CN1141089A - 橡胶改性热塑性塑料的静电调色剂接受层 - Google Patents

橡胶改性热塑性塑料的静电调色剂接受层 Download PDF

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CN1141089A
CN1141089A CN94194777A CN94194777A CN1141089A CN 1141089 A CN1141089 A CN 1141089A CN 94194777 A CN94194777 A CN 94194777A CN 94194777 A CN94194777 A CN 94194777A CN 1141089 A CN1141089 A CN 1141089A
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R·S·斯蒂尔曼
E·J·汉森
J·珍妮特
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Abstract

一种包含丙烯酸树脂，乙烯基树脂，溶液或分散体级橡胶和增塑剂的混合物的静电调色剂接受层。当将所得的接受层施加在抗龟裂膜上，并随后应用于软侧面交通工具时，所述的接受层能提供耐久性和柔韧性。

Description

橡胶改性热塑性塑料的静电调色剂接受层
技术领域
本发明涉及一种静电调色剂接受层，更具体地是涉及一种含橡胶改性热塑性塑料的接受层。
本发明的背景
以前，高质量的图形限于大批量以降低费用，或是小批量而成本高昂。随着Scotchprint图形的出现，可以用能承受的成本制造数量有限的高质量的图形。而且，Scotchcal 8620和8640接受体涂层膜允许对数量有限刚性表面使用这种高质量的图形。这些标记膜包含乙烯膜基，该膜基面涂有含丙烯酸共聚物，乙烯基氯/乙酸乙烯酯共聚物和增塑剂的溶剂热塑性混合物。该表面涂层是在室温下中等柔韧性的无粘性的固体。高于70℃时，热塑性塑料熔融并粘合至先前印刷到转移介质上的静电调色剂上。冷却后，标记膜可从转移介质上分离出来，而调色剂被标记膜保留。
理想化地，热塑性塑料层(1)很好地粘合在基膜上，(2)不会粘附到转移介质上未上色(未形成图象)的区域，(3)不会破坏基膜的物理性质(张力，伸长率，颜色等)，(4)完好地粘合至调色剂上，允许从转移介质上去除调色剂而不允许在通常使用过程中去除调色剂，(5)在通常使用过程中无粘性，和(6)与附加操作如透明涂覆或预掩蔽是相容的。
然而，连续的挠曲表面(例如在世界上大部分地区普遍使用的具有增塑聚氯乙烯涂层织物侧面的运输工具和交通工具)对接受体涂层膜来说是一个问题。增塑聚氯乙烯涂层织物典型地为一种在板壁(siding)使用期过程中多次挠曲，滚压，拍打和冷挠曲的热塑性材料。因此，任何粘合或以其它方式粘附在这种板壁上的图形图象必须能经得起同等的应力而不损坏。
本发明的概述
简言之，本发明的一个方面，接受层包含涂覆在抗龟裂压敏粘合剂背衬膜上的丙烯酸树脂，乙烯基树脂，溶液或分散体级橡胶和增塑剂的混合物。简单地讲，现在的接受层允许Scotchprint图形施加在增塑聚氯乙烯涂层织物上以在软侧面(soft-sided)交通工具上使用。
有利地，最终的图形图象制品，即施加在增塑聚氯乙烯涂层织物板壁上的在抗龟裂压敏粘合剂背衬膜上的已形成图象的接受层，与任何合适的保护透明涂层一起将经得住在软侧面交通工具上，尤其是在低温下所发生的极端环境应力，而这在目前的Scotchprint材料是无法经受得起的。较好实例的描述
正如在美国专利No.5,114,520和5,262,259中所述，图象通常由先前已印刷到转移介质上的热粘合静电调色剂施加到本发明的接受层上，这些描述在此引用结合在本发明中。冷却后，接受体涂层标记膜可从转移介质上分离，而调色剂则由接受体涂层标记膜保留。
较可取地，最终的图形图象制品经得住下述试验：
(1)涂层粘合性试验；和
(2)在-20℃时抗龟裂试验。
当最终的图形图象制品由多于一块的板组成(例如含有重叠接缝的并列板或一块板部分或全部粘合在另一块板上)时，则最终的图形图象制品最好能经得住下述附加试验：(3)一层形成图象的膜与下一层形成图象的膜的重叠粘合性。将“板”定义为在抗龟裂压敏粘合剂背衬膜上的形成图象接受层的片，它可包含或不包含合适的保护透明涂层。
将“涂层粘合性”定义为在水中浸渍16小时之后，从水中取出并用毛巾擦干后即刻对样品进行试验，达到由ASTM试验D3359，试验方法B的4B或5B额定值。将“抗龟裂”定义为在反复挠曲后，较好地按DIN 53359试验B在-20℃下在挠曲试验机上操作4000次双挠曲后对表面的最小限度损害。除了被试验的形成图象膜粘合至已粘合到PVC一涂层织物基材上同样的形成图象膜部分上外，“重叠”粘合性按ASTM D1000确定。在试验前，将这种多层复合物(即至少两块板相互重叠)在65℃下老化至少16小时。对所有颜色和未上色部分该重叠粘合性较好地为每英寸宽至少1.0磅。
含氨基甲酸乙酯基层的标记膜(例如Scotchcal 190标记膜)是用于增塑的聚氯乙烯涂层织物的。尽管氨基甲酸乙酯为基的膜具有显著的抗龟裂，抗增塑剂和耐湿性，但标准Scotchprint接受体涂层不能在氨基甲酸乙酯为基或其它抗龟裂标记膜上加工。
当将用于常规乙烯基氯为基的标记膜的静电调色剂接受体涂层施加在用于标记软侧面交通工具的抗龟裂膜上时，这种涂层膜不符合抗龟裂标准且通常不符合涂层粘合性标准。然而，当抗龟裂膜(例如氨基甲酸乙酯为基的膜)涂有本发明的接受体时，涂层膜基本上保持了基膜在不含这种涂层的情况下的所有性质，而且更重要的是该涂层膜符合上述性能指标。对由调色剂转移形成图象来说，使用不含任何接受体涂层的氨基甲酸乙酯为基的膜通常是不能接受的，原因是热层压导致无法从未上色区域松脱和在上色区域上差的重叠粘合性。
众所周知热塑性涂层的柔韧性可通过加入增塑剂得以提高。室温下用于乙烯基膜的涂层的柔韧性部分可归功于增塑剂。提高增塑剂的用量已显示出改进了抗低温龟裂。然而，随着增塑剂含量更高，尤其是在含丙烯酸的涂层中，那么在通常处置温度下表面会变得发粘。这种表面发粘会引起处理困难，污垢沉积，较小的耐磨性，较差的内部强度，图象脱层和辊堵塞等问题。
大家知道的柔韧的聚氯乙烯基材典型地包含高含量(每一百份树脂中60-100份)的单体增塑剂。这种单体增塑剂趋于迁移到任何粘合在表面的图形标记膜上，这样导致与加入过量增塑剂相同类型的问题。
亦已发现涂覆在氨基甲酸乙酯为基的膜上的包含丙烯酸树脂，乙烯基树脂，溶液或分散体级橡胶和增塑剂的混合物的接受体涂层组合物将符合性能指标，同时最大程度地降低增塑剂在通常处置温度下的影响。较为可取的是，接受体涂层组合物含至少5％—55％的溶液或分散体级别橡胶，含7％—30％的溶液或分散体级别橡胶则更好。在此范围内所得的印刷图形符合抗龟裂指标。
一旦静电调色剂接受体涂层被施加到抗龟裂膜上，调色剂图象可被热转移至该接受层上。然后可由本领域技术熟练者已知的技术，例如筛网印刷透明涂层或淹没涂覆(flood coating)透明涂层，施加耐磨涂层，保护层或透明涂层。
而且，亦已发现如在转让给本申请相同受让人的Attorney Docket No.49516 USA 4A中所述，加入图形外层复合物(与保护层相邻的预掩蔽层)可提高最终图形图象板的重叠粘合性。
用于图象接受体涂层的特别有用的丙烯酸树脂包括甲基丙烯酸甲酯聚合物和共聚物，例如可购自Rohm & Haas的Acryloids B-44和B-48，和甲基丙烯酸甲酯/丙烯酸乙酯/N-叔丁基丙烯酰胺。用于图象接受体涂层的特别有用的乙烯基树脂包括乙烯基氯/乙酸乙烯酯共聚物，例如以商品名为“UCAR”购自Union Carbide的共聚物。任何分散体或溶液级橡胶都可用于本发明，其合适的例子包括但不局限于溶液氯化橡胶(例如以商品名为Hydrin CG购自ZeonChemicals的表氯醇)和氨基甲酸乙酯分散体橡胶(例如购自Zeneca Chemical的NeoPac R-9000)。
本发明的目的和优点将进一步地由下述实施例加以阐述，但不应将在这些实施例中所述的具体的物料及其量，以及其它条件和细节看作是对本发明的过分限制。除非另有阐明或是显而易见的，所有的物料都是可商品购得或对本领域的技术熟练者来说是已知的。
材料名称汇编
    A11 以商品名“Acryloid A-11”购自Rohm & Haas的甲基丙烯酸甲酯聚合物
    B44 购自Rohm & Haas的甲基丙烯酸甲酯共聚物
Aromatic 150 购自Exxon Chemical标记的闭杯闪点为150℃，含98％C8＋芳香族化合物的石脑油芳香溶剂
 Hydrin CG70橡胶 购自Zeon Chemicals的溶液表氯醇橡胶
MMA/EA/t-BAM三元聚合物 甲基丙烯酸甲酯(CAS#80-62-6)/丙烯酸乙酯(CAS#140-88-5)/N-叔丁基丙烯酰胺；比率为55/20/25，在MEK中有40.88％固体，在60rpm LV4下的Brookfield粘度为7120cps.，Mw为186，326，多分散性，Mw/Mn＝3.7479(以一批为基准)。各单体购自Aldrich Chemical。
    NeoPacR-9000 购自Zeneca，Sward硬度为36且自由膜伸长率为620％的脂族聚氨酯-丙烯酸胶乳共聚物分散体橡胶
 Palatinol 711-9 购自BASF的C7-11邻苯二甲酸酯增塑剂
   UCAR 525 购自Union Carbide的54％固体丙烯酸-乙烯基氯改性胶乳
  Uniflex 312 购自Union Camp的增塑剂
VAGH 以商品名“UCAR VAGH”购自Union Carbide的羟基官能团乙烯基氯/乙酸乙烯酯三元聚合物
VYES 以商品名“UCAR VYES”购自Union Carbide的羟基官能团乙烯基氯/乙酸乙烯酯三元聚合物
    VYHH 以商品名“UCAR VYHH”购自Union Carbide的乙烯基氯/乙酸乙烯酯共聚物
VYNC 以商品名“UCAR VYNC”购自Union Carbide的乙烯基氯/乙酸乙烯酯共聚物，供应时在乙酸异丙酯中有40％固体。
                 乙烯基树脂特性
树脂 乙烯基氯     乙酸乙烯酯 羟基   固有粘度1 Tg(℃)   平均Mw
 VAGH    90％     4％    2.3％     0.53     79  23,000
 VYES    67％     11％    3.0％     0.15     40  4,000
 VYHH    86％     14％     0％     0.50     72  20,000
 VYNC    60％     32％     0％     0.32     51  12,000
       (1)ASTM D-1243
       丙烯酸聚合物特性
 丙烯酸  TG(℃)  硬度(KHN)     化学组成
  A-11   100   18-19    MMA聚合物
  B-44    60   15-16    MMA共聚物
                     实施例实施例1
将概括于表1的量的组分进行混和制备接受体涂层。然后将这种混合物涂覆到主要组分比率为33/41/26的二氧化钛，Zeneca Chemicals R-9000和Zeneca Chemicals R-962的带有压敏粘合剂背衬的膜上。接受层的涂层重量为19.4g/m2。使这种涂层膜形成图象并通过涂层粘合性和抗龟裂试验。
                         表1所用的量(磅)                             组分
11.49                        MMA/EA/t-BAM三元聚合物
37.97                              甲乙酮(MEK)
14.65                                 甲苯
13.80                                 VYNC
5.52                                  VYHH
5.17                            Hydrin CG 70橡胶
11.40                           Palatinol 711-9实施例2
将概括于表2的量的组分进行混和制备接受体涂层。然后将这种混合物涂覆到主要组分比率为33/45/22的二氧化钛，Miles Bayhydrol 123和ZenecaChemicals R-9000的压敏粘合剂膜上。接受层的涂层重量为19.4g/m2。将这种涂层膜形成图象并通过涂层粘合性和抗龟裂试验。表5概括了Zeneca和Miles产品的膜性能。
                       表2所用的量(磅)                              组分
4.28                             Rohm & Haas B-44
52.75                             甲乙酮(MEK)
10.32                                 甲苯
12.56                                 VYNC
5.02                                  VYHH
4.70                             Hydrin CG 70橡胶
10.37                            Palatinol 711-P实施例3
透明涂层/预掩蔽层是这样制备的：先用主要由表3所述配方组成的一层、而后用表4中所述的一层涂覆在其两面含有高密度聚乙烯(在其光泽一面为13磅和在其粗糙一面为11磅，购自HP Smith)、基重为94磅/令(3000平方英尺)的纸质预掩蔽背衬上。涂覆第一层获得的干涂层重量为4.5g/m2。涂覆第二层获得的干涂层重量为10.3g/m2。
                        表3所用的量(磅)                          组分
19.5                           Acryloid A-11
60.0                               MEK
4.9                               VAGH
13.4                           Uniflex 312
                        表4所用的量(磅)                         组分
10.0                              VYES
42.7                              MEK
38.2                              甲苯
6.1                           Hydrin CG 70橡胶
3.3                           Palatinol 711-P
表5膜组分的物理性能
    产品 NeoPac R-9000  NeoRez R-962  Bayhydrol 123
张力(psi)     4000     3500     5000
伸长率(％)     620     800     350
100％模量(psi)     2000     900     800
将实施例2的材料(带有由脱卸衬里保护的压敏粘合剂层)与上述预掩蔽层/透明涂层相接触，并通过下述的热辊层压操作：一个9”钢辊，一个肖氏D硬度为58的9″橡胶辊，辊隙压力为55磅/线英寸以及速度为46厘米/分。所得的复合物通过下述过程粘合到柔韧的聚氯乙烯涂层织物上，(1)除去保护压敏粘合剂的衬里，(2)使粘合剂与聚氯乙烯涂层织物接触，(3)将压敏粘合剂紧密地压紧聚氯乙烯涂层织物使图形粘合到柔韧的聚氯乙烯涂层织物上，和(4)除去预掩蔽背衬，将带有透明涂层的最终图形留在柔韧的聚氯乙烯涂层织物上。使这种涂层膜形成图象并进行试验，符合三个性能指标。实施例4
先用主要由表3所述配方组成的一层、而后用表4中所述的一层涂覆2密尔的聚酯预掩蔽背衬。涂覆第一层获得的干涂层重量为4.5g/m2。涂覆第二层获得的干涂层重量为10.3g/m2。如实施例3中所述对物料进行层压，并如实施例1中所述对之进行试验。使这种涂层膜形成图象并进行试验，符合三个性能指标。实施例5
将概括于表6的量的组分进行混和制备接受体涂层。然后将这种混合物涂覆到主要组分比率为33/41/26的二氧化钛，Zeneca Chemicals R-9000和Zeneca Chemicals R-962的带有压敏粘合剂背衬的膜上。接受层的涂层重量为19.4g/m2。使这种涂层膜形成图象并进行试验，符合三个性能指标。
                      表6所用的量(磅)                              组分
79.5                                UCAR 525
10.0                               NeoPac R-9000
10.0                                Uniflex 312
0.5                        乙二醇氧基丙基三甲氧基硅烷
使用230筛目的筛网对涂层制品进行透明涂层筛网印刷，使之通过单次涂覆，然后在150°F下烘箱干燥10分钟。透明涂层组合物用环己酮稀释至粘度值为700厘泊，用Brookfied粘度计，LV-2，RPM-60测量。透明涂层主要由下述组分组成：
                   表7所用的量(磅)                           组分
21.7                                环己酮
17.6                            乙氧基丙酸乙酯
9.5                             纤维素乙酸丁酯
12.2                              Aromatic 150
20.1                                 A-11
5.1                                  VAGH
13.8                              Uniflex 312
在不偏离本发明的范围和原则的基础上本发明的各种改进和改变对本领域技术熟练者来说将是显而易见的，而且应明白的是本发明并不局限于上面列举的实例。在此参考引用所有的出版物和专利，就好象各个出版物或专利被具体和分别加以参考引用一样。

Claims (13)

1.一种静电调色剂接受层，它包含丙烯酸树脂，乙烯基树脂，溶液或分散体级橡胶和增塑剂的混合物。
2.如权利要求1所述的静电调色剂接受层，其中溶液或分散体级橡胶的含量为5-55重量％。
3.如权利要求1所述的静电调色剂接受层，其中溶液级橡胶为氯化橡胶。
4.如权利要求1所述的静电调色剂接受层，其中分散体级橡胶为聚氨酯分散橡胶。
5.如权利要求1所述的静电调色剂接受层，其中丙烯酸树脂为甲基丙烯酸甲酯/丙烯酸乙酯和N-叔丁基丙烯酰胺的三元聚合物。
6.一种图形制品，它包含粘合在抗龟裂膜的第一主表面上的静电调色剂接受层，其中所述的静电调色剂接受层包含丙烯酸树脂，乙烯基树脂，溶液或分散体级橡胶和增塑剂的混合物。
7.如权利要求6所述的图形制品，它还包含粘合在抗龟裂膜的第二主表面上的压敏粘合剂层，其中第二主表面与第一主表面相对。
8.如权利要求6所述的图形制品，其中丙烯酸树脂为甲基丙烯酸甲酯/丙烯酸乙酯和N-叔丁基丙烯酰胺的三元聚合物。
9.如权利要求6所述的图形制品，其中该制品还包含叠加在调色剂接受层上的形成图象层。
10.如权利要求9所述的图形制品，其中该制品还包含叠加在形成图象层上的透明涂层。
11.如权利要求10所述的图形制品，其中透明涂层为图形外层复合物。
12.一种图形图象制品，它包含施加在增塑聚氯乙烯涂层织物上的，在带有压敏粘合剂背衬的抗龟裂膜上的形成图象接受层。
13.如权利要求12所述的图形图象制品，它还包含叠加在形成图象接受层上的保护透明涂层。
CN94194777A 1994-01-07 1994-11-30 橡胶改性热塑性塑料的静电调色剂接受层 Pending CN1141089A (zh)

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