CN1149303A - 新磺化聚酯及其在织物漂洗、软化和处理洗涤剂组合物中防污剂的用途 - Google Patents
新磺化聚酯及其在织物漂洗、软化和处理洗涤剂组合物中防污剂的用途 Download PDFInfo
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- CN1149303A CN1149303A CN95193288.8A CN95193288A CN1149303A CN 1149303 A CN1149303 A CN 1149303A CN 95193288 A CN95193288 A CN 95193288A CN 1149303 A CN1149303 A CN 1149303A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
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Abstract
新的水分散性或水溶性磺化聚酯,其数均分子量低于20000,含硫重量为约0.5到10%,羟基官能团含量用OH等效量/kg聚酯表示为大于0.2。它们可用作防污剂和/或抗再污染剂,并选择性的在洗涤剂组合物、漂洗、软化或防污处理组合物中用作洗涤剂,用于有或没有预处理的织物,特别是聚酯基的织物的洗涤、漂洗、软化或防污处理。
Description
本发明涉及新的水分散性或水溶性磺化聚酯,其制备方法,及其在漂洗、软化或防污(“后处理”)处理组合物中作为防污剂和/或抗再污染剂和洗涤剂组合物中视具体情况存在的洗涤剂,用于对织物,特别是聚酯基的织物在有或没有预处理的条件下进行洗涤、漂洗、软化或防污处理。
根据本发明,它们是水分散性或水溶性磺化聚酯,其特征在于它们是通过单体组合物的酯化反应和/或酯基转移反应和缩聚反应制备的,所说的单体组合物基于:
-未磺化的二酸单体(A),是由至少一个选自对苯二酸、间苯二酸和2,6-萘二甲酸的二羧酸或酐或酐类或它们的二酯类组成,其用量对应于摩尔比(A)/(A)+(SA)为约95/100到60/100,优选约93/100到65/100
-磺化二酸单体(SA),是由至少一个磺化芳族或磺化脂族二羧酸或酐,或其酯组成,其用量对应于摩尔比(SA)/(A)+(SA)为约5/100到40/100,优选约7/100到35/100,其中有待被羟基化二酸单体(HA)代替的未磺化二酸单体(A)和/或磺化二酸单体(SA)的量多达50%摩尔,优选多达30%摩尔,所说的羟基化二酸单体(HA)是由至少一种羟基化芳族或脂族二羧酸或酐或所说羟基化芳族或脂族二羧酸的二酯组成
-和多羟基单体(P),是由至少一种选自乙二醇、丙二醇、二乙二醇、二丙二醇、丙三醇、1,2,4-丁三醇和1,2,3-丁三醇的多羟基化合物组成,其用量与多羟基单体(P)的OH官能团数/二酸单体(A)+(SA)+(HA)的COOH官能团或等效官能团数的比是约1.05到4相对应,优选约1.1到3.5,特别优选约1.8到3
其特征还在于当多羟基单体(P)不含任何二醇以外的多羟基化合物或当没有羟基化二酸单体(HA)存在时,磺化二酸单体(SA)是由至少一种磺化芳族二羧酸或酐,或磺化芳族酸或酐和磺化脂族酸或酐或其二酯的混合物组成其特征还在于所述的磺化聚酯呈现下列特性
-分子量低于20000,
-含硫量为约0.5到10%重量,优选约1.2到8%重量,
-用OH等效量/Kg聚合物表示的羟基官能团含量大于0.2。
羟基官能团含量是通过质子NMR测算的;测量在二甲基亚砜中进行。
数均分子量是在含有10-2N的LiBr的二甲基乙酰胺中,在25℃通过凝胶渗透色谱法测量。结果用聚苯乙烯当量表示。
在单体(A)、(SA)或(HA)摩尔的定义中所说的基本单元对于二酸是指COOH官能团,对于其酐或其二酯是COOH的等效官能团。
未磺化二酸单体(A)优选由50到100%摩尔,特别优选70到90%摩尔的对苯二酸或酐或其低级(甲基、乙基、丙基、异丙基、丁基的)二酯的其中之一,和0到50%摩尔,更特别是10到30%摩尔的间苯二酸或酐和/或2,6-萘二羧酸或酐或其低级(甲基、乙基、丙基、异丙基、丁基)二酯的其中之一组成;优选的二酯是甲基二酯。
在未磺化二酸单体(A)中,另外还存在上述未提到的微量芳族二酸,如邻苯二酸、蒽、1,8-萘、1,4-萘和联苯二羧酸,或脂族二酸,如以酸、酐或低级(甲基、乙基、丙基、异丙基、丁基)二酯形式存在的己二酸、戊二酸、丁二酸、三甲基己二酸、庚二酸、壬二酸、癸二酸、辛二酸、亚甲基丁二酸和马来酸等等。
磺化的二酸单体(SA)含有至少一个磺酸基团,优选呈碱金属(优选钠)磺酸盐形式,并且在涉及芳族二羧酸或酐或其二酯的情况下连接在一个或多个芳环上的,或者在涉及脂族二羧酸或酐或其二酯的情况下连接在脂族链上的两个酸官能团或酸官能团等效物(也就是说一个酐官能团或两个酯官能团)。
在磺化二酸单体(SA)中,芳族磺化二羧酸或酐可以是例如:磺基间苯二酸、磺基对苯二酸、磺基邻苯二酸或酐、4-磺基-2,7-萘二羟酸或酐,磺基4,4’-双(羟基羰基)二苯基砜、磺基二苯基二羧酸或酐、磺基-4,4’-双(羟基羰基)二苯基甲烷、磺基-5-苯氧基间苯二酸或酐或其低级(甲基、乙基、丙基、异丙基、丁基)二酯和磺化脂族磺化二羧酸或酐如磺基琥珀酸或酐或其低级(甲基、乙基、丙基、异丙基、丁基)二酯。优选的磺化二酸单体(SA)是磺基间苯二酸和磺基丁二酸或酐和其甲基二酯,并特别是5-钠代氧磺基间苯二酸二甲酯。
羟基化二酸单体(HA)含有至少一个羟基,当它是芳族单体时,该羟基连接在一个或多个芳环上,当它是脂族单体时,连接在脂肪链上。
在羟基化二酸单体(HA)中,可以有5-羟基间苯二酸、4-羟基间苯二酸、4-羟基苯二酸、2-羟基甲基丁二酸、羟基甲基戊二酸和羟基戊二酸或酐等等,或它们的低级(甲基、乙基、丙基、异丙基、丁基)二酯。
多羟基单体(P)优选一乙二醇和/或甘油。
所说的水溶性和/或水分散性磺化聚酯可以通过通常的酯化反应和/或酯基转移反应和缩聚反应制备,例如在多羟基单体(P)与各种二酸单体的酯化反应和/或酯基转移反应的催化剂存在下,通过酯化反应和/或酯基转移反应制备,每个二酸都是以酸或酐的形式存在,或以其二酯的其中之一的形式,并且多羟基酯的缩聚反应是在减压、存在缩聚反应催化剂的情况下进行。
根据优选制备方法,所说水溶性和/或水分散性磺化聚酯是通过进行下列连续步骤制备的:
-酯基转移反应(互换反应)阶段,是在一方面,以二酯形式存在并且占以二酯形式存在的未磺化二酸单体(A)总量的50到100%摩尔,特别是30到90%摩尔的磺化二酸单体(SA),和,另一方面一定量的多羟基单体(P)之间的反应,多羟基单体(P)的用量对应于其中OH官能团的数量/所说以二酯形式存在的单体(A)和(SA)的COOH官能团等效物的数量之间的比为约1.05到4,优选约1.1到3.5,更优选是约1.8到3.0
-视具体情况存在的酯化反应阶段,是在以二酸或酐形式存在的未磺化二酸单体(A)可能存在的量,和一定量多羟基单体(P)之间的反应,多羟基单体(P)的用量对应于其中OH官能团数/以二酸或酐形式存在的未磺化二酸单体(A)的COOH官能团数之间的比是约1.05到4,优选约1.1到3.5,更优选是约1.8到3.0。
-缩聚反应阶段
用于酯基转移(互换)反应阶段的未磺化(A)和磺化(SA)二羧酸的二酯优选是甲基二酯。
互换阶段是在高于或等于130℃,优选约140到220℃,并特别优选约180到220℃的温度下进行的;在此温度下,优选通过蒸馏将形成的甲醇(在优选情况下是甲基二酯)从反应混合物中去除。这种互换反应优选是在有金属酯基转移催化剂,尤其是金属羟酸盐如乙酸锰、乙酸锌、乙酸钴或乙酸钙,或者有机或无机钛酸盐如丁基钛酸盐、2,2’,2”-氮基三乙基钛酸盐(或钛氨基三乙醇盐)或钛酸钙存在下进行的。优选的催化剂是有机钛酸盐;它的采用量相对于存在的反应物量,以钛表示至少是约0.001%重量,优选约0.002%到0.02%重量。
互换反应持续的时间是1到4小时;通常是2到3小时。
当大于理论值90%的甲醇被蒸出以后,过量的多羟基化合物通过将反应混合物的温度提高到230℃来去除。
酯化反应是通过往反应混合物中加入以二酸形式存在的未磺化二酸单体(A)的和预先悬浮的多羟基单体(P)的残留部分,在互换反应终了温度下进行;添加阶段为1小时。
酯化反应是在约230到280℃,优选约250到260℃温度下,在存在与酯基转移反应同样的催化剂情况下进行;优选的催化剂是有机钛酸盐;它的采用量相对于引入酯化阶段的反应物量,以钛表示至少是0.001%重量,优选0.002%到0.02%重量;反应从除去水开始,水是与过量的多羟基化合物一起从反应器中去除的。
缩聚反应优选是在约230到280℃,更优选约240到260℃的温度下,在预先加热到此温度的另一个反应器中,并且逐渐排空至可能高达10Pa的压力的情况下进行;压力减小到约10毫巴持续约40分钟。
缩聚反应随着多羟基分子的脱除而发生。在7.5-升反应器中,当反应物温度为250℃,锚型转子的搅拌速度为80转/分钟,搅拌器轴的驱动转力矩是0与大约0.5到5牛顿米等同的数值时,停止反应;转矩测量器采用Kyowa型,测量范围在0到100牛顿米之间。
接着,通入氮气破坏真空,将聚合物倾入坯料模;冷却后,将聚酯研磨。
优选的磺化聚酯是由下列物质制备的:
-(优选甲基)二酯形式的对苯二酸(A1)和二酸或酐形式的间苯二酸(A2),或者(优选甲基)二酯形式的对苯二酸(A1)和二酸或酐形式的羟基化的对苯二酸或羟基化的间苯二酸(HA),选择性的与二酸或酐形式的间苯二酸(A2)混合,(A1)/(A1)+(A2)、(A1)/(A1)+(HA)或(A1)/(A1)+(HA)+(A2)的摩尔比是约100/100到50/100,优选约90/100到70/100[以单体(A)或单体(A)和(HA)计]
-(优选甲基)二酯形式的磺基间苯二酸[以单体(SA)计]
-一乙二醇和/或甘醇[以多羟基单体(P)计]。
它们可以按照上述的优选方法制备,通过下列连续步骤进行:
-酯基转移反应(互换反应)阶段,是在一方面,(优选甲基)二酯形式的对苯二酸(A1)和(优选甲基)二酯形式的磺基间苯二酸(SA),和另一方面一乙二醇和/或甘醇(P)之间进行,(P)的OH官能团数/(A1)+(SA)的COOH官能团等效物的数量之间的比是约1.05到4,优选约1.1到3.5,更优选是约1.8到3.0
-酯化反应阶段,是在间苯二酸(A2)和/或羟基(间-或对-)苯二酸(HA)和一乙二醇和/或甘醇(P)之间进行,(P)的OH官能团数量/(A2)+/或(HA)的官能团COOH的数量之间的比是约1..05到4,优选约1.1到3.5,更优选是约1.8到3.0
-缩聚反应阶段。
构成本发明主题的磺化聚酯在洗涤剂组合物中,在用于织物,特别是聚酯基织物的有或没有预处理的洗涤、漂洗、软化或防污处理的漂洗、软化、或防污(“后处理”)处理组合物中,作为防污剂和/或抗再污染剂和视需要而存在的洗涤剂是特别有效的。
本发明的另一个主题是洗涤剂组合物,它含有占所说组合物量的约0.01到10%,优选约0.1%到5%,更优选约0.2到3%的所说的构成了本发明主题的磺化聚酯。
本发明的其他主题包括在用于洗涤特别是基于聚酯纤维的纺织品的洗涤剂组合物中,采用能够通过基于下列物质的单体组合物的酯化反应和/或酯基转移反应和缩聚反应制备的水分散性或水溶性磺化聚酯作为防污剂的用途:
-未磺化二酸单体(A),是由至少一个选自对苯二酸、间苯二酸和2,6-萘二羧酸或酐或其二酯的二羧酸或酐组成,其用量对应于摩尔比(A)/(A)+(SA)为约95/100到60/100,优选约93/100到65/100
-磺化二酸单体(SA),是由至少一个磺化芳族或磺化脂族二羧酸或酐或它们的酯组成,其用量对应于摩尔比(SA)/(A)+(SA)约为5/100到40/100,优选约7/100到35/100,有待被羟基化二酸单体(HA)代替的未磺化二酸单体(A)和/或磺化二酸单体(SA)的量高达50%摩尔,优30%摩尔,羟基化二酸单体(HA)是由至少一种羟基化芳族或脂族二羧酸或酐或所说的羟基化芳族或脂族二羧酸的二酯组成
-和多羟基单体(P),它是由至少一种选自乙二醇、丙二醇、二乙二醇、二丙二醇、丙三醇、1,2,4-丁三醇和1,2,3-丁三醇的多羟基化合物组成,其用量对应于多羟基单体(P)的OH官能团的数量/二酸单体(A)+(SA)+(HA)的COOH官能团或官能团等效物的数量之比是约1.05到4,优选约1.1到3.5,特别优选约1.8到3
所说的磺化聚酯的
-数均分子量低于20000,
-含硫重量为约0.5到10%,优选约1.2到8%
-并且,以OH等效物/Kg聚酯表示,羟基官能团含量大于0.2。
单体(A)、(SA)、(HA)和(P)的实例已在前面提到;制备所说的磺化聚酯的反应条件与前述的相同或等效。
用于洗涤纺织制品,特别是基于聚酯纤维的纺织制品的洗涤剂组合物,在生态毒理学性质方面非常有利,它们包括:
-约0.01到10%重量,优选约0.1到5%重量,更优选约0.2到3%重量的水分散性或水溶性的上述磺化聚酯防污剂
-和约3到40%重量,优选约5到35%重量的阴离子表面活性剂,它其中的至少一种是选自可选择性的与约0.5到30摩尔环氧乙烷缩合的C5-C24饱和的脂族醇的硫酸盐,
不超过5%重量的所说的洗涤剂组合物能够由其他类型的缺乏优良的生态毒理学性质的阴离子表面活性剂组成,如C1-C18烷基苯磺酸盐。
在可采用的选择性被乙氧基化的醇的硫酸盐中,可以提及的是未乙氧基化的C8-C18(优选C10-C15)醇的硫酸盐、与约1到30(优选1到10)摩尔的环氧乙烷缩合的C5-C13(优选C10-C13)脂肪醇的硫酸盐,和与约4到30(优选4到10)摩尔的环氧乙烷缩合的C14-C20(优选C14-C18)脂肪醇的硫酸盐。
下面描述除了本发明所说的磺化聚酯之外,洗涤剂组合物还可以包括的其他类型的添加剂。-表面活性剂,量约为洗涤剂组合物的3-40%重量的表面活性剂如阴离子表面活性剂-烷基磺酸盐,通式为R-CH(SO3M)-COOR’,其中R表示C8-C20,优选C10-C16烷基,R’表示C1-C6,优选C1-C3烷基,M表示碱金属(钠、钾、锂)阳离子,取代的或未取代的铵(甲基、二甲基、三甲基、四甲基铵、二甲基哌啶翁等等)或一个链烷醇胺(一乙醇胺、二乙醇胺、三乙醇胺等等)的衍生物。更具体的说,可以是其中R是C14-C20的甲磺酸盐;-通式为ROSO3M的烷基硫酸盐,其中R表示C5-C24,优选C10-C18烷基或羟烷基,M表示氢原子或与上述限定一样的阳离子,和它们平均含0.5到30,优选0.5到10个EO和/或PO单元的乙氧基化(EO)和/或丙氧基化(PO)的衍生物;-通式为RCONHR’OSO3M的烷基酰胺的硫酸盐,其中R表示C2-C22,优选C6-C20烷基,R’表示C2-C3烷基,M表示氢原子或与上述限定一样的阳离子,和它们平均含0.5到60个EO和/或PO单元的乙氧基化(EO)和/或丙氧基化(PO)的衍生物;-C8-C24,优选C14-C20的饱和或不饱和脂肪酸的盐,C9-C20烷基苯磺酸盐,伯或仲C8-C22烷基磺酸盐,磺酸烷基甘油酯盐,在GB-A-1082179中所述的磺化聚羧酸,石蜡磺酸盐,N-酰基-N-烷基牛磺酸盐,烷基磷酸盐,异硫代硫酸盐,烷基丁二酸盐,烷基磺基丁二酸盐,磺基丁二酸一酯或二酯盐,N-酰基肌氨酸盐,烷基苷硫酸盐,和聚乙氧基羧酸盐
阳离子是碱金属(钠、钾、锂)、取代的或未取代的铵残基(甲基、二甲基、三甲基、四甲基铵、二甲基哌啶翁等等)或一个链烷醇胺(一乙醇胺、二乙醇基胺、三乙醇胺等等)的衍生物;非离子表面活性剂-聚氧亚烷基化(聚乙氧亚乙基化、聚氧亚丙基化,聚氧亚丁基化)的烷基酚,其中烷基取代基是含有5到25个氧亚烷基单元的C6-C12;实例是由Rohm & Haas Co.市售的Tritons X-45,X-114,X-100或X-102,-葡糖酰胺,葡糖胺,甘油酰胺;-聚氧亚烷基化C8~22脂族醇,含有1到25个氧亚烷基(氧亚乙基、氧亚丙基)单元;可提到的实例是由Union Carbide Corp.市售的Tergitol 15-S-9、Tergitol 24-L-6NMW,由Shell Chemical Co.市售的Neodol 45-9、Neodol 23-65、Neodol 45-7、Neodol 45-4,由Procter & Gamble Co市售的Kyro EOB;-通过环氧乙烷的缩合反应制得的产物,通过环氧丙烷与丙二醇的缩合反应制得的化合物,如由BASF市售的Pluronics;-通过环氧乙烷的缩合反应制得的产物,通过环氧丙烷与乙二胺的缩合反应制得的化合物,如由BASF市售的Tetronics;-胺氧化物,如(C10-C18烷基)二甲基胺氧化物和(C8-C22烷氧基)乙基二羟基乙基胺氧化物;-在US-A-4 565 647中描述的烷基聚苷;-C8-C20脂肪酰胺-乙氧基化脂肪酸-乙氧基化脂肪酰胺-乙氧基化胺阳离子表面活性剂-烷基二甲基铵卤化物两性的和两性离子的表面活性剂-烷基二甲基甜菜碱,烷基酰氨基丙基二甲基甜菜碱,烷基三甲基磺基甜菜碱,脂肪酸和蛋白的水解产物的缩合产物-其中烷基含6到20个碳原子的烷基两性乙酸盐或烷基两性二乙酸盐-改良表面活性剂性质的辅助剂(“助洗”剂),其量为占液态洗涤剂配方的约5-50%,优选5-30%重量或占粉状洗涤剂配方的约10-80%,优选15-50%重量,增效助剂如无机(“增效助剂”)辅助剂-碱金属、铵或链烷醇胺聚磷酸盐(三聚磷酸盐,焦磷酸盐,正磷酸盐,六偏磷酸盐)-四硼酸盐或硼酸盐前体-硅酸盐,特别是SiO2/Na2O的比例是约1.6/1到3.2/1的硅酸盐和在US-A-4 664 839描述的片状硅酸盐-碱金属或碱土金属碳酸盐(碳酸氢盐,倍半碳酸盐)-水合碱金属硅酸盐和富含Q2或Q3形式的硅原子的碱金属(钠或钾)碳酸盐的共颗粒,如在EP-A-488 868中所述-晶状或无定型碱金属(钠、钾)或铵的氨基硅酸盐如沸石A,P,X等等;优选粒度约为0.1-10微米的沸石A有机(“增效助剂”)辅助剂-水溶性聚磷酸盐(1-羟基-1,1-二磷酸乙酯盐,亚甲基二磷酸酯盐等等)-羧酸聚合物或共聚物的水溶性盐,或它们的水溶性盐,如
-聚羟酸酯醚(氧二丁二酸和其盐,酒石酸一丁二酸和其盐,酒石酸二丁二酸和其盐)
-羟基聚羧酸酯醚
-柠檬酸和其盐,苯六甲酸,丁二酸及其盐
-聚乙酸的盐(亚乙基二胺四乙酸盐,次氮基三乙酸盐,N-(2-羟基乙基)次氮基二乙酸盐)
-C5-C20烷基丁二酸和它们的盐(2-十二烷基丁二酸盐,月桂基丁二酸盐)
-羧基聚缩醛酯
-聚天冬氨酸,聚谷氨酸和它们的盐-由天冬氨酸和/或谷氨酸的缩聚反应衍生的聚酰亚胺;-谷氨酸或其它氨基酸的聚羧基甲基化衍生物;-漂白剂,其量约为0.1-20%,优选约1-10%重量,可选择性的与漂白活性剂结合,其量为0.1-60%,优选约0.5-40%重量,漂白剂和活性剂如漂白剂-过硼酸盐,如高硼酸钠一水或四水合物-过氧化物,如碳酸钠过氢氧化物,焦磷酸过氢氧化物,脲过氢氧化物,过氧化钠,过硫酸钠,优选与漂白活性剂结合使用,这种漂白活性剂在洗涤介质中即时形成过氧羟酸;在这些活性剂中,可以是四乙酰基乙二胺,四乙酰基甲二胺,四乙酰基甘脲,对乙酰氧苯磺酸钠,五乙酰基葡萄糖,八乙酰基乳糖等等。-过羧酸和它们的盐(叫做“过碳酸盐”),如一过氧邻苯二甲酸镁六水合物,间氯过苯甲酸镁,4-壬基氨基-4-氧代过氧丁酸,6-壬基氨基-6-氧代过氧己酸,二过氧十四双酸,过氧丁二酸的壬酰胺和癸基二过氧丁二酸。
这些试剂可以与至少一种下述防污剂或抗再污染剂结合使用。
还需提到的是未氧化的通过存在氧的光敏化反应而起作用的漂白剂,如磺化的铝和/或酞青锌之类的试剂-其他防污剂,量为约0.01-10%,优选约0.1-5%,并特别优选约0.2-3%重量,如-纤维素衍生物,如羟基醚纤维素,甲基纤维素,乙基纤维素,羟丙基甲基纤维素,羟丁基甲基纤维素-在聚亚烷基主链上接枝的聚乙烯基酯,如在聚氧亚乙基主链上接枝的聚乙烯基乙酸酯(EP-A-219048)-聚乙烯基醇-基于对苯二酸乙二醇酯和/或对苯二酸丙二醇酯和聚氧亚乙基对苯二酸酯单元的聚酯共聚物,其中对苯二酸乙二醇酯和/或对苯二酸丙二醇酯(单元数)/聚氧亚乙基对苯二酸酯(单元数)的摩尔比是约1/10到10/1,优选1/1到9/1,聚氧亚乙基对苯二酸酯具有数均分子量为约300到5000,优选约600到5000的聚氧亚乙基单元(US-A-3959230,US-A-3893929,US-A-4116896,US-A-4702857,和US-A-4770666);-磺化聚酯低聚物,是通过从乙氧基化的烯丙醇、从对苯二酸二甲酯和从1,2-丙二醇衍生的低聚物的磺化反应制备的,含有1到4个磺化基(US-A-4968451)。-基于对苯二酸丙二醇酯和聚氧亚乙基对苯二酸酯单元的聚酯共聚物,并且以乙基或甲基单元(US-A-4711730)为端基,或者以烷基聚乙氧基(US-A-4702857)或磺基聚乙氧基(US-A-4721580)或磺基芳酰基(US-A-4877896)阴离子基团为端基的聚酯低聚物-其他抗再污染剂,量约是粉状洗涤剂组合物的0.01-10%重量,是液态洗涤剂组合物的约0.01-5%重量,试剂如-乙氧基化的-胺或聚胺,乙氧基化的胺聚合物(US-A-4597898,EP-A-11984)-羧甲基纤维素-磺化聚酯低聚物,是通过间苯二酸、磺基丁二酸二甲酯和二乙二醇的缩合反应制备的(FR-A-2236926)-聚乙烯基吡咯烷酮-铁离子和镁离子的螯合剂,量为约0.1-10%,优选约0.1-3%重量,试剂如-氨基羧酸盐,如乙二胺四乙酸盐、羟基乙基乙二胺三乙酸盐、次氮基三乙酸盐-氨基磷酸盐,如次氮基三(亚甲基磷酸盐)-多官能的芳香化合物,如二羟基二磺基苯;-聚合物分散剂,量为0.1-7%重量,用于控制钙和镁的硬度,试剂如-数均分子量为约2000到100000的聚羧酸的水溶性盐,是通过烯属不饱和羧酸,如丙烯酸、马来酸或酐、富马酸、衣康酸、乌头酸、中康酸、柠康酸或亚甲基丙二酸,并且特别是数均分子量为约2000到10000(US-A-3308067)的聚丙烯酸酯的和丙烯酸和数均分子量为约5000到75000(EP-A-66915)的马来酸酐的共聚物的聚合反应或缩聚反应制备的,-数均分子量为约1000到50000的聚乙二醇;-荧光剂(增亮剂),量为约0.05-1.2%重量,试剂如1,2-二苯乙烯衍生物、吡唑啉、香豆素、富马酸、肉桂酸、吡咯、次甲基花清、噻吩等等(“The production and application of fluorescent brighening agents”-M.Zahradnik,published by John Wiley & Sons,New York-1982);-抑泡剂,量多达5%重量,试剂如-C10-C24一羧基脂肪酸或它们的碱金属、铵或链烷醇胺盐、脂肪酸甘油三酯-脂族、脂环、芳族或杂环饱和的或未饱和的烃,如石蜡和蜡类-N-烷基氨基三嗪-单硬酯酰磷酸盐、十八烷醇磷酸盐-可选择性与氧化硅颗粒结合的聚有机硅油或树脂;-软化剂,相对于约0.5-10%重量,试剂如粘土;-酶,量为每克洗涤剂组合物为5毫克,优选0.05-3毫克活性酶,酶如-蛋白酶、淀粉酶、脂肪酶、纤维素酶、过氧酶(US-A-3553139,US-A-4101457,US-A-4507219,US-A-4261868);-其他添加剂,如-醇类(甲醇、乙醇、丙醇、异丙醇、丙二醇、乙二醇、丙三醇)-缓冲剂-芳香剂-颜料。
下面给出实施例进行说明。实施例1
磺化聚酯的制备
7.5升不锈钢反应器装配有转速为80转/分钟的锚式搅拌器,与Kyowa转矩计、传热流体循环夹套和由电磁阀控制的蒸馏柱连接,往其中加入:
-12.17摩尔的对苯二酸二甲酯 (2363g)
-1.99摩尔的5-二甲基磺酸间苯二酸钠 (590g)
-40.16摩尔的乙二醇 (2493g)
-54ppm(重量)的丁基原钛酸盐形式的钛。
将混合物预热到130℃。
再在约130分钟内将其加热到220℃,将大于理论量的90%的甲醇蒸出。
接着将反应混合物在30分钟内加热到230℃。当反应物达到230℃时, 开始加入含下列物质的悬浮液:
-2.99摩尔的间苯二酸 (497g)
-8.00摩尔的乙二醇 (497g)
加入是在60分钟内完成,同时将反应物保持在230℃。
继续加热,使反应物在60分钟内达到250℃。
在加入间苯二酸和乙二醇混合物的过程中和在加热到250℃的过程中,在无需增加成本的条件下便可以蒸出水和乙二醇的混合物。
反应混合物接着被转移到预热到250℃的高压釜中,在38分钟内将压力减到10毫巴,相当于3Nm的驱动转力矩。
将反应物倾出;冷却后得到水分散性聚酯,其具有下列性质:
-数均分子量=10480
-磺化官能团含量为:11.6%摩尔
-OH官能团含量:0.48eq./kg实施例2
磺化聚酯的制备
在相同反应条件下重复实施例1的步骤, 采用
-7.99摩尔的苯二酸二甲酯 (1551g)
-5.38摩尔的5-二甲酯磺酸间苯二酸钠 (1594g)
-37.5摩尔的乙二醇 (2325g)
-54ppm (重量)的丁基原钛酸盐形式的钛 (1.34g)
接着加入230℃的悬浮物,其含有
-2.00摩尔的间苯二酸 (332.6g)
-5.36摩尔的乙二醇 (332.8g)
将反应混合物在驱动转力矩为3Nm,相当于减压到100毫巴时倾出。
得到水分散性聚酯,其具有下列性质:
-数均分子量=9100
-磺化的官能团含量为:35%摩尔
-OH官能团含量:0.39eq./kg。实施例3
磺化聚酯的制备
在同样的反应条件下重复实施例1的步骤,采用
-9.04摩尔的对苯二酸二甲酯 (1736g)
-1.46摩尔的5-二甲基磺酸间苯二酸钠 (433g)
-29.4摩尔的乙二醇 (1825g)
-54ppm(重量)的氨基三乙醇钛形式的钛 (1.34g)
接着加入230℃的悬浮液,其含有
-2.40摩尔的羟基间苯二酸 (400g)
-19.33摩尔的乙二醇 (1200g)
将反应混合物在驱动转力矩为3Nm,相当于减压到13毫巴时倾出。
得到水分散性聚酯,其具有下列性质:
-数均分子量=13310
-磺化的官能团含量为:11.3%摩尔
-OH官能团含量:0.54eq./kg。实施例4
磺化聚酯的制备
在同样的反应条件下重复实施例1的步骤, 采用
-12.17摩尔的对苯二酸二甲酯 (2363g)
-1.99摩尔的5-二甲基磺酸间苯二酸钠 (590g)
-40.16摩尔的乙二醇 (2493g)
-54ppm(重量)的丁基原钛酸盐形式的钛
接着加入230℃的悬浮液,其含有
-2.99摩尔的间苯二酸 (497g)
-2.99摩尔甘油 (275g)
-5.01摩尔的乙二醇 (261g)
将反应混合物在驱动转力矩为3Nm,相当于减压至13毫巴时倾出。
得到水分散性聚酯,其具有下列性质:
-数均分子量=12130
-磺化的官能团含量为:11.6%摩尔
-OH官能团含量:0.41eq./kg。实施例5
制备洗衣机用洗涤剂组合物
洗涤粉组合物 份(重量)
-沸石4A 25
-碱式碳酸盐 15
-R2A焦硅酸盐 5
-Sokalan CP5丙烯酸/马来酸的共聚物(BASF) 5
-Na的硫酸盐 10.7
-羧甲基纤维素 1
-过硼酸盐一水合物 15
-四乙酰乙二胺 5
-直链十二烷基苯磺酸盐 6
-Synperonic A3(用3个EO乙氧基化 3
的C12-C15脂肪醇)
-Synperonic A9(用9个EO乙氧基化 9
的C12-C15脂肪醇)
-Esperase 4.0T酶 0.3
-防污剂。实施例6
防污性质
将试验的防污聚合物加入到实施例5的洗涤剂组合物中,聚合物活性物质的量为1%。试验
预洗
将面积大小为10×10cm的聚酯或聚酯/棉花(65/35)在涤垢仪中预洗20分钟,温度为40℃,洗涤粉配方含有1%重量的试验聚合物活性物质;所用水的硬度为30°TH;所用的洗涤粉的量为1升水5g。
将方形织物用冷水(14℃)洗涤3次,历时5分钟,并两次通过打光机干燥。
污染
将4滴发动机污油滴在6个预洗了的方形物上,为了确保污渍牢固,将织物置于60℃的炉中1小时。为了使结果能够良好的重现,将织物在24小时内洗涤。
洗涤
在与预洗同样的条件下完成洗涤(即在40℃洗涤20分钟,用5g每1升硬度为30°TH的水中含1%防污聚合物活性物质的洗涤粉,接着用冷水在5分钟内洗涤3次,在打光机上干燥两次)。
评价
用Dr.Lange/Luci 100比色计测量织物在洗涤之前和之后的反射度。
试验聚合物用作防污剂的效果用去除污渍的%表示,由下面的通式计算:
E的%=100×(R3-R2)/(R1-R2)
R1表示未污织物在洗涤前的反射度
R2表示被污染的织物在洗涤前的反射度
R3表示被污染的织物在洗涤后的反射度
对每一个试验产物计算去除污渍的平均%。
所得结果列于下表1。
聚合物 E的%
- 10
实施例1的 63
实施例2的 80
实施例3的 50
GerolPS 32* 13
*由Rhone-Poulenc市售的含有11.62%摩尔的磺化官能团并且数均数均分子量为25000的水分散性磺化聚酯
实施例7
主要的洗涤性质
由CFT(试验材料中心)制造的标准织物的试件如下
-棉皮脂10D
-聚酯/棉(65/35)皮脂20D
-聚酯皮脂30D
将大小为10x10cm的试件在涤垢仪中用往其中加入了1%重量的聚合物活性物质的上述配方的洗涤剂在40℃洗涤20分钟;所用水的硬度为30°TH。
将织物在5分钟清洗3次,在打光机中干燥。
采用Xenocolor(Dr.Lange)反射计,根据“L”、“a”和“b”系统(从黑到白、从绿到红和从兰到黄的程度)测定试件在洗涤前和洗涤和干燥后的反射度。
通过将在污染织物洗涤前和洗涤后的色差ΔL、Δa和Δb进行几何加和来计算每一类型织物的ΔE值,即
ΔE=(ΔL2+Δa2+Δb2)1/2
所得结果列于下表
聚合物 ΔE
- 40
实施例1的 42
实施例2的 51.3
实施例3的 43.6
GerolPS 32 46.2实施例8
洗衣机用洗涤剂组合物的配方
洗涤粉的组成 重量份
-沸石4A 25
-碱式碳酸盐 15
-焦硅酸盐R2A 5
-Sokalan CP5丙烯酸/马来酸共聚物(BASF) 5
-硫酸钠 5.7
-羧甲基纤维素 1
-过硼酸盐一水合物 15
-四乙酰乙二胺 5
-乙氧基化月桂酰基醚硫酸盐(一个氧化乙烯单元) 10
-Synperonic A3(被3个EO乙氧基化的C12-C15脂肪醇)3
-Synperonic A9(被9个EO乙氧基化的C12-C15脂肪醇)9
-Esperase4.0T酶 0.3
-实施例2的防污聚合物 1
重复实施例6所述的试验,去除污渍E的平均%是75%。实施例9
洗衣机用洗涤剂组合物的配方
洗涤粉的组成 重量份
-沸石4A 25
-碱式碳酸盐 15
-焦硅酸盐R2A 5
-Sokalan CP5丙烯酸/马来酸共聚物(BASF) 5
-硫酸钠 5.7
-羧甲基纤维素 1
-过硼酸盐一水合物 15
-四乙酰乙二胺 5
-乙氧基化月桂酰基醚硫酸盐(两个氧化乙烯单元) 10
-Synperonic A3(被3个EO乙氧基化的C12-C15脂肪醇)3
-Synperonic A9(被9个EO乙氧基化的C12-C15脂肪醇)9
-Esperase4.0T酶 0.3
-实施例2的防污聚合物 1
重复实施例6所述的试验,去除污渍E的平均%是71%。
Claims (15)
1.水分散性或水溶性磺化聚酯,其特征在于:它们是通过以下列物质为基的单体组合物的酯化反应和/或酯基转移反应和缩聚反应制备的:
-未磺化的二酸单体(A),是由至少一个选自对苯二酸、间苯二酸和2,6-萘二甲酸的二羧酸或酐类或它们的二酯类组成,其用量对应于摩尔比(A)/(A)+(SA)约为95/100到60/100,优选约93/100到65/100
-磺化二酸单体(SA),是由至少一个磺化芳族或磺化脂族二羧酸或酐,或其二酯组成,其用量对应于摩尔比(SA)/(A)+(SA)为约5/100到40/100,优选约7/100到35/100,有待被羟基化二酸单体(HA)代替的未磺化二酸单体(A)和/或磺化二酸单体(SA)的量多达50%摩尔,优选多达30%摩尔,所说的羟基化二酸单体(HA)是由至少一种羟基化芳族或脂族二羧酸或酐或所说羟基化芳族或脂族二羧酸的二酯组成
-和多羟基单体(P),是由至少一种选自乙二醇、丙二醇、二乙二醇、二丙二醇、丙三醇、1,2,4-丁三醇和1,2,3-丁三醇的多羟基化合物组成,其用量对应于多羟基单体(P)的OH官能团数/二酸单体(A)+(SA)+(HA)的COOH官能团或等效官能团数的比是约1.05至4,优选约1.1至3.5,特别优选约1.8至3其特征在于当多羟基单体(P)不含任何非二元醇多羟基化合物或当没有羟基化二酸单体(HA)存在时,磺化二酸单体(SA)是由至少一种磺化芳族二羟酸或酐,或磺化芳族酸或酐和磺化脂族酸或酐或其二酯的混合物组成其特征还在于所述的磺化聚酯呈现下列行性
-数均分子量低于20000,
-含硫重量为约0.5到10%,优选约1.2到8%,
-用OH等效量/Kg聚合物表示的羟基官能团含量大于0.2。
2.根据权利要求1所述的聚酯,其特征在于:未磺化二酸单体(A)是由50到100%摩尔的对苯二酸或酐或其低级二酯的其中之一和0到50%摩尔的间苯二酸或酐和/或2,6-萘二羧酸或酐或其低级二酯的其中之一组成。
3.根据权利要求1或2所述的聚酯,其特征在于:磺化单体(SA)选自:磺基间苯二酸、磺基对苯二酸、磺基邻苯二酸或酐、4-磺基-2,7-萘二羧酸或酐、磺基-4,4’-双(羟基羰基)二苯基砜、磺基二苯基二羟酸或酐、磺基-4,4’-双(羟基羰基)二苯基甲烷、磺基-5-苯氧基间苯二酸或酐、磺基丁二酸或酐或其低级二酯。
4.根据权利要求1到3的其中之一所述的聚酯,其特征在于:羟基化的二酸单体(HA)选自5-羟基间苯二酸、4-羟基间苯二酸、4-羟基苯二酸、2-羟基甲基丁二酸、羟基甲基戊二酸和羟基戊二酸或酐或它们的低级二酯。
5.根据权利要求1到4的其中之一所述的聚酯,其特征在于:多羟基单体(P)是一乙二醇和/或甘油。
6.根据前述权利要求中的任意一个所述的聚酯,其特征在于:它们能够由下述物质制备:-(优选甲基)二酯形式的对苯二酸(A1)和二酸或酐形式的间苯二酸(A2),或者(优选甲基)二酯形式的对苯二酸(A1)和二酸或酐形式的羟基化的对苯二酸或羟基化的间苯二酸(HA),可选择性的与二酸或酐形式的间苯二酸(A2)混合,(A1)/(A1)+(A2)、(A1)/(A1)+(HA)或(A1)/(A1)+(HA)+(A2)的摩尔比是约100/100到50/100,优选约90/100到70/100-(优选甲基)二酯形式的磺基间苯二酸-一乙二醇和/或甘醇。
7.制备构成上述任意一个权利要求主题的聚酯的方法,其特征在于采用下列连续步骤:-酯基转移反应(互换反应)阶段,是在一方面,以二酯形式的并且占以二酯形式存在的未磺化二酸单体(A)总量的50到100%摩尔,特别是30到90%摩尔的磺化二酸单体(SA),和,另一方面一定量的多羟基单体(P)之间的反应,多羟基单体(P)的用量对应于该单体中OH官能团的数量/所说二酯形式的单体(A)和(SA)的COOH官能团等效物的数量之间的比约为1.05到4,优选约1.1到3.5,更优选是约1.8到3.0-可选择的酯化反应阶段,是在二酸或酐形式的未磺化二酸单体(A)以可能存在的量,和一定量多羟基单体(P)之间的反应,其中多羟基单体(P)的用量对应于该单体中OH官能团数/二酸或酐形式的未磺化二酸单体(A)的COOH官能团数之间的比是约1.05到4,优选约1.1到3.5,更优选是约1.8到3.0-缩聚反应阶段缩聚反应是通过去除多羟基分子进行的,并且在7.5升反应器中反应物质温度为250℃,锚型转子的转速为80转/分钟,当搅拌器轴的驱动转力矩约是0.5到5牛顿米时,反应终止。
8.洗涤剂组合物,其含有占所说组合物重量约0.01到10%重量的构成权利要求1到6主题的聚酯。
9.水分散性或水溶性磺化聚酯在洗涤剂组合物中作为防污剂的用途,这种磺化聚酯是通过以下列物质为基的单体组合物的酯化反应和/或酯基转移反应和缩聚反应制备的:
-未磺化的二酸单体(A),是由至少一个选自对苯二酸、间苯二酸和2,6-萘二甲酸的二羧酸或酐类或它们的二酯类组成,其用量对应于摩尔比(A)/(A)+(SA)约为95/100到60/100,优选约93/100到65/100
-磺化二酸单体(SA),是由至少一个磺化芳族或磺化脂族二羧酸或酐,或其二酯组成,其用量对应于摩尔比(SA)/(A)+(SA)约为5/100到40/100,优选约7/100到35/100,有待被羟基化二酸单体(HA)代替的未磺化二酸单体(A)和/或磺化二酸单体(SA)的量高达50%摩尔,优选高达30%摩尔,所说的羟基化二酸单体(HA)是由至少一种羟基化芳族或脂族二羧酸或酐或所说羟基化芳族或脂族二羧酸的二酯组成
-和多羟基单体(P),是由至少一种选自乙二醇、丙二醇、二乙二醇、二丙二醇、丙三醇、1,2,4-丁三醇和1,2,3-丁三醇的多羟基化合物组成,多羟基单体(P)的用量对应于该单体中OH官能团数/二酸单体(A)+(SA)+(HA)的COOH官能团或等效官能团数的比是约1.05至4,优选约1.1至3.5,特别优选约1.8至3
所述磺化聚酯呈现下列特性
-数均分子量低于20000,
-含硫重量约为0.5到10%,优选约1.2到8%,
-用OH等效量/Kg聚合物表示的羟基官能团含量大于0.2。
10.根据权利要求9所说的用途,其特征在于:未磺化二酸单体(A)由50到100%摩尔的对苯二酸或酐或其低级二酯的其中之一和0到50%摩尔的间苯二酸或酐和/或2,6-萘二羧酸或酐或其低级二酯的其中之一组成。
11.根据权利要求9或10所说的用途,其特征在于:磺化单体(SA)选自:磺基间苯二酸、磺基对苯二酸、磺基邻苯二酸或酐、4-磺基-2,7-萘二羧酸或酐、磺基-4,4’-双(羟基羰基)二苯基砜、磺基二苯基二羟酸或酐、磺基-4,4’-双(羟基羰基)二苯基甲烷、磺基-5-苯氧基间苯二酸或酐、磺基丁二酸或酐或其低级二酯。
12.根据权利要求9到11中任意一个所说的用途,其特征在于:羟基化二酸单体(HA)选自5-羟基间苯二酸、4-羟基间苯二酸、4-羟基苯二酸、2-羟基甲基丁二酸、羟基甲基戊二酸和羟基戊二酸或酐或它们的低级二酯。
13.根据权利要求9到12中任意一个所说的用途,其特征在于:多羟基单体(P)是一乙二醇和/或甘油。
14.根据权利要求9到13中任意一个所说的用途,其特征在于:所述水溶性或水分散性磺化聚酯可以通过下列物质制备:-(优选甲基)二酯形式的对苯二酸(A1)和二酸或酐形式的间苯二酸(A2),或者(优选甲基)二酯形式的对苯二酸(A1)和二酸或酐形式的羟基化的对苯二酸或羟基化的间苯二酸(HA),可选择性的与二酸或酐形式的间苯二酸(A2)混合,(A1)/(A1)+(A2)、(A1)/(A1)+(HA)或(A1)/(A1)+(HA)+(A2)的摩尔比是约100/100到50/100,优选约90/100到70/100-(优选甲基)二酯形式的磺基间苯二酸-一乙二醇和/或甘醇。
15.用于洗涤织物,特别是以聚酯纤维为基的织物的洗涤剂组合物,其特征在于含有:-约0.01到10%重量,优选约0.1到5%重量,更优选约0.2到3%重量的水分散性或水溶性的磺化聚酯防污剂,它的用途构成了权利要求9到14中任意一个的主题-和约3到40%重量,优选约5到35%重量的至少一种选自可选择性与约0.5到30摩尔的环氧乙烷缩合的C5-C24饱和脂族醇硫酸盐的阳离子表面活性剂,不超过5%重量的所说的洗涤剂组合物,能够由其他类型的生态毒理学性质较差的阴离子表面活性剂,如C1-C18烷基苯磺酸盐组成。
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FR94/10857 | 1994-09-12 | ||
FR9410857A FR2720400B1 (fr) | 1994-05-30 | 1994-09-12 | Nouveaux polyesters sulfones et leur utilisation comme agent anti-salissure dans les compositions détergentes, de rinçage, d'adoucissage et de traitement des textiles. |
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EP0029620A1 (en) * | 1979-11-19 | 1981-06-03 | Agfa-Gevaert N.V. | Aqueous copolyester dispersions suited for the subbing of polyester film, subbed polyester film and photographic materials containing a subbed polyester base |
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-
1994
- 1994-09-12 FR FR9410857A patent/FR2720400B1/fr not_active Expired - Lifetime
-
1995
- 1995-05-19 CN CN95193288A patent/CN1082515C/zh not_active Expired - Lifetime
- 1995-05-19 WO PCT/FR1995/000658 patent/WO1995032997A1/fr active IP Right Grant
- 1995-05-19 CZ CZ963497A patent/CZ349796A3/cs unknown
- 1995-05-19 DK DK95920961T patent/DK0763068T3/da active
- 1995-05-19 JP JP08500417A patent/JP3054196B2/ja not_active Expired - Lifetime
- 1995-05-19 AU AU26199/95A patent/AU701126B2/en not_active Expired
- 1995-05-19 ES ES95920961T patent/ES2163513T3/es not_active Expired - Lifetime
- 1995-05-19 DE DE69522563T patent/DE69522563T2/de not_active Expired - Lifetime
- 1995-05-19 NZ NZ287469A patent/NZ287469A/en not_active IP Right Cessation
- 1995-05-19 EP EP95920961A patent/EP0763068B1/fr not_active Expired - Lifetime
- 1995-05-19 PL PL95317321A patent/PL182842B1/pl not_active IP Right Cessation
- 1995-05-19 AT AT95920961T patent/ATE205229T1/de not_active IP Right Cessation
- 1995-05-19 MX MX9604798A patent/MX9604798A/es unknown
- 1995-05-19 HU HUP9603294A patent/HU216028B/hu not_active IP Right Cessation
- 1995-05-19 CA CA002190291A patent/CA2190291C/fr not_active Expired - Lifetime
- 1995-05-19 SI SI9520053A patent/SI9520053A/sl unknown
- 1995-05-19 BR BR9507790A patent/BR9507790A/pt not_active IP Right Cessation
-
1996
- 1996-11-28 BG BG101018A patent/BG101018A/xx unknown
- 1996-11-28 NO NO965082A patent/NO965082L/no not_active Application Discontinuation
-
1997
- 1997-11-20 US US09/887,664 patent/US6579466B1/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103608380A (zh) * | 2011-06-15 | 2014-02-26 | 巴斯夫欧洲公司 | 具有磺酸盐基团的支化聚酯 |
CN103608380B (zh) * | 2011-06-15 | 2016-08-31 | 巴斯夫欧洲公司 | 具有磺酸盐基团的支化聚酯 |
Also Published As
Publication number | Publication date |
---|---|
HU9603294D0 (en) | 1997-01-28 |
MX9604798A (es) | 1998-05-31 |
ES2163513T3 (es) | 2002-02-01 |
HUT76124A (en) | 1997-06-30 |
PL317321A1 (en) | 1997-04-01 |
CN1082515C (zh) | 2002-04-10 |
ATE205229T1 (de) | 2001-09-15 |
BG101018A (en) | 1998-03-31 |
FR2720400A1 (fr) | 1995-12-01 |
AU2619995A (en) | 1995-12-21 |
NO965082L (no) | 1997-01-30 |
NZ287469A (en) | 1997-12-19 |
HU216028B (hu) | 1999-04-28 |
EP0763068B1 (fr) | 2001-09-05 |
CZ349796A3 (en) | 1997-03-12 |
CA2190291A1 (fr) | 1995-12-07 |
AU701126B2 (en) | 1999-01-21 |
JP3054196B2 (ja) | 2000-06-19 |
DK0763068T3 (da) | 2001-11-26 |
CA2190291C (fr) | 2002-07-16 |
JPH09506139A (ja) | 1997-06-17 |
NO965082D0 (no) | 1996-11-28 |
DE69522563T2 (de) | 2002-07-11 |
US6579466B1 (en) | 2003-06-17 |
BR9507790A (pt) | 1997-09-23 |
DE69522563D1 (de) | 2001-10-11 |
WO1995032997A1 (fr) | 1995-12-07 |
SI9520053A (en) | 1997-04-30 |
EP0763068A1 (fr) | 1997-03-19 |
FR2720400B1 (fr) | 1996-06-28 |
PL182842B1 (pl) | 2002-03-29 |
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