CN101553353A - 薄壁二轴拉伸聚酯瓶 - Google Patents
薄壁二轴拉伸聚酯瓶 Download PDFInfo
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- CN101553353A CN101553353A CNA2007800444871A CN200780044487A CN101553353A CN 101553353 A CN101553353 A CN 101553353A CN A2007800444871 A CNA2007800444871 A CN A2007800444871A CN 200780044487 A CN200780044487 A CN 200780044487A CN 101553353 A CN101553353 A CN 101553353A
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- Prior art keywords
- biaxially stretched
- stretched polyester
- polyester bottles
- bottle
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- 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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- 238000001237 Raman spectrum Methods 0.000 description 5
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- 230000033228 biological regulation Effects 0.000 description 2
- 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 2
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- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
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- 235000011037 adipic acid Nutrition 0.000 description 1
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- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
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- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 1
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- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
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- 230000001856 erectile effect Effects 0.000 description 1
- RWLDAJMGAVDXSH-UHFFFAOYSA-N ethane-1,1,2-tricarboxylic acid Chemical class OC(=O)CC(C(O)=O)C(O)=O RWLDAJMGAVDXSH-UHFFFAOYSA-N 0.000 description 1
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 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 class OC(=O)CCC(C(O)=O)CCC(O)=O ROTJZTYLACIJIG-UHFFFAOYSA-N 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
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- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- B29C49/08—Biaxial stretching during blow-moulding
- B29C49/10—Biaxial stretching during blow-moulding using mechanical means for prestretching
- B29C49/12—Stretching rods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
-
- 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
- B29C49/08—Biaxial stretching during blow-moulding
- B29C49/16—Biaxial stretching during blow-moulding using pressure difference for pre-stretching, e.g. pre-blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
-
- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
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- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/22—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at neck portion
-
- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/24—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at flange portion
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- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/26—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at body portion
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- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/28—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at bottom portion
-
- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3024—Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique
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- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3024—Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique
- B29C2949/3026—Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique having two or more components
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- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3032—Preforms or parisons made of several components having components being injected
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- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3032—Preforms or parisons made of several components having components being injected
- B29C2949/3034—Preforms or parisons made of several components having components being injected having two or more components being injected
- B29C2949/3036—Preforms or parisons made of several components having components being injected having two or more components being injected having three or more components being injected
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- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3056—Preforms or parisons made of several components having components being compression moulded
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- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
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- B29C2949/3058—Preforms or parisons made of several components having components being compression moulded having two or more components being compression moulded
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/06—Injection blow-moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
本发明提供一种薄壁二轴拉伸聚酯瓶,瓶身部的中央部满足(i)和(ii)中的至少一方,(i)在室温下的抗拉试验中,圆周方向的伸长率大于纵向的伸长率、(ii)拉曼光谱法的圆周方向的取向参数小于纵向的取向参数,由此,即使瓶身部的平均壁厚薄壁化成250μm以下,外观特性也优异且具有耐落下冲击性。
Description
技术领域
本发明涉及瓶身部被高度薄壁化了的二轴拉伸聚酯瓶(biaxially stretched polyester bottle),更加详细地涉及耐落下冲击性和外观特性优异的薄壁二轴拉伸聚酯瓶。
背景技术
以往以来,公知有对由聚对苯二甲酸乙二醇酯等聚酯树脂构成的预成型件进行二轴拉伸吹塑成形而形成的二轴拉伸聚酯瓶,该二轴拉伸聚酯瓶在透明性、表面光泽、耐冲击性、气体阻隔性方面优异,作为各种饮料、食品、液体清洗剂等的容器而被广泛地使用。
通常用于饮料容器的二轴拉伸聚酯瓶具有0.25~0.30mm左右的平均壁厚,但是从降低成本和轻量化等方面考虑,对进一步降低树脂的使用量的要求增高。
从这样的方面考虑,例如在日本特开平7-257534号公报中提出了一种将瓶身部的平均壁厚设为0.25mm以下,使平均拉伸倍率为10倍以上地吹塑成形而形成的瓶状容器。
可是,该瓶状容器存在如下问题:即使在5000mL等大容量的容器的情况下也能谋求轻量化,但在2000mL以下的容量比较小的容器的情况下难以谋求轻量化。此外,该瓶状容器的制法是使二轴拉伸吹塑成形的平均拉伸倍率为10倍以上,但纵拉伸倍率通常是在2~2.7倍的范围内,若将纵拉伸倍率提高到该范围以上,则会产生由过拉伸引起白化或层叠剥离(脱层)、破裂(burst)等问题,存在难以成形这样的问题。
此外,还提出了能通过使容器的一部分薄壁化来谋求轻量化的薄壁瓶,例如在日本特开2001-122237号公报中公开了如下的技术:将500mL左右的瓶的肩部平均壁厚设为0.2~0.3mm,将瓶身部的平均壁厚设为0.02~0.05mm,在瓶身部上形成提高变形强度的横肋的技术。可是,在拉伸吹塑成形这样的壁厚变化量大的瓶的情况下,存在如下的问题:在预先注射模塑成形预成型件时需要限制壁厚的变化,或难以设定拉伸吹塑成形预成型件时的成形条件。
本申请人在日本特开2003-191819号公报中还提出了平均壁厚被薄壁化成0.1~0.2mm的聚酯制的二轴拉伸吹塑瓶,该二轴拉伸吹塑瓶不会由过拉伸而造成白化,能成形可竖立的薄壁的瓶状容器,能谋求削减树脂的使用量和轻量化。
可是,以上述制造方法成形的二轴拉伸吹塑瓶在吹塑成形的初始阶段无论是在产生破裂还是在不产生破裂的情况下,有时温度降低了的部分作为环状的厚壁部而残留,存在外观特性差且耐落下冲击性差这样的问题。
发明内容
因此,本发明的目的在于提供一种二轴拉伸聚酯瓶,该二轴拉伸聚酯瓶的瓶身部薄壁化成250μm以下、较佳的是薄壁化成平均壁厚为200μm以下,是具有优异的外观特性且耐落下冲击性的二轴拉伸聚酯瓶。
根据本发明,提供一种二轴拉伸聚酯瓶,其特征在于,在对由聚酯树脂构成的预成型件进行二轴拉伸吹塑成形而形成的二轴拉伸聚酯瓶中,瓶身部的中央部满足(i)和(ii)中的至少一方,(i)在室温下的抗拉试验中,圆周方向的伸长率大于纵向的伸长率、(ii)拉曼光谱法的圆周方向的取向参数小于纵向的取向参数。
在本发明的二轴拉伸聚酯瓶中,优选:
1.瓶身部的平均壁厚为250μm以下,
2.圆周方向的伸长率为100%以上,特别是在100~1000%的范围内,
3.圆周方向的取向参数为3.5以下,特别是在1.5~3.5的范围内,
4.利用具有如下特征的制造方法来制造二轴拉伸聚酯瓶:在利用拉伸杆拉伸被加热到拉伸温度的聚酯制预成型件、并且利用空气吹塑进行拉伸以形成二轴拉伸聚酯瓶的制造方法中,在利用上述拉伸杆进行拉伸时,使如下流量的吹塑空气流入到预成型件内部,该流量的吹塑空气使预成型件与拉伸杆顶端以外的部分和模具表面不接触。
在本发明的二轴拉伸聚酯瓶中,即使瓶身部的平均壁厚为250μm以下的薄壁,也不会形成有产生于以往的二轴拉伸聚酯瓶上的环状的厚壁部,外观特性优异且耐落下冲击性也优异。
又因为是非常薄的壁,所以能降低树脂的使用量,且能谋求轻量化。
另外,在本说明书中,所谓“薄壁”的二轴拉伸聚酯瓶是指瓶身部的平均壁厚在大约250μm以下的范围内的聚酯瓶。在此,瓶身部的平均壁厚(t)是指由瓶的颈环以下的部分(除了颈环和盖紧固用的螺纹部之外的部分)的颈下重量(G)和使用树脂的比重(γ)求出瓶的颈下体积(V),并且算出瓶的颈环以下的部分的颈下表面积(S),用瓶的颈下体积(V)除以瓶的颈下表面积而获得的值(t=V/S)。
如上所述,在成形瓶身部的平均壁厚为小于250μm的薄壁的二轴拉伸聚酯瓶时,在成形中途多产生破裂,即使是不产生破裂而能成形的容器,外观特性和耐落下冲击性也会变差。
本申请人从这样的方面考虑,作为瓶身部的平均壁厚为200μm以下的薄壁二轴拉伸聚酯瓶的成形方法,提出了具有如下特征的成形方法(WO2007/83396):在利用拉伸杆拉伸被加热到拉伸温度的聚酯制预成型件、且利用空气吹塑拉伸以形成二轴拉伸聚酯瓶的制造方法中,在利用上述拉伸杆进行拉伸时,将使预成型件与拉伸杆顶端以外的部分和模具表面不接触的流量的吹塑空气流入到预成型件内部。
在由该制法获得的本发明的二轴拉伸聚酯瓶中,发现了在利用上述本申请人在日本特开2003-191319号公报记载的方法所获得的瓶身部的平均壁厚为200μm以下的薄壁二轴拉伸聚酯瓶(以下、将该瓶称为“以往薄壁瓶”)、瓶身部的平均壁厚比250μm大的以往的通常壁厚的二轴拉伸聚酯瓶(以下、将该瓶称为“通常壁厚瓶”)中未发现的如下特性:瓶身部的中央部在室温下的抗拉试验中,圆周方向的伸长率大于纵向的伸长率,而且瓶身部的中央部的拉曼光谱法的圆周方向的取向参数小于纵向的取向参数,并且发现了满足该特性的薄壁二轴拉伸聚酯瓶比以往薄壁瓶外观特性优异且耐落下冲击性明显提高。
图1是表示对利用下述的实施例和比较例作成的、本发明的二轴拉伸聚酯瓶(实施例1)、以往薄壁瓶(比较例1)、通常壁厚瓶(比较例2),用从瓶身部切出的5×40mm的大小的试验片,以夹头间距离5mm、拉伸速度10mm/分钟的条件进行抗拉试验时的伸长率和应力的关系。
从该图1的结果显而易见,以往薄壁瓶在纵向和圆周方向的任一方向上均无太大伸长率,而且纵向和圆周方向上的伸长率几乎没有差别。此外,通常壁厚瓶具有纵向的伸长率大于横向的伸长率这样的共同的倾向。
对此,可知本发明的薄壁二轴拉伸聚酯瓶具有如下在其它的瓶中未发现的特征:圆周方向的伸长率比比较例1、2的瓶显著增大,圆周方向的伸长率也比纵向的伸长率显著增大。
此外,图2是表示对利用下述的实施例和比较例作成的、本发明的二轴拉伸聚酯瓶(实施例1)、以往薄壁瓶(比较例1)、通常壁厚瓶(比较例2),用波长532nm的激光在1800~600cm-1的测量范围内,在5秒的测量秒数、2次积分的测量条件下的拉曼光谱的取向。
从该图2显而易见,以往薄壁瓶[图2的(B)]的圆周方向的取向大于纵向的取向,此外,通常壁厚瓶[图2的(C)]也是圆周方向的取向大于纵向的取向。
对此,可知本发明的薄壁二轴拉伸聚酯瓶[图2的(A)]具有如下在其它的瓶中未发现的特征:在厚度方向的任一位置上纵向的取向大于圆周方向的取向。
从下述的实施例的结果显而易见,具有这样的特征的本发明的二轴拉伸聚酯瓶与以往薄壁瓶、通常壁厚瓶相比,能谋求降低树脂使用量、瓶的轻量化的同时,具有优异的外观特性和耐落下冲击性的所有特性。
即,以往薄壁瓶通过瓶身部的平均壁厚为200μm以下能减少树脂使用量、谋求轻量化,但会形成厚壁的环部,外观特性变差,而且耐落下冲击性的落下容许高度为90cm,与本发明的二轴拉伸聚酯瓶相比较差(比较例1)。此外,通常壁厚瓶满足耐落下冲击性这一点,但因为瓶身部的平均壁厚为大于0.25mm且小于等于0.30mm,所以无法谋求降低树脂使用量和轻量化(比较例2)。
对此,显而易见,本发明的二轴拉伸聚酯瓶的瓶身部的平均壁厚为250μm以下、特别是200μm以下,能谋求树脂使用量少且轻量化的同时,具有均匀的壁厚且外观特性也优异。而且落下容许高度为120cm,耐落下冲击性更优异(实施例1)。
附图说明
图1是表示各种二轴拉伸聚酯瓶的抗拉试验的伸长率和应力的关系的图。
图2是表示各种二轴拉伸聚酯瓶的拉曼光谱的取向和距外表面的距离关系的图。
图3是表示本发明的二轴拉伸聚酯瓶的一个例子的侧视图。
图4是表示本发明的二轴拉伸聚酯瓶的成形工序的一个例子的图。
具体实施方式
二轴拉伸聚酯瓶
图3是表示本发明的二轴拉伸聚酯瓶的一个例子的侧视图,聚酯瓶10由未拉伸的口部11和支承环12、被拉伸的肩部13、瓶身部14和底部15构成,被成形为利用设于底部15的凹部16能竖立的形状。
该聚酯瓶10能谋求轻量化且谋求降低使用树脂的量,被拉伸的肩部13、瓶身部14和底部15的平均壁厚是0.05~0.25mm的范围,更优选是0.07~0.20mm的范围,特别优选0.07~0.15mm的范围内,由此,该壁厚变化量在0.1mm以内、优选0.05mm以内,能谋求大幅度的轻量化。
本发明的二轴拉伸聚酯瓶随着轻量化、薄壁化的同时不是特别需要用于加强刚性、强度的加强用加强筋等加强部分,但也可以在瓶身部的中央形成有呈环状的向内侧凹下的加强用肋。
聚酯树脂
构成本发明的二轴拉伸聚酯瓶的聚酯树脂,能采用以往以来二轴拉伸吹塑成形所采用的、公知的聚酯树脂。
作为构成聚酯树脂的二羧酸成分,从机械的性质和热的性质上考虑,优选二羧酸成分的50%以上、特别是80%为对苯二甲酸,但当然也可以含有对苯二甲酸以外的羧酸成分。作为对苯二甲酸以外的羧酸成分,能够举出间苯二甲酸、萘二羧酸、p-β-氧基乙氧基安息香酸、联苯-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、六氢苯对二甲酸、己二酸、癸二酸等。
另一方面,作为二醇成分,从机械的性质和热的性质上考虑,优选二醇成分的50%以上、特别是80%以上为乙二醇,作为乙二醇以外的二醇成分,能举出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的双氧乙烷加成物、丙三醇、三羟甲基丙烷等。
另外,也可以含有苯偏三酸、苯均四酸、连苯三酸、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、联苯-3,4,3’,4’-四羧酸等,或季戊四醇、丙三醇、三羟甲基丙烷、1,2,6-己三醇、山梨糖醇、1,1,4,4-四(羟甲基)环己烷等三官能以上的多元酸及多元醇。
再有,在聚酯树脂中,在不损坏最终成形件的品质的范围内,可以按照公知处方配合其自身公知的树脂用配合剂,例如着色剂、抗氧化剂、稳定剂、各种带电防止剂,离模剂,润滑剂、核剂等。
成形方法
本发明的用于成形二轴拉伸聚酯瓶的预成型件可以使用上述聚酯树脂,由以往公知的制法,例如,注射模塑成形或者压缩成形等成形,根据需要加热已成形的预成型件的口部并使其热结晶化。
本发明所使用的预成型件可以是上述聚酯树脂的单层结构,或者也可以是多层结构,该多层结构是将上述聚酯树脂设为内外层,作为中间层使用其它热塑性树脂、或具有阻气性、氧吸收性、氧吸收阻气性等功能的以往公知的功能性树脂组成物等。
成形了的预成型件在拉伸吹塑成形之前被加热到拉伸温度,但优选预成型件的外表面的温度处于100~130℃、特别是处于115~125℃的范围,且预成型件外表面和内表面的温度差为2℃以内地加热预成型件。在预成型件的外表面温度高于130℃的情况下,因为预成型件会热结晶化而白化,所以不佳。此外,通过预成型件的内外表面的温度差在2℃以内,沿壁厚方向均匀地加热,能使拉伸时产生的热应力在内外表面大致相同,能均匀地进行拉伸,有效地防止由过拉伸造成的白化、异常收缩造成的破裂。其结果,能成品率高地成形更薄壁化了的二轴拉伸聚酯瓶。
接着,参照图4所示的工序图对拉伸吹塑成形的一实施方式的概略进行说明。
自如图4的(A)所示的状态、即将根据上述的加热条件被均匀且高温加热的预成型件20固定在口部、并放入到吹塑模21内的状态,如图4的(B)所示那样,将使预成型件与拉伸杆顶端以外的部分和模具表面不接触的流量的吹塑空气一边流入到预成型件内部,一边开始利用拉伸杆22沿其轴向(纵)拉伸预成型件20。
在图4所示的具体例子中,拉伸杆22进行了从最终成形件10的颈下到接地面的距离的大致95%左右的拉伸[图4的(C)],此时刻正在被成形的预成型件仍未与模具表面接触。
在利用拉伸杆拉伸完成的时刻,在本发明的一实施方式中,通过使吹塑空气的流量不变化,保持该流量直到形成最终成形件地进行吹塑成形,实质上进行周向拉伸,预成型件接触到模具表面而能成形为最终成形件的形状[图4的(D)]。
此外,在本发明的二轴拉伸聚酯瓶的成形方法的另一实施方式中,在完成拉伸杆的拉伸的时刻,进行比上述流量大的流量的主吹塑,由此实质上进行周向拉伸,预成型件接触到模具表面而能成形为最终成形件的形状[图4的(D)]。
吹塑成形后的瓶在被热固定之后,被冷却而作为最终成形件完成。热固定既能够用在吹塑成形模具中进行的一模(onemould)法来进行,也能够用在与吹塑成形模具相互独立的热固定用的模具中进行的二模(two mould)法进行。热固定的温度通常在60~180℃的范围是适当的。
在上述的利用拉伸杆22的拉伸中,相当于最终成形件10的肩部13的部分被拉伸,并且与其连接的、相当于瓶身部14上部的部分被拉伸,接着,预成型件20的相当于聚酯瓶10的瓶身部14下部和底部15的部分的大部分被拉伸。此外,如上所述,利用拉伸杆拉伸时流入规定流量的吹塑空气,从而不论拉伸杆的直径大小都可预防预成型件接触到拉伸杆。
使该预成型件与拉伸杆顶端以外的部分和模具表面不接触的流量是根据预成型件的大小、拉伸杆的直径或最终成形件的形状等的不同而不同,无法统一规定,但能使用被调整为0.05~0.5MPa的压力的吹塑空气,在最终形状为如图4所示那样的横截面为圆形状的2000mL的二轴拉伸聚酯瓶的情况下,优选为0.05~0.1MPa的范围。这样,通过降低吹塑空气的流量,能抑制由从空气罐内流入到预成型件的吹塑空气的隔热膨胀造成的温度变化,能以在空气罐中设定的温度进行拉伸吹塑成形。
此外,该吹塑空气优选被调整为以空气罐内的设定温度计为60~300℃,特别是100~200℃的范围的温度。这样,通过将吹塑空气调整为高温,能抑制预成型件的温度降低,由此能进行均匀的拉伸,能抑制二轴拉伸聚酯瓶的圆周方向的取向,并且能进行高度地薄壁化。
本发明的二轴拉伸聚酯瓶直到拉伸吹塑成形结束时,流入预成型件的吹塑空气的流量是使预成型件与拉伸杆的顶端以外的部分和模具表面不接触的流量,即使进行拉伸吹塑,也能不产生破裂等地进行成形,但是从缩短拉伸所需时间而能提高生产率的方面考虑,特别优选将在利用拉伸杆进行拉伸时的吹塑空气的流入作为预吹塑来进行,在利用拉伸杆进行拉伸结束的同时预吹塑结束,之后进行主吹塑的拉伸。
在该情况下,较佳的是,利用拉伸杆拉伸时进行的预吹塑空气流入作为最终成形件的二轴拉伸聚酯瓶的内部容积的10~50%、特别是25~40%的量。
此外,较佳的是,拉伸杆将预成型件沿纵向拉伸至瓶的最终尺寸的从颈下到接地面的距离(从图3的支承环12到接地面的垂直距离)的70%以上的距离。若小于70%,则由吹塑空气产生的拉伸量过多,特别是在分预吹塑和主吹塑进行拉伸的情况下,由于在主吹塑中急剧的拉伸,有可能会产生过拉伸、成形不良,或容易产生破裂。
利用拉伸杆进行纵向拉伸的上限当然是比如下所述距离小的距离,该所述距离是瓶的最终尺寸的从颈下到接地面的距离减去底部中央的壁厚和在底部中央设有凹部的情况下的凹部的深度后的距离。通常在2000mL的聚酯瓶的情况下,优选是瓶的最终尺寸的从颈下到接地面的距离的95%左右。
在利用拉伸杆的拉伸中,优选拉伸杆的最高速度为700mm/秒以下,特别是在200~500mm/秒的范围内,拉伸杆顶端与预成型件底部内表面接触时的速度是200mm/秒以下或暂时停止。
这样,通过缓慢地进行拉伸杆的拉伸,能进行均匀地拉伸,能够抑制成形了的二轴拉伸聚酯瓶的纵向伸长率和取向,在具备上述特性的同时,能够有效地预防由于急剧的拉伸而产生的过拉伸、成形不良,或产生破裂。
利用拉伸杆拉伸结束后的主吹塑优选被调整为0.5~4.0MPa的压力、且被调整为60~300℃的温度的吹塑空气,以与预吹塑所使用的吹塑空气相同的温度,使用被调整为预吹塑以上的压力的吹塑空气,这样能够将拉伸吹塑成形装置中的空气罐设为一个,因此从生产率方面来看是优选的。
在本发明的二轴拉伸聚酯瓶的制造方法中,拉伸倍率优选纵拉伸倍率为2.7倍以上且面积倍率为12~25倍,由此,能得到薄壁化、轻量化了的二轴拉伸聚酯瓶。
实施例
实施例1
使用聚酯树脂由注射模塑成形机成形质量19g的预成型件,将该预成型件加热到115℃,以200mm/秒的速度进行拉伸杆的拉伸,作为预吹塑,将使预成型件与拉伸杆的顶端以外的部分和模具表面不接触的流量(0.07MPa)的吹塑空气流入到预成型件内部,而且以2MPa进行主吹塑,成形了内部容积为2000mL的瓶。
对于所得到的瓶(N=5个)求出距底部12cm的位置的瓶身部的平均壁厚,为90μm。
此外,使用自距底部12cm的位置的瓶身部切出的5×40mm大小的试验片,在夹头间距离为5mm、拉伸速度为10mm/分钟的条件下进行了抗拉试验。结果表示于图1。
此外,对所得到的瓶自距底部12cm的位置的瓶身部切出试样,使用波长532nm的激光在1800~600cm-1的测量范围内,以5秒的测量秒数、2次积分的测量条件测量了拉曼光谱的取向。将取向参数(OP)相对于距外表面的距离的值表示于图2的(A)。
对所得到的瓶进行了耐落下冲击性的评价,落下容许高度是120cm。
另外,落下容许高度的测量方法如下。
在涂敷有树脂的地面上,对灌满(fully-filled,全填充)状态的瓶进行(1)使瓶以直立状态底部首先落下、和(2)使瓶侧面首先落下,按该顺序反复进行了5次。将不产生瓶身部破裂或底破裂的最大高度作为落下容许高度。
比较例1
使用聚酯树脂由注射模塑成形机成形质量19g的预成型件,将该预成型件加热到124℃,以200mm/秒的速度进行拉伸杆的拉伸,作为预吹塑,使0.8MPa的吹塑空气流入到预成型件内部,而且以3MPa进行主吹塑,成形了内部容积为2000mL的瓶。
对所得到的瓶与实施例1相同地测量出瓶身部的平均壁厚为80μm。
此外,与实施例1相同地测量拉伸试验和拉曼光谱的取向,结果表示于图1和图2的(B)。
与实施例1相同地还对耐落下冲击性进行了评价,落下容许高度是90cm。
比较例2
使用聚酯树脂由注射模塑成形机成形质量45g的预成型件,将该预成型件加热到110℃,以800mm/秒的速度进行拉伸杆的拉伸,作为预吹塑,使0.8MPa的吹塑空气流入到预成型件内部,而且以2MPa进行主吹塑,成形了内部容积为2000mL的瓶。
对所得到的瓶与实施例1相同地测量出瓶身部的平均壁厚为260μm。
此外,与实施例1相同地测量拉伸试验和拉曼光谱的取向,结果表示于图1和图2的(C)。
与实施例1相同地还对耐落下冲击性进行了评价,落下容许高度是120cm。
Claims (5)
1.一种二轴拉伸聚酯瓶,是对由聚酯树脂构成的预成型件进行二轴拉伸吹塑成形而形成的,其特征在于,瓶身部的中央部满足(i)和(ii)中的至少一方,(i)在室温下的抗拉试验中,圆周方向的伸长率大于纵向的伸长率、(ii)拉曼光谱法的圆周方向的取向参数小于纵向的取向参数。
2.根据权利要求1所述的二轴拉伸聚酯瓶,其特征在于,上述瓶身部的平均壁厚为250μm以下。
3.根据权利要求1所述的二轴拉伸聚酯瓶,其特征在于,上述圆周方向的伸长率为100%以上。
4.根据权利要求1所述的二轴拉伸聚酯瓶,其特征在于,上述圆周方向的取向参数为3.5以下。
5.根据权利要求1所述的二轴拉伸聚酯瓶,其特征在于,利用具有如下特征的制造方法来制造二轴拉伸聚酯瓶:在利用拉伸杆拉伸被加热到拉伸温度的聚酯制预成型件、并且利用空气吹塑进行拉伸以形成二轴拉伸聚酯瓶的制造方法中,在利用上述拉伸杆进行拉伸时,使如下流量的吹塑空气流入到预成型件内部,该流量的吹塑空气使预成型件与拉伸杆顶端以外的部分和模具表面不接触。
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CN103826826A (zh) * | 2011-10-04 | 2014-05-28 | 大日本印刷株式会社 | 预制坯和塑料瓶 |
CN107922077A (zh) * | 2015-08-28 | 2018-04-17 | 株式会社吉野工业所 | 合成树脂制容器以及其制造方法 |
CN109415134A (zh) * | 2016-06-28 | 2019-03-01 | 东洋制罐株式会社 | 聚酯制拉伸吹塑成形容器及其生产方法 |
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US10239267B2 (en) * | 2010-10-26 | 2019-03-26 | Basell Poliolefine Italia S.R.L. | Process for producing injection stretch blow molded polyolefin containers |
JP2018083630A (ja) * | 2016-11-21 | 2018-05-31 | 東洋製罐株式会社 | ポリエステル製延伸ブロー成形容器及びその製造方法 |
JP6862698B2 (ja) * | 2016-06-28 | 2021-04-21 | 東洋製罐株式会社 | ポリエステル製ブロー容器 |
WO2018003790A1 (ja) * | 2016-06-28 | 2018-01-04 | 東洋製罐株式会社 | ポリエステル製延伸ブロー成形容器及びその製造方法 |
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CN103826826A (zh) * | 2011-10-04 | 2014-05-28 | 大日本印刷株式会社 | 预制坯和塑料瓶 |
CN103826826B (zh) * | 2011-10-04 | 2016-08-17 | 大日本印刷株式会社 | 预制坯和塑料瓶 |
CN107922077A (zh) * | 2015-08-28 | 2018-04-17 | 株式会社吉野工业所 | 合成树脂制容器以及其制造方法 |
CN107922077B (zh) * | 2015-08-28 | 2020-07-03 | 株式会社吉野工业所 | 合成树脂制容器的制造方法 |
US10934048B2 (en) | 2015-08-28 | 2021-03-02 | Yoshino Kogyosho Co., Ltd. | Synthetic resin container and method for manufacturing the same |
CN109415134A (zh) * | 2016-06-28 | 2019-03-01 | 东洋制罐株式会社 | 聚酯制拉伸吹塑成形容器及其生产方法 |
CN109415134B (zh) * | 2016-06-28 | 2021-03-12 | 东洋制罐株式会社 | 聚酯制拉伸吹塑成形容器及其生产方法 |
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