WO2019077746A1 - Organic resin coated surface-treated metal plate - Google Patents

Organic resin coated surface-treated metal plate 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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WIPO (PCT)
Prior art keywords
organic resin
metal plate
resin
acid
treated metal
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PCT/JP2017/038035
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French (fr)
Japanese (ja)
Inventor
拓也 柏倉
新 櫻木
Original Assignee
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/en
Publication of WO2019077746A1 publication Critical patent/WO2019077746A1/en

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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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Abstract

The present invention is an organic resin coated surface-treated metal plate which is obtained by forming, on at least one surface of a metal plate, a surface treatment film layer and an organic resin coating layer that is on the surface treatment film layer, and which is characterized in that: the surface treatment film layer contains a polycarboxylic acid polymer as a main component, while containing a polyalcohol as a crosslinking component for the polycarboxylic acid polymer. An organic resin coated surface-treated metal plate according to the present invention enables the achievement of a can body and a can lid, which have hot water-resistant adhesion that is able to deal with a pasteurization treatment after filling of the content and a sterilization treatment such as a retort treatment.

Description

有機樹脂被覆表面処理金属板Organic resin coated surface treated metal plate
　本発明は、飲料缶等の缶体・缶蓋用途に用いられる有機樹脂被覆表面処理金属板に関するものであり、より詳細には、内容品充填後に施される殺菌処理にも対応可能な優れた耐熱水密着性を有する缶体、缶蓋を提供可能であると共に、経済性にも優れ、かつ環境への負荷が小さい有機樹脂被覆表面処理金属板に関する。 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.
　アルミニウム等の金属板を有機樹脂で被覆した有機樹脂被覆金属板は、缶用材料として古くから知られており、この有機樹脂被覆金属板を絞り加工或いは絞り・しごき加工に付して、飲料等を充填するためのシームレス缶とし、或いはこれをプレス成形してイージーオープンエンド等の缶蓋とすることもよく知られている。例えば、エチレンテレフタレート単位を主体としたポリエステル樹脂から成る熱可塑性樹脂フィルムを有機樹脂被覆層として有する有機樹脂被覆金属板は、シームレス缶用の製缶材料として使用されている（特許文献１）。 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. For example, 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).
　また、このような缶体・缶蓋用途の有機樹脂被覆金属板に用いられる金属板としては、一般に、耐食性や有機樹脂被覆層との密着性を確保することを目的として、化成処理等の表面処理を施した表面処理金属板が用いられる。このような表面処理としては、例えばリン酸クロメート処理があり、リン酸クロメート処理を施した表面処理金属板から成る有機樹脂被覆表面処理金属板は、それを用いてシームレス缶等を成形した場合において、製缶適性に優れると共に、内容物充填・密封後の殺菌処理時における有機樹脂被覆層と金属基材間の密着性（耐熱水密着性）に優れることから、広く使用されてきたが、環境保護の観点からノンクロム系表面処理への要請が高まっている。 Moreover, as 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.
　これまでに缶用材料向けのノンクロム系表面処理が数多く提案されてきた。例えば有機樹脂被覆シームレスアルミニウム缶向けとして、ジルコニウム化合物とリン化合物、及びフェノール化合物を用いた有機無機複合系の化成処理が提案されており、優れた製缶適性や耐熱水密着性を発現し得るものである（特許文献２）。しかしながら、上記で提案されている表面処理は、処理後に水洗が必要な化成型（反応型）の表面処理であることから、廃水が大量に発生するため、廃水処理にコストがかかり、かつ環境への負荷が大きいことが懸念される。 Many non-chromium surface treatments for can materials have been proposed so far. For example, for organic resin-coated seamless aluminum cans, chemical conversion treatment of organic-inorganic composites using a zirconium compound, a phosphorus compound, and a phenol compound has been proposed, and can exhibit excellent can-making aptitude and hot water adhesion. (Patent Document 2). However, since the surface treatment proposed above is a surface treatment of chemical forming (reactive type) that requires washing after treatment, a large amount of wastewater is generated, so the cost of wastewater treatment increases, and There is a concern that the load on
　一方で化成型の表面処理と異なり、処理後に水洗が不要で、廃水処理にかかるコストを低減でき、かつ環境への負荷も小さい塗布型の表面処理（塗布型処理）によるノンクロム系表面処理も缶用材料向けに提案されている。例えばジルコニウム化合物とジルコニウム架橋されたポリアクリル酸が含有されて成る塗布型下地皮膜が形成された樹脂被覆アルミニウム板が提案されている（特許文献３）。 On the other hand, unlike chemical surface processing, there is no need for water washing after processing, the cost for wastewater treatment can be reduced, and the load on the environment is small. Coating surface treatment (coating type treatment) can also be used for non-chromium surface treatment It has been proposed for use in materials. For example, 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).
日本国特開２００１－２４６６９５号公報Japanese Patent Laid-Open No. 2001-246695 日本国特開２００７－７６０１２号公報Japanese Patent Application Publication No. 2007-76012 日本国特開２００７－１７６０７２号公報Japanese Patent Application Publication No. 2007-176072
　しかしながら、上記特許文献３で提案されている塗布型下地皮膜は、特にキャップ成型用の樹脂被覆アルミニウム板向けに提案されており、加工量の少ないキャップへの成形には適したものであったとしても、キャップに比してより過酷な成形加工により形成されるシームレス缶用の有機樹脂被覆金属板に適用した場合には、以下のような問題点がある。即ち、それを用いてシームレス缶を形成した場合に、内容物充填・密封後のパストライズ処理（熱水シャワー処理）やレトルト処理などの殺菌処理の際に、主に缶体成形の後加工（ネッキング加工やフランジ加工）を施した部分において、有機樹脂被覆層と金属基材間の耐熱水密着性の不足により、有機樹脂被覆層が剥離する場合があり、シームレス缶用の有機樹脂被覆金属板に適用するためには、さらなる改善が必要である。 However, 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. Also when applied to 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.
　従って、本発明の目的は、内容品充填後のパストライズ処理やレトルト処理等の高温・湿潤環境下に賦された場合においても、フランジ部における有機樹脂被覆層の剥離を抑制できる優れた耐熱水密着性を有すると共に、経済性に優れ、かつ環境への負荷が小さいノンクロム系の塗布型処理により形成される表面処理皮膜層を有する有機樹脂被覆表面処理金属板を提供することである。 Therefore, 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.
　本発明者らは鋭意検討した結果、金属板の少なくとも片面に、主成分としてポリアクリル酸等のポリカルボン酸系重合体と該ポリカルボン酸系重合体の架橋成分としてポリアルコールを含有し、ポリカルボン酸系重合体とポリアルコールが架橋構造を形成している表面処理皮膜層、及び該表面処理皮膜層上に形成された有機樹脂被覆層を有する有機樹脂被覆表面処理金属板が、内容品充填後のパストライズ処理やレトルト処理等の高温・湿潤環境下に賦された場合においても、フランジ部における有機樹脂被覆層の剥離を抑制できる優れた耐熱水密着性を有する缶体を提供可能であることを見出し、本発明を完成するに至った。
　即ち本発明によれば、金属板の少なくとも片面に、表面処理皮膜層及び該表面処理皮膜層上に有機樹脂被覆層が形成されて成る有機樹脂被覆表面処理金属板であって、該表面処理皮膜層が主成分としてポリカルボン酸系重合体及び該ポリカルボン酸系重合体の架橋成分としてポリアルコールを含有することを特徴とする有機樹脂被覆表面処理金属板が提供される。 As a result of intensive investigations, the present inventors have found that 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. An organic resin-coated surface-treated metal plate having a surface-treated film layer in which a carboxylic acid polymer and a polyalcohol form a crosslinked structure, and an organic resin-coated layer formed on the surface-treated film layer is filled with contents It is possible to provide a can having 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 later pass try treatment or retort treatment. 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.
　本発明の有機樹脂被覆表面処理金属板においては、
１．前記表面処理皮膜層における前記ポリアルコールの含有量が、前記ポリカルボン酸系重合体の固形分１００質量部に対して２０質量部以下であること、
２．前記ポリカルボン酸系重合体が、ポリアクリル酸であること、
３．前記ポリアルコールが、ポリビニルアルコール、または澱粉類であること、
４．前記表面処理皮膜層の単位面積当たりの皮膜重量が、炭素原子換算で２～１００ｍｇ／ｍ２であること、
５．前記有機樹脂被覆層が、ポリエステル樹脂フィルムであること、
６．前記金属板が、アルミニウム板であること、
が好適である。 In the organic resin-coated surface-treated metal plate of the present invention,
1. 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.
　本発明によればまた、上記有機樹脂被覆表面処理金属板から成ることを特徴とする缶体又は缶蓋が提供される。 According to the present invention, there is also provided a can or a can lid comprising the above organic resin-coated surface-treated metal plate.
　本発明の有機樹脂被覆表面処理金属板により、内容品充填後に施される殺菌処理にも対応可能な優れた耐熱水密着性を有する缶体・缶蓋を提供することが可能になる。
　しかも本発明の表面処理皮膜層は、ノンクロム系の塗布型処理により形成されることから、経済性に優れていると共に環境への負荷が少ないという利点がある。 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.
　本発明の上述する作用効果は後述する実施例の結果からも明らかである。
　主成分としてポリアクリル酸等のポリカルボン酸系重合体と該ポリカルボン酸系重合体の架橋成分としてポリアルコールを含有する表面処理皮膜層、及び該表面処理皮膜層上に有機樹脂被覆層を形成して成る有機樹脂被覆表面処理金属板を用いて作製したシームレス缶では、耐熱水密着性評価においても、有機樹脂被覆の剥離が防止されている（実施例１～１８）。
　これに対して、架橋成分であるポリアルコールを配合することなく、ポリカルボン酸系重合体のみで形成された表面処理皮膜層を有する有機樹脂被覆表面処理金属板、或いはポリアルコールのみで、ポリカルボン酸系重合体を含有しない表面処理皮膜層を有する有機表面処理金属板を用いて作成したシームレス缶では、フランジ部で有機樹脂被覆層の剥離が生じている（比較例１及び２）。 The above-described effects of the present invention are also apparent from the results of the examples described below.
A surface treatment film layer containing a polycarboxylic acid polymer such as polyacrylic acid as a main component and a polyalcohol as a crosslinking component of the polycarboxylic acid polymer, and an organic resin coating layer formed on the surface treatment film layer In the seamless can produced using the organic resin coated surface-treated metal plate, the peeling of the organic resin coating is prevented also in the evaluation of hot water adhesion (Examples 1 to 18).
On the other hand, 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).
本発明の有機樹脂被覆表面処理金属板の断面構造の一例を示す図である。It is a figure which shows an example of the cross-section of the organic resin coating surface treatment metal plate of this invention.
（表面処理皮膜層）
　本発明の有機樹脂表面処理金属板における表面処理皮膜層は、少なくとも主成分としてポリカルボン酸系重合体及び該ポリカルボン系重合体の架橋成分としてポリアルコールを含有していることが重要な特徴であり、それにより優れた耐熱水密着性を有する缶体を提供することが可能となる。本発明の作用効果は以下のように推察している。
　ポリカルボン酸系重合体とポリアルコールを含有する表面処理皮膜層が金属板上に形成された後、特定の条件下での熱処理（２００℃程度）に賦された際、表面処理皮膜層中において、ポリカルボン酸系重合体に含まれるカルボキシル基とポリアルコールに含まれる水酸基との間でエステル化反応が起こり、ポリカルボン酸系重合体がポリアルコールにより架橋された架橋構造が形成されると考えられる。この架橋により、主成分であるポリカルボン酸系重合体の耐熱水性が顕著に向上され、殺菌処理のような高温・湿潤環境下に賦された場合においても、皮膜が充分な強度を保持することが可能となる。一方、ポリカルボン酸系重合体に含まれる遊離のカルボキシル基（ポリアルコールの水酸基とエステル結合を形成していないカルボキシル基）は、表面処理皮膜層上に形成される有機樹脂被覆層と強い相互作用を形成するため、高温・湿潤環境下に賦された場合においても、この遊離のカルボキシル基を介して、皮膜と有機樹脂被覆層は良好に密着することができる。これらの効果が組み合わさることにより、本発明の有機樹脂被覆表面処理金属板から成形された缶体は、内容物充填後に殺菌処理に賦された際にも、有機樹脂被覆層の剥離が抑制され、優れた耐熱水密着性を発現するものと考えている。 (Surface treatment film layer)
It is an important feature that 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.
When a surface treatment film layer containing a polycarboxylic acid polymer and a polyalcohol is formed on a metal plate and then subjected to heat treatment (about 200 ° C.) under specific conditions, in the surface treatment film layer It is believed that an esterification reaction occurs between the carboxyl group contained in the polycarboxylic acid polymer and the hydroxyl group contained in the polyalcohol to form a crosslinked structure in which the polycarboxylic acid polymer is crosslinked by the polyalcohol. Be By this crosslinking, the hot water resistance of the polycarboxylic acid-based polymer which is the main component is significantly improved, and the film maintains sufficient strength even when applied under high temperature and wet environment such as sterilization treatment. Is possible. On the other hand, 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.
　本発明の有機樹脂被覆表面処理金属板における表面処理皮膜層の組成としては、ポリカルボン酸系重合体の固形分１００質量部に対して、ポリアルコールが２０質量部以下、特に０．１～２０質量部、好ましくは０．１～１０質量部未満、特に好ましくは０．５～５質量部の量で含有されていることが好適である。上記範囲よりもポリアルコールが多い場合は、上記範囲にある場合に比して、過度に架橋が形成されることで缶体の成形のような過酷な加工に際して表面処理皮膜層が金属基材に追従することが困難になり、その結果、缶体成形後に有機樹脂被覆層の歪みを緩和するために施される熱処理工程において、缶口端で有機樹脂被覆層が剥離する場合があり、製缶適性が顕著に劣化するおそれがあり、また耐熱水密着性も劣化するおそれがある。一方、上記範囲よりもポリアルコールが少ない場合には、上記範囲にある場合に比して、十分に架橋が形成されないことで表面処理皮膜層の耐熱性及び耐水性が不足し、殺菌処理時に皮膜強度を保持できず内部破壊しやすくなる。その結果、有機樹脂被覆層が剥離するおそれがあり、耐熱水密着性が劣化する場合がある。また缶体成形後の熱処理工程においても、耐熱性の不足により、皮膜が内部破壊しやすくなる。その結果、有機樹脂被覆層が剥離する場合があり、製缶適性が劣化するおそれがある。 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. Suitably, 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. When 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. It becomes difficult to follow, and as a result, 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. On the other hand, when 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.
　本発明において、表面処理皮膜層の単位面積当たりの皮膜重量は、炭素原子換算で２～１００ｍｇ／ｍ２、特に５～５０ｍｇ／ｍ２の範囲にあることが好適である。上記範囲より皮膜重量が大きい場合には、皮膜が必要以上に厚膜となり、不経済である。一方で上記範囲よりも含有量が小さい場合には、皮膜が必要とされる膜厚よりも薄くなり、有機樹脂被覆層との耐熱水密着性が充分に得られないおそれがある。また、表面処理皮膜層の厚みとしては０．１μｍ未満であることが好ましく、特に０．００５～０．０５μｍの範囲にあることが特に好ましい。 In the present invention, 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 μm, and particularly preferably in the range of 0.005 to 0.05 μm.
（ポリカルボン酸系重合体）
　本発明において表面処理皮膜層を構成するポリカルボン酸系重合体としては、既存のポリカルボン酸系重合体を用いることができるが、既存のポリカルボン酸系重合体とは、分子内に２個以上のカルボキシル基を有する重合体の総称である。具体的には、重合性単量体として、エチレン性不飽和カルボン酸を用いた単独重合体、単量体成分として、エチレン性不飽和カルボン酸のみからなり、それらの少なくとも２種の共重合体、またエチレン性不飽和カルボン酸と他のエチレン性不飽和単量体との共重合体、さらにアルギン酸、カルボキシメチルセルロース、ペクチンなどの分子内にカルボキシル基を有する酸性多糖類を例示することができる。これらのポリカルボン酸系重合体は、それぞれ単独で、または少なくとも２種のポリカルボン酸系重合体を混合して用いることができる。 (Polycarboxylic acid polymer)
In the present invention, 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. Specifically, a homopolymer using an ethylenically unsaturated carboxylic acid as a polymerizable monomer, and only a ethylenically unsaturated carboxylic acid as a monomer component, and at least two of them copolymers In addition, 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.
　ここでエチレン性不飽和カルボン酸としては、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマール酸、クロトン酸等が代表的なものであり、その中でもアクリル酸、メタクリル酸、イタコン酸、マレイン酸が好適である。またそれらと共重合可能なエチレン性不飽和単量体としては、エチレン、プロピレン等のα－オレフィン類、酢酸ビニル等のカルボン酸ビニルエステル類、アルキルアクリレート、アルキルメタクリレート、アルキルイタコネート等の不飽和カルボン酸エステル類、アクリロニトリル、塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、アクリルアミド、スチレン等が代表的なものである。 Here, as the ethylenically unsaturated carboxylic acid, 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. Further, as ethylenically unsaturated monomers copolymerizable with them, α-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.
　このようなポリカルボン酸系重合体の中でも、アクリル酸、メタクリル酸、イタコン酸、マレイン酸の中から選ばれる少なくとも１種の重合性単量体から誘導される構成単位を含む重合体、または該重合体の混合物であることが好ましい。なお、該重合体は、単独重合体でも、共重合体でもよい。また、該重合体において、前記アクリル酸、マレイン酸、メタクリル酸、およびイタコン酸の中から選ばれる少なくとも１種の重合性単量体から誘導される構成単位が６０ｍｏｌ％以上、好ましくは８０ｍｏｌ％以上、最も好ましくは１００モル％の量で含まれていることが望ましい（ただし全構成単位を１００ｍｏｌ％とする。）。すなわち、ポリカルボン酸系重合体が前記アクリル酸、マレイン酸、メタクリル酸、およびイタコン酸の中から選ばれる少なくとも１種の重合性単量体のみから成る重合体であることが好ましい。なお、上記構成単位以外の構成単位が含まれる場合には、その他の構成単位としては、例えば前述のエチレン性不飽和カルボン酸と共重合可能なエチレン性不飽和単量体などが挙げられる。更にポリカルボン酸系重合体が前記アクリル酸、マレイン酸、メタクリル酸、およびイタコン酸の中から選ばれる少なくとも１種の重合性単量体のみから成る重合体である場合には、それら重合性単量体の単独重合体、共重合体、或いはそれらの混合物を用いることができる。より好ましくは、ポリアクリル酸、ポリメタクリル酸、ポリイタコン酸、ポリマレイン酸、及びそれらの混合物を用いることができる。本発明においては、ポリカルボン酸系重合体がポリアクリル酸であることが特に好ましい。 Among such 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. In the polymer, 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%). That is, it is preferable that 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. In addition, when structural units other than the said structural unit are contained, 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. Furthermore, when 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. In the present invention, the polycarboxylic acid polymer is particularly preferably polyacrylic acid.
　また、本発明に用いるポリカルボン酸系重合体は、本発明の目的を損なわない範囲でポリカルボン酸系重合体の有するカルボキシル基の一部が、予め塩基性化合物で中和されていてもよい。塩基性化合物としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム等のアルカリ金属の水酸化物やアンモニア等の各種アミン化合物を挙げることができる。 Further, in the polycarboxylic acid-based polymer used in the present invention, 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 . Examples of basic compounds include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and various amine compounds such as ammonia.
　本発明の表面処理皮膜層を構成するポリカルボン酸系重合体は、これに限定されないが、重量平均分子量（Ｍｗ）が３，０００～１，０００，０００、好ましくは１０，０００～１，０００，０００の範囲にあることが望ましい。上記範囲よりも重量平均分子量が小さい場合には、表面処理皮膜層の耐熱水密着性が劣化する場合がある。一方で、上記範囲よりも重量平均分子量が大きい場合には、表面処理液の安定性が低下し、経時でゲル化するおそれがあり、生産性に劣る場合がある。 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.
（ポリアルコール）
　本発明において表面処理皮膜層を構成するポリアルコールとは、分子内に２個以上の水酸基を有する低分子量ポリアルコールや、ポリアルコール系重合体、糖類等を挙げることができる。
　低分子量ポリアルコールとしては、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、ネオペンチルグリコール、１，６－ヘキシレングリコール、ジエチレングリコール、トリエチレングリコール、シクロヘキサンジメタノール、ビスフェノールＡのエチレンオキサイド付加物、トリメチロールプロパン、エリスリトール、ペンタエリスリトール、グリセリン、キシリトール、アラビトール、ソルビトール、マンニトール等を挙げることができる。
　またポリアルコール系重合体としては、ポリビニルアルコール（以下、「ＰＶＡ」ということがある）、ポリ酢酸ビニルの部分けん化物、ブテンジオール－ビニルアルコール共重合樹脂、ポリヒドロキシエチル（メタ）アクリレート、ポリエチレングリコール、ポリプロピレングリコール、エチレンービニルアルコール共重合体等を挙げることができる。
　更に糖類としては、アラビノース、キシロース、リボース、リキソース、グルコース、マンノース、ガラクトース、フラクトース等の単糖類、サッカローズ、マルトース、セロビオース、ラクトース等のオリゴ糖類、或いは澱粉類、デキストリン等の多糖類が挙げられる。
　本発明においては、上記ポリアルコールの中でもＰＶＡ、ブテンジオール－ビニルアルコール共重合樹脂、澱粉類、グリセリン、ポリエチレングリコールを好適に使用することができ、特にＰＶＡ、澱粉類が好適である。
　ＰＶＡとしては、特に限定されないが、けん化度が８５％以上、好ましくは９５％以上であり、平均重合度が５０～５０００の範囲にあるものを好適に使用することができる。
　澱粉類としては、水溶性の可溶性澱粉が好適に使用できる。 (Poly alcohol)
Examples of 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.
As 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.
Further, as 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.
Furthermore, as 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 .
In the present invention, among the above polyalcohols, 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.
As starches, water soluble soluble starch can be suitably used.
（触媒）
　ポリカルボン酸系重合体とポリアルコールの熱処理によるエステル化反応を促進する目的で、触媒として無機酸または有機酸の金属塩を適宜添加することができる。金属としてはリチウム、ナトリウム、カリウム等のアルカリ金属を挙げることができる。無機酸または有機酸の金属塩の具体的な例としては、塩化リチウム、塩化ナトリウム、塩化カリウム、臭化ナトリウム、次亜リン酸ナトリウム、亜リン酸水素二ナトリウム、リン酸二ナトリウム、アスコルビン酸ナトリウム、酢酸ナトリウム、安息香酸ナトリウム、次亜硫酸ナトリウム等が挙げられ、特に次亜リン酸ナトリウムが好適である。無機酸および有機酸の金属塩の添加量は、ポリカルボン酸系重合体の固形分１００質量部対して、０．１～１０質量部、好ましくは０．２～５質量部である。 (catalyst)
In order to accelerate the esterification reaction of the polycarboxylic acid polymer and the polyalcohol by heat treatment, a metal salt of an inorganic acid or an organic acid can be appropriately added as a catalyst. Examples of 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.
　また、本発明における表面処理皮膜層は、本発明の目的を損なわない範囲で、ジルコニウムや亜鉛、カルシウム、アルミニウム等の多価金属化合物が含まれていても良い。 In addition, 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.
（表面処理液）
　本発明の表面処理皮膜層を形成する表面処理液は、ポリカルボン酸系重合体、ポリアルコール、水性媒体、及び必要に応じてエステル化反応触媒を含有する表面処理液から形成することができる。このような表面処理液においては、ポリカルボン酸系重合体の固形分１００質量部に対して、ポリアルコールが０．１～２０質量部、好ましくは０．１～１０質量部未満、特に好ましくは０．５～５質量部の量で含有されていることが好適である。また表面処理液に触媒として無機酸および有機酸の金属塩を配合する場合には、ポリカルボン酸系重合体１００質量部当たり、無機酸および有機酸の金属塩の添加量が固形分換算で０．１～１０質量部、好ましくは０．２～５質量部の量で配合することが好適である。 (Surface treatment solution)
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. In such 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. When metal salts of inorganic acids and organic acids are blended as a catalyst in the surface treatment solution, 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.
　前記水性媒体としては、蒸留水、イオン交換水、純粋水等の水を使用することができ、公知の水性組成物と同様に、アルコール、多価アルコール、その誘導体等の有機溶媒を含有することができる。このような共溶剤を用いる場合には、水に対して５～３０重量％の量で有機溶媒を含有することができる。上記範囲で有機溶媒を含有することにより、製膜性能が向上する。このような有機溶媒としては例えば、メチルアルコール、エチルアルコール、イソプロピルアルコール、プロピレングリコールモノプロピルエーテル、エチレングリコールモノブルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、３－メチル３－メトキシブタノールなどが挙げられる。 As the 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. When such co-solvents are used, 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. As such 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.
（金属板上への表面処理皮膜層の形成方法）
　金属板上への表面処理皮膜層の形成方法としては特に限定されず、例えば、金属板に圧延油や防錆油等を除去するための表面洗浄（前処理）として、脱脂処理を施し、水洗や表面調整をし、次いで、前述の表面処理液を金属板上に塗布し、加熱乾燥することで表面処理皮膜層を形成させることができる。 (Method of forming surface treatment film layer on metal plate)
The method for forming the surface treatment film layer on the metal plate is not particularly limited. For example, 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.
　上記脱脂処理としては特に限定されず、例えば、従来アルミニウムやアルミニウム合金等の金属板の脱脂処理に用いられてきたアルカリ洗浄や酸洗浄を挙げることができる。本発明においては、表面処理皮膜層と金属基材の密着性の点から、アルカリ洗浄の後、更に、酸洗浄を行う方法、又は、上記アルカリ洗浄を行うことなく、酸洗浄を行う方法が好ましい。上記脱脂処理において、通常、アルカリ洗浄はアルカリ性クリーナーを用いて行われ、酸洗浄は酸性クリーナーを用いて行われる。 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. In the present invention, from the viewpoint of adhesion between the surface treatment film layer and the metal substrate, 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 . In the above-mentioned degreasing treatment, usually, alkaline cleaning is performed using an alkaline cleaner, and acid cleaning is performed using an acidic cleaner.
　上記アルカリ性クリーナーとしては特に限定されず、例えば、通常のアルカリ洗浄に用いられるものを用いることができ、例えば、日本ペイント社製「サーフクリーナー４２０Ｎ－２」等が挙げられる。上記酸性クリーナーとしては特に限定されず、例えば、硫酸、硝酸、塩酸等の無機酸等の水溶液が挙げられる。上記脱脂処理を行った後は、金属板表面に残存する脱脂剤を除去するために、水洗処理を行なった後、エアーブロー若しくは熱空気乾燥等の方法にて、金属板表面の水分を除去する。 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. .
　表面処理液は、ロールコート法、スプレー法、浸漬法、刷毛塗り法、スプレー絞り法（スプレーにより、金属板上に表面処理液を塗布した後、ロールやエアーで液膜を絞りとり乾燥する）、浸漬絞り法（金属板を表面処理液に浸漬させた後、ロールやエアーで液膜を強く絞りとり乾燥する）等の従来公知の方法で金属板に塗布処理することができる。表面処理後の乾燥条件は、５０～３００℃、５秒～５分であり、特に１５０～２５０℃、１０秒～２分であることが好ましい。 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.
（金属板）
　本発明に用いる金属板としては、特に限定されないが、各種鋼板やアルミニウム板などが使用される。鋼板としては、冷圧延鋼板を焼鈍した後二次冷間圧延したものを用いることができ、他にクラッド鋼板なども用いることができる。また、アルミニウム板としては、いわゆる純アルミニウムの他にアルミニウム合金から成るアルミニウム板を用いることができ、本発明においては、特にアルミニウム合金から成るアルミニウム板を好適に使用できる。上記アルミニウム板としては、例えば、アルミニウム合金５１８２材、アルミニウム合金５０２１材、アルミニウム合金５０２２材、アルミニウム合金５０５２材、アルミニウム合金３００４材、アルミニウム合金３００５材、アルミニウム合金３１０４材、アルミニウム合金１１００材等が好適に用いられる。
　金属板の元厚は、特に限定はなく、金属の種類、容器の用途或いはサイズによっても相違するが、金属板としては一般に０．１０～０．５０ｍｍの厚みを有するのがよく、この中でも鋼板の場合には０．１０～０．３０ｍｍの厚み、アルミニウム板の場合は０．１５～０．４０ｍｍの厚みを有するのがよい。０．１５ｍｍ未満では、蓋成形が困難で、かつ所望の蓋強度が得られず、一方０．４０ｍｍを超えると、経済性が悪くなるためである。 (Metal plate)
Especially as a metal plate used for the present invention, although not limited, various steel plates, an aluminum plate, etc. are used. As the steel plate, 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. In addition to so-called pure aluminum, 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. As 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. Used for
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.
　尚、本発明においては、金属板として、あらかじめ従来公知の化成処理やめっき等の表面処理を施したものを使用しても良い。
　前述の表面処理としては、金属板として鋼鈑を用いる場合には、亜鉛メッキ、錫メッキ、ニッケルメッキ、電解クロム酸処理、クロム酸処理、リン酸塩処理等の表面処理の一種又は二種以上行ったものを挙げることができる。金属板としてアルミニウム板を用いる場合には、リン酸クロメート処理、リン酸ジルコニウム処理、リン酸塩処理等の無機系の化成処理、及び無機系の化成処理にアクリル樹脂、フェノール樹脂などの水溶性樹脂、タンニン酸等の有機成分を組み合わせた有機無機複合化成処理等を挙げることができる。 In the present invention, as 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.
In the case of using a steel plate as the metal plate as the above-mentioned surface treatment, 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. In the case of using an aluminum plate as the metal plate, 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 And organic-inorganic composite chemical conversion treatment in which organic components such as tannic acid are combined.
（有機樹脂被覆層）
　本発明の有機樹脂被覆塗装金属板において、金属板に形成された表面処理皮膜層上に直接施される有機樹脂被覆層を構成する有機樹脂としては、特に限定されず、例えば、結晶性ポリプロピレン、結晶性プロピレン－エチレン共重合体、結晶性ポリブテン－１、結晶性ポリ４－メチルペンテン－１、低－、中－、或いは高密度ポリエチレン、エチレン－酢酸ビニル共重合体（ＥＶＡ）、エチレン－アクリル酸エチル共重合体（ＥＥＡ）、イオン架橋オレフィン共重合体（アイオノマー）等のポリオレフィン類；ポリスチレン、スチレン－ブタジエン共重合体等の芳香族ビニル共重合体；ポリ塩化ビニル、塩化ビニリデン樹脂等のハロゲン化ビニル重合体；アクリロニトリル－スチレン共重合体、アクリロニトリル－スチレン－ブタジエン共重合体の如きニトリル重合体；ナイロン６、ナイロン６６、パラ又はメタキシリレンアジパミドの如きポリアミド類；ポリエチレンテレフタレート（ＰＥＴ）、ポリテトラメチレンテレフタレート等のポリエステル類；各種ポリカーボネート；ポリオキシメチレン等のポリアセタール類等の熱可塑性樹脂が挙げられる。これらの熱可塑性樹脂から構成された熱可塑性樹脂フィルムを有機樹脂被覆層として用いることができる。これらの中でも、特に熱可塑性樹脂としてポリエステル樹脂から構成されたポリエステル樹脂フィルムが好適である。 (Organic resin coating layer)
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-butadiene copolymer Nitrile polymers such as bodies; Polyamides such as nylon 6, nylon 66, para or metaxylylene adipamide; Polyesters such as polyethylene terephthalate (PET), polytetramethylene terephthalate; various polycarbonates; polyacetals such as polyoxymethylene And thermoplastic resins such as The thermoplastic resin film comprised from these thermoplastic resins can be used as an organic resin coating layer. Among these, a polyester resin film composed of a polyester resin as a thermoplastic resin is particularly preferable.
　前記ポリエステル樹脂フィルムを構成するポリエステル樹脂としては、ホモポリエチレンテレフタレートであってもよいし、テレフタル酸以外の酸成分を酸成分基準で３０モル％以下の量で、またエチレングリコール以外のアルコール成分をアルコール成分基準で３０モル％以下の量で含有する共重合ポリエステル単体またはそれらのブレンド物であってもよい。
　前記テレフタル酸以外の酸成分としては、イソフタル酸、ナフタレンジカルボン酸、シクロヘキサンジカルボン酸、Ｐ－β－オキシエトキシ安息香酸、ジフェノキシエタン－４，４’－ジカルボン酸、５－ナトリウムスルホイソフタル酸、ヘキサヒドロテレフタル酸、コハク酸、アジピン酸、セバシン酸、ドデカンジオン酸、ダイマー酸、トリメリット酸、ピロメリット酸等を挙げることができる。
　前記エチレングリコール以外のアルコール成分としては、プロピレングリコール、１，４－ブタンジオール、ネオペンチルグリコール、１，６－ヘキシレングリコール、ジエチレングリコール、トリエチレングリコール、シクロヘキサンジメタノール、ビスフェノールＡのエチレンオキサイド付加物、トリメチロールプロパン、ペンタエリスリトールなどのグリコール成分を挙げることができる。
　また、ホモポリエチレンテレフタレート樹脂及び／又はポリエチレンテレフタレートを主体とした共重合ポリエステル樹脂とこれら以外の結晶性ポリエステル樹脂、たとえばホモポリブチレンテレフタレート樹脂及び／又はポリブチレンテレフタレート樹脂を主体とした共重合ポリエステル樹脂、或いは、ホモポリエチレンナフタレート樹脂及び／又はポリエチレンナフタレート樹脂を主体とした共重合ポリエステル樹脂とをブレンドした樹脂であってもよい。その場合においては、ホモポリエチレンテレフタレート樹脂及び／又はポリエチレンテレフタレート樹脂を主体とした共重合ポリエステル樹脂に対して、ホモポリエチレンテレフタレート樹脂及びポリエチレンテレフタレート樹脂を主体とした共重合ポリエステル樹脂以外の前記結晶性ポリエステル樹脂の配合量が５～５０ｗｔ％であることが好ましい。 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.
Examples of acid components other than terephthalic acid include isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, P-β-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.
Examples of 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.
In addition, 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, Alternatively, the resin may be a blend of a homopolyethylene naphthalate resin and / or a copolyester resin mainly composed of a polyethylene naphthalate resin. In that case, 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%.
　上記ポリエステル樹脂の中でも特に、エチレンテレフタレート単位からなるポリエチレンテレフタレート樹脂、ポリエチレンテレフタレート／ポリエチレンイソフタレート共重合樹脂、ポリエチレンテレフタレート／ポリブチレンテレフタレート共重合樹脂、ポリエチレンテレフタレート／ポリエチレンナフタレート共重合樹脂、ポリエチレンテレフタレート樹脂とポリブチレンテレフタレート樹脂のブレンド樹脂、ポリエチレンテレフタレート／ポリエチレンイソフタレート共重合樹脂とポリブチレンテレフタレート樹脂のブレンド樹脂の何れかであることが好ましく、特に、ポリエチレンテレフタレート／ポリエチレンイソフタレート共重合樹脂、ポリエチレンテレフタレート／ポリエチレンイソフタレート共重合樹脂とポリブチレンテレフタレート樹脂のブレンド樹脂が好ましい。なお、ポリエチレンテレフタレート／ポリエチレンイソフタレート共重合樹脂としては、イソフタル酸の含有量が２０モル％以下（酸成分基準）のものが好ましい。前記ポリエチレンテレフタレート／ポリエチレンイソフタレート共重合樹脂とポリブチレンテレフタレート樹脂のブレンド樹脂としては、ポリエチレンテレフタレート／ポリエチレンイソフタレート共重合樹脂に対して、ポリブチレンテレフタレート樹脂を１０～５０ｗｔ％の範囲でブレンドしたものが好ましい。 Among the above polyester resins, 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). As 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.
　有機樹脂被覆層として使用するポリエステル樹脂は、フィルム形成範囲の分子量を有するべきであり、溶媒として、フェノール／テトラクロロエタン混合溶媒を用いて測定した固有粘度〔η〕が０．５以上、特に０．５２～０．７０の範囲にあることが腐食成分に対するバリヤー性や機械的性質の点から好ましく、またガラス転移点が５０℃以上、特に６０℃～８０℃の範囲にあることが好ましい。 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.
　ポリエステル樹脂フィルム等の熱可塑性樹脂フィルムには、それ自体公知のフィルム用配合剤、滑剤、アンチブロッキング剤、顔料、各種帯電防止剤、酸化防止剤等を公知の処方によって配合することができる。
　ポリエステル樹脂フィルム等の熱可塑性樹脂フィルムの厚みは、一般に５～４０μｍの範囲にあることが好ましい。
　熱可塑性樹脂フィルムから成る有機樹脂被覆層は二層構成にすることもでき、熱可塑性樹脂としてポリエステル樹脂を用いる場合には、下層として、エチレンテレフタレート単位を主体とし、イソフタル酸、ナフタレンジカルボン酸等の少なくとも一種を１～３０モル％（酸成分基準）の量で含有し、上層となるポリエステル樹脂における上記酸成分の配合量よりも、その量が多いポリエステル樹脂から形成することが、加工密着性、耐デント性等の点から特に好適である。 A 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 μm.
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.
　熱可塑性樹脂フィルムから成る有機樹脂被覆層は、エポキシフェノール系やポリエステルフェノール系等の従来公知の接着プライマー層を介して、表面処理皮膜層の上に形成しているものであっても良い。接着プライマー層は、表面処理皮膜層と有機樹脂被覆層との両方に優れた接着性を示すものである。
　エポキシフェノール系の接着プライマーとしては、特にエポキシ樹脂とフェノール樹脂を５０：５０～９９：１の重量比、特に６０：４０～９５：５の重量比で含有する塗料から形成されることが、密着性と耐食性の観点から好ましい。
　ポリエステルフェノール系の接着プライマーとしては、特にポリエステル樹脂とフェノール樹脂を５０：５０～９９：１の重量比、特に６０：４０～９５：５の重量比で含有する塗料から形成されることが、密着性と耐食性の観点から好ましい。
　上記接着プライマー層は一般に０．１～１０μｍの厚みに設けるのがよい。接着プライマー層は予め表面処理金属板上の表面処理皮膜層上に設けても良く、あるいは上記ポリエステル樹脂フィルム等の有機樹脂被覆層上に設けても良い。 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.
As an adhesive bond of epoxy phenol type, 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. It is preferable from the viewpoint of resistance and corrosion resistance.
The adhesion primer layer is generally provided in a thickness of 0.1 to 10 μm. 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.
　また本発明の有機樹脂被覆表面処理金属板において、樹脂塗料組成物から成る塗膜を有機樹脂被覆層とすることもできる。好適に使用できる樹脂塗料組成物としては、熱硬化性樹脂塗料、例えば、フェノール樹脂、メラミン樹脂、アルキド樹脂、不飽和ポリエステル樹脂、エポキシ樹脂、エポキシアクリル樹脂、エポキシフェノール樹脂、エポキシユリア樹脂、ビスマレイミド樹脂、トリアリルシアヌレート樹脂、熱硬化型アクリル樹脂、シリコーン樹脂、油性樹脂等を用いた樹脂塗料、或いは熱可塑性樹脂塗料、例えばビニルオルガノゾル、塩化ビニル－酢酸ビニル共重合体、塩化ビニル－酢酸ビニル共重合体部分ケン化物、塩化ビニル－マレイン酸共重合体、塩化ビニル－マレイン酸－酢酸ビニル共重合体、アクリル重合体、飽和ポリエステル樹脂等を用いた樹脂塗料を挙げることができる。これらの樹脂塗料は単独でも２種以上の組合せでも使用される。これらの中でもポリエステル樹脂、フェノール樹脂、エポキシ樹脂、エポキシアクリル樹脂、エポキシフェノール樹脂、エポキシユリア樹脂、ビニルオルガノゾルのうちの１種、又は２種以上を用いた樹脂塗料から成る塗膜が好適である。
　尚、上記塗膜の好適な乾燥塗膜質量は５～２００ｍｇ／ｄｍ２が好ましい。 Moreover, the organic resin coating surface-treated metal plate of this invention WHEREIN: The coating film which consists of a resin coating composition can also be made into an organic resin coating layer. As 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. or thermoplastic resin paint such as vinyl organosol, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acetate acetate Examples of 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 .
（表面処理金属板上への有機樹脂被覆層の形成方法）
　表面処理金属板上への有機樹脂被覆層の形成方法としては、有機樹脂被覆層が熱可塑性樹脂フィルムである場合には、例えば、熱可塑性樹脂フィルムを予め従来公知の方法により形成した後、表面処理金属板上に熱接着法で被覆する方法や、加熱溶融した熱可塑性樹脂を押出機を用いてフィルム状に押出し、直接表面処理金属板上に被覆する押出ラミネート法などが好適である。また、熱可塑性樹脂フィルムを形成した後で被覆する場合、フィルムは延伸されていてもよいが、未延伸フィルムであることが成形加工性及び耐デント性の点からは好ましい。
　有機樹脂被覆層が塗膜である場合には、ロールコート法、スプレー法等、従来公知の方法で表面処理板上に塗料組成物を塗工し、乾燥・焼き付けすることで形成させることができる。 (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. Moreover, 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.
When 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. .
　図１は、本発明の有機樹脂被覆表面処理金属板の断面構造の一例を示すものであり、この有機樹脂被覆表面処理金属板１は、金属板２の両面に施された表面処理皮膜層３ａ，３ｂ、有機樹脂被覆層４ａ，４ｂとから成っている。図１に示す具体例においては、金属板２の容器内外面の両方に表面処理皮膜層３ａ，３ｂを介して有機樹脂被覆層４ａ，４ｂが形成されているが、本発明の有機樹脂被覆表面処理金属板において、表面処理皮膜層３及び有機樹脂被覆層４は、少なくとも片面に形成されていればよく、もう一方の面には、異なる表面処理皮膜層および有機樹脂被覆層を形成することもできる。 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. In the specific example shown in FIG. 1, 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. In the treated metal plate, 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.
（缶体及びその製法）
　本発明の有機樹脂被覆表面処理金属板から成る缶体は、従来公知の成形法により製缶することができる。
　本発明の有機樹脂被覆表面処理覆金属板は、有機樹脂被覆層が優れた加工密着性を有していることから、絞り加工、絞り・深絞り加工、絞り・しごき加工、絞り・曲げ伸ばし加工・しごき加工等の過酷な加工により成形されるシームレス缶を、破胴やフランジ形成部の樹脂被覆の剥離を生じることなく成形することができる。
　シームレス缶の側壁部は、有機樹脂被覆表面処理金属板の絞り－再絞り加工による曲げ伸ばし或いは更にしごき加工により、有機樹脂被覆表面処理金属板の元厚の２０～９５％、特に２５～８５％の厚みとなるように薄肉化されていることが好ましい。
　得られたシームレス缶は、少なくとも一段の熱処理に付し、加工により生じるフィルムの残留歪みを除去し、加工の際用いた滑剤を表面から揮散させ、更に表面に印刷した印刷インキを乾燥硬化させる。熱処理後の容器は急冷或いは放冷した後、所望により、一段或いは多段のネックイン加工に付し、フランジ加工を行って、巻締用の缶とする。また、シームレス缶を成形した後、シームレス缶の上部を変形させてボトル形状にすることも可能である。 (Can and its manufacturing method)
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.
（缶蓋及びその製法）
　本発明の有機樹脂被覆表面処理金属板から成る缶蓋は、従来公知の缶蓋の製法により成形することができる。
　特に缶蓋の成形に適した有機樹脂被覆表面処理金属板としては、前述したエポキシフェノール系やポリエステルフェノール系等の接着プライマー層を介して、有機樹脂被覆層としてポリエステル樹脂フィルムが形成された有機樹脂被覆表面処理金属板を挙げることができ、上記接着プライマー層は、乾燥膜厚で０．３～３μｍの厚みで形成されていることが好ましい。
　また有機樹脂被覆層として、エポキシフェノール系塗料、エポキシアクリル系塗料、ポリエステル系塗料、エポキシユリア系塗料、ビニルオルガノゾル系塗料等から成る塗膜が形成された有機樹脂被覆表面処理金属板も好適に使用することができる。 (Can lid and its manufacturing method)
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.
In particular, 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 μm.
In addition, 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.
　また缶蓋の形状は、内容物注出用開口を形成するためのスコア及び開封用のタブが設けられたイージーオープン蓋等の従来公知の形状を採用することができ、フルオープンタイプ又はパーシャルオープンタイプ（ステイ・オン・タブタイプ）の何れであってもよい。
　イージーオープン蓋の成形は、先ずプレス成形工程で、有機樹脂被覆金属板を円板の形に打抜くと共に、所望の蓋形状に成形する。次いで、スコア刻印工程で、スコアダイスを用いて、蓋の外面側からスコアが金属素材の厚み方向の途中に達するようにスコアの刻印を行う。リベット形成工程において、リベット形成ダイスを用いてスコアで区画された開口予定部に外面に突出したリベットを形成させ、タブ取付工程で、リベットに開口用タブを嵌合させ、リベットの突出部を鋲出してタブを固定させることにより、イージーオープン蓋が成形される。 Further, 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).
In forming 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. In the rivet forming step, 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.
　以下、具体的な実施例を挙げて本発明を詳細に説明するが、本発明は以下の実施例により限定されるものではない。なお、以下において「部」とあるのは「質量部」を意味する。 Hereinafter, the present invention will be described in detail by way of specific examples, but the present invention is not limited by the following examples. In the following, “parts” means “parts by mass”.
［実施例１～１８］
（表面処理液の調製）
　ポリカルボン酸系重合体をイオン交換水中に溶解させ、２質量％のポリカルボン酸系重合体水溶液を得た。ポリアルコールをイオン交換水中に溶解させ、２質量％のポリアルコール水溶液を得た。次いでポリカルボン酸系重合体水溶液に、ポリアルコール水溶液を所定の配合比となるように、常温にて攪拌しながら徐々に添加した。さらに触媒を配合する場合においては、触媒の水溶液を調製し、所定の配合比となるように、常温にて攪拌しながらポリカルボン酸系重合体及びポリアルコールを含む水溶液中に添加した。次いで攪拌しながらイオン交換水を加え、水溶液中のポリカルボン酸系重合体の固形分濃度が０．５～１質量％となるように調製し、表面処理液を得た。 [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. Next, 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. Further, in the case of blending the catalyst, 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. Next, while stirring, 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.
　ポリカルボン酸系重合体としては、ポリアクリル酸（東亞合成社製「ジュリマーＡＣ－１０Ｌ、Ｍｗ＝約５０，０００」：表中「ＰＡＡ１」と表記、「ジュリマーＡＣ－１０Ｈ、Ｍｗ＝約８００，０００」：表中「ＰＡＡ２」と表記）を用いた。ポリアルコールとしてはポリビニルアルコール（和光純薬社製「ポリビニルアルコール５００　完全けん化型、平均重合度４００～６００、けん化度９６％以上」：表中「ＰＶＡ１」と表記、「ポリビニルアルコール３５００　部分けん化型、平均重合度＝３１００～３９００、けん化度＝８６～９０％」：表中「ＰＶＡ２」と表記）、可溶性澱粉（和光純薬社製「でんぷん、溶性」）、ブテンジオール－ビニルアルコール共重合樹脂（日本合成化学社製「ニチゴーＧポリマーＡＺＦ８０３５Ｗ」：表中「ＢＶＯＨ」と表記）、グリセリン（和光純薬社製「グリセリン」）、ポリエチレングリコール（和光純薬社製「ポリエチレングリコール２００、平均分子量＝１８０～２００」：表中「ＰＥＧ」と表記）を用いた。触媒としては次亜リン酸ナトリウム（和光純薬社製「ホスフィン酸ナトリウム一水和物」）を用いた。各実施例において、用いたポリカルボン酸系重合体とポリアルコールの種類、及び表面処理液におけるポリカルボン酸系重合体の固形分１００部に対するポリアルコール及び触媒の固形分配合量を表１に示す。 As a polycarboxylic acid type polymer, polyacrylic acid (made by Toagosei Co., Ltd. "Jurimer AC-10L, Mw = about 50,000": It describes with "PAA1" in the table, "Jurimer AC-10H, Mw = about 800, 000 ":" PAA2 "is used in the table). As a polyalcohol, polyvinyl alcohol (Wako Pure Chemical Industries, Ltd. "polyvinyl alcohol 500 complete saponification type, average polymerization degree 400 to 600, saponification degree 96% or more": "PVA1" in the table, "polyvinyl alcohol 3500 partially saponification type, Average degree of polymerization = 3100 to 3900, degree of saponification = 86 to 90% ":" PVA2 "in the table), soluble starch (" starch, soluble "manufactured by Wako Pure Chemical Industries, Ltd.), butenediol-vinyl alcohol copolymer resin ( "Nichigo G Polymer AZF 8035W" manufactured by Nippon Gohsei Chemical Co., Ltd .: "BVOH" in the table, glycerin ("Glycerin" manufactured by Wako Pure Chemical Industries, Ltd.), polyethylene glycol ("Polyethylene glycol 200 manufactured by Wako Pure Chemical Industries, Ltd., average molecular weight = 180 To 200 ":" PEG "in the table) was used. As a catalyst, sodium hypophosphite ("sodium phosphinate monohydrate" manufactured by Wako Pure Chemical Industries, Ltd.) was used. 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. .
（表面処理金属板の作製）
　金属板として、アルミニウム板（３１０４合金板　板厚：０．２８ｍｍ　板寸法：２００×３００ｍｍ）を使用した。まず、日本ペイント社製のアルカリ性クリーナー「サーフクリーナー４２０Ｎ－２」（商品名）の２％水溶液中（６０℃）に、６秒間浸漬してアルカリ洗浄を行った。アルカリ洗浄後、水洗してから、２％硫酸水溶液中（６０℃）に６秒間浸漬して酸洗浄を行い、水洗してから乾燥した。得られた金属板の両面に表面処理液を塗布し、２００℃に設定したオーブン内に６０秒間保持して乾燥させ、表面処理金属板を作製した。 (Preparation of surface-treated metal plate)
As a metal plate, an aluminum plate (3104 alloy plate thickness: 0.28 mm plate size: 200 × 300 mm) was used. First, 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.
（皮膜重量測定）
　得られた表面処理金属板における表面処理皮膜層中のポリカルボン酸系重合体、及びポリアルコールに由来する炭素（Ｃ）の単位面積当たりの重量（ｍｇ／ｍ２）は、蛍光Ｘ線分析装置を用いて測定した。測定に際して、まず、単位面積当たりの炭素の重量が既知で炭素の重量が異なるサンプルをそれぞれ複数測定し、この際の強度より、強度－重量の検量線を作製した。同様の条件で、各実施例における表面処理金属板についても測定し、得られた測定強度を検量線に基づき、炭素の重量に変換することにより、表面処理皮膜層の炭素換算の皮膜重量を測定した。測定結果を表１に示す。
　使用機器：理学電機製　ＺＳＸ１００ｅ
　測定条件：測定径　２０ｍｍ
　　　　　　Ｘ線出力　５０ｋＶ－７０ｍＡ (Measurement of film weight)
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. In the measurement, first, 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. Under the same conditions, 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.
Equipment used: Rigaku Denki ZSX100e
Measurement condition: Measuring diameter 20mm
X-ray output 50kV-70mA
（有機樹脂被覆表面処理金属板の作製）
　缶体用の有機樹脂被覆表面処理板は、以下の方法により作製した。得られた表面処理金属板を、予め板温度２５０℃に加熱しておき、表面処理金属板の両面に、有機樹脂被覆層としてポリエステル樹脂フィルムを、ラミネートロールを介して熱圧着した後、直ちに水冷することにより有機樹脂被覆表面処理金属板を得た。尚、ポリエステル樹脂フィルムとしては、１２μｍ厚のポリエチレンテレフタレート／ポリエチレンイソフタレート共重合樹脂フィルムを用いた。 (Preparation of organic resin coated surface treated metal plate)
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 μm thick polyethylene terephthalate / polyethylene isophthalate copolymer resin film was used.
（シームレス缶の作製）
　作製した缶体用の有機樹脂被覆表面処理金属板の両面に、パラフィンワックスを静電塗油した後、直径１５６ｍｍの円形に打ち抜き、浅絞りカップを作成した。次いで、この浅絞りカップを、再絞り－しごき加工及びドーミング成形を行い、開口端縁部のトリミング加工を行い、２０１℃で７５秒間、次いで２１０℃で８０秒間熱処理を施し、開口端をネッキング加工、フランジング加工を行い、缶胴２１１径でネック部２０６径の容量５００ｍｌのシームレス缶を作製した。シームレス缶の諸特性は以下の通りであった。
　　缶体径：６６ｍｍ
　　缶体高さ：１６８ｍｍ
　　元板厚に対する缶側壁部の平均板厚減少率：６０％ (Manufacture of seamless cans)
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%
（比較例１）
　表１に示すように、ポリアルコールを含有しない表面処理液を使用した以外は、実施例１と同様にしてシームレス缶を作製した。 (Comparative 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.
（比較例２）
　表１に示すように、ポリカルボン酸系重合体を含有しない表面処理液を使用した以外は、実施例１と同様にしてシームレス缶を作製した。 (Comparative example 2)
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 polycarboxylic acid polymer was used.
（比較例３）
　金属板として、リン酸クロメート処理（化成型処理）を施した表面処理アルミニウム板（３１０４合金板　板厚：０．２８ｍｍ　板寸法：２００×３００ｍｍ　表面処理皮膜中のクロム含有量：２０ｍｇ／ｍ２）を用いて、前記「有機樹脂被覆表面処理金属板の作製」の項に記載した通りに、有機樹脂被覆表面処理金属板を作製し、前記「シームレス缶の作製」の項に記載した通りにシームレス缶を作製した。 (Comparative example 3)
Surface-treated aluminum plate (3104 alloy plate thickness: 0.28 mm plate size: 200 × 300 mm, chromium content in surface-treated film: 20 mg / m 2 ) treated with phosphate chromate treatment (chemical formation treatment) as metal plate An organic resin-coated surface-treated metal plate is produced as described in the above-mentioned "Production of an organic resin-coated surface-treated metal plate" using the above, and seamless as described in the above-mentioned "Production of a seamless can". A can was made.
（シームレス缶の評価方法）
　実施例１～１８及び比較例１～３により得られたシームレス缶について、下記の評価を行い、結果を表１に示した。 (Evaluation method of seamless can)
The following evaluations were performed on the seamless cans obtained in Examples 1 to 18 and Comparative Examples 1 to 3, and the results are shown in Table 1.
（製缶適性評価）
　熱処理時フランジ部剥離性評価は、前記「シームレス缶の作製」の項に記載した通りに、缶体をトリミング加工まで行った後、オーブンを用いて、２０１℃で７５秒間、次いで２１０℃で８０秒間の熱処理を行った後、缶体の開口端（フランジ形成部）を顕微鏡で観察し、缶体の開口端より有機樹脂被覆層の剥離度合いで評価した。評価結果を表１に示す。
　　◎：剥離した部分の最大長さが０．１ｍｍ未満
　　○：剥離した部分の最大長さが０．１ｍｍ以上０．２ｍｍ未満
　　△：剥離した部分の最大長さが０．２ｍｍ以上０．３ｍｍ未満
　　×：剥離した部分の最大長さが０．３ｍｍ以上 (Can making ability evaluation)
During heat treatment, 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 Δ: 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
（耐熱水密着性評価）
　耐熱水密着性評価は、前記「シームレス缶の作製」の項に記載した通りにシームレス缶を作製した後、内面側ネック部の最小径部に内面から缶周に沿ってカッターナイフで金属面まで達するキズを付与した状態で、１００℃の熱水に１０分間浸漬後のネック部の有機樹脂被覆層の剥離状態を観察して評価した。評価結果を表１に示す。
　　◎：全周に渡って剥離が認められない
　　○：一部剥離が認められるが、その剥離部分の長さが缶全周長さの５％未満
　　△：一部剥離が認められるが、その剥離部分の長さが缶全周長さの５％以上１０％
　　　未満
　　×：剥離部分の長さが全周方向の１０％以上 (Heat water adhesion evaluation)
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 | attainment flaw, the peeling state of the organic resin coating layer of the neck part after 10-minute immersion in a 100 degreeC hot water was observed and evaluated. The evaluation results are shown in Table 1.
:: Peeling is not observed all around ○: Some peeling is observed, but the length of the peeling portion is less than 5% of the entire circumferential length of the can Δ: Partial peeling is observed, but peeling Part length is 5% or more 10% of the entire circumference of the can
Less than ×: Peeling part length is 10% or more of all circumferential
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　本発明の有機樹脂被覆表面処理金属板は、それを用いてシームレス缶等を成形した場合に、殺菌工程のような高温・湿潤環境下に賦された場合にも、有機樹脂被覆層の剥離を抑制できる優れた耐熱水密着性を発現可能であるため、缶体及び缶蓋に好適に使用することができ、しかも過酷な成形加工に賦された場合にも優れた耐熱水密着性を有することから、特に絞りしごき缶等のシームレス缶に好適に利用することができる。 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.
１　有機樹脂被覆表面処理金属板、２　金属板、３　表面処理皮膜層、４　有機樹脂被覆層。 1 Organic resin coated surface treated metal plate, 2 metal plate, 3 surface treated film layer, 4 organic resin coated layer.

Claims (9)

  1. 　金属板の少なくとも片面に、表面処理皮膜層及び該表面処理皮膜層上に有機樹脂被覆層が形成されて成る有機樹脂被覆表面処理金属板であって、該表面処理皮膜層が主成分としてポリカルボン酸系重合体及び該ポリカルボン酸系重合体の架橋成分としてポリアルコールを含有することを特徴とする有機樹脂被覆表面処理金属板。 A surface-treated film layer and an organic resin-coated surface-treated metal plate having an organic resin coating layer formed on the surface-treated film layer on at least one side of a metal plate, wherein the surface-treated film layer is polycarboxylic acid as a main component. An organic resin-coated surface-treated metal sheet comprising an acid polymer and a polyalcohol as a crosslinking component of the polycarboxylic acid polymer.
  2. 　前記表面処理皮膜層における前記ポリアルコールの含有量が、前記ポリカルボン酸系重合体の固形分１００質量部に対して、２０質量部以下であることを特徴とする請求項１記載の有機樹脂被覆表面処理金属板。 The organic resin coating according to claim 1, wherein 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. Surface-treated metal plate.
  3. 　前記ポリカルボン酸系重合体が、ポリアクリル酸であることを特徴とする請求項１又は請求項２記載の有機樹脂被覆表面処理金属板。 The organic resin coated surface-treated metal sheet according to claim 1 or 2, wherein the polycarboxylic acid-based polymer is polyacrylic acid.
  4. 　前記ポリアルコールが、ポリビニルアルコール、または澱粉類であることを特徴とする請求項１～３の何れかに記載の有機樹脂被覆表面処理金属板。 The organic resin-coated surface-treated metal sheet according to any one of claims 1 to 3, wherein the polyalcohol is polyvinyl alcohol or starch.
  5. 　前記表面処理皮膜層の単位面積当たりの皮膜重量が、炭素原子換算で２～１００ｍｇ／ｍ２であることを特徴とする請求項１～４の何れかに記載の有機樹脂被覆表面処理金属板。 The organic resin-coated surface-treated metal plate according to any one of claims 1 to 4, wherein a film weight per unit area of the surface treatment film layer is 2 to 100 mg / m 2 in terms of carbon atoms.
  6. 　前記有機樹脂被覆層が、ポリエステル樹脂フィルムであることを特徴とする請求項１～５の何れかに記載の有機樹脂被覆表面処理金属板。 The organic resin-coated surface-treated metal plate according to any one of claims 1 to 5, wherein the organic resin-coated layer is a polyester resin film.
  7. 　前記金属板が、アルミニウム板であることを特徴とする請求項１～６の何れかに記載の有機樹脂被覆表面処理金属板。 The organic resin-coated surface-treated metal plate according to any one of claims 1 to 6, wherein the metal plate is an aluminum plate.
  8. 　請求項１～７の何れかに記載の有機樹脂被覆表面処理金属板から成ることを特徴とする缶体。 A can comprising the organic resin-coated surface-treated metal plate according to any one of claims 1 to 7.
  9. 　請求項１～７の何れかに記載の有機樹脂被覆表面処理金属板から成ることを特徴とする缶蓋。 A can lid comprising the organic resin-coated surface-treated metal plate according to any one of claims 1 to 7.
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WO2016195081A1 (en) * 2015-06-03 2016-12-08 日本ペイント・サーフケミカルズ株式会社 Hydrophilization treatment agent, hydrophilic film formation method, and hydrophilic film
WO2017138230A1 (en) * 2016-02-08 2017-08-17 東洋鋼鈑株式会社 Organic resin-coated steel sheet, method for producing same, and can and can lid each using said organic resin-coated steel sheet

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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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