CN1954116A - 处理柔性基材的方法 - Google Patents
处理柔性基材的方法 Download PDFInfo
- Publication number
- CN1954116A CN1954116A CNA2005800151053A CN200580015105A CN1954116A CN 1954116 A CN1954116 A CN 1954116A CN A2005800151053 A CNA2005800151053 A CN A2005800151053A CN 200580015105 A CN200580015105 A CN 200580015105A CN 1954116 A CN1954116 A CN 1954116A
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- parent metal
- alkyl
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Classifications
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- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
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Abstract
本发明涉及一种处理基材的方法,其中使至少一种选自(A1)聚丙烯酸酯、聚酯、聚硅氧烷、聚酰胺或(A2)一种或多种基于通式(I)的单体的聚合物的基材(A)与至少一种含水配制剂接触,其中通式(I)中的R1选自-Cl、C1-C10烷基、-CH=CH2、-C(Cl)=CH2、-C(CH3)=CH2和-COOC1-C10烷基,所述含水配制剂含有(B)至少一种以共聚形式包含60-95重量%乙烯和5-40重量%至少一种烯属不饱和羧酸的乙烯共聚物蜡以及至少一种选自(C)至少一种颜料和(D)至少一种染料的着色剂。
Description
本发明涉及一种处理柔性基材的方法,包括使至少一种柔性基材(A)与至少一种含水配制剂接触,所述柔性基材选自由(A1)聚丙烯酸酯(polyacrylic)、聚酯、聚硅氧烷、聚酰胺或者(A2)一种或多种基于通式I的单体的聚合物组成的基材:
其中R1选自-Cl、C1-C10烷基、-CH=CH2、-C(Cl)=CH2、-C(CH3)=CH2和-COOC1-C10烷基,
所述含水配制剂包含(B)至少一种以共聚形式包含60-95重量%乙烯和5-40重量%至少一种烯属不饱和羧酸的乙烯共聚物蜡,以及至少一种选自(C)至少一种颜料和(D)至少一种染料的着色剂。
对柔性基材如薄片或纤维状基材如纺织物、成圈编织物或非织造织物进行涂敷、染色或印花的方法要求进行配制。一个具体的挑战涉及例如与聚丙烯有关的印花的配制剂。用常规配制剂印花的聚丙烯基材通常表现出牢度不足,例如就耐洗牢度和湿耐摩牢度而言。类似地,其他例如由聚氯乙烯或聚硅氧烷组成的柔性基材要求例如允许具有良好牢度的印花或染色的处理方法。
此外,例如在形成粘合剂结合中需要避免温度超过聚丙烯的熔点或软化点时聚丙烯的粘合剂结合具有限制。确实可以通过电晕处理对聚丙烯进行改性,以使粘合剂随后能够保持。然而,电晕处理通常昂贵、通常并不非常有效且对于储存中的改性仅具有有限稳定性。
因此,本发明的目的是提供一种没有现有技术缺点的处理柔性基材的方法。本发明的目的进一步在于提供处理过的柔性基材。本发明的目的还在于提供可以用来处理柔性基材的印花糊和染色液。
我们发现该目的由开头所定义的方法实现。
本发明方法由至少一种基材(A)开始,所述基材优选为柔性基材,即可以在室温下非破坏性地手工变形,例如扭结、卷紧、卷开、折叠或弯曲至少一次的基材。柔性基材的优选实例是纺织品,下文也称为纺织品基材,薄片和可手工变形的中空结构体如瓶子。
对本发明而言,纺织品或纺织品基材是纺织品纤维,纺织品中间产品和终产品以及由其制造的成品纺织品制品,后者除了用于服装工业的纺织品外还包括例如地毯和其他家用纺织品以及用于工业目的的纺织品结构体如凉蓬。这些还包括未成型的结构体如短纤维,线性结构体如细绳、长丝、纱线、线、索、绳索、丝以及三维结构体如毡、纺织物、成圈编织物、非织造织物、绒料和衬垫。
柔性基材(A)选自由如下材料制成的基材:
(A1)聚丙烯酸酯、聚酯、聚硅氧烷、聚酰胺,例如α,ω-二酰胺与α,ω-二羧酸或环状酰胺如∈-己内酰胺的缩聚物,或优选
(A2)一种或多种基于通式I的单体的聚合物:
其中R1选自:
氯,
支化或未支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、正壬基、正癸基;更优选C1-C4烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基,最优选甲基,
-CH=CH2、-C(Cl)=CH2、-C(CH3)=CH2
和-COOC1-C10烷基,其中C1-C10烷基可以是支化或未支化的且如上所定义。
由上述聚合物之一组成的基材还包括包含一定比例,例如不低于30重量%,优选不低于50重量%的至少一种上述聚合物的基材。说明性实例是由棉-聚酯或棉-聚酰胺组成的混纺织物。
对本发明而言,基于至少一种通式I的单体的聚合物不仅包括均聚物,而且包括可能以共聚形式含有显著比例,例如不低于50mol%的至少一种通式I的单体的共聚物。有用的共聚物例如还包括可能以共聚形式含有不低于50mol%丙烯的乙烯-丙烯共聚物。
非常特别优选由聚氯乙烯(PVC)和聚丙烯(PP)组成的基材,它们各自可以通过任何所需方法生产。例如聚丙烯可以通过齐格勒-纳塔催化或通过茂金属催化而生产。
根据本发明,将至少一种柔性基材与至少一种含水配制剂接触,所述含水配制剂包含至少一种以共聚形式包含60-95重量%,优选65-85重量%乙烯和5-40重量%,优选15-35重量%至少一种烯属不饱和羧酸的乙烯共聚物蜡,其中重量百分数基于整个乙烯共聚物蜡。
优选至少一种烯属不饱和羧酸为通式II的羧酸:
其中
R2选自氢;
-C1-C10烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、正壬基、正癸基;更优选C1-C4烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基;
-COOH、COOCH3、COOC2H5;
R3选自氢;
-C1-C10烷基,如甲基、乙基、正丙基,异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、正壬基、正癸基;更优选C1-C4烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基。
最优选R2为氢且R3为氢或甲基。
包括在本发明所用含水配制剂中的乙烯共聚物蜡可以共聚形式包含至多40重量%,优选至多35重量%(百分数各自基于乙烯和共聚的烯属不饱和羧酸的总和)的一种或多种其他单体,例如:
-乙酸乙烯酯,
-一种或多种烯属不饱和羧酸酯,优选式III的烯属不饱和羧酸酯:
R4选自氢;
-C1-C10烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、正壬基、正癸基;更优选C1-C4烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基;
R5选自氢;
-C1-C10烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、正壬基、正癸基;更优选C1-C4烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基;
-COOH、COOCH3、COOC2H5;
R6选自C1-C10烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、正壬基、正癸基;更优选C1-C4烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基。
最优选R5为氢且R4为氢或甲基。
最优选R5为氢,R4为氢或甲基且R6选自甲基、乙基、正丁基和2-乙基己基。
乙烯和烯属不饱和羧酸的前述乙烯共聚物蜡可以有利地通过在高压条件下例如在搅拌的高压釜中或在高压管式反应器中自由基引发共聚而制备。优选在搅拌的高压釜中的制备。搅拌的高压釜本身是已知的,有关说明可以在Ullmann’s Encyclopedia of Industrial Chemistry,第5版,标题:蜡,第A28卷,第146及随后各页,Verlag Chemie Weinheim,Basel,Cambridge,New York,Tokyo,1996中找到。其长度/直径比主要在5∶1-30∶1,优选10∶1-20∶1的间隔内变化。同样可以使用的高压管式反应器同样在Ullmann’s Encyclopedia of Industrial Chemistry,第5版,标题:蜡,第A28卷,第146及随后各页,Verlag Chemie Weinheim,Basel,Cambridge,New York,Tokyo,1996中找到。
聚合的合适压力条件是500-4000巴,优选1500-2500巴。反应温度为170-300℃,优选200-280℃。
聚合可以在调节剂存在下进行。有用的调节剂例如包括氢气或通式IV的脂族醛或脂族酮:
或其混合物。
在该式中,R7和R8相同或不同且各自选自:
-氢;
-C1-C6烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基,更优选C1-C4烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基;
-C3-C12环烷基,如环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环壬基、环癸基、环十一烷基和环十二烷基;优选环戊基、环己基和环庚基。
在一个特定实施方案中,R7和R8共价键合在一起形成4-13元环。例如R7和R8可以结合为-(CH2)4-、-(CH2)5-、-(CH2)6-、-(CH2)7-、-CH(CH3)-CH2-CH2-CH(CH3)-或-CH(CH3)-CH2-CH2-CH2-CH(CH3)-。
非常有用的调节剂包括烷基芳族化合物,例如甲苯、乙苯或二甲苯的一种或多种异构体。优选不使用通式IV的醛和酮作为调节剂。特别优选除了所谓的减敏剂(phlegmatizer)外不加入任何其他调节剂,所述减敏剂可以加入有机过氧化物中以改进处理且可能同样具有分子量调节剂的功能。
自由基聚合的有用引发剂包括常规自由基引发剂如有机过氧化物、氧气或偶氮化合物。两种或更多种自由基引发剂的混合物也是合适的。
选自市售物质的合适过氧化物是
-过氧化二癸酰、2,5-二甲基-2,5-二(2-乙基己酰基过氧)己烷、过氧-2-乙基己酸叔戊基酯、过氧化二苯甲酰、过氧-2-乙基己酸叔丁基酯、过氧化二乙基乙酸叔丁基酯、过氧化二乙基异丁酸叔丁基酯、异构体混合物形式的1,4-二(叔丁基过氧羰基)环己烷、过异壬酸叔丁基酯、1,1-二(叔丁基过氧)-3,3,5-三甲基环己烷、1,1-二(叔丁基过氧)环己烷、甲基异丁基酮过氧化物、碳酸叔丁基过氧异丙基酯、2,2-二叔丁基过氧丁烷或过氧乙酸叔丁基酯;
-过氧苯甲酸叔丁基酯、过氧化二叔戊基、过氧化二枯基、异构的(叔丁基过氧异丙基)苯、2,5-二甲基-2,5-二叔丁基过氧己烷、过氧化叔丁基枯基、2,5-二甲基-2,5-二(叔丁基过氧)己-3-炔、过氧化二叔丁基、1,3-二异丙基苯单氢过氧化物、氢过氧化枯烯或氢过氧化叔丁基;或
-通式Va-Vc的二聚或三聚酮过氧化物。
在这些式中,R9-R14相同或不同且各自选自:
-C1-C8烷基,如甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、仲戊基、异戊基、正己基、正庚基、正辛基;优选线性C1-C6烷基,如甲基、乙基、正丙基、正丁基、正戊基、正己基,更优选线性C1-C4烷基,如甲基、乙基、正丙基或正丁基,非常特别优选乙基;
-C6-C14芳基,如苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基和9-菲基,优选苯基、1-萘基和2-萘基,更优选苯基。
通式Va-Vc的过氧化物及其制备方法由EP-A 0 813 550已知。
特别合适的过氧化物是过氧化二叔丁基、过氧新戊酸叔丁基酯、过氧异壬酸叔丁基酯、过氧化二苯甲酰或其混合物。偶氮化合物的示例是偶氮二异丁腈(“AIBN”)。自由基引发剂以常用于加成聚合的量加入。
在销售之前将许多市售有机过氧化物与所谓的减敏剂混合以改进其处理。合适的减敏剂实例包括白油或烃类,尤其如异十二烷。在自由基高压加成聚合条件下,这类减敏剂可以起调节分子量的作用。对本发明而言,任何有关使用分子量调节剂的提及都应看作是指除了使用这类减敏剂外还额外使用了上述其他分子量调节剂。
乙烯和烯属不饱和羧酸单体在进料中的比例通常并不准确对应于本发明所用配制剂中所包括的乙烯共聚物蜡中的单元比例,因为通常而言,烯属不饱和羧酸比乙烯更易掺入乙烯共聚物蜡中。
单体通常一起或单独计量加入。
可以在压缩机中将单体调至聚合压力。在本发明方法的另一实施方案中,首先借助泵将单体调至例如150-400巴,优选200-300巴,尤其是250巴的高压,然后使用压缩机调至实际聚合压力。
聚合可以在溶剂存在和不存在下选择性地进行;就此而言,对本发明来说在聚合过程中存在于反应器中且已经用于减敏自由基引发剂的矿物油、白油和其他溶剂不能被认为是溶剂。
在一个实施方案中,聚合在不存在溶剂下进行。
当然还可以通过首先使乙烯与至少一种通式III的烯属不饱和羧酸酯共聚,然后例如用氢氧化钾水溶液或氢氧化钠水溶液以类似于聚合物的反应皂化酯基而制备乙烯共聚物蜡。
本发明所用含水配制剂优选包含0.05-40重量%,优选10-35重量%的一种或多种乙烯共聚物蜡,优选呈完全或部分中和形式。
为了进行部分或完全中和,本发明所用含水配制剂通常包含一种或多种具有碱性作用的物质,例如碱金属的氢氧化物和/或碳酸盐和/或碳酸氢盐,氨,有机胺如三乙胺、二乙胺、乙胺、三甲胺、二甲胺、甲胺、乙醇胺、二乙醇胺、三乙醇胺、甲基二乙醇胺、正丁基二乙醇胺、N,N-二甲基乙醇胺。本发明所用含水配制剂优选包含足以中和乙烯共聚物蜡的羧基的至少一半,优选至少四分之三的碱性物质。碱性物质例如可以在乙烯共聚物蜡的分散过程中加入本发明所用配制剂中。
在本发明的一个实施方案中,本发明所用含水配制剂包含足以定量中和乙烯共聚物蜡的羧基的碱性物质。
本发明所用含水配制剂通常具有碱性pH,优选pH为7.5-14,更优选pH为8或更高,最优选pH为8.5或更高。
本发明所用含水配制剂优选不包括保护性胶体。本发明所用含水配制剂甚至在没有这类表面活性助剂下也是稳定的;即当在100cm-1下剪切时,以纯水作为参照测定,固含量为0.1%的分散体的透光率的变化不超过2%。
本发明所用含水配制剂除了乙烯共聚物蜡(B)外还包含至少一种选自如下的着色剂:
(C)至少一种颜料,和
(D)至少一种染料。
对本发明而言,颜料(C)是按照德国标准规范DIN 55944中的定义基本不溶、精细分散的有机或无机着色剂。优选至少选择有机颜料和/或金属颜料。
有机颜料的说明性实例是:
-单偶氮颜料:C.I.颜料棕25;C.I颜料橙5,13,36和67;C.I.颜料红1,2,3,5,8,9,12,17,22,23,31,48∶1,48∶2,48∶3,48∶4,49,49∶1,52∶1,52∶2,53,53∶1,53∶3,57∶1,63,112,146,170,184,210,245和251;C.I.颜料黄1,3,73,74,65,97,151和183;
-双偶氮颜料:C.I颜料橙16,34和44;C.I.颜料红144,166,214和242;C.I.颜料黄12,13,14,16,17,81,83,106,113,126,127,155,174,176和188;
-二苯并芘二酮颜料:C.I.颜料红168(C.I.瓮橙3);
-蒽醌颜料:C.I.颜料黄147和177;C.I.颜料紫31;
-蒽醌颜料:C.I.颜料黄147和177;C.I.颜料紫31;
-蒽素嘧啶(anthrapyrimidine)颜料:C.I.颜料黄108(C.I.瓮黄20);
-喹吖啶酮颜料:C.I.颜料红122,202和206;C.I.颜料紫19;
-喹酞酮(quinophthalone)颜料:C.I.颜料黄138;
-二嗪颜料:C.I.颜料紫23和37;
-黄烷士酮颜料:C.I.颜料黄24(C.I.瓮黄1);
-阴丹酮颜料:C.I.颜料蓝60(C.I.瓮蓝4)和64(C.I.瓮蓝6);
-异吲哚啉颜料:C.I.颜料橙69;C.I.颜料红260;C.I.颜料黄139和185;
-异吲哚啉酮颜料:C.I.颜料橙61;C.I.颜料红257和260;C.I.颜料黄109,110,173和185;
-异宜和蓝酮颜料:C.I.颜料紫31(C.I.瓮紫1);
-金属配合物颜料:C.I.颜料黄117,150和153;C.I.颜料绿8;
-紫环酮(perinone)颜料:C.I.颜料橙43(C.I.瓮橙7);C.I.颜料红194(C.I.瓮红15);
-苝系颜料:C.I.颜料黑31和32;C.I.颜料红123,149,178,179(C.I.瓮红23),190(C.I.瓮红29)和224;C.I.颜料紫29;
-酞菁颜料:C.I.颜料蓝15,15∶1,15∶2,15∶3,15∶4,15∶6和16;C.I.颜料绿7和36;
-皮蒽酮颜料:C.I.颜料橙51;C.I.颜料红216(C.I.瓮橙4);
-硫靛颜料:C.I.颜料红88和181(C.I.瓮红1);C.I.颜料紫38(C.I.瓮紫3);
-三芳基碳颜料:C.I.颜料蓝1,61和62;C.I.颜料绿1;C.I.颜料红81,81∶1和169;C.I.颜料紫1,2,3和27;C.I.颜料黑1(苯胺黑);
-C.I.颜料黄101(醛连氮黄);
-C.I.颜料棕22。
特别优选的颜料(C)的实例是C.I.颜料黄138,C.I.颜料红122,C.I.颜料紫19,C.I.颜料蓝15∶3和15∶4,C.I.颜料黑7,C.I.颜料橙5,38和43和C.I.颜料绿7。
其他合适的颜料(C)是金属颜料如金色铜粉、银色铜粉(silver bronze)、Iriodin颜料、云母。
本发明方法所用颜料(C)的中径通常为20nm至1.5μm,优选300-500nm。
在本发明的一个实施方案中,本发明方法所用颜料(C)以球形或基本球形颗粒形式存在,即最长直径与最短直径之比为1.0-2.0,优选至多1.5。
在本发明的另一实施方案中,本发明方法所用颜料(C)以针或钉形式存在。
合适的染料(D)是所有纺织品染料,例如瓮染料如靛蓝及其衍生物,直接染料,分散染料,酸性染料,金属配位染料,萘酚染料,硫化染料,活性染料和有机颜料。
本发明所用含水配制剂例如可以如下所述生产。一种方案是首先将一种或多种乙烯共聚物蜡分散于水中。可以将一种或多种上述乙烯共聚物蜡用于此。将其置于容器如烧瓶、高压釜或罐中。在一个方案中,将乙烯共聚物蜡加热到其熔点以上。有利的是加热到比乙烯共聚物蜡的熔点高至少10℃,更有利的是高至少30℃的温度。当使用多种不同的乙烯共聚物蜡时,将它们加热到在最高温度下熔融的乙烯共聚物蜡的熔点以上的温度。在使用多种不同乙烯共聚物蜡的情况下,有利的是加热到比在最高温度下熔融的乙烯共聚物蜡的熔点高至少10℃的温度。在使用多种不同乙烯共聚物蜡的情况下,特别有利的是加热到比在最高温度下熔融的乙烯共聚物蜡高至少30℃的温度。
然后对于水的加入和碱性物质以及其他成分的加入,以任何顺序加入水和一种或多种碱性物质以及合适的话其他成分如乙二醇。当温度高于100℃时,有利的是在高压下操作并且相应地选择容器。例如通过机械或压气搅拌或通过振摇而均化所得乳液。随后可以冷却如此生产的含水配制剂。
然后可以加入至少一种选自(C)至少一种颜料和(D)至少一种染料的着色剂。此后将水、乙烯共聚物蜡(B)和着色剂混合。
为了加入作为着色剂的至少一种颜料(C),优选以所谓的颜料制剂形式,即用水和合适的话至少一种表面活性物质分散的形式加入颜料(C)。
本发明处理柔性基材的方法通过使至少一种柔性基材(A)与至少一种本发明所用含水配制剂接触而进行。
在本发明的一个实施方案中,使(A)与含水配制剂在20-100℃的温度,优选室温下接触。
在本发明的一个实施方案中,接触在0.5-10巴的压力,尤其是大气压力下进行。
在本发明的一个实施方案中,使(A)与含水配制剂在70-180℃,优选90-120℃的温度下接触并且对此使用超过大气压力的压力,例如至多10巴。
本发明的接触例如可以进行0.1秒至60分钟,优选0.5秒至30分钟。
基材(A)与本发明所用含水配制剂的接触例如可以通过喷涂、轧染、涂敷、浸渍和印花进行,例如通过喷墨法进行。
基材(A)与本发明所用含水配制剂接触一次或连续接触多次。
本发明方法优选通过使柔性基材与至少一种本发明所用含水配制剂接触并随后干燥而进行。
特别优选在实际干燥之前将根据本发明处理过的基材预干燥到例如残留含湿量为0.5-2重量%。
预干燥/干燥可以在常用设备中进行。例如为了处理纺织品基材,可以在所有常用于纺织工业中的定形和干燥设备上进行预干燥/干燥。合适的干燥或预干燥温度范围例如为50-300℃,优选70-180℃。
之后可以在50-300℃,优选100-160℃,更优选110-130℃的温度下例如热处理10秒至60分钟,优选0.5-7分钟。聚酰胺、聚酯、聚氯乙烯、改性聚酯、聚酯混纺织物、聚酰胺混纺织物、聚丙烯腈、聚碳酸酯有利地在130-250℃的温度下热处理。聚丙烯织物优选在80-130℃,更优选110-130℃下热处理。这里的温度通常指待处理柔性基材周围的介质温度。
在本发明的一个实施方案中,本发明所用含水配制剂包含至少一种可以选自增稠剂、交联剂、牢度改进剂、增塑剂、消泡剂、润湿剂和匀染剂的其他物质(E)。
有用的交联剂例如包括脲-甲醛和蜜胺-甲醛加成产物,合适的话与无机盐如MgCl2·6H2O或NH4Cl结合。有用的交联剂例如进一步包括游离或封端异氰酸酯或多异氰酸酯,如通式VI的化合物:
其中
Y1选自N-R15、氧和N-H,
Z1选自氢和CO-O-R15,
R15在每次出现时相同或不同且选自C1-C10烷基,特别优选甲基和正丁基。
有用的交联剂进一步包括多官能环氧化物如多元醇的多缩水甘油醚,例如季戊四醇多缩水甘油醚,还有多官能氮丙啶如三羟甲基丙烷三(β-吖丙啶基丙酸酯)。
例如可以加入膜抑制剂以抑制在接触期间例如在轧染机(pad-mangle)的辊上成膜。有用的膜抑制剂例如包括多重烷氧基化醇的混合物,尤其是多重乙氧基化脂肪醇的混合物。
作为增稠剂可以使用天然或合成增稠剂。天然增稠剂的实例是藻酸盐,瓜尔胶,淀粉,角豆粉醚,山扁豆胶,罗望子纤维素醚,糊精如天然树胶、半乳甘露聚糖、黄原胶、多糖及其混合物。优选使用合成增稠剂,例如使用合成(共)聚合物在例如白油中的室温液体溶液或其水溶液或油包水乳液,它们优选包含约40重量%(共)聚合物。
增稠剂的优选实例为包含85-95重量%丙烯酸、4-14重量%丙烯酰胺和约0.01-1重量%式VII的(甲基)丙烯酰胺衍生物且分子量Mw为100,000-200,000g/mol的共聚物:
其中R16或甲基或优选氢。
本发明的配制剂可以包含30-70重量%白油。含水增稠剂通常基于整个增稠剂总共包含至多25重量%(共)聚合物且在某些情况下包含至多50重量%(所谓的增稠剂分散体)。当希望使用增稠剂的含水配制剂时,通常加入氨水。甚至可以使用增稠剂的颗粒状固体配制剂以便能够例如无释放地产生颜料印花。
有用的牢度改进剂例如包括室温液体硅油和聚硅氧烷。在本发明的优选方案中,省略牢度改进剂的使用。
合适的增塑剂实例是选自被链烷醇完全酯化的脂族或芳族二元羧酸或多元羧酸和至少被链烷醇单酯化的磷酸的酯化合物。
在本发明的一个实施方案中,链烷醇为C1-C10链烷醇。
被链烷醇完全酯化的芳族二元羧酸或多元羧酸的优选实例是被链烷醇完全酯化的邻苯二甲酸、间苯二甲酸和苯六甲酸;说明性实例为邻苯二甲酸二正辛基酯、邻苯二甲酸二正壬基酯、邻苯二甲酸二正癸基酯、间苯二甲酸二正辛基酯、间苯二甲酸二正壬基酯、间苯二甲酸二正癸基酯。
被链烷醇完全酯化的脂族二元羧酸或多元羧酸的优选实例例如为己二酸二甲酯、己二酸二乙酯、己二酸二正丁基酯、己二酸二异丁基酯、戊二酸二甲酯、戊二酸二乙酯、戊二酸二正丁基酯、戊二酸二异丁基酯、琥珀酸二甲酯、琥珀酸二乙酯、琥珀酸二正丁基酯、琥珀酸二异丁基酯及其混合物。
至少被链烷醇单酯化的磷酸的优选实例是磷酸C1-C10烷基二-C6-C14芳基酯如磷酸异癸基二苯基酯。
增塑剂的其他合适实例是被C1-C10烷基羧酸至少单酯化的脂族或芳族二醇或多元醇。
2,2,4-三甲基戊烷-1,3-二醇单异丁酸酯为被C1-C10烷基羧酸至少单酯化的脂族或芳族二醇或多元醇的优选实例。
其他合适的增塑剂是可以通过脂族二元羧酸和脂族二醇,例如己二酸或琥珀酸和1,2-丙二醇的缩聚得到的Mw尤其为200g/mol的聚酯,以及聚丙二醇烷基苯基醚,优选Mw为450g/mol的聚丙二醇烷基苯基醚。
其他合适的增塑剂是被两种不同醇醚化且分子量Mw为400-800g/mol的聚丙二醇,其中优选醇之一可以为链烷醇,尤其是C1-C10链烷醇,且另一醇可以优选为芳族醇,例如邻甲酚、间甲酚、对甲酚,尤其是苯酚。
有用的消泡剂例如包括含聚硅氧烷的消泡剂如式HO-(CH2)3-Si[OSi(CH3)3]2的那些。不含聚硅氧烷的消泡剂也是合适的,例如多重烷氧基化的醇,例如脂肪醇烷氧基化物,优选2-50倍乙氧基化的优选未支化C10-C20链烷醇,未支化C10-C20链烷醇和2-乙基己-1-醇。
有用的润湿剂例如包括非离子、阴离子或阳离子表面活性剂,尤其是脂肪醇的乙氧基化和/或丙氧基化产物或氧化丙烯-氧化乙烯嵌段共聚物,乙氧基化或丙氧基化脂肪醇或羰基合成醇,还有油酸或烷基酚的乙氧基化物,烷基酚醚硫酸盐,烷基聚苷,烷基膦酸盐,烷基苯基膦酸盐,磷酸烷基酯或烷基苯基磷酸酯。
有用的匀染剂例如包括分子量Mn为500-5000g/mol,优选800-2000g/mol的氧化乙烯和氧化丙烯的嵌段共聚物。特别优选例如式EO8PO7EO8的氧化丙烯/氧化乙烯嵌段共聚物,其中EO代表氧化乙烯且PO代表氧化丙烯。
本发明进一步提供由本发明方法处理的基材。本发明基材包含至少一种交联或未交联形式的乙烯共聚物蜡。本发明基材具有良好的性能特征,例如良好的牢度,尤其是耐洗牢度以及耐摩擦牢度如干和湿耐摩牢度。
本发明的特殊实施方案是一种通过本发明方法生产印花的柔性基材,尤其是印花的纺织品的方法,下文也称为本发明纺织品印花方法。
本发明纺织品印花方法例如可以通过加工至少一种本发明含水配制剂以形成印花糊,下文也称为本发明印花糊,然后通过本身已知的方法将纺织品基材印花而进行。
本发明印花糊有利地通过将至少一种本发明所用含水配制剂与常见印花法助剂和至少一种颜料(C)混合而生产。色调深度有利地通过调节颜料(C)与本发明所用含水配制剂的比例而控制。
优选将颜料以颜料制剂形式加入本发明印花糊。颜料制剂通常包含20-60重量%颜料、水和一种或多种表面活性化合物,例如一种或多种乳化剂,实例是多重烷氧基化的C10-C30链烷醇。
颜料与本发明所用含水配制剂的比例可以在宽范围内变化。例如,颜料和本发明所用含水配制剂可以20∶1-1∶100的重量比使用。在本发明的优选实施方案中,调节颜料与本发明所用含水配制剂的比例以使颜料与本发明所用含水配制剂的固体级分的重量比为1∶1-1∶30。
当然还可以首先以20∶1-10∶1的重量比将颜料和本发明所用含水配制剂预混并且仅在印花之前立即进一步加入本发明所用含水配制剂或加入常规丙烯酸酯类粘合剂。
用于纺织品印花中的印花糊的其他常规助剂由Ullmann,Handbuchder technischen Chemie und Verfahrenstechnik例如参见Ullmann’sEnyclopedia of Industrial Chemistry,第5版,标题:纺织品助剂,第A26卷,第286及随后各页以及第296及随后各页,Verlag Chemie,Weinheim,Deerfield/Florida,Basel;1996以及Textil-Hilfsmittel-Katalog,KonradinVerlag Robert Kohlhammer GmbH,D-70771 Leinfelden-Echterdingen已知。作为常规助剂,可以举例提到增稠剂、固色剂、手感改进剂、消泡剂、流变改进剂、酸供体和乳化剂。
在本发明的另一改进实施方案中,本发明印花糊进一步包含选自聚硅氧烷,尤其是聚二甲基硅氧烷以及脂肪酸C1-C10烷基酯的手感改进剂。可以加入本发明印花糊中的市售手感改进剂的实例是AcraminWeichmacher SI(Bayer AG)、Luprimol SIG、Luprimol TX 4732和Luprimol CW(BASF Aktiengesellschaft)。
在本发明的优选实施方案中,本发明印花糊包括作为其他成分的一种或多种乳化剂,尤其当该印花糊含有含白油的增稠剂且以水包油乳液得到时。合适乳化剂的实例是芳基-或烷基取代的聚乙二醇醚。合适乳化剂的市售实例是Emulgator W(Bayer)、Luprintol PE New和LuprintolMP(BASF Aktiengesellschaft)。
本发明印花糊例如可以通过将水合适的话与消泡剂如基于聚硅氧烷的消泡剂混合并在例如通过搅拌而混合下加入至少一种本发明所用含水配制剂而生产。然后可以加入一种或多种乳化剂和一种或多种颜料。
接下来可以加入一种或多种手感改进剂,例如一种或多种聚硅氧烷乳液。
然后可以加入一种或多种增稠剂并通过进一步混合,例如搅拌而均化。
本发明的典型印花糊包含(在每种情况下为每kg本发明印花糊):
0.5-400g,优选10-250g乙烯共聚物蜡(B),
0-100g,优选1-5g乳化剂,
1-500g,优选3-100g增稠剂,
0-500g,优选0.1-250g,优选0.5-120g颜料(C),
合适的话其他助剂;
余量优选为水。
在本发明的一个实施方案中,本发明印花糊的20℃粘度为0.3-4000dPa·s,优选20-200dPa·s,更优选60-100dPa·s。粘度可以由常规方法,尤其例如用旋转粘度计,例如来自Haake Mess-Technik GmbH u.Co.,Karlsruhe的VT02或VT24粘度计测定。
使用至少一种本发明印花糊的颜料印花可以根据各种本身已知的方法进行。通常使用筛网,用刮刀迫使本发明印花糊通过该筛网。该方法属于筛网印花法。使用至少一种本发明印花糊的本发明颜料印花方法提供了特别高的印花亮度和色调深度相结合的具有优良手感的印花基材。本发明因此提供了使用本发明印花糊由本发明印花方法印花的柔性基材。
本发明的另一实施方案是利用至少一种本发明配制剂的颜料染色方法,下文也称为本发明颜料染色方法。本发明染色方法优选通过用至少一种包含至少一种本发明配制剂的染色液处理至少一种柔性基材,优选纺织品基材而进行。包含至少一种本发明配制剂的染色液在下文也称为本发明染色液。
本发明染色液可以进一步包含润湿剂添加剂,优选被认为是低泡润湿剂的润湿剂,因为染色操作中因高湍流起泡使得形成不均匀染色而使染色质量受损。
用于连续颜料染色的该类干燥纺织品织物、成圈编织物或绒头织物含有大量空气。本发明颜料染色方法因此有利地使用脱泡剂实施。这些脱泡剂例如基于聚醚硅氧烷共聚物。它们可以0.01-2g/l的量包括在本发明染色液中。
本发明染色液可以进一步包含抗迁移剂。有用的抗迁移剂包括例如分子量Mn为500-5000g/mol,优选800-2000g/mol的氧化乙烯和氧化丙烯的嵌段共聚物。
本发明染色液可以进一步包括加入的一种或多种手感改进剂。手感改进剂通常为聚硅氧烷或蜡。聚硅氧烷在这里的优点在于持久性,而蜡在使用中逐渐被洗掉。
本发明染色液的粘度优选低于100mPa·s。调节本发明染色液的表面张力以使材料可以被润湿。工业上利用的表面张力小于50mN/m。
在本发明的一个实施方案中,典型的本发明染色液每升包含:
0.5-400g,优选20-300g乙烯共聚物蜡(B),
0-100g,优选0.1-10g润湿剂,
0-100g,优选0.1-10g消泡剂,
0-300g,优选1-20g防成膜剂,
0-100g,优选1-50g抗迁移剂,
0-100g,优选1-50g匀染剂,
0.5-25g,优选1-12g颜料(C)。
本发明的另一方面是一种生产本发明染色液的方法。本发明方法包括将着色剂,例如优选以包含一种或多种表面活性化合物及颜料和水的颜料制剂形式的颜料(C)与上述添加剂如其它溶剂、消泡剂、手感改进剂、乳化剂和/或生物杀伤剂混合并用水补足。为了实施制备本发明染色液的方法,通常将本发明染色液的组分在混合容器中搅拌,混合容器的尺寸和形状并不重要。优选搅拌后进行澄清过滤。
本发明的另一方面是一种通过使用上述本发明染色液染色柔性基材的方法,下文中也称作本发明染色方法,尤其是本发明颜料染色方法。本发明染色方法可以在常用染色机中进行。优选轧染机,其中主要元件是两个压浆辊,通过压浆辊引导柔性基材,尤其是纺织品。本发明染色液在辊上方引入并润湿柔性基材或纺织品。辊的压力使得柔性基材或纺织品被挤出并且确保恒定的添加水平。
实际的染色之后通常进行热干燥步骤和任选的定形步骤。干燥优选在25-300℃的温度下进行10秒至60分钟,优选30秒至10分钟。需要定形的话,定形在150-190℃的温度下进行30秒至5分钟。
优选通过轧染的颜料染色方法。
根据本发明印花和染色的基材的突出之处在于相应印花和染色的基材具有色彩亮度和良好手感。本发明的另一方面因此是通过使用本发明染色液由上述方法染色的基材。
本发明进一步提供了可以通过本发明颜料染色方法得到的染色的柔性基材。本发明的染色的柔性基材的突出之处例如在于良好的耐洗牢度,良好的干和湿耐摩牢度以及良好的坚牢度,这尤其是由于在沸腾刷洗过程中产生的色调深度降低程度最小之故。
在本发明的另一实施方案中,使由聚丙烯组成的柔性基材(A),尤其是薄片或纺织品与不含颜料的含水配制剂接触,然后干燥。均匀分布在柔性基材上的未交联乙烯共聚物蜡起底漆的作用且使得与任何其他材料的粘合剂结合成为可能。
在本发明的另一实施方案中,本发明对柔性基材印花的方法可以作为转移印花方法进行。为此,用至少一种本发明印花糊对涂有蜡如聚硅氧烷蜡的纸张进行印花,然后将该印花的纸张在室温至300℃,优选室温至180℃下干燥。在热压机或热轧光机上于70-300℃将该干燥且印花的纸张用纺织品材料处理,优选在100-120℃下处理10-100秒。在该操作过程中,印花糊软化/熔融并从纸张转移和固定于待印花的二维或三维柔性基材如纺织品基材或薄片上。
工作实施例说明本发明。
工作实施例
1.制备乙烯共聚物蜡
在文献(M.Buback等,Chem.Ing.Tech.1994,66,510)中所述的高压釜中使表1所示的乙烯和丙烯酸或甲基丙烯酸共聚。在1700巴的反应压力下,将乙烯以12.0kg/h的速率供入高压釜中。首先单独将表1所示量的丙烯酸或甲基丙烯酸压缩至260巴的中间压力,然后在1700巴的反应压力下供入高压釜中。单独地将由在异十二烷中的过氧新戊酸叔丁基酯组成的引发剂溶液(量和浓度见表1)在1700巴的反应压力下供入高压釜中。首先单独将表1所示量的由在异十二烷中的丙醛组成的调节剂(浓度见表1)压缩至260巴的中间压力,然后借助另一压缩机供入高压釜中。反应温度为220℃。按照表1得到分析数据如表2所示的乙烯共聚物蜡。
乙烯和丙烯酸或甲基丙烯酸在乙烯共聚物蜡中的含量分别通过NMR光谱法和滴定(酸值)测定。根据德国标准规范DIN 53402以滴定方式测定乙烯共聚物蜡的酸值。KOH的消耗对应于乙烯共聚物蜡中的丙烯酸或甲基丙烯酸含量。根据德国标准说明DIN 53735,在160℃和325g的负荷下测定MFI。
表1:制备乙烯共聚物蜡
序号 | T反应器[℃] | 乙烯[kg/h] | AS[l/h] | AS[kg/h] | MAS[l/h] | MAS[kg/h] | ID中的PA[ml/h] | C(PA) | ID中的PO[l/h] | c(PO) | 转化率[wt%] | ECW产物[kg/h] |
1.1 | 220 | 12 | 0.79 | 0.80 | - | - | 650 | 25 | 1.95 | 0.07 | 23 | 3.0 |
1.2 | 220 | 12 | - | - | 1.01 | 1.03 | 600 | 25 | 2.10 | 0.07 | 25 | 3.2 |
T反应器指高压釜的最高内部温度。
表2:乙烯共聚物蜡的分析数据
序号 | 乙烯含量[wt%] | AS含量[wt%] | MAS含量[wt%] | 酸值[mgKOH/g ECW] | MFI[g/min] | T熔点[℃] | ρ[g/cm3] |
1.1 | 79.0 | 21.0 | - | 165 | 10 | 78-88 | 0.96 |
1.2 | 73.4 | - | 26.6 | 173 | 10 | 65-80 | 未检测出 |
“含量”指在各乙烯共聚物蜡中共聚的乙烯或丙烯酸或甲基丙烯酸的分数。
缩写:AS:丙烯酸,MAS:甲基丙烯酸,PA:丙醛,ID:异十二烷,PO:氢过氧化叔丁基,ECW:乙烯共聚物蜡。
2.生产乙烯共聚物蜡水分散体
向装有锚式搅拌器的2升高压釜中加入表3所示量的根据实施例1的乙烯共聚物蜡。加入表3所示量的去离子水以及氨并在搅拌下将温度升至120℃。在120℃下30分钟后将温度在15分钟内降至室温,得到分散体2.1和2.2。
表3:生产乙烯共聚物蜡的水分散体
序号 | ECW序号 | ECW量[g] | NH3量[g] | 水量[g] | 固含量[%] | 粘度[s] | pH |
2.1 | 1.1 | 25.0 | 3.4 | 71.6 | 25 | 85 | 9.0 |
2.2 | 1.2 | 25.0 | 3.4 | 71.6 | 25 | 40 | 8.8 |
使用5mm杯在23℃下根据ISO 2431测定粘度。
“NH3量”指25重量%氨水溶液的量。
3.生产本发明印花糊
3.1生产蓝色颜料制剂
在Drais DCP SF 12 Superflow搅拌球磨机中将下列成分在一起研磨:
2640g 颜料蓝15∶3
460g 正C18H37O(CH2CH2O)25H
600g 甘油
2300g 蒸馏水
继续研磨直到颜料颗粒的中径为100nm。
3.2.生产原浆
在搅拌容器中将表4所示成分在一起搅拌并通过以表4所示顺序将各成分相互合并并在一起搅拌而得到原浆3.1-3.4。然后在Ultra-Turrax型高速搅拌器中在约6000转/分钟下搅拌15分钟,然后测试pH。当pH低于8时,通过加入浓氨水将pH设定为8.5。
表4:生产原浆3.1-3.4
原浆 | 3.1 | 3.2 | 3.3 | 3.4 |
成分[g] | ||||
蒸馏水 | - | 380 | - | 380 |
2.1 | 980 | 600 | - | - |
2.2 | - | - | 980 | 600 |
增稠剂 | 20 | 20 | 20 | 20 |
总和 | 1000 | 1000 | 1000 | 1000 |
2.1和2.2指来自实施例2的相应水分散体2.1或2.2。
所用增稠剂在每种情况下为丙烯酸(92重量%)、丙烯酰胺(7.6重量%)、亚甲基二丙烯酰胺(0.4重量%)的共聚物的分散体,该共聚物用氨(25%水溶液)定量中和且分子量Mw为约150,000g/mol;该分散体为矿物油包水分散体(体积比为2.6∶1)(矿物油沸点:190-230℃),固含量:24重量%;用脱水山梨糖醇单油酸酯(基于所有增稠剂为2.5重量%)稳定。
3.3.原浆与来自实施例3.2的蓝色颜料制剂的混合
按照表5的本发明印花糊通过将在每种情况下为970g的按照表4的原浆与在每种情况下为30g的来自实施例3.1的蓝色颜料制剂混合而生产。
得到按照表5的本发明印花糊4.1-4.4。
表5:生产本发明印花糊
原浆序号 | 印花糊序号 |
3.1 | 4.1 |
3.2 | 4.2 |
3.3 | 4.3 |
3.4 | 4.4 |
4.印花试验,印花品测试
将由机织聚丙烯纺织物组成的基重为170g/m2的基材筛网印花。
印花参数为15mm刮刀,ESTAL MONO E 55筛网,磁拉水平(magnetpull level)6,简单印花,无图案。
在干燥箱中于80℃下干燥后,在固定箱中通过在110℃下用热空气加热5分钟而固定。
这得到本发明基材5.1和5.2,也分别称为根据本发明印花的基材5.1和5.2。
为了对比,用类似于本发明印花糊4.1生产的对比印花糊V4.5进行印花,不同的是乙烯共聚物蜡分散体2.1用下列共聚物的分散体(丙烯酸酯粘合剂分散体)代替:
丙烯酸正丁酯(66重量%),
笨乙烯(31重量%),
丙烯酸(1重量%),
羟甲基丙烯酰胺(1重量%)、丙烯酰胺(1重量%);用氨(25重量%水溶液)定量中和,基于共聚物含有2重量%的如下化合物作为乳化剂:
固含量:35重量%。
得到对比基材V5.5。
根据DIN EN ISO 105-X12测试本发明基材的干和湿耐摩牢度并根据DIN EN ISO 105-C03测试耐洗牢度。最好的可能结果:等级为5,最坏的可能结果:等级为1。
得到表6所示的下列本发明基材和测试结果。
表6:根据本发明印花的基材和测试结果
印花糊序号 | 基材序号 | 干耐摩牢度 | 湿耐摩牢度 | 耐洗牢度 |
4.1 | 5.1 | 3-4 | 4 | 3 |
4.2 | 5.2 | 3-4 | 3-4 | 3 |
4.3 | 5.3 | 3-4 | 4 | 3 |
4.4 | 5.4 | 3-4 | 3-4 | 3 |
V4.5 | V5.5 | 3 | 1 | 1-2 |
6.生产本发明染色液和颜料染色液
6.1.生产本发明染色液
通用配方:
通过在搅拌容器中一起搅拌而将下列成分混合在一起:
完全脱盐的水 774g
实施例3.1的颜料制剂 20g/l(以颜料制剂计)
水分散体2.1或2.2 180g/l(以固含量计)
EO8PO7EO8 20g/l作为抗迁移剂
正C12H25O(C2H4O)7H 4g/l作为防成膜剂
HO-(CH2)3-Si[OSi(CH3)3]2 20g/l作为消泡剂
并用完全脱盐的水配成1升。使用水分散体2.1得到本发明染色液F6.1;使用水分散体2.2得到本发明染色液F6.2。
抗迁移剂:在通用配方中所用的EO8PO7EO8抗迁移剂中,EO总是代表氧化乙烯且PO总是代表氧化丙烯。其具有下列性能:在水中的浊点为40℃,平均摩尔质量Mw为1100g/ml,固化点<5℃,25℃粘度:175mPa·s。
6.2.用本发明染色液将基材染色
使用Mathis HVF12085轧染机在每种情况下用根据6.1生产的本发明染色液将纺织品基材(聚丙烯纺织物)染色。辊的轧点压力为2.6巴。所得纤维吸湿率为55%。施加速度为2m/min。然后将纺织品在来自Mathis的LTF89534循环空气箱中于80℃干燥60秒(空气循环为50%)。随后在110℃和空气循环(100%)下定形5分钟。
这得到表7所示的下列本发明基材,也称为根据本发明染色的基材和试验结果。
通过用对比液染色而生产对比基材,该对比液对应于本发明染色液F6.1,不同的是代替分散体2.1使用的是相同量的也用于生产对比印花糊V4.5的丙烯酸酯粘合剂分散体。
表7:根据本发明染色的基材和试验结果
染色液序号 | 基材序号 | 干耐摩牢度 | 湿耐摩牢度 | 耐洗牢度 |
F6.1 | 7.1 | 3-4 | 4 | 3 |
F6.2 | 7.2 | 3-4 | 3-4 | 3 |
对比染色液 | V7.3 | 2 | 1 | 1-2 |
7.生产转移印花品
7.1.生产本发明转移印花色浆
表8:生产本发明转移印花色浆8.1-8.2
转移印花色浆 | 8.1 | 8.2 |
成分[g/kg] | ||
2.1 | 958 | --- |
2.2 | - | 600 |
完全脱盐的水 | --- | 358 |
HO-(CH2)3-Si[OSi(CH3)3]2 | 2 | 2 |
实施例3.2的增稠剂 | 20 | 20 |
蓝色颜料制剂3.1 | 20 | 20 |
总和 | 1000 | 1000 |
7.2.生产转移印花品
用本发明印花糊如8.1和8.2对涂有聚硅氧烷蜡的纸张进行印花,然后在100℃下干燥。将印花并干燥的纸张在热压机上于120℃下与纺织品一起处理1分钟。在此操作期间,印花糊软化/熔融并从纸张转移和固定于待印花的纺织品上。
Claims (10)
2.根据权利要求1的方法,其中所述至少一种烯属不饱和羧酸为通式II的羧酸:
其中
R2选自氢、支化或未支化C1-C10烷基或COOH、COOCH3、COOC2H5,
R3选自氢、支化或未支化C1-C10烷基。
3.根据权利要求1或2的方法,其中所述柔性基材选自薄片和纺织品基材。
4.根据权利要求1-3中任一项的方法,其中所述柔性基材选自(A2)聚丙烯。
5.根据权利要求1-4中任一项的方法,其中所述柔性基材选自纺织物、成圈编织物和非织造织物。
6.根据权利要求1-5中任一项的方法,其中所述至少一种含水配制剂包含(A)至少一种选自增稠剂、交联剂、膜抑制剂、牢度改进剂、增塑剂、消泡剂、润湿剂和匀染剂的其他材料。
7.根据权利要求1-6中任一项的方法,其中在所述接触之后将已处理的柔性基材干燥。
8.由根据权利要求1-7中任一项的方法处理的柔性基材。
9.印花糊,包含:
(B)至少一种包含至少一种以共聚形式包含60-95重量%乙烯和5-40重量%至少一种烯属不饱和羧酸的乙烯共聚物蜡的含水配制剂,和
(C)至少一种颜料。
10.染色液,包含:
(B)至少一种包含至少一种以共聚形式包含60-95重量%乙烯和5-40重量%至少一种烯属不饱和羧酸的乙烯共聚物蜡的含水配制剂,和
(C)至少一种颜料,或
(D)至少一种染料。
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US3405200A (en) * | 1965-07-08 | 1968-10-08 | Toyo Boseki | Polyolefin composition containing a copolymer of ethylene-acrylamide-ethylenically unsaturated compound |
US3650664A (en) * | 1968-04-04 | 1972-03-21 | Inmont Corp | Textile printing method |
US3959534A (en) * | 1973-04-23 | 1976-05-25 | Union Carbide Corporation | Process for producing fibers |
DE2801577A1 (de) * | 1978-01-14 | 1979-07-19 | Sandoz Ag | Textilfaerbeverfahren |
US5378755A (en) * | 1993-08-27 | 1995-01-03 | Reichhold Chemicals, Inc. | Binding agent |
AR001122A1 (es) | 1995-03-06 | 1997-09-24 | Akzo Nobel Nv | Procedimiento de polímerizacion que utiliza una composición de peróxidos (co)polímero funcionalizadoobtenido por el proceso y uso de una composición de peróxidos |
AU2204797A (en) * | 1996-03-13 | 1997-10-01 | Foto-Wear, Inc. | Application to fabric of heat-activated transfers |
DE19805121A1 (de) * | 1998-02-09 | 1999-08-12 | Basf Ag | Verfahren zur Herstellung farbstoffenthaltender, wässriger Polymerisatdispersionen |
-
2004
- 2004-05-12 DE DE102004023894A patent/DE102004023894A1/de not_active Withdrawn
-
2005
- 2005-05-04 WO PCT/EP2005/004809 patent/WO2005113886A1/de not_active Application Discontinuation
- 2005-05-04 EP EP05745338.3A patent/EP1749129B1/de not_active Not-in-force
- 2005-05-04 US US11/578,948 patent/US20080022466A1/en not_active Abandoned
- 2005-05-04 CN CNA2005800151053A patent/CN1954116A/zh active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101680160B (zh) * | 2007-06-12 | 2013-07-10 | 巴斯夫欧洲公司 | 用于浸渍赋予对抗害虫的保护活性的非活体材料的含水配制剂及方法 |
CN108560288A (zh) * | 2018-04-28 | 2018-09-21 | 句容市茂源织造厂 | 一种提高彩色包装材料染色牢度的染色方法 |
CN110317420A (zh) * | 2019-06-25 | 2019-10-11 | 安徽英泰利科技有限公司 | 一种抗老化空气流量计连接胶管材料及其制备方法 |
Also Published As
Publication number | Publication date |
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DE102004023894A1 (de) | 2005-12-08 |
EP1749129B1 (de) | 2014-01-01 |
WO2005113886A1 (de) | 2005-12-01 |
US20080022466A1 (en) | 2008-01-31 |
EP1749129A1 (de) | 2007-02-07 |
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