CN103038416A - 用于无纺基材的甲醛含量极低的粘合剂 - Google Patents

用于无纺基材的甲醛含量极低的粘合剂 Download PDF

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CN103038416A
CN103038416A CN2011800375810A CN201180037581A CN103038416A CN 103038416 A CN103038416 A CN 103038416A CN 2011800375810 A CN2011800375810 A CN 2011800375810A CN 201180037581 A CN201180037581 A CN 201180037581A CN 103038416 A CN103038416 A CN 103038416A
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J·R·博伊兰
C·W·佩里
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Abstract

用于提高无纺基材的湿抗拉强度和干抗拉强度的甲醛含量低的粘合剂组合物,其中所述组合物包含a)使用非离子型、阳离子型或两性型分散体稳定剂的乙酸乙烯酯乙烯共聚物含水分散体,b)壳聚糖,及c)一种或多种不含分散体稳定剂的表面活性剂;其中所述粘合剂组合物的自由甲醛含量不大于10ppm,至少90重量%的所述一种或多种表面活性剂是非离子型、阳离子型、两性型或它们的组合,所述分散体中的共聚物不含产生甲醛的部分。

Description

用于无纺基材的甲醛含量极低的粘合剂
技术领域
含有作为自交联官能单体的N-羟甲基丙烯酰胺(NMA)的乙酸乙烯酯乙烯(VAE)共聚物分散体经常被施加在无纺基材上以提供良好的干抗拉强度和湿抗拉强度以及良好的水吸收率。此类基材的例子包括用于湿巾最终用途应用的干法无纺基材。湿巾含有含水组合物,例如洗液,其浸入基材中以提供湿的织物。
背景技术
然而在VAE交联期间,产生作为非期望的副产物的甲醛。此外,在许多情况下,在交联之前由于使用了甲醛次硫酸钠作为在形成VAE共聚物时的氧化还原自由基引发剂,甲醛也存在于分散体中。由于使用了特定的防腐剂,也可能存在甲醛。然而在交联反应之后在分散体以及在基材中存在甲醛,对于基材的制造商以及最终使用的用户而言都是非期望的。然而使用不含NMA或其他交联单体的VAE树脂的努力通常导致干抗拉强度和湿抗拉强度不足及水吸收率不足。因此,存在能够提供可接受的湿抗拉强度和干抗拉强度以及吸收率而不会产生甲醛的方法和组合物的需求。
发明内容
一方面,本发明提供低甲醛含量的粘合剂组合物,以提高无纺基材的湿抗拉强度和干抗拉强度。该组合物包含
a)使用了非离子型、阳离子型或两性型分散体稳定剂的乙酸乙烯酯乙烯共聚物含水分散体,
b)壳聚糖,及
c)一种或多种不含分散体稳定剂的表面活性剂。
粘合剂组合物的自由甲醛含量不大于10ppm,一种或多种表面活性剂的至少90重量%是非离子型、阳离子型、两性型或它们的组合,分散体中的共聚物不含产生甲醛的部分。
另一方面,本发明提供包含用本发明的粘合剂组合物处理的无纺基材的无纺产品。在某些方面,本发明提供用含水组合物浸渍的该产品。
具体实施方式
本发明提供组合物和方法,以使无纺基材具有良好的湿强度和干强度以及吸收率,几乎不或者不形成甲醛。现在公开了使用壳聚糖(经改性的天然多糖聚合物)、一种或多种非离子型和/或阳离子型和/或两性型润湿表面活性剂以及甲醛含量低的不含NMA的VAE的三组份组合,在作为粘合剂施加至纤维素纤维(例如,在无纺基材是纸的情况下)或者施加至纤维素/合成纤维无纺基材时,提供良好的湿强度和干强度性能和良好的亲水性特性。不同于含有NMA的VAE强度试剂,该组合在分散体和用作为粘合剂的组合物处理的无纺基材中均获得非常低(接近0ppm)水平的自由甲醛。与此不同,使用典型的含有NMA的分散体,则获得含有>10ppm甲醛的基材,而且根据ASTM D5910-96所测,分散体本身通常可能含有至少40ppm的自由甲醛。(在经处理的基材中的甲醛水平可以采用该方法的改变的方案进行测量,其中在通过D5910-96进行测试之前对基材实施水萃取。)
由实施例可以看出,VAE与壳聚糖的组合产生了出人意料的合作效应,与预期相比提供了明显更高的干抗拉强度和湿抗拉强度。含有润湿表面活性剂,以提供含水液体对于用该组合物处理的无纺基材的适当吸收率。经处理的无纺基材具有高水平的湿抗拉强度和干抗拉强度,以及极低水平的自由甲醛。这些特性使其可用于湿巾或干巾产品。现在分别描述这些组份,然后描述合适的组合物及其用途。
VAE共聚物分散体
出于本发明的目的,VAE共聚物不含NMA单元或任何其他的含有羟甲基的单体,并且不含任何在粘合剂组合物中或者在经处理的基材上产生甲醛的单体。由此,该共聚物不含产生甲醛的部分。与使用将产生甲醛的甲醛次硫酸钠(SFS)用作还原剂的更加典型的氧化还原对引发剂的情况不同,优选还通过利用不含产生甲醛的部分的引发剂引发乙酸乙烯酯/乙烯分散体聚合作用制备该共聚物。一般而言,氧化还原对的合适的不产生甲醛的还原剂包括以下非限制性实例,在现有技术中已知的基于抗坏血酸、亚硫酸氢盐、异抗坏血酸盐或酒石酸的化学试剂,以及由德国Heilbronn的Bruggeman Chemical公司生产的称作
Figure BDA00002796150100031
FF6M的商购还原剂。还可以使用非氧化还原引发剂,例如过硫酸盐、过氧化物和偶氮型引发剂,它们均是在现有技术中已知的。
一种合适的VAE共聚物是购自德国慕尼黑的Wacker化学股份公司的称作
Figure BDA00002796150100032
RB18的非离子型聚乙烯醇(PVOH)稳定化的VAE。根据ASTM D5910-96测得的作为55%非挥发性物质的分散体的
Figure BDA00002796150100033
RB18的自由甲醛水平的平均值为6.3ppm,其中通过液相色谱测定分散体聚合物中的自由甲醛,而类似的利用SFS制得的PVOH稳定化的分散体测得的数值则>40.0ppm。优选使用PVOH或某些其他的非离子型、阳离子型或两性型分散体稳定剂,而不是阴离子型,其原因在下面进行描述。合适的稳定剂包括聚合物稳定剂,例如纤维素化合物(例如羟乙基纤维素)、糊精、聚乙烯吡咯烷酮和聚丙烯酰胺。其他可使用的稳定剂可以包括阳离子型、两性型或非离子型表面活性剂。例子包括乙氧基化的脂肪族胺、氧化胺、环氧乙烷/环氧丙烷嵌段共聚物、醇乙氧基化物、烷基酚乙氧基化物、二醇酯、酰胺、苯甲基季铵化合物、两性乙酸盐、两性丙酸盐、两性磺酸盐和氨基丙酸盐。
在配制品中VAE的功能是为无纺基材提供更高水平的干抗拉强度,超过壳聚糖作为唯一的粘合剂可以提供的干抗拉强度。VAE的低的玻璃态转变温度(Tg=17℃,在RB18的情况下)还预期为无纺基材提供改善的拉伸和伸长特性,克服壳聚糖(Tg>140℃)的脆性特性。在用于将其转化成最终产品的设备上处理无纺基材时,这些特性是重要的。
壳聚糖
壳聚糖β-(1,4)-2-氨基-2-脱氧-D-葡糖直链均聚物。其是通过由蟹壳获得的壳多糖的碱性脱乙酰作用制备的。其结构如下:
Figure BDA00002796150100042
壳聚糖为无纺基材提供优异的湿抗拉强度和干抗拉强度。但是由该结构可以看出,壳聚糖并不形成或释放甲醛。
壳聚糖通常以粉末形式供应,并且可以分散在水中,但是不可溶。其可以通过以1%的水平添加乙酸至分散的壳聚糖粉末而溶解。虽然其他壳聚糖也可能表现良好,在开发本发明时发现的可用的一个等级的壳聚糖由Aldrich供应,并且具有以下规格:
脱乙酰作用百分比: >75%
1%溶液的粘度      20至200cps
粒径:            <150微米
润湿表面活性剂
需要一种或多种润湿剂以克服壳聚糖的疏水性特性,并为无纺基材提供吸收率,以在用于湿巾中时允许无纺基材吸收水或其他含水组合物(例如含水洗液)。
用于本发明的润湿表面活性剂必须基本上是非离子型、阳离子型、两性型或者它们的组合,以与阳离子型壳聚糖相容。大量的阴离子型表面活性剂与壳聚糖不相容,因此至少90重量%或者至少95重量%或者至少98重量%的一种或多种表面活性剂是非离子型和/或阳离子型和/或两性型。在某些情况下,所述一种或多种表面活性剂100%是非离子型和/或阳离子型和/或两性型。本发明的发明人发现,即使阴离子型润湿剂被广泛使用并且在其中使用可交联的含有NMA的VAE粘合剂的系统中是有效的,阴离子型润湿剂对于改善本发明的组合物的吸收率也是无效的。若干类型的非离子型润湿表面活性剂适合于使用,并且不会为无纺基材提供甲醛。一种类型包括乙氧基化的乙炔二醇,例如
Figure BDA00002796150100051
465(Air Products & Chemicals,Allentown,PA)。可以使用的还有分支醇乙氧基化物,例如BC720、十三烷醇乙氧基化物,及直链醇乙氧基化物,例如
Figure BDA00002796150100053
LA-9(Rhodia,Cranbury,NJ)。其他合适的润湿剂包括环氧乙烷/环氧丙烷嵌段共聚物、烷基酚乙氧基化物、氧化胺、乙氧基化的脂肪族胺、苯甲基季铵化合物、两性乙酸盐、两性丙酸盐、两性磺酸盐和氨基丙酸盐。
粘合剂组合物
在针对无纺应用配制时,VAE、壳聚糖和表面活性剂通常一共构成粘合剂组合物的2重量%至25重量%,余量是水(及乙酸,用于溶解壳聚糖)。更典型地,该范围是5重量%至15重量%,或者是7重量%至13重量%。
VAE共聚物及其相关的一种或多种乳液稳定剂通常构成粘合剂组合物中所有非挥发性物质的至少77重量%或者至少85重量%或者至少90重量%。通常构成最多99.7重量%或者最多98重量%或者最多97重量%。在此,术语“非挥发性物质”是指在≥100℃下对组合物进行干燥直至达到恒重之后残留的残余物,由CSC Scientific公司,Inc.,Fairfax,VA生产的CSC Digital Moisture Balance测得。
壳聚糖通常构成粘合剂组合物中所有非挥发性物质的至少0.2重量%或者至少1重量%或者至少2重量%。通常构成最多20重量%或者最多15重量%或者最多10重量%。
表面活性剂通常构成粘合剂组合物中所有非挥发性物质的至少0.1重量%或者至少0.2重量%或者至少0.3重量%。通常构成最多3重量%或者最多2.5重量%或者最多2重量%。
施加至基材
本发明的粘合剂组合物可以通过任何以下的施加方法施加至无纺基材,包括但不局限于喷涂、浸透、起泡和印刷。含纤维的无纺基材可以通过各种不同的方法制造,包括但不局限于干法(气流成网)、湿法、梳理和水刺。
用于无纺基材中的含纤维的材料可以是天然纤维,例如(但不局限于)纤维素纤维,或合成纤维,包括但不局限于一种或多种和聚酯、聚乙烯、聚丙烯和聚乙烯醇、或黏胶纤维、或它们的任意组合。
实施例
用于喷涂的粘合剂组合物
适合于喷涂施加至干法无纺基材的粘合剂是通过混合以下成分制备的,产生10%非挥发性物质的组合物:
Figure BDA00002796150100061
*55%非挥发性物质
非织物喷涂施加/测试
将上述配制品喷涂在基重为85g/m2的纤维素纤维/合成纤维无纺基材的两面。基于基材干重,粘合剂施加量的目标为10%的干粘合剂混合物。将经喷涂的基材在通风炉中在320°F(160℃)的温度下干燥三分钟。然后根据ASTM方法D5035-95对经处理的无纺基材评估干拉伸断裂强度和湿拉伸断裂强度,并利用Sherwood Instruments ATS 600吸收性测试系统吸收性测试仪测试吸收性能。该仪器测量无纺基材的水吸收率和最大吸收能力。
实施例1–VAE分散体中自由甲醛的量
下面表1所示为VAE分散体中自由甲醛的量,其中使用1)基于甲醛次硫酸钠的氧化还原引发剂或者2)不含形成甲醛的部分的氧化还原引发剂(“NFI”),作为形成VAE共聚物时的自由基引发剂。还显示了利用N-羟甲基丙烯酰胺制备的分散体聚合物以及利用不含形成甲醛的部分的氧化还原引发剂制备的非离子型聚乙烯醇稳定化的分散体
Figure BDA00002796150100071
RB18)的自由甲醛水平。
Figure BDA00002796150100072
产品可购自德国慕尼黑的Wacker化学股份公司。
表1
Figure BDA00002796150100073
Figure BDA00002796150100074
可以看出,与利用SFS或NMA制备的分散体相比,利用非甲醛引发剂和聚乙烯醇制备的非离子稳定化的
Figure BDA00002796150100081
RB18具有明显更低的甲醛含量。
实施例2–单独的组份对于物理性能的贡献
将用于制备根据本发明的配制品的三种组份作为单独的组份及以组合方式喷涂施加至干法无纺基材,以确定它们对于无纺基材的物理性能的作用。未经处理的无纺基材具有以下特性:
基重–~85克/m2
纤维组成
纤维素–88%
合成双组份纤维–12%(用聚乙烯外壳包围的聚酯核心)
厚度–0.81mm
横向干抗拉强度–590克/5cm
横向湿抗拉强度–330克/5cm
用于制备溶解壳聚糖和将所有成分混合在一起的过程如下:
1、通过搅拌将壳聚糖分散在水中。
2、将乙酸添加至分散的壳聚糖,并在壳聚糖溶解时继续搅拌。
3、将表面活性剂添加至溶解的壳聚糖。
4、在搅拌的情况下,将壳聚糖/表面活性剂混合物添加至RB18,并继续搅拌30分钟。
将表2中所述的配制品喷涂至纤维素/合成无纺基材的两面。将经喷涂的基材在通风炉中在320°F(160℃)的温度下干燥三分钟。如上所述测定干拉伸断裂强度和湿拉伸断裂强度和吸收性能,并利用ThwingAlbert厚度测试仪测量以毫米计的厚度。
如表2中的配制品#1所示,
Figure BDA00002796150100083
192是一种含有NMA的自交联VAE共聚物分散体(52%非挥发性物质),其通常用作干法无纺基材的粘合剂,并在此显示为比较例。在表2中,
Figure BDA00002796150100084
192条目表明,将NH4Cl(催化剂)和OT二辛基磺基丁二酸钠(阴离子型表面活性剂)添加至
Figure BDA00002796150100092
192,导致在沉积在基材上的非挥发性物质中,98重量%是VAE共聚物/乳液稳定剂,1重量%是NH4Cl,1重量%是
Figure BDA00002796150100093
OT。
表2–单独的组份对于物理性能的贡献
Figure BDA00002796150100094
非织物测试结果
基重克/m2 97.10 92.40 83.38 88.20 90.89 93.30
施加量(%) 10.00% 9.83% 0.4%* 0.1%* 9.66% 9.67%
厚度(mm) 1.18 1.09 1.08 1.69 1.11 1.18
密度克/cm3 0.082 0.85 0.077 0.52 0.082 0.079
横向干抗拉强度克/5cm 2473 3036 1137 895 2925 3035
峰值应变% 24.6% 22.3% 26.7% 34.4% 20.9% 23.1%
横向湿抗拉强度克/5cm 1215 512 513 303 905 868
吸收率克/克/秒 1.04 0.03 0.79 1.43 0.11 0.45
*理论施加率–在用于精确重量测量的非织物上的材料过少
如上表所示,三种配制品组份均没有单独地提供无纺基材所需的主要的干强度、湿强度和吸收特性,它们在这些方面与现有技术的标准添加剂
Figure BDA00002796150100095
192均是不可比的。然而,配制品#6(包含所有的组份)提供的基材则具有所有主要的物理性能的可接受的数值。这能够通过甲醛含量非常低的配制品实现是令人吃惊和意外的。
实施例3–壳聚糖水平对物理性能影响
下面表3所示为提高在混合配制品中的壳聚糖水平的影响。壳聚糖从1%升高至5%(干重%),并喷涂施加至前述的干法无纺基材。以与实施例1所述相同的方式测试经处理的基材。
表3–壳聚糖含量对物理性能的影响
Figure BDA00002796150100101
非织物测试结果
基重克/m2 89.7 89.7 95.2 91.5 96.1 94.5 92.1
施加量% 9.4% 9.8% 9.8% 9.8% 9.4% 9.7% 9.9%
厚度mm 1.24 1.17 1.19 1.21 1.24 1.22 1.27
密度克/cm3 0.072 0.077 0.080 0.076 0.078 0.077 0.073
横向干抗拉强度克/5cm 2250 3266 3238 2977 3149 2990 3149
峰值应变% 26.9 24.5 25 24.9 25.9 24.1 23.4
横向湿抗拉强度克/5cm 1263 560 715 800 883 855 970
吸收率克/克/秒 1.07 0.04 0.30 0.36 0.43 0.45 0.40
能力克/克 13.1 10.4 10.1 10.0 10.4 9.8 10.0
从表3可以看出,提高粘合剂配制品中的壳聚糖水平,提高了湿强度。RB18VAE单独地为无纺基材提供560克/5cm的湿强度(配制品#2),但是以1%添加壳聚糖(配制品#3)时,湿强度提高了28%。相对于用100%的
Figure BDA00002796150100112
RB18(配制品#2)处理的无纺基材,以5%添加壳聚糖(配制品#7)时,湿强度提高了73%。
实施例4–表面活性剂对物理性能的影响
表4(见下)所示为粘合剂配制品中的润湿表面活性剂对所获得的无纺基材性能的影响。与阴离子型表面活性剂二辛基磺基丁二酸钠
Figure BDA00002796150100113
OT,Cytec Industries Inc.,Woodland Park,NJ)类似地,
评估三种非离子型表面活性剂
Figure BDA00002796150100114
465、
Figure BDA00002796150100115
LA-9和
Figure BDA00002796150100116
BC720。
在本研究中使用的无纺基材如实施例2中所述。将粘合剂配制品喷涂施加至无纺基材,并以与实施例2所述相同的方式进行测试。
表4–表面活性剂对物理性能的影响
Figure BDA00002796150100117
非织物测试结果
基重克/m2 94.20 94.10 94.40 96.10 97.30 96.20
施加量% 10.70% 11.30% 10.50% 10.60% 10.60% 11.50%
横向干抗拉强度克/5cm 2924 3359 2502 3039 2835 2884
横向湿抗拉强度克/5cm 552 1025 786 1011 925 782
吸收率克/克/秒 0.02 0.16 0.03 0.54 0.83 0.79
吸收能力克/克 4.0 8.4 7.9 10.5 12.2 11.7
不含表面活性剂的配制品#1和#2分别获得0.02和0.16克/克/秒的非常低的吸收率。由配制品#3可以看出,添加阴离子型表面活性剂
Figure BDA00002796150100121
OT对于改善吸收率而言基本上没有作用。其在改善吸收能力方面也很差。与此不同,所有的非离子型表面活性剂对于吸收率及吸收能力具有突出的积极效果,而不会明显地干扰经处理的基材的抗拉性能。
与非离子型表面活性剂相比,使用阴离子型
Figure BDA00002796150100122
OT也获得明显更低的湿抗拉强度和干抗拉强度。OT是一种已知的润湿剂,其通常用于改善利用阴离子稳定化的分散体粘结的基材的润湿(吸收率),在这些应用中并不会干扰强度发展。然而,使用阴离子型
Figure BDA00002796150100124
OT则获得差的湿抗拉性能和干抗拉性能和非常差的吸收性能。因此,在本发明的组合物中可能容许少量的阴离子型表面活性剂,一种或多种表面活性剂必须至少主要是非离子型和/或阳离子型和/或两性型,优选100%是非离子型和/或阳离子型和/或两性型。
实施例5–VAE与壳聚糖的协同效应
为了阐明VAE和壳聚糖对于湿抗拉强度和干抗拉强度的贡献,在四种不同的条件下评估Whatman第4号色谱纸:用三种含有添加剂的配制品之一进行处理,及一种其中不进行处理的空白。三种配制品如下:
#1
Figure BDA00002796150100131
RB18分散体9%非挥发性物质
#2RB18分散体/5%壳聚糖9%非挥发性物质,用乙酸调节至pH=3.8
#3100%壳聚糖0.45%非挥发性物质,用乙酸调节至pH=3.8
壳聚糖具有低分子量,并且75%至85%被脱乙酰化。以如下方式将每种配制品施加至纸张:
对纸张在260°F下干燥2分钟,以去除水分,并在四位(four place)分析天平上称重以获得干重。将称重的样品放在含有所指定的配制品的盘中,并吸收材料至浸透(饱和)。使浸透的纸张通过Atlas Padder的压制间隙,以去除多余的配制品。用所施加的配制品处理的纸张放入300°F的对流炉中5分钟以进行干燥。取出经干燥的样品,再称重以确定配制品施加量。
在测试之前,将经处理的纸张在受控制的温度和湿度条件下进行调节24小时。切割样品以在纸张的横向(CD)上进行抗拉测量,并且进行湿抗拉测量和干抗拉测量。结果在表5中所示。
若假设基材、VAE和壳聚糖的强度贡献是简单加和的,则基于表5中所示的四种条件的各自的平均值,含有VAE和壳聚糖的组合物(#2)的干抗拉强度比预期高约32%。更加令人惊叹的是,湿抗拉强度比预期高约117%;超过其强度的两倍。这些结论的基准可以参见下表,其中#1至#4是指在表5中详细描述的试验。下面所示的增加值是指所计算的VAE或壳聚糖对于强度的单独贡献,而预期值则假定强度作为VAE或壳聚糖的量的函数的线性响应。可以看出,VAE与壳聚糖的组合为干抗拉强度和湿抗拉强度提供了突出的合作或协同效应。
Figure BDA00002796150100141
虽然在此参考特殊的实施方案描述和阐明本发明,但是本发明不应当被限制于所示的细节。可以在不背离本发明的前提下,在权利要求的等效范围内详细地进行各种改变。
表5–VAE与壳聚糖结合的效果
Figure BDA00002796150100151

Claims (19)

1.用于提高无纺基材的湿抗拉强度和干抗拉强度的甲醛含量低的粘合剂组合物,其中所述组合物包含
a)使用非离子型、阳离子型或两性型分散体稳定剂的乙酸乙烯酯乙烯共聚物含水分散体,
b)壳聚糖,及
c)一种或多种不含分散体稳定剂的表面活性剂;
其中所述粘合剂组合物的自由甲醛含量不大于10ppm,至少90重量%的所述一种或多种表面活性剂是非离子型、阳离子型、两性型或它们的组合,所述分散体中的共聚物不含产生甲醛的部分。
2.权利要求1的粘合剂组合物,其中所述分散体稳定剂是聚合的。
3.权利要求1的粘合剂组合物,其中所述分散体稳定剂是非离子型。
4.权利要求1的粘合剂组合物,其中所述分散体稳定剂包含聚乙烯醇。
5.权利要求1的粘合剂组合物,其中所述分散体稳定剂包含羟乙基纤维素。
6.权利要求1的粘合剂组合物,其中至少98重量%的所述一种或多种表面活性剂是非离子型、阳离子型、两性型或它们的组合。
7.权利要求1的粘合剂组合物,其中所述一种或多种表面活性剂包含醇乙氧基化物。
8.权利要求7的粘合剂组合物,其中所述分散体稳定剂包含聚乙烯醇。
9.权利要求1的粘合剂组合物,其中所述一种或多种表面活性剂包含乙氧基化的乙炔二醇。
10.权利要求1的粘合剂组合物,其中所述乙酸乙烯酯乙烯共聚物分散体是通过由不产生甲醛的引发剂系统引发的乳液聚合作用形成的。
11.权利要求1的粘合剂组合物,其中所述乙酸乙烯酯乙烯共聚物分散体是通过由不产生甲醛的氧化还原对系统引发的乳液聚合作用形成的。
12.权利要求1的粘合剂组合物,其中所述共聚物构成99.7重量%至77重量%的非挥发性物质,壳聚糖构成0.2重量%至20重量%的非挥发性物质,所述一种或多种表面活性剂构成0.1重量%至3重量%的非挥发性物质。
13.包含用权利要求1的组合物处理的无纺基材的无纺产品。
14.权利要求13的无纺产品,其中所述无纺基材是干法所制的,并且包含合成纤维和纤维素。
15.权利要求13的无纺产品,其中所述无纺基材是湿法基材。
16.包含无纺基材的无纺湿巾,所述无纺基材用权利要求1的组合物处理,然后用足以提供湿织物的量的含水组合物浸渍。
17.权利要求16的无纺湿巾,其中所述含水组合物是洗液。
18.权利要求16的无纺湿巾,其中所述无纺基材是干法所制的,并且包含合成纤维和纤维素。
19.权利要求16的无纺湿巾,其中所述无纺基材是湿法基材。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103882764A (zh) * 2014-03-12 2014-06-25 金红叶纸业集团有限公司 湿用成膜组合物及其制造方法

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015032726A1 (en) * 2013-09-03 2015-03-12 Celanese Emulsions Gmbh Emulsion polymerization methods
CN114195926A (zh) 2015-12-09 2022-03-18 国际人造丝公司 羧化乙酸乙烯酯/乙烯共聚物分散体及其用途
US20190242055A1 (en) * 2016-03-11 2019-08-08 Georgia-Pacific Nonwovens LLC Blended chitosan-latex binder for high performance nonwoven fabrics
CN110582203B (zh) * 2017-05-03 2022-06-21 瓦克化学股份公司 与非离子结合剂结合的抗微生物非织造湿巾
WO2019097885A1 (ja) * 2017-11-16 2019-05-23 三菱電機株式会社 全熱交換素子および全熱交換器
US20210289778A1 (en) * 2018-12-14 2021-09-23 Wacker Chemie Ag Antimicrobial nonwoven wet wipe bonded with a cationic binder
WO2022122120A1 (de) * 2020-12-08 2022-06-16 Wacker Chemie Ag Textile flächengebilde
WO2024096808A1 (en) 2022-11-03 2024-05-10 Organoclick Ab Biobased binder compositions for nonwoven materials

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000303360A (ja) * 1999-02-08 2000-10-31 Gunze Ltd 消臭繊維及びその製造方法
CN1403163A (zh) * 2002-10-23 2003-03-19 东南大学 可吸收纤维增强多层膜材料及其制备方法
US20040242106A1 (en) * 2003-05-28 2004-12-02 Rabasco John Joseph Nonwoven binders with high wet/dry tensile strength ratio
CN1714186A (zh) * 2002-12-20 2005-12-28 赛拉尼斯国际公司 高湿强度基材粘结剂
US20060052018A1 (en) * 2004-09-07 2006-03-09 Boylan John R Vinyl acetate/ethylene and vinyl chloride polymer blends as binders for nonwoven products

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5030507A (en) * 1990-01-12 1991-07-09 National Starch And Chemical Investment Holding Corporation Formaldehyde-free nonwoven binder composition
JP2788961B2 (ja) * 1990-06-28 1998-08-20 工業技術院長 生分解性不織布
EP0596318B1 (en) * 1992-11-04 1998-09-16 National Starch and Chemical Investment Holding Corporation Emulsion binders containing low residual formaldehyde and having improved tensile strength
US6709709B1 (en) * 1999-02-08 2004-03-23 Gunze Limited Deodorizing fibers and process for producing the same
US7056847B2 (en) * 2002-01-18 2006-06-06 Celanese International Corporation Binder for high wet-strength substrates
US7772138B2 (en) * 2002-05-21 2010-08-10 Kimberly-Clark Worldwide, Inc. Ion sensitive, water-dispersible polymers, a method of making same and items using same
US7153791B2 (en) * 2004-09-07 2006-12-26 Air Products Polymers, L.P. Vinyl acetate/ethylene and ethylene/vinyl chloride blends as binders for nonwoven products
US7485590B2 (en) * 2006-09-29 2009-02-03 Wacker Chemical Corporation Self-crosslinking vinyl acetate-ethylene polymeric binders for nonwoven webs
US7884037B2 (en) * 2006-12-15 2011-02-08 Kimberly-Clark Worldwide, Inc. Wet wipe having a stratified wetting composition therein and process for preparing same
EP1958601A1 (en) * 2007-02-13 2008-08-20 The Procter & Gamble Company Absorbent article comprising an ink composition
US20090035340A1 (en) * 2007-07-30 2009-02-05 Kimberly-Clark Worldwide, Inc. Preservative compositions for moist wipes
US8273414B2 (en) * 2009-03-05 2012-09-25 Wacker Chemical Corporation Phosphate-containing binders for nonwoven goods

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000303360A (ja) * 1999-02-08 2000-10-31 Gunze Ltd 消臭繊維及びその製造方法
CN1403163A (zh) * 2002-10-23 2003-03-19 东南大学 可吸收纤维增强多层膜材料及其制备方法
CN1714186A (zh) * 2002-12-20 2005-12-28 赛拉尼斯国际公司 高湿强度基材粘结剂
US20040242106A1 (en) * 2003-05-28 2004-12-02 Rabasco John Joseph Nonwoven binders with high wet/dry tensile strength ratio
US20060052018A1 (en) * 2004-09-07 2006-03-09 Boylan John R Vinyl acetate/ethylene and vinyl chloride polymer blends as binders for nonwoven products

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103882764A (zh) * 2014-03-12 2014-06-25 金红叶纸业集团有限公司 湿用成膜组合物及其制造方法

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