CN1715038A - 可模切的双轴取向薄膜 - Google Patents
可模切的双轴取向薄膜 Download PDFInfo
- Publication number
- CN1715038A CN1715038A CNA2005100790909A CN200510079090A CN1715038A CN 1715038 A CN1715038 A CN 1715038A CN A2005100790909 A CNA2005100790909 A CN A2005100790909A CN 200510079090 A CN200510079090 A CN 200510079090A CN 1715038 A CN1715038 A CN 1715038A
- Authority
- CN
- China
- Prior art keywords
- film
- copolymer
- label
- die
- layer
- 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
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
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- 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
- B29K2023/04—Polymers of ethylene
- B29K2023/08—Copolymers of ethylene
- B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
-
- 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
-
- 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
- C08J2323/14—Copolymers of propene
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/334—Applications of adhesives in processes or use of adhesives in the form of films or foils as a label
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
- C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/006—Presence of polyolefin in the substrate
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/14—Layer or component removable to expose adhesive
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2848—Three or more layers
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
- Y10T428/31917—Next to polyene polymer
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
本发明涉及具有适应性的、可模切的双轴拉伸取向的单层或多层薄膜,该薄膜包括聚乙烯,聚丙烯或它们的混合物。该薄膜的横向拉伸模量为约150000磅/平方英寸或以下,该薄膜特别适用于制造含粘合剂的标签材料。
Description
发明领域
本发明涉及具有适应性和可模切的双轴取向薄膜和标签材料,更具体地说,涉及双轴拉伸取向的单层和多层薄膜以及标签材料。
背景技术
供标签用的压敏粘合材料的制造与切分是早已知道的,这种压敏粘合材料是由用作标签或标志的面层或面层材料,涂在其背面的一层压敏粘合剂以及覆盖在粘合剂上的剥离衬或载体所构成的。剥离衬或载体在运输和贮存期间起保护粘合剂的作用,便于在标签经模切后能顺利地转移一排单个标签,并在贴标签生产线上能使载体顺利地从表面材料层上剥下直到依次分送单个标签的位置。从模切至分送期间,剥离衬或载体保持未切状态,并可卷绕和退卷以利于载持在衬上的一排单个标签的贮存、移动和使用。
一般来说,标签未能可靠地实施分送的特征是指标签随着载体沿剥离板移动时没有实现分送,即没有“离开”载体贴合于被贴物体上。这种未能实施分送可认为是和标签面层材料与剥离衬之间的剥离值过大有关。可分送性也取决于面层材料的劲度。未能实施分送的特征也在于因标签的劲度不够,因而在从载体转移到被贴物体的分送速度下标签发生了折皱。在各种粘贴标签的场合中的另一特定要求是能以高的生产速度粘贴聚合物膜标签,因为提高生产速度具有显著节省费用的优点。
在各种粘贴标签的场合中,希望面层材料是具有纸类所缺乏的性能的聚合物膜,这种性能包括诸如透明度、耐久性、强度、耐水性、耐磨性、光泽度和其它性能。从历史上说,为了保证在自动贴标签机上实现分送性,已经采取了厚度大于约3密耳(75微米)的聚合物面层材料。例如在粘贴标签的场合中,已采用了厚度约3.5-4.0密耳(87.5-100微米)的增塑聚氯乙烯薄膜,因为它具有所要求的柔软性。然而,已经认识到,为使刚性薄膜转变为柔软薄膜而添加在PVC薄膜中的增塑剂的迁移是引起这类薄膜所需性能(如粘合性、着色性、收缩率和柔软性)下降的主要原因。最终,增塑剂的迁移会使面层和/或标签出现折皱、龟裂和目视可见的损坏。同时,也希望降低厚度或降低面层材料的厚度,以节省材料费用。面层材料厚度的降低常常会使劲度下降,因而不能采用自动化机械以可靠的工业上认可的方式对标签实施模切和分送。从环境保护要求考虑也要用聚合物面层材料代替聚氯乙烯来制造标签。
先有技术中用于制造标签的聚合物材料包括厚度低至约2.0密耳(50微米)的双轴取向聚丙烯(“BOPP”)。这些材料由于价格较低,因而可节省费用,并具有足够的劲度而能很好地实现分送。然而,这些材料沿纵向(MD)和横向(CD)都具有较高的拉伸模量,因而形成的标签适应性很差。
对于刚性表面如玻璃来说,已经遇到了适应性问题,例如,当双轴取向薄膜粘贴到刚性物体如玻璃瓶上时,该粘贴过程不能成功地完成。劲度较高的标签往往会在瓶子成形过程中形成的表面凹陷和模塑接缝处形成桥接,这样就在粘贴的标签上形成了类似捕集的空气泡那样的不符要求的表面外观。这一问题已经在一定程度上妨碍了以压敏粘合剂标签来替代先有的玻璃瓶贴标签技术,如在玻璃瓶制造过程中直接将瓷漆粘合在瓶子表面上,但顾客认为这种外观不吸引人。由于有害的油墨组分及回收碎玻璃瓶过程中油墨的污染,因而这种瓷漆技术是不符合环保要求的。对于柔软物体如塑料瓶来说,采用劲度较高的取向聚丙烯薄膜的试验也没有完全成功,这是由于这种标签不具有与柔软塑料容器相符所要求的柔软性所致。取向聚丙烯薄膜还较PVC或聚乙烯薄膜难以印刷。
其它可采用的材料是价格较低的、具有适应性的未取向聚乙烯和聚丙烯薄膜。然而,当这两种薄膜较薄时,都难以模切且不能进行分送。在欧洲,一种未取向的较厚的聚乙烯面层材料已成功地用于制造标签。该面层材料是可模切的,且可在高速运转的自动分送装置上进行分送。这种欧洲的“标准”聚乙烯面层材料的常规厚度为约4.0密耳(100微米)。为降低成本而实施的降低聚乙烯面层材料厚度的试验还没有取得任何进展,这是由于较薄的聚乙烯面层不易进行模切,模切后在衬上会留下模头的印记,以及在模切的标签上会留上切纹。此外,较薄的面层材料因其劲度较低而难以在较高的运转速度下沿剥离板进行分送。
发明概述
本发明的一个实施方案是可模切的双轴取向单层薄膜,该薄膜包括密度约0.940克/立方厘米或以下的聚乙烯,丙烯聚合物或共聚物,或它们的混合物,其中薄膜的纵向拉伸模量高于横向拉伸模量,横向拉伸模量为约150000磅/平方英寸或以下,该薄膜不含乙烯与烯属不饱和羧酸或酯的共聚物。在一个实施方案中,双轴取向单层薄膜已经过双轴拉伸取向和热定形。
在另一个实施方案中,本发明涉及可模切的拉伸取向多层薄膜,该薄膜包含:
(A)具有上表面和下表面的基材层,该基材层包括密度约0.940克/立方厘米或以下的聚乙烯,丙烯均聚物或共聚物,或它们的混合物,该基材层不含乙烯与烯属不饱和羧酸或酯的共聚物,以及
(B)粘贴在基材层上表面上的热塑性聚合物第一表层,其中多层薄膜的纵向拉伸模量高于横向拉伸模量,横向拉伸模量为约150000磅/平方英寸或以下。该双轴取向多层薄膜特别适用于制造含有粘合剂的用于涂胶标签的面层材料。
在还有一个实施方案中,本发明涉及包括至少一种聚烯烃的可模切的双轴拉伸取向单层薄膜,其中薄膜已经过拉伸取向,纵向拉伸比为约9∶1-约10∶1,横向拉伸比为大于1∶1-约3∶1。
优选实施方案的说明
在一个实施方案中,本发明涉及双轴拉伸取向的单层和多层薄膜的制造,其中薄膜的特征是具有良好的适应性、模切性和/或分送性。在一些实施方案中可制成高透明度薄膜。虽然具有适应性的薄膜通常模切性较差,但本发明提供的具有适应性的薄膜具有符合要求的模切性,因此,这些薄膜可用于粘贴瓶子、管子的标签的场合,或用于其它需要透明和具有适应性的标签的场合。可按照本发明方法制造多层膜结构,这种结构包含用于提供印刷适性的表层,或是用于提供其它所需特性(如劲度)因而可降低薄膜厚度的表层,或者是两种性能兼有的表层。
在一个实施方案中,本发明的双轴拉伸取向单层薄膜包括密度约0.940克/立方厘米或以下的聚乙烯,丙烯聚合物或共聚物,或它们的混合物,其中薄膜的纵向拉伸模量高于横向拉伸模量,横向拉伸模量为约150000磅/平方英寸或以下,该薄膜不含乙烯与烯属不饱和羧酸或酯的共聚物。
适用的乙烯均聚物包括密度为约0.940或以下的聚乙烯。密度为约0.850-约0.925克/立方厘米的聚乙烯通常称为低密度聚乙烯,而密度在约0.925与约0.940克/立方厘米之间的聚乙烯在技术上称为中密度聚乙烯。低密度和中密度聚乙烯也可由熔体指数(根据ASTM试验方法D1238,条件E测定)为0.5-约25来表征。除上述密度和熔体指数外,低密度聚乙烯还可由拉伸强度为约2200与约3200磅/平方英寸之间(通常为约2700磅/平方英寸)来表征,而中密度聚乙烯可由拉伸强度为约3000与约4000磅/平方英寸之间(通常为约3400磅/平方英寸)来表征。
适用作本发明面层材料的第一表层的低密度和中密度聚乙烯,有多种货源可供商购。适用的聚乙烯实例汇于下表1中。
表1
商购聚乙烯
商购产品牌号 | 制造公司 | 熔体流动指数(克/10分钟) | 密度(g/cm3) |
Rexene1017 | Rexene | 2.0 | 0.920 |
Rexene1058 | Rexene | 5.5 | 0.922 |
Rexene1080 | Rexene | 2.0 | 0.930 |
Rexene2030 | Rexene | 5.0 | 0.919 |
Rexene2034 | Rexene | 7.5 | 0.925 |
Rexene2038 | Rexene | 9.0 | 0.917 |
Rexene2040 | Rexene | 12.0 | 0.917 |
Rexene2049 | Rexene | 20.0 | 0.917 |
NA-334 | Equistar | 6.0 | 0.918 |
NA-217 | Equistar | 5.5 | 0.923 |
NA285-003 | Equistar | 6.2 | 0.930 |
Exact3027 | Exxon | 3.5 | 0.900 |
Exact3022 | Exxon | 9.0 | 0.905 |
Exact3139 | Exxon | 7.5 | 0.900 |
SLP9053 | Exxon | 7.5 | 0.900 |
AffinityPF1140 | Dow Chemical | 1.6 | 0.895 |
Sclair11G1 | Nova | 0.72 | 0.920 |
Dowlex2027 | Dow Chemical | 4.0 | 0.941 |
单层薄膜可包括丙烯均聚物或共聚物、或丙烯均聚物与至少一种丙烯共聚物的共混物。当采用均聚物与共聚物的共混物制作薄膜时,该共混物可包含约5%-约95%(重量)的均聚物和约95%-约5%(重量)的共聚物。可单独使用或如上所述与丙烯共聚物混合使用的丙烯均聚物包括各种丙烯均聚物如熔体流动速率(MFR)为约1-约20(按ASTM试验方法D1238,条件L测定)的丙烯均聚物。熔体流动速率至少约4(优选至少为约8)的丙烯均聚物是特别适用的,它能赋予薄膜好的模切性。适用的丙烯均聚物也可表征为密度为约0.88-约0.92克/立方厘米。
对许多适用的丙烯均聚物来说,有多种货源可供商购。一些适用的均聚物汇于下表II中。
表2
商购丙烯均聚物
商购产品牌号 | 制造公司 | 熔体流动指数(克/10分钟) | 密度(g/cm3) |
WRD5-1057 | Union Carbide | 12.0 | 0.90 |
DX5E66 | Union Carbide | 8.8 | 0.90 |
5A97 | Union Carbide | 3.9 | 0.90 |
5E98 | Union Carbide | 3.2 | 0.90 |
Z9470 | Fina | 5.0 | 0.89 |
Z9470HB | Fina | 5.0 | 0.89 |
Z9550 | Fina | 10.0 | 0.89 |
6671XBB | Fina | 11.0 | 0.89 |
3576X | Fina | 9.0 | 0.89 |
3272 | Fina | 1.8 | 0.89 |
SF6100 | Montell | 11.0 | 0.90 |
可采用的丙烯共聚物通常包括丙烯与至多约40%(重量)的至少一种选自乙烯和含4-约8个碳原子的α-烯烃的α-烯烃的共聚物。适用的α-烯烃的实例包括乙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯和1-辛烯。通常可用于本发明的丙烯共聚物包括丙烯与乙烯、1-丁烯或1-辛烯的共聚物。适用于本发明的丙烯α-烯烃共聚物包括无规共聚物和嵌段共聚物,尽管无规共聚物通常是优选的。共聚物的共混物以及共聚物与丙烯均聚物的共混物都可用作基材层的成分。在一个优选的实施方案中,丙烯共聚物是乙烯含量为约0.2%-约10%(重量)的丙烯-乙烯共聚物。优选的是,乙烯含量为约3%-约10%(重量),而更优选为约3%-约6%(重量)。对于丙烯-1-丁烯共聚物来说,1-丁烯含量为至多约15%(重量)是适用的。在一个实施方案中,1-丁烯含量通常在约3%(重量)-至多约15%(重量),在其它实施方案中,该含量范围可从约5%-约15%(重量)。适用于本发明的丙烯-1-辛烯共聚物可含至多约40%(重量)的1-辛烯。通常,丙烯-1-辛烯共聚物可含至多约20%(重量)的1-辛烯。
适用于本发明的丙烯共聚物可通过技术人员已知的技术来制备,而且许多这类共聚物是可商购的。例如,适用于本发明的共聚物可通过丙烯与α-烯烃如乙烯或1-丁烯,在单点金属茂催化剂存在下进行共聚合而制得。一些适用的可商购的丙烯共聚物列于下表III中。适用于本发明的丙烯共聚物的MFR为约1-约20,优选为约1-约12。
表3
商购丙烯均聚物
商购产品名 | 制造厂商 | %乙烯 | %1-丁烯 | 熔体流动速率(克/10分钟) | 密度(g/cm3) |
DS4D05 | Union Carbide | - | 14 | 6.5 | 0.890 |
DS6D20 | Union Carbide | 3.2 | - | 1.9 | 0.890 |
DS6D81 | Union Carbide | 5.5 | - | 5.0 | 0.900 |
SRD4-127 | Union Carbide | - | 8 | 8.0 | NA |
SRD4-104 | Union Carbide | - | 11 | 5.0 | NA |
SRD4-105 | Union Carbide | - | 14 | 5.0 | NA |
上述本发明的单层薄膜也是以不含乙烯单体与烯属不饱和羧酸或酯共聚单体的共聚物为特征的。当薄膜中这类共聚物的含量低于约0.1%(重量)时可认为该薄膜中不含此类共聚物。不在本发明实施方案的薄膜所考虑范围之内的共聚物的具体实例是乙烯-醋酸乙烯酯(EVA),乙烯丙烯酸甲酯(EMA)和乙烯丙烯酸正丁酯(EnBA)的共聚物。
虽然本发明薄膜可含其它聚合物和共聚物,但当要求获得透明(低雾度)薄膜时,不相容的聚合物和共聚物的含量应降至最低限度,或者应基本上避免采用。可包括的不相容聚合物的含量随具体聚合物(例如不相容性程度)和所允许的雾度程度而定。
本发明的单层薄膜可掺入各种成核剂和微粒状填料。成核剂的添加量应足以对结晶结构作所需的改进,但又不会对所要求的薄膜性能产生不利的影响。通常希望利用成核剂来改进结晶结构并提供大量的相当小的晶体或球粒以改进薄膜的透明度、劲度和模切性。显然,添加到薄膜配方中的成核剂量不应对薄膜的透明性有不利的影响。至今已用于聚合物薄膜的成核剂包括无机成核剂和有机成核剂。无机成核剂的实例包括炭黑、二氧化硅、高岭土和滑石。已被推荐可用于聚烯烃薄膜的有机成核剂包括脂族一元或二元酸或芳基烷基酸的盐如琥珀酸钠、戊二酸钠、癸酸钠、4-甲基戊酸钠、苯基乙酸铝和肉桂酸钠。芳族和脂环族羧酸的碱金属盐和铝盐如苯甲酸铝、苯甲酸钠或钾、β-萘甲酸钠、苯甲酸锂和叔丁基苯甲酸铝都是适用的有机成核剂。取代的山梨醇衍生物如双(亚苄基)山梨醇和双(烷基亚苄基(benzilidine))山梨醇等也是适用的成核剂,其中烷基基团含约2-约18个碳原子。更具体地说,诸如1,3,2,4-二亚苄基山梨醇;1,3,2,4-二对甲基亚苄基山梨醇和1,3,2,4-二对甲基亚苄基山梨醇等山梨醇衍生物是聚丙烯的适用成核剂。对适用的成核剂来说,有多种货源可供商购。Millad 8C-41-10是一种10%Millad3988(山梨醇成核剂)和90%聚丙烯的母料,购自Milliken Chemical Co.
当成粒剂掺入薄膜中时,掺入本发明薄膜配方中的成粒剂用量通常是相当低的,约为薄膜的100-约2000或4000ppm。成核剂的优选用量应不超过2000ppm,在一个实施方案中,最佳浓度为约300-500ppm。
薄膜可含有其它添加剂和微粒状填料以改进薄膜的性能。例如薄膜中可包含着色剂如TiO2、CaCO3等。例如少量TiO2的存在会形成白色面料。基材层中也可含有防粘连剂。AB-5是一种购自Schulman Inc.,(3550West Market Street,Akron,Ohio 44333)的、包括5%固态合成的无定形二氧化硅与95%低密度聚乙烯的防粘连母料。ABPPO5SC是一种购自Schulman含5%合成无定形二氧化硅的丙烯共聚物防粘连母料。防粘连剂(二氧化硅)在基材层中的用量可为约500-约5000ppm,而约1000ppm是优选的。
在一些实施方案中,特别是在要求薄膜为透明的情况中,虽然薄膜不含惰性微粒状填料,但由于杂质等的原因,薄膜中仍可存在极少量的微粒状填料。术语“不含”是指薄膜中微粒状填料的含量低于约0.1(重量)%。不含微粒状填料的薄膜特别适用于要求制造透明薄膜的场合,这种透明薄膜可由低雾度例如低于10%或低于6%雾度,在某些情况下低于约2%来表征。雾度或透明度是以技术上已知的BYK-Gardner雾度-光泽度计测定的。已经观察到,本发明不含填料微粒的双轴拉伸取向薄膜具有高透明性,而在某些情况下,该薄膜是清澈透明的。如上所述,当要求透明薄膜时,薄膜中应不含或只含少量不相容的聚合物和共聚物。
本发明的单层薄膜可通过技术人员了解的各种技术来成形,这类技术包括吹胀挤出或平挤挤出、挤出贴面或是这些技术的组合。如上所述,本发明薄膜是双轴拉伸取向的。在制备本发明薄膜时,可采用同时双轴取向或顺序双轴取向。一种优选的制造单层薄膜的方法是同时双轴取向方法。
虽然,可以通过以纵向(MD)拉伸量等于或高于横向(CD)拉伸量的拉伸方法来制造本发明所要求的可模切双轴拉伸取向单层薄膜,但在一个实施方案中,优选的是MD拉伸取向高于CD拉伸取向至少约10%,或甚至20%。MD取向的拉伸比可为约3∶1-约10∶1或以上,尽管通常MD拉伸比为约5∶1-约10∶1。在其它实施方案中,MD拉伸比可为约9∶1-约10∶1或以上。如上所述,CD拉伸比常常低于MD拉伸比。于是,CD拉伸比可为高于1∶1-约5∶1,或高于1∶1-约3∶1或高于1∶1-约2∶1。在后一个实施方案的具体实例中,将MD拉伸比为9∶1-10∶1的拉伸取向聚烯烃单层薄膜以拉伸比高于1∶1-约2∶1或3∶1或4∶1进行CD拉伸取向。可用于该实施方案的聚烯烃包括聚乙烯、聚丙烯、丙烯与至多约40(重量)%的至少一种选自乙烯和如上所述含4-约8个碳原子的α-烯烃的α-烯烃的共聚物和它们的混合物。因此,在该具体实施方案中,聚烯烃包括低密度聚乙烯、中密度聚乙烯和高密度聚乙烯,尽管低密度和中密度聚乙烯是较常用的。高密度聚乙烯是指密度高于约0.940-约0.965克/立方厘米的聚乙烯。
本发明的单层薄膜是在等于或高于薄膜软化温度下,经热拉伸而形成双轴取向的。热拉伸步骤中所采用的温度尤其随薄膜的组成和是否有成核剂的存在而定。当采用顺序取向时,MD拉伸温度可以不同于CD拉伸时的温度。一般来说,MD取向是在低于CD取向温度下实施的。例如,对丙烯均聚物来说,实施MD取向的温度可为约140℃,而实施CD取向的温度为约180℃。
在本发明的一个实施方案中,使在加热条件下,经拉伸取向达到所需拉伸比的单层薄膜再通过退火辊以实施退火或热定形操作。在热定形或退火操作后,再使薄膜通过冷却辊以完成热拉伸和热定形操作。在另一个实施方案中,在经退火或热定形步骤前,先使经热拉伸的薄膜沿MD和CD进行松驰达约5%-约25%,通常为约10%-约20%。实施热拉伸步骤和热定形步骤的温度随用于形成单层薄膜的具体聚合物而定,其温度范围为约110℃-约180℃。实施热拉伸和热定形步骤的温度可以是相同的,尽管在一些情况中,实施热定形步骤的温度稍高于实施热拉伸步骤的温度。因此,热定形步骤可在高达约180℃下实施。当本发明的热拉伸薄膜经历热定形或退火步骤时,通常使薄膜热定形或退火约5-约25秒,更常见为约10-约20秒。本发明经热定形或退火的拉伸取向单层薄膜,基本上没有在热的作用下会回复到先前构型的“记忆”效应。这就是说,本发明经热定形和退火的薄膜在以后经受高温的情况下不再会发生收缩或变形。
上述单层薄膜的厚度可随薄膜的预期用途而定,其范围可为约0.5密耳(12.5微米)-约6密耳(150微米)。然而,一般来说,本发明双轴拉伸取向单层薄膜的厚度为约1密耳-约3.5或4密耳。在一个实施方案中,薄膜厚度为约2-约2.5密耳。
上述本发明双轴拉伸取向单层薄膜具有可使薄膜用于如作为可模切标签材料等用途中的劲度特性。因此,本发明双轴拉伸取向单层薄膜的纵向Gurley劲度可为约3-约50,通常为约5或10至高达约50。本发明单层薄膜的横向Gurley劲度通常低于纵向Gurley劲度。本发明单层薄膜的Gurley劲度是按照TAPPI Gurley劲度试验T543pm方法测定的。
如上所述,本发明薄膜也可包括可模切的拉伸取向多层薄膜,该薄膜包含:
(A)具有上表面和下表面的基材层,该基材层包括密度为约0.940克/立方厘米或以下的聚乙烯,丙烯均聚物或共聚物,或它们的混合物,该基材层不含乙烯与烯属不饱和羧酸或酯的共聚物,以及
(B)粘贴在基材层上表面上的热塑性聚合物第一表层,其中多层薄膜的纵向拉伸模量高于横向拉伸模量,横向拉伸模量为约150000磅/平方英寸或以下。
上述任何一种单层薄膜在取向前都可用作多层薄膜的基材层。这就是说,本发明多层薄膜的基材层可包括上述任何聚乙烯,任何丙烯均聚物或共聚物,或它们的混合物,其中基材层不含乙烯与烯属不饱和羧酸或酯的共聚物。基材层也可含有如上述单层薄膜中任选的、任何成分如填料、着色剂、成核剂、防粘连剂等。如果要求获得透明的多层薄膜,基材层应不含惰性微粒状填料。如果要求获得不透明的多层薄膜,基材层可含有上述微粒状填料。
第一表层可包括任何其它各种热塑性聚合物。适用作本发明多层薄膜组成第一表层的热塑性聚合物和共聚物的实例包括聚烯烃、聚酰胺、聚苯乙烯、聚苯乙烯-丁二烯、聚酯、聚酯共聚物、聚氨酯、聚砜、聚偏二氯乙烯、苯乙烯-马来酸酐共聚物、苯乙烯-丙烯腈共聚物、乙烯甲基丙烯酸钠盐或锌盐基的离聚物、聚甲基丙烯酸甲酯、纤维素、氟塑料、丙烯酸聚合物和共聚物,聚碳酸酯、聚丙烯腈、乙烯-醋酸乙烯酯共聚物,以及它们的混合物。第一表层组成的选择是随对第一表层所要求的性能(如成本、耐候性、印刷适性等)而定的。
第一表层可含有、实际上的确常常含有聚烯烃(如聚乙烯、丙烯聚合物和共聚物)和乙烯与烯属不饱和羧酸或酯的共聚单体的共聚物如EVA的混合物。例如一种适用的表层组成包含聚丙烯与EVA之比为50∶50的混合物。
第一表层也可含其它添加剂例如如上所述的微粒状填料、防粘连剂、成核剂等。当要求获得透明的多层薄膜时、第一表层(以及基材层)通常不含微粒状填料。如果要求获得不透明的薄膜,表层(和/或基材层)可含微粒状填料。因此,可制得本发明的从不透明至透明的多层薄膜,透明薄膜可以雾度低于10%或低于6%,或甚至低于约2%来表征。
在本发明的还有一个实施方案中,包含具有上表面和下表面的基材层以及粘贴在基材层上表面上的热塑性聚合物第一表层的多层薄膜,也可包含粘贴在基材层下表面的第二表层,该第二表层可包括上述适用于第一表层的任何热塑性聚合物,第二表层的组成可与第一表层相同,也可以不相同。一般来说,由于对两表层的性能要求不同,因而两表层是不相同的。对第一表层来说需要有印刷适性、耐候性等,而对第二表层来说需要对粘合层有良好的粘合性能。
本发明的多层薄膜可通过技术人员了解的各种技术来制造,此类技术包括吹账挤出或平挤挤出或挤出贴面或是这些技术的组合。美国专利5186782(Freedman)和美国专利5242650(Rackovan等人)与5435963(Rackovan等人)公开了适用于制造多层薄膜的方法。这些专利已列入本文供参考。多层薄膜可以适用的已知类型共挤出模头通过同时挤出成形,然后将各层彼此粘合成永久性复合体,从而形成整体共挤塑体。或者,先将基材层挤出在基体上形成基材层,然后再通过挤出贴面技术在基材层上成形第一表层(和任选第二表层),从而形成两层或三层结构,其中各层彼此粘合成永久性的复合体。再一个实施方案的制造方法是先通过挤出技术分别成形两层膜材或三层膜材,随后再经加热和加压而层合在一起。
一般来说,基材层较第一表层和第二表层厚一些。在另一个虽然通常不是优选的实施方案中,第一表层可较基材层厚。因此,三层膜的厚度比可为约90∶5∶5-5∶5∶90。然而,三层膜的优选厚度比(基材层∶第一表层∶第二表层)包括90∶5∶5,80∶10∶10,70∶15∶15,85∶5∶10和80∶5∶15。
如上所述,本发明的多层薄膜是双轴拉伸取向的。同时双轴取向或顺序双轴取向技术都可用来制备本发明的多层薄膜。在一个本发明的实施方案中,制造本发明多层薄膜的优选方法是同时双轴取向技术。
在一些例子中,可通过薄膜的纵向(MD)拉伸和横向(CD)拉伸而制得上述本发明可模切的双轴拉伸取向多层薄膜,其中纵向拉伸量等于或高于横向拉伸量,且MD拉伸取向常高于CD拉伸取向至少约10%,或甚至20%。MD取向的拉伸比可为约3∶1-约10∶1或以上,但优选的MD拉伸比为约5∶1-约10∶1。在另一些实施方案中,MD的位伸比为约9∶1-约10∶1或以上。如上所述,CD的拉伸比通常低于MD拉伸比。因此,CD拉伸比为高于1∶1-约5∶1,或高于1∶1-约3∶1或高于1∶1至约2∶1。
上述多层薄膜的厚度随预期的薄膜的用途而定,为约0.5密耳(12.5微米)-约6密耳(150微米)。然而,一般来说,本发明的多层薄膜的厚度可为约1-约3.5或4密耳,或约2-约3密耳。这种厚度特别适用于制造贴在刚性和柔软物体上的标签。如前所述,本发明多层薄膜面层材料的具体特征是能制成适用于制作标签的很薄的薄膜(即1-3密耳)。
用作第二表层的具体聚合物的选择随对第二表层所要求的性质和特征而定。用作第二表层的聚合物应与基材层聚合物相容,以保证对基材层有足够的粘附性。例如,如果基材层含有丙烯聚合物,则含有至少某种丙烯聚合物的第二表层就会与基材层相粘附而不会形成中间过渡层。业已发现,如第二表层的组成不同于第一表层,则面层材料卷绕时会降低相互粘连的倾向。
在一个实施方案中,第二表层包括较用于制造基材层的丙烯聚合物或共聚物,或丙烯聚合物与共聚物的共混物柔软的聚合物是优选的,尤其是当第二表层借助粘合剂粘接在剥离衬上时,具体地说,第二表层材料的拉伸模量较构成基材层的材料的拉伸模量为低是优选的。当与第二表层材料的拉伸模量高于基材层材料的面层材料相比时,采用较低拉伸模量的第二表层会使面层材料具有更好的模切性。
本发明多层薄膜的劲度对于以较高线速度沿剥离板适时地分送标签是很重要的。多层薄膜的双轴取向增大了纵向拉伸模量和横向拉伸模量。纵向拉伸模量的增大有助于达到尺寸稳定性和良好的印刷对版性能。
纵向取向多层薄膜的劲度通常应至少为约2或3,且可高达50或60Gurley。通常,纵向取向多层薄膜的劲度范围为约5或10,至多约25或35Gurley(按照TAPPI Gurley stiffness Test T543pm测定)。横向Gurley劲度通常与纵向有相同的范围,但CD劲度低于MD劲度。
上述本发明的双轴拉伸取向单层薄膜和多层薄膜还以横向拉伸模量为约150000磅/平方英寸或以下来表征。薄膜的拉伸模量可按ASTMTest D882题为“Tensile Propertise of Thin Plastic Sheeting”进行测定。在本发明的一个实施方案中,本发明薄膜的横向拉伸模量低于纵向拉伸模量。由这种薄膜制造的标签具有更好的适应性。因此,在一个实施方案中,本发明薄膜的纵向拉伸薄膜可高达200000磅/平方英寸或甚至高达250000磅/平方英寸,而横向拉伸模量为150000磅/平方英寸或以下。在其它实施方案中,纵向拉伸模量为150000或以下,甚至为125000或以下,横向拉伸模量低于100000磅/平方英寸。
汇于表IV中的下列实施例说明了本发明的单层薄膜。在下列实施例中以及在说明书和权利要求中,除非另有说明,所有份数和百分比都以重量计,温度为摄氏温度,压力为大气压或接近大气压。
表IV中所列的薄膜是由熔融物料通过挤塑模头后流延在冷却辊上而制得的。将挤出物料切成10×10平方厘米的片状,接着在实验室薄膜拉伸机上以表IV中规定的拉伸比,以400%/秒的拉伸速度进行双轴热拉伸。拉伸机是KARO IV型拉伸机(Brckner MaschinenbaU制造)。如表IV所示,对取向薄膜进行松驰和退火(热定形)。实施例1-11的单层薄膜的一些性能列于表V中。
表IV
双轴拉伸取向单层薄膜
实施例 | 薄膜组成 | 拉伸比 | 取向温度(℃) | 松驰%1 | 退火时间(秒)2 | 厚度(密耳) | |
MD | CD | ||||||
1 | 11G1 | 7∶1 | 5∶1 | 122 | 10 | 20 | 2.26 |
2 | 11G1 | 8∶1 | 5∶1 | 118 | 10 | 20 | 1.82 |
3 | 11G1 | 8∶1 | 5∶1 | 122 | 10 | 20 | 1.40 |
4 | 6D81 | 5∶1 | 5∶1 | 122 | 10 | 20 | 3.28 |
5 | 6D81 | 8∶1 | 4∶1 | 130 | 10 | 20 | 2.58 |
6 | 6D81 | 9∶1 | 4∶1 | 130 | 10 | 20 | 2.30 |
7 | DS4D05 | 8∶1 | 4∶1 | 130 | 10 | 20 | 2.46 |
8 | DS4D05 | 10∶1 | 2.5∶1 | 130 | 10 | 20 | 3.24 |
9 | DS4D05 | 10∶1 | 4∶1 | 130 | 10 | 20 | 2.16 |
10 | 5E98+2%NA3 | 10∶1 | 2.5∶1 | 160 | 10 | 10 | 2.86 |
11 | DS5E98 | 10∶1 | 2.5∶1 | 160 | 10 | 10 | 2.07 |
1MD和CD拉伸比减少的百分比
2退火温度与取向温度相同
3Millad 8C41-10
表V
双轴拉伸取向单层薄膜的性能
实施例 | 厚度(密耳) | Gurley劲度 | 2%割线模量(psi) | 雾度(%) | ||
MD | CD | MD | CD | |||
1 | 2.26 | 7.0 | 5.8 | 63,600 | 33,100 | 1.7 |
2 | 1.82 | 3.9 | 3.4 | 42,200 | 28,500 | 2.1 |
3 | 1.40 | 1.7 | 1.6 | 42,200 | 32,700 | 4.6 |
4 | 3.28 | 28.3 | 27.2 | 73,300 | 72,800 | 1.1 |
5 | 2.58 | 15.2 | 10.1 | 80,000 | 74,700 | 1.3 |
6 | 2.30 | 11.8 | 7.2 | 89,100 | 67,800 | 1.3 |
7 | 2.46 | 16.6 | 12.6 | 113,300 | 87,800 | 0.9 |
8 | 3.24 | 43.6 | 29.6 | 152,000 | 93,300 | 0.9 |
9 | 2.16 | 12.8 | 7.2 | 134,500 | 99,800 | 0.7 |
10 | 2.86 | 51.9 | 32.4 | 234,300 | 149,400 | 4.9 |
11 | 2.07 | 18.6 | 11.3 | 235,600 | 145,500 | 5.2 |
下列实施例12-14说明了本发明多层薄膜。该多层薄膜是通过如上所述共挤塑技术制造的。该薄膜是在表VI所示的温度和拉伸比的条件下实施双轴取向的。拉伸速度为400%/秒。实施例12-14薄膜的一些性能列于表VII中。
表VI
双轴拉伸取向多层薄膜
实施例 | 基材层 | 表层 | 总厚度(密耳) | 拉伸比 | 取向温度(℃) | 松驰(%)1 | 退火时间(秒)2 | |
MD | CD | |||||||
12 | 11G1 | 2027 | 2.14 | 7∶1 | 5∶1 | 118 | 10 | 20 |
13 | 11G1 | 2027 | 2.52 | 8∶1 | 4∶1 | 130 | 10 | 20 |
14 | 6D81 | 50%5E98 50%EVA* | 2.76 | 8∶1 | 4∶1 | 130 | 10 | 20 |
*Equistar UESP242F;含18%VA的EVA
1MD和CD拉伸比减少的百分比
2退火温度与取向温度相同
表VII
双轴拉伸取向多层薄膜的性能
实施例 | 总厚度(密耳) | Gurley劲度 | 2%割线模量(psi) | 雾度(%) | ||
MD | CD | MD | CD | |||
12 | 2.14 | 4.8 | 4.4 | 43,700 | 33,600 | 2.6 |
13 | 2.52 | 17.4 | 11.3 | 86,900 | 71,100 | 5.6 |
14 | 2.76 | 16.8 | 12.2 | 73,000 | 63,000 | 71.1 |
实施例1-14的双轴取向薄膜的可模切性按下述方法进行评价:将薄膜模切成一定形状的切片,然后测定从模切切片上分离基质所需的摩擦能。低摩擦能值(如约150克-厘米或以下)表示该薄膜具有好的模切性。摩擦能值低于120,低于100甚至低于80是特别理想的。该试验方法的细节已公开在美国专利5961766题为“Method For Selecting A SubstrateIntended For Use In A Cuttng Operation”中,该专利内容已列入本文供参考。
使尺寸为7×10英寸(17.8×25.4厘米)的每种薄膜和纸衬构成的受试片材通过模切机将该薄膜切成10块但不切及纸衬。模切机具有圆柱形型面。模切辊的直径为3英寸(76.2毫米),并带有一个横向模槽和周围十个模槽。每个模槽为6英寸(152.4毫米)长(或横向),15/16英寸(22.25毫米)宽(或深)并有直径为3/32英寸(2.38毫米)圆角。相邻模槽的间距为1/8英寸(3.175毫米)。砧辊直径为5英寸(127毫米)。砧辊与模具尖端之间的间隙为2.2密耳(0.0559毫米)。模压为300磅/平方英寸(208500千克/平方米),模具运行速度为15米/分钟。
每一受试片材模切深度要足以贯穿薄膜但不切及衬材。形成的切片形状为长方形,并按横向一个切片纵向10个切片并排排列在试片上。每张切片的长边与下一相邻切片的长边相平行。切片的尺寸为7/8×6英寸(22.25毫米×152.4毫米),彼此等距离排列。每张切片间的间距为1/8英寸(3.175毫米)。在模切过程中,在切片周围会产生需废弃的部分面层材料(基质)。
沿一张切片的长边中心线,然后沿下一张相邻切片的长边中心线切割模切受试片材而切成受试试样。切口是彼此相互平行的。每一受试试样由一张切片的二分之一,下一张邻近切片的二分之一、切片周围的部分基质所构成。
采用改进型TA-XT2织物分析仪(Stable Micro System,Unit105,Blackdown Rural Industries,Haste Hill,Haslemere,SurreyGU273AY,England)测定每一试样中基质与模切切片分离所需的摩擦能。TA-XT2织物分析仪是一种拉伸试验设备。对该试验仪作如下改进:折除上横梁上的夹具,由上L形固定夹取代之,上L形固定夹的一臂与上框架相连,折除安装在基座上的平台,由下L形固定夹取代之。每一受试试样的测定过程如下:将受试试样的基质边缘系在上L形固定夹上,将邻近所系基质边缘的每一切片部分的边缘系到下L形固定夹上。开动织物分析仪,使基质以5毫米/秒的速度与切片部分分离。
利用TA-XT2织物分析仪提供的软件,以分离过程中分离基质所施的力和力作用下受试试样沿长度方向的位移作图。利用TA-XT2织物分析仪的软件测定曲线下的面积。该曲线下面积是以克-秒为单位的。将测得结果乘以剥离速度(5毫米/秒),并对单位(即毫米变换成厘米)作适当的校正,以克-厘米(g-cm)表示算得的摩擦能。试样的摩擦能较高,说明面层材料切割性能不良或粘合剂回流不良。实施例1-14薄膜的试验结果汇于表VIII。对每一薄膜来说,以大约七个受试试样进行试验,这些试样的试验结果的平均值列于表VIII中。
表VIII
摩擦能试验结果
实施例薄膜 | 摩擦能(g-cm) |
1 | 68 |
2 | 93 |
3 | 109 |
4 | 54 |
5 | 51 |
6 | 41 |
7 | 74 |
8 | 85 |
9 | 43 |
10 | 40 |
11 | 65 |
12 | 57 |
13 | 54 |
14 | 36 |
在本发明另一个实施方案中,本发明的双轴取向单层或多层薄膜可用来制造用于涂胶标签的标签材料。该标签材料包含上述单层膜或多层膜以及与薄膜的一个表面以粘附相接合的粘合层。
在一个实施方案中,含粘合剂的用于涂胶标签的标签材料包含:
(A)可模切的双轴取向的多层薄膜,该多层薄膜包含:
(A-1)具有上表面和下表面的基材层,该基材层包括密度约0.940克/立方厘米或以下的聚乙烯,丙烯聚合物或共聚物,或它们的混合物,该基材层不含乙烯与烯属不饱和羧酸或酯的共聚物,以及
(A-2)粘贴在基材层上表面上的热塑性聚合物第一表层,其中多层薄膜的纵向拉伸模量高于横向拉伸模量,横向拉伸模量为150000磅/平方英寸或以下,以及
(B)具有上表面和下表面的粘合层,其中粘合层的上表面粘附于基材层的下表面。
以上已对适用作这类标签材料的多层薄膜作了详细说明。本实施方案中的粘合层是粘附在基材层的下表面上的。此外,双轴取向多层薄膜(A)还可包含粘附在基材层下表面的第二表层(A-3),此时,第二表层位于基材层与粘合层之间。如上所述的第二表层是可采用的。
粘合层可直接涂敷在基材层的下表面上,或在有第二表层的情况可涂在第二表层上,或者粘合层可从与多层薄膜相复合的衬上转移过来。一般来说,粘合层的厚度为约0.1-约2密耳(2.5-50微米)。适用于本发明标签材料的粘合剂在本领域是可商购的。通常,这些粘合剂包括压敏粘合剂,热活化粘合剂,热熔型粘合剂等。压敏粘合剂是特别优选的。这些粘合剂包括丙烯酸粘合剂以及其它弹性体如天然橡胶或含有苯乙烯、丁二烯、丙烯腈、异戊二烯和异丁烯的聚合物或共聚物的合成橡胶。压敏粘合剂在技术上是众所周知的,任何一种已知的粘合剂都可用于本发明的面层材料中。在一个优选实施方案中,压敏粘合剂的主要成分是丙烯酸酯例如丙烯酸2-乙基己酯与极性共聚单体如丙烯酸的共聚物。
在由上述根据本发明的单层和多层薄膜制造标签材料时,可附加衬或载体材料。该衬或载体可包括如美国专利4713273公开的方法制得的多层衬(该专利公开内容已列入本文供参考),或者可以是由单层纸张或薄膜层构成的常规衬或载体,这种纸或薄膜可以成卷绕形态供应。如果衬或载体事先不具有剥离涂层,其本身也不包含在与粘合剂相接触的表面上能内在产生剥离表面的组分,则衬或载体可涂以剥离涂层(如聚硅氧烷)。如果采用剥离涂层,则在涂布后,采用适当方法使其干燥或固化。
剥离衬或载体的剥离面上可涂布一层随后要转移到待粘上此剥离衬或载体的标签材料上的压敏粘合剂。当标签材料与衬或载体相复合时,该粘合剂粘附到双轴取向薄膜上。其后,撕去衬或载体使粘合剂暴露,此时粘合剂仍能持久地粘附在双轴取向薄膜上。
在一些用途中,粘合层可以是热活化粘合剂或热熔型粘合剂,它们不同于压敏粘合剂,可应用于模内标签的用途中。如果粘合剂是热活化粘合剂或热熔型粘合剂,就不需要象采用压敏粘合剂时所需的具有固有剥离性的剥离衬。
由上述根据本发明的双轴取向薄膜制造的压敏粘合标签材料的方法说明如下:衬或载体材料可以包含多层衬或是由具有剥离涂层的单层纸张或薄膜层构成的常规衬或载体,这种纸或薄膜可以成卷绕形态供应。剥离衬或载体的剥离面上可以涂布一层随后要转移到待粘上此剥离衬或载体的取向膜上的压敏粘合剂。当薄膜与衬或载体相复合时,该粘合剂会粘附到薄膜上。其后,撕去衬或载体使粘合剂暴露,此时粘合剂仍能持久地粘附在双轴取向薄膜上。
双轴取向薄膜在模切成单张标签之前可进行印刷。印刷步骤可在衬与取向薄膜复合前或复合后,但应在标签材料模切成单张标签之前进行。为了获得高质量的图象或文字,薄膜在各印刷步骤间(例如在不同颜色的连续印刷之间)必须保持精确的定位,为了使图象和文字准确地处于标签上,薄膜在印刷和随后的模切步骤间必须准确对齐。薄膜在印刷期间受张力的作用,有可能会使温度有某些升高,例如当UV油墨固化时,因此必须使薄膜保持纵向尺寸的稳定性。
如上所述,本发明双轴拉伸取向薄膜是可模切的,载持在衬上的标签材料可模切成一列有间隔的、载持在剥离衬或载体上的压敏标签。模切步骤可按照众所周知的方式以冲切模(例如旋转冲切模)来实施,模切步骤还涉及模切后应废弃的梯子形薄膜即所形成的标签周围的边料的剥离(梯子的“横档”代表连续标签间的间隔)。剥离后,标签仍以一定的间隔保留在衬上。在这一操作过程中,一种失效的形态涉及标签模切不良,在剥离载体时标签仍保留在基质上。对于这种失效形态,由于剥离程度降低,在剥离基质和分离标签时,不良的模切更易引起标签滞留而附着在基质材料上。另一种失效形态是因模切贯穿粘合剂和部分衬而在衬上留下了切痕。再一种失效形态是因被模切的薄膜的强度不足引起的,由于基质材料强度较低,当模切标签周围的基质材料从衬上剥去时,该材料往往会被撕裂。本发明的薄膜具有足够的强度,可避免或减少剥离时发生破裂的现象。
通过技术人员了解的技术可将衬上或载体上的模切标签分送和粘贴在各种物体上。例如,采用反向剥离边缘,以渐进方式将衬或载体剥去以使标签的粘合面外露,并使标签投向正在通过的工件与之相接触,从而将标签分送和粘贴到正在通过的工件上。在本发明的前后文中,工件可以是诸如玻璃瓶或其它刚性物品等的被粘贴物体,其中刚性物品往往有不规则表面,因而需要柔软的、能严密地粘贴(适应)在其表面上而不会出现因桥接引起的局部表面凹陷的标签。该被粘贴物体也可以是柔软的塑料容器。
虽然已参照优选实施方案对本发明作了说明,但大家都知道,对阅读本说明书后的技术人员来说,对本发明作各种各样的变更是不难的。因此,本文公开的本发明内容包括了属于所附权利要求书范围内的这类变更。
Claims (5)
1.一种可模切的双轴拉伸取向单层薄膜,该薄膜包括至少一种聚烯烃,其中薄膜已经过拉伸取向,纵向拉伸比为约9∶1-约10∶1,横向拉伸比高于1∶1-约3∶1。
2.权利要求1的薄膜,其中横向拉伸比低于2∶1。
3.权利要求1的薄膜,其中薄膜包括聚乙烯,丙烯聚合物或共聚物,或它们的混合物。
4.权利要求1的薄膜,其中薄膜包括丙烯与乙烯或至少一种含4-约8个碳原子的α-烯烃的共聚物。
5.一种可模切的拉伸取向多层薄膜,该薄膜包含:
(A)具有上表面和下表面并包括至少一种聚烯烃的基材层,
(B)粘贴在基材层上表面上的热塑性聚合物第一表面,其中多层薄膜已经过拉伸取向,纵向拉伸比为9∶1-约10∶1,横向拉伸比高于1∶1-约3∶1。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/531,978 US20030039826A1 (en) | 2000-03-20 | 2000-03-20 | Conformable and die-cuttable biaxially oriented films and labelstocks |
US09/531,978 | 2000-03-20 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB018084486A Division CN1243633C (zh) | 2000-03-20 | 2001-03-16 | 可模切的双轴取向薄膜 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1715038A true CN1715038A (zh) | 2006-01-04 |
CN100408310C CN100408310C (zh) | 2008-08-06 |
Family
ID=24119876
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2005100790909A Expired - Fee Related CN100408310C (zh) | 2000-03-20 | 2001-03-16 | 可模切的双轴取向薄膜 |
CNB018084486A Expired - Fee Related CN1243633C (zh) | 2000-03-20 | 2001-03-16 | 可模切的双轴取向薄膜 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB018084486A Expired - Fee Related CN1243633C (zh) | 2000-03-20 | 2001-03-16 | 可模切的双轴取向薄膜 |
Country Status (10)
Country | Link |
---|---|
US (3) | US20030039826A1 (zh) |
EP (1) | EP1272328B1 (zh) |
CN (2) | CN100408310C (zh) |
AU (2) | AU2001247571B2 (zh) |
BR (1) | BR0109759A (zh) |
CA (1) | CA2403466A1 (zh) |
DE (1) | DE60131635T2 (zh) |
MX (1) | MXPA02009180A (zh) |
PL (1) | PL357139A1 (zh) |
WO (1) | WO2001070484A1 (zh) |
Families Citing this family (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101186268B1 (ko) | 2002-06-26 | 2012-09-27 | 애버리 데니슨 코포레이션 | 폴리프로필렌/올레핀 탄성체 혼합물을 포함하는 배향된 필름 |
KR101092056B1 (ko) * | 2002-09-16 | 2011-12-12 | 다우 글로벌 테크놀로지스 엘엘씨 | 고 투명도, 고 강성도 필름 |
EP1617990A4 (en) * | 2003-05-01 | 2006-08-09 | Avery Dennison Corp | MULTILAYER FOIL |
US7399509B2 (en) * | 2003-12-23 | 2008-07-15 | Kari Virtanen | Thin polyethylene pressure sensitive labels |
EP1740376A4 (en) | 2004-03-10 | 2008-10-15 | Avery Dennison Corp | LABELS AND LABELING PROCEDURES |
US7836888B2 (en) * | 2004-09-21 | 2010-11-23 | Pavad Medical, Incorporated | Airway implant and methods of making and using |
US7882842B2 (en) * | 2004-09-21 | 2011-02-08 | Pavad Medical, Inc. | Airway implant sensors and methods of making and using the same |
MX2007007214A (es) * | 2004-12-16 | 2007-08-14 | Applied Extrusion Technologies | Etiquetas de plastico desprendible, claras. |
BRPI0503167A (pt) * | 2005-07-29 | 2007-03-13 | Brasileira De Filmes Flexiveis | filme de polipropileno biorientado multicamada, processo para preparar um filme de polipropileno biorientado multicamada e artigo compreendendo o referido filme |
JP4825508B2 (ja) * | 2005-12-14 | 2011-11-30 | フタムラ化学株式会社 | 表面保護フィルム用支持基材及び表面保護フィルム |
EP2049333B1 (en) | 2006-06-14 | 2012-12-05 | Avery Dennison Corporation | Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing |
US9636895B2 (en) | 2006-06-20 | 2017-05-02 | Avery Dennison Corporation | Multilayered polymeric film for hot melt adhesive labeling and label stock and label thereof |
AU2007275336B2 (en) | 2006-07-17 | 2012-03-22 | Avery Dennison Corporation | Asymmetric multilayered polymeric film and label stock and label thereof |
JP4999413B2 (ja) * | 2006-09-22 | 2012-08-15 | 日東電工株式会社 | 剥離ライナー付き感圧接着シート |
JP5121043B2 (ja) * | 2007-03-09 | 2013-01-16 | 日東電工株式会社 | 剥離ライナー付き感圧接着シート |
US20080233373A1 (en) * | 2007-03-22 | 2008-09-25 | Theodore Coburn | Method of reducing film density and related product |
US20100301510A1 (en) * | 2007-03-22 | 2010-12-02 | Coburn Theodore R | Method of reducing film density and related product |
US8282754B2 (en) | 2007-04-05 | 2012-10-09 | Avery Dennison Corporation | Pressure sensitive shrink label |
KR101232572B1 (ko) | 2007-04-05 | 2013-02-12 | 애브리 데니슨 코포레이션 | 감압 수축 라벨 |
US20090269566A1 (en) * | 2008-04-23 | 2009-10-29 | Berry Plastics Corporation | Pre-stretched multi-layer stretch film |
US8574694B2 (en) | 2009-11-03 | 2013-11-05 | Curwood, Inc. | Packaging sheet with improved cutting properties |
WO2011094117A2 (en) | 2010-01-28 | 2011-08-04 | Avery Dennison Corporation | Label applicator belt system |
US9174377B2 (en) | 2011-05-12 | 2015-11-03 | Chevron Phillips Chemical Company Lp | Multilayer blown films for shrink applications |
CA2851488A1 (en) | 2011-10-11 | 2013-04-18 | Jindal Films Americas Llc | Squeezable and conformable oriented polypropylene label |
US9676532B2 (en) | 2012-08-15 | 2017-06-13 | Avery Dennison Corporation | Packaging reclosure label for high alcohol content products |
CN115416956A (zh) | 2014-02-10 | 2022-12-02 | Upm拉弗拉塔克公司 | 印刷的无内衬可洗涤面层压件,贴有标签的物品和向物品贴标签的方法 |
WO2015118212A1 (en) * | 2014-02-10 | 2015-08-13 | Upm Raflatac Oy | Linerless washable label, apparatus and method for preparing a label |
WO2015118214A1 (en) * | 2014-02-10 | 2015-08-13 | Upm Raflatac Oy | Washable label and method for preparing thereof |
WO2015118213A1 (en) * | 2014-02-10 | 2015-08-13 | Upm Raflatac Oy | Method for preparing a label web and labels obtained with said method |
WO2015187646A1 (en) | 2014-06-02 | 2015-12-10 | Avery Dennison Corporation | Films with enhanced scuff resistance, clarity, and conformability |
CN105644088B (zh) * | 2014-11-11 | 2017-11-17 | 苏州莫立克新型材料有限公司 | 一种农用复合拉伸膜 |
JP2018505266A (ja) | 2014-12-30 | 2018-02-22 | アベリー・デニソン・コーポレイションAvery Dennison Corporation | フィルムおよびフィルムレーザー変換装置 |
EP3426489B1 (en) | 2016-03-08 | 2024-01-03 | Avery Dennison Corporation | Face films and pressure sensitive laminates for printing, manufacturing process |
CN113039072A (zh) * | 2018-11-01 | 2021-06-25 | 陶氏环球技术有限责任公司 | 层压物和并入有层压物的制品 |
Family Cites Families (255)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US358667A (en) * | 1887-03-01 | Low-water alarm and indicator for boilers | ||
US377289A (en) * | 1888-01-31 | Car-coupling | ||
US617660A (en) * | 1899-01-10 | Explosion engine or motor | ||
US554406A (en) * | 1896-02-11 | John west | ||
US160607A (en) * | 1875-03-09 | Improvement in apparatus for cutting goods on bias | ||
US73064A (en) * | 1868-01-07 | Aibin warth | ||
US146314A (en) * | 1874-01-13 | Improvement in safety-valves | ||
CA888148A (en) | 1971-12-14 | A. Shmidt Donald | Composite release film | |
US852611A (en) * | 1905-12-29 | 1907-05-07 | Walter G Perkins | Process of agglomerating minerals. |
US888148A (en) * | 1907-11-11 | 1908-05-19 | Frederick G Dokkenwadel | Insecticide-fertilizer. |
US1404018A (en) * | 1921-05-16 | 1922-01-17 | Gauthier Emile | Resilient wheel |
US1578517A (en) * | 1924-12-23 | 1926-03-30 | George N Hein | Valve piston and barrel construction for hypodermic syringes |
US2112030A (en) * | 1935-04-03 | 1938-03-22 | Klinkenstein Gustave | Laminated material |
US2718666A (en) | 1951-09-24 | 1955-09-27 | Du Pont | Process of longitudinally stretching film of organic linear polymeric material |
US2920352A (en) * | 1954-04-23 | 1960-01-12 | Du Pont | Process of casting and stretching film |
US3036945A (en) * | 1958-10-27 | 1962-05-29 | Dymo Industries Inc | Embossable plastic assembly |
BE588116A (zh) | 1959-03-03 | 1900-01-01 | ||
US3154461A (en) | 1960-03-07 | 1964-10-27 | Minnesota Mining & Mfg | Matte-finish polymeric film and method of forming the same |
US3187982A (en) * | 1960-07-21 | 1965-06-08 | Union Carbide Corp | Method for forming coated uniaxially oriented films and the product formed thereby |
BE623938A (zh) * | 1961-10-23 | 1900-01-01 | ||
US3354506A (en) | 1962-04-30 | 1967-11-28 | Union Carbide Corp | Apparatus for melt extrusion of multi-wall plastic tubing |
BE636331A (zh) * | 1962-08-22 | |||
US3309452A (en) * | 1962-09-11 | 1967-03-14 | Toyo Rayon Co Ltd | Thermoplastic film and its process of manufacture |
GB1100423A (en) | 1964-02-24 | 1968-01-24 | American Can Co | Method and device for treating a smooth plastic sheet surface to reduce its coefficient of friction with respect to a smooth body surface |
US3468744A (en) | 1964-08-13 | 1969-09-23 | Minnesota Mining & Mfg | Color changeable embossable label tape |
US3515626A (en) * | 1965-02-22 | 1970-06-02 | Ici Ltd | Thermoplastic laminates having improved surface properties |
US3382206A (en) * | 1965-09-03 | 1968-05-07 | Du Pont | Pencil receptive film |
US3381717A (en) * | 1966-06-03 | 1968-05-07 | Nat Distillers Chem Corp | Blown polypropylene tubular films |
GB1145199A (en) | 1966-06-13 | 1969-03-12 | Nat Distillers Chem Corp | Heat-sealable oriented polypropylene film laminate |
US3422302A (en) * | 1967-04-11 | 1969-01-14 | Wagner Electric Corp | Lamp lead wire terminal |
JPS4640794B1 (zh) * | 1968-03-26 | 1971-12-02 | ||
US3841943A (en) | 1968-03-26 | 1974-10-15 | Mitsubishi Petrochemical Co | Apparatus for making synthetic paper |
US3501726A (en) * | 1968-08-14 | 1970-03-17 | Karl Richard Olesen | Rotary solenoid |
US3565985A (en) * | 1969-04-10 | 1971-02-23 | Dow Chemical Co | Method of preparing multilayer plastic articles |
JPS491782B1 (zh) | 1969-12-28 | 1974-01-16 | ||
US3854229A (en) | 1970-02-04 | 1974-12-17 | Morgan Adhesives Co | Laminated label or similar article |
US3690909A (en) | 1970-02-27 | 1972-09-12 | Phillips Petroleum Co | Supported releasable polyolefin films |
DE2112030C3 (de) | 1970-03-13 | 1984-03-15 | Toyo Boseki K.K., Osaka | Verfahren zur Herstellung einer papierähnlichen polymeren Folie |
CA949869A (en) | 1970-07-06 | 1974-06-25 | Takashi Toyoda | Production of synthetic papers |
US3842152A (en) | 1970-08-19 | 1974-10-15 | Du Pont | Embossed polyester film preparation |
US3924051A (en) | 1970-09-08 | 1975-12-02 | American Can Co | Oriented saran coextrudate |
US3773608A (en) | 1970-09-16 | 1973-11-20 | Toyo Boseki | Paper-like polymeric films and production thereof |
US4051293A (en) | 1971-03-29 | 1977-09-27 | Cosden Oil & Chemical Company | Co-extrusion of polyvinylidene fluoride/polystyrene multiple-layered sheeting |
US3968196A (en) | 1971-03-29 | 1976-07-06 | Cosden Oil & Chemical Company | Method of co-extrusion of polyvinylidene fluoride/polystyrene multiple-layered sheeting |
US3767523A (en) | 1971-04-12 | 1973-10-23 | Kimberly Clark Co | Synthetic paper base and method of manufacture |
JPS5029738B2 (zh) | 1971-08-06 | 1975-09-26 | ||
US3963851A (en) * | 1971-08-06 | 1976-06-15 | Kabushiki Kaisha Oji Yuka Goseishi Kenkyujo | Paper for adhesive stickers and the like |
GB1384556A (en) | 1971-12-22 | 1975-02-19 | Mitsubishi Petrochemical Co | Synthetic papers and method of making the same |
US4057667A (en) | 1972-03-24 | 1977-11-08 | American Can Company | Oriented saran coextrudate |
US3854581A (en) | 1972-04-10 | 1974-12-17 | Monarch Marking Systems Inc | Pressure-sensitive material and supporting material combination |
US3871947A (en) | 1973-01-15 | 1975-03-18 | Minnesota Mining & Mfg | Biaxially oriented polyethylene terephthalate film having a surface suitable for writing thereon |
CA1070069A (en) * | 1973-03-26 | 1980-01-22 | James Jack | Thermoplastics compositions |
US3817177A (en) * | 1973-05-07 | 1974-06-18 | Avery Products Corp | Hand labeler |
US3894904A (en) * | 1973-06-11 | 1975-07-15 | Crown Zellerbach Corp | Method of manufacturing synthetic paper laminates |
US4082880A (en) * | 1973-11-22 | 1978-04-04 | Du Pont Of Canada Limited | Paper-like thermoplastic film |
US3936567A (en) * | 1974-03-25 | 1976-02-03 | W. H. Brady Co. | Light-reflective adhesive label |
US3908065A (en) | 1974-04-15 | 1975-09-23 | Minnesota Mining & Mfg | Magnetic embossable label tape laminate |
US3971866A (en) | 1974-06-07 | 1976-07-27 | Minnesota Mining And Manufacturing Company | Thermoformable release liner |
US3968195A (en) * | 1974-06-17 | 1976-07-06 | Marilyn Bishop | Method for making sterile connections |
US4011358A (en) * | 1974-07-23 | 1977-03-08 | Minnesota Mining And Manufacturing Company | Article having a coextruded polyester support film |
US4071597A (en) * | 1974-09-13 | 1978-01-31 | Owens-Illinois, Inc. | Container with improved heat-shrunk cellular sleeve |
US3979000A (en) | 1974-09-13 | 1976-09-07 | Owens-Illinois, Inc. | Container with improved heat-shrunk cellular sleeve |
DE2548875A1 (de) | 1974-10-31 | 1976-05-13 | Cosden Technology | Verfahren zur herstellung von zusammengesetztem bahnmaterial |
US4020215A (en) * | 1975-05-30 | 1977-04-26 | Crown Zellerbach Corporation | Extrusion of polyolefin onto paper at decreased temperatures |
GB1495776A (en) | 1975-06-11 | 1977-12-21 | Ici Ltd | Film-forming olefin polymer compositions |
US4331727A (en) * | 1975-09-17 | 1982-05-25 | Stanley Maas | Adhesive transfer device |
US4118438A (en) | 1975-11-06 | 1978-10-03 | Toyo Boseki Kabushiki Kaisha | Transparent non-blocking polypropylene film and its preparation |
US4008115A (en) * | 1976-02-25 | 1977-02-15 | Dennison Manufacturing Company | Method for making durable overcoated labels |
US4166464A (en) | 1976-06-23 | 1979-09-04 | Johnson & Johnson | Absorbent dressing |
US4024312A (en) * | 1976-06-23 | 1977-05-17 | Johnson & Johnson | Pressure-sensitive adhesive tape having extensible and elastic backing composed of a block copolymer |
US4233367A (en) | 1977-01-06 | 1980-11-11 | American Can Company | Coextruded multilayer film |
FR2393676A1 (fr) | 1977-06-07 | 1979-01-05 | Ugine Kuhlmann | Materiau composite resine acrylonitrile-butadiene-styrene-resine polyfluorure de vinylidene |
US4166706A (en) | 1977-08-01 | 1979-09-04 | Johnson & Johnson | Lift-off tape and process |
US4147827A (en) * | 1977-11-04 | 1979-04-03 | Mobil Oil Corporation | Coextruded heat sealable laminar thermoplastic films |
DE2814311B2 (de) | 1978-04-03 | 1981-03-12 | Hoechst Ag, 6000 Frankfurt | Heißsiegelfähige, opake Kunststoffolie, Verfahren zu ihrer Herstellung |
US4188443A (en) * | 1978-08-30 | 1980-02-12 | W. R. Grace & Co. | Multi-layer polyester/polyolefin shrink film |
US4172163A (en) | 1978-06-05 | 1979-10-23 | Dennison Manufacturing Company | Chemically-resistant adhesives and labels |
US4189519A (en) * | 1978-08-30 | 1980-02-19 | American Can Company | Heat sealable resin blends |
GB2029317A (en) | 1978-09-06 | 1980-03-19 | British Cellophane Ltd | Heat-sealable polypropylene films |
US4235341A (en) | 1978-09-19 | 1980-11-25 | The Dow Chemical Company | Spirally wound container with strippable layer |
CH633481A5 (en) | 1978-10-04 | 1982-12-15 | Ugine Kuhlmann | Acrylonitrile-butadiene-styrene resin/polyvinylidene fluoride resin composite material |
US4254169A (en) * | 1978-12-28 | 1981-03-03 | American Can Company | Multi-layer barrier film |
US4246058A (en) * | 1979-01-19 | 1981-01-20 | Avery International Corporation | Label matrix stripping |
DE2906856C2 (de) * | 1979-02-22 | 1984-02-02 | Esselte Meto International Gmbh, 6932 Hirschhorn | Handgerät zum Ausgeben oder Anbringen von auf einem Trägerband haftenden Etiketten |
US4379806A (en) * | 1979-07-05 | 1983-04-12 | Johnson & Johnson | Pressure-sensitive adhesive tape and process |
US4289821A (en) | 1979-09-24 | 1981-09-15 | Scott Paper Company | Surface replication on a coated substrate |
US4322450A (en) * | 1979-09-24 | 1982-03-30 | Scott Paper Company | Surface replication on a coated substrate |
US4407897A (en) | 1979-12-10 | 1983-10-04 | American Can Company | Drying agent in multi-layer polymeric structure |
JPS57123050A (en) | 1980-12-01 | 1982-07-31 | Toray Industries | Polyester composite film |
US4398985A (en) | 1980-02-08 | 1983-08-16 | Kimberly-Clark Corporation | Releasable, self-detackifying laminate construction |
CA1138817A (en) | 1980-04-01 | 1983-01-04 | Leco Inc. | Coextruded product and process for the manufacture thereof |
US4343851A (en) | 1980-04-14 | 1982-08-10 | American Can Company | Multi-ply laminae |
US4429015A (en) * | 1980-04-14 | 1984-01-31 | American Can Company | Multi-ply laminae and identification card |
US4439478A (en) * | 1980-05-23 | 1984-03-27 | W. R. Grace & Co., Cryovac Division | Heat sealable, multi-ply polypropylene film |
NL8003192A (nl) | 1980-05-31 | 1982-01-04 | Stamicarbon | Biaxiaal verstrekte voortbrengselen uit kunststoffen op basis van polypropeen en werkwijze voor het vervaardigen van dergelijke voortbrengselen. |
JPS5725953A (en) | 1980-07-22 | 1982-02-10 | Toray Industries | Multilayer laminated polypropylene film |
US4346855A (en) | 1980-07-24 | 1982-08-31 | Elizabeth S. Biggar | Stripping method and apparatus for the processing of a continuous laminated web |
US4427732A (en) * | 1980-10-02 | 1984-01-24 | Scott Paper Company | Surface replication on a coated substrate |
JPS5764551A (en) * | 1980-10-09 | 1982-04-19 | Mitsui Petrochemical Ind | Composite film |
US4410582A (en) | 1980-12-10 | 1983-10-18 | Toray Industries, Inc. | Multi-layered polyolefin laminated film |
US4402172A (en) | 1980-12-22 | 1983-09-06 | American Can Company | Flexible packaging structure and process for making it |
US4361628A (en) | 1981-02-20 | 1982-11-30 | American Can Company | Coextruded film of polypropylene, polypropylene blend, and nylon |
US4389450A (en) * | 1981-02-26 | 1983-06-21 | American Can Company | Multiple layer packaging film |
US4384024A (en) * | 1981-03-19 | 1983-05-17 | Imperial Chemical Industries Limited | Composite heat-sealable films |
JPS57181829A (en) | 1981-05-06 | 1982-11-09 | Oji Yuka Gouseishi Kk | Manufacture of stretched film by composite polyolefine resin |
US4377050A (en) * | 1981-06-01 | 1983-03-22 | Renholts Roy J | Laminated tape for imprinting |
US4414275A (en) | 1981-07-13 | 1983-11-08 | Loctite (Ireland) Limited | UV Curable adhesive tape |
US4405401A (en) | 1981-07-15 | 1983-09-20 | Stahl Ted A | Thermoplastic labeling and method of making same |
US4447485A (en) * | 1981-08-04 | 1984-05-08 | Mitsubishi Plastics Industries Limited | Adhesive tape and process for its production |
US4465729A (en) | 1981-08-05 | 1984-08-14 | Clopay Corporation | Cross-tearable plastic films |
US4440824A (en) * | 1981-10-23 | 1984-04-03 | Composite Container Corporation | Thermoformable coextruded multilayered structure |
JPS5874774A (ja) | 1981-10-27 | 1983-05-06 | Mitsubishi Plastics Ind Ltd | 粘着テ−プ |
US4517044A (en) * | 1981-11-18 | 1985-05-14 | Advanced Graphic Technology | Dry transfer decal and method of manufacture |
US4377616A (en) * | 1981-12-30 | 1983-03-22 | Mobil Oil Corporation | Lustrous satin appearing, opaque film compositions and method of preparing same |
US4475971A (en) | 1981-12-30 | 1984-10-09 | Mobil Oil Corporation | Method for forming strong cross-laminated films |
US4386135A (en) * | 1982-01-11 | 1983-05-31 | Minnesota Mining And Manufacturing Company | Stable silicone-coated release liner for pressure-sensitive adhesive sheets |
CA1191006A (en) | 1982-01-14 | 1985-07-30 | Sekisui Kaseihin Kogyo Kabushiki Kaisha | Sheet for forming sleeve and process for producing the same |
US4568403A (en) * | 1982-03-17 | 1986-02-04 | Miller Products, Inc. | Method of making laminated member |
US4544590A (en) | 1982-03-17 | 1985-10-01 | Miller Products, Inc. | Laminated member and method of making same |
US4478663A (en) | 1982-03-22 | 1984-10-23 | American Can Company | Plastic sheet having high gloss and low coefficient of friction and method for producing the same |
JPS58186744A (ja) * | 1982-04-26 | 1983-10-31 | Fuji Photo Film Co Ltd | 感光物質用包装材料及びその製造方法 |
DE3216603A1 (de) * | 1982-05-04 | 1983-11-10 | Hoechst Ag, 6230 Frankfurt | Klebeband |
US4454179A (en) * | 1982-05-10 | 1984-06-12 | Minnesota Mining And Manufacturing Company | Dry transfer article |
US4424256A (en) * | 1982-08-06 | 1984-01-03 | American Can Company | Retortable foil-based packaging structure |
US4501797A (en) * | 1982-12-01 | 1985-02-26 | American Can Company | Unbalanced oriented multiple layer film |
US4528055A (en) | 1982-12-17 | 1985-07-09 | Graphic Resources, Inc. | Method of manufacturing an elongated label supply |
DE3247998C2 (de) * | 1982-12-24 | 1986-02-06 | Hoechst Ag, 6230 Frankfurt | Siegelbare transparente polyolefinische Mehrschichtfolie |
MX156476A (es) * | 1983-02-04 | 1988-08-28 | Maquinas Fabricacion Sa De | Tapon irrellenable e inviolable mejorado |
DE3306189A1 (de) * | 1983-02-23 | 1984-08-23 | Hoechst Ag, 6230 Frankfurt | Mehrschichtige folie mit einer gas- und aroma-sperrschicht, verfahren zu ihrer herstellung und ihre verwendung |
IT1159842B (it) * | 1983-02-23 | 1987-03-04 | Manuli Autoadesivi Spa | Perfezionamento al procedimento per la preparazione di nastri autoadesivi |
US4617199A (en) | 1983-02-23 | 1986-10-14 | Manuli Autoadesivi Spa | Process for the manufacturing of adhesive tapes |
DE3311728A1 (de) | 1983-03-30 | 1984-10-04 | Hoffmann & Engelmann Ag, 6730 Neustadt | Traeger fuer abzieh- oder abschiebebilder |
US4522887A (en) * | 1983-04-18 | 1985-06-11 | Toray Industries, Inc. | Laminated film of biaxially oriented polypropylene and an olefin polymer film |
US4438175A (en) * | 1983-04-28 | 1984-03-20 | Mobil Oil Corporation | Synthetic film with a paper-like surface and method of forming same |
GB8315001D0 (en) * | 1983-06-01 | 1983-07-06 | Ici Plc | Multiple-layer polyolefin films |
GB2150881A (en) * | 1983-11-23 | 1985-07-10 | Bcl Ltd | Decorative packaging films |
US4661188A (en) * | 1983-11-28 | 1987-04-28 | Owens-Illinois, Inc. | Method of applying a plastic label to a container |
US4650721A (en) * | 1983-12-23 | 1987-03-17 | Mobil Oil Corporation | Polypropylene barrier film and method of forming same |
US4617241A (en) | 1984-01-23 | 1986-10-14 | W. R. Grace & Co., Cryovac Div. | Linear polyethylene stretch/shrink films |
US4587158A (en) * | 1984-09-04 | 1986-05-06 | Ewing William D | Deformable label |
US4613643A (en) | 1984-02-09 | 1986-09-23 | Tokuyama Soda Kabushiki Kaisha | Porous sheet |
US4551380A (en) | 1984-05-10 | 1985-11-05 | W. R. Grace & Co., Cryovac Div. | Oriented heat-sealable multilayer packaging film |
DE3422302A1 (de) | 1984-06-15 | 1985-12-19 | Hoechst Ag, 6230 Frankfurt | Klebeband |
JPS613748A (ja) * | 1984-06-18 | 1986-01-09 | 王子油化合成紙株式会社 | 高光沢の印刷が可能な合成紙 |
US4585752A (en) * | 1984-08-15 | 1986-04-29 | W. R. Grace & Co. | Catalyst composition for ultra high temperature operation |
US4604324A (en) | 1984-09-28 | 1986-08-05 | Mobil Oil Corporation | Multi-layer polypropylene film structure and method of forming the same |
US4585679A (en) * | 1985-01-14 | 1986-04-29 | Owens-Illinois, Inc. | Coextruded multilayer sheet and tough sleeve label made therefrom |
US4581262A (en) * | 1985-01-14 | 1986-04-08 | Owens-Illinois, Inc. | Coextruded multilayer sheet and sleeve label made therefrom |
US4626455A (en) | 1985-01-14 | 1986-12-02 | Owens-Illinois, Inc. | Coextruded multilayer sheet and sleeve label for bottles |
DE3501726A1 (de) | 1985-01-19 | 1986-07-24 | Hoechst Ag, 6230 Frankfurt | Polypropylen-klebeband |
US4837088A (en) * | 1985-02-05 | 1989-06-06 | Avery International Corporation | Coextruded core laminates |
DE335425T1 (de) | 1985-02-05 | 1993-04-29 | Avery International Corp., Pasadena, Calif. | Verbundfutter. |
US5143570A (en) | 1985-02-05 | 1992-09-01 | Avery Dennison Corporation | Composite facestocks and liners |
US4888075A (en) | 1985-02-05 | 1989-12-19 | Avery International Corporation | Composite facestocks and liners |
US4946532A (en) | 1985-02-05 | 1990-08-07 | Avery International Corporation | Composite facestocks and liners |
US5372669A (en) | 1985-02-05 | 1994-12-13 | Avery Dennison Corporation | Composite facestocks and liners |
JPS61248740A (ja) | 1985-04-26 | 1986-11-06 | 住友化学工業株式会社 | ポリプロピレン多層フイルム |
US4724186A (en) * | 1985-05-13 | 1988-02-09 | The Dow Chemical Company | Weatherable three layer films |
US4680234A (en) | 1985-05-13 | 1987-07-14 | The Dow Chemical Company | Weatherable coextruded flexible films and laminated structure |
US4626460A (en) | 1985-07-11 | 1986-12-02 | Mobil Oil Corporation | Coextruded pressure sensitive label stock material with integral peelable backing |
US4582752A (en) * | 1985-07-11 | 1986-04-15 | Mobil Oil Corporation | Heat shrinkable, lustrous satin appearing, opaque film compositions |
US4582753A (en) * | 1985-07-11 | 1986-04-15 | Mobil Oil Corporation | Polymer laminate possessing an intermediate water vapor transmission barrier layer |
US4582736A (en) * | 1985-07-11 | 1986-04-15 | Mobil Oil Corporation | Coextruded pressure sensitive label stock material with integral peelable backing |
US4702954A (en) | 1985-07-11 | 1987-10-27 | Mobil Oil Corporation | Polymer laminate possessing an intermediate water vapor transmission barrier layer |
US4966795A (en) | 1985-11-29 | 1990-10-30 | American National Can Company | Multiple layer sheet structures and package |
US4695503A (en) | 1986-03-07 | 1987-09-22 | Mobil Oil Corporation | Coated, oriented, polymer film laminate |
US4865908A (en) | 1986-03-07 | 1989-09-12 | Mobil Oil Corporation | Coated, oriented polymer film laminate |
US4923722A (en) * | 1987-03-02 | 1990-05-08 | Okura Industrial Co., Ltd. | Heat shrinkable composite film and packaging method using same |
DE3715308A1 (de) * | 1987-05-08 | 1988-11-24 | Feldmuehle Ag | Transparente verpackung fuer stueckige gueter |
GB2210581B (en) | 1987-10-05 | 1992-01-02 | Courtaulds Films & Packaging | Polymeric films |
DE3743791A1 (de) * | 1987-12-23 | 1989-07-13 | Hoechst Ag | Opake mehrschichtfolie mit inhaerenter delaminierungsstabilitaet |
GB8817239D0 (en) | 1988-07-20 | 1988-08-24 | Adhesive Materials Ltd | Adhesive labels & methods for their manufacture |
US5176954A (en) | 1989-03-16 | 1993-01-05 | Mobil Oil Corporation | High opacity film and method thereof |
US5151309A (en) | 1989-07-05 | 1992-09-29 | The Dow Chemical Company | Die-cuttable and dispensable deformable labels |
JPH0645226B2 (ja) | 1989-08-29 | 1994-06-15 | チッソ株式会社 | 不透明積層延伸成形物およびその製造方法 |
US5182168A (en) | 1989-12-18 | 1993-01-26 | Mobil Oil Corporation | Biaxially oriented polypropylene film |
US5064893A (en) * | 1990-03-08 | 1991-11-12 | Rexene Corporation | Flexible label film from polyethylene and calcium carbonate-polymer mixture |
DE4031125A1 (de) | 1990-10-02 | 1992-04-09 | Hoechst Ag | Biaxial orientierte polypropylenfolie fuer den dreheinschlag |
US5186782A (en) * | 1990-10-17 | 1993-02-16 | Avery Dennison Corporation | Method for high speed labelling of deformable substrates |
JP3070023B2 (ja) | 1990-11-13 | 2000-07-24 | モービル・オイル・コーポレーション | 切断抵抗を改良したポリプロピレンシート材料 |
US5273798A (en) | 1991-08-01 | 1993-12-28 | Watson Label Products, Corp. | Heat and solvent resistant pressure-sensitive label |
JP2681557B2 (ja) | 1991-08-08 | 1997-11-26 | リンテック株式会社 | スクイズ容器用ラベル |
TW200424B (zh) * | 1991-09-09 | 1993-02-21 | Avery Dennison Corp | |
US5242650A (en) | 1991-09-09 | 1993-09-07 | Avery Dennison Corporation | In-mold labelling a coextruded, stretched and annealed label |
CA2118807A1 (en) | 1991-11-12 | 1993-04-01 | Harvey C. Tung | Labelstock for squeezable pressure-sensitive labels |
US5240789A (en) | 1992-02-20 | 1993-08-31 | Rand Mcnally & Company | Multi-layer labels |
DE4210969A1 (de) | 1992-04-02 | 1993-10-07 | Hoechst Ag | Seidenmatte, biaxial orientierte Polyolefin-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
US5284688A (en) * | 1992-04-16 | 1994-02-08 | Unique Label Systems, Inc. | Pressure sensitive adhesive labels and manufacture thereof |
US5288548A (en) * | 1992-07-31 | 1994-02-22 | Mobil Oil Corporation | Label face stock |
NZ247073A (en) * | 1992-08-26 | 1994-12-22 | Lintec Corp | Pressure sensitive adhesive label sheet with label film being polyethylene resin of a density of .925-.95 g/cc |
CA2077103C (en) | 1992-08-28 | 2003-06-10 | Moore U.S.A. Inc. | Multipurpose label construction |
US5275886A (en) | 1992-10-08 | 1994-01-04 | Mobil Oil Corporation | Polypropylene film |
US5525287A (en) * | 1992-10-09 | 1996-06-11 | Signode Corporation | Method for producing oriented plastic strap |
US5660787A (en) | 1992-10-09 | 1997-08-26 | Illinois Tool Works Inc. | Method for producing oriented plastic strap |
US5707660A (en) * | 1992-10-09 | 1998-01-13 | Signode Corporation | Apparatus for producing oriented plastic strap |
US5387388A (en) * | 1992-10-09 | 1995-02-07 | Illinois Tool Works Inc. | Method for producing oriented plastic strap |
DE4308854A1 (de) | 1993-03-19 | 1994-09-22 | Hoechst Ag | Siegelfähige orientierte Polyolefin-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE4310684A1 (de) | 1993-04-01 | 1994-10-06 | Hoechst Ag | Siegelflähige orientierte Polyolefin-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE4311422A1 (de) | 1993-04-07 | 1994-10-13 | Hoechst Ag | Opake, matte, biaxial orientierte Polypropylen-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE4311950A1 (de) | 1993-04-10 | 1994-10-13 | Hoechst Ag | Opake, matte Polypropylen-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE4313640A1 (de) | 1993-04-27 | 1994-11-03 | Hoechst Ag | Matte, biaxial orientierte Polypropylen-Mehrschichtfolie mit hohem Schrumpf, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE4313431A1 (de) | 1993-04-27 | 1994-11-03 | Hoechst Ag | Matte, siegelbare, schrumpffähige, biaxial orientierte Polypropylen-Mehrschichtfolie, Verfahren zu ihrer Hestellung und ihre Verwendung |
DE4313430A1 (de) | 1993-04-27 | 1994-11-03 | Hoechst Ag | Matte, biaxial orientierte Polypropylen-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
US5516393A (en) * | 1993-04-29 | 1996-05-14 | Avery Dennison Corporation | Labelling of substrates |
US5338790A (en) | 1993-07-14 | 1994-08-16 | Shell Oil Company | Polymer compositions |
US5451283A (en) | 1993-07-16 | 1995-09-19 | Avery Dennison Corporation | Method of making a uniaxially oriented label film with compatibilizer |
US5585193A (en) | 1993-07-16 | 1996-12-17 | Avery Dennison Corporation | Machine-direction oriented label films and die-cut labels prepared therefrom |
IT1271418B (it) | 1993-08-11 | 1997-05-28 | Himont Inc | Manufatti in film cast costituiti da polimeri propilenici |
WO1995006556A1 (en) | 1993-09-02 | 1995-03-09 | Quantum Chemical Corporation | Biaxially-oriented polypropylene film with improved gas barrier |
DE4336560A1 (de) | 1993-10-27 | 1995-05-04 | Hoechst Ag | Biaxial orientierte Polyolefinfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
IT1266781B1 (it) | 1993-11-08 | 1997-01-21 | Grace W R & Co | Pellicole multistrato orientate biassialmente e termoretraibili, procedimento per produrle e loro uso per confezionare prodotti |
US5861201A (en) * | 1994-02-15 | 1999-01-19 | Owens-Illinois Labels Inc. | Multilayer label material |
US6150035A (en) | 1994-04-01 | 2000-11-21 | Avery Dennison Corporation | Multi-layer composites and sheet labels |
US6534189B1 (en) | 1994-07-15 | 2003-03-18 | Exxonmobil Oil Corporation | Uniaxially shrinkable biaxially oriented polypropylene film and method for use as tobacco pack overwrap |
US6322883B1 (en) | 1994-07-15 | 2001-11-27 | Exxonmobil Oil Corporation | Uniaxially shrinkable biaxially oriented polypropylene film with HDPE skin |
US5709937A (en) * | 1995-01-13 | 1998-01-20 | Avery Dennison Corporation | Clear conformable oriented films and labels |
US5637366A (en) | 1995-06-07 | 1997-06-10 | Qpf, Inc. (Delaware Corporation) | Polyester-containing biaxially-oriented polypropylene films and method of making the same |
DK0850278T3 (da) * | 1995-09-14 | 2000-07-10 | Dow Chemical Co | Forbedret filmoversidemateriale og produkter til visuel præsentation |
JPH11512765A (ja) * | 1995-09-26 | 1999-11-02 | ザ・ダウ・ケミカル・カンパニー | 透明な単層ラベルフィルム材料 |
US5949971A (en) | 1995-10-02 | 1999-09-07 | International Business Machines Corporation | Method and system for performance monitoring through identification of frequency and length of time of execution of serialization instructions in a processing system |
EP0863183B2 (en) | 1995-11-24 | 2008-05-28 | Chisso Corporation | Propylene composition, process for preparing the same, polypropylene composition, and molded articles |
US6150013A (en) | 1996-02-23 | 2000-11-21 | Avery Dennison Corporation | Low thermal conductivity in-mold label films |
US5922471A (en) | 1996-03-04 | 1999-07-13 | Union Carbide Chemicals & Plastics Technology Corporation | Metallizable polypropylene random copolymer compositions |
JP3707858B2 (ja) * | 1996-03-05 | 2005-10-19 | 株式会社ユポ・コーポレーション | 感圧粘着ラベル |
US5712031A (en) * | 1996-03-06 | 1998-01-27 | The Dow Chemical Company | Plastic adhesive labels for glass substrates |
US5662985A (en) | 1996-05-21 | 1997-09-02 | Mobil Oil Corporation | Two-side coated label facestock |
JPH09310059A (ja) | 1996-05-24 | 1997-12-02 | Nitto Denko Corp | 粘着剤組成物とその粘着シ―ト類 |
US6183856B1 (en) * | 1996-07-25 | 2001-02-06 | Mobil Oil Corporation | Opaque polymeric films and processes for making same |
US6583227B2 (en) * | 1996-09-04 | 2003-06-24 | Exxonmobil Chemical Patents Inc. | Propylene polymers for films |
US6576306B2 (en) * | 1996-09-04 | 2003-06-10 | Exxonmobil Chemical Patents Inc. | Propylene polymers for films |
WO1998010076A2 (en) * | 1996-09-05 | 1998-03-12 | Onyx Pharmaceuticals, Inc. | Phospholipase d and dna sequences |
US20020028340A1 (en) * | 1996-10-22 | 2002-03-07 | Atsushi Fujii | Soft transparent polyolefin resin sheet and method for producing the same |
US6231975B1 (en) | 1997-01-24 | 2001-05-15 | Mobil Oil Corporation | Sealable film |
US6110552A (en) * | 1997-01-31 | 2000-08-29 | Flexcon Company, Inc. | Release liners for pressure sensitive adhesive labels |
WO1998041571A1 (en) * | 1997-03-18 | 1998-09-24 | Exxon Chemical Patents Inc. | Die-cuttable labels |
EP0888866B1 (en) | 1997-07-01 | 2002-11-06 | Nan Ya Plastics Corporation | A process for the production of a biaxially oriented polypropylene synthetic paper of high gloss and easy drying printability |
CN1128163C (zh) * | 1998-04-08 | 2003-11-19 | 出光石油化学株式会社 | 薄膜用聚丙烯及薄膜的制造方法 |
US6461706B1 (en) * | 1998-04-17 | 2002-10-08 | Avery Dennison Corporation | Multilayer films and labels |
US5961766A (en) | 1998-04-17 | 1999-10-05 | Avery Dennison Corporation | Method for selecting a substrate intended for use in a cutting operation |
US6451446B1 (en) | 1998-05-21 | 2002-09-17 | Dow Global Technologies Inc. | Polypropylene/polystyrene multilayer film structures |
DE19823162A1 (de) * | 1998-05-23 | 1999-11-25 | Hoechst Trespaphan Gmbh | Polyolefinfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
KR20010075346A (ko) | 1998-09-25 | 2001-08-09 | 우쯔기 미쯔루 | 열가소성 수지 필름 및 이를 포함한 라벨용지 |
US6391425B1 (en) | 1999-03-30 | 2002-05-21 | Exxonmobil Oil Corporation | Polyolefin film with embossed surface |
JP4516165B2 (ja) * | 1999-08-04 | 2010-08-04 | 株式会社ユポ・コーポレーション | 多層樹脂延伸フィルム |
US6364988B1 (en) * | 1999-09-13 | 2002-04-02 | Nan Ya Plastics Corporation | Process for producing a 3-layer co-extruded biaxially oriented polypropylene synthetic paper of thickness 25-250 μm |
US6379605B1 (en) * | 1999-10-22 | 2002-04-30 | Nan Ya Plastics Corporation | Process for producing a 3-layer co-extruded biaxial-oriented polypropylene synthetic paper and transparent film for in-mold label |
US6503635B1 (en) | 1999-11-08 | 2003-01-07 | Exxon Mobil Oil Corporation | Metallized multi-layer film |
US6641913B1 (en) | 1999-12-03 | 2003-11-04 | Fina Technology, Inc. | Heat-sealable films |
US6472077B1 (en) | 1999-12-20 | 2002-10-29 | Exxon Mobil Oil Corporation | Block-resistant film |
US6376058B1 (en) * | 1999-12-21 | 2002-04-23 | Avery Dennison Corporation | Polypropylene based compositions and films and labels formed therefrom |
US6455171B2 (en) | 2000-02-03 | 2002-09-24 | Ferro Corporation | Multilayer structure with acrylic cap layer, polyolefin core layer, and intermediate tie layer |
US20020115795A1 (en) * | 2000-03-16 | 2002-08-22 | Sherwin Shang | Autoclavable, non-adherent, heat sealable polymer films for fabricating monolayer and multiple layered films and containers |
US6576329B2 (en) * | 2001-06-12 | 2003-06-10 | Exxonmobil Oil Corporation | Multilayer thermoplastic film |
US6583209B2 (en) * | 2001-09-06 | 2003-06-24 | Equistar Chemicals, Lp | Propylene polymer composites having improved melt strength |
ATE314932T1 (de) * | 2001-10-12 | 2006-02-15 | Toray Plastics America Inc | Polyolefinfolie zur verwendung in kohäsiven kaltsiegelanwendungen |
-
2000
- 2000-03-20 US US09/531,978 patent/US20030039826A1/en not_active Abandoned
-
2001
- 2001-03-16 EP EP01920528A patent/EP1272328B1/en not_active Expired - Lifetime
- 2001-03-16 MX MXPA02009180A patent/MXPA02009180A/es unknown
- 2001-03-16 PL PL01357139A patent/PL357139A1/xx not_active Application Discontinuation
- 2001-03-16 AU AU2001247571A patent/AU2001247571B2/en not_active Ceased
- 2001-03-16 DE DE60131635T patent/DE60131635T2/de not_active Expired - Lifetime
- 2001-03-16 CN CNB2005100790909A patent/CN100408310C/zh not_active Expired - Fee Related
- 2001-03-16 BR BR0109759-8A patent/BR0109759A/pt not_active Application Discontinuation
- 2001-03-16 CN CNB018084486A patent/CN1243633C/zh not_active Expired - Fee Related
- 2001-03-16 WO PCT/US2001/008774 patent/WO2001070484A1/en active IP Right Grant
- 2001-03-16 AU AU4757101A patent/AU4757101A/xx active Pending
- 2001-03-16 CA CA002403466A patent/CA2403466A1/en not_active Abandoned
-
2002
- 2002-09-06 US US10/236,769 patent/US6835462B2/en not_active Expired - Lifetime
-
2004
- 2004-09-01 US US10/931,619 patent/US20050025947A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
CA2403466A1 (en) | 2001-09-27 |
CN1243633C (zh) | 2006-03-01 |
US20050025947A1 (en) | 2005-02-03 |
CN100408310C (zh) | 2008-08-06 |
EP1272328B1 (en) | 2007-11-28 |
AU2001247571B2 (en) | 2004-10-28 |
BR0109759A (pt) | 2003-04-08 |
MXPA02009180A (es) | 2003-03-12 |
DE60131635D1 (de) | 2008-01-10 |
AU4757101A (en) | 2001-10-03 |
WO2001070484A1 (en) | 2001-09-27 |
US6835462B2 (en) | 2004-12-28 |
DE60131635T2 (de) | 2008-10-30 |
US20030113535A1 (en) | 2003-06-19 |
PL357139A1 (en) | 2004-07-12 |
EP1272328A1 (en) | 2003-01-08 |
US20030039826A1 (en) | 2003-02-27 |
EP1272328A4 (en) | 2005-03-02 |
CN1426349A (zh) | 2003-06-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1243633C (zh) | 可模切的双轴取向薄膜 | |
US6461706B1 (en) | Multilayer films and labels | |
EP1244743B1 (en) | Films and labels formed from polypropylene based compositions | |
CN103121320B (zh) | 可顺应和可冲切的轴向定向的标签原料和标签及制备方法 | |
AU2001247571A1 (en) | Die-cuttable biaxially oriented films | |
CN101053004A (zh) | 模内标签及其用途 | |
CN1659030A (zh) | 包括聚丙烯/烯烃弹性体混合物的取向膜 | |
EP3149097A1 (en) | Films with enhanced scuff resistance, clarity, and conformability | |
EP1617990A2 (en) | Multilayered film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080806 Termination date: 20190316 |
|
CF01 | Termination of patent right due to non-payment of annual fee |