CN117460765A - 具有抗微生物特性的包装材料 - Google Patents
具有抗微生物特性的包装材料 Download PDFInfo
- Publication number
- CN117460765A CN117460765A CN202280040803.2A CN202280040803A CN117460765A CN 117460765 A CN117460765 A CN 117460765A CN 202280040803 A CN202280040803 A CN 202280040803A CN 117460765 A CN117460765 A CN 117460765A
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- Prior art keywords
- package
- coating
- antimicrobial
- mixtures
- silicone
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- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims abstract description 12
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
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- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- 235000019486 Sunflower oil Nutrition 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 5
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
- C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
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Abstract
具有抗微生物特性的包装材料,包含基材和涂层,其中所述涂层包含:‑第一聚合组分,其选自聚丙烯酸类树脂、聚乙烯醇缩丁醛、聚氨酯、聚酯、聚乙烯醇、纤维素聚合物及其混合物,‑低粘附性、滑爽或防粘剂,其选自聚硅氧烷、巴西棕榈蜡、卵磷脂、脂肪酸、脂肪族酰胺、脂肪酸酯、硬脂酸镁、植物油及其混合物,‑抗微生物剂,以及任选的一种或多种功能试剂,其选自:‑消泡剂‑聚结剂‑润湿剂‑交联剂‑及其混合物,其中所述涂层包含:‑50至99.49重量%的第一聚合组分;‑0.5至35重量%的低粘附性、滑爽或防粘剂,以及‑0.01至15重量%的抗微生物剂,‑0至10重量%的功能试剂‑所述重量百分数相对于100重量份干燥涂层。
Description
本发明涉及具有抗微生物特性(特别是抗病毒特性)的包装材料。
特别地,本发明涉及用于包装食物产品的包装材料。
包装被设计用于容纳其内容物和保护其内容物免受外部环境的影响,因此起阻隔作用;此外,它作为与客户交流的表面发挥着重要作用;因此,包装必须被视为阻隔和表面,从安全的角度来看,这两个方面都是相关的。
当表面暴露于受控制造之外的环境时,它将收集堆积的碎片,其可能包括致病微生物。这可包括含有微生物(或更具体是病毒)的液滴,其落入包装表面并停留一段时间。消毒表面的做法可以通过灭活微生物阻止疾病传播的风险,但在生产设施之外以及通向市场和家庭的供应链沿途并不总是可能的。因此,能够防止微生物污染的活性表面具有吸引力并为客户增加价值。
由于包装表面在整个分销链中暴露于环境中,并且一旦其离开生产设备就难以进行消毒,需要抗微生物的活性包装表面,其将降低疾病从人传播到表面和从表面传播到人的风险,由此保护供应链和最终客户。在包装的整个使用期限内,包装表面的持续和稳健的抗微生物活性对于确保沿着通过仓库和销售点向客户住宅的供应链的保护是必要的。
此外,希望消除或减少抗微生物剂向外部环境的迁移,从而延长抵抗通过接触包装表面而传播的任何潜在疾病的抗微生物和活性效果。因此,必须将特定的制剂放置在适当的位置以使包装能够保持从生产日期到有效期的活性。
本发明的一个目的是提供具有改进的抗微生物特性的包装和/或包装材料,其适于减少通过与包装表面接触而传播疾病的风险。
特别地,本发明的一个目的是提供这样的包装,其通过不粘、低粘附性或滑爽特性阻止或减少微生物和病毒通过附着在包装表面的碎片、液滴或任何载体而粘附到包装表面,并且同时,通过灭活任何粘附的微生物抑制微生物感染(抗微生物特性)。本发明也适用于通过冷链分销的包装,因为在一些情况下,在冷藏条件下的储存可能延长传染源的活性。
因此,本发明的目的是如所附权利要求中所定义的包装,其被认为包括在本公开中。
发明概述
如所附权利要求中所定义,本发明的主题是具有抗微生物特性、抗病毒特性以及使液滴和碎片滑落或更少粘附的能力的包装,其包括基材和涂层,其中所述涂层组合了抗微生物特性和低粘附性特性。涂层的低粘附性、滑爽或防粘(release)特性作用于减少污染物在包装表面的堆积同时抗微生物行为作用于灭活任何残留污染物中存在的微生物。
如本文中所使用的,术语“包装”适用于具有柔性基材的包装片或膜和具有刚性或自支撑基材的包装,例如容器及其类似物。
本发明提供了可施加在任何种类的包装上的活性涂层表面的广泛领域,所述包装包括通过挤出和注射成型获得的包装,例如保护具有半刚性或刚性一致性和外观的托盘、盒子和任何包装。此外,由于所配制涂层的特定另外发现的特性,本发明还可以赋予包装膜表面和热成型后的材料密封性。这开启了生产其中将柔性元件密封在刚性部分上的组合包装和盒子的可能性,为销售主张和客户提供了活性表面的更广泛的领域。
在本发明的一些涉及可热密封的涂层的实施方案中,由涂层介导的密封可以在70-150℃的温度和25ms至20s的时间出现,取决于基材。优选约100℃和0.5秒。在适用的情况下,涂层可降低塑料基材的密封温度,使低温下能够进行密封,或者缩短完成密封所需要的时间。
所述涂层包含:
-第一聚合组分,其选自聚丙烯酸类树脂、聚乙烯醇缩丁醛、聚氨酯、聚乙烯醇(完全水解(DH>98)或部分水解)、纤维素聚合物、聚酯,优选选自聚羟基脂肪酸酯、聚丁二酸丁二醇酯和聚乳酸及其混合物;
-低粘附性、滑爽或防粘剂,其选自聚硅氧烷、聚乙二醇、聚乙烯、巴西棕榈蜡、卵磷脂、聚酰胺、脂肪族酰胺、脂肪酸、脂肪酸酯、硬脂酸镁、植物油、石蜡及其混合物;以及
-抗微生物剂。
所述制剂可额外包括一种或多种以下功能试剂:
-消泡剂
-聚结剂
-润湿剂
-交联剂
-及其混合物
在涂料组合物中,就重量而言,第一聚合组分通常是主要组分,并且单独或与低粘附性、滑爽或防粘剂组合形成连续相或基体,抗微生物剂分散或溶解在其中。
用作第一聚合组分的聚丙烯酸类树脂包括聚丙烯酸、聚丙烯酸酯和聚甲基丙烯酸酯。
用作第一聚合组分的聚酯类树脂包括聚对苯二甲酸乙二醇酯、聚羟基脂肪酸酯、聚己内酯、聚丁二酸丁二醇酯、聚乳酸或其混合物。
优选的聚羟基脂肪酸酯包括乳酸聚酯、聚羟基丁酸酯、聚羟基丁酸酯-戊酸酯、聚羟基丁酸酯-丙酸酯、聚羟基丁酸酯-己酸酯、聚羟基丁酸酯-癸酸酯、聚羟基丁酸酯-十二烷酸酯、聚羟基丁酸酯-十六烷酸酯、聚羟基丁酸酯-十八烷酸酯、聚-3-羟基丁酸酯-4-羟基丁酸酯、聚-3-羟基丁酸酯-共-3-羟基己酸酯或其混合物。
纤维素聚合物包括纤维素、硝化纤维素、壳聚糖、乙酸纤维素、羧甲基纤维素、甲氧基纤维素、羟甲基纤维素、乙酸丁酸纤维素、乙酸丙酸纤维素、纤维素-2-羟乙基甲基醚、纤维素-十六烷基2-羟乙基醚、乙酸丁酯纤维素或其混合物。
尽管第一聚合物组分可以是疏水的或亲水的,但低粘附性、滑爽或防粘剂通常是疏水的或超疏水的材料或物质,或两亲性类材料或物质。
如本文中所使用的,术语“疏水的”和“超疏水的”意指防水的,并且具有其在化学与聚合物领域的通常和一般意义。特别地,如本文关于材料所使用的,术语“疏水的”是指材料具有至少90度的水接触角。并且术语“超疏水”意指它具有高于150度的接触角。
如本文中所使用的,术语两亲性意指同时具有疏水的和亲水的部分的物质且具有其在化学与聚合物领域的通常和一般意义。
优选的聚硅氧烷包括二甲基聚硅氧烷、有机硅乙烯基聚合物、有机硅乳液和硅油以及烷基化硅氧烷聚合物(或硅酮蜡)及其混合物。特别优选的是二甲基聚硅氧烷和硅酮蜡及其混合物。
优选的植物油包括大豆油、蓖麻油、菜籽油、棕榈油、葵花籽油、和椰子油及其混合物。
根据本发明的适合使用的抗微生物剂包括金属(例如钛、银、金、铜、铂、锌)、所述金属的氧化物或盐、合金、包含所述金属氧化物或盐的粘土或玻璃;所述金属可以是纳米颗粒的形式或者可以负载在纳米-、微米-或大(macro)-二氧化硅、或有机硅基或粘土基载体上;还包括的是作为抗微生物剂的抗微生物肽、有机硅基抗微生物剂以及季铵阳离子(QuaTs)。
此外,抗微生物剂也可采取消毒剂的形式,任选地封装于热、湿度或温度敏感的聚合物中。消毒剂可包括过氧化物、丙二醇、三乙二醇、十二烷酸、甲醛、戊二醛、百里酚、丁香油、肉桂油、西柚(grape frui t)提取物、桉树提取物、抗微生物植物提取物、氯或碘在溶剂例如水、乙醇、异丙醇中的溶液或其混合物。
优选的抗微生物剂包含银离子材料例如氯化银、钛、磷酸银、氧化锌、有机硅拴系季胺、百里酚、丁香油、肉桂油、西柚籽提取物、桉树提取物或前述的混合物。
在所有实施方案中银离子是优选的抗微生物剂。
涂料被配制成溶液、分散体、悬浮液或熔体,其包括第一聚合组分、低粘附性组分、抗微生物剂以及适当时适合的溶剂。适合的溶剂包括水、乙酸乙酯、乙醇、异丙醇、甲醇、十六烷、十二烷及其混合物。
涂料溶液、分散体或浆料可具有0.5至70重量%的干含量;10至25重量%的干含量,更优选大约15重量%的干含量是优选的。
在涂料溶液或分散体中抗微生物组分的负载可以是最终制剂的0.001%至60%的干含量,优选0.01至15重量%。
在涂覆和干燥过程之后,残留涂层的溶剂保持率应优选地少于15g/sqm,与所使用的溶剂和基材组合无关。
根据本发明的合适的涂覆方法包括轮转凹版印刷、柔性版印刷、平版印刷、数码印刷和挤出涂布。第一聚合组分、抗微生物剂和低粘附性、滑爽或防粘组分的组合同样可以被挤出和/或注射。
在轮转凹版印刷的情况下,滚筒应进行雕刻,以使涂层重量干克数达到以下范围:
0.1–20g/sqm
用于轮转凹版印刷的滚筒可被任意种技术雕刻,如日光反射信号(hel io)、电击或激光。
在柔性版印刷的情况下,考虑到连续接合技术,利用网纹辊雕刻以避免柔性版印刷过程中的不连续性。
提供抗微生物特性的涂层可以以一道或若干道施加。
本发明的涂料可被直接施加在包装材料基材的表面上或其可被施加在油墨、防潮或抗氧化的阻隔涂层、密封漆、防粘漆、低粘附性或食物接触漆的顶部或与其组合,能够使特性和各种包装图案结合。
在优选实施方案中,包装包含一层或多层在基材与抗微生物涂层之间的粘附性增强层。粘合增强层使表面准备好接收涂层并导致了改进的功能性。它们的作用是改善涂层与基材的粘附性,并有助于将涂层保持在表面,阻止涂层通过分层、磨损或吸收到基材中而被去除。将涂层保持在表面上的效果导致增强的功能性,因为涂层特性在包装的供应链沿途保持了更长时间;此外,用较低的涂层量可以获得相同的性能,因为在包装的表面有更多可用涂层。
粘附性增强层包括具有印刷油墨的印刷层、黏粒胶膜、阻隔涂层与底漆层或涂层。
油墨和底漆可改变基材的表面能,增强涂层粘附性。粘土和其他阻隔涂层也会改变基材的表面能并且可以额外减少基材的孔隙率,在不增加施加量的情况下增加包装表面涂层的可用性。
在印刷过程中,通常情况下在将下一层施加在其顶部之前,上一层未完全干燥和/或固化。这意指一旦结构完全装配,这个结构的层之间会发生带有各种化学和物理相互作用的进一步的干燥/固化。这种固化是暂时状态,根据所使用的具体底漆、油墨或清漆,可认为其在24-72小时内完成。一旦系统经装配,发现这种固化和相互作用除了如上述改进的粘附性还进一步增强了涂覆层的活性。
合适的底漆包括丙烯酸类清漆,优选具有添加的异氰酸酯,任选地与使用印刷油墨印刷的层组合。
在涂料组合物中,在固化和/或干燥后,第一聚合组分、低粘附性、滑爽或防粘剂和抗微生物剂的重量优选如此以获得疏水的表面。在第一聚合组分本身不疏水的情况下低粘附性、滑爽或防粘剂必须以足够高的浓度存在于涂层的表面以提供疏水的表面。通常,这是通过低粘附性、滑爽或防粘剂在干燥或固化过程中迁移到涂层的表面实现的,由此为涂层提供与涂层本体相比增强浓度的该材料,导致疏水表面。因此,少量组分的低粘附性、滑爽或防粘剂足够提供疏水性表面。
通常,涂层在干燥时、在固化之后和转化过程之后包含:
-50至99.49重量%的第一固化组分;优选70%至99.49%
-0.5至35重量%的低粘附性、滑爽或防粘剂,优选1%至10%;以及
-0.01至15重量%的抗微生物剂,优选0.01%至10%,更优选0.01%
-2%,所述重量百分数相对于100重量份干燥涂层,其中百分数总计100%。
用于基材的适合的材料包含纸、纸板、玻璃、金属和塑料材料,特别是例如聚丙烯(PP)、聚乙烯(PE)、聚乙烯-聚丙烯共聚物、聚苯乙烯(PS)、聚对苯二甲酸乙二醇酯(PET)和生物塑料,例如聚羟基脂肪酸酯(PHA),聚丁二酸丁二醇酯(PBS)或聚乳酸(PLA)。
在一个实施方案中,所述基材包括由上述的材料制成或含有上述的材料的膜或片且这种膜或片具有金属涂层。所述包装基材还包括上述膜或片的多层层压体和包括层压或涂覆在纸上的聚合物层的层压体。所述膜或片在多种环境中可以是或可以不是可堆肥的和/或可生物降解的。
膜或片形式的基材,可能具有可热密封的涂层;在具有可热密封涂层的柔性基材的情况下,经涂覆的基材可被密封在其他表面上,例如托盘或盒子,或它可被折叠,例如以管状形式,以获得在其外侧或内侧具有抗微生物涂层的包装。所述膜或片形式的基材可以是热成型的,并且在热成型以获得成形的包装结构之前可以将抗微生物涂层施加到基材上。
如之前提到的,如本文中所使用的,术语“包装”也包括其中所述基材是成形结构,例如刚性或半刚性容器、盒子或硬纸盒,玻璃、金属、塑料、纸或纸板中的任一种。这种材料可以通过注射成型、热成型、折叠或其它合适的成型技术形成。
在热成型和折叠的刚性或半刚性基材的情况下,涂料可以被印刷或喷涂在平坦时的基材上。涂层的抗微生物活性在折叠或热成型过程中保持或通过该过程被激活,由此赋予刚性或半刚性结构抗微生物活性。用于该过程的适合的基材包括纸和纸板、聚丙烯、聚乙烯、聚乙烯-聚丙烯共聚物、ABS、聚对苯二甲酸乙二醇酯、聚苯乙烯、聚乳酸、聚丁二酸丁二醇酯、聚羟基脂肪酸酯。
如以下所提到的,所述涂料组合物包含第一聚合组分、抗微生物剂和低粘附性、滑爽或防粘剂,也可以被挤出、共挤出和注射、在热处理后保持抗微生物特性,从而形成刚性或半刚性抗微生物包装。
适用于注射成型的聚合物与涂料组合物的组合包含所述第一聚合组分、抗微生物剂和低粘附性、滑爽或防粘剂,包括:聚丙烯、聚乙烯、聚乙烯-聚丙烯共聚物、ABS、聚对苯二甲酸乙二醇酯、聚苯乙烯、聚乳酸、聚丁二酸丁二醇酯、聚羟基脂肪酸酯。
根据本发明的实施方案,包装包含基材,其是通过注射成型或挤出聚合物共混物获得的注射成型或挤出包装结构,所述聚合物共混物包含:
聚合物,其选自聚丙烯、聚乙烯、聚乙烯-聚丙烯共聚物、ABS、聚苯乙烯、聚对苯二甲酸乙二醇酯和生物塑料,优选聚羟基脂肪酸酯、聚丁二酸丁二醇酯或聚乳酸及其混合物,以及涂料组合物的组分,其包含如前述所定义的抗微生物剂和低粘附性、滑爽或防粘剂和任选的如前述所定义的所述第一聚合组分。
涂料组合物的组分(包含抗微生物剂、低粘附性、滑爽或防粘剂和任选的所述第一聚合组分)也可与合适的聚合物(例如在前述段落中提到的用于注塑成型的那些)配混并直接挤出或注射,或者它们可以与载体树脂混合以形成母料,其随后与所述合适的聚合物注射或挤出。
在优选实施方案中,母料应以0.1至10重量%加入注射成型聚合物,所述母料包含:
-45至97重量%的载体聚合物(注射成型树脂);优选80%至97%
-1至30重量%的第一聚合组分
-1至5重量%的低粘附性、滑爽或防粘剂,优选1%至3%;以及
-1至20重量%的抗微生物剂,优选1%至10%
所述制剂可额外包括
-成核剂以及
-表面活性剂和稳定剂
在不使用母料组合材料的情况下,以下是优选实施方案:
-73重量%至99.399重量%的注射成型聚合物,
-0.5重量%至20重量%的所述第一聚合组分,
-0.1重量%至2重量%的低粘附性、滑爽或防粘剂,优选少于1.5%;以及
-0.001至5重量%的抗微生物剂,优选0.1%至1%。
取决于对基材的选择,如之前所描述的涂层可以直接施加到未经处理的基材表面或预先经例如电晕处理、底漆、油墨及其类似物处理过的基材表面。在施加涂层之后必须进行固化,从涂层中去除溶剂(当存在时)并且能够进行物理或化学交联。在升高的温度下延长固化时间可能是对稳定涂层行为所必需的。
根据本发明,涂层,包括以上提到的低粘附性、滑爽或防粘剂组分的使用,提供了水滴和其它碎片的粘附性降低的包装表面,这进而减少了微生物的积累和停留时间。这与涂层的抗微生物特性一起作用,导致增强抗微生物特性并降低抗微生物剂的负载量。抗微生物特性与防粘或滑爽特性的组合益处额外地可以促进材料的涂层卷轴的退绕。
附图说明
附图的图1至图6以举例方式示出了本发明包装的优选分层结构。
活性涂覆层2被施加在作为包装结构的最外层的基材4上,任选地具有插入的油墨或印刷层6或具有插入的阻隔涂覆层8。适于提供热密封特性的密封剂层或漆层10可以施加在与活性涂覆层相对的包装的另一侧上。然而,在一些实施方案中,活性涂覆层可以是可热密封的。金属化层12可以施加在与活性涂覆层相对的封装的外表面上。所述包装可以包括一个或多个基材层4A和4B。
本发明的优选实施方案
上文所提供的涂覆层组分的公开应被解释为每种所列出的聚合组分与每种所列出的滑爽剂或防粘剂和/或每种所列的抗微生物剂的特定组合的公开。
在优选实施方案(其提供了适于轮转凹版印刷的涂覆层,然后热密封经涂覆的表面)中,所述聚合组分优选丙烯酸类、聚氨酯或纤维素聚合物。
在这个实施方案中,优选的低粘附性、滑爽或防粘剂选自聚硅氧烷例如有机硅乙烯基聚合物、有机硅乳液、二甲基聚硅氧烷、硅油和烷基化有机硅聚合物(或硅酮蜡),聚乙二醇、聚乙烯、巴西棕榈蜡、卵磷脂、聚酰胺、脂肪酸、脂肪酸酯、硬脂酸镁、植物油例如大豆油、菜籽油、棕榈油、葵花籽油、椰子油和蓖麻油、石蜡及其混合物。
本文中之前提到的任何抗微生物剂都可以和上述聚合组分和/或滑爽或防粘剂中的每一种组合;然而,抗微生物剂优选选自氯化银、钛、磷酸银、有机硅拴系季胺、氧化锌、抗微生物植物提取物或其混合物。在这些实施方案中,涂料组合物优选在水性溶剂中配制。
本文中之前所公开的涂料组合物组分的重量的范围也适用于根据以下优选实施方案的组分。
优选的实施方案也是具有涂层的包装,其中:
A)第一聚合组分是丙烯酸类聚合物或聚乙烯醇缩丁醛,
滑爽或防粘剂选自以下:石蜡、含有机硅的聚合物、巴西棕榈蜡或植物基油。
抗微生物剂是银离子,优选在水性溶液中配制。
B)第一聚合组分是丙烯酸类或聚氨酯聚合物,
滑爽或防粘剂选自石蜡、含有机硅的聚合物、巴西棕榈蜡或植物油,
抗微生物剂是磷酸银玻璃;涂料优选在水性溶液中配制。
C)第一聚合组分是丙烯酸类或聚氨酯聚合物,
滑爽或防粘剂选自石蜡或含有机硅的聚合物,
抗微生物剂是磷酸银陶瓷;优选在水性溶液中配制。
D)第一聚合组分是纤维素聚合物,
滑爽或防粘剂选自石蜡或含有机硅的聚合物、椰子油、巴西棕榈蜡或植物油,优选椰子油,
抗微生物剂是磷酸银陶瓷;优选在水性溶液中配制。
E)第一聚合组分是纤维素聚合物,
滑爽或防粘剂选自石蜡或含有机硅的聚合物、巴西棕榈蜡、植物油,优选椰子油,
抗微生物剂是百里酚、肉桂油、丁香油或其混合物;优选在水性溶液中配制。
进一步优选的实施方案(其中涂覆层适于通过轮转凹版印刷进行印刷,但是因为化学交联的存在不适于热密封)是其中涂料的第一聚合组分是聚酯、聚乙烯醇缩丁醛、聚氨酯或纤维素聚合物的包装,特别这样的包装,其中在涂料中:
F)第一聚合组分是聚酯、聚乙烯醇缩丁醛、聚氨酯或纤维素聚合物,
滑爽或防粘剂选自石蜡、含有机硅的聚合物、巴西棕榈蜡、聚酰胺及其混合物,
抗微生物剂选自氯化银、钛、磷酸银、有机硅拴系季胺或其混合物,其中涂料组合物优选包含基于异氰酸酯或醛衍生物的交联剂。这些涂料优选使用乙酸乙酯作为溶剂配制。
G)第一聚合组分是聚酯、聚乙烯醇缩丁醛、聚氨酯或纤维素聚合物,
滑爽或防粘剂选自石蜡、巴西棕榈蜡、椰子油、聚酰胺及其混合物,
抗微生物剂是有机硅拴系季胺,或氯化银、钛、磷酸银、有机硅拴系季胺、抗微生物植物提取物的混合物,其中涂料组合物优选包含基于异氰酸酯或醛衍生物的交联剂。这些涂料优选使用乙酸乙酯作为溶剂配制。
在以下工作实施例中,除非另有说明,百分数是以重量计的。
实施例1
所制备的涂料包含:
硝化纤维素基聚合物(相对于干物质为85%)
含有机硅的聚合物,相对于干物质为7%
银离子,相对于干物质为1%
功能试剂(相对于干物质为7%)
以及乙酸乙酯(相对于以上所有干组分为85%)。
涂料通过轮转凹版印刷被施加到作为基材的聚丙烯或聚乙烯的膜上;涂层重量为0.5-3g/sqm,线速度为250m/min,然后在环境温度下固化24h。得到R值>1的杀病毒活性,当针对甲型流感和NL63人类冠状病毒根据ISO21702:2019以24h的接触时间测试时。
实施例2
所制备的涂料包含:
聚酯(优选相对于干物质为91%)
聚二甲基硅氧烷7%,有机硅拴系季胺0.02%至2%干含量
使用基于异氰酸酯的交联剂,以及
作为溶剂的乙酸乙酯,(相对于以上所有干组分为40%)
涂料通过轮转凹版印刷技术被施加到聚丙烯或聚乙烯的膜上,涂层重量为0.5-2.5g/sqm,线速度为200m/min,异氰酸酯交联,然后在环境温度下固化72h。得到R值>1的杀病毒活性,当针对NL63人类冠状病毒根据ISO21702:2019以24h的接触时间测试时。
实施例3
所制备的涂料包含:
聚氨酯(相对于干物质为92%)
巴西棕榈蜡7%
银离子1%
以及水性溶剂(相对于以上所有干组分为85%)
涂料通过轮转凹版印刷技术被施加到聚丙烯膜上,具有1-3g/sqm的涂层重量。得到R值>2的杀病毒活性,当针对猫杯状病毒根据ISO21702:2019以24h的接触时间测试时。
实施例4
所制备的涂料包含:
丙烯酸类聚合物(相对于干物质为90-92.9%)
植物油(相对于干物质为7%)
银离子(相对于干物质为0.1-3%)
以及水性溶剂(相对于以上所有干组分为85%)
使用轮转凹版印刷技术将涂料施加到聚丙烯膜上,具有1至2g/sqm的涂层重量。得到>3的对数下降值的抗细菌活性,当针对大肠杆菌和金黄色葡萄球菌根据ISO22196以24h的接触时间测试时。
实施例5
所制备的涂料包含:
壳聚糖(相对于干物质为90-92.9%)
椰子油(相对于干物质为7%)
丁香油、肉桂油和百里酚油的混合物(相对于干物质为0.1-3%)
以及水性溶剂(相对于以上所有干组分为85%)
将涂料手动施加到聚丙烯膜上,涂层重量1至4g/sqm,并得到延迟的霉菌生长。
实施例6
在纸基材(重量60g/m2)上施加黏粒胶膜并且通过连续轮转凹版印刷将黏粒胶膜印刷1至9种颜色;然后将以下抗微生物涂层施加到印刷层上:
丙烯酸类聚合物(相对于干物质为90%)
聚硅氧烷(相对于干物质为4%)
无机载体上的银离子(相对于干物质为1.4%)
功能试剂(相对于干物质为4.6%)
以及水性溶剂(相对于以上所有干组分为70%)
通过轮转凹版印刷技术以1.4-2g/m2施加涂料并且得到关于细菌的>2对数下降值,当针对大肠杆菌和金黄色葡萄球菌根据ISO22196以24h的接触时间测试时。
实施例6a
使用聚丙烯膜作为基材重复实施例6的步骤。根据ISO 22196,在抗微生物活性方面获得了基本相同的结果。
实施例7
通过轮转凹版印刷用7种颜色印刷由铝膜组成的基材,并施加以下抗微生物涂层:
聚乙烯醇缩丁醛(相对于干物质为92%)
聚硅氧烷(相对于干物质为4%)
无机载体上的银离子(相对于干物质为0.8%)
功能试剂(相对于干物质为3.2%)
以及乙酸乙酯溶剂(相对于以上所有干组分为75%)和交联剂(相对于以上描述的涂层制剂为15%)
涂料通过轮转凹版印刷技术以180m/min以1.4-2g/m2施加,并且得到对细菌的>4的对数下降值,当针对大肠杆菌和金黄色葡萄球菌根据ISO22196以24h的接触时间测试时以及关于病毒滴度>1的对数下降值,根据ISO21702以24h的接触时间。
实施例8
以0.2至1.5g/m2将底漆层印刷至由聚丙烯膜组成的基材上,所述底漆层由丙烯酸类清漆和添加的异氰酸酯组成;根据图形的需要,具有印刷油墨的印刷层被施加在底漆层上。以下抗微生物剂然后被施加在印刷层上
丙烯酸类聚合物(相对于干物质为90%)
脂肪酸(相对于干物质为4%)
无机载体上的银离子(相对于干物质为1%)
功能试剂(相对于干物质为5%)
以及水性溶液(相对于以上所有干组分为70%)。
发现当施加在底漆和油墨上时,涂层的固化起到增强涂层本身的抗微生物活性的作用。
实施例9
所制备的涂料包含:
丙烯酸酯聚合物(相对于干物质为90%)
聚硅氧烷/硅酮蜡(相对于干物质为4%)
无机载体上的银离子(相对于干物质为1.4%)
功能试剂(相对于干物质为4.6%)
以及水性溶剂(相对于以上所有干组分为70%)。
实施例10
所制备的涂料包含:
聚乙烯醇缩丁醛(相对于干物质为92%)
聚硅氧烷/硅酮蜡(相对于干物质为4%)
无机载体上的银离子(相对于干物质为0.8%)
功能试剂(相对于干物质为3.2%)
以及乙酸乙酯溶剂(相对于以上所有干组分为75%)和交联剂(相对于以上描述的涂层制剂为15%)
Claims (28)
1.一种具有抗微生物特性的包装,其包含基材和涂层,其中所述涂层包含:
-第一聚合组分,其选自聚丙烯酸类树脂、聚乙烯醇缩丁醛、聚氨酯、聚乙烯醇、纤维素聚合物和聚酯,优选选自聚羟基脂肪酸酯、聚丁二酸丁二醇酯和聚乳酸及其混合物;
-低粘附性、滑爽或防粘剂,其选自聚硅氧烷、巴西棕榈蜡、卵磷脂、脂肪酸、脂肪酸酰胺、脂肪酸酯、硬脂酸镁、植物油及其混合物;
-抗微生物剂,以及
任选的一种或多种功能试剂,其选自:
-消泡剂
-聚结剂
-润湿剂
-交联剂
-及其混合物,
其中所述涂层包含:
-50至99.49重量%的第一聚合组分;
-0.5至35重量%的低粘附性、滑爽或防粘剂,以及
-0.01至15重量%的抗微生物剂,
-0至10重量%的功能试剂
-所述重量百分数相对于100重量份干燥涂层。
2.根据权利要求1所述的包装,其中所述第一聚合组分是聚丙烯酸类树脂,并且所述低粘附性滑爽或防粘剂是聚硅氧烷,优选二甲基聚硅氧烷和硅酮蜡的混合物。
3.根据权利要求1所述的包装,其中所述第一聚合组分是聚乙烯醇缩丁醛,并且所述低粘附性滑爽或防粘剂是聚硅氧烷,优选二甲基聚硅氧烷和硅酮蜡的混合物。
4.根据权利要求1或2所述的包装,其中所述聚丙烯酸类树脂选自聚丙烯酸、聚丙烯酸酯和聚甲基丙烯酸酯。
5.根据权利要求1、2或3所述的包装,其中所述聚硅氧烷选自二甲基聚硅氧烷、有机硅乙烯基聚合物、有机硅乳液以及硅油、硅酮蜡及其混合物。
6.根据权利要求1所述的包装,其中所述聚酯选自聚羟基脂肪酸酯、聚对苯二甲酸乙二醇酯、聚己内酯、聚丁二酸丁二醇酯、聚丁二酸乙烯酯、聚乳酸及其混合物。
7.根据权利要求1中任一项所述的包装,其中所述植物油选自大豆油、蓖麻油、菜籽油、棕榈油、葵花籽油和椰子油及其混合物。
8.根据权利要求1至7中任一项所述的包装,其中所述抗微生物剂是金属,其选自钛、银、金、铜、铂和锌、所述金属的氧化物或盐、合金、包括所述金属氧化物的粘土或玻璃,其中所述金属可以是纳米颗粒的形式,或者可以负载在纳米-、微米-或大-二氧化硅、有机硅或粘土载体上。
9.根据权利要求1至7中任一项所述的包装,其中所述抗微生物剂选自抗微生物肽、有机硅基抗微生物剂以及季铵阳离子(Qua Ts)。
10.根据权利要求1至7中任一项所述的包装,其中所述抗微生物剂是消毒剂,其选自过氧化物、丙二醇、三乙二醇、十二烷酸、甲醛、戊二醛、百里酚、丁香油、肉桂油、西柚籽提取物、桉树提取物、抗微生物植物提取物、氯或碘在溶剂如水、乙醇、异丙醇或其混合物中的溶液,其中所述消毒剂任选封装在热、湿度或温度敏感的聚合材料中。
11.根据权利要求1至10中任一项所述的包装,其中所述涂层得自溶液或分散体,其包括所述第一聚合组分、所述滑爽或防粘剂和所述抗微生物剂和溶剂,所述溶剂选自水、乙酸乙酯、乙醇、异丙醇、甲醇、十六烷、十二烷及其混合物。
12.根据权利要求1所述的包装,其中在所述涂层中:
所述第一聚合组分是聚酯,
所述滑爽或防粘剂选自聚硅氧烷、巴西棕榈蜡、脂肪酸、脂肪酸酰胺及其混合物,
所述抗微生物剂选自氯化银、钛、磷酸银、有机硅拴系季胺、百里酚、西柚籽提取物、丁香油、肉桂油或其混合物,所述涂层任选进一步包含基于异氰酸酯的交联剂。
13.根据前述权利要求任一项所述的包装,其中所述基材由以下制成或包含:纸、纸板、玻璃、金属或选自以下的聚合材料:聚丙烯、聚乙烯、聚乙烯-聚丙烯共聚物、聚苯乙烯、聚对苯二甲酸乙二醇酯和生物塑料,其优选聚羟基脂肪酸酯、聚丁二酸丁二醇酯或聚乳酸,以及所述聚合材料的混合物。
14.根据前述权利要求任一项所述的包装,其中所述涂层被施加以提供0.01至20g/sqm的涂层克重,以干燥涂层计。
15.根据前述权利要求任一项所述的包装,其中所述基材包含单层或多层膜或片,其包含以下或由以下组成:纸、纸板、聚丙烯、聚乙烯、聚乙烯-聚丙烯共聚物、聚苯乙烯、聚对苯二甲酸乙二醇酯以及生物塑料,其优选聚羟基脂肪酸酯、聚丁二酸丁二醇酯或聚乳酸以及所述聚合材料的混合物,任选包括金属化层。
16.根据前述权利要求任一项所述的包装,其中涂覆层被施加到柔性基材上并且所述涂层是可热密封的,以使基材能够相对于其自身或相对于例如托盘或盒子的其它表面密封。
17.根据权利要求16所述的包装,其中所述包装以管状形式密封,其中所述涂层在所述管状形式的内侧上。
18.根据前述权利要求任一项所述的包装,其中所述涂层在所述基材随后热成型之前被施加在纸、纸板或塑料基材上。
19.根据前述权利要求任一项所述的包装,其中所述涂层在基材被折叠成刚性或半刚性形式之前被施加在纸、纸板或塑料基材上。
20.根据权利要求1所述的包装,其中所述基材是注射成型或挤出的包装结构并且通过使聚合物共混物注射成型或挤出聚合物共混物获得,所述聚合物共混物包含:
聚合物,其选自聚丙烯、聚乙烯、聚乙烯-聚丙烯共聚物、ABS、聚苯乙烯、聚对苯二甲酸乙二醇酯以及生物塑料,其优选聚羟基脂肪酸酯、聚丁二酸丁二醇酯或聚乳酸及其混合物,
抗微生物剂,其选自钛、银、金、铜、铂、锌、所述金属的氧化物或盐、合金、包含所述金属氧化物的粘土或玻璃、抗微生物肽、有机硅基抗微生物剂、季铵阳离子(Qua Ts)、消毒剂,所述消毒剂选自过氧化物、丙二醇、三乙二醇、十二烷酸、甲醛、戊二醛、百里酚、丁香油、肉桂油、西柚籽提取物、桉树提取物、抗微生物植物提取物、氯或碘在溶剂中的溶液,其中所述消毒剂任选封装在热、湿度、或温度敏感的聚合材料中,以及
低粘附性、滑爽或防粘剂,其选自有机硅乙烯基聚合物、有机硅乳液、二甲基聚硅氧烷、硅油、硅酮蜡、巴西棕榈蜡、卵磷脂、脂肪酸、脂肪酸酯、硬脂酸镁、植物油,优选大豆油、菜籽油、棕榈油、葵花籽油、椰子油、蓖麻油及其混合物,及其混合物。
21.根据权利要求20所述的包装,其中所述基材是注射成型或挤出的包装结构,其通过使聚合物共混物注射成型或挤出聚合物共混物获得,所述聚合物共混物包含:
聚合物,其选自聚丙烯、聚乙烯、聚乙烯-聚丙烯共聚物、ABS、聚苯乙烯、聚对苯二甲酸乙二醇酯以及生物塑料,其优选聚羟基脂肪酸酯、聚丁二酸丁二醇酯或聚乳酸及其混合物,其中母料包含:
-聚合组分,其选自聚氨酯、聚丙烯酸类树脂、聚对苯二甲酸乙二醇酯、聚乙烯醇、聚羟基脂肪酸酯、聚乳酸、纤维素聚合物及其混合物,
-低粘附性、滑爽或防粘剂,其选自有机硅乙烯基聚合物、有机硅乳液、二甲基聚硅氧烷、硅油、西棕榈蜡、卵磷脂、脂肪酸、脂肪酸酯、硬脂酸镁、植物油,优选大豆油、菜籽油、棕榈油、葵花籽油、椰子油、蓖麻油及其混合物,及其混合物以及;
-抗微生物剂,其选自钛、银、金、铜、铂、锌、所述金属的氧化物或盐、合金、包含所述金属氧化物的粘土或玻璃、抗微生物肽、有机硅基抗微生物剂、季铵阳离子(Qua Ts)、消毒剂,所述消毒剂选自过氧化物、丙二醇、三乙二醇、十二烷酸、甲醛、戊二醛、百里酚、丁香油、肉桂油、西柚籽提取物、桉树提取物、抗微生物植物提取物、氯或碘在溶剂中的溶液,其中所述消毒剂任选封装在热、湿度或温度敏感的聚合材料中。
22.根据权利要求20或21所述的包装,其中所述基材是挤出包装结构,并且所述涂层与所述基材共挤出。
23.根据权利要求1至21中任一项所述的包装,其中所述涂层在形成包装结构之后被施加于刚性或半刚性包装结构以赋予抗微生物特性。
24.根据权利要求1至22中任一项所述的包装,所述包装包含放置在所述基材和所述抗微生物涂层之间的粘附性增强层,所述粘附性增强层选自黏粒胶膜、用印刷油墨印刷的印刷层、阻隔涂层和丙烯酸类底漆。
25.一种组合物,其包含:
-第一聚合组分,其选自聚丙烯酸类树脂、聚乙烯醇缩丁醛及其混合物,
-低粘附性、滑爽或防粘剂,其选自聚硅氧烷,优选有机硅乙烯基聚合物、有机硅乳液、二甲基聚硅氧烷、硅油和硅酮蜡,及其混合物,以及
-抗微生物剂。
26.根据权利要求25所述的组合物,其中所述抗微生物剂选自抗微生物剂,所述抗微生物剂选自钛、银、金、铜、铂、锌、所述金属的氧化物或盐、合金、包含所述金属氧化物的粘土或玻璃、抗微生物肽、有机硅基抗微生物剂、季铵阳离子(Qua Ts)、消毒剂,所述消毒剂选自过氧化物、丙二醇、三乙二醇、十二烷酸、甲醛、戊二醛、百里酚、丁香油、肉桂油、西柚籽提取物、桉树提取物、抗微生物植物提取物、氯或碘在溶剂中的溶液,其中所述消毒剂任选封装于热、湿度或温度敏感的聚合材料中。
27.一种生产具有抗微生物特性的包装的方法,其包括将根据权利要求25或26所述的组合物施加于包装柔性或刚性基材的步骤。
28.一种生产具有抗微生物特性的包装的方法,其包括共混根据权利要求25或26所述的组合物与热塑料聚合材料,并且使所述共混物成型或热成型以提供所述包装的步骤。
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LU500140A LU500140B1 (en) | 2021-05-07 | 2021-05-07 | Packaging material having anti-microbial properties |
PCT/EP2022/062242 WO2022234062A1 (en) | 2021-05-07 | 2022-05-06 | Packaging material having anti-microbial properties |
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JP (1) | JP2024518939A (zh) |
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US20030091767A1 (en) * | 2001-11-02 | 2003-05-15 | Podhajny Richard M. | Anti-microbial packaging materials and methods for making the same |
JP2004269836A (ja) * | 2003-03-07 | 2004-09-30 | Sutetsupu Moa:Kk | 透明性を有する鮮度保持シール |
KR101291584B1 (ko) * | 2011-07-29 | 2013-08-01 | (주) 피러스 | 피톤치드를 함유하는 코팅제와 그 제조 방법 및 코팅제를 함유하는 과일 봉지 및 필름 |
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