CN1063455C - 压敏粘合剂用分散液 - Google Patents
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- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
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Abstract
本发明涉及一种生产压敏粘合剂用分散液的方法,该分散液基于由丙烯酸正丁酯单元和(甲基)丙烯酸组成的共聚物;为此含有丙烯酸丁酯及阴离子型和非离子型乳化剂一起在水相中,在加热下,在至少一种式(Ⅰ)的水溶性引发剂存在下聚合
MR1(Ⅰ)
引发剂的用量为0.5~1.5%(重),然后将(甲基)丙烯酸乳化在其中,同时保持在高温;随后加入第二引发剂使聚合完全。
Description
本发明涉及用于压敏粘合剂的、含有(甲基)丙烯酸烷基酯的含水分散液。
压敏粘合剂(有时称为“自粘化合物”)在常温、稍加压力下形成一层永久性粘合剂膜,它立刻粘着到各种表面上。(见1985,“Ullmann's Encyclopedia of IndustrialChemistry”,5th Ed.,Vol Al,pub.VCH,pp 235~236.)
压敏粘合剂主要用于涂覆支撑物,例如得到自粘合标签、粘合带、自粘合膜等,支撑物主要是纸或聚合物薄膜或片材。这类产品在特性上有很宽的性质范围,例如从
-粘合膜对基材表面的短接触时间粘合(“粘性”)到
-耐水粘合剂层。
可理解的是,单一的压敏粘合剂不能显示出所有所需的性质(特别是有些性质是相斥的)。因此,对于每一应用场合,必须找出一组折衷的“优化的”性质。常常,产品的优化通过使用各种辅助物质如合成树脂、增粘剂、交联剂、粘度调节剂等来实现。特定的粘合剂以其溶液、分散液甚至熔体的形式涂覆到基材上,视其组成而定。粘合剂固化后,压敏粘合剂层在支撑物上作为薄膜存在。在使用前,压敏粘合剂层常常用适合的防粘合材料,特别是硅酮化的薄膜覆盖。但是,可以使用没有覆盖层的粘合带(见“Ullmarr's Encyclopedia”,loc.cit.,258)。天然的和合成的橡胶(以改性形式)可用作压敏粘合剂用粘合材料。聚(甲基)丙烯酸酯、聚乙烯醚和聚异丁烯(常常与酚醛树脂或烃类树脂组合)也经常用作粘合剂。
聚丙烯酸酯分散液或醋酸乙烯酯共聚物常用作所谓的“分散型压敏粘合剂”。常常可将各种树脂加到其中。
作为例子,将参考基于(电晕处理的)聚丙烯带材的粘合带更详细地说明这一问题。这样的粘合带最好用作如硬纸盒的包装带。在这一应用领域中最重要的要求是带对盒的表面有良好的粘合物以及粘合剂层有很好的内强度(很好的内聚作用)。在大多数情况下,同时满足这两个要求是不可能的,因为许多产生良好内聚作用的方法对良好的粘合性都有损害。例如,已知内聚作用随聚合物分子量的增加而增加,而粘合性相应要下降。
在Ullmann百科全书中指出:
“有迹象表明,压敏粘合剂总是必含有
-高聚合物主树脂,它提供内聚作用和特殊的粘合性,以及
-所谓的增粘剂,
在许多体系甲,后者可用主树脂的低分子量组分代替。为了提高内聚作用,在许多体系中主树脂在涂覆后被交联(或在橡胶的情况下被硫化)。”
实现乳液聚合的一些主要经验规则已得到支持,尽管已知有许多变种。例如,使用过二硫酸铵(APS)作为引发剂已变成标准步骤。文献提到使用0.001~0.05%(重)(按单体重量计)过二硫酸盐化合物作为引发剂(见Houben and Weyl,1961,“Methoden der Organischen Chemie”,4th Ed.,Vol XIV/I,pub.G.Thieme,P.1049;and 1968,Rauch.puntigam,H.and Voelker,Th.,“Acryl-und Methacrylvergindungen”,pub.Springer-Verlag,221)。
本发明的根本问题是要改善已知的丙烯酸酯压敏粘合剂的性质,特别是它们的粘合性和内聚作用。
解决这一问题的出发点是主树脂由丙烯酸丁酯以及相对少量(<1.5%(重))的(甲基)丙烯酸组成。
本发明指出,粘合剂层的内强度的确可通过与不同浓度的各种交联剂体系共聚合得到提高(可提到例如(甲基)丙烯酸丙烯基酯、二甲基丙烯酸乙二醇酯、甲基丙烯酰胺、N-(羟甲基)甲基丙烯酰胺和氰脲酸三丙烯基酯)(见1968,Rauch-puntigam,H.andVoelker,Th.,loc.cit.),但是以这一方式交联的体系通常有低的粘合性,而且通过调节乳液聚合中的分子量不能使粘合性提高到明显的程度。
令人吃惊的是,在本发明方面,已发现如果使用特殊的水溶性引发剂,而与常规使用的浓度相比,其引发剂的用量很大,那么乳液聚合生产的聚合物可达到所需的一组性质-很好的内聚作用以及极好的粘合性,该聚合物是以丙烯酸正丁酯和(甲基)丙烯酸为基础。
而且,已观测到,只要当压敏粘合剂用分散液用芯壳聚合法聚合,就完全能达到压敏粘合剂薄膜所需的一组性质。(本发明采用的方法将称为“芯壳”法(“core and shell”method))。在芯壳聚合中,芯由丙烯酸丁酯组成。如果想均匀的引入(甲基)丙烯酸或改变芯壳条件,其结果是例如耐温性显著变坏。
因此,本发明涉及一种生产压敏粘合剂用分散液的方法,该分散液基于由丙烯酸正丁酯单元和少量(甲基)丙烯酸组成的共聚物。在第一步中,丙烯酸丁酯在水相中优选在芯壳聚合条件下,在式Ⅰ的水溶性引发剂存在下聚合,优选作为芯,
MR1 (Ⅰ)其中M表示金属阳离子如钠或钾,以及R1表示过氧酸或含偶氮基的酸的阴离子,其中引发剂的用量为1±0.5%(重)(按水相重量计);在第二步中,丙烯酸丁酯和(甲基)丙烯酸聚合,其总的重量比为99.5∶0.5~90∶10,优选的是98∶2~96∶4,以此得到的芯壳重量比优选为30∶70~70∶30,特别优选为50∶50。聚合进行完全,优选在聚合结束时,用氨中和(甲基)丙烯酸基(中和PH值为9.5)。步骤是根据常规乳液聚合方法,例如半连续“进料”法或间歇法(见Houben and Weyl,loc.cit,Vol.XIV/I)。
引发剂本身是已知的(见Brandrup,J.,and Immergut,E.H.,1989,“Polymer Handbook”,3rd Ed.,Vol.Ⅱ-1,pub.J.Wiley)。引发剂如为偶氮化合物,最好选自式Ⅰ-A表示的偶氮化合物其中R2表示CH3,以及
n表示从1至4的一个数字。
特别是,式Ⅰ的引发剂选自过二硫酸的金属盐(例如过二硫酸钾(KPS)、过二硫酸钠(NaPS))和4,4′-偶氮双-(4-氰戊酸)的金属盐(如K盐或Na盐)。但是不应使用常用的铵盐。
通过加入氧化还原引发剂可明显促进最后的聚合。
在可得到的知识基础上,
-均匀的引入(甲基)丙烯酸和
-超出所述的范围显著改变芯/壳比都会使得耐温性明显下降。如果在聚合结束时用氨中和(甲基)丙烯酸基,那么可提高分散液的可加工性(剪切稳定性)和应用特性(薄膜的形成)。在分散液中酸分布的测定揭示相当大比例的含酸基的低聚物(Mw≤400克/摩尔)在乳清中,该低聚物由于大量起始基团(低聚物基团)及其反应性的结果,在水相中生成。可以假设(但不作为对本发明范围的限制),在分散液的乳清中,含酸基的低聚物的含量的增加是造成观测到的在聚合物薄膜的粘合性以增粘剂的方式大大增加的原因。
本发明的压敏粘合剂通过本身已知的乳液聚合法生产(见Houben and Weyl,1987,loc.cit.,Vol.E20,PP1150~1156;1992,“Ullmann'S”,lol.cit.,Vol.21A;and Rauch-Puntigam and Voelker,1967,loc.cit.,pp 217-230)。
在该法中采用的一般路线依靠该技术的状况。优选的是,使用亲水亲油平衡值>12的表面活性物质作为乳化剂,例如低聚乙二醇醚的硫酸盐和磺酸盐阴离子型乳化剂,特别是具有12~20个碳原子的烷基酚和链烷醇的乙氧基化产物的非离子型乳化剂。可以提到的阴离子型乳化剂的例子是磺基琥珀酸酯,在中和点以下的PH值下它是有效的。
具体地说,步骤可如下:
优选的是,将以下物质加入到装有搅拌设备、控温设备和加料设备的反应器中:完全脱盐的水(约35%水相)、乳化剂(可提到,约0.03%磺基琥珀酸酯)和含丙烯酸酯的接种乳胶(粒度例如为50毫微米)。
将如此加入的混合物加热到如80℃,然后加入约10%(重)引发剂(用适合的碱如碳酸氢钠中和,然后溶于约两倍数量的水中)。
在所选的温度下,在搅拌下,将丙烯酸丁酯在(脱盐)水中的乳液在几小时内(如4小时)分批添加到该溶液中,该乳液含有非离子型表面活性剂以及阴离子型乳化剂(表面活性剂与乳化剂的重量比约为1∶4)。
乳液可含有如丙烯酸丁酯和水(重量比约为2∶1),最好还含有约0.5%(重)式Ⅰ的引发剂,优选用适合的碱金属碳酸氢盐中和。
约加料时间一半以后,最好在不中断进料的情况下,将(甲基)丙烯酸乳化在进料中。
优选的是,将反应混合物在高温下保持一段时间,例如1小时,然后将它冷却到室温。
然后可进行最后的聚合,如在稍低的温度下(如70℃),可加入氧化还原引发剂,引发剂可为叔丁基过氧化氢/硫酸亚铁/羟甲基亚磺酸钠。
最后,优选的是加入消泡剂,如烃类-脂肪乳液,並用氨把PH值调节到碱性(PH值9.5±0.5)。
压敏粘合剂用分散液可以简单的方式涂覆到基材(支撑物)上,例如它可为(可能经电晕处理的)聚丙烯带材。例如可用刮板法涂覆达到这一厚度,以致在水蒸发和形成薄膜后,留下的压敏粘合剂层的膜重在20~30克/平方米范围内。
用本发明的压敏粘合剂用分散液形成的粘合剂膜在技术试验中有良好的粘合性以及良好的耐温性。应当指出,本发明的粘合剂分散液单独在本发明生产方法的基础上就能形成有良好粘合性和耐热性的粘合剂膜,而不需要加增粘剂或缩合树脂。
粘合性用PSTC(压敏粘带联合会)的试验方法No.1测量。
用测量的耐温性来表征粘合剂膜的内聚作用(PSTC试验方法No.7)。
“粘性”用PSTC试验方法No.6测定(见PSTC,“TestMethods for pressure Sensitive Tapes”,9thEd.)。
正如从下表可看出的那样,当足够数量的含金属盐的引发剂用于生产该分散液时,粘合剂膜具有一组所需的性质(高粘合性和高耐温性)。当相应的氨中形式的引发剂(如APS)用于聚合时,其温度稳定性大大下降。如果引发剂的用量显著下降(如4,4'-偶氮双-
(4-氰戊酸)的用量为0.25%,用NaHCO3中和),形成的粘合剂膜具有不能接受的很差的性质。
以下的实施例用来说明本发明:
实施例
A.粘合剂分散液的生产
实施例1
将11.22公斤脱盐水、0.0033公斤磺基琥珀酸二异己酯(Rewopol(R)SB MB 80)和0.042公斤含丙烯酸酯的接种乳胶(粒度50毫微米)在装有搅拌器、控温设备和进料设备的反应器中加热到80℃。在这一温度下,将0.028公斤引发剂(如溶于0.052公斤水中的並用0.018公斤NaHCO3中和的5,5'-偶氮双-(5-次氮基戊酸))加入。在80℃、搅拌下,在4小时内,将由以下组分生成的乳液加到该溶液中:
41.16公斤丙烯酸丁酯
20.04公斤脱盐水
0.175公斤磺基琥珀酸二异己酯
0.175公斤25%非离子型表面活性剂水溶液(Marlipal(R)013/400)(有40摩尔环氧乙烷的C13酮醇)
2.1公斤由0.21公斤“偶氮”化合物、1.89公斤水和0.135公斤NaHCO3组成的4,4'-偶氮双-(4-氰戊酸)(“偶氮”)溶液
分批加入乳液2小时后,在不中断所述进料的情况下,将0.84公斤甲基丙烯酸乳化在进料中。所述的进料完成后,将反应混合物在80℃下再保持1小时,然后冷却到室温。在这一冷却期间,在70℃通过加入0.035公斤叔丁基过氧化氢、0.0003公斤硫酸亚铁和0.028公斤羟甲基亚磺酸钠来完成最后的聚合。在40℃下加入0.011公斤消泡剂)(Nopco(R)NXZ,一种烃类/脂肪乳液),並用氨调节PH值。
压敏粘合剂分散液的标准特性:
固含量(%) 53±1
粘度(毫帕-秒) 100~600
颗粒半径,rNS(毫微米)
用Nanosizer(R)通过
光相关显微镜测量 250±50
PH值 9.5±0.5
下表报道了类似实施例1的其他实施例,其中,聚合物组成是相同的,压敏粘合剂用分散液仅在所用的引发剂体系和数量不同。
表
a | b | c(N/25mm) | d(h) | e(mm) |
2.3.4.5.6.7.8.9.10. | 0.75%"f"(NaHCO3)1.0%"f"(NaHCO3)1% g0.75% g1%NaPS h0.35%"f"(NaHCO3)+0.5% g0.25%"f"(NaHCO3)1% i1%"f"(NH4HCO3) | 7.07.18.37.58.38.55.29.57.1 | >170>170>120>100>100>170<10<2<1 | 709090602060 |
表的关键词:(a)实施例号;(b)引发剂IN(%(重),按水相重计);(c)粘合性(牛/25毫米),按PSTC试验方法№1测量;(d)耐温性(小时),按PSTC试验方法№7测量;(e)粘性(毫米),按PSTC试验方法№6测量;(f)“A20”为4,4′-偶氮双-(4-氰戊酸);(g)“KPS”为过二硫酸钾;(h)“NaPS”为过二硫酸钠;(i)“APS”为过二硫酸铵。
Claims (12)
1.一种生产压敏粘合剂用分散液的方法,该分散液基于由丙烯酸正丁酯单元和(甲基)丙烯酸组成的共聚物,两种单体的重量比为99.5∶0.5至大于85∶低于15,该法的特征在于,在水相中,在加热下,在至少一种式(Ⅰ)的水溶性引发剂存在下使含有丙烯酸丁酯和阴离子型和非离子型乳化剂一起聚合
MR1 (Ⅰ)其中M表示金属阳离子,以及
R1表示过氧酸或含偶氮基的酸的阴离子,引发剂的用量为0.5-1.5%(重),按单体的重量计;然后将(甲基)丙烯酸乳化在其中,同时保持在高温;随后加入第二引发剂使聚合完全。
2.根据权利要求1的方法,其特征在于,该法在芯壳聚合的条件下进行。
3.根据权利要求1的方法,其特征在于,聚合按乳液进料半连续法进行。
4.根据权利要求1的方法,其特征在于,聚合按间歇法进行。
5.根据权利要求1~4中任一项的方法,其特征在于,丙烯酸丁酯与(甲基)丙烯酸的重量比在99.5∶0.5~90∶10的范围内。
6.根据权利要求2的方法,其特征在于,芯与壳的重量比在30∶70~70∶30范围内。
7.根据权利要求1、2或6的方法,其特征在于,芯由丙烯酸丁酯单元组成。
8.根据权利要求1-4中任一项的方法,其特征在于,引发剂选自
-过二硫酸钾和过二硫酸钠,以及
-式Ⅰ-A表示的偶氮化合物其中R2表示甲基,
M表示金属阳离子,以及
n表示1~4的数字。
9.根据权利要求8的方法,其特征在于,式(Ⅰ-A)的化合物是4,4′-偶氮双-(4-氰戊酸)的钠盐或钾盐。
10.根据权利要求1的方法,其特征在于,式(Ⅰ)的化合物是过二硫酸钾盐或钠盐。
11.根据权利要求1-4中任一项的方法,其特征在于,使用非离子型乳化剂,为环氧乙烯加成到酮醇或烷基酚上的产物。
12.根据权利要求1-4中任一项的方法,其特征在于,使用阴离子型乳化剂,为磺基琥珀酸酯的形式。
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US5928783A (en) * | 1998-03-09 | 1999-07-27 | National Starch And Chemical Investment Holding Corporation | Pressure sensitive adhesive compositions |
US6569968B1 (en) * | 1999-08-19 | 2003-05-27 | Kurita Water Industries Ltd. | Polymer of a water-soluble radical-polymerizable monomer, process for producing the polymer and flocculant comprising the polymer |
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