CN1745107A - 水性分散液的制备方法 - Google Patents

水性分散液的制备方法 Download PDF

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CN1745107A
CN1745107A CN200480003055.2A CN200480003055A CN1745107A CN 1745107 A CN1745107 A CN 1745107A CN 200480003055 A CN200480003055 A CN 200480003055A CN 1745107 A CN1745107 A CN 1745107A
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aqueous liquid
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methyl
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CN100393752C (zh
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佐川俊正
达春美
堀内雅可
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Unimatec Co Ltd
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Abstract

将含有多氟烷基的(甲基)丙烯酸酯和不含氟原子的聚合性单体在表面活性剂和分子量250～5000的聚丙二醇系化合物的存在下进行乳化处理后，在聚合引发剂的存在下使其发生共聚反应从而制备水性分散液。所得到的水性分散液，即使是含有，含有以碳数12或以的全氟烷基的混合全氟烷基作为多氟烷基的(甲基)丙烯酸酯，将其作为水性分散液制备时，乳化稳定性优良，因而可以作为防水防油剂而有效使用。

Description

水性分散液的制备方法
技术领域
本发明涉及水性分散液的制备方法。进而更详细地涉及乳化稳定性优良、适合用作防水防油剂的水性分散液的制备方法。
背景技术
使用以含有多氟烷基、通常含有全氟烷基的(甲基)丙烯酸酯共聚物作为有效成分的防水防油剂，广泛地进行赋予纤维防水防油性处理。具有全氟烷基(Rf基)的(甲基)丙烯酸酯由化合物RfI通过各种反应而制备，在此，使用的全氟烷基碘RfI通过以C2F5I为起始物质的调聚反应而合成，形成以通式CnF2n+1I表示的化合物，但该化合物是具有各种n值链长分布的混合物。
通常，C6F13I～C14F29I的成分被作为有效成分使用，C16F33I或以上的成分没有有效的利用方法，此外，实际情况是C12F25I～C14F29I的各成分生成量与消耗量不平衡而被废弃。然而，从近年的环境保护的规定和经济方面的观点看来，强烈要求有效利用这些未被利用的资源以及废弃成分。此外，若由含有C12F25或以上长链Rf基的(甲基)丙烯酸酯聚合物制备该水性分散液，会出现水性分散液的乳化稳定性不足的问题。
已公开了以下各种方法：在制备含有全氟烷基的(甲基)丙烯酸酯共聚物的水性分散液时，添加三甘醇二甲醚、四甘醇二甲醚、双丙甘醇、1，6-己二醇，1，5-戊二醇、琥珀酸二乙酯等的方法等(日本特公平4-32873号公报、日本特公平6-74409号公报、美国专利第6,180,740号说明书)，但在这些方法中可以确认，含有混合全氟烷基的(甲基)丙烯酸酯共聚物的水性分散液的乳化稳定性完全不足，其中该混合全氟烷基含有碳数12或以上，特别是碳数16或以上的全氟烷基。
此外，本申请人先前公开了使用甜菜碱型和非离子型乳化剂，在pH2～5.5的条件下，使含有多氟烷基的(甲基)丙烯酸酯和(甲基)丙烯酸硬脂基酯乳化聚合而制备水性乳液的方法(日本特开平11-255,995号公报)，谋求以沉淀重量率或10％粒径、50％粒径、90％粒径等表示的水性分散液乳化稳定性方面的进一步改善。
发明内容
本发明的目的是提供以下水性分散液的制备方法：即使是含有含有以碳数12或以上的全氟烷基的混合全氟烷基作为多氟烷基的(甲基)丙烯酸酯共聚物，将其作为水性分散液制备时，乳化稳定性优良，因而可以作为防水防油剂而有效使用。
本发明的目的是通过将含有多氟烷基的(甲基)丙烯酸酯和不含氟原子的聚合性单体在表面活性剂和分子量为250～5000的聚丙二醇系化合物的存在下进行乳化处理后，在聚合引发剂的存在下进行共聚反应而制备水性分散液而达到的。在此，(甲基)丙烯酸酯这种表达方式是指丙烯酸酯或甲基丙烯酸酯。
作为含有多氟烷基的(甲基)丙烯酸酯，使用由通式：
               CH2＝CRCOOR1Rf
                    R：氢原子或甲基
                    R1：2价有机基团，优选以通式CmH2m
                    (m：1～6)或CmH2mN(R’)SO2(m：1～
                    6，R’：碳数1～5的低级烷基)表示的
                    2价有机基团
                    Rf：碳数4～20的多氟烷基
表示的物质，例如有如下含有多氟烷基的(甲基)丙烯酸酯化合物。
               CH2＝CHCOOCH2CnF2nH
               CH2＝C(CH3)COOCH2CnF2nH
               CH2＝CHCOOCH2CnF2n+1
               CH2＝C(CH3)COOCH2CnF2n+1
               CH2＝CHCOOC2H4CnF2n+1
               CH2＝C(CH3)COOC2H4CnF2n+1
               CH2＝CHCOOC3H8CnF2n+1
               CH2＝C(CH3)COOC3H6CnF2n+1
            CH2＝CHCOOC4H8CnF2n+1
            CH2＝C(CH3)COOC4H6CnF2n+1
            CH2＝CHCOOC2H4N(CH3)SO2CnF2n+1
            CH2＝C(CH3)COOC2H4N(CH3)SO2CnF2n+1
            CH2＝CHCOOC2H4N(C2H5)SO2CnF2n+1
            CH2＝C(CH3)COOC2H4N(C2H5)SO2CnF2n+1
            CH2＝CHCOOC2H4N(C3H7)SO2CnF2n+1
            CH2＝C(CH3)COOC2H4N(C3H7)SO2CnF2n+1
            CH2＝CHCOOC2H4CnF2nCF(CF3)2
            CH2＝C(CH3)COOC2H4CnF2nCF(CF3)2
这些含有多氟烷基的(甲基)丙烯酸酯中的全氟烷基可以是具有各种n值的混合CnF2n+1基团，但是即使使用这里的含有多氟烷基的(甲基)丙烯酸酯的共聚物，在本发明中也可以形成乳化稳定性优良的水性分散液，其中该多氟烷基中混合存在具有碳数12或以上，依据情况是碳数16或以上的全氟烷基。这些多氟烷基(甲基)丙烯酸酯在制备水性分散液时使用的共聚物中以10重量％或以上，优选25～75重量％的比例进行共聚，以体现防水防油性。
作为与含有多氟烷基的(甲基)丙烯酸酯共聚的不含氟原子的聚合性单体，可以列举用甲基、乙基、丙基、异丙基、正丁基、正己基、2-乙基己基、正辛基、月桂基、硬脂基等烷基；环己基等环烷基；苄基等芳烷基；甲氧甲基、2-甲氧乙基、2-乙氧乙基、2-丁氧乙基、3-乙氧丙基等烷氧烷基进行酯化的丙烯酸酯或甲基丙烯酸酯；富马酸或马来酸的二甲基、二乙基、二丙基、二丁基、二辛基等二烷基酯；乙酸乙烯酯、辛酸乙烯酯等乙烯酯。其中在防水性、防油性的平衡方面，优选使用丙烯酸月桂基酯、(甲基)丙烯酸硬脂基酯、甲基丙烯酸环己基酯、甲基丙烯酸苄基酯等，特别优选单独使用丙烯酸硬脂基酯或组合使用甲基丙烯酸环己基酯、甲基丙烯酸苄基酯等。这些不含氟原子的聚合性单体在水性分散液制备时使用的共聚物中以90重量％或以下，优选75～25重量％的比例使用。
在共聚物中，在无损于其特性的范围内，例如可以以在共聚物中占30重量％或以下的比例使其他可共聚的单体共聚。作为该可共聚的单体可以举出苯乙烯、乙烯基甲苯、α-甲基苯乙烯、乙烯基萘、丙烯腈、甲基丙烯腈、丙酮丙烯酰胺、异戊二烯、戊二烯、丁二烯、丙烯酸-2-羟乙基酯、丙烯酸-4-羟丁基酯、(甲基)丙烯酸-2-羟基-3-氯丙基酯、聚乙二醇单(甲基)丙烯酸酯、聚丙二醇单(甲基)丙烯酸酯、氯乙烯、1，1-二氯乙烯、氟乙烯、1，1-二氟乙烯、2-氯乙基乙烯基醚、2-羟乙基乙烯基醚、4-羟丁基乙烯基醚等乙烯基化合物或异戊二烯、戊二烯、丁二烯等二烯烃。
此外，根据需要，可以以在共聚物中占30重量％或以下的比例使多官能性单体或低聚物共聚。作为该多官能性单体或低聚物可以举出乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1，4-丁二醇二(甲基)丙烯酸酯、1，6-己二醇二(甲基)丙烯酸酯、1，9-壬二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、四甘醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、双酚A·环氧乙烷加成物二丙烯酸酯、二羟甲基三环癸烷二丙烯酸酯、甘油甲基丙烯酸酯丙烯酸酯、3-丙烯酰基氧基甘油单甲基丙烯酸酯等聚(甲基)丙烯酸酯或聚丁二烯低聚物、聚戊二烯低聚物等低聚物。
使这些各聚合性单体在表面活性剂乳化剂和分子量250～5000，优选300～3000聚丙二醇系化合物乳化助剂的存在下共聚。
相对于共聚单体总计量，以1～20重量％，优选5～15重量％的比例使用作为乳化剂而作用的表面活性剂，优选聚环氧乙烷系非离子表面活性剂和阳离子性表面活性剂中的至少一种。作为聚环氧乙烷系非离子表面活性剂可以使用聚环氧乙烷与己基苯酚、辛基苯酚、壬基苯酚、多环苯基醚、十六醇、油酸、C12～C18的烷胺、脱水山梨醇单脂肪酸酯等的缩合生成物，优选使用聚环氧乙烷(n＝10～90)与辛基苯酚或与壬基苯酚的缩合生成物。此外，作为阳离子性表面活性剂可以使用季铵盐，例如氯化硬脂基三甲基铵、乙酸月桂基三甲基铵、氯化月桂基三甲基铵、氯化十四烷基三甲基铵、氯化十六烷基三甲基铵、氯化十八烷基三甲基铵、氯化月桂基苯基三甲基铵、氯化月桂基甲基二(聚环氧乙烷)铵、氯化双十八烷基二甲基铵等或烷基吡啶鎓盐。
作为与这些乳化剂组合使用的乳化助剂的聚丙二醇系化合物，以相对于共聚单体总计量，10～100重量％，优选15～70重量％的比例使用聚丙二醇、其末端单甲基醚、甘油的丙二醇加成物等。使用这些分子量小于250的聚丙二醇系化合物时、或不使用它们时、再或使用双丙甘醇(分子量134)或1，6-己二醇代替它们时，以沉淀重量率、10％粒径、50％粒径、90％粒径表示的水性分散液的乳化稳定性将降低。
在共聚反应前，首先进行在表面活性剂乳化剂和聚丙二醇系化合物乳化助剂存在下的含有多氟烷基的(甲基)丙烯酸酯和含有不含氟的聚合性单体的聚合性单体混合物的乳化处理。乳化处理用高压匀浆机等充分进行。
经乳化处理的聚合性单体的共聚反应是，在其中添加的自由基聚合引发剂的存在下进行。作为自由基聚合引发剂，可以使用有机过氧化物、偶氮化合物、过硫酸盐等中的任意一种，但优选使用过硫酸钾、过硫酸铵、2，2’-偶氮双(2-脒基丙烷基)·2盐酸盐等水溶性自由基聚合引发剂。反应在水介质中约40～80℃下进行约1～10小时左右，从而形成固形分浓度约15～35重量％的水性分散液(水性乳液)。
此时，在加入自由基聚合引发剂的同时，加入含有交联性基的单体，例如丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、N-甲氧基甲基丙烯酰胺、N-丁氧基(甲基)丙烯酰胺等丙烯酰胺或其衍生物、缩水甘油甲基丙烯酸酯等，在共聚物中占10重量％或以下，优选占约0.5～7重量％的比例下共聚。进一步使该含有交联性基的单体共聚时，与纤维表面的羟基交联或自身交联，可以提高防水防油剂的耐久性。此外，可以在水性分散液中添加封端异氰酸酯、蜜胺树脂、尿素树脂等作为交联剂。
根据防水防油剂用途在水性分散液中进一步添加必要的添加剂作为其他添加剂：聚合体延长剂、硅树脂或油、蜡等其他的防水剂、防虫剂、防静电剂、染料稳定剂、防皱剂、防污剂等。
如上所述得到的水性分散液作为防水防油剂有效地适用于纸、薄膜、纤维、布、织物、毛毡或由长丝、纤维、线等制成的布料·丝织物等。作为应用方法，一般使用涂覆、浸渍、喷雾、浸轧、辊涂或其组合方法等，例如通过使轧染浴的固形分浓度为约0.1～10重量％，作为浸轧浴使用。在该浸轧浴中浸轧被处理材料，然后用挤压辊除去过剩的溶液干燥，以相对于被处理材料共聚体量为约0.01～10重量％完成附着。然后，根据被处理材料的种类，一般在约100～200℃温度下进行干燥约1分钟到约2小时左右，完成防水防油处理。
具体实施方式
下面，以实施例说明本发明。
实施例1
全氟烷基乙基聚丙烯酸酯                          133.5重量份
(全氟烷基：C6 6％，C8 52％，C10 24％，C12 7％，C14 2％总计91％的混合物，平均碳数8.8)
硬脂基丙烯酸酯                                  148.5重量份
月桂基硫醇                                      0.9重量份
聚丙二醇                                        57.0重量份
(日本油脂制品ユニオ一ルD-400；分子量400)
聚氧乙烯(n：30)单(壬基酚)醚                     2.5重量份
聚氧乙烯(n：50)单(壬基酚)醚                     8.6重量份
氯化硬脂基三甲基铵                              15.6重量份
离子交换水                                      400.7重量份
将以上各成分加入反应器中，用高压匀浆机在60MPa下乳化处理，将得到的乳液用氮气置换30分钟。然后，缓缓升高反应器内温度，达到40℃后，加入溶解在100重量份离子交换水中的N-羟甲基丙烯酰胺11.8重量份和溶解在100重量份离子交换水中的2，2’-偶氮双(2-脒基丙烷)·2盐酸盐5.9重量份，然后从内部温度缓缓上升到70℃后，反应4小时。反应结束后冷却，得到978重量份的固形分浓度32重量％的水性分散液。
实施例2
在实施例1中，使用相同量的其他的全氟烷基乙基聚丙烯酸酯(全氟烷基：C6 2％，C8 39％，C10 37％，C12 10％，C14 2％、C16 0.6％、C18 0.1％总计91％的混合物，平均碳数9.4)。
实施例3
在实施例1中，使用相同量的其他的全氟烷基乙基丙烯酸酯(全氟烷基：C6 2.5％，C8 65％，C10 26％，C12 1％总计95％的混合物，平均碳数8.1)。
比较例1
使用相同量的双丙甘醇(分子量134)代替实施例1中的聚丙二醇(分子量400)。
比较例2
使用相同量的1，6己二醇代替实施例1中的聚丙二醇(分子量400)。
将以上各实施例和比较例得到的水性分散液的固形分浓度用离子交换水稀释至0.5重量％的浓度，在其中浸渍棉/聚酯混纺布、聚酯布、聚酰胺布，测定防水性(依据JIS L1092标准)和防油性(依据AATCC-TM118-1966标准；结果如表-2所示以防油性数值表示)。此时的挤压后的吸湿率(wet pick up)为：棉/聚酯混纺布100％、聚酯布：40％、聚酰胺布60％，干燥条件均为80℃、10分钟，焙烘温度为：棉/聚酯混纺布、聚酯布150℃、3分钟，聚酰胺布170℃、1.5分钟。
此外，将离子交换水稀释前的800mL水性分散液置于800mL离心管中，以3000rpm分离30分钟后，由沉淀在120℃下干燥3小时后的重量计算沉淀率。然后用粒度分布计MICROTRAC UPA 150，从小粒径依次测定累积频数为10％、50％、90％时的粒径，以其分别作为10％粒径、50％粒径(平均粒径)、90％粒径。
得到的结果，如下表1所示。
                                             表1
  测定项目     实施例-1   实施例-2   实施例-3   比较例-1   比较例-2
  [防水性]棉/聚酯混纺布聚酯布聚酰胺布[防油性]棉/聚酯混纺布聚酯布聚酰胺布[水性分散液]沉淀重量率    (％)10％粒径      (μm)50％粒径      (μm)90％粒径      (μm) 100100l0077850.0020.02780.04300.0678 1001001007850.0080.03140.04770.0718 1001001007850.0000.02650.04270.0718 100100907840.8920.06230.08930.1384 1001001007850.4530.03700.06970.1210
实施例4
用苄基甲基丙烯酸酯代替实施例1中的148.5重量份硬脂基丙烯酸酯中的26.5重量份，此外用其他的聚丙二醇(日本油脂制品ユニオ一ルD-250；分子量250)，配制乳液。
实施例5
使用相同量的环己基甲基丙烯酸酯代替实施例4中的苄基甲基丙烯酸酯。
实施例6
用相同量的其他聚丙二醇(日本油脂制品ユニオ一ルD-600；分子量600)。
实施例7
使用相同量的聚丙二醇单甲醚(日本油脂制品ユニオ一ルMME；分子量400)代替实施例5中的聚丙二醇。
实施例8
用同量的甘油的聚丙二醇加成物HO(C3H6O)pCH[CH2O(C3H6O)qH][CH2O(C3H6)rH](日本油脂制品ユニオ一ルTG-330；分子量330；分子量330)代替实施例1中聚丙二醇。
以上实施例4～8中测定结果，如下表2所示。
                                     表2
    测定项目   实施例-4 实施例-5   实施例-6 实施例-7 实施例-8
[防水性]棉/聚酯混纺布聚酯布聚酰胺布[防油性]棉/聚酯混纺布聚酯布聚酰胺布[水性分散液]沉淀重量率    (％)10％粒径      (μm)50％粒径      (μm)90％粒径      (μm) 1001001007850.0110.02880.04640.0789 1001001007850.0030.03140.04730.0742 1001001007850.0090.02720.04410.0732 1001001007850.0160.03330.05220.0811 1001001007850.0100.02740.04410.0732
产业实用性
本发明涉及的水性分散液，如沉淀重量率和10％、50％、90％粒径的数据所示，乳化稳定性非常优异，由于其在使用了表面活性剂乳化剂的同时使用了聚丙二醇系化合物乳化助剂，使形成乳化处理的均一性、混合稳定性优良的水性分散液成为可能，因此将其作为防水防油剂使用时，可以赋予被处理材料优异的防水防油性。
即使使用含有全氟烷基的(甲基)丙烯酸酯共聚物也能使之形成乳化稳定性优良的水性分散液，其中，该全氟烷基含有碳数为12或以上，有时碳数为16或以上的混合存在的全氟烷基物质。

Claims (14)

1.一种水性分散液制备方法，其特征为：将含有多氟烷基的(甲基)丙烯酸酯和不含氟原子的聚合性单体在表面活性剂和分子量250～5000的聚丙二醇系化合物的存在下进行乳化处理后，在聚合引发剂的存在下使其发生共聚反应。
2.权利要求1所述的水性分散液制备方法，其特征为：使用在生成的共聚体中至少占10重量％量的含有多氟烷基的(甲基)丙烯酸酯。
3.权利要求1所述的水性分散液制备方法，其特征为：使用含有，含有以碳数为12或以上的全氟烷基的混合全氟烷基作为多氟烷基的(甲基)丙烯酸酯。
4.权利要求1所述的水性分散液制备方法，其特征为：使用(甲基)丙烯酸酯、富马酸或马来酸的二烷基酯或乙烯基酯作为不含氟原子的聚合性单体。
5.权利要求4所述的水性分散液制备方法，其特征为：作为(甲基)丙烯酸酯使用月桂基丙烯酸酯、硬脂基(甲基)丙烯酸酯、环己基甲基丙烯酸酯或苄基甲基丙烯酸酯。
6.权利要求5所述的水性分散液制备方法，其特征为：作为(甲基)丙烯酸酯，单独使用硬脂基丙烯酸酯、或将其与环己基甲基丙烯酸酯、或苄基甲基丙烯酸酯组合使用。
7.权利要求1所述的水性分散液制备方法，其特征为：表面活性剂为聚环氧乙烷系非离子表面活性剂或阳离子表面活性剂。
8.权利要求1所述的水性分散液制备方法，其特征为：使用聚丙二醇、其末端单甲基醚或甘油的聚丙二醇加成物作为聚丙二醇系化合物。
9.权利要求1所述的水性分散液制备方法，其特征为：将含有交联性基的聚合性单体进一步共聚。
10.权利要求9所述的水性分散液制备方法，其特征为：使用丙烯酰胺或其衍生物或缩水甘油(甲基)丙烯酸酯作为含有交联性基的聚合性单体。
11.一种按照权利要求1所述的方法制备的水性分散液。
12.一种按照权利要求9所述的方法制备的水性分散液。
13.一种作为防水防油剂使用的权利要求11所述的水性分散液。
14.一种作为防水防油剂使用的权利要求12所述的水性分散液。
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US20090286931A1 (en) 2009-11-19
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