TW200300774A

TW200300774A - Stabilization of dispersions of halogen-containing polymers

Info

Publication number: TW200300774A
Application number: TW91134859A
Authority: TW
Inventors: Karl-Josef Kuhn; Hans-Helmut Friedrich; Kornelia Malzacher
Original assignee: Crompton Vinyl Additives Gmbh
Priority date: 2001-12-04
Filing date: 2002-11-29
Publication date: 2003-06-16
Also published as: AR037617A1; WO2003048233A1; GT200200254A; AU2002361969A1

Abstract

The invention relates to a process for stabilizing halogen-containing polymers in aqueous dispersion by adding a stabilizer mixture compatible with the polymer dispersion, and also to polymer dispersions stabilized by this process, and to their use in the coating of articles.

Description

200300774 玖、發明說明【發明所屬之技術領域】本發明係關於一種藉由添加與聚合物分散液相容的安定劑混合物來安定水性懸浮液中之含鹵聚合物的方法，亦關於藉此方法所安定的聚合物分散液，以及關於它們在物件塗佈方面的用途。【先前技術】迄今一直不可能將熱成形方法直接用於含鹵聚合物之分散液（大部分是但非完全是水性），例如PVC淤漿上。含鹵聚合物原有的熱不安定性對此類型方法而言是一大障礙，而另一個存在因素的例子是作用爲降解催化劑之水的存在。一直無法得到可使聚合反應期間所製得之水性聚合物分散液可直接加工的水溶性聚合物安定劑。習用安定劑，例如金屬皂或錫安定劑，在水性聚合物分散液的直接加工方面是失敗的，可能只是因爲在水中的不溶性或與水的不相容性或是水解的立即開始。有許多可安定PVC的添加劑。重金屬鉛、鋇及鎘之化合物特別適合此目的之用，但現今因環境因素或由於其重金屬含量而有所爭議；亦已知有其他以Ca/Zn或錫爲主或是以有機材料爲主的安定化系統，但因上述原因而無法用於預安定作用中（參見”塑膠添加劑（Kunststoffadditive)”， R. Gachter/H. Muller，Carl Hanser 出版社，第 3 版，1989，第303_311頁（亦見2001年的第4版）；”塑膠手冊PVC (Kunststoff Handbuch PVC)，，，第 2/1 卷，W. Becker/D. Braun 200300774 ，Carl Hansei·出版社，第 2 版，1985，第 531-538 頁；及 Kirk-〇thmer·· “化學技術百科全書（Encyclopedia of Chemical Technology)”，第4版，1994，第12卷，熱安定劑，第 1071-1091 頁）。【發明內容】本發明之目的是提供一種安定含鹵聚合物之分散液的方法。本發明提供一種安定水性分散液中之含鹵聚合物的方法，其中係將與聚合物分散液相容的安定劑混合物添加至含鹵聚合物之水性分散液中。特別適合的安定劑混合物包含過氯酸鹽化合物及/或烷醇胺及/或此等的鹽類。可根據本發明使用的安定劑混合物係與大部分的水性聚合物分散液相容，或甚至可溶於其中，且對聚合物之分散液沒有任何不利的效應，例如分散液的破壞（凝結）。就本發明之目的而言，分散液一詞亦包括懸浮液、膠體系統及乳化液。此處的分散液（或懸浮液、膠體系統或乳化液）爲含鹵聚合物在適當分散或懸浮媒質中者，正如在 SPVC、微SPVC或EPVC生產中所產生者。本發明方法的提供現今使得第一次有可能實現例如未經增塑之PVC覆蓋物與塗層，而無需事先乾燥PVC粉末且無需使用增塑劑。不過，本發明之安定方法亦可在增塑劑或潤滑劑存在下應用，只要這些不會破壞聚合物分散液即可。本發明方法所提出的安定劑系統係在聚合反應之後用 200300774 於聚合物分散液中，或者是在聚合程序之前或期間使用。200300774 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for stabilizing a halogen-containing polymer in an aqueous suspension by adding a stabilizer mixture compatible with the polymer dispersion, and also to a method by which Stabilized polymer dispersions and their use in coating objects. [Prior art] Until now, it has not been possible to apply the thermoforming method directly to a dispersion (mostly but not completely water) of a halogen-containing polymer, such as a PVC slurry. The inherent thermal instability of halogen-containing polymers is a major obstacle to this type of process, and another example of a factor is the presence of water acting as a degradation catalyst. Water-soluble polymer stabilizers which allow the aqueous polymer dispersion prepared during the polymerization to be directly processed have not been obtained. Conventional stabilizers, such as metal soaps or tin stabilizers, have failed in the direct processing of aqueous polymer dispersions, possibly simply because of insolubility in water or incompatibility with water or the immediate start of hydrolysis. There are many additives that stabilize PVC. Compounds of heavy metals lead, barium, and cadmium are particularly suitable for this purpose, but are currently controversial due to environmental factors or due to their heavy metal content; other Ca / Zn or tin-based or organic materials are also known Stabilization system, but cannot be used for pre-stabilization due to the above reasons (see "Kunststoffadditive", R. Gachter / H. Muller, Carl Hanser Press, 3rd edition, 1989, pp. 303_311 ( See also 4th edition 2001); "Plastic Handbook PVC (Kunststoff Handbuch PVC)," Vol. 2/1, W. Becker / D. Braun 200300774, Carl Hansei · Press, 2nd Edition, 1985, No. 531-538 pages; and Kirk-〇thmer · "Encyclopedia of Chemical Technology", 4th edition, 1994, vol. 12, thermal stabilizer, pages 1071-1091) [Contents of the invention] The purpose of the present invention is to provide a method for stabilizing a dispersion of a halogen-containing polymer. The present invention provides a method for stabilizing a halogen-containing polymer in an aqueous dispersion, wherein a stabilizer compatible with the polymer dispersion is mixed Addition to aqueous dispersions of halogen-containing polymers. Particularly suitable stabilizer mixtures include perchlorate compounds and / or alkanolamines and / or these salts. The stabilizer mixtures which can be used according to the invention are Most aqueous polymer dispersions are compatible, or even soluble in them, without any adverse effects on the polymer dispersion, such as destruction (coagulation) of the dispersion. For the purposes of the present invention, dispersions The term also includes suspensions, colloidal systems, and emulsions. Dispersions (or suspensions, colloidal systems, or emulsions) here are those containing halogenated polymers in a suitable dispersion or suspension medium, as in SPVC, micro SPVC, or Produced in EPVC production. The provision of the method of the present invention now makes it possible for the first time to achieve, for example, unplasticized PVC coverings and coatings without the need to dry the PVC powder in advance and without the use of plasticizers. However, the present invention The stabilization method can also be applied in the presence of plasticizers or lubricants, as long as these do not damage the polymer dispersion. The stabilizer system proposed in the method of the present invention is a polymerization The polymer dispersion, or during or after the use should be used prior to the polymerization procedure 200,300,774.

所得安定PVC分散液，同樣係由本發明所提供者，可藉由噴霧裝置或刮刀，或者是藉由熱熔輥而使用於所欲塗佈之物件上，且可經熱處理以除去黏附的分散媒質（例如水）。熱處理同時使聚合物熔化、燒結或凝膠於所欲塗佈之物件上。本方法產物的實例爲施於木材、毛氈、紙材、金屬等之上的聚合物塗層，例如藉由將所提及材料浸漬於聚合物分散液（淤漿）中，然後（短暫地）在高溫下乾燥。因此本發明亦包括本發明聚合物於生產物件與塗層方面的用途。【實施方式】現在已經發現，由至少一種通式（I)烷醇胺及/或至少一種過氯酸鹽（特別是鹼土金屬過氯酸鹽或鹼金屬過氯酸鹽 )所組成的系統，特別適合所述用來安定含鹵聚合物（尤其是PVC)的方法。The obtained stable PVC dispersion liquid is also provided by the present invention, and can be used on the object to be coated by a spray device or a doctor blade, or by a hot-melt roller, and can be heat-treated to remove the adhered dispersion medium. (E.g. water). Heat treatment also melts, sinters, or gels the polymer onto the object to be coated. Examples of products of this method are polymer coatings applied to wood, felt, paper, metal, etc., for example by immersing the mentioned material in a polymer dispersion (slurry) and then (temporarily) Dry at high temperature. The invention therefore also includes the use of the polymers of the invention in the production of articles and coatings. [Embodiment] It has now been found that a system consisting of at least one alkanolamine of the general formula (I) and / or at least one perchlorate (especially alkaline earth metal perchlorate or alkali metal perchlorate), It is particularly suitable for the method described for stabilizing halogen-containing polymers, especially PVC.

本發明因此提供一種安定水性分散液中之含鹵聚合物的方法，其中係將安定劑混合物添加至含鹵聚合物之水性分散液中，該安定劑混合物至少包含： a) —種過氯酸鹽，及/或 b) —種下式⑴之烷醇胺 R2 Η 一議 Ή χ 200300774 其中 1、2 或 3 ; y= 1、2、3、4、5 或 6 ; n= 1至1〇；The present invention therefore provides a method for stabilizing a halogen-containing polymer in an aqueous dispersion, wherein a stabilizer mixture is added to the aqueous dispersion of the halogen-containing polymer, the stabilizer mixture comprising at least: a) a perchloric acid Salt, and / or b)-an alkanolamine R2 of the formula Η Ή 200300774 where 1,2 or 3; y = 1, 2, 3, 4, 5 or 6; n = 1 to 1〇 ;

Ri和R2彼此獨立地=Η、CVC22·烷基、-[-((：服3丄-CHR3b-〇-]n_H、-[-(CHR3a)y-CHR3b-〇_]n-C〇-R4、C2-C20-烯基、 C2-C18-醯基、c4_c8-環烷基（其可在β_位上具有〇H取代度 )、C6-C1Q-芳基、C7-C1(r烷芳基或（VG。-芳烷基，或者，若x=l ’ R1與R2亦可與N —起形成一個4至10員的封閉環’其係由碳原子與（適當時）至高2個雜原子所組成，或者，若x=2，Ri亦可爲C2-C18-伸烷基，其在兩β-碳原子上可具有〇Η取代度及/或可被一或多個〇原子及/或一或多個NR2基團中斷，或爲經二羥基取代之四氫伸聯環戊二烯基、經二羥基取代之乙基伸環己基、經二羥基取代之伸 4,4’-(雙酚Α二丙基醚）基、伸異佛爾酮基、二甲基伸環己基、二環己基亞甲基或3,3’-二甲基二環己基亞甲基，以及若x = 3 ’則R1亦可爲經三羥基取代之（異氰脲酸三丙酯）二基； R3a與R3b彼此獨立地= CrC22-烷基、C2-C6-烯基、C6-C10·芳基、Η或CH2-X-R5，其中X=〇、s、-〇-C〇-或-C〇-〇- R4=CrC18-烷基/烯基或苯基；及 R5 = Η、CrC22-烷基、C2-C22-烯基或 C6-C1(r芳基，及/ 200300774 c) a)與b)的鹽。本發明進一步提供一種其中使用安定劑混合物的安定化方法，該安定劑混合物至少包含： a) —種過氯酸鹽，及/或 b) —種單或多官能環氧化物與氨或分別與單或多官能二烷基（芳基）或單烷基（芳基）胺的反應產物，及/或 c) a)與b)的鹽。通式⑴烷醇胺之實例爲其中R1與R2=甲基、乙基、丙基、丁基、環己基、辛基、月桂基、十四烷基、十六烷基、硬脂基、油基、烯丙基、苯基或基或羥烷基且R3=H 、甲基、乙基、丙基或丁基之化合物。優先選擇係給予其中Ri =月桂基、十四烷基、十六烷基、硬脂基、油基且其中R2=羥烷基之烷醇胺。亦可能使用三乙醇胺和三異丙醇胺以及植物或動物來源之脂肪胺的乙氧基化物和丙氧基化物。優先選擇係給予其中R3 = Η或甲基且y = 1之三院醇胺和單烷基/烯基二烷醇胺，特別是已經與氧化乙烯或與氧化丙烯反應二次之脂肪胺。其他具有非常高度適合性的化合物可見於下列淸單。與氧化乙烯或氧化丙烯反應一次或二次之甲胺或二甲胺。與氧化乙烯或氧化丙烯反應一次或二次之丙胺或二丙胺。與氧化乙烯或氧化丙烯反應一次或二次之異丙胺或二異丙胺。 200300774 與氧化乙烯或氧化丙烯反應一次或二次之丁胺或二丁胺。與氧化乙烯或氧化丙烯反應一次或二次之異丁胺或二異丁胺。與氧化乙烯或氧化丙烯反應一次或二次之戊胺或二戊胺。與氧化乙烯或氧化丙烯反應一次或二次之異戊胺或二異戊胺。與氧化乙烯或氧化丙烯反應一次或二次之己胺或二己胺。與氧化乙烯或氧化丙烯反應一次或二次之異己胺或二異己胺。與氧化乙烯或氧化丙烯反應一次或二次之庚胺或二庚胺。與氧化乙烯或氧化丙烯反應一次或二次之異庚胺或二異庚胺。與氧化乙烯或氧化丙烯反應一次或二次之辛胺或二辛胺。與氧化乙烯或氧化丙烯反應一次或二次之異辛胺或二異辛胺。與氧化乙烯或氧化丙烯反應一次或二次之壬胺或二壬胺。與氧化乙烯或氧化丙烯反應一次或二次之異壬胺或二異壬胺。 11 200300774 與氧化乙烯或氧化丙烯反應一次或二次之癸胺或二癸胺。與氧化乙烯或氧化丙烯反應一次或二次之異癸胺或二異癸胺。與氧化乙烯或氧化丙烯反應一次或二次之十一胺或雙十一胺。與氧化乙烯或氧化丙烯反應一次或二次之異十一胺或二異十一胺。與氧化乙烯或氧化丙烯反應一次或二次之十二胺或雙十二胺。與氧化乙烯或氧化丙烯反應一次或二次之異十二胺或二異十二胺。與氧化乙烯或氧化丙烯反應一次或二次之十三胺或雙十三胺。與氧化乙烯或氧化丙烯反應一次或二次之異十三胺或二異十三胺。與氧化乙烯或氧化丙烯反應一次或二次之十四胺或雙十四胺。與氧化乙烯或氧化丙烯反應一次或二次之十六胺或雙十六胺。與氧化乙烯或氧化丙烯反應一次或二次之十八胺或雙十八胺。與氧化乙烯或氧化丙烯反應一次或二次之二十胺或雙二十胺。 12 200300774 與氧化乙烯或氧化丙烯反應一次或二次之二十二胺或雙二十二胺。與氧化乙烯或氧化丙烯反應一次或二次之N-甲基丁胺。與氧化乙烯或氧化丙烯反應一次或二次之N-乙基丁胺。與氧化乙烯或氧化丙烯反應一次或二次之烯丙胺或二烯丙胺。與氧化乙烯或氧化丙烯反應一次或二次之巴豆胺或二巴豆胺。與氧化乙烯或氧化丙烯反應一次或二次之十八烯胺或雙十八烯胺。與氧化乙烯或氧化丙烯反應一次或二次之胺或二胺。與氧化乙烯或氧化丙烯反應一次或二次之環己胺或二環己胺。與氧化乙烯或氧化丙烯反應一次或二次之N-甲基環己胺。與氧化乙烯或氧化丙烯反應一次或二次之N-乙基環己胺。與二乙醇胺或二異丙醇胺反應二次之雙環氧化4-乙烯基-1-環己烯。與二乙醇胺或二異丙醇胺反應二次之雙環氧化二聚環戊二烯。與二乙醇胺或二異丙醇胺反應二次之雙酚A二縮水甘油醚。 13 200300774 與二乙醇胺或二異丙醇胺反應二次之異氰脲酸三縮水甘油酯。優先選擇係給予其中R3a與R3b彼此獨立地=H或甲基且y = 1的三烷醇胺和單烷基/烯基二烷醇胺。其中y = 1至6之通式（I)化合物，亦即在胺基與經羥基取代之碳原子之間含有至高6個亞甲基者，已經被發現適合配合過氯酸鹽用作PVC安定劑。根據本發明，亦可能使用是其中x=2之通式（I)化合物，亦即每分子含有二個羥烷基胺基的化合物。這些化合物的實例包括：N，N，N’，N’-肆（2-羥乙基）伸乙基二胺、 N，N，N’，N’-肆（2-羥基-1-丙基）伸乙基二胺、N，N，N’，N’-肆（2-羥乙基）伸丙基二胺和N，N，N’，N’-肆（2-羥基-1-丙基）伸丙基二胺及N，N，N’，N’-肆（2-羥乙基）伸己基二胺，優先選擇係給予1,6-伸己基二胺或1，8-伸辛基二胺或新戊烷二胺與氧化乙烯或與氧化丙烯之四次反應，或是雙胺基甲基環己烷或異佛爾酮二胺或4,4’-二胺基二環己基甲烷或3,3’-二甲基-4,4’-二胺基二環己基甲烷之類似反應。根據本發明，亦可能使用其中X= 3之通式（I)化合物，亦即每分子含有三個羥烷基胺基者。這些化合物的一個實例爲異氰脲酸三縮水甘油酯與單或二乙醇胺或單或二丙醇胺之反應產物。通式⑴烷醇胺爲可購得之化學品，或可藉已知方法經由適當胺或氨的N-烷基化反應而製得（參見Kirk & Othmer ，第2卷，烷醇胺）。 14 200300774 較佳的通式（I)烷醇胺的實例有：參（2-羥基乙基）胺、參 (2-羥基_1_丙基）胺、雙（2-羥基乙基）-2-羥基-1-丙胺、N-正丁基-N，N-雙（2-羥基乙基）胺、N，N-雙（正丁基）二（2-羥基乙基）胺、N-(3_正丁氧基-2-羥基-1-丙基）-N，N-雙（2·羥基乙基）胺、N-(l，3-二羥基-2-羥基甲基-2-丙基）-N，N-雙（2-羥基乙基) 胺、Ν，Ν·雙（2-羥基乙基）_N-棕櫚胺、N，N-雙（2-羥基乙基）-N-油胺、N，N-雙（2-羥基乙基）-义硬脂胺、N，N-雙（2-羥基乙基）-N-硬脂胺、N-(2-羥基乙基）嗎啉與N-(2,3-二羥基-1-丙基）嗎啉、雙羥乙基呢啡和雙羥異丙基派啡，及縮水甘油醚與單或二烷基胺或氨之反應產物，以及自其衍生之烷醇胺，如乙醇胺、二乙醇胺、單與二正丙醇胺及單與二異丙醇胺。極特別優先選擇係給予烯烴氧化物如氧化辛烯、氧化癸烯、氧化十二烯、氧化十四嫌、氧化十六烯、氧化十八烯、氧化二十烯和氧化二十二烯及環氧硬脂醇等與二乙醇胺或二異丙醇胺之加成產物。這些化合物在相當長烷基鏈的兩端之β-位上具有OH官能度，舉例而言’ N-(2-羥基十六烷基）二乙醇胺、N-(2-羥基-3-辛氧基丙基）)二乙醇胺、N-(2-羥基-3-癸氧基丙基）二乙醇胺、N-(2-羥基-3-辛氧基丙基）二乙醇胺及雙-N-(2-羥基-3_苯氧基丙基）乙醇胺爲本發明安定劑系統中特別適合的成份。此淸單僅供作實例。過氯酸鹽爲熟諳此技藝者所已知者。實例爲具有分子式 M(Cl〇4)n 者，其中 Μ 爲H、Li、Na、K、Mg、Ca、Sr、 Ba、Ζη、Al、La、Ce或ΝΗ4 ; η依Μ之價數戶斤需而爲1、2 15 ΡΠ500774 或3 ◦當使用水性分散系統時，亦可使用過氯酸或以媒質中的活性成份形成此物。在此可使用過氯酸鹽之各種常用供應形式（調配物） :例如鹽或溶於水或有機溶劑中之溶液。這些過氯酸鹽調配物的其他實例爲利用醇類（多元醇、環糊精）或利用醚醇類或酯醇類或冠醚使之溶解或錯合的過氯酸鹽，而另一個實例是過氯酸的稀薄水溶液。其他具體實例係敘述於EP 0 394 547、EP 0 457 471 和 W〇 94/24200 中。最好係使用鈉/鉀過氯酸鹽。所定義過氯酸乙醇銨鹽類於抑制含氯樹脂脫色作用的用途亦已經揭示於JP-A 61-9457中，而用於”非水性”PVC 安定化。這些過氯酸鹽具有銨鹽結構，且可藉由將一級、二級或三及乙醇胺添加至過氯酸溶液中而獲得。此應用亦使得經由根據本發明使用溶解的水性安定劑系統而可第一次無風險地使用過氯酸銨。本發明亦提供一種安定化方法，其中包含至少一種過氯酸鹽與至少一種通式⑴化合物之安定劑混合物的組合，係配合至少一種其他習用添加劑或安定劑來使用。優先選擇係給予多元醇與雙糖醇、菱水鎂鋁石、沸石（鹼金屬或鹼土金屬的鋁矽酸鹽）、塡料、金屬皂、鹼金屬或鹼土金屬的其他化合物、染料、均染助劑、潤滑劑、增塑劑、顏料、環氧化脂肪酯與其他環氧化合物、抗氧化劑、UV吸收劑、光安定劑、螢光增白劑及發泡劑。類似聚合物者，這些添加劑或其他安定劑可細微地分 16 200300774 佈於分散液中，因而可經由後續的進一步加工而均勻地混入聚合物中。所使用成份之可能反應產物亦爲所包含者。這些外加成份之實例係在下文中列舉與解釋（參見E. J. Wickson 所著之 “PVC 調配手冊 ”(Handbo〇k of PVC Formulating, John Wiley & Sons, New York 1993)) o 多元醇與雙糖醇此類之可能化合物的實例有：新戊四醇、二新戊四醇、三新戊四醇、三羥甲基乙烷、雙（三羥甲基丙烷）、聚乙烯醇、雙（三羥甲基乙烷）、三羥甲基丙烷、糖類、糖醇。當然，優先選擇係給予雙糖醇。亦可能使用多元醇糖漿，如山梨醇糖漿、甘露糖醇糖漿及麥芽糖醇糖漿。以100重量份PVC爲基準，多元醇用量之實例爲0.01至20重量份，最好是0.1至20重量份，且尤其是0.1至10重量份。菱水鎂鋁石這些化合物之化學組成爲熟諳此技藝者已知，例如得知於專利 DE 3 843 58卜 US 4,000，100、EP 0 062 813 及 W〇 93/20135 。得自菱水鎂鋁石系列之化合物可由下通式描述： M2+ 1.xM3+x(OH)2 (Ab-)x/b · d H20 ^ 其中 M2+ =—或多種選自Mg、Ca、Sr、Zn及Sn所成群組之金屬， 17 200300774 M3+ = A1 或 B，Ri and R2 are independently of each other = Η, CVC22 · alkyl,-[-((: server 3 丄 -CHR3b-〇-] n_H,-[-(CHR3a) y-CHR3b-〇_] nC〇-R4, C2 -C20-alkenyl, C2-C18-fluorenyl, c4-c8-cycloalkyl (which may have a degree of substitution of 0H at the β-position), C6-C1Q-aryl, C7-C1 (r alkylaryl or ( VG. -Aralkyl, or, if x = l 'R1 and R2 can also form a closed ring of 4 to 10 members with N', which consists of a carbon atom and (where appropriate) up to 2 heteroatoms Or, if x = 2, Ri may also be C2-C18-alkylene, which may have a degree of substitution of 0 on two β-carbon atoms and / or may be substituted by one or more 0 atoms and / or one or Multiple NR2 groups are interrupted, or tetrahydroextended cyclopentadienyl substituted with dihydroxy, ethylcyclohexyl substituted with dihydroxy, and 4,4 '-(bisphenol A disubstituted with dihydroxy substituted Propyl ether), isophorone, dimethylcyclohexyl, dicyclohexylmethylene or 3,3'-dimethyldicyclohexylmethylene, and if x = 3 'then R1 It may also be a tri-substituted (tripropyl isocyanurate) diyl group; R3a and R3b are independent of each other = CrC22-alkyl, C2-C6-alkenyl, C 6-C10 · aryl, hydrazone, or CH2-X-R5, where X = 0, s, -0-C〇- or -C〇-〇- R4 = CrC18-alkyl / alkenyl or phenyl; = Hydrazone, CrC22-alkyl, C2-C22-alkenyl or C6-C1 (raryl, and / 200300774 c) a) and b) salts. The present invention further provides a stabilization method in which a stabilizer mixture is used The stabilizer mixture contains at least: a) a perchlorate, and / or b) a mono- or polyfunctional epoxide with ammonia or with a mono- or polyfunctional dialkyl (aryl) or monoalkane, respectively. (Aryl) amine reaction products, and / or c) a) and b) salts. Examples of the general pinanolamines are where R1 and R2 = methyl, ethyl, propyl, butyl, cyclohexyl, octyl, lauryl, tetradecyl, cetyl, stearyl, oil Compounds based on alkyl, allyl, phenyl, or hydroxyalkyl, and R3 = H, methyl, ethyl, propyl, or butyl. Preference is given to alkanolamines where Ri = lauryl, tetradecyl, cetyl, stearyl, oleyl and R2 = hydroxyalkyl. It is also possible to use triethanolamine and triisopropanolamine and ethoxylates and propoxylates of fatty amines of vegetable or animal origin. Preference is given to tertiary alcohol amines and monoalkyl / alkenyl dialkanolamines where R3 = hydrazone or methyl and y = 1, especially fatty amines that have reacted twice with ethylene oxide or with propylene oxide. Other compounds with very high suitability can be found in the following list. Methylamine or dimethylamine which reacts once or twice with ethylene oxide or propylene oxide. Propylamine or dipropylamine which reacts once or twice with ethylene oxide or propylene oxide. Isopropylamine or diisopropylamine which reacts once or twice with ethylene oxide or propylene oxide. 200300774 One or two reactions of butylamine or dibutylamine with ethylene oxide or propylene oxide. Isobutylamine or diisobutylamine which reacts once or twice with ethylene oxide or propylene oxide. Pentylamine or dipentylamine which reacts once or twice with ethylene oxide or propylene oxide. Isoamylamine or diisoamylamine reacted once or twice with ethylene oxide or propylene oxide. Hexylamine or dihexylamine reacted once or twice with ethylene oxide or propylene oxide. Isohexylamine or diisohexylamine reacted once or twice with ethylene oxide or propylene oxide. Heptylamine or diheptylamine which reacts once or twice with ethylene oxide or propylene oxide. Isoheptylamine or diisoheptylamine which reacts once or twice with ethylene oxide or propylene oxide. Octylamine or dioctylamine reacted once or twice with ethylene oxide or propylene oxide. Isooctylamine or diisooctylamine which reacts once or twice with ethylene oxide or propylene oxide. Nonylamine or dinonylamine that reacts once or twice with ethylene oxide or propylene oxide. Isononylamine or diisononylamine that reacts once or twice with ethylene oxide or propylene oxide. 11 200300774 One or two reactions of decylamine or didecylamine with ethylene oxide or propylene oxide. Isodecylamine or diisodecylamine which is reacted once or twice with ethylene oxide or propylene oxide. Undecylamine or bisundecylamine reacted once or twice with ethylene oxide or propylene oxide. Isoundecylamine or diisoundecylamine reacted once or twice with ethylene oxide or propylene oxide. Dodecylamine or dodecylamine which reacts once or twice with ethylene oxide or propylene oxide. Isododecylamine or diisododecylamine which is reacted once or twice with ethylene oxide or propylene oxide. Tridecylamine or bistridecylamine reacted once or twice with ethylene oxide or propylene oxide. Isotridecylamine or diisotridecylamine reacted once or twice with ethylene oxide or propylene oxide. Tetradecylamine or ditetradecylamine reacted once or twice with ethylene oxide or propylene oxide. Hexadecylamine or bishexadecylamine reacted once or twice with ethylene oxide or propylene oxide. Octadecylamine or octadecylamine reacted once or twice with ethylene oxide or propylene oxide. Eicosylamine or diicosylamine reacted once or twice with ethylene oxide or propylene oxide. 12 200300774 One or two reactions of behenylamine or biscosenediamine with ethylene oxide or propylene oxide. N-methylbutylamine which reacts once or twice with ethylene oxide or propylene oxide. N-ethylbutylamine which reacts once or twice with ethylene oxide or propylene oxide. Allylamine or diallylamine which reacts once or twice with ethylene oxide or propylene oxide. Crotamine or dicrotamine which reacts once or twice with ethylene oxide or propylene oxide. Octadecenylamine or dioctadecenylamine reacted once or twice with ethylene oxide or propylene oxide. An amine or diamine that reacts once or twice with ethylene oxide or propylene oxide. Cyclohexylamine or dicyclohexylamine which reacts once or twice with ethylene oxide or propylene oxide. N-methylcyclohexylamine reacted once or twice with ethylene oxide or propylene oxide. N-ethylcyclohexylamine reacted once or twice with ethylene oxide or propylene oxide. Bi-epoxidized 4-vinyl-1-cyclohexene reacted twice with diethanolamine or diisopropanolamine. Diepoxidized dicyclopentadiene which reacts with diethanolamine or diisopropanolamine twice. Bisphenol A diglycidyl ether reacted twice with diethanolamine or diisopropanolamine. 13 200300774 Triglycidyl isocyanurate which reacts with diethanolamine or diisopropanolamine twice. Preference is given to trialkanolamines and monoalkyl / alkenyldialkanolamines where R3a and R3b are independently H or methyl and y = 1. Compounds of general formula (I) in which y = 1 to 6, that is, those containing up to 6 methylene groups between an amine group and a carbon atom substituted with a hydroxyl group, have been found suitable for use with PVC as a stabilizer Agent. According to the invention, it is also possible to use compounds of the general formula (I) in which x = 2, i.e. compounds containing two hydroxyalkylamino groups per molecule. Examples of these compounds include: N, N, N ', N'-Di (2-hydroxyethyl) ethylenediamine, N, N, N', N'-Di (2-hydroxy-1-propyl) ) Ethylenediamine, N, N, N ', N'-methyl (2-hydroxyethyl) propylenediamine and N, N, N', N'-methyl (2-hydroxy-1-propane) Phenyldiamine and N, N, N ', N'-(2-hydroxyethyl) hexyldiamine, preference is given to 1,6-hexyldiamine or 1,8-heptane Four reactions of ethylenediamine or neopentanediamine with ethylene oxide or with propylene oxide, or bisaminomethylcyclohexane or isophoronediamine or 4,4'-diaminodicyclohexyl Similar reactions with methane or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane. According to the invention, it is also possible to use compounds of the general formula (I) in which X = 3, that is, those containing three hydroxyalkylamine groups per molecule. An example of these compounds is the reaction product of triglycidyl isocyanurate and mono- or diethanolamine or mono- or dipropanolamine. Pinanolamines of the general formula are either commercially available chemicals or can be prepared by known methods via N-alkylation of an appropriate amine or ammonia (see Kirk & Othmer, Volume 2, alkanolamines) . 14 200300774 Examples of preferred alkanolamines of the general formula (I) are: ginseng (2-hydroxyethyl) amine, ginseng (2-hydroxy_1_propyl) amine, bis (2-hydroxyethyl) -2 -Hydroxy-1-propylamine, N-n-butyl-N, N-bis (2-hydroxyethyl) amine, N, N-bis (n-butyl) bis (2-hydroxyethyl) amine, N- ( 3-n-butoxy-2-hydroxy-1-propyl) -N, N-bis (2 · hydroxyethyl) amine, N- (l, 3-dihydroxy-2-hydroxymethyl-2-propane -N, N-bis (2-hydroxyethyl) amine, N, N · bis (2-hydroxyethyl) _N-palmamine, N, N-bis (2-hydroxyethyl) -N-oil Amine, N, N-bis (2-hydroxyethyl) -stearylamine, N, N-bis (2-hydroxyethyl) -N-stearylamine, N- (2-hydroxyethyl) morpholine Reaction products with N- (2,3-dihydroxy-1-propyl) morpholine, bishydroxyethylmorphine and bisisopropylpyrophine, and glycidyl ether with mono- or dialkylamine or ammonia , And alkanolamines derived from it, such as ethanolamine, diethanolamine, mono- and di-n-propanolamine, and mono- and diisopropanolamine. Very particular preference is given to olefin oxides such as octene oxide, decene oxide, dodecene oxide, tetradecyl oxide, hexadecene oxide, octadecyl oxide, eicosene oxide and docosadiene oxide and cyclic Addition products of oxystearyl alcohol and diethanolamine or diisopropanolamine. These compounds have OH functionality at the β-positions at both ends of a fairly long alkyl chain, such as' N- (2-hydroxyhexadecyl) diethanolamine, N- (2-hydroxy-3-octyloxy) Propyl)) diethanolamine, N- (2-hydroxy-3-decoxypropyl) diethanolamine, N- (2-hydroxy-3-octyloxypropyl) diethanolamine and bis-N- (2 -Hydroxy-3_phenoxypropyl) ethanolamine is a particularly suitable ingredient in the stabilizer system of the present invention. This list is for example only. Perchlorate is known to those skilled in the art. Examples are those with the molecular formula M (ClO4) n, where M is H, Li, Na, K, Mg, Ca, Sr, Ba, Zη, Al, La, Ce or ΝΗ4; η depends on the price of M Need to be 1, 2 15 Π 500774 or 3 ◦ When using an aqueous dispersion system, it can also be formed using perchloric acid or the active ingredients in the medium. Various common supply forms (formulations) of perchlorate can be used here: for example, salts or solutions dissolved in water or organic solvents. Other examples of these perchlorate formulations are perchlorates that are dissolved or complexed with alcohols (polyols, cyclodextrins) or with ether alcohols or ester alcohols or crown ethers, while another example It is a thin aqueous solution of perchloric acid. Other specific examples are described in EP 0 394 547, EP 0 457 471 and WO 94/24200. It is best to use sodium / potassium perchlorate. The use of the defined ammonium perchlorate ethanol salts to inhibit the decolorization of chlorine-containing resins has also been disclosed in JP-A 61-9457, and is used for the stabilization of "non-aqueous" PVC. These perchlorates have an ammonium salt structure and can be obtained by adding primary, secondary or tri- and ethanolamines to a perchloric acid solution. This application also makes it possible to use ammonium perchlorate for the first time without risk via the use of a dissolved aqueous stabilizer system according to the invention. The invention also provides a stabilization method, which comprises a combination of a stabilizer mixture of at least one perchlorate and at least one compound of the general formula VII, which is used in combination with at least one other conventional additive or stabilizer. Preference is given to polyols and disaccharide alcohols, magnesite, zeolites (alkali or alkaline earth metal aluminosilicates), fodder, metal soaps, other compounds of alkali or alkaline earth metals, dyes, levelling Additives, lubricants, plasticizers, pigments, epoxidized fatty esters and other epoxy compounds, antioxidants, UV absorbers, light stabilizers, fluorescent whitening agents and foaming agents. Similar to polymers, these additives or other stabilizers can be finely divided into the dispersion 16 200300774 and can be uniformly mixed into the polymer through subsequent further processing. The possible reaction products of the ingredients used are also included. Examples of these additional ingredients are listed and explained below (see "Handbook of PVC Formulating by John J. Wickson" (HandboOk of PVC Formulating, John Wiley & Sons, New York 1993)) o Polyols and disaccharides Examples of such possible compounds are: neopentaerythritol, dipentaerythritol, trinepentaerythritol, trimethylolethane, bis (trimethylolpropane), polyvinyl alcohol, bis (trimethylol) Ethane), trimethylolpropane, sugars, sugar alcohols. Of course, preference is given to disaccharide alcohol. Polyol syrups such as sorbitol syrup, mannitol syrup, and maltitol syrup are also possible. Examples of the amount of the polyol used are 0.01 to 20 parts by weight, preferably 0.1 to 20 parts by weight, and especially 0.1 to 10 parts by weight based on 100 parts by weight of PVC. Magnesite. The chemical composition of these compounds is known to those skilled in the art, for example in patents DE 3 843 58 and US 4,000,100, EP 0 062 813 and WO 93/20135. The compound obtained from the magnesite series can be described by the formula: M2 + 1.xM3 + x (OH) 2 (Ab-) x / b · d H20 ^ where M2 + = — or more selected from Mg, Ca, Sr Metals in the group of Zn, Zn and Sn, 17 200300774 M3 + = A1 or B,

An 價數n之陰離子， b爲1至2之數， 0 < x < 0.5， d爲0至20之數。優先選擇係給予其中An anion with an valence n, b is a number from 1 to 2, 0 < x < 0.5, and d is a number from 0 to 20. Preference is given to them

An 二〇H_、Cl〇4_、HC〇3-、CH3C〇〇-、C6H5C〇Cr、 C〇32- 、（CH〇HC〇〇）22- 、（CH2C〇〇）22- 、 CH3CH〇HC〇〇-、 hp〇3·或HP〇42·之化合物。菱水鎂鋁石之實例有：An ２〇H_, Cl〇4_, HC〇3-, CH3CO〇-, C6H5 CoCr, Co32-, (CH〇HC〇〇) 22-, (CH2C〇) 22-, CH3CH〇HC. 〇-, hp〇3 · or HP〇42 · compounds. Examples of magnesite are:

Al2〇3.6Mg〇.C〇2.12H2〇（i)、Mg4.5Al2(〇H)13.C〇3.3.5H2〇 (ii)、4Mg〇.Al2〇3.C〇2_9H2〇（iii)、4Mg〇.Al2〇3.C〇2.6H2〇、 Zn03Mg〇_Al2〇3.C〇2_8-9H2〇及 Zn〇*3Mg〇，Al2(VC〇2.5-6H2〇。極特別優先選擇係給予下列種類：Alkamizer 2、 Alkamizer P 93_2 (得自Kyowa)及L-CAM (經鋰改性之菱水鎂錯石，得自富士（Fuji))。最好使用無水菱水鏡鋁石。沸石（鹼金屬及/或鹼土金屬之鋁矽酸鹽此等可由通式Mx/n[(Al〇2)x(Si〇2)y]_wH2〇描述，其中η 爲陽離子Μ上之價數； Μ爲第一或第二主族的元素，例如Li、Na、Κ、Mg、 Ca、Sr 或 Ba ; y : x爲0.8至15之數，較佳爲0.8至1.2 ;及 w爲0至300之數，較佳爲0.5至30。沸石之實例爲下列各式之鈉鋁矽酸鹽： 18 200300774Al2〇3.6Mg.CO2.2.1H2O (i), Mg4.5Al2 (〇H) 13.C3.3.5H2O (ii), 4Mg0.Al2O3.C2_9H2O (iii), 4Mg 〇.Al2〇3.C〇2.6H2〇, Zn03Mg〇_Al2〇3.C〇2_8-9H2〇 and Zn〇 * 3Mg〇, Al2 (VC〇2.5-6H2〇. Very special preference is given to the following categories: Alkamizer 2, Alkamizer P 93_2 (available from Kyowa) and L-CAM (lithium-modified rhodochrosite, obtained from Fuji). Anhydrous rhodochroite is preferred. Zeolite (alkali metal and / Or alkaline earth metal aluminosilicates. These can be described by the general formula Mx / n [(Al〇2) x (Si〇2) y] _wH2〇, where η is the valence on the cation M; M is the first or the first Elements of the two main groups, such as Li, Na, K, Mg, Ca, Sr, or Ba; y: x is a number from 0.8 to 15, preferably 0.8 to 1.2; and w is a number from 0 to 300, preferably 0.5 to 30. Examples of zeolites are the following sodium aluminosilicates: 18 200300774

Na12Al12Si12〇48.27 H2〇[沸石 A] ; Na6Al6Si6〇24.2 NaX.7.5 H2〇，X=〇H、鹵素、Cl〇4 [方鈉石];Na6Al6Si30〇72.24 H2〇，Na8Al8Si40O96-24 H20 ; Na16Al16Si24〇8〇, 16 H2〇；Na12Al12Si12〇48.27 H2〇 [zeolite A]; Na6Al6Si6〇24.2 NaX.7.5 H2〇, X = 〇H, halogen, Cl〇4 [sodium stone]; Na6Al6Si30〇72.24 H20, Na8Al8Si40O96-24 H20; Na16Al16Si24〇8〇 , 16 H2〇;

Na16Al16Si32〇96.16 H2〇；Na56Al56Si136〇384.250 H2〇[、沸石 Y]; Na86Al86Si106O 384 · 264 H2〇[沸石X]; 或爲可經由用Li原子、K原子、Mg原子、Ca原子、 Sr原子或Zn原子部份或完全交換Na原子所製得之沸石，例如（Na，K)1()Al1()Si22〇64.20 H2〇；Ca4.5Na3[(Al〇2)12(Si〇2)12].30 H2〇，(Al〇2)i2(Si〇2)i2].27 H2〇。極特別優先選擇係給予Na沸石A和Na沸石P。以100重量份含鹵聚合物爲基準，菱水鎂鋁石及/或沸石可以例如0.1至20重量份，最好是0.1至10重量份且尤其是0.1至5重量份的量使用。塡料所使用的是諸如碳酸銷、白雲石、砂灰石、氧化鎂、氫氧化鎂、矽酸鹽、瓷土、滑石、玻璃纖維、玻璃珠、木粉、雲母、金屬氧化物或金屬氫氧化物、碳黑、石墨、岩粉、重晶石、玻璃纖維、滑石、高嶺土和白堊之類的塡料。優先選擇係給予白堊（PVC調配手冊（HANDBOOK〇F PVC FORMULATING, E. J. Wickson, John Wiley & Sons, Inc., 1993)第393-449頁）和增強劑（塑膠添加劑手冊 (TASCHENBUCH der Kunststoffadditive, R. Gachter & Η. Muller，Carl Hanser，1990)第 549-615 頁）。以100重量份PVC爲基準，塡料可以較佳至少一重量 19 200300774 份，例如5至200重量份，最好是5至150重量份且尤其是5至100重量份的量使用。金屬皂金屬皂主要是金屬羧酸鹽，較佳是相當長鏈羧酸的鹽。此等之著名實例爲硬脂酸鹽和月桂酸鹽，還有油酸鹽及相當短鏈脂族或芳族羧酸如乙酸、丙酸、丁酸、戊酸、己酸、山梨酸；草酸、丙二酸、琥珀酸、穀胺酸、己二酸、反丁烯二酸、檸檬酸、苯甲酸、水楊酸、鄰苯二甲酸、苯連三酸、偏苯三酸、1，2,4,5-苯四酸的鹽類。應提及之金屬有：Li、Na、K、Mg、Ca、Sr、Ba、Zn 、Ab La、Ce及稀土金屬。經常使用所謂的協同混合物，例如鋇/鋅安定劑、鎂/鋅安定劑、鈣/鋅安定劑或鈣/鎂/鋅安定劑。金屬皂可單獨使用或以混合物使用。常用金屬皂之綜述係見於Ullmann氏工業化學百科全書（Ullmann’s Encyclopedia of industrial Chemistry )，第 5 版，第 A16 卷 (1985)，第361頁及以下。以100重量份PVC爲基準，金屬皂或此等混合物可以例如0.001至10重量份，最好是0.01至8重量份，特佳爲 0.05至5重量份的量使用。鹼金屬和鹼土金屬化合物就本發明目的而言，此等主要是上述酸的殘酸鹽，以及相應的氧化物，或者分別爲氫氧化物或碳酸鹽。此等與有機酸之混合物亦爲可行者。實例有：LiOH、NaOH、K0H 、Ca〇、Ca(〇H)2、Mg〇、Mg(〇H)2、Sr(〇H)2、A1(〇H)3、 20 200300774Na16Al16Si32〇96.16 H2〇; Na56Al56Si136〇384.250 H2〇 [, zeolite Y]; Na86Al86Si106O 384 · 264 H2〇 [zeolite X]; or can be through the use of Li atom, K atom, Mg atom, Ca atom, Sr atom or Zn atom Zeolites prepared by partial or complete exchange of Na atoms, such as (Na, K) 1 () Al1 () Si22〇64.20 H2〇; Ca4.5Na3 [(Al〇2) 12 (Si〇2) 12] .30 H2O, (Al2O2) i2 (Si02) i2]. 27 H2O. Very particular preference is given to Na Zeolite A and Na Zeolite P. The magnesite and / or zeolite may be used in an amount of, for example, 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and particularly 0.1 to 5 parts by weight based on 100 parts by weight of the halogen-containing polymer. The materials used are such as carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicate, porcelain clay, talc, glass fibers, glass beads, wood flour, mica, metal oxides or metal hydroxides. Concrete, carbon black, graphite, rock powder, barite, fiberglass, talc, kaolin and chalk. Preference is given to chalk (HANDBOOK〇F PVC FORMULATING, EJ Wickson, John Wiley & Sons, Inc., pp. 393-449) and reinforcing agents (TASCHENBUCH der Kunststoffadditive, R. Gachter & M. Muller, Carl Hanser, 1990) pp. 549-615). Based on 100 parts by weight of PVC, the concrete may be used in an amount of preferably at least one weight 19 200300774 parts, for example, 5 to 200 parts by weight, most preferably 5 to 150 parts by weight, and especially 5 to 100 parts by weight. Metal soaps Metal soaps are mainly metal carboxylates, preferably relatively long-chain carboxylic acid salts. Famous examples of these are stearates and laurates, but also oleates and fairly short-chain aliphatic or aromatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, and sorbic acid; , Malonic acid, succinic acid, glutamic acid, adipic acid, fumaric acid, citric acid, benzoic acid, salicylic acid, phthalic acid, trimellitic acid, trimellitic acid, 1, 2 , 4,5-Pyromellitic acid salts. The metals to be mentioned are: Li, Na, K, Mg, Ca, Sr, Ba, Zn, Ab La, Ce and rare earth metals. So-called synergistic mixtures are often used, such as barium / zinc stabilizers, magnesium / zinc stabilizers, calcium / zinc stabilizers or calcium / magnesium / zinc stabilizers. Metal soaps can be used alone or as a mixture. A review of commonly used metal soaps is found in Ullmann's Encyclopedia of industrial Chemistry, 5th edition, Vol. A16 (1985), pages 361 and below. Based on 100 parts by weight of PVC, metal soap or these mixtures can be used, for example, in an amount of 0.001 to 10 parts by weight, preferably 0.01 to 8 parts by weight, and particularly preferably 0.05 to 5 parts by weight. Alkali and alkaline earth metal compounds For the purposes of the present invention, these are mainly the residual acid salts of the aforementioned acids, and the corresponding oxides, or hydroxides or carbonates, respectively. Mixtures of these with organic acids are also feasible. Examples are: LiOH, NaOH, K0H, Ca0, Ca (〇H) 2, Mg〇, Mg (〇H) 2, Sr (〇H) 2, A1 (〇H) 3, 20 200300774

CaC〇3及MgC〇3 (以及鹼式碳酸鹽，例如白鎂氧和碳銘鎂礦），以及Na和K之脂肪酸鹽。在鹼土金屬羧酸鹽和Zn 羧酸鹽之情況中，亦可能使用此等與MO或M(OH)2 (M = Ca、Mg、Sr或Zn )之加合物，即所謂的”高鹼性”化合物。除了根據本發明之安定劑外，最好使用鹼金屬羧酸鹽、鹼土金屬羧酸鹽及/或鋁羧酸鹽。濶滑劑可能潤滑劑之實例爲：褐煤蠟、脂肪酸酯、PE蠛、醯胺躐、氯代鏈烷烴、甘油酯與鹼土金屬皂及脂肪酮，以及列舉於EP 0 259 783之潤滑劑或潤滑劑組合。以硬脂酸鈣較佳。增塑劑有機增塑劑之實例爲選自於下列群組者： A) 鄰苯二甲酸酯：例如較佳爲鄰苯二甲酸二-2-乙基己酯、二異壬酯及二異癸酯，亦以常用縮寫DOP (鄰苯二甲酸二辛酯，鄰苯二甲酸二-2-乙基己酯）、DINP (鄰苯二甲酸二異壬酯）、DIDP (鄰苯二甲酸二異癸酯）等爲人所知。 B) 脂族二羧酸之酯類，特別是己二酸、壬二酸和癸二酸之酯類：較佳爲己二酸二-2-乙基己酯及己二酸二異辛酯。 C) 偏苯三酸酯，例如偏苯三酸三-2-乙基己酯、偏苯三酸三異癸酯（混合物）、偏苯三酸三異十三酯、偏苯三酸三異辛酯（混合物），以及偏苯三酸三-C6-C8-烷基酯、三_ C6-C1Q-烷基酯、三-C7-C9-烷基酯及三-C9-Cn-烷基酯。常用縮寫爲TOTM (偏苯三酸三辛酯，偏苯三酸三-2-乙基己酯 21 200300774 )、TIDTM (偏苯三酸三異癸酯）及TITDTM (偏苯三酸三異十三酯）。 D) 環氧增塑劑：這些主要是環氧化不飽和脂肪酸，例如環氧化大豆油。 E) 聚合物增塑劑：製備聚酯增塑劑最常用的原料爲：二羧酸，如己二酸、鄰苯二甲酸、壬二酸或癸二酸；二醇，如 1,2-丙二醇、1,3-丁二醇、1,4-丁二醇、1，6-己二醇、新戊二醇及二乙二醇。 F) 磷酸酯：這些酯類之定義係示於上述”塑膠添加劑手冊 ”（Taschenbuch der Kunststoffadditive )第 5.9.5 章，第 408-412頁中。這些磷酸酯類之實例有：磷酸三丁酯、磷酸三-2-乙基丁酯、磷酸三-2-乙基己酯、磷酸三氯乙酯、磷酸 2-乙基己基二苯酯、磷酸甲苯基二苯酯、磷酸三苯酯、磷酸三甲苯酯及磷酸參二甲苯酯。優先選擇係給予磷酸參（2-三乙基己基）酯及得自汽巴特用化學品之Reofos® 50和 Reofos® 95 〇 G) 氯化碳氫化合物（鏈烷烴） H) 碳氫化合物 I) 一元酯，例如油酸丁酯、油酸苯氧基乙酯、油酸四氫糠酯及烷基磺酸酯。 J) 乙二醇酯類，例如苯甲酸二乙二醇酯。這些增塑劑之定義及其實例係示於“塑膠添加劑手冊” (Kunststoffadditive, R. Gachter/H. Muller, Carl Hanser Verlag，3rd Ed·，1989 )第 5.9.6 章，第 412-415 頁及”PVC 技 22 200300774 術”（PVC Technology，W. V. Titow，4th Ed·，Elserier Publ. 1984 )第165-170頁中。亦可能使用各種增塑劑之混合物。以100重量份PVC爲基準，增塑劑可以例如5至20重量份，最好是10至20重量份的量使用。剛性或半剛性 PVC較佳包含至高1〇%，特佳至高5%之增塑劑，或者無增塑劑。顏料適當物質爲熟練工作者所已知。無機顏料之實例爲 Τι〇2、以氧化锆爲主之顏料、BaS04、氧化鋅（鋅白）與鋅鋇白（硫化鋅/硫酸鋇）、碳黑、碳黑-二氧化鈦混合物、氧化鐵顏料、Sb2〇3、（Ti，Ba，Sb)〇2、Cr2〇3、尖晶石如鈷藍和鈷綠、Cd(S，Se)、群青。有機顏料之實例爲偶氮顏料、肽菁顏料、喹吖啶酮顏料、花顏料、二酮吡咯并吡咯顏料及憩醌顏料。微粒化形式之Ti02亦爲較佳者。定義與進一步說明係見於”PVC 調配手冊”（Handbook of PVC Formulating，E. J. Wickson，John Wiley & Sons, New York, 1993)中。環氬化脂肪酸酯及其他環氧化合物本發明之安定劑組合可另外且最好包含至少一種環氧化脂肪酸酯。此處之可能化合物尤其是天然來源脂肪酸之酯類（脂肪酸甘油酯），例如大豆油或菜子油。然而，亦可能使用合成產物’例如環氧化油酸丁酯。亦可使用環氧化聚丁二烯和聚異戊二烯，若需要亦可呈部份羥基化之形式，或丙烯酸縮水甘油酯與甲基丙烯酸縮水甘油酯來作爲均聚物或共聚物。這些環氧化合物亦可能已經應用於鋁鹽化合物；在此相關部份亦參見DE-A-4 031 818。 200300774 抗氣化劑烷基化一元酚，如2,6-二第三丁基-4-甲基酚，院基硫代甲基酚，如2,4-二辛基硫代甲基-6-第三丁基酚，院基化氫醌，如2,6-二第三丁基-4-甲氧基酚，羥基化硫代二苯醚，如2,2’-硫代雙（6-第三丁基-4-甲基酚），伸烷基雙酣，如 2,2’-亞甲基雙（6-第三丁基冬甲基酚），苄基化合物，如 3,5,3’，5’-四第三丁基-4,4’-二羥基二苄基醚，羥苄基化丙二酸酯，如2,2-雙（3,5-二第三丁基-2-羥苄基）丙二酸雙十八酯，羥苄基芳族烴，如1，3,5-參（3,5-二第三丁基-4-羥苄基）_ 2,4,6-三甲基苯，三啡化合物，如2,4-雙辛基锍基-6-(3,5_二第三丁基-4-羥基苯胺基）-1,3,5-三啡，膦酸酯與亞膦酸酯，如2,5-二第三丁基-4-羥苄基膦酸二甲酯，醯胺基酚，如仁羥基金醯苯胺，β-(3,5-二第三丁基-4-羥苯基）丙酸、β-(5-第三丁基-4-羥基-3-甲基苯基）丙酸、β-(3,5-二環己基_4_羥苯基 )丙酸等之酯類，3,5-二第三丁基-4-羥苯基乙酸與一元或多元醇之酯類，β-(3,5-二第三丁基-4-羥苯基）丙酸之醯胺類，如Ν，Ν’-雙（3,5-二第三丁基-4-羥苯基-丙醯基）伸己基二胺，維生素Ε (生育酚）及衍生物。以100重量份PVC爲基準，抗氧化劑用量之實例爲 0.01至10重量份，最好是0.1至10重量份，且尤其是至5重量份。 UV吸收劑和光安定劑此等之實例有：2-(2’-羥苯基）苯并***，如2-(2’_羥基-5’-甲基苯基）苯并***，2-羥基二苯酮，未經取代或經取代 24 200300774 苯甲酸之酯類，如水楊酸4-第三丁基苯酯、水楊酸苯酯，丙烯酸酯，鎳化合物，草醯胺，如4,4’·二辛氧基草醯二苯胺、2,2’-二辛氧基-5,5’-二第三丁基草醯二苯胺，2-(2-羥苯基）-1，3,5-三啡，如2,4,6-參（2-羥基-4-辛氧基苯基）-1，3,5-三啡、2-(2-羥基-4-辛氧基苯基）-4,6-雙（2,4-二甲基苯基）-1,3,5-三啡，立體受阻胺，如癸二酸雙（2,2,6,6-四甲基派啶-4-酯）、琥珀酸雙（2,2,6,6-四甲基派啶-4-酯）。發泡齊ί 發泡劑之實例爲有機偶氮化合物及有機亞肼基化合物、四唑、腭啡、靛紅酸酐，以及蘇打和碳酸氫鈉。優先選擇係給予偶氮二醯胺和碳酸氫鈉，以及其混合物。其他可使用的添加劑有：衝擊改性劑及加工助劑、膠凝劑、抗靜電劑、殺生物劑、金屬減活劑、螢光增白劑、阻燃劑、防霧劑、相容劑及分散劑，例如烷基磺酸酯、芳基磺酸酯、聚乙烯醇、脫水山梨糖醇酯、黃原酸酯、烷基醚衍生物等等（亦參見”界面活性劑手冊（Tensid-Taschenbuch)”， H. Stache、K. Kossvig，Carl Hanser 出版社，第3版，1990)。添加劑的一般敘述係示於“塑膠添加劑 ”（Kunststoffadditive，R. Gachter/H. Muller，Carl Hanser 出版社，第3版，1989與第4版，2001 )、聚氯乙烯調配手冊(Handbook of Polyvinyl Chloride Formulating, E. J. Wilson, J. Wiley & Sons，1993 )及”塑膠添加劑”（"Plastics additives”，G· Pritchard，Chapman & Hall，London，第 1 版， 1998 )等之中。 25 200300774 衝擊改性劑亦詳細描述於”PVC之衝擊改性劑”（Impact Modifiers for PVC, J. T. Lutz/D. L. Dunkelberger, John Wiley & Sons, 1992 )中。本發明進一步提供包含已藉本發明方法安定化之含鹵聚合物的組成物。此組成物的實例爲聚合物分散液或者是乾燥之後的聚合物粉末。此處的安定劑混合物在聚合物中有幾乎均質的分佈。根據本發明所安定化之聚合物分散液的特色是，（直到進一步加工之前）它們保持安定而不凝結，它們因而不會展現出非常細微分佈之聚合物粒子（該粒子在分散液中無法持久）的聚集作用，因而維持未被破碎。爲達成含氯聚合物在這些組成物中的安定化，以整體分散液爲基準，有利的是使用0.01至10重量份，較佳0.1 至5重量份的列於（b)中之通式（I)化合物。 (a)項中中之過氯酸鹽或此等之溶液的用量實例爲：以整體分散液爲基準，最好是0.01至3重量份，特佳是0.01 至2重量份。最後，可使用份量從0.01至10重量份，較佳從0.1至 5重量份的（c)項中a)與b)的鹽。優先選擇係給予其中⑻項中通式⑴化合物（或其混合物）對（a)項中之過氯酸鹽的比例，以重量計係在0.01 : 1 至50 : 1範圍內的組成物。含鹵聚合物最好是含氯聚合物，特別是PVC。所欲安定化之含氯聚合物的實例有： 26 200300774 氯乙烯聚合物、偏二氯乙嫌聚合物，結構中含有氯乙烯單元之乙烯基樹脂，如氯乙烯與脂肪酸乙烯酯（特別是乙酸乙烯酯）之共聚物，氯乙烯與（甲基）丙烯酸酯及與丙烯腈之共聚物，氯乙烯與二烯化合物及與不飽和二羧酸或其酸酐之共聚物，如氯乙烯與馬來酸二乙酯、富馬酸二乙酯或馬來酸酐之共聚物，氯乙烯之後氯化聚合物及共聚物，氯乙烯和偏二氯乙烯與不飽和醛類、酮類及其他如丙烯醛、巴豆醛、乙烯基甲基酮、乙烯基甲基醚、乙烯基異丁基醚等化合物之共聚物；偏二氯乙烯聚合物及其與氯乙烯和其他可聚合化合物之共聚物；氯乙酸乙烯酯之聚合物和二氯二乙烯基醚之共聚物；乙酸乙烯酯之氯化聚合物，丙烯酸及經α取代丙烯酸之氯化聚酯；氯化苯乙烯如二氯苯乙烯之聚合物；氯化橡膠；乙烯之氯化聚合物；氯丁二烯之聚合物與後氯化聚合物，及此等與氯乙烯之共聚物，氯化天然或合成橡膠，以及所提及之聚合物與彼此之間或與其他可聚合化合物的混合物。就本發明之目的而言，PVC包括與可聚合化合物如丙烯腈、乙酸乙烯酯或ABS之共聚物，這些材料可包括懸浮、本體或乳化等聚合物。優先選擇係給予PVC均聚物，或是與聚丙烯酸酯或聚乙烯醇和聚乙酸乙烯酯結合之PVC均聚物。亦可使用PVC與EVA、ABS和MBS之接枝聚合物。其他較佳的基質爲上述均聚物及共聚物（特別是氯乙烯均聚物）與其他熱塑性或/及彈性聚合物的混合物，特別是與 ABS、MBS、NBR、SAN、EVA、CPE、MBAS、PMA、 27 200300774 PMMA、EPDM的摻合物，及與特別是選自ABS、NBR、 NAR、SAN及EVA所成群組之聚內酯的摻合物。用於共聚物之縮寫爲熟練工作者所熟習，且具有下列意義：ABS :丙烯腈-丁二烯-苯乙烯；SAN ··苯乙烯-丙烯腈；NBR :丙烯腈 -丁二烯；NAR :丙烯腈-丙烯酸酯；EVA :乙烯-乙酸乙烯酯；其他可使用的特定材料爲以丙烯酸酯爲主之苯乙烯-丙烯腈共聚物（ASA)。包含所提及作爲成份（i)和（ii)之25至75重量％PVC和 75至25重量％共聚物之混合物的聚合物組成物爲此處較佳者。由⑴100重量份PVC與（ϋ) 0至300重量份ABS及/或經SAN改性之ABS和0至80重量份共聚物NBR、NAR及/ 或 EVA、PMA、PMMA (而特別是 EVA、PMA 和 PMMA) 所組成的組成物爲特別重要的成份。就本發明之目的而言，安定作用亦可特別經由利用非常細微分散之含鹵聚合物的分散液或懸浮液來達成，此處的聚合物爲更詳細說明於上文者，其已經由加工、使用或貯存而經受些許降解作用。特別優先選擇係給予回收的 PVC材料。可根據本發明伴隨使用且同時又爲含氯聚合物之化合物’係爲熟練工作者所熟知且係詳細描述於”塑膠添加劑” (Kunststoffadditive，R. Gachter/H. Muller，Carl Hanser 出版社，第 3 版，1989 ) ; 1999 年 3 月 17 日之 DE 197 41 778 和EP-A 99 105 418.0中，其特別以引用方式倂入本文。本發明之經安定含鹵（特別是含氯）聚合物組成物係 28 200300774 經增塑或未經增塑者，或是不含增塑劑或實質上不含增塑劑的組成物。呈未經增塑調配物形式之本發明組成物特別適合包裝薄膜、防衝墊薄膜（汽車）、管材、設備罩殻（電腦和家庭用品）、含PVC塗料、任意類型之塗佈基材如紙張、紙板、地毯、織物、墓材、金屬、玻璃、毛氈、纖維材料、纖維、高充塡模塑物、經塗佈裝飾薄膜、屋頂薄膜、事務用薄膜或壁紙。可伴隨使用潤滑劑或增塑劑，只要含鹵聚合物之分散液保持未破碎即可。本發明亦提供本發明組成物於生產或塗佈物件的用途及所得的物件。本發明特別包括一種經由將物件浸漬於根據本發明被安定之聚合物分散液中而製造未經增塑PVC塗層的方法。本發明組成物作爲塑料溶膠替代品使用的實例爲人造革、地板覆蓋物、織物塗層、壁紙、螺管塗層及汽車用底封層。本發明組成物之燒結PVC應用的實例爲脂膏、塗凝模具、螺管塗層、模塑物及層壓物。下列用以摻混安定劑的方法是有利的：在聚合反應期間或之後，以溶液（本發明與這種供應形式的結合有其優點，因爲彳谷劑可爲水）、乳化液或分散液，或是直接添加至聚合物分散液（聚合反應分散液）中。根據本發明安定之含鹵聚合物可以本身已知之方式製得，但亦可能不用聚合物粉末的乾燥，而使用整體聚合物 29 200300774 分散液（聚合反應分散液）供進一步加工’並在適當時將其他添加劑與聚合物混合。安定劑可個別添加或以混合物添加，或者以所知爲母料的形式添加。這對於pvc是特別可應用的。根據本發明安定化之PVC特別適合的用途實例爲包裝薄膜、片材、發泡體、重質型材、充塡模塑物、建築型材、副材、事務用薄膜與設備罩殻（電腦和家庭用品）、地板覆蓋物、壁紙及塗層，這些是特別加者。關於這點之更多細節參見”塑膠手冊PVC ( Kunststoffhandbuch PVC) ”，第 2/2 卷，W. Becker/H. Braun ，第 2 版 ’ 1985 ’ Carl Hanser 出版社，第 1236_1277 頁。以下實例係說明本發明而非限制之。在說明之其餘部分中，份數與％係以重量爲基準來表示。聚合物分散液的一項特色是，它們直到被加工（製造模塑物）之前，都是維持安定而不凝結。表1 所使用的安定劑安定劑 1 "30%過氯酸鈉單水合物於水中的溶液 " 2 二乙醇胺 -- 3 "π%過氯酸鈉單水合物於二乙醇胺中的溶液 ~—— 4 Ί3%過氯酸鈉單水合物於三異丙醇胺中的溶液 ~— 5 13%過氯酸鈉單水合物於經雙(2-羥基乙基)取代之天溶液 6 ^雙(2_羥基乙基)取代之大丑胺： ~— 7 "2_0%氯化鋅於水中的溶液 -- 8 飽和碳酸氫鈉水溶液 '一''— 9 環氧化大旦油 ' 10 Mark T 682有機錫女定劑（購自Crompton乙烯基的市售產品） -----___ 30 200300774 實施例1 :靜熱試驗（熱安定性）將1克100份水性PVC分散液（1)與[X]份表1所述之安定劑的混合物置於鋁盤上，並在乾燥橱中於190°C乾燥10 秒鐘，然後於190°c膠凝另10秒鐘。利用2分鐘的間隔，然後使樣本於190°C接受10分鐘的加熱老化。如根據ASTM D1925-70之黃度指數（YI)測定樣本的脫色作用。低數値表示良好的起始顏色，因此有良好的安定作用。 PVC分散液（1):由約40%的PVC和60%的水與添加劑所組成，該添加劑係由聚乙烯醇、硬脂酸酯和鄰苯二甲酸酯所組成。表2 編號安定劑 [X】份數 10分鐘後之YI 1 無安定劑 103.0 2 1 0.5 77.9 3 2 0.5 64.4 4 3 0.5 47.8 5 4 0.5 55.5 6 5 1.0 49.9 —7 6 1.0 86.2 —8 7 0.1 116.0 9 8 1.0 111.0 10 9 1.0 97.0 11 10 0.1 92.2CaC03 and MgC03 (as well as basic carbonates such as white magnesia and carborite), and fatty acids salts of Na and K. In the case of alkaline earth metal carboxylates and Zn carboxylates, it is also possible to use these adducts with MO or M (OH) 2 (M = Ca, Mg, Sr or Zn), the so-called "high alkalis" Sex "compounds. In addition to the stabilizers according to the present invention, alkali metal carboxylates, alkaline earth metal carboxylates and / or aluminum carboxylates are preferably used. Examples of possible lubricants for lubricating agents are montan wax, fatty acid esters, PE 蠛, amidine 躐, chloroparaffins, glycerides and alkaline earth metal soaps and fatty ketones, as well as the lubricants listed in EP 0 259 783 or Lubricant combination. Calcium stearate is preferred. Examples of plasticizers Organic plasticizers are those selected from the group consisting of: A) Phthalates: For example, di-2-ethylhexyl phthalate, diisononyl ester and di Isodecyl, also commonly used abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), DINP (diisononyl phthalate), DIDP (phthalic acid Diisodecyl ester) and others. B) esters of aliphatic dicarboxylic acids, especially esters of adipic acid, azelaic acid, and sebacic acid: di-2-ethylhexyl adipate and diisooctyl adipate are preferred . C) Trimelates, such as tri-2-ethylhexyl trimellitate, triisodecyl trimellitate (mixture), triisotridecyl trimellitate, triisotrimellitic acid Octyl esters (mixtures), and tri-C6-C8-alkyl esters of trimellitic acid, tri-C6-C1Q-alkyl esters, tri-C7-C9-alkyl esters, and tri-C9-Cn-alkyl esters . Common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate 21 200300774), TIDTM (triisodecyl trimellitate), and TITDTM (triisotrimellitic acid Triester). D) Epoxy plasticizers: These are mainly epoxidized unsaturated fatty acids, such as epoxidized soybean oil. E) Polymer plasticizers: The most common raw materials for preparing polyester plasticizers are: dicarboxylic acids such as adipic acid, phthalic acid, azelaic acid or sebacic acid; glycols such as 1,2- Propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol. F) Phosphate esters: The definition of these esters is shown in the "Plastic Additives Handbook" (Taschenbuch der Kunststoffadditive), Chapter 5.9.5, pages 408-412. Examples of these phosphates are: tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyl diphenyl phosphate, phosphoric acid Tolyl diphenyl ester, triphenyl phosphate, tricresyl phosphate, and paraxylyl phosphate. Preference is given to ginseng (2-triethylhexyl) phosphate and Reofos® 50 and Reofos® 95 ° C from Cibabat Chemicals) Chlorinated hydrocarbons (paraffins) H) Hydrocarbons I) Monobasic esters such as butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkyl sulfonates. J) Glycol esters, such as diethylene glycol benzoate. The definitions and examples of these plasticizers are shown in the "Handbook of Plastic Additives" (Kunststoffadditive, R. Gachter / H. Muller, Carl Hanser Verlag, 3rd Ed., 1989), Chapter 5.9.6, pages 412-415 and "PVC Technology 22 200300774" (PVC Technology, WV Titow, 4th Ed., Elserier Publ. 1984) pages 165-170. It is also possible to use mixtures of various plasticizers. The plasticizer may be used in an amount of, for example, 5 to 20 parts by weight, preferably 10 to 20 parts by weight based on 100 parts by weight of PVC. Rigid or semi-rigid PVC preferably contains up to 10%, particularly preferably up to 5% of a plasticizer, or no plasticizer. Pigments Suitable substances are known to the skilled worker. Examples of inorganic pigments are Ti02, zirconia-based pigments, BaS04, zinc oxide (zinc white) and zinc barium white (zinc sulfide / barium sulfate), carbon black, carbon black-titanium dioxide mixture, iron oxide pigments, Sb203, (Ti, Ba, Sb) 02, Cr203, spinels such as cobalt blue and cobalt green, Cd (S, Se), ultramarine. Examples of organic pigments are azo pigments, peptide cyanine pigments, quinacridone pigments, flower pigments, diketopyrrolopyrrole pigments, and quinone pigments. Micronized Ti02 is also preferred. Definitions and further explanations are found in the "Handbook of PVC Formulating," E. J. Wickson, John Wiley & Sons, New York, 1993. Cyclized fatty acid esters and other epoxy compounds The stabilizer combination of the present invention may additionally and preferably include at least one epoxylated fatty acid ester. Possible compounds here are in particular esters of fatty acids of natural origin (fatty acid glycerides), such as soybean oil or rapeseed oil. However, it is also possible to use synthetic products' such as epoxidized butyl oleate. Epoxylated polybutadiene and polyisoprene can also be used, if necessary, in the form of partial hydroxylation, or glycidyl acrylate and glycidyl methacrylate as homopolymers or copolymers. These epoxy compounds may also have been applied to aluminum salt compounds; see also DE-A-4 031 818 for related parts. 200300774 Anti-gasification agents alkylated monohydric phenols, such as 2,6-di-tert-butyl-4-methylphenol, and noctylthiomethylphenols, such as 2,4-dioctylthiomethyl-6 -Third-butylphenol, hydroquinone hydroquinone, such as 2,6-di-tert-butyl-4-methoxyphenol, hydroxylated thiodiphenyl ether, such as 2,2'-thiobis (6 -Third-butyl-4-methylphenol), alkylidene bisfluorene, such as 2,2'-methylenebis (6-third-butyl aspartyl phenol), benzyl compounds, such as 3,5 , 3 ', 5'-tetratert-butyl-4,4'-dihydroxydibenzyl ether, hydroxybenzyl malonate, such as 2,2-bis (3,5-ditert-butyl 2-Hydroxybenzyl) dioctadecyl malonate, hydroxybenzyl aromatic hydrocarbons, such as 1,3,5-ginseng (3,5-di-third-butyl-4-hydroxybenzyl) _ 2, 4,6-trimethylbenzene, a triphine compound, such as 2,4-bisoctylfluorenyl-6- (3,5-di-tert-butyl-4-hydroxyaniline) -1,3,5- Trisphine, phosphonates and phosphinates, such as 2,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dimethyl esters, amidophenols, such as p-hydroxyanilide, β- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionic acid, β- (5-Third-butyl-4-hydroxy-3-methylphenyl) propionic acid, β- (3,5-Di Cyclohexyl_4 _Hydroxyphenyl) propionic acid and other esters, 3,5-di-third-butyl-4-hydroxyphenylacetic acid and mono- or polyhydric alcohols, β- (3,5-di-third-butyl- 4-Hydroxyphenyl) propionic acid amines, such as N, N'-bis (3,5-di-tertiary-butyl-4-hydroxyphenyl-propanyl) hexyldiamine, vitamin E (fertility Phenol) and derivatives. Examples of the amount of the antioxidant based on 100 parts by weight of PVC are 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, and especially 5 to 5 parts by weight. Examples of UV absorbers and light stabilizers are 2- (2'-hydroxyphenyl) benzotriazole, such as 2- (2'_hydroxy-5'-methylphenyl) benzotriazole, 2 -Hydroxybenzophenone, unsubstituted or substituted 24 200300774 Benzoic acid esters, such as 4-tert-butylphenyl salicylate, phenyl salicylate, acrylates, nickel compounds, chloramphenicol, such as 4 , 4 '· dioctyloxyoxadiphenylaniline, 2,2'-dioctyloxy-5,5'-di-tert-butyloxadiphenylaniline, 2- (2-hydroxyphenyl) -1, 3,5-triphine, such as 2,4,6-ginseng (2-hydroxy-4-octyloxyphenyl) -1,3,5-triphine, 2- (2-hydroxy-4-octyloxy) Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triorphine, a sterically hindered amine, such as sebacic acid bis (2,2,6,6-tetramethyl) Bispyridin-4-ester), bis (2,2,6,6-tetramethylpyridin-4-ester) succinate. Examples of foaming agents are examples of organic azo compounds and organic hydrazine compounds, tetrazole, pyrene, isatoic anhydride, and soda and sodium bicarbonate. Preference is given to azodiamidamide and sodium bicarbonate, and mixtures thereof. Other additives that can be used are: impact modifiers and processing aids, gelling agents, antistatic agents, biocides, metal deactivators, fluorescent whitening agents, flame retardants, anti-fog agents, compatibilizers And dispersants, such as alkyl sulfonates, aryl sulfonates, polyvinyl alcohols, sorbitan esters, xanthates, alkyl ether derivatives, etc. (see also the Handbook of Surfactants (Tensid- Taschenbuch) ", H. Stache, K. Kossvig, Carl Hanser Press, 3rd edition, 1990). General descriptions of additives are shown in "Plastic Additives" (Kunststoffadditive, R. Gachter / H. Muller, Carl Hanser Press, 3rd Edition, 1989 and 4th Edition, 2001), Handbook of Polyvinyl Chloride Formulating, EJ Wilson, J. Wiley & Sons, 1993) and "Plastics additives", G. Pritchard, Chapman & Hall, London, 1st edition, 1998, etc. 25 200300774 Impact Modifiers are also described in detail in "Impact Modifiers for PVC" (JT Lutz / DL Dunkelberger, John Wiley & Sons, 1992). The present invention further provides a method comprising the stabilization by the method of the present invention. Composition of a halogen-containing polymer. Examples of this composition are polymer dispersions or polymer powders after drying. The stabilizer mixture here has an almost homogeneous distribution in the polymer. It is stabilized according to the invention Polymer dispersions are distinguished by the fact that they remain stable and do not condense (until further processing), so they do not exhibit very fine The aggregation effect of the polymer particles of the cloth (the particles cannot be sustained in the dispersion), so that they remain unbroken. In order to achieve the stabilization of the chlorinated polymer in these compositions, it is advantageous to use the overall dispersion as a benchmark 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight of the compound of the general formula (I) listed in (b) are used. Examples of the amount of the perchlorate or the solution thereof in the item (a) are: Based on the entire dispersion, it is preferably from 0.01 to 3 parts by weight, particularly preferably from 0.01 to 2 parts by weight. Finally, a portion (c) of from 0.01 to 10 parts by weight, preferably from 0.1 to 5 parts by weight can be used The salts of a) and b). Preference is given to the ratio of the compound of general formula IX (or a mixture thereof) in item (i) to the perchlorate salt in (a), in the range of 0.01: 1 to 50 by weight. : Composition in the range of 1. The halogen-containing polymer is preferably a chlorine-containing polymer, especially PVC. Examples of the chlorine-containing polymer to be stabilized are: 26 200300774 vinyl chloride polymer, vinylidene chloride polymerization Materials, vinyl resins containing vinyl chloride units in the structure, such as vinyl chloride and fatty acid vinyl (Especially vinyl acetate) copolymers, copolymers of vinyl chloride and (meth) acrylates and acrylonitrile, copolymers of vinyl chloride and diene compounds, and unsaturated dicarboxylic acids or anhydrides thereof, such as chlorine Copolymers of ethylene with diethyl maleate, diethyl fumarate or maleic anhydride, chlorinated polymers and copolymers after vinyl chloride, vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and Copolymers of other compounds such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether; vinylidene chloride polymer and its copolymerization with vinyl chloride and other polymerizable compounds Polymers; copolymers of polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, acrylic acid and chlorinated polyesters substituted for alpha acrylic acid; chlorinated styrenes such as dichlorostyrene Polymers; chlorinated rubber; chlorinated polymers of ethylene; polymers of chloroprene and post-chlorinated polymers, and copolymers of these with vinyl chloride, chlorinated natural or synthetic rubber, and the mentioned Polymer and each other Mixture with other polymerizable compounds. For the purposes of the present invention, PVC includes copolymers with polymerizable compounds such as acrylonitrile, vinyl acetate or ABS. These materials may include polymers such as suspensions, bulks or emulsions. Preference is given to PVC homopolymers or PVC homopolymers combined with polyacrylate or polyvinyl alcohol and polyvinyl acetate. Graft polymers of PVC and EVA, ABS and MBS can also be used. Other preferred substrates are mixtures of the above homopolymers and copolymers (especially vinyl chloride homopolymers) with other thermoplastic or / and elastic polymers, especially with ABS, MBS, NBR, SAN, EVA, CPE, MBAS , PMA, 27 200300774 PMMA, EPDM blends, and blends with polylactones especially selected from the group consisting of ABS, NBR, NAR, SAN and EVA. The abbreviations used for copolymers are familiar to skilled workers and have the following meanings: ABS: acrylonitrile-butadiene-styrene; SAN ·· styrene-acrylonitrile; NBR: acrylonitrile-butadiene; NAR: propylene Nitrile-acrylate; EVA: ethylene-vinyl acetate; other specific materials that can be used are styrene-acrylonitrile copolymers (ASA) based on acrylates. A polymer composition comprising the mixture of 25 to 75% by weight of PVC and 75 to 25% by weight of a copolymer mentioned as ingredients (i) and (ii) is preferable here. From ⑴100 parts by weight of PVC and (ϋ) 0 to 300 parts by weight of ABS and / or SAN modified ABS and 0 to 80 parts by weight of copolymers NBR, NAR and / or EVA, PMA, PMMA (and especially EVA, PMA And PMMA) are particularly important ingredients. For the purposes of the present invention, stabilization can also be achieved in particular through the use of very finely dispersed dispersions or suspensions of halogen-containing polymers. The polymers herein are described in more detail above, which have been processed by , Used or stored subject to some degradation. Special preference is given to recycled PVC materials. Compounds which can be used in accordance with the present invention and which are also chlorinated polymers are well known to skilled workers and described in detail in "Plastic Additives" (Kunststoffadditive, R. Gachter / H. Muller, Carl Hanser Press, 3 Edition, 1989); DE 197 41 778 and EP-A 99 105 418.0, March 17, 1999, which are specifically incorporated herein by reference. The stabilized halogen-containing (especially chlorine-containing) polymer composition of the present invention 28 200300774 Plasticized or unplasticized composition, or a composition containing no plasticizer or substantially no plasticizer. The composition of the present invention in the form of an unplasticized formulation is particularly suitable for packaging films, impact cushion films (automotive), pipes, equipment housings (computers and household goods), PVC coatings, and any type of coated substrate such as Paper, cardboard, carpet, fabric, cemetery, metal, glass, felt, fibrous material, fiber, high-filled molding, coated decorative film, roofing film, office film or wallpaper. Lubricants or plasticizers can be used concomitantly, as long as the dispersion of the halogen-containing polymer remains unbroken. The invention also provides the use of the composition of the invention in the production or coating of articles and the articles obtained. The present invention particularly includes a method for making an unplasticized PVC coating by immersing an article in a polymer dispersion stabilized according to the present invention. Examples of the use of the composition of the present invention as a plastisol substitute are artificial leather, floor coverings, fabric coatings, wallpaper, solenoid coatings, and automotive underseals. Examples of sintered PVC applications of the composition of the present invention are greases, gel coat molds, solenoid coatings, moldings, and laminates. The following methods for admixing stabilizers are advantageous: during or after the polymerization, in solution (the combination of the invention with this form of supply has its advantages, since cereals can be water), emulsions or dispersions , Or directly added to the polymer dispersion (polymerization dispersion). The halogenated polymers stabilized according to the present invention can be prepared in a manner known per se, but it is also possible to use the bulk polymer 29 200300774 dispersion (polymerization dispersion) for further processing without drying the polymer powder, and where appropriate Mix other additives with the polymer. Stabilizers can be added individually or in a mixture, or in a form known as a masterbatch. This is particularly applicable for PVC. Examples of particularly suitable uses of stabilized PVC according to the present invention are packaging films, sheets, foams, heavy profiles, filling mouldings, building profiles, auxiliary materials, office films and equipment housings (computers and households) Supplies), floor coverings, wallpaper and coatings, these are special additions. For more details on this, see “Plastic Handbook PVC (Kunststoffhandbuch PVC)”, Vol. 2/2, W. Becker / H. Braun, 2nd edition ’1985’ Carl Hanser Press, pages 1236_1277. The following examples illustrate the invention without limiting it. In the rest of the description, parts and% are expressed on a weight basis. A special feature of polymer dispersions is that they remain stable and do not set until they are processed (molded). Table 1 Stabilizers used Stabilizer 1 " 30% sodium perchlorate monohydrate solution in water " 2 diethanolamine-3 " π% sodium perchlorate monohydrate solution in diethanolamine ~ —— 4 Ί 3% sodium perchlorate monohydrate solution in triisopropanolamine ~ 5 13% sodium perchlorate monohydrate solution in bis (2-hydroxyethyl) substituted day 6 ^ Bis (2-hydroxyethyl) substituted uglyamine: ~ — 7 " 2_0% zinc chloride solution in water-8 saturated sodium bicarbonate aqueous solution 'a'-9 epoxidized big oil '' 10 Mark T 682 organic tin female fixative (commercially available product from Crompton vinyl) -----___ 30 200300774 Example 1: Static heat test (heat stability) 100 grams of water-based PVC dispersion (1) The mixture with [X] parts of the stabilizer described in Table 1 was placed on an aluminum pan and dried in a drying cabinet at 190 ° C for 10 seconds, and then gelled at 190 ° C for another 10 seconds. Using a 2-minute interval, the samples were then subjected to heat aging at 190 ° C for 10 minutes. For example, the decolorization effect of the sample is determined according to the yellowness index (YI) of ASTM D1925-70. A low number 値 indicates a good starting color and therefore good stability. PVC dispersion (1): It is composed of about 40% of PVC and 60% of water and additives. The additive is composed of polyvinyl alcohol, stearates and phthalates. Table 2 Number of stabilizers [X] YI after 10 minutes 1 No stabilizer 103.0 2 1 0.5 77.9 3 2 0.5 64.4 4 3 0.5 47.8 5 4 0.5 55.5 6 5 1.0 49.9 —7 6 1.0 86.2 —8 7 0.1 116.0 9 8 1.0 111.0 10 9 1.0 97.0 11 10 0.1 92.2

在表2中的比較實施例8至11顯示較差的熱安定性，如從10分鐘之YI値所可見者。實施例2 :靜熱試驗（起始顏色）受試樣本係如實施例1中所述者製得。使用相同的 31 200300774 PVC懸浮液（1)。表3 編號安定劑 [X】份數 2分鐘後之YI 1 無安定劑 18.5 2 1 0.5 1.6 3 2 0.5 3.9 4 3 0.5 3.6 5 6 1.0 5.6 6 7 0.1 9.9 7 8 1.0 20.8 8 9 1.0 4.4 9 10 0.1 5.0Comparative Examples 8 to 11 in Table 2 show poor thermal stability, as can be seen from the YI 値 of 10 minutes. Example 2: Static heat test (starting color) The samples were prepared as described in Example 1. Use the same 31 200300774 PVC suspension (1). Table 3 Number of stabilizers [X] YI after 2 minutes 1 No stabilizer 18.5 2 1 0.5 1.6 3 2 0.5 3.9 4 3 0.5 3.6 5 6 1.0 5.6 6 7 0.1 9.9 7 8 1.0 20.8 8 9 1.0 4.4 9 10 0.1 5.0

表3顯示，根據本發明之安定化作用提供改良的起始顏色。實施例3 :靜熱試驗（熱安定性）受試樣本係如實施例1中所述者製得。 PVC分散液（2):由約60%的PVC和40%的水與添加劑所組成’該添加劑係由烷基苯甲酸衍生物、硬脂酸酯和一種醇所組成。Table 3 shows that the stabilization effect according to the present invention provides an improved starting color. Example 3: Static heat test (thermal stability) The subject sample was prepared as described in Example 1. PVC dispersion (2): composed of about 60% of PVC and 40% of water and additives. The additive is composed of an alkyl benzoic acid derivative, a stearic acid ester, and an alcohol.

表4 編號安定劑 [X]份數 10分鐘後之YI 1 無安定劑 87.3 2 1 0.5 74.6 3 2 0.5 78.2 4 3 0.5 32.9 5 3 1.0 44.4 6 4 0.5 63.2 7 5 1.0 46.8 8 6 1.0 69.3 9 7 〇7\ 110.0 10 8 1.0 102.0 11 10 0.1 90.3 32 200300774 在表4中的比較實施例9至11顯示較差的熱安定性，如從10分鐘之YI値所可見者。實施例4 :靜熱試驗（起始顏色）受試樣本係如實施例3中所述者製得。使用相同的 PVC分散液（2)。表5 編號安定劑【X臟 2分鐘後之YI 1 無安定劑 16.4 2 1 0.5 6.8 3 2 0.5 4.3 4 3 0.5 7.2 5 3 1.0 0.1 6 4 0.5 2.3 7 5 1.0 3.2 8 6 1.0 3.7 10 8 1.0 20.6 11 10 0.1 9.4Table 4 Number of stabilizers [X] YI after 10 minutes 1 No stabilizer 87.3 2 1 0.5 74.6 3 2 0.5 78.2 4 3 0.5 32.9 5 3 1.0 44.4 6 4 0.5 63.2 7 5 1.0 46.8 8 6 1.0 69.3 9 7 〇 7 \ 110.0 10 8 1.0 102.0 11 10 0.1 90.3 32 200300774 Comparative Examples 9 to 11 in Table 4 show poor thermal stability, as can be seen from the YI 値 of 10 minutes. Example 4: Static heat test (starting color) The subject samples were prepared as described in Example 3. Use the same PVC dispersion (2). Table 5 Numbered stabilizers [YI after 2 minutes of dirty X 1 Stabilizer-free 16.4 2 1 0.5 6.8 3 2 0.5 4.3 4 3 0.5 7.2 5 3 1.0 0.1 6 4 0.5 2.3 7 5 1.0 3.2 8 6 1.0 3.7 10 8 1.0 20.6 11 10 0.1 9.4

表5顯示，根據本發明之安定化作用提供較佳的起始顏色。實施例5 :靜熱試驗鲁受試樣本係如實施例1中所述者製得。 PVC分散液（3):由約40%的PVC和60%的水與添加劑所組成’該添加劑係由烷基磺酸酯、脫水山梨糖醇酯和硬脂酸酯所組成。 33 200300774 表6 編號安定劑 [X】份數 YI 2分鐘 10分鐘 1 無安定劑 7.9 99.6 2 1 0.5 6.4 68.3 3 2 0.5 2.4 38.3 4 3 0.5 2.5 Ϊ5Λ 5 4 0.5 2.5 31.4 本發明安定化的作用方式顯然是在改良起始顏色（2分鐘後之YI)和較佳的熱安定性（1 〇分鐘後之YI)方面。實施例6 :靜熱試驗受試樣本係如實施例1中所述者製得。 PVC分散液（4):由約40%的PVC和60%的水與添加劑所組成，該添加劑係由脫水山梨糖醇酯所組成。表7 編號安定劑 [X】份數 YI 2分鐘 1〇分鐘 1 無安定劑 0.1 89.6 2 1 0.5 0.5 61.9 3 2 0.5 -0.2 89.6 4 3 0.5 -2.7 16.3 5 4 0.5 -0.7 36.0 本發明安定化的作用方式顯然是在改良起始顏色（2分鐘後之YI)和較佳的熱安定性（10分鐘後之YI)方面。實施例7 :靜熱試驗受試樣本係如實施例1中所述者製得。 PVC分散液（5):由約50%的PVC和50%的水與添加劑所組成，該添加劑係由4-烷基苯磺酸衍生物與一種潤滑劑 34 200300774 所組成。表8 編號安定劑 [X】份數 YI 2分鐘 10分鐘 1 無安定劑 5.6 66.8 2 1 0.5 2.7 44.1 3 2 0.5 1.1 37.4 4 3 0.5 1.2 24.4 5 4 0.5 0.9 24.5 本發明安定化的作用方式顯然是在改良起始顏色（2分鐘後之YI)和較佳的熱安定性（10分鐘後之YI)方面。實施例8 :分散液安定性藉由摻合100份水性PVC分散液（1)與[X]份安定劑來製備一種立即可用塗料淤漿，並在製備後隨即及在30天之後評估安定性。 PVC分散液（1):由約40%的PVC和60%的水與添加劑所組成，該添加劑係由聚乙烯醇、硬脂酸酯及鄰苯二甲酸酯所組成。表9 編號安定劑 [X]份數安定性在製備之後在30天之後 1 無安定劑分散液分散液 2 1 0.5 分散液分散液 3 2 0.5 分散液分散液 4 3 0.5 分散液分散液 5 4 0.5 分散液分散液 8 7 0.1 凝結物凝結物 9 8 1.0 凝結物凝結物 10 9 1.0 分散液凝結物 11 10 0.1 凝結物凝結物 35 200300774 顯然，利用本發明之安定劑可製得安定的立即可用 PVC分散液。實施例9 : PVC塗層將2克100份水性PVC分散液（1)與1.0份如表1所述之安定劑的混合物塗敷至“K-300”纖維素過濾板上（直徑6 公分）（得自Seitz公司），然後在乾燥櫥中於60°C加熱 30分鐘。然後使經塗佈過濾板於190°C接受加熱老化。如根據ASTM D1925-70之黃度指數（YI)測定樣本之脫色作用。低數値表示良好的起始顏色，因此有良好的安定作用〇 PVC分散液（1):由約40%的PVC和60%的水與添加劑所組成，該添加劑係由聚乙烯醇、硬脂酸酯和鄰苯二甲酸酯所組成。表10 編號安定劑 ίο分鐘後之γι 1 無安定劑 80.6 2 1 52.0 3 2 51.6 4 3 45.2 5 4 51.9 6 5 50.6 7 6 60.7 8 1 7 >120 9 8 111.0 10 9 1 97.0 11 10 112.4Table 5 shows that the stabilization effect according to the present invention provides a better starting color. Example 5: Static-heat test Lu acceptance sample This system was prepared as described in Example 1. PVC dispersion (3): It is composed of about 40% of PVC and 60% of water and additives. The additive is composed of alkyl sulfonate, sorbitan ester and stearate. 33 200300774 Table 6 Numbered stabilizer [X] Parts YI 2 minutes 10 minutes 1 No stabilizer 7.9 99.6 2 1 0.5 6.4 68.3 3 2 0.5 2.4 38.3 4 3 0.5 2.5 Ϊ5Λ 5 4 0.5 2.5 31.4 Mode of action of stabilization of the present invention Obviously in terms of improving the starting color (YI after 2 minutes) and better thermal stability (YI after 10 minutes). Example 6: Static heat test The subject was prepared as described in Example 1. PVC dispersion (4): It is composed of about 40% of PVC and 60% of water and additives, and the additive is composed of sorbitan ester. Table 7 Number of stabilizers [X] Parts YI 2 minutes 10 minutes 1 No stabilizer 0.1 89.6 2 1 0.5 0.5 61.9 3 2 0.5 -0.2 89.6 4 3 0.5 -2.7 16.3 5 4 0.5 -0.7 36.0 The stabilizer of the present invention The mode of action is obviously in terms of improving the initial color (YI after 2 minutes) and better thermal stability (YI after 10 minutes). Example 7: Static-heat test The subject sample was prepared as described in Example 1. PVC dispersion (5): It is composed of about 50% PVC and 50% water and additives. The additive is composed of 4-alkylbenzenesulfonic acid derivative and a lubricant 34 200300774. Table 8 Numbered stabilizer [X] Parts YI 2 minutes 10 minutes 1 No stabilizer 5.6 66.8 2 1 0.5 2.7 44.1 3 2 0.5 1.1 37.4 4 3 0.5 1.2 24.4 5 4 0.5 0.9 24.5 The stabilization mode of the present invention is obviously In terms of improved starting color (YI after 2 minutes) and better thermal stability (YI after 10 minutes). Example 8: Stability of Dispersion A 100% aqueous PVC dispersion (1) and [X] parts of stabilizer were blended to prepare a ready-to-use coating slurry, and the stability was evaluated immediately after preparation and after 30 days . PVC dispersion (1): It is composed of about 40% of PVC and 60% of water and additives. The additive is composed of polyvinyl alcohol, stearates and phthalates. Table 9 Number of stabilizers [X] Parts stability After preparation after 30 days 1 stabilizer-free dispersion liquid dispersion 2 1 0.5 dispersion liquid dispersion 3 2 0.5 dispersion liquid dispersion 4 3 0.5 dispersion liquid dispersion 5 4 0.5 Dispersion dispersion 8 7 0.1 Condensate condensate 9 8 1.0 Condensate condensate 10 9 1.0 Dispersion condensate 11 10 0.1 Condensate condensate 35 200300774 Obviously, the stabilizer of the present invention can be used to prepare a stable and ready-to-use product. PVC dispersion. Example 9: PVC coating A mixture of 2 g of 100 parts of an aqueous PVC dispersion (1) and 1.0 part of a stabilizer as described in Table 1 was applied to a "K-300" cellulose filter plate (6 cm in diameter) (Available from Seitz) and then heated in a drying cabinet at 60 ° C for 30 minutes. The coated filter plate was then subjected to heat aging at 190 ° C. Such as the yellowness index (YI) of ASTM D1925-70 to determine the decolorization of the sample. A low number 値 indicates a good starting color, so it has good stability. PVC dispersion (1): It is composed of about 40% of PVC and 60% of water and additives. The additive is made of polyvinyl alcohol and stearin. Esters and phthalates. Table 10 Number of stabilizers γι minutes later 1 No stabilizer 80.6 2 1 52.0 3 2 51.6 4 3 45.2 5 4 51.9 6 5 50.6 7 6 60.7 8 1 7 > 120 9 8 111.0 10 9 1 97.0 11 10 112.4

很明顯地，利用本發明之安定劑可製得適用的安定 PVC塗層。 36Obviously, suitable stabilizer PVC coatings can be made using the stabilizers of the present invention. 36

Claims

200300774 拾、申請專利範圍 1 · 一種安定水性分散液中含鹵聚合物之方法，其中係將與聚合物分散液相容的安定劑混合物添加至含鹵聚合物的水性分散液中。 2.根據申請專利範圍第1項之方法，其特徵在於該安定劑混合物包含過氯酸鹽化合物及/或烷醇胺及/或此等的鹽 ❿ 3·根據申請專利範圍第1項或第2項之方法，其特徵在於該穩定劑混合物至少包含： a) —種過氯酸鹽，及/或 b) —種下式（I)之烷醇胺： R2 I (CHR|)-CHRf~〇 Η χ = 1、2 或 3 ; y=l、2、3、4、5或6; n= 1 至 10 ; R1和R2彼此獨立地=Η、CrC22-烷基、+((：1^^ CHR3b-〇-]n-H、-[-(CHR3a)y-CHR3b-〇-]n-C〇-R4、C2-C20-烯基、 C2-C18-醯基、C4-C8-環烷基（其可在β-位上具有OH取代度 )、C6-C1Q-芳基、c7-c1(r烷芳基或C7-C1Q-芳烷基，或者，若x = 1，R1與R2亦可與N —起形成一個4至10員的封閉 37 200300774 環，其係由碳原子與（適當時）至高2個雜原子所組成，或者，若x=2，R1亦可爲C2-C18-伸烷基，其在兩β-碳原子上可具有ΟΗ取代度及/或可被一或多個〇原子及/或一或多個NR2基團中斷，或爲經二羥基取代之四氫伸聯環戊二烯基、經二羥基取代之乙基伸環己基、經二羥基取代之伸 4,4’-(雙酚Α二丙基醚）基、伸異佛爾酮基、二甲基伸環己基、二環己基亞甲基或3,3’-二甲基二環己基亞甲基，以及若x = 3，則R1亦可爲經三經基取代之（異氰脲酸三-N-丙酯) 二基； R3a與R3b彼此獨立地= CVC22-烷基、C2-C6-烯基、C6-C10-芳基、Η或CH2-X-R5，其中x=〇、s、-〇-C〇-或_C〇-〇-， R4=CrC18-烷基/烯基或苯基；及 R5= Η、CVCf 烷基、C2-C22-烯基或 C6-C1(r芳基，及/ 或 c) a)與b)的鹽。 4. 根據申請專利範圍第1項或第2項之方法，其特徵在於該穩定劑混合物至少包含： a) —種過氯酸鹽，及/或 b) —種單或多官能環氧化物與氨或分別與單或多官能二烷基（芳基）胺或單烷基（芳基）胺的反應產物，及/或 c) a)與b)的鹽。 5. 根據申請專利範圍第1項或第2項之方法，其特徵在於該多官能環氧化物爲雙環氧化二聚環戊二烯、雙環氧化 38 200300774 乙烯基環己烯、雙酚A二縮水甘油醚或異氰脲酸三縮水甘油酯’二烷基胺爲二乙醇胺或二異丙醇胺，而單烷基胺爲單乙醇胺或單異丙醇胺。 6·根據申請專利範圍第1項或第2項之方法，其特徵在於該過氯酸鹽爲具有分子式M(C104)n的化合物，其中Μ是 Η、Li、Na、Κ、Mg、Ca、Sr、Ba、Ζη、Α卜 La、Ce 或 ΝΗ4 ，而n依M之價數所需而可爲1、2或3。 7 ·根據申g靑專利範圍第1項或第2項之方法，其特徵在於在具通式（I)之化合物中，R3a和R3b彼此獨立地爲Η或 CH3，而 y = 1 〇 8. 根據申請專利範圍第1項或第2項之方法，其中在具通式⑴之化合物中，RkRLCIVCHRlOH。 9. 根據申請專利範圍第1項或第2項之方法，其中在該過氯酸鹽中，M = Na或K，而n=l。 10. 根據申請專利範圍第1項或第2項之方法，其中通式⑴之化合物爲：參（2-羥基-1-丙基）胺、參（2-羥基乙基）胺、雙（2-羥基乙基）-2-羥基-1-丙胺或烷基/烯基雙（2-羥基乙基）胺或烷基/烯基（2-羥基-1-丙基）胺、N-(2-羥基十六烷基）二乙醇胺、N-(2-羥基-3-辛氧基丙基）二乙醇胺、N-(2-羥基-3-癸氧基丙基）二乙醇胺或此等之混合物。 11. 根據申請專利範圍第1項至第2項之安定含鹵聚合物之方法，其特徵在於該聚合物爲含氯聚合物’較佳爲 PVC。 12. —種組成物，其包含已經藉由根據申請專利範圍第 39 200300774 1項至第11項中任一項之方法安定化的含鹵聚合物。 13. 根據申請專利範圍第12項之組成物，其特徵在於有安定含鹵聚合物之分散液存在。 14. 根據申請專利範圍第12項或第13項之組成物，其特徵在於··以整體含氯聚合物之分散液爲基準，（b)項中通式（I)化合物的存在量最好是0.01至10重量份，較佳係從 0.1至5重量份。 15. 根據申請專利範圍第12項或第13項之組成物，其特徵在於：以整體含氯聚合物之分散液爲基準，（a)項中過氯酸鹽或此等之溶液的存在量係從0.001至5重量份，最好是0.01至3重量份，特佳是0.01至2重量份。 16. 根據申請專利範圍第12項或第13項之組成物，其特徵在於：以整體含氯聚合物之分散液爲基準，（c)項中（a) 與（b)之鹽類的存在量是0.01至10重量份，較佳係從0.1至 5重量份。 Π.根據申請專利範圍第12項或第13項之組成物，其特徵在於：以重量計，（b)項中通式化合物（或此等之混合物）對（a)項中過氯酸鹽的比例是在0.01:1至50:1的範圍內。 18. —種根據申請專利範圍第12項至第17項中任一項之組成物的用途，其係用於物件的製造。 19. 一種根據申請專利範圍第12項至第17項中任一項之組成物的用途，其係用於物件之塗佈。 20. 根據申請專利範圍第19項之用途，其係用來製造未經增塑之PVC塗層。 200300774 21·—種製造增塑PVC塗層之方法，其係將物件浸漬於根據申請專利範圍第13項至第17項中任一項之組成物中〇 22. —種藉由根據申請專利範圍第18項至第21項中任一項之用途或方法所製得的物件。拾壹、圖式 (無）200300774 Patent application scope 1 · A method for stabilizing a halogen-containing polymer in an aqueous dispersion, wherein a stabilizer mixture compatible with the polymer dispersion is added to the aqueous dispersion of the halogen-containing polymer. 2. The method according to item 1 of the scope of patent application, characterized in that the stabilizer mixture contains a perchlorate compound and / or an alkanolamine and / or these salts. 3. According to item 1 or The method of item 2, characterized in that the stabilizer mixture comprises at least: a) a perchlorate, and / or b) an alkanolamine of the formula (I): R2 I (CHR |) -CHRf ~ 〇Η χ = 1, 2, or 3; y = 1, 2, 3, 4, 5 or 6; n = 1 to 10; R1 and R2 are independent of each other = Η, CrC22-alkyl, + ((: 1 ^ ^ CHR3b-〇-] nH,-[-(CHR3a) y-CHR3b-〇-] nC〇-R4, C2-C20-alkenyl, C2-C18-fluorenyl, C4-C8-cycloalkyl (which can be With a degree of OH substitution at the β-position), C6-C1Q-aryl, c7-c1 (r-alkaryl or C7-C1Q-aralkyl, or, if x = 1, R1 and R2 may also be N- To form a 4 to 10 member closed 37 200300774 ring consisting of a carbon atom and (where appropriate) up to 2 heteroatoms, or if x = 2, R1 can also be a C2-C18-alkylene group, It may have a degree of substitution of 0Η on two β-carbon atoms and / or may be interrupted by one or more 0 atoms and / or one or more NR2 groups, Or it is tetrahydroextended cyclopentadienyl substituted with dihydroxy, ethylcyclohexyl substituted with dihydroxy, 4,4 '-(bisphenol A dipropyl ether) group substituted with dihydroxy, Isophorone, dimethylcyclohexyl, dicyclohexylmethylene or 3,3'-dimethyldicyclohexylmethylene, and if x = 3, then R1 can also be a trisyl group Substituted (tri-N-propyl isocyanurate) diyl; R3a and R3b are independent of each other = CVC22-alkyl, C2-C6-alkenyl, C6-C10-aryl, fluorene or CH2-X-R5 , Where x = 〇, s, -0-C〇- or _C〇-〇-, R4 = CrC18-alkyl / alkenyl or phenyl; and R5 = fluorene, CVCf alkyl, C2-C22-alkenyl Or C6-C1 (raryl, and / or c) a) and b) salt. 4. The method according to item 1 or 2 of the patent application scope, characterized in that the stabilizer mixture contains at least: a) -A perchlorate, and / or b)-a reaction product of a mono- or polyfunctional epoxide with ammonia or with a mono- or polyfunctional dialkyl (aryl) amine or monoalkyl (aryl) amine, respectively And / or c) a) and b) salts. 5. The method according to item 1 or 2 of the scope of patent application, characterized in that the polyfunctional epoxide is diepoxydicyclopentadiene, diepoxy 38 200300774 vinyl cyclohexene, bisphenol A di shrink The glyceryl ether or triglycidyl isocyanurate 'dialkylamine is diethanolamine or diisopropanolamine, and the monoalkylamine is monoethanolamine or monoisopropanolamine. 6. The method according to item 1 or 2 of the scope of patent application, characterized in that the perchlorate is a compound having a molecular formula M (C104) n, where M is Η, Li, Na, K, Mg, Ca, Sr, Ba, Zn, Ab La, Ce or NΗ4, and n may be 1, 2 or 3 depending on the valence of M. 7. The method according to item 1 or 2 of the patent scope of claim g, characterized in that in the compound of the general formula (I), R3a and R3b are independently 独立 or CH3, and y = 1 〇8. The method according to item 1 or item 2 of the scope of patent application, wherein RkRLCIVCHRlOH is the compound of the general formula ⑴. 9. The method according to item 1 or 2 of the scope of patent application, wherein in the perchlorate, M = Na or K, and n = 1. 10. The method according to item 1 or item 2 of the scope of patent application, wherein the compound of the general formula ⑴ is: ginseng (2-hydroxy-1-propyl) amine, ginseng (2-hydroxyethyl) amine, bis (2 -Hydroxyethyl) -2-hydroxy-1-propylamine or alkyl / alkenylbis (2-hydroxyethyl) amine or alkyl / alkenyl (2-hydroxy-1-propyl) amine, N- (2 -Hydroxyhexadecyl) diethanolamine, N- (2-hydroxy-3-octyloxypropyl) diethanolamine, N- (2-hydroxy-3-decyloxypropyl) diethanolamine or mixtures thereof . 11. The method for stabilizing a halogen-containing polymer according to items 1 to 2 of the scope of patent application, characterized in that the polymer is a chlorine-containing polymer ', preferably PVC. 12. A composition comprising a halogen-containing polymer that has been stabilized by a method according to any one of claims 39 to 200300774 1 to 11. 13. The composition according to item 12 of the scope of patent application, characterized in that a stable dispersion of a halogen-containing polymer is present. 14. The composition according to item 12 or item 13 of the scope of patent application, which is characterized in that: based on the dispersion of the entire chlorine-containing polymer, the compound of the general formula (I) in item (b) has the best amount It is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. 15. The composition according to item 12 or item 13 of the scope of patent application, characterized in that the amount of perchlorate or the solution in the item (a) is based on the dispersion of the entire chlorinated polymer. It is from 0.001 to 5 parts by weight, preferably from 0.01 to 3 parts by weight, particularly preferably from 0.01 to 2 parts by weight. 16. The composition according to item 12 or item 13 of the scope of patent application, which is characterized by the presence of the salts of (a) and (b) in (c) based on the entire chloropolymer dispersion The amount is from 0.01 to 10 parts by weight, preferably from 0.1 to 5 parts by weight. Π. The composition according to the 12th or 13th of the scope of the patent application, characterized in that, by weight, the compound of the general formula (or a mixture of these) in (b) vs. the perchlorate in (a) The ratio is in the range of 0.01: 1 to 50: 1. 18.-Use of a composition according to any one of claims 12 to 17 of the scope of patent application, which is used for the manufacture of articles. 19. Use of a composition according to any one of claims 12 to 17 of the scope of patent application, which is used for coating objects. 20. Use according to item 19 of the scope of patent application, which is used to make unplasticized PVC coatings. 200300774 21 · —A method for manufacturing a plasticized PVC coating, which is immersed in a composition according to any one of claims 13 to 17 of the scope of patent application. Articles made by the use or method of any one of items 18 to 21. Pick up, schema (none)

41 200300774 陸、（一）、本案指定代表圖爲：第（無）圖 (二）、本代表圖之元件代表符號簡單說明：41 200300774 Lu, (I), the designated representative of this case is: (None) Figure (II), the component representative symbols of this representative map are simply explained:

柒、本案若有化學式時，請揭示最能顯示發明特徵的化學式： R2 -(CHRj)-CHRj—〇 Ή柒 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: R2-(CHRj) -CHRj—〇 Ή

χ 4x 4