WO2019077746A1 - Tôle métallique traitée en surface revêtue de résine organique - Google Patents

Tôle métallique traitée en surface revêtue de résine organique Download PDF

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Publication number
WO2019077746A1
WO2019077746A1 PCT/JP2017/038035 JP2017038035W WO2019077746A1 WO 2019077746 A1 WO2019077746 A1 WO 2019077746A1 JP 2017038035 W JP2017038035 W JP 2017038035W WO 2019077746 A1 WO2019077746 A1 WO 2019077746A1
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Prior art keywords
organic resin
metal plate
resin
acid
treated metal
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PCT/JP2017/038035
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English (en)
Japanese (ja)
Inventor
拓也 柏倉
新 櫻木
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東洋製罐グループホールディングス株式会社
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Priority to PCT/JP2017/038035 priority Critical patent/WO2019077746A1/fr
Publication of WO2019077746A1 publication Critical patent/WO2019077746A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • B32B15/082—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 vinyl resins; comprising acrylic resins
    • 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
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
    • B65D25/14—Linings or internal coatings
    • 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
    • B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
    • B65D25/34—Coverings or external coatings
    • 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
    • B65D43/00—Lids or covers for rigid or semi-rigid containers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the present invention relates to an organic resin-coated surface-treated metal plate used for cans and can lids such as beverage cans, and more particularly, it is excellent for being able to cope with the sterilization treatment applied after filling the contents.
  • the present invention relates to an organic resin-coated surface-treated metal sheet which can provide a can and a lid having heat-resistant water adhesion, is excellent in economic efficiency, and has a small environmental load.
  • Organic resin-coated metal sheets in which metal sheets such as aluminum are coated with an organic resin, have long been known as materials for cans, and the organic resin-coated metal sheets are subjected to drawing processing, drawing, ironing and processing It is also well known to use as a seamless can for filling or as a can lid such as an easy open end by pressing it.
  • an organic resin-coated metal plate having, as an organic resin coating layer, a thermoplastic resin film composed of a polyester resin mainly composed of ethylene terephthalate units is used as a can-making material for a seamless can (Patent Document 1).
  • a metal plate used for the organic resin coated metal plate for such a can body / can lid use generally surfaces, such as a chemical conversion treatment, for the purpose of ensuring corrosion resistance and adhesiveness with an organic resin coating layer.
  • a treated surface-treated metal plate is used.
  • Such surface treatment includes, for example, phosphate chromate treatment, and an organic resin-coated surface-treated metal plate composed of a surface-treated metal plate subjected to phosphate chromate treatment is used when it is used to form a seamless can or the like. It has been widely used because it is excellent in can-making ability and excellent in adhesion (heat-resistant water adhesion) between the organic resin coating layer and the metal substrate at the time of sterilization treatment after filling and sealing the contents. From the viewpoint of protection, the demand for non-chromium surface treatment is increasing.
  • Coating surface treatment can also be used for non-chromium surface treatment It has been proposed for use in materials.
  • a resin-coated aluminum plate has been proposed in which a coating-type undercoat film comprising a zirconium compound and a zirconium-crosslinked polyacrylic acid is formed (Patent Document 3).
  • the coating type undercoating film proposed in the above-mentioned Patent Document 3 has been proposed especially for a resin-coated aluminum plate for cap molding, and is suitable for molding into a cap with a small amount of processing.
  • an organic resin-coated metal plate for a seamless can formed by severer forming processing than a cap there are the following problems. That is, when it is used to form a seamless can, it is mainly processed after can forming (can be necked) during sterilization treatment such as pass try treatment (hot water shower treatment) or retort treatment after content filling and sealing. In the part subjected to processing and flange processing, the organic resin coating layer may peel off due to the lack of heat resistant water adhesion between the organic resin coating layer and the metal substrate, and the organic resin coated metal plate for seamless can Further improvements are needed to apply.
  • an object of the present invention is to provide excellent hot water adhesion which can suppress peeling of the organic resin coating layer at the flange portion even when applied under high temperature and wet environment such as pass try treatment and retort treatment after content filling. It is an object of the present invention to provide an organic resin-coated surface-treated metal sheet having a surface-treated coating layer formed by a non-chromium coating type treatment having excellent properties and economical efficiency and small environmental load.
  • polycarboxylic acid polymers such as polyacrylic acid and polyalcohol as a crosslinking component of the polycarboxylic acid polymer are contained as main components on at least one side of a metal plate.
  • the present invention has been completed. That is, according to the present invention, it is an organic resin-coated surface-treated metal plate having a surface-treated coating layer and an organic resin coating layer formed on the surface-treated coating layer on at least one surface of a metal plate. There is provided an organic resin-coated surface-treated metal plate characterized in that the layer contains a polycarboxylic acid-based polymer as a main component and a polyalcohol as a crosslinking component of the polycarboxylic acid-based polymer.
  • the content of the polyalcohol in the surface treatment film layer is 20 parts by mass or less with respect to 100 parts by mass of the solid content of the polycarboxylic acid-based polymer, 2.
  • the polycarboxylic acid polymer is polyacrylic acid, 3.
  • the polyalcohol is polyvinyl alcohol or starch. 4.
  • the film weight per unit area of the surface treatment film layer is 2 to 100 mg / m 2 in carbon atom conversion, 5.
  • the organic resin coating layer is a polyester resin film, 6.
  • the metal plate is an aluminum plate, Is preferred.
  • a can or a can lid comprising the above organic resin-coated surface-treated metal plate.
  • the metal sheet coated with an organic resin coated surface of the present invention makes it possible to provide a can / lid having excellent heat resistant water adhesion which can cope with the sterilization treatment applied after filling the contents. Furthermore, since the surface treatment film layer of the present invention is formed by the non-chromium coating type treatment, it is advantageous in that it is excellent in economic efficiency and has a small impact on the environment.
  • a polycarboxylic acid polymer such as polyacrylic acid as a main component and a polyalcohol as a crosslinking component of the polycarboxylic acid polymer
  • an organic resin-coated surface-treated metal plate having a surface-treated film layer formed only of a polycarboxylic acid-based polymer without blending a polyalcohol as a crosslinking component, or a polyalcohol alone In a seamless can prepared using an organic surface-treated metal plate having a surface-treated film layer containing no acid polymer, peeling of the organic resin coating layer occurs in the flange portion (Comparative Examples 1 and 2).
  • the surface-treated film layer in the organic resin surface-treated metal plate of the present invention contains at least a polycarboxylic acid-based polymer as a main component and a polyalcohol as a crosslinking component of the polycarboxylic acid-based polymer. It is possible to provide a can having excellent hot water adhesion.
  • the action and effect of the present invention are presumed as follows.
  • the free carboxyl group (carboxyl group which does not form an ester bond with the hydroxyl group of polyalcohol) contained in the polycarboxylic acid polymer interacts strongly with the organic resin coating layer formed on the surface treatment film layer. Even when applied under high temperature and wet environment, the film and the organic resin coating layer can be well adhered to each other through this free carboxyl group. By combining these effects, peeling of the organic resin coating layer is suppressed even when the can body formed from the organic resin coated surface-treated metal plate of the present invention is subjected to sterilization treatment after filling the contents. , It is believed that it exhibits excellent hot water adhesion.
  • the composition of the surface treatment film layer in the organic resin coated surface-treated metal plate of the present invention is 20 parts by mass or less of polyalcohol, particularly 0.1 to 20 parts by mass with respect to 100 parts by mass of solid content of the polycarboxylic acid polymer.
  • it is contained in an amount of parts by weight, preferably 0.1 to less than 10 parts by weight, particularly preferably 0.5 to 5 parts by weight.
  • the amount of polyalcohol is more than the above range, the surface treatment film layer becomes a metal substrate at the time of severe processing such as molding of a can due to excessive crosslinking being formed as compared with the case of being in the above range.
  • the organic resin coating layer may peel off at the end of the can in the heat treatment process applied to relieve distortion of the organic resin coating layer after the can is molded. There is a risk that the suitability may be significantly degraded, and the hot water adhesion may also be degraded.
  • the amount of polyalcohol is less than the above range, the heat resistance and the water resistance of the surface treatment film layer are insufficient due to the insufficient crosslinking formation as compared with the case of the above range, The strength can not be maintained and the internal breakage is likely to occur. As a result, the organic resin coating layer may be peeled off, and the hot water adhesion may deteriorate. Also in the heat treatment process after forming the can, the film is easily broken internally due to the lack of heat resistance. As a result, the organic resin coating layer may peel off, and the can-making ability may be deteriorated.
  • the film weight per unit area of the surface treatment film layer is preferably in the range of 2 to 100 mg / m 2 , particularly 5 to 50 mg / m 2 in terms of carbon atom. If the film weight is larger than the above range, the film becomes thicker than necessary, which is uneconomical. On the other hand, when the content is smaller than the above range, the film becomes thinner than the required film thickness, and there is a possibility that the hot water adhesion to the organic resin coating layer can not be sufficiently obtained.
  • the thickness of the surface treatment film layer is preferably less than 0.1 ⁇ m, and particularly preferably in the range of 0.005 to 0.05 ⁇ m.
  • an existing polycarboxylic acid-based polymer can be used as the polycarboxylic acid-based polymer constituting the surface treatment film layer, but the existing polycarboxylic acid-based polymer has two in the molecule. It is a generic term of the polymer which has the above carboxyl group.
  • copolymers of an ethylenically unsaturated carboxylic acid and other ethylenically unsaturated monomers, and acid polysaccharides having a carboxyl group in the molecule such as alginic acid, carboxymethyl cellulose and pectin can be exemplified.
  • These polycarboxylic acid polymers can be used alone or as a mixture of at least two polycarboxylic acid polymers.
  • acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like are representative, and among them, acrylic acid, methacrylic acid, itaconic acid, maleic acid Is preferred.
  • ⁇ -olefins such as ethylene and propylene
  • carboxylic acid vinyl esters such as vinyl acetate
  • unsaturated acids such as alkyl acrylate, alkyl methacrylate and alkyl itaconate
  • Carboxylic acid esters acrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylamide, styrene and the like are representative.
  • polycarboxylic acid polymers polymers containing a structural unit derived from at least one polymerizable monomer selected from acrylic acid, methacrylic acid, itaconic acid and maleic acid, or the polymer It is preferably a mixture of polymers.
  • the polymer may be a homopolymer or a copolymer.
  • a structural unit derived from at least one polymerizable monomer selected from acrylic acid, maleic acid, methacrylic acid and itaconic acid is 60 mol% or more, preferably 80 mol% or more. Most preferably, it is contained in an amount of 100 mol% (however, the total structural unit is 100 mol%).
  • the polycarboxylic acid-based polymer is a polymer composed only of at least one type of polymerizable monomer selected from among acrylic acid, maleic acid, methacrylic acid and itaconic acid.
  • the ethylenic unsaturated monomer etc. which can be copolymerized with the above-mentioned ethylenically unsaturated carboxylic acid etc. are mentioned as another structural unit, for example.
  • the polycarboxylic acid-based polymer is a polymer consisting only of at least one polymerizable monomer selected from among the above-mentioned acrylic acid, maleic acid, methacrylic acid and itaconic acid
  • those polymerizable monomers may be used. It is possible to use homopolymers, copolymers or mixtures thereof of monomers. More preferably, polyacrylic acid, polymethacrylic acid, polyitaconic acid, polymaleic acid, and mixtures thereof can be used.
  • the polycarboxylic acid polymer is particularly preferably polyacrylic acid.
  • a part of the carboxyl groups possessed by the polycarboxylic acid-based polymer may be neutralized in advance by the basic compound within the range not impairing the object of the present invention .
  • basic compounds include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and various amine compounds such as ammonia.
  • the polycarboxylic acid-based polymer constituting the surface treatment film layer of the present invention is not limited thereto, but the weight average molecular weight (Mw) is 3,000 to 1,000,000, preferably 10,000 to 1,000. It is desirable to be in the range of 1,000. When the weight average molecular weight is smaller than the above range, the hot water adhesion of the surface treatment film layer may be deteriorated. On the other hand, when the weight average molecular weight is larger than the above range, the stability of the surface treatment liquid may be lowered, and there is a possibility that the gelation may occur with time, and the productivity may be inferior.
  • Mw weight average molecular weight
  • polyalcohols constituting the surface treatment film layer in the present invention include low molecular weight polyalcohols having two or more hydroxyl groups in the molecule, polyalcohol polymers, saccharides and the like.
  • low molecular weight polyalcohols ethylene oxide, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, cyclohexane dimethanol, ethylene oxide adduct of bisphenol A, Trimethylol propane, erythritol, pentaerythritol, glycerin, xylitol, arabitol, sorbitol, mannitol and the like can be mentioned.
  • polyalcohol polymers polyvinyl alcohol (hereinafter sometimes referred to as "PVA"), partially saponified polyvinyl acetate, butenediol-vinyl alcohol copolymer resin, polyhydroxyethyl (meth) acrylate, polyethylene glycol And polypropylene glycol, ethylene-vinyl alcohol copolymer and the like.
  • PVA polyvinyl alcohol
  • partially saponified polyvinyl acetate partially saponified polyvinyl acetate
  • butenediol-vinyl alcohol copolymer resin polyhydroxyethyl (meth) acrylate
  • polyethylene glycol And polypropylene glycol polyethylene glycol And polypropylene glycol
  • ethylene-vinyl alcohol copolymer ethylene-vinyl alcohol copolymer and the like.
  • saccharides monosaccharides such as arabinose, xylose, ribose, lyxose, glucose, mannose, galactose and fructose, oligosaccharides such as sucrose, maltose, cellobiose and lactose, or polysaccharides such as starches and dextrin .
  • PVA butenediol-vinyl alcohol copolymer resin
  • starches, glycerin and polyethylene glycol can be suitably used, and PVA and starches are particularly preferable.
  • the PVA is not particularly limited, but a PVA having a degree of saponification of 85% or more, preferably 95% or more, and an average degree of polymerization of 50 to 5000 can be suitably used.
  • a PVA having a degree of saponification of 85% or more, preferably 95% or more, and an average degree of polymerization of 50 to 5000 can be suitably used.
  • starches water soluble soluble starch can be suitably used.
  • a metal salt of an inorganic acid or an organic acid can be appropriately added as a catalyst.
  • the metal include alkali metals such as lithium, sodium and potassium.
  • Specific examples of metal salts of inorganic acids or organic acids include lithium chloride, sodium chloride, potassium chloride, sodium bromide, sodium hypophosphite, disodium hydrogen phosphite, disodium phosphate, sodium ascorbate Sodium acetate, sodium benzoate, sodium hyposulfite and the like, with sodium hypophosphite being particularly preferred.
  • the addition amount of the metal salt of the inorganic acid and the organic acid is 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the solid content of the polycarboxylic acid-based polymer.
  • the surface treatment film layer in the present invention may contain a polyvalent metal compound such as zirconium, zinc, calcium, or aluminum, as long as the object of the present invention is not impaired.
  • the surface treatment solution for forming the surface treatment film layer of the present invention can be formed from a surface treatment solution containing a polycarboxylic acid polymer, a polyalcohol, an aqueous medium, and, if necessary, an esterification reaction catalyst.
  • a surface treatment liquid 0.1 to 20 parts by mass, preferably 0.1 to less than 10 parts by mass, and particularly preferably 0.1 to 20 parts by mass of polyalcohol relative to 100 parts by mass of solid content of the polycarboxylic acid-based polymer. It is preferred that the content is 0.5 to 5 parts by mass.
  • the amount of metal salts of inorganic acids and organic acids added is 100% by mass in terms of solid content per 100 parts by mass of the polycarboxylic acid polymer. It is suitable to blend in an amount of 1 to 10 parts by mass, preferably 0.2 to 5 parts by mass.
  • aqueous medium water such as distilled water, ion-exchanged water, pure water or the like can be used, and it contains an organic solvent such as alcohol, polyhydric alcohol, its derivative or the like as well as known aqueous compositions. Can.
  • the organic solvent can be contained in an amount of 5 to 30% by weight with respect to water. By containing the organic solvent in the above range, film forming performance is improved.
  • an organic solvent for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, propylene glycol monopropyl ether, ethylene glycol monostable ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether
  • examples include butyl ether, tripropylene glycol monomethyl ether, 3-methyl 3-methoxybutanol and the like.
  • the method for forming the surface treatment film layer on the metal plate is not particularly limited.
  • the metal plate is subjected to a degreasing treatment as surface cleaning (pretreatment) for removing rolling oil, rust preventive oil, etc.
  • the surface treatment film layer can be formed by applying the above-mentioned surface treatment solution onto a metal plate and performing heat drying.
  • the degreasing treatment is not particularly limited, and examples thereof include alkali washing and acid washing which have been conventionally used for degreasing treatment of metal plates such as aluminum and aluminum alloys.
  • alkali washing and acid washing which have been conventionally used for degreasing treatment of metal plates such as aluminum and aluminum alloys.
  • a method of carrying out acid washing after alkali washing or a method of carrying out acid washing without carrying out the above alkali washing is preferable .
  • alkaline cleaning is performed using an alkaline cleaner
  • acid cleaning is performed using an acidic cleaner.
  • the alkaline cleaner is not particularly limited, and for example, those used for ordinary alkaline cleaning can be used, and examples thereof include "surf cleaner 420N-2" manufactured by Nippon Paint Co., Ltd. It does not specifically limit as said acidic cleaner, For example, aqueous solution, such as inorganic acids, such as a sulfuric acid, nitric acid, and hydrochloric acid, is mentioned. After the above degreasing treatment, in order to remove the degreasing agent remaining on the surface of the metal plate, water washing treatment is performed, and then the moisture on the surface of the metal plate is removed by a method such as air blowing or hot air drying. .
  • the surface treatment solution is roll coating method, spray method, immersion method, brush coating method, spray drawing method (After applying the surface treatment solution on a metal plate by spray, squeeze the liquid film with a roll or air and dry it)
  • the metal plate can be coated by a conventionally known method such as immersion drawing (in which the liquid film is strongly drawn with a roll or air after being dipped in a surface treatment solution and dried). Drying conditions after the surface treatment are preferably 50 to 300 ° C., 5 seconds to 5 minutes, and particularly preferably 150 to 250 ° C., 10 seconds to 2 minutes.
  • Metal plate Especially as a metal plate used for the present invention, although not limited, various steel plates, an aluminum plate, etc. are used.
  • a cold-rolled steel plate may be annealed and then subjected to secondary cold rolling, and a clad steel plate or the like may also be used.
  • an aluminum plate made of an aluminum alloy can be used as the aluminum plate, and in the present invention, an aluminum plate made of an aluminum alloy can be preferably used.
  • the aluminum plate for example, aluminum alloy 5182 material, aluminum alloy 5021 material, aluminum alloy 5022 material, aluminum alloy 5052 material, aluminum alloy 3004 material, aluminum alloy 3005 material, aluminum alloy 3104 material, aluminum alloy 1100 material and the like are preferable.
  • the original thickness of the metal plate is not particularly limited and may differ depending on the type of metal, the use of the container or the size of the container, but the metal plate should generally have a thickness of 0.10 to 0.50 mm. In the case of the above, it is preferable to have a thickness of 0.10 to 0.30 mm, and in the case of an aluminum plate, the thickness of 0.15 to 0.40 mm. If it is less than 0.15 mm, it is difficult to mold the lid and a desired lid strength can not be obtained, while if it exceeds 0.40 mm, the economy is deteriorated.
  • the metal plate one which has been subjected to surface treatment such as chemical conversion treatment and plating conventionally known in the prior art may be used in advance.
  • surface treatment such as chemical conversion treatment and plating conventionally known in the prior art
  • one or two or more kinds of surface treatments such as zinc plating, tin plating, nickel plating, electrolytic chromic acid treatment, chromic acid treatment, and phosphate treatment The thing which went is mentioned.
  • water-soluble resin such as acrylic resin and phenol resin for inorganic chemical conversion treatment such as phosphate chromate treatment, zirconium phosphate treatment and phosphate treatment and inorganic chemical conversion treatment
  • organic-inorganic composite chemical conversion treatment in which organic components such as tannic acid are combined.
  • the organic resin coated coated metal sheet of the present invention is not particularly limited as the organic resin constituting the organic resin coated layer directly applied on the surface treatment film layer formed on the metal sheet, for example, crystalline polypropylene, Crystalline propylene-ethylene copolymer, crystalline polybutene-1, crystalline poly 4-methylpentene-1, low-, medium- or high-density polyethylene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic Polyolefins such as ethyl acid copolymer (EEA), ionically cross-linked olefin copolymer (ionomer); aromatic vinyl copolymers such as polystyrene and styrene-butadiene copolymer; halogens such as polyvinyl chloride and vinylidene chloride resin Vinyl chloride polymer; acrylonitrile-styrene copolymer, acrylonitrile-styrene-buta
  • the polyester resin constituting the polyester resin film may be homopolyethylene terephthalate, or an acid component other than terephthalic acid in an amount of 30 mol% or less based on the acid component, and an alcohol component other than ethylene glycol as an alcohol.
  • the copolyester alone or a blend thereof may be contained in an amount of 30 mol% or less based on the component.
  • acid components other than terephthalic acid include isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, P- ⁇ -oxyethoxybenzoic acid, diphenoxyethane-4,4'-dicarboxylic acid, 5-sodium sulfoisophthalic acid, and hexa Hydroterephthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, trimellitic acid, pyromellitic acid and the like can be mentioned.
  • alcohol components other than ethylene glycol include propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, cyclohexane dimethanol, and an ethylene oxide adduct of bisphenol A, Glycol components such as trimethylolpropane and pentaerythritol can be mentioned.
  • homopolyethylene terephthalate resin and / or copolyester resin mainly composed of polyethylene terephthalate and crystalline polyester resins other than these for example, copolyester resin mainly composed of homopolybutylene terephthalate resin and / or polybutylene terephthalate resin
  • the resin may be a blend of a homopolyethylene naphthalate resin and / or a copolyester resin mainly composed of a polyethylene naphthalate resin.
  • the above-mentioned crystalline polyester resin other than the copolyester resin mainly composed of the homopolyethylene terephthalate resin and the polyethylene terephthalate resin with respect to the copolyester resin mainly composed of the homopolyethylene terephthalate resin and / or the polyethylene terephthalate resin Preferably, the compounding amount of is 5 to 50 wt%.
  • polyethylene terephthalate resin consisting of ethylene terephthalate units, polyethylene terephthalate / polyethylene isophthalate copolymer resin, polyethylene terephthalate / polybutylene terephthalate copolymer resin, polyethylene terephthalate / polyethylene naphthalate copolymer resin, polyethylene terephthalate resin It is preferably any one of a blend resin of polybutylene terephthalate resin and a blend resin of polyethylene terephthalate / polyethylene isophthalate copolymer resin and polybutylene terephthalate resin, and in particular, polyethylene terephthalate / polyethylene isophthalate copolymer resin, polyethylene terephthalate / polyethylene Isophthalate copolymer resin and polybutylene Blend resin of terephthalate resin is preferable.
  • the polyethylene terephthalate / polyethylene isophthalate copolymer resin preferably has a content of isophthalic acid of 20 mol% or less (based on the acid component).
  • a blend resin of the polyethylene terephthalate / polyethylene isophthalate copolymer resin and the polybutylene terephthalate resin a blend of polybutylene terephthalate resin in a range of 10 to 50 wt% with the polyethylene terephthalate / polyethylene isophthalate copolymer resin preferable.
  • the polyester resin used as the organic resin coating layer should have a film forming molecular weight, and has an intrinsic viscosity [.eta.] Of 0.5 or more, particularly 0.D., as measured using a phenol / tetrachloroethane mixed solvent as a solvent.
  • the range of 52 to 0.70 is preferable from the viewpoint of the barrier property to corrosive components and mechanical properties, and the glass transition point is preferably 50 ° C. or more, particularly 60 ° C. to 80 ° C.
  • thermoplastic resin film such as a polyester resin film can be compounded with a known compounding agent for film, a lubricant, an antiblocking agent, a pigment, various antistatic agents, an antioxidant and the like known per se. It is preferable that the thickness of the thermoplastic resin film such as polyester resin film is generally in the range of 5 to 40 ⁇ m.
  • the organic resin coating layer made of a thermoplastic resin film can be made to have a two-layer structure, and when using a polyester resin as a thermoplastic resin, an ethylene terephthalate unit is mainly used as a lower layer, such as isophthalic acid and naphthalene dicarboxylic acid Process adhesion, containing at least one type in an amount of 1 to 30 mol% (based on the acid component), and forming from a polyester resin whose amount is larger than the compounding amount of the acid component in the polyester resin to be the upper layer. It is particularly preferable in terms of dent resistance and the like.
  • the organic resin coating layer made of a thermoplastic resin film may be formed on the surface treatment film layer via a conventionally known adhesion primer layer such as epoxy phenol type or polyester phenol type.
  • the adhesion primer layer exhibits excellent adhesion to both the surface treatment film layer and the organic resin coating layer.
  • adhesion is particularly made from a paint containing an epoxy resin and a phenol resin in a weight ratio of 50:50 to 99: 1, particularly 60:40 to 95: 5. It is preferable from the viewpoint of resistance and corrosion resistance.
  • As an adhesive primer of polyester phenol type in particular, it is formed from a paint containing a polyester resin and a phenol resin in a weight ratio of 50:50 to 99: 1, particularly 60:40 to 95: 5.
  • the adhesion primer layer is generally provided in a thickness of 0.1 to 10 ⁇ m.
  • the adhesion primer layer may be provided in advance on the surface treatment film layer on the surface treated metal plate, or may be provided on the organic resin coating layer such as the polyester resin film.
  • the coating film which consists of a resin coating composition can also be made into an organic resin coating layer.
  • a resin paint composition which can be suitably used thermosetting resin paints, for example, phenol resin, melamine resin, alkyd resin, unsaturated polyester resin, epoxy resin, epoxy acrylic resin, epoxy phenol resin, epoxy urea resin, bismaleimide Resin paint containing triallyl cyanurate resin, thermosetting acrylic resin, silicone resin, oil resin, etc.
  • thermoplastic resin paint such as vinyl organosol, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acetate acetate
  • the resin paint include vinyl copolymer partial saponified product, vinyl chloride-maleic acid copolymer, vinyl chloride-maleic acid-vinyl acetate copolymer, acrylic polymer, saturated polyester resin and the like. These resin paints may be used alone or in combination of two or more. Among these, a coating film made of a resin paint using one or more of polyester resin, phenol resin, epoxy resin, epoxy acrylic resin, epoxy phenol resin, epoxy urea resin, vinyl organosol is preferable. .
  • the preferred dry coating weight of the above coating is preferably 5 to 200 mg / dm 2 .
  • Method of forming an organic resin coating layer on a surface-treated metal plate As a method of forming an organic resin coating layer on a surface-treated metal plate, when the organic resin coating layer is a thermoplastic resin film, for example, a thermoplastic resin film is formed in advance by a conventionally known method, and then the surface is formed.
  • the method of coating by heat adhesion on a treated metal plate, the extrusion laminating method of extruding a heat-melted thermoplastic resin into a film shape using an extruder and directly coating it on a surface-treated metal plate are suitable.
  • the film when coating after forming a thermoplastic resin film, the film may be stretched, but it is preferable that it is an unstretched film from the viewpoint of molding processability and dent resistance.
  • the organic resin coating layer is a coating film, it can be formed by applying a coating composition on a surface-treated plate by a conventionally known method such as roll coating or spraying, and drying and baking it. .
  • FIG. 1 shows an example of the cross-sectional structure of the organic resin-coated surface-treated metal plate of the present invention.
  • This organic resin-coated surface-treated metal plate 1 is a surface-treated film layer 3a applied to both surfaces of a metal plate 2 , 3b, and organic resin coating layers 4a, 4b.
  • the organic resin coating layers 4a and 4b are formed on both the inner and outer surfaces of the container of the metal plate 2 via the surface treatment film layers 3a and 3b.
  • the surface treatment film layer 3 and the organic resin coating layer 4 may be formed on at least one side, and different surface treatment film layers and an organic resin coating layer may be formed on the other side. it can.
  • the can comprising the organic resin-coated surface-treated metal plate of the present invention can be produced by a conventionally known forming method.
  • the organic resin-coated surface-coated metal sheet of the present invention has excellent processing adhesion to the organic resin-coated layer, and therefore drawing, drawing, deep drawing, drawing, ironing, drawing, bending, drawing -A seamless can formed by severe processing such as ironing can be formed without causing peeling of the resin coating of the rupture cylinder or the flange forming portion.
  • the side wall of the seamless can is 20 to 95% of the original thickness of the organic resin-coated surface-treated metal plate, particularly 25 to 85%, by bending-stretching or further ironing of the organic resin-coated surface-treated metal plate by drawing-redrawing. It is preferable to be thinned so as to have a thickness of
  • the obtained seamless can is subjected to at least one step of heat treatment to remove residual distortion of the film generated by processing, to evaporate the lubricant used during processing from the surface, and to dry and cure the printing ink printed on the surface. After heat treatment, the container is rapidly cooled or allowed to cool, optionally subjected to one or more stages of neck-in processing, and flanged to form a can for winding. In addition, after forming the seamless can, it is also possible to deform the upper portion of the seamless can into a bottle shape.
  • the can lid made of the organic resin-coated surface-treated metal plate of the present invention can be formed by a conventionally known method of producing a can lid.
  • an organic resin coated surface-treated metal plate suitable for forming a can lid is an organic resin in which a polyester resin film is formed as an organic resin coating layer through the aforementioned adhesion primer layer of epoxy phenol type or polyester phenol type.
  • a coated surface-treated metal plate can be mentioned, and the adhesion primer layer is preferably formed to have a dry film thickness of 0.3 to 3 ⁇ m.
  • an organic resin coated surface-treated metal plate on which a coating film composed of an epoxy phenol based paint, an epoxy acrylic based paint, a polyester based paint, an epoxy urea based paint, a vinyl organosol based paint etc. is formed as the organic resin coated layer is also suitable. It can be used.
  • the shape of the can lid can adopt a conventionally known shape such as an easy open lid provided with a score for forming the content dispensing opening and a tab for opening, and a full open type or a partial open It may be of any type (stay on tab type).
  • the easy open lid first, in the press forming step, the organic resin-coated metal plate is punched into a disk shape and is molded into a desired lid shape. Next, in a score imprinting process, using a score die, the score is imprinted so that the score reaches the middle of the thickness direction of the metal material from the outer surface side of the lid.
  • a rivet forming die is used to form an outwardly projecting rivet on the opening planned portion divided by the score, and in the tab attaching step, the opening tab is fitted to the rivet and the rivet projection is removed. By taking out and fixing the tab, the easy open lid is formed.
  • parts means “parts by mass”.
  • Examples 1 to 18 (Preparation of surface treatment solution)
  • the polycarboxylic acid polymer was dissolved in ion-exchanged water to obtain a 2 mass% aqueous polycarboxylic acid polymer solution.
  • the polyalcohol was dissolved in ion exchange water to obtain a 2% by mass aqueous polyalcohol solution.
  • an aqueous polyalcohol solution was gradually added to the aqueous solution of polycarboxylic acid-based polymer while stirring at normal temperature so as to obtain a predetermined blending ratio.
  • an aqueous solution of the catalyst was prepared and added to the aqueous solution containing the polycarboxylic acid polymer and the polyalcohol while stirring at normal temperature so as to obtain a predetermined blending ratio.
  • ion-exchanged water was added, and the solid content concentration of the polycarboxylic acid-based polymer in the aqueous solution was adjusted to 0.5 to 1% by mass to obtain a surface treatment liquid.
  • polyalcohol polyvinyl alcohol (Wako Pure Chemical Industries, Ltd.
  • sodium hypophosphite sodium phosphinate monohydrate manufactured by Wako Pure Chemical Industries, Ltd.
  • Table 1 shows the types of polycarboxylic acid polymers and polyalcohols used in each example, and the blending amounts of the polyalcohol and the catalyst with respect to 100 parts of the solid content of the polycarboxylic acid polymer in the surface treatment liquid. .
  • an aluminum plate (3104 alloy plate thickness: 0.28 mm plate size: 200 ⁇ 300 mm) was used.
  • alkaline cleaning was performed by immersion for 6 seconds in a 2% aqueous solution (60 ° C.) of an alkaline cleaner “surf cleaner 420N-2” (trade name) manufactured by Nippon Paint Co., Ltd. After alkali washing, after washing with water, it was immersed in a 2% aqueous sulfuric acid solution (60 ° C.) for 6 seconds to carry out acid washing, washed with water and then dried.
  • the surface treatment liquid was applied to both sides of the obtained metal plate, and was held for 60 seconds in an oven set at 200 ° C. for drying to prepare a surface-treated metal plate.
  • the weight (mg / m 2 ) per unit area of the polycarboxylic acid-based polymer in the surface-treated coating layer of the obtained surface-treated metal plate and carbon (C) derived from polyalcohol is a fluorescent X-ray analyzer It measured using.
  • a plurality of samples each having a known weight of carbon per unit area and a different weight of carbon were measured, and a strength-weight calibration curve was prepared from the strength at this time.
  • measure the surface-treated metal plate in each example convert the measured strength obtained to carbon weight based on the calibration curve, and measure the film weight in carbon conversion of the surface-treated film layer. did.
  • the measurement results are shown in Table 1.
  • the organic resin coated surface treatment board for cans was produced by the following method.
  • the obtained surface-treated metal plate is previously heated to a plate temperature of 250 ° C., and a polyester resin film as an organic resin coating layer is thermocompression-bonded to both surfaces of the surface-treated metal plate via a laminating roll, Thus, an organic resin-coated surface-treated metal plate was obtained.
  • As the polyester resin film a 12 ⁇ m thick polyethylene terephthalate / polyethylene isophthalate copolymer resin film was used.
  • Paraffin wax was electrostatically coated on both sides of the manufactured organic resin-coated surface-treated metal plate for cans, and then punched into a circle having a diameter of 156 mm to prepare a shallow drawn cup. Then, the shallow drawing cup is subjected to redrawing-ironing and doming forming, trimming of the opening edge, heat treatment at 201 ° C. for 75 seconds, and then at 210 ° C. for 80 seconds, necking the opening end Then, flanging was performed to prepare a seamless can having a diameter of can barrel 211 and a diameter of neck portion 206 and a capacity of 500 ml.
  • the characteristics of the seamless can were as follows. Can body diameter: 66 mm Can height: 168 mm Average thickness reduction ratio of can side wall to original thickness: 60%
  • Example 1 As shown in Table 1, a seamless can was produced in the same manner as in Example 1 except that a surface treatment solution containing no polyalcohol was used.
  • flange portion removability evaluation is carried out until trimming of the can as described in the above-mentioned "Production of Seamless Can", and then using an oven, it is performed at 201 ° C for 75 seconds and then at 210 ° C for 80 seconds. After heat treatment for 2 seconds, the open end (flanged portion) of the can was observed with a microscope, and the degree of peeling of the organic resin coating layer was evaluated from the open end of the can. The evaluation results are shown in Table 1.
  • the maximum length of the peeled portion is less than 0.1 mm ⁇ : The maximum length of the peeled portion is 0.1 mm or more and less than 0.2 mm ⁇ : The maximum length of the peeled portion is 0.2 mm or more and less than 0.3 mm X: The maximum length of the peeled part is 0.3 mm or more
  • Heat resistance water adhesion evaluation is as described in the above-mentioned "Production of seamless can", and after producing a seamless can, the inner diameter from the inner surface to the smallest diameter part of the inner side neck portion to the metal surface with a cutter knife along the can circumference In the state which gave the reach
  • the organic resin-coated surface-treated metal sheet of the present invention peels off the organic resin-coated layer even when it is applied to a high temperature / wet environment such as a sterilization process when a seamless can or the like is molded using it. Since it can exhibit excellent heat resistant water adhesion which can be suppressed, it can be suitably used for cans and can lids, and it has excellent heat water resistant adhesion even when subjected to severe forming processing. In particular, it can be suitably used for seamless cans such as drawn and ironed cans.

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  • Chemical & Material Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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  • Laminated Bodies (AREA)

Abstract

L'invention concerne une tôle métallique traitée en surface revêtue de résine organique qui est constituée par formation d'une couche de film de traitement de surface et d'une couche de revêtement de résine organique sur cette couche de film de traitement de surface, sur au moins une face d'une tôle métallique, et qui est caractéristique en ce que la couche de film de traitement de surface comprend un polymère à base d'acide polycarboxylique en tant que composant principal, et un polyalcool en tant que composant de réticulation du polymère à base d'acide polycarboxylique. La tôle métallique traitée en surface revêtue de résine organique de l'invention permet de fournir un corps et un couvercle de boîte de conserve qui présentent une adhérence résistant à l'eau chaude leur permettant d'être appropriés à une stérilisation par traitement de pasteurisation, traitement en autoclave, ou similaire, après remplissage d'un contenu.
PCT/JP2017/038035 2017-10-20 2017-10-20 Tôle métallique traitée en surface revêtue de résine organique WO2019077746A1 (fr)

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Cited By (1)

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US20230132293A1 (en) * 2020-04-03 2023-04-27 Toyo Kohan Co., Ltd. Multilayered polyester resin-coated metal sheet, multilayered polyester resin film, and can lid

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WO2016195081A1 (fr) * 2015-06-03 2016-12-08 日本ペイント・サーフケミカルズ株式会社 Agent de traitement d'hydrophilisation, procédé de formation de film hydrophile, et film hydrophile
WO2017138230A1 (fr) * 2016-02-08 2017-08-17 東洋鋼鈑株式会社 Tôle d'acier revêtue de résine organique, procédé pour sa production, boîte et couvercle de boîte utilisant chacun ladite tôle d'acier revêtue de résine organique

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US5534082A (en) * 1992-04-01 1996-07-09 Henkel Corporation Composition and process for treating metal
JPH07205379A (ja) * 1994-01-26 1995-08-08 Kureha Chem Ind Co Ltd ガスバリヤー性積層体及びその製造方法
US6605344B1 (en) * 1998-04-15 2003-08-12 Kureha Chemical Industry Co., Ltd. Gas-barrier films
JP2002086059A (ja) * 2000-09-13 2002-03-26 Unitika Ltd 塗装金属材料及びその製造方法
JP2002302150A (ja) * 2001-02-01 2002-10-15 Toyo Seikan Kaisha Ltd 耐レトルト性に優れたガスバリアー材
JP2004249614A (ja) * 2003-02-20 2004-09-09 Tohcello Co Ltd 二軸延伸ポリプロピレン複合フィルム及びその製造方法
JP2005146027A (ja) * 2003-11-12 2005-06-09 Toyobo Co Ltd コーティング剤およびそれを用いたフィルム
JP2008001080A (ja) * 2006-05-25 2008-01-10 Furukawa Sky Kk アルミニウム塗装板及びこれを用いたプレコートアルミニウムフィン材
WO2016195081A1 (fr) * 2015-06-03 2016-12-08 日本ペイント・サーフケミカルズ株式会社 Agent de traitement d'hydrophilisation, procédé de formation de film hydrophile, et film hydrophile
WO2017138230A1 (fr) * 2016-02-08 2017-08-17 東洋鋼鈑株式会社 Tôle d'acier revêtue de résine organique, procédé pour sa production, boîte et couvercle de boîte utilisant chacun ladite tôle d'acier revêtue de résine organique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230132293A1 (en) * 2020-04-03 2023-04-27 Toyo Kohan Co., Ltd. Multilayered polyester resin-coated metal sheet, multilayered polyester resin film, and can lid
US12049060B2 (en) * 2020-04-03 2024-07-30 Toyo Kohan Co., Ltd. Multilayered polyester resin-coated metal sheet, multilayered polyester resin film, and can lid

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