CN106585017A - 层叠片材和成形容器 - Google Patents
层叠片材和成形容器 Download PDFInfo
- Publication number
- CN106585017A CN106585017A CN201510677358.2A CN201510677358A CN106585017A CN 106585017 A CN106585017 A CN 106585017A CN 201510677358 A CN201510677358 A CN 201510677358A CN 106585017 A CN106585017 A CN 106585017A
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- CN
- China
- Prior art keywords
- poly
- resin layer
- biodegradable resin
- laminated sheet
- sheet material
- 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.)
- Pending
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- 239000011347 resin Substances 0.000 claims abstract description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000001301 oxygen Substances 0.000 claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 45
- 229920006167 biodegradable resin Polymers 0.000 claims abstract description 39
- 230000004888 barrier function Effects 0.000 claims abstract description 26
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 20
- 230000035699 permeability Effects 0.000 claims abstract description 11
- 229920000954 Polyglycolide Polymers 0.000 claims abstract description 7
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- 239000008107 starch Substances 0.000 claims abstract description 6
- 235000019698 starch Nutrition 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 49
- -1 poly- butanedioic acid butanediol Ester Chemical class 0.000 claims description 21
- 239000004626 polylactic acid Substances 0.000 claims description 20
- 239000000853 adhesive Substances 0.000 claims description 19
- 230000001070 adhesive effect Effects 0.000 claims description 19
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 5
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 239000004633 polyglycolic acid Substances 0.000 claims description 5
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- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
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- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 230000000813 microbial effect Effects 0.000 abstract description 2
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 abstract 1
- 229920000331 Polyhydroxybutyrate Polymers 0.000 abstract 1
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
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- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 229960004424 carbon dioxide Drugs 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
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- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
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- 238000010276 construction Methods 0.000 description 2
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- KFUSEUYYWQURPO-UHFFFAOYSA-N 1,2-dichloroethene Chemical compound ClC=CCl KFUSEUYYWQURPO-UHFFFAOYSA-N 0.000 description 1
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N 4-Methylcyclohexylamine Chemical class CC1CCC(N)CC1 KSMVBYPXNKCPAJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
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- 239000004698 Polyethylene Substances 0.000 description 1
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
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- 150000004984 aromatic diamines Chemical class 0.000 description 1
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- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 1
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- LMHUKLLZJMVJQZ-UHFFFAOYSA-N but-1-ene;prop-1-ene Chemical compound CC=C.CCC=C LMHUKLLZJMVJQZ-UHFFFAOYSA-N 0.000 description 1
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- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
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- 239000001530 fumaric acid Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- WGOROJDSDNILMB-UHFFFAOYSA-N octatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WGOROJDSDNILMB-UHFFFAOYSA-N 0.000 description 1
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007920 subcutaneous administration Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
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Classifications
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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
- B32B1/00—Layered products having a non-planar shape
-
- 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
-
- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明提供一种层叠片材和成形容器。其中层叠片材具有氧阻隔性树脂层和生物降解性树脂层,该生物降解性树脂层通过粘接层层叠于该氧阻隔性树脂层的两面,生物降解性树脂层的质量百分率之和为片材整体的90%以上,并且各个生物降解性树脂层的质量百分率为片材整体的10%以上,片材整体的氧渗透率为10cc/m2·day以下。构成生物降解性树脂层的生物降解性树脂使用从聚乳酸、聚琥珀酸丁二醇酯、聚羟基丁酸酯、聚己内酯、聚羟基烷酸、聚乙醇酸、改性聚乙烯醇、淀粉中选择的至少一种。本发明的层叠片材同时具有优良的热成形性、氧阻隔性,且通过堆肥时的微生物分解(生物降解)变为二氧化碳、水,能返回到自然。
Description
技术领域
本发明涉及一种层叠片材,具体地,涉及完全分解型的生物降解性阻隔片材和将其热成形而成的容器。
背景技术
近年来,塑料废弃物增多成为大的社会问题。以往,高分子材料多数是以高性能和长期稳定性为目的开发、生产的,所以在自然环境中不容易分解。因此,如何处置、管理不要的大量塑料废弃物在世界规模上都成为社会问题。在这些塑料废弃物中,由聚乙烯、聚丙烯等聚烯烃类树脂、聚对苯二甲酸乙二酯(PET)等聚酯类树脂、聚氯乙烯树脂等各种合成树脂所形成的容器因为体积庞大,所以特别成为问题。
其中,在包装业界由可再生资源制造的塑料的需求提高。随着与塑料对环境带来的影响有关的消费者意识提高,消费者要求包装产品的容器由可再生资源制造。
其中,如以聚乳酸(PLA)为代表的生物降解性塑料能作为各种各样的包装材料来利用,但是与聚烯烃相比气体渗透性高,因此,不太适合在氧存在时劣化的产品的包装。因此,要求赋予了如抑制氧渗透的功能性的材料。
例如在专利文献1中对由聚乳酸和除氧剂构成的物品进行了记载。该除氧剂选自下述组。
·可氧化的化合物和过渡金属催化剂
·烯类不饱和烃和过渡金属催化剂
·抗坏血酸盐
·异抗坏血酸盐
·亚硫酸盐
·抗坏血酸盐和过渡金属催化剂(该催化剂由单纯金属或者盐构成)
·过渡金属的化合物、络合物或者螯合剂
·聚羧酸、水杨酸或者聚胺的过渡金属络合物或者螯合剂
·单宁
另外,物品的形状可以是膜、涂层、覆面层、其它的形式。
但是,关于在专利文献1中提出的由PLA和除氧剂构成的物品,所谓除氧剂,一般是出于在具有有限的空间的密闭环境中制成脱氧状态的目的而使用的,对于进行热成形来抑制来自大气的氧渗透的用途有限。
另外,在专利文献2中提出了如下生物降解性氧吸收性的塑料:其包含生物降解性基材和还原铁粒子,该还原铁粒子在适当浓度下存在而吸收氧,并指定比铁粒子不存在的情况下的变形温度实际上降低的充分的浓度。
但是,作为专利文献2记载的构成,提出了一种多层层叠结构,其由箔层、粘接剂层、具有铁基的氧吸收剂的PLA层以及密封材料层构成,容易预想到具有该结构的构成不具有完全分解型的分解度。
现有技术文献
专利文献
专利文献1:美国专利第6908652号
专利文献2:WO2011/142871号
发明内容
本发明是鉴于上述情况完成的,其目的在于提供如下层叠片材和将其热成形而成的容器:该层叠片材同时具有优良的热成形性、氧阻隔性,且通过堆肥时的微生物分解(生物降解)变为二氧化碳、水,能返回到自然。
本发明的层叠片材具有氧阻隔性树脂层和生物降解性树脂层,该生物降解性树脂层通过粘接层层叠于该氧阻隔性树脂层的两面,所述生物降解性树脂层的质量百分率之和为片材整体的90%以上,并且各个生物降解性树脂层的质量百分率为片材整体的10%以上,片材整体的氧渗透率为10cc/m2·day以下。
另外,在上述的层叠片材中,构成所述生物降解性树脂层的生物降解性树脂使用从聚乳酸、聚琥珀酸丁二醇酯、聚羟基丁酸酯、聚己内酯、聚羟基烷酸、聚乙醇酸、改性聚乙烯醇、淀粉中选择的至少一种。
另外,在上述的层叠片材中,优选所述生物降解性树脂使用聚乳酸。
而且,在上述的层叠片材中,优选片材整体的厚度为200~1300μm,氧阻隔性树脂层的厚度为10~50μm。
另一方面,本发明的成形容器是将上述的各种层叠片材热成形而成的。
根据本发明的层叠片材和成形容器,同时具有优良的热成形性、氧阻隔性,且通过堆肥时的微生物分解(生物降解)变为二氧化碳、水,能返回到自然。
附图说明
图1是示出本发明的实施方式所涉及的层叠片材的层叠结构的一例的概略纵侧视截面图。
具体实施方式
作为本发明的一实施方式,如图1所示,本发明的层叠片材是在氧阻隔性树脂层(12)上通过粘接层(11a)在最表面层叠有成为表皮层的生物降解性树脂层(10a),另外在该生物降解性树脂层(10a)的相反侧同样通过粘接层(11b)层叠有成为皮下层的生物降解性树脂层(10b)而成的。片材整体的厚度为200~1300μm,氧阻隔性树脂层的厚度为10~50μm。
以下详细地说明。
<层叠片材>
本发明的一实施方式所涉及的层叠片材的层构成如上所述,是生物降解性树脂层/粘接层/氧阻隔性树脂层/粘接层/生物降解性树脂层,简单地可表述为表皮层/粘接层/氧阻隔层/粘接层/皮下层。也可以设为在皮下层新设有如下层的构成:该层是将在制造本发明的层叠片材、成形容器的工序中产生的碎屑不废弃而细细地粉碎、或者在热熔融后粒化而作为再生品回收的层。
另外,在皮下层侧没有特别限定,可以设为如下构成:通过例如直接印刷、将印刷的膜层叠的方法设有印刷面。
本发明中的层叠片材的片材整体的厚度优选200~1300μm。当不足200μm时,热成形后的容器形成有厚度薄的部位,由此,由于被称为压曲强度的表示相对于压缩、压力的耐性的容器强度的降低,例如,由于在容器的里面收纳有内容物的状态下搬运、保管时的振动、压缩,有可能发生容器的变形、破损。另一方面,当片材整体的厚度超过1300μm时,难以在热成形时在片材的厚度方向充分地传导热,有可能发生成形不良。
作为层叠片材的挤出成形的方法没有特别限定,可列举如下方法:例如,使用4台或者4台以上的单螺杆或者多螺杆挤出机熔融挤出各个原料树脂,通过送料区块和T形模具进行层叠的方法,或者使用多歧管模具进行层叠的方法。
<生物降解性树脂层(10a、10b)>
作为生物降解性树脂层的厚度,如果是生物降解性树脂层的质量百分率之和相对于片材整体设为片材整体的90%以上的构成,则无论是将表皮层和皮下层设为相同厚度的上下对称型还是设为不同厚度的上下不对称型,哪一方都可以。在上下不对称型的情况下,为了防止特别是由于进行深拉的容器成形时的削薄导致的构成层的断裂、破裂,优选各个生物降解性树脂层的质量百分率为片材整体的10%以上。
作为构成本发明的生物降解性树脂层的生物降解性树脂,可以使用选自聚乳酸、聚琥珀酸丁二醇酯、聚羟基丁酸酯、聚己内酯、聚羟基烷酸、聚乙醇酸、改性聚乙烯醇、淀粉的1种,也可以使用将选自这些生物降解性树脂的2种以上混合的物质,关于混合2种以上时的配合比例没有特别限定。另外,在使用选自这些生物降解性树脂的1种的情况下,特别优选使用通用的聚乳酸。
一般,生物降解性树脂大多结晶速率慢,所以有如下倾向:将假定了用于需要提高耐热性的用途的结晶度提高,或者仅以生物降解性树脂难以出现片材的硬度,所以不特别限定于此,也可以添加滑石、亚乙基双硬脂酸酰胺(EBS)等改性剂。此外,作为这些改性剂的添加量,为了改质发挥较大的效果,优选相对于生物降解性树脂设为0.1~30%。
本发明记载的生物降解性树脂的熔体流动速率(Melt FlowRate。以下仅称为MFR)适用一般进行的如下方法:在一定温度和载荷条件下,测定从通过活塞设置于气缸底部的规定口径的模具挤出10分钟左右的树脂量;本发明的测定条件为:温度设定为190℃,载荷为2.16kgf。优选本发明记载的生物降解性树脂的MFR为1.0~20g/10min.。若是不足1.0g/10min.,有可能片材挤出成形加工时的加工性降低。当超过20g/10min.时,有可能在挤出成形时、容器成形时通过加热使片材垂下的耐垂伸性变差,并且耐冲击性也降低。
<氧阻隔性树脂层(12)>
作为构成氧阻隔性树脂层的氧阻隔性树脂,代表性地可列举例如乙烯-乙烯基醇共聚物树脂、聚酰胺树脂、聚乙烯醇、聚偏二氯乙烯,但是并不限定于此。其中,在挤出成形性的方面优选乙烯-乙烯基醇共聚物树脂。
乙烯-乙烯基醇共聚物树脂通常是将乙烯-乙酸乙烯酯共聚物皂化而得到的,为了使其具备氧阻隔性、挤出成形性,乙烯含有量为10~65摩尔%,优选为20~50摩尔%,皂化度为90%以上,优选为95%以上。
另外,作为聚酰胺树脂,可列举己内酰胺、十二内酰胺等内酰胺聚合物、6-氨基己酸、11-氨基十一酸、12-氨基十二酸等氨基羧酸的聚合物、己二胺、葵二胺、十二甲撑二胺、2,2,4-或者2,4,4-三甲基六亚甲基二胺等脂肪族二胺、1,3-或者1,4-双(氨基甲基)环己烷、双(对-氨基环己基甲烷)等脂环族二胺、间苯二甲胺或者对-苯二甲胺等芳香族二胺等的二胺单元与己二酸、辛二酸、葵二酸等脂肪族二羧酸、环己烷二羧酸等脂环族二羧酸、对苯二甲酸、间苯二甲酸等芳香族二羧酸等的二羧酸单元的缩聚物、以及这些的共聚物等。
作为聚酰胺树脂,具体地有尼龙6、尼龙9、尼龙11、尼龙12、尼龙66、尼龙610、尼龙611、尼龙612、尼龙6T、尼龙6I、尼龙MXD6、尼龙6/66、尼龙6/610、尼龙6/6T、尼龙6I/6T等,其中尼龙6、尼龙MXD6较佳。
氧阻隔性树脂层的厚度优选为10~50μm,更优选为20~40μm。当不足10μm时,在将片材热成形后的容器中,氧阻隔性树脂层的厚度极其薄,由此得不到可抑制由于收纳于容器内的内容物氧化劣化导致的质量下降程度的氧阻隔性能,另外,当超过50μm时,有可能在热成形后实施的容器的冲剪加工加工时产生被称为所谓的须状毛刺的外观不良。
片材整体的氧渗透率为10cc/m2·day以下,更优选为5cc/m2·day以下。当超过10cc/m2·day时,在热成形容器的内容物氧化劣化的情况下,有可能不能出现充分抑制氧化劣化的功能。
<粘接层(11a、11b)>
作为构成粘接层的树脂,优选改性聚烯烃类聚合物。作为构成粘接层的改性聚烯烃类聚合物,代表性地可列举如下:将乙烯、丙烯、1-丁烯、3-甲基1-丁烯、1-戊烯、4-甲基1-戊烯、1-己烯、1-辛烯、1-十二碳烯等碳原子数为2~20程度的其它的聚烯烃、醋酸乙烯、氯乙烯、丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯、聚苯乙烯等与乙烯化合物的共聚物等聚烯烃类树脂、乙烯-丙烯共聚物、乙烯-丙烯-二烯共聚物、乙烯-丁烯-1共聚物、丙烯-丁烯-1共聚物等聚烯烃类橡胶,用丙烯酸、甲基丙烯酸、丁烯酸、异丁烯酸、马来酸、富马酸、衣康酸、柠康酸、四氢邻苯二甲酸等不饱和羧酸或者其酰卤、酰胺、酰亚胺、酐、酯等衍生物具体地为马来酰氯、马来酰亚胺、无水马来酸、无水柠康酸、马来酸单甲酯、马来酸二甲酯、马来酸缩水甘油酯等在接枝反应条件下改性所得的物质。
作为改性聚烯烃类聚合物,其中由不饱和二羧酸或者其酸酐、特别是马来酸或者其酸酐改性的乙烯类树脂、丙烯类树脂、或者乙烯-丙烯或者丁烯-1共聚物橡胶较佳。
对于改性聚烯烃类聚合物层的厚度,哪个层都优选5~50μm,更优选为10~30μm。当不足5μm时,有可能得不到充分的层间的粘接强度,另外,当超过50μm时,有可能在热成形后实施的容器的冲剪加工加工时发生被称为所谓的须状毛刺的外观不良。
<成形容器>
本发明的成形容器是通过将本发明的层叠片材热成形而成的。作为热成形方法,可列举如下方法等:一般的真空成形,压空成形,作为这些的应用使柱塞与片材的单面接触而进行成形的助压模塞法,另外,使呈一对的凸凹模具与片材的两面接触而进行成形的被称为所谓的合模(matched mould)的方法,但是并不限定于此。另外,作为在成形前使片材加热软化的方法,能适用如下等公知的片材加热方法:通过非接触加热的红外线加热器等进行辐射加热,使片材与加热的热盘直接接触而使其软化的热盘加热。
热成形时的成形温度是考虑到树脂的熔点等而适当设定的,但是当片材加热温度过低时,加热成形后的容器的赋型状态不充分,反之,当片材加热温度过高时,有可能发生引起热盘熔化等不良情况,所以优选设定为适当的温度。
【实施例】
以下列举实施例和比较例更具体地说明本发明,但是本发明完全不限定于实施例等的内容。
在实施例中使用的树脂原料如下。
(1)生物降解性树脂
①聚乳酸“4032D”
(美国NatureWorks公司制造,密度:1.24g/cm3、MFR:4.0g/10min.(190℃,2.16kgf))
②聚乳酸“GH501H”
(湖北光合生物科技有限公司制造,密度:1.24g/cm3,MFR:4.5g/10min.(190℃,2.16kgf))
③聚乳酸“REVODE 190”
(浙江海正生物材料股份有限公司制造,密度:1.24g/cm3,MFR:2.5g/10min.(190℃,2.16kgf))
④聚琥珀酸丁二醇酯树脂“FD92”
(三菱化学株式会社制造,密度:1.24g/cm3,MFR:4.0g/10min.(190℃,2.16kgf))
(2)氧阻隔性树脂
乙烯-乙烯基醇共聚物(EVOH)“eval J171B”
(可乐丽(Kuraray)株式会社制造,密度:1.18g/cm3,MFR:1.7g/10min.(190℃,2.16kgf),乙烯含量32mol%)
(3)粘接层用树脂
①改性聚酯类聚合物“frimalloy GK320”
(三菱化学株式会社制造,密度:1.03g/cm3,MFR:10g/10min.(230℃,2.16kgf))
②改性聚烯烃类聚合物(改性PO)“MODIC F563”
(三菱化学株式会社制造,密度:1.03g/cm3,MFR:3.0g/10min.(190℃,2.16kgf))
<实施例1>
通过使用送料区块的挤出成形加工,在表皮层和皮下层使用作为①的聚乳酸“4032D”作为生物降解性树脂,使用①的改性聚酯类聚合物“FRIMALLOY GK320”作为粘接层用树脂,得到如下多层层叠片材:其具有成为生物降解性树脂层(10a)140μm/粘接层(11a)15μm/氧阻隔性树脂层(12)30μm/粘接层(11b)15μm/生物降解性树脂层(10b)700μm的层构成,总厚度为900μm,生物降解性树脂层的质量百分率成为片材整体的94%。
<实施例2>
除了使用②的改性聚烯烃类聚合物“MODIC F563”作为粘接层用树脂以外,得到与实施例1同样的多层层叠片材。
<实施例3>
除了在表皮层和皮下层使用②的聚乳酸“GH501H”作为生物降解性树脂以外,得到与实施例1同样的多层层叠片材。
<实施例4>
除了在表皮层和皮下层使用③的聚乳酸“REVODE 190”作为生物降解性树脂以外,得到与实施例1同样的多层层叠片材。
<实施例5>
除了将为百分之95质量的树脂①的聚乳酸“4032D”和百分之5质量的树脂④的聚琥珀酸丁二醇酯树脂“FD92”混合作为生物降解性树脂以外,得到与实施例1同样的多层的层叠片材。
<比较例1>
通过使用送料区块的挤出成形加工,在表皮层和皮下层使用①的聚乳酸“4032D”作为生物降解性树脂,得到如下多层层叠片材:其具有成为生物降解性树脂层(10a)30μm/粘接层(11a)15μm/氧阻隔性树脂层(12)30μm/粘接层(11b)15μm/生物降解性树脂层(10b)110μm的层构成,总厚度为200μm,生物降解性树脂层的质量百分率之和成为片材整体的72%。
<比较例2>
使用1台单螺杆挤出机,使用①的聚乳酸“4032D”作为生物降解性树脂,得到总厚度为700μm的单层片材。
另一方面,以下说明本发明记载的层叠片材的氧渗透率的测定方法。
用以下方法测定片材整体的氧渗透率。氧渗透率测定是在向以下高温高湿环境下投入前后进行测定的。
[测定方法]依据GB/T 1038
使用设备:济南兰光机电技术有限公司制造VAC-V1
测定条件:23℃×65%R.H.
样品设置:基本上鉴定容器成形后的实用性,在氧从片材样品的皮下层侧渗透的方向上设置样品。
用以下方法评价片材的生物降解性。
[基于土壤埋设试验的层叠片材的质量变化]
在微生物活性的土壤中将片材埋设180天,通过外观观察、质量测定等计算分解度。
[生物降解性的评价方法]
在培养温度设为58℃±2℃的堆肥条件下保管180天后,用依据ISO 14855的方法评价生物降解性。此外,如果分解度为90%以上,则评价为完全分解。
在表1中归纳出各实施例和比较例的相对于层叠片材的氧渗透率的测定和生物降解性的评价结果。
此外,在上述实施例1~4中,使用聚乳酸作为生物降解性树脂,在实施例5中,使用将聚乳酸和聚琥珀酸丁二醇酯混合的物质作为生物降解性树脂,但是不特别限定于此,在上述实施例1~4中,也可以使用选自聚琥珀酸丁二醇酯、聚羟基丁酸酯、聚己内酯、聚羟基烷酸、聚乙醇酸、改性聚乙烯醇、淀粉的1种作为生物降解性树脂,或者也可以使用将选自选自聚乳酸、聚琥珀酸丁二醇酯、聚羟基丁酸酯、聚己内酯、聚羟基烷酸、聚乙醇酸、改性聚乙烯醇、淀粉的2种以上混合的物质作为生物降解性树脂。在该情况下,能得到与上述各实施例相同的效果。
【表1】
根据上述表1的结果,在实施例1至5中氧渗透率均被控制得较低,另外,生物降解度为90%以上,为完全分解,与此相对,在比较例1中,氧渗透率虽低,但是其分解度为70%,为不充分分解,在另一个比较例2中分解度为100%,关于生物降解性没有问题,但是氧渗透率为350cc/m2·day,非常高,因而其受到氧成分影响的氧化劣化的抑制效果低。
因此,通过设为由本发明的实施例记载的构成树脂构成的多层片材,能提供如下完全分解型生物降解性阻隔片材和将其热成形而成的容器:该完全分解型生物降解性阻隔片材同时具有优良的热成形性、氧阻隔性,且通过堆肥时的微生物分解(生物降解)变为二氧化碳、水,能返回到自然。
Claims (5)
1.一种层叠片材,其具有氧阻隔性树脂层和生物降解性树脂层,该生物降解性树脂层通过粘接层层叠于该氧阻隔性树脂层的两面,所述生物降解性树脂层的质量百分率之和为片材整体的90%以上,并且各个生物降解性树脂层的质量百分率为片材整体的10%以上,片材整体的氧渗透率为10cc/m2·day以下。
2.如权利要求1所述的层叠片材,其特征在于,构成所述生物降解性树脂层的生物降解性树脂使用从聚乳酸、聚琥珀酸丁二醇酯、聚羟基丁酸酯、聚己内酯、聚羟基烷酸、聚乙醇酸、改性聚乙烯醇、淀粉中选择的至少一种。
3.如权利要求2所述的层叠片材,其特征在于,所述生物降解性树脂使用聚乳酸。
4.如权利要求1至3中任一项所述的层叠片材,其特征在于,片材整体的厚度为200~1300μm,氧阻隔性树脂层的厚度为10~50μm。
5.一种成形容器,其为将如权利要求1至4中任一项所述的层叠片材热成形而成。
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WO2023080498A1 (ko) * | 2021-11-02 | 2023-05-11 | 에스케이마이크로웍스 주식회사 | 다층 배리어 필름, 이의 제조방법 및 이를 포함하는 포장재 |
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EP2781351A1 (en) * | 2011-11-11 | 2014-09-24 | The Nippon Synthetic Chemical Industry Co., Ltd. | Biodegradable laminate |
JP2013199059A (ja) * | 2012-03-26 | 2013-10-03 | Toray Ind Inc | 積層フィルム |
JP2014000683A (ja) * | 2012-06-15 | 2014-01-09 | Nippon Synthetic Chem Ind Co Ltd:The | 多層延伸フィルムの製造方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111278650A (zh) * | 2017-10-04 | 2020-06-12 | 日本制纸株式会社 | 阻隔材料 |
US11504952B2 (en) | 2017-10-04 | 2022-11-22 | Nippon Paper Industries Co., Ltd. | Barrier material |
CN116034150A (zh) * | 2020-08-12 | 2023-04-28 | 株式会社可乐丽 | 乙烯醇系聚合物及其用途 |
Also Published As
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WO2017069127A1 (ja) | 2017-04-27 |
JPWO2017069127A1 (ja) | 2018-08-02 |
EP3366470A1 (en) | 2018-08-29 |
US20180304573A1 (en) | 2018-10-25 |
TW201722727A (zh) | 2017-07-01 |
EP3366470A4 (en) | 2019-05-08 |
JP6996978B2 (ja) | 2022-01-17 |
TWI781086B (zh) | 2022-10-21 |
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