CN1141984A - 起皱剥离剂 - Google Patents

起皱剥离剂 Download PDF

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CN1141984A
CN1141984A CN96108414A CN96108414A CN1141984A CN 1141984 A CN1141984 A CN 1141984A CN 96108414 A CN96108414 A CN 96108414A CN 96108414 A CN96108414 A CN 96108414A CN 1141984 A CN1141984 A CN 1141984A
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composition
creping adhesives
wrinkling
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A·J·艾伦
G·A·洛克
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Hercules LLC
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Abstract

一种使纤维纸幅起皱的组合物，包括：(1)多胺/表卤醇树脂起皱粘合剂，和(2)作为多胺/表卤醇树脂增塑剂、润胀比至少0.10、溶解度参数大于20MPa1/2的起皱剥离剂。另外还分开了一种使纤维纸幅起皱的方法，其中起皱粘合剂和剥离剂可一起或单独地施加至纤维纸幅用的干燥表面上。

Description

起皱剥离剂
本发明涉及湿抄纸产品的起皱。
在某些湿抄纸产品如搽面纸、浴巾纸或毛巾纸的制造过程中，通常要使纸幅进行起皱，以便使它具有希望的结构特性，如柔软度和松厚度。该起皱过程通常涉及：将纸幅粘着至旋转的起皱烘缸如称为扬克式烘缸的装置上，然后用刮刀刀片将粘着的纸幅取出。纸幅相对于刮刀刀片的冲击使纸幅内的一些纤维对纤维的键破裂，并使纸幅卷曲或起皱。
这种起皱作用的程度取决于许多因素，其中包括纸幅和起皱烘缸表面之间的粘着程度。较大的粘着力能产生增加的柔软度，尽管通常要损失一些强度。为了增加粘着力，使用起皱粘合助剂，以增强该纸幅由于其水份而可能具有的自然产生的粘着作用，该水份将随纸幅预干燥的程度而大大地变化。另外，起皱助剂还将防止对烘缸表面的磨损，提供刮刀刀片和烘缸表面之间的润滑，并减少化学腐蚀，以及控制起皱度。使纸面正合适地粘着至辊筒上的涂层将给出良好的起皱，在能最少地损失纸强度下赋予纸以吸收性和柔软性。如果粘着至干燥辊筒上的粘着作用太强，那么纸页可能会掉毛或甚至于“堵塞”，即在刮刀刀片下重叠并沿干燥辊筒缠绕。如果没有足够的粘着力，那么纸页将太容易剥离，并进行太少的起皱作用。
作为水溶液或水分散体的起皱粘合剂通常被喷淋至起皱烘缸例如扬克式烘缸的表面上。这等改善热传递，并使纸页能更有效的干燥。如果纸浆配料粘着至起皱烘缸太强的话，可将脱模剂喷淋至该烘缸上。通常脱摸剂为烃油。这些脱模剂将帮助薄页纸纸幅在起皱刀片处均匀的剥离，另外还将润滑和保护刀片免于过多的磨损。
在us5187219中公开了一种起皱粘合剂组合物，该组合物会有水溶性的、乙醛酸化的丙烯酰胺/二烯丙基二甲基氯化铵的聚合物，和作为该聚合物增塑剂、分子量低于3000的水溶性多元醇。us5246544公开了一种可以逆交联的起皱粘合剂，该粘合剂含有非自交联的材料和至少一种四价或更高价的金属阳离子交联剂；所述非自交联材料是含有可通过离子交联而交联的官能团的聚合物或低聚物。该粘合剂还可含有改善交联聚合物机械性能的添加剂，例如乙二醇，聚乙二醇，和其它的多无醇如单糖和低聚糖。例如在us5338807和加拿大专利(Ca)979579中披露的那些多酰氨基胺/表氯醇起皱粘合剂通常与烃油一起使用。这些烃油与起皱粘合剂是不相容的，并因此不能在干燥烘缸上形成均匀的涂层。
由于目前用作起皱剥离助剂的烃油与起皱粘合剂不相容，因此需要改进的起皱组合物，特别是供多酰氨基胺/表氯醇起皱粘合剂用的起皱组合物。
用于使纤维幅起皱的本发明的组合物含有(a)多胺/表卤醇树脂起皱粘合剂，和(b)作为多胺/表卤醇树脂的增塑剂、润胀比至少0.10、溶解度参数大于20Mpa1/2的起皱剥离剂。这些剥离剂与起皱粘合剂相容，并可溶于其中。
另外，本发明还公开了一种纤维幅的起皱方法，在该方法中，将上述的起皱粘合剂和剥离剂或者一起或者分开地施加至纤维幅的干燥表面上。
结合使用上述的起皱粘合剂和剥离剂，能够更好地控制起皱方法，即，在控制纸张粘着至干燥表面，和将纸张在起皱刀片处剥离时有更大的灵活性。
任何多胺/表卤醇树脂均可作为起皱粘合剂用于本发明的组合物中。这些起皱粘合剂是表氯醇和多胺树脂的反应产物，多胺树脂例如包括多亚烷基多胺树脂和被称为多酰氨基胺(pAA)树脂的多胺树脂的特殊种类。多亚烷基多胺包括例如二乙三胺和双六亚甲基三胺。例如在us2595935；3248353和3655506中叙述了聚亚烷基多胺/表氯醇树脂的制备。通过至少带一个仲胺基的聚亚烷基多胺与饱和的脂族二羧酸或二羧酸酯反应，制得pAA树脂。例如在us5338807和Ca979579中叙述了多酰氨基胺/表氯醇树脂的制备。这些多胺/表卤醇树脂通常是水溶性的和可交联的。合适的树脂包括KYMENER557H湿强度树脂和CrepetrolR73，80E和190阳离子聚合物，这些均得自Hercules Incorporated(WilMington，DE，usa)。优选多酰氨基胺/表卤醇树脂，特别是表氯醇和由己二酸和甲基双(氨基丙胺)制得的多酰氨基胺及应产物的树脂，表氯醇对聚酰胺中胺基的摩尔比为0.25。
在所选择的特定的多胺/表卤醇起皱粘合剂中，用于本发明组合物中的剥离剂的润胀比至少为0.10，溶解度参数大于20Mpa1/2。取决于所选择的起皱粘合剂和剥离剂的特定组合，润胀比可选择高达18或更高，溶解度参数可选择高达30或更高。通过下述方法测定润胀比和溶解度参数。合适的剥离剂包括例如，数均分子量低于600的脂族多元醇或它们的低聚物，多链烷醇胺，芳族磺酰胺，吡咯烷酮，和它们的混合物。剥离剂的具体例子包括例如乙二醇，丙二醇，二甘醇，甘油，吡咯烷酮，三乙醇胺，二乙醇胺，聚乙二醇，二丙二醇，Uniplex108[得自Unitex Chemical Corporation(Greenville，NC，USA)]的芳族磺酰胺]，以及它们的混合物。优选乙二醇，丙二醇，二甘醇和甘油。最优选的是乙二醇。这些化合物与多胺/表氯醇起皱粘合剂是相容的，并能溶于其中，并且用作该粘合剂的增塑剂。
在实施本发明时所用的起皱粘合剂和剥离剂的相应用量取决于许多因素，例如所用多胺/表卤醇树脂的种类，所抄造的纸张种类，用来造纸的机器条件，所希望的纸张性能和操作条件(例如轻-重起皱，造纸机运行的快慢，以及用作增塑剂的剥离剂的有效性)之间的平衡。这些因素还将对特定造纸体系所选择的起皱粘合剂和剥离剂的优选组合的选择产生影响。以组合物总重量计，剥离剂用量通常在0.01-90％的范围内。
用本发明的组合物通过(1)将上述组合物施加至纤维纸幅的干燥表面上，(2)将纤维纸幅紧压至干燥表面上以使纸幅粘着至干燥表面上，和(3)利用起皱装置，如使纤维纸幅起皱的刮刀刀片从干燥表面上取出纸幅，从而使纤维幅起皱。
另外，可首先施加多胺/表卤醇树脂起皱粘合剂，然后施加剥离剂。也可以在将纸幅紧压至干燥表面上之前，将起皱粘合剂掺入纤维纸幅中。当利用这种方法时，单独地将剥离剂施加至干燥表面上，或将剥离剂加上另外的起皱粘合剂一起施加至干燥表面上。为方便起见，组合物或两种单独的组分通常以水溶液的形式施加。
实施例
为了定量候选增塑剂与起皱粘合剂的相容性，测量在许多增塑剂和溶剂中起皱粘合剂试样的润胀。在加或不加增塑剂的情况下，通过将起皱粘合剂的水溶液置于整个喷有脱模剂的铝盘上而制备流延聚合物薄膜。根据下面的方式在强制热风炉中加热这些铝盘：
35℃4小时
40℃4小时
45℃过夜
第二天，50℃4小时
60℃4小时
80℃过夜
在从铝盘上取出试样之前，通过ASTM法D2240-86测量肖氏A硬度。使用PTC仪(306L型A型硬度计)进行测量。刻度从零(液体的硬度)至100(如玻璃这样的硬表面)。在从盘上取出后，将试样储存在干燥器中以防吸收水份。
称取重量在0.4和0.6g之间的每个薄膜试样，精确至0.0001g，并置于过量(30ml)的候选增塑剂中。使用每种起皱粘合剂/增塑剂组合的三个试样进行这些试验。只是除水以外，在一周内每天对三个试样进行称重。在水中的溶胀在24小时进行测量。在称重前，用镊子操作试样并用薄页纸进行轻拍干燥以除去表面上过量的增塑剂。试样吸收的增塑剂量除以原始试样重量来计算润胀比{Q(t)]。
Q(t)＝[M(t)－M(o)]/M(o)式中M(o)为原始试样重量，M(t)为时间t时润胀试样的重量。
在某些场合，如水和乙二醇的场合，润胀试样碎成许多小片。当发生这种情况时，在标出皮重的钢制筛网漏斗(-50mm直径×50mm高，100目，蒙及尔合金钢)中收集润胀的试样。通过用薄页纸轻拍漏斗底面，除去过量的增塑剂。然后称重润胀的试样。
通过使用装有2100型控制分析器的DuPont910遥控DSC的差示扫描量热仪(DSC)在-100℃-120℃测量玻璃化转变温度(Tg)。在用氮吹洗的开口盘中，以20℃分的扫描频率进行展示。所报告的Tg值为从第二加热循环起呈现的温度。
这些试验的结果列于表1-6中。在表中EG＝乙二醇，PG＝丙二醇，DEG＝二甘醇，GLY＝甘油，PEG-200＝聚乙二醇、数均分子量200，PEG-300＝聚乙二醇、数均分子量300，K-557H＝KymeneR557H湿强度树脂，U-108＝Uniplex 108[得自Unitex Chemical Corporation(Greenville NC，USA)的一种芳族磺酰胺]。起皱粘合剂A是Hercules Incorporated(Wilmington，DE)以商品名Crepetrol R190出售的多酰氨基胺/表氯醇树脂。起皱粘合剂B是HerculesIncorporated以商品名CrepetrolR80E出售的多酰氨基胺/表氯醇树脂。在表3-6中，所添加的增塑剂和最终增塑剂的浓度的百分数均是以起皱粘合剂为准的重量百分数。在试样加热期间损失掉水和一些增塑剂。
                     表1，起皱粘合剂的溶剂润胀
    溶剂 溶解度参数 润胀比Q(150)1
水2甘油吡咯烷酮乙二醇四亚甲基砜3三乙醇胺丙二醇二乙醇胺N，N一二甲基甲酰胺二甘醇1，4一丁二醇U-108异丙醇吗啉三乙二醇二丙二醇聚乙二醇，200MW聚乙二醇，300MW (MPa1/2) K-557H     A     B
    47.933.830.129.927.426.925.825.624.824.824.824.323.522.121.920.5  5.920.5020.2066.100.001630.03990.3060.09500.5901.620.329-0.03180.01711.050.3560.00600.07610.0215  13.91.9414.915.50.07320.67214.00.4320.33317.59.862.380.8060.43510.11.883.250.768  23.10.5380.24712.9-0.02570.3791.360.1610.01931.550.7290.4570.02660.1590.6500.07620.2380.0547
1.Q(150)＝150小时时的润胀比。2.在24小时时测定在水中的润胀。3.该溶剂具有中等的氢键键合值，所有其它溶剂均为良好的氢键键合剂。
                      表2，含有EG和PG的起皱粘合剂组合物
聚合物 添加的增塑剂 最终增塑剂浓度 肖氏A级硬度 Tg(℃)
 K-557HK-557HK-557HK-557HK-557H     无5％EG10％EG5％EG10％EG 1.49％4.48％6.72％7.46％     9488848484     20.0-3.0-12.3-9.2-12.1
    AAAAA     无5％EG10％EG5％EG10％EG 2.27％5.30％2.27％5.30％     6573536453     -0.2-3.8-27.3-0.7-14.7
    BBBBB     无5％EG10％EG5％EG10％EG 2.89％6.14％3.97％7.22％     84    -19.2-18.4-31.8-25.4-29.4
                  表3，含有DEG和GLY的起皱粘合剂组合物
聚合物 添加的增塑剂 最终增塑剂浓度 肖氏A级硬度 Tg(℃)
 K-557HK-557HK-557HK-557HK-557H     无5％DEG10％DEG5％GLY10％GLY 3.76％8.27％3.76％8.27％     9286828483  21.513.310.4-4.0-1.4
    AAAAA     无5％DEG10％DEG5％GLY10％GLY 3.79％6.81％4.55％9.09％     6566536354  -0.2-6.5-19.1-15.9-27.5
    BBBBB     无5％DEG10％DEG5％GLY10％GLY 3.60％7.55％3.60％8.63％     8775758064 -2.3-16.1-19.5-12.1-21.6
                 表4，含有EG和PG的起皱粘合剂组合物
聚合物 添加的增塑剂 最终增塑剂浓度 肖氏A级硬度 Tg(℃)
 K-557HK-557HK-557HK-557HK-557H     无15％EG20％EG15％PG20％PG 8.27％10.5％9.02％11.3％     8667727264     17.80.6-7.4-0.1-5.2
    AAAAA     无15％EG20％EG15％PG20％PG 6.77％6.77％6.02％10.5％     77445837     -4.7-24.4-30.8-23.0-28.0
    BBBBB     无15％EG20％EG15％PG20％pG 7.91％10.4％8.99％11.9％     8250455654      8.7-11.5-21.0-8.9-15.9
                表5，含有DEG和GLY的起皱粘合剂组合物
聚合物 添加的增塑剂 最终增塑剂浓度 肖氏A级硬度  Tg(℃)
 K-557HK-557HK-557HK-557HK-557H     无15％DEG20％DEG15％GLY20％GLY 11.2％14.2％11.9％16.4％     9181778275     14.3-6.9-16.4-3.7-14.8
    AAAAA     无15％DEG20％DEG15％GLY20％GLY 10.6％12.9％12.1％16.7％     8863466464     -18.8-43.4-45.8-40.3-55.0
    BBBBB     无15％DEG20％DEG15％GLY20％GLY 10.8％14.4％12.6％16.2％     9066636555     7.5-6.6-11.9-29.0-37.0
    表6，含有PEG-200和PEG-300的起皱粘合剂组合物
聚合物 添加的增塑剂 最终增塑剂浓度 肖氏A级硬度 Tg(℃)
 K-557HK-557HK-557HK-557HK-557H     无5％PEG-20010％pEG-2005％PEG-30010％PEG-300 5.1％9.5％4.4％10.2％     7468626962 -4.5-11.7-16.0-9.8-14.5
    AAAAA     无5％PEG-20010％PEG-2005％PEG-30010％PEG-300 3.7％6.6％3.7％7.4％     5445353738 -11.5-18.4-22.3-15.0-19.8
    BBBBB     无5％PEG-20010PEG-2005％pEG-30010％PEG-300 4.2％7.7％4.5％7.3％     5758485963 -6.8-11.3-14.8-10.0-15.3
这些增塑剂添加至起皱粘合剂中将导致玻璃化转变温度(Tg)的明显下降，这种下降与所加的增塑剂量成正比。当增加所添加的增塑剂用量时，还将降低这些材料的硬度。这些数据表明，作为增塑剂而进行试验的化合物对于起皱粘合剂是有效的。业已知道，这些增塑剂能降低增塑剂添加至其中的材料的Tg和硬度。
在此，并不打算将这里所给出的例子构成对本发明的限定，这些例子只是用来阐明本发明的某些具体的实施方案。在不脱离所附权利要求范围下，可对本发明作出各种改进和变更。

Claims (17)

1.一种对纤维纸幅进行起皱的组合物，包括(a)多胺/表卤醇树脂起皱粘合剂，和(b)用作多胺/表卤醇树脂增塑剂，润胀比至少0.10，溶解度参数大于20MPa 1/2的至少一种起皱剥离剂。
2.权利要求1的组合物，其中剥离剂选自由数均分子量小于600的脂族多元醇或它们的低聚物，多链烷醇胺，芳族磺酰胺和吡咯烷酮组成的组。
3.前述任一项权利要求的组合物，其中剥离剂选自由乙二醇，丙二醇，二甘醇，甘油，吡咯烷酮，三乙醇胺，二乙醇胺，聚乙二醇，二丙二醇，芳族磺酰胺，以及它们的混合物组成的组。
4.前述任一项权利要求的组合物，其中剥离剂选自由乙二醇，丙二醇，二甘醇和甘油组成的组。
5.前述任一项权利要求的组合物，其中剥离剂为乙二醇。
6.前述任一项权利要求的组合物，其中起皱粘合剂为聚亚烷基多胺/表卤醇树脂。
7.前述任一项权利要求的组合物，其中起皱粘合剂为多酰氨基胺/表卤醇树脂。
8.权利要求7的组合物，其中多酰氨基胺为聚亚烷基多胺和饱和脂族二羧酸或酸的衍生物的反应产物。
9.权利要求7和8的组合物，其中多酰氨基胺是己二酸和甲基双(氨基丙胺)的反应产物，起皱粘合剂含有：每摩尔多酰氨基胺中的胺基0.25摩尔的表氯醇。
10.前述任一项权利要求的组合物，其中表卤醇为表氯醇。
11.前述任一项权利要求的组合物，其中，以剥离剂和起皱粘合剂总重量计，剥离剂用量为0.01-90％重量。
12.一种使纤维纸幅进行起皱的方法，包括：(1)将前述任一项权利要求的组合物施加至纤维纸幅用的干燥表面上，(2)将该纤维纸幅紧压至干燥表面，以使纸幅粘着至干燥表面上，和(3)利用起皱装置，从干燥表面移位纸幅使纤维纸幅起皱。
13.权利要求12的方法，其中起皱粘合剂和起皱剥离剂以水溶液的形式施加。
14.权利要求12和13的方法，其中起皱粘合剂在剥离剂施加之前施加至干燥表面上。
15.权利要求12和13的方法，其中起皱粘合剂作为纤维纸幅的组分施加至干燥表面上。
16.权利要求12-15的方法，其中纤维纸幅为纤维素纤维纸幅。
17.一种由权利要求12-16的方法制得的皱纹纸。
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