CN105579497B - 膜及其生产方法 - Google Patents

膜及其生产方法 Download PDF

Info

Publication number
CN105579497B
CN105579497B CN201480050563.XA CN201480050563A CN105579497B CN 105579497 B CN105579497 B CN 105579497B CN 201480050563 A CN201480050563 A CN 201480050563A CN 105579497 B CN105579497 B CN 105579497B
Authority
CN
China
Prior art keywords
film
layer
crosslinking
polyvinyl
mooney viscosity
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
Application number
CN201480050563.XA
Other languages
English (en)
Other versions
CN105579497A (zh
Inventor
约瑟夫·马尼
福尔克尔·许尓斯韦德
托马斯·马尔内
于尔根·比林
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.)
Benek Kellico Co Ltd
Original Assignee
Benek Kellico Co Ltd
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 Benek Kellico Co Ltd filed Critical Benek Kellico Co Ltd
Publication of CN105579497A publication Critical patent/CN105579497A/zh
Application granted granted Critical
Publication of CN105579497B publication Critical patent/CN105579497B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/002—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/005—Surface shaping of articles, e.g. embossing; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • 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
    • C08L23/06—Polyethene
    • 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
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
    • B29C2035/0877—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/02—Combined thermoforming and manufacture of the preform
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0094—Condition, form or state of moulded material or of the material to be shaped having particular viscosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/253—Preform
    • B29K2105/256—Sheets, plates, blanks or films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/004—Semi-crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
    • B29L2031/3005—Body finishings
    • B29L2031/3041—Trim panels
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Thermal Sciences (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

本发明涉及一种膜及其生产方法。该膜可以是单层或多层的，并且特别地用于机动车辆的内部装饰。该膜的至少顶层包括15至90phr的至少一种具有50至80门尼单位的门尼粘度(ML1+4，121℃)的乙烯基聚合物和10至85phr的至少一种具有大于或等于400MPa的ISO 178挠曲模量的聚丙烯。该膜的特征为其特别良好的抗刮性。

Description

膜及其生产方法
技术领域
本发明涉及一种膜并且涉及其生产方法。这种膜可以是单层或多层并且特别地用于汽车内部装饰。
背景技术
基于聚氯乙烯(PVC)或基于热塑性聚烯烃(TPO)或基于聚氨酯(PU或PUR)的膜和膜层合件，即，多层膜已经从现有技术中熟知。它们在各种不同的领域，例如，在包装工业中或者在汽车行业中使用。对于在不同行业中的使用，特别是在汽车内部装饰的行业中，这些膜或膜层合件通过热成型操作或其他变形操作被进一步加工以便获得所希望的形式–例如，一种汽车内部装饰形式。就这些膜或膜层合件的化学和物理特性而言对其施加了严格的要求；例如，颗粒化的膜特别地是具有良好的纹理稳定性并且同时良好的抗刮性。EP 1149858A1例如，使用电子束为一种TPO膜，提供了改进的纹理稳定性。EP 1688460 B1披露了一种TPO膜，该膜事实上已经具有良好的纹理稳定性但是其抗刮性是不足的。用于汽车内部的TPO膜通过与PVC或PU膜相比典型地展现出低得多的抗刮性。
同时，在热成型之后获得小于1.5的光泽水平是令人希望的，以便实现用于该膜的高级的光学品质并且使例如在挡风玻璃中的反射最小化。通过引入一种限定的表面粗糙度和这产生的扩散光散射完成降低光泽水平。在不同的纵向比例上引入该表面粗糙度。总体上，通过纹理化引入具有光学效应的最粗糙的粗糙度。更精细粗糙度的引入通常是借助于在涂覆层中的消光剂完成的。然而，两种措施一起迄今被证明在热成型之后不足以获得1.5的光泽单位。此外，对于该膜配方必要的是展现出非常精细的表面粗糙度(凭借其形态学)。独立于纹理化和涂覆，直接在该热成型挤出的样品上可以确定通过该膜配方的形态学对粗糙度的贡献。只有当该挤出热成型的样品具有低光泽水平时，该涂覆的纹理化的部件可以被预期展现出所要求的光泽水平。
实用新型
因此本发明的一个目的是提供一种单层或多层TPO膜，该膜的特征是良好的抗刮性和一个足够的光泽水平。该膜在一个正热成型操作中能够被加工并且在一个负热成型过程中或在IMG过程中能够展现出良好的纹理复制和部件几何结构的形成。在该IMG过程(模具内纹理化过程)的情况下，通过与其中从一种基础部件真空层压出颗粒化的膜的常规层压操作相比，晶粒施加在层压操作之前立即发生。这通过一种已经包括纹理结构并且将这种结构转移给热膜的模具完成。在这种预成型状态下，这种纹理化的膜被直接施加到该基础部件上。在该正热成型过程的情况下，该膜在该层压阶段本身处配备有一种纹理，换言之，借助于一种现有压花程序具有一种三维表面结构。由于在热成型操作过程中该膜的拉伸可以改变这种晶粒，其方式仅仅为使得该最终部件的光学品质对应于消费者的要求。为了实现这种稳定性，已知的实践是在热成型之前借助于电子束交联该膜。通过添加交联助剂可以支持该交联操作。
这些表面对刮擦物品的耐受性越来越获取重要性。根据具有0.75mm的针直径的Erichsen 318测试抗刮性，并且对于一种具有300μm下的纹理深度的似皮革纹理，具有至少3N或更大的抗刮性。一个另外的边界条件是在该部件上的低水平的光泽。
该目的借助于一种单层或多层膜实现，其中至少该顶层包括15至90phr的至少一种具有50至80门尼单位的门尼粘度(ML1+4，121℃)的乙烯基聚合物和10至85phr的至少一种具有大于或等于400MPa的ISO 178挠曲模量的聚丙烯。
这种类型的膜出人意料地能够在一个正热成型过程中被加工，并且展现出不同的抗刮性连同继续良好的纹理稳定性。同时，在该IMG过程中存在该纹理的有效复制和该部件几何结构的形成。
该乙烯基聚合物在此被称为软相并且具有50至80门尼单位(MU)、优选54至70的门尼单位的门尼粘度(ML1+4，121℃)。根据ASTM D1646确定门尼粘度。该门尼粘度可以借助于这些聚合物的高支化度和/或高分子量进行调节。该乙烯基聚合物是以15至90phr的量、优选以50至70phr的量使用。
在一个特别优选的实施例中，该乙烯基聚合物的结晶度是小于或等于30％、优选地小于或等于20％。该结晶度是借助于DSC根据ISO11357-1:2009确定的。
该乙烯基聚合物具有至少50wt％的乙烯单元和小于0.90g/cm3的密度。
可以使用的软的、乙烯基聚合物的实例包括乙烯基共聚物和/或乙烯-丙烯共聚物(PEP)和/或乙烯-丙烯橡胶(EPR)、EPM橡胶、EPDM橡胶和/或聚乙烯。
根据本发明存在的聚丙烯在此被称为硬相。值得注意的是，对于挠曲模量大于或等于400Mpa、优选地大于或等于800Mpa、更优选地大于或等于1200MPa。该聚丙烯是以10至85phr的量、优选以30至50phr的量使用。可以使用的聚丙烯包括在本领域中所有的聚丙烯，例如像，PP均聚物(聚丙烯，均聚物)、PP共聚物(聚丙烯，共聚物)、PP无规(聚丙烯)、RAHECO(无规多相共聚物)和PP化合物。
在一个特别优选的实施例中，该膜的层进一步包括至少一种增容剂，特别是当使用PP均聚物时。该聚丙烯，尤其该PP均聚物，在此通常形成分散相，而该乙烯基聚合物形成连续基体。这些产生的相的可混和性和尺寸由在这些聚合物之间的相互作用并且还通过添加增容剂进行确定。在此使用的增容剂优选地是PP无规和/或PE-PP共聚物，该共聚物附接在该相界面处。其结果是，可获得良好的机械和化学特性。当使用至少一种乙烯-丙烯共聚物时，该乙烯部分应当优选地是在1与10wt％之间、更优选地在3与5wt％之间。
该增容剂优选地具有0.1至4.0g/10min、更优选地0.2至1.0g/10min、非常优选地0.3至0.5g/10min的熔体流动指数MFI(230℃，2.16kg)。
总体上，当使用PP无规作为硬相时，对于增容剂不存在需要。
除了这些聚合物成分之外，对于膜生产使用的组合物优选地可包含一系列助剂，如交联助剂、抗氧化剂、光稳定剂、颜料、润滑剂和/或老化抑制剂。
已经证明特别有利的是对于所使用的抗氧化剂包括苯酚衍生物、内酯和/或亚磷酸酯，并且对于所使用的光稳定剂包括空间位阻胺或苯并三嗪，其量为基于该组合物的重量小于约5wt％、优选地最高达3.5wt％、更特别是从0.2至2.5wt％。
为了获得在正热成型情况下该膜良好的纹理稳定性，如果该单层或多层膜的顶层在该正热成型过程内在该形成晶粒结构的压花步骤和该交联之后具有在沸腾的二甲苯中24小时提取之后测量的10至80wt％、优选地25至50wt％的凝胶含量，这是一个优点。具有这种类型的凝胶含量的膜可被热成型和/或另外被变形而没有该纹理结构的实质改变或损伤。
在该压花之后，在热成型和/或变形过程中存在另一个用于高纹理稳定性的材料的交联。在该形成纹理结构的压花步骤之后发生的另外的交联可通过化学手段或物理地发生。
在物理交联的情况下，如果该另外的交联借助于电子束完成的话，这已经证明是有利的。这产生了特别良好的网络节点的分布，这对于在热成型之后有效的纹理保留并且对于在该部件上该膜的均匀的拉伸是重要的。在致密膜的情况下，在此辐射优选地用10至300kGy、更特别地30至150kGy的辐射剂量发生，在膜层合件的情况下，用20至150kGy、更特别地30至100kGy的辐射剂量发生。
对于在负热成型过程中或者在该IMG过程中的膜的使用，最初不存在对于通过电子束的交联的需要。在此，首先层压该膜而不压花。为了实现在该IMG过程中的良好的晶粒复制，在对于该纹理化操作相关的条件下该膜的足够低的熔体粘度是一个优点。在该IMG操作中，该膜优选地在大于160℃的温度下变形并且纹理化。在该IMG操作中引入的纹理必须在至少三周的时段内在120℃下热储存时在该部件上保持稳定。
在该形成纹理结构的压花步骤过程中和/或之前和/或之后和/或在该交联之前和/或之后，该膜可以被层压以产生一种多层复合结构和/或例如用一种PUR涂剂进行涂覆，并且随后进一步交联，它可被热成型，以产生一种多层、纹理化的模制品，例如作为一种机动车辆的内部装饰部件。
如果该膜具有以一种复合结构或膜层合件的形式的多层设计，则包括本发明的组合物的层形成该顶层，该顶层被称为顶膜或上部膜。因此，该多层膜由至少一个根据本发明的顶膜和一个底部膜构成。该底部膜可以是致密的或发泡的和/或可包括一种织物。
该多层膜可以配备有一个例如ABS或天然纤维的背衬，在这种情况下如果该背衬直接在该颗粒化的、多层膜的生产中该热成型操作过程中被连接到该纹理化的、多层膜层合件上，将是一个优点。背衬和底部膜可以在此借助于一种粘合剂***进行连接。
具体实施方式
现在使用工作实例说明本发明。为此目的，如下文描述的生产热成型的、纹理化的模制品：
在以下表1和2中配制的组合物，其中这些物质的量以重量份计，在一个双螺杆挤出机上被挤出以形成具有0.5mm厚度的膜。用于这些单独成分的量数字根据在该橡胶工业内通常使用的phr(每百份橡胶的份数)量数字进行报道。
该凝胶含量根据以下方法确定：
通过提取法获得这些凝胶含量。将这些样品切割成大约1mm尺寸的条并且在一个已知净重的网眼片上称量到0.1g±0.01g的精确度。将该网片折叠使得这些条被包封在该网片中。然后将每个网片引入至一个测试管内。向每个测试管中，添加50mL的二甲苯。为了防止该样品漂浮，将钢丝网悬浮在该管内，确保完全浸没到该二甲苯中。将这些样品用铝箔密封并放置到预热至145℃的油浴中持续16小时。随后将这些测试管从该油浴中移除。
将这些网片各自放置在铝托盘上并且在150℃下的干燥箱中干燥持续5小时。在冷却至室温之后，将它们与这些铝托盘一起再称重，对此在此还必要的是知道该单独铝托盘的净重。
在挤出之后表2中的光泽的确定是在此在60°的角度下使用Byk Gardner Mikro光泽仪器完成的。表2中在热成型之后的光泽的确定是在此用60％至100％的拉伸以未涂覆的形式下在60°的角度下使用Byk Gardner Mikro光泽仪器完成的。
表1描述了借助于正热成型过程产生的膜。表2描述了借助于IMG过程可以被进一步加工的膜。
在每种情况下“C”标记对比实例，而这些标记“I”的实例在每种情况下是本发明的。
本发明实例I1至I4各自展现出色的抗刮性。
表1：用于正热成型施加的膜组合物
TPE-V共混物：由35wt％PP和65wt％的EPM组成的热塑性弹性体，MFI 15g/10min(230℃/10kg)、凝胶含量28％
PE 1：乙烯-丁烯共聚物，门尼粘度ML[121℃1+4]：47MU，软化点约50℃
PE 2：乙烯-丁烯共聚物，门尼粘度ML[121℃1+4]：54MU，软化点约50℃
PE 3：EPDM、ENB部分4.9％，门尼粘度ML[121℃1+4]：70MU，软化点约50℃
PP 1：均-PP，挠曲模量＝1200MPa，在230℃、2.16kg下的MFI＝2.6g/10min，熔点＝164℃
PP 2：无规-PP，挠曲模量＝800MPa，在230℃、2.16kg下的MFI＝0.3g/10min，熔点＝143℃
PP/EPM共混物：20wt％的均-PP和80wt％的EPM，挠曲模量＝380MPa，MFI 0.8g/10min(230℃/2.16kg)，软化点约140℃
光稳定剂：苯并***衍生物
抗氧化剂：位阻酚
表2：用于IMG施加的膜组合物
TPE-V共混物：由35wt％PP和65wt％的EPM组成的热塑性弹性体，MFI 15g/10min(230℃/10kg)、凝胶含量28％
PE 1：乙烯-丁烯共聚物，门尼粘度ML[121℃1+4]：47MU，软化点约50℃
PE 2：乙烯-丁烯共聚物，门尼粘度ML[121℃1+4]：54MU，软化点约50℃
PE 3：EPDM、ENB部分4.9％，门尼粘度ML[121℃1+4]：70MU，软化点约50℃
PP 1：均-PP，挠曲模量＝1200MPa，在230℃、2.16kg下的MFI＝2.6g/10min，熔点＝164℃
PP 2：无规-PP，挠曲模量＝800MPa，在230℃、2.16kg下的MFI＝0.3g/10min，熔点＝143℃
PP/EPM共混物：20wt％的均-PP和80wt％的EPM，挠曲模量＝380MPa，MFI 0.8g/10min(230℃/2.16kg)，软化点约140℃
光稳定剂：苯并***衍生物
抗氧化剂：位阻酚

Claims (8)

1.一种单层或多层膜，其特征在于，至少该顶层由下述组成：50至70phr的至少一种具有50至80门尼单位的门尼粘度的乙烯基聚合物，门尼粘度在ML1+4，121℃条件下测定；和10至85phr的至少一种具有大于或等于400MPa的ISO 178挠曲模量的聚丙烯；以及增容剂和/或助剂，其中所述单层或多层膜具有3N至5N的抗刮性。
2.如权利要求1所述的单层或多层膜，其特征在于，该乙烯基聚合物的结晶度是小于或等于30％。
3.如权利要求2所述的单层或多层膜，其特征在于，该增容剂具有0.1至4.0g/10min的熔体流动指数MFI，熔体流动指数MFI在230℃，2.16kg的条件下测定。
4.一种用于生产如权利要求1至3中任一项所述的膜的方法，其特征在于，借助于一个IMG过程在大于160℃的温度下将所述膜进一步加工成一种部件。
5.一种用于生产如权利要求1至3中任一项所述的膜的方法，其特征在于，在一个正热成型过程中用至少一个形成纹理结构的压花切割和随后的交联生产所述膜。
6.如权利要求5所述的方法，其特征在于，在该形成纹理结构的压花步骤和该交联之后该膜具有在沸腾的二甲苯中24小时提取之后测量的10至80wt％的凝胶含量。
7.如权利要求5或6所述的方法，其特征在于，该交联借助于电子束交联发生。
8.机动车辆的内部装饰，包括如权利要求1至3中任一项所述的膜。
CN201480050563.XA 2013-09-12 2014-07-15 膜及其生产方法 Active CN105579497B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE201310110036 DE102013110036A1 (de) 2013-09-12 2013-09-12 Folie und Verfahren zu deren Herstellung
DE102013110036.8 2013-09-12
PCT/EP2014/065062 WO2015036148A1 (de) 2013-09-12 2014-07-15 Folie und verfahren zu deren herstellung

Publications (2)

Publication Number Publication Date
CN105579497A CN105579497A (zh) 2016-05-11
CN105579497B true CN105579497B (zh) 2019-10-11

Family

ID=51177075

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480050563.XA Active CN105579497B (zh) 2013-09-12 2014-07-15 膜及其生产方法

Country Status (5)

Country Link
US (1) US9938385B2 (zh)
EP (1) EP3044251A1 (zh)
CN (1) CN105579497B (zh)
DE (1) DE102013110036A1 (zh)
WO (1) WO2015036148A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106380616A (zh) * 2016-08-30 2017-02-08 贝内克-长顺汽车内饰材料（张家港）有限公司 一种带有金属质感低光泽汽车内饰材料的制备方法
JP2022529129A (ja) 2019-04-17 2022-06-17 ダウ グローバル テクノロジーズ エルエルシー 熱可塑性オレフィン組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101835837A (zh) * 2007-10-22 2010-09-15 陶氏环球技术公司 用于模制制品的聚合物组合物和方法
EP2263856A1 (de) * 2009-06-18 2010-12-22 Benecke-Kaliko AG Verfahren zur Herstellung eines Formkörpers und nach diesem Verfahren herstellbarer Formkörper
CN102482465A (zh) * 2009-07-02 2012-05-30 陶氏环球技术有限责任公司 Tpo组合物，制品，和所述组合物制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR960007011B1 (ko) * 1988-01-29 1996-05-27 미쓰이세끼유 가가꾸 고오교오 가부시끼가이샤 적층성형체 및 그 제조방법
DE10018196A1 (de) 2000-04-12 2001-11-22 Benecke Kaliko Ag Verfahren zur Herstellung einer Polyolefinfolie und deren Verwendung
DE102005005576A1 (de) 2005-02-07 2006-08-17 Benecke-Kaliko Ag Verfahren zur Herstellung einer genarbten Folie und deren Verwendung
DE102011053224A1 (de) 2011-09-02 2013-03-07 Benecke-Kaliko Ag Thermoplastische Elastomerzusammensetzung, Folie und Verwendung
BR112014024333B1 (pt) * 2012-04-04 2020-12-22 Borealis Ag composição de polipropileno reforçada com fibra de alto fluxo

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101835837A (zh) * 2007-10-22 2010-09-15 陶氏环球技术公司 用于模制制品的聚合物组合物和方法
EP2263856A1 (de) * 2009-06-18 2010-12-22 Benecke-Kaliko AG Verfahren zur Herstellung eines Formkörpers und nach diesem Verfahren herstellbarer Formkörper
CN102482465A (zh) * 2009-07-02 2012-05-30 陶氏环球技术有限责任公司 Tpo组合物，制品，和所述组合物制备方法

Also Published As

Publication number Publication date
US20160222176A1 (en) 2016-08-04
WO2015036148A1 (de) 2015-03-19
EP3044251A1 (de) 2016-07-20
CN105579497A (zh) 2016-05-11
DE102013110036A1 (de) 2015-03-12
US9938385B2 (en) 2018-04-10

Similar Documents

Publication Publication Date Title
EP2291438B1 (en) Biaxially oriented lldpe blends
JP6284685B2 (ja) ポリマー組成物および押出被覆された物品
CN107405871B (zh) 单轴取向的多层流延膜
WO2012020106A1 (en) Easy tear polypropylene film without notch
WO2014110657A1 (en) Improved multilayer blown films
CN111727224A (zh) 聚乙烯膜组合物，层压体，及其制造方法
WO2017073751A1 (ja) ポリエチレンフィルム、積層体およびこれらを用いた包装体
CN100540296C (zh) 压花模塑件的制备方法以及按其制备的模塑件
CN105579497B (zh) 膜及其生产方法
EP3554809A1 (de) Verfahren zur herstellung einer lackierten genarbten folie, die lackierte genarbte folie und deren verwendung
JP2020192695A (ja) 積層体
JP2014124797A (ja) 発泡積層体の製造方法及びその発泡積層体
US11628648B2 (en) Method of making coextruded crosslinked polyolefin foam with polyamide cap layers
JP6705347B2 (ja) ポリプロピレン樹脂製多層発泡シート
US11479016B2 (en) Coextruded crosslinked polyolefin foam with polyamide cap layers
JP6331347B2 (ja) 発泡積層体の製造方法及び発泡積層体
EP2263856B1 (de) Verfahren zur Herstellung eines Formkörpers
JP6800406B2 (ja) 発泡用積層体及び発泡積層体
JP7387831B2 (ja) ポリプロピレン樹脂組成物およびこれにより製造された成形品
DE102017221414A1 (de) Kunststofffolienlaminat mit Schaum mittlerer Dichte
JP6673157B2 (ja) ポリプロピレン樹脂製多層発泡シート並びに発泡容器及びその製造方法
JP6662733B2 (ja) 積層体フィルム
JP6958281B2 (ja) 加飾フィルムおよびそれを用いた加飾成形体の製造方法
TW202413116A (zh) 包裝膜、包裝材以及食品包裝體
TW202413115A (zh) 包裝膜、包裝材以及食品包裝體

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant