CN107001882A - 用于聚烯烃膜的热熔性粘合剂 - Google Patents
用于聚烯烃膜的热熔性粘合剂 Download PDFInfo
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- CN107001882A CN107001882A CN201580066528.1A CN201580066528A CN107001882A CN 107001882 A CN107001882 A CN 107001882A CN 201580066528 A CN201580066528 A CN 201580066528A CN 107001882 A CN107001882 A CN 107001882A
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- Prior art keywords
- weight
- polyolefin
- hot
- melt adhesive
- resin
- Prior art date
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 60
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- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 20
- -1 adhesion promotor Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000004806 packaging method and process Methods 0.000 claims abstract description 16
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- 239000002759 woven fabric Substances 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000000945 filler Substances 0.000 claims abstract description 4
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- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 229920013639 polyalphaolefin Polymers 0.000 claims description 10
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 9
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- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 8
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 8
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
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- 125000003118 aryl group Chemical group 0.000 claims description 4
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
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- XPVIQPQOGTVMSU-UHFFFAOYSA-N (4-acetamidophenyl)arsenic Chemical compound CC(=O)NC1=CC=C([As])C=C1 XPVIQPQOGTVMSU-UHFFFAOYSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
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- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 2
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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
-
- 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
- B32B1/00—Layered products having a non-planar shape
-
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Abstract
本发明涉及一种热熔性粘合剂,其含有a)25至95重量%,优选50至85重量%的至少一种基于聚烯烃的聚合物;b)1至75重量%,优选1至40重量%的至少一种增粘树脂;c)0至15重量%的至少一种增塑剂;和d)0至30重量%的至少一种添加剂和/或助剂,其选自稳定剂、粘合促进剂、填料或颜料、蜡和/或其他聚合物或其任意组合,其特征在于,所述至少一种基于聚烯烃的聚合物是以下物质的混合物:a1)相对于所述基于聚烯烃的聚合物的总量,20至80重量%的量的至少一种分子量Mn<10,000g/mol的第一基于聚烯烃的聚合物,以及a2)相对于所述基于聚烯烃的聚合物的总量,20至80重量%的量的至少一种分子量Mn>10,000g/mol的第二基于聚烯烃的聚合物。本发明还涉及所述热熔性粘合剂用于胶合膜状基材,特别是聚烯烃膜、织织物或无纺织物的用途。本发明还涉及使用本发明的热熔性粘合剂制造包装的具体方法以及由所述方法得到的包装。
Description
本发明涉及用于胶合膜状基材、机织织物或无纺织物,特别是聚烯烃膜的热熔性粘合剂,与其他添加剂一起,基于聚烯烃基聚合物进行制造,得到具有改善的迁移性能的热熔性粘合剂。此外,描述了这种热熔性粘合剂和含有这些粘合剂的产品和/或可以使用这些粘合剂制造的产品的合适用途。本发明还涉及使用本发明的特定热熔性粘合剂制造由聚烯烃膜制成的包装的方法。
由聚烯烃制成的市售袋和小袋通常通过热焊接彼此叠置的两个塑料网,或者通过将彼此叠置的两个塑料网粘在两侧(侧缝)上以及底部(底盖)上来制造。
多年来,在袋和小袋的制造过程中,已经使用基于苯乙烯-异戊二烯-苯乙烯和苯乙烯-丁二烯-苯乙烯橡胶的压敏粘合剂来胶合这些基于聚烯烃的材料。
由于难以胶合的基于聚烯烃的材料和在-20℃至80℃的宽温度范围内的粘合和凝聚性的严格要求,必须在这些橡胶中加入大量的助剂以提高它们的粘合,因为没有这种助剂,粘合的质量不足。尤其是,粘合剂树脂和油在这里用作助剂。
粘合剂树脂可以是化学上非常多样的物质,但它们通常是松香酸(松香)的酯或萜烯酚醛树脂。一方面,矿物油-石蜡油,和另一方面所谓的环烷油已经被证明特别适合于实现这些橡胶粘合剂的足够柔软和表面粘性的膜。
然而,先前使用的橡胶粘合剂在许多方面是不利的。一方面,它们需要大量基于石油原料的特殊树脂,这些原料的可用性常常受到限制。此外,这些树脂的合成是昂贵的。鉴于这些事实,这些树脂在成本方面是不利的。此外,它们具有特有的内在气味,可以传递到袋/小袋的内容物,特别是在食品工业中是不受欢迎的。
而且,使用的油也有严重的缺点。与树脂类似,它们基于原油,因此在成本和资源减少方面已经是不利的。此外,它们含有大量化合物,特别是包括多环芳烃级分,这些化合物被传递到填充的产品,因此对消费者,尤其是在食品和制药领域具有很高的潜在危害。在这种情况下,特别不利的是,由于即使在室温下它们的低分子量和低极性,这些油是非常低粘度的液体,因此即使在与树脂和聚合物混合时也保持高迁移能力。这种迁移能力既指胶合材料的渗透性,也指渗透到填充产品中。
因此,需要另外的粘合剂,其中可以减少或甚至完全避免使用这些助剂,以为消费者确保更好的产品安全性。然而,同时,所使用的粘合剂应该具有与已知粘合剂相当的粘合效果(粘合/凝聚)和柔性。
本发明通过提供基于基于聚烯烃的聚合物的新型粘合剂,特别是热熔性粘合剂来解决这个问题。
因此,在第一方面,本发明涉及热熔性粘合剂,其含有
a)25至95重量%,优选50至85重量%的至少一种基于聚烯烃的聚合物;
b)1至75重量%,优选1至40重量%的至少一种增粘树脂;
c)0至15重量%的至少一种增塑剂;和
d)0至30重量%的至少一种添加剂和/或助剂,其选自稳定剂、粘合促进剂、填料或颜料、蜡和/或其他聚合物或其任意组合,
其特征在于,所述至少一种基于聚烯烃的聚合物是以下的混合物:
a1)相对于所述基于聚烯烃的聚合物的总量,20至80重量%的量的至少一种分子量Mn<10,000g/mol的第一基于聚烯烃的聚合物,以及
a2)相对于所述基于聚烯烃的聚合物的总量,20至80重量%的量的至少一种分子量Mn>10,000g/mol的第二基于聚烯烃的聚合物。
另一方面,本发明还涉及根据本发明的热熔性粘合剂用于胶合膜状基材,特别是聚烯烃膜、机织织物或无纺织物的用途。
本发明的另一方面涉及制造由聚烯烃膜制成的包装的方法,特别是由聚烯烃制成的小袋,其包括以纵向和/或底部胶合的方式,对至少两个聚烯烃膜进行部分表面粘合,根据本发明的热熔性粘合剂用于胶合。本发明还涉及用于制造胶合的机织织物或无纺织物的方法,其包括对至少两个基材进行部分表面或全表面胶合,其特征在于至少一个基材是机织织物或无纺织物,并且根据本发明的热熔性粘合剂用于胶合。
最后,在另一方面,本发明还涉及由聚烯烃膜制成的包装,特别是袋或小袋,其包括由根据本发明的方法可获得的聚烯烃制成的一种或多种膜。
通过研究以下详细描述,本发明的这些和其他方面、特征和优点对于本领域技术人员将变得显而易见。本发明的一个方面的任何特征可用于本发明的任何其他方面。此外,容易理解,本文包含的实施例旨在描述和说明而不是限制本发明,并且特别地,本发明不限于这些实施例。除非另有说明,显示的所有百分比均为重量百分比。以“从x到y”的格式表示的数值范围也包括提到的值。如果以这种格式表示多个优选的数值范围,则不言而喻,也包括由各端点的组合产生的所有范围。
除非另有说明,本文中指出的分子量是指数均分子量(Mn)。分子量Mn可以根据端基分析(根据DIN 53240-1:2013-06的羟基数),或用THF作为洗脱液,通过根据DIN 55672-1:2007-08的凝胶渗透色谱法(GPC)来确定。除非另有说明,所列分子量是通过GPC测定的分子量。如前所述,重均分子量Mw也可以通过GPC测定。
本文所用的“至少一个”是指1个或多个,即1、2、3、4、5、6、7、8、9或更多个。对于成分,所述表述是指成分的类型,而不是分子的绝对数量。因此,“至少一种树脂”是指至少一种类型的树脂,例如可以使用一种类型的树脂或几种不同树脂的混合物。与重量数据一起,所述表述是指包含在组合物/混合物中所含的所指示类型的所有化合物,即组合物不含有超过所指示量的相应化合物的任何其他化合物。
本发明的热熔性粘合剂含有至少一种基于聚烯烃的聚合物,相对于其总重量,所述聚合物含有20至80重量%的量的至少一种分子量Mn<10,000g/mol的第一基于聚烯烃的聚合物,和20至80重量%的量的至少一种分子量Mn>10,000g/mol的第二基于聚烯烃的聚合物,总和为100%。在更优选的实施方案中,本发明的热熔性粘合剂含有至少一种基于聚烯烃的聚合物,相对于其总重量,所述聚合物含有50至80重量%的至少一种分子量Mn<10,000g/mol的第一基于聚烯烃的聚合物和20至50重量%的至少一种分子量Mn>10,000g/mol的第二基于聚烯烃的聚合物,其总和为100%。
在优选的实施方案中,在根据本发明的热熔性粘合剂中,a1)的Mn为<10,000g/mol,a2)的Mn>25,000g/mol;更优选的是,a1)的Mn为<9000g/mol,a2)的Mn为>50,000g/mol,最优选的是,a1)的Mn为<8,000g/mol,a2)的Mn为>100,000g/mol。在其他优选实施方案中,除了上述范围之外,a1)的下限为1,000g/mol,a2)的上限为500,000g/mol。
作为基于聚烯烃的聚合物,聚烯烃的均聚物和共聚物特别优选选自聚-α-烯烃,优选基于乙烯、丙烯和/或丁烯的无规立构聚-α-烯烃(APAO),和乙烯/α-烯烃和丙烯/α-烯烃共聚物,优选乙烯和丙烯、1-丁烯、1-己烯、1-辛烯的共聚物,或其任意组合。
根据本发明合适的共聚物可以是嵌段共聚物,并且嵌段可以任选地具有不同的单体组成。
在优选的实施方案中,基于聚烯烃的聚合物的特征在于它们具有窄的分子量分布。以Mw/Mn表示的分子量分布应优选为2.5,更优选小于2.3。这些聚合物在文献中是已知的,可以从各制造商商购获得。
在例如专利申请EP 0912646 A1、WO 00/00565A1、WO 2001/46277 A2、WO 2006/102150 A2、WO 2005/090426A1、WO 2010/026172 A1和WO 2010/070046 A1,以及US6586543 B1中描述了乙烯/丙烯与至少一种(C3至C20)-α-烯烃单体,特别是茂金属催化的聚合物一起的合适的共聚物。这种共聚物可商购获得,例如商品名为Infuse TM(Dow ChemicalCorporation)的烯烃嵌段共聚物,特别是Infuse TM 9807或9808或Queo TM(Borealis),特别是Queo TM 8230。其他合适的烯烃塑性体也可以以商品名VistamaxxTM(Exxon)和AffinityTM(Dow Chemical Company)得到。得自Evonik的商品名为的聚-α-烯烃也适用于本发明。
根据本发明的热熔性粘合剂还含有至少一种树脂。树脂旨在增粘基础聚合物。相对于热熔性粘合剂的总重量,其通常以1至75重量%,特别是1至40重量%的量使用。根据本发明,优选选择的树脂的量尽可能少,例如在热熔性粘合剂的总重量的1至10重量%的范围内。
原则上,可以使用已知的树脂,例如芳族、脂族或脂环族烃树脂,其各自也是完全或部分水合的形式,以及改性或水合的天然树脂。可用于本发明的合适的树脂包括脂环族烃树脂、萜烯树脂如三元共聚物或萜烯共聚物、基于松香的天然树脂或妥尔油树脂,包括其衍生物,例如其甲基、季戊四醇,或甘油酯,其他改性天然树脂,例如来自香脂树脂的树脂酸、妥尔油树脂或根树脂,任选还有氢化松香醇和其酯、丙烯酸共聚物如苯乙烯-丙烯酸共聚物或乙烯、丙烯酸酯和马来酸酐的共聚物,或基于官能烃树脂的树脂。
特别是从针叶树获得基于松香或妥尔油树脂的天然树脂作为纸张制造的副产物。松香树脂通常是8种树脂酸,即松香酸、新松香酸、脱氢松香酸、长叶松酸、左旋海松酸、海松酸、异海松酸和山达海松酸的混合物。树脂可以通过氢化、酯化,优选用醇,如甲醇、三甘醇、甘油和季戊四醇,二聚化和官能化进行改性。官能化优选是指多元醇酯(例如上述那些)与二酸如马来酸或富马酸的进一步酯化。合适的树脂可以例如以商品名(ArizonaChemical),特别是 RE85、Staybelite TM A松香酸(Pinova Inc.)、StaybeliteTM E松香酯(EASTMan)和PEXALYN T100(Pinova Inc)获得。
至少一种增粘树脂可以是单种树脂,或者优选上述树脂的混合物。
在各种实施方案中,所述树脂包含完全或部分水合的烃树脂和/或至少一种基于松香或妥尔油树脂的天然树脂,或甲基、季戊四醇或甘油酯,或其任意组合。特别地,至少一种完全或部分水合的烃树脂可以是脂环族树脂、芳香族改性树脂、多萜烯、萜烯酚醛树脂、1,3-戊二烯树脂、环戊二烯树脂、2-甲基-2-丁烯共聚物,或其衍生物或上述树脂的任意组合。
一种示例性混合物由软化点在95℃和105℃之间的芳烃改性的C5烃树脂组成,例如可以商品名Wingtack TM Extra Flakes(Cray Valley,USA)商购的那些,在室温下为液体的芳族改性的水合C9烃树脂,例如可以商品名Regalite TM R(EASTMan,USA)商购的那些。
通常,优选使用具有80-130℃的软化点的树脂或树脂混合物。另一个特殊实施方案使用软化点低于50℃的树脂;特别地,这些也可以是液体。
软化点使用环球法(ASTM方法E28;ISO 4625)测定。
可以包含在热熔性粘合剂中的另一组分是增塑剂。这些组分通常可以选自矿物油、聚(异)丁烯、以及液体或糊状水合烃。它们优选是根据DIN51818的稠度值为000、00、00、1、2、3、4或5的水合烃。
合适的增塑剂包括但不限于医用白油、环烷矿物油、聚丙烯、聚异丁烯和聚异戊二烯低聚物、水合聚异戊二烯和/或聚丁二烯低聚物、苯甲酸酯、邻苯二甲酸酯、己二酸酯、植物或动物油及其衍生物。例如,水合增塑剂选自石蜡烃油。聚丙二醇和聚丁二醇以及聚亚甲基二醇也是合适的。诸如液体聚酯和甘油酯的酯也可以用作增塑剂。聚丁烯低聚物的分子量Mw应优选在200至6,000g/mol的范围内,聚烯烃应具有至多约2,000g/mol,特别是至多1,000g/mol的分子量Mw。特别地,聚(异)丁烯和液体或糊状水合烃是合适的。分子量Mw小于5000的聚异丁烯是非常特别优选的。在各种优选实施方案中,根据本发明的粘合剂不含增塑剂和/或增塑剂组分不含矿物油,特别是石蜡和/或环烷烃油,和芳烃。
在本发明中,“不含”是指相对于组合物的总重量,相应组分的浓度<0.1重量%,优选<0.01重量%。
增塑剂的量应在0至最大15重量%之间。过多的增塑剂含量可导致粘合剂的凝聚特性降低。
任选地,可将蜡以0.5至5重量%的量加入到热熔性粘合剂中。计量该量,使得粘度降低到所需范围,而不会不利地影响粘合。蜡可以是天然来源的,或者它也可以是化学改性形式或合成来源的。植物蜡、动物蜡、矿物蜡或石化蜡可用作天然蜡。硬蜡如褐煤酯蜡、沙索蜡等可用作化学改性的蜡。聚亚烷基蜡以及聚乙二醇蜡被用作合成蜡。优选地,使用石油化学蜡如凡士林、石蜡、微晶蜡和合成蜡。石蜡和/或微晶蜡和/或其水合型是特别优选的,特别是具有根据ASTM D-3954测定的滴点为50℃至170℃的聚丙烯或聚乙烯蜡。
除了上述组分之外,根据本发明的热熔性粘合剂可以含有通常用于热熔性粘合剂中作为添加剂的其他组分。这些包括例如稳定剂、粘合促进剂、抗氧化剂、填料和/或颜料。以这种方式,可以影响粘合剂的某些特性,例如其凝聚力、稳定性、粘合性或强度。添加剂和助剂的量优选为0至3重量%。特别优选的添加剂包括耐热和氧化降解以及由UV辐射造成的分解的稳定剂。
添加剂如稳定剂或粘合促进剂是本领域技术人员已知的。这些是商业产品,并且本领域技术人员可以根据期望的特性来选择它们。必须确保与聚合物共混物具有相容性。例如,可以以商品名(BASF SE)获得的抗氧化剂可用作稳定剂,优选为所述组合物的0.5至1重量%。
作为任选的组分,根据本发明的热熔性粘合剂可以含有0至8重量%,特别是2至5重量%的与根据本发明的共聚物不同的另外的聚合物。特别地,这些聚合物的量应该小于根据本发明所需的烯烃聚合物的量。这些聚合物可以改善热熔性粘合剂的各种应用相关特征,例如负载下的热稳定性、低温柔韧性、凝聚力和所施加的粘合剂的粘合性。这些另外的聚合物优选地不具有在制造和储存条件下交联的基团。
在其他实施方案中,热熔性粘合剂因此可以另外含有至少一种基于烯烃的弹性聚合物和具有羧基和/或酸酐基团的(甲基)丙烯酸酯。烯烃单体可以选自已知的C2至C5烯烃,特别是乙烯或丙烯。(甲基)丙烯酸酯选自具有低分子量的C1至C8链烷醇的(甲基)丙烯酸酯;特别地,(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯或(甲基)丙烯酸-2-乙基己酯单独或混合使用是合适的。共聚物也必须具有羧基和/或酸酐基团。这可以通过与相应的官能单体的聚合或通过随后的聚烯烃共聚物的改性而发生。例如,可以通过氧化引入COOH基团。此外,可以通过例如与马来酸酐、COOH或酸酐基团的自由基接枝反应将COOH或酸酐基团引入到聚合物中。来自乙烯、丙烯酸酯和马来酸酐的三元共聚物在190℃和2.6kg的测试载荷下(根据ISO 1133)的熔体流动指数为100-300/10分钟,是特别优选的。
这样的聚合物通常具有3,000至50,000g/mol,特别是8,000至25,000g/mol的分子量(Mn)。COOH/酸酐基团的量特别为1至100mg KOH/g,特别优选为5至50mg KOH/g。如果羧基的数量高,则热熔性粘合剂的组分的相容性是有问题的。软化点可以在50℃至150℃,特别是90℃至110℃的范围内。带有COOH基团的聚合物的量应为0至15重量%,特别是0.5至10重量%。具有羧基的合适的聚合物是市售的并且是本领域技术人员已知的。
虽然弹性聚合物影响热熔性粘合剂的柔性,但是可以通过附加的非柔性热塑性聚合物的含量来提高凝聚力。特别地,已知的热塑性聚合物如EVA和高分子量聚烯烃如聚-1-丁烯是合适的。
在优选的实施方案中,所述热熔性粘合剂不含多环芳烃。
根据本发明的热熔性粘合剂通过在熔体中混合的已知方法制造。所有的组分可以同时放入,加热,然后均化,或者首先放入并混合更容易熔化的组分,然后是较硬的树脂组分。在挤出机中连续制造热熔性粘合剂也是可能的和优选的。合适的热熔性粘合剂是固体,除杂质外,不含溶剂。
根据本发明合适的热熔性粘合剂优选在160℃(Brookfield RVT,转子27)下测量的粘度为约500mPa·s至100,000mPa·s,特别优选5,000mPa·s至20,000mPa·s。还优选其具有大于70℃,特别是大于80℃的软化点(环球法,ASTM E 28)。
本文所述的热熔性粘合剂特别适用于胶合膜状基材,优选作为用于胶合至少两个膜网的热熔性粘合剂,更优选以侧面或底部接缝的形式。制造膜容器的另一个优选的可能性在于,例如通过心轴(mandrel)折叠单个膜片或单个膜网,并且至少部分地将由折叠产生的膜部分粘合在一起,优选地至少在一个边缘区域。例如,如果将膜网折叠并且将以这种方式制造的膜部分沿着膜网的整个长度胶合在一起,制成膜管,然后将膜管以与膜网的纵轴成直角的方式切割,并且可以任选地在另一边缘区域中胶合。
可以以这种方式生产各种各样的膜包装,例如袋或小袋。本发明的热熔性粘合剂也适用于胶合的机织织物或无纺织物。
作为这些膜状基材的材料,特别是用于袋和小袋中,优选使用聚烯烃,特别是聚乙烯(PE)和聚丙烯(PP),可以将其用作网材料或以具有或不具有表面处理或涂层的另一种形式的包装中。例如,表面预处理的材料包括PE和PP,并且预处理可以涉及电晕处理或用于增大表面张力的相关技术或用丙烯酸酯预涂布聚烯烃。可选地,也可以设想其他预处理,例如用气体火焰或乙烯-乙酸乙烯酯(EVA)涂层。
通常的助剂可以与聚烯烃膜材料混合。使用这些助剂以产生更好的印刷性,以产生抗静电效果,以确保作为卷材的可展开性(unrollability)等。然而,所有这些材料都具有相应的聚烯烃作为主要组分,即相对于聚烯烃膜材料的总重量至少80重量%。
可以使用各种技术和方法来制造这样的膜袋和小袋。例如,压力涂布、共挤出涂布、平膜共挤出和吹膜共挤出是合适的(参见Plastics Extrusion Technology,FriedhelmHensen(编辑),Carl Hanser Verlag Munich,1988)。
对于纵向和底部胶合,可以使用本领域技术人员为此目的已知的技术,例如使用喷嘴、轮子或印刷块的施加。
为了使其能够用于粘合剂相关目的,本发明的粘合剂优选以垫或颗粒的形式存在,所述垫或颗粒本身通过在高温下挤出并随后切割,特别是股线切割(strand cutting)(冷却之后,例如通过冷水冷却)来制备。
在特别粘稠的产品的情况下,将粘合剂包装在硅油纸或适当的塑料膜中是有利的。在制造包装期间,可以将本发明的热熔性粘合剂施加在至少两种材料之间。
本发明的一个方面是针对这种包装,特别是用于食品的包装,其含有所述胶合的膜。
如上面已经多次描述的,所述包装可以是袋或小袋的形式。以这种方式制造的包装可以用于许多应用:例如作为食品包装,特别是用于面包、烘焙食品、糖果、香料、茶、咖啡、奶酪、香肠和在食用前在烤箱或微波炉中加热的食品。这种包装也适用于药物、毛巾、清洁布等,可以向布中加入清洁乳液或化妆活性物质。
以下实施例旨在解释本发明,但本发明不受其限制。
实施例
实施例1:粘合剂配制物
下文中,术语“烃树脂”也称为“HC树脂”。
玻璃化转变温度Tg根据DIN EN 1427测定。
熔体粘度根据DIN 53019测定。
如上所述,根据DIN 55672测定分子量Mn。
制备相对于组合物含有以下组分的粘合剂组合物:
配制物1:
聚-α-烯烃(Mn 5,000g/mol;Tg 96℃;熔体粘度2,500mPa·s)70.0重量%
聚-α-烯烃(Mn 18,100g/mol;Tg 107℃;熔体粘度50,000mPa·s)15.0重量%
Escorez 5400(ExxonMobil Chemical),脂环族HC树脂5.0重量%
Polybut 10(Productos Uhpon),聚异丁烯9.5重量%
Irganox 1010(BASF SE),抗氧化剂0.5重量%
以这种方式获得的产品在基于聚烯烃的袋材料上显示非常好的粘合性和非常高的凝聚力。
配制物2:
聚-α-烯烃(Mn 5,000g/mol;Tg 96℃;熔体粘度2,500mPa·s)70.0重量%
聚-α-烯烃(Mn 18,100g/mol;Tg 107℃;熔体粘度50,000mPa·s)15.0重量%
Sylvatac RE 85(Arizona Chemical),松香甘油酯5.0重量%
Polybut 10(Productos Uhpon)聚异丁烯9.5重量%
Irganox 1010(BASF SE),抗氧化剂0.5重量%
以这种方式获得的产品具有比配制物1更强的粘合性。
配制物3:
聚-α-烯烃(Mn 5,000g/mol;Tg96℃;熔体粘度2,500mPa·s)15.0重量%
聚-α-烯烃(Mn 18,100g/mol;Tg 107℃;熔体粘度50,000mPa·s)40.0重量%
Regalite S1100(EASTMan Chemical Company),脂环族HC树脂29.5重量%
Polybut 10(Productos Uhpon),聚异丁烯12.0重量%
Polybut 30(Productos Uhpon),聚异丁烯3.0重量%
Irganox 1010(BASF SE),抗氧化剂0.35重量%
Irganox PS 802FL(BASF SE),抗氧化剂0.15重量%
该粘合剂在160℃(Brookfield RVT转子21)下的粘度为约11300mPa·s,软化点为87.8/87.9℃(ASTM E 28)。在150℃粘合温度下,使用加热台/加热片涂覆40g/m2的50μmPET,粘合剂在钢和PE上在20分钟后分别显示31N/25mm和15N/25mm的粘合力(adhesivebond),24小时后,在钢和玻璃上分别为33N/25mm和32N/25mm。在重新胶合(130℃,30秒,5kg/100cm2)后,在24小时后在钢和PE和玻璃上分别实现35N/25mm(70%粘合失效)和17N/25mm和24N/25mm的粘合力。
配制物4:
聚-α-烯烃(Mn 5,000g/mol;Tg 96℃;熔体粘度2,500mPa·s)15.0重量%
聚-α-烯烃(Mn 18,100g/mol;Tg 107℃;熔体粘度50,000mPa·s)35.0重量%
Regalite R1010(EASTMan Chemical Company),脂环族HC树脂5.0重量%
Regalite S1100(EASTMan Chemical Company),脂环族HC树脂29.5重量%
Polybut 10(Productos Uhpon),聚异丁烯12.0重量%
Polybut 30(Productos Uhpon),聚异丁烯3.0重量%
Irganox 1010(BASF SE),抗氧化剂0.35重量%
Irganox PS 802FL(BASF SE),抗氧化剂0.15重量%
该粘合剂在160℃(Brookfield RVT转子21)下的粘度为约7500mPa·s,软化点为85.2/85.4℃(ASTM E 28)。在150℃粘合温度下,使用加热台/加热片涂覆40g/m2的50μmPET,粘合剂在钢和PE和玻璃上在20分钟后分别显示23N/25mm和17N/25mm和26N/25mm的粘合力,24小时后,在钢和PE和玻璃上分别为37N/25mm和8N/25mm和41N/25mm。在重新胶合(130℃,30秒,5kg/100cm2)后,在24小时后在钢和PE和玻璃上分别实现35N/25mm(80%粘合失效)和23N/25mm和37N/25mm(80%凝聚失效)的粘合力。
Claims (11)
1.热熔性粘合剂,其含有以下组分,优选由以下组分组成:
a)25至95重量%,优选50至85重量%的至少一种基于聚烯烃的聚合物;
b)1至75重量%,优选1至40重量%的至少一种增粘树脂;
c)0至15重量%的至少一种增塑剂;和
d)0至30重量%的至少一种添加剂和/或助剂,其选自稳定剂、粘合促进剂、填料或颜料、蜡和/或其他聚合物,其优选为(甲基)丙烯酸酯,或其任意组合,
其特征在于,所述至少一种基于聚烯烃的聚合物是以下物质的混合物:
a1)相对于所述基于聚烯烃的聚合物的总量,20至80重量%的量的至少一种分子量Mn<10,000g/mol的第一基于聚烯烃的聚合物,以及
a2)相对于所述基于聚烯烃的聚合物的总量,20至80重量%的量的至少一种分子量Mn>10,000g/mol的第二基于聚烯烃的聚合物。
2.根据权利要求1所述的热熔性粘合剂,其特征在于,所述至少一种基于聚烯烃的聚合物选自聚烯烃的均聚物和共聚物,特别是选自由聚-α-烯烃组成的组,优选基于乙烯、丙烯和/或丁烯的无规立构聚-α-烯烃(APAO),和乙烯/α-烯烃和丙烯/α-烯烃共聚物,优选乙烯和丙烯、1-丁烯、1-己烯、1-辛烯的共聚物,或其任意组合。
3.根据权利要求1或2所述的热熔性粘合剂,其特征在于,所述至少一种增粘树脂是树脂或树脂混合物,其包含至少一种完全或部分水合的烃树脂和/或至少一种基于松香或妥尔油树脂的天然树脂或其甲基、季戊四醇或甘油酯,所述至少一种完全或部分水合的烃树脂任选地含有脂环族树脂、芳族改性树脂、多萜烯、萜烯酚醛树脂、1,3-戊二烯树脂、环戊二烯树脂、2-甲基-2-丁烯共聚物,或上述树脂的衍生物。
4.根据权利要求1至3中任一项所述的热熔性粘合剂,其特征在于,所述增塑剂选自聚(异)丁烯和液体或糊状水合烃,特别是分子量Mw小于5,000g/mol的聚异丁烯。
5.根据权利要求1至4中任一项所述的热熔性粘合剂,其特征在于,相对于所述热熔性粘合剂,所述至少一种添加剂和/或助剂包含0.1至3重量%的添加剂,特别是耐热、氧化和UV引起的降解的稳定剂。
6.根据权利要求1至5中任一项所述的热熔性粘合剂,其特征在于,所述热熔性粘合剂在160℃(Brookfield CAP,转子8)下的粘度在500至100,000mPa·s的范围内。
7.根据权利要求1至6中任一项所述的热熔性粘合剂的用途,其用于胶合膜状基材,特别是聚烯烃膜、机织织物或无纺织物。
8.制造由聚烯烃膜制成的包装、包含由聚烯烃制成的膜的包装袋或小袋的方法,其包括以纵向和/或底部胶合的形式,对至少两个聚烯烃膜进行部分表面胶合,其特征在于,使用权利要求1至6中任一项所述的热熔性粘合剂用于胶合。
9.根据权利要求7所述的用途或根据权利要求8所述的方法,其特征在于,相对于聚烯烃膜的总重量,所述聚烯烃膜是由至少80重量%任选地表面处理的或表面涂覆的聚乙烯(PE)或聚丙烯(PP)组成的膜。
10.由聚烯烃膜制成的包装,特别是包含由聚烯烃制成的膜的袋或小袋,其能够根据权利要求8所述的方法获得。
11.制造胶合的机织织物或无纺织物的方法,其包括对至少两个基材进行部分表面或全表面胶合,其特征在于至少一个基材是机织织物或无纺织物,并且使用权利要求1至6中任一项所述的热熔性粘合剂用于胶合。
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CN112585209B (zh) * | 2018-07-26 | 2024-03-12 | 科莱恩国际有限公司 | 热塑性成形物质 |
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Also Published As
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JP6682525B2 (ja) | 2020-04-15 |
WO2016062797A1 (de) | 2016-04-28 |
BR112017007686B1 (pt) | 2022-08-30 |
EP3209742A1 (de) | 2017-08-30 |
JP2017538803A (ja) | 2017-12-28 |
RU2017117584A3 (zh) | 2019-04-09 |
CN116179115A (zh) | 2023-05-30 |
MX2017005118A (es) | 2017-07-14 |
RU2701826C2 (ru) | 2019-10-01 |
AU2015334922B2 (en) | 2019-08-08 |
RU2017117584A (ru) | 2018-11-26 |
KR102494179B1 (ko) | 2023-01-31 |
PL3209742T3 (pl) | 2022-03-21 |
AR102910A1 (es) | 2017-04-05 |
AU2015334922A1 (en) | 2017-05-18 |
BR112017007686A2 (pt) | 2017-12-19 |
CL2017000973A1 (es) | 2017-11-24 |
EP3209742B1 (de) | 2021-12-01 |
US20170226388A1 (en) | 2017-08-10 |
KR20170072289A (ko) | 2017-06-26 |
US11655400B2 (en) | 2023-05-23 |
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