CN1229462C - 用于非纤维素型基材的氯乙烯/乙酸乙烯酯/乙烯/自交联聚合物 - Google Patents

用于非纤维素型基材的氯乙烯/乙酸乙烯酯/乙烯/自交联聚合物 Download PDF

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CN1229462C
CN1229462C CNB031410901A CN03141090A CN1229462C CN 1229462 C CN1229462 C CN 1229462C CN B031410901 A CNB031410901 A CN B031410901A CN 03141090 A CN03141090 A CN 03141090A CN 1229462 C CN1229462 C CN 1229462C
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J·E·戈德斯泰恩
J·A·韦尔蒂
D·A·马特兰
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Abstract

本发明涉及用于无纺产品的粘合用聚合粘合剂的改进和该无纺产品。基础聚合粘合剂包括乙酸乙烯酯、乙烯和自交联单体，例如N-羟甲基丙烯酰胺的乳液聚合单元。用于形成主要包括合成纤维的无纺织物的粘合用聚合粘合剂的改进在于聚合到乙酸乙烯酯/乙烯聚合物骨架上的氯乙烯的存在。

Description

用于非纤维素型基材的 氯乙烯/乙酸乙烯酯/乙烯/自交联聚合物
                      技术领域
用于制备吸收性一次应用产品如抹布的无纺产品已经广泛应用。这种无纺产品或织物包括用粘合用聚合粘合剂粘结在一起的松散组装的纤维织物(web)或纤维体。这些纤维包括纤维素或聚合材料如聚酯、聚酰胺、聚丙烯酸酯等。用于无纺织物的许多粘合用聚合物以通过乳液聚合形成的乙酸乙烯酯、乙烯和自交联单体，例如N-羟甲基丙烯酰胺(NMA)的水性聚合物或等同物为基础。自交联机理的引入提供了增强的湿强度和耐有机溶剂性。
                      背景技术
以下专利是现有技术的代表：
US3,380,851公开了粘结于松散组装的纤维的包括乙酸乙烯酯、作为内增塑剂的另一可聚合的化合物和后固化性共聚单体如N-羟甲基丙烯酰胺的聚合物的无纺粘结剂。公开了以天然和合成纤维，包括纤维素、羊毛、聚酰胺、聚酯、聚乙烯等为基础的各种纤维。
US 4,449,978公开了用少量甲醛产生的粘合用聚合物粘结的在US3,380,851中公开的那类无纺织物。特定体系以乙酸乙烯酯、乙烯及丙烯酰胺和N-羟甲基丙烯酰胺的共混物为基础。
US 3,758,429公开了用于生产无纺织物的以乙烯、氯乙烯和N-羟甲基丙烯酰胺的三元共聚物为基础的粘合剂。该三元共聚物提供来提高湿强度。
US 3,752,733公开了用乙烯/氯乙烯/丙烯酰胺三元共聚物粘结的以来自天然和合成来源的纤维为基础的无纺产品。专利人公开了用硫化合物固化这些聚合物，以提供增强的拉伸强度、柔软度、柔性等。
US 3,137,589公开了包括在氮上被至少一个羟甲基取代的α，β-不饱和羧酸酰胺和另一不饱和可聚合的化合物的共聚物的粘合剂，用于制备无纺织物。
现有技术的乙酸乙烯酯/乙烯型粘合剂的缺点是对合成非纤维素型织物缺乏粘合力，因此缺乏提供良好湿拉伸强度的能力。显然，因为没有反应活性部位，或在许多情况下，相对于能够与标准自交联乙酸乙烯酯/乙烯型聚合物反应的纤维素，反应活性部位很少，所以很难获得具有良好湿拉伸和溶剂强度的成品织物。
                     发明内容
本发明涉及用于无纺产品的粘合用聚合粘合剂的改进和该无纺产品。基础聚合粘合剂包括乙酸乙烯酯、乙烯和自交联单体，例如N-羟甲基丙烯酰胺的聚合单元，该聚合粘合剂通过乳液聚合形成和配制用于形成无纺产品。用于形成主要包括合成纤维的无纺织物的粘合用聚合粘合剂的改进在于存在聚合到乙酸乙烯酯/乙烯聚合物骨架上的氯乙烯。
显著的优点是可能存在的，它们包括：
对基本不含反应活性部位，例如羟基官能度的合成纤维增强粘合力；
使用用现有自交联乙酸乙烯酯/乙烯粘合剂体系制备无纺织物的普通设备，而没有为该转变而需要较大费用的能力；和
在等同强度下通过减少粘合剂用量而减少游离甲醛水平的能力。
总之，该粘合剂体系的主要优点是该聚合粘合剂表现出对合成纤维的改进粘合力，从而可供许多无纺织物的新结构用。该增加的粘合力导致了织物的强度高于在工业上用任何其它已知乙酸乙烯酯/乙烯型粘合剂体系可能获得的那些，并且可以使用较少的粘合剂制造出与目前可商购的那些具有等同的强度的结构来。该后一优点不仅节约了原料，而且能够成为性能优点，因为它能提供具有较低甲醛水平、无条痕(streaking)、改进吸收性以及更软手感的成品。
本发明涉及通过通过乳液聚合形成的改进水性乙酸乙烯酯/乙烯聚合物，它用作无纺织物的粘合剂。该无纺织物包括作为该无纺织物的组分的合成非纤维素型纤维。该聚合物的改进骨架包括乙酸乙烯酯、氯乙烯和乙烯与有限量的引入到该聚合物中的自交联单体的聚合单元。在改进粘合剂的形成中使用的自交联单体一般以N-羟甲基衍生物，例如N-羟甲基丙烯酰胺为基础。还可以使用C1-C5烷氧基取代的丙烯酰胺如N-羟甲基甲基丙烯酰胺和异丁氧基甲基丙烯酰胺。
改进聚合物的组成类似于在过去适合于无纺织物的那些乙酸乙烯酯/乙烯型粘合剂，不同的是引入了氯乙烯的聚合单元。该乙酸乙烯酯可在60-90wt％，优选70-80wt％范围内，乙烯为5-40wt％，优选10-25wt％，氯乙烯为5-40wt％，优选10-25wt％，以及自交联单体，如N-羟甲基丙烯酰胺为2-10wt％，优选3-8wt％，基于聚合物中的单体总重量。对于降低游离甲醛散发的聚合物，优选的聚合物含有约3-10wt％的N-羟甲基丙烯酰胺/丙烯酰胺的混合物。优选，在聚合物的配方中使用约1.75-3.5wt％的N-羟甲基丙烯酰胺和约1.25-8.25wt％的丙烯酰胺。设想作为N-羟甲基丙烯酰胺的功能等同物的丙烯酰胺单体以约1∶1，即约等摩尔的N-羟甲基丙烯酰胺∶丙烯酰胺摩尔比存在。
在形成该改进聚合物时，乙酸乙烯酯、乙烯、氯乙烯和N-羟甲基丙烯酰胺或N-羟甲基丙烯酰胺/丙烯酰胺单体混合物在水性介质中在不超过100个大气压的压力下在催化剂和至少一种乳化剂的存在下共聚，该水性体系通过适合的缓冲剂保持在2-6的pH下，该催化剂递增添加。该方法是分批法，包括首先均化，其中将悬浮在水中的乙酸乙烯酯在乙烯的存在下在工作压力下充分搅拌，以获得乙烯在乙酸乙烯酯中的溶液，同时将反应介质逐渐加热到聚合温度。反应温度能够通过催化剂添加速度和散热速度来控制。一般，已发现，有利的是，在单体的聚合过程中保持约50℃的平均温度和避免温度大大超过80℃。
均化阶段之后是聚合阶段，在此期间，递增添加由主催化剂或引发剂组成且可以包括活化剂的催化剂。类似地递增添加氯乙烯和N-羟甲基丙烯酰胺或N-羟甲基丙烯酰胺/丙烯酰胺混合物，体系中的压力通过施加恒定的乙烯压力来保持基本不变。
在进行单体的聚合时能够使用各种自由基形成催化剂，如过氧化合物。还能够使用同时应用还原剂和氧化剂的结合型催化剂。这类结合催化剂的使用在本领域中一般称之为“氧化还原聚合”或“氧化还原体系”。该还原剂还常常被称之为活化剂和该氧化剂被称之为引发剂。适合的还原剂或活化剂包括亚硫酸氢盐，次硫酸盐，BruggoliteFF-6(由Bruggemann出售的一种还原剂)，抗坏血酸或异抗坏血酸，或具有还原性能的其它化合物如亚铁盐，和叔芳族胺，例如N，N-二甲基苯胺。氧化剂或引发剂包括过氧化氢，有机过氧化物如过氧化苯甲酰，叔丁基氢过氧化物(t-bhp)等，过硫酸盐如过硫酸铵或钾，过硼酸盐等。能够使用的特定结合型催化剂或氧化还原体系包括叔丁基过氧化物和甲醛合次硫酸锌或异抗坏血酸；过氧化氢，过硫酸铵，或过硫酸钾，与焦亚硫酸钠，亚硫酸氢钠，硫酸亚铁，二甲基苯胺，甲醛合次硫酸锌或甲醛合次硫酸氢钠。还能够使用本领域公知的其它类型的催化剂来聚合这些单体。
该催化剂以0.1-2％，优选0.25-0.75％的量使用，基于引入到该系统中的乙酸乙烯酯的重量。活化剂通常以水溶液的形式添加，以及活化剂的量一般是催化剂量的0.25-1倍。
适合使用的乳化剂一般是阴离子、非离子乳化剂，或它们的共混物。适合的非离子乳化剂包括聚氧乙烯缩合物。聚氧乙烯缩合物可以用通式：R-(CH2CH2O-)nH来表示，其中R是含有10-18个碳原子的脂肪醇，烷基酚，含有10-18个碳原子的脂肪酸，酰胺，胺或硫醇的残基，和其中n是1或1以上的整数。适合的阴离子乳化剂包括上述非离子型的硫酸盐的单价盐，磺基丁二酸半酯或二酯的单或二钠盐，烷基苯磺酸的钠盐。能够使用单一乳化剂，或能够结合使用这些乳化剂。当使用乳化剂的混合物时，有利的是使用相对疏水的乳化剂与相对亲水试剂的混合物。相对疏水试剂是在1％水溶液中具有低于190°F(88℃)的浊点的试剂和相对亲水试剂是在1％水溶液中具有等于或超过190°F(88℃)的浊点的试剂。使用的乳化剂总量的浓度范围是0.5-5％，基于胶乳的水相，不考虑固体含量。表面活性剂包装用物(surfactant package)一般以乳液的2-7wt％的量使用。
如果希望将体系的pH保持在所需值，那么可以适当添加与该稳定剂相容的任何适宜类型的碱性缓冲剂。缓冲剂的量一般是约0.1-0.5wt％，基于单体。
反应通常持续，直到残留乙酸乙烯酯含量为0.5％以下为止。然后将完全反应的产物冷却到大约室温，同时密封，与大气隔绝。然后将pH适当调节到4.5-7，优选6-6.5范围内的值，以确保最高稳定性。
能够直接生产出较高固体含量的胶乳，因此，产物一般具有55-65％的固体含量。当然，它们能够容易地通过加水稀释以降低任何所需值的固体含量。
乙酸乙烯酯/乙烯/氯乙烯/N-羟甲基丙烯酰胺聚合粘合剂用于通过本领域已知的各种方法制备无纺产品，或织物，这一般包括用粘合剂胶乳浸渍松散组装的纤维体，随后适度加热，以干燥该纤维体。在本发明的情况下，该适度加热还用于通过形成交联聚合物来固化该粘合剂。在应用粘合剂之前，它当然可以与N-羟甲基丙烯酰胺的适合催化剂混合。因此，如本领域已知的那样，适合使用酸催化剂如无机酸，例如氯化氢，或有机酸，例如草酸，或酸式盐如氯化铵。催化剂的量一般是总聚合物的大约0.5-2％。
应用于纤维起始织物的粘合剂的量(按干基计算)应该至少是大约2.5wt％和适宜在约10到约50wt％的范围内，或者比这更高，基于起始织物的重量，优选为约5到约25wt％，基于起始织物的重量。然后干燥和固化浸渍织物。这样，通过让织物经过热空气箱或类似物和然后经过固化烘箱来适当干燥它们。获得最佳交联的典型条件是充足的时间和温度如在150-200°F(65-94℃)下干燥4-6分钟，随后在300-310°F(149-155℃)下固化3-5分钟或更多时间。然而，如本领域公知的那样，能够使用其它时间-温度关系，在较高温度下使用较短时间或在较低温度下使用较长时间。
用于与乙酸乙烯酯/氯乙烯型聚合物一起形成无纺织物的合成纤维包括聚酯，聚乙烯，聚丙烯，聚丙烯酸酯和聚酰胺纤维。包括聚乙烯和聚酯纤维的织物在湿拉伸强度上显示了显著的改进，当使用该改进的粘合剂时。即使在其中大多数纤维是纤维素，但在织物中混入约10-20％合成纤维的织物中也看到了该改进。一般，织物主要由合成纤维制成，通常为整个织物的至少90％。
                   具体实施方式
提供以下实施例来说明本发明，但不用来限制它的范围。
                     实施例1
    乙酸乙烯酯/乙烯/氯乙烯/N-羟甲基丙烯酰胺聚合物
向1加仑压力反应器加入800.0g的去离子水，305g的PolystepCOP-3S表面活性剂，即由Stepan制备的辛基酚乙氧基化物磺酸钠和辛基酚乙氧基化物的65∶35共混物的20％水溶液，0.91g乙酸钠，3.11g的乙酸，2.3g的硫酸铁铵和312.0g的乙酸乙烯酯。反应器用氮气吹扫，搅拌到900rpm和将温度调至50℃。将乙烯(240g)加入到反应器中，还加入15.0g的甲醛合次硫酸氢钠的15％水溶液。以0.5ml/min的速度开始引入t-bhp的3％水溶液。在反应的开始，以5.2g/min的速度添加934.4g的乙酸乙烯酯，以1.73g/min的速度添加311.6g的氯乙烯和以1.35g/min的速度添加324.0g的N-羟甲基丙烯酰胺(NMA)的30％水溶液。在花费总共3个小时完成的单体延迟的过程中添加另外100.0g的乙烯。在1小时后，以保持2.5∶1的活性甲醛合次硫酸氢钠与活性t-bhp的比率的速度将水延迟(aqueous delay)的甲醛合次硫酸氢钠15％水溶液加入到该反应器中。残留单体使用较多的t-bhp的水溶液和甲醛合次硫酸氢钠的水溶液转化。让反应冷却，脱除大多数残留气体。测定残留的氯乙烯量，和如果必要，将其它等分部分的乙酸乙烯酯与等分部分的甲醛合次硫酸氢钠水溶液和t-bhp水溶液一起加入到储存容器中。重复该方法，直到残留氯乙烯水平是在由联邦政府设定的法定界限以下为止。固体是52.2％，在60rpm下用3号LV心轴测定的粘度为226cps。聚合物的Tg是12.0℃。
                     实施例2
                 合成织物的测试
        氯乙烯对乙酸乙烯酯-乙烯粘合剂的影响
在本实施例中，根据实施例1的工序制备使用聚合物的无纺产品，只是聚合物的组成不同。聚合物的添加量是无纺纤维的20wt％。纤维包括起绒聚酯。这些聚合物以具有约85wt％乙酸乙烯酯，12wt％乙烯和3wt％的N-羟甲基丙烯酰胺和丙烯酰胺的1∶1摩尔混合物的工业表面活性剂稳定化的乙酸乙烯酯/乙烯/N-羟甲基丙烯酰胺聚合物为基础(标记为A-190对照)。在制备包括氯乙烯的聚合物时，乙酸乙烯酯在A-190中的含量要减去氯乙烯单体(VCM)的添加量。
聚合物的性能概括在附图1中：
在附图1中柱的次序与图例说明中的相同；即A-190对照是第一根柱；A-190+5％VCM是第二根柱；A-190+10％VCM是第三根柱；A-190+15％VCM是第四根柱；和A-190+20％VCM是最后一根柱。直方图显示，用乙酸乙烯酯/乙烯/N-羟甲基丙烯酰胺粘合剂粘结的无纺织物或聚酯纤维的性能可以通过用氯乙烯替换少量乙酸乙烯酯而得到改进。虽然在试验工序中会有一些误差界限，但至多10wt％的聚合物用氯乙烯取代获得了湿拉伸强度的显著改进。
                     实施例3
                  合成织物的测试
        丙烯酸酯对乙酸乙烯酯/乙烯粘合剂的影响
按照实施例2的工序，只是用各种丙烯酸酯代替氯乙烯。在本实施例中，EA是指丙烯酸乙酯，BA是指丙烯酸丁酯和EHA是指丙烯酸2-乙基己酯。附图2提供了结果。
在附图2中柱的次序与图例说明中的相同；即A-190对照是第一根柱，具有EA的A-190是第二根柱；具有BA的A-190是第三根柱；和具有EHA的A-190是最后一根柱。结果表明，将丙烯酸类单体聚合到乙酸乙烯酯/乙烯/NMA骨架上没有如氯乙烯那样提供湿拉伸强度的改进。
                     实施例4
     乙酸乙烯酯/乙烯/N-羟甲基丙烯酰胺型粘合剂
在本实施例中，根据实施例2的一般工序制备无纺产品，只是使用的聚合物的组成不同。聚合物的添加重量是无纺纤维的20wt％。以具有约78wt％乙酸乙烯酯，18wt％乙烯和4wt％N-羟甲基丙烯酰胺的乳液聚合的工业乙酸乙烯酯/乙烯/N-羟甲基丙烯酰胺聚合物(标记为A-105对照)为基础制备该聚合物。在制备氯乙烯型体系时，乙酸乙烯酯的含量要减去氯乙烯的添加量。
在本实施例中，A-105是指表面活性剂稳定化乳液型，包括如实施例1使用的烷基壬基酚乙氧基化物，A-177是工业乙酸乙烯酯/乙烯/NMA型粘合剂乳液，但以无烷基酚乙氧基化物的稳定化体系为基础(无APE)。
在以下附图3和4中给出了对以聚酯纤维为基础的无纺产品的效率的测试结果：
在附图3中柱的次序与图例说明中的相同；即A-105对照是第一根柱；和A-105+10％VCM是第二根柱。
在附图4中柱的次序与图例说明中的相同；即，A-105对照是第一根柱；A-177是第二根柱；A-105+10％VCM是第三根柱；和A-177+10％VCM是最后一根柱。该直方图显示，通过添加氯乙烯从而形成乙酸乙烯酯/乙烯/氯乙烯/N-羟甲基丙烯酰胺型粘合剂，显著增强了乙酸乙烯酯/乙烯/N-羟甲基丙烯酰胺性粘合剂的湿拉伸强度。

Claims (7)

1.一种无纺织物，所述无纺织物含有通过乳液聚合形成的自交联乙酸乙烯酯/乙烯聚合粘合剂粘结在一起的松散组装的纤维，改进在于：
所述织物包括合成纤维作为该织物的组分，和
所述自交联乙酸乙烯酯/乙烯聚合物包括以60-80wt％的量存在的乙酸乙烯酯、以10-25wt％的量存在的乙烯、以5-25wt％的量存在的氯乙烯和一种以2-10wt％的量存在的含N-羟甲基丙烯酰胺的自交联单体的聚合单元，所述wt％基于聚合物中的单体的总重量。
2.权利要求1的无纺织物，其中氯乙烯以5-20wt％的量存在。
3.权利要求2的无纺织物，其中乙酸乙烯酯以65-80wt％的量存在。
4.权利要求3的无纺织物，其中乙烯以12-18wt％的量存在。
5.权利要求4的无纺织物，其中N-羟甲基丙烯酰胺以3-8wt％的量存在。
6.权利要求5的无纺织物，其中合成纤维选自聚酯、聚酰胺、聚丙烯酸酯、聚乙烯和聚丙烯。
7.权利要求1的无纺织物，其中N-羟甲基丙烯酰胺是N-羟甲基丙烯酰胺和丙烯酰胺的等摩尔混合物。
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