CN103502000B - 包装及其制备材料 - Google Patents
包装及其制备材料 Download PDFInfo
- Publication number
- CN103502000B CN103502000B CN201280012883.7A CN201280012883A CN103502000B CN 103502000 B CN103502000 B CN 103502000B CN 201280012883 A CN201280012883 A CN 201280012883A CN 103502000 B CN103502000 B CN 103502000B
- Authority
- CN
- China
- Prior art keywords
- density polyethylene
- low density
- laminated material
- layer
- starch
- 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.)
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 239000002648 laminated material Substances 0.000 claims abstract description 120
- 229920002472 Starch Polymers 0.000 claims abstract description 84
- 239000008107 starch Substances 0.000 claims abstract description 84
- 235000019698 starch Nutrition 0.000 claims abstract description 84
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000010410 layer Substances 0.000 claims description 137
- 229920001684 low density polyethylene Polymers 0.000 claims description 82
- 239000004702 low-density polyethylene Substances 0.000 claims description 82
- 239000004698 Polyethylene Substances 0.000 claims description 58
- 229920005989 resin Polymers 0.000 claims description 52
- 239000011347 resin Substances 0.000 claims description 52
- 230000004888 barrier function Effects 0.000 claims description 51
- 239000010408 film Substances 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 229920000881 Modified starch Polymers 0.000 claims description 34
- 239000004368 Modified starch Substances 0.000 claims description 34
- 235000019426 modified starch Nutrition 0.000 claims description 34
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 32
- 239000010409 thin film Substances 0.000 claims description 30
- -1 polyethylene Polymers 0.000 claims description 26
- 229920001903 high density polyethylene Polymers 0.000 claims description 23
- 239000004700 high-density polyethylene Substances 0.000 claims description 23
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 20
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 19
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 19
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 19
- 229920000573 polyethylene Polymers 0.000 claims description 16
- 239000005030 aluminium foil Substances 0.000 claims description 15
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 15
- 241000446313 Lamella Species 0.000 claims description 14
- 239000004677 Nylon Substances 0.000 claims description 12
- 229920001778 nylon Polymers 0.000 claims description 12
- 229920003023 plastic Polymers 0.000 claims description 12
- 239000004033 plastic Substances 0.000 claims description 12
- 239000013047 polymeric layer Substances 0.000 claims description 12
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims description 10
- 235000014655 lactic acid Nutrition 0.000 claims description 10
- 239000004310 lactic acid Substances 0.000 claims description 10
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 10
- 229920000098 polyolefin Polymers 0.000 claims description 10
- 238000012958 reprocessing Methods 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 7
- 229920008262 Thermoplastic starch Polymers 0.000 claims description 7
- 239000011140 metalized polyester Substances 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- 239000004628 starch-based polymer Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 4
- 239000002985 plastic film Substances 0.000 claims description 4
- 229920006255 plastic film Polymers 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000000565 sealant Substances 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims 2
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 239000005020 polyethylene terephthalate Substances 0.000 claims 1
- 229920000139 polyethylene terephthalate Polymers 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 10
- 239000000606 toothpaste Substances 0.000 abstract description 10
- 229940034610 toothpaste Drugs 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
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- 239000011112 polyethylene naphthalate Substances 0.000 description 9
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000551 dentifrice Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920001059 synthetic polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 239000011846 petroleum-based material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940095688 toothpaste product Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
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- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
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- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/046—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
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- B32B15/00—Layered products comprising a layer of metal
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- 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
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- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
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- B32B2597/00—Tubular articles, e.g. hoses, pipes
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- 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
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- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/31703—Next to cellulosic
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- 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
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- 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
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-
- 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
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- Y10T428/31855—Of addition polymer from unsaturated monomers
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-
- 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
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Tubes (AREA)
- Wrappers (AREA)
Abstract
本发明提供一种包含淀粉/聚合物混合物的新的柔韧性、基本不透气层压材料,所述材料可用于制造分配管,例如,用于牙膏的分配管,该材料轻、弹性并且便宜,可几乎完全由可再生材料制造,并且可以循环。
Description
相关申请交叉引用
本申请要求2011年3月11日提交的美国临时申请61/451,945的权益。以上申请的公开内容通过引用结合到本文中。
发明领域
本发明涉及新的可变形层压材料和用它制造的容器,例如,用于牙膏、化妆品、调味品、胶水和具有糊、凝胶或乳脂稠度的其它物质的分配管。
发明背景
分配管提出重要的技术挑战。它们需要基本不透其内容物,并且不与内容物反应。例如,牙膏可包含挥发性或反应性组分,例如活性成分、水、盐、金属离子、甜味剂和挥发性香料。管应使内容物避光,因为组分在光存在下降解,特别是UV光。优选管应结实,能够经受运输、温度变化和消费者使用的严酷环境。管优选薄得足以容易变形,以便能够将糊容易地从管挤出,然而仍足够硬,以在填充和使用中经受显著压力。最后,材料和制造成本应尽可能低,因为包装可构成使用分配管的很多产品的商品成本的显著部分。
因此,需要提供等于或优于现有管的性能但也对环境无害并且廉价的分配管。
发明概述
本发明特别提供一种新的柔韧性、基本不透气层压材料,所述层压材料包含内聚合物层、基本不透气的阻挡层和外聚合物层,其中外聚合物层包含淀粉,例如,下述层压材料1和2,该材料可用于制造比铝轻且不易破裂或渗漏的分配管,可几乎完全由可再生材料制造,这将代替不可再生材料(例如,由石油化工源制造的塑料)。
包含可再生材料的多层牙膏管的独特之处在于保持各层的优良功能,但增加的益处是,减小对石油基材料的依赖性,提高可持续性,减小商品成本,并通过产品寿命周期减小对环境的影响。
通过以下提供的详述,本发明适用性的进一步范围将变得显而易见。应了解,虽然指出了本发明的优选实施方案,但详述和具体实施例仅作为说明给出,并且不意味限制本发明的范围。
发明详述
在第一实施方案,本发明提供一种新的柔韧性、基本不透气层压材料,所述层压材料包含内聚合物层、基本不透气的阻挡层和外聚合物层,其中外聚合物层包含淀粉,例如,淀粉/聚乙烯混合物,并且淀粉百分比为至少40%,例如50-70%或约60%。
例如,在一个实施方案中,本发明提供新的柔韧性、基本不透气层压材料,层压材料1,所述层压材料包含以下层(从在使用中与内容物直接的内层到外层):
a.非反应性树脂薄膜内层,例如,线型低密度聚乙烯(LLDPE);
b.任选的树脂薄膜层,例如,选自
i.低密度聚乙烯(LDPE);
ii.与改性淀粉混合的低密度聚乙烯;
iii.塑性薄膜层,包括一个或多个与改性淀粉混合的低密度聚乙烯层和一个或多个低密度聚乙烯(LDPE)层;和
iv.三片层,所述三片层包含:
1.任选与改性淀粉混合的低密度聚乙烯,
2.热塑性淀粉,
3.任选与改性淀粉混合的低密度聚乙烯;
c.任选的例如粘合树脂材料粘结层,例如,包含酐改性的聚烯烃或乙烯-酸共聚物;
d.由基本不透气(例如,不透水蒸气和氧)材料制成的阻挡层,例如,选自
i.铝箔,例如循环铝箔;
ii.金属化聚(乳酸);
iii.聚(乳酸)(PLA);
iv.金属化纸;
v.树脂涂覆纸,例如,用乙烯-乙烯醇共聚物(EVOH)涂覆的纸;
vi.乙烯-乙烯醇共聚物薄膜;
vii.尼龙;
viii.金属化聚酯,例如,聚(对苯二甲酸乙二酯)(PET)和聚(萘二甲酸乙二酯)(PEN);
e.任选的例如粘合树脂材料粘结层,例如,包含酐改性的聚烯烃或乙烯-酸共聚物;
f.树脂薄膜外层,例如,选自
i.与改性淀粉混合的低密度聚乙烯;
ii.塑性薄膜,包括一个或多个与改性淀粉混合的低密度聚乙烯层和一个或多个低密度聚乙烯(LDPE)层;
iii.三片层,所述三片层包含:
1.任选与改性淀粉混合的低密度聚乙烯,
2.热塑性淀粉,
3.任选与改性淀粉混合的低密度聚乙烯;
g.任选的贴标层,例如,包括白色聚乙烯薄膜,例如,具有密封特征。
因此,本发明提供层压材料1的不同实施方案,例如,
1.1.层压材料1,其中阻挡层(d)选自树脂涂覆纸(例如,用乙烯-乙烯醇共聚物(EVOH)涂覆的纸)和乙烯-乙烯醇共聚物薄膜;
1.2.层压材料1或1.1,其中内层(a)包括线型低密度聚乙烯薄膜;
1.3.任何前述层压材料,其中层b和层c共挤出,并且/或者层e和层f共挤出;
1.4.任何前述层压材料,其中任选的树脂薄膜层(b)存在,并且包括低密度聚乙烯薄膜;
1.5.任何前述层压材料,所述层压材料包括与改性淀粉混合的低密度聚乙烯,其中例如通过与淀粉上的羟基反应使淀粉改性,以减小其亲水性,例如,通过用疏水残基酯化;
1.6.前述层压材料,其中树脂薄膜(b)和/或(f)的层的总淀粉含量为至少40%;
1.7.任何前述层压材料,其中树脂薄膜(b)存在,并且包括与改性淀粉混合的低密度聚乙烯;或三片层,所述三片层包含:
1.任选与改性淀粉混合的低密度聚乙烯,
2.热塑性淀粉,
3.任选与改性淀粉混合的低密度聚乙烯;
1.8.任何前述层压材料,其中层压材料的总淀粉含量为至少40%;
1.9.任何前述层压材料,其中任选的树脂薄膜层(b)和/或(f)存在,并且包括生物可降解或可再生树脂;
1.10.任何前述层压材料,其中任选的树脂薄膜层(b)和/或(f)存在,并且包括由循环塑料制成的树脂;
1.11.任何前述层压材料,其中任选的树脂薄膜层(b)和/或(f)存在,并且包括由乙醇衍生单体聚合产生化学相同聚烯烃制成的低密度聚乙烯;
1.12.任何前述层压材料,其中粘结层(c)和(e)包括酐改性的聚烯烃。
1.13.任何前述层压材料,其中粘结层(c)和(e)包括乙烯-酸共聚物,例如乙烯-丙烯酸共聚物或乙烯-甲基丙烯酸共聚物;
1.14.任何前述层压材料,其中阻挡层(d)为循环的铝箔;
1.15.任何前述层压材料,其中阻挡层(d)包括金属化聚(乳酸);
1.16.任何前述层压材料,其中阻挡层(d)包括聚(乳酸)(PLA);
1.17.任何前述层压材料,其中阻挡层包括用乙烯-乙烯醇共聚物(EVOH)涂覆的聚(乳酸)(PLA);
1.18.任何前述层压材料,其中阻挡层(d)包括金属化纸;
1.19.任何前述层压材料,其中阻挡层(d)包括树脂涂覆纸;
1.20.任何前述层压材料,其中阻挡层(d)包括用乙烯-乙烯醇共聚物(EVOH)涂覆的纸;
1.21.任何前述层压材料,其中阻挡层(d)包括乙烯-乙烯醇共聚物(EVOH)薄膜;
1.22.任何前述层压材料,其中阻挡层(d)包括尼龙;
1.23.任何前述层压材料,其中阻挡层(d)包括由可再生材料制成的尼龙,例如,包含来自癸二酸的单体;
1.24.任何前述层压材料,其中阻挡层(d)包括金属化聚酯,例如,聚(对苯二甲酸乙二酯)(PET)和聚(萘二甲酸乙二酯)(PEN);
1.25.任何前述层压材料,其中外层(g)包括聚乙烯,例如,白色聚乙烯;
1.26.任何前述层压材料,所述层压材料基本可循环;
1.27.任何前述层压材料,所述层压材料基本可生物降解。
在另一个实施方案中,本发明提供新的柔韧性、基本不透气层压材料,层压材料2,所述层压材料包含以下层(从在使用中与内容物直接接触的内层到外层):
a.非反应性树脂薄膜内层,例如,线型低密度聚乙烯(LLDPE);
b.任选的树脂薄膜层,例如,选自
i.低密度聚乙烯(LDPE);
ii.与改性淀粉混合的低密度聚乙烯;
iii.塑性薄膜层,包括一个或多个与改性淀粉混合的低密度聚乙烯层和一个或多个低密度聚乙烯(LDPE)层;和
iv.三片层,所述三片层包含:
1.任选与改性淀粉混合的低密度聚乙烯,
2.热塑性淀粉,
3.任选与改性淀粉混合的低密度聚乙烯;
c.任选的例如粘合树脂材料粘结层,例如,包含酐改性的聚烯烃或乙烯-酸共聚物;
d.由基本不透气(例如,不透水蒸气和氧)材料制成的阻挡层,例如,选自
i.铝箔,例如循环铝箔;
ii.金属化聚(乳酸);
iii.聚(乳酸)(PLA);
iv.金属化纸;
v.树脂涂覆纸,例如,用乙烯-乙烯醇共聚物(EVOH)涂覆的纸;
vi.乙烯-乙烯醇共聚物薄膜;
vii.尼龙;
viii.金属化聚酯,例如,聚(对苯二甲酸乙二酯)(PET)和聚(萘二甲酸乙二酯)(PEN);
e.任选的例如粘合树脂材料粘结层,例如,包含酐改性的聚烯烃或乙烯-酸共聚物;
f.外层或多层,所述层包含具有至少40%(例如,50-70%或约60%)淀粉的淀粉/聚乙烯混合物,例如,塑性薄膜,所述塑性薄膜包括一个或多个与改性淀粉混合的低密度聚乙烯层和一个或多个低密度聚乙烯(LDPE)层;例如,包括三片层(从内至外)
1.具有50-70%或约60%淀粉百分数的淀粉/聚乙烯混合物;
2.具有50-70%或约60%淀粉百分数和8%重量颜料的淀粉/聚乙烯混合物;
3.线性低密度聚乙烯和/或低密度聚乙烯;
g.任选的标签层,例如,包括白色聚乙烯,例如,任选包含密封剂。
因此,本发明提供层压材料2的不同实施方案,例如,
2.
2.1.层压材料2,其中阻挡层(d)选自树脂涂覆纸(例如,用乙烯-乙烯醇共聚物(EVOH)涂覆的纸)和乙烯-乙烯醇共聚物薄膜;
2.2.层压材料2或2.1,其中内层(a)包括线型低密度聚乙烯薄膜;
2.3.任何前述层压材料,其中层b和层c共挤出,并且/或者层e和层f共挤出;
2.4.任何前述层压材料,其中任选的树脂薄膜层(b)存在,并且包括低密度聚乙烯薄膜;
2.5.任何前述层压材料,其中树脂薄膜(b)存在,并且包括与改性淀粉混合的低密度聚乙烯,其中例如通过与淀粉上的羟基反应使淀粉改性,以减小其亲水性,例如,通过用疏水残基酯化;
2.6.前述层压材料,其中树脂薄膜层(b)的总淀粉含量为至少40%;
2.7.任何前述层压材料,其中层压材料的总淀粉含量为至少40%;
2.8.任何前述层压材料,其中任选的树脂薄膜层(b)存在,并且包括生物可降解树脂;
2.9任何前述层压材料,其中任选的树脂薄膜层(b)存在,并且包括由循环塑料制成的树脂;
2.10.任何前述层压材料,其中任选的树脂薄膜层(b)存在,并且包括由乙醇衍生单体聚合产生化学相同聚烯烃制成的低密度聚乙烯;
2.11任何前述层压材料,其中粘结层(c)和(e)包括酐改性的聚烯烃。
2.12.任何前述层压材料,其中粘结层(c)和(e)包括乙烯-酸共聚物,例如乙烯-丙烯酸共聚物或乙烯-甲基丙烯酸共聚物;
2.13.任何前述层压材料,其中阻挡层(d)为循环的铝箔;
2.14.任何前述层压材料,其中阻挡层(d)包括金属化聚(乳酸);
2.15.任何前述层压材料,其中阻挡层(d)包括聚(乳酸)(PLA);
2.16.任何前述层压材料,其中阻挡层包括用乙烯-乙烯醇共聚物(EVOH)涂覆的聚(乳酸)(PLA);
2.17.任何前述层压材料,其中阻挡层(d)包括金属化纸;
2.18.任何前述层压材料,其中阻挡层(d)包括树脂涂覆纸;
2.19.任何前述层压材料,其中阻挡层(d)包括用乙烯-乙烯醇共聚物(EVOH)涂覆的纸;
2.20.任何前述层压材料,其中阻挡层(d)包括乙烯-乙烯醇共聚物(EVOH)薄膜;
2.21.任何前述层压材料,其中阻挡层(d)包括尼龙;
2.22.任何前述层压材料,其中阻挡层(d)包括金属化聚酯,例如,聚(对苯二甲酸乙二酯)(PET)和聚(萘二甲酸乙二酯)(PEN);
2.23.任何前述层压材料,其中阻挡层(d)包括由可再生材料制成的尼龙,例如,包含来自癸二酸的单体;
2.24.任何前述层压材料,其中外层(g)存在,并且包括聚乙烯,例如,白色聚乙烯;
2.25.任何前述层压材料,所述层压材料基本可循环;
2.26.任何前述层压材料,所述层压材料基本可生物降解。
本发明进一步提供一种分配管,所述分配管包括上述层压材料,例如,包括柔韧性、基本不透气的层压材料,所述层压材料包含内聚合物层、基本不透气的阻挡层和外聚合物层,其中外聚合物层包含淀粉,例如,淀粉/聚乙烯混合物,并且淀粉百分比为至少40%,例如50-70%或约60%(本发明的层压材料);例如,选自前述层压材料1等系列或层压材料2等系列的层压材料。在一个实施方案中(容器1),分配管包括具有由本发明的层压材料制成的顶端、底端和柔韧壁的管,其中在底端的壁卷曲成密封部分,其中顶端具有密封到并且近似垂直于壁的肩部,其中肩部由比壁更刚性的材料制成,所述肩部包括或提供管口的支持体,并且管口具有盖,这样可将容器密封。因此,本发明提供容器1的不同实施方案,例如,
3.1.容器1,其中肩部由高密度聚乙烯(HDPE)制成;
3.2.前述容器,其中HDPE为再处理HDPE;
3.3.任何前述容器,其中壁进一步包括内肋,以例如提供另外的强度和抗裂性;
3.4.任何前述容器,所述容器包括使容器内容物从肩部材料分离的香味阻挡插件;
3.5.前述容器,其中香味阻挡插件由可再生材料制成,例如再处理聚(对苯二甲酸乙二酯)(RPET);
3.6.任何前述容器,其中盖由可循环或可再生材料制成,例如,循环聚丙烯;
3.7.任何前述材料,其中盖由任选用铝涂覆的PLA树脂制成。
3.8.任何前述容器,其中盖由生物可降解材料制成,例如,与至少40%淀粉混合的树脂,优选至少50%淀粉;
3.9.任何前述容器,其中整个容器可循环;
3.10.任何前述容器,其中容器包括约25%重量可再生或循环材料。
在另一个实施方案中,本发明提供一种牙膏产品,所述牙膏产品包含关于容器1所述任何实施方案的容器中的牙膏。
在另一个实施方案中,本发明提供一种循环塑性层压材料牙膏管的方法,例如,关于容器1所述任何实施方案的牙膏管,所述方法包括将牙膏出售给消费者,在使用后从消费者收回牙膏管,并使牙膏管循环进入基于树脂的产品。
在本说明书中有时使用以下缩略语:
Al:铝
EAA:乙烯-丙烯酸共聚物
EVOH:乙烯-乙烯醇共聚物
HDPE:高密度聚乙烯
LDPE:低密度聚乙烯
LLDPE:线型低密度聚乙烯
PE:聚乙烯
PP:聚丙烯
PET:聚(对苯二甲酸乙二酯)
PLA:聚(乳酸)
TPS:热塑性淀粉
优选的材料包括用改性淀粉作为PP或PE的填料。可将淀粉用于注模盖和淀粉填充的薄膜中。其它可再生基材料也可以为填料,例如种子、竹、植物纤维等。
在一个实施方案中,如下制造层压材料:通过挤出薄的塑料圆环,将圆环向上拉成充气泡,制造泡吹膜。用模隙和旋转扩幅辊的组合控制厚度。在扩幅组件顶部使泡塌缩入辊,该辊围绕泡旋转,用于控制厚度和在辊内分配。可以此方式制造很宽的片。流延薄膜作为平片制造,从直模隙挤出和拉伸到冷却辊上。用此制造方法比用吹泡方法控制厚度更好。
在一个实施方案中,在管层压材料中外PE层是用于特殊印刷和密封功能的吹塑薄膜和熔融挤出PE的复杂布置。内流延PE薄膜利用共挤出层压到EAA粘结层,并层压到铝箔层上。EAA粘结层也匹配到铝箔的外侧。这些层在工厂一起单程通过层压机。
将层压材料转移到制管机,以形成管侧壁,并熔接到肩部,产生管口。总厚度为100至500微米。
在一些实施方案中,一个或多个层压材料层包含高比例淀粉。淀粉是市场上最廉价的生物聚合物,实际上只是聚乙烯价格的约四分之一。因此,通过研发也具有高百分比淀粉的高性能层压材料,申请人能够减小对石油衍生聚合物的依赖性,并且也降低了成本。
用于本发明的“改性淀粉”包括经改性以提高其在混合物中与聚合物的相容性的淀粉,例如,通过使淀粉塑化,以破坏其结晶结构,并任选使淀粉化学改性,以减小其亲水性。用于本发明的淀粉/塑料混合物优选利用预塑化淀粉。如果天然淀粉颗粒简单地与合成聚合物(加入的塑化剂)作为填料混合,而不对淀粉进行其它改性,则由于淀粉的高结晶性和与合成聚合物的不良相容性,加入到这些化合物的淀粉的最高百分数为15-20%。因此,使淀粉塑化,以在一定程度上破坏其结晶性,这使淀粉更容易地热处理。然后将经塑化淀粉与具有亲水官能团(例如,羟基,羧基)的可与淀粉上的羟基或者与小分子相容剂反应的一些聚合物混合。这些混合物的淀粉含量可达到50-80%。例如,在具有PE的塑化淀粉的混合物中,淀粉含量为例如在混合物中约60%重量。在一个实施方案中,只有外或倒数第二薄膜层用淀粉/PE混合物改性,以使此改性对经包装牙膏的潜在干扰最大限度地减小。外层不与牙膏直接接触,通过阻挡层与其隔离。
在其它实施方案中,本发明在一个或多个层中使用热塑可处理淀粉TPS。TPS是可与不同合成聚合物混合的100%淀粉物质。如US5,362,777中所述,为了产生TPS,将塑化剂与天然淀粉混合,并通过施加热和机械能使混合物熔融。在使淀粉和塑化剂的混合物熔融后,将熔融物混合到至少几乎均匀。在没有水存在下进行混合过程。
前述优选实施方案说明只为示例性质,不以任何方式限制本发明、其应用或用途。
在全文中,范围作为描述此范围内各个和每一个值的简略表达。可选择此范围内的任何值作为范围的端点。另外,在本文中引用的所有参考文献全文通过引用结合到本文中。在本公开中的定义和所引用参考中的定义冲突的情况下,以本公开为准。
除非另外说明,应了解,在此和说明书其它地方表达的所有百分比和量均指重量百分比。所给的量基于物质的活性重量。
实施例1
用可再生和可循环材料制备牙膏管,然后试验其性能。制备层压材料,层压材料从内侧到外侧具有以下结构:
a.LLDPE/LDPE/粘结层/循环Al箔/粘结层/LDPE/白色PE混合物
b.LLDPE/来自乙醇的LDPE/粘结层/金属化PLA/粘结层/来自乙醇的LDPE/白色PE混合物再处理的HDPE
c.LLDPE/来自乙醇的LDPE/粘结层/PLA/粘结层/来自乙醇的LDPE/白色PE混合物再处理的HDPE
d.LLDPE/来自乙醇的LDPE/粘结层/金属化纸/粘结层/来自乙醇的LDPE/白色PE混合物再处理的HDPE
e.LLDPE/来自乙醇的LDPE/粘结层/EVOH涂覆纸(两侧)/粘结层/来自乙醇的LDPE/白色PE混合物再处理的HDPE
f.LLDPE/具有淀粉填充的LDPE/粘结层/可再生尼龙阻挡层/粘结层/具有淀粉填充的LDPE/白色PE混合物
对管顶端的改进包括在香味阻挡插件中使用再处理PET。在插件中的预期应力破裂性质用设计变化改进,包括用内肋提供环向强度和抗应力破裂性。盖用循环PP树脂制造,而不是用原生树脂。或者,盖由PLA树脂制成,并用铝溅射涂覆,这是较佳阻挡层所需的。HDPE肩部用通过安全和审美筛选(老化研究)的再处理HDPE制造。与再处理PET或另一种聚酯的组合中,消除来自再处理HDPE的任何迁移问题。
从糖甘蔗乙醇或其它可再生源制成的可再生PE得自Braskem或DowChemical。在用铝箔作为阻挡层时,使用循环铝箔。代替铝箔作为阻挡层的选择包括PLA或金属化PLA、金属化纸、EVOH涂覆纸、EVOH涂覆PLA薄膜或金属化聚酯,例如PET和PEN;
最后,作为阻挡层材料试验来自可再生源的尼龙,例如,用癸二酸制成的尼龙。
淀粉填充,使树脂与改性淀粉混合以减小塑料量和增强生物可降解性,也通过淀粉填充内LDPE层并制造用50%淀粉填充的盖树脂评价。
实施例2
用以下层压材料结构(从外侧到内侧)制管:
淀粉填充,使树脂与改性淀粉混合以减小塑料量和增强生物可降解性,也通过淀粉填充内LDPE层评价。
实施例3
用以下层压材料结构(从外侧到内侧)制管:
淀粉填充,使树脂与改性淀粉混合以减小塑料量和增强生物可降解性,也通过淀粉填充内LDPE层评价。
实施例4
用以下层压材料结构(从外侧到内侧)制管:
实施例4:
用塑化淀粉与PE的混合物制造层压材料。淀粉含量为在混合物中60%重量。只用淀粉/PE混合物改进外薄膜,以使此改进对经包装牙膏的潜在干扰最大限度地减小。外薄膜不与牙膏直接接触,并且通过阻挡层与其隔离。包括淀粉/PE层的外薄膜层压材料单独制备,然后层压到阻挡层上。已发现,在不包括LLDPE最外层时,在与其它层共挤成层压材料时,淀粉/PE混合物外薄膜层破裂。然而,也已发现,包括增加LLDPE外薄膜层可对淀粉/PE混合物外薄膜层提供结构支撑,以防止在层压材料挤出期间破裂。在此实施方案中,改进的结构从外侧到内侧显示如下:
外薄膜层1 LLDPE |
外薄膜层2 92%重量:淀粉/PE,淀粉60%;8%重量颜料母料 |
外薄膜层淀粉/PE,淀粉60% |
粘结层:共挤出的PE/EAA |
阻挡层 – 铝箔 |
粘结层:共挤出的PE/EAA |
内薄膜三片层PE |
在此实施方案中,总外薄膜层厚度为185μ,外薄膜层1和3厚度分别为27.5μ,外薄膜层2厚度为130μ。淀粉/PE混合物具有60%淀粉含量。外薄膜经3层共挤出,随后薄膜吹塑。
将此层压材料与具有PE/阻挡层/PE结构并且在PE和阻挡层之间具有粘结层的常规层压材料比较。内PE层和外PE层二者均具有不同总厚度的多片层。阻挡层为Al箔或其它阻挡层材料。粘结层为共挤出的PE/EAA层,以使PE薄膜粘合到阻挡层。
在新层压材料和常规层压材料中使用的外薄膜的薄膜性质在表1中比较。
表1:常规和外薄膜的机械性质
用具有高淀粉外薄膜的层压材料制造牙膏管。用内气爆、落下、内层粘合强度试验(表2)试验管性质,发现可以接受。
表2.对淀粉管的鉴定试验
实施例5:二片层压材料
在此实施例中,外薄膜具有二片结构,并且除去在共挤出粘结层中的PE。由于PE/淀粉混合物和EAA之间良好的相容性,并且减少结构中更多石油基材料,以增加生物基材料含量,因此进行该方案。结构从外侧到内侧如下:
外薄膜层92%重量:淀粉/PE,淀粉60%;8%重量颜料母料 |
粘结层: EAA |
阻挡层 – 铝箔 |
粘结层: EAA |
内薄膜层:LLDPE/密封剂 |
Claims (20)
1.一种柔韧性、不透气层压材料,所述层压材料包括以下层:
a.非反应性树脂薄膜内层;
b.任选的树脂薄膜层
c.任选的粘合树脂材料粘结层;
d.不透气材料阻挡层,选自
i.循环铝箔,
ii.聚乳酸,
iii.金属化纸,
iv.树脂涂覆纸,
v.乙烯-乙烯醇薄膜,
vi.尼龙,和
vii.金属化聚酯;
e.任选的粘合树脂材料粘结层;
f.包含淀粉的外聚合物层;
g.任选的外标签层;
其中包含淀粉的外聚合物层(f)包括与改性淀粉混合的低密度聚乙烯,其中淀粉经改性以减小其亲水性。
2.权利要求1的层压材料,其中层b和c和/或层e和f共挤出。
3.权利要求1或2的层压材料,其中内层(a)包括线型低密度聚乙烯薄膜。
4.权利要求1或2的层压材料,其中任选的树脂薄膜层(b)存在,并且包括低密度聚乙烯薄膜和/或与改性淀粉混合的低密度聚乙烯,其中淀粉经改性以减小其亲水性。
5.权利要求1或2的层压材料,其中任选的树脂薄膜层(b)和/或包含淀粉的外聚合物层(f)包括一个或多个选自下列的层
i.与改性淀粉混合的低密度聚乙烯;
ii.塑性薄膜层,包括一个或多个与改性淀粉混合的低密度聚乙烯层和一个或多个低密度聚乙烯(LDPE)层;
iii.三片层,所述三片层包含:
1.任选与改性淀粉混合的低密度聚乙烯,
2.热塑性淀粉,
3.任选与改性淀粉混合的低密度聚乙烯。
6.权利要求1或2的层压材料,其中粘结层c和e包括酐改性的聚烯烃或乙烯-酸共聚物。
7.权利要求1的层压材料,其中不透气材料阻挡层为金属化聚乳酸。
8.权利要求1的层压材料,其中树脂涂覆纸为用乙烯-乙烯醇共聚物涂覆的纸。
9.权利要求1的层压材料,其中金属化聚酯为金属化聚对苯二甲酸乙二酯或聚萘二甲酸乙二酯。
10.一种柔韧性、不透气层压材料,所述层压材料包括以下层:
a.非反应性树脂薄膜内层;
b.任选的树脂薄膜层
c.任选的粘结层;
d.由不透气材料制成的阻挡层;
e.任选的粘结层;
f.外聚合物层,所述外聚合物层包括具有50-70wt%淀粉百分数的淀粉/聚乙烯混合物;
g.任选的外层;
任选其中层b和c和/或层e和f共挤出;
其中任选的树脂薄膜层(b)存在,并且包括低密度聚乙烯薄膜和/或与改性淀粉混合的低密度聚乙烯,其中淀粉经改性以减小其亲水性。
11.权利要求10的层压材料,其中内层(a)包括线型低密度聚乙烯薄膜。
12.权利要求10或11的层压材料,其中任选的树脂薄膜层(b)存在,并且包括
i.低密度聚乙烯(LDPE);
ii.与改性淀粉混合的低密度聚乙烯;
iii.塑性薄膜,包括一个或多个与改性淀粉混合的低密度聚乙烯层和一个或多个低密度聚乙烯(LDPE)层;或
iiv.三片层,所述三片层包含:
a.任选与改性淀粉混合的低密度聚乙烯,
b.热塑性淀粉,
c.任选与改性淀粉混合的低密度聚乙烯。
13.权利要求10或11的层压材料,其中粘结层c和e包括酐改性的聚烯烃或乙烯-酸共聚物。
14.权利要求10或11的层压材料,其中外聚合物层包括线型低密度聚乙烯和具有60wt%淀粉百分数的淀粉/聚乙烯混合物。
15.权利要求10的层压材料,其中任选的外层包括白色聚乙烯,任选包含密封剂。
16.权利要求1-2、7-9和10-11中任一项的层压材料,其中阻挡层(d)包括由来自癸二酸的单体制成的尼龙。
17.权利要求1-2、7-9和10-11中任一项的层压材料,其中外层(g)包括聚乙烯。
18.权利要求1-2、7-9和10-11中任一项的层压材料,其包括:
a.从内侧到外侧的以下层:
i.线型低密度聚乙烯
ii.低密度聚乙烯
iii.粘结层
iv.循环铝箔
v.粘结层
vi.低密度聚乙烯
vii.白色聚乙烯混合物;
或者
b.从内侧到外侧的以下层:
i.线型低密度聚乙烯
ii.来自乙醇的低密度聚乙烯
iii.粘结层
iv.金属化聚乳酸
v.粘结层
vi.来自乙醇的低密度聚乙烯
vii.白色聚乙烯混合物再处理的高密度聚乙烯;
或者
c.从内侧到外侧的以下层:
i.线型低密度聚乙烯
ii.来自乙醇的低密度聚乙烯
iii.粘结层
iv.聚乳酸
v.粘结层
vi.来自乙醇的低密度聚乙烯
vii.白色聚乙烯混合物再处理的高密度聚乙烯;
或者
d.从内侧到外侧的以下层:
i.线型低密度聚乙烯
ii.来自乙醇的低密度聚乙烯
iii.粘结层
iv.金属化纸
v.粘结层
vi.来自乙醇的低密度聚乙烯
vii.白色聚乙烯混合物再处理的高密度聚乙烯;
或者
e.从内侧到外侧的以下层:
i.线型低密度聚乙烯
ii.来自乙醇的低密度聚乙烯
iii.粘结层
iv.两侧以乙烯-乙烯醇共聚物涂覆的纸
v.粘结层
vi.来自乙醇的低密度聚乙烯
vii.白色聚乙烯混合物再处理的高密度聚乙烯;
或者
f.从内侧到外侧的以下层:
i.线型低密度聚乙烯
ii.具有淀粉填充的低密度聚乙烯
iii.粘结层
iv.可再生尼龙阻挡层
v.粘结层
vi.具有淀粉填充的低密度聚乙烯
vii.白色聚乙烯混合物。
19.一种管,所述管具有由前述权利要求中任一项的层压材料制成的顶端、底端和柔韧壁,其中在底端的壁卷曲成密封部分,其中顶端具有密封到并且近似垂直于壁的肩部,肩部由比壁更刚性的材料制成,所述肩部包括或提供管口的支持体,并且管口具有盖,这样可将容器密封。
20.权利要求19的管,其中整个管可循环;或者其中管的25%用循环材料制成。
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WO2015176867A1 (en) * | 2014-05-19 | 2015-11-26 | Unilever Plc | Toothpaste tube and composition |
RU2016147224A (ru) | 2014-06-02 | 2018-07-10 | Дзе Проктер Энд Гэмбл Компани | Многослойные термопластичные полимерные пленки, содержащие полимолочную кислоту |
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JP2014512982A (ja) | 2014-05-29 |
RU2013145552A (ru) | 2015-04-20 |
AU2012228823B2 (en) | 2014-11-27 |
CA2829501A1 (en) | 2012-09-20 |
SG192802A1 (en) | 2013-09-30 |
WO2012122898A1 (en) | 2012-09-20 |
EP2683548B1 (en) | 2020-05-06 |
EP2683548A1 (en) | 2014-01-15 |
US9138968B2 (en) | 2015-09-22 |
MX2013010412A (es) | 2013-10-17 |
CN103502000A (zh) | 2014-01-08 |
AU2012228823A1 (en) | 2013-05-09 |
EP2683548A4 (en) | 2014-08-06 |
US20130333787A1 (en) | 2013-12-19 |
BR112013022143A2 (pt) | 2016-12-06 |
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