CN1096522C - 纤维制品的处理方法 - Google Patents
纤维制品的处理方法 Download PDFInfo
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Abstract
纤维制品先用金属盐和磷酸化合物两者或从金属盐和羧酸制备的羧酸金属配合物处理,然后用氟烃防水防油剂处理。处理后的纤维制品即使是重复洗涤和摩擦也能保持防水性,同时又不丧失其固有的触感、手感和柔软性。
Description
本发明涉及纤维制品的处理方法及其所处理的纤维制品。更详细地说,涉及通过纤维制品的改性处理,使得即使经过包括洗涤等在内的长期使用也能保持耐久的防水防油性,进而在处理后也能保持纤维本来的触感·手感·柔软性的纤维制品处理方法。
先有技术
众所周知,含有氟烷基的含氟化合物对纤维制品显示出优异的防水防油性能,具体地说含有氟烷基的丙烯酸聚合物类处理剂已得到实际应用。然而,用含有氟烷基的丙烯酸聚合物类处理剂处理时,所处理的纤维制品除了有本来的触感·手感·柔软性等显著损失这样的缺点外,所得到的防水性也会因洗涤或磨损而显著降低。近年来,作为提高防水防油性的耐久性的尝试,采用了在处理时能与含有氟烷基的丙烯酸聚合物一起使用的并用剂。例如,可以列举蜜胺类树脂、脲醛树脂等,但若并用这些树脂,虽说其耐久性比聚合物单独使用时略有提高,但有使纤维本来的触感、手感、柔软性进一步受损的趋势。因此,可以说,在使用氟类聚合物时,其耐久性与纤维本来的触感、手感、柔软性有相反的关系。特开平5-98568号公报中公开了用磷酸烷酯盐处理兽毛纤维能赋与防水性和柔软性,但由于没有用氟类防水防油剂进行处理,因而在严酷的使用条件下其耐久性很差。
此外,在先有技术上,羧酸的铬配合物也可以作为纤维制品或纸的加工剂用来达到赋与防水性的目的,尤其含有全氟烷基的羧酸铬配合物除了能赋与防水性外还能用来赋与防油性(例如,可参阅特公昭33-466号公报、特公昭44-3274号公报)。然而,这些铬配合物的效果未必充分,还有使其效果进一步增强之需求。
本发明要解决的课题
本发明的目的是即使经过包括洗涤等在内的长期使用也能保持耐久的防水防油性,进而在纤维制品处理后也能保持纤维本来的触感、手感·柔软性。
解决这一课题的手段
[式中,R1和R2可以相同或不同,是氢原子或碳原数4~20的饱和或不饱和直链或支链烃基(碳-碳键之间也可以插入氧原子、氮原子。磺酰基或芳香环)(其中R1和R2不能同时是氢原子);A是氧原子、硫原子或直连键;n是1或2]所示磷酸衍生物或其盐构成的改性剂和金属盐化合物组成的固定剂互为先后处理纤维制品后,或
(ii)在用由通式
R3-COOH
[式中,R3是碳原子数4-28的饱和或不饱和直链或支链烃基或氟烷基)碳-碳键之间可以插入氧原子·氮原子·磺酰基或芳香环)]所示羧酸与金属盐化合物形成的金属配合物处理纤维制品后,
(B)用氟类防水防油剂处理。
本发明也提供用上述处理方法处理的纤维制品。
本说明书中,所谓“处理”系指含有改性剂、固定剂、金属配合物或氟类防水防油剂的处理液与纤维制品接触。处理可以用诸如浸渍、含浸、浸轧法、涂布法等方法进行。
在第一阶段处理中,可以在纤维制品用固定剂处理后用改性剂处理。此外,也可以在纤维制品用改性剂处理后用固定剂处理。
在第一阶段处理中使用的改性剂是上述通式(I)所示磷酸衍生物或其盐。磷酸衍生物是含有P-OH键且同时具有烃基的化合物。所谓烃基,通常是脂肪族烃基,包括饱和或不饱和的、直链或支链的脂肪族烃基,但也包括那些在碳-碳键之间插入了氧原子·氮原子·磺酰基以及芳香环的烃基。烃基较好的是烷基。作为磷酸衍生物的盐,可以列举一价金属盐如钠盐,钾盐·锂盐等,或有机胺盐如二乙醇胺盐、三乙胺盐、丙胺盐、吗啉盐等,或铵盐等。上述磷酸衍生物或其盐的分子量通常因通式而异,但较好是在2000以下。
以下列举磷酸衍生物具体例,但不只是限定于这些。
此外,所谓作为第一阶段处理中使用的固定剂的金属盐化合物的金属,可以是能与磷原子上键合的羟基形成离子键的2价以上金属,通常较好的是铬、锆、钛、铝等。此外,金属盐化合物较好的是水溶性化合物,例如,较好的是氯化物、硝酸盐、硫酸盐、氢氧化物等。具体地说,从耐久性的观点来看,尤其好的是碱式硫酸铬、碱性硫酸锆。
[式中,R1是氢或甲基,R2是低级烷基,X是2价有机基团,m是1-4的整数,n是5-21的整数。]
含氟聚合物的平均分子量通常是5,000-500,000。
[式中,Rf是CmFm+1(m是5~21的整数),n是0~4。]
这些氟类防水防油剂也可以与各种并用剂一起使用,作为并用剂,可以列举诸如蜜胺树脂、脲醛树脂、封闭的异氰酸酯·乙二醛等。
在本发明的第一阶段处理中,纤维制品用改性剂和固定剂处理。改性剂和固定剂的使用顺序如以下所示,先用哪一种都可以。在用改性剂和固定剂的处理方法方面,可以列举以下所示方法(1)、(2)和(3)。
(1)现在说明先用固定剂处理然后用改性剂处理的方法。在固定剂溶液中浸渍纤维制品,从该浴中提起纤维制品、排水。然后,纤维制品在改性剂溶液中浸渍后,在同一浴液中加入酸溶液把pH调至1-5、较好调至3-4,放置,排水、充分水洗后再排水、干燥。或者,在改性剂溶液中浸渍,排水后,在酸溶液(pH1~5)中浸渍,排水,充分水洗后再排水、干燥。
(2)固定剂溶液浸渍和改性剂溶液浸清的顺序也可以反过来。首先,在改性剂溶液中浸渍纤维制品,从该浴中提起纤维制品、排水。然后,纤维制品在固定剂溶液中浸渍后,在同一浴液中加入酸溶液把pH调至1~5、较好调至3~4,放置,排水,充分水洗后再排水、干燥。或者,在固定剂溶液中浸渍、排水后,在酸溶液中浸渍、排水,充分水洗后·排水、干燥。
(3)此外,这一连串处理也可以在同一种浴液中进行。例如,在固定剂溶液中浸渍纤维制品后,向该溶液中添加改性剂,浸渍。进而再添加酸溶液把pH调至1~5、较好调至3~4,放置、排水·充分水洗后、排水、干燥、此外,也可以在改性剂溶液中浸渍后添加固定剂溶液。
在上述方法(1)、(2)和(3)中,作为固定剂的金属盐化合物溶液是0.01-10%(重量)、较好是0.03-3%(重量)水溶液。固定剂溶液的温度通常是20-70℃。作为改性剂的磷酸衍生物的溶液是0.01-10%(重量)、更好的是0.03-3%(重量)水溶液或低级醇溶液。作为低级醇,可以列举甲醇、乙醇、异丙醇、等。改性剂的温度通常是5~90℃、较好是20~70℃。
浸渍或pH调整时使用的酸溶液,是含有盐酸、硫酸等无机酸或甲酸、乙酸、丙酸等有机酸的溶液,较好是水溶液。酸溶液的浓度没有限定,但通常是0.05~30%(重量)、较好是0.1~5%(重量)。酸溶液的温度通常是5~90℃、较好是20~70℃。在固定剂溶液·改性剂溶液和酸溶液中各自的浸渍时间通常在10秒以上,较好是1-120分钟,更好的是1-30分钟。在调整至pH1-5的溶液中的放置时间通常在10秒以上,较好是1-30分钟。干燥温度通常是10~70℃、较好是在室温。干燥时间因干燥条件(尤其干燥温度)而异,通常在24小时以内,较好是0.1-10小时。此外,在上述(3)所示同种溶液的情况下,溶液中固定剂与改性剂的重量比通常是0.1∶1~10∶1。
以下说明使用羧酸衍生物的纤维处理方法。羧酸金属配合物是通过金属盐化合物与羧酸反应得到的。
[式中,R3的意义同上]。铬配合物是通过羧酸与铬化合物在无溶剂或加溶剂的情况下加热得到的。
羧酸的具体例列举如下,但不只限定于这些。
金属盐化合物可以是上述作为固定剂所示的金属盐化合物。
按照本发明的方法,首先作为第一阶段处理,是用由羧酸的金属配合物组成的处理剂处理纤维制品。在本发明的方法中,纤维制品在含有0.01-30%(重量)、更好的是0.1~10%(重量)羧酸金属配合物的水溶液(液温20~70℃、更好的是30~50℃)中浸渍10秒以上,较好浸清1~120分钟,从溶液中把纤维制品提起、排水,然后干燥。干燥温度可以在10~140℃的范围内,但在实用上,在室温风干就足够了。
在第一阶段处理中,水溶液可以含有酸。酸是,例如,盐酸、硫酸等无机酸,甲酸、乙酸、丙酸等有机酸。
对进行了以上第一阶段处理的纤维制品,再进行第二阶段处理(B),即以下所示通常用氟类防水防油剂的处理。其方法可以是先有技术上可进行的方法,例如,用含浸·浸轧法或涂布法等进行,然后干燥。此时,也可以与蜜胺树脂或脲醛树脂等并用剂组合。必要时也可以进一步进行热处理或轧光加工等。此外,也可以与氟类化合物以外的处理剂如硅类化合物并用。
氟类防水防油剂的形态可以是乳液或有机溶剂溶液中任何一种。在乳液的情况下,从氟类防水防油剂的渗透观点来看,更好的是添加占乳液0.1~10%(重量)、较好1-5%(重量)的水溶性低级醇或酮类(尤其好的是异丙醇)。
第二阶段处理对任何一种纤维制品都可以进行。例如,可以对成品地毯(或布)进行第二阶段处理。或者,也可以在用于地毯的原丝和原毛阶段进行第二阶段处理,然后再用这样处理的原丝、原毛编织地毯。还可以对原丝或原毛进行第一阶段处理,然后对成品地毯进行第二阶段处理。
按照本发明,由于首先使磷酸衍生物或羧酸金属配合物渗透到纤维束内部之后加以固定,因而不仅具备了能在纤维织物表面上得到防水防油性这样的条件,而且即使是厚织物也能赋与其深达内部的效果。进而,由于在这上面又用氟类防水防油剂进行第二阶段处理,因而耐久性变得更强了,在进一步使用磷酸衍生物的情况下,以前单独用氟类防水防油剂处理时不可避免的纤维制品原有手感、柔软性的下降得到了令人惊讶的改善,而且即使是在氟类防水防油剂与蜜胺树脂、封闭的异氰酸酯等并用剂一起使用的情况下,也能得到保持与未处理品毫无区别的手感这样完全出乎预料的效果。这些效果不受纤维制品各种形态所左右,对纤维、丝线、织物、编织物、无纺布·由极细纤维形成的人造革等,都取得同等效果。
在本发明中,供给的纤维制品,除纤维本身的形态外,还包括由纤维形成的丝线,织物、编织物、无纺布·人造革等。纤维,当然可以用棉花、羊毛、蚕丝等天然纤维,但也可以用包括聚酯、尼龙等合成纤维在内的任何一种化学纤维。还可以用天然纤维与合成纤维的混纺物。此外,近年来得到显著发展的由极细纤维组成的织物、人造革等,从重视其手感(或外观)、触感的观点来看,也适用于本发明。极细纤维通常是1旦以下,较好是0.8旦以下、更好的是0.8-0.0001旦、最好是0.1-0.001旦。
按照本发明得到的纤维制品,由于具有以上那样出色的特长,因而适合于对防水防油性或防污性等有特殊要求的用途。作为适用于本发明的纤维制品实例之一,可以列举地毯。所供给的地毯,其原材料没有特别限定,可以是尼龙等聚酰胺、聚酯、聚丙烯酸类、羊毛等,但本发明对于通常在严酷条件下使用的尼龙地毯特别有效。而且,也不受地毯构造、编织类型、绒头长度等的制约。
按照本发明得到的纤维制品可用于室外暴露于雨水中的用途。例如,可以列举帐蓬类、汽车覆盖物、自行车覆盖物、卡车车厢蓬布、工程用苫布、雨伞、衣料[尤其雨衣类(例如雨衣、雨大氅等)]。
此外,作为难清洗纤维制品、易污纤维制品、不能经过多次洗涤的纤维制品的用途也很好。例如,可以用于作为帽子、鞋类(例如鞋、拖鞋)、箱包类、口袋类、座套(例如,小轿车座套、其它座套、沙发套、椅套)用的纤维制品,窗帘,台布,建筑物或运载工具(例如,汽车、火车、飞机、轮船等)的墙壁。天井等的内装饰品,以及各种引人注目的展示品。
本发明的较好实施方式
以下提供实施例和比较例,具体地说明本发明。
实施例和比较例中所示的防水性是按照JIS-L-1092-1977测定、用表1所示的数字表示,而防油性则按照AATTC TM-118-1975的方法测定,滴下表2所示表面张力各异的油,以30秒后未观察到任何渗透的最高油代号作为防油性指标。
表1
防水性 状态
100 在表面上不附着湿润
90 在表面上显示出稍微附着湿润
80 在表面上显示部分湿润
70 在表面上显示湿润
50 在整个表面上显示湿润
0 表里两面都显示完全湿润
表2
防油性 表面张力 试液
0 - 防油性不到1的试液
1 31.45 液体石蜡
2 29.6 液体石蜡/正十六烷=
65/35(体积%)
3 27.3 正十六烷
4 26.35 正十四烷
5 24.7 正十二烷
6 23.5 正癸烷
7 21.4 正辛烷
8 19.75 正庚烷
此外,洗涤耐久性按照JIS-L-0217-103测定,以洗涤20次前后的防水性、防油性表示。其中,防水性或防油性数值凡带有“+”号者,均表示该性能比各该指标稍好。
吸水性按照JIS-K-6550-1976测定,系将各样品在纯水中浸渍30分钟,以浸渍前后的重量增加(%)表示。
进而,耐水度按照JIS-K-6550-1976测定,系将样品装入口径50mm、具有能产生恒定水压的构造的耐水度试验机((株)安田精机制作所制)中,让水柱一点一点上升,以样品表面漏水时的水柱高度表示。
处理后纤维的手感根据触感按表3的基准判定。
表3
符号 触感
○ 柔软
△ 稍硬
× 硬
实施例1(用磷酸衍生物和固定剂处理(i)的情况)
第一阶段处理
由极细纤维组成的布(商品名:人工皮革ソフリナシヤル,(株)ワラレ制)在30℃的0.5%碱式硫酸铬(商品名:バイクロムF、バイエル公司制(水溶液)溶比10∶1)中浸渍,用染色试验机(过井染机工业公司制)族转处理30分钟后,排水后,用表4所示化合物1(磷酸衍生物)的50℃ 0.5%水溶液(溶比10∶1)浸渍、旋转处理30分钟。向浴中添加0.3%甲酸水溶液调整至pH=3后,旋转30分钟,排水,在40℃水洗,然后在室温干燥。
第二阶段处理
氟类防水防油剂(商品名:ラツワスガ-ド TG-520,ダイキン工业公司制)用自来水稀释成固形物浓度为1%,再添加作为并用剂的2%エラストロン BN-69(第一工业制药公司制封闭的异氰酸酯)、0.2%エラストロンキヤタリスト(第一工业制药公司制催化剂)、3%异丙醇,配制成处理液。把第一阶段处理毕的试验布浸渍在此处理液中,用轧液机绞干至吸湿率为50%,在110℃干燥3分钟,进而在160℃热处理1分钟。
测定洗涤前后的手感和防水性、防油性、吸水性、耐水度、其结果列于表5中。
比较例1
只进行第二阶段处理
对实施例1使用的纤维制品样品只进行与实施例1第二阶段处理相同的处理。测定洗涤前后的手感、防水性·防油性、吸水性、耐水度、其结果列于表5中。
比较例2
只进行第一阶段处理
对实施例1使用的纤维制品样品只进行与实施例1第一阶段处理相同的处理。测定洗涤前后的手感、防水性、防油性、吸水性、耐水度、其结果列于表5中。
表4
表5
手感 防水性 防油性 吸水性(%) 耐水度(cm)实施例1 L0 ○ 100+ 4 5.8 140
L20 ○ 70 1 29.4 114比較例1 L0 × 100+ 4 10.6 109
L20 × 50 0 72.6 79比較例2 L0 ○ 70+ 0 10.4 76
L20 ○ 50 0 79.0 71
注:L0表示洗涤前,L20表示洗涤20次后。
实施例2(用羧酸金属配合物处理(ii)的情况)
第一阶段处理
由极细纤维组成的人造革)商品名:ソフリナシヤル,(株)クラレ制(浸渍在含有2%(以固形物计)下式所示含全氟烷基的羧酸铬配合物(商品名:スコツチガ-ド 233A スリ-エム公司制)和0.4%甲酸的水溶液(溶比250%)中,用染色试验机(过井染机工业公司制)在40℃旋转处理30分钟后,排水,绞干至吸湿率为80%后,在室温风干。
第二阶段处理
氟类防水防油剂(商品:ラツクスガ-ド TG520,ダイキン工业公司制)用自来水稀释成固形物浓度为1%,再添加作为并用剂的エラストロンBN-69(第一工业制药公司制封闭的异氰酸酯)2%、エラストロンキヤタリスト(第一工业制药公司制催化剂)0.2%、异丙醇3%,配制成处理液。把第一阶段处理完毕的试验布浸渍此处理液中,用轧液机绞干至吸湿率为50%,在110℃干燥3分钟,进而在160℃热处理1分钟。
测定洗涤前后的防水性、防油性、吸水性、耐水度。其结果列于表6中。
比较例3
只进行第二阶段处理
把氟类防水防油剂的固形物浓度配制成实施例2的2倍,对实施例2使用的纤维制品样品只进行与实施例2第二阶段处理相同的处理。测定洗涤前后的防水性、防油性、吸水性、耐水度、其结果列于表6中。
比较4
只进行第一阶段处理
把羧酸铬配合物的固形物浓度配制成实施例2的2倍,对实施例2使用的纤维制品样品只进行与实施2第一阶段处理相同的处理。测定洗涤前后的防水性、防油性、吸水性、耐水度。其结果列于表6中。
表6
防水性 防油性 吸水性(%) 耐度(cm)实施例2 L0 100+ 4 5.3 150
L20 70 1 6.8 112比較例3 L0 100+ 4 10.6 109
L20 50 0 72.6 79比較例4 L0 80+ 3 7.1 124
L20 50 0 14.2 109注:L0表示洗涤前,L20表示洗涤20次。
发明效果
按照本发明,即使是包括洗涤或磨擦等在内长期使用的也能保持耐久的防水性,进而在用磷酸衍生物和固定剂处理的情况下,纤维制品处理后也能保持纤维本来的触感、手感、柔软性等,因而可以同时解决在先有技术中用氟类防水防油剂处理时呈相反关系的耐久性和柔软性这两个课题。
Claims (2)
1.处理纤维制品的方法,其特征在于
(A)
(i)在用由通式(I)表示的磷酸衍生物或其盐构成的改性剂和金属盐化合物组成的固定剂互为先后处理纤维制品后,式中,R1和R2可以相同或不同,是氢原子或碳原子数4-20的饱和或不饱和直链或支链烃基,碳-碳键之间可以插入氧原子、氮原子、磺酰基或芳香环,其中R1和R2不同时是氢原子;A是氧原子、硫原子或直连键;n是1或2,或
(ii)在用由下述通式表示的羧酸与金属盐化合物形成的金属配合物处理纤维制品后,
R3-COOH式中,R3是碳原子数4-28的饱和或不饱和直链或支链烃基或氟烷基,碳-碳键之间可以插入氧原子、氮原子、磺酰基或芳香环,
(B)用氟类防水防油剂处理,其中该防水防油剂为具有全氟烷基的含氟化合物。
2.权利要求1的处理纤维制品的方法,其中组成固定剂和金属配合物的金属盐化合物是铬盐、锆盐、钛盐或铝盐。
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CN (1) | CN1096522C (zh) |
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DE (1) | DE69430873T2 (zh) |
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US7811949B2 (en) | 2003-11-25 | 2010-10-12 | Kimberly-Clark Worldwide, Inc. | Method of treating nonwoven fabrics with non-ionic fluoropolymers |
EP2302130A1 (de) * | 2009-09-26 | 2011-03-30 | Huntsman Textile Effects (Germany) GmbH | Zusammensetzung für die Öl- und/oder Wasserabweisende Ausrüstung von Fasermaterialien |
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JPS598568A (ja) * | 1982-07-07 | 1984-01-17 | Nissan Motor Co Ltd | キツキングプレ−ト |
JPS63105175A (ja) * | 1986-10-23 | 1988-05-10 | カネボウ株式会社 | 合成繊維構造物を帯電防止ならびに撥水加工する方法 |
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NL7505229A (nl) * | 1974-05-07 | 1975-11-11 | Hoechst Ag | Werkwijze en middel voor het vuilafstotend en antistatisch afwerken van vezelmateriaal. |
JPH03193975A (ja) * | 1989-12-22 | 1991-08-23 | Minnesota Mining & Mfg Co <3M> | 撥水撥油処理剤 |
JP2796385B2 (ja) * | 1989-12-22 | 1998-09-10 | ミネソタ マイニング アンド マニユフアクチユアリング カンパニー | 撥水撥油処理剤 |
JPH0598568A (ja) * | 1991-10-09 | 1993-04-20 | Senka Kk | 獣毛繊維の処理方法 |
WO1993015254A1 (en) * | 1992-01-27 | 1993-08-05 | Daikin Industries, Ltd. | Treatment agent for fiber product, method of treating fiber product, and fiber product treated thereby |
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JPS598568A (ja) * | 1982-07-07 | 1984-01-17 | Nissan Motor Co Ltd | キツキングプレ−ト |
JPS63105175A (ja) * | 1986-10-23 | 1988-05-10 | カネボウ株式会社 | 合成繊維構造物を帯電防止ならびに撥水加工する方法 |
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EP0737773A1 (en) | 1996-10-16 |
WO1995018258A1 (fr) | 1995-07-06 |
CN1139965A (zh) | 1997-01-08 |
TW327198B (en) | 1998-02-21 |
DE69430873T2 (de) | 2002-11-28 |
JPH07197377A (ja) | 1995-08-01 |
EP0737773A4 (en) | 1998-06-10 |
EP0737773B1 (en) | 2002-06-26 |
DE69430873D1 (de) | 2002-08-01 |
EP1039018A1 (en) | 2000-09-27 |
ATE219804T1 (de) | 2002-07-15 |
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