WO2020057553A1 - 一种聚酯覆铁膜以及覆膜金属板 - Google Patents

一种聚酯覆铁膜以及覆膜金属板 Download PDF

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Publication number
WO2020057553A1
WO2020057553A1 PCT/CN2019/106467 CN2019106467W WO2020057553A1 WO 2020057553 A1 WO2020057553 A1 WO 2020057553A1 CN 2019106467 W CN2019106467 W CN 2019106467W WO 2020057553 A1 WO2020057553 A1 WO 2020057553A1
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WIPO (PCT)
Prior art keywords
polyester film
copolyester
film
homopolyester
polyester
Prior art date
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PCT/CN2019/106467
Other languages
English (en)
French (fr)
Inventor
谢龙
陈红星
戴竞舸
Original Assignee
宝山钢铁股份有限公司
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Filing date
Publication date
Application filed by 宝山钢铁股份有限公司 filed Critical 宝山钢铁股份有限公司
Priority to US17/277,170 priority Critical patent/US20210371644A1/en
Priority to ES19863378T priority patent/ES2955213T3/es
Priority to EP19863378.6A priority patent/EP3854584B1/en
Publication of WO2020057553A1 publication Critical patent/WO2020057553A1/zh
Priority to PH12021550586A priority patent/PH12021550586A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • 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
    • B29K2067/003—PET, i.e. poylethylene terephthalate
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • 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
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/04—4 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
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    • B32B2255/20—Inorganic coating
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    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
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    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to the field of coated metal plates for metal packaging, and more particularly to a polyester iron-clad film and a coated metal plate.
  • modified polyester films for metal-coated metal sheets for metal packaging can basically meet various molding requirements, but functional iron-clad films that meet both the molding requirements and the chemical resistance such as acid and alkali resistance still exist. Large technical optimization space.
  • An object of the present invention is to provide a coated metal plate having excellent processability, excellent chemical resistance such as acid and alkali, and excellent uniformity, which is prepared by using a polyester iron-clad film.
  • the present invention adopts the following technical solutions.
  • a blended polyester film includes a copolyester and a homopolyester, and the blended polyester film includes upper, middle, and lower layers, three Each of the layers is a homogeneous mixture of the copolyester and the homopolyester, and the copolyester includes 800-2000 ppm of SiO 2 in parts by mass.
  • SiO 2 in the copolyester is added by in-situ polymerization.
  • the glycol component in the copolyester includes ethylene glycol, 1,4-cyclohexanedimethanol, and 1,4-butanediol.
  • a mass fraction ratio of the copolymerized polyester and the homopolyester in the blended polyester film is 8: 2 to 5: 5.
  • a mass fraction ratio of the copolyester and the homopolyester in each layer is 8: 2 to 5: 5.
  • the mass parts ratios of the copolyester and the homopolyester are 8: 2, 7: 3, and 5: 5, respectively.
  • the melting point of the copolyester is between 200-240 ° C.
  • the blended polyester film is prepared by a biaxial stretching method at a manufacturing temperature of 250-270 ° C.
  • a coated metal plate including a metal substrate and a blended polyester film as described above covered on the surface of the metal substrate.
  • the metal substrate material is selected from the group consisting of a chrome-plated steel sheet, a tin-plated steel sheet, a low-tin steel sheet (ie, a steel sheet having a tin plating amount of 1.1 g / m 2 or less), a galvanized steel sheet, One of cold rolled steel sheet and stainless steel sheet.
  • the blended polyester film is directly hot-laminated on the surface of the metal substrate at a pressure of 2 to 10 Kg and a temperature of 180 to 260 ° C by a hot-melt lamination method.
  • the metal substrate has a thickness of 0.10 to 0.50 mm.
  • a metal container for food and beverage packaging which is made of a coated metal plate as described above.
  • the present invention has the following beneficial effects:
  • the present invention adopts a method of laminating a blended polyester film to a metal plate by thermal lamination, so that the coated metal plate prepared from the blended polyester film can simultaneously satisfy complex molding processing and food with high corrosion resistance Performance requirements for metal containers for beverage packaging. Because the copolyester of the polyester iron-clad film is added with 800-2000ppm of SiO 2 by in-situ polymerization, no ordinary silicon-containing polyester chips are used, and there is no high-temperature polyester resin (melting point greater than 245 ° C). The intervention not only meets the basic requirements of traditional SiO 2 opener, but also can significantly improve the comprehensive performance of the film.
  • Adding SiO 2 to the polymer through in situ polymerization uniformly improves the crystallization properties of the polyester film as a whole; and by improving the traditional method of adding SiO 2 in the form of master batches, high-melting resin is avoided from being added to the film.
  • the two points mentioned above significantly improve the overall performance of the polyester film, and significantly improve the complex processability and corrosion resistance of the coated iron including the film of the present invention.
  • the blended polyester film according to the present invention includes a copolyester and a homopolyester, the blended polyester film includes upper, middle, and lower layers, and each of the three layers is the copolymerized polyester and the
  • the homopolyester is a homogeneously mixed mixture
  • the copolyester includes 800-2000 ppm of SiO 2 in parts by mass.
  • the SiO 2 is added to the copolyester by in-situ polymerization.
  • the mass fraction of SiO 2 in the copolyester is 1300-2000 ppm.
  • the “in-situ polymerization addition” described herein refers to mixing SiO 2 with a monomer for synthesizing the copolyester, and then polymerizing to obtain the copolyester according to the present invention.
  • the polyester is obtained by polymerizing terephthalic acid and a diol.
  • the glycol component includes ethylene glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol.
  • the amount of the diol component is selected so that the melting point of the copolymerized polyester obtained by the polymerization is between 200-240 ° C.
  • the copolymerized polyester of the present invention can be obtained by polymerization using a polymerization method known in the art.
  • the homopolyester of the present invention is obtained by polymerizing terephthalic acid with ethylene glycol or butanediol.
  • a vacuum of 20-50 ppm is used in the polycondensation process, the reaction temperature is 270-290 ° C, and the reaction time is 2-4 h.
  • the melting point of the homopolyester used in the present invention is 250-265 ° C, preferably 255-265 ° C.
  • the mass fraction of the copolyester and the homopolyester in the blended polyester film according to the present invention is 8: 2 to 5: 5.
  • the mass fraction ratio of the copolyester and the homopolyester in each layer may be the same or different, and may range from 8: 2 to 5: 5. Within the range, such as 8: 2, 7: 3, and 5: 5.
  • the blended polyester film according to the present invention is prepared by a biaxial stretching method at a manufacturing temperature of 250-270 ° C.
  • the invention also provides a method for manufacturing a blended polyester film, the method comprising:
  • the polyester film is manufactured by using a biaxial stretching method at 250-270 ° C.
  • the invention also provides the application of SiO 2 in improving the crystallization property of the polyester film.
  • the blended polyester film is as described in any embodiment herein.
  • a method for producing a polyester iron-clad film is manufactured by a biaxial stretching method at a manufacturing temperature of 250-270 ° C.
  • the polyester iron-clad film includes 7 parts of a copolymerized polyester and 3 parts of a homopolymer.
  • the diol in the copolyester is a mixture of ethylene glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol, and the melting point is 200 ° C.
  • the polyester iron-clad film is manufactured by a three-layer co-extrusion biaxial stretching method, and the uniformly mixed copolyester and the homopolyester mixture are divided into upper, middle, and lower three layers. Contains 1300 ppm of SiO 2 .
  • the prepared biaxially stretched polyester film is thermally bonded to a surface of a thin metal plate of 0.10 to 0.50 mm under a pressure of 2 to 10 Kg and a temperature of 180 to 260 ° C to obtain a coated metal plate.
  • a method for producing a polyester iron-clad film is manufactured by a biaxial stretching method at a manufacturing temperature of 250-270 ° C.
  • the polyester iron-clad film includes 5 parts of a copolymerized polyester and 5 parts of a homopolymer.
  • the diol in the copolyester is a mixture of ethylene glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol, and the melting point is 230 ° C.
  • the polyester iron-clad film is manufactured by a three-layer co-extrusion biaxial stretching method, and the uniformly mixed copolyester and the homopolyester mixture are divided into upper, middle, and lower three layers. Contains 2000 ppm of SiO 2 .
  • the prepared biaxially stretched polyester film is thermally bonded to a surface of a thin metal plate of 0.10 to 0.50 mm under a pressure of 2 to 10 Kg and a temperature of 180 to 260 ° C to obtain a coated metal plate.
  • a method for producing a polyester iron-clad film is manufactured by a biaxial stretching method at a manufacturing temperature of 250-270 ° C.
  • the polyester iron-clad film includes 8 parts of a copolymerized polyester and 2 parts of a homopolymer.
  • the diol in the copolyester is a mixture of ethylene glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol, and the melting point is 240 ° C.
  • the polyester iron-clad film is manufactured by a three-layer co-extrusion biaxial stretching method, and the uniformly mixed copolyester and the homopolyester mixture are divided into upper, middle, and lower three layers. Contains 800 ppm of SiO 2 .
  • the prepared biaxially stretched polyester film is thermally bonded to a surface of a thin metal plate of 0.10 to 0.50 mm under a pressure of 2 to 10 Kg and a temperature of 180 to 260 ° C to obtain a coated metal plate.
  • a method for producing a polyester iron-clad film The polyester iron-clad film is manufactured by a casting method at a manufacturing temperature of 250-270 ° C.
  • the polyester iron-clad film includes 8 parts of a copolymerized polyester and 2 parts of a homopolymerized polymer. ester.
  • the diol in the copolyester is a mixture of ethylene glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol, and the melting point is 220 ° C.
  • the polyester iron-clad film is manufactured by a three-layer co-extrusion biaxial stretching method, and the uniformly mixed copolyester and the homopolyester mixture are divided into upper, middle, and lower three layers. Contains 1500 ppm of SiO 2 .
  • the prepared biaxially stretched polyester film is thermally bonded to a surface of a thin metal plate of 0.10 to 0.50 mm under a pressure of 2 to 10 Kg and a temperature of 180 to 260 ° C to obtain a coated metal plate.
  • a method for producing a polyester iron-clad film The polyester iron-clad film is manufactured by a casting method at a manufacturing temperature of 250-270 ° C.
  • the polyester iron-clad film includes 5 parts of a copolymerized polyester and 5 parts of a homopolymerized polymer. ester.
  • the diol in the copolyester is a mixture of ethylene glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol, and the melting point is 200 ° C.
  • the polyester iron-clad film is manufactured by a three-layer co-extrusion biaxial stretching method, and the uniformly mixed copolyester and the homopolyester mixture are divided into upper, middle, and lower three layers. Contains 1800 ppm of SiO 2 .
  • the prepared biaxially stretched polyester film is thermally bonded to a surface of a thin metal plate of 0.10 to 0.50 mm under a pressure of 2 to 10 Kg and a temperature of 180 to 260 ° C to obtain a coated metal plate.
  • a method for producing a polyester iron-clad film is manufactured by a biaxial stretching method at a manufacturing temperature of 250-270 ° C.
  • the polyester iron-clad film includes 7 parts of a copolymerized polyester and 3 parts of a homopolymer.
  • the diol in the copolyester is a mixture of ethylene glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol, and the melting point is 230 ° C.
  • the polyester iron-clad film is manufactured by a three-layer co-extrusion biaxial stretching method, and the uniformly mixed copolyester and the homopolyester mixture are divided into upper, middle, and lower three layers. Contains 1300 ppm of SiO 2 .
  • the prepared biaxially stretched polyester film is thermally bonded to a surface of a thin metal plate of 0.10 to 0.50 mm under a pressure of 2 to 10 Kg and a temperature of 180 to 260 ° C to obtain a coated metal plate.
  • a single-layer polyester film is made from a modified PET resin having a melting point of 210 ° C by a casting method.
  • the single-layer polyester film prepared by the casting method is thermally bonded to the surface of a 0.19mm chrome-plated steel plate at a pressure of 2 to 10 Kg and a temperature of 180 to 260 ° C to obtain a coated iron.
  • a three-layer biaxially stretched polyester film The upper resin is 3 ⁇ m PET resin, the middle layer is 14 ⁇ m of 265 ° C PET and 210 ° C PET blended resin (blending ratio is 7: 3), and the lower layer is 3 ⁇ m.
  • Modified PET resin with a melting point of 210 ° C.
  • the proportion of copolyester in this polyester film is less than 30%.
  • the prepared biaxially stretched polyester film is thermally laminated with a steel layer using a lower layer, and heat-laminated on a surface of a chrome-plated steel plate of 0.19 mm under a pressure of 2 to 10 Kg and a temperature of 180 to 260 ° C. iron.
  • the coated metal plates obtained in Examples 1-6 and Comparative Examples 1-2 were respectively subjected to a drawing and drawing method (DRD: Draw and Redraw) according to the processing conditions shown below, and were formed into a can body by three stampings.
  • the 20 ⁇ m films prepared in the examples are located on both sides of the tank and outside the tank.
  • Blanking diameter 172mm.
  • Blank holding force 4000kg
  • Mold component temperature before molding 55 ° C.
  • Blank holding force 3000kg
  • Mold component temperature before molding 55 ° C.
  • Mold component temperature before molding 55 ° C.
  • necking and flanging are carried out by the conventional method of can making.
  • Acid resistance performance The performance of corrosion resistance was evaluated by evaluating the acid resistance after the coated iron was washed in a can (type 691). Fill the coated tank with a 20g / L citric acid solution, cook it at 121 ° C for 60min after capping, and take out the sample after cooling to observe the occurrence of acid spots on the surface to evaluate the resistance of the coated iron. Acid performance.
  • Anti-sulfur performance After the coated iron is washed into a can (type 691), the anti-sulfur performance evaluation is used to represent the corrosion resistance evaluation.
  • the coated can was filled with a 1% Na 2 S solution, and after being capped, it was cooked at 121 ° C for 60 minutes. After cooling, the sample was taken out to observe the occurrence of sulfide spots on the surface to evaluate the resistance of the coated iron. Sulfur properties.
  • the film was formed by blending a copolymerized polyester and a homopolyester, and the moldability was good in both the casting method and the biaxial stretching method, and a thin polyester iron-clad film could be prepared.
  • the coated metal plate prepared by using the polyester iron-clad film has excellent stamping resistance and extensibility, and excellent chemical resistance such as acid and alkali resistance.
  • SiO 2 through in-situ synthesis in the copolyester, it is obvious that there is no intervention of high-temperature polyester resin (melting point greater than 245 °C) because ordinary silicon-containing polyester chips are not used in the polyester iron-clad film. Improve the uniformity of the comprehensive performance of the coated metal sheet.
  • the addition of SiO 2 is beneficial to the winding and unwinding of the polyester iron-clad film.
  • Adding SiO 2 to the polymer through in situ polymerization uniformly improves the crystallization properties of the polyester film as a whole; and by improving the traditional method of adding SiO 2 in the form of master batches, high-melting resin is avoided from being added to the film.
  • the two points mentioned above significantly improve the overall performance of the polyester film, and significantly improve the complex processability and corrosion resistance of the coated iron including the film of the present invention.

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Abstract

本发明公开一种共混聚酯薄膜，包括共聚聚酯和均聚聚酯，由上、中、下三层构成，三层中的每一层为所述共聚聚酯和所述均聚聚酯均匀混合的混合物，共聚聚酯包括通过原位聚合加入质量份数为800-2000ppm的SiO 2。共聚聚酯中的二元醇成份包括乙二醇、1，4-环己烷二甲醇、1，4-丁二醇。共聚聚酯的熔点在200-240℃之间。本发明的共混聚酯薄膜具有优良加工性能、优良耐酸、碱等耐化学性，优良均匀性。由共混聚酯薄膜制备的覆膜金属板可以同时满足复杂成型加工和高耐蚀性的食品饮料包装用金属容器的性能需求。

Description

一种聚酯覆铁膜以及覆膜金属板 技术领域
本发明涉及金属包装用覆膜金属板领域，更具体地指一种聚酯覆铁膜以及覆膜金属板。
背景技术
近年来，聚对苯二甲酸乙二醇酯(聚酯)工业发展十分迅速，国内外已有一大批著名的生产聚酯材料及聚酯设备的公司，1987年聚酯的世界产量已跃居工程塑料的第五位。薄膜是聚酯材料应用领域中的一个重要分支，广泛应用于食品、饮料的包装领域。近年来，由于金属覆膜技术的兴起，将覆铁膜与金属板通过热熔覆合的方式相结合，克服了传统金属罐内侧必须经过涂装加工所导致的有害物质——双酚A类(Bis-phenol A)的析出问题，而这一问题已受到全球范围的高度重视。随着金属板覆膜技术的逐步推广，覆铁膜替代涂料以提升灌装的食品安全性已得到广泛认可。
现有技术中，改性聚酯薄膜用于金属包装用覆膜金属板基本可以满足各种成型要求，然而既满足成型要求又满足耐酸、碱性等耐化学性的功能性覆铁膜还存在较大的技术优化空间。
发明内容
本发明的目的是提供一种具有优良加工性能的、优良耐酸、碱等耐化学性的，优良均匀性的，采用聚酯覆铁膜制备的覆膜金属板。
为了实现上述目的，本发明采用以下技术方案。
根据本发明的一个方面，提供一种共混聚酯薄膜，所述共混聚酯薄膜包括共聚聚酯和均聚聚酯，所述共混聚酯薄膜包括上、中、下三层，三层中的每一层为所述共聚聚酯和所述均聚聚酯均匀混合的混合物，所述共聚 聚酯包括质量份数为800-2000ppm的SiO 2。
根据本发明的一个方面的共混聚酯薄膜中，所述共聚聚酯中的SiO 2通过原位聚合加入。
根据本发明的一个方面的共混聚酯薄膜中，所述共聚聚酯中的二元醇成份包括乙二醇、1,4-环己烷二甲醇和1,4-丁二醇。
根据本发明的一个方面的共混聚酯薄膜中，所述共混聚酯薄膜中所述共聚聚酯和所述均聚聚酯的质量份数比8：2到5：5。
根据本发明的一个方面的共混聚酯薄膜中，每一层中所述共聚聚酯和所述均聚聚酯的质量份数比8：2到5：5。
根据本发明的一个方面的共混聚酯薄膜中，所述共聚聚酯和所述均聚聚酯的质量份数比分别为8:2、7:3、以及5:5。
根据本发明的一个方面的共混聚酯薄膜中，所述共聚聚酯的熔点在200-240℃之间。
根据本发明的一个方面的共混聚酯薄膜中，所述共混聚酯薄膜采用双向拉伸方法在250-270℃的制造温度下制备而成。
在上述方案中，在共聚聚酯中通过原位加入质量份数为800-2000ppm的SiO 2，不仅达到开口剂的基板需求，同时有利于明显提升薄膜的综合性能。
根据本发明的另一个方面，提供一种覆膜金属板，其包括金属基板和覆盖在所述金属基板表面上的如上所述的共混聚酯薄膜。
根据本发明的另一个方面的覆膜金属板中，所述金属基板材料选自镀铬钢板、镀锡钢板、低锡钢板(即镀锡量≤1.1g/m 2的钢板)、镀锌钢板、冷轧钢板、以及不锈钢板中的一种。
根据本发明的另一个方面的覆膜金属板中，所述共混聚酯薄膜采用热熔覆合的方式在压力2～10Kg、温度180～260℃下直接热覆合到金属基板表面上。
根据本发明的另一个方面的覆膜金属板中，所述金属基板厚0.10～0.50mm。
根据本发明的再一个方面，提供一种应用于食品饮料包装用的金属容 器，其由如上所述的覆膜金属板制成。
与现有技术相比，本发明具有如下有益效果：
本发明通过采用将共混聚酯薄膜通过热覆合的方式覆合到金属板，使得由所述共混聚酯薄膜制备的覆膜金属板可以同时满足复杂成型加工和高耐蚀性的食品饮料包装用金属容器的性能需求。由于所述聚酯覆铁膜的共聚聚酯中采用原位聚合方式加入了800-2000ppm的SiO 2，没有使用普通的含硅聚酯切片，不存在高温聚酯树脂(熔点大于245℃)的介入，不仅达到了传统SiO 2开口剂的基本需求，同时可明显提升薄膜的综合性能。
聚合物中通过原位聚合加入SiO 2，从整体上均匀地改善聚酯薄膜的结晶性能；并且通过改善传统以母粒形式加入SiO 2的方式，避免了高熔点树脂加入薄膜中。上述两点使聚酯薄膜的综合性能得到明显提升，包含本发明薄膜的覆膜铁的耐复杂加工性、覆膜铁的耐腐蚀性能等得到显著提高。
具体实施方式
以下在具体实施方式中通过对非限制性实施例所作的详细描述，本发明的目的、特征、和优点将变得更清楚明显。其内容足以使本领域技术人员了解和实施本发明。
根据本发明的共混聚酯薄膜包括共聚聚酯和均聚聚酯，所述共混聚酯薄膜包括上、中、下三层，三层中的每一层为所述共聚聚酯和所述均聚聚酯均匀混合的混合物，所述共聚聚酯包括质量份数为800-2000ppm的SiO 2。优选地，该SiO 2通过原位聚合加入到所述共聚聚酯中。优选地，SiO 2在共聚聚酯中的质量份数为1300-2000ppm。本文所述的“原位聚合加入”指将SiO 2与合成共聚聚酯的单体一起混合，然后进行聚合，制造得到本发明所述的共聚聚酯。
本发明中，聚酯由对苯二甲酸与二元醇聚合而成。优选地，本发明所述的共聚聚酯中，二元醇成份包括乙二醇、1,4-环己烷二甲醇和1,4-丁二醇。优选地，二元醇成份用量的选择使得所聚合得到的共聚聚酯的熔点在200-240℃之间。可采用本领域周知的聚合方法聚合获得本发明的共聚聚酯。
优选地，本发明的均聚聚酯由对苯二甲酸与乙二醇或丁二醇聚合得到。 在一些实施方案中，缩聚过程中采用20-50ppm的真空度，反应温度为270-290℃，反应时间为2-4h。优选地，本发明使用的均聚聚酯的熔点为250～265℃，优选为255～265℃。
优选地，根据本发明的共混聚酯薄膜中所述共聚聚酯和所述均聚聚酯的质量份数比8：2到5：5。优选地，根据本发明的共混聚酯薄膜中，每一层中所述共聚聚酯和所述均聚聚酯的质量份数比可相同或不同，可在8：2到5：5的范围内，如分别为8:2、7:3、以及5:5。
根据本发明的共混聚酯薄膜中，所述共混聚酯薄膜采用双向拉伸方法在250-270℃的制造温度下制备而成。
本发明还提供一种共混聚酯薄膜的制造方法，所述方法包括：
(1)提供本文任一实施方案所述的共聚聚酯和均聚聚酯的混合物；和
(2)在250-270℃下采用双向拉伸方法制造得到所述聚酯薄膜。
本发明还提供SiO 2在改善聚酯薄膜的结晶性能中的应用。优选地，所述共混聚酯薄膜如本文任一实施方案所述。
实施例1
一种聚酯覆铁膜的生产方法，所述聚酯覆铁膜采用双向拉伸方法制造，制造温度250-270℃，所述聚酯覆铁膜包括7份共聚聚酯，3份均聚聚酯。所述共聚聚酯中二醇为乙二醇、1,4-环己烷二甲醇和1,4-丁二醇的混合物，且熔点为200℃。所述聚酯覆铁膜采用三层共挤双向拉伸方法制造，将均匀混合的所述共聚聚酯和所述均聚聚酯混合物分成上、中、下三层，所述共聚聚酯中含有1300ppm的SiO 2。
将制备好的双向拉伸聚酯薄膜在压力2～10Kg温度180～260℃下热贴合在0.10～0.50mm的薄金属板表面制得覆膜金属板。
实施例2
一种聚酯覆铁膜的生产方法，所述聚酯覆铁膜采用双向拉伸方法制造，制造温度250-270℃，所述聚酯覆铁膜包括5份共聚聚酯，5份均聚聚酯。 所述共聚聚酯中二醇为乙二醇、1,4-环己烷二甲醇和1,4-丁二醇的混合物，且熔点为230℃。所述聚酯覆铁膜采用三层共挤双向拉伸方法制造，将均匀混合的所述共聚聚酯和所述均聚聚酯混合物分成上、中、下三层，所述共聚聚酯中含有2000ppm的SiO 2。
将制备好的双向拉伸聚酯薄膜在压力2～10Kg温度180～260℃下热贴合在0.10～0.50mm的薄金属板表面制得覆膜金属板。
实施例3
一种聚酯覆铁膜的生产方法，所述聚酯覆铁膜采用双向拉伸方法制造，制造温度250-270℃，所述聚酯覆铁膜包括8份共聚聚酯，2份均聚聚酯。所述共聚聚酯中二醇为乙二醇、1,4-环己烷二甲醇和1,4-丁二醇的混合物，且熔点为240℃。所述聚酯覆铁膜采用三层共挤双向拉伸方法制造，将均匀混合的所述共聚聚酯和所述均聚聚酯混合物分成上、中、下三层，所述共聚聚酯中含有800ppm的SiO 2。
将制备好的双向拉伸聚酯薄膜在压力2～10Kg温度180～260℃下热贴合在0.10～0.50mm的薄金属板表面制得覆膜金属板。
实施例4
一种聚酯覆铁膜的生产方法，所述聚酯覆铁膜采用流延法制造，制造温度250-270℃，所述聚酯覆铁膜包括8份共聚聚酯，2份均聚聚酯。所述共聚聚酯中二醇为乙二醇、1,4-环己烷二甲醇和1,4-丁二醇的混合物，且熔点为220℃。所述聚酯覆铁膜采用三层共挤双向拉伸方法制造，将均匀混合的所述共聚聚酯和所述均聚聚酯混合物分成上、中、下三层，所述共聚聚酯中含有1500ppm的SiO 2。
将制备好的双向拉伸聚酯薄膜在压力2～10Kg温度180～260℃下热贴合在0.10～0.50mm的薄金属板表面制得覆膜金属板。
实施例5
一种聚酯覆铁膜的生产方法，所述聚酯覆铁膜采用流延法制造，制造 温度250-270℃，所述聚酯覆铁膜包括5份共聚聚酯，5份均聚聚酯。所述共聚聚酯中二醇为乙二醇、1,4-环己烷二甲醇和1,4-丁二醇的混合物，且熔点为200℃。所述聚酯覆铁膜采用三层共挤双向拉伸方法制造，将均匀混合的所述共聚聚酯和所述均聚聚酯混合物分成上、中、下三层，所述共聚聚酯中含有1800ppm的SiO 2。
将制备好的双向拉伸聚酯薄膜在压力2～10Kg温度180～260℃下热贴合在0.10～0.50mm的薄金属板表面制得覆膜金属板。
实施例6
一种聚酯覆铁膜的生产方法，所述聚酯覆铁膜采用双向拉伸方法制造，制造温度250-270℃，所述聚酯覆铁膜包括7份共聚聚酯，3份均聚聚酯。所述共聚聚酯中二醇为乙二醇、1,4-环己烷二甲醇和1,4-丁二醇的混合物，且熔点为230℃。所述聚酯覆铁膜采用三层共挤双向拉伸方法制造，将均匀混合的所述共聚聚酯和所述均聚聚酯混合物分成上、中、下三层，所述共聚聚酯中含有1300ppm的SiO 2。
将制备好的双向拉伸聚酯薄膜在压力2～10Kg温度180～260℃下热贴合在0.10～0.50mm的薄金属板表面制得覆膜金属板。
比较例1
采用流延法由熔点为210℃的改性PET树脂制成单层聚酯薄膜。
覆膜铁的制备：将流延法制备好的单层聚酯薄膜在压力2～10Kg温度180～260℃下热贴合在0.19mm的镀铬钢板表面制得覆膜铁。
比较例2
一种三层双向拉伸聚酯薄膜，上层树脂为3μm的PET树脂，中间层为14μm的265℃的PET与210℃的PET共混的树脂(共混比例为7：3)，下层为3μm熔点为210℃的改性PET树脂。此聚酯薄膜中共聚聚酯的比例小于30％。
覆膜铁的制备：将制备好的双向拉伸聚酯薄膜，采用下层与钢板热覆 合，在压力2～10Kg温度180～260℃下热贴合在0.19mm的镀铬钢板表面制得覆膜铁。
测试例
分别使用实施例1-6、比较例1-2获得的覆膜金属板，根据以下所示的加工条件进行冲拔拉深法(DRD：Draw and Redraw)加工，经过三次冲压成型为罐体。各实施例制备得到的20μm膜同时处于罐内、罐外两侧。
成型加工条件(冲拔拉深法)
1.落料直径：172mm。
2.第一道加工条件
冲头直径：114.5mm；
模具间隙：0.36mm；
压边力：4000kg；
成型前模具组件温度：55℃。
3.第二道加工条件
冲头直径：88mm；
模具间隙：0.4mm；
压边力：3000kg；
成型前模具组件温度：55℃。
4.第三道加工条件
冲头直径：65.3mm；
模具间隙：0.43mm；
压边力：2000kg；
成型前模具组件温度：55℃。
成型后采用制罐的常规方法进行缩颈翻边加工。
采用以下所示方法评价上述方法所制备的罐子，其结果见表1。
(1)树脂薄膜的加工粘合性
用肉眼评价上述成形加工条件下所制备的冲拔拉伸罐的加工工序中覆合于钢板表面的树脂膜层是否发生剥离，直到最终工序尚未发生剥离的 状态为优。
(2)抗酸性能：将覆膜铁冲罐(罐型691)后以抗酸性能评价来代表耐蚀性能评价。将覆膜罐灌装20g/L的柠檬酸溶液，封盖后在121℃温度条件下蒸煮60min，待冷却后将试样取出观察表面产生酸化斑的情况，以此来评价覆膜铁的抗酸性能。
(3)抗硫性能：将覆膜铁冲罐(罐型691)后以抗硫性能评价来代表耐蚀性能评价。将覆膜罐灌装1％的Na 2S溶液，封盖后在121℃温度条件下蒸煮60min，待冷却后将试样取出观察表面产生硫化斑的情况，以此来评价覆膜铁的抗硫性能。
表1：耐深冲成型性、耐腐蚀性评价结果
Figure PCTCN2019106467-appb-000001
注：表1中╳表示较差；△表示一般；○表示较好；◎表示很好；-表示不具备评价的条件。
上述六个实施例中通过共聚聚酯和均聚聚酯共混后制膜，在流延法制膜和双向拉伸法制膜的成型性都良好，能制备出厚度较薄的聚酯覆铁膜。且采用该聚酯覆铁膜制备的覆膜金属板有优良的耐冲压成型性和延伸性，以及优良的耐酸、碱性等耐化学性能。并且通过在共聚聚酯中通过原位合成加入SiO 2，因没有在聚酯覆铁膜中使用普通的含硅聚酯切片，不存在高温聚酯树脂(熔点大于245℃)的介入，可以明显提升覆膜金属板综合性 能的均匀性。同时，SiO 2的加入有利于聚酯覆铁膜收放卷。
聚合物中通过原位聚合加入SiO 2，从整体上均匀地改善聚酯薄膜的结晶性能；并且通过改善传统以母粒形式加入SiO 2的方式，避免了高熔点树脂加入薄膜中。上述两点使聚酯薄膜的综合性能得到明显提升，包含本发明薄膜的覆膜铁的耐复杂加工性、覆膜铁的耐腐蚀性能等得到显著提高。
最后，需要指出的是，虽然本发明已参照当前的具体实施例来描述，但是本技术领域中的普通技术人员应当认识到，以上的实施例仅是用来说明本发明，而并非用作为对本发明的限定，在不脱离本发明构思的前提下还可以作出各种等效的变化或替换，因此，只要在本发明的实质精神范围内对上述实施例的变化、变型都将落在本发明的权利要求书范围内。

Claims (12)

  1. 一种共混聚酯薄膜，其特征在于：所述共混聚酯薄膜包括共聚聚酯和均聚聚酯，所述共混聚酯薄膜包括上、中、下三层，三层中的每一层为所述共聚聚酯和所述均聚聚酯均匀混合的混合物，所述共聚聚酯包括通过原位聚合加入的质量份数为800-2000ppm的SiO 2。
  2. 如权利要求1所述的共混聚酯薄膜，其特征在于：所述共聚聚酯中的二元醇成份包括乙二醇、1,4-环己烷二甲醇和1,4-丁二醇。
  3. 如权利要求1或2所述的共混聚酯薄膜，其特征在于：所述共混聚酯薄膜中，所述共聚聚酯和所述均聚聚酯的质量份数比在8：2到5：5的范围内。
  4. 如权利要求3所述的共混聚酯薄膜，其特征在于：所述共聚聚酯和所述均聚聚酯的质量份数比分别为8:2、7:3、以及5:5。
  5. 如权利要求1或2所述的共混聚酯薄膜，其特征在于：所述共聚聚酯的熔点在200-240℃之间。
  6. 如权利要求1所述的共混聚酯薄膜，其特征在于：所述均聚聚酯为对苯二甲酸与乙二醇或丁二醇的均聚物。
  7. 权利要求1所述的共混聚酯薄膜的制造方法，其特征在于，所述方法包括：
    (1)提供所述共聚聚酯和均聚聚酯的混合物；和
    (2)在250-270℃的制造温度下采用双向拉伸方法制造得到所述聚酯薄膜。
  8. 一种覆膜金属板，其特征在于：包括金属基板和所述金属基板表面上覆盖的如权利要求1-6中任一项所述的共混聚酯薄膜。
  9. 如权利要求8所述的覆膜金属板，其特征在于：所述金属基板材料选自镀铬钢板、镀锡钢板、低锡钢板、镀锌钢板、冷轧钢板、以及不锈钢板中的一种。
  10. 如权利要求8所述的覆膜金属板，其特征在于：所述金属基板厚0.10～0.50mm。
  11. 权利要求6所述的覆膜金属板的制造方法，其特征在于：所述方法包括，采用热熔覆合的方式在压力2～10Kg、温度180～260℃下将所述共混聚酯薄膜直接热覆合到金属基板表面上。
  12. 一种应用于食品饮料包装用的金属容器，其特征在于，所述金属容器由如权利要求8-10中任一项所述的覆膜金属板制成。
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