CN100523057C - 用于浸渍合成纤维的两步法 - Google Patents
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Abstract
本发明涉及一种浸渍合成纤维的两步法,其中首先用含水预浸渍组合物浸渍纤维,然后用间苯二酚-甲醛胶乳(RFL)组合物浸渍,其特征在于预浸渍组合物包含具有至少三官能异氰酸酯基团的封端异氰酸酯和胶乳,其中封端异氰酸酯与胶乳的重量比在9和0.7之间,优选在4和1之间。本发明进一步涉及用于浸渍合成纤维的预浸渍组合物,其包含封端的至少三官能异氰酸酯化合物和胶乳,而且包含水、乳化剂和2-乙烯基吡啶其聚物;并且涉及纤维、帘线和橡胶与纤维或帘线的复合物品,其中纤维或帘线具有至少分布在其表面部分的(1)封端三官能异氰酸酯化合物,优选HDI-三聚体;(2)RFL粘合剂;和(3)现场硫化橡胶化合物。
Description
本发明涉及用于浸渍合成纤维两步法,其中所述纤维首先用预浸渍组合物浸渍,然后用间苯二酚-甲醛胶乳(RFL)组合物浸渍。
用于粘合到橡胶化合物上的纤维,例如芳族聚酰胺,通常经过浸渍处理以增强这种合成纤维与橡胶的结合。这种组合物可用于制造复合材料,例如轮胎,其中增强纤维与轮胎橡胶化合物结合。
在橡胶复合材料(它们包括纤维、连续纤维线、帘线或切短纤维形式的纤维增强材料)的制造中,重要的是增强复合材料的橡胶基体与增强纤维之间的粘合性能。
例如,芳族聚酰胺是一种用于轮胎加固的纤维。由于纤维的结晶表面,在芳族聚酰胺与橡胶之间提供粘合是非常困难的。因此,有效的预浸渍处理是必要的,以便获得纤维与橡胶之间理想的粘合性能。这种预浸渍处理的标准方法是使用环氧粘合剂预浸渍,然后用间苯二酚甲醛胶乳(RFL)浸渍,该方法提供了芳族聚酰胺增强材料与硫化橡胶的良好粘合。
例如,已经提出用环氧化物和聚乙烯亚胺作为芳族聚酰胺纤维的助粘剂。Lyengar提出了一种将芳族聚酰胺纤维粘合到橡胶上的两步粘合***。第一步骤或预浸渍应包括环氧化合物。(J.AppI.Polym.Sci.,2311,第11卷(1967))。G.E.van Gills(The general Tire and Rubbers Co.)在美国专利3,872,939中披露使用2%的甘油二缩水甘油基醚溶液作为初层和面层,其包括1,3-丁二烯-苯乙烯-2-乙烯基吡啶共聚物和热反应性2,5-二(2,4-二羟基苯基甲基)-4-氯酚。
在EP 353473中,除了使用传统的环氧预浸渍组合物外,还使用了包含苯基封端的4,4′-二苯基甲烷二异氰酸酯的预浸渍组合物。这些溶液不包含除水和异氰酸酯之外的任何其他组分。我们已经发现含水的封端二异氰酸酯预浸渍组合物导致纤维和帘线与橡胶的粘合性能不充分。
用于聚酯纤维的包含三异氰酸酯和更高级异氰酸酯化合物的预浸渍组合物已经在JP 57187238中描述。这种包含多官能异氰酸酯和二异氰酸酯混合物的预浸渍组合物已经在JP 51037174中描述,而且包含封端多异氰酸酯和粘土(例如斑脱土)混合物的预浸渍组合物已经在JP 55062269描述。但是,这些组合物中没有一个在粘合橡胶方面非常有效并且其中没有一个可工业化使用。
从那时起开发的粘合技术实际上一直以使用环氧化物为基础,但是由于卫生保健问题和政府规章的要求日益严格,使用环氧化物目前是不合需要的。根据HSE条例,人体暴露于环氧化物是不符合要求的。因此越来越要求获得安全的浸渍程序,其不使用有毒材料并且与基于环氧化物的粘合剂基本等效。
为此,发明了用于浸渍合成纤维的两步法,其中纤维首先用含水预浸渍组合物浸渍,然后用间苯二酚-甲醛胶乳(RFL)组合物浸渍,其特征在于所述预浸渍组合物包含具有至少三官能异氰酸酯基的封端异氰酸酯和胶乳,其中封端异氰酸酯与胶乳的重量比在9和0.7之间,优选在4和1之间。
这样浸渍的纤维保持与使用传统环氧化物预浸渍获得的相同粘合性能,而完全可以避免这种环氧化物处理。因此,优选的实施方式是使用基本上、或甚至完全不含含环氧化物的衍生物的预浸渍组合物进行浸渍程序。
在另一实施方式中,预浸渍组合物可包含封端的至少三官能的异氰酸酯化合物和胶乳,其进一步包含水、乳化剂和2-乙烯基吡啶共聚物。
预浸渍的胶乳部分可以与RFL组合物的胶乳部分相同或不同,并且是共轭烯烃嵌段和芳族嵌段的嵌段共聚物。这种嵌段共聚物在本领域是公知的。已经发现,当预浸渍和RFL组合物的胶乳部分为乙烯基-吡啶嵌段共聚物时,获得了特别好的结果。合适的共聚物包含2-乙烯基吡啶、苯乙烯和丁二烯残基。优选地,所述共聚物中10-20%的单元为类2-乙烯基吡啶的结构。例如,合适的共聚物具有通式[(C7H7N)1(C8H8)m(C4H6)n]x,其中l:(m+n)比(重量%)为1:9-1:4,并且m:n比为2:3-4:1。最优选的是,l:m:n=约15:35:50。
本发明方法原则上可以用于任何通常在轮胎、传送带等所用橡胶复合材料中用作增强纤维的合成纤维。这种纤维优选包含芳族聚酰胺、聚酯和聚对苯二甲酸酯中的至少一种。在本发明中,特别适合的纤维至少包含芳族聚酰胺,优选包含PPTA和/或PPODPTA。
本发明方法适于浸渍其中纤维以纺纱使用的纤维。
所述封端的异氰酸酯具有至少三官能异氰酸酯基团。这种异氰酸酯的实例为1,6-六亚甲基二异氰酸酯(HDI)三聚体等。封端基团在本领域是公知的,并且选自酮肟基团,如甲基乙基酮肟;吡唑衍生物,如3,5-二甲基吡唑;酯,如丙二酸酯;己内酰胺和烷基化的酚。最优选的封端异氰酸酯是封端的HDI-三聚体,例如甲基乙基酮肟或3,5-二甲基吡唑封端的六亚甲基二异氰酸酯三聚体。最优选的封端基是3,5-二甲基吡唑。
所述RFL浸渍可包含乳化剂。合适的乳化剂选自包含橡胶胶乳的乳化剂。
非常适合的本发明预浸渍是包含下述组分的组合物:2.5-4重量%水分散的3,5-二甲基吡唑封端的异氰酸酯化合物(HDI-三聚体),1-2.5重量%的2-乙烯基吡啶共聚物(胶乳)和90-96重量%水(基于固体的重量%)。
必要的是,封端异氰酸酯与胶乳的重量比在9和0.7之间。包含过多或过少胶乳的组合物不能提供与传统环氧预浸渍相当的粘合性能。
更具体地,本发明提供了将芳族聚酰胺纤维与可硫化的橡胶粘合的方法,其包括步骤:(1)将纤维浸入包含下述组分的水分散体中以产生涂覆的纤维:(a)2.5-4重量%水分散的3,5-二甲基吡唑封端的异氰酸酯化合物(HDI-三聚体),(b)1-2.5重量%的2-乙烯基吡啶共聚物和(c)90-96重量%水;(2)干燥并固化该涂覆的纤维,以生产预浸渍的纤维;(3)对预浸渍的纤维进行RFL粘合剂浸渍,以产生浸渍纤维;(4)干燥并固化该浸渍纤维以产生浸渍纤维;(5)使固化的浸渍纤维与可硫化橡胶接触;和(6)固化该可硫化的橡胶(基于固体的重量%)。
本发明的另一实施方式中涉及纤维和帘线,其中纤维和帘线具有至少分布在其表面部分的(1)封端的三官能异氰酸酯,如水分散的3,5-二甲基吡唑封端的异氰酸酯化合物(HDI-三聚体);(2)RFL粘合剂;和(3)现场硫化的橡胶化合物。
还提供了橡胶和纤维的复合物品,其中纤维具有至少分布在其表面部分的(1)封端的三官能异氰酸酯,如水分散的3,5-二甲基吡唑封端的异氰酸酯化合物(HDI-三聚体);(2)RFL粘合剂;和(3)现场硫化的橡胶化合物。
本发明将通过下述非限定实施例加以说明。
实施例1
本实施例提供使用芳族聚酰胺试样的试验,以证明在芳族聚酰胺纤维上结合使用三官能封端异氰酸酯和2-乙烯基吡啶共聚物的效果。
用于芳族聚酰胺纤维的对比粘合剂是环氧和RFL双涂层。芳族聚酰胺纤维用多官能环氧树脂预浸渍和RFL面层浸渍以进行比较。实验粘合剂(初层)包括作为预浸渍的3.5重量%的BI 7986(3,5-二甲基吡唑封端HDI三聚体;来自Baxenden Chemicals Ltd.,UK)和1.5重量%VP106S(2-乙烯基吡啶共聚物胶乳;来自GoodyearChemicals Ltd.,USA)(基于固体)和作为面层的RFL。
帘线处理
芳族聚酰胺帘线用2股纱线制备。1680 dtex PPTA纱线来自Teijin)或1670dtex PPODPTA纱线来自Teijin)以330tpm以Z方向加捻。通过成缆,双绞纱线结合在一起,并以330tpm以S方向加捻。这种原坯帘线在预浸渍粘合剂中浸渍并于150℃干燥120秒,于240℃固化90秒,浸入RFL,于235℃固化90秒。
用于试验的化合物
浸渍过的芳族聚酰胺帘线在用于客车轮胎层橡胶的化合物中测试。主要组分是天然橡胶。
结果和讨论
在本实施例和其后各实施例中,静态剥离粘合性和粘合耐热性试验是指将帘线埋置于橡胶、并且橡胶在金属模具中固化的试验(根据ASTM D4393;SPAF=带剥离粘合力)。该复合材料试样然后在室温大气下(静态)或120℃大气下(耐热性)施加荷载直到橡胶与帘线层分离,其中的荷载以牛顿(N)表示。
1HDI-三聚体/胶乳浸渍(HDI-三聚体/2-乙烯基吡啶(Vp)胶乳重量比)
2环氧化物浸渍而不是HDI-三聚体/胶乳浸渍
3括号内的值表示剥离表面的橡胶覆盖率%
实施例2
通过应用标准帘线(即1000,1680dtex/2,1Z330×2S330)和标准橡胶(5320,NR橡胶)并且应用轮胎胎体用橡胶(重量比,NR/SBR=70/30)测定根据本发明的无环氧预浸渍和根据现有技术的环氧预浸渍的粘合性能。
纱线和帘线
浸渍
标准现有技术浸渍(环氧预浸渍)(2%三官能缩水甘油基甘油醚(环氧化物)/RFL)
根据本发明的浸渍(无环氧预浸渍)(非环氧化物/RFL)
(HDI三聚体/Vp胶乳重量比=75/25,浓度5%)
顺序
预浸渍;120s×150℃(9N)-90s×240℃(9N)
RFL浸渍;90s×235℃(9N)
评估(SPAF)
BS/FS橡胶(cra)(NR/SBR)160℃×20分钟
原坯和浸渍帘线的断裂强度示于表II
表II
浸渍类型 | 加捻机械 | 断裂强度原坯(N) | 断裂强度浸渍(N) |
环氧化物/RFL | 两步 | 425 | 423 |
非环氧化物/RFL* | 两步 | 425 | 435 |
环氧化物/RFL | 直接成缆 | 410 | 455 |
非环氧化物/RFL* | 直接成缆 | 410 | 453 |
*根据本发明
粘合性能
使用NR橡胶和NR/SBR橡胶针对两步和直接成缆的环氧化物/RFL(现有技术)和非环氧/RFL(本发明)确定SPAF性能,并且表明在所有条件下都几乎相同。所有的值均在280和320N/2cm之间。
橡胶覆盖率
橡胶覆盖率按如下步骤确定。在测量剥离粘合性后,观察剥离的表面并测定残留橡胶的比率。结果示于表III。
表III
浸渍类型 | 加捻机械 | NR橡胶 | NR/SBR橡胶 |
环氧化物/RFL | 两步 | R-R,R-C65-70% | R-R100% |
非环氧化物/RFL* | 两步 | R-R,R-C60-65% | R-R100% |
环氧化物/RFL | 直接成缆 | R-R,R-C60-65% | R-R100% |
非环氧化物/RFL* | 直接成缆 | R-R,R-C55-60% | R-R100% |
NR=天然橡胶
SBR=苯乙烯-丁烯橡胶
R-R=橡胶断裂
R-C=橡胶与帘线之间断裂
*依照本发明
这些结果说明无环氧的预浸渍与现有技术环氧化物预浸渍相当,因此可作为一种新的粘合方法。
Claims (16)
1.一种浸渍合成纤维的两步法,其中首先用含水预浸渍组合物浸渍纤维,然后用间苯二酚-甲醛胶乳RFL组合物浸渍,其特征在于所述预浸渍组合物包含具有至少三官能异氰酸酯基团的封端异氰酸酯和胶乳,其中所述预浸渍组合物的封端异氰酸酯与胶乳的重量比在9和0.7之间。
2.根据权利要求1所述的方法,其中所述预浸渍组合物的封端异氰酸酯与胶乳的重量比在4和1之间。
3.根据权利要求1或2所述的方法,其中所述预浸渍组合物基本不含含环氧化物的衍生物。
4.根据权利要求1或2所述的方法,其中所述预浸渍组合物和RFL组合物的胶乳部分为共轭烯烃嵌段与芳族嵌段的嵌段共聚物。
5.根据权利要求4所述的方法,其中所述胶乳部分为乙烯基-吡啶嵌段共聚物。
6.根据权利要求1或2所述的方法,其中所述合成纤维为包含芳族聚酰胺和聚酯中至少一种的纤维。
7.根据权利要求6所述的方法,其中所述聚酯是聚对苯二甲酸酯。
8.根据权利要求1或2所述的方法,其中所述合成纤维为至少包含芳族聚酰胺的纤维。
9.根据权利要求8所述的方法,其中所述芳族聚酰胺为PPTA和/或PPODPTA。
10.根据权利要求1或2所述的方法,其中使用初纺纤维。
11.根据权利要求1或2所述的方法,其中所述封端异氰酸酯是封端的1,6-六亚甲基二异氰酸酯HDI三聚体。
12.一种用于浸渍合成纤维的预浸渍组合物,其包含封端的至少三官能异氰酸酯化合物和胶乳,其中封端异氰酸酯与胶乳的重量比在9和0.7之间,而且该预浸渍组合物还包含水、乳化剂和2-乙烯基吡啶共聚物。
13.根据权利要求12所述的预浸渍组合物,其中封端异氰酸酯与胶乳的重量比在4和1之间。
14.将芳族聚酰胺纤维与可硫化的橡胶粘合的方法,包括下列步骤:
(1)将纤维浸入包含下述组分的水分散体中以产生涂覆的纤维:(a)2.5至4重量%水分散的3,5-二甲基吡唑封端的异氰酸酯化合物,(b)1至2.5重量%的2-乙烯基吡啶共聚物和(c)90至96重量%水;
(2)干燥并固化该涂覆的纤维,以生产预浸渍的纤维;
(3)对预浸渍的纤维进行间苯二酚-甲醛胶乳RFL粘合剂浸渍,以产生浸渍纤维;
(4)干燥并固化该浸渍纤维以产生固化的浸渍纤维;
(5)使该固化的浸渍纤维与可硫化橡胶接触;和
(6)固化该可硫化的橡胶,
其中所述百分比为基于固体的重量%。
15.权利要求14所述的方法,其中所述封端的异氰酸酯化合物是封端的1,6-六亚甲基二异氰酸酯HDI三聚体。
16.根据权利要求14或15所述的方法获得的与可硫化的橡胶粘合的芳族聚酰胺纤维。
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