CN110023441A - 适用于可再封闭包装的基于聚1-丁烯聚合物和苯乙烯共聚物的可挤出压敏粘合剂 - Google Patents
适用于可再封闭包装的基于聚1-丁烯聚合物和苯乙烯共聚物的可挤出压敏粘合剂 Download PDFInfo
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- CN110023441A CN110023441A CN201780072176.XA CN201780072176A CN110023441A CN 110023441 A CN110023441 A CN 110023441A CN 201780072176 A CN201780072176 A CN 201780072176A CN 110023441 A CN110023441 A CN 110023441A
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- Prior art keywords
- sensitive adhesive
- pressure
- adhesive composition
- weight
- polymer
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Classifications
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/06905—Using combined techniques for making the preform
- B29C49/0691—Using combined techniques for making the preform using sheet like material, e.g. sheet blow-moulding from joined sheets
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- 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
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- 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
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- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
-
- 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- 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
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
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- B32—LAYERED PRODUCTS
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Abstract
本发明涉及压敏粘合剂组合物,其包含:i)至少一种1‑丁烯(共)聚合物;ii)至少一种液体增粘剂;iii)至少一种固体增粘剂;iv)至少一种苯乙烯共聚物;v)任选存在的至少一种不同于i)和iv)的其它(共)聚合物;vi)任选存在的至少一种添加剂。此外,本发明涉及根据本发明的压敏粘合剂组合物的用途,其用作食品包装单元的封闭构件,用于在微波炉或烘箱中加热的包装单元,用于药物、卫生纸巾、清洁纸巾或化妆纸巾的包装单元的封闭构件。本发明还涉及包含根据本发明的压敏粘合剂组合物的制品和获得所述制品的方法。
Description
技术领域
本发明涉及基于聚1-丁烯(共)聚合物并且进一步包含液体增粘剂、固体增粘剂和苯乙烯共聚物的压敏粘合剂(在下文中称为PSA),所述压敏粘合剂适用于可再封闭(reclosable)包装,特别是用于食品工业。此外,本发明涉及根据本发明的压敏粘合剂组合物的用途,其用作食品包装单元的封闭构件,用于在微波炉(microwave)或烘箱中加热的包装单元,用于药物、卫生纸巾、清洁纸巾或化妆纸巾的包装单元的封闭构件。此外,本发明涉及包含根据本发明的粘合剂作为两个基材之间的粘合剂层的制品以及制备所述制品的方法。
背景技术
WO 2012/052429 A1概括公开了聚1-丁烯(共)聚合物在PSA中的使用。然而,该参考文献仅教导了使用单一的室温固体增粘剂。由此获得的粘合剂适用于可再封闭包装。然而,它们对基材(如PE或PET)的粘合力在初始粘合力、再封闭后的粘合力和粘度方面是中等的(mediocre),而这些性能对于在制备步骤中施加粘合剂是重要的。因此,需要基于聚1-丁烯(共)聚合物的PSA,其具有改善的粘合性能(特别是可再封闭性)以及足够的粘度,并且适用于可再封闭包装。
发明内容
本发明的发明人惊奇地发现,如果PSA包含两种增粘剂,特别是液体增粘剂和固体增粘剂,则可以改善基于聚1-丁烯(共)聚合物的PSA的粘合性,并且可以达到足够的粘度。此外,惊奇地发现,加入苯乙烯共聚物带来改善的可再封闭特性。此外,已经发现,根据本发明的PSA显示出在低温下的高柔性、良好的粘合性和良好的成膜特性,同时对于挤出成型是优异的。
具体实施方案
下面更详细地描述本发明。除非另有明确说明,否则所描述的每个实施方案可以与任何其它一个或多个实施方案组合。特别地,任何被指示为优选或有利的特征可以与任何其它被指示为优选或有利的一个或多个特征组合。
本文所用的单数形式“一种或一个(a和an)”和“所述(the)”应解释为“至少一种或至少一个”。
本文所用的术语“包含(comprising、comprises和comprised of)”与“包括(including、includes)”或“含有(containing、contains)”同义,并且是包括性的或开放式的,并且不排除另外的、未描述的构件、元件或方法步骤。
数值端点的描述包括包含在相应范围内的所有数字和分数,以及所描述的端点。
除非另有定义,否则说明书中使用的所有术语,包括技术和科学术语,都具有本领域普通技术人员通常理解的含义。
在本发明的上下文中,术语“基本上不含”应解释为基于组合物的总重量,相应化合物在组合物中的含量小于5重量%、4重量%、3重量%、2重量%、1.5重量%、1重量%、0.75重量%、0.5重量%、0.25重量%或0.1重量%,其中所述量分别以降序更优选。例如,4重量%比5重量%更优选,3重量%比4重量%更优选。
术语“氢化烃树脂”是指至少95%氢化,优选至少98%,更优选至少99%氢化,最优选完全氢化的烃树脂。
术语“(共)聚合物”包括均聚物、共聚物、嵌段共聚物和三元共聚物。
具体地,本发明涉及:
1.压敏粘合剂组合物,其包含以下物质,优选由以下物质组成:
i)至少一种1-丁烯(共)聚合物;
ii)至少一种液体增粘剂;
iii)至少一种固体增粘剂;
iv)至少一种苯乙烯共聚物;
v)任选存在的至少一种不同于i)和iv)的其它(共)聚合物;
vi)任选存在的至少一种添加剂。
2.根据第1项所述的压敏粘合剂组合物,其中
基于所述1-丁烯(共)聚合物,所述至少一种1-丁烯(共)聚合物具有85-100摩尔%的1-丁烯含量;
更优选地,基于所述1-丁烯(共)聚合物,所述至少一种1-丁烯(共)聚合物具有85-99摩尔%的1-丁烯含量,并且其中共聚单体选自α-烯烃,更优选乙烯和/或丙烯;
和/或优选地,所述1-丁烯(共)聚合物具有至多10,更优选至多5的熔体指数(根据DIN EN ISO 1133-1:2012-03测量;2.16kg,190℃/10min);
和/或优选地,所述1-丁烯(共)聚合物具有低于4的分子量分布Mw/Mn(通过GPC并且使用聚苯乙烯标准品测量);
和/或优选地,所述1-丁烯(共)聚合物具有1-4dL/g,更优选1.5-2.5dL/g的特性粘度(在135℃在四氢化萘中测量);
和/或优选地,所述1-丁烯(共)聚合物具有小于40%,更优选小于30%,最优选小于20%的结晶度(通过X射线测量);
和/或优选地,所述1-丁烯(共)聚合物具有0.899g/cm3或更小,更优选0.895g/cm3或更小,甚至更优选小于0.875g/cm3的密度;
和/或优选地,所述1-丁烯(共)聚合物具有低于90,更优选低于70的肖氏A硬度(根据DIN EN ISO 868:2003-10测量)。
3.根据第2项所述的压敏粘合剂组合物,其中
所述至少一种(在25℃)液体增粘剂具有15-40Pa*s的粘度(用BrookfieldThermosel根据DIN 53019-1:2008-09在140℃测量);
优选地,所述至少一种液体增粘剂是烃树脂;
更优选氢化烃树脂;
最优选地,所述至少一种液体增粘剂包括选自季戊四醇、甘油酯、萜烯酚醛树脂(terpen-phenol resins)、环戊二烯树脂或它们的混合物的化合物;
和/或所述至少一种液体增粘剂具有0-25℃,更优选5-10℃的软化点(根据ASTME28-99测量)。
4.根据第1-3项中任一项所述的压敏粘合剂组合物,其中
所述至少一种(在25℃)固体增粘剂具有0.5-5Pa*s的粘度(用BrookfieldThermosel根据DIN 53019-1:2008-09在140℃测量);
优选地,所述至少一种固体增粘剂是烃树脂;
更优选氢化烃树脂;
最优选地,所述至少一种固体增粘剂包括选自芳族改性树脂、萜烯酚醛树脂、间戊二烯、2-甲基-2-丁烯共聚物、环戊二烯树脂或它们的混合物的化合物;
和/或所述至少一种固体增粘剂具有80-150℃,更优选85-130℃,最优选90-115℃的软化点(根据ASTM E28-99测量)。
5.根据第4项所述的压敏粘合剂组合物,其中在所述组合物中包含至少两种在140℃具有0.5-5Pa*s的粘度的固体增粘剂。
6.根据第1-5项中任一项所述的压敏粘合剂组合物,其中所述至少一种不同于i)和iv)的其它聚合物包括烯烃(共)聚合物,优选α-烯烃(共)聚合物,更优选茂金属催化的α-烯烃(共)聚合物,甚至更优选乙烯或辛烷α-烯烃(共)聚合物,最优选辛烷乙烯α-烯烃共聚物;
和/或其中所述至少一种其它(共)聚合物具有至多100,更优选至多20的熔体指数(根据DIN EN ISO 1133-1:2012-03测量;2.16kg,190℃/10min)。
7.根据第1-6项中任一项所述的压敏粘合剂组合物,其中所述至少一种添加剂包括选自以下的化合物:增塑剂,如聚异丁烯或油;蜡,如石蜡和微晶蜡以及它们的氢化形式、费-托蜡(fischer-tropsch-wax);稳定剂,如紫外线稳定剂;和改性剂,如乙烯、丙烯酸酯和马来酸酐的三元共聚物;抗氧化剂或它们的混合物。
8.根据第1-7项中任一项所述的压敏粘合剂组合物,其中所述组合物在200℃具有300-2,000Pa*s,更优选600-1600Pa*s,最优选800-1500Pa*s的粘度(用BrookfieldThermosel根据DIN 53019-1:2008-09在200℃测量)。
9.根据第1-8项中任一项所述的压敏粘合剂组合物,其中当所述组合物用作两个基材之间的20μm厚的粘合剂层时,在将所述两个基材彼此剥离时,所述组合物具有5-8N/15mm,优选6N/15mm的粘合力,并且在将所述两个基材再次压在一起之后,所述组合物具有0.5-2N/15mm,优选1N/15mm的粘合力(根据DIN EN ISO 11339:2010-06测量),优选地,所述基材基于聚乙烯(PE)、聚丙烯(PP)、取向聚丙烯(OPP)、聚对苯二甲酸乙二醇酯(PET)、无定形聚对苯二甲酸乙二醇酯(APET)及它们的改性材料。
10.根据第1-9项中任一项所述的压敏粘合剂组合物,其中所述苯乙烯共聚物是基于所述苯乙烯共聚物的总重量,苯乙烯含量为8-12重量%的苯乙烯嵌段共聚物,和/或其中所述苯乙烯共聚物选自苯乙烯-丁二烯-苯乙烯(SBS)、苯乙烯-乙烯-丙烯(SEP)、苯乙烯-异戊二烯-苯乙烯(SIS)、苯乙烯-乙烯/丁烯-苯乙烯(SEBS)和苯乙烯-异戊二烯/丁二烯-苯乙烯(SIBS)共聚物,更优选地,这些苯乙烯共聚物是嵌段共聚物,甚至更优选SIS嵌段共聚物,最优选星形SIS嵌段共聚物。
11.根据第1-10项中任一项所述的压敏粘合剂组合物,其中基于所述压敏粘合剂组合物的总重量,所述组合物包含以下物质,优选由以下物质组成:
35-74重量%,优选40-60重量%的i);
5-50重量%,优选8-40重量%,更优选9-20重量%的ii);
10-50重量%,优选15-40重量%,更优选20-35重量%的iii);
3-40重量%,优选5-30重量%,更优选8-25重量%的iv);
0-30重量%,优选1-25重量%,更优选5-20重量%的v);以及
0-30重量%,优选0.1-20重量%,更优选1-15重量%的vi)。
12.根据第1-11项中任一项所述的压敏粘合剂组合物的用途,其用作食品(如奶酪、香肠、肉)包装单元的封闭构件,用于在微波炉或烘箱中加热的包装单元,用于药物、卫生纸巾、清洁纸巾或化妆纸巾的包装单元的封闭构件。
13.制品,其包含根据第1-11项中任一项所述的组合物作为两个基材之间的粘合剂层;优选其中所述基材材料独立地选自PE、低密度聚乙烯(LDPE)或PET基材,更优选其中两个基材均为PE、LDPE或PET基材,最优选其中一个基材是PE并且另一个基材是PET。
14.根据第13项所述的制品,其中所述粘合剂层具有5-30μm,优选10-25μm,更优选13-20μm的厚度。
15.根据第13或14项所述的制品,其中所述制品是包装单元,优选食品包装单元,更优选可再封闭包装单元,最优选可再封闭的食品包装单元。
16.根据第13或14项所述的制品,其中所述制品是用于药物、卫生纸巾、清洁纸巾或化妆纸巾的包装单元,优选用于药物、卫生纸巾、清洁纸巾或化妆纸巾的可再封闭包装单元。
17.制备根据第13-16项中任一项所述的制品的方法,其包括以下步骤:
i)通过吹塑薄膜机头(blow film head)形成根据第1-11项中任一项所述的压敏粘合剂组合物的膜;
ii)使步骤i)形成的膜作为中间层与另外两层接触。
根据本发明的至少一种1-丁烯(共)聚合物i)可以例如通过WO 2012/052429 A1中公开的任何一种方法获得。商购获得的1-丁烯(共)聚合物可例如以商品名Koattro,如Koattro KT MR05从Lyondell Basell购得。在包含共聚物或三元共聚物的实施方案中,基于相应聚合物的总单体含量,1-丁烯单体的含量优选为至少55%,更优选至少60%,最优选至少80%。
根据本发明的至少一种液体增粘剂ii)可选自液体烃树脂和氢化烃树脂、液体聚苯乙烯、液体松香酯、液体多萜烯、来自聚合的和氢化的C9烃流(streams)的液体树脂;来自聚合的和氢化的二环戊二烯物质的液体树脂;来自聚合的和氢化的纯单体物质(例如苯乙烯、乙烯基甲苯、α-甲基苯乙烯)的液体树脂。液体增粘树脂包括下述液体烃树脂,所述液体烃树脂包含主要衍生自含有4至6个碳原子的脂族石油衍生物流(包括二烯烃和单烯烃)的聚合结构。该聚合产物可以任选地进一步氢化。示例性液体增粘剂(具有低于25℃的环球软化点)包括多萜烯,例如可从Sartomer商购获得的Wingtack 10和可从ExxonMobilChemical商购获得的Escorez 2520。
另一种有用的液体增粘剂主要包括已经聚合和氢化的环戊二烯物质。这种增粘树脂可从Exxon Chemical Company作为ECR-327商购获得。另一种液体增粘树脂是通过包含苯乙烯、乙烯基甲苯和α-甲基苯乙烯的纯单体原料聚合和氢化产生的树脂,例如可从Eastmann Chemical Company作为Regalrez 1018购得的树脂。另一种有用的液体增粘树脂是聚合的α-蒎烯树脂,其软化点约为25℃,可从Arizona Chemical Company作为ZonarezA-25购得。
在优选实施方案中,通过使用聚苯乙烯标准品的GPC测量,所述至少一种液体增粘剂的数均分子量为150-1000g/mol,优选250-950g/mol,更优选300-900g/mol。
根据本发明的至少一种固体增粘剂iii)可选自脂族烃树脂、芳族改性脂族烃树脂、氢化聚环戊二烯树脂、聚环戊二烯树脂、脂松香、脂松香酯、木松香、木松香酯、妥尔油松香、妥尔油松香酯、多萜烯、芳族改性多萜烯、萜烯酚醛树脂(terpene phenolics)、芳族改性氢化聚环戊二烯树脂、氢化脂族树脂、氢化脂族芳族树脂、氢化萜烯和改性萜烯、氢化松香酸和氢化松香酯。在一些实施方案中,所述增粘剂是氢化的。
在优选实施方案中,所述至少一种固体增粘剂是非极性的,这表明所述增粘剂基本上不含具有极性基团的单体。
用作增粘剂或改性剂的优选的烃树脂包括:
树脂,例如C5/C6萜烯树脂、苯乙烯萜烯、α-甲基苯乙烯萜烯树脂、C9萜烯树脂、芳族改性C5/C6、芳族改性环状树脂、芳族改性二环戊二烯基树脂或它们的混合物。通常,这些树脂是通过含有一种或多种以下单体的组合物的阳离子聚合获得的:C5二烯烃(例如1-3戊二烯、异戊二烯等);C5烯烃(例如2-甲基丁烯、环戊烯等);C6烯烃(例如己烯)、C9乙烯基芳族化合物(例如苯乙烯、α-甲基苯乙烯、乙烯基甲苯、茚、甲基茚等);环状化合物(例如二环戊二烯、甲基二环戊二烯等);和/或萜烯(例如苎烯、蒈烯等)。在该段中,C是指碳原子。例如,C5表示5个碳原子。
通过以下方法获得树脂:二环戊二烯的热聚合,任选地与乙烯基芳族化合物(例如苯乙烯、α-甲基苯乙烯、乙烯基甲苯、茚、甲基茚)热聚合;和/或环戊二烯和/或甲基环戊二烯的二聚物或低聚物的热聚合,任选地与乙烯基芳族化合物(例如苯乙烯、α-甲基苯乙烯、乙烯基甲苯、茚、甲基茚)热聚合。在聚合和分离未反应的材料之后获得的树脂优选进行氢化。
在优选实施方案中,组合物包含至少两种固体增粘剂。在更优选的实施方案中,第一固体增粘剂包含氢化烃树脂,第二增粘剂包含松香。
使用氢化烃树脂作为增粘剂(固体以及液体)使得与本发明的聚合物i)的相容性提高。在另一优选实施方案中,增粘剂ii)和iii)基本上不含芳族改性增粘剂。
所述至少一种苯乙烯共聚物可以是技术人员已知的任何苯乙烯共聚物。合适的苯乙烯共聚物包括热塑性弹性体。合适材料的说明性实例是苯乙烯-丁二烯-苯乙烯(SBS)、苯乙烯-乙烯-丙烯(SEP)、苯乙烯-异戊二烯-苯乙烯(SIS)、苯乙烯-乙烯/丁烯-苯乙烯(SEBS)和苯乙烯-异戊二烯/丁二烯-苯乙烯(SIBS)共聚物,更优选地,这些苯乙烯共聚物是嵌段共聚物,甚至更优选SIS嵌段共聚物,最优选星形SIS嵌段共聚物。此类共聚物例如可从KratonPolymer Group以通用商品名“Kraton”,例如Kraton D-1102、Kraton HT 1200KT-N商购获得。三元共聚物也是本发明的合适材料。Kraton Polymer Group出售的一种这样的三元共聚物是“Tacky G”。这种三元共聚物是在主链上具有接枝SI二嵌段的SEBS嵌段共聚物。
苯乙烯-丁二烯和苯乙烯-异戊二烯嵌段共聚物可以是对应于一般构型A-B-A或A-B-A-B-A的线性共聚物,或对应于一般构型(AB-)n的自由基共聚物,其中聚合物嵌段A是非弹性的含苯乙烯的聚合物嵌段,并且聚合物嵌段B是弹性的含丁二烯或含异戊二烯的聚合物嵌段。“n”是(AB-)嵌段重复的整数。
在本发明的一个优选实施方案中,优选使用线性苯乙烯-丁二烯嵌段共聚物。苯乙烯-丁二烯嵌段共聚物和苯乙烯-异戊二烯嵌段共聚物各自包含至少约25重量%,优选约25重量%至约50重量%,更优选约35重量%至约45重量%的苯乙烯。苯乙烯-丁二烯嵌段共聚物和苯乙烯-异戊二烯嵌段共聚物各自具有约3至约50,优选约8至约40的熔体流动指数(通过ASTM-D 1238-95测定)。用于制备物理共混物的丁二烯-异戊二烯嵌段共聚物与苯乙烯-异戊二烯嵌段共聚物的比率可以概括地在约1:3至约3:1重量份的范围内,优选为约1:1。
在本发明的另一优选实施方案中,苯乙烯共聚物是星形嵌段共聚物,更优选星形SIS嵌段共聚物。基于苯乙烯共聚物的总重量,这些共聚物的苯乙烯含量优选为8-12重量%。US 4077893、US 4116917、US 4141847和US 4427834公开了示例性星形苯乙烯共聚物及其制备方法,这些专利通过引用并入本文。
苯乙烯共聚物的使用提高了可再封闭特性。
任选存在的至少一种不同于i)和iv)的其它聚合物v)包括烯烃(共)聚合物。示例性的商购获得的共聚物以商品名Vistamaxx、Infuse、Affinity和Engage由Dow ChemicalCompany和ExxonMobil出售。这些烯烃(共)聚合物是热熔体领域的技术人员公知的。示例性聚合物及其制备方法描述于WO 2005/108442 A1、WO 2005/113622 A1、WO 2004/046214和US20150065638 A1中。
PSA通过公知的捏合机或挤出方法获得。当使用吹塑挤出膜(blow extrusion-film)技术时,有利的是,PSA在200℃的粘度为300-2,000Pa*s,更优选在200℃为600-1,600Pa*s,最优选在200℃为800-1500Pa*s,所述粘度用Brookfield Thermosel根据DIN53019-1:2008-09在200℃测量。
待粘合的基材的材料优选为PE(聚乙烯)、LDPE(低密度聚乙烯)、PP(聚丙烯)、OPP(取向聚丙烯)、PET(聚对苯二甲酸乙二醇酯)、APET(无定形PET)、CPET(结晶PET)。材料可以被修饰,例如含有压印(imprint)。
实施例
使用以下化合物:
Koattro KT MR 05:来自Lyondell Basell的聚1-丁烯共聚物
LR 1:来自Eastman的液体树脂Regalite R1010,氢化烃树脂
SR 1:来自Eastman的固体树脂Regalite R 1090,氢化烃树脂,软化点为85-91℃(环球法;根据ASTM E 28测量)
SR 2:来自ExxonMobil的Escorez 2203,增粘树脂,软化点为约93℃(环球法;根据ASTM E 28测量)
SCOP:Kraton HT 1200KT,苯乙烯-异戊二烯-苯乙烯星形嵌段共聚物
可再封闭性的测试方法:分别制备具有下述组成的PSA。将化合物作为在环己烷中的15%溶液回流6小时。用涂布刀将混合物涂布在PE上(300μm),并在室温下干燥1天,随后在90℃干燥1小时。干燥层(干燥层的厚度约20μm)粘合在PE上,卷起25mm厚的条带。24小时后测量粘合力并测量初始值。在测量之后立即再次卷起条带(用1kg辊),并测量粘合力。重复该步骤三次。根据DIN EN ISO 11339:2010-06测量粘合力(单位N/25mm;测量300mm/Min)。在第四步骤中评估了表1中给出的可再封闭性。
表1:根据本发明的实施例,所有数字均指基于粘合剂的总重量的重量%
化合物 | 实施例1 | 比较例2 | 比较例3 |
Koattro KT MR 05 | 40 | 60 | 60 |
LR 1 | 9.5 | 9.5 | 9.5 |
SR 1 | 30.0 | ||
SR 2 | 30.0 | 30.0 | |
SCOP | 20.0 | - | - |
稳定剂 | 0.5 | 0.5 | 0.5 |
粘度(200℃) | ++ | ++ | + |
可再封闭性 | ++ | o | + |
结果以--(坏)、-(不足)、o(可接受)、+(良好)、++(非常好)给出
根据本发明的实施例1显示出非常好的粘度,同时具有非常好的可再封闭性。相反,比较例仅具有可接受的或良好的可再封闭性。
Claims (14)
1.压敏粘合剂组合物,其包含:
i)至少一种1-丁烯(共)聚合物;
ii)至少一种液体增粘剂;
iii)至少一种固体增粘剂;
iv)至少一种苯乙烯共聚物;
v)任选存在的至少一种不同于i)和iv)的其它(共)聚合物;
vi)任选存在的至少一种添加剂,其中
基于所述1-丁烯(共)聚合物的总单体含量,所述至少一种1-丁烯(共)聚合物具有至少55%的1-丁烯含量。
2.根据权利要求1所述的压敏粘合剂组合物,其中所述至少一种液体(在25℃)增粘剂ii)在140℃具有15-40Pa*s的粘度。
3.根据权利要求1或2所述的压敏粘合剂组合物,其中所述至少一种固体(在25℃)增粘剂iii)在140℃具有0.5-5Pa*s的粘度。
4.根据权利要求3所述的压敏粘合剂组合物,其中在所述组合物中包含至少两种在140℃具有0.5-5Pa*s的粘度的固体增粘剂iii)。
5.根据权利要求1-4中任一项所述的压敏粘合剂组合物,其中所述至少一种不同于i)和iv)的其它聚合物包括烯烃(共)聚合物。
6.根据权利要求1-5中任一项所述的压敏粘合剂组合物,其中所述至少一种添加剂包括选自以下的化合物:增塑剂;蜡;稳定剂;和改性剂;抗氧化剂或它们的混合物。
7.根据权利要求1-6中任一项所述的压敏粘合剂组合物,其中所述组合物在200℃具有300-2,000Pa*s的粘度。
8.根据权利要求1-7中任一项所述的压敏粘合剂组合物,其中当所述组合物用作两个基材之间的20μm厚的粘合剂层时,在将所述两个基材彼此剥离时,所述组合物具有5-8N/15mm的粘合力,并且在将所述两个基材再次压在一起之后,所述组合物具有0.5-2N/15mm的粘合力。
9.根据权利要求1-8中任一项所述的压敏粘合剂组合物,其中基于所述压敏粘合剂组合物的总重量,所述组合物包含:
35-74重量%的i);
5-50重量%的ii);
10-50重量%的iii);
3-40重量%的iv);
0-30重量%的v);以及
0-30重量%的vi)。
10.根据权利要求1-9中任一项所述的压敏粘合剂组合物的用途,其用作食品包装单元的封闭构件,用于在微波炉或烘箱中加热的包装单元,用于药物、卫生纸巾、清洁纸巾或化妆纸巾的包装单元的封闭构件。
11.制品,其包含根据权利要求1-9中任一项所述的组合物作为两个基材之间的粘合剂层。
12.根据权利要求11所述的制品,其中所述制品是包装单元。
13.根据权利要求11所述的制品,其中所述制品是用于药物、卫生纸巾、清洁纸巾或化妆纸巾的包装单元。
14.制备根据权利要求11-13中任一项所述的制品的方法,其包括以下步骤:
i)通过吹塑薄膜机头形成根据权利要求1-10中任一项所述的压敏粘合剂组合物的膜;
ii)使步骤i)形成的膜作为中间层与另外两层接触。
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CN110591617B (zh) * | 2019-08-20 | 2022-02-08 | 佛山南宝高盛高新材料有限公司 | 一种立体芯体成型热熔胶及其制备方法与应用 |
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ES2749111T3 (es) | 2020-03-19 |
PL3323866T3 (pl) | 2020-01-31 |
RU2019119220A3 (zh) | 2020-12-24 |
US20190264075A1 (en) | 2019-08-29 |
EP3323866A1 (en) | 2018-05-23 |
JP6957619B2 (ja) | 2021-11-02 |
JP2020513439A (ja) | 2020-05-14 |
RU2752564C2 (ru) | 2021-07-29 |
CN110023441B (zh) | 2022-03-01 |
RU2019119220A (ru) | 2020-12-24 |
PT3323866T (pt) | 2019-08-21 |
EP3323866B1 (en) | 2019-07-24 |
WO2018095744A1 (en) | 2018-05-31 |
KR20190087489A (ko) | 2019-07-24 |
US11485884B2 (en) | 2022-11-01 |
KR102395335B1 (ko) | 2022-05-06 |
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