CN1092430A - 纸张涂料组合物用的胶乳共聚物 - Google Patents
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Abstract
本发明涉及一种胶乳共聚物,它以聚合的形式包
含一种或多种烯属不饱和聚(乙二醇)单体和一种或
多种共聚单体,上述聚(乙二醇)单体由以下通式表
示:其中R1是烯属不饱和官能团,R是H、OH或
OCH3,n是3—20。包含这种胶乳共聚物的纸张涂
料组合物改进了所涂布的纸的纸页光泽度和干掉毛
性能。另外的具体方案包括制备含有烯属不饱和聚
(乙二醇)单体的胶乳共聚物和纸张涂料组合物的方
法。
Description
本发明涉及用于纸张涂料配方以改进和优化纸张性能例如纸页光泽度、印刷面光泽和平滑度的胶乳,本发明还涉及制备这些胶乳的方法和纸张涂料组合物。
造纸工业广泛使用包含胶乳共聚物的纸张涂料配方。通过开发包含在纸张涂料配方中的新胶乳,不断地寻求在一些性能例如纸页光泽度、印刷面光泽和平滑度上的改进。
用颜料例如白土和使颜料稳定和分散在水淤浆中的其他成分,制备涂布的纤维素幅或纸幅。用粘合剂配制淤浆以形成涂料,一种用于涂布纸幅或纸的纸张涂料组合物。涂料的成分对涂布纸幅的方法的实施和对涂布的纸的性能产生影响。如果纸是较高质量等级的纸,成品的涂布纸幅应该具有高的亮度,平滑度和光泽,以及在纸幅被压光后具有优良的光洁度和手感。
为了能印刷涂布的纸而没有“掉毛”,即没有涂料从纸的表面或者从涂层中分离,涂料必须具有足够的强度和粘合性。
US 4440896公开了在包含胶乳的粘合剂配方中使用乙二醇的水溶性聚合物。
US 4717502公开了在含水的光学增白剂组合物中使用聚乙二醇。
最好是具有一些新的胶乳,这些胶乳为纸张涂料配方和涂料提供改进了的物理特性,而没有现有技术中与聚乙二醇的混合物有关的那些缺点。
本发明涉及一种胶乳共聚物,它以聚合的形式包含一种或多种烯属不饱和聚(乙二醇)单体和一种或多种共聚单体;上述聚(乙二醇)单体由以下通式表示:
其中R1是烯属不饱和官能团,R是H、OH或OCH3,n是3-20;上述共聚单体选自单乙烯基芳族单体、脂族共轭二烯单体、丙烯酸酯单体、偏二卤乙烯单体、卤乙烯单体、含有1-18个碳原子的羧酸的乙烯基酯、甲基丙烯腈、丙烯腈和单烯属不饱和羧酸单体。
在本发明的范围内,本发明包括制备胶乳共聚物的方法,它包括乳液聚合一种聚合混合物,该混合物含有基于胶乳共聚物中单体总重量1-15%的一种或多种烯属不饱和聚(乙二醇)单体和一种或多种共聚单体;上述烯属不饱和聚(乙二醇)单体由以下通式表示:
其中R1是烯属不饱和官能团,R是H、OH或OCH3,n是3-20;上述共聚单体选自单乙烯基芳族单体、脂族共轭二烯单体、丙烯酸酯单体、偏二卤乙烯单体、卤乙烯单体、含1-18个碳原子的羧的乙烯基酯、甲基丙烯腈、丙烯腈和单烯属不饱和羧酸单体。
在另一实例中,本发明涉及一种包含胶乳共聚物和与该共聚物混合的其他成分的纸张涂料组合物;这种胶乳共聚物以聚合的形式包含一种或多种烯属不饱和聚(乙二醇)单体和一种或多种共聚单体;上述聚(乙二醇)单体由以下通式表示:
其中R1是烯属不饱和官能基,R是H、OH或OCH3,n是3-20;上述共聚单体选自单乙烯基芳族单体、脂族共轭二烯单体、丙烯酸酯单体、偏二卤乙烯单体、卤乙烯单体、含1-18个碳原子的羧酸的乙烯基酯、甲基丙烯腈、丙烯腈和单烯属不饱和羧酸单体;上述与胶乳共聚物混合的其他成分是:一种或多种颜料、可有可无的一种或多种粘合剂、可有可无的一种或多种稳定剂和可有可无的消泡剂。
在本发明的范围内,本发明包括制备纸张涂料组合物的方法,该方法包括乳液聚合一种聚合混合物,该混合物含有基于胶乳共聚物中单体总重量1-15%的一种或多种烯属不饱和聚(乙二醇)单体和一种或多种共聚单体;上述烯属不饱和聚(乙二醇)单体由以下通式表示:
其中R1是烯属不饱和官能团,R是H、OH或OCH3,n是3-20;上述共聚单体选自乙烯基芳族单体、脂族共轭二烯单体、丙烯酸酯单体、偏二卤乙烯单体、卤乙烯单体、含1-18个碳原子的羧酸的乙烯基酯、甲基丙烯腈、丙烯腈和单烯属不饱和羧酸单体;该方法还包括以任何顺序将上述乳液聚合产物与以下成分混合,这些成分是:一种或多种颜料、可有可无的一种或多种粘合剂、可有可无的一种或多种稳定剂和可有可无的消泡剂。
在本发明的胶乳共聚物和其制备方法的一些优选实例中,R1是乙烯基或丙烯基,n是7-15,R是OH。
最好是存在于胶乳共聚物中的烯属不饱和聚(乙二醇)单体的量为基于胶乳共聚物中单体和共聚单体总重量的1-15%,优选为5-10%。
在本发明中适于与烯属不饱和聚(乙二醇)单体共同使用的共聚单体和共聚单体的混合物包括单乙烯基芳族单体、脂族共轭二烯单体、丙烯酸酯单体、偏二卤乙烯或卤乙烯单体、含1-18个碳原子的羧酸的乙烯基酯例如乙酸乙烯酯或硬脂酸乙烯酯、甲基丙烯腈和丙烯腈。也可以使用单烯属不饱和羧酸,单乙烯基芳族单体和脂族共轭二烯单体是优选的。
本文中所用的“单乙烯基芳族单体”意指具有直接与含6-10个碳原子的芳核连接的通式为
的基团的那些单体,其中R是氢或低级的烷基的例如1-4个碳原子的烷基,这些单体包括其中的芳核被烷基或卤素取代基所取代的那些单体。一些例子包括苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、叔丁基苯乙烯、乙烯基甲苯和卤代苯乙烯。优选的单体是苯乙烯。
与烯属不饱和聚(乙二醇)单体并存的单乙烯基芳族共聚单体的有效量,一般将取决于(ⅰ)包含烯属不饱和聚(乙二醇)的胶乳共聚物单独起粘合剂的作用,或者(ⅱ)使包含烯属不饱和聚(乙二醇)的胶乳与按常规所知的胶乳混合在一起用作粘合剂。对于用作粘合胶乳的本发明的那些胶乳来说,单乙烯基芳族共聚单体含量的典型范围是基于单体总重量的30-70%。对于与粘合胶乳混合的本发明的胶乳来说,单乙烯基芳族共聚单体的含量的范围是比较灵活的。例如,如果要将本发明的胶乳在纸张涂料配方中起塑性颜料的作用,那么单乙烯基芳族单体的含量可以高达单体总重量的95%。
本文中所用的“脂族共轭二烯”,意思是包括象异戊二烯、1,3-丁二烯、2-甲基-1,3丁二烯、戊间二烯(1,3-戊二烯)和1,3-丁二烯的其他烃类似物那样的共聚单体化合物。与聚(乙二醇)共聚单体并存的脂族共轭二烯单体的含量一般取决于所选用的单体,但是,如果单乙烯基芳族单体是共聚单体,脂族共轭二烯含量的典型的范围是共聚单体总重量的30-70%。与粘合胶乳混合的本发明胶乳有比较灵活的脂族共轭二烯含量范围。
也适合于本发明的“偏二卤乙烯”和“卤乙烯单体”可包括优选的偏二氯乙烯和氯乙烯单体,也可以使用偏二溴乙烯和溴乙烯。
本文中所用的“丙烯酸酯”,意思是包括丙烯酸酯和甲基丙烯酸酯共聚单体。丙烯酸酯可包括酸、酯、酰胺和它们的取代衍生物。通常,优选的丙烯酸酯是丙烯酸或甲基丙烯酸的C1-C8烷基酯,这种丙烯酸酯的一些例子包括丙烯酸丁酯、丙烯酸己酯、丙烯酸2-乙基己基酯、丙烯酸叔丁基酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸乙酯、甲基丙烯酸己酯、甲基丙烯酸异丁基酯和甲基丙烯酸异丙基酯。优选的丙烯酸酯是丙烯酸丁酯和甲基丙烯酸甲酯。
与聚(乙二醇)共聚单体并存的丙烯酸酯的含量将取决于所选的单体,但是,所希望的含量范围是单体总重量和0-95%。
本文中所用的“单烯属不饱和羧酸单体”,意思是包括象丙烯酸和甲基丙烯酸那样的单羧酸单体,象衣康酸、富马酸、马来酸和它们的单酯那样的二羧酸单体。
单烯属不饱和羧酸共聚单体的含量是提高胶乳颗粒稳定性所必需的那个含量。尽管在没有羧酸共聚单体存在的情况下该胶乳颗粒可能是足够稳定的,但是典型的稳定含量是存在于共聚物中的单体总重量的2-10%。
用以下通式表示烯属不饱和聚(乙二醇)单体:
其中R1是烯属不饱和官能团,R是H、OH或OCH3,n是3-20,优选为5-10。
优选的烯属不饱和聚(乙二醇)单体是其中R1为乙烯基或丙烯基,n为7-15,R为OH的那些单体。
R1基团是指起官能团的作用,通过该官能团单体键合形成聚合物链,技术熟练的技术人员将容易确定对R1的各种选择。
虽然不希望被本发明实施的任何特定理论所约束,但是据认为烯属不饱和的聚(乙二醇)起官能团的作用,该官能团与象涂料中的白土那样的无机颜料反应。通过与白土的反应,可以认为涂料提高了纸的光泽,而没有损失强度和粘合性。
存在于本发明胶乳中的聚(乙二醇)单体的有效的定性的含量一般为存在于胶乳共聚物中单体总量的1-15%。存在于胶乳中的聚(乙二醇)单体的优选含量为存在于胶乳中单体总量的5-10份。
一般来说,可以在本发明的纸张涂料组合物中适当地将按常规已知的粘合剂与含聚(乙二醇)的胶乳混合。这些粘合剂包括天然的粘合剂和合成粘合剂,天然粘合剂包括淀粉,改性淀粉例如氧化淀粉、酶转化的淀粉或羟基-乙基化的淀粉,大豆蛋白和酪蛋白。合成粘合剂包括苯乙烯-丁二烯胶乳。粘合剂还可以是各种粘合物质的混合物。
可以将含有烯属不饱和聚(乙二醇)的胶乳与这些常规的粘合胶乳混合,含聚(乙二醇)的胶乳的量一般为粘合胶乳为10-50%重量。含聚(乙二醇)的胶乳的优选含量为20-45%重量。含烯属不饱和聚(乙二醇)的胶乳的优选含量大约为25%重量。
纸张涂料配方
该涂料一般包含:含有65-100份白土的100份颜料,0-35份辅助颜料,0.01-0.5份分散剂或稳定剂,0.5-25份含烯属不饱和聚(乙二醇)的胶乳,0-25份共一粘合剂,0-0.2份消泡剂,以及其量足以维持想要的固体含量的水,固体通常占重量的35-70%。该涂料的改进和配方是在该技术中技术熟练人员的知识范围内。
与含有聚(乙二醇)的胶乳颗粒反应的无机或矿物颜料,可以选自细碎的白土(特别是高岭土型的)、碳酸钙、二氧化钛、缎光白等等。也可以采用含有颜料的物质,例如滑石、钡白、赭石、碳黑、铝。
可以用常规的方法,例如用气刀涂布机、拖刀涂布机、倒置式刮刀涂布机、辊式涂布机和short dwell涂布机,将纸张涂料组合物,也称为涂料,涂到纸基上。
然后将纸基干燥,并根据要生产的纸的质量等级可将纸压光或超级压光。
说明本发明应用的纸张涂料性能包括,但是并不限于干掉毛(dry pick)和纸页光泽度。纸页光泽度往往是通过不出现干掉毛(说明涂料与纸的粘合是多么好)来获得。本发明使纸张涂料能保持干掉毛并且同时增加纸页光泽度。用标准方法分析纸张的纸页光泽度和表面结合强度性能。
借助于Westvaco Rod Applicator,通过使用TAPPI标准方法,试验纸的抗粘性能。用TAPPI标准方法T480-OS-78试验纸在75度时的镜面光泽。在有粘合剂胶乳的配方中含有烯属不饱和聚(乙二醇)单体的胶乳共聚物的实施例
实施例1
1.用以下方法制备含烯属不饱和聚(乙二醇)单体的胶乳。向1加仑的加压不锈钢反应器中加入813克水、1.23克浓度为45%的活性的表面活性剂溶液、0.89克浓度为10%的硫酸、11.1克浓度为1%的二亚乙基三胺五乙酸钠活性水溶液和26.35克种子胶乳,其中,种子胶乳将提供直径大约为1400A的颗粒尺寸。用氮气吹洗反应器并将反应器加热至90℃,经过5小时的时间后,再向反应器中加入单体流。上述单体流包含:530克丁二烯;140克烯属不饱和聚(乙二醇)单体,该单体是α-(2-甲基-1-氧代-2-丙烯基)-ω-羟基-聚(氧-1,2-乙烯二基),它具有大约20个环氧乙烷单元(此后表示为“HEM20”,它是从Alcolac作为聚(乙二醇)单甲基丙烯酸酯购得的;9.0克硫醇链转移剂;726克苯乙烯。与上述单体流同时加入485克水、24.26克浓度为45%的活性的表面活性剂溶液、24克浓度为10%的氢氧化钠溶液和19克过硫酸钠。加入单体流和含水流之后,将反应器在90℃保温约1小时,然后冷却。
用以下方法制备纸张涂料配方。向混合器中加入足够量的水和0.1份作为分散剂的聚丙烯酸钠,其中的水是为了配制浓度为72%的淤浆用的,淤浆中含有2000克干的1号涂料白土。将白土总量的大约2/3加入到混合器中,用低速使混合器转动直到白土被湿润为止。再加入剩余的白土用低速转动混合器直到所有的白土都湿润为止。然后用高速将颜料分散1分钟。
将100克颜料浆放入一个装有胶乳粘合剂的8盎司的瓶中。用空气搅拌器以不引起涡流的速度将涂料混合物搅拌大约3-5分钟。然后在手工搅拌配方的同时,用氢氧化铵或氢氧化钠将配方的PH值调到8.5-9。
将涂料配方涂到上面的纸或原纸是28磅/3300英尺2的含有磨木浆的印刷用纸浆。用由Modern Metalcraft of Midland,Michigan制造的Dow Bench Blade Coater涂布原纸。在用加热的钢质辊筒进行干燥的情况下,用槽式刮刀涂布机以大约12英尺/分钟的速度涂布12英寸的纸幅。为了加热使循环的乙二醇在205°F至215°F通过辊筒是足够的。将纸干燥后,将样品剪成适合于试验的尺寸。
胶乳粘合剂由75%羧化的苯乙烯-丁二烯胶乳和25%上面制备的含烯属不饱和聚(乙二醇)单体的胶乳所组成。用该涂料配方涂布过的纸的纸页光泽度为62,干掉毛为225。
实施例2-5
2、用类似于实施例1中制备胶乳的方法所制备的胶乳来制备类似的涂料,但是,该胶乳是用基于单体总重量的5份α-(2-甲基-1-氧代-2-丙烯基)-ω-羟基-聚(氧-1,2-乙烯二基)制备的,该化合物具有大约10个环氧乙烷单元(以后表示为“HEM10”),它是从Alcolac作为聚(乙二醇)单甲基丙烯酸酯买到的,上述涂料是用75%羧化的苯乙烯-丁二烯胶乳和25%HEM10胶乳制备的。用该涂料配方涂布过的纸的纸页光泽度为61,干掉毛为206。
3、用类似于实施例1中制备胶乳的方法所制备的胶乳来制备类似的涂料,但是,用基于单体总重量为10份的HEM10制备胶乳,用75%羧化的苯乙烯-丁二烯胶乳和25%HEM10胶乳制备该涂料。用该涂料配方涂布的纸的纸页光泽度为64,干掉毛为222。
4、用类似于实施例1中制备胶乳的方法所制备的胶乳来制备类似的涂料,但是,用基于单体总重量为15份的HEM10制备胶乳,用75%羧化的苯乙烯-丁二烯胶乳和25%HEM10胶乳制备该涂料。用该涂料配方涂布的纸的纸页光泽度为65,干掉毛为195。
5、用类似于实施例1中制备胶乳的方法所制备的胶乳来制备类似的涂料,但是,用基于单体总重量为10份的HEM10制备胶乳,用50%羧化的苯乙烯-丁二烯胶乳和50%HEM10胶乳制备该涂料。用该涂料配方涂布的纸的纸页光泽度为65,干掉毛为210。
比较例
只用羧化的苯乙烯-丁二烯制备类似的涂料,因此只用羧化的苯乙烯-丁二烯胶乳制备该涂料。与实施例5中所述的比较合乎要求的纸页光泽度为65和干掉毛为210相比,用本比较例的涂料配方涂布的纸的纸页光泽度为57,干掉毛为188。
上述数据说明,当在涂料中加入含烯属不饱和聚(乙二醇)单体的胶乳时,想要的纸页光泽度增加了,而且显示出纸是干掉毛的。
Claims (11)
2、权利要求1的胶乳共聚物,其中R1是乙烯基或丙烯基,n是7-15,R是OH。
3、权利要求1或2的胶乳共聚物,其中存在于胶乳共聚物中的烯属不饱和聚(乙二醇)单体的量为基于存在于胶乳共聚物中的单体和共聚单体的总重量的1-15%,或者5-10%。
5、权利要求4的方法,其中R1是乙烯基或丙烯基,n是7-15,R是OH。
6、权利要求4或5的方法,其中存在于聚合混合物中的烯属不饱和聚(乙二醇)单体的量为基于存在于胶乳共聚物中的单体和共聚单体的总重量的1-15%,或者5-10%。
8、权利要求7的纸张涂料组合物,其中的粘合剂选自淀粉、改性淀粉、氧化淀粉、酶转化的淀粉和羟基-丁基化的淀粉、大豆蛋白、酪蛋白、苯乙烯-丁二烯共聚物胶乳、苯乙烯-丁二烯丙烯酸酯共聚物胶乳以及它们的混合物。
9、权利要求7或8的纸张涂料组合物,其中,以该组合物的总重量为基准,包含0.5-25份胶乳共聚物、65-100份白土颜料、0-35份选自碳酸钙、二氧化钛和缎光白的辅助颜料、0.01-0.5份稳定剂、0-0.2份消泡剂,该组合物的固体含量为35-70%重量。
10、权利要求7的纸张涂料组合物,其中胶乳共聚物占它和粘合剂重量的10-50%,或者20-45%。
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CN93104060A CN1092430A (zh) | 1989-10-25 | 1993-03-16 | 纸张涂料组合物用的胶乳共聚物 |
US08/207,007 US5491209A (en) | 1989-10-25 | 1994-03-07 | Latex copolymers for paper coating compositions |
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US42624489A | 1989-10-25 | 1989-10-25 | |
US86474892A | 1992-04-07 | 1992-04-07 | |
CN93104060A CN1092430A (zh) | 1989-10-25 | 1993-03-16 | 纸张涂料组合物用的胶乳共聚物 |
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Cited By (2)
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CN102251437A (zh) * | 2011-06-30 | 2011-11-23 | 金东纸业(江苏)股份有限公司 | 涂布纸及其生产方法 |
CN102747651A (zh) * | 2012-06-08 | 2012-10-24 | 太仓市新星轻工助剂厂 | 一种涂布纸胶粘剂及其制备方法 |
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US5900451A (en) * | 1997-05-15 | 1999-05-04 | Reichhold Chemicals, Inc. | Collaidally stabilized butadiene emulsions |
US6417249B1 (en) | 1997-10-31 | 2002-07-09 | Hewlett-Packard Company | Ink-jet printing ink compositions having superior smear-fastness |
DE69820897T2 (de) * | 1997-10-31 | 2004-12-09 | Hewlett-Packard Co. (N.D.Ges.D.Staates Delaware), Palo Alto | Haltbare, filmformende, wasserdispergierbare polymere |
AU1379699A (en) * | 1997-10-31 | 1999-05-24 | Hewlett-Packard Company | Printing ink compositions having superior smear-fastness |
EP0930395A1 (en) * | 1998-01-20 | 1999-07-21 | Dow Europe S.A. | Low foaming paper surface sizing composition |
IT1304499B1 (it) * | 1998-12-22 | 2001-03-19 | Enichem Spa | Procedimento per ridurre il peso molecolare di copolimeri eterpolimeri dell'etilene. |
DE50015912D1 (de) | 1999-07-15 | 2010-06-10 | Clariant Produkte Deutschland | Wasserlösliche Polymere und ihre Verwendung in kosmetischen und pharmazeutischen Mitteln |
US6599638B1 (en) | 1999-09-10 | 2003-07-29 | Dow Reichhold Specialty Latex Llc | Colloidally stabilized emulsions |
FR2846978B1 (fr) * | 2002-11-08 | 2007-05-18 | Coatex Sas | Utilisation d'un copolymere disposant d'au moins une fonction greffee alkoxy ou hydroxy polyalkylene glycol, comme agent ameliorant l'activation de l'azurage optique et produits obtenus |
FR2846971B1 (fr) * | 2002-11-08 | 2006-09-29 | Omya Ag | Utilisation d'un copolymere disposant d'au moins une fonction greffee alkoxy ou hydroxy polyalkylene glycol, comme agent ameliorant la brillance du papier et produits obtenus |
US7276549B2 (en) * | 2004-01-12 | 2007-10-02 | United States Gypsum Company | Surface enhancing coating for gypsum-containing floor underlayments |
FR2893031B1 (fr) * | 2005-11-04 | 2008-02-08 | Coatex Sas | Procede de fabrication d'une resine thermoplastique avec une resistance a l'impact amelioree mettant en oeuvre un polymere peigne avec au moins une fonction greffee oxyde de polyalkylene et resines obtenues. |
FR2894998A1 (fr) * | 2005-12-16 | 2007-06-22 | Coatex Sas | Procede de fabrication de sauces de couchage a la retention d'eau et a la viscosite brookfield ameliorees mettant en oeuvre un polymere peigne avec au moins une fonction greffee oxyde de polyalkylene. |
FR2925077A1 (fr) * | 2007-12-17 | 2009-06-19 | Coatex Soc Par Actions Simplif | Epaississant acrylique a chaine hydrophobe et ramifiee pour sauce de couchage papetiere a retention d'eau amelioree |
FR2926558B1 (fr) * | 2008-01-17 | 2010-03-05 | Coatex Sas | Amelioration d'un procede de fabrication de polymeres peignes par ajout d'un antioxydant, polymeres obtenus et leurs applications |
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US4003870A (en) * | 1973-11-21 | 1977-01-18 | Dulux Australia Ltd. | Polymeric thickeners |
US4265977A (en) * | 1979-04-24 | 1981-05-05 | Asahi-Dow Limited | Paper coating composition of unsaturated acid and mono-olefin polymerized in the presence of a preformed styrene/butadiene latex |
FR2511008B1 (fr) * | 1981-08-10 | 1985-10-04 | Rhone Poulenc Spec Chim | Procede de preparation de latex de polymeres d'acetate de vinyle |
GB8321119D0 (en) * | 1982-10-01 | 1983-09-07 | Ici Plc | Polymerisation process |
JPS6038415A (ja) * | 1983-08-12 | 1985-02-28 | Nippon Zeon Co Ltd | 共重合体ラテツクスの製造方法 |
DE3502038A1 (de) * | 1985-01-23 | 1986-07-24 | Sandoz-Patent-GmbH, 7850 Lörrach | Waessrige aufhellerpraeparate und deren verwendung im papierstrich |
JPS62169868A (ja) * | 1986-01-21 | 1987-07-27 | Nippon Zeon Co Ltd | 弾性塗料組成物 |
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1993
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Cited By (2)
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CN102251437A (zh) * | 2011-06-30 | 2011-11-23 | 金东纸业(江苏)股份有限公司 | 涂布纸及其生产方法 |
CN102747651A (zh) * | 2012-06-08 | 2012-10-24 | 太仓市新星轻工助剂厂 | 一种涂布纸胶粘剂及其制备方法 |
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