CN1344206A - 由丙烯聚合物材料制成的复合多层包装薄膜 - Google Patents
由丙烯聚合物材料制成的复合多层包装薄膜 Download PDFInfo
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 37
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- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
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- 230000033912 thigmotaxis Effects 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
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Abstract
一种用来包装新鲜摘取产品的复合多层膜由以下组分组成:(1)乙烯/丙烯/4-8Cα-烯烃三元共聚物的外层;(2)中间层,它至少包括以下(a)和(b)中的一种:(a)0-100%的如(1)所述的三元共聚物和(b)0-100%的如下所述的混合物,所述的混合物的组成如下:(i)大约99.5-95%的烯烃共聚物组合物,该组合物由至少两个阶段的序列聚合得到,(ii)大约0.5-5%的低密度聚乙烯,其中,(a)与(b)的和等于100%;(3)内层,它至少包含下(a)和(b)中的一种:(a)0-100%的乙烯和C4-C8α-烯烃共聚物和(b)0-100%的层(2)所述的混合物(b),其中,所述(a)的共聚物由茂金属催化剂制得,具有0.89-0.91g/cm3的密度,(a)与(b)的和等于100%。这些层的厚度比例,以及当两种组分都存在时层(2)和(3)的混合物中各自的聚合物的量能被改变,以与被包装的产品的透气率相匹配。
Description
技术领域
本发明涉及由丙烯聚合物材料制得的多层薄膜。
背景技术
新鲜摘取的水果和蔬菜在被摘取、冲洗和切割之后继续呼吸着,并且要以这样的方式包装,即该包装的氧气和二氧化碳的透过率和产品的呼吸速率相匹配。每一种水果或蔬菜有其自身的呼吸速率,因而需要不同的包装。
聚烯烃膜的各种各样的组合物已被用作食物的包装材料。例如,美国专利第5500284号公开了特别适用于制造用来包装固体和/或液体产品的袋子的复合膜,和/或用来保藏必须在低温下保存的产品的袋子的复合膜。该膜的构成如下:(A)单层或多层双定向(bioriented)膜,其中,该双定向膜的单层或至少一层是结晶的丙烯均聚物;和(B)单层或多层流延薄膜,其中该膜的单层或至少一层是包括丙烯聚合物的组合物层,例如乙烯与丙烯和/或C4-C8α-烯烃的共聚物。
美国专利第5318842公开了双轴取向膜或片状制品,包括(A)由C3-C10α-烯烃均聚物或共聚物制得的基层或内层的膜,该共聚物是如丙烯和两种不向烯烃的共聚物,该烯烃选自乙烯和C4-C10α-烯烃;和(B)至少有一层宽分子量分布的丙烯聚合物,可任选地包含其它的丙烯聚合物,如丙烯和至少两种不同的烯烃的共聚物,该烯烃选自乙烯和C4-C8α-烯烃。该膜被描述为相对于通常的膜用等级聚烯烃树脂具有改进的刚性和透潮率。
美国专利第5741565号公开了一种多层流延薄膜,它包括(A)至少一层丙烯均聚物、丙烯和乙烯和/或C4-C8α-烯烃的共聚物或三元共聚物;(B)至少一层丙烯均聚物、丙烯和乙烯和/或C4-C8α-烯烃的共聚物或三元共聚物,或者丙烯与乙烯和/或C4-C10α-烯烃无规共聚物的组合物。较佳的膜由三层组成,其中(B)夹在两层(A)外层之间,或者(A)夹在两层(B)外层之间。该膜特别适用于糖果点心店的包装。
还需要一种包装材料,该包装材料用来包装新鲜产品,能与所包装的具体的水果或蔬菜的透气率相匹配,从而满足各种生产者的需要。
发明内容
本发明的复合多层膜包含以下层:
(1)三元共聚物外层,它包括(a)大约85-96%的丙烯,(b)大约0.5-5.0%的乙烯和(c)大约2.5-10%的C4-C8α-烯烃,其中,(b)和(c)的总量大约是4.0-15.0%;
(2)中间层,它至少包括下(a)和(b)中的一种:(a)0-100%(1)所描述的三元共聚物和(b)0-100%的烯烃聚合物混合物,其中(b)包括
(i)大约99.5-95%的烯烃聚合物的组合物,该组合物由至少两个阶段的序列聚合制得,该组合物包括:
(A)重量百分比为大约5-25%的丙烯与乙烯和C4-C8α-烯烃的共聚物,该共聚物包含大约80-96%的丙烯、大约2-10%乙烯和大约2-10%的C4-C8α-烯烃;和
(B)重量百分比为大约95-75%的直链低密度聚乙烯,它包含重量百分比高达20%的C4-C8α-烯烃。
(ii)重量百分比为大约0.5-5%的低密度聚乙烯,其密度为0.916-0.922g/cm3,熔体指数为0.2-20g/10分钟;
其中,(a)+(b)=100%;
(3)内层,它至少下(a)和(b)中的一种:包括(a)0-100%乙烯与C4-C8α-烯烃的共聚物,由茂金属催化剂制得,具有0.89-0.91g/cm3的密度,和(b)0-100%第(2)层所描述的烯烃聚合物混合物,(a)+(b)=100%。
该膜能用来包装新鲜的产品。通过改变这些层的厚度比例,或者当组分(a)和(b)都存在时,改变第(2)和第(3)层混合物的组分比例,能使膜与具体类型的被包装的产品的呼吸速率相匹配,并且同时改进了膜的刚性和光学透明度。
本发明的详细描述
本发明的膜的外层(1)包括乙烯/丙烯/C4-C8α-烯烃三元共聚物,该共聚物包含大约0.5-5%乙烯、大约2.5-10%C4-C8α-烯烃和大约85-96%丙烯,其中,乙烯含量大约为1-3%较佳,C4-C8α-烯烃含量大约为3-6%较佳。此层大约占该膜总厚度的15-35%。
C4-C8α-烯烃较佳为选自丁烯-1、己烯-1、辛烯-1和4-甲基-1-戊烯。丁烯-1更佳。
第(1)层的三元共聚物可以由单体经过多阶段序列聚合制得,该反应在支承于活性二卤化镁的立体定向齐铬勒-纳塔催化剂的存在下进行。在美国专利第5486419号里较详细地描述了这种三元共聚物的制备,本文引入该文内容作为参考。
复合膜的中间层(2)包括至少下(a)和(b)中的一种:(a)0-100%的第(1)层所述的三元共聚物和(b)0-100%以下(i)和(ii)的混合物,其中(i)大约99.5-95%、较佳为大约98-95%的烯烃聚合物组合物,该组合物由至少两个阶段的序列聚合制得,(ii)大约0.5-5%、较佳为大约1-5%、最佳为2-5%的低密度聚乙烯;其中,(a)+(b)=100%。
在第(2)层的混合物(b)中,由至少两个阶段的序列聚合制得的烯烃聚合物组合物包括:
(A)重量百分比在大约5-25%、较佳在5-15%的丙烯与乙烯和C4-C8α-烯烃的共聚物,其中,丙烯含量大约为80-96%,乙烯含量大约为2-10%,较佳为约2-7%,C4-C8α-烯烃含量大约为2-10%、较佳为大约2-8%;和
(B)重量百分比为大约95-75%、较佳为大约85-95%的直链低密度聚乙烯,它包含重量百分比最高达20%、较佳为大约5-14%的C4-C8α-烯烃。
该烯烃聚合物组合物较佳地具有0.4-1.10g/10分钟的总熔体指数(MIE),0.8-1.10g/10分钟更佳,其密度为0.905-0.9135g/cm3。
当第(2)层中(a)和(b)都存在时,混合物(b)的重量百分比含量为大约30-70%。
用来制备烯烃聚合物组合物的C4-C8α-烯烃包括如丁烯-1、己烯-1、辛烯-1和4-甲基-1-戊烯。C4-C8α-烯烃是丁烯-1较佳。
烯烃聚合物组合物能用聚合方法制备,该方法包括两个阶段,在每个阶段中有一个或一个以上的反应器,其中,在一个阶段里,组分(A)在一个或一个以上的反应器中被聚合,在另一个阶段里,组分(B)在一个或一个以上的反应器中制备。制备各组分的次序并不重要。然而,在第一阶段制备组分(A)较佳。
聚合在气相中进行,在每个阶段中使用到分开的流化床反应器(separate fluidbed reator),在所有的阶段里使用同样的催化剂。
氢气在需要控制分子量时被作为链转移剂加入。
组分(A)和(B)的聚合反应温度可以相同或不同,通常是从40℃-120℃,60℃-100℃较佳。
聚合反应中用到的催化剂包括反应(i)固相催化剂组分,(ii)不含卤素的烷基铝化合物,以及可任选地(iii)电子供体化合物。其中,固相催化剂组分包括钛化合物,该钛化合物包含至少一个支承于活性卤化镁的Ti-卤素键,还可任选地包含电子供体化合物。
较佳的是,在进行气相聚合反应之前,先让催化剂和少量的相同烯烃单体接触(称为预聚合),使催化剂维持在烃类溶剂的悬浮液中,然后在室温到60℃的温度里聚合足够长的时间,以产生0.5到3倍于催化剂重量的聚合物。
更佳的是,该催化剂包含具有规则的形态结构,如球状的或球体的组分。这些催化剂的例子在美国专利第5221651号、已公开的欧洲专利申请第553805号和553806号中描述到。
在美国专利第5455303号中详细地描述了烯烃聚合物组合物的制备,本文引入该文内容作为参考。
第(2)层的混合物(b)中的低密度聚乙烯可以是任何的市售低密度聚乙烯,根据ASTM D-1238、条件E(190℃,2.16Kg)测量该低密度聚乙烯,它具有0.2-20g/10分钟的熔体指数,熔体指数为1.8-2.6g/10分钟较佳,它的密度为0.916-0.922g/cm3。
中间层占膜总厚度的35-60%。
常与包装的产品邻近的复合膜的内层(3)包含下(a)和(b)中的至少一种:(a)0-100%的乙烯/C4-C8α-烯烃共聚物,该共聚物的密度为0.89-0.91g/cm3,较佳为0.89-0.906g/cm3,由茂金属催化剂制备;(b)0-100%的第(2)层所述的烯烃聚合物混合物(b);其中,(a)+(b)=100%。
当第(3)层中(a)和(b)都存在时,乙烯/α-烯烃共聚物的用量大约在30-70%,烯烃聚合物混合物的用量大约在70-30%。
第三层大约占膜总厚度的15-35%。
能用来以茂金属催化剂制备乙烯共聚物的C4-C8α-烯烃包括丁烯-1、、戊烯-1、己烯-1、辛烯-1和4-甲基-1-戊烯。以辛烯-1为较佳。
本发明用来制造多层膜或片状材料的不同层的聚合物组合物也可以包含常规的添加剂,例如稳定剂(如抗氧化剂)、增量油(如石腊油和环烷油)、填充剂(如CaCO3、滑石和氧化锌)、增滑剂、防结块剂、阻燃剂,以及成核剂,如苯甲酸钠和Millad山梨糖醇衍生物(可由Milliken化学公司市售得到)。
当用来制备第(2)和第(3)层的混合物的两种组分都存在时,通常使用标准的混合设备以小丸的形态将其混合。
通过三个不同的挤出机,用三层共挤出模头用标准吹塑薄膜方法制成复合膜。其吹胀直径比为2.5∶1。在挤出机的外面用40°-45°F的冷空气吹着。虽然实施例中的膜是依吹塑薄膜方法而制成的,但是,本发明膜的生产方法并不限于此。该膜也可以是用本领域周知的标准方法制得的流延薄膜,这些方法包括将成膜组合物加到挤出机中,通过平膜模头挤出,然后在冷却锟上淬火。
膜的总厚度通常小于5mil。三个层的厚度比例,以及当两种组分都存在时,第(2)和第(3)层的混合物的组分比例依膜最终的使用要求而改变。从而,膜层的厚度和组成能改变,以与具体的包装产品的呼吸速率相匹配。例如,在23℃和100%氧气的条件下测量的透氧率能从100cm3/100in2/天改变到800cm3/100in2/天,其刚性(2%割线模量)的改变为35-75Kpsi,同时雾度维持在10%以下。
膜的特性依其总厚度而变化,例如,氧气和二氧化碳的透过率随着厚度的降低而增加。
对于一个2mil的膜,它的特性较佳为:
雾度(%):4.5-10.0(越低越好)
光泽度(45°):65-80(越高越好)
2%割线模量(psi):纵向(MD):45000-54000;横向(TD):46000-55000
透氧率(em3/100in2/天):150-300
二氧化碳透过速率(cm3/100in2/天):800-1300
在实施例中用到的试验方法:
落镖冲击 ASTM D-1709
爱尔门道夫式撕裂强度强度 ASTM D-1922
2%割线模量 ASTM D-822
透潮率 ASTM E-96
透氧率 ASTM D-3985
二氧化碳透过率 ASTM D-3985
%雾度 ASTM D-1003
%透明度 ASTM D-1003
45°光泽度 ASTM D-2457
熔体指数(190℃,2。16Kg) ASTM D-1238
通过Instron4202型试验设备,用2001b的测力传感器测量膜的刺孔抗性。19mm(0.750in)的镖探针以254mm/分钟(10in/分钟)的速度移动,穿透厚度大约为0.010英寸(10mil)的150mm(6in)的平方的膜样本上的直径为4英寸的部分。该试验在温度为23+2℃(73.4+3.5°F)和相对湿度为50±5%的标准实验室气氛中进行。测量破裂负荷、最大负载量和探针穿透度。
在本说明书中,除非有另外的说明,所有的份和百分比都以重量表示。
实施例1
本实施例描述三层膜的制备,在该膜中,层(A)占总厚度的35%。层(B)占50%,层(C)占15%。
层(A)由含有100份丙烯、乙烯和丁烯-1的三元共聚物制成,其中,丙烯占92.5%,乙烯占2.5%,丁烯-1占5.5%,其中还包含增滑剂和防结块剂(可从美国Basell公司市售的得到)、苯甲酸钠0.25份/每100份(pph)三元共聚物、0.05pph的DHT-4A抗酸剂化合物(可从Kyowa Chemical Industry有限公司得到)、0.15pph的Irganox B225抗氧化剂(可从Ciba Specially Chemicals公司得到)、0.10pph的Sylobloc 45抗结块剂(可从W.R.Grace公司得到),以及0.15pph的芥酸酰胺(erucamide)。
Irganox B225抗氧化剂是50/50的四〔亚甲基(3,5-二-叔丁基-4-羟基苯基丙酯)〕甲烷和三(2,4-二-叔丁基苯基)亚磷酸酯的混合物。
层(B)由如下所述混合物制得,该混合物包括(i)30%层(1)的三元共聚物组合物;(ii)70%的聚合物组合物,该组合物由至少两个阶段的序列聚合制得,包含可从美国Basell公司得到的增滑剂和抗结块剂,该组合物包含(a)重量百分比大约为95%的烯烃聚合物组合物,以及(b)约5%的可从EquistarChemicalLP.得到的NA951-100低密度聚乙烯,其中,所述(a)中的组合物包括(I)15%由91.5%的丙烯、2.5%的乙烯和6.0%的丁烯-1构成的三元共聚物,和(II)85%的由90.8%的乙烯和9.2%丁烯构成的直链低密度聚乙烯。
层(C)由如下所述混合物制得,该混合物包括(a)70%的、可从Dow Plastic公司得到的含有增滑剂的Affinity PL 1881乙烯/辛烯-1共聚物,该共聚物用茂金属催化剂制备,具有0.902g/cm3的密度;(b)30%的层(B)中使用的聚合物组合物(ii)。
用三个挤出机通过共挤出三个层制得1.8mil的多层膜。挤出机(A)有直径为60mm的槽进给螺杆,挤出机(B)有直径为3.5″的光滑内腔螺杆,挤出机(C)有2.5″的光滑内腔螺杆。该冲膜是11″的通常用在吹塑薄膜复合方法中的环行冲膜。进料导管的温度和冲膜的温度都是410°F。该冲膜没有内在气囊降温。挤出条件如下。
挤出机A 挤出机B 挤出机C熔融温度(°F) 395-400 420-425 420-425排出压力(psi) 1700-1800 2500-3200 2000-2500机筒温度1(°F) 360 360 375机筒温度2(°F) 420 380 420机筒温度3(°F) 400 390 410机筒温度4(°F) NA 380 410机筒温度5(°F) NA 380 410筛网变换器(°F) 415 400 415适应器(°F) 415 400 415
该膜具有下述特性。其中MD表示纵向,TD表示横向,MVTR表示透潮率,TR表示透过率。落镖冲击(g) 77.0爱尔门道夫式撕裂强度强度,MD(g) 37爱尔门道夫式撕裂强度强度,TD(g) 916刺孔抗性(ft.lb/in3) 41.92%割线模量,MD,(psi) 565002%割线模量,TD,(psi) 53600MVTR(g/100in2/24小时) 0.518透氧率(cm3/100in2/24小时) 172.7二氧化碳透过率(cm3/100in2/24小时) 965.2%雾度 5.5%透明度 94.945°光泽度 76.2
实施例2
本实施例描述三层膜的制备,在该膜中层(A)占膜总厚度的35%,层(B)占50%。层(C)占15%。
(A)与实施例1一样。
层(B)由如下所述的混合物制成,该混合物由70%的层(A)的三元共聚物组合物和30%的实施例1层(B)所述的聚合物组合物(ii)组成。
层(C)由如下所述的混合物制成,该混合物由30%的实施例1所述的DowPL1881乙烯/辛烯-1共聚物和70%的实施例1层(B)所述的聚合物组合物(ii)组成。
如实施例1所述共挤出2.0mil的膜。该膜有如下特性:落镖冲击(g) 81.0爱尔门道夫式撕裂强度强度,MD(g) 29爱尔门道夫式撕裂强度强度,TD(g) 93刺孔抗性(ft.lb/in3) 36.82%割线模量,MD,(psi) 721002%割线模量,TD,(psi) 64300MVTR(g/100in2/24小时) 0.466透氧率(cm3/100in2/24小时) 136.8二氧化碳透过率(cm3/100in2/24小时) 1905.7%雾度 7.7%透明度 94.645°光泽度 68.0
普通的技术人员在阅读完前面所公开的部分后,能容易地实现本发明在这里所公开的其它的特征、优点和实施例。为此,本发明的特殊的实施例已被相当详细地描述,对于这些实施例的改变和修改,在没有偏离本发明的描述和要求的实质和范围的情况下能够实现。
Claims (12)
1.一种复合多层膜,它包括:
(a)三元共聚物外层,它包括(i)大约85-96%的丙烯,(ii)大约0.5-5.0%的乙烯和(iii)大约2.5-10%的C4-C8α-烯烃,其中,(ii)和(iii)的总量大约是4.0-15.0%;
(b)中间层,它至少包括以下(i)和(ii)中的一种:(i)0-100%在层(a)中描述的三元共聚物和(ii)0-100%的烯烃聚合物混合物,其中(ii)包括
(A)大约99.5-95%的烯烃聚合物的组合物,该组合物由至少两个阶段的序列聚合制得,该组合物包括:
(1)重量百分比为大约5-25%的丙烯与乙烯和C4-C8α-烯烃的共聚物,该共聚物包含大约80-96%的丙烯、大约2-10%乙烯和大约2-10%的C4-C8α-烯烃;和
(2)重量百分比为大约95-75%的直链低密度聚乙烯,它包含重量百分比高达20%的C4-C8α-烯烃;
(B)重量百分比为大约0.5-5%的低密度聚乙烯,其密度为0.916-0.922g/cm3,熔体指数为0.2-20g/10分钟;
其中,所述(i)与(ii)的和等于100%;
(c)内层,它至少包括以下(i)和(ii)中的一种(i)0-100%的用茂金属催化剂制得的密度为0.89-0.91g/cm3的乙烯与C4-C8α-烯烃的共聚物和(ii)0-100%在层(b)中描述的烯烃聚合物混合物,(i)与(ii)的和等于100%。
2.如权利要求1所述的膜,其中,层(a)的4-8Cα-烯烃是丁烯-1。
3.如权利要求1所述的膜,其中,层(b)中的(A)(1)是丙烯、乙烯和丁烯-1的共聚物。
4.如权利要求1所述的膜,其中,层(b)中的直链低密度聚乙烯(A)(2)是乙烯与丁烯-1的共聚物。
5.如权利要求1所述的膜,其中,层(c)的(i)包括乙烯与辛烯-1的共聚物。
6.如权利要求1所述的膜,其中,外层(a)大约占该膜总厚度的15-35%。
7.如权利要求1所述的膜,其中,中间层(b)大约占该膜总厚度的35-60%。
8.如权利要求1所述的膜,其中,内层(c)大约占该膜总厚度的15-35%。
9.如权利要求1所述的膜,其中,层(a)占该膜总厚度的35%,层(b)占50%,层(c)占15%。
10.如权利要求1所述的膜,其中,所述膜的总厚度小于5密耳。
11.如权利要求1所述的膜,其中,中间层(b)的(i)的含量大约为30-70%,(ii)的含量大约为70-30%。
12.如权利要求1所述的膜,其中,内层(c)的(i)的含量大约为30-70%,(ii)的含量大约为70-30%。
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CN100448667C (zh) * | 2003-04-03 | 2009-01-07 | 普瑞曼聚合物株式会社 | 包装用膜 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4411072B2 (ja) * | 2001-10-03 | 2010-02-10 | トータル・ペトロケミカルズ・リサーチ・フエリユイ | ポリエチレンのポリプロピレンへの接着 |
US6899249B2 (en) * | 2001-10-26 | 2005-05-31 | Fresh Advantage, Inc. | Tray for storing and transporting products |
KR101186271B1 (ko) | 2002-06-26 | 2012-09-27 | 애버리 데니슨 코포레이션 | 폴리프로필렌/올레핀 탄성체 혼합물을 포함하는 배향된필름 |
US20040219198A1 (en) * | 2003-05-01 | 2004-11-04 | 3M Innovative Properties Company | Transdermal drug delivery device with multilayer backing |
GB0314189D0 (en) * | 2003-06-18 | 2003-07-23 | Borealis Tech Oy | Food packaging |
EP1780009B1 (en) * | 2004-08-17 | 2013-10-30 | Japan Polyethylene Corporation | Layered product |
PL2049333T3 (pl) | 2006-06-14 | 2013-07-31 | Avery Dennison Corp | Łatwo dopasowujące się i nadające się do sztancowania zorientowane wzdłużnie materiały do produkcji etykiet, i etykiety oraz sposób ich otrzymywania |
CN101484315B (zh) | 2006-06-20 | 2013-04-10 | 艾利丹尼森公司 | 用于热熔粘合剂标记和标签原料以及此种标签的多层聚合膜 |
JP5579436B2 (ja) | 2006-07-17 | 2014-08-27 | エーブリー デニソン コーポレイション | 非対称の多層高分子フィルム、並びにラベルストック及びそのラベル |
US20120263924A1 (en) | 2011-04-12 | 2012-10-18 | Paul Thomas Weisman | Multi-Layer Films And Methods Of Forming Same |
US9676532B2 (en) | 2012-08-15 | 2017-06-13 | Avery Dennison Corporation | Packaging reclosure label for high alcohol content products |
US9095152B2 (en) * | 2012-09-12 | 2015-08-04 | Munger Bros., LLC | Method for disinfecting, sanitizing, and packaging ready-to-eat produce |
WO2015187646A1 (en) | 2014-06-02 | 2015-12-10 | Avery Dennison Corporation | Films with enhanced scuff resistance, clarity, and conformability |
CN107487535A (zh) * | 2017-07-04 | 2017-12-19 | 北京印刷学院 | 功能集成保鲜包装袋及在小油菜保鲜中的应用 |
CN107826502A (zh) * | 2017-11-14 | 2018-03-23 | 北京印刷学院 | 一种芒果常温贮藏用保鲜袋 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW221700B (zh) | 1990-11-01 | 1994-03-11 | Himont Inc | |
CZ5693A3 (en) | 1992-01-23 | 1993-10-13 | Himont Inc | Elastic yarn of polypropylene polymer and articles made therefrom |
US5318842A (en) | 1992-12-03 | 1994-06-07 | Himont Incorporated | Biaxially oriented propylene polymer film or sheet articles |
US5331047A (en) | 1993-02-17 | 1994-07-19 | Himont Incorporated | Olefin polymer films |
IT1271418B (it) | 1993-08-11 | 1997-05-28 | Himont Inc | Manufatti in film cast costituiti da polimeri propilenici |
IT1265452B1 (it) | 1993-12-27 | 1996-11-22 | Himont Inc | Film poliolefinici compositi adatti per imballaggio |
US5455303A (en) | 1994-06-20 | 1995-10-03 | Montell North America Inc. | Linear low density polyethylene based compositions with improved optics |
IT1276120B1 (it) * | 1995-11-14 | 1997-10-24 | Montell Technology Company Bv | Film multistrato estensibili basati su lldpe |
US6218023B1 (en) * | 1997-04-21 | 2001-04-17 | Montell North America, Inc. | Co-extruded laminate comprising at least one propylene graft copolymer layer |
IT1292138B1 (it) * | 1997-06-12 | 1999-01-25 | Montell Technology Company Bv | Film multistrato estensibili |
-
1999
- 1999-12-21 US US09/468,438 patent/US6333096B1/en not_active Expired - Fee Related
-
2000
- 2000-12-20 DE DE2000603390 patent/DE60003390T2/de not_active Expired - Lifetime
- 2000-12-20 WO PCT/IB2000/001925 patent/WO2001045938A1/en active IP Right Grant
- 2000-12-20 BR BR0008389A patent/BR0008389A/pt not_active Application Discontinuation
- 2000-12-20 JP JP2001546464A patent/JP2003517952A/ja active Pending
- 2000-12-20 EP EP20000983437 patent/EP1152894B1/en not_active Expired - Lifetime
- 2000-12-20 CA CA 2364382 patent/CA2364382A1/en not_active Abandoned
- 2000-12-20 PL PL34936100A patent/PL349361A1/xx unknown
- 2000-12-20 KR KR1020017010633A patent/KR20010102303A/ko not_active Application Discontinuation
- 2000-12-20 AU AU20191/01A patent/AU2019101A/en not_active Abandoned
- 2000-12-20 CN CN00805454A patent/CN1344206A/zh active Pending
- 2000-12-21 AR ARP000106809 patent/AR031544A1/es unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100448667C (zh) * | 2003-04-03 | 2009-01-07 | 普瑞曼聚合物株式会社 | 包装用膜 |
CN100410151C (zh) * | 2005-03-30 | 2008-08-13 | 李光球 | 无菌包装袋 |
Also Published As
Publication number | Publication date |
---|---|
DE60003390T2 (de) | 2004-04-22 |
PL349361A1 (en) | 2002-07-15 |
JP2003517952A (ja) | 2003-06-03 |
AR031544A1 (es) | 2003-09-24 |
DE60003390D1 (de) | 2003-07-24 |
EP1152894B1 (en) | 2003-06-18 |
WO2001045938A1 (en) | 2001-06-28 |
CA2364382A1 (en) | 2001-06-28 |
AU2019101A (en) | 2001-07-03 |
KR20010102303A (ko) | 2001-11-15 |
EP1152894A1 (en) | 2001-11-14 |
BR0008389A (pt) | 2002-01-29 |
US6333096B1 (en) | 2001-12-25 |
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