CN1219150A - 有双面涂层的标签用片料 - Google Patents
有双面涂层的标签用片料 Download PDFInfo
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- CN1219150A CN1219150A CN97194814A CN97194814A CN1219150A CN 1219150 A CN1219150 A CN 1219150A CN 97194814 A CN97194814 A CN 97194814A CN 97194814 A CN97194814 A CN 97194814A CN 1219150 A CN1219150 A CN 1219150A
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Abstract
描述了一种标签用片料结构,它包括高分子膜基材,在该高分子膜基材的第一表面上有(A)粘合剂锚固层,第二表面上有(B)油墨色浆层,(A)和(B)层选自:(i)底涂层,其外表面上有一层以下二种成分的共聚物的功能性涂层:(a)α,β－单烯型不饱和羧酸和(b)包括丙烯酸烷基酯和甲基丙烯酸烷基酯的中性单体酯;(ii)亚胺化聚合物;或者,(A)粘合剂锚固层选自:(iii)(i)的功能性涂层与(ii)的亚胺化聚合物的混合物;(iv)线型的水可离解的聚酯缩合物;和(v)聚酯;或者,(B)油墨色浆层选自:(vi)底涂层,其外表面上有一层丙烯酸类共聚物的功能性涂层;(vii)底涂层,其外表面上有一层苯乙烯共聚物的功能性涂层,其条件是,(A)粘合剂锚固层与(B)油墨色浆层各不相同。
Description
本发明涉及一种有双面涂层的可印刷的膜。更具体地说，本发明涉及一种压敏标签用片料(facestock)和包含该标签用片料的标签结构及其制造方法。
为用作标签用片料而制备的膜通常用能提高油墨粘着性的涂料在其印刷面上进行涂布。例如，美国专利No.5,380,587公开了一种多层包装材料即具有优良的可印刷性和非粘连性的标签用料膜。该膜先进行底涂，然后涂布共聚酯涂料。美国专利No.5,382,473描述了另一种可提高油墨粘着性的涂料。
丙烯酸类涂料也已施用于膜上以提高其热稳定性，这在美国专利No.3,753,769中有叙述。在该专利中，揭示了一种由甲基丙烯酸酯、丙烯酸低级烷基酯和丙烯酸制得的热封性涂料树脂。
压敏粘合剂不用加热即可进行粘合是公知的。美国专利No.4,898,787和5,070,164公开了一类特别的压敏粘合剂。这种粘合剂是由丙烯酸低级烷基酯(如丙烯酸乙酯)、甲基丙烯酸低级烷基酯(如甲基丙烯酸甲酯)和酸(如丙烯酸)的乳液聚合而制得的。
本发明涉及标签用片料结构，这些片料或是透明的，或是不透明的、白色不透明的，或镀有金属。
更具体地说，这种膜是这样一种可印刷的片料结构，它包括高分子膜基材，在该高分子膜基材的第一表面上有(A)粘合剂锚固层，第二表面上有(B)油墨色浆(ink base)层，(A)和(B)层选自：
(ⅰ)底涂层，其外表面上有一层以下二种成分的共聚物的功能性涂层：(a)α,β-单烯型不饱和羧酸和(b)包括丙烯酸烷基酯和甲基丙烯酸烷基酯的中性单体酯；
(ⅱ)甲基丙烯酸甲酯、甲基丙烯酸C2-C8烷基酯或丙烯酸C1-C8烷基酯和烯不饱和羧酸的亚胺化聚合物。
或者，(A)粘合剂锚固层选自：
(ⅲ)(ⅰ)中所述共聚物与(ⅱ)中所述亚胺化聚合物的混合物；
(ⅳ)由下述单体或它们的形成聚酯的等价物与化学计量的约100摩尔％的至少一种可共聚的C2-C11脂族或脂环族亚烷基二醇形成的的线型的水可离解的聚酯缩合物：对苯二甲酸、脂族二羧酸、含连接在二羧酸型芳香环上的磺酸碱金属盐基团的磺基化单体；
(ⅴ)包含下述组分的重复单元的聚酯：间苯二甲酸、5-磺基间苯二甲酸、1,4-环己烷二甲醇和二甘醇；
或者，(B)油墨色浆层选自：
(ⅵ)底涂层，其外表面上有一层C1-C8丙烯酸酯、C1-C8甲基丙烯酸酯和丙烯酸或甲基丙烯酸的共聚物的功能性涂层；
(ⅶ)底涂层，其外表面上有一层C1-C8丙烯酸酯、C1-C8甲基丙烯酸酯和丙烯酸或甲基丙烯酸的苯乙烯共聚物的功能性涂层，
其条件是，(A)粘合剂锚固层与(B)油墨色浆层各不相同。
本发明还涉及一种复合标签结构，它包含膜形式的衬垫、粘附在衬垫外表面的粘合剂涂层、邻近膜片料(膜片料包括热塑性基材)的外表面、被固定在粘合剂涂层表面上的膜片料，该膜片料包括位于粘合剂涂层与热塑性基材之间的粘合剂锚固层，粘合剂锚固层选自：
(ⅰ)底涂层，其外表面上有一层以下二种成分的共聚物的粘合剂锚固涂层：(a)选自丙烯酸、甲基丙烯酸和它们的混合物的α,β-单烯型不饱和羧酸；(b)包括丙烯酸烷基酯和甲基丙烯酸烷基酯的中性单体酯；
(ⅱ)甲基丙烯酸甲酯、甲基丙烯酸C2-C8烷基酯或丙烯酸C1-C8烷基酯和烯不饱和羧酸的亚胺化聚合物；
(ⅲ)(ⅰ)共聚物与(ⅱ)亚胺化聚合物的混合物，所述(ⅱ)共聚物为(a)选自丙烯酸、甲基丙烯酸和它们的混合物的α,β-单烯型不饱和羧酸与(b)包括丙烯酸烷基酯和甲基丙烯酸烷基酯的中性单体酯的共聚物，所述(ⅱ)亚胺化聚合物为甲基丙烯酸甲酯、甲基丙烯酸C2-C8烷基酯或丙烯酸C1-C8烷基酯和烯不饱和羧酸的亚胺化聚合物；
(ⅳ)由下述单体或它们的形成聚酯的等价物与化学计量的约100摩尔％的至少一种可共聚的C2-C11脂族或脂环族亚烷基二醇形成的线型的水可离解的聚酯缩合物：对苯二甲酸、脂族二羧酸、含连接在二羧酸型芳香环上的磺酸碱金属盐基团的磺基化单体；
(ⅴ)包括下述组分的重复单元的聚酯：间苯二甲酸、5-磺基间苯二甲酸、1,4-环己烷二甲醇和二甘醇；
本发明的一个目的是提高压敏胶(即粘合剂)在标签用片料上的锚固性。
本发明的一个特征是在标签用片料上形成一个涂布表面，该涂布表面将压敏胶锚固在片料上，为的是当将片料从剥离衬或另一个表面(如产品或产品容器)上剥下时，所有(如果不是几乎所有的话)压敏胶仍留在片料上。
本发明的一个优点是当将标签用片料从剥离衬或另一个表面(如产品或产品容器)上剥下或重新粘上时，胶水将有留在标签用片料上而不是在另一个表面上的倾向。
本发明的另一个优点是当基材各侧面的涂层不相同时，膜的涂层与涂层之间不易粘连。
通常，“粘合剂锚固”一词是指片料能牢固地将粘合剂材料(包括制造压敏标签所用的胶水和粘性材料)粘固住的性能。这些胶水和粘性材料在压敏标签制造领域是公知的。粘合剂锚固层(A)和油墨色浆层(B)共聚物(ⅰ)
如果粘合剂锚固层(A)和油墨色浆层(B)各不相同，则它们含(a)选自丙烯酸、甲基丙烯酸和它们的混合物的α,β-单烯型不饱和羧酸和(b)包括丙烯酸烷基酯和甲基丙烯酸烷基酯的中性单体酯的共聚物(ⅰ)。该树脂涂层的玻璃化温度(Tg)的计算值应在100-140°F(38-60℃)之间。
Tg的定义通常为聚合物从玻璃状的脆性固体转变成粘性很大的液体时的温度(Bueche,“Physical Properties of Polymers”,Interscience Publishers出版，1962)。在低于或略高于Tg的温度，聚合物对粘性流动具有很大的阻力，因此，无论施加多大的压力或使聚合物表面彼此接触多长时间也不会发生封合。
多元共聚物的制备方法是，在合适的链转移剂(例如硫醇或卤代烃)的存在下，选择下述各类合适的化合物进行共聚：A．高Tg单体；B．低Tg单体；和C．含酸的单体。
可使用的高Tg单体的例子包括甲基丙烯酸乙酯、甲基丙烯酸甲酯等。
可使用的低Tg单体的例子包括丙烯酸低级烷基酯，如丙烯酸甲酯、乙酯或丁酯。
可使用的酸单体的例子包括丙烯酸、甲基丙烯酸、马来酸、巴豆酸和它们的混合物。
聚合反应可方便地按以下方法进行：在反应过程中逐步添加混合单体，以在多元共聚物分子中得到更接近均一的单体分布。
可用来产生多元共聚物涂层的单体的相对比率可在以下范围内变化：2-15重量％(较好的是2.5-6重量％)的α,β-不饱和羧酸或其混合物(如丙烯酸或甲基丙烯酸)，85-98重量％(较好的是94-97.5重量％)的中性单体酯。通常，中性单体酯包括(a)丙烯酸烷基酯，如丙烯酸甲酯、乙酯或丁酯；(b)甲基丙烯酸烷基酯，如甲基丙烯酸甲酯、甲基丙烯酸乙酯。在可用此方法制备的三元共聚物中，所用单体组分之比率应为，甲基丙烯酸烷基酯单体占三元共聚物组合物总重量的至少10％，较好的是占20-80％，丙烯酸烷基酯单体组分占涂料组合物总重量的至少10％，较好的是占80-20％。通常，用已知的聚合方法(如乳液聚合法)进行共聚。可使用标准的聚合方法(如溶液聚合法、本体聚合法或乳液聚合法)制备本发明的三元共聚物涂料组合物。这种共聚物在美国专利No.3,753,769中有叙述。
有用的共聚物市售品有Valspar公司生产的“Valspar 90XW067”。亚胺化聚合物(ⅱ)
在本发明的另一实施方式中，(A)粘合剂锚固层或(B)油墨色浆层是(ⅱ)甲基丙烯酸甲酯、甲基丙烯酸C2-C8烷基酯或丙烯酸C1-C8烷基酯和烯不饱和羧酸的亚胺化聚合物。
亚胺化聚合物可含甲基丙烯酸甲酯、丙烯酸烷基酯或甲基丙烯酸烷基酯和可与亚烷基亚胺(如吖丙啶或2-甲基吖丙啶)反应的烯不饱和羧酸的丙烯酸类聚合物。更具体地说，亚胺化聚合物含具有以下成分的聚合物：(1)甲基丙烯酸甲酯、(2)其烷基含2-12个(更好的是2-8个)碳原子的甲基丙烯酸烷基酯或其烷基含1-12个(更好的是2-8个)碳原子的丙烯酸烷基酯、和(3)可与亚烷基亚胺反应的烯不饱和羧酸，通常，该丙烯酸类聚合物是用常规的溶液聚合法或本体聚合法制备的，在这些方法中，将单体、聚合催化剂和溶剂加入到聚合容器中并加热，形成具有用聚合物粘度表示的所需分子量的聚合物，然后与亚烷基亚胺反应。美国专利No.3,705,076提供了一种制备这些丙烯酸类聚合物的方法。
甲基丙烯酸烷基酯中的烷基的典型例子包括乙基、丙基、异丙基、丁基、叔丁基、己基甲基、2-乙基己基、辛基等。丙烯酸烷基酯中的烷基的典型例子包括乙基、丙基、丁基、异丁基、丙基、己基、2-乙基己基、辛基、壬基、癸基、月桂基等。
烯不饱和酸的典型例子包括甲基丙烯酸、乙基丙烯酸、丙烯酸、衣康酸等。
美国专利No.3,705,076中所述的所有亚烷基亚胺均可用来使丙烯酸类聚合物亚胺化。其具体例子包括吖丙啶和2-甲基吖丙啶，它们的使用量通常为丙烯酸类聚合物的4-6重量％。
本发明的典型的丙烯酸类聚合物是(1)70-90重量％的甲基丙烯酸甲酯、(2)9-19重量％的丙烯酸C2-C12烷基酯和(3)可与约1-8重量％的亚烷基亚胺反应的1-11重量％的丙烯酸或甲基丙烯酸。本发明的另一典型的丙烯酸类聚合物是(1)78-82重量％的甲基丙烯酸甲酯、(2)9-17重量％的丙烯酸乙酯和(3)可与约4-6重量％的亚烷基亚胺反应的5-9重量％的甲基丙烯酸。又一典型的丙烯酸类聚合物基本上由重量比为80/13/7的甲基丙烯酸甲酯/丙烯酸乙酯/甲基丙烯酸组成，并与4-5重量％的2-甲基吖丙啶反应。
亚胺化聚合物有Zeneca Resins公司以产品名“Neocryl”销售的产品，如“Neocryl XK-90”和“Neocryl XA-5090”。共聚物与亚胺化聚合物的混合物(ⅲ)
(A)粘合剂锚固层可以是前面(ⅰ)中所述的共聚物与前面(ⅱ)中所述的亚胺化聚合物的混合物。通常，(ⅰ)与(ⅱ)之比在约10∶90至90∶10之间，较好的为40∶60至60∶40。聚酯缩合物(ⅳ)和(ⅴ)
(A)粘合剂锚固层可以是聚酯缩合物(ⅳ)或(ⅴ)中的一个。
聚酯缩合物(ⅳ)通常是由下述草体或它们的形成聚酯的等价物与化学计量的约100摩尔％的至少一种可共聚的C2-C11脂族或脂环族亚烷基二醇形成的线型的水可离解的聚酯缩合物：对苯二甲酸、脂族二羧酸、含连接在二羧酸型芳香环上的磺酸碱金属盐基团的磺基化单体。该共聚聚酯通常可由下述单体或它们的形成聚酯的等价物的聚酯缩合物组成：
(a)60-75摩尔％的对苯二甲酸；
(b)15-25摩尔％的至少一种式HOOC(CH2)nCOOH的脂族二羧酸，其中n在1-11之间；
(c)6-15摩尔％的至少一种含连接在二羧酸型芳香环上的磺酸碱金属盐基团的磺基化单体；
(d)化学计量的100摩尔％的至少一种可共聚的C2-C11脂族或脂环族亚烷基二醇。该聚酯缩合物在美国专利No.5,380,587和4,525,419中有叙述。这些聚酯缩合物的市售品有Eastman Chemical公司的“EastekTM31125”。
在本发明的又一实施方式中，粘合剂锚固层是聚酯缩合物(ⅴ)，它通常是包含下述组分的重复单元的聚酯：间苯二甲酸、5-磺基间苯二甲酸、1,4-环己烷二甲醇和二甘醇。通常，该涂层是线型的水可离解的聚酯，以0.5g聚酯在100ml溶剂中的浓度于重量份之比为60/40的苯酚/四氯乙烷溶液中在25℃测得的比浓对数粘度至少为0.1，该聚酯含基本上等摩尔比率的酸部分重复单元(100摩尔％)和羟基部分重复单元(100摩尔％)，该聚酯包含下述组分(a)、(b)、(c)和(d)的重复单元(其中，所述的所有摩尔百分率均以所有酸部分重复单元和羟基部分重复单元之总和为200摩尔％计)：(a)90-70摩尔％的间苯二甲酸；(b)3-10摩尔％的5-磺基间苯二甲酸或其碱金属盐；(c)70-85摩尔％的1,4-环己烷二甲醇；(d)15-30摩尔％的二甘醇。这些聚酯已描述过，为具有上述比浓对数浓度并具有上述等摩尔比率的酸和羟基部分的线型的水可离解的聚酯。这些聚酯在美国专利No.5,006,598和5,382,473中有叙述。共聚物(ⅵ)
油墨色浆层可选自共聚物(ⅵ)。共聚物(ⅵ)是丙烯酸类共聚物。该丙烯酸类共聚物通常包括C1-C8丙烯酸酯、C1-C8甲基丙烯酸酯与选自丙烯酸、甲基丙烯酸、衣康酸和马来酸的酸的共聚物。丙烯酸烷基酯中的烷基的例子包括甲基、乙基、己基和异辛基。甲基丙烯酸烷基酯中的烷基的例子包括甲基、乙基和异丁基。该共聚物通常有含上述各单体中的至少一种的单体物料制得。
一般地，该共聚物由以下组分制得并含这些组分：40-75重量％(较好的是60-70重量％)的第一单体、15-50重量％(较好的是25-35重量％)的第二单体和0.1-10重量％(较好的是约1-5重量％)的第三单体。所有比率均以单体物料总重量计。
这些乳液型聚合物由凝胶渗透色谱法(GPC)测得的的平均分子量为20.000-150,000，较好的为50,000-90,000，Tg计算值为-15℃至+15℃，较好的为-10℃至+1℃。三元共聚物颗粒的直径一般在0.05-0.3微米之间。有用的三元共聚物是按美国专利No.5,070,164中所述的方法制得的。苯乙烯共聚物(ⅶ)
油墨色浆层可以是其外表面上有苯乙烯共聚物(ⅶ)的底涂层。
该苯乙烯共聚物(ⅶ)通常是C1-C8丙烯酸酯、C1-C8甲基丙烯酸酯和丙烯酸或甲基丙烯酸的苯乙烯共聚物。通常，该共聚物是用常规的乳液聚合法制得的水溶性乳液。该单体物料包含苯乙烯、丙烯酸烷基酯(如丙烯酸丁酯)、甲基丙烯酸烷基酯(如甲基丙烯酸丁酯)和丙烯酸或甲基丙烯酸。通常，苯乙烯共聚物含20-60％(较好的是30-50％)的苯乙烯；75-30％(较好的是65-45％)的丙烯酸烷基酯、甲基丙烯酸烷基酯和它们的混合物；及3-10％(较好的是4-7％)的丙烯酸或甲基丙烯酸。苯乙烯共聚物的市售品有Zeneca Resins公司的“NeoCryl XK-64”。
本发明的一个重要特征是(A)粘合剂锚固层与(B)油墨色浆层各不相同。只要这些层不相同，则这些层的表面之间的粘连性就低。
“粘连性”是指当膜的二个或多个表面压在一起时(例如，膜的片材或叠卷在贮存期中叠放在一起时)，膜之间互相粘附的倾向。在较高温度和高的相对湿度下更容易出现粘连。在一般的贮存条件下，所遇到的最高温度通常为100-110°F(38-43℃)，相对湿度可高达90-100％。在这些条件下抗粘连的膜具有重要的商业意义。根据本发明，可将有双面涂层的片料卷成卷筒或以片材叠放，这样，粘合剂锚固层和印刷色浆层接触但不粘连。
在将涂料组合物施用在合适的基材之前，通常，先对基材表面进行处理以确保涂层将牢固地粘附在膜上，消除或避免涂层从膜上剥离的现象。该处理通常用已知的方法进行，例如，可用膜氯化法(即，将膜暴露在氯气中)、氧化剂(如铬酸)处理法、热气或蒸气处理法、电晕或火焰处理法等。虽然所有这些方法均可有效地用来对膜表面进行预处理，但一个非常有用的处理方法是将膜表面暴露于高压电晕放电下，同时使膜在一对留有间距的电极之间通过，由此对膜表面进行电子处理。电子处理后，即可对表面进行涂布。
底涂涂涂料(它尤其在层(ⅰ)、(ⅵ)和(ⅶ)中是有用的)可以是环氧基底涂剂或聚吖丙啶。通常，底涂涂料选自(A)酸化了的氨乙基化乙烯基聚合物和环氧树脂的反应产物，(B)聚吖丙啶、和(C)它们的混合物。环氧底涂剂与层(ⅳ)和(ⅴ)的磺化聚酯一起特别有用。
合适的酸化了的氨乙基化乙烯基聚合物底涂涂料在美国专利No.5,066,434中有叙述。
底涂剂材料包括环氧树脂与酸化了的氨乙基化乙烯基聚合物的反应产物。可使用的环氧树脂有多羟基化合物的缩水甘油醚。可使用的典型多羟基化合物包括双酚A、环取代的双酚A、间苯二酚、氢醌、酚醛树脂、酚醛清漆树脂、脂族二醇(如乙二醇、丙二醇、1,4-丁二醇、1,6-己二醇、丙三醇、低级烷基乙内酰脲)和它们的混合物。
合乎要求的环氧树脂有环氧氯丙烷与双酚A的缩水甘油化反应产物。该类型的环氧树脂一般是以其环氧基当量(EEW)进行分类的，所谓环氧基当量的定义是含1克当量环氧基的树脂的重量(克)。可使用EEW为170-280(较好的为180-210)的树脂。
环氧树脂组分的组合物中的一个变化是用乙内酰脲类混合物代替双酚A。例如，可在低分子量环氧树脂中使用1,1-二甲基乙内酰脲，因为以该物质为基的树脂是完全溶于水的，从而无需进行乳化。
虽然环氧树脂的具体结构对所用的底涂剂不是决定性的，但在选择环氧树脂时必须对其物理状态予以认真考虑。例如，环氧树脂必须是液态的且能容易地用下面所述的第二组分即固化剂进行分散或溶解是很重要的。若环氧树脂的粘度低，则可直接将其搅拌到第二组分(例如固化剂)中，然而，使用水性乳液形式的环氧树脂较有利。
环氧底涂剂中的第二组分是水溶性的氨基改性的丙烯酸类聚合物。该聚合物是环氧化合物的固化剂。具体物质在美国专利No.3,719,629中有叙述，一般可描述为在侧端具有氨基烷基化物基团的酸化了的氨乙基化共聚物。该物质的制备方法是，将丙烯酸酯、甲基丙烯酸酯、苯乙烯或其他合适单体与足量的甲基丙烯酸或丙烯酸聚合，使-COOH含量为7.5-12.5％。优选溶剂聚合法。然后将该聚合物与吖丙啶单体反应，并用盐酸进行酸化，使该聚合物变得溶于水。
可以分散液或溶液的形式将底涂剂涂料施用在基材上，分散液或溶液中所用的有机载体例如可以是醇或芳香烃(如二甲苯)或它们的混合物。
在本发明的一个实施方式中，通过快速搅拌将液态环氧树脂乳化于固化剂溶液中。然后用水将所得分散液稀释至涂布所需浓度，通常将分散液稀释至固含量为2-25％。
当将环氧树脂与固化剂混合时，一般需要使用化学计量当量平衡的环氧基和氨基。然而，业已发现，化学计量比可在一个较宽的范围内变化，例如，环氧基与氨基之比可为1∶3至3∶1(也可为1∶2至2∶1)而不会对底涂剂的效用产生严重的影响。
环氧树脂和固化剂的溶液或分散液可含少量的湿润剂以使底涂材料更容易地施用于膜表面。可使用的常用的非离子型湿润剂包括乙二醇的己醚或苄醚、二甘醇的己醚、丁醇、己醇、辛醇、双丙酮醇等。
虽然环氧树脂和固化剂的混合物会交联或固化而无需添加催化剂，但业已发现，在某些情况下使用胺催化剂是有用的。这些催化剂包括丙二胺、己二胺等。已知的另一种底涂涂料(B)聚吖丙啶是PEI。PEI用作膜基材(如玻璃纸和聚烯烃)上的高分子涂层的底涂涂料如英国专利No.766827和910875中所揭示的是公知的。该物质在美国专利No.3,230,175中也有叙述。该类物质的市售品称为EPOMIN L50(日本触媒株式会社产品)。该物质可用水介质或有机溶剂介质(如乙醇)配制成含0.1-0.6重量％的聚吖丙啶的溶液供施用。
亚胺底涂剂使具有粘合剂活性的整个表面充分又牢固地与以后施用的本发明的涂料组合物粘结。该底涂剂通常用常规的溶液涂布法(如直接凹槽辊涂布法或逆向直接凹槽辊涂布法)施用在已处理过的基膜上。可用水介质或有机溶剂介质(如乙醇)配制成含0.5重量％的聚吖丙啶的有效涂布溶液供施用。当使用环氧底涂剂与聚吖丙啶的混合物时，其比率可以是任意的。
当粘合剂锚固层或油墨色浆层为(ⅰ)的共聚物或油墨色浆层为(ⅵ)或(ⅶ)的共聚物时，已表面处理过的底涂涂层良好地粘附在基材上是重要的。
可以用例如各种有机溶剂(如醇、酮、酯等)配制的组合物非水溶液将涂料组合物施用于膜基材的表面。然而，由于如下面所述的，涂料可能含胶态无机物质，且由于这些物质难以很好地分散在有机溶剂中，因此，以水溶液(通常是碱性水溶液)的形式施用涂料是重要的。
将涂料以任何常规的已知方法(如凹槽辊涂布法、逆向直接凹槽辊涂布法、辊涂布法、浸涂法、喷涂法等)施用于通常已进行过电晕放电或火焰处理的材料的表面上，在某些情况下，施用在已表面处理过且已底涂过的材料的表面上。可用挤压辊或刮刀等将过量的水溶液除去。一般而言，施用的涂料厚度和分布须能将粘合剂锚固在基材上。在大多数情况下，施用的涂料量在干燥之后须能形成厚度或涂层重量为0.9-1.1g/m2的光滑而又分布均匀的层。
通常，接着用热空气、辐射热或其他任何方便的方法使膜上的涂料干燥。氨气在干燥过程中挥发，膜上留下一层非水溶性的透明而又有光泽的涂层。
涂料中可使用防粘连物质。合适的防粘连物质包括蜡和蜡样物质，虽然在某些情况下蜡可能抑制粘合剂的锚固性。
可在本发明中使用的热塑性膜的具体类型有聚烯烃，通常是取向的聚丙烯。然而，可使用的基材可包括任何热塑性材料，只要其可形成能用来包装、标记或装饰的薄膜即可。此类材料有聚烯烃、耐纶、聚对苯二甲酸乙二醇酯和聚碳酸酯。可使用的基材还包括前述材料的共挤出物、这些材料中的任何二种或多种的层压物或作为单一基膜挤出的这些材料的任何共混物。聚烯烃均聚物和丙烯与乙烯的共聚物是有用的。尤其优选的是含至少80重量％全同聚丙烯的聚丙烯。基材层可以是熔点为320-330°F(160-166℃)的丙烯均聚物°市售材料包括Exxon4252和FINA3371。该基材可与至少一种表层共挤出，或者可将其层压在至少一种其他膜上。当膜是共挤出物时，表层厚度通常占膜的总厚度的2-18％。表层可以是丙烯与另一种烯烃(如乙烯和/或1-丁烯)的共聚物。在共聚物中可存在另一种烯烃。优选的基材是具有至少一层表层的聚丙烯，所述表层选自聚乙烯、聚丙烯、丙烯与乙烯的共聚物、乙烯与1-丁烯的共聚物、上述任何物质的三元共聚物及马来酸酐改性的聚合物。
另一种有用的基材是与小量的下述聚合物共混的聚丙烯：聚乙烯、乙烯与α-烯烃的共聚物、丙烯与α-烯烃的共聚物、烯烃的三元共聚物及马来酸酐改性的聚合物。
白色不透明的、多孔的聚丙烯也是有用的基材。这些膜在美国专利No.4,758,462、4,965,123和5,209,884中有叙述。
也可使用镀有金属的膜。通常包含或由聚丙烯或聚乙烯(中或高密度聚乙烯)组成的已电晕或火焰处理过的膜表面一般通过铝真空沉积来镀金属。将涂料施用在镀有金属的表面上。
如前面所间接提到的，可使用具有3层或更多层(例如5层，有时甚至7层)的多层膜。在5层的膜中，如美国专利No.5,209,854和5,397,635所揭示的，通常在芯层的两面有聚丙烯中间层。
所用的膜可以是单轴取向的或是双轴取向的。通常在纵向上拉伸4-10倍，在横向上拉伸7-12倍。膜厚度可在10-100微米之间。
为使生产的标签用片料具有进行机械加工和便于处理的良好的滑爽性，可用起滑爽剂作用的固态的磨细的不溶于水的无机材料(如胶态二氧化硅)配制涂料。其他可用来提高滑爽性的磨细的无机材料包括不溶于水的固体，如硅藻土、硅酸钙、膨润土、滑石粉和磨细的粘土。这些磨细的无机材料的粒径可在0.1-10微米之间，稳定化了的二氧化硅碱性分散体是优选的材料。也可使用能提高不透明性的微粒，如二氧化钛。
在拟定的标签用片料结构中，压敏粘合剂在有双面涂层片料的粘合剂锚固层与剥离衬的剥离表面之间。用冲刀将压敏的标签用片料裁切成粘附在连续的剥离层上的标签。典型的压敏粘合剂有热熔性粘合剂，如苯乙烯/异戊二烯/苯乙烯嵌段共聚物(National Starch公司生产的“Duro-tak”系列，包括“Duro-tak 9866”和“Duro-tak 4206”)、苯乙烯/乙烯丁烯/苯乙烯嵌段共聚物(National Starch公司生产的“Duro-tak 9684”)；水基压敏粘合剂，如丙烯酸类乳液(Unocal公司生产的产品号为9612、9646和9202的产品、Air Products公司生产的产品名为GP-2、LC-31和SP-27的产品、Rohm&Haas公司生产的产品名为PS-67的产品以及National Starch公司生产的产品名为Nacor-4537的产品)、乙烯/乙酸乙烯酯共聚物乳液(National Starch公司生产的产品名为“EVA-Tak 9685”和“EVA-Tak 9715”的产品)、橡胶-树脂乳液(Dyna-tech公司生产的产品号为2412的产品)；溶剂基压敏粘合剂，如热塑性丙烯酸类(National Starch公司生产的产品名为“Duro-tak 2434”的产品)、自交联的丙烯酸类(National Starch公司生产的产品名为“Duro-tak 1068”和“Duro-tak 1077”的产品)和橡胶基化合物(National Starch公司生产的产品名为“Duro-tak 6172”和“Duro-tak9718”的产品)。
可使用的剥离衬有具有聚硅氧烷剥离涂层的基材。可使用的基材有超级压光的牛皮纸、玻璃纸、聚丙烯、聚酯(如对苯二甲酸乙二醇酯)、有聚乙烯涂层的牛皮纸、有聚丙烯涂层的牛皮纸、或Mobil Chemical公司生产的产品名为“Proliner”的热塑性基材。这些基材通常涂有用热固化的聚硅氧烷剥离涂层，如乙烯基官能化的聚二甲基硅氧烷(Dow Corning公司生产的产品名为“Syl-off7686”的产品)。在该体系中，交联剂通常是二甲基氢聚硅氧烷(DowCorning公司生产的产品名为“Syl-off 7048”的产品)。
包含基材(如玻璃纸、有多层涂层的牛皮纸、聚对苯二甲酸乙二醇酯、取向的或铸塑聚丙烯、聚乙烯或聚苯乙烯)的剥离衬可用可辐射或电子束固化的聚硅氧烷(如可UV固化的聚硅氧烷(GE生产的产品名为“UV9300”、“UV9315”的产品，这些产品使用“UV9310C”作为光引发剂)和可电子束固化的聚硅氧烷(Goldschmidt公司生产的产品名为“RC726”和“RC705”的产品))进行涂布。通常，压敏粘合剂涂布在剥离衬上并在其温度通常为35-120℃的烘箱中干燥。然而，干燥温度往往取决于粘合剂的类型。溶剂基粘合剂的干燥温度通常为66℃，而水基粘合剂的干燥温度则通常为93℃。干燥之后，将剥离衬层压在标签用片料的有粘合剂锚固层的一面。
实施例
测试根据下面的实施例制得的膜的粘连性和粘合剂锚固性。
粘连性的测定方法是，在各种温度、压力和时间的条件下，在实验室用压机中使膜的有涂层的表面互相接触。测定在Instron试验机中将膜拉开所需的力(单位：g/英寸(g/m))，由此确定将膜分离所需的力。实施例1
在本实施例中，由市售的3层共挤出的双轴取向的基膜(Mobil公司生产的196LLB3)制造有双面涂层的标签用片料结构。该膜是A/B/C结构，其中膜的B芯层是聚丙烯，A表层是乙烯/丙烯共聚物，C表层是含0.2％十二烷基磺酸钠(siponate)和1800ppm二氧化硅防粘连剂的乙烯/丙烯共聚物。膜总厚度为1.96密耳(约50微米)。各表层占膜总厚度的10％。将A表层火焰处理成40达因/cm。将C表层电晕处理成40达因/cm。
用逆向直接凹槽辊涂布法往A表层施用由亚胺化聚合物(100phr,ZenecaXA-5090,19％固含量)和二氧化硅防粘连剂(0.4phr,W.R.Grace公司生产的Siloblock S42)配制的涂料。涂层重量为1.09g/m2。用逆向直接凹槽辊涂布法往C层施用环氧底涂剂，然后涂布磺化聚酯树脂涂料，其方法在美国专利No.5,382,473的实施例2中有叙述。
测定A层涂层对C层涂层在140°F(60℃)的粘着力小于15g/英寸(5.9g/cm)。在A表层上涂布的涂层的粘合剂锚固性的测定方法为，往有涂层的表面施加Tesa7475胶带并在环境条件下老化24小时。TLML机以180°的角度和300英寸/分(762cm/min)将胶带从有涂层的表面剥离。记录用TLML测得的剥离力并用肉眼观察表面，确定是否有粘合剂残留。由于具有良好粘合剂锚固性的表面能将粘合剂从胶带上除去，因此，最好将粘合剂从Tesa胶带转移到有涂层的表面上。测得的剥离力为3829g/英寸(1507g/cm)，肉眼观察的结果表明，粘合剂从胶带上转移到了有涂层的表面。实施例2
在本实施例中，由白色不透明的双轴取向的膜制造有双面涂层的标签用片料结构。该膜是5层A/B/C/D/E结构，其中C芯层是空隙化聚丙烯，空隙化剂是聚对苯二甲酸丁二醇酯。A层是中密度聚乙烯，B层是配混8重量％TiO2的聚丙烯，D层是丙烯均聚物，E层是丙烯均聚物和二氧化硅防粘连剂。膜总厚度约为3密耳(约76微米)。中间层B和D的厚度之和占膜厚度的17％，而表层A和E的厚度之和占膜厚度的3％。
往A层外表面施用由亚胺化聚合物(100phr,Zeneca XA-5090,19％固含量)和二氧化硅防粘连剂(0.4phr,W.R.Grace公司生产的Siloblock S42)配制的涂料。涂层重量为0.6-0.7g/msi(0.93-1.09g/m2)。
往E层外表面施用由以下组分混合而成的涂料：亚胺化聚合物(50phr,Zeneca XA-5090,19％固含量)、Mobil公司生产的丙烯酸类共聚物(50phr,22％固含量)、滑石粉(0.5phr,10％固含量)和二氧化硅(5phr,40％固含量)。涂层重量为0.6-0.7g/msi(0.93-1.09g/m2)。
在各种条件下对A层涂层对E层涂层的粘着力进行测定，结果列在下面。在对照试样中，于130°F(54℃)以750磅/英寸2(5,171kPa)的压力加压1小时后，有涂层的A面对已处理(无涂层)的E面的粘连严重，只有撕裂才能使两者分离。在另一对照试样中，施加的压力和时间与前者相同，但温度为约70°F(20℃)，测得的粘着力为200-300g/英寸(79-118g/cm)。
测试条件 粘着力
压力(kPa)/温度(℃)/时间(小时) (g/cm)
5,171/38/1 4
5,171/49/1 10
5,171/54/1 18
861/52/72 8
861/29/72 6
上面的结果表明，在各种条件下，这些膜的A层涂层对E层涂层的粘连性较小。
将标签复合物裁切成约50mm的片条测试其粘合剂锚固性。将剥离衬从膜上剥离并将膜的外露的粘合剂表面放置在不锈钢板上。用1kg的橡胶辊将膜滚压在钢板上并使其粘附在其上面。用TLML机以180°的角度和300英寸/分钟(762cm/min)将标签从钢板上剥离。记录用TLML测得的剥离力。用肉眼观察表面，确定粘合剂是否从标签表面除去。具有良好粘合剂锚固性的膜在不锈钢板上不留任何粘合剂痕迹。
有涂层的膜在上述粘合剂锚固试验中显示出良好的性能。在试验中使用了几种市售的粘合剂。膜在钢板上未留下粘合剂。
Claims (10)
1．一种可印刷的片料结构，它包括高分子膜基材，该高分子膜基材的第一表面上有(A)粘合剂锚固层，在其第二表面上有(B)油墨色浆层，(A)和(B)层选自：
(ⅰ)底涂层，其外表面上有一层以下二种成分的共聚物的功能性涂层：(a)选自丙烯酸、甲基丙烯酸和它们的混合物的α,β-单烯型不饱和羧酸和(b)包括丙烯酸烷基酯和甲基丙烯酸烷基酯的中性单体酯；
(ⅱ)甲基丙烯酸甲酯、甲基丙烯酸C2-C8烷基酯或丙烯酸C1-C8烷基酯和烯不饱和羧酸的亚胺化聚合物；
或者，(A)粘合剂锚固层选自：
(ⅲ)(ⅰ)共聚物与(ⅱ)亚胺化聚合物的混合物，所述(ⅰ)共聚物为(a)选自丙烯酸、甲基丙烯酸和它们的混合物的α,β-单烯型不饱和羧酸与(b)包括丙烯酸烷基酯和甲基丙烯酸烷基酯的中性单体酯的共聚物，所述(ⅱ)亚胺化聚合物为甲基丙烯酸甲酯、甲基丙烯酸C2-C8烷基酯或丙烯酸C1-C8烷基酯和烯不饱和羧酸的亚胺化聚合物；
(ⅳ)由下述单体或它们的形成聚酯的等价物与化学计量的100摩尔％的至少一种可共聚的C2-C11脂族或脂环族亚烷基二醇形成的线型的水可离解的聚酯缩合物：对苯二甲酸、脂族二羧酸、含连接在二羧酸型芳香环上的磺酸碱金属盐基团的磺基化单体；
(ⅴ)包含下述组分的重复单元的聚酯：间苯二甲酸、5-磺基间苯二甲酸、1,4-环己烷二甲醇和二甘醇；
或者，(B)油墨色浆层选自：
(ⅵ)底涂层，其外表面上有一层C1-C8丙烯酸酯、C1-C8甲基丙烯酸酯和丙烯酸或甲基丙烯酸的共聚物的功能性涂层；
(ⅶ)底涂层，其外表面上有一层C1-C8丙烯酸酯、C1-C8甲基丙烯酸酯和丙烯酸或甲基丙烯酸的苯乙烯共聚物的功能性涂层，
其条件是，(A)粘合剂锚固层与(B)油墨色浆层各不相同。
2．如权利要求1所述的可印刷的膜，其中，高分子膜基材包含丙烯均聚物。
3．如权利要求1所述的可印刷的膜结构，其中，(A)粘合剂锚固层是(ⅳ)由下述单体或它们的形成聚酯的等价物与化学计量的100摩尔％的至少一种可共聚的C2-C11脂族或脂环族亚烷基二醇形成的线型的水可离解的聚酯缩合物：对苯二甲酸、脂族二羧酸、含连接在二羧酸型芳香环上的磺酸碱金属盐基团的磺基化单体；(B)油墨色浆层是(ⅱ)甲基丙烯酸甲酯、甲基丙烯酸C2-C8烷基酯或丙烯酸C1-C8烷基酯和烯不饱和羧酸的亚胺化聚合物。
4．如权利要求3所述的可印刷的膜，其中，高分子膜基材包含丙烯均聚物芯层，在该芯层的一面至少另有一层高分子层，该另一层高分子层选自丙烯均聚物、乙烯均聚物、乙烯/丙烯共聚物和丙烯/乙烯/1-丁烯三元共聚物。
5．如权利要求4所述的可印刷的膜，其中，丙烯均聚物芯层包含聚丙烯基质芯层，在该聚丙烯基质芯层内有空隙层，空隙密度需能产生显著的不透明性。
6．如权利要求1所述的可印刷的膜结构，其中，(A)粘合剂锚固层是(ⅲ)(ⅰ)共聚物与(ⅱ)亚胺化聚合物的混合物，所述(ⅰ)共聚物为(a)选自丙烯酸、甲基丙烯酸和它们的混合物的α,β-单烯型不饱和羧酸与(b)包括丙烯酸烷基酯和甲基丙烯酸烷基酯的中性单体酯的共聚物，所述(ⅱ)亚胺化聚合物为甲基丙烯酸甲酯、甲基丙烯酸C2-C8烷基酯或丙烯酸C1-C8烷基酯和烯不饱和羧酸的亚胺化聚合物；(B)油墨色浆层是(ⅱ)甲基丙烯酸甲酯、甲基丙烯酸C2-C8烷基酯或丙烯酸C1-C8烷基酯和烯不饱和羧酸的亚胺化聚合物。
7．如权利要求6所述的可印刷的膜，其中，高分子膜基材包含丙烯均聚物芯层和施加在该芯层表面的至少另一层高分子层，该另一层高分子层选自丙烯均聚物、乙烯均聚物、乙烯/丙烯共聚物和丙烯/乙烯/1-丁烯三元共聚物。
8．如权利要求7所述的可印刷的膜，其中，丙烯均聚物芯层包含聚丙烯基质芯层，在该聚丙烯基质芯层内有空隙层，空隙密度需能产生显著的不透明性。
9．如权利要求8所述的可印刷的膜，其中，高分子基材是5层，第一外表层是中密度聚乙烯，第二外表层是聚丙烯，第一高分子中间层在第一外表层与芯层之间，第二高分子中间层在第二外表层与芯层之间。
10．如权利要求9所述的可印刷的膜，其中，第一中间层包含聚丙烯和不透明剂，第二中间层包含聚丙烯并基本上没有不透明剂。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/646,784 US5662985A (en) | 1996-05-21 | 1996-05-21 | Two-side coated label facestock |
| US08/646,784 | 1996-05-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1219150A true CN1219150A (zh) | 1999-06-09 |
Family
ID=24594443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97194814A Pending CN1219150A (zh) | 1996-05-21 | 1997-03-28 | 有双面涂层的标签用片料 |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US5662985A (zh) |
| EP (1) | EP0912332B1 (zh) |
| JP (1) | JP2000512223A (zh) |
| KR (1) | KR20000015828A (zh) |
| CN (1) | CN1219150A (zh) |
| AR (1) | AR007210A1 (zh) |
| AU (1) | AU706538B2 (zh) |
| BR (1) | BR9709017A (zh) |
| CA (1) | CA2254062A1 (zh) |
| DE (1) | DE69731201T2 (zh) |
| ES (1) | ES2225962T3 (zh) |
| ID (1) | ID16955A (zh) |
| MY (1) | MY132462A (zh) |
| TW (1) | TW333553B (zh) |
| WO (1) | WO1997044187A1 (zh) |
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| CN100383561C (zh) * | 2004-02-26 | 2008-04-23 | 日东电工株式会社 | 防静电性粘合型光学薄膜及图像显示装置 |
| CN101432379B (zh) * | 2006-04-25 | 2012-10-17 | 埃克森美孚石油公司 | 涂覆的聚合物薄膜 |
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-
1997
- 1997-03-28 CN CN97194814A patent/CN1219150A/zh active Pending
- 1997-03-28 DE DE69731201T patent/DE69731201T2/de not_active Expired - Fee Related
- 1997-03-28 BR BR9709017A patent/BR9709017A/pt not_active Application Discontinuation
- 1997-03-28 AU AU25933/97A patent/AU706538B2/en not_active Ceased
- 1997-03-28 JP JP09542338A patent/JP2000512223A/ja active Pending
- 1997-03-28 KR KR1019980709378A patent/KR20000015828A/ko not_active Application Discontinuation
- 1997-03-28 EP EP97917670A patent/EP0912332B1/en not_active Expired - Lifetime
- 1997-03-28 CA CA002254062A patent/CA2254062A1/en not_active Abandoned
- 1997-03-28 ES ES97917670T patent/ES2225962T3/es not_active Expired - Lifetime
- 1997-03-28 WO PCT/US1997/005062 patent/WO1997044187A1/en active IP Right Grant
- 1997-05-16 TW TW086106514A patent/TW333553B/zh active
- 1997-05-19 MY MYPI97002163A patent/MY132462A/en unknown
- 1997-05-20 AR ARP970102138A patent/AR007210A1/es unknown
- 1997-05-21 ID IDP971707A patent/ID16955A/id unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383561C (zh) * | 2004-02-26 | 2008-04-23 | 日东电工株式会社 | 防静电性粘合型光学薄膜及图像显示装置 |
| CN101432379B (zh) * | 2006-04-25 | 2012-10-17 | 埃克森美孚石油公司 | 涂覆的聚合物薄膜 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2593397A (en) | 1997-12-09 |
| EP0912332A4 (en) | 1999-11-24 |
| EP0912332B1 (en) | 2004-10-13 |
| JP2000512223A (ja) | 2000-09-19 |
| TW333553B (en) | 1998-06-11 |
| EP0912332A1 (en) | 1999-05-06 |
| ES2225962T3 (es) | 2005-03-16 |
| AU706538B2 (en) | 1999-06-17 |
| CA2254062A1 (en) | 1997-11-27 |
| MY132462A (en) | 2007-10-31 |
| AR007210A1 (es) | 1999-10-13 |
| KR20000015828A (ko) | 2000-03-15 |
| BR9709017A (pt) | 1999-08-03 |
| DE69731201T2 (de) | 2006-02-23 |
| ID16955A (id) | 1997-11-27 |
| WO1997044187A1 (en) | 1997-11-27 |
| DE69731201D1 (de) | 2004-11-18 |
| US5662985A (en) | 1997-09-02 |
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