CN115768842A - 用于涂覆植物鞣制皮革的方法 - Google Patents

用于涂覆植物鞣制皮革的方法 Download PDF

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CN115768842A
CN115768842A CN202180045690.0A CN202180045690A CN115768842A CN 115768842 A CN115768842 A CN 115768842A CN 202180045690 A CN202180045690 A CN 202180045690A CN 115768842 A CN115768842 A CN 115768842A
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leather
vegetable
leather sheet
coating layer
tanned leather
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CN115768842B (zh
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马尔科·托斯卡诺
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Jorino Technology Co ltd
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Abstract

一种用于涂覆植物鞣制皮革的方法，该方法包括以下步骤：将由聚氨酯树脂的水分散体构成的涂覆层(C)沉积在具有防粘性质的载体(R)上，将该涂覆层(C)固化在该载体(R)上，将由聚氨酯树脂的水分散体构成的粘合剂层(A)沉积到固化的涂覆层(C)上，放置皮革片(P)以与粘合剂层(A)接触，该皮革是植物鞣制皮革片，在连续烤炉(44)中，固化粘合剂层(A)以将皮革片(P)附接到涂覆层(C)，以及从该载体(R)移除经涂覆的皮革片(P)，其中，在连续烤炉(44)内，皮革片(P)达到介于65℃与75℃之间的最高温度，其中在烤炉中的停留时间介于180秒与210秒之间。

Description

用于涂覆植物鞣制皮革的方法
本发明涉及一种用于涂覆植物鞣制皮革(vegetable-tanned leather)的方法。
鉴于对具有低环境影响的产品的日益增长的市场需求，有一种趋势是使用可持续鞣制体系(诸如，无铬或无金属鞣制)在皮革上施加各种膜涂饰剂(film finish)。
因此决定将保护性膜涂饰剂和可能的美学涂饰剂施加到源自最生态可持续的鞣制体系的基材上：植物鞣制。
来自植物鞣制的皮革经过一种工艺，在这种工艺中，所谓的鞣剂是单宁(tannin)，是专门从植物来源(诸如栗子(chestnut)或桦木(birch wood)或白坚木(quebracho)、五倍子(gall nuts)、塔拉豆荚(Tara pod)等)提取的天然提取物。
一方面，植物鞣制赋予皮革“自然”的外观，这是市场非常喜欢的；然而，另一方面，它对鞣制工艺的本质存在一些固有的限制，例如：非常低的化学-物理强度性质，其低于市场的平均要求；广泛且非常频繁的表面缺陷，因此这使得切削产量非常低；或者甚至是外观的再现性大规模降低。因此，这是一种非常昂贵并且主要在工匠规模上可用的备受关注的皮革。
因此，需要制造一种工业产品，该工业产品保持典型的工匠价值，同时增加物理机械性能，并且确定产生的所制造的产品的更大耐久性。
在这方面，从申请人自己的文件IT TO 950 145A1中已知一种涂覆皮革的方法，该方法包括以下步骤：
将由聚氨酯树脂和溶剂的混合物构成的涂覆层沉积在具有剥离性质的载体(support)上，
允许涂覆层在载体上固化，
将由聚氨酯树脂和溶剂的混合物构成的粘合剂层沉积在固化的涂覆层上，
放置皮革片以与粘合剂层接触，
在连续烤炉(continuous oven)中，允许粘合剂层固化，以将皮革片结合到涂覆层，以及
将涂覆的皮革片从载体分离。
IT TO 950 145A1中所描述的方法是为矿物鞣制皮革(mineral-tannedleather)、特别是铬鞣制皮革而设计的。因此，该方法不适合于植物鞣制皮革。实际上，植物鞣制由于使用单宁来源的鞣剂，赋予皮革对于热应力有限的稳定性。因此，任何将植物皮革暴露于主要热源的涂饰方法都会导致所述皮革的劣化，这损害了植物皮革随时间的稳定性，甚至损害了其在制造的产品的生产中的用途。
温度对皮革的影响的最直接的后果之一是，在没有达到更严重的劣化水平的情况下，通过颜色的明显变化来证明，实际上可以通过由于水分含量的损失导致的纤维的自然收缩来识别。
本发明的目的是提供一种用于涂饰植物鞣制皮革的方法。
因此，本发明涉及一种用于涂覆植物鞣制皮革的方法，该方法包括以下步骤：
使用粒度(grit size)在80与600FEPA单位之间的纸对植物鞣制皮革片(vegetable-tanned leather piece)进行抛光操作(buffing operation)，
将由聚氨酯树脂的水分散体(aqueous dispersion of polyurethane resin)构成的涂覆层沉积在具有防粘性质的支承剥离纸(support release paper)上，所述支承剥离纸具有预定的进送速率，
将涂覆层固化在支承剥离纸上，
将由水性聚氨酯树脂分散体构成的粘合剂层沉积在固化的涂覆层上，
放置所述皮革片以与粘合剂层接触，
在连续烤炉中，固化粘合剂层，以将皮革片结合到涂覆层，以及
将涂覆的皮革片从支承剥离纸移除，
其中，调节所述支承剥离纸的进送速率，由此所述皮革片在所述连续烤炉中具有介于180秒与210秒之间的停留时间，并且调节所述连续烤炉，由此所述皮革片达到65℃与75℃之间的最高温度。
申请人已经发现，采用上述方法，可以以最佳方式涂饰植物皮革，从而保持植物皮革独特的特性，并且同时赋予植物皮革机械强度和工业再现性的优异性能。
根据本发明的方法的进一步的特征和优点将从以下对本发明的实施方案的详细描述变得显而易见，该实施方案是参照附图的并且被提供仅用于说明性和非限制性目的，在附图中：
-图1a、图1b、图1c、图1d共同表示用于涂覆皮革的已知设备的示意性侧视图，其中，根据本发明的方法的实施从图1a的左侧开始并在图1d的右侧结束；
-图2至图5是局部示意性截面图，具有非常夸大的厚度，展示了施加皮革片的层到支承条带的连续阶段；
-图6为从图1c中VI所示的设备区域的放大比例的俯视平面示意图；
-图7为图6中所示设备区域的示意性侧视图；
-图8是图1d中所展示的剥离工位(stripping station)的局部竖直示意性截面图；以及
-图9为示出了对于不同温度值，皮革收缩率随连续烤炉中停留时间变化的实验曲线的图表。
现在将描述根据本发明的方法，该方法从图1a中左侧的设备的起点处开始，到图1d中右侧的设备结束。
在这些图中，主要旋转部件的旋转方向由弧形的、未参引的箭头表示。
下面描述的设备和方法可以获得覆盖有涂覆层的植物鞣制皮革，该涂覆层通过粘合剂层联接到皮革片。植物鞣制皮革通常被定义为用植物单宁鞣制的皮革。
涂层(包括涂覆层和粘合剂层)由水系聚氨酯树脂(water-based polyurethaneresin)制成。例如，这种树脂可以是具有20％至98％范围的干百分比的脂肪族(aliphatic)或芳香族聚氨酯(aromatic polyurethane)、聚醚系(polyether-based)或聚酯系(polyester-based)的树脂。在粘合剂基材的情况下，基于干百分比为30％至50％的聚醚，使用脂肪族或芳香族性质的水相中的聚氨酯树脂。
优选地，涂层包含水系、生物系脂肪族或芳香族聚氨酯树脂，其具有百分比范围为40％至90％的源自可再生来源的多元醇。它们分散在水相中，使用温度范围为60℃至160℃。
涂饰基材(涂覆层加上粘合剂层)的总重量为50g/m2至140g/m2，其中粘合剂部分为15g/m2至50g/m2。
由于覆盖皮革的膜具有热塑性，因此成品皮革随后可以再加工，也可以通过热冲压等来增强或改善皮革的美学性质。
组成膜的层可以是无色的或着色的，以赋予皮革不同于天然颜色的所需颜色。
支承条带R在所述设备中运行，该设备在由若干未参引的线性箭头指示的方向上延伸。
条带R由具有剥离性质的材料制成，并且优选地由本领域技术人员称为“剥离纸”的强力纸条带构成。
条带R从进送滚筒10展开，穿过缓冲器12，并到达第一涂覆工位14。如图2所示，在该第一工位14处，由聚氨酯树脂的水分散体构成的第一涂覆层C1或所谓的“预表皮”涂层被施加到条带R。
然后，条带R穿过第一连续干燥烤炉16，在此处，层C1进行固化。
在烤炉16的出口处，条带R穿过牵引单元17，然后穿过处理工位18。该工位18可以用作附加的涂覆工位或用作涂饰工位，以赋予第一涂覆层C1图案或颜色效果。
然后，涂覆带子穿过第二干燥烤炉20，第二干燥烤炉仅在相同材料的后续层(未示出)已经被施加到层C1时使用。
在第二烤炉20的出口处，条带穿过牵引单元21，然后穿过另一个涂覆工位22，如图3所示，在该涂覆工位处，与第一层C1具有类似组成的第二涂覆层C2被施加在第一干燥涂覆层C1上。
如图3所示，涂覆的条带然后进入第三连续干燥烤炉24，该第三连续干燥烤炉具有与第一烤炉16基本相同的特征。
在烤炉24的出口处，如图4中的C所示，具有相同性质的两个干燥层C1和C2实际上熔合在一起，以形成皮革件的最终涂层，如稍后将会看到。
在第二烤炉20的出口处，携带有完全干燥的涂覆层C的条带R穿过牵引单元25，然后穿过最终涂覆工位26，在该最终涂覆工位处，粘合剂A层以流体状态施加到层C，该粘合剂由聚氨酯树脂的水分散体组成。
必要时，如果与第二阶段相同的第三涂覆阶段C3可用并安装以补充体系(未示出)，则可以使用该第三涂覆阶段。涂层厚度的规格和工艺操作与层C2的生产相同。
当层A的粘合剂仍然是流体或软化的时，条带穿过联接工位28，也在图6中可见。
联接工位主要包括平台30，涂覆的条带R在该平台上滑动。
当经涂覆的条带滑离台30时，操作者或专用机器(未示出)将连续的皮革片P施加到粘合剂层A，使粒面(grain side)或肉面(flesh side)与所述粘合剂接触。所述皮革片P预先用粒度在80至600FEPA(Fédération Européenne des Fabricants de ProduitsAbrasifs，欧洲磨料生产商联合会)单位的纸进行抛光操作，并且优选地还进行了拉软操作(staking operation)，拉软操作可以根据皮革的手感和待完成的制品的类型包括一至四个循环。上述方法有助于准备皮革片用于与涂层粘合。
在台30的下游，该条带穿过压延工位(calendering station)32，该压延工位用于施加压力以将皮革片P粘附在粘合剂层A上。
在所示的情况下，如图7可以看见的，压延工位32包括从滚筒36展开并回绕到滚筒38上的纸条带34。
条带34与多个联接层R、C、A、P一起在成对的机动化压力辊40和42之间通过。
替代地，压延工位可以简单地包括一对或多对压力辊。
特别地，在压延工位32的入口处的成对的机动化压力辊40优选地包括具有例如由钢制成的高硬度表面的辊和具有例如由弹性材料制成的较低硬度表面的相对辊，以使条带R附带有联接层，从而避免形成折痕或缺陷。
一旦皮革片P已经在压延工位牢固地粘附在粘合剂层A，复合条带R、C、A、P就穿过最后的连续干燥烤炉44，在该干燥烤炉中，层A的粘合剂发生固结或固化。
虽然前面的烤炉16、20、24的条件并不严格，但是干燥烤炉44必须满足相当严格的条件，现在将对这些条件进行详细说明。这些条件如下面所述根据实验来确定。
为了固化层A的粘合剂，使热空气在烤炉44中循环，由此皮革P的温度不超过75℃，并且暴露于该温度的时间在180秒与210秒之间。在烤炉长度为17m的情况下，这意味着条带的进送速率在大约4.9m/min与大约5.5m/min之间。
在烤炉44的出口处，由于粘合剂的固化，皮革片P胶合在其上的复合条带R、C、A、P穿过牵引单元46，并且到达分离工位48，如图8中所示。
在分离工位48中，进入的复合条带首先经过辊50，在辊处，由涂层C、粘合剂A和皮革片P形成的层地组合从支承条带R上分离。支承条带R继续水平运动，直到它最终缠绕在重绕滚筒52上(图1d)而被回收。
另一方面，层C、A、P的组合在环形带式输送机52上竖直地连续。
沿着竖直路径，相继的皮革片再次通过由涂层C和粘合剂A的层形成的薄膜接合在一起，如图8中的F所示。
在输送带52的循环路径的顶部，所述输送带经过返回滚筒54，而由皮革片P和膜F构成的条带从所述条带分离，例如由操作者A分离。在拉动皮革片P后，使皮革片互连的膜F裂开，并且涂覆的皮革片可以被一个接一个地拾取和堆叠，并从设备中取出。
实验部分
如上所述，温度对皮革的影响的最直接后果之一是，由于水分含量的损失而导致的纤维的自然收缩。本发明人使用该参数评估植物皮革在热处理后的稳定性，得到确定0.5％的皮革最大收缩率的最佳热应力窗口，该最大收缩率被确定为热收缩率的最大极限，以免于遭受内在降解，从而丧失稳定性和独特的手感特征以及成品的再现性。
为了确定该方法是适用于植物鞣制的最佳方法，执行了许多尺寸稳定性试验。主要变量是涂覆带的温度和速度，然后，一旦设定烤炉的长度(对于手边的样品为17延米)，则主要变量为皮革的暴露时间。
这项研究是通过用接触式温度计进行测量而直接地检测皮革上的温度来进行的，由于所述皮革的加热过程的热惯性，这些温度自然低于烤炉的温度。鉴于所用皮革片的厚度非常低(小于2mm)，由所述皮革片内部的热扩散确定的效果被认为是可忽略不计的。
可变的带速导致在烤炉中停留时间不同，这些停留时间是根据在皮革片上测量的温度和检查的皮革的收缩百分比值(percent shrinkage value)进行插值得到的。
作为指示，下表显示了在60秒与240秒之间的停留时间间隔内，在皮革上测量的一些温度作为烤炉温度的函数。
表1
烤炉中的温度 皮革片上检测到的温度
80℃ 60℃-65℃
90℃ 68℃-76℃
100℃ 77℃-88℃
130℃ 93℃-100℃
160℃ 127℃-140℃
然后在不同的烤炉温度下进行许多测试，改变皮革的停留时间，并确定所得的平均收缩百分比。下面是对应于80℃与160℃之间的设定温度范围的一些测量值。
表2
Figure BDA0004018281710000071
应当注意的是，皮革的收缩百分比通过增加停留时间而显著变化，显示了对降解过程的参考参数的恶化的甚至三倍的影响。同时，由于多头涂覆工艺固有的原因，停留时间不能太短，这实际上提供了在恒定的带速度下相对于每个阶段对膜沉积和固化的最佳和伴随的调节。因此，必须找到停留时间与皮革在烤炉中所经受的温度之间的理想折衷。
图9的图表中概括地示意了优化过程。收缩率为0.5％的水平线所对的区域表示植物皮革内在稳定的区域。所报道的测试在80℃至160℃的温度范围内进行。停留时间(带速度的函数)在一分钟与四分钟之间(60秒-240秒)调节。在每个预设温度下，随着带速度的变化，测量植物皮革的收缩百分比。应当注意的是，一旦设定了特定的烤炉温度并且增加了停留时间，皮革的收缩百分比(P)显著增加，直到确定的值超过0.5％的阈值极限，该收缩百分比与在同一皮革中引起的不稳定性成正比。还应注意的是，在烤炉温度高于90℃时，对应于皮革上的温度高达75℃，收缩百分比曲线几乎立即超过0.5％的值，从而导致皮革上产生不稳定性的情况。因此，可以确定的是，植物皮革在生产周期期间在与整个涂覆过程相适应的速度(设定在4.9米/分钟至5.5米/分钟的范围内)下可能经受的最高温度是90℃。在较低温度(例如80℃，对应于在皮革上测量的最高温度为65℃)下的加工周期可以允许停留时间甚至高于180秒-210秒，这不利于生产率和优化层C1、C2、C3和A的硫化过程。

Claims (3)

1.一种用于涂覆植物鞣制皮革的方法，所述方法包括以下步骤：
用粒度介于80与600FEPA单位之间的纸抛光植物鞣制皮革片(P)，
将由聚氨酯树脂的水分散体构成的涂覆层(C)沉积到具有防粘性质的支承剥离纸(R)上，所述支承剥离纸具有预定的进送速率，
将所述涂覆层(C)固化在所述支承剥离纸(R)上，
将由聚氨酯树脂的水分散体构成的粘合剂层(A)沉积到固化的所述涂覆层(C)上，
放置所述植物鞣制皮革片(P)以与所述粘合剂层(A)接触，
在连续烤炉(44)中，固化所述粘合剂层(A)，以将所述植物鞣制皮革片(P)结合到所述涂覆层(C)，以及
从所述支承剥离纸(R)移除经涂覆的所述皮革片(P)，
其中，调节所述支承剥离纸(R)的进送速率，由此所述植物鞣制皮革片(P)在所述连续烤炉(44)中具有介于180秒与210秒之间的停留时间，并且调节所述连续烤炉(44)，由此所述植物鞣制皮革片(P)达到介于65℃与75℃之间的最高温度。
2.根据权利要求2所述的方法，其中，所述植物鞣制皮革片在被施加到所述粘合剂层(A)上之前进行拉软操作。
3.根据权利要求1或2所述的方法，其中，所述涂覆层(C)的聚氨酯树脂和所述粘合剂层(A)的聚氨酯树脂是源自可再生来源的、重量百分比范围为40％至90％的脂肪族或芳香族聚醚系聚氨酯树脂。
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CN101724719A (zh) * 2009-09-14 2010-06-09 陕西科技大学 一种无金属鞣制山羊皮服装革的鞣制方法
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CN110628966A (zh) * 2019-10-08 2019-12-31 浙江合力革业有限公司 一种透气皮革的制作工艺

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