CN107848186A - 多层预制品和多层拉伸吹塑成形容器 - Google Patents
多层预制品和多层拉伸吹塑成形容器 Download PDFInfo
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- CN107848186A CN107848186A CN201680041693.6A CN201680041693A CN107848186A CN 107848186 A CN107848186 A CN 107848186A CN 201680041693 A CN201680041693 A CN 201680041693A CN 107848186 A CN107848186 A CN 107848186A
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- multilayer
- prefabrication
- low
- intermediate layer
- resin
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- 238000000071 blow moulding Methods 0.000 claims abstract description 34
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- 239000003595 mist Substances 0.000 claims abstract description 20
- 238000010276 construction Methods 0.000 claims abstract description 18
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 238000002347 injection Methods 0.000 description 24
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
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- 125000003118 aryl group Chemical group 0.000 description 3
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- XDZMPRGFOOFSBL-UHFFFAOYSA-N 2-ethoxybenzoic acid Chemical compound CCOC1=CC=CC=C1C(O)=O XDZMPRGFOOFSBL-UHFFFAOYSA-N 0.000 description 2
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- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 125000002252 acyl group Chemical group 0.000 description 2
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-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
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- NVEUWWMNWPNXOC-UHFFFAOYSA-N 2,2-dimethyltridecane Chemical compound CCCCCCCCCCCC(C)(C)C NVEUWWMNWPNXOC-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- 101100109101 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) APE3 gene Proteins 0.000 description 1
- 101100499769 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) APE4 gene Proteins 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
- 150000007513 acids Chemical class 0.000 description 1
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- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
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- AVVFWBDWRGVOJI-UHFFFAOYSA-N ethane-1,2-diol;hexane-1,6-diol Chemical compound OCCO.OCCCCCCO AVVFWBDWRGVOJI-UHFFFAOYSA-N 0.000 description 1
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- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexamethylene diamine Natural products NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
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- 150000003951 lactams Chemical class 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ROTJZTYLACIJIG-UHFFFAOYSA-N pentane-1,3,5-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CCC(O)=O ROTJZTYLACIJIG-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
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- 238000006068 polycondensation reaction Methods 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/03—Injection moulding apparatus
- B29C45/13—Injection moulding apparatus using two or more injection units co-operating with a single mould
-
- 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
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/14—Making preforms characterised by structure or composition
-
- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
-
- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
- B29C45/1642—Making multilayered or multicoloured articles having a "sandwich" structure
- B29C45/1646—Injecting parison-like articles
-
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Abstract
本发明涉及具有各自由对苯二甲酸乙二醇酯系聚酯树脂形成的内层和外层以及至少一层至少由低结晶性对苯二甲酸乙二醇酯系聚酯树脂和阻气性芳香族聚酰胺树脂形成的中间层的多层预制品。所述低结晶性对苯二甲酸乙二醇酯系聚酯树脂含有15‑20摩尔%的环己烷二甲醇或7.5‑15摩尔%的间苯二甲酸作为共聚合组分;低结晶性对苯二甲酸乙二醇酯系聚酯树脂与阻气性芳香族聚酰胺树脂的重量比在50:50至75:25的范围内;所述中间层在预制品整体中的重量比例为1重量%以上且小于10重量%;具有多层结构的部分的雾度为5%以上。因此,该多层预制品能够提供具有优异的透明性、阻气性和机械强度的拉伸吹塑成形容器。
Description
技术领域
本发明涉及多层预制品和将该多层预制品双轴拉伸吹塑成形而得到的多层拉伸吹塑成形容器。更具体地,本发明涉及能够成形具有优异的透明性、层间粘接性和机械强度的多层拉伸吹塑成形容器的多层预制品。
背景技术
由聚对苯二甲酸乙二醇酯代表的聚酯树脂具有优异的如成形性、透明性、机械强度和耐化学品性等性质,因此,已广泛用于包装容器领域。为了改进包含聚酯树脂的容器对氧等气体的阻气性,已知在聚酯树脂的内层与外层之间形成乙烯-乙酸乙烯酯共聚物的皂化产物或聚酰胺的层作为中间层的多层结构的包装材料。为了进一步改进上述多层结构的包装材料的阻气性,还尝试使中间层共混有粘土(专利文献1)。
在该多层结构的包装材料中,如果聚酰胺树脂用作中间层,则聚酰胺树脂与构成内外层的聚酯树脂之间的粘接性变差。因此,已提出了将聚酯树脂和聚酰胺树脂、或聚酯树脂和含粘土的聚酰胺树脂的共混物的树脂组合物用作中间层(专利文献2和3)。
然而,当将聚酯树脂和聚酰胺树脂,特别是聚酰胺树脂中具有特别优异的阻气性的如聚己二酰间苯二甲胺(MXD6)等芳香族聚酰胺树脂的共混物的树脂组合物用作中间层时,发生损害由聚酯树脂具有的优异透明性的问题。作为用于改进聚酯树脂和聚酰胺树脂的共混物的透明性的方法,以下专利文献4公开了一种透明聚合物共混物,其为包含特定的共聚聚酯树脂的第一组分和作为特定的酰胺-交换共混物的第二组分的非混溶性共混物的聚合物组合物,并调节第一组分与第二组分之间的折射率的差。然而,通过将此类聚合物共混物的预制品双轴拉伸吹塑成形而得的拉伸吹塑成形容器并没有表现出优异的透明性。
为了解决上述问题,本发明人已提出了通过使用低结晶性聚酯树脂作为待添加到聚酰胺树脂的聚酯树脂来兼顾实现双轴拉伸吹塑成形容器的阻气性和透明性的技术(专利文献5)。
现有技术文献
专利文献
专利文献1:JP-A-2004-142444
专利文献2:JP-A-2005-59859
专利文献3:国际公开WO2010/035654
专利文献4:日本专利第5296385号公报
专利文献5:JP-A-2015-157468
发明内容
发明要解决的问题
根据上述由本发明人提出的专利申请(专利文献5),发现了在特定的拉伸条件下,低结晶性聚酯树脂展现接近于聚酰胺树脂的折射率。因此,使得可以提供具备阻气性和优异的透明性的双轴拉伸吹塑成形容器。
然而,低结晶性聚酯树脂的使用带来了双轴拉伸吹塑成形容器呈现机械强度降低的新问题。也就是说,一般而言通过双轴拉伸吹塑成形使聚酯树脂取向并结晶,因而使其获得机械强度。然而,当使用低结晶性聚酯树脂时,取向和结晶发生得不太多且机械强度变低。因此,当试图获得用于容纳碳酸饮料等自发产生压力的内容物的耐压性容器时,容器应对诸如落下等情况的强度可能变得不足。
因此,本发明的目的是提供一种拉伸吹塑成形容器,其具有包括由聚酯树脂形成的内层和外层以及由聚酯树脂和芳香族聚酰胺树脂的共混物形成的中间层的多层结构,展现出优异的透明性、阻气性和机械强度,以及提供一种能够成形为上述拉伸吹塑成形容器的多层预制品。
用于解决问题的方案
根据本发明,提供一种多层预制品,其具有由对苯二甲酸乙二醇酯系聚酯树脂形成的内层和外层,以及至少一层至少由低结晶性对苯二甲酸乙二醇酯系聚酯树脂和阻气性芳香族聚酰胺树脂形成的中间层,其中低结晶性对苯二甲酸乙二醇酯系聚酯树脂含有作为共聚合组分的以15~20摩尔%范围内的量的环己烷二甲醇或以7.5~15摩尔%范围内的量的间苯二甲酸;低结晶性对苯二甲酸乙二醇酯系聚酯树脂和所述阻气性芳香族聚酰胺树脂的重量比在50:50~75:25的范围内;所述中间层相对于预制品整体的重量比例为1重量%以上且小于10重量%;和已形成有多层结构的部分的雾度为5%以上。
在本发明的多层预制品中,期望:
1.低结晶性对苯二甲酸乙二醇酯系聚酯树脂和阻气性芳香族聚酰胺树脂满足下式,
0≤RIE-RIA≤0.03 …(1)
其中,RIE和RIA为分别由低结晶性对苯二甲酸乙二醇酯系聚酯树脂和阻气性芳香族聚酰胺树脂制成的注射成形板在同时双轴拉伸3×3倍后的折射率。
2.在口颈部未形成中间层。
3.中间层含有包含氧化催化剂和氧化性有机组分的氧吸收性组分、或层状硅酸盐的至少之一。
4.阻气性芳香族聚酰胺树脂为末端氨基浓度为40eq/106g以上的含有亚二甲苯基的聚酰胺树脂。
根据本发明,还提供一种多层拉伸吹塑成形容器,其通过将多层预制品双轴拉伸吹塑成形而得,已形成有多层结构的部分的雾度为3%以下。
本发明的多层拉伸吹塑成形容器特别优选为耐压性容器。
发明的效果
本发明人在先已提出了一种双轴拉伸吹塑成形容器,其通过在共混有芳香族聚酰胺系阻气性树脂的中间层中选择低结晶性聚酯树脂用作基质(matrix),使低结晶性聚酯树脂在拉伸后展现接近于芳香族聚酰胺树脂的折射率,折射率的差△RI(=∣RIE-RIA∣)为0.03以下,具有壁部的雾度为3%以下的如此优异的透明性且还维持优异的阻气性。然而,发现当将双轴拉伸吹塑成形容器用作用于容纳碳酸饮料的耐压性容器时,容器的机械强度不足。
本发明中,作为如下的结果,使得可以提供一种多层预制品,其能够成形为具有令人满意的机械强度还维持优异的阻气性和透明性的双轴拉伸吹塑成形容器:
(i)低结晶性对苯二甲酸乙二醇酯系聚酯树脂含有作为共聚合组分的以15~20摩尔%范围内的量的环己烷二甲醇或以7.5~15摩尔%范围内的量的间苯二甲酸;
(ii)低结晶性对苯二甲酸乙二醇酯系聚酯树脂和阻气性芳香族聚酰胺树脂的重量比在50:50~75:25的范围内;
(iii)中间层相对于预制品整体的重量比例为1重量%以上且小于10重量%。
从后述实施例的结果来看,本发明的上述作用效果将变得明显。也就是说,尽管中间层使用满足上述式(1)的聚酰胺树脂和低结晶性聚酯树脂的共混物形成,但是如果不满足上述(i)至(iii)中的任何一个要求,也不会获得足够程度的透明性或阻气性,将发生中间层剥离或瓶的强度降低(比较例1至7)。另一方面,由本发明的多层预制品获得的双轴拉伸吹塑成形容器在透明性、阻气性、抑制中间层剥离以及瓶的强度方面是令人满意的(实施例1至4)。
另外,在本发明的多层预制品中,存在中间层的部分具有5%以上的雾度且是不透明的。因此,可以目视确认预制品中形成包括中间层的多层结构的位置。因而,使得容易判断阻气性树脂是否确实存在于在拉伸吹塑成形步骤后成为呈现最小厚度且必须具有阻气性的主体部的位置,提供了在生产步骤中便于检查的优点。
附图说明
[图1]其为说明本发明的多层预制品的截面结构的图。
[图2]其为说明本发明的多层预制品的另一截面结构的图。
[图3]其为示出本发明的多层拉伸吹塑成形容器的图。
具体实施方式
(多层预制品)
本发明的多层预制品为具有由对苯二甲酸乙二醇酯系聚酯树脂(下文通常称作“PET树脂”)形成的内层和外层,以及至少一层至少由低结晶性对苯二甲酸乙二醇酯系聚酯树脂(下文通常称作“低结晶性PET树脂”)和阻气性芳香族聚酰胺树脂(下文通常称作“阻气性聚酰胺树脂”)形成的中间层的多层预制品,其中,如上所述,重要的特征在于(i)低结晶性PET树脂含有作为共聚合组分的以15~20摩尔%范围内的量的环己烷二甲醇或以7.5~15摩尔%范围内的量的间苯二甲酸;(ii)低结晶性PET树脂和阻气性聚酰胺树脂的重量比在50:50~75:25、并且特别是60:40~75:25的范围内;(iii)中间层相对于预制品整体的重量比例为1重量%以上且小于10重量%,特别是在3至8重量%的范围内。
(内层和外层)
用于形成本发明的内层和外层的PET树脂为二羧酸组分的50摩尔%以上、特别是80摩尔%以上为对苯二甲酸,和二醇组分的50摩尔%以上、特别是80摩尔%以上为乙二醇的聚酯树脂。上述PET树脂具有优异的机械性质和热性质以及优异的拉伸性,因此,在拉伸成形时能够使中间层也均匀地拉伸。
PET树脂可包含除对苯二甲酸和乙二醇以外的共聚合组分。
作为除对苯二甲酸以外的羧酸组分,可以示例间苯二甲酸、萘二甲酸,对-β-羟基乙氧基苯甲酸、联苯基-4,4’-二羧酸、二苯氧基乙烷-4,4’-二羧酸、间苯二甲酸5-磺酸钠、六氢对苯二甲酸、己二酸和癸二酸。
作为除乙二醇以外的二醇组分,可以示例1,4-丁二醇、丙二醇、新戊二醇、1,6-己二醇、二甘醇、三甘醇、环己烷二甲醇、双酚A的环氧乙烷加成物、甘油和三羟甲基丙烷。
另外,二羧酸组分和二醇组分可以包括三官能以上的多官能多元酸和多元醇。例如,可以示例如偏苯三酸、苯均四酸、苯连三酸、1,1,2,2-乙烷四羧酸、1,1,2-乙烷三羧酸、1,3,5-戊烷三羧酸、1,2,3,4-环戊烷四羧酸和联苯基-3,4,3’,4’-四羧酸等多元酸,以及如季戊四醇、甘油、三羟甲基丙烷、1,2,6-己三醇、山梨糖醇和1,1,4,4-四(羟基甲基)环己烷等多元醇。
期望用于形成本发明的内层和外层的PET树脂的通过使用重量比为1:1的苯酚和四氯乙烷的混合溶剂、在30℃的温度下测量的特性粘度在0.60-1.40dL/g的范围内。此外,期望PET树脂的熔点(Tm)为200至275℃,从而改进多层容器的耐热性和加工性。期望其玻璃化转变点为不低于30℃、特别是在50至120℃的范围内。
用于形成本发明的内层和外层的PET树脂可以在不损害最终成形品的品质的范围内根据已知的配方与本身已知的树脂用共混剂如着色剂、抗氧化剂、稳定剂、抗静电剂、脱模剂(parting agent)、润滑剂和成核剂等共混。
(阻气性中间层)
本发明的多层预制品的中间层至少包括低结晶性PET树脂和阻挡性聚酰胺树脂。这里,重要的特征在于(i)低结晶性PET树脂含有作为共聚合组分的以15~20摩尔%范围内的量的环己烷二甲醇或以7.5~15摩尔%范围内的量的间苯二甲酸,(ii)低结晶性PET树脂和阻气性芳香族聚酰胺树脂的重量比在50:50~75:25、特别是60:40~75:25的范围内,和(iii)中间层相对于预制品整体的重量比例为1重量%以上且小于10重量%,特别是在3至8重量%的范围内。
如果环己烷二甲醇或间苯二甲酸在低结晶性PET树脂中的含量变得大于上述范围,则结晶性大幅降低并变得难以维持容器的机械强度。另一方面,如果环己烷二甲醇或间苯二甲酸的含量变得小于上述范围,则变得难以维持容器的透明性。
另外,对于低结晶性PET树脂和阻挡性聚酰胺树脂的重量比,如果低结晶性PET树脂的量大于上述范围,容器呈现降低的机械强度。另一方面,如果低结晶性PET树脂的量小于上述范围,形成其中在阻挡性聚酰胺树脂的连续相中存在多个低结晶性PET树脂分散相的海岛分散结构。因此,内层和外层之间的层间密合性(interlayer close adhesion)可能受损,且在受到冲击的情况下可能容易发生层间剥离性。
此外,如果阻挡性中间层占预制品整体的重量比例小于上述范围,则无法实现足够程度的阻气性。另一方面,如果中间层的重量比例大于上述范围,则机械强度倾向于降低。
期望以如下组合选择构成阻挡性中间层的低结晶性PET树脂和阻挡性聚酰胺树脂:使得由上式(1)表示的折射率的差△RI(=RIE–RIA)落入0至0.03的范围内。即,低结晶性PET树脂和阻挡性芳香族聚酰胺树脂的折射率的差落入上述范围内,使得可以通过甚至是少量的拉伸来赋予取向结晶性,因而改进双轴拉伸吹塑成形容器的机械强度还维持通过双轴拉伸吹塑成形多层预制品而得的容器的透明性并防止低结晶性PET树脂的结晶性变得过低。
上式(1)的拉伸条件符合多层预制品将要双轴拉伸吹塑成形时的拉伸条件。后述实施例表明,如果在上述拉伸条件下制备的样品的折射率的差在上述范围内,则多层拉伸吹塑成形容器具有3%以下的雾度。
[低结晶性PET树脂]
构成本发明的中间层的低结晶性PET树脂确保与构成内层和外层的PET树脂的粘接性,改进层间粘接性,具有在1.56~1.58的范围内的拉伸之前的折射率,具有在1.58~1.62的范围内的在上述式(1)的条件下拉伸之后的折射率,即,具有与随后将描述的阻挡性聚酰胺树脂的在拉伸之后的折射率接近的折射率,并且因此,不损害拉伸吹塑成形容器的透明性。
即,一般用于拉伸吹塑成形容器的PET树脂为用于赋予容器机械强度和耐热性的结晶性聚酯树脂。然而,如果拉伸,则结晶性聚酯树脂取向结晶并且结晶度上升。因此,取决于拉伸,其折射率的变化大。因此,如果与阻挡性聚酰胺树脂组合使用,它们的折射率之间的差增大,导致双轴拉伸吹塑成形容器的透明性降低。
另一方面,本发明使用特定的低结晶性PET树脂来防止双轴拉伸吹塑成形容器由过低的结晶性引起的机械强度的降低,并通过拉伸赋予取向结晶而不损害透明性。
在说明书中,短语“低结晶性”PET树脂代表以下PET树脂:当在差示扫描量热法(DSC)中以10℃/分钟的速度升温时,不显示结晶熔解(crystal fusion)峰,或者如果其显示结晶熔解峰,则具有40J/g以下的对应于结晶熔解峰的结晶熔解热量(△Hm)。
作为低结晶性PET树脂,期望可以使用包含相对于100摩尔%的二醇组分为15~20摩尔%的环己烷二甲醇和余量的乙二醇的PET树脂,或者包含相对于100摩尔%的二羧酸组分为7.5~15摩尔%的间苯二甲酸组分和余量的对苯二甲酸的PET树脂。
具体地,在上述范围内,期望可以使用包含15~19摩尔%的环己烷二甲醇或10~15摩尔%的间苯二甲酸的低结晶性PET树脂。
上述共聚合组分可以通过共聚方法或使聚合物共混的方法引入低结晶性PET树脂。
期望用于本发明的中间层的低结晶性PET树脂具有0.60dL/g以上、特别是在0.70~1.40dL/g范围内的如通过使用重量比1:1的苯酚/四氯乙烷混合溶剂在30℃的温度下测量的特性粘度(IV)。通过使用具有大特性粘度(IV)的低结晶性PET树脂,使得可以改进机械强度并有效地防止由落下时的冲击引起的层间剥离的发生。
构成本发明的中间层的低结晶性PET树脂还可以以在它们不损害期望的低结晶性PET树脂的低结晶性和折射率的范围内的量包含除上述的那些以外的共聚合组分。
作为除对苯二甲酸以外的羧酸组分,可以示例间苯二甲酸、萘二甲酸、对-β-羟基乙氧基苯甲酸、联苯基-4,4’-二羧酸、二苯氧基乙烷-4,4’-二羧酸、间苯二甲酸5-磺酸钠、六氢对苯二甲酸、己二酸和癸二酸。
作为除了乙二醇以外的二醇组分,可以示例1,4-丁二醇、丙二醇、新戊二醇、1,6-己二醇、二甘醇、三甘醇、环己烷二甲醇、双酚A的环氧乙烷加成物、甘油和三羟甲基丙烷。
上述二羧酸组分和二醇组分可以包括三官能以上的多元酸和多元醇。它们的实例包括如偏苯三酸、苯均四酸、苯连三酸、1,1,2,2-乙烷四羧酸、1,1,2-乙烷三羧酸、1,3,5-戊烷三羧酸、1,2,3,4-环戊烷四羧酸和联苯基-3,4,3’,4’-四羧酸等多元酸,以及如季戊四醇、甘油、三羟甲基丙烷、1,2,6-己三醇、山梨糖醇和1,1,4,4-四(羟基甲基)环己烷等多元醇。
当低结晶性PET树脂包含15~20摩尔%的量的环己烷二甲醇并包含间苯二甲酸作为二羧酸组分时,间苯二甲酸的量不应超过4摩尔%。或者,当低结晶性PET树脂包含7.5~15摩尔%的量的间苯二甲酸并包含环己烷二甲醇作为二醇组分时,环己烷二甲醇的含量不应超过4摩尔%。
还期望低结晶性PET树脂包含不超过4摩尔%的量的二甘醇。
[阻挡性聚酰胺树脂]
构成本发明的中间层的芳香族聚酰胺型阻气性树脂具有优异的阻气性,具有在1.57~1.59的范围内的拉伸之前的折射率,具有在1.57~1.60的范围内的在上述式(1)的条件下拉伸之后的折射率,并且当其与上述低结晶性PET树脂组合使用时,具有在0~0.03范围内的由上述式(1)表示的折射率的差。
作为具有上述优异的阻气性的芳香族聚酰胺树脂,期望使用包含亚二甲苯基的聚酰胺,特别是由主要包含间苯二甲胺和/或对苯二甲胺的二胺组分、和脂肪族二羧酸和/或芳香族二羧酸获得的聚酰胺。
具体地,可以示例如聚己二酰间苯二甲胺、聚癸二酰间苯二甲胺、聚辛二酰间苯二甲胺、聚庚二酰对苯二甲胺和聚壬二酰间苯二甲胺等均聚物;如己二酰间苯二甲胺/己二酰对苯二甲胺共聚物、庚二酰间苯二甲胺/庚二酰对苯二甲胺共聚物、癸二酰间苯二甲胺/癸二酰对苯二甲胺共聚物、和壬二酰间苯二甲胺/壬二酰对苯二甲胺共聚物等共聚物;或者通过使其均聚物或共聚物组分与如六亚甲基二胺等脂肪族二胺、如哌啶(piperadine)等脂环族二胺、如对-双(2-氨乙基)苯等芳香族二胺、如对苯二甲酸等芳香族二羧酸、如ε-己内酰胺等内酰胺、如7-氨基庚酸等ω-氨基羧酸、或如对氨基甲基苯甲酸等芳香族氨基羧酸共聚获得的共聚物。
这些芳香族聚酰胺树脂还应当具有足以形成膜的大的分子量,并且应当具有1.1以上、特别是1.5以上的例如在浓硫酸(浓度为1.0g/dl)中在30℃下测量的相对粘度。
此外,如果添加后述氧吸收性组分,则期望使用通过二羧酸组分与主要包含苯二甲胺的二胺组分缩聚获得的、末端氨基浓度为40eq/106g以上的聚酰胺树脂,这是因为不发生在吸收氧时的氧化劣化,且容器的机械强度不降低。
[其它组分]
在本发明的拉伸吹塑成形容器中,期望中间层包含含有氧化催化剂和氧化性有机组分的氧吸收性组分、或层状硅酸盐的至少之一。
氧吸收性组分包含常规的氧化催化剂和氧化性有机组分的组合。在共混有其时,中间层变得能够遮断或捕捉从容器外部透过至容器内的氧,或者能够捕捉容器内部残留的氧,并且能够改进内容物的保存性。
作为氧化性有机组分,可以示例可以氧化的有机物,或者具体地,丁二烯,如马来酸酐改性的丁二烯等由酸或酸酐改性的多烯低聚物或聚合物,以及具有不饱和键的低分子化合物。
作为氧化催化剂,可以使用如铁、钴和镍等周期表第VIII族的金属成分,尽管不仅限于此。
在期望以换算为金属至少为300ppm的量添加氧化催化剂的同时,期望以相对于100重量份的阻挡性聚酰胺树脂为2~10重量份的量添加氧化性有机组分。
共混有层状硅酸盐的中间层由于层状硅酸盐的迂回效果而显示进一步改进的阻气性。
作为层状硅酸盐,可以示例云母、蛭石和蒙脱石。优选的层状硅酸盐为电荷密度为0.25~0.6的2-八面体型或3-八面体型的层状硅酸盐。作为2-八面体型层状硅酸盐,可以示例蒙脱土、贝得石和绿脱石。作为3-八面体型层状硅酸盐,可以示例锂蒙脱石和皂石。层状硅酸盐优选为通过用如季铵盐等有机化剂(organificating agent)处理而溶胀的层状硅酸盐。作为季铵盐,可以使用具有至少一个或多个的、碳原子数为12以上的烷基的季铵盐,或者具体地,三甲基十二烷基铵盐或三甲基十四烷基铵盐。
期望以相对于100重量份的阻挡性聚酰胺树脂为1~10重量份、特别是1~8重量份的量添加层状硅酸盐。
上述氧吸收性组分和/或层状硅酸盐可以添加至低结晶性PET树脂或阻挡性聚酰胺树脂,但特别优选添加至阻挡性聚酰胺树脂。即,如果用作中间层的基质的低结晶性PET树脂包含氧吸收性组分和/或层状硅酸盐,则成形性变差并且可能发生层间剥离。因此,使这些组分存在于包含阻挡性聚酰胺树脂的分散相中,从而抑制成形性和层间密合力的降低。
构成中间层的低结晶性PET树脂或阻挡性聚酰胺树脂可以在不损害本发明目的的范围内根据已知配方与如脱氧剂、填料、着色剂、耐热稳定剂、耐候稳定剂、抗氧化剂、防老剂、光稳定剂、紫外线吸收剂、抗静电剂、像金属皂或蜡等润滑剂,以及改性用树脂或橡胶等已知的树脂用共混剂共混。
如果将上述组分添加至构成中间层的低结晶性PET树脂或阻挡性聚酰胺树脂,则期望添加的组分的量少于用作基材的低结晶性PET树脂或芳香族聚酰胺树脂的量,从而使得对折射率的变化影响较小。在该情况下,在由上式(1)表示的折射率的测量中,可以通过测量使不含有添加的物质的用作基材的低结晶性PET树脂或芳香族聚酰胺树脂注射成形而获得的板在同时双轴拉伸3×3倍之后的折射率来求得折射率的差。
(多层结构)
本发明的多层预制品可以采用各种层构成,只要它们具有由PET树脂形成的内层和外层以及至少一层由上述低结晶性PET树脂和阻挡性聚酰胺树脂形成的中间层即可。如图1所示,多层预制品可以呈现在由PET树脂形成的内层1与外层2之间包括由低结晶性PET树脂和阻挡性聚酰胺树脂形成的阻挡性中间层3的2种3层构成。或者如图2所示,多层预制品也可以呈现包括由PET树脂形成的内层1与外层2,在由PET树脂形成的内层1与由PET树脂形成的中间层4之间和在由PET树脂形成的外层2与由PET树脂形成的中间层4之间的由低结晶性PET树脂和阻挡性聚酰胺树脂形成的两层阻挡性中间层3a和3b的2种5层构成。
在本发明中,改进了内层、外层和中间层之间的层间粘接性。因此,在制造多层容器时,不需要将粘接剂树脂插入树脂层之间。然而,当然粘接剂树脂也可以插入树脂层之间。作为粘接剂树脂,可以使用在其主链或侧链上具有浓度为1~700毫当量(meq)/100g树脂、特别是10~500meq/100g树脂的源自羧酸、羧酸酐、羧酸盐、羧酸酰胺或羧酸酯的羰基(-CO-)的热塑性树脂。粘接剂树脂的优选实例包括乙烯-丙烯酸共聚物、离子交联烯烃共聚物、马来酸酐-接枝的聚乙烯、马来酸酐-接枝的聚丙烯、丙烯酸-接枝的聚烯烃、乙烯-乙酸乙烯酯共聚物和共聚聚酯。
在本发明的多层预制品中,期望:
阻挡性中间层在整个容器中的重量比例为1重量%以上且小于10重量%,特别是在3~8重量%的范围内。如果阻挡性中间层的重量比例小于上述范围,不能获得充分程度的阻气性。另一方面,如果阻挡性中间层的重量比大于上述范围,变得难以维持容器的机械强度。
另外,如上所述,如果存在由低结晶性PET树脂和阻挡性聚酰胺树脂形成的多个阻挡性中间层,期望全部阻挡性中间层的重量比例落在上述范围内。
(制造方法)
本发明的多层预制品可通过任何常规方法来制造,例如其中使由低结晶性PET树脂和阻挡性聚酰胺树脂形成的中间层用树脂组合物与内层和外层形成用PET树脂一起共挤出的共挤出成形法;其中将中间层用树脂组合物与PET树脂同时注射至模具内的同时注射成形法;其中将PET树脂、中间层用树脂组合物和PET树脂逐次注射至模具内的逐次注射法;或其中通过使用核模具和凹模具使中间层用树脂组合物和PET树脂的共挤出物压缩成形的压缩成形法。
在多层预制品中,重要的是,至少在变为在拉伸之后呈现最薄的厚度的主体部的部分形成多层结构。这使得可以赋予容器必要的阻气性并且确保容器的透明性。即,在本发明的中间层已拉伸的情况下,低结晶性PET树脂和阻挡性聚酰胺树脂呈现变得彼此接近的折射率,因此,变得透明。因此,从维持整个容器的透明性的观点,期望预制品中仅在要充分拉伸的部分形成多层结构。
在具有使其热结晶化的口颈部的耐热容器中,口颈部透明与否不重要。即,如果预制品的口颈部变为容器的口部则其不拉伸。因此,期望在预制品的口颈部不形成多层结构。
在拉伸之前的预制品中,形成多层结构的部分具有5%以上的雾度并且比仅由PET树脂形成的部分和没有形成多层结构的部分较不透明。因此,在预制品中,容易目视确认是否形成了多层结构。
本发明中,当中间层要与氧吸收性组分或层状硅酸盐共混时,期望如上所述通过预先将其添加至阻挡性聚酰胺树脂来制备丸粒化母料。期望通过将该母料与低结晶性PET树脂以低结晶性PET树脂和阻挡性聚酰胺树脂的量的比成为如上所述的量共混在一起来制备中间层用树脂组合物。
本发明的多层拉伸吹塑成形容器通过将具有上述本发明的多层结构的多层预制品双轴拉伸吹塑成形来制造。
期望多层预制品的成形和双轴拉伸吹塑成形通过冷型坯体系进行。然而,它们还可通过执行拉伸吹塑成形而完全不冷却所形成的多层预制品的热型坯体系进行。
另外,在进行双轴拉伸吹塑成形之前,将预制品在90~120℃的拉伸温度下通过诸如热风、红外线加热器或高频感应加热等手段加热。
将加热的预制品供给至已知的拉伸吹塑成型机中,置于模具中,通过推入拉伸棒而沿轴向牵引拉伸,并通过吹入流体而沿周向拉伸。这里,如上所述,本发明的双轴拉伸吹塑成形容器具有优异的阻气性和机械强度,并可优选地用作耐压容器。在该情况下,容器可制造成广泛公知的耐压性底部形状,例如所谓的花瓣状的形状(petaloidal shape)和其底部的中心部形成凹部的香槟状的形状。
从构成中间层的低结晶性PET树脂与阻挡性聚酰胺树脂在拉伸之后二者之间的折射率的差(△RI)在0~0.03的范围内的观点,期望作为本发明的最终制品的多层拉伸吹塑成形容器以2.0~4.0倍、特别是2.5~3.5倍的面积倍率拉伸,以沿轴向为2.0~4.0倍、特别是2.5~3.5倍的倍率拉伸,或者以沿周向为2.0~4.0倍、特别是2.5~3.5倍的倍率来拉伸。这能够使拉伸之后的中间层中低结晶性PET树脂和阻挡性聚酰胺树脂的折射率变得彼此接近,因此,△RI的值落在上述范围内,因此使得可以获得具有主体部的雾度为3%以下的优异的透明性的拉伸吹塑成形容器。
在本发明的多层拉伸吹塑成形容器中,主体部的厚度根据容器的容积(重量)或者容器的用途而变化,但期望为小于0.36mm、特别是在0.20~0.30mm的范围内。本发明规定的主体部的厚度为在容器的主体部的最薄部分测量的值。
实施例
1.材料
以下描述为用于实施例的材料。
(1)对苯二甲酸乙二醇酯系聚酯树脂。
PET1:间苯二甲酸(共聚比例=1.8mol%),二甘醇(共聚比例=2.3mol%)共聚聚对苯二甲酸乙二醇酯树脂(5015w:由Shinkong Synthetic Fibers Co.制造,IV=0.83)。
(2)低结晶性对苯二甲酸乙二醇酯系聚酯树脂。
APET1:间苯二甲酸(共聚比例=15摩尔%),二甘醇(共聚比例=3.6摩尔%)共聚聚对苯二甲酸乙二醇酯树脂(IV=0.70)。
APET2:间苯二甲酸(共聚比例=10摩尔%),二甘醇(共聚比例=3.0摩尔%)共聚聚对苯二甲酸乙二醇酯树脂(IV=0.74)。
APET3:1,4-环己烷二甲醇(共聚比例=30摩尔%),二甘醇(共聚比例=2.3摩尔%)共聚聚对苯二甲酸乙二醇酯树脂(S2008:由SK Chemicals Co.,Ltd.制造,IV=0.78)。
APET4:间苯二甲酸(共聚比例=20摩尔%),二甘醇(共聚比例=3.3摩尔%)共聚聚对苯二甲酸乙二醇酯树脂(IV=0.75)。
(3)芳香族聚酰胺。
PA1:聚己二酰间苯二甲胺树脂(S6007:由Mitsubishi Gas Chemical Company,Inc.制造)。
2.多层预制品的成形
通过使用共注射成形机,成形2种3层构成(PET/中间层/PET)的多层预制品。向内外PET层形成用注射成形机的料斗内,投入已干燥的对苯二甲酸乙二醇酯系树脂,并且向中间层形成用注射成形机的料斗内,投入已干燥的且以预定的比例共混在一起的低结晶性对苯二甲酸乙二醇酯系树脂和芳香族聚酰胺系阻气性树脂。将这些材料共注射成形。在中间层在260至280℃的温度下成形的同时,将内外PET层设定在290℃的温度下。将称重为24g的预制品以中间层不到达口颈部也不到达底部的方式成形。
3.多层瓶的成形
将多层预制品的主体部从外侧通过使用红外线加热器在100℃的表面温度下加热,通过使用拉伸棒沿瓶的轴向机械拉伸,然后通过向其中吹入空气而双轴拉伸吹塑,从而成形主体部被拉伸纵向大致3倍、横向大致3倍、由此面积为9倍的图3所示的容量为500ml的拉伸吹塑瓶。将模具温度设定在60℃,并吹入室温(20℃)的3.5MPa的高压空气。
4.注射成形板的成形。
已干燥的上述材料单独或者以预定的比例干式共混供给至注射成形机(NN75JS:由Niigata Engineering Co.,Ltd.制造)的料斗。通过将料筒(barrel)的温度设定在260至280℃,使材料注射成形为尺寸为90×90×1.5mm的板。
5.双轴拉伸片材的成形。
通过使用双轴拉伸试验机(x6H-S:由Toyo Seiki Seisaku-sho,Ltd.制造),将上述注射成形板在以下条件下双轴拉伸成形。
腔室内温度:100℃
拉伸之前的加热时间:2分30秒
拉伸方法:同时双轴拉伸
拉伸倍率:纵向3倍、横向3倍
拉伸速度:沿两个方向10m/分
6.测量。
(1)瓶主体部的雾度的测量。
将多层瓶主体部切出并且通过使用彩色计算机(SM-4:由Suga Test InstrumentsCo.,Ltd.制造)测量其雾度。测量值为任意的三点的平均值。
(2)预制品主体部的雾度的测量。
从多层预制品的主体部的中央切出高度为30mm的筒状试样,并且沿预制品的高度方向切成两部分,从而获得半圆筒状试样。通过使用附带有积分球装置的分光光度计(UV-3100PC:由Shimadzu Corporation制造),根据下述步骤测量试样的雾度。扫描条件为测量覆盖400~700nm的范围的透过率的模式。
<1>将标准白板安装至试样侧和基准侧双方,并且沿基线扫描。然后,进行测量以计算400-700nm内的透过率积分值(T0)。
<2>除去试样侧标准白板,并且测量由装置散射的光的光谱以计算400-700nm内的透过率积分值(T1)。
<3>将试样预制品安装至试样侧。此处,半圆状预制品的外面侧与积分球紧密接触使得入射光从预制品的内面侧照射。在该状态下,测量由试样散射的光的光谱,从而计算400-700nm内的透过率积分值(Td)。
<4>在上述<3>的状态下,将标准白板安装至试样侧,并且测量透过试样的光的全部光谱,从而计算400-700nm内的透过率积分值(Tt)。
由以上获得的透过率积分值,根据下式计算预制品的雾度,
预制品的雾度(%)={Td–Tt×(T1/T0)}/Tt×100
测量值为从由各试样获得的两个半圆筒状试样测量的值的平均值。
(3)瓶的碳酸气体阻挡性的测量。
通过考虑瓶的内容积,将使得初期内压为0.4MPa的必要量的干冰放入瓶内。然后用塑料盖密封瓶。在维持在22℃50%RH下的恒温恒湿室贮存6周之后,瓶主体部的中央通过使用FT-IR(FTS7000SERIES:由VARIAN Co.制造)测量4990cm-1附近出现的源自CO2的双峰面积和使用游标卡尺测量主体部的直径。根据下式来计算气体损失率
A1=S1×(D0/D1)
气体损失率(%)=(A1–A0)/A0×100
A0:初期峰面积
S1:随时间的峰面积
A1:随时间的峰面积(主体直径校正之后)
D0:初期主体直径
D1:随时间的主体直径
(4)同时双轴拉伸3×3倍之后的折射率的测量。
从如上所述成形的双轴拉伸片材中,切出尺寸为30×10mm的试样以使短边方向为测量方向。通过使用具有带偏光板的目镜的阿贝折射计(NAR-1T:由Atago Co.,Ltd.制造),测量试样沿纵横拉伸方向的折射率,并且其平均值被认为是从试样测量的值。
(5)层间剥离试验。
通过使用切刀,将瓶的主体部切入30mm,并评价外观。从切入部(incisedportion),目视确认是否发生层间剥离。
(6)瓶耐压性试验。
通过使用PET瓶破裂试验机(PTP-25K-1500,由Kazama Engineering Co.,Ltd.制造),测量瓶的破裂强度(bursting strengths)。
(实施例1)
通过使用共注射成形机,成形2种3层构成(PET/中间层/PET)的多层预制品。向内外PET层形成用注射成形机的料斗内,投入干燥的PET1,并且向中间层形成用注射成形机的料斗内,投入以70:30的重量比共混的已干燥的APET1和PA1,并且使这些材料共注射成形。在260℃的温度下成形中间层的同时,将内外PET层设定在290℃的温度下。预制品的重量为24g并且中间层的比例为整个瓶的6重量%。使得中间层不到达口颈部也不到达底部而成形预制品。
接着,将多层预制品通过上述方法双轴拉伸吹塑成形为多层瓶。对于获得的预制品和瓶,通过上述方法测量预制品主体部的雾度、瓶主体部的雾度、瓶的碳酸气体阻挡性、层间剥离的有无以及破裂强度。
此外,将干燥的APET1供给至注射成形机的料斗并且在将料筒的温度设定在280℃的同时注射成形,从而获得尺寸为90×90×1.5mm的注射成形板。通过上述方法将注射成形板同时双轴拉伸3×3倍,从而获得双轴拉伸片材。PA1也同样地注射成形为板并且双轴拉伸为片材。然而,此处,料筒的温度设定在260℃。通过上述方法测量拉伸的片材的折射率,从而计算它们的折射率和折射率的差△RI(=RIE–RIA)。
(实施例2)
除了将重量比为70:30的APET2和PA1的干混物投入中间层形成用注射成形机的料斗内以外,以与实施例1相同的方式成形并测量预制品和瓶。
此外,除了将APET2供给至注射成形机的料斗以外,以与实施例1相同的方式成形并测量双轴拉伸片材。
(实施例3)
除了将重量比为35:35:30的APET3、PET1和PA1的干混物投入中间层形成用注射成形机的料斗内,并且在使中间层在280℃的温度下成形以外,以与实施例1相同的方式成形并测量预制品和瓶。
此外,除了将重量比为1:1的APET3和PET1的干混物供给至注射成形机的料斗以外,以与实施例1相同的方式成形并测量双轴拉伸片材。
(实施例4)
除了将重量比为30:30:40的APET3、PET1和PA1的干混物投入中间层形成用注射成形机的料斗内以外,以与实施例3相同的方式成形并测量预制品、瓶和双轴拉伸片材。
(比较例1)
通过使用共注射成形机但不运行中间层形成用注射成形机,通过将PET1投入内外PET层形成用注射成形机的料斗内并将温度设定在290℃而成形重量为24g的单层预PET制品。通过上述方法将单层PET预制品双轴拉伸吹塑成形为单层PET瓶。
对于获得的预制品和瓶,通过上述方法测量预制品主体部的雾度、瓶主体部的雾度、瓶的碳酸气体阻挡性、和瓶的破裂强度。
(比较例2)
除了将重量比为70:30的PET1和PA1的干混物投入中间层形成用注射成形机的料斗内以外,以与实施例1相同的方式成形并测量预制品和瓶。
此外,除了将PET1供给至注射成形机的料斗以外,以与实施例1相同的方式成形并测量双轴拉伸片材。
(比较例3)
除了将重量比为70:30的APET3和PA1的干混物投入中间层形成用注射成形机的料斗内以外,以与实施例3相同的方式成形并测量预制品和瓶。
此外,除了将APE3供给至注射成形机的料斗以外,以与实施例3相同的方式成形并测量双轴拉伸片材。
(比较例4)
除了将重量比为70:30的APET4和PA1的干混物投入中间层形成用注射成形机的料斗内以外,以与实施例1相同的方式成形并测量预制品和瓶。
此外,除了将APE4供给至注射成形机的料斗以外,以与实施例1相同的方式成形并测量双轴拉伸片材。
(比较例5)
除了将重量比为20:20:60的APET3、PET1和PA1的干混物投入中间层形成用注射成形机的料斗内以外,以与实施例3相同的方式成形并测量预制品、瓶和双轴拉伸片材。然而,如表1所示,在层间剥离试验中确认了层间剥离。因此,未进行瓶的耐压性试验。
(比较例6)
除了将重量比为40:40:20的APET3、PET1和PA1的干混物投入中间层形成用注射成形机的料斗内以外,以与实施例3相同的方式成形并测量预制品、瓶和双轴拉伸片材。
(比较例7)
除了将中间层在瓶中的比例设定为10重量%以外,以与实施例3相同的方式成形并测量预制品、瓶和双轴拉伸片材。
产业上的可利用性
本发明的通过将多层预制品双轴拉伸吹塑成形获得的双轴拉伸吹塑成形容器不仅具有优异的阻气性和透明性而且还具有优异的机械强度,并可有利地用作需要特别高度的阻气性和对内压的机械强度的耐压性容器。
附图标记说明
1内层 2外层
3阻挡性中间层 4中间层
Claims (7)
1.一种多层预制品,其具有由对苯二甲酸乙二醇酯系聚酯树脂形成的内层和外层,以及至少一层至少由低结晶性对苯二甲酸乙二醇酯系聚酯树脂和阻气性芳香族聚酰胺树脂形成的中间层,其中:
所述低结晶性对苯二甲酸乙二醇酯系聚酯树脂含有作为共聚合组分的以15~20摩尔%范围内的量的环己烷二甲醇或以7.5~15摩尔%范围内的量的间苯二甲酸;
所述低结晶性对苯二甲酸乙二醇酯系聚酯树脂和所述阻气性芳香族聚酰胺树脂的重量比在50:50~75:25的范围内;
所述中间层相对于预制品整体的重量比例为1重量%以上且小于10重量%;和
已形成有多层结构的部分的雾度为5%以上。
2.根据权利要求1所述的多层预制品,其中所述低结晶性对苯二甲酸乙二醇酯系聚酯树脂和所述阻气性芳香族聚酰胺树脂满足下式,
0≤RIE-RIA≤0.03
其中,RIE和RIA为分别由所述低结晶性对苯二甲酸乙二醇酯系聚酯树脂和所述阻气性芳香族聚酰胺树脂制成的注射成形板在同时双轴拉伸3×3倍后的折射率。
3.根据权利要求1或2所述的多层预制品,其中在口颈部未形成所述中间层。
4.根据权利要求1至3任一项所述的多层预制品,其中所述中间层含有包含氧化催化剂和氧化性有机组分的氧吸收性组分、或层状硅酸盐的至少之一。
5.根据权利要求4所述的多层预制品,其中所述阻气性芳香族聚酰胺树脂为末端氨基浓度为40eq/106g以上的含有亚二甲苯基的聚酰胺树脂。
6.一种多层拉伸吹塑成形容器,其通过将根据权利要求1至5任一项所述的多层预制品双轴拉伸吹塑成形而得,已形成有多层结构的部分的雾度为3%以下。
7.根据权利要求6所述的多层拉伸吹塑成形容器,所述多层拉伸吹塑成形容器具有耐压性。
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EP3842353A4 (en) * | 2018-08-24 | 2021-10-13 | Mitsubishi Gas Chemical Company, Inc. | MULTI-LAYER CONTAINER AND METHOD OF MANUFACTURING THEREOF |
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USD966895S1 (en) * | 2018-12-13 | 2022-10-18 | Integrated Plastics Pty Ltd | Pre-form with handle |
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