CN86103073A - 可热灌装抗塌陷聚酯容器的生产方法 - Google Patents

可热灌装抗塌陷聚酯容器的生产方法 Download PDF

Info

Publication number
CN86103073A
CN86103073A CN86103073.7A CN86103073A CN86103073A CN 86103073 A CN86103073 A CN 86103073A CN 86103073 A CN86103073 A CN 86103073A CN 86103073 A CN86103073 A CN 86103073A
Authority
CN
China
Prior art keywords
ingot
container
polyester
post bake
intermediate products
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.)
Withdrawn
Application number
CN86103073.7A
Other languages
English (en)
Other versions
CN1013259B (zh
Inventor
格拉德·T·克里恩斯
威尼·N·科莱特
马丁·H·贝克
理查德·E·克拉克
伊尤安·L·哈里
苏帕严·克里施纳库马
布里安·H·米勒
理查德·尼科尔斯
戴维德·彼希奥利
露斯·D·塔希奥
埃利尼·M·沃索维茨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Graham Packaging Pet Technologies Inc
Original Assignee
Continental PET Technologies Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=24933965&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN86103073(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Continental PET Technologies Inc filed Critical Continental PET Technologies Inc
Publication of CN86103073A publication Critical patent/CN86103073A/zh
Publication of CN1013259B publication Critical patent/CN1013259B/zh
Expired legal-status Critical Current

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D1/00Containers 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
    • B65D1/40Details of walls
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/08Biaxial stretching during blow-moulding
    • B29C49/085Biaxial stretching during blow-moulding without pre-stretching, e.g. simple blowing step
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/4273Auxiliary operations after the blow-moulding operation not otherwise provided for
    • B29C49/4278Cutting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/64Heating or cooling preforms, parisons or blown articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/64Heating or cooling preforms, parisons or blown articles
    • B29C49/6409Thermal conditioning of preforms
    • B29C49/6418Heating of preforms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/78Measuring, controlling or regulating
    • B29C2049/7879Stretching, e.g. stretch rod
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2793/00Shaping techniques involving a cutting or machining operation
    • B29C2793/009Shaping techniques involving a cutting or machining operation after shaping
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/07Preforms or parisons characterised by their configuration
    • B29C2949/0715Preforms or parisons characterised by their configuration the preform having one end closed
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/07Preforms or parisons characterised by their configuration
    • B29C2949/079Auxiliary parts or inserts
    • B29C2949/08Preforms made of several individual parts, e.g. by welding or gluing parts together
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/07Preforms or parisons characterised by their configuration
    • B29C2949/081Specified dimensions, e.g. values or ranges
    • B29C2949/0811Wall thickness
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/20Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
    • B29C2949/22Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at neck portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/20Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
    • B29C2949/24Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at flange portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/20Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
    • B29C2949/26Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at body portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/20Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
    • B29C2949/28Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at bottom portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3008Preforms or parisons made of several components at neck portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3012Preforms or parisons made of several components at flange portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3016Preforms or parisons made of several components at body portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/302Preforms or parisons made of several components at bottom portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3024Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3024Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique
    • B29C2949/3026Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique having two or more components
    • B29C2949/3028Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique having two or more components having three or more components
    • B29C2949/303Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique having two or more components having three or more components having more than three components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3032Preforms or parisons made of several components having components being injected
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3032Preforms or parisons made of several components having components being injected
    • B29C2949/3034Preforms or parisons made of several components having components being injected having two or more components being injected
    • B29C2949/3036Preforms or parisons made of several components having components being injected having two or more components being injected having three or more components being injected
    • B29C2949/3038Preforms or parisons made of several components having components being injected having two or more components being injected having three or more components being injected having more than three components being injected
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3041Preforms or parisons made of several components having components being extruded
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3041Preforms or parisons made of several components having components being extruded
    • B29C2949/3042Preforms or parisons made of several components having components being extruded having two or more components being extruded
    • B29C2949/3044Preforms or parisons made of several components having components being extruded having two or more components being extruded having three or more components being extruded
    • B29C2949/3046Preforms or parisons made of several components having components being extruded having two or more components being extruded having three or more components being extruded having more than three components being extruded
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/06Injection blow-moulding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/08Biaxial stretching during blow-moulding
    • B29C49/087Means for providing controlled or limited stretch ratio
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/42394Providing specific wall thickness
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/64Heating or cooling preforms, parisons or blown articles
    • B29C49/6604Thermal conditioning of the blown article
    • B29C49/6605Heating the article, e.g. for hot fill
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/76Neck calibration
    • B29C49/761Forming threads, e.g. shaping neck thread between blowing means and mould
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2067/00Use of polyesters or derivatives thereof, as moulding material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0094Condition, form or state of moulded material or of the material to be shaped having particular viscosity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25Solid
    • B29K2105/253Preform
    • B29K2105/258Tubular
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/26Scrap or recycled material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2667/00Use of polyesters or derivatives thereof for preformed parts, e.g. for inserts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B29K2995/0017Heat stable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/004Semi-crystalline
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0041Crystalline
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/005Oriented
    • B29K2995/0053Oriented bi-axially
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0063Density
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0068Permeability to liquids; Adsorption
    • B29K2995/0069Permeability to liquids; Adsorption non-permeable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00Other particular articles
    • B29L2031/712Containers; Packaging elements or accessories, Packages
    • B29L2031/7158Bottles
    • B29L2031/716Bottles of the wide mouth type, i.e. the diameters of the bottle opening and its body are substantially identical
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/907Direct application of fluid pressure differential to shape, reshape, i.e. distort, or sustain an article or preform and crystallizing of nonstretched or molecularly unoriented portion thereof
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/909Direct application of fluid pressure differential to stretch an article or preform and heat shrinking of stretched article or preform

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

本文涉及生产用来灌装热产品的高取向的、抗热塌陷的聚酯容器的一种方法。按照此方法,对一块聚酯锭料进行二次加热,然后放在吹塑模腔里,使锭料扩张并模塑成包括一个容器的中间产品,容器有一个取向的放端盖的颈口,颈口直径比锭料直径大得多。此方法的特征在于:对上述锭料中聚酯成分、锭料扩张时的拉伸比以及二次加热条件均加以控制,使容器侧壁及颈口密度在1.350到接近(但低于)1.370克/厘米3范围内。

Description

本发明所涉及的是一种用来生产可热灌装的抗塌陷的聚酯容器的方法,在这里不需要用变定工艺(Set    Process)技术,且具有传统容器的几何外形。
过去几年中,用双轴取向的聚对苯二甲酸乙二醇酯(PET)材料做的各种形状的容器(包括小口瓶、大口瓶和罐头盒)的市场需求量日益增加。
这些容器中绝大多数只能用来在低温或中温下灌装产品,诸如软饮料,食物油、芥末,网球等。假若聚合物容器能在160~200°F温度下灌装产品的话,则现在由金属容器和玻璃容器占据的二千万件以上的食品包装市场的25%肯定可以用聚合物容器来代替。
然而,众所周知,采用传统的注射吹塑,二次加热吹塑及其他工艺生产的PET容器在热灌装和密封时出现两种变形现象。
第一种变形为,当容器处于接近或超过PET的玻璃态转变温度(Tg)或软化温度(大约170°F)时,容器由于过分的热收缩而导致变形。
产生第二种变形是由于容器热灌装和在接近灌装温度下密封以后容器内部形成了部分真空。由于产品本身及其热空间的气体冷却,使体积收缩,从而形成部分真空,这样就在容器侧壁上产生一个向里的净力,使容器产生皱曲或塌陷。
这两种现象使得用传统方法生产的PET容器在提高灌装温度时不能满足商用要求。
正如技术上已介绍过的,用二次成形的热处理工艺可以减少热收缩已经知道,把“精加工”的聚合物百分结晶度增加到远远高于非晶态或锭料的(preform)百分数,可以提高PET的变形温度(Tg)。在吹塑的容器中,要达到这一点可通过:(1)预先取向工艺(它产生变形诱导的结晶过程)(2)加热的吹塑模中,在稍高于产品工作温度的温度下进行被迫的二次吹塑调节(它产生热诱导的结晶过程)。已经知道,单靠变形诱导的结晶过程也能明显地增加百分结晶度,但其值仍远远低于热变定(heat    set)温度调节所能达到的百分结晶度(即Tg)。
因此,以前是用热调节技术来制备热灌装用的PET容器。然而,由于下列几个关键问题使这种技术(所谓“热变定”工艺)商业应用的寿命缩短了。问题包括(1)热调节和从吹塑模中取出之前冷却容器壁所需时间;(2)PET结晶过程的性能随链的形态变化很大,因此,取向和拉伸水平直接影响到容器的外观和物理性能。
例如,所建立的提高PET容器壁Tg的方法,要求有相当长的塑模停留时间(5-20秒)以产生所期望的热调节水平(在190°F灌装时通常规定的最大容器体积收缩为1%)。然而,绝大多数的现有PET产品是两步成形的,如果采用上述塑模停留时间的话,高产量、间歇运行的二次加热的吹塑机将会大大降低生产率(即单位时间的产量)。产量及其他经济方面的类似缺点也存在于轮流二次加热及注射吹塑转换技术中。
除塑模停留时间过长外,热变定技术的商业应用还受到下列限制:未取向的基本上是无定形的PET在结晶时有转变为乳白色的不透明材料的倾向。这样,如果希望得到全透明的容器,通常需要对双轴取向的PET容器的低取向的颈口部、肩部和底部进行冷却,以防止这些部位在热变定温度调节期间过分结晶及增白。当然,尽管有高水平的热诱导的结晶过程,高取向的瓶子侧壁仍然是透明的。这些形态学上的现象迫使瓶子生产者要末(1)冒失去市场的风险(在外观方面)和牺牲物理性能(降低未取向结晶部位的抗冲击性能),故意使容器未取向部位过分结晶和增白,要末(2)尽量减少未取向材料结晶过程,使容器在热灌装时可能产生热变形。(对变形问题的共同解决办法是增加未取向、未结晶部位的壁厚以增强这些部位并降低热变形的可能性。但是成本的增加又严重限制了这种办法。)
除了热变形外,先前技术介绍了几种减轻真空塌陷的办法。增加容器壁厚连同采用加强肋、轮圈和其它结构上的措施是有效的,但也带来了成本及几何尺寸方面的缺点。此外,专利文献也介绍了一些解决方案,使得在产品温度影响下向内变形的容器部位故意发生热弹变形和压力变形,从而使产生的局部真空与之抵销或减少。这种办法的主要缺点是:改变了传统容器径向的几何形状,涉及到产品的形象、消费者的接受能力等许多复杂的市场问题。
一种在热和真空作用下都不会变形的,而且经济上及商业上都有竞争力的PET容器将会开辟新的市场,提供轻的、透明的并抗震的PET包装。但先前技术对这些问题的捷决办法仅仅是对容器的经济性(单位成本)和市场接受能力(非传统的几何形状)进行折衷。
因此,本发明的主要目的是提供一种改进的方法来生产价格可行的可热灌装的PET容器,容器的热变形是商业上可接受的,没有真空塌陷(在高达200°F温度下热灌装及密封),无需作二次成形热处理,而且具有传统容器的几何形状。
解决真空引起的容器变形问题的新办法是由于运用了特殊的工艺控制和产品设计技术(在容器生产及灌装过程中),使容器收缩及“得到控制的”真空塌陷控制在所要求的水平上,从而得到最小的内部真空度,满足被灌装容器的尺寸稳定性要求。
实现本发明的这些目标及其他目标部分地借助于运用授予Beck等人的美国专利No.4,496,064中描述的大口PET容器制造技术。
上面所说的大口技术利用由传统技术生产的PET锭料来生产带有双轴取向的螺纹或凸边部位的大口瓶和罐头盒。生产出的容器口的取向控制在一定程度,克服了非取向的无定形聚酯在热变定/热灌装过程中的那些缺点。
为了上述目的及将在下文中指出的其它目的,通过下面的详细说明,附加的权利要求以及附图中的一些视图,将会更清楚地理解本发明的实质内容。
图1A是用传统技术生产的聚酯容器的立视图。
图1B是同一个容器在灌装190°F的热产品以后的主视图。
图1C是图1中容器的立视图,其中的容器用热变定技术改进后再在190°F灌装,显示出体积减少1%并有回旋形的几何形状,没有传统的真空塌陷。
图2是从与本发明相连的一个典型锭料上切取的半个剖面图。
图3是一个标准模具的半个剖面图,它限定一个吹塑模腔,在模腔中放有预先吹塑模塑的图2的锭料。
图4是用放在图3模腔内的图2的锭料吹塑模塑成的中间产品的半个立视图。
图5是聚酯罐头盒的半个立视图,它是沿图4上箭头A的轨迹切开中间产品而得到的。
图6是瓶口带有螺纹的瓶子的半个立视图,瓶子是中间产品的一部分,用图3表示的同样的方法成形的。
图7是图5罐头盒的半个剖面图,罐头盒灌装190°F的热产品后用两道接缝将其端部封闭,在双锁边后允许5%的体积收缩。
图8是从图6的瓶子上切取的半个剖面图,瓶子灌装了190°F的产品以后用一个盖子封闭,在封闭后允许5%的体积收缩。
图9是一个曲线图,表示容器典型的侧壁密度测量结果和计算得的百分结晶度,把用前面提到过的Beck等人的专利生产的和用传统的方法生产的大口容器进行对比。
图10是类似于图5罐头盒的半个剖面图,它用本发明中提出的图7上的方法密封。在进行灌装和密封时允许的体积收缩小于1%。
图11是类似于图10的半个剖面图,但罐头盒是用图8的方法密封,允许的体积收缩小于1%。
图12是一个喷淋冷却装置的立式示意图,该装置用来减少热灌装及密封时容器的收缩。
图13上曲线表示聚酯密度是拉伸比的函数。
图14上曲线表示190°F时聚酯收缩量是拉伸比的函数。
图15上曲线表示一定拉伸比下密度同锭料温度的关系。
图16上曲线表示在一定的锭料温度和拉伸比下,密度同聚酯共聚体含量的关系。
图17上曲线表示用各种方法生产的容器的典型体积收缩量,它是热灌装时温度的函数。
图18是从典型锭料上切取的局部放大的剖面图,其中的锭料是叠层结构的锭料。
用传统的二次加热或注射吹塑技术生产的聚酯容器表现出过大的热收缩,在190°F下灌装时体积收缩为15~50%。这种容器的一个例子见图1。如前所述,先前技术解决聚酯热变形问题是采取调节加热的吹塑模中的吹塑容器的方法,把聚酯的Tg(即软化温度)提高到稍高于190°F。用增加瓶子侧壁上百分结晶度的热变定工艺达到上述目的。高结晶度聚酯(>50%结晶度)的Tg超过350℃(即Tg随百分结晶度的增加而增加)。用ASTM1505的方法侧得密度就可以测定结晶度。
百分结晶度= (ds-da)/(dc-da) ×100
其中,ds=样品密度,克/厘米3
da=1.333克/厘米3(无定形)
dc=1.455克/厘米3(100%晶体)
表1
图1A,B    图1C
颈口密度,克/厘米31.341 1.388
颈口横截面缩小,%    1.22    0.08
侧壁密度,克/厘米31.357 1.372
侧壁横截面缩小,%    10.5    0.52
侧壁高度缩小,%    8.8    0.40
表1列出图1上述容器的密度与百分收缩率的数据。
一般说来,热变定容器在190°F下灌装时体积收缩率低于1%,侧壁密度的测定结果大于1.365克/厘米3,通常高于1.370克/厘米3(分别相当于26%和30%结晶度)。
虽然热变定容器在190°F下灌装显示的热变形性是可接受的,但它们对于真空引起的塌陷仍然是敏感的。在刚性容器中,当装入的产品冷却到环境温度时,可显示的典型的真空度超过8-16psi(磅/英寸)(取决于灌装量,产品灌装温度等)。为了防止柔性的聚酯侧壁变形,使用如回旋形的镶板这样一些非传统几何形状的容器,为了控制形变,还常常使用加强肋、轮圈等,并增加侧壁厚度。除了增加成本外,还影响市场销路。
此外,先前的热变定容器必须防止热灌装时容器口过分变形,这种变形会影响加盖及密封。例如,某些瓶子使用预结晶的不透明的瓶口以减少变形。此方法虽有效,但明显地增加了成本。其他瓶子保持瓶口透明,就用增加壁厚(相对于传统的非热灌装容器)来减少变形。这些方法都增加成本,从而限制了其使用。
下面要指出一种生产可热灌装的聚酯容器的新办法,这种并不否定热变定工艺。
图2-6示出的罐头盒,小口瓶和大口瓶是用传统的一层或多层注射模塑或挤塑的锭料生产的,这与前述的Beck等人的专利一致,因此凸边和颈口有高的取向。
现在请参看图2,图上示出本发明特别提供的锭料。锭料的横截面是围绕中心轴20的环,锭料包括一个上部22,这是开口端,位于支承突缘24的上面。在图2上更清楚地看到,突缘及颈口22从相应的吹塑模中向外突出。在传统的模塑操作中,一个吹塑管装在颈口22上并与之密封。锭料(用26表示)在突缘24下面有一个筒体部分28,28下面厚度向外增加的部位用30来表示。30下面的部分则由细长的圆筒32组成,32在内、外两个方向上都有一点圆锥形,以便于从注射模中抽出,但其芯体部分的厚度保持不变。锭料26的底部成半球形,厚度往中心方向减少。
然而,可以理解到:锭料的尺寸是直接由要做的中间产品的大小决定的。
虽然专门介绍过注射模塑的锭料26,但应当理解,锭料可以用一个挤塑管来成形。
现在参看图18,图上表示具有叠层结构的一个典型锭料的放大横截面。这种锭料有PET材料的外层36和内层38。这两层的里面有相当薄的隔层40,42,隔层可由SARAN这样的材料构成。最后是芯部44,它可由PET或相似的聚合物构成。
图3表示一个典型的吹塑模,它被劈成一半,用46表示。吹塑模46有一个或几个吹塑模腔48,模腔形状加工成可塑造出下面一部分的形状为一个罐头盒的中间产品。把锭料26放在模腔48内,支承在突缘24上。传统的适当的吹塑器械包括一根吹塑杆(未示出),它把压缩气体直接吹进锭料26,使锭料26轴向伸长或拉伸。可以理解,要根据模腔48形状决定锭料26的外形,以达到一个预定的拉伸比。还要控制由内部气体产生的锭料26在模腔48轴向的伸长或拉伸以及锭料的膨胀,以便控制容器及其侧壁的厚度和拉伸比。
图4上示出中间产品50,它是吹塑模腔48中的锭料26塑成的。产品50下部是一个罐头盒,包括底部54以及同底部整体相连的盒身或侧壁56,侧壁56到向外突出的突缘58为止。如果想要的话,侧壁56可带垂直方向上可以向里收缩的轮圈60,以适应产品冷却时容器内部体积的减少。轮圈60通过吹塑模46的内部肋62制成。
中间产品50的上部用64表示,把它当作连接部分。沿着图4上箭头A所指的线切开中间产品,把连接部分64同容器或罐头盒52分开,然后把切下来的连接部分64重新研磨,用在以后的锭料中。
图5上清楚地示出分离以后的容器或罐头盒52,图上凸边58成为用双锁边把端部卷缝到盒身56上的通常的凸边。
虽然,可以修改模腔48的形状,使塑成的中间产品(未示出)的下部呈大口瓶形状(如图6所示,用66表示)。大口瓶66有一个封闭侧壁或瓶身70下部的瓶底68。瓶子上部是敞开的,与卷边的凸边58不同,瓶身上端向里形成一个环形凸边72,凸边72再向上轴向延伸形成颈口74,瓶口可以扣上传统的带螺纹的或有突缘的帽盖。如果想要的话,瓶身70可以用类似于肋60的空心肋76来加强。
图7上示出的罐头盒52已装上热的产品78并且由端盖80封闭。端盖是金属的或是复合材料的,用传统的带凸边58的双锁边82固定在罐头盒上。
图9上示出的大口瓶66已装上热的产品并且用端盖86封闭。端盖86是传统的带罩裙88的罩子,罩裙88同瓶口74连接。显然,罩子86的端板由瓶口74的端部密封面90(图6)密封。
如前所述,当图5的罐头盒52和图6的大口瓶66用Beck等人专利中描述的PET锭料制造(用传统方法)时,它们能适应灌装热产品时高的收缩百分数。
图7和图8示出在190°F下灌装以后罐头盒及大口瓶的情况。用不是最佳的工艺条件生产的这些容器的总体积收缩率为6-10%,这可与图1示出的用先前的技术生产的这类容器的收缩情况(为15-50%)相对比。
性能上的主要改进是由于消除了传统方法生产的容器中大面积的低取向及无定形部位(例如放端盖的瓶口及肩部与侧壁的过渡区)。
图13是结晶化聚酯的密度与拉伸比的典型曲线。拉伸比确定如下:
DRt=( (Db-Dp)/(Dp) + (Lb-Lp)/(Lp) )×100
这里,Db=瓶子的最大外径
Dp=锭料的最小内径
Lb=瓶口以下的瓶子长度
Lp=瓶口以下的锭料长度
根据最终容器的瓶口以及肩部的取向情况,图5和图6所示的总密度(即百分结晶度及Tg)较高的容器(与传统的容器相比)在热灌装时产生的热变形就低(不需要用热结晶及“热变定”)。
图13-16表示的各种关系曲线,它是相对于用热变定方法生产的容器中聚酯的最大密度而作出的。这些曲线介绍了工具设计、聚酯成分及工艺条件(全部是非热变定的变量)的作用及相互关系,这些因素影响容器中聚酯的百分结晶度。
例如,图13表示变形引起的结晶过程对提高聚酯密度的影响,对典型的聚酯来说,当总的拉伸率大于8/1但小于12/1时,聚酯密度增加到最大,其值略低于1.37克/厘米3
图14表示拉伸比超出最大变形硬化范围后对百分收缩率的负效应。已知在改进密度方面的控制因素是总的拉伸比。例如,轴向拉伸与环向拉伸的比率是意义不大的。
作为已知的密度最佳化技术的另一个例子,图15和16指出工艺条件及聚酯成分对密度的影响。
把Beck等人取向的瓶口技术(oriented finish techology)同先前的工艺技术结合起来,不用热变定热调节就可以生产出总的体积收缩在3-5%范围内(在190°F下灌装时)的聚酯容器。用这种方法生产的容器的侧壁及凸边/瓶口平均密度超过1.350克/厘米,最大可达1.365克/厘米3(22-30%结晶度)。
190°F下体积收缩率为3-5%的容器与其他容器相比,在外观上不会有很大变化,而且用于热灌装在商业上也有竞争力。
3-5%的体积收缩对于降低内部真空实际上是有利的,这种真空是由于密封以后容器中产品及空间气体冷下来而产生的。通常,在190°F下灌装时,容器体积因收缩而减少2-5%就足以抵消使容器塌陷的压力。为了有效地消除可能出现的真空塌陷,希望减少热灌装时和密封以前出现的容器收缩。这就要求缩短从开始灌装到密封完毕这一段时间间隔,最好为5秒或更短时间。如果因灌装线和/或产品的限制做不到这一点,则在灌装期间和密封之前必须冷却容器的外部。
用图12上所示的喷淋系统可有效地增加灌装/密封的允许时间间隔,可增加10倍或者更多。
现在参看图12,把罐头盒52看成是用本发明的方法制造的,罐头盒在灌装后进行密封。罐头盒52放在图上示出的支承件90上,此时,罐头盒52位于装罐机92的下面,从装罐机把热的产品灌装到罐头盒52里。在灌装的同时,用喷淋管94进行冷却。喷淋管94可在罐头盒52上喷淋冷水或合适的冷却气体。
罐头盒52装完以后,过一般时间再把它送到密封机械上(用96表示),用传统的方法加上端盖80并用双锁边82密封。图上只表示支承夹头(backup    chuck)98和密封机械的成型滚筒100或双锁边96。
喷淋管102与密封机械相连,用它对被密封的罐头盒52进行喷淋。与喷淋管94相似,喷淋管102可以把冷水或冷空气喷到正在密封的罐头盒52上。
上面“可控制的”收缩过程有效地消除对于容器的径向几何形状及过分的壁厚的要求。然而,希望用图5和图6所示的加强肋或加强轮圈60、76来防止塌陷,这种塌陷是由于产品在货架上长期存放时长期的水蒸汽传输及部分内部真空引起的。
下面的例子是想要更充分地证明本发明的实质,但并不限制在这个范围内。
例1
这个例子表明411×501聚酯罐头盒的生产情况,在190°F下灌装时其体积收缩率为6-8%。图3上所示的一块62克的锭料,其在突缘以下的长度为4.95英寸,外表面直径为1.56英寸,平均壁厚为0.180英寸,它是用PET共聚物(2%的)间苯二酸酯)生产的,其特征性粘度为0.80±0.1。
锭料在传统的拉伸吹塑模塑机中二次加热,模塑机带有石英绝缘电阻的二次加热炉,机器的全部周期为5.0秒。拉伸吹塑开始之前锭料的温度为200°F(用绝缘电阻高温计测得)。吹塑模温度保持在35°F。
修整后的容器在190°F下充水,充到离凸边0.625英寸以内,再让它冷到室温。测得总的体积损失为8.2%。平均侧壁密度为1.348克/厘米3,就这一点来说,来能获得充分发展的热变形诱导的晶体结构。
例2
这个例子表明用例1中的工具、材料和最佳工艺条件生产的聚酯罐头盒在190°F下灌装时它产生3-4%的体积收缩。
以同样的炉子停留时间对例1中用的同样的锭料进行二次加热,但增加了石英真空管的能量输出以提高锭料温度(在明显的结晶过程开始之前)。此外,改变了锭料的垂直温度分布和开始膨胀前锭料的轴向拉伸程度,并把吹塑容器的壁厚减小到0.015英寸。其他所有的工艺及评价条件均与例1中的相同。
总的体积收缩为4.2%,平均侧壁密度为1.362克/厘米3。就这一点来说,得到了充分发展的、热变形诱导的晶体结构。
例3
这个例子表明被控制的容器收缩对防止真空引起起的塌陷的作用。
如例2所生产的10个聚酯罐头盒,充入190°F的水,一直充到凸边下面0.625英寸的水平面上,在双锁边以前让其停留10秒钟。结果所有样品均出现真空引起的塌陷(如图10实施)。
用同-批料再做10个罐头盒,充入190°F的水,在2秒钟以内双锁边并立即放在水浴中冷到室温。结果所有样品在取出之前均塌陷。
用同-批料做最后一组10个罐头盒,充入190°F的水,在2秒钟以内双锁边并让其在室温下收缩。结果所有样品均未出现真空引起的变形。
例4
这个例子表明控制颈口及侧壁收缩率的聚酯大口瓶的生产情况。
以特性粘度为0.80±0.1的聚酯均聚物为原料,用传统的注射技术生产80克锭料,其颈口以下长度为6.31英寸,平均壁厚为0.185。
锭料在石英炉中二次加热到225°F,对温度垂直分布曲线及拉伸吹塑条件进行调整以生产出一个70mmCT,24(盎司)的容器(如图6所示),其颈口壁厚为0.025英寸,侧壁平均厚度为0.015英寸。
容器修整后在190°F下灌装,容器总体积减少5.2%,颈口直径减少2.0%,而底板直径减少3.2%。测得颈口及瓶身侧壁的密度分别为1.360和1.356。结果表明用以前的注射模塑精加工技术得到的控制颈口收缩率的容器(如图1B所示),在变形及体积总收缩率方面是不可接受的。
例5
这个例子表明把原有的Glastik取向的颈口或凸边的优点同已知的热变定技术结合起来所产生的协同效应。
对例1和例2中的锭料,用例2的方法进行二次加热,再把它在与例1和例2相同的吹塑模中拉伸吹塑。但250°F时在吹塑模中保温10秒钟(例1和例2是在35°F时保温1.5秒)。
这样产生的容器在190°F下热灌装时,体积收缩率为0.4%。
例4中的锭料作同样的二次加热,然后在与例4相同的吹塑模中拉伸吹塑。但250°F时保温时间为10秒钟(例2为35°F时保温2秒钟)。
产生的容器在颈口及肩部均是透明的,在190°F时其体积收缩为0.8%。
相比之下,用传统的注射吹塑工艺和热变定工艺生产的同样形状和尺寸的49克容器在颈口及肩部是半透明的,它在190°F时体积收缩率为1.6%。
图17上的曲线表示用下列工艺生产的容器的情况:
曲线a,传统的非热变定技术
曲线b,Beck等人的非热变定技术
曲线c,先前的传统的热变定技术
曲线d,Beck等人的热变定技术

Claims (18)

1、生产用来灌装热产品的高取向的抗热塌陷的聚酯容器的一种方法,上述方法包括下列步骤:
a)提供一块聚酯锭料,对锭料二次加热,把锭料放在吹塑模腔里,使其扩张并与吹塑模腔配合模塑成包括一个容器的中间产品,容器有一个取向的放端盖的颈口,颈口直径比锭料直径大得多;
b)方法的特征在于:对上述锭料中聚酯的成分、锭料扩张时的拉伸比以及二次加热条件都加以控制,使得容器侧壁及颈口的密度在1.350到接近(但低于)1.370克/厘米3的范围内,相应的结晶度为14~28%。
c)从塑模中取出中间产品并使容器与中间产品的其余部分分开。
2、如权利要求1所述的方法,其中,中间产品的其余部分重复使用在另一锭料的成型中。
3、如权利要求1所述的方法,其中,聚酯成分的特性粘度控制在0.80±0.1左右。
4、如权利要求1所述的方法,其中,侧壁的总拉伸比范围为8~10比1。
5、权利要求1所述的方法,其中,锭料二次加热的温度范围通常为180°F到250°F之间。
6、如权利要求3所述的方法,其中,侧壁的总拉伸比范围为8~10比1。
7、如权利要求6所述的方法,其中,锭料二次加热的的温度范围通常为180°F到250°F之间。
8、如权利要求4所述的方法,其中,锭料二次加热的的温度范围通常为180°F到250°F之间。
9、如权利要求1所述的方法,其中,锭料二次加热的的温度大约为225°F,并且温度是轴向分布的。
10、如权利要求1所述的方法,其中,所述锭料是多层结构的锭料。
11、生产用来灌装热产品的高取向的抗热塌陷的聚酯容器的一种方法,上述方法包括下列步骤:
a)提供一种聚酯锭料,对锭料二次加热,把锭料放在吹塑模腔里,使其扩张并与吹塑模腔配合模塑成包括一个容器的中间产品,容器有一个取向的放端盖的颈口,颈口直径比锭料直径大得多;
b)方法的特征在于:对上述锭料中聚酯的成分、锭料扩张时的拉伸比以及二次加热条件都加以控制;
c)在温度保持在190°F以上的吹塑模中将中间产物保温2~5秒钟,至少对侧壁及颈口进行热调节,由此把容器的平均密度提高到接近(但低于)1.370克/厘米3;
d)从塑模中取出中间产品并使容器与中间产品的其余部分分开。
12、如权利要求11所述的方法,从塑模中取出中间产品之前还要加上从内部冷却器的步骤。
13、如权利要求11所述的方法,其中,进行热调节之前容器的侧壁及颈口的密度范围为1.350到接近但小于1.370克/厘米3
14、如权利要求11所述的方法,其中,所提供的锭料是多层结构的锭料。
15、如权利要求11所述的方法,其中,每个容器在灌装热的产品以后密封,对每个这样的容器在热灌装期间及密封之前进行冷却,以便使由于热灌装而引起的容器收缩绝大部分出现在密封之后。
16、如权利要求15所述的方法,其中,用来冷却容器的流体冷却剂是水或气体。
17、如权利要求1所述的方法,其中,每个容器在灌装热产品后密封,对每个这样的容器在热灌装期间及密封之前进行冷却,以便使由于热灌装而引起的容器收缩绝大部分出现在密封之后。
18、如权利要求17所述的方法,其中,用来冷却容器的流体冷却剂是水或气体。
CN86103073.7A 1985-05-03 1986-05-03 可热灌装抗塌陷聚酯容器的生产方法 Expired CN1013259B (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/730,113 US4665682A (en) 1985-05-03 1985-05-03 Method for producing a hot fillable, collapse resistant polyester container without the need to utilize set process techniques and/or non-conventional container geometries
US730,113 1985-05-03

Publications (2)

Publication Number Publication Date
CN86103073A true CN86103073A (zh) 1987-04-08
CN1013259B CN1013259B (zh) 1991-07-24

Family

ID=24933965

Family Applications (1)

Application Number Title Priority Date Filing Date
CN86103073.7A Expired CN1013259B (zh) 1985-05-03 1986-05-03 可热灌装抗塌陷聚酯容器的生产方法

Country Status (13)

Country Link
US (1) US4665682A (zh)
EP (2) EP0200564A3 (zh)
JP (1) JPS6230021A (zh)
CN (1) CN1013259B (zh)
AT (1) ATE163591T1 (zh)
AU (1) AU575253B2 (zh)
CA (1) CA1254010A (zh)
DE (1) DE3650667T2 (zh)
DK (1) DK168064B1 (zh)
FI (1) FI861848A (zh)
MX (1) MX165124B (zh)
NO (1) NO174413C (zh)
SG (1) SG50632A1 (zh)

Families Citing this family (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3786258T2 (de) * 1986-12-02 1993-11-04 Dainippon Printing Co Ltd Herstellung eines behaelters mit metalldeckel.
US4936473A (en) * 1988-09-16 1990-06-26 Continental Pet Technologies, Inc. Hot-fill product container with multi-layer wall structure
US5011648A (en) * 1989-02-14 1991-04-30 Van Dorn Company System, method and apparatus for hot fill PET container
US5250335A (en) * 1989-06-23 1993-10-05 Toyo Seikan Kaisha, Ltd. Polyester vessel for drink and process for preparation thereof
US5067622A (en) * 1989-11-13 1991-11-26 Van Dorn Company Pet container for hot filled applications
US5066528A (en) * 1990-03-05 1991-11-19 Continental Pet Technologies, Inc. Refillable polyester container and preform for forming the same
US5251424A (en) * 1991-01-11 1993-10-12 American National Can Company Method of packaging products in plastic containers
WO1994001269A1 (en) 1992-07-07 1994-01-20 Continental Pet Technologies, Inc. Method of forming container with high-crystallinity sidewall and low-clystallinity base
CA2159169C (en) * 1994-09-27 2006-05-16 Tony Salemi Modified plastic bottle injection blow-molding apparatus and process
JPH09277361A (ja) * 1996-04-18 1997-10-28 Nippon Steel Chem Co Ltd 多層ブロー成形体および多層ブロー成形方法
USD419882S (en) 1996-04-19 2000-02-01 Snapple Beverage Corporation Bottle
USD420592S (en) 1996-04-19 2000-02-15 Snapple Beverage Corporation Bottle
IT1285525B1 (it) 1996-10-18 1998-06-08 Sinco Eng Spa Procedimento perfezionato per la stabilizzazione dimensionale di manufatti in polietilentereftalato
US6062408A (en) * 1997-04-09 2000-05-16 Dtl Technology Limited Partnership Wide mouth hot fill container
US5988416A (en) 1998-07-10 1999-11-23 Crown Cork & Seal Technologies Corporation Footed container and base therefor
US6109006A (en) * 1998-07-14 2000-08-29 Advanced Plastics Technologies, Ltd. Process for making extruded pet containers
US6228317B1 (en) * 1998-07-30 2001-05-08 Graham Packaging Company, L.P. Method of making wide mouth blow molded container
US6296471B1 (en) * 1998-08-26 2001-10-02 Crown Cork & Seal Technologies Corporation Mold used to form a footed container and base therefor
US6264050B1 (en) 1998-10-06 2001-07-24 Plastipak Packaging, Inc. Container with improved neck portion and method for making the same
RU2164887C1 (ru) * 2000-03-24 2001-04-10 Общество с ограниченной ответственностью "Водолей 2001" Банка для продуктов и способ ее изготовления
AU2001267004A1 (en) * 2000-06-27 2002-01-08 Graham Packaging Company, L.P. Preform and method for manufacturing a multi-layer, blown finish container
US6523720B1 (en) 2000-06-30 2003-02-25 Ocean Spray Cranberries, Inc. Dispensing consumable liquids
US6536617B2 (en) * 2001-02-15 2003-03-25 Colgate-Palmolive Company Bottle with closure holding structure
US6814923B2 (en) * 2001-12-27 2004-11-09 Graham Packaging Company, L.P. Preform, intermediate article and method for manufacturing a blown finish container
US20040026827A1 (en) * 2002-06-28 2004-02-12 Issam Dairanieh Method for the fabrication of crystallizable resins and articles therefrom
US6827228B2 (en) * 2002-08-08 2004-12-07 Pepsico., Inc. Plastic container with decorative recessed features and associated method and apparatus for manufacture thereof
US20060255049A1 (en) * 2002-08-09 2006-11-16 Fort James Corporation Stretch blow-molded stackable tumbler
US20040035874A1 (en) * 2002-08-20 2004-02-26 Sonoco Development, Inc. Extrusion blow molding methods and articles made thereby
US7153466B2 (en) * 2002-08-20 2006-12-26 Sonoco Development, Inc. Method and apparatus for blow-molding an article having a solid radially outwardly projecting flange
US6997336B2 (en) * 2002-09-23 2006-02-14 Graham Packaging Company, L.P. Plastic cafare
US20040091651A1 (en) * 2002-11-01 2004-05-13 Mark Rule Pet copolymer composition with enhanced mechanical properties and stretch ratio, articles made therewith, and methods
US20050260371A1 (en) * 2002-11-01 2005-11-24 Yu Shi Preform for low natural stretch ratio polymer, container made therewith and methods
US20040146673A1 (en) * 2003-01-24 2004-07-29 Larsen W. Bruce Container preform assembly and method of manufacture
BRPI0411557A (pt) * 2003-06-18 2006-08-01 Coca Cola Campany recipiente preparado por meio de um processo de moldagem a sopro com estiramento curado com calor, e, processos de moldagem a sopro com estiramento curado com calor para produzir um recipiente, e para enchimento a quente de um recipiente
US20050017013A1 (en) * 2003-07-24 2005-01-27 Alberto Peisach Container for hot fill food packaging applications
US7531125B2 (en) * 2003-08-25 2009-05-12 Ring Container Technologies Blow molded wide mouth pet container and method of manufacture
US20050221036A1 (en) * 2004-04-01 2005-10-06 The Coca-Cola Company Polyester composition with enhanced gas barrier, articles made therewith, and methods
US7481961B2 (en) * 2004-04-01 2009-01-27 Graham Packaging Pet Technologies, Inc. Multilayer container trimming
US7820257B2 (en) * 2005-05-11 2010-10-26 The Coca-Cola Company Preforms for preparing lightweight stretch blow molded PET copolymer containers and methods for making and using same
US7572493B2 (en) * 2005-05-11 2009-08-11 The Coca-Cola Company Low IV pet based copolymer preform with enhanced mechanical properties and cycle time, container made therewith and methods
CA2552105A1 (en) * 2005-07-12 2007-01-12 Pretium Packaging, Llc Container with improved crush resistance
EP2065164A1 (fr) * 2007-11-27 2009-06-03 Aisapack Holding SA Procédé de fabrication d'un emballage pour remplissage à chaud ainsi qu'un tel emballage
US20110017753A1 (en) * 2009-07-24 2011-01-27 Graham Packaging Company, L.P. Hot-fillable and Retortable Plastic Container
DE102010012211A1 (de) 2010-03-19 2011-09-22 Krones Ag Vorrichtung und Verfahren zum Heißabfüllen von Getränken
US10087344B2 (en) * 2015-10-30 2018-10-02 E Ink Corporation Methods for sealing microcell containers with phenethylamine mixtures
CA2914315C (en) * 2015-12-09 2023-04-25 Nova Chemicals Corp. Hot fill process with closures made from high density unimodal polyethylene
CA2914353C (en) * 2015-12-10 2023-01-24 Nova Chemicals Corp. Hot fill process with closures made from high density polyethylene compositions
USD802422S1 (en) * 2016-01-15 2017-11-14 Owens-Brockway Glass Container Inc. Container
USD802423S1 (en) * 2016-01-15 2017-11-14 Owens-Brockway Glass Container Inc. Container
GB2552023B (en) 2016-07-08 2020-03-25 Gr8 Eng Ltd Container and manufacture thereof
USD846992S1 (en) 2017-10-23 2019-04-30 Pretium Packaging, L.L.C. Container
USD859994S1 (en) 2017-10-23 2019-09-17 Pretium Packaging, L.L.C. Container
USD847653S1 (en) 2017-10-23 2019-05-07 Pretium Packaging, L.L.C. Container

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1479801B2 (de) * 1964-12-03 1974-08-08 Enka Glanzstoff Ag, 5600 Wuppertal Verfahren zur Herstellung von Formkörpern aus Polyäthylenterephthalat
US3822332A (en) * 1970-08-07 1974-07-02 Ciba Geigy Ag Process for the production of amorphous transparent polyethylene mouldings by the combined injection and blow moulding technique
US3733309A (en) * 1970-11-30 1973-05-15 Du Pont Biaxially oriented poly(ethylene terephthalate)bottle
BE792927A (fr) * 1971-12-23 1973-04-16 Valyi Emery I Appareil pour la fabrication d'articles plastiques
US4235837A (en) * 1975-10-31 1980-11-25 Standard Oil Company (Indiana) Method of making oriented containers
FR2389478B1 (zh) * 1977-05-04 1980-11-28 Rhone Poulenc Ind
GB2024087B (en) * 1978-06-29 1982-08-25 Yoshino Kogyosho Co Ltd Blow moulding polyester container
US4318882A (en) * 1980-02-20 1982-03-09 Monsanto Company Method for producing a collapse resistant polyester container for hot fill applications
NL8102376A (nl) * 1980-05-29 1981-12-16 Plm Ab Werkwijze en inrichting voor het vormen van een houder.
JPS5881131A (ja) * 1981-11-10 1983-05-16 Mitsubishi Plastics Ind Ltd プラスチツク製びん及びその製法
US4496064A (en) * 1981-11-23 1985-01-29 The Continental Group, Inc. Blow molded container and method of forming the same
US4512948A (en) * 1982-03-03 1985-04-23 Owens-Illinois, Inc. Method for making poly(ethylene terephthalate) article
US4618515A (en) * 1985-04-05 1986-10-21 Continental Pet Technologies, Inc. Polyester container with oriented, crystallized thread finish for hot fill applications and method of making same

Also Published As

Publication number Publication date
SG50632A1 (en) 1998-07-20
DE3650667D1 (de) 1998-04-09
EP0511720A1 (en) 1992-11-04
US4665682A (en) 1987-05-19
NO174413C (no) 1994-05-04
DK202486D0 (da) 1986-05-02
FI861848A (fi) 1986-11-04
AU575253B2 (en) 1988-07-21
DK202486A (da) 1986-11-04
AU5709486A (en) 1986-11-06
DK168064B1 (da) 1994-01-31
EP0200564A2 (en) 1986-11-05
EP0511720B1 (en) 1998-03-04
EP0200564A3 (en) 1989-10-18
MX165124B (es) 1992-10-28
CA1254010A (en) 1989-05-16
FI861848A0 (fi) 1986-05-02
NO861754L (no) 1986-11-04
DE3650667T2 (de) 1998-07-09
JPS6230021A (ja) 1987-02-09
ATE163591T1 (de) 1998-03-15
NO174413B (no) 1994-01-24
CN1013259B (zh) 1991-07-24

Similar Documents

Publication Publication Date Title
CN86103073A (zh) 可热灌装抗塌陷聚酯容器的生产方法
JPH07304088A (ja) 二軸延伸ブロー容器の製造方法
JPS6071207A (ja) 延伸ブロー成形用多層プリフォームの製造方法
CN1089226A (zh) 成型具有高结晶度的侧壁和低结晶度的底部的容器的方法
JPH04144731A (ja) 2軸延伸結晶性樹脂容器およびその製造方法
BRPI0707317A2 (pt) recipiente moldado a sopro tendo ranhura rosqueada
EP1897676B1 (en) Polyester resin container and molding process thereof
JP2003053823A (ja) ボトル状容器のブロー成形用プリフォーム
JPS5892536A (ja) 2軸延伸プラスチツクびん
CA2455873C (en) Method for producing bottle-shaped container mainly made of polyethylene terephthalate resin
US4235837A (en) Method of making oriented containers
TWI248865B (en) Biaxial orientation blow molding process
JPS5892535A (ja) プラスチツクびん
JPH07242222A (ja) 耐圧・耐熱性ボトル
JPS60201909A (ja) 多層延伸ブロ−ボトルの製造方法
JPH07112729A (ja) 耐熱性プラスチック容器
JP2020049779A (ja) プリフォーム
WO2005115722A1 (en) Method for producing heat-set base of a plastic container and the produced container
JP3178538B2 (ja) 2軸延伸ブロー成形壜体とその成形方法
JPH06143397A (ja) 熱固定ポリエステル成形容器及びその製法
JPH11152123A (ja) 延伸樹脂容器
JP2022056259A (ja) プリフォームおよびプラスチックボトル
JP5345804B2 (ja) 合成樹脂製のカップ型容器及びそのカップ型容器の製造方法
JPS58203012A (ja) カツプ状薄肉容器の製造方法
JPH0532247A (ja) プラスチツクブロー成形容器

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR02 Examined patent application
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee