CN1189618C - 用于含纤维素材料的无甲醛阻燃处理 - Google Patents
用于含纤维素材料的无甲醛阻燃处理 Download PDFInfo
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- CN1189618C CN1189618C CNB008134235A CN00813423A CN1189618C CN 1189618 C CN1189618 C CN 1189618C CN B008134235 A CNB008134235 A CN B008134235A CN 00813423 A CN00813423 A CN 00813423A CN 1189618 C CN1189618 C CN 1189618C
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- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
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- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
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- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
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- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
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Abstract
用于含纤维素的材料的含水整理组合物，包括羟烷基官能化有机磷阻燃剂(它含有在固化温度下的基本无挥发组分)和无甲醛交联剂(如多羧酸交联剂)，以及用这种组合物处理的材料。用于含水整理组合物的任选成分包括交联剂和/或低廉的饱和α-羟基多羧酸如柠檬酸(更昂贵的优选多羧酸的部分替代)。
Description
本发明的背景
本发明涉及用于含纤维素的材料，如棉花或棉花混纺物(棉花/聚酯和棉花/尼龙)的无甲醛阻燃处理，它能够耐受浆洗和干洗操作。
目前，有几种不同类型的化学整理剂能够应用于含纤维素的材料以赋予阻燃(FR)性。在这些体系当中，只有几种获得了能够进行浆洗和干洗而不损失它们的FR质量的整理织物。这些处理一般称之为耐久FR整理。在这些整理剂当中，跟本发明最相关的是PROBAN和PYROVATEX商标材料。来自Albright & Wilson的PROBAN技术以使用氯化四-(羟甲基)鏻(“THPC”)型产物和氨化室为基础。它在以下U.S.专利Nos.4,078,101；4,145,463；4,311,855和4,494,951中均有详细描述，所有这些专利都属于Albright and Wislson。PYROVATEX CP工艺，最初由Ciba-Geigy开发，利用(N-羟甲基氨基甲酰基-乙基)膦酸二甲酯或类似的羟甲基官能化含磷类似物作为阻燃剂。由于市场受到了在工业中的PROBAN和PYROVATEX产品控制，依次常常难以令人理解的是，人们会普遍忍受与使用这些产品和它们所应用的各种化学过程相关的负面影响。
在近年来，对所使用的THPC交联化学过程提出了几种变型。例如，预缩合-NH3方法(例如PROBAN)技术是这些变型的最近一种。虽然它可能是市场上最耐久的处理，但该技术包括使用氨化室和严格的操作条件，以获得织物没有显著强度损失的一致结果。除了困难的操作条件以外，实施该整理工艺的启动成本和与氨气相关的法规问题使得它不那么吸引人，尤其对于市场的新的到来者。
在许多方面，PYROVATEX技术遭到了与PROBAN技术几乎同样的衰落。无论它是以使用(N-羟甲基氨基甲酰基-乙基)膦酸二甲酯为基础的最初PYROVATEX CP工艺，或者是使用不同N-羟甲基官能化含磷类似物的其它方法，所有这些产物含有和排放毒性组分甲醛(已知的致癌物质)。除了构成PYROVATEX型方法的基础的该分子以外，还需要含甲醛的交联树脂，如N-羟甲基脲(例如，1，3-二羟甲基-4，5-二羟亚乙基脲-“DMDHEU”)，N-羟甲基酰胺，或N-羟甲基蜜胺以确保化学整理的充足的耐久性。这些树脂也独立用作纺织品工业中的耐久压烫交联剂。N-羟甲基含磷类似物和N-羟甲基交联树脂的结合，或者单独使用这两种试剂的任一种经常导致在织物应用过程中和衣服的整个使用期间释放大量的甲醛。因此，全工业中限制和仔细规定甲醛释放水平。甲醛释放仍然被忍受的唯一理由是由于缺乏可接受的无甲醛替代技术。
由于甲醛对人健康的负面影响，棉服和纺织品整理工业主要集中在创造等效的无甲醛技术。因为它们广泛的用途，目前的大多数研究努力花费在用于含纤维素材料的新型无甲醛交联剂的制造和设计上。这些试剂能够用于许多不同的应用，包括在耐久压烫整理中的使用到用于产物的通用固定添加剂如PYROVATEX型FR添加剂。在过去几年里，研究努力已经导致了几种新的低甲醛型体系的发现。这些整理剂一般以DMDHEU的结构改性，即通过侧挂羟甲基官能团的取代或消除为基础。虽然如此，这些新整理剂从未曾获得广泛的赞同，由于它们作为交联剂性能不充分。一般，对DMDHEU分子的最高活性部分的去除或改性仅仅导致了无活性的产生和得到不需要的整理剂。
除了改性DMDHEU以外，其它技术也开始被开发。更有希望的无甲醛体系之一以多羧酸的使用为基础。这些分子通过五元环酐的原位形成和它们随后与在处理纺织品内含有的羟基结构部分的反应产生了交联纤维素材料。该技术在Clark Welch的指导下在新奥尔良的theUnited States Department of Agriculture开发，以使用1，2，3，4-丁烷四羧酸(BTCA)为基础。描述该方法的代表性专利是：U.S.专利Nos.4,820,307；4,936,865；4,975,209；和5,221,285。
因为BTCA技术的发明，其它研究者已经开始用多羧酸处理来改进它们的商业吸引力。一些最近的工作已经集中在使用聚马来酸和在一些情况下使用柠檬酸，或含柠檬酸的混合物。聚马来酸(PMA)是廉价、可商购的材料，通常用作水处理化学品。该工作的一些方面描述在PCT国际专利公开No.WO98/30387中。除了PMA以外，有各种各样的供选择的无甲醛交联树脂能够用来获得用于含纤维素材料的耐久无甲醛FR处理。这些树脂中的许多目前可以购得并用于抑制结垢的水处理行业中，它们中的一些甚至含有少量的磷。这些无甲醛含磷树脂的使用甚至可以提供与无磷交联树脂如PMA相比的附加优点。将磷物质引入到交联树脂本身可以使得不需要外部交联催化剂和/或加入的磷可以获得处理含纤维素材料的改进FR性能。这些树脂的实例能够在以下U.S.专利Nos.4,046,707；4,105,551；4,621,127；5,376,731；5,386,038；5,496,476；5,705,475；和5,866,664中看到。
本发明的概述
本发明涉及用于含纤维素材料的含水整理组合物和用这种组合物处理的材料。含水整理组合物在它最宽的实施方案中包括了羟烷基官能化有机磷阻燃剂和无甲醛交联剂，任选还有包括在其中的交联催化剂。
优选实施方案的描述
根据本发明的目的用于处理含纤维素材料的含水整理组合物含有两种必需组分：(1)羟烷基官能有机磷阻燃剂(排除N-羟甲基，及其醚，和潜在的甲醛释放剂)；和(2)无甲醛交联剂。
单体、低聚(一般含有大约2-10个重复单元)和聚合(一般含有超过大约10个重复单元)羟烷基官能化有机磷阻燃添加剂希望在这里使用。
描述在U.S.专利No.3,695,925(E.D.Weil)和4,199,534,4,268,633,和4,335,178(R.B.Fearing)中的那类反应性低聚含磷阻燃剂是能够根据本发明使用的羟烷基官能化有机磷阻燃剂的实例之一。优选的实施方案具有下式结构：
其中R1独立选自甲基和羟乙基，R2独立选自甲基，甲氧基和羟基乙氧基，和n等于或大于1。该实施方案通过多步法从甲基膦酸二甲酯、五氧化磷、乙二醇和环氧乙烷来制备，并可以注册商标FYROL51从Akzo Nobel Chemicals Inc.获得。端基主要是羟基。
用于这里使用的另一类物质包括水溶性低聚烯基膦酸酯物质，它们的实例描述在U.S.专利Nos.3,855,359和4,017,257中，二者都属于E.D.Weil。在这些物质中烯基取代基的存在提供了利用自由基永久固化条件的其它机理(描述在以上专利中)。这类优选物质可以商标FYROL76从Akzo Nobel Chemicals Inc.获得，并通过使双(2-氯乙基)乙烯基膦酸酯和甲基膦酸二甲酯反应，以及基本清除氯甲烷来生产。
能够使用的另一类羟烷基官能化有机磷阻燃剂是如描述在U.S.专利Nos.2,909,559，3,099,676，3,228,998，3,309,427，3,472,919，3,767,732，3,850,859，4,244,893，4,382,042，4,458,035，4,697,030，4,820,854，4,886,895，5,117,033，和5,608,100中的携带羟基烷氧基的低聚磷酸酯。
阻燃剂一般以含水整理组合物的大约1-大约60wt％，优选大约10-大约40wt％存在。
无甲醛交联剂，即本发明含水整理组合物的第二必要组分，一般以组合物总重量的大约1-大约40wt％，优选大约5-大约20wt％存在。
多羧酸交联剂形成了可以在这里使用的一类交联剂。有效作为根据本发明的纤维素交联剂的多羧酸包括烯属饱和或不饱和脂族、脂环族和芳族酸，具有至少三个和优选三个以上羧基/分子或具有两个羧基/分子，如果碳-碳双键存在于一个或两个羧基的α，β位。其它要求是：它在酯化纤维素羟基中是反应活性的，在脂族或脂环族多羧酸中的既定羧基应该被不少于两个的碳原子和不多于三个的碳原子与第二羧基分开。在芳族酸中，如果第一羧基在酯化纤维素羟基中是有效的，羧基必须是第二个羧基的邻位。从这些要求可以发现，羧基必需是反应性的，它应该能够与多羧酸分子中的相邻羧基形成环状5-或6-元酸酐环。在两个羧基被碳-碳双键分开或二者连接于同一环上，两个羧基应该彼此成顺式结构，倘若它们要以这种方式相互作用的话。脂族或脂环族多羧酸还可以在羧基所连接的链或环中含有氧或硫原子。
在含有三或多个羧基/分子的脂族酸中，连接于羧基的α位碳原子上的羟基不受纤维素被酸酯化和交联的干扰。然而，羟基的存在可以引起材料在热固化过程中的显著发黄。这种α羟基酸适合用于适宜染色的棉布的耐久压烫整理，因为染料的颜色掩盖了可由羟基存在引起的变色。用不仅在一个羧基的α、β位上具有烯属双键，而且在第二个羧基的β、γ位上具有烯属双键的不饱和酸同样发现了织物的变色。
通过用α-羟基酸如柠檬酸交联而在白色含纤维素材料中产生的变色能够通过用含有0.5-5wt％的选自一过氧邻苯二甲酸镁，过硼酸钠，四硼酸钠，硼酸，硼氢化钠，次氯酸钠，和氯化氢中的脱色剂的水溶液浸渍变色材料来消除。将该材料浸渍在脱色剂的溶液中并在室温下，或者必要的话，在升温至不超过60℃温度的这种溶液中浸泡5-120分钟。材料随后用水冲洗以除去过量的化学品和溶解着色产物，然后干燥。
用于这里使用的特别优选的多羧酸交联剂是1，2，3，4-丁烷四甲酸。
用于这里使用的其它优选的多羧酸交联剂是聚马来酸。
用于该组分的其它方案是马来酸酐与乙酸乙烯酯和丙烯酸乙酯的水解三元共聚物。马来酸酐与乙酸乙酯和丙烯酸乙酯的总摩尔数的摩尔比优选是大约2.5∶1-大约5∶1并且乙酸乙烯酯与丙烯酸乙酯的摩尔量优选是大约1∶4-大约4∶1，最优选大约1∶2-大约2∶1。三元共聚物的分子量具有大约4,000的上限。这类产物可以商标BELCLENE283从FMC Corporation购得。
在本发明范围内的其它具体的多羧酸的实例是以下物质：马来酸；柠康酸，也称为甲基马来酸；柠檬酸，也称为2-羟基-1，2，3-丙烷三羧酸；衣康酸，也称为亚甲基丁二酸；丙三羧酸，也称为1，2，3-丙烷三羧酸；反式乌头酸，也称为反式-1-丙烯-1，2，3-三羧酸；1，2，3，4-丁烷四羧酸；全顺式-1，2，3，4-环戊烷四羧酸；苯六甲酸，也称为苯六羧酸；氧联丁二酸，也称为2，2’-氧双-(丁二酸)；硫二丁二酸；描述在U.S.专利Nos.4,046,707；4,105,551；4,621,127；5,376,731；5,386,038；5,496,476；5,705,475；5,866,664中的含磷多羧酸树脂；以及其它等等。
如果使用前面提及的体系没有获得充分的交联，也许有必要添加适合的交联催化剂以增强所要处理的含纤维素材料、羟烷基官能化有机磷阻燃剂，和无甲醛交联剂之间的反应，该催化剂能够以含水整理组合物总重量的至多大约30wt％，优选至多大约10wt％存在。如在PCT国际专利公开No.WO98/303387和U.S.专利Nos.4,820,307，4,936,865，4,975,209和5,221,285中所述，所选择的适合催化剂类型的实例包括已知的次磷酸盐、亚磷酸盐、焦磷酸盐、磷酸二氢盐、磷酸盐和磷酸一氢盐类的一种或多种碱金属盐，以及诸如聚磷酸、次磷酸、亚磷酸和烷基次膦酸的一种或多种的这类酸。还能够使用供选择的碱性交联催化剂如NaHCO3和Na2CO3。
在一些情况下，为了升高处理溶液的pH以改进浴或添加剂的相容性和/或用于改进强度保持率，一部分多羧酸可以盐的形式使用，尤其作为水溶性盐。适合于该目的的是酸的碱金属盐。另外，或者与盐形式的多羧酸的使用相结合，可以升高处理溶液的pH，或者溶液通过添加碱，优选水溶性碱，如碱金属氢氧化物，氢氧化铵或胺来部分中和。为此，pH可以升高至大约2.3-大约5，优选大约2.5-4。
本发明进一步通过以下的实施例来说明。
实验背景资料
所使用的阻燃(“FR”)添加剂
#1样品化合物：改性FYROL51阻燃剂(低OH#)
#2样品化合物：PEEOP(低OH#)
#3样品化合物：改性PEEOP(高OH#)
#4样品化合物：FYROL51阻燃剂(高OH#)
#5样品化合物：FYROL6阻燃剂
#6样品化合物：FYROL76阻燃剂
在以上给出的列举中，“PEEOP”是在U.S.序列No.08/677,283中所述的那类聚(乙基亚乙基氧基)磷酸酯，具有大约915(数均)/1505(重均)的分子量，和在大约5mg KOH/g之下(低羟基值型)和大约150mg KOH/g(高羟基值型)的典型羟基值。改性FYROL51阻燃剂具有在大约5mg KOH/g之下的羟基值，以及FYROL51牌的产品的高羟基型具有大约125mg KOH/g的羟基值。FYROL6阻燃剂具有大约440mg KOH/g的羟基值，而FYROL76阻燃剂具有大约100mg KOH/g的羟基值。
所使用的多羧酸树脂和其它化学品
Belclene 283：马来酸酐、乙酸乙烯酯和丙烯酸乙酯的三元共聚物(TMPA)的水解产物的35％水溶液。
Belclene 200：聚马来酸(PMA)的35％水溶液。
BTCA：1，2，3，4-丁烷四甲酸(固体)。
NaH2PO2(水合物)：用作交联催化剂。
所用设备
浸轧涂敷装置(实验室规格)：用于以规定水平将溶液涂布于织物上的仪器(％纤维吸液率)。
固化烘箱(实验室规格)：用于在高温下干燥和随后固化化学处理的织物的烘箱。
洗衣机(家用规格)：用于在化学处理和固化之前和之后机洗织物(用Tide洗衣粉)。
所用织物
中厚(大约1mm厚)，白色，预洗涤，100％棉织物(12×16英寸样品)。
实验细节
初步工作：
浆洗该棉织物以确保它的清洁，然后切割成大约12×16英寸样品用于以后使用。使用水和织物样品，设置浸轧涂敷装置至大约75％的纤维吸液率(液体的附加重量除以干布的初始重量)。将水的75％纤维吸液率换算成化学品溶液的大约80％纤维吸液率。
一般操作程序：
制备有和没有FR的涂布溶液。各溶液含有FR(空白除外)，多羧酸，NaH2PO2，和水。已知纤维吸液率为80％，调节溶液浓度以获得各化学品的所需加合重量。
在制备后，在5小时内使用各涂布溶液。
然后将各溶液涂布于织物样品。将织物浸渍在溶液中，从浸轧涂敷装置中过一下，再次浸渍在溶液中，以及再次从浸轧涂敷装置中过一下以确保整个织物样品具有充分的均匀性。
在涂布后，各织物样品放置在金属框架上和送入80℃的烘箱以进行干燥(3-5分钟)。
在干燥后，将各样品再次放入180℃的烘箱中以固化该化学处理(1.5-2分钟)。
然后从金属架上取出各固化样品，并记录它的物理性能。还记录在干燥和固化织物同时所做的任何观测。
非正式点燃试验：
将各织物样品保持在水平位置和用丙烷打火机点燃。记录各织物样品的可燃性。
实验数据
第一次试验涂布：
| BELELENE 283树脂 | BTCA | |||||
| 样品化合物#2 | 样品化合物#4 | 样品化合物#5 | 样品化合物#2 | 样品化合物#4 | 样品化合物#5 | |
| 干燥添加重量 | 10％ FR#24％ TMPA2％ NaH2PO2 | 10％ FR#44％ TMPA2％ NaH2PO2 | 10％ FR#54％ TMPA2％ NaH2PO2 | 10％ FR#24％ BTCA2％ NaH2PO2 | 10％ FR#44％ BTCA2％ NaH2PO2 | 10％ FR#54％ BTCA2％ NaH2PO2 |
| 涂布溶液配方 | 26.6g FR#230.4gBELCLENE2835.4g NaH2PO2137.6g H2O | 26.6g FR#430.4gBELCLENE2835.4g NaH2PO2137.6g H2O | 26.6g FR#530.4gBELCLENE2835.4g NaH2PO2137.6g H2O | 26.6g FR#210.7g BTCA5.4g NaH2PO2157.3g H2O | 26.6g FR#410.7g BTCA5.4g NaH2PO2157.3g H2O | 26.6g FR#510.7g BTCA5.4g NaH2PO2157.3g H2O |
| 干燥条件 | 3分钟@80℃ | 3分钟@80℃ | 3分钟@80℃ | 3分钟@80℃ | 3分钟@80℃ | 3分钟@80℃ |
| 固化条件 | 1.5分钟@180℃ | 1.5分钟@180℃ | 1.5分钟@180℃ | 1.5分钟@180℃ | 1.5分钟@180℃ | 1.5分钟@180℃ |
| 燃烧(在洗涤前) | 不良-织物燃烧 | 不良-织物燃烧 | 不良-织物燃烧 | 不良-织物燃烧 | 不良-织物燃烧 | 不良～织物燃烧 |
第二次试验涂布：
| 空白样品(没有FR) | |||
| BELCENE 283 (TMPA) | BTCA | BELCLENE 200 (PMA) | |
| 干燥添加重量 | 8％ TMPA4％ NaH2PO2 | 8％ TMPA4％ NaH2PO2 | 8％ TMPA4％ NaH2PO2 |
| 涂布溶液配方 | 57.1g BELCLENE 28310.0g NaH2PO2132.9g H2O | 57.1g BELCLENE 28310.0g NaH2PO2132.9g H2O | 57.1g BELCLENE 28310.0g NaH2PO2132.9g H2O |
| 干燥条件 | 5分钟@80℃ | 5分钟@80℃ | 5分钟@80℃ |
| 固化条件 | 2分钟@180℃ | 2分钟@180℃ | 2分钟@180℃ |
| 燃烧试验(在洗涤前) | 不良-织物燃烧 | 不良-织物燃烧 | 不良-织物燃烧 |
| 织物颜色 | 轻微米色 | 白色 | 黄色 |
| 织物手感 | 非常硬 | 硬 | 非常硬 |
| 其它发现 | 无烟 | 无烟 | 无烟 |
| BELELENE 283树脂(TMPA) | ||||||
| 样品化合物#1 | 样品化合物#2 | 样品化合物#3 | 样品化合物#4 | 样品化合物#5 | 样品化合物#6 | |
| 干燥添加重量 | 20％ FR#18％ TMPA4％ NaH2PO2 | 20％ FR#28％ TMPA4％ NaH2PO2 | 20％ FR#38％ TMPA4％ NaH2PO2 | 20％ FR#48％ BTCA4％ NaH2PO2 | 80％ FR#58％ BTCA4％ NaH2PO2 | 20％ FR#68％ BTCA4％ NaH2PO2 |
| 涂布溶液配方 | 50.0g FR#157.1gBELCLENE28310.0g NaH2PO282.9g H2O | 50.0g FR#257.1gBELCLENE28310.0g NaH2PO282.9g H2O | 50.0g FR#357.1gBELCLENE28310.0g NaH2PO282.9g H2O | 50.0g FR#457.1gBELCLENE28310.0g NaH2PO282.9g H2O | 50.0g FR#557.1gBELCLENE28310.0g NaH2PO282.9g H2O | 50.0g FR#657.1gBELCLENE28310.0g NaH2PO282.9g H2O |
| 干燥条件 | 5分钟@80℃ | 5分钟@80℃ | 5分钟@80℃ | 5分钟@80℃ | 5分钟@80℃ | 5分钟@80℃ |
| 固化条件 | 2分钟@180℃ | 2分钟@180℃ | 2分钟@180℃ | 2分钟@180℃ | 2分钟@180℃ | 2分钟@180℃ |
| 燃烧试验(在洗涤之前) | 良好 | 良好 | 良好 | 良好 | 不良-织物燃烧 | 良好 |
| 燃烧试验(在1次水洗后) | 可以接受 | 不良-织物燃烧 | 良好 | 良好 | 不良-织物燃烧 | 良好 |
| 燃烧试验(在5次洗涤后) | - | - | 可接受 | 良好 | - | 可接受 |
| 织物颜色 | 粉红色 | 暗粉红色 | 粉红色 | 暗粉红色 | 粉红色 | 浅粉红色 |
| 织物手感 | 硬 | 柔软 | 非常硬 | 非常硬 | 非常硬 | 非常硬 |
| 其它发现 | 在固化过程中冒烟 | 溶解性问题-FR | 无烟 | 无烟 | 在固化过程中冒烟 | 无烟 |
| 样品化合物#1 | 样品化合物#2 | 样品化合物#3 | 样品化合物#4 | 样品化合物#5 | 样品化合物#6 | |
| 干燥添加重量 | 20％ FR#15％ BTCA2.5％ NaH2PO2 | 20％ FR#25％ BTCA2.5％ NaH2PO2 | 20％ FR#35％ BTCA2.5％ NaH2PO2 | 20％ FR#45％ BTCA2.5％ NaH2PO2 | 20％ FR#55％ BTCA2.5％ NaH2PO2 | 20％ FR#65％ BTCA2.5％ NaH2PO2 |
| 涂布溶液配方 | 50.0g FR#112.5g BTCA6.3g NaH2PO2131.2g H2O | 50.0g FR#212.5g BTCA6.3g NaH2PO2131.2g H2O | 50.0g FR#312.5g BTCA6.3g NaH2PO2131.2g H2O | 50.0g FR#412.5g BTCA6.3g NaH2PO2131.2g H2O | 50.0g FR#512.5g BTCA6.3g NaH2PO2131.2g H2O | 50.0g FR#612.5g BTCA6.3g NaH2PO2131.2g H2O |
| 干燥条件 | 5分钟@80℃ | 5分钟@80℃ | 5分钟@80℃ | 5分钟@80℃ | 5分钟@80℃ | 5分钟@80℃ |
| 固化条件 | 2分钟@180℃ | 2分钟@180℃ | 2分钟@180℃ | 2分钟@180℃ | 2分钟@180℃ | 2分钟@180℃ |
| 燃烧试验(在洗涤之前) | 良好 | 良好 | 良好 | 良好 | 不良-织物燃烧 | 良好 |
| 燃烧试验(在1次水洗后) | 可以接受 | 不良-织物燃烧 | 良好 | 良好 | 不良-织物燃烧 | 良好 |
| 燃烧试验(在5次洗涤后) | - | - | 良好 | 良好 | - | 良好 |
| 织物颜色 | 白色 | 白色 | 白色 | 白色 | 浅黄色 | 白色 |
| 织物手感 | 半柔软 | 柔软 | 硬 | 非常硬 | 硬 | 非常硬 |
| 其它发现 | 在固化过程中冒烟 | 溶解性问题-FR | 无烟 | 无烟 | 在固化过程中冒烟 | 无烟 |
| BELCLENE 200(PMA) | ||||
| 样品化合物#1 | 样品化合物#3 | 样品化合物#4 | 样品化合物#6 | |
| 干燥添加重量 | 20％ FR#18％ PMA4％ NaH2PO2 | 20％ FR#38％ PMA4％ NaH2PO2 | 20％ FR#48％ PMA4％ NaH2PO2 | 20％ FR#68％ PMA4％ NaH2PO2 |
| 涂布溶液配方 | 50.0g FR#157.1gBELCLENE 20010.0g NaH2PO282.9g H2O | 50.0g FR#357.1gBELCLENE 20010.0g NaH2PO282.9g H2O | 50.0g FR#457.1gBELCLENE 20010.0g NaH2PO282.9g H2O | 50.0g FR#457.1gBELCLENE 20010.0g NaH2PO282.9g H2O |
| 干燥条件 | 5分钟@80℃ | 5分钟@80℃ | 5分钟@80℃ | 5分钟@80℃ |
| 固化条件 | 2分钟@180℃ | 2分钟@180℃ | 2分钟@180℃ | 2分钟@180℃ |
| 燃烧试验(在洗涤之前) | 良好 | 良好 | 良好 | 良好 |
| 燃烧试验(在1次水洗后) | 可以接受 | 良好 | 良好 | 良好 |
| 燃烧试验(在5次洗涤后) | - | - | 良好 | - |
| 织物颜色 | 黄色 | 黄色 | 黄色 | 黄色 |
| 织物手感 | 硬 | 非常硬 | 硬 | 非常硬 |
| 其它发现 | 在固化过程中冒烟 | 无烟 | 无烟 | 无烟 |
第三次试验涂布：
| #5样品化合物 | |||
| BELCLENE 283(TMPA) | BTCA | BELCLENE 200(PMA) | |
| 干燥添加重量 | 40％ FR#58％ TMPA4％ NaH2PO2 | 40％ FR#55％ BTCA2.5％ NaH2PO2 | 40％ FR#58％ PMA4％ NaH2PO2 |
| 涂布溶液配方 | 100.0g FR#557.1g BELCLENE 28310.0g NaH2PO232.9g H2O | 100.0g FR#512.5g BTCA6.3g NaH2PO281.2g H2O | 100.0g FR#557.1g BELCLENE 20010.0g NaH2PO232.9g H2O |
| 干燥条件 | 5分钟@80℃ | 5分钟@80℃ | 5分钟@80℃ |
| 固化条件 | 2分钟@180℃ | 2分钟@180℃ | 2分钟@180℃ |
| 燃烧试验(在1次水洗后) | 不良-织物燃烧 | 不良-织物燃烧 | 不良-织物燃烧 |
| 织物颜色 | 黄色 | 黄色 | 黄色 |
| 织物手感 | 柔软 | 柔软 | 柔软 |
| 其它发现 | 在固化过程中冒烟 | 在固化过程中冒烟 | 在固化过程中冒烟 |
所选织物样品的分析
#3样品化合物(20％用量)与TMPA和BTCA(样品-在洗涤前，在1次水洗后，和在5次浆洗后)。
#4样品化合物(20％用量)与TMPA，BTCA，和PMA(样品-在洗涤前，在1次水洗后，和在5次浆洗后)。
#6样品化合物(20％用量)与TMPA和BTCA(样品-在洗涤前，在1次水洗后，和在5次浆洗后)。
#5样品化合物(40％用量)与TMPA，BTCA，和PMA(样品-在1次水洗后)。
对选择织物样品的百分数磷测定
| 样品标识(干燥添加重量) | 在洗涤前(％P) | 在1次水洗后(％P) | 在5次浆洗后(％P) |
| 20％ FR#3，5.0％ BTCA，2.5％NaH2PO2 | 2.8 | 1.9 | 1.6 |
| 20％ FR#3，8.0％ TMPA，4.0％NaH2PO2 | 3.6 | 2.1 | 2.1 |
| 20％ FR#4，5.0％ BTCA，2.5％NaH2PO2 | 3.4 | 2.0 | 2.1 |
| 20％ FR#4，8.0％ TMPA，4.0％NaH2PO2 | 4.2 | 2.7 | 2.5 |
| 20％ FR#4，8.0％ PMA，4.0％NaH2PO2 | 3.9 | 2.2 | 2.3 |
| 20％ FR#6，5.0％ BTCA，2.5％NaH2PO2 | 3.9 | 2.6 | 2.3 |
| 20％ FR#6，8.0％ TMPA，4.0％NaH2PO2 | 4.5 | 1.5 | 1.5 |
| 40％ FR#5，5.0％ BTCA，2.5％NaH2PO2 | - | 0.35 | - |
| 40％ FR#5，8.0％ TMPA，4.0％NaH2PO2 | - | 0.37 | - |
| 40％ FR#5，8.0％ PMA，4.0％NaH2PO2 | - | 0.34 | - |
对选择织物样品的百分数钠测定
| 样品标识(干燥添加重量) | 在5次浆洗后(％Na) |
| 20％ FR#3，5.0％ BTCA，2.5％ NaH2PO2 | 72ppm* |
| 20％ FR#3，8.0％ TMPA，4.0％ NaH2PO2 | 58ppm* |
| 20％ FR#4，5.0％ BTCA，2.5％ NaH2PO2 | 55ppm* |
| 20％ FR#4，8.0％ TMPA，4.0％ NaH2PO2 | 95ppm* |
| 20％ FR#4，8.0％ PMA，4.0％ NaH2PO2 | 92ppm* |
| 20％ FR#6，5.0％ BTCA，2.5％ NaH2PO2 | 51ppm* |
| 20％ FR#6，8.0％ TMPA，4.0％ NaH2PO2 | 76ppm* |
*数字用空白修正(空白样品的钠水平是~75ppm)
从以上结果可以看出，几种FR/树脂涂布混合物获得了FR耐久性，即使在用洗涤剂5次浆洗后(所使用的洗涤的最大数字)。对于以上报道的成功试验和其它没有获得所需结果的实施方案，后者是由于缺乏阻燃反应活性(羟基官能度不足)或由于阻燃添加剂的挥发性，一种趋势变得非常明显。需要OH官能团在阻燃添加剂中存在以获得最令人满意的FR耐久性。含有#3，#4和#6样品化合物的涂布混合物(OH官能化)获得了所记录的最耐久的FR处理。
根据OH官能团，似乎很可能的是，#5样品化合物将被证明是所评价的最耐久的FR添加剂。然而，这不是在所进行的实验过程中的实际情况。对此最可能的解释是FR添加剂在烘箱固化阶段中蒸发。这不是令人惊奇的，因为#5化合物的TGA和DSC分析结果显示了在大约160℃下，即在设定固化温度(180℃)以下大约20℃，重量显著损失(TGA& DSC)。蒸发也解释了在处理织物的固化步骤过程中所观察到的大量烟雾和蒸汽。在已知这些结果的情况下，当实施本发明时，还需要考虑选择FR添加剂的挥发性。有潜力的FR添加剂应该具有在固化温度下基本无挥发的、反应活性的组分，以确保在FR添加剂的挥发之前发生交联。固化温度被定义为交联反应发生的温度。
除了所使用的FR添加剂的类型以外，对所使用的交联树脂的类型也进行了观察。除了在试验过程中记录的各种特性以外，织物的颜色和手感是最重要的。一般，BTCA树脂获得了最柔软的手感和最白的颜色，二者是非常理想的质量。PMA和TMPA然而获得了不太优选的结果。一般来说，由两种树脂赋予的手感比用BTCA要僵硬得多，这很可能是由所使用的高树脂水平引起的性质。通过减少这些树脂的用量或通过使用软化剂，可以改进织物的手感。PMA和TMPA的另一负面作用是它们在织物上赋予的颜色。PMA处理的织物产生了浅黄色。通过降低固化温度和/或添加增白剂这两种通常用于工业中以矫正这类问题的工艺可能会降低质量。除了PMA以外，TMPA也对织物着色。然而，由该树脂产生的粉红色是更强烈和显著的。
在这些初步试验中，除了使用样品化合物#3、#4和#6的一个以外的所有织物样品在一次水洗后保持了56-68％的应用磷。另外，经第一次洗涤后附着于织物的磷似乎在经过所有5次浆洗后都保留在其中。
除了百分数磷测定以外，还决定来证实钠在浆洗样品中的水平。高水平的钠将不良地影响所测试的FR处理的长期耐久性。众所周知的事实是，水解和随后的钠离子交换至来自洗涤剂的磷FR处理剂中将随时间推移显著影响处理的FR性能(即，磷酯的钠盐使得FR低劣)。除了水解和磷从织物中除去以外，钠离子交换至FR处理剂中是在浆洗后FR性能损失的首要原因之一。如以上数据所显示的那样，所有的浆洗样品都含有非常低水平的钠，这意味着该结合磷对浆洗稳定并应该在5次洗涤后保持良好的FR性能。
前述实施例应该不以限制的方式来解释，因为它们仅用于阐述本发明的某些优选实施方案。请求保护范围在所附权利要求书中阐明。
Claims (9)
1.应用于包含纤维素的材料的含水整理组合物，包括占组合物的1-60wt％的羟烷基官能化有机磷酯阻燃剂，和占组合物的1-40wt％的无甲醛交联剂，其中有机磷酯阻燃剂选自低聚磷酸酯，聚合磷酸酯，低聚膦酸酯，或混合磷酸酯/膦酸酯阻燃剂组合物。
2.如权利要求1中所要求的组合物，其中羟烷基官能化有机磷酯阻燃剂具有下式结构：
其中R1独立选自烷基和羟烷基，R2独立选自烷基、烯基、烷氧基和羟基烷氧基，和n等于或大于1。
3.如权利要求2中所要求的组合物，其中羟烷基官能化有机磷酯阻燃剂具有下式结构：
其中R1独立选自甲基和羟乙基，R2独立选自甲基，甲氧基和羟基乙氧基，和n等于或大于1。
4.如权利要求1中所要求的组合物，其中无甲醛交联剂选自在相邻碳原子上具有一个或多个二羧酸，任选含有磷的多羧酸，多羧酸盐，和它们的混合物。
5.如权利要求4中所要求的组合物，其中多羧酸交联剂是1，2，3，4-丁烷四甲酸。
6.如权利要求4中所要求的组合物，其中多羧酸交联剂是聚马来酸。
7.如权利要求1中所要求的组合物，进一步包括占组合物的至多30wt％的交联催化剂。
8.如权利要求1中所要求的组合物，进一步包括至少一种饱和α-羟基多羧酸，和/或它的盐，其具有连接于相邻碳的至少两个羧基。
9.已经用权利要求1-8之一的含水整理组合物处理的包括纤维素的材料。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/406,529 | 1999-09-27 | ||
| US09/406,529 US6309565B1 (en) | 1999-09-27 | 1999-09-27 | Formaldehyde-free flame retardant treatment for cellulose-containing materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1376225A CN1376225A (zh) | 2002-10-23 |
| CN1189618C true CN1189618C (zh) | 2005-02-16 |
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| CNB008134235A Expired - Fee Related CN1189618C (zh) | 1999-09-27 | 2000-09-22 | 用于含纤维素材料的无甲醛阻燃处理 |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US6309565B1 (zh) |
| EP (1) | EP1226302B1 (zh) |
| JP (1) | JP2003510478A (zh) |
| KR (1) | KR100701717B1 (zh) |
| CN (1) | CN1189618C (zh) |
| AT (1) | ATE393258T1 (zh) |
| AU (1) | AU4024201A (zh) |
| CA (1) | CA2388781A1 (zh) |
| DE (1) | DE60038689D1 (zh) |
| HK (1) | HK1047150A1 (zh) |
| MX (1) | MXPA02003180A (zh) |
| WO (1) | WO2001023663A1 (zh) |
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- 1999-09-27 US US09/406,529 patent/US6309565B1/en not_active Expired - Lifetime
-
2000
- 2000-09-22 DE DE60038689T patent/DE60038689D1/de not_active Expired - Lifetime
- 2000-09-22 EP EP00963746A patent/EP1226302B1/en not_active Expired - Lifetime
- 2000-09-22 AT AT00963746T patent/ATE393258T1/de not_active IP Right Cessation
- 2000-09-22 WO PCT/US2000/026133 patent/WO2001023663A1/en active Application Filing
- 2000-09-22 JP JP2001527037A patent/JP2003510478A/ja active Pending
- 2000-09-22 AU AU40242/01A patent/AU4024201A/en not_active Abandoned
- 2000-09-22 CA CA002388781A patent/CA2388781A1/en not_active Abandoned
- 2000-09-22 CN CNB008134235A patent/CN1189618C/zh not_active Expired - Fee Related
- 2000-09-22 KR KR1020027003898A patent/KR100701717B1/ko not_active IP Right Cessation
- 2000-09-22 MX MXPA02003180A patent/MXPA02003180A/es active IP Right Grant
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Also Published As
| Publication number | Publication date |
|---|---|
| EP1226302B1 (en) | 2008-04-23 |
| DE60038689D1 (de) | 2008-06-05 |
| US6309565B1 (en) | 2001-10-30 |
| AU4024201A (en) | 2001-04-30 |
| CN1376225A (zh) | 2002-10-23 |
| WO2001023663A1 (en) | 2001-04-05 |
| US6365070B1 (en) | 2002-04-02 |
| KR20020059414A (ko) | 2002-07-12 |
| MXPA02003180A (es) | 2003-08-20 |
| JP2003510478A (ja) | 2003-03-18 |
| HK1047150A1 (zh) | 2003-02-07 |
| CA2388781A1 (en) | 2001-04-05 |
| US20020050588A1 (en) | 2002-05-02 |
| EP1226302A1 (en) | 2002-07-31 |
| ATE393258T1 (de) | 2008-05-15 |
| KR100701717B1 (ko) | 2007-03-29 |
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