CN1143660A - 用于调节气体阻隔性的包装粘合剂混合物 - Google Patents

用于调节气体阻隔性的包装粘合剂混合物 Download PDF

Info

Publication number
CN1143660A
CN1143660A CN96108869A CN96108869A CN1143660A CN 1143660 A CN1143660 A CN 1143660A CN 96108869 A CN96108869 A CN 96108869A CN 96108869 A CN96108869 A CN 96108869A CN 1143660 A CN1143660 A CN 1143660A
Authority
CN
China
Prior art keywords
day
transmission rate
oxygen transmission
otr oxygen
latex
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.)
Granted
Application number
CN96108869A
Other languages
English (en)
Other versions
CN1105764C (zh
Inventor
R·M·兰伯特
H·D·舍曼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roman Haas chemical Limited Liability Company
Original Assignee
Morton International LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Morton International LLC filed Critical Morton International LLC
Publication of CN1143660A publication Critical patent/CN1143660A/zh
Application granted granted Critical
Publication of CN1105764C publication Critical patent/CN1105764C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C09J121/00—Adhesives based on unspecified rubbers
    • C09J121/02—Latex
    • 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
    • B32B27/08—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 of synthetic resin
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • 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
    • C09J127/00—Adhesives 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 a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives 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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/04—Adhesives 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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • 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
    • C09J127/00—Adhesives 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 a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives 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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/04—Adhesives 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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09J127/08—Homopolymers or copolymers of vinylidene chloride
    • 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
    • C09J133/00—Adhesives 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09J133/00—Adhesives 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

以一定的比例将一种高气体阻隔性的丙烯酸/氯化乙烯基或丙烯酸/氯化乙烯基/乙烯基胶乳粘合剂组分以及一种低气体阻隔性的丙烯酸/乙烯基胶乳粘合剂组分混合，并用该混合物粘合低气体阻隔性材料的膜(如聚烯烃膜)，从而得到能调节气体阻隔性能的粘合层。

Description

用于调节气体阻隔性的包装粘合剂混合物
本发明涉及粘合剂组分的混合物，特别涉及丙烯酸或丙烯酸/乙烯基胶乳粘合剂组分的混合物，这种胶乳粘合剂组分是由占大部分的氯化乙烯基单体制得的。这种粘合剂组分的混合物提供的包装材料具有能调节的气体阻隔性能。
发明的背景
在许多种食品包装的应用中(如包装肉和乳酪)，要求包装材料的透气性越小越好。因此，可以使用高气体阻隔性的材料，如尼龙、乙烯/乙烯醇或聚偏氯乙烯膜或涂层。
另一方面，如果包装材料具有一定的透气性，某些食品，特别是水果和蔬菜可以更长时间地保持其新鲜度。收割后的水果和蔬菜在长时间内仍具有呼吸功能，所以最好用能使产物呼吸的材料对其进行包装。每个人都知道常用于出售柑桔水果的尼龙网袋，这种多孔袋使水果完全暴露在空气中。如果用不透气的口袋包装柑桔水果，那么它将很快腐烂。
收割后的水果放出加快水果腐烂的气体，特别是环氧乙烷。不透气的水果包装显然会使这种气体聚集。事实上，已知水果具有产生这种气体的本能。水果毕竟是一种物种再生的种子的载体，如果水果不被吃掉并且水果中的种子不被动物所移动，那么水果就需要腐烂以使种子长成植物。收割后的蔬菜同样也具有一些呼吸功能，尽管这种功能常常弱于水果。
研究表明不同的水果和蔬菜具有不同的“呼吸”需求，在具体的气体隔离包装中，各种水果或蔬菜具有各自最长的储存寿命。因此要求包装材料的制造商能根据具体的包装用途，调节包装材料的气体阻隔性能。
一种提出调节气体阻隔性的方法是改变膜或叠层中特定几层的厚度或规格。但由于在材料的加工和设备的调节(由一种包装转而生产另一种包装时要改变膜层的厚度)方面存在困难，所以包装材料，特别是多层叠合膜的生产难以使用这种方法。本发明披露粘合剂组分的混合物，该混合物的比例能很容易地进行调节，从而能用于调节气体的阻隔性能。
本发明的综述
本发明一方面提供一种混合物，该混合物由下列物料组成：第一高气体阻隔性的胶乳粘合剂组分，该组分含有由丙烯酸单体、氯化乙烯基单体和任选的其它乙烯基单体制得的聚合物，以及第二低气体阻隔性的胶乳粘合剂组分，该组分含有由丙烯酸单体和任选的乙烯基单体(包括氯化乙烯基单体)制得的聚合物。完全由高气体阻隔性的胶乳粘合剂组分制得的膜的氧气透过率(OTR)比完全由低气体阻隔性粘合剂组分制得的膜的氧气透过率(OTR)至少低50ccO2/100in.2/天(775mlO2/m2/天)，较好的为至少低100ccO2/100in.2/天(1550mlO2/m2/天)，最好的为至少低200ccO2/100in.2/天(3100mlO2/m2/天)。这里，OTR是以涂布重量3.5lbs/ream(3.5lbs/3000ft2)(5.71kg/1000m2)为基准的，这是一种常规的涂布重量。第一胶乳粘合剂组分聚合物占第一和第二胶乳粘合剂聚合物总重量的约5-95％(重量)，第二胶乳粘合剂组分聚合物占第一和第二胶乳粘合剂聚合物总重量的约95-5％(重量)，从而使胶乳粘合剂混合物制得的膜的气体阻隔性介于单独由第一或第二胶乳粘合剂组分制得的膜的气体阻隔性之间。
本发明的另一方面是一种制备具有能调节气体阻隔性的粘合层的多层叠合膜的方法，该叠合膜是将两层或多层低气体阻隔性膜用高气体阻隔性的胶乳粘合剂粘合而成的。胶乳粘合剂组合物是用适量的高气体阻隔性的第一胶乳粘合剂组分和适量的低气体阻隔性的第二胶乳粘合剂组分制得的，从而使得到的粘合层的OTR在高气体阻隔性的胶乳粘合剂组分的OTR与低气体阻隔性的胶乳粘合剂组分的OTR的范围内。某些优选实例的详细描述
这里粘合层的气体阻隔性用以3.5lbs/3000ft2(5.71kg/1000m2)涂布重量为基准的氧气透过率表示。尽管其它气体如CO2、乙烯和环氧乙烷也是影响食物新鲜度的因素，但是这些气体的透过率通常与氧气透过率具有相同的变化趋势。多层(两层或多层)包装叠层的气体阻隔性当然不仅取决于一层或多层粘合层的气体阻隔性，还取决于膜层和粘合剂的气体阻隔性。但是，本发明主要应用于叠层，在这种叠层中所有膜的气体阻隔性都相对弱于粘合层。最具体地说，本发明涉及由聚烯烃(如聚乙烯和聚丙烯)片制得的多层叠层。聚烯烃的气体阻隔性差，其OTR通常为50-500ccO2/100in.2/天/mil(775-7750mlO2/m2/天/0.025mm)。这种片由相同或不同的聚合物组成。因此，这里所讨论的气体阻隔性仅指涂布重量为3.5lbs/3000ft2(5.71kg/1000m2)的胶乳粘合剂提供的粘合层的气体阻隔性。包装材料的制造商也必须考虑(factor)膜层的气体阻隔性以使包装适应专门的用途。
这里用于描述胶乳粘合剂组分的术语“高阻隔性”和“低阻隔性”是相对的，指一种粘合剂组分的气体阻隔性明显高于另一种。
多数水果和蔬菜的适宜的OTR约为50-300，最好约为70-225cc/100in.2/天(775-6450，最好为1085-3488mlO2/m2/天)，尽管OTR可在本文描述的胶乳粘合剂组分的类型能给出的任何范围内变化，但本发明提供的OTR主要在上述范围内。
用于制备高气体阻隔性和低气体阻隔性粘合剂组分的合适的丙烯酸单体有(但不局限于)丙烯酸、甲基丙烯酸和这两种酸的C1-C12烷基酯。高气体阻隔性的胶乳粘合剂组分也含有部分氯化乙烯基单体，如氯乙烯和优选的偏氯乙烯。一般认为由于大的氯分子使聚合物堆砌紧密从而增强其气体阻隔性。制备高气体阻隔性的胶乳粘合剂组分时优选偏氯乙烯而非氯乙烯，这是因为它含有两个氯原子并(与气态氯乙烯相反)在环境温度下是液体。在一种或两种粘合剂组分中还可含有可共聚的乙烯基单体如乙酸乙烯酯。
高气体阻隔性胶乳粘合剂组分的聚合物通常由约40-95％(重量)偏氯乙烯和/或氯乙烯，最好约50-95％的偏氯乙烯和/或氯乙烯制得。高气体阻隔性胶乳粘合剂组分由约5-60％(重量)、最好约5-50％丙烯酸单体制得。高气体阻隔性胶乳粘合剂组分还可由高达约55％(重量)的可共聚的乙烯基单体制得。高气体阻隔性胶乳粘合剂组分不需要含酸官能度，但可以由高达约5％具有羧酸官能度的单体制得。尽管高气体阻隔性胶乳粘合剂组分不需要羟基官能度，但它可以含有(如丙烯酸羟乙酯提供的)羟基官能度。最好约2-15％(重量)用于制备高气体阻隔性胶乳组分的单体具有羟基官能度。一般认为羟基官能度可增加粘性。高气体阻隔性胶乳粘合剂聚合物的重均分子量约为25,000-200,000。
低气体阻隔性胶乳粘合剂组分的聚合物主要由丙烯酸单体(即约50-100％(重量)丙烯酸单体)组成，其余单体是可共聚的乙烯基单体，如乙酸乙烯酯。与高气体阻隔性胶乳粘合剂组分相同，低气体阻隔性胶乳粘合剂组分的聚合物可由部分偏氯乙烯和/或氯乙烯制得，但使用的比例大大低于高气体阻隔性胶乳粘合剂组分中的比例。低气体阻隔性胶乳粘合剂组分不需要含酸官能度，但可以由高达约10％具有羧酸官能度的单体制得。尽管低气体阻隔性胶乳粘合剂组分不需要羟基官能度，但它可以含有(如丙烯酸羟乙酯提供的)羟基官能度。最好约2-10％(重量)用于制备低气体阻隔性胶乳粘合剂组分的单体具有羟基官能度。低气体阻隔性胶乳粘合剂聚合物的重均分子量约为2千万-1亿。
除聚合物之外，高气体阻隔性胶乳粘合剂组分和低气体阻隔性胶乳粘合剂组分都含有表面活性剂，该表面活性剂量足以使聚合物乳化并保持水性聚合物乳液。表面活性剂常为阴离子型表面活性剂和/或非离子型表面活性剂。一些常用的阴离子表面活性剂包括：RhodocalDS-10和ArosolMA-80。一些常用的非离子型表面活性剂包括CO660Igepal和TritonX405.在高气体阻隔性粘合剂组分和低气体阻隔性粘合剂组分中，表面活性的用量通常约为0.1-5％(按聚合物重量计)。
用任何常规的制备胶乳聚合物的方法制备胶乳粘合剂组分。最为方便的是，用常规的水介质中的乳液聚合制备胶乳粘合剂组分，这样现制胶乳。胶乳粘合剂组分也可以是市售的胶乳粘合剂，只要两种胶乳粘合剂能各自形成具有明显不同气体阻隔性的粘合层。
在应用中，包装材料的制造商将提供两种粘合剂组分，这两种粘合剂组分各自形成具有不同OTR的粘合层，从而使得OTR范围满足复合包装应用的要求。尽管出于某些包装的需要，可单独使用高气体阻隔性的粘合剂组分或低气体阻隔性的粘合剂组分以得到要求的气体阻隔性，但以适当的量混合两种胶乳粘合剂组分可得到适中的气体阻隔性。一般，至少使用约5％(按两种组分聚合物总重量计)的一种(或另一种)组分才能明显改变另一种组分的气体阻隔性。由两种组分的混合物提供的气体阻隔性一般是线性的。在任何情况下，对两种已知组分的任何给定的混合物，可以预先确定一根气体阻隔性曲线。这种曲线证明完全是可重复的。因此，当由一种包装用途转到另一种包装用途(各自具有不同的最佳气体阻隔性要求)时，包装材料的制造商仅需要计算出两种组分的相对用量。由于粘合剂层的气体阻隔性可以调节，所以由一种包装用途转到另一种包装用途时，不需要改变膜的类型、膜厚度以及涂布重量。
本发明使用的胶乳组分的类型具有良好的相互间的混溶性。这不是不同胶乳混合时所常有的。混合后的胶乳(甚至属于相同总类的胶乳)所遇到的问题是常会发生凝聚。本发明使用的胶乳组分的类型是形成均相的粘合层，没有相分离的趋向。一般认为正由于这种混溶性才使得气体阻隔性是基本线性、两种胶乳粘合剂组分的相对量间具有可预测的关系和由该混合物制得的膜具有气体阻隔性。
本发明体系的另一个优点是制得的膜的气体阻隔性取决于高气体阻隔性和低气体阻隔性组分的相对量，而较不依赖于涂布重量。粘合剂的涂布重量常约为2-5lbs/ream(2-5lbs/3000ft2)(3.26-8.15kg/1000m2)，一般为3.5lbs/ream(5.71kg/1000m2)。但是难以得到始终准确的涂布重量，在叠合工艺中在各个方向上的涂布重量的差异可高达20％。在通常的涂布误差范围内，制得的粘合层的气体阻隔性会相当均匀。
包装叠层是用常规方法(通常是干粘叠合方法)由聚合物片和胶乳粘合剂制得的。将水性乳液施涂于一层膜上，干燥后形成粘合层，然后将其与另一膜相接触。粘合剂组分和最终粘合剂混合物的固体含量约为35-60％(重量)，通常为46％。为简单起见，在混合前最好使各个粘合剂组分具有大致相同的固体含量以使混合物具有相同的固体含量，而与两个组分的相对比例无关。
下面，将通过具体的实施例对本发明作更详细的描述。
                实施例1
由下面单体混合物和氧化还原混合物制备高气体阻隔性胶乳粘合剂组分：
单体混合物
重量％            单   体
60               偏氯乙烯
30               丙烯酸(2-乙基己)酯
10               丙烯酸羟乙酯
氧化还原剂
份/100单体
0.10             过硫酸铵
0.20             过氧化氢(35％)
0.27             erythorbic acid
下面是制备高气体阻隔性胶乳粘合剂组分的配方制备下述溶液。
1.GafacRE9601               10.0g
去离子水                       89.1g
注1：阴离子表面活性剂用
去离子水                       3.6g
氨水                           1.9g将该溶液中和至pH为6.5-6.8
2.去离子水                   107.0g
AerosolA-1962(97％)       12.2g
IgepalCO 8873(70％)       6.3g
注2：阴离子表面活性剂
注3：非离子表面活性剂取下列物料以制备预乳液
去离子水                     743.7g
SEM钠盐(5％)                 888.1g
溶液1                        104.6g
  溶液2               125.5g
  去离子水             82.4g
很好地混合上述物料后，边搅拌边加入下列物料：
  丙烯酸羟乙酯               450.5g
  丙烯酸(2-乙基己)酯         889.2g
  偏氯乙烯                  3115.8g
搅拌直至形成稳定的预乳液。
            反应器加料
制备下列溶液：
  3.柠檬酸二铵               6.6g
  去离子水                   8.9g
  4.IgepalCO 887(70％)   15.8g
  去离子水                  26.8g
  5.AerosolA-196(97％)    3.9g
  去离子水                  26.8g
  6.ethorbic酸              10.2g
  去离子水                 935.9g
  7.过氧化氢(35％)          18.7g
  去离子水                 267.4g
取一反应釜，加入下列物料：
  去离子水                2050.0g
  溶液3                     15.5g
  过硫酸铵                   4.5g
  溶液                     442.6g
  溶液5                     30.7g
  去离子水                  71.3g
将反应釜加热至46-48。并向其中加入：
  过氧化氢(35％)             4.5g
  预乳液(投入种子)         128.4g
混合并将温度稳定在46-48℃；然后开始加入活化剂(溶液6)，加料时间为11.6小时。
15分钟后，以35.5克/10分钟的速率开始加入预乳液。
10分钟后，将加料速率提高70.6克/分钟。
20分钟后，将加料速率提高至107.0克/分钟。(总加料时间约为450分钟)。
105分钟后，以6克/10分钟的速率开始加入引发剂(溶液7)(总加料时间约为450分钟)。
加完预乳液后，用64.2g去离子水冲洗输料管。
冲洗完后，向反应釜中加入：
    8.去离子水         17.8g
      过氧化氢(35％)    1.2g然后用
    去离子水            8.9g冲洗，将温度在46-48℃保持30-35分钟，然后加热至64-67℃。在64-67℃，加入：
  9.去离子水        8.9g
    过氧化氢(35％)  1.2g
    去离子水冲洗    8.9g
  10.去离子水      17.6g
     erythorbic酸  3.6g
     去离子水冲洗   8.9g
将温度在64-67℃保持1小时，然后冷却至27-30℃。加入氨水将pH调节至2.0-2.5；每次氨水的补加量为5g。将溶液过滤，并测定其物理性能，结果应符合下列指标：
  固体含量                    44.0-46.0％
  pH                          2.0-2.5
  重量/加仑(4.55×10-3m3)   10.0lbs.(4.5kg)
  粘度                        最大为350.0cps
如果使该粘合剂组分以3.5lbs/3000ft2(5.71kg/1000m2)的涂布重量单独成膜，其OTR为75ccO2/100in.2/天(1159mlO2/m2/天)。
                实施例2
由下面单体混合物制备低气体阻隔性胶乳粘合剂组分：
单体混合物
重量％         单    体
71            丙烯酸丁酯
17            酸乙烯酯
6             丙烯酸羟乙酯
6             丙烯酸
氧化还原剂
份/100单体    组分
0.04          过硫酸铵
0.03          过氧化氢(35％)
0.38          erythorbic acid
下面是制备低气体阻隔性胶乳粘合剂组分的配方
            预乳液向一个混合容器这加入下列物料：
去离子水                      1114.6g
硼酸钠                          13.9g
Triton X 4054(70％)           108.0g
Aerosol A-196(97％)             23.0g
SEM钠盐(5％)                   470.9g
丙烯酸丁酯                    3435.7g
乙酸乙烯酯                     651.3g
丙烯酸羟乙酯                   280.7g
丙烯酸                         280.7g
去离子水(洗涤)                  97.5g
注4：非离子型表面活性剂混合直至形成稳定的预乳液。
            反应器加料
去离子水                      1949.8g
硼酸钠                           4.6g
Triton X 405(70％)               5.6g
Aerosol A-196(97％)              0.6g
1％铁溶液                        4.6g将反应釜加热至50-53℃。在加热反应釜的同时，制备下列溶液：
1.去离子水                      31.9g
过硫酸铵                         9.3g
2.去离子水         243.7g
过硫酸铵            11.1g
3.去离子水         493.2g
ethorbic酸          17.4g
反应釜的温度为50-53℃，将制得的稳定的预乳液和三种溶液：
A.将溶液1加至反应釜
B.开始在8小时内加入溶液3
C.开始在7小时内加入预乳液。
开始加入预乳液30分钟后，在6.5小时内加入溶液2。
加料时将温度保持在50-53℃；
就在预乳液和溶液2加完前，制备下列溶液：
4.去离子水        29.0g
过氧化氢(35％)     5.2g
当加完预乳液和溶液2后，开始在30分钟内向反应釜中加入溶液4。
当加完溶液4后，溶液3的加料还应再持续30分钟。
当加完所有溶液后，将温度在50-53℃保持1小时。冷却至环境温度，测定物理性能。如有必要可加入去离子水调节固体含量。
          物理性能的指标
  固体含量：                49.0-51.0％
  pH：                      2.0-3.0
  粘度                      最大350.0cps
  重量/加仑(4.55×10-3m3) 8.7lbs(3.95kg)
如果使该粘合剂组分以3.5lbs/3000ft2的涂布重量单独成膜，其OTR为240ccO2/100in.2/天(3720mlO2/m2/天)。
                  实施例3
以各种的比例(按各个组分中聚合物含量计)混合实施例1和2的胶乳粘合剂组分。混合物用于叠合两层聚乙烯膜。由混合物给出的膜的OTR列于下表：
高气体阻隔性组分的重量％  OTR(15.5mlO2/m2/天)
            90                    113
            80                    167
            70                    198

Claims (11)

1.一种含有下列混合物的水性胶乳粘合剂形成的组合物：
A)第一胶乳粘合剂组分含有由包括约40-95％(重量)偏氯乙烯、氯乙烯或两者的混合物、约5-60％(重量)丙烯酸单体以及约0-55％(重量)可共聚的乙烯基单体的单体混合物制得的聚合物加上用于保持所述聚合物乳液的足量的表面活性剂，以及
B)第二胶乳粘合剂组分含有由约50-100％(重量)丙烯酸单体、和其余的可共聚的乙烯基单体制得的聚合物，加上用于保持所述聚合物乳液的足量的表面活性剂，
所述第一胶乳粘合剂组分A)的氧气透过率比所述第二胶乳粘合剂组分B)的氧气透过率至少低约50ccO2/100in.2/天(775mlO2/m2/天)，
混合所述第一和第二胶乳组分，使所述第一胶乳粘合剂聚合物的量占所述第一和第二胶乳粘合剂聚合物总量的约5-95％(重量)并使所述第二胶乳粘合剂聚合物的量占所述第一和第二胶乳粘合剂聚合物总量的约95-5％(重量)。
2.如权利要求1中所述的组合物，其特征在于所述第一胶乳粘合剂组分A)的氧气透过率比低于所述第二胶乳粘合剂组分B)的氧气透过率至少低约100ccO2/100in.2/天(1 550mlO2/m2/天)。
3.如权利要求1中所述的组合物，其特征在于所述第一胶乳粘合剂组分A)的氧气透过率比低于所述第二胶乳粘合剂组分B)的氧气透过率至少低约200ccO2/100in.2/天(3100mlO2/m2/天)。
4.如权利要求1中所述的组合物，该组合物以3.5lbs/3000ft2(5.71kg/1000m2)的涂布重量涂布并干燥后形成的粘合层的氧气透过率约为50-300ccO2/100in.2/天(775-4650mlO2/m2/天)。
5.如权利要求1中所述的组合物，该组合物以3.5lbs/3000ft2(5.71kg/1000m2)的涂布重量涂布并干燥后形成的粘合层的氧气透过率约为70-225ccO2/100in.2/天(1 085-3488mlO2/m2/天)。
6.一种制备叠层的方法，该叠层由第一和第二聚合物片经可调节氧气透过率的粘合层粘合而成的，该方法包括：
提供能成膜的第一水性胶乳丙烯酸系粘合剂组分，当以涂布重量为3.5lbs/3000ft2施涂时，形成的膜具有第一氧气透过率，
提供能成膜的第二水性胶乳丙烯酸系粘合剂组分，当以涂布重量为3.5lbs/3000ft2(5.71kg/1000m2)施涂时，形成的膜具有第二氧气透过率，所述第一氧气透过率比所述第二氧气透过率至少低约50ccO2100in.2/天(775mlO2/m2/天)，
以一定的比例将部分所述第一组分和部分所述第二组分混合，该比例根据要求的氧气透过率而定，制得粘合剂组合物混合物，
用所述粘合剂组合物混合物将所述第一片粘合至所述第二片上。
7.如权利要求6中所述的方法，其特征在于所述第一和第二片是聚烯烃。
8.如权利要求6中所述的方法，其特征在于所述第一氧气透过率比所述第二氧气透过率至少低约100ccO2/100in.2/天(1550mlO2/m2/天)。
9.如权利要求6中所述的方法，其特征在于所述第一氧气透过率比所述第二氧气透过率至少低约200ccO2/100in.2/天(3100mlO2/m2/天)。
10.如权利要求6中所述的方法，其特征在于所述粘合剂混合物以3.5lbs/3000ft2(5.71kg/1000m2)的涂布重量施涂并干燥后形成的粘合层的氧气透过率约为50-300ccO2/100in.2/天(775-4650mlO2/m2/天)。
11.如权利要求6中所述的方法，其特征在于所述粘合剂混合物以3.5lbs/3000ft2(5.71kg/1000m2)的涂布重量施涂并干燥后形成的粘合层的氧气透过率约为70-225ccO2/100in.2/天(1085-3488mlO2/m2/天)。
CN96108869A 1995-07-27 1996-07-22 用于调节气体阻隔性的包装粘合剂混合物 Expired - Fee Related CN1105764C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US50795695A 1995-07-27 1995-07-27
US507956 1995-07-27

Publications (2)

Publication Number Publication Date
CN1143660A true CN1143660A (zh) 1997-02-26
CN1105764C CN1105764C (zh) 2003-04-16

Family

ID=24020789

Family Applications (1)

Application Number Title Priority Date Filing Date
CN96108869A Expired - Fee Related CN1105764C (zh) 1995-07-27 1996-07-22 用于调节气体阻隔性的包装粘合剂混合物

Country Status (13)

Country Link
US (2) US6358357B1 (zh)
EP (1) EP0755990B1 (zh)
JP (1) JP3048127B2 (zh)
KR (1) KR0169874B1 (zh)
CN (1) CN1105764C (zh)
AR (1) AR002916A1 (zh)
AU (1) AU682289B2 (zh)
BR (1) BR9603151A (zh)
CA (1) CA2180410C (zh)
CO (1) CO4560483A1 (zh)
ES (1) ES2196125T3 (zh)
MX (1) MX9602779A (zh)
TW (1) TW436517B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100430220C (zh) * 2001-12-25 2008-11-05 东洋制罐株式会社 具有气体阻隔性能的多层结构
CN106833437A (zh) * 2017-01-25 2017-06-13 江阴宝柏包装有限公司 一种阻酸型泡罩包装铝箔盖膜的制备方法、盖膜及应用

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7935375B2 (en) * 2002-08-02 2011-05-03 Basf Corporation Process and coating composition for extending the shelf life of post harvest produce
SE527531C2 (sv) * 2002-08-28 2006-04-04 Amcor Flexibles Lund Ab Material för förpackningsändamål, förfarande för framställning av materialet och förpackningsförfarande
CN100353650C (zh) * 2003-04-29 2007-12-05 建准电机工业股份有限公司 无刷直流电动机
US20160278949A1 (en) * 2011-04-08 2016-09-29 Ifit Prosthetics, Llc Modular prosthetic devices and prosthesis systems
US9181460B2 (en) 2013-03-06 2015-11-10 H.B. Fuller Company Gas transmitting polyurethane adhesive
MX2020001151A (es) 2017-07-31 2020-03-24 Dow Global Technologies Llc Estructuras de película laminada completamente de polietileno con capa adhesiva de barrera.
MX2021006413A (es) 2018-12-04 2021-08-19 Dow Global Technologies Llc Película de laminación y adhesivo para esta.

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3274328A (en) * 1963-06-06 1966-09-20 Polymer Corp Dielectric for circuit board and strip lines
US3460944A (en) * 1964-04-28 1969-08-12 Du Pont Polymer compositions,strata and elements
US3753828A (en) * 1968-05-23 1973-08-21 Tee Pak Inc Method of preparing oxygen impermeable film laminate
US4032487A (en) * 1974-03-21 1977-06-28 Borden, Inc. Aqueous acrylate-epoxy silane crosslinker adhesive dispersion composition
JPS606784B2 (ja) * 1979-01-12 1985-02-20 凸版印刷株式会社 包装材料
JPS57202043A (en) 1981-06-08 1982-12-10 Nippon Hoso Kyokai <Nhk> Image pickup tube
JPS5993646A (ja) * 1982-11-19 1984-05-30 東洋製罐株式会社 ラベル付プラスチツク容器
GB8402345D0 (en) * 1983-02-21 1984-02-29 Ici Plc Vinylidene chloride copolymer aqueous latex composition
US4619960A (en) * 1983-06-01 1986-10-28 The B. F. Goodrich Company Stable blends of vinyl chloride and acrylic latexes
US4762731A (en) * 1983-09-12 1988-08-09 The Dow Chemical Company Barrier film structures using carbon monoxide-containing polymers
GB8528244D0 (en) * 1984-12-06 1985-12-18 Ici Plc Latex compositions
JPH04238771A (ja) * 1991-01-11 1992-08-26 Daifuku Co Ltd 複式トロリーコンベヤのトロリー乗り移し装置
US5468526A (en) * 1993-09-20 1995-11-21 The Dow Chemical Company Multilayer barrier film for ostomy applications

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100430220C (zh) * 2001-12-25 2008-11-05 东洋制罐株式会社 具有气体阻隔性能的多层结构
CN106833437A (zh) * 2017-01-25 2017-06-13 江阴宝柏包装有限公司 一种阻酸型泡罩包装铝箔盖膜的制备方法、盖膜及应用

Also Published As

Publication number Publication date
KR0169874B1 (ko) 1999-01-15
JP3048127B2 (ja) 2000-06-05
TW436517B (en) 2001-05-28
AR002916A1 (es) 1998-04-29
KR970006447A (ko) 1997-02-21
EP0755990A3 (en) 1999-07-28
US6358357B1 (en) 2002-03-19
JPH09104853A (ja) 1997-04-22
EP0755990B1 (en) 2003-04-09
CN1105764C (zh) 2003-04-16
US20020117261A1 (en) 2002-08-29
ES2196125T3 (es) 2003-12-16
MX9602779A (es) 1998-04-30
US6673865B2 (en) 2004-01-06
CO4560483A1 (es) 1998-02-10
BR9603151A (pt) 1998-05-05
AU682289B2 (en) 1997-09-25
EP0755990A2 (en) 1997-01-29
CA2180410C (en) 2001-12-18
AU5834696A (en) 1997-01-30
CA2180410A1 (en) 1997-01-28

Similar Documents

Publication Publication Date Title
CN1219816C (zh) 等规聚丙烯和接枝等规聚丙烯为主要成分的组合物
CN1105764C (zh) 用于调节气体阻隔性的包装粘合剂混合物
CN1067941C (zh) 阻气复合薄膜及其制造方法
CN1095746C (zh) 一种树脂组合物
CN1203123C (zh) 包含接枝的由茂金属催化获得的全同立构聚丙烯的组合物
CN1088077C (zh) 树脂组合物和多层结构
CN1235952C (zh) 透气膜
CN1281674C (zh) 具有改进的密封性能和光学性能并具有减低的溶解度的晶状丙烯共聚物组合物
CN1847269A (zh) 多级乳液聚合物水分散体的制备方法
CN1167802A (zh) 以共接枝聚烯烃混合物为主要组分的共挤出粘合剂
CN1098727A (zh) 具有增强的凝胶强度的高吸水性聚合物
CN1138827C (zh) 由良好层间粘接性的乙烯-乙烯醇共聚物构成的树脂组合物
CN1165554C (zh) 生产聚乙烯基酯树脂乳液的方法
CN100339015C (zh) 包含保护胶体稳定的聚丙烯酸酯分散体的食品涂料组合物,其用途和由其制备的涂覆食品
CN1078232C (zh) 粘性液体脱氧剂及用其制造的脱氧片和脱氧片的制造方法
CN1062278C (zh) 含乙烯-乙烯醇共聚物层的多层薄膜
CN1829768A (zh) 1,1－二氯乙烯类树脂膜、肉糜制品用肠衣和包装肉糜制品
CN1408896A (zh) 沉积薄膜及其制造方法
CN1277879C (zh) 偏氯乙烯系树脂组合物、其制造方法及其薄膜
CN1533888A (zh) 阻透性层积膜及其制造方法
MXPA96002779A (en) Adhesive mixtures of packaging with controlled barrier properties
CN1594376A (zh) 用聚合稳定剂制备多峰型聚合物分散体的方法及该分散体的用途
CN1529654A (zh) 包装薄膜
CN106905491B (zh) 聚丙烯基酸改性接枝物以及含有该接枝物的粘合剂
CN1495229A (zh) 制备包含聚乙烯醇和表面活性剂的引发剂组合物的方法

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C53 Correction of patent of invention or patent application
CB02 Change of applicant information

Applicant after: Autoliv ASP Inc.

Applicant before: Morton International, Inc.

COR Change of bibliographic data

Free format text: CORRECT: APPLICANT; FROM: MERTON INTERNATIONAL CO., LTD. TO: AUTOLIV ASPCO., LTD.

C53 Correction of patent of invention or patent application
CB02 Change of applicant information

Applicant after: Morton International, Inc.

Applicant before: Autoliv ASP Inc.

COR Change of bibliographic data

Free format text: CORRECT: APPLICANT; FROM: AUTOLIV ASPCO., LTD. TO: MERTON INTERNATIONAL CO., LTD.

C14 Grant of patent or utility model
GR01 Patent grant
C56 Change in the name or address of the patentee

Owner name: ROHM AND HAAS CHEMICALS CO., LTD.

Free format text: FORMER NAME OR ADDRESS: MERTON INTERNATIONAL CO., LTD.

CP03 Change of name, title or address

Address after: American Pennsylvania

Patentee after: Roman Haas chemical Limited Liability Company

Address before: Illinois

Patentee before: Morton International, Inc.

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20030416

Termination date: 20140722

EXPY Termination of patent right or utility model