CN112334531B - 水性乙烯-乙烯醇共聚物分散体和涂覆有所述分散体的氧阻隔多层膜 - Google Patents
水性乙烯-乙烯醇共聚物分散体和涂覆有所述分散体的氧阻隔多层膜 Download PDFInfo
- Publication number
- CN112334531B CN112334531B CN201980039974.1A CN201980039974A CN112334531B CN 112334531 B CN112334531 B CN 112334531B CN 201980039974 A CN201980039974 A CN 201980039974A CN 112334531 B CN112334531 B CN 112334531B
- Authority
- CN
- China
- Prior art keywords
- ethylene
- vinyl alcohol
- alcohol copolymer
- mol
- aqueous dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C08J7/048—Forming gas barrier coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
- C08L23/0861—Saponified vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
-
- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
乙烯‑乙烯醇共聚物的水性分散体适合用作实现用于柔性基底或刚性基底二者的薄涂层的漆,特征在于优异的氧和二氧化碳阻隔性能,特别是在高湿度条件下的优异的氧和二氧化碳阻隔性能。所述分散体包含乙烯含量为24mol%至38mol%的呈胶囊形式的第一乙烯‑乙烯醇共聚物和乙烯含量低于15mol%的第二乙烯‑乙烯醇共聚物。
Description
本发明涉及乙烯-乙烯醇(通常缩写为EVOH)共聚物的水性分散体,其适合用作涂覆柔性基底或刚性基底的漆,以实现优异的氧阻隔特性,特别是对于满足食品包装领域中的要求的优异的氧阻隔特性。
乙烯乙烯醇(EVOH)是乙烯和乙烯醇的形式上的共聚物,通常通过使乙烯和乙酸乙烯酯聚合以及随后使获得的乙烯-乙酸乙烯酯(EVA)水解来制备。EVOH共聚物通常由其以mol%测量的乙烯含量限定,因此,高乙烯EVOH和低乙烯EVOH二者均可以商购获得。
关于本发明的应用领域,公知的是,当进入到包装中的氧与食品反应性组分反应或促进好氧细菌的生长时,通过氧化现象可能发生优质食品的损失、保存期限减少和变质现象。因此,食品包装领域中近来研究的一个重要部分已聚焦于制备具有低氧渗透率(即高阻隔)的聚合物材料。如以上所预期的,通过限制从环境中到氧敏感性食品物品或药用产品中的氧传递,可以保持产品的品质,可以增加保存期限,从而减少浪费并节约成本。
除高阻隔要求之外,用于塑料包装的材料还应具有各种其他特性,例如机械强度、耐热性、耐化学性、透明度和柔性。
合成聚合物材料广泛用于制造用于食品包装的各种制品,但存在已常规地用于提供具有氧阻隔特性的涂层或层的特定聚合物,例如乙烯-乙烯醇共聚物(EVOH)、聚酰胺(PA)、聚乙烯醇共聚物(PVOH)和聚氯乙烯(PVC)。
EVOH的特征在于在干燥条件下,在0%相对湿度(RH)下更好的氧阻隔性能,关于其用作阻隔材料的最相关的问题涉及其水分敏感性。实际上,当直接暴露于高湿度条件(通常高于60%RH)时,EVOH的亲水性质导致吸收大量的水,由于使聚合的组合物溶胀并使其结晶相部分地软化(melt)的水分的作用,从而增加最终的氧渗透率。因此,需要考虑EVOH作为食品包装中的阻隔物的性能与包装暴露于的加工条件和储存条件之间的紧密联系,特别是当涉及高水分和/或高温的严苛条件时。
EP 2164898描述了包含以下组分的共混物的阻隔膜:基于共混物重量,以65重量%至95重量%的量的具有21mol%至30mol%的乙烯-乙烯醇共聚物含量的第一聚合物组分,和以5重量%至35重量%的量的具有41mol%至50mol%范围内的乙烯-乙烯醇共聚物的第二阻隔组分。
重要的是注意到,在以上欧洲现有技术文献中,最终的阻隔膜是通过挤出技术获得的,例如管状成型共挤出、管状成型挤出或平板成型挤出、吹泡挤出(用于单层膜)或共挤出(用于多层膜)。无论如何,挤出过程要求待使用的材料的可能限制其适用性,特别是在生物相容的包装领域中的适用性的一些特性,例如适合于过程温度的软化温度(meltingtemperature)、在高温加工条件和标准大气下的热力学稳定性(氧化/降解风险)、在压缩和剪切应力下的机械稳定性以及由于高温加工而在添加剂或填料选择方面的限制。
因此,为了在包装解决方案中实现以上相关特征,最相关的步骤之一由包含适合于制造例如漆涂层的EVOH的基于水的制剂的制备来表示。
在本领域中,术语漆通常表示用于生产包装涂层的液体制剂,其需要合适的耐物理和化学特性以保护包装产品免于任何变质并实现用于制造过程的技术效果,例如基底润湿、柔性、粘合性提升和润滑性。
在这方面,JP 2001172443公开了水性组合物,其包含乙烯含量为16mol%至70mol%(高乙烯含量)的乙烯-乙烯醇共聚物和乙烯含量为2mol%至15mol%(低乙烯含量)的乙烯-乙烯醇共聚物。第一乙烯-乙烯醇共聚物以细颗粒的形式分散在水中,然后分散在第二乙烯-乙烯醇共聚物的水性分散体中。在JP 2001172443中,具有高乙烯含量的EVOH被认为是在高湿度条件下的最佳性能体系,因此,从将其用作主要组分开始,他们其次添加了具有低乙烯含量的EVOH以改善组合物的可加工性(即溶剂相容性)。具体地,JP 2001172443报道了,基于100重量份的第一EVOH,低乙烯EVOH的量为0.05重量份至100重量份,因此,他们公开了其中高乙烯EVOH的量通常大于或等于低乙烯EVOH的量的组合物。
EP 1816159公开了水性的基于乙烯-乙烯醇的共聚物分散体,其特征在于气体阻隔性能、长期储存稳定性和良好的成膜特性。EP 1816159具体使用乙烯含量为15mol%至65mol%且皂化度不低于80mol%的EVOH共聚物、碱中和的基于乙烯/α,β-不饱和羧酸的共聚物以及具有75mol%至100mol%的皂化度、100至3500的聚合度和以每100重量份EVOH共聚物的0.5重量份至100重量份的含量的聚乙烯醇。直接得到的层合体显示出当涂层厚度为15μm时,在20℃和85%相对湿度的条件下测量的氧渗透率不高于0.286fm/Pa·s,优选不高于0.229fm/Pa·s。
本发明的目的是提供水性的基于乙烯-乙烯醇的共聚物分散体,其在成膜特性方面是优异的,同时保留与膜相关的所有优点,还具有小于10μm的减小的厚度,特征在于高气体阻隔性能。
具体地,本发明涉及水性分散体,其包含分散在乙烯含量低于15mol%(低乙烯含量)的第二乙烯-乙烯醇共聚物中的乙烯含量为24mol%至38mol%(高乙烯含量)的呈胶囊形式的第一乙烯-乙烯醇共聚物,特征在于,所述第一乙烯-乙烯醇共聚物与所述第二乙烯-乙烯醇共聚物之间的重量比为0.40至0.70。
考虑以上引用的现有技术文献,虽然本发明也公开了特征分别在于低乙烯含量和高乙烯含量的两种类型的EVOH的使用,但显然,本发明中实现的最终组合物是完全不同的并且是新的。
如果与现有技术相比,则本发明要求的组合物的特征在于相对于低乙烯EVOH的较低量的高乙烯EVOH,特别是以0.40至0.70的重量比,因为相对于低乙烯EVOH的较高量的高乙烯EVOH使得在低于60%RH的中等相对湿度下的氧阻隔性能降低。此外,所要求的乙烯含量低于15mol%的低乙烯EVOH的相对量允许获得水溶性体系,而所要求的具有较高乙烯含量(即乙烯含量在24mol%至38mol%的范围内)的EVOH的相对量允许增加在高湿度条件的存在下的稳定性。
更具体地,相对于现有技术,本发明要求的高乙烯含量聚合物与低乙烯含量聚合物之间的比率是相反的,考虑在高湿度条件下使用本发明的气体阻隔物的目的,我们的发明报道了更好的氧渗透率性能,具体地特征在于,相对于JP 2001172443的10[cc天-1m-2]至15[cc天-1m-2]的值,在20℃和80%RH下的氧渗透率量度(OTR)低于10[cc天-1m-2]。
此外,本发明人发现,为了通过稳定EVOH结晶形式来改善其阻隔特性,采用一些胶囊制备途径,例如喷雾干燥、乳化、纳米沉淀和超临界流体技术。特别地,采用喷雾干燥加工来生产高乙烯EVOH胶囊。获得的在湿润环境中保持其结晶度的最终水性分散体的胶囊的特征在于体积平均直径为0.1μm至10.0μm的颗粒尺寸分布,并且对于直径大于1.0μm的颗粒存在内腔。所述体积平均直径(Volume Mean Diameter,VMD)可以定义为通过干式分散激光衍射测量并通过使用Fraunhofer理论计算的样品的体积加权平均颗粒尺寸。
在一些实施方案中,水性分散体可以以低于10重量%的量任选地包含醇例如乙醇或异丙醇以改善涂层的均匀性。
此外,为了改善最终阻隔物的性能,本发明的分散体还可以包含以0.1重量%至7重量%的量添加的活性填料或惰性填料二者。特别地,活性填料如沸石,例如Linde型A(LTA)沸石的使用可以改善在低湿度条件(低于60%RH)和高湿度条件(80%RH)二者下在引起较高阻隔性能的水分溶解度方面的聚合物性能。另一方面,惰性填料如石墨烯、氧化石墨烯或磷酸锆的添加可以通过降低氧在聚合网络中的扩散系数来改善在干燥条件(即0%相对湿度)下的氧阻隔性能。
通过以相对于EVOH量的优选25重量%至100重量%的浓度使用一些分散剂如四乙氧基硅烷(TEOS),或者可以以相对于EVOH量的优选低于7重量%的浓度添加填料例如纤维素,可以改善涂层的机械稳定性和粘合性。此外,可以优选以相对于EVOH重量的0.5%至5%的量添加添加剂例如壳聚糖以改善涂层的再循环相容性。
作为通过本发明实现的第二方面,可以获得具有减小的厚度的经涂覆的阻隔层合体,以在保持高阻隔性能的同时保持重要特性,如透明度、雾度水平、对塑料基底的粘合性、可加工性、较高的再循环相容性、机械稳定性和降低的成本。
实际上,已知,如在EP 1816159中报道的,为了达到高阻隔性能,特别是在高湿度条件下的高阻隔性能,需要最终膜的较大的厚度,通常大于10μm。
然而,在本公开内容中,本发明人能够制备涂漆的阻隔层合体,其包括至少基底和至少涂层,特征在于,所述涂层包含乙烯含量为24mol%至38mol%的第一乙烯-乙烯醇共聚物的胶囊和乙烯含量低于10mol%的第二乙烯-乙烯醇共聚物,所述第一共聚物和所述第二共聚物的相应的重量比为0.40至0.70,其中所述涂层的厚度为0.1μm至10.0μm。
对于特征在于低厚度值的涂漆的阻隔层合体的制备,可以通过使用螺旋棒成型(流延,casting),使溶剂蒸发并使获得的涂层在80℃至150℃,优选130℃至150℃的温度下经受烘烤过程来获得分散体。替代的制备过程可以为刮涂、旋涂、浸涂、凹版涂覆、三辊涂覆、槽模涂覆、针分配(needle dispensing)、喷射分配(jet dispensing)。获得的薄涂层在保持对于包装应用中所需的通常特性如透射率和雾度值的优异性能的同时提供优异的OTR值。
此外,漆涂层的组合物的特征还在于作为用于CO2的阻隔物的相关性能,其使漆涂层的组合物以及相应的层合体适合于在受控气氛中的食品包装的应用。
在一些实施方案中,层合体结构的厚度为8μm至150μm的基底可以选自由以下组成的非限制性组:聚对苯二甲酸乙二醇酯(PET)、聚酰胺(PA)、聚呋喃二甲酸乙二醇酯(Polyethylene Furanoate,PEF)、聚乙烯(PE)、聚丙烯(PP)、聚己二酸对苯二甲酸丁二醇酯(Polybutylene Adipate Terephthalate,PBAT)、聚丁二酸丁二醇酯(PBS)、聚乳酸(PLA)、聚羟基烷酸酯(PHA)、淀粉共混物、木质素纤维素共混物和玻璃纸。
在另一些可能的实施方案中,所述涂漆的层合体可以为多层体系,所述多层体系还包括可以定位成与涂层、与基底、或与其二者接触的粘合剂层(如聚氨酯层合粘合剂)。
在下文中,将参照以下实施例更详细地说明本发明。
根据本发明,在样品A至H中,通过向保持在搅拌(在100rpm和80℃下)下的水醇溶液中添加乙烯-乙烯醇共聚物制备高乙烯EVOH胶囊。在聚合物溶解之后,将所得制剂喷雾干燥,如有需要,进一步经受喷射研磨处理以获得体积平均直径为5μm(±20%)且D90低于10μm(其中D90定义为在90%的累积颗粒尺寸分布处的颗粒尺寸)的单分散胶囊。然后将该制剂添加到乙烯含量低于15mol%的低乙烯EVOH共聚物的水性制剂中以得到具有目标气体阻隔特性的最终水性分散体。最后,对于涂漆的阻隔层合体的制备,使用螺旋棒成型分散体,使溶剂蒸发并使获得的涂层在80℃至150℃的温度下经受烘烤过程。
用上述方法但使用在本发明要求的范围之外的EVOH共聚物之间的相对比率制备比较样品1、2和3。
根据EP 1816159制备比较样品4。具体地,通过将丙烯酸和NaOH在搅拌下在80℃下溶解在H2O中来制备第一溶液(A)。对于第二溶液(B),将27mol%量的EVOH在搅拌下在80℃下溶解在2-丙醇和H2O中。随后,将第一溶液(A)注入到第二溶液(B)中并使所得溶液在5℃下冷却12小时,然后与基于低乙烯EVOH(15mol%)的溶液混合,随后进行成型。
表1样品和比较样品的列表
样品组合物A至H符合本发明,并且对于单位厚度的相对OTR值(OTR/μm),相比于特征在于两种EVOH组分之间的不同比率的比较样品1、2和3的值以及相比于根据EP 1816159制备的比较样品4好得多。
对于所有以上样品和比较样品获得的结果(总结在表1中),指出在本发明要求的范围之外的高乙烯含量EVOH与低乙烯含量EVOH之间的重量比(低于0.4或高于0.7)导致不适合于具有减小的厚度(即小于10.0μm)的膜和在高湿度条件下的高气体阻隔要求的氧渗透率值。
作为可以通过使用根据本发明的组合物获得的次要技术效果的代表,表2和表3示出了对于一些样品的透射率、雾度和CO2渗透率的观察值。
表2:光学特性
CO2渗透率是通过将样品的两个表面暴露在50%RH(50%RH/50%RH)下,然后将阻隔层合体的涂漆的表面上的相对湿度增加至80%RH的值(80%RH/50%RH)来测量的。
特别地,实验数据显示出根据本发明的组合物获得的涂层还充当CO2阻隔物的能力,如果与现有技术相比(样品B对比较样品1),在不同湿度条件下具有更好的性能。
表3:CO2阻隔特性
Claims (16)
1.一种水性分散体,包含
- 乙烯含量为24 mol%至38 mol%的呈胶囊形式的第一乙烯-乙烯醇共聚物,和
- 乙烯含量低于15 mol%的第二乙烯-乙烯醇共聚物,
其中,所述第一乙烯-乙烯醇共聚物与所述第二乙烯-乙烯醇共聚物之间的重量比在0.40至0.70的范围内。
2.根据权利要求1所述的水性分散体,其中呈胶囊形式的所述第一乙烯-乙烯醇共聚物的乙烯含量为27 mol%至32 mol%。
3.根据权利要求1所述的水性分散体,还包括:
量为5重量%至10重量%的醇。
4. 根据权利要求1所述的水性分散体,其中所述第一乙烯-乙烯醇共聚物胶囊具有体积平均直径为0.1 μm至10.0 μm的颗粒尺寸分布。
5.根据权利要求4所述的水性分散体,其中直径大于1.0 μm的所述第一乙烯-乙烯醇共聚物胶囊包含内腔。
6.根据权利要求1所述的水性分散体,还包括:
量为0.1重量%至7重量%的填料。
7.根据权利要求6所述的水性分散体,其中所述填料选自沸石、石墨烯、氧化石墨烯、纤维素和磷酸锆。
8.根据权利要求1所述的水性分散体,还包括:
相对于所述第一乙烯-乙烯醇共聚物和所述第二乙烯-乙烯醇共聚物,量为25重量%至100重量%的四乙氧基硅烷TEOS。
9.根据权利要求1所述的水性分散体,还包括:
相对于所述第一乙烯-乙烯醇共聚物和所述第二乙烯-乙烯醇共聚物,量为0.5重量%至5重量%的壳聚糖。
10.一种涂漆的阻隔层合体,包括:
至少基底;和
至少涂层,
其中,所述涂层包含乙烯含量为24 mol%至38 mol%的呈胶囊形式的第一乙烯-乙烯醇共聚物和乙烯含量低于15 mol%的第二乙烯-乙烯醇共聚物,其中所述第一乙烯-乙烯醇共聚物与所述第二乙烯-乙烯醇共聚物之间的重量比为0.40至0.70。
11.根据权利要求10所述的涂漆的阻隔层合体,其中所述基底选自聚对苯二甲酸乙二醇酯PET、聚酰胺PA、聚呋喃二甲酸乙二醇酯PEF、聚乙烯PE、聚丙烯PP、聚己二酸对苯二甲酸丁二醇酯PBAT、聚丁二酸丁二醇酯PBS、聚乳酸PLA、聚羟基烷酸酯PHA、淀粉共混物、木质素纤维素共混物和玻璃纸。
12.根据权利要求10所述的涂漆的阻隔层合体,其中所述基底的厚度为8 μm至150 μm。
13.根据权利要求10所述的涂漆的阻隔层合体,其中所述涂层的厚度为0.1 μm至10.0μm。
14.根据权利要求10所述的涂漆的阻隔层合体,还包括:
粘合剂层。
15.根据权利要求14所述的涂漆的阻隔层合体,其中所述涂层接触所述粘合剂层。
16.根据权利要求14所述的涂漆的阻隔层合体,其中所述粘合剂层为聚氨酯层合粘合剂。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT102018000007179A IT201800007179A1 (it) | 2018-07-13 | 2018-07-13 | Dispersione acquosa di copolimeri di alcool etilene-vinilico e film multistrato di barriera all'ossigeno rivestito con detta dispersione |
IT102018000007179 | 2018-07-13 | ||
PCT/IB2019/055909 WO2020012396A1 (en) | 2018-07-13 | 2019-07-11 | Aqueous ethylene-vinyl alcohol copolymer dispersion and oxygen barrier multilayer film coated with said dispersion |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112334531A CN112334531A (zh) | 2021-02-05 |
CN112334531B true CN112334531B (zh) | 2021-09-14 |
Family
ID=63762885
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201980039974.1A Active CN112334531B (zh) | 2018-07-13 | 2019-07-11 | 水性乙烯-乙烯醇共聚物分散体和涂覆有所述分散体的氧阻隔多层膜 |
Country Status (10)
Country | Link |
---|---|
US (1) | US11041067B1 (zh) |
EP (1) | EP3797136B1 (zh) |
JP (1) | JP7235775B2 (zh) |
KR (1) | KR102418209B1 (zh) |
CN (1) | CN112334531B (zh) |
BR (1) | BR112021000541B1 (zh) |
ES (1) | ES2905436T3 (zh) |
IT (1) | IT201800007179A1 (zh) |
TW (1) | TWI773908B (zh) |
WO (1) | WO2020012396A1 (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT202000005449A1 (it) * | 2020-03-13 | 2021-09-13 | Getters Spa | Composizioni polimeriche induribili aventi proprietà di barriera all'ossigeno migliorate |
IT202000018589A1 (it) | 2020-07-30 | 2022-01-30 | Getters Spa | Imballaggio flessibile multistrato con proprietà antiossidanti |
US20230159785A1 (en) * | 2021-11-19 | 2023-05-25 | E Ink California, Llc | Sealing film compositions for sealing microcells of electro-optic devices |
CN114808544B (zh) * | 2022-05-06 | 2023-07-14 | 山东金麦材料科技股份有限公司 | 一种高阻隔包装纸及其加工工艺 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0207440A2 (en) * | 1985-06-26 | 1987-01-07 | Kuraray Co., Ltd. | Laminate having good gas barrier properties |
JP2001172443A (ja) * | 1999-12-15 | 2001-06-26 | Kuraray Co Ltd | バリア性に優れたエチレン−ビニルアルコール共重合体水性組成物 |
CN1430627A (zh) * | 2000-05-19 | 2003-07-16 | 谢弗龙菲利普斯化学公司 | 通过改性乙烯/乙烯醇共聚物(evoh)提高氧阻隔性 |
CN101065439A (zh) * | 2004-11-25 | 2007-10-31 | 住友精化株式会社 | 乙烯/乙烯醇类共聚物水性分散液 |
CN101679706A (zh) * | 2007-05-08 | 2010-03-24 | 纳幕尔杜邦公司 | 乙烯乙烯醇组合物 |
CN105073840A (zh) * | 2013-02-25 | 2015-11-18 | 巴斯夫欧洲公司 | 粒状微胶囊组合物 |
CN105849183A (zh) * | 2013-12-27 | 2016-08-10 | 日本合成化学工业株式会社 | 含乙烯-乙烯基酯系共聚物皂化物的成形材料 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3400128B2 (ja) * | 1994-08-30 | 2003-04-28 | 株式会社クラレ | 水性組成物および積層体 |
JP4077927B2 (ja) * | 1998-04-27 | 2008-04-23 | 住友化学株式会社 | 樹脂組成物および積層体 |
JP2000052501A (ja) | 1998-06-03 | 2000-02-22 | Kuraray Co Ltd | 積層体およびその製造方法 |
WO2008153980A1 (en) | 2007-06-11 | 2008-12-18 | Cryovac, Inc. | Evoh blend providing improved oxygen resistance |
CN104350103B (zh) * | 2012-06-13 | 2016-06-15 | 株式会社可乐丽 | 乙烯-乙烯醇树脂组合物、多层片材、包装材料和容器 |
CN105555860B (zh) * | 2013-09-20 | 2018-04-03 | 日本合成化学工业株式会社 | 乙烯‑乙烯醇共聚物组合物,以及使用其的层叠体和二次成形品 |
CN105131483A (zh) * | 2015-09-09 | 2015-12-09 | 沈阳化工大学 | 一种多层结构的高阻隔共混材料 |
-
2018
- 2018-07-13 IT IT102018000007179A patent/IT201800007179A1/it unknown
-
2019
- 2019-07-11 KR KR1020207037082A patent/KR102418209B1/ko active IP Right Grant
- 2019-07-11 CN CN201980039974.1A patent/CN112334531B/zh active Active
- 2019-07-11 BR BR112021000541-2A patent/BR112021000541B1/pt active IP Right Grant
- 2019-07-11 US US17/059,549 patent/US11041067B1/en active Active
- 2019-07-11 WO PCT/IB2019/055909 patent/WO2020012396A1/en unknown
- 2019-07-11 ES ES19769859T patent/ES2905436T3/es active Active
- 2019-07-11 JP JP2020568506A patent/JP7235775B2/ja active Active
- 2019-07-11 EP EP19769859.0A patent/EP3797136B1/en active Active
- 2019-07-12 TW TW108124662A patent/TWI773908B/zh active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0207440A2 (en) * | 1985-06-26 | 1987-01-07 | Kuraray Co., Ltd. | Laminate having good gas barrier properties |
JP2001172443A (ja) * | 1999-12-15 | 2001-06-26 | Kuraray Co Ltd | バリア性に優れたエチレン−ビニルアルコール共重合体水性組成物 |
CN1430627A (zh) * | 2000-05-19 | 2003-07-16 | 谢弗龙菲利普斯化学公司 | 通过改性乙烯/乙烯醇共聚物(evoh)提高氧阻隔性 |
CN101065439A (zh) * | 2004-11-25 | 2007-10-31 | 住友精化株式会社 | 乙烯/乙烯醇类共聚物水性分散液 |
CN101679706A (zh) * | 2007-05-08 | 2010-03-24 | 纳幕尔杜邦公司 | 乙烯乙烯醇组合物 |
CN105073840A (zh) * | 2013-02-25 | 2015-11-18 | 巴斯夫欧洲公司 | 粒状微胶囊组合物 |
CN105849183A (zh) * | 2013-12-27 | 2016-08-10 | 日本合成化学工业株式会社 | 含乙烯-乙烯基酯系共聚物皂化物的成形材料 |
EP3088462A1 (en) * | 2013-12-27 | 2016-11-02 | The Nippon Synthetic Chemical Industry Co., Ltd. | Molding material comprising ethylene-vinyl ester copolymer saponification product |
Also Published As
Publication number | Publication date |
---|---|
CN112334531A (zh) | 2021-02-05 |
US20210206952A1 (en) | 2021-07-08 |
BR112021000541A8 (pt) | 2023-01-10 |
US11041067B1 (en) | 2021-06-22 |
EP3797136A1 (en) | 2021-03-31 |
KR102418209B1 (ko) | 2022-07-08 |
IT201800007179A1 (it) | 2020-01-13 |
JP2021529844A (ja) | 2021-11-04 |
JP7235775B2 (ja) | 2023-03-08 |
BR112021000541A2 (pt) | 2021-04-06 |
ES2905436T3 (es) | 2022-04-08 |
WO2020012396A1 (en) | 2020-01-16 |
KR20210031864A (ko) | 2021-03-23 |
BR112021000541B1 (pt) | 2023-03-14 |
TW202006078A (zh) | 2020-02-01 |
TWI773908B (zh) | 2022-08-11 |
EP3797136B1 (en) | 2021-12-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112334531B (zh) | 水性乙烯-乙烯醇共聚物分散体和涂覆有所述分散体的氧阻隔多层膜 | |
JP6422932B2 (ja) | 包装材料、真空断熱体、包装材料の製造方法、及び真空断熱体の製造方法 | |
KR101384029B1 (ko) | 필름 및 구조물용 배리어 코팅 | |
US6709735B2 (en) | Oxygen barrier coating and coated film | |
CA2843762C (en) | Barrier coatings for films and structures | |
US7807272B2 (en) | Coating solution, and gas barrier film, gas barrier laminate and gas barrier multilayer film, using the coating solution, and their manufacturing methods | |
TW201504047A (zh) | 阻氣性包裝材料 | |
JP5590439B2 (ja) | 透明ハイガスバリア膜用コーティング液及びそれを用いて得られるコーティング膜並びに積層フィルム | |
CN114517049B (zh) | 一种高阻隔性能的涂布液及其应用 | |
KR101823914B1 (ko) | 프라이머층을 포함하는 가스 배리어 필름 및 이의 제조 방법 | |
JP4864818B2 (ja) | 積層フィルム | |
Liu et al. | Improvement of Hydrophobicity and Gas Permeability of the Polyvinyl Alcohol Film Utilizing Monoglyceride Coating and Diatomaceous Earth Filling and Its Application to Fresh-Cut Mango | |
WO2006138597A2 (en) | Barrier film with enhanced adhesive properties | |
EP2014733A1 (en) | Coating liquid, gas barrier film using same, gas barrier laminate, gas barrier multilayer film, and their production methods | |
JP2003268183A (ja) | 樹脂組成物および用途 | |
JP7136382B2 (ja) | ガスバリア性積層体及び包装材料 | |
JP2001114966A (ja) | 樹脂組成物、その製造法および用途 | |
JP3131505B2 (ja) | 多層構造体 | |
US20220064394A1 (en) | Multilayer film with biomolecule based barrier coating |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |