CN104693927A - 可印刷涂料 - Google Patents
可印刷涂料 Download PDFInfo
- Publication number
- CN104693927A CN104693927A CN201510090072.4A CN201510090072A CN104693927A CN 104693927 A CN104693927 A CN 104693927A CN 201510090072 A CN201510090072 A CN 201510090072A CN 104693927 A CN104693927 A CN 104693927A
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- Prior art keywords
- film
- coating composition
- coating
- arbitrary
- ink
- Prior art date
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- Pending
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- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
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- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
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- 239000004902 Softening Agent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N methyl ethyl ketone Substances CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
-
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Abstract
用于面材的无底涂涂料组合物，其包含：为水分散性聚合物的粘合剂；水分散性的并可与水分散性聚合物混合或结合至水分散性聚合物的烯键式不饱和化合物，其中烯键式不饱和化合物能够与墨形成共价键；以及交联剂，其中交联剂适于将涂料粘合至所述面材。可以将涂料组合物涂覆至基底来形成可印刷膜。可以将本发明的印刷膜施用于标签，例如用于在诸如瓶子的容器上的标签。
Description
本发明涉及改进的涂料，所述涂料为能够向涂料实施印刷的涂料。特别地，但排他地，本发明涉及当与可辐射固化墨一起使用时具有良好粘附性的改进的可印刷膜。
近些年，印刷产品的多样化已需要在更多元化的片状材料上进行印刷；例如，纸、合成纸、诸如热塑性树脂膜的聚合物膜、金属箔、金属化片等。通过诸如胶版印刷、凹版印刷、柔性版印刷、丝网印刷和凸版印刷的方法来印刷这些印刷物品。在这些印刷方法中，由于可辐射固化墨迅速固化，并且使用可辐射固化墨的印刷方法具有优越的操做性，因此使用可辐射固化墨的方法近来已经广受欢迎。可辐射固化墨已知用在包装材料、标签和非吸收性印刷材料的印刷过程中。可辐射固化印刷墨通常包含不饱和丙烯酸酯、聚酯、光引发剂和添加剂。然而，在电子束固化墨中，可以不使用光引发剂。
可辐射固化墨在可印刷物品上的沉积之后，将印刷图案暴露于辐射，并且在转眼间内使其硬化。在连续印刷过程中，实现最高达到300m/min的印刷速度。目前，对于片状可印刷物品存在巨大的需求。
在印刷方法中，印刷片期望具有良好的片操作性和防粘连性以及抗静电性，所述防粘连性是在片材表面上形成墨的均匀分布。除了这些常规期望的特性，在使用可辐射固化墨的印刷方法中，印刷片材特别需要对辐射固化墨的强力粘附性能。
特别地，旨在例如在瓶子标签市场中用作标签的可辐射固化墨印刷的聚合物膜应抵御冻结水条件(以使所获得的产品在冷却器或冰桶中能够存贮)并抵御例如通过暴露于蒸汽的杀菌方法(以确保预先标记的瓶子适用于填充)。
欧洲专利申请EP-A1-410051公开了印刷片，其包含支撑层和在所述支撑层的至少一个面上的表面层，所述表面层至少包含丙烯酸酯基聚合物和不饱和化合物(肉桂酸或其衍生物)。该文献没有教导关于可能使用其它单体来代替肉桂酸的任何事情。
WO-A-02/048260公开了所谓的改进粘合剂、吸墨组合物和包含粘合剂、微粒填充物和媒染剂的涂覆基底。优选的粘合剂包含用至少一种耐湿磨性-增强单体制备的一种或多种丙烯酸共聚物。该文公开的涂料组合物是完全饱和的，其具有由媒染剂和/或填充物提供的吸墨性。
WO-A-01/60878公开了共混的聚氨酯-聚乙烯酯组合物，其被用作保护性而非吸墨性的涂料。该文献提出在制备过程中完全固化的水分散性UV-混合涂料的用途。
US 2002/0098340公开了包含基底并且至少包含表面层的可印刷膜，所述表面层覆盖所述基底的至少一面并且包含水分散性聚合物和烯键式不饱和化合物。然而，所述产品很昂贵，并且由于其多组分性质因而难以制备。该文献教导了使用基底和表面层之间的底涂中间层来提供符合要求的粘附水平。
然而，在印刷和固化之后，以上列出的形成片状的材料，特别是聚合物膜不能充分地粘附至放射可固化墨，特别是在这些极端情况中。因此，印刷且辐射固化的墨的问题在于将印刷且辐射固化的墨与聚合物膜分离。
在可印刷膜领域需要改进，从而获得经济、易于制备的产品，并且其还具有适当的粘附性能。
从第一方面，本发明提供了用于面材的无底涂涂料，其包含为水分散性聚合物的粘合剂；水分散性的并可与水分散性聚合物混合或结合至水分散性聚合物的烯键式不饱和化合物，其中所述烯键式不饱和化合物能够与墨形成共价键；以及交联剂，其中所述交联剂适用于将涂料粘合至面材。
能够在本发明中用作面材的合适基底为聚合物膜、特别是聚烯烃膜、纸、合成纸、机织物、无纺织物、陶瓷片、金属板以及通过上述材料组合而形成的多层复合片。对于用作标签的可印刷膜，聚烯烃膜是优选的，特别是取向的聚丙烯膜，并且甚至更优选的是EP-A-0202812的取向聚丙烯膜。
本文涉及的可印刷膜为能够直接着墨的膜，即表面层牢固足以抵御粘性墨拉扯的膜，否则表面层区域可以从表面扯掉，产生称为摘取物的缺陷。
涂料制剂、生成的涂层和涂覆产品不包含底涂。这不仅产生成本方面的优势，并且产生制备装置和简单性方面的优势。此外，无底涂体系改进了可印染性。相当多数量的公开底涂的现有技术教导的内容与本申请的无底涂体系完全不同。
在某些现有技术体系中，通过聚合物(例如丙烯酸聚合物)和烯键式不饱和聚合物(例如Cytec Industries Inc.的)之间的相互作用来提供开放式可印刷表面。当印刷膜时，将湿墨粘附至涂覆的表面，然后当将该印刷膜辐射固化时，UV引发剂(含在墨中)引起Ebecryl自交联和与墨交联的自由基固化反应，由此将墨粘合至膜的表面上。由于担心产生硬的、不可印刷的膜，技术人员通常避免使用交联剂来使涂料粘合至膜；而相反，在现有技术体系中，在膜和涂料之间通常使用单独的底涂层来将膜与涂料粘合。
出乎意料地，本发明人已经发现在涂料制剂中可以使用交联剂来形成粘合，而不损害其它特性，例如良好的可印染性。本发明人已经发现可以使用交联剂来使膜表面上的官能团与涂料组合物组分中的官能团粘合。交联剂还提供了具有防水性的膜，而不使产品过度硬化，由此意味着仍然能够容易印刷该表面。实际上，得到可印染性的改进。
使用交联剂从而其能够提供有效的粘附(并且还任选提供防水性)，同时还获得有效的可印染性。非异氰酸酯交联剂是优选的，这是由于本发明人已经发现异氰酸酯能够自交联从而产生硬的、抗印染的聚脲组分。采用碳二亚胺交联剂，特别是氮丙啶交联剂，本发明人已经获得了良好结果，因此这些交联剂是优选的。技术人员将意识到提供粘合效果并且获得有效的可印染性的其它交联剂也在本发明的范围之内。
能够再次将本发明的体系与现有技术的底涂基体系进行对比，其中通过单独底涂层来形成结合，并且该单独底涂层仅在膜与面涂层间界面存在，而在面涂层自身中不存在。
在本发明中，交联剂通常能够与烯键式不饱和化合物反应，所述化合物可以形成或不形成水分散性聚合物主链的部分，和/或可以是或不是水分散性聚合物主链的侧链。任选地，该化学相互作用是包含这两种材料以及聚合物的三元相互作用，由此在膜表面上有效形成用于接收墨的预聚物，然后通过辐射固化来进行固化。
此外，交联剂通常以超出水分散聚合物的化学当量交联所需量的量存在于涂料组合物中。这能够剩余一些可用于与烯键式不饱和化合物反应的交联剂。
在本发明的无底涂体系中，交联剂优选存在遍及整个涂层。交联剂优选通过面涂层的所有方向从膜(基底)到达表面，其中在基底中交联剂与基底上的官能团(例如，其上的酸、羟基和氨基)粘合，在面涂层中交联剂将聚合物交联并且与烯键式不饱和化合物进行化学相互作用，在表面中交联剂将烯键式不饱和化合物固定并且仍然留下在烯键式不饱和化合物上可用的官能团来粘合墨。本发明的关键特征是存在于体系中的烯键式不饱和化合物在将墨涂覆至体系时保留其至少部分的不饱和性。换而言之，涂料包含烯键式不饱和化合物，所述烯键式不饱和化合物没有被固化至完全从化合物中除去烯基不饱和性并且其不能与涂覆至涂层表面的墨粘合的程度。在本发明的涂料制剂中使用的烯键式不饱和化合物必须能够(通过一个或多个其烯键式不饱和基团)与涂覆至涂层的墨粘合。最初用烯键式不饱和化合物制备涂料制剂，但然后在着墨之前将其固化，从而在涂层中保留了不够用于墨粘附的烯键式不饱和基团，这种涂料制剂与本发明无关。
组分的组合能够使用过量的交联剂，而不导致过分地交联、硬的不可印刷的膜。相反，某些优选的交联剂能够通过水解避免过度交联的缺点。以下也能够起作用，并且可以由技术人员进行相应的改变：与烯键式不饱和化合物的反应；考虑聚合物的三元相互作用；材料的特殊官能度，包括例如在聚合物组成中有限水平的酸官能度；交联剂的量；以及当进行初始聚合反应时所选择的单体。
交联剂和烯键式不饱和化合物间的化学相互作用的机理可以任选地为碱诱导的不饱和(烯基)键的亲核加成反应，例如Michael加成或可选择的/另外的Baylis-Hillman反应。
涂料组合物优选为水基组合物；能够可选择地使用基于溶剂(例如，MEK-甲基乙基酮或乙酸异丙酯)的体系。可以任选地将基于有机溶剂的体系与聚酯粘合剂和/或芳香性交联剂组合使用。
优选地，烯键式不饱和化合物为可分散在水中或可混合在水中(而不是可溶解)。
本发明的涂料可以形成覆盖上述基底的至少一个面的层。通过非限制性实例，水分散性聚合物可以选自水分散性聚丙烯酸酯、水分散性聚氨酯、水分散性聚氨酯丙烯酸酯、水分散性苯乙烯丁二烯/马来酸酐共聚物及其混合物。水分散性聚合物形成光滑、成膜并亲墨的表面。
用作水分散性聚合物的丙烯酸聚合物包括通过至少一种(甲基)丙烯酸型单体的自由基加成聚合反应以及任选的其它乙烯基化合物或烯丙基化合物的自由基加成聚合反应而获得的聚合物(共聚物)。丙烯酸聚合物提供了光滑、成膜并亲墨的表面。
许多丙烯酸聚合物能够满足这样的要求。合适的丙烯酸聚合物为(甲基)丙烯酸或烷基(甲基)丙烯酸酯的均聚物，所述烷基具有1个至10个碳原子，或者两个或两个以上的所述(甲基)丙烯酸型单体的共聚物以及任选的其它乙烯基化合物或烯丙基化合物的共聚物。
如上所述，还可以适当地使用水分散性聚氨酯聚合物。如同丙烯酸聚合物，重要的是这种聚氨酯聚合物应当能够提供光滑、成膜和亲墨的表面。
许多聚氨酯化合物能够满足这样的要求。例如，合适的聚氨酯化合物为异氰酸酯封端的聚氨酯预聚物和活性含氢扩链剂的反应产物，所述异氰酸酯封端的聚氨酯预聚物通过至少过量的有机聚异氰酸酯、包含至少两个异氰酸酯反应基团的有机化合物与包含阳离子盐官能团(或随后可以转化为这种阳离子盐基团的酸基团)或非离子基团的异氰酸酯反应化合物反应而形成。
水分散性聚合物具有足够低水平的反应官能团以限制交联密度，从而为成品膜的性能提供充足的防水性，同时留下亲印刷墨的表面，所述墨为可UV固化的、水基或基于溶剂的。优选地，具有小于10重量％的反应官能团。
例如，基于涂料组合物干燥后的重量，水分散性聚合物的量为10％至98％，优选为60％至95％，更优选为74％至92％。
表面层还包含烯键式不饱和化合物。
选择烯键式不饱和化合物以在湿润阶段其可混合在水相中并且在干燥阶段其可与水分散性聚合物本身相容。因此，表面层一旦硬化，烯键式不饱和化合物充当表面层的增塑剂，使其上的可辐射固化墨易于渗透。或者，可以提供烯键式不饱和化合物作为水分散性聚合物的一部分，例如，作为其官能侧链。
当将印刷膜经受辐射从而固化墨时，烯键式不饱和化合物还必须能够与已经渗入表面层的墨的不饱和组分反应。
表面层的烯键式不饱和化合物与可辐射固化墨的不饱和化合物间的反应形成这些化合物间的化学键，同时将表面层交联，由此生成最终的抗性产品。
优选地，烯键式不饱和化合物每个分子包含1个至10个双键，并且甚至更优选每个分子(或每个官能团，前提是提供化合物作为水分散性聚合物的侧链或作为水分散性聚合物的部分)包含2个至5个双键。
适当的烯键式不饱和化合物为α-烯键式不饱和酸、β-烯键式不饱和酸与多元醇或烷氧基化多元醇的酯衍生物，所述烯键式不饱和酸例如丙烯酸或甲基丙烯酸、衣康酸或宁康酸、马来酸或富马酸等。其它合适的烯键式不饱和化合物包括与烯键式不饱和醇及其乙氧基化变体反应的异氰酸酯预聚物或低聚物的衍生物，例如，与羟基甲基丙烯酸乙酯反应的Desmodur(Bayer)三官能异氰酸酯。换而言之，本发明使用的烯键式不饱和化合物除一个或多个酯键之外还可以包含一个或多个氨基甲酸酯键，或可以包含一个或多个氨基甲酸酯键而不包含一个或多个酯键。
合适的多元醇包括饱和脂肪族二醇，例如乙二醇、二甘醇、三甘醇、丙二醇、二丙二醇、三丙二醇、丁二醇、新戊二醇、1,3-丁二醇和1,4-丁二醇、1,5-戊二醇、1,6-己二醇和2-甲基-1,3丙二醇。还可以使用丙三醇、1,1,1-三羟甲基丙烷、双酚A及其氢化衍生物。合适的烷氧基化多元醇包括以上列举的多元醇的乙氧基化衍生物或丙氧基化衍生物。
本发明能够使用的烯键式不饱和化合物的实例为诸如二官能丙烯酸酯、三官能丙烯酸酯、四官能丙烯酸酯等的多官能丙烯酸酯，其中二官能丙烯酸酯例如1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三乙基二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、2,2-二醇二丙烯酸酯、双酚A二丙烯酸酯等，三官能丙烯酸酯例如季戊四醇三丙烯酸酯、三羟甲基丙烷三丙烯酸酯等。
应当明白还能够使用与这些丙烯酸酯衍生物相对应的甲基丙烯酸酯衍生物。
此外，已经发现诸如四烯丙氧基乙烷等的聚烯丙基衍生物也是合适的。在这方面，合适的材料购买自Cytec Industries Inc，其商品名为Ebecryl。
例如，烯键式不饱和化合物的量为丙烯酸聚合物的约2％重量比至约90％重量比，并且优选为约2％重量比至约15％重量比，或2％重量比至10％重量比(在本说明书中，所有百分比以干燥重量为基准)。
合适的交联剂包括碳二亚胺交联剂和氮丙啶交联剂，以及在例如WO02/31016中公开的交联剂。交联剂可以在基底和面涂层间界面形成羧基官能团、羟基官能团或胺官能团间的键。
交联剂还可以提高沉积在膜上的表面层的硬度和/或防水性，并因此提高成品的硬度和/或防水性，同时生成的表面层，其一旦硬化，能够使其上的可辐射固化墨易于渗透。
例如，可以使用1％至10％的交联剂，更优选1％至5％或2％至5％。
例如，当聚合物为丙烯酸聚合物，交联剂的量能够最高达到丙烯酸聚合物的10％重量比，优选为丙烯酸聚合物的1％重量比至5％重量比。
为了防止一片与另一片粘连，并且为了提高片操作性、抗静电性、不透明性等，若需要，表面层可以包含所有其它的添加剂。通常以不超过丙烯酸聚合物的约40％重量比的总量来加入这些添加剂。例如，对于所述添加剂，可以使用颜料，例如聚氧化乙烯、二氧化硅、硅胶、粘土、滑石、硅藻土、碳酸钙、硫酸钙、硫酸钡、硅酸铝、合成沸石、氧化铝、氧化锌、氧化钛、锌钡白、缎光白等；以及阳离子抗静电剂；阴离子抗静电剂和非离子抗静电剂等。
例如，可以使用墨粘附促进剂和表面硬化剂，例如胶体二氧化硅。例如，墨粘附促进剂和表面硬化剂能够以5％至20％的量存在。
可以使用的合适的防粘连材料包括二氧化硅、粘土、不成膜聚合物(例如PMMA分散液和PMMA珠)，例如，其添加量为0.1％至3％，优选为0.1％至1.0％。
可以向涂料固体提供约5％至20％的水。
根据本发明，通过辊涂、刮涂、喷涂、气刀涂覆、杆棒涂覆、反转凹印等方法可以在基底上以约0.5g/m2至约2.5g/m2的水性分散液涂覆表面层，然后干燥，例如在热风烘箱中干燥。
在干燥步骤之后，表面层由此包含通过交联剂平滑地交联的水分散性聚合物和包含在丙烯酸聚合物基体中的烯键式不饱和化合物。这样可使可辐射固化墨易于渗透入表面层并随后与烯键式不饱和化合物反应。
本发明没有使用底涂。然而，在涂覆表面层之前，如果在基底表面不能获得足够的官能度，能够任选以常规方法对其预处理，从而改进湿润性和粘附性。为了这个目的，例如，可能通过电晕效应、电晕放电、火焰或氧化化学品来预处理基底，但是应当明白从组合物应用的角度，旨在改进片状物品表面的已知技术是合适的。
能够使用由常用压敏粘合剂组成的压敏粘合层来覆盖基底的反面，即没有被表面层覆盖的面。此外，若需要，由剥离剂组成的剥离膜或剥离片可以覆盖压敏粘合层。可以将包含本发明印刷片的该层压材料用作粘贴标签，可以将该粘贴标签贴至大多数类型的表面。
因此，本发明的另一方面涉及用于标签的包含基底的可印刷膜，所述基底仅一面用表面层涂覆并且反面用压敏粘合层涂覆，所述压敏粘合层自身用剥离膜或剥离片来覆盖。
本发明的另一方面涉及制备可印刷膜的方法，其包括用水性分散液涂覆基底的至少一面的步骤，并且还包括将所获得的涂层干燥的步骤，所述水性分散液包含水分散性聚合物、烯键式不饱和化合物和合适的交联剂以及任选的常规添加剂。
制备可印刷膜的方法可以任选包括在涂覆基底的至少一面的步骤之前将基底进一步预处理的步骤(例如电晕放电处理)。
在涉及制备标签的特别实施方案中，所述基底的仅一面用表面层涂覆，并且用压敏粘合剂涂覆所获得的已涂覆一面的基底。可以将压敏粘合剂从与涂覆基底结合的剥离衬垫上转移。
本发明的另一个目的涉及包含基底的印刷膜，所述基底的至少一面用表面层涂覆，所述表面层包含水性分散液聚合物，烯键式不饱和化合物以及合适的交联剂，使用可辐射固化墨，通过诸如胶印、凹版印刷、柔性版印刷、丝网印刷和凸版印刷的常规方法来印刷基底的所述涂覆面，然后辐射固化。
辐射固化的墨制剂通常包含颜料、赋形剂、溶剂和添加剂。这些体系中的溶剂为低粘度的能够自反应的单体(即，用作反应稀释剂)。赋形剂通常由树脂组成，所述树脂源自能够与表面层的烯键式不饱和化合物反应的不饱和单体、预聚物或低聚物，例如丙烯酸酯衍生物。对于UV墨，“添加剂”包含大量的对UV光光子有反应的光引发剂以开始体系的反应。
UV制剂可归纳为：
对于可电子束固化墨，“添加剂”通常不包含光引发剂。
有时称为稀释剂的低粘度单体能够进行化学反应从而使其完全合并在最终聚合物基体中。
赋形剂提供了制剂的“硬树脂”部分。通常，其源自通过与具有烯基的化合物反应而被改性的合成树脂，己内酯与具有羟基的不饱和化合物的反应产物等，所述合成树脂例如聚氨酯、环氧树脂、聚酯，所述具有烯基的化合物例如(甲基)丙烯酸、(甲基)丙烯酸羟乙酯。
可以对使用的预聚体和单体的选择进行适当的调整，从而实现本申请不同方法的所期望的粘度。
本发明的另一方面涉及制备印刷膜的方法，其包括步骤：
a)用水性分散液涂覆基底，所述水性分散液包含水分散性聚合物、烯键式不饱和化合物以及合适的交联剂；
b)将所获得的涂层干燥；
c)用可辐射固化墨将干燥的涂层着墨；
d)用UV辐射或EB辐射将墨固化。
注意在与常规表面层相同的条件(速度、成本等)中，可以实行本方法的不同步骤。
最后，本发明还涉及通过将本发明的可印刷膜着墨而获得的印刷膜，特别涉及所获得的印刷标签。
本发明的涂膜的实例示意性地并且未按比例地显示在图1中。
实施例
给出以下实施例老说明本发明，并且可以按照标准技术在基底膜上涂覆以下实施例。
在这些实施例中使用的原材料来源于下列供应商：Cytec SurfaceSpecialties S.A./N.V.Anderlechtstraat，33，1620Drogenbos；AlberdingkBoley GmbH Europe Headquarters，Duesseldorfer Str.53，47829Krefeld，德国；Cray Valley Laporte Road，Stallingborough，North East Lincolnshire，DN418DR；Xama Aziridenes Flevo Chemie(荷兰)B.V.，Havendijk 8a，3846AD Harderwijk，荷兰；Gasil Silica INEOSSilicas Limited，Warrington，英格兰WA51AB；Baxenden Chemicals Ltd，Paragon Works，Worsley Street，Rising Bridge，Accrington，BB52SL；Bayer Material Science 100BayerRoad，Pittsburgh，PA 15205；Grace Davison Oak Park Business Centre，Alington Road，Little Barford，St.Neots，Cambs PE196WL；NIPPONSHOKUBAI EUROPE N.V.Haven 1053，Nieuwe Weg1，B-2070Zwijndrecht，比利时；Nissando Industries Inc.1-2-3，Onodai Midori-ku，中国；DSM NeoResins+Sluisweg 12，PO Box 1235140AC Waalwijk，荷兰。
样品1
样品2
样品3
(在以上样品1至样品3的括号中所示的范围为所指定材料的优选范围，并且在括号前所示数值是在建议优选范围内的预期配方的具体实例。)
根据本发明来制备下列更具体的制剂，或在不存在指定的防粘连组分的情况下，以适合实验室测试的形式制备下列更具体的制剂，并且对其进行如下测试：
实施例1
| 组分 | 干燥百分比 | 描述 |
| Alberdingk U3305 | 76.96 | 聚氨酯丙烯酸酯分散液 |
| Ludox X30 | 10.00 | 胶体二氧化硅 |
| 防粘连剂 | 1.00 | 微粒PMMA |
| Sartomer CN133 | 7.00 | 脂肪族低聚物三丙烯酸酯 |
| Dowfax 2A1 | 0.04 | 分散表面活性剂 |
| CX 100 | 5.00 | 氮丙啶交联剂(DSM) |
实施例2
实施例3
| 组分 | 干燥百分比 | 描述 |
| Alberdingk U3305 | 76.96 | 聚氨酯丙烯酸酯分散液 |
| Ludox X30 | 10.00 | 胶体二氧化硅 |
| 防粘连剂 | 1.00 | 微粒PMMA |
| Sartomer CN133 | 7.00 | 脂肪族低聚物三丙烯酸酯 |
| Dowfax 2A1 | 0.04 | 分散表面活性剂 |
| Carbodilite E-03A | 5.00 | 碳二亚胺交联剂(Nissindo Industries) |
实施例4
实施例5
符合本发明预期的其它更具体的制剂如下：
实施例6
| 组分 | 干燥百分比 | 描述 |
| Alberdingk U3305 | 76.96 | 聚氨酯丙烯酸酯分散液 |
| Bindzil 30/310 | 10.00 | 胶体二氧化硅 |
| 防粘连剂 | 1.00 | 微粒PMMA |
| Ebecryl 1160 | 7.00 | 乙氧基化TMPTA(Cytec) |
| Dowfax 2A1 | 0.04 | 分散表面活性剂 |
| CX 100 | 4.00 | 氮丙啶交联剂 |
实施例7
| 组分 | 干燥百分比 | 描述 |
| Alberdingk U3305 | 76.96 | 聚氨酯丙烯酸酯分散液 |
| Bindzil 30/310 | 10.00 | 胶体二氧化硅 |
| 防粘连剂 | 1.00 | 微粒PMMA |
| Sartomer 454 | 7.00 | 乙氧基化TMPTA |
| Dowfax 2A1 | 0.04 | 分散表面活性剂 |
| Ucarlink XL29SE | 5.00 | 碳二亚胺交联剂(Dow Chemicals) |
这些样品和实施例的体系在交联剂耗尽之前应具有约8小时至12小时的可用期。然而，另外的交联剂的加入激活了该制剂，而不显著影响成品膜性能。
在膜上涂覆上述实施例1至实施例5的具体制剂之后，将涂覆的膜在热风烘箱中干燥，然后通过丝网印刷方法，使用市售的UV可固化丝印墨，以5g/m2至15g/m2进行印刷。实施例为来自FUJIFILM SERICOL的RN752&650-CWHD墨、来自PARAGON INKS的UVSF-172墨、来自NORCOTE的RSP系列墨或来自FLINT INKS的CombiwhiteUSW90004&UVOSCREEN II(tm)墨。
以通常50m/min至100m/min的印刷速度，使用100W/cm至200W/cm UV灯功率的通常商用条件，将所获得的印刷膜UV固化。
按照下列方法来测试最终获得的印刷膜：
在高温(通常>90℃)和低温(0℃)暴露于极端潮湿的条件下，然后立即进行划痕测试。实施例1至实施例5各自通过高温测试，并且实施例3通过了在4℃的改进的低温测试。
实施例6和实施例7和按照样品1至样品3配制的具体实施例得到预期相似的结果。
结果显示本发明新型无底涂体系提供了适于在诸如饮料工业中标记的优异印刷膜。
Claims (22)
1.用于面材的无底涂涂料组合物，其包含：为水分散性聚合物的粘合剂；水分散性的并能与所述水分散性聚合物混合或结合至所述水分散性聚合物的烯键式不饱和化合物，其中所述烯键式不饱和化合物能够与墨形成共价键；以及交联剂，其中所述交联剂适于将所述涂料粘合至所述面材。
2.如权利要求1所述的涂料组合物，其中成品中的粘合发生在所述交联剂和所述烯键式不饱和化合物之间。
3.如权利要求1或2所述的涂料组合物，其能够形成光滑膜并提供适于印刷的亲墨表面。
4.如前述任一权利要求所述的涂料组合物，其中在将所述涂料组合物干燥之后，所述水分散性聚合物的存在量为10％重量比至98％重量比。
5.如前述任一权利要求所述的涂料组合物，其中在将所述涂料组合物干燥之后，所述烯键式不饱和化合物的存在量为2％重量比至90％重量比。
6.如前述任一权利要求所述的涂料组合物，其中在将所述涂料组合物干燥之后，所述交联剂的存在量为1％重量比至5％重量比。
7.如前述任一权利要求所述的涂料组合物，其中所述水分散性聚合物选自水分散性聚丙烯酸酯、水分散性聚氨酯、水分散性聚氨酯丙烯酸酯、水分散性苯乙烯丁二烯/马来酸酐共聚物及其混合物。
8.如前述任一权利要求所述的涂料组合物，其中所述交联剂为碳二亚胺交联剂或氮丙啶交联剂。
9.如权利要求1至8中任一权利要求所述的涂料组合物，其中所述烯键式不饱和化合物在向所述涂料涂覆墨时能够通过存在于所述涂料中的烯键式不饱和基团与墨形成共价键。
10.如权利要求9所述的涂料组合物，其中当通过涂覆步骤已将所述涂料涂覆至膜上并且已将涂覆的膜提供至印刷台上时，将所述墨涂覆至所述涂料。
11.可印刷膜，其包含基底和由前述任一权利要求所述的涂料组合物形成的至少一个表面层，所述表面层不包含底涂层。
12.可印刷膜，其包含：基底；适于印刷的由权利要求1至10中任一权利要求所述的涂料组合物形成的第一表面层，所述第一表面层不包含底涂层；以及适于粘附的第二表面层。
13.如权利要求12所述的可印刷膜，其中所述第二表面层是由权利要求1至10中任一权利要求所述的涂料组合物形成，所述第二表面层不包含底涂层。
14.如权利要求11至13中任一权利要求所述的可印刷膜，其中所述基底选自聚合物膜、聚烯烃膜、纸、合成纸、机织物、无纺织物、陶瓷片、金属纤维片、镀金属片(膜)、金属箔、金属板以及通过上述材料的组合而形成的多层复合片。
15.如权利要求11至14中任一权利要求所述的可印刷膜，其中所述基底为取向的聚丙烯膜。
16.如权利要求11至15中任一权利要求所述的可印刷膜，其中所述基底的仅一面用表面层涂覆，并且所述基底的反面用压敏粘合层覆盖。
17.包含权利要求11至16中任一权利要求所述的可印刷膜的印刷膜，其还具有印刷图案。
18.用于制备权利要求11至16中任一权利要求所述的可印刷膜的方法，其包括用水性分散液涂覆所述基底的至少一个面的步骤，所述水性分散液包含权利要求1至10中任一权利要求所述的涂料，并且还包括将所获得的涂层干燥的步骤。
19.用于制备权利要求17所述的印刷膜的方法，其包括权利要求18所述的步骤，并且还包括以下步骤：用可辐射固化的墨将所述干燥的涂层着墨；以及用UV辐射或EB辐射将所述墨固化。
20.印刷膜，其通过权利要求19所述的方法获得。
21.如权利要求17或20所述的标签形式的印刷膜，在印刷之前或之后，所述膜与压敏粘合层结合，并任选与剥离膜结合。
22.容器，例如瓶子，其用权利要求21所述的标签标记。
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| GB0822412.3 | 2008-12-09 | ||
| GBGB0822412.3A GB0822412D0 (en) | 2008-12-09 | 2008-12-09 | Printable coating |
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| CN2009801475132A Pending CN102227315A (zh) | 2008-12-09 | 2009-12-08 | 可印刷涂料 |
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| JP (3) | JP5912581B2 (zh) |
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| CN (2) | CN104693927A (zh) |
| AU (1) | AU2009326206B2 (zh) |
| BR (1) | BRPI0921545B1 (zh) |
| CA (1) | CA2743388C (zh) |
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| HK (1) | HK1207105A1 (zh) |
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| MY (1) | MY145643A (zh) |
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| CN1209777A (zh) * | 1996-01-25 | 1999-03-03 | Ucb公司 | 可印刷薄膜 |
| US20020146559A1 (en) * | 2001-04-06 | 2002-10-10 | Touhsaent Robert Edward | Printable plastic film with printable coating comprising epoxy acrylate |
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| CN107513327A (zh) * | 2017-09-13 | 2017-12-26 | 纳印（北京）技术服务有限公司 | 亲水性涂料组合物及其应用以及用于喷墨打印直接制版的环保型板材 |
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