CN1281403C - 可整合的全息标签 - Google Patents

可整合的全息标签 Download PDF

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Publication number
CN1281403C
CN1281403C CNB028128761A CN02812876A CN1281403C CN 1281403 C CN1281403 C CN 1281403C CN B028128761 A CNB028128761 A CN B028128761A CN 02812876 A CN02812876 A CN 02812876A CN 1281403 C CN1281403 C CN 1281403C
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China
Prior art keywords
integrating
plane materiel
copolymer
cortex
polymer film
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Expired - Lifetime
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CNB028128761A
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CN1520355A (zh
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R·G·罗迪克
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Avery Dennison Corp
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Avery Dennison Corp
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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Holo Graphy (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)

Abstract

一种可整合的面材包括具有上和下表面的聚合物膜(11),和具有粘附到聚合物膜的下表面上的上表面(15)的全息层(12)。

Description

可整合的全息标签
本发明的领域
本发明涉及整合性的包含全息图像的标签和面材。更具体地,本发明涉及一种包含整合性的和/或可挤压的全息图像层的标签和面材,如全息图像不开裂或剥落。
本发明的背景
全息图和其它种类的衍射光栅通常附着到文件或其它制品上。全息图已经用作文件以及信用卡中的安全方式以鉴别其真实性和增加伪造那些制品的难度。全息图还附着到印刷文件和其它制品上用于装饰和美学目的。对于消费品,包含全息图的标签提供一种引人注意的产品显示。
在标签中使用全息图的一个问题是,全息图往往是坚硬的。标签内的全息图往往开裂或剥落。在标签中,全息图可提供市场吸引力,但由于图像在处理过程中或在使用包含全息标签的产品的过程中被破坏而通常被回避。需要在标签内具有全息图,其中图像对于可挤压的瓶或可挤压的容器是可整合的。
本发明的综述
本发明涉及一种包含聚合物膜的面材,和一种在面材表面上的全息层,其中膜是可整合的。本发明还涉及由该面材制成的标签原料,和由其制成的标签。该标签可用于可挤压的容器。这些标签的一个优点在于全息图像较少和没有开裂或剥落。
附图的简要描述
图1a是包含图像压花的膜层的本发明面材的横截面。
图1b是包含膜层和全息层,具有覆盖全息层整个表面的反射材料的本发明面材的横截面。
图1c是包含膜层和全息层,具有仅覆盖全息层的图像区域的反射材料的本发明面材的横截面。
图2是包含具有两层的多层膜和全息层的本发明面材的横截面。
图3是包含具有三层的多层膜和全息层的本发明面材的横截面。
图4是包含图1b所示面材与粘合剂层和释放衬里的按照本发明的标签原料的横截面。
图5是包含图3所示面材与粘合剂层和释放衬里的按照本发明的标签原料的横截面。
图6是其中保护层覆盖在全息层上的按照本发明的标签原料的横截面。
优选实施方案的详细描述
如本文所述,本发明涉及标签和用于其中的面材。该标签可用于可变形的和可挤压的瓶。变形可如同牙膏管是永久的或如同洗发剂瓶,牙膏管,手洗剂瓶和管,等是非永久的。
本文所用的术语″可整合的″是指,膜或标签能够屈服于弯曲的或粗糙的表面的轮廓。可整合的全息标签整合于它所应用的容器或基材而没有全息图像的开裂或剥落。
全息层
面材和标签原料包含全息层。如图1a所示,面材10具有聚合物膜层11,后者具有上表面和下表面,其中下表面粘附于全息层12。聚合物膜11的底表面可直接粘附于全息层12,或通过粘接层或粘合剂层(未示)间接粘附于全息层。全息层12在聚合物膜层11的相对表面上具有图像13。
在一个实施方案中,具有上表面和图像表面的全息层在图像表面上具有反射材料。如图1b所示,聚合物膜11粘附于全息层12,后者具有上表面15和具有图像13的图像表面16。反射材料14,如铝或本领域技术人员已知的其它材料覆盖图像表面16和在全息层12的表面上形成全息图。
在另一实施方案中,如图1c所示,面材具有粘附于全息层12(具有图像13)的聚合物层11。反射材料14覆盖全息层12的仅一部分图像表面16,即图像13的区域。
全息层包含用本领域技术人员已知的反射材料处理的图像。该图像可在聚合物面材上通过压花该膜并随后金属化该膜的图像区域或整个图像表面而形成。图像也可使用液体铸塑树脂而形成。该树脂可以是涂覆在面材膜上的辐射可固化树脂。图像使用全息图模板或本领域技术人员已知的其它方式提供给该铸塑树脂。辐射可固化树脂包括Cellofilm,如Cellofilm C-200和Radcure树脂,如Radcure#801。
辐射可固化树脂一般用作低聚物。低聚物是可购自各种来源。氨基甲酸乙酯丙烯酸酯低聚物以品名Uvithane 782和Uvithane 783得自Morton Thiokol,和以品名PURELAST得自聚合物体系公司,Orlando,Florida。Ebecryl 270是一种得自UCB Radcure,Atlanta,Ga的丙烯酸酯脂族氨基甲酸乙酯低聚物。环氧丙烯酸酯低聚物例如,以品名Novacure 3600得自UCB Radcure,Atlanta,Ga.和以品名Epocryl25A60得自Shell Chemical Company。尽管Epocryl 25A60包含一些挥发性溶剂,该产品可与丙烯酸酯单体如,例如,1,6-己烷二醇二丙烯酸酯混合,和可去除起始存在的溶剂。市售丙烯酸丙烯酸酯低聚物的一个例子是Novacure 6700(来自UCB Radcure)。市售多元胺丙烯酸酯低聚物的一个例子是Novacure 7100(来自UCB Radcure)。该丙烯酸酯官能低聚物胺是一种具有在25℃下的粘度500-1500CPs和理论分子量800的液体,和该低聚物包含低于10%的己烷二醇二丙烯酸酯。
将图像提供给全息层的方法和其中使用的材料(包括用作铸塑树脂的材料)描述于US专利,4,728,377(Gallagher);4,913,858(Mallik等人);4,933,120(D′Amato);5,003,915(D′Amato);5,083,850(Miekk等人),5,116,548(Mallik);4,906,315(McGrew);5,948,199(McGrew);5,164,227(Miekka等人);和5,643,678(Boswell),在此将整个公开内容作为参考并入本发明。
在另一实施方案中,全息图图像使用箔/复合片材制成。U.S.专利Nos.5,810,957,5,783,017,5,759,683,5,753,349,5,674,580,5,670,003,5,643,678和5,464,690涉及具有印入箔中的全息图像或衍射光栅图像和一个或多个复合层的箔/复合片材。这些专利公开,如,直接在基材如文件上热冲压包含全息图像的芯片。公开于5,810,957的箔/复合片材,例如,顺序包括,塑料载体膜,释放涂层,硬大漆涂层,软大漆涂层,金属层和压花接受涂层。如果加热压花垫片在压力下作用于压花接受层,软大漆涂层,金属层和压花接受涂层被压花以全息图像。热活化粘合剂然后施用到压花接受涂层上,以将芯片施用到文件上。也可称作释放涂层的压花接受涂层可以是蜡如微晶蜡或部分皂化褐煤蜡或可以是硅氧烷。金属是,如,铝。软大漆涂层可以是包含丙烯酸或硝基纤维素或氯化橡胶的热软化聚合物。该组中的其它专利公开了类似箔/复合片材结构,其中全息图像施用到箔/复合片材上以形成芯片,和然后芯片通过,如,热冲压施用到文件或其它基材上。U.S.专利Nos.5,810,957;5,783,017;5,759,683;5,753,349;5,674,580;5,670,003;5,643,678和5,464,690涉及在箔/复合片材上形成这些热可冲压的全息图像的教导分别在此作为参考并入本发明。
聚合物面材
面材包括全息层和聚合物膜。该膜可以是单层聚合物膜或多层聚合物膜。这些多层膜一般包含基层和视需要,一个或多个其它的层。层可通过共挤塑层压在一起或可使用粘合剂粘附在一起。在一个实施方案中,本发明面材具有改进的机器方向Gurley挺度和模切能力,尤其当聚合物膜仅在机器方向上取向时。如果聚合物膜是多层膜,基层仅可被取向或多层膜的所有层可在机器方向上取向。其中仅基层已被机器方向取向的本发明多层膜可通过制备机器方向取向聚丙烯膜和然后在取向聚丙烯层上共挤塑涂布粘接层和第一皮层以形成三层膜而得到。但更常见的是,整个膜在形成之后优选通过共挤塑进行机器方向取向。
在一个实施方案中,多层膜和/或整个多层膜的基层在机器方向上在拉伸比率至少约2∶1,和/或在拉伸比率约3∶1-约9∶1下取向。在另一实施方案中,单或多层膜在机器方向上在比率约4∶1-约6∶1下取向。取向膜随后通常热固或退火以提供尺寸稳定性(即,以防膜的收缩,松弛或任何扭曲)。
面材的厚度是约0.5密耳(12.5微米)-约10密耳(250微米),取决于面材的预期用途。但更常见的是,本发明面材的厚度低于6密耳(150微米)。约1-约6密耳(25-150微米),更通常约1-约4密耳(25-100微米)和最通常约1.5-约2.5密耳(37.5-62.5微米)的面材厚度尤其可用于制备施用到刚性和柔性基材上的标签。如上所述,本发明面材的一个特殊特点在于,非常薄的膜(即,1-2.5密耳,或25-62.5微米)可被制成并可用于形成标签。在此和在说明书和权利要求的其它部分,范围和比率限度可被组合。
膜可由可用于形成聚合物面材和标签的任何聚合物或聚合物组合而制成。聚合物膜可衍生自包括聚苯乙烯,聚烯烃,聚酰胺,聚酯,聚碳酸酯,聚乙烯基醇,聚(乙烯乙烯基醇),聚氨酯,聚丙烯酸酯,聚(乙酸乙烯酯),离聚体和其混合物的聚合物。在一个实施方案中,聚合物膜材料是聚烯烃。在另一实施方案中,聚烯烃膜材料一般特征在于具有例如通过ASTM试验方法1238测定的低于30,更通常低于20,和最通常低于10的熔体指数或熔体流速。本发明的聚合物膜是可整合的。
在一个实施方案中,聚合物膜是(a)丙烯均聚物或共聚物,(b)聚乙烯或(c)(i)丙烯均聚物或聚乙烯和(ii)至少一种丙烯共聚物的共混物。如果使用均聚物和共聚物的共混物,该共混物可包含约5%-约95%均聚物和相应约95%-约5%重量共聚物。可单独在与本文所述丙烯共聚物结合用作基材的丙烯均聚物包括各种丙烯均聚物如具有例如通过ASTM试验D1238,条件L测定的熔体流速(MFR)约1-约20的那些。具有MFR至少约4,或至少约8的丙烯均聚物尤其可用和提供具有改进的模切能力的面材。有用的丙烯均聚物还可特征在于具有密度约0.88-约0.92g/cm3
许多有用的丙烯均聚物可购自各种来源。一些有用的均聚物在下表I中列举和描述。
表I
商品丙烯均聚物
  商品名称   公司   熔体流动g/10min   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
  Z9470   Fina   5.0   0.89
  Z9470HB   Fina   5.0   0.89
  Z9550   Fina   10.0   0.89
  6671×BB   Fina   11.0   0.89
  3576×   Fina   9.0   0.89
  3272   Fina   1.8   0.89
  SF6100   Montell   11.0   0.90
可用于基层的丙烯共聚物一般包含丙烯和最高约40%重量至少一种选自乙烯和包含4-约8个碳原子的α-烯烃的α-烯烃的共聚物。有用的α-烯烃包括乙烯,1-丁烯,1-戊烯,4-甲基-1-戊烯,1-己烯,1-庚烯,和1-辛烯。更通常,采用在本发明中的丙烯共聚物包括丙烯与乙烯,1-丁烯或1-辛烯的共聚物。可用于本发明的丙烯α-烯烃共聚物包括无规以及嵌段共聚物,但无规共聚物一般是优选的。共聚物的共混物以及共聚物与丙烯均聚物的共混物可作为组合物用于基层。在一个优选实施方案中,丙烯共聚物是具有烯属含量约0.2%-约10%重量的丙烯-乙烯共聚物。
在一个实施方案中,乙烯含量是约3%-约10%重量和更优选约3%-约6%重量。对于丙烯-1-丁烯共聚物,最高约15%重量的1-丁烯含量是有用的。在一个实施方案中,1-丁烯含量一般可以是约3%重量至最高约15%重量,和在其它实施方案,该范围可以是约5%-约15%重量。可用于本发明的丙烯-1-辛烯共聚物可包含最高约40%重量1-辛烯。更通常,丙烯-1-辛烯共聚物包含最高约20%重量1-辛烯。
在一个实施方案中,用于本发明的丙烯共聚物通过丙烯与α-烯烃如乙烯或1-丁烯使用单中心金属茂催化剂的共聚反应而得到。对一些有用的市售丙烯共聚物的列举在下表II中找到。可用于本发明的丙烯共聚物具有MFR约1-约20,优选约1-约12。改进的模切能力在丙烯共聚物具有MFR至少约4时得到。
在一个实施方案中,聚合物膜特征在于是透明或晶体透明的。膜是一种在机器方向和截面方向上具有不透明度约10%和雾度约10%或更低的仅机器方向取向的膜。在一个实施方案中,雾度是约5%或更低。膜的不透明度使用TAPPI试验425测定,和雾度按照ASTM试验方法D-1003测定。乙烯在丙烯乙烯共聚物中的百分数和1-丁烯在丙烯-1-丁烯共聚物中的百分数,和在机器方向上的牵引或拉伸比被控制并可改变以提供所需透明性。
一般来说,随着乙烯或1-丁烯在丙烯共聚物中的浓度的增加,膜的雾度下降。例如,如果共聚物膜包含一种包含约5%-约6%乙烯的聚丙烯-乙烯共聚物,透明膜可在约7或更低,和更通常约5或更低的在机器方向上的拉伸比率下得到。如果共聚物是包含约3%-约6%乙烯的丙烯乙烯共聚物,约4或更低的拉伸比率是有用的。尤其是,包含约5.5%乙烯的丙烯-乙烯共聚物当在拉伸比约5∶1下在机器方向上取向时提供透明膜。如果共聚物膜是包含3.2%乙烯的丙烯-乙烯共聚物,约4∶1的拉伸比提供透明膜。透明膜还当包含约8%-14%1-丁烯的丙烯-1-丁烯共聚物在拉伸比率约4∶1-5∶1下拉伸时得到。
在一个实施方案中,聚合物膜包含单层的(a)丙烯均聚物或共聚物和(b)烯烃-丙烯酸烷基酯或甲基丙烯酸烷基酯共聚物的共混物。烯烃可以是包含约2-约8个碳原子的α-烯烃。烷基-丙烯酸酯可以是丙烯酸C1-C8烷基酯或甲基丙烯酸C1-C8烷基酯。在一个实施方案中,烯烃-丙烯酸烷基酯是乙烯-丙烯酸丁酯共聚物。丙烯均聚物或共聚物在共混中的量一般是40-90%重量和烯烃-丙烯酸烷基酯或甲基丙烯酸烷基酯共聚物在共混中的量一般是10-60%重量。
商品丙烯共聚物
  商品名称   来源   %乙烯   %1-丁烯   熔体流速(g/10mins)   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   NA
  SRD4-127   Union Carbide   ----   8   8.0   NA
  SRD4-104   Union Carbide   ----   11   5.0   NA
  SRD4-105   Union Carbide   ----   14   5.0   NA
在本发明另一实施方案中,膜可包含聚乙烯,如低密度,线性低密度,高密度,非常高密度聚乙烯以及乙烯共聚物。在一个实施方案中,聚亚乙基可在机器方向上取向。拉伸比率可以是约2∶1-约9∶1。
膜可包含其它添加剂以调整基层和面材膜的性能。例如,着色剂如TiO2,CaCO3,等可被包括在基层中。少量TiO2的存在例如,得到白色面材。抗粘剂还可被包括在基层中。AB-5是一种得自A.SchulmanInc.,3550 West Market Street,Akron,Ohio 44333的抗粘浓缩物,包含在95%低密度聚乙烯中的5%固体合成无定形硅石。ABPP05SC是一种来自Schulman的抗粘浓缩物,包含在丙烯共聚物中的5%合成无定形硅石。存在于基层中的抗粘剂(硅石)的量可以是约500-约5000ppm,其中约1000ppm的量是优选的。在一些实施方案中,还有利地将柔性聚烯烃加入基层以降低粒度和降低截面方向(CD)分裂。有用的柔性聚烯烃(聚丙烯共聚物)在商品名W-105,W-107,和W-113得自Rexene。
如图2所示,膜可以是多层膜。面材20包括具有上和下表面的基层21。基层21的上表面粘附于皮层24。基层21可直接(这对于共挤出膜是常见的),或间接地通过粘接层或粘合剂层粘附于皮层。基层的下表面粘附于其中具有图像23的全息层22。
本发明的多层膜可进一步包含至少一位于基层和第一皮层之间的粘接层位。粘接层可包含用于提高第一皮层与基层的粘附性的任何聚合物材料。在一个实施方案中,粘接层包含丙烯均聚物或共聚物和软极性添加剂(″SPA″)如乙烯乙酸乙烯酯共聚物(EVA)的混合物。上述可用于基层的任何丙烯均聚物或共聚物可用于粘接层。丙烯聚合物或共聚物和SPA在共混中的重量比可以是约50/50-60/40。软极性添加剂一般包含烯烃和更极性部分的无规共聚物。除了是乙烯乙酸乙烯酯共聚物(EVA)的优选软极性添加剂,粘接层可包括其它软极性添加剂如乙烯丙烯酸甲酯(EMA)和丙烯腈丁二烯橡胶。
粘接层的这些共混的特定例子包括包含50%EVA和50%包含约6%乙烯的无规丙烯共聚物的共混物;60%EVA和40%丙烯均聚物的共混物;和50%EMA和50%丙烯均聚物。可用于本发明的乙烯乙酸乙烯酯共聚物的具体例子是包含18%乙酸乙烯酯和28%乙酸乙烯酯的那些。
粘接层还可包含极性添加剂如乙烯丙烯酸甲酯(EMA)而没有任何其它的丙烯聚合物。有用的市售EMA的例子包括EM-803-115(熔体指数=3.5),EM 806-009(熔体指数=6.0)和EM 802-009(熔体指数=2.0),得自Equistar,1221 McKinney,Houston,Texas 77252。
可单独或与其它热塑性聚合物结合用于皮层的热塑性成膜聚合物包括聚烯烃(线性或支化),聚酰胺,聚苯乙烯,尼龙,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,基于乙烯甲基丙烯酸的钠或锌盐的离聚体,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,和乙烯-乙酸乙烯酯共聚物。第二皮层的热塑性塑料的一些具体例子包括丙烯酸酯如乙烯甲基丙烯酸,乙烯丙烯酸甲酯,乙烯丙烯酸和乙烯丙烯酸乙酯。在一个实施方案中,皮层包含聚乙烯和丙烯均聚物或共聚物的混合物。对用于皮层的特殊聚合物的选择取决于通过存在皮层所要引入的性能和特性。用于皮层的聚合物应该与基层聚合物相容以提供基层在不存在粘接层时的充分粘附。
在图2中,基层21的下表面还粘附于具有全息图像23的全息层22。如上所述,粘附可直接或间接地通过使用粘接层进行。简便起见,反射层没有在图2中给出。如上所述,反射材料可覆盖仅一部分或所有的全息层。
在一个实施方案中,在多层膜本发明面材中通过粘接层粘接到基层上表面上的皮层包含至少一种具有密度约0.940g/cm3或更低的聚乙烯。这些聚乙烯一般在本领域中称作低密度或中密度聚乙烯,和这些聚乙烯均聚物可通过本领域熟练技术人员熟知的技术制备,包括高压,自由基催化工艺和使用金属茂催化剂的工艺。低密度聚乙烯和用于制备这些聚乙烯的金属茂催化工艺描述于U.S.专利5,358,792;5,462,809;5,468,440;5,475,075;和5,530,054。这些专利关于金属茂催化剂,聚乙烯,和用于制备聚乙烯的方法的公开内容在此作为参考并入本发明在此作为参考并入本发明。金属茂-催化聚乙烯一般具有密度约0.850-约0.925g/cm3,和更通常约0.870-约0.920g/cm3
可用于皮层的乙烯均聚物包括具有密度0.850至最高约0.940或更低的那些。具有密度0.850-约0.925g/cm3的聚乙烯一般称作低密度聚乙烯,和具有密度约0.925和0.940的聚乙烯在本领域中称作中密度聚乙烯。可用于皮层的低和中密度聚乙烯还可特征在于具有熔体指数(例如通过ASTM试验D1238,条件E测定)0.5-约25。除了以上密度,和熔体指数,低密度聚乙烯可特征在于拉伸强度约2200-约3200psi(通常约2700psi),和中密度聚乙烯可特征在于具有拉伸强度约3000和约4000psi(通常约3400psi)。低密度或中密度聚乙烯是否用作皮层的确定部分地取决于皮的厚度和面材的总体厚度。较低密度聚乙烯的较厚膜由于低密度聚乙烯的柔软度和相对低拉伸强度而一般是优选的。相反,中密度聚乙烯的内膜可用于本发明面材。
可用于本发明面材的皮层的低和中密度聚乙烯可购自各种来源。
有用的聚乙烯的例子汇总于下表III。
表III
商品聚乙烯
  商品名称   公司   熔体指数(g/10mins)   密度(g/cm3)
  Rexene 1017   Rexene   2.0   0.920
  Rexene 1058   Rexene   5.5   0.922
  Rexene 1080   Rexene   2.0   0.930
  Rexene 2030   Rexene   5.0   0.919
  Rexene 2034   Rexene   7.5   0.925
  Rexene 2038   Rexene   9.0   0.917
  Rexene 2040   Rexene   12.0   0.917
  Rexene 2049   Rexene   20.0   0.917
  NA-334   Equistar   6.0   0.918
  NA-217   Equistar   5.5   0.923
  NA 285-003   Equistar   6.2   0.930
  Exact 3027   Exxon   3.5   0.900
  Exact 3022   Exxon   9.0   0.905
  Exact 3139   Exxon   7.5   0.900
  SLP 9053   Exxon   7.5   0.900
  Affinity PF1140   Dow Chemical   1.6   0.895
皮层也可包含其它添加剂如上述用于基层的抗粘剂。一种或多种抗粘剂在第一皮层中的量可以是约500-约5000ppm,其中约1000ppm的量一般是优选的。
各种成核剂和颜料可被引入本发明的膜配方中。优选成核剂被引入基层和/或粘接层,但不被引入第一皮层。成核剂的加入量应该足以提供晶体结构的所需改性,同时对面材的所需性能没有不利影响。一般理想地采用成核剂以改性晶体结构和提供大量的明显较小晶体或球晶以提高膜的透明度(透明性),和挺度,和模切能力。显然,成核剂加入膜配方的量应该对膜的透明性没有有害影响。迄今用于聚合物膜的成核剂包括无机成核剂和有机成核剂。无机成核剂的例子包括炭黑,硅石,高岭土和滑石。已被建议可用于聚烯烃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,己酸钠,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和铝盐如苯甲酸铝,苯甲酸钠或钾,β-萘酸钠,苯甲酸锂和叔-丁基苯甲酸铝也是有用的有机成核剂。取代的山梨醇衍生物如二(亚苄基)和二(烷基亚苄基)山梨醇(其中烷基基团包含约2-约18个碳原子)是有用的成核剂。更尤其,山梨醇衍生物如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-甲基亚苄基山梨醇是有效地用于聚丙烯的成核剂。有用的成核剂可购自许多来源。Millad 8C-41-10,Millad 3988和Millad3905是得自Milliken Chemical Co.的山梨醇成核剂。
被引入本发明膜配方的成核剂的量一般非常小且是总面材的约100-约2000或4000ppm。优选成核剂的量不应超过约2000ppm,和在一个实施方案中,浓度约300-500ppm时出现最佳值。
在一个实施方案中,面材膜包括在其每个表面上具有皮层的基层。如图3所示,面材30包括具有上和下表面的基层31。基层31的上表面粘附于第一皮层34和下表面粘附于第二皮层35。具有图像33的全息层32粘附于第二皮层35的下表面。反射材料(未示)可涂覆到具有图像33的全息层32的一部分或整个下表面上。
第二皮层35的组成可与第一皮层34相同或不同于第一皮层的组成。在一个实施方案中,第二皮层可基本上由与存在于第一皮层中的相同的聚合物或共混组成,或第二皮层可包含不同的聚合物或共混。尤其有用的多层膜是聚丙烯皮层(聚丙烯和乙烯乙酸乙烯酯(18%乙酸乙烯酯)(重量比75∶25)的一种共混物)和丙烯丁烯共聚物(3.2%丁烯),二氧化钛,和碳酸钙(重量比50∶30∶20)的基层的共挤出产品。
本发明多层膜包括,在一个实施方案中,具有上表面和下表面的基层,和至少通过粘接层粘接到基层上表面上的第一皮层,其中基层包含(a)丙烯均聚物或共聚物,(b)聚乙烯,或(c)丙烯均聚物和至少一种丙烯共聚物的共混物。第一皮层包含(a)丙烯均聚物,或共聚物,(b)聚乙烯,或(c)丙烯均聚物和至少一种丙烯共聚物的共混物。
面材的层可通过各种本领域熟练技术人员已知的技术形成,包括吹塑或铸塑,或挤涂或通过这些技术的组合。U.S.专利5,186,782(Freedman),和U.S.专利5,242,650(Rackovan等人)和5,435,963(Rackovan等人)公开了可用于制备多层膜的步骤,和这些专利在此作为参考完全并入本发明。该层可通过由合适的已知类型的共挤模头同时挤塑而形成,和三层以一种永久结合的状态相互粘附以提供整体共挤物。另外,基层可通过在基材上挤塑基层随后将粘接层和第一皮层共挤塑涂布到基层上而形成,这样形成三层结构,其中这些层以一种永久结合的状态相互粘附以。在另一替代实施方案中,三层可通过挤塑而单独形成和然后通过施加热和压力而层压在一起。
一般,基层相对第一皮层和粘接层较厚。在另一尽管一般不优选的实施方案中,第一皮层可相对基层和粘接层较厚。因此,三层膜的厚度比率可以是约90∶5∶5-5∶5∶90(基层∶粘接层∶第一皮层)。但一般优选的三层膜的厚度比率(基层∶粘接层∶第一皮层)包括90∶5∶5;80∶10∶10;70∶15∶15;85∶5∶10;和80∶5∶15。
如果面材的至少基层,和更优选,整个多层化膜已仅在机器方向上取向,可提高本发明面材的多层膜的理想的性能,尤其对于机器方向Gurley挺度和模切能力。一般,基层和/或整个多层膜在机器方向上在拉伸比率至少约2∶1,和更优选在拉伸比率约3∶1-约9∶1下取向。在另一优选的实施方案中,膜在机器方向上在比率约4∶1-约6∶1下取向。取向膜随后优选热固或退火以提供尺寸稳定性(即,以防膜的收缩,松弛或任何扭曲)。
在一个实施方案中,第二皮层的组成不同于第一皮层的组成,和,在该实施方案中,第二皮层可包含不同于第一皮层所用聚乙烯(包括低和中密度聚乙烯)的聚乙烯或不是具有密度约0.940g/cm3或更低的聚乙烯的热塑性成膜聚合物。可单独或结合用于第二皮层的热塑性成膜聚合物包括聚烯烃(线性或支化),聚酰胺,聚苯乙烯,尼龙,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,基于乙烯甲基丙烯酸的钠或锌盐的离聚体,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,和乙烯-乙酸乙烯酯共聚物。第二皮层的热塑性塑料的具体例子包括丙烯酸酯如乙烯甲基丙烯酸,乙烯丙烯酸甲酯,乙烯丙烯酸和乙烯丙烯酸乙酯。
在一个实施方案中,第二皮层包含聚乙烯和丙烯均聚物或共聚物的混合物。对用于第二皮层的特殊聚合物的选择取决于通过存在第二皮层所要引入的性能和特性。用于第二皮层的聚合物应该与基层的聚合物显然以提供在不存在粘接层时与基层的充分粘附。例如,如果基层包含丙烯聚合物,包含至少一些丙烯聚合物的第二皮层粘附于基层而没有中间粘接层。还已经发现,不同于第一皮层组成的第二皮层组成的使用降低了在面材自身进行辊压时的粘连倾向。
在一个实施方案中,第二皮层包含一种软于用于基层的丙烯聚合物或共聚物,或丙烯聚合物和共聚物的共混物的聚合物,尤其当第二皮层使用粘合剂结合到释放涂覆衬里上时。尤其是,优选的是,第二皮层的材料的拉伸模量低于构成基层的材料的拉伸模量。较低拉伸模量第二皮层的使用导致在与其中第二皮层材料的拉伸模量高于基层材料的面材相比时面材具有改进的模切能力。
在一个实施方案中,可整合的面材包括具有上表面和下表面的聚合物膜,在聚合物膜的上表面上的全息层和在全息层的上表面上的保护层。聚合物膜可以是单层或多层膜。保护层可以是具有与聚合物膜时本文所述的相同的聚合物组成的膜。保护膜可用粘合剂层压到全息层上或可热封到全息层是。另外,保护层可包含施用到全息层上的固化树脂涂层。保护层可向面材提供抗静电性能,耐摩性,UV-阻断性能,等。保护层是透明的和可整合的。
标签原料
包含全息图的上述面材标签。如图4所示,标签40由具有上表面和下表面的聚合物膜41,和具有粘附于聚合物膜41下表面的图像43的全息层42组成。可有可无的反射材料44涂覆在全息层42的下表面上。全息层42(视需要与反射材料)粘附于粘合剂45,后者又可释放地粘附于释放衬里46。
图5说明涉及用于制备粘合剂标签的多层标签原料的本发明另一实施方案。标签原料50包括具有粘附于基层52表面的皮层53和54的多层膜聚合物膜51。第二皮层54还粘附于具有图像56的全息层55。全息层55粘附于粘合剂57,后者又可释放地粘附于释放衬里58。图5的多层膜面材51类似于图3的多层面材。本发明还考虑到粘合剂多层标签原料,包括具有一,两,三或甚至四层的多层膜面材和粘合剂层。这些标签原料可通过将粘合剂层加入图1-3所示的面材而说明,其中粘合剂层分别与图1,2和3中的全息层12,22,和32接触。
在图6所示的另一实施方案中,标签原料60包括具有上表面和下表面的聚合物膜61,具有粘附于聚合物膜61上表面的图像63的全息层62,和粘附于全息层62上表面的保护层64。粘合剂层65粘附于聚合物膜61的下表面和可释放地粘附于释放衬里66。聚合物膜61可以是单层或多层膜。
本发明标签原料一般具有总体厚度最高约20密耳。在一个实施方案中,标签原料的厚度是约0.6密耳-约12密耳。
通常,粘合剂层具有厚度约0.1-约2密耳(2.5-50微米)。适用于本发明标签原料的粘合剂通常是本领域可得的。一般,这些粘合剂包括压敏粘合剂,热活化粘合剂,热熔粘合剂,和类似物。压敏粘合剂是尤其优选的。这些包括丙烯酸基粘合剂以及其它弹性体如天然橡胶或包含苯乙烯,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。压敏粘合剂是本领域熟知的和任何已知的粘合剂可与本发明面材一起使用。在一个优选实施方案中,压敏粘合剂基于丙烯酸酯,如,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。
在最高约160℃(约320)的任何温度下粘性的粘合剂是尤其有用的。在环境温度下粘性的PSAs尤其可用于本发明的共挤出粘合剂结构。可以使用各种常规PSAs,前提是粘度类似于正与粘合剂共挤的聚合物膜材料的粘度或可调整如此。有用的PSA组合物在用于熔体处理的温度下是流体或可抽吸的。另外,粘合剂组合物在所用的温度下在熔体处理和挤塑所需的时间内不应明显降解或胶凝。通常,粘合剂组合物在处理温度下具有粘度1000泊-1,000,000泊。
粘合剂一般可分为以下种类:
无规共聚物粘合剂如基于丙烯酸酯和/或甲基丙烯酸酯共聚物,α-烯烃共聚物,硅氧烷共聚物,氯丁二烯/丙烯腈共聚物,和类似物的那些,
嵌段共聚物粘合剂,包括基于线性嵌段共聚物(即,A-B和A-B-A型),支化嵌段共聚物,星嵌段共聚物,接枝或径向嵌段共聚物,和类似物的那些,和
天然和合成橡胶粘合剂。
对有用的压敏粘合剂的描述可在聚合物科学和工程百科全书,Vol.13.Wiley-Interscience出版社(New York,1988)中找到。对有用的压敏粘合剂的其它描述可在聚合物科学和技术百科全书,Vol.1,Interscience出版社(New York,1964)中找到。
市售压敏粘合剂可用于本发明。这些粘合剂的例子包括作为HM-1597,HL-2207-X,HL-2115X,HL-2193-X得自H.B.FullerCompany,St.Paul,Minn.的热熔压敏粘合剂。其它有用的市售压敏粘合剂包括得自Century粘合剂公司,Columbus,Ohio的那些。
常规PSAs,包括硅氧烷-基PSAs,橡胶-基PSAs,和丙烯酸-基PSAs是有用的。热熔粘合剂的另一商业例子是H2187-01,由AtoFindley,Inc.(Wauwatusa,Wisconsin)销售。另外,描述于U.S.专利3,239,478(Harlan)的橡胶基嵌段共聚物PSAs还可用于本发明的共挤出粘合剂结构,且该专利在此将有关这些热熔粘合剂的公开内容作为参考并入本发明。
在一个优选实施方案中,采用在本发明中的压敏粘合剂包含橡胶基弹性体材料如表示为二嵌段结构A-B,三嵌段A-B-A,径向或偶联结构(A-B)n的线性,支化,接枝,或径向嵌段共聚物,和这些的组合,其中A表示在室温下是非橡胶状或玻璃状或结晶的但在较高温度下上流体的硬热塑性相或嵌段,和B表示在服务温度或室温下是橡胶状或弹性体的软嵌段。这些热塑性弹性体可包含约75%-约95%重量橡胶状链段和约5%-约25%重量非橡胶状链段。
非橡胶状链段或硬嵌段包含单-和多环芳族烃,和更尤其可以是单环或双环性质的乙烯基-取代的芳族烃的聚合物。优选的橡胶状嵌段或链段是脂族共轭二烯的均聚物或共聚物的聚合物嵌段。橡胶状材料如聚异戊二烯,聚丁二烯,和苯乙烯丁二烯橡胶可用于形成橡胶状嵌段或链段。尤其优选的橡胶状链段包括聚二烯和乙烯/丁烯或乙烯/丙烯共聚物的饱和烯烃橡胶。后者橡胶可由相应的不饱和聚亚烷基部分如聚丁二烯和聚异戊二烯通过其氢化而得到。
可以使用的乙烯基芳族烃和共轭二烯的嵌段共聚物包括任何具有弹性体性能的那些。嵌段共聚物可以是二嵌段,三嵌段,多嵌段,星嵌段,聚嵌段或接枝嵌段共聚物。在该说明书和权利要求中,有关嵌段共聚物结构特点的术语二嵌段,三嵌段,多嵌段,聚嵌段,和接枝或接枝-嵌段按照在文献中定义的其正常含义给出,如聚合物科学和工程百科全书,Vol.2,(1985)John Wiley & Sons,Inc.,New York,pp.325-326,和J.E.McGrath的嵌段共聚物,科学技术,Dale J.Meier,Ed.,HarwoodAcademic Publishers,1979,页数1-5。
这些嵌段共聚物可包含各种比率的共轭二烯与乙烯基芳族烃,包括包含最高约40%重量乙烯基芳族烃的那些。因此,可采用线性或径向对称的或非对称的和具有表示为结构式A-B,A-B-A,A-B-A-B,B-A-B,(AB)0,1,2...BA,等的结构的多嵌段共聚物,其中A是乙烯基芳族烃的聚合物嵌段或共轭二烯/乙烯基芳族烃锥形共聚物嵌段,和B是共轭二烯的橡胶状聚合物嵌段。
嵌段共聚物可通过任何熟知的嵌段聚合反应或共聚反应步骤而制成,包括单体的顺序加入,单体的增量加入,或例如描述于U.S.专利3,251,905;3,390,207;3,598,887;和4,219,627的偶联技术。熟知的是,锥形共聚物嵌段可通过共轭二烯和乙烯基芳族烃单体利用其共聚反应性速率差异进行共聚而被引入多嵌段共聚物。各种专利描述了包含锥形共聚物嵌段的多嵌段共聚物的制备,包括U.S.专利3,251,905;3,639,521;和4,208,356,在此作为参考并入本发明。
可用于制备聚合物和共聚物的共轭二烯是包含4-约10个碳原子和更一般,4-6个碳原子的那些。例子包括1,3-丁二烯,2-甲基-1,3-丁二烯(异戊二烯),2,3-二甲基-1,3-丁二烯,氯丁二烯,1,3-戊二烯,1,3-己二烯,等。也可使用这些共轭二烯的混合物。优选的共轭二烯是异戊二烯和1,3-丁二烯。
可用于制备共聚物的乙烯基芳族烃的例子包括苯乙烯和各种取代的苯乙烯如o-甲基苯乙烯,p-甲基苯乙烯,p-叔-丁基苯乙烯,1,3-二甲基苯乙烯,α-甲基苯乙烯,β-甲基苯乙烯,p-异丙基苯乙烯,2,3-二甲基苯乙烯,o-氯苯乙烯,p-氯苯乙烯,o-溴苯乙烯,2-氯-4-甲基苯乙烯,等。优选的乙烯基芳族烃是苯乙烯。
共轭二烯和乙烯基芳族化合物的许多上述共聚物是市售的。嵌段共聚物在氢化之前的数均分子量是约20,000-约500,000,优选约40,000-约300,000。
共聚物内的各个嵌段的平均分子量可在某些限度内变化。在大多数情况下,乙烯基芳族嵌段具有数均分子量约2000-约125,000,和优选约4000-60,000。共轭二烯嵌段在氢化前后具有数均分子量约10,000-约450,000和更优选约35,000-150,000。
另外,在氢化之前,共轭二烯部分的乙烯基含量一般是约10%-约80%,和乙烯基含量优选为约25%-约65%,尤其35%-55%,如果需要改性的嵌段共聚物具有橡胶状弹性。嵌段共聚物的乙烯基含量可利用核磁共振测定。
二嵌段共聚物的具体例子包括苯乙烯-丁二烯(SB),苯乙烯-异戊二烯(SI),和其氢化衍生物。三嵌段聚合物的例子包括苯乙烯-丁二烯-苯乙烯(SBS),苯乙烯-异戊二烯-苯乙烯(SIS),α-甲基苯乙烯-丁二烯-α-甲基苯乙烯,和α-甲基苯乙烯-异戊二烯α-甲基苯乙烯。本发明粘合剂的市售嵌段共聚物的例子包括得自Shell Chemical Company和在下表III中列举的那些。
表III
  Kraton   类型   苯乙烯/橡胶比率(w)   熔体指数
  D1101   线性SBS   31/69   <1
  D1107P   线性SIS   15/85   11
  D1111   线性SIS   22/78   3
  D1112P   线性SIS   15/85   23
  D1113P   线性SIS   16/84   24
  D1117P   线性SIS   17/83   33
  D1320X   多臂(SI)n   10/90   NA
Vector 4111是得自Dexco(Houston,Texas)的SIS嵌段共聚物。
通过氢化包含1,4和1,2异构体的混合物的橡胶状链段的SBS共聚物,得到苯乙烯-乙烯-丁烯苯乙烯(SEBS)嵌段共聚物。类似地,氢化SIS聚合物得到苯乙烯-乙烯丙烯-苯乙烯(SEPS)嵌段共聚物。
嵌段共聚物的选择氢化可通过各种熟知的工艺进行,包括在存在这些催化剂作为Raney镍,贵金属如铂,钯,等,和可溶过渡金属催化剂的情况下氢化。可以使用的合适的氢化工艺是其中含二烯的聚合物或共聚物溶解在惰性烃稀释剂如环己烷中和在存在可溶氢化催化剂的情况下通过与氢反应而氢化的那些。这些步骤描述于U.S.专利3,113,986和4,226,952,在此作为参考并入本发明。嵌段共聚物的这些氢化进行使得,生产出在聚二烯嵌段中的残余不饱和度含量是在氢化之前其原始不饱和度含量的约0.5%-约20%的选择氢化共聚物。
在一个实施方案中,嵌段共聚物的共轭二烯部分是至少90%饱和的和更通常至少95%饱和的,而乙烯基芳族部分不明显氢化。尤其有用的氢化嵌段共聚物是苯乙烯-异戊二烯-苯乙烯的嵌段共聚物如苯乙烯-(乙烯/丙烯)-苯乙烯嵌段聚合物的氢化产物。如果聚苯乙烯-聚丁二烯-聚苯乙烯嵌段共聚物被氢化,聚合物中的1,2-聚丁二烯与1,4-聚丁二烯比率最好是约30∶70-约70∶30。如果这种嵌段共聚物被氢化,所得产物类似乙烯和1-丁烯(EB)的规则共聚物嵌段。如上所述,如果共轭二烯用作异戊二烯,所得氢化产物类似乙烯和丙烯(EP)的规则共聚物嵌段。
许多选择氢化嵌段共聚物可在一般商品名″Kraton G″购自ShellChemical Company。一个例子是Kraton G1652,它是包含约30%重量苯乙烯端嵌段的氢化SBS三嵌段和中嵌段(是乙烯和1-丁烯(EB)的共聚物)。G1652的一种较低分子量变型以品名Kraton G1650得自Shell。Kraton G1651是包含约33%重量苯乙烯的另一SEBS嵌段共聚物。Kraton G1657是包含约13%w苯乙烯的SEBS二嵌段共聚物。该苯乙烯含量低于Kraton G1650和Kraton G1652中的苯乙烯含量。
在另一实施方案中,选择氢化嵌段共聚物具有结构式
Bn(AB)oAp
其中n=0或1;o是1-100;p是0或1;
每个B在氢化之前主要是具有数均分子量约20,000-约450,000的聚合共轭二烯烃嵌段;每个A主要是具有数均分子量约2000-约115,000的聚合乙烯基芳族烃嵌段;A的嵌段占共聚物的约5%-约95%重量;和嵌段B的不饱和度低于约10%原始不饱和度。
在其它实施方案,嵌段B的不饱和度通过氢化而降低至低于其原始值的5%,和氢化嵌段共聚物的平均不饱和度降低至其原始值的低于20%。
嵌段共聚物也可包括例如可通过将α,β-烯属不饱和单羧酸或二羧酸试剂反应到乙烯基芳族烃和共轭二烯的上述选择氢化嵌段共聚物上而得到的官能化聚合物。接枝嵌段共聚物中的羧酸试剂之间的反应可在溶液中或通过熔体工艺在存在自由基引发剂的情况下进行。
的已接枝有羧酸试剂的共轭二烯和乙烯基芳族烃的各种选择氢化嵌段共聚物的制备描述于许多专利,包括U.S.专利4,578,429;4,657,970;和4,795,782,和在此将这些专利涉及共轭二烯和乙烯基芳族化合物的接枝选择氢化嵌段共聚物,和这些化合物的制备的公开内容作为参考并入本发明。U.S.专利4,795,782描述和给出了通过溶液工艺和熔体工艺制备接枝嵌段共聚物的例子。U.S.专利4,578,429包含一个使用2,5-二甲基-2,5-二(t-丁基过氧)己烷通过在双螺杆挤出机中的熔体反应将Kraton G1652(SEBS)聚合物接枝以马来酸酐的例子。(参见栏8,行40-61。)
苯乙烯和丁二烯的市售马来酸化选择氢化共聚物的例子包括来自Shell的Kraton FG1901X,FG1921X,和FG1924X,通常称作马来酸化选择氢化SEBS共聚物。FG1901X包含约1.7%重量的作为琥珀酸酐的键接官能度和约28%w苯乙烯。FG 1921X包含约1%w的作为琥珀酸酐的键接官能度和29%w苯乙烯。FG1924X包含约13%苯乙烯和约1%的作为琥珀酸酐的键接官能度。
有用的嵌段共聚物也可得自Nippon ZeonCo.,2-1,Marunochi,Chiyoda-ku,Tokyo,日本。例如,Quintac 3530得自Nippon Zeon和据信是线性苯乙烯-异戊二烯-苯乙烯嵌段共聚物。
用于形成本发明结构的聚合物膜材料和粘合剂组合物可以是净的,或它们可以是乳液或溶剂-基的。乳液和溶剂-基丙烯酸基PSAs是已知的和相应描述于,例如,U.S.专利No.5,639,811和5,164,444,和这些专利的这些公开内容在此作为参考并入本发明。
本标签原料具有用于良好的分配和基质剥离的足够挺度。多层膜面材在机器方向上的取向增加在机器方向上的拉伸模量,这有助于尺寸稳定性和良好的印刷记录。本发明多层膜面材可在机器方向上通过本领域熟练技术人员熟知的步骤如通过在拉伸比率至少2,和一般在拉伸比率约2-约9下热拉伸多层膜面材而取向。在从软化面材的预加热辊周围经过之后,软化面材随后被拉伸和然后退火或热固,和最后,在急冷辊上冷却以完成热拉伸操作。面材可随后以卷形式收集和储存。
在由按照本发明的上述多层膜面材制造标签原料时,可提供衬里或载体原料。衬里或载体原料可包含例如按照U.S.专利4,713,273(在此作为参考并入本发明)所述制成的多层衬里,或可以是由可以卷形式供给的膜层的单个纸组成的常规衬里或载体。如果它事先不具有释放涂层和本身不包括固有地在其粘合剂-接触面上产生释放表面的组分,衬里或载体可涂有释放涂层(如,硅氧烷)。如果施加释放涂层,它在施用之后通过任何合适的方式干燥或固化。
释放衬里或载体的释放面可涂有一层压敏粘合剂用于随后转移粘合剂至衬里或载体所采用的面材上。如果面材与衬里或载体结合,粘合剂结合到面材上。随后,去除衬里或载体以暴露粘合剂,和粘合剂保持永久地结合到面材上。
在一些情况下,粘合剂层可以是例如用于模内标签场合的热活化粘合剂或热熔粘合剂,这不同于压敏粘合剂。如果粘合剂是热活化粘合剂或热熔粘合剂,无需提供例如在使用压敏粘合剂时所需的用于固有释放能力的释放衬里。
尽管本发明已根据其优选的实施方案描述,可以理解,本领域熟练技术人员在阅读说明书之后可以对其进行各种改进。因此可以理解,本文公开的本发明意味着覆盖落入所附权利要求书范围内的这些改进。

Claims (54)

1.一种包括具有上表面和下表面的聚合物膜,和具有上表面和下表面的全息层的可整合的面材,其中全息层的上表面粘附于聚合物膜的下表面。
2.权利要求1的可整合的面材,其中全息层包含固化铸塑树脂和覆盖在至少一部分铸塑树脂上的反射材料。
3.权利要求2的可整合的面材,其中铸塑树脂中具有至少一种图像。
4.权利要求2的可整合的面材,其中反射材料覆盖铸塑树脂的整个表面。
5.权利要求3的可整合的面材,其中反射材料覆盖其中具有图像的那部分铸塑树脂。
6.权利要求1的可整合的面材,其中聚合物膜选自聚苯乙烯,聚烯烃,聚酰胺,聚酯,聚碳酸酯,聚乙烯基醇,聚(乙烯乙烯基醇),聚氨酯,聚丙烯酸酯,聚(乙酸乙烯酯),离聚体和其混合物。
7.权利要求1的可整合的面材,其中聚合物膜包含聚烯烃。
8.权利要求1的可整合的面材,其中聚合物膜包含单层膜。
9.权利要求1的可整合的面材,其中聚合物膜包括多层膜。
10.权利要求9的可整合的面材,其中多层膜包括具有上表面和下表面的基层,和至少粘接到基层的上表面的第一皮层。
11.权利要求10的可整合的面材,其中基层包含(a)聚乙烯,(b)丙烯均聚物或共聚物,或(c)(i)聚乙烯或丙烯均聚物和(ii)至少一种丙烯共聚物的共混物。
12.权利要求11的可整合的面材,其中基层包含丙烯均聚物。
13.权利要求11的可整合的面材,其中基层的丙烯共聚物包含丙烯和最高为40%重量至少一种选自乙烯和包含4-8个碳原子的α-烯烃的α-烯烃的共聚物。
14.权利要求13的可整合的面材,其中α-烯烃包含乙烯,1-丁烯,或1-辛烯。
15.权利要求10的可整合的面材,其中基层包含(a)丙烯均聚物和(b)丙烯-乙烯或丙烯-1-丁烯共聚物的共混物。
16.权利要求10的可整合的面材,其中皮层包含(a)聚乙烯,(b)丙烯均聚物和(c)丙烯-乙烯或丙烯-1-丁烯共聚物的共混物。
17.权利要求11的可整合的面材,其中基层进一步包含至少一种成核剂。
18.权利要求10的可整合的面材,其中基层在机器方向上在拉伸比率为3∶1-9∶1下取向。
19.权利要求10的可整合的面材,其中基层在机器方向上在拉伸比率至少为2∶1下取向。
20.权利要求1的可整合的面材,其中聚合物膜在机器方向上在拉伸比率为3∶1-9∶1下取向。
21.权利要求9的可整合的面材,其中聚合物膜包含共挤出膜。
22.权利要求10的可整合的面材,进一步包含粘接到基层的下表面上的第二皮层。
23.权利要求22的可整合的面材,其中第二皮层的组成不同于第一皮层的组成。
24.权利要求22的可整合的面材,其中第二皮层的组成基本上与第一皮层的组成相同。
25.权利要求22的可整合的面材,其中第二皮层包含热塑性聚合物。
26.权利要求22的可整合的面材,其中第二皮层包含至少一种选自聚烯烃,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,基于乙烯甲基丙烯酸的钠或锌盐的离聚体,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-乙酸乙烯酯共聚物,和其混合物的聚合物。
27.权利要求22的可整合的面材,其中第二皮层包含聚乙烯和丙烯均聚物或共聚物的混合物。
28.权利要求22的可整合的面材,其中第二皮层通过粘接层粘接到基层的下表面上。
29.权利要求28的可整合的面材,其中第二皮层的组成不同于第一皮层的组成。
30.权利要求28的可整合的面材,其中第二皮层包含至少一种选自聚烯烃,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,基于乙烯甲基丙烯酸的钠或锌盐的离聚体,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-乙酸乙烯酯共聚物,和其混合物的聚合物。
31.权利要求28的可整合的面材,其中聚合物膜在机器方向上在拉伸比率至少为2∶1下取向。
32.权利要求28的可整合的面材,其中聚合物膜包含共挤出膜。
33.权利要求32的可整合的面材,其中聚合物膜在机器方向上在拉伸比率为3∶1-9∶1下取向。
34.权利要求8的可整合的面材,其中聚合物膜包含(a)丙烯均聚物或共聚物和(b)烯烃-丙烯酸烷基酯或甲基丙烯酸烷基酯共聚物的共混物;其中聚合物膜在机器方向取向。
35.权利要求34的可整合的面材,其中(b)的烯烃是包含2-8个碳原子的α-烯烃。
36.权利要求34的可整合的面材,其中(b)的烷基-丙烯酸酯是丙烯酸C1-C8烷基酯或甲基丙烯酸C1-C8烷基酯。
37.权利要求34的可整合的面材,其中(b)是乙烯丙烯酸丁酯共聚物。
38.权利要求1的可整合的面材,其中聚合物膜的厚度为0.5密耳-为10密耳。
39.权利要求1的可整合的面材,其中聚合物膜的厚度低于6密耳。
40.权利要求1的可整合的面材,进一步包括覆盖在全息层的下表面上的保护层。
41.一种用于粘合剂标签的可整合的标签原料,包括:
可整合的面材,所述面材包括具有上表面和下表面的聚合物膜和具有上表面和下表面的全息层,其中全息层的上表面粘附于聚合物膜的下表面;和
具有上表面和下表面的粘合剂层,其中粘合剂层的上表面粘附于全息层的下表面。
42.一种用于粘合剂标签的可整合的标签原料,包括:
可整合的面材,所述面材包括具有上表面和下表面的聚合物膜和具有上表面和下表面的全息层,其中全息层的上表面粘附于聚合物膜的下表面;和
具有上表面和下表面的粘合剂层,其中粘合剂层的下表面粘附于聚合物膜的上表面。
43.权利要求42的可整合的标签原料,进一步包含粘附于全息层的下表面的保护层。
44.权利要求41的可整合的标签原料,其中粘合剂是压敏粘合剂。
45.权利要求42的可整合的标签原料,其中粘合剂是压敏粘合剂。
46.权利要求41的可整合的标签原料,进一步包括可释放地粘附到粘合剂层的下表面上的释放衬里。
47.权利要求42的可整合的标签原料,进一步包括可释放地粘附到粘合剂层的上表面上的释放衬里。
48.一种用于粘合剂标签的可整合的标签原料,包括:
(a)多层可整合的面材,包括具有上表面和下表面的基层,通过粘接层粘接到基层的上表面上的第一皮层,和在基层的下表面上的全息层;其中基层包含(i)丙烯均聚物或共聚物,或(ii)丙烯均聚物和至少一种丙烯共聚物的共混物;
(b)具有上表面和下表面的粘合剂层,其中粘合剂层的上表面粘附结合到全息层上。
49.权利要求48的可整合的标签原料,具有厚度最高为20密耳。
50.权利要求48的可整合的标签原料,具有厚度为0.6-12密耳。
51.权利要求48的可整合的标签原料,进一步包括接触和可释放地结合到粘合剂层的下表面上的释放涂覆衬里。
52.一种由权利要求1的可整合的面材制成的标签。
53.一种由权利要求41的可整合的标签原料模切的压敏粘合剂标签。
54.一种由权利要求42的可整合的标签原料模切的压敏粘合剂标签。
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US6821592B2 (en) 2004-11-23
EP1423262A4 (en) 2007-06-27
PL365064A1 (en) 2004-12-27
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BR0211324A (pt) 2004-09-28
AU2002326492B2 (en) 2008-07-17
CA2449829A1 (en) 2003-02-13
US20030107709A1 (en) 2003-06-12
US20050031824A1 (en) 2005-02-10
BR0211324B1 (pt) 2014-06-10
US7410706B2 (en) 2008-08-12
US20050214558A1 (en) 2005-09-29
WO2003011584A1 (en) 2003-02-13

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