CN1268087A - 具有含蜡间同立构屏蔽层的多层薄膜 - Google Patents
具有含蜡间同立构屏蔽层的多层薄膜 Download PDFInfo
- Publication number
- CN1268087A CN1268087A CN98808508A CN98808508A CN1268087A CN 1268087 A CN1268087 A CN 1268087A CN 98808508 A CN98808508 A CN 98808508A CN 98808508 A CN98808508 A CN 98808508A CN 1268087 A CN1268087 A CN 1268087A
- Authority
- CN
- China
- Prior art keywords
- layer
- wax
- multilayer film
- film
- screen 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- 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
-
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
-
- 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
- B32B2331/00—Polyvinylesters
- B32B2331/04—Polymers of vinyl acetate, e.g. PVA
-
- 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
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- 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
- B32B2377/00—Polyamides
-
- 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
- B32B2391/00—Waxes
-
- 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
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/91—Product with molecular orientation
-
- 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]
- Y10T428/31725—Of polyamide
- Y10T428/31739—Nylon type
- Y10T428/31743—Next to addition polymer from unsaturated monomer[s]
- Y10T428/31746—Polymer of monoethylenically unsaturated hydrocarbon
-
- 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]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31797—Next to 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]
- Y10T428/31801—Of wax or waxy material
-
- 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
Abstract
一种取向的多层膜,它包含:(a)至少一层包含如全同立构聚丙烯的烯烃聚合物的层,和(b)毗邻(a)层的屏蔽层,该层包含间同立构的聚丙烯均聚物,以及至少10%的蜡材料,该蜡材料例如是聚乙烯蜡,其分子量在300至800之间,熔点在52℃-72℃之间。
Description
本发明涉及包含取向聚丙烯的屏蔽层。该屏蔽层改进了防潮性能并减少了氧气传递。
已知取向聚丙烯膜可用于包装操作。美国专利No.4,604,324(授予Nahmias等人)公开了一种多层聚丙烯膜结构,它包括高度立构规整的聚丙烯基层和立构规整性相对较低的含有防粘连添加剂的皮层的共挤塑层。另外,皮层可含有高达10%(重量)(%重量)的蜡,以改进膜的热封合性或光学性质。美国专利No.5,254,394(授予Bothe等人)公开了一种用于包装的聚烯烃膜,它包含全同立构聚丙烯基层和间同立构聚丙烯顶层,它具有高的封合线缝强度和优良的光学性质。该层可含有润滑添加剂,例如相对于各层高达2%(重量)的蜡。
美国专利5,155,160(授予Yeh等人)公开了通过在间同立构聚烯烃中掺入3至10%(重量)的蜡(如石蜡)来改进晶状或全同立构聚烯烃屏蔽性能的方法。该篇文献公开了通过改变冷辊条件来影响屏蔽性能。
本发明涉及一种多层薄膜,该膜能有效地防潮、防氧而不需要采用诸如多萜、脂环烃、或高度屏蔽性的聚偏二氯乙烯涂层的屏蔽剂。
本发明涉及一种取向的多层膜,它包含:
(a)至少一层含有烯烃聚合物的层,以及
(b)毗邻(a)层的屏蔽层,它包含间同立构聚丙烯均聚物,该均聚物的全同立构性低于25%,以及水分和氧气渗透性减少量的蜡。更具体地说,(a)层与(b)层不同。
本发明还涉及一种取向的多层膜,该膜含有间同立构性丙烯聚合物,以及用量足以使水蒸汽透过率低于0.2,具体地说是在38℃和90%相对湿度下低于1.6克/100平方英寸/密尔/天的蜡。
另外,本发明还涉及一种制备取向的多层膜的方法,该方法包括熔融共挤塑包含下列物质的组合物:
(a)至少一层含有烯烃聚合物的层,和
(b)毗邻(a)层的屏蔽层,该层包含间同立构聚丙烯均聚物,该均聚物的全同立构性低于25%,以及用量使水分和氧气渗透性减少的蜡;
和取向所述共挤塑组合物。
层(a)
多层膜的至少一层层(a)包含烯烃聚合物(例如丙烯聚合物),较佳的是,它主要(至少90%(重量))由丙烯组成,较佳的是熔点为140℃或更高,更佳的是其熔点为150℃或更高。
用于该基层的烯烃聚合物的较佳例子是:正庚烷溶解度为15%(重量)或更少的全同立构聚丙烯,乙烯含量为10%(重量)或更少的乙烯和丙烯的共聚物,以及(C4-C8)α烯烃含量为10%(重量)或更少的聚丙烯和(C4-C8)α烯烃的共聚物。
在230℃、21.6N(DIN 53735)的负载下,层(a)的丙烯聚合物宜具有0.5克/10分钟至8克/10分钟的熔体流动指数,更佳的有1.5克/10分钟至4克/10分钟的熔体流动指数。这些层(a)丙烯聚合物的例子包括Fina 3371(购自Fina Oil and ChemicalCompany)和PP 4252(购自Exxon Corporation)。
屏蔽层
屏蔽层含有间同立构聚丙烯与蜡成分的共混物。间同立构聚丙烯宜具有低于25%、特别是低于6%的全同立构性。间同立构序列的序列平均长度nr宜大于20,更佳的大于25。摩尔质量分布对应于关系式
Mw=k×Mn,其中Mw代表摩尔质量分布的平均重量,
Mn代表摩尔质量分布的平均数,和
k是1至5之间、较佳的在2和3之间的系数。
平均重量宜在60000至250000之间,特别是在90000和160000之间。平均摩尔质量可根据常规方法测定,其中,经证实,凝胶渗透色谱法是特别合适的。
适用于本发明的间同立构聚丙烯树脂包括购自Fina Oil and Chemical Company的EOD 93-06和EOD 95-01。
所用的蜡通常是烃类蜡,它可以是矿物蜡或合成蜡。平均链长度在22和65个碳原子间、分子量在300和800间、熔点在125和190°F(52和88℃)间的聚乙烯型蜡是特别佳的。这些蜡包括石蜡、微晶蜡和中间产物蜡。最佳的是石蜡,它通常具有22至40个碳原子之间的平均链长度,分子量在300和450之间,熔点在125至160°F(52至71℃)之间。石蜡通常由正链烷和支链烷的混合物组成,正链烷的含量宜在35至90%(重量)之间。石蜡通常具有较宽的分子量分布。例如,每一部分含一定数量碳原子的链宜少于蜡的25%,更佳的少于蜡的20%。分子量分布较宽的石蜡提供了比分子量分布较窄的石蜡更好的屏蔽性能,认为这是因为分子量分布较宽的蜡所形成的晶粒具有与聚烯烃非晶形区域的形态更好匹配的形态。一种特别合适的蜡是Chevron 143。其熔点为143°F(62℃),平均链长度为29个碳原子,平均分子量为416,正链烷含量为74%,并含有12%的C28级分,12%C29级分,和11%C30级分(蜡中最大的三个级分)。
蜡加入在间同立构聚丙烯的量应使所得膜制品的水蒸汽透过率(WVTR)和氧透过(TO2)减少。为了这个目的,可以根据ASTM E96和TAPPI T464标准,在100°F(38℃)和90%相对湿度下测定WVTR。根据ASTM D3985-81(cc/100平方英寸/24小时)测定TO2。通常,加入屏蔽层的蜡用量可取决于聚烯烃的非晶度,而该非晶度则取决于聚烯烃的类型、含有聚烯烃的挤塑膜的冷却方法以及膜厚度。通常,屏蔽层含有大于10%(重量)的蜡,具体是至少为12%(重量)的蜡,或至少为15%(重量)的蜡。
通常,含蜡屏蔽层不是外露面,以避免蜡使表面开花模糊。因此,屏蔽层通常被夹在芯层和外皮层之间。在另一个实施方案中,屏蔽层是多层膜的芯层。
外层
本发明的外层可以任一已知的、可挤塑的、双轴取向的成膜树脂。这些材料包括上面讨论的适用于(a)层的那些材料,包括全同立构聚丙烯、聚丙烯与聚丁烯-1的共混物,以及乙烯-丙烯共聚物,包括分级的乙烯-丙烯共聚物。合适的乙烯-丙烯共聚物包括乙烯-丙烯的无规共聚物和乙烯-丙烯的嵌段共聚物。另外,聚乙烯、聚丁烯-1、乙烯-丙烯-1-丁烯三元共聚物、聚酯、尼龙、乙烯-乙酸乙烯酯以及乙烯-乙烯醇也可用作外层。在一个实施方案中,皮层的组成可以和(a)层相同。
适于用作本发明外层的乙烯-丙烯-1-丁烯无规三元共聚物包括含有1-5%(重量)无规乙烯和5至25%(重量)无规1-丁烯的那些聚合物。这些共聚物中无规乙烯和1-丁烯组成的量,以共聚物的总量计,通常在10-25%(乙烯加上1-丁烯)范围内。
这些共聚物的熔体流动速率通常在5至10范围内,密度为0.9,熔点在115℃至130℃范围内。
在本发明的一个方面,外层来源于低密度聚乙烯。这可以是线性低密度聚乙烯(LLDPE)或标准的低密度聚乙烯。这些聚合物的熔体指数通常为0.5至10。低密度聚乙烯应具有0.88-0.93的密度,而线性材料可能具有高达0.94的密度,通常在0.90至0.94范围内,例如0.918或0.921,熔体指数为1至10。线性低密度聚乙烯可以从乙烯以及其它高级共聚单体(如1-丁烯、1-己烯或1-辛烯)衍生获得。
每一外层的厚度在0.5至3微米之间,较佳的在0.5至1.0微米之间,例如从0.5到0.75微米。
添加剂
为了进一步改进本发明的多层膜的某些性能,其中的一层或多层可以含有有效量的合适添加剂。较佳的添加剂包括抗静电剂、防粘连剂、润滑剂、稳定剂、和/或低分子量树脂。这些添加剂在美国专利No.5,254,394中有进一步的描述。
表面处理
可对本发明多层膜的一层或多层外露层进行表面处理,以使它们能吸收例如油墨。表面处理可根据本领域已知的一种方法来进行。已知的方法包括,例如,两极间的电喷雾放电,即电晕放电处理、火焰处理或利用极化火焰的处理。
涂层
本发明的间同立构聚丙烯/蜡屏蔽层提供了高效防潮和屏蔽氧透过的多层膜,而不需要采用屏蔽涂层(其存在通常会使产品回收利用变得困难)。然而,在需要的时候,可以用诸如涂布丙烯酸聚合物、聚偏二氯乙烯(PVDC)或聚乙烯醇的技术来进一步增强防潮能力。
丙烯酸涂层可以从美国专利No.3,753,769和4,865,908中公开的任一三元共聚物组合物衍生获得。这些涂层组合物含有一种树脂作为成膜组分,该树脂基本上由下列物质的共聚体组成:(a)2至15、较佳的是2.5至6重量份的α-β单烯键式不饱和羧酸,这些羧酸选自丙烯酸、甲基丙烯酸以及它们的混合物;和(b)85至98、较佳的是94至97.5重量份的中性单体酯,所述中性单体酯宜包含(1)丙烯酸甲酯或丙烯酸乙酯,以及(2)甲基丙烯酸甲酯。这些共聚体组成的特征还在于,宜包含30-55%(重量)的甲基丙烯酸甲酯(当所述丙烯酸烷酯是丙烯酸甲酯),以及52.5-69%(重量)的甲基丙烯酸甲酯(当所述丙烯酸烷酯是丙烯酸乙酯)。如上文更详细的描述,这些涂层组合物可以各种方式,包括氨溶液形式,施加到膜上。
同样有用的是从前述中性单体酯制得的共聚物涂层组合物。这些涂层组合物宜用乳剂形式施加到膜层压物上。
涂层还可基于任何已知的和常规的、至今用作膜生产中的涂层的聚偏二氯乙烯(PVDC)组合物,例如美国专利No.4.214,039;4,447,494;4,961,992;5,019,447以及5,057,177中描述的任何一种PVDC材料。
美国专利No.5,230,963公开了一种增强膜屏蔽氧性能的方法,该方法涉及一种涂布方法,较佳的是先施加一层底涂层,以增强PVDC涂层与其待施加PVDC涂层的膜表面的粘合。可采用1,1-二氯乙烯含量至少为50%,更佳的为75至92%的市售PVDC乳胶。PVDC也可以1,1-二氯乙烯与一种或多种其它烯键式不饱和共聚单体的共聚物形式提供,这些共聚单体包括:α,β烯键式不饱和酸,如丙烯酸和甲基丙烯酸;含有1至18个碳原子的所述酸的烷酯,如甲基丙烯酸甲酯,丙烯酸乙酯,丙烯酸丁酯等。另外,可以采用α,β烯键式不饱和腈(如丙烯腈和甲基丙烯腈)以及单乙烯基芳族化合物(如苯乙烯和氯乙烯共聚单体)。考虑的具体的PVDC乳胶包含82%(重量)的1,1-二氯乙烯、14%(重量)的丙烯酸乙酯和4%(重量)的丙烯酸。另外,同样可采用含80%(重量)1,1-二氯乙烯、17%丙烯酸甲酯和3%(重量)甲基丙烯酸的聚合物乳胶。
可用作涂层的乙烯醇聚合物可以是任何市售的材料。例如,购自Air Products,Inc的Vinol 125,99.3+%超水解的聚乙烯醇或Vinol 325,98%水解的聚乙烯醇。在美国专利No.5,230,963中还描述了采用PVOH涂层。
在将涂层组合物施加到合适的基材上之前,最好如上所述那样处理膜的上表面,以提高其表面能,因此确保该涂层能牢固粘合于其上,从而减少涂层从膜上剥离或脱落的可能。这种处理可用已知技术来实现,例如用膜氯化技术,即,使膜表面暴露在气态氯下,用氧化剂(如铬酸)、热空气或蒸汽处理、火焰处理等。尽管任一这些技术均能用来有效地预处理膜表面,但是一种特别希望的处理方法是所谓的电子处理方法,该方法包括在膜通过一对一定间距的电极时,使膜表面暴露在高压电晕放电处理下。在膜表面经电子处理后,将涂层组合物施加于其上。
在需要更高的涂层-膜粘合性(即高于用前述方法处理膜表面所得的粘合性)的场合下,可采用中间底涂层来提高涂层组合物与膜的粘合性。在这种情况下,有利地是首先用前述一种方法来处理膜,以在其上提供增加的活性粘合部位(从而促进底涂剂粘合),随后在经如此处理的膜表面上施加一层底涂材料的连续涂层。这些底涂材料是现有技术中熟知的,它们包括,例如,环氧材料和聚(乙烯亚胺)(PEI)材料。美国专利No.3,753,769(授予Steiner)和4,439,493(授予Hein等人)公开了采用这些底涂剂的应用。底涂剂为与随后施加的涂层组合物充分牢固结合提供了一个有整体粘合活性的表面,它可用常规的溶液涂布方法(例如用啮合轧辊)施加到膜上。
涂层组合物能以溶液形式,例如用有机溶剂(如醇、酮、酯等)配制的溶液,施加到膜上。然而,由于涂层组合物可含有很难充分分散在有机溶剂中的不溶的、细分的无机材料,因此涂层组合物宜以任何常规方式,例如凹槽辊涂布、辊涂、浸涂、喷涂等方式,施加到经处理的表面上。过量的水溶液可用挤压辊、刮刀等除去。
膜可以在机器方向上拉伸,用涂层组合物涂布,然后在横向上垂直拉伸。在另一个实施方案中,涂布可在双轴取向完成后进行。双轴取向的膜通常在机器方向(MD)上拉伸4.5至6次,在横向(TD)上拉伸6至13次。整体取向(MD×TD)可在25至80范围内。
涂层组合物的施加量应在干燥光滑的、均匀分布的层后沉积成大致约为0.01至0.2密尔(0.25至5.08微米)的厚度(等价于0.2至3.5克/6451.6平方厘米的膜)。通常,施加涂层的厚度应足以为所得膜提供所需的可密封性、屏蔽氧和水蒸汽的性质。通常,涂层包含1至25%(重量)、较佳的是7至15%(重量)的完整涂布的膜组成。随后用热空气、辐射热或任何其它常规方式干燥膜上的涂层。
在各实施例中,用下列方法测试膜的屏蔽性能。
实施例1至3
用市售的用于共挤塑树脂的系统制得本发明的5层多层膜。每一多层膜具有ABCBA的结构,其中A是皮层,B是屏蔽层,C是基层。用于所有三个实施例中的基层是Fina 3371,一种常规的全同立构丙烯均聚物。屏蔽层是间同立构聚丙烯(EOD9306),实施例2和3中的间同立构聚丙烯中加入了15%(重量)的蜡。实施例1的皮层是购自Chisso的乙烯-丙烯三元共聚物(XPM 7702),实施例2和3的皮层分别是购自Fina的Z9470和8573HB。
实施例中的多层膜如下制得:
使聚合物成熔融态,并通过平的挤片模头从常规挤塑机中共挤塑出来,在从模头中挤塑出来之前,将熔融的流体限制在注嘴接头内。在离开模头后,冷却多层膜结构,然后重新加热骤冷后的片材并取向。
对膜双轴取向。取向后,对膜修边,将膜卷成一卷。
通常,多层膜结构的总体膜厚度具有的结构可以描述成层ABCBA,其中层A是外层,层B是中间层,层C是芯层。本发明的屏蔽层通常用于层B和C。膜厚度通常为10至64微米,较佳的为12至50微米。层之间的厚度关系有时很重要。特别是,提供B层的相对厚度为膜总厚度的5至40%,其中10-25%是较佳的。当膜的总厚度为例如0.8密尔(20.32微米)时,较佳的A层厚度为1微米至5微米。
芯层C宜占膜总厚度的40-95%,较佳的为50-85%。
下表中的数据显示了根据本发明制得的膜的优点。实施例2和3是本发明的组合物,它们显示了在水蒸汽透过率(WVTR)方面比实施例1(对比例)的改进之处。
实施例2的膜的“C”层厚度为29微米,每一“B”层厚度为4.3微米,每一“A”层厚度为1.3微米,膜厚度为40.2微米。
实施例3的膜的“C”层厚度为28.7微米,每一“B”层厚度为2.9微米,每一“A”层厚度为0.99微米,膜厚度为36.5微米。
表
WVTR1 | ||||
蜡(%重量) | 实施例编号 | 总数 | 室温 | OTR2 |
0 | 1 | 0.365 | ||
15 | 2 | 1.58 | 0.13 | 21.2* |
15 | 3 | 1.44 | 0.112 | 22.5* |
注意:1.WVTR=克/645.16平方厘米/25.4微米/天,在38℃和90%相对湿度下测得
2.OTR*=cc/645.16平方厘米/天,在1个大气压、23℃和0%相对湿度下
*在1个大气压、23℃和0%相对湿度下,常规聚丙烯的OTR通常为150cc/645.16平方厘米/天。
Claims (6)
1.一种取向的多层膜,它包含:
(a)至少一层包含烯烃聚合物的层,和
(b)毗邻(a)层的屏蔽层,该层包含间同立构丙烯均聚物,该均聚物的全同立构度低于25%,以及减少水分和氧渗透的蜡,蜡的用量为至少10%。
2.根据权利要求1所述的多层膜,它还包含:
(c)毗邻屏蔽层的包含聚烯烃的皮层。
3.根据权利要求1所述的多层膜,它还包含:
(c)毗邻屏蔽层的外层,该层包含选自全同立构聚丙烯、乙烯-丙烯无规共聚物、乙烯-丙烯嵌段共聚物、乙烯-丙烯-1-丁烯共聚物、聚丁烯-1、聚酯、尼龙、乙烯-乙酸乙烯酯和乙烯-乙烯醇。
4.根据权利要求3所述的取向的多层膜,其中外层(c)用选自聚偏二氯乙烯、聚乙烯醇和丙烯酸的涂层涂布。
5.根据权利要求1所述的取向的多层膜,其中屏蔽层(b)的蜡是聚乙烯型蜡,其平均链长度在22和65个碳原子之间,分子量在300和800之间,熔点在52℃至71℃之间。
6.一种取向的多层膜,它包含至少一层屏蔽层,该屏蔽层含有间同立构的丙烯聚合物以及用量足以使在38℃和90%相对湿度下的水蒸汽透过率低于0.2克/645.16平方厘米/25.4微米/天的蜡。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/918,172 | 1997-08-25 | ||
US08/918,172 US6159612A (en) | 1997-08-25 | 1997-08-25 | Multi-layer films with syndiotactic barrier layer containing a wax |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1268087A true CN1268087A (zh) | 2000-09-27 |
Family
ID=25439916
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN98808508A Pending CN1268087A (zh) | 1997-08-25 | 1998-07-17 | 具有含蜡间同立构屏蔽层的多层薄膜 |
Country Status (11)
Country | Link |
---|---|
US (1) | US6159612A (zh) |
EP (1) | EP1007353A4 (zh) |
JP (1) | JP2001514094A (zh) |
KR (1) | KR20010023250A (zh) |
CN (1) | CN1268087A (zh) |
AR (1) | AR016859A1 (zh) |
AU (1) | AU750316B2 (zh) |
BR (1) | BR9811383A (zh) |
CA (1) | CA2301743A1 (zh) |
ID (1) | ID24648A (zh) |
WO (1) | WO1999010172A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1863876B (zh) * | 2003-10-06 | 2010-09-22 | 花王株式会社 | 生物降解性蜡组合物 |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE59909402D1 (de) * | 1998-02-12 | 2004-06-09 | Trespaphan Gmbh | Siegelfähige biaxial orientierte polypropylenfolie mit verbesserten eigenschaften hinsichtlich barriere |
DE19836657A1 (de) * | 1998-08-13 | 2000-02-17 | Hoechst Trespaphan Gmbh | Mehrschichtig biaxial orientierte Polypropylenfolie mit verbesserter Barriere, Verfahren zu ihrer Herstellung und ihre Verwendung |
US20010055692A1 (en) * | 1999-03-17 | 2001-12-27 | Michael T. Heffelfinger | Multi-layer film with core layer of syndiotactic polypropylene |
WO2003020516A1 (en) * | 2001-08-30 | 2003-03-13 | Toray Plastics (America), Inc. | Polyolefin oil resistant film using a wax-containing layer |
JP2003136655A (ja) * | 2001-10-30 | 2003-05-14 | Toray Ind Inc | 感熱転写材用積層フィルム |
US20030211350A1 (en) * | 2002-05-10 | 2003-11-13 | Migliorini Robert A. | Multilayer heat sealable polyolefin film comprising skin layer and transition layer of differing melting points |
US6884450B2 (en) * | 2002-10-03 | 2005-04-26 | Pactiv Corporation | Polypropylene containers |
US20040191445A1 (en) * | 2003-03-27 | 2004-09-30 | Baranowski Thomas R. | Transparent closure cap liner having oxygen barrier properties |
US20080003384A1 (en) * | 2006-06-29 | 2008-01-03 | Polymer Ventures, Inc. | Multi-layer coatings to increase water and grease resistance of porous materials and materials having such protection |
US7282273B2 (en) * | 2005-10-26 | 2007-10-16 | Polymer Ventures, Inc. | Grease resistance and water resistance compositions and methods |
US7745527B2 (en) * | 2006-12-15 | 2010-06-29 | Fina Technology, Inc. | Polyethylene-syndiotactic polypropylene composition and processing thereof |
US20090098303A1 (en) * | 2007-10-15 | 2009-04-16 | Polymer Ventures, Inc. | Coatings to increase water and grease resistance of porous materials and materials having such protection |
WO2021140382A1 (en) | 2020-01-06 | 2021-07-15 | Flint Hills Resources, Lp | Polymeric substrate including a barrier layer |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4604324A (en) * | 1984-09-28 | 1986-08-05 | Mobil Oil Corporation | Multi-layer polypropylene film structure and method of forming the same |
US4794096A (en) * | 1987-04-03 | 1988-12-27 | Fina Technology, Inc. | Hafnium metallocene catalyst for the polymerization of olefins |
US4975403A (en) * | 1987-09-11 | 1990-12-04 | Fina Technology, Inc. | Catalyst systems for producing polyolefins having a broad molecular weight distribution |
US5155160A (en) * | 1988-05-02 | 1992-10-13 | James River Ii, Inc. | Polyolefin films having improved barrier properties |
US5141801A (en) * | 1988-05-02 | 1992-08-25 | James River Ii, Inc. | Coextruded polyolefin films having improved barrier properties |
JP2609545B2 (ja) * | 1988-05-02 | 1997-05-14 | プリントパック・イリノイ・インク | 遮断性のすぐれたポリオレフィンフィルム |
US4892851A (en) * | 1988-07-15 | 1990-01-09 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
US5155080A (en) * | 1988-07-15 | 1992-10-13 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
US5162278A (en) * | 1988-07-15 | 1992-11-10 | Fina Technology, Inc. | Non-bridged syndiospecific metallocene catalysts and polymerization process |
DE4035344A1 (de) * | 1990-11-07 | 1992-05-14 | Hoechst Ag | Heisssiegelfaehige verpackungsfolie |
EP0499216B1 (en) * | 1991-02-15 | 1998-01-07 | MITSUI TOATSU CHEMICALS, Inc. | Transparent impact-resistant molded articles |
DE4228812A1 (de) * | 1992-08-29 | 1994-03-03 | Hoechst Ag | Siegelbare Polypropylen-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
WO1995002630A1 (en) * | 1993-07-16 | 1995-01-26 | Exxon Chemical Patents Inc. | Polymeric films with low water vapor transmission rates |
US5462807A (en) * | 1993-08-20 | 1995-10-31 | Exxon Chemical Patents Inc. | Heat sealable films and articles |
WO1995006556A1 (en) * | 1993-09-02 | 1995-03-09 | Quantum Chemical Corporation | Biaxially-oriented polypropylene film with improved gas barrier |
US5491019A (en) * | 1994-03-28 | 1996-02-13 | W. R. Grace & Co.-Conn. | Oxygen-permeable multilayer film |
US5468440B1 (en) * | 1994-05-06 | 1997-04-08 | Exxon Chemical Patents Inc | Process of making oriented film or structure |
JP3258831B2 (ja) * | 1994-09-29 | 2002-02-18 | 株式会社興人 | ポリプロピレン系熱収縮性積層フィルム |
DE19622083A1 (de) * | 1996-05-31 | 1997-12-04 | Brueckner Maschbau | Verfahren zur Herstellung einer biaxial orientierten Polypropylenfolie |
-
1997
- 1997-08-25 US US08/918,172 patent/US6159612A/en not_active Expired - Fee Related
-
1998
- 1998-07-17 BR BR9811383A patent/BR9811383A/pt not_active Application Discontinuation
- 1998-07-17 ID ID20000347A patent/ID24648A/id unknown
- 1998-07-17 JP JP2000507529A patent/JP2001514094A/ja active Pending
- 1998-07-17 CN CN98808508A patent/CN1268087A/zh active Pending
- 1998-07-17 KR KR1020007001881A patent/KR20010023250A/ko not_active Application Discontinuation
- 1998-07-17 EP EP98934614A patent/EP1007353A4/en not_active Withdrawn
- 1998-07-17 WO PCT/US1998/014820 patent/WO1999010172A1/en not_active Application Discontinuation
- 1998-07-17 AU AU84100/98A patent/AU750316B2/en not_active Ceased
- 1998-07-17 CA CA 2301743 patent/CA2301743A1/en not_active Abandoned
- 1998-08-21 AR ARP980104172 patent/AR016859A1/es unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1863876B (zh) * | 2003-10-06 | 2010-09-22 | 花王株式会社 | 生物降解性蜡组合物 |
Also Published As
Publication number | Publication date |
---|---|
EP1007353A4 (en) | 2002-03-13 |
BR9811383A (pt) | 2001-10-16 |
AR016859A1 (es) | 2001-08-01 |
WO1999010172A1 (en) | 1999-03-04 |
KR20010023250A (ko) | 2001-03-26 |
US6159612A (en) | 2000-12-12 |
AU750316B2 (en) | 2002-07-18 |
EP1007353A1 (en) | 2000-06-14 |
ID24648A (id) | 2000-07-27 |
JP2001514094A (ja) | 2001-09-11 |
AU8410098A (en) | 1999-03-16 |
CA2301743A1 (en) | 1999-03-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1268087A (zh) | 具有含蜡间同立构屏蔽层的多层薄膜 | |
CN1088649C (zh) | 聚烯烃系统多层薄膜 | |
EP0426382B1 (en) | Oriented multilayer heat sealable packaging film | |
AU709579B2 (en) | High moisture barrier polypropylene-based film | |
DE69730028T2 (de) | Metallisierter, mehrschichtiger verpackungsfilm | |
US6623866B2 (en) | Multilayer films including anti-block | |
CN1310750C (zh) | 多层热收缩密封膜 | |
CN101287598A (zh) | 多层薄膜、制备方法和由其制备的制品 | |
JPH0625439A (ja) | プロピレン重合体フィルムの製造法およびそれによって得られるラミネートおよび製品 | |
US20020182391A1 (en) | Multilayer matte films | |
CN1290207A (zh) | 间同立构聚丙烯多层包装膜 | |
US6270912B1 (en) | Multi-layer films with core layer of metallocene-catalyzed polypropylene | |
CN1136291A (zh) | 带表层的取向hdpe膜 | |
US6391467B1 (en) | Cast film made from metallocene-catalyzed polypropylene | |
CN1392836A (zh) | 层合用薄膜及层合体 | |
US6632383B1 (en) | Method for producing improved polymeric films | |
EP0376560A2 (en) | Slip coated thermoplastic films | |
CN1246879A (zh) | 用于塑料薄膜的底涂料 | |
US5073458A (en) | Polypropylene-polybutylene laminated packaging film with improved tear strength | |
CN1750931A (zh) | 具有防渗透性能的镀金属不透明膜 | |
KR102587753B1 (ko) | 폴리프로필렌 수지 조성물 및 이로부터 제조된 성형품 | |
EP0459742A2 (en) | Laminated film with improved tear strength | |
JP2021187056A (ja) | バリア性積層フィルムおよびバリア性包装体 | |
AU2002254200A1 (en) | Multilayer matte films | |
JPH09104791A (ja) | オレフィン重合体組成物およびその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |