JP6650286B2 - Organic resin-coated steel sheet, method for producing the same, and can and can lid using this organic resin-coated steel sheet - Google Patents
Organic resin-coated steel sheet, method for producing the same, and can and can lid using this organic resin-coated steel sheet Download PDFInfo
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- JP6650286B2 JP6650286B2 JP2016022052A JP2016022052A JP6650286B2 JP 6650286 B2 JP6650286 B2 JP 6650286B2 JP 2016022052 A JP2016022052 A JP 2016022052A JP 2016022052 A JP2016022052 A JP 2016022052A JP 6650286 B2 JP6650286 B2 JP 6650286B2
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- Prior art keywords
- organic resin
- resin
- layer
- steel sheet
- adhesive layer
- Prior art date
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- 239000011347 resin Substances 0.000 title claims description 133
- 229910000831 Steel Inorganic materials 0.000 title claims description 38
- 239000010959 steel Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000010410 layer Substances 0.000 claims description 67
- 239000012790 adhesive layer Substances 0.000 claims description 64
- 229910052751 metal Inorganic materials 0.000 claims description 53
- 239000002184 metal Substances 0.000 claims description 53
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- 239000004645 polyester resin Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 24
- -1 phosphorus compound Chemical class 0.000 claims description 23
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- 239000011651 chromium Substances 0.000 claims description 10
- 150000002927 oxygen compounds Chemical class 0.000 claims description 10
- 229930185605 Bisphenol Natural products 0.000 claims description 9
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
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- 239000002585 base Substances 0.000 description 23
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- 239000000654 additive Substances 0.000 description 17
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- 230000007797 corrosion Effects 0.000 description 10
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- 239000005029 tin-free steel Substances 0.000 description 5
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 description 1
- UPSIAUXDGWYOFJ-UHFFFAOYSA-N formaldehyde;furan Chemical compound O=C.C=1C=COC=1 UPSIAUXDGWYOFJ-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B32B15/04—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
- B32B15/098—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 condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- 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
- B65D43/00—Lids or covers for rigid or semi-rigid containers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、接着剤層(プライマー)を介して有機樹脂層を基材に被覆した有機樹脂被覆鋼板及びその製造方法、並びにこの有機樹脂被覆鋼板を用いた缶あるいは缶蓋に関する。 The present invention relates to an organic resin-coated steel sheet having an organic resin layer coated on a substrate via an adhesive layer (primer), a method for producing the same, and a can or can lid using the organic resin-coated steel sheet.
飲食品、医薬品などを長期保存するのに好適な容器として、缶胴・蓋からなるいわゆる2ピースタイプの缶(以下、2ピース缶とも称する)や、缶底・缶胴・蓋からなる3ピースタイプの缶(以下、3ピース缶とも称する)などが従来から広く用いられている。
典型的にこれらの缶では、基材表面に熱可塑性樹脂が被覆されたラミネート材が用いられており、耐食性が要求される用途においては熱可塑性樹脂と基材との間に更に接着剤層を介在させている。
As containers suitable for long-term storage of foods, drinks, pharmaceuticals, etc., so-called two-piece cans (hereinafter also referred to as two-piece cans) having a can body and a lid, and three-piece cans having a can bottom, a can body, and a lid Conventionally, cans of the type (hereinafter also referred to as three-piece cans) have been widely used.
Typically, these cans use a laminate material in which the surface of the substrate is coated with a thermoplastic resin, and in applications where corrosion resistance is required, an additional adhesive layer is provided between the thermoplastic resin and the substrate. It is interposed.
一方、近年においては、環境負荷を低減する物質の導入や、人体に影響のある物質を排除する動きが活発化している。
例えばラミネート缶に用いられる接着剤についても、いわゆる内分泌(エンドクリン)撹乱物質を排除する動きから、BPA(ビスフェノールA)を含有しない材料の開発が加速している(例えば特許文献1参照)。
また、BPAフリーであると共に、加工性及び耐食性を向上可能な接着剤、およびこの接着剤を用いた熱可塑性樹脂ラミネート金属板なども提案されている(例えば特許文献2参照)。
On the other hand, in recent years, there has been an increasing movement to introduce substances that reduce environmental load and to eliminate substances that have an effect on the human body.
For example, as for an adhesive used for a laminate can, development of a material containing no BPA (bisphenol A) has been accelerated due to the movement to eliminate so-called endocrine disrupting substances (for example, see Patent Document 1).
Further, an adhesive which is BPA-free and which can improve processability and corrosion resistance, and a thermoplastic resin-laminated metal plate using this adhesive have been proposed (for example, see Patent Document 2).
特許文献1や特許文献2のごとくBPAフリーとすることは社会的な要請の上で必須であるが、その場合においても缶の性能が低下するのは避けねばならない。
この点において熱可塑性樹脂などの有機樹脂が被覆された鋼板は、家電用、車両用、建材用あるいは食品や飲料などを保存する容器用として様々な用途に適用されるが、特に食品を保存する用途においてはレトルト密着性も要求される。
たしかに上述した特許文献によれば加工性や耐食性がある程度は向上するものの、レトルト密着性を含めると未だに改善の余地があると言える。すなわち、これらの特許文献に記載された接着剤では有機樹脂と基材との密着性が十分でなく、特に缶に加工を行った際の缶側壁部の密着性が十分でないという課題を有していることが判明した。
As described in Patent Literature 1 and Patent Literature 2, it is essential to be BPA-free in view of social demands, but even in such a case, it is necessary to avoid a decrease in the performance of the can.
In this regard, a steel sheet coated with an organic resin such as a thermoplastic resin is applied to various uses as a container for storing home appliances, vehicles, building materials or foods and beverages, and particularly for storing foods. In applications, retort adhesion is also required.
Although the workability and the corrosion resistance are improved to some extent according to the above-mentioned patent documents, it can be said that there is still room for improvement when the retort adhesion is included. That is, the adhesives described in these patent documents have a problem that the adhesion between the organic resin and the base material is not sufficient, and particularly the adhesion of the can side wall portion when the can is processed is not sufficient. Turned out to be.
本発明は、かような課題を解決することを鑑みてなされ、BPAを用いずに有機樹脂との高い加工密着性とレトルト密着性を同時に実現したプライマーを含む有機樹脂被覆鋼板及び缶や缶蓋、並びにこれらの製造方法を提供することを目的とする。 The present invention has been made in view of solving such problems, and has an organic resin-coated steel sheet, a can, and a can lid containing a primer that simultaneously achieves high processing adhesion with an organic resin and retort adhesion without using BPA. , And a method for producing these.
上記課題を解決するため、本発明の一実施形態にかかる有機樹脂被覆鋼板は、(1)基材と、前記基材に被覆される有機樹脂層と、前記基材と前記有機樹脂層との間に介在するとともに、ビスフェノール類に由来する成分をそれぞれ含まないポリエステル樹脂とレゾール型フェノール樹脂が、前記ポリエステル樹脂/前記レゾール型フェノール樹脂の比として5.7〜19の割合で含有されてなる接着剤層と、を含み、前記接着剤層は、前記ポリエステル樹脂と前記フェノール樹脂との合計の重量に対する重量比が、アクリル樹脂/(ポリエステル樹脂とフェノール樹脂との合計)の比として、0.015〜0.06の重量比であるアクリル樹脂を含むことを特徴とする。
さらに、前記した(1)の特徴を備えた有機樹脂被覆鋼板においては、(2)前記ポリエステル樹脂の数平均分子量が8000〜30000であってガラス転移温度が50℃以上85℃未満であり、かつ前記ポリエステル樹脂の酸価が7〜15mgKOH/gであることが好ましい。
In order to solve the above problems, an organic resin-coated steel sheet according to one embodiment of the present invention includes (1) a base material, an organic resin layer coated on the base material, and the base material and the organic resin layer. Bonding in which a polyester resin and a resole-type phenol resin that do not contain components derived from bisphenols and that are interposed therebetween are contained in a ratio of 5.7 to 19 as a ratio of the polyester resin / the resole-type phenol resin. adhesive layer and, only including, the adhesive layer, the weight ratio to the total weight of the polyester resin and the phenol resin is, as the ratio of the acrylic resin / (the total of the polyester resin and phenol resin), 0. An acrylic resin having a weight ratio of 015 to 0.06 is included .
Further, in the organic resin-coated steel sheet having the above-mentioned feature (1), (2) the polyester resin has a number average molecular weight of 8,000 to 30,000, a glass transition temperature of 50 ° C. or more and less than 85 ° C., and The polyester resin preferably has an acid value of 7 to 15 mgKOH / g.
また、前記した(1)又は(2)の特徴を備えた有機樹脂被覆鋼板においては、(3)前記接着剤層と前記有機樹脂層との厚みの比(接着剤層の厚み/有機樹脂層の厚み)が、3%〜50%であることが好ましい。
また、前記した(1)〜(3)のいずれかの特徴を備えた有機樹脂被覆鋼板においては、(4)前記有機樹脂層がポリエステル樹脂であることが好ましい。
Further, in the organic resin-coated steel sheet having the features of the above (1) or (2) , ( 3 ) the ratio of the thickness of the adhesive layer to the thickness of the organic resin layer (thickness of the adhesive layer / organic resin layer) Is preferably 3% to 50%.
In addition, in the organic resin-coated steel sheet having any one of the features (1) to ( 3 ), ( 4 ) the organic resin layer is preferably a polyester resin.
また、前記した(1)〜(4)のいずれかの特徴を備えた有機樹脂被覆鋼板においては、
(5)前記基材のうち少なくとも前記接着剤層と接する側には表面処理層が形成されてなり、前記表面処理層は、クロム、ジルコニウム、アルミニウム及びチタンのいずれかを含む酸素化合物から成ることが好ましい。
また、前記した(5)の特徴を備えた有機樹脂被覆鋼板においては、(6)前記表面処理層は、更にリン化合物を含むことが好ましい。
なお、本発明の缶あるいは缶蓋は、上記した(1)〜(6)のいずれかの特徴を具備した有機樹脂被覆鋼板を用いて形成されてなる。
Further, in the organic resin-coated steel sheet having any one of the features (1) to ( 4 ),
( 5 ) A surface treatment layer is formed on at least a side of the substrate that contacts the adhesive layer, and the surface treatment layer is made of an oxygen compound containing any of chromium, zirconium, aluminum, and titanium. Is preferred.
Further, in the organic resin-coated steel sheet having the feature of ( 5 ), it is preferable that ( 6 ) the surface treatment layer further contains a phosphorus compound.
The can or can lid of the present invention is formed using an organic resin-coated steel sheet having any one of the features (1) to ( 7 ) described above.
また、上記課題を解決するため、本発明の一実施形態にかかる有機樹脂被覆鋼板の製造方法は、ビスフェノール類に由来する成分をそれぞれ含まないポリエステル樹脂とレゾール型フェノール樹脂が、前記ポリエステル樹脂/前記レゾール型フェノール樹脂の比として5.7〜19の割合で含有されてなる接着剤層を、基材または有機樹脂層の少なくとも一方の表面に形成する工程と、前記接着剤層が介在するように前記基材上に前記有機樹脂層を形成する工程と、前記有機樹脂層が形成された基材に対し、180℃〜280℃の温度範囲で前加熱処理を行う工程と、前記前加熱処理の後で、前記有機樹脂層が形成された基材に対して160℃〜240℃の温度範囲内で後加熱処理を行う工程と、を含むことを特徴とする。 Further, in order to solve the above problems, the method for producing an organic resin-coated steel sheet according to one embodiment of the present invention is characterized in that the polyester resin and the resole-type phenol resin each containing no component derived from bisphenols are the polyester resin / Forming an adhesive layer containing the resole type phenol resin at a ratio of 5.7 to 19 on at least one surface of the base material or the organic resin layer; A step of forming the organic resin layer on the base material, a step of performing a pre-heat treatment on the base material on which the organic resin layer is formed, in a temperature range of 180 ° C to 280 ° C, And performing a post-heating treatment within a temperature range of 160 ° C. to 240 ° C. on the substrate on which the organic resin layer is formed.
本発明によれば、BPAを用いずに、缶に加工を行った場合でも缶側壁部で有機樹脂の剥離が生じず、かつ耐食性に優れた缶や缶蓋を実現することができる。これにより、有機樹脂と金属板との高い加工密着性に加えてレトルト密着性を同時に実現することも可能となる。 ADVANTAGE OF THE INVENTION According to this invention, even if it processes to a can without using BPA, the peeling of an organic resin does not generate | occur | produce in a can side wall part, and also can and the can and the can lid excellent in corrosion resistance can be implement | achieved. This makes it possible to simultaneously achieve retort adhesion in addition to high processing adhesion between the organic resin and the metal plate.
≪第1実施形態≫
以下、本発明を実施するための実施形態について説明する。
図1に示すとおり、本実施形態に係る有機樹脂被覆鋼板10は、基材1、有機樹脂層4、及びこの基材1と有機樹脂層4の間に介在する接着剤層3を含み、この接着剤層3が、ビスフェノール類に由来する成分をそれぞれ含まないポリエステル樹脂とレゾール型フェノール樹脂が特定比の割合(ポリエステル樹脂/レゾール型フェノール樹脂の比として、5.7〜19)で含有されていることを特徴としている。
以下、本実施形態に係る有機樹脂被覆鋼板10につき個々の構成要素を詳述していく。
<< 1st Embodiment >>
Hereinafter, embodiments for carrying out the present invention will be described.
As shown in FIG. 1, the organic resin-coated steel sheet 10 according to the present embodiment includes a base material 1, an organic resin layer 4, and an adhesive layer 3 interposed between the base material 1 and the organic resin layer 4. The adhesive layer 3 contains a polyester resin and a resole-type phenol resin each containing no component derived from a bisphenol at a specific ratio (5.7 to 19 as a ratio of polyester resin / resol-type phenol resin). It is characterized by having.
Hereinafter, individual components of the organic resin-coated steel sheet 10 according to the present embodiment will be described in detail.
<基材>
有機樹脂被覆鋼板10のベース部材である基材1としては、鉄や各種の合金などの金属板が用いられる。
より具体的に基材となる金属板は、0.1mm〜0.5mm程度の鉄や各種の合金などの鋼板が用いられる。また、本実施形態では例えばアルミニウムを基材とした金属板も好適である。
<Substrate>
As the base material 1 which is a base member of the organic resin-coated steel sheet 10, a metal plate such as iron or various alloys is used.
More specifically, a steel plate of about 0.1 mm to 0.5 mm such as iron or various alloys is used as the metal plate serving as the base material. In the present embodiment, for example, a metal plate made of aluminum as a base material is also suitable.
また、本実施形態に好適な鋼板としては、例えば一般的に缶用に用いられる炭素量0.01〜0.15質量%の低炭素アルミキルド鋼を用いることもできる。更にはニオブやチタンを添加した炭素量0.01質量%未満の非時効性極低炭素アルミキルド鋼も適用可能である。なお、これらのアルミキルド鋼の熱間圧延板を電解酸洗等で酸洗して表面のスケールを除去した後、冷間圧延し、次いで、電解洗浄、焼鈍、圧延など施したものを冷延鋼板として用いてもよい。 Further, as a steel sheet suitable for the present embodiment, for example, a low carbon aluminum killed steel having a carbon amount of 0.01 to 0.15% by mass generally used for cans can also be used. Further, a non-ageing ultra-low carbon aluminum killed steel having a carbon content of less than 0.01% by mass to which niobium or titanium is added is also applicable. The hot-rolled aluminum-killed steel sheet was pickled by electrolytic pickling or the like to remove the scale on the surface, then cold-rolled, and then subjected to electrolytic cleaning, annealing, rolling, etc. to obtain a cold-rolled steel sheet. May be used.
なお、上述した金属板には、各種の表面処理による表面処理層2が施されていてもよい。すなわち、本実施形態に適用可能な鋼板には、例えば、ぶりき、TFS(ティンフリースチール)、ニッケルめっき金属板などの各種の表面処理がなされたものも含まれる。
かような表面処理層2は、基材1のうち少なくとも接着剤層3と接する側に形成されていればよく、基材1の両面側に形成されていてもよい。
In addition, the surface treatment layer 2 by various surface treatments may be given to the above-mentioned metal plate. That is, the steel plate applicable to the present embodiment includes, for example, a steel plate subjected to various surface treatments such as tinplate, TFS (tin-free steel), and a nickel-plated metal plate.
Such a surface treatment layer 2 may be formed on at least the side of the substrate 1 that is in contact with the adhesive layer 3, and may be formed on both sides of the substrate 1.
また、この表面処理層2としては、ジルコニウム、アルミニウム、チタンのいずれかの酸素化合物を含んでいることが好ましい。これらの酸素化合物は、接着剤層と金属板との接着力を向上させる効果を奏する点で特に有効である。なお、ジルコニウム酸素化合物であれば、Zr量5〜150mg/m2、アルミニウム酸素化合物であれば、Al量3〜50mg/m2、チタン酸素化合物であれば、Ti量10mg〜100mg/m2であることが好ましい。また、表面処理層2には、これらの酸素化合物のうち単一の酸素化合物をだけでなく、複数の酸素化合物が存在してもよい。 The surface treatment layer 2 preferably contains an oxygen compound of zirconium, aluminum or titanium. These oxygen compounds are particularly effective in that they exhibit an effect of improving the adhesive strength between the adhesive layer and the metal plate. The zirconium oxygen compound has a Zr content of 5 to 150 mg / m 2 , the aluminum oxygen compound has an Al content of 3 to 50 mg / m 2 , and the titanium oxygen compound has a Ti content of 10 mg to 100 mg / m 2 . Preferably, there is. The surface treatment layer 2 may include not only a single oxygen compound among these oxygen compounds but also a plurality of oxygen compounds.
なお、表面処理層2には、リン化合物が更に含まれていてもよい。本実施形態の「リン化合物」には、リン酸系化合物が含まれるが、より具体的にはリン酸もしくはその塩、縮合リン酸もしくはその塩、リン酸ジルコニウム、リン酸チタンなどが挙げられる。また、塩としてはアンモニウム塩、ナトリウム塩、カリウム塩などのアルカリ金属塩を挙げることができる。また密着性を向上させる目的で有機ケイ素化合物を含有させてもよい。
かようなリン化合物を表面処理層2が含むことにより、接着剤層と金属板との接着力がさらに向上する効果を奏する点で有効である。なお、このリン化合物におけるリンの量としては、P量=0.1〜20mg/m2であることが好ましい。
The surface treatment layer 2 may further contain a phosphorus compound. The “phosphorus compound” of the present embodiment includes a phosphoric acid compound, and more specifically, phosphoric acid or a salt thereof, condensed phosphoric acid or a salt thereof, zirconium phosphate, titanium phosphate and the like. Examples of the salt include an alkali metal salt such as an ammonium salt, a sodium salt, and a potassium salt. Further, an organosilicon compound may be contained for the purpose of improving adhesion.
The inclusion of such a phosphorus compound in the surface treatment layer 2 is effective in that the effect of further improving the adhesive strength between the adhesive layer and the metal plate is exhibited. In addition, it is preferable that the amount of phosphorus in this phosphorus compound is P amount = 0.1 to 20 mg / m 2 .
<有機樹脂層>
本実施形態の有機樹脂層4は、後述する接着剤層3を介して基材1を被覆している。なお、有機樹脂層4は、上述した基材1の片面または両面を被覆していてもよい。
かような有機樹脂層4としては、例えば熱可塑性樹脂が好適に用いられる。本実施形態で使用可能な熱可塑性樹脂の例としては、種々の公知の樹脂が適用可能であるが、例えばポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリルエステル共重合体、アイオノマー等のオレフィン系樹脂フィルム、ポリエチレンテレフタレートやポリブチレンテレフタレート等のポリエステルフィルム、ポリ塩化ビニルフィルムやポリ塩化ビニリデンフィルム等の未延伸フィルム又は二軸延伸したフィルム、又はナイロン6、ナイロン6,6、ナイロン11、ナイロン12等のポリアミドフィルムなどを用いることができる。
その中でも、ポリエチレンテレフタレートのフィルムが好ましく、この場合において共重合される酸成分としてはイソフタル酸が好適である。しかしながら酸成分はイソフタル酸に限られず、テレフタル酸、オルソフタル酸、ナフタレンジカルボン酸、コハク酸、グルタル酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジオン酸などがあげられる。
<Organic resin layer>
The organic resin layer 4 of the present embodiment covers the substrate 1 via an adhesive layer 3 described later. Note that the organic resin layer 4 may cover one or both surfaces of the base material 1 described above.
As such an organic resin layer 4, for example, a thermoplastic resin is suitably used. As examples of the thermoplastic resin that can be used in the present embodiment, various known resins can be applied. For example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acryl Ester copolymers, olefin-based resin films such as ionomers, polyester films such as polyethylene terephthalate and polybutylene terephthalate, unstretched films such as polyvinyl chloride films and polyvinylidene chloride films or biaxially stretched films, or nylon 6, nylon For example, polyamide films such as 6, 6, nylon 11, and nylon 12 can be used.
Among them, a polyethylene terephthalate film is preferable, and isophthalic acid is preferable as the acid component to be copolymerized in this case. However, the acid component is not limited to isophthalic acid, but includes terephthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecandioic acid, and the like.
また、有機樹脂層4としては、無延伸フィルムでも適用可能ではあるが、二軸延伸フィルムを用いることが好ましい。また、有機樹脂層(熱可塑性樹脂)4のガラス転移温度(Tg)は、50から80℃であることが好ましい。
また、これらの熱可塑性樹脂(有機樹脂層4)は、1種の単層樹脂層として基材1に接着剤層3を介して被覆されてもよいし、異なる有機材料がブレンドされて単層樹脂層として基材1に接着層を介して被覆されてもよいし、2種以上の複層樹脂層として基材1に接着剤層3を介して被覆されてもよい。
なお複数層の熱可塑性樹脂を用いる場合には、例えば基材1側の下層としては密着性に優れた組成のポリエステル樹脂を選択する一方で、上層には耐食性やフレーバー成分の非吸着性に優れた組成のポリエステル樹脂を選択してもよい。
Further, as the organic resin layer 4, although a non-stretched film is applicable, it is preferable to use a biaxially stretched film. The glass transition temperature (Tg) of the organic resin layer (thermoplastic resin) 4 is preferably 50 to 80 ° C.
Further, these thermoplastic resins (organic resin layer 4) may be coated on the base material 1 via the adhesive layer 3 as one kind of single-layer resin layer, or different organic materials may be blended to form a single-layer resin layer. The substrate 1 may be coated as a resin layer via an adhesive layer, or the substrate 1 may be coated as an at least two kinds of multilayer resin layers via an adhesive layer 3.
When a plurality of thermoplastic resins are used, for example, a polyester resin having an excellent adhesion is selected as the lower layer on the base material 1 side, while the upper layer is excellent in corrosion resistance and non-adsorption of flavor components. May be selected.
なお有機樹脂層4の厚み(膜厚)としては、5〜40μm、より好ましくは10〜20μmであることが好ましい。このとき、接着剤層3と有機樹脂層4との厚み比(接着剤層3の厚み/有機樹脂層4の厚み)は、絞り加工、しごき加工、ストレッチ加工など大きな成形加工履歴を受けるシームレス缶(2ピース缶)用途においては14〜50%、さらに好ましくは14〜40%となっていることが望ましい。絞り缶の缶側壁部では加工により残留応力が生じることがあり、特に缶側壁部上部では有機樹脂層(熱可塑性樹脂)の収縮の残留応力が生じている。このため、上記厚み比が14%未満では、有機樹脂層(熱可塑性樹脂)の収縮を抑制できず、有機樹脂層(熱可塑性樹脂)との密着性が低下し、剥離が生じやすくなる。一方で上記厚み比が50%を超えると、有機樹脂層(熱可塑性樹脂)との密着性、耐食性はそれ以上改善されず、コスト的に不利となるからである。
一方で、成形加工履歴の小さい溶接缶(3ピース缶)用途又は蓋用途では接着剤層3を薄くしてもよく、かような場合においては接着剤層3と有機樹脂層4との厚み比(接着剤層3の厚み/有機樹脂層4の厚み)は3〜50%、より好ましくは8〜20%とすることができる。
The thickness (film thickness) of the organic resin layer 4 is preferably 5 to 40 μm, more preferably 10 to 20 μm. At this time, the thickness ratio of the adhesive layer 3 to the organic resin layer 4 (thickness of the adhesive layer 3 / thickness of the organic resin layer 4) is determined by a seamless can that has undergone a large forming history such as drawing, ironing, and stretching. In a (two-piece can) application, it is desirable that the content be 14 to 50%, more preferably 14 to 40%. Processing may cause residual stress in the can side wall portion of the drawn can, and in particular, a residual stress due to shrinkage of the organic resin layer (thermoplastic resin) occurs in the upper portion of the can side wall portion. For this reason, when the thickness ratio is less than 14%, the shrinkage of the organic resin layer (thermoplastic resin) cannot be suppressed, the adhesion to the organic resin layer (thermoplastic resin) decreases, and peeling tends to occur. On the other hand, if the thickness ratio exceeds 50%, the adhesion to the organic resin layer (thermoplastic resin) and the corrosion resistance are not further improved, and this is disadvantageous in cost.
On the other hand, the adhesive layer 3 may be thinner in a welding can (three-piece can) application or a lid application having a small forming history, and in such a case, the thickness ratio of the adhesive layer 3 to the organic resin layer 4 may be reduced. (Thickness of adhesive layer 3 / thickness of organic resin layer 4) can be 3 to 50%, more preferably 8 to 20%.
<接着剤層>
接着剤層3は、基材1と有機樹脂層4との間に介在する。例えば上記したシームレス缶用途では、この接着剤層3の厚みは、2〜10μmの範囲内に、より好ましくは2〜4μmであることが望ましい。また、上記した溶接缶用途又は蓋用途では、接着剤層3の厚みは0.5〜6μm、より好ましくは1〜3μmとすることができる。
本実施形態に用いられる接着剤層3は、ポリエステル樹脂とレゾール型フェノール樹脂の割合が、樹脂粘度、加工性及び硬化性のバランスの観点から、ポリエステル樹脂/レゾール型フェノール樹脂の比として、5.7〜19であることが好ましい。更に、このポリエステル樹脂/レゾール型フェノール樹脂の比として、より好ましくは10〜17、さらに好ましくは14〜16である。
上記範囲よりレゾール型フェノールが少ない場合には接着剤の硬化が不十分となり、結果として、密着性や耐食性が低下しやすい。
<Adhesive layer>
The adhesive layer 3 is interposed between the base material 1 and the organic resin layer 4. For example, in the above-mentioned seamless can application, it is desirable that the thickness of the adhesive layer 3 is in the range of 2 to 10 μm, more preferably 2 to 4 μm. Further, in the above-mentioned welding can use or lid use, the thickness of the adhesive layer 3 can be 0.5 to 6 μm, more preferably 1 to 3 μm.
In the adhesive layer 3 used in the present embodiment, the ratio of the polyester resin to the resol-type phenolic resin is set at a ratio of polyester resin / resol-type phenolic resin from the viewpoint of the balance of resin viscosity, processability, and curability. It is preferably 7 to 19. Further, the ratio of the polyester resin to the resol-type phenol resin is more preferably 10 to 17, and further preferably 14 to 16.
When the amount of the resol-type phenol is less than the above range, the curing of the adhesive becomes insufficient, and as a result, the adhesion and the corrosion resistance are apt to decrease.
一方で上記範囲よりレゾール型フェノールが多い場合には、接着剤層3がもろくなり、有機樹脂被覆金属板を加工する際に、接着剤層3と基材1との間、あるいは接着剤層3内で剥離が生じ、密着性や耐食性が低下しやすい。また、接着剤を熱可塑性樹脂上に塗布・乾燥後に巻き取った際に、接着剤を塗布していない面に接着剤が転写される可能性がある。
なおフェノール樹脂がレゾール型以外のフェノール樹脂の場合では、上述した十分な密着性を得ることは難しい。
On the other hand, when the resol-type phenol is more than the above range, the adhesive layer 3 becomes brittle, and when the organic resin-coated metal plate is processed, the gap between the adhesive layer 3 and the base material 1 or the adhesive layer 3 Separation occurs in the inside, and adhesion and corrosion resistance are likely to decrease. Further, when the adhesive is applied onto the thermoplastic resin, dried, and then wound up, the adhesive may be transferred to a surface on which the adhesive is not applied.
When the phenol resin is a phenol resin other than the resol type, it is difficult to obtain the above-mentioned sufficient adhesiveness.
また、接着剤層3に含まれるレゾール型フェノール樹脂は、ビスフェノール類に由来する構成成分を含まないことが好ましい。かような接着剤層3に含まれるレゾール型フェノール樹脂としては、3官能以上のフェノール化合物を50質量%以上含有するフェノール化合物とホルムアルデヒドの共重合体であることが好ましい。フェノール化合物としては、フェノール、m−クレゾール、m−エチルフェノール、m−メトキシフェノール、キシレノールなどがあげられる。また、o−クレゾール、p−クレゾール、p−エチルフェノールなどのフェノール化合物を添加してよい。 The resol-type phenol resin contained in the adhesive layer 3 preferably does not contain a component derived from bisphenols. The resol-type phenol resin contained in the adhesive layer 3 is preferably a copolymer of a phenol compound containing at least 50% by mass of a phenol compound having three or more functional groups and formaldehyde. Examples of the phenol compound include phenol, m-cresol, m-ethylphenol, m-methoxyphenol, xylenol and the like. Further, a phenol compound such as o-cresol, p-cresol, and p-ethylphenol may be added.
本実施形態の接着剤層3に含有されるポリエステル樹脂は、酸成分として、特に制限されるものではないが、例えば、ジカルボン酸成分としてテレフタル酸、イソフタル酸、オルソフタル酸、ナフタレンジカルボン酸、コハク酸、グルタル酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジオン酸など、その他のポリカルボン酸成分としてトリメリット酸などがあげられる。また、グリコール成分として、特に限定されるものではないが、例えばエチレングリコール、プロピレングリコールなど、その他のポリオール成分としてはトリメチロールプロパン、ペンタエリスリトールなどがあげられる。 The polyester resin contained in the adhesive layer 3 of the present embodiment is not particularly limited as an acid component. For example, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, and succinic acid are used as dicarboxylic acid components. Other polycarboxylic acid components such as, for example, glutaric acid, adipic acid, azelaic acid, sebacic acid and dodecandioic acid include trimellitic acid. The glycol component is not particularly limited, but examples thereof include ethylene glycol and propylene glycol, and examples of other polyol components include trimethylolpropane and pentaerythritol.
また、本実施形態の接着剤層3に含有されるポリエステル樹脂は、数平均分子量(Mn)が8,000〜30,000であり、より好ましくは10,000〜25,000である。数平均分子量(Mn)が8,000未満では、有機樹脂層4との密着力が弱く、接着剤層3と有機樹脂層4との間での界面剥離を生じる恐れがある。また、数平均分子量(Mn)が30,000を超えると、粘度が高くなり、生産が困難となる場合がある。 The polyester resin contained in the adhesive layer 3 of the present embodiment has a number average molecular weight (Mn) of 8,000 to 30,000, and more preferably 10,000 to 25,000. If the number average molecular weight (Mn) is less than 8,000, the adhesive strength with the organic resin layer 4 is weak, and there is a possibility that the interface peeling between the adhesive layer 3 and the organic resin layer 4 may occur. On the other hand, when the number average molecular weight (Mn) exceeds 30,000, the viscosity becomes high and production may be difficult.
また、本実施形態の接着剤層3に含有されるポリエステル樹脂のガラス転移温度は、50℃以上85℃未満であり、より好ましくは50〜80℃未満である。ガラス転移温度が50℃未満では、接着剤を塗布した熱可塑性樹脂の巻き取り、あるいは巻き取り後の経時によりブロッキングが生じるおそれがある。一方でガラス転移温度が85℃を超えると、室温付近での弾性率が高くなり、樹脂自体が硬すぎて、熱可塑性樹脂との接着性が発現しない可能性がある。 Further, the glass transition temperature of the polyester resin contained in the adhesive layer 3 of the present embodiment is 50 ° C. or more and less than 85 ° C., and more preferably 50-80 ° C. When the glass transition temperature is lower than 50 ° C., there is a possibility that the thermoplastic resin to which the adhesive has been applied is wound up or blocking occurs with the elapse of time after winding up. On the other hand, when the glass transition temperature exceeds 85 ° C., the elastic modulus near room temperature becomes high, and the resin itself is too hard, so that there is a possibility that the adhesiveness with the thermoplastic resin may not be exhibited.
さらに、本実施形態の接着剤層3に含有されるポリエステル樹脂の酸価が7〜15mgKOH/gであり、より好ましくは8〜14mgKOH/gである。
また、本実施形態の接着剤層3には、アクリル樹脂が添加されていてもよい。かようなアクリル樹脂は、アクリル樹脂/(ポリエステル樹脂とフェノール樹脂との合計)の比として、0.015〜0.06、より好ましくは、0.02〜0.04の割合で含まれる接着剤層3に添加されていることが好ましい。
アクリル樹脂の酸価は0〜500(mgKOH/g)であることが好ましい。500以上では、アクリル樹脂がゲル化しやすくなる傾向がある。また、水酸基価は0〜300(mgKOH/g)であることが好ましい。
また、本実施形態で用いるアクリル樹脂は、機械的性質や耐薬品性、接着性などを向上させるために、エポキシ基で変性されていてもよい。
アクリル樹脂を構成しうるモノマーとしては、アクリル酸、メタアクリル酸;メチル(メタ)アクリレート、エチル(メタ)アクリレート、n−プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert−ブチル(メタ)アクリレート、n−オクチル(メタ)アクリレート、ラウリル(メタ)アクリレート、トリデシル(メタ)アクリレート、ステアリル(メタ)アクリレート等のアルキル(メタ)アクリレート;2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、3−ヒドロキシプロピル(メタ)アクリレート、2,3−ジヒドロキシブチル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレート及びポリエチレングリコールモノ(メタ)アクリレート等の多価アルコールとアクリル酸又はメタクリル酸とのモノエステル化物;そのモノエステル化物のε-カプロラクトン付加体;マレイン酸、フマル酸、アクリルアミド、アクリロニトリル、酢酸ビニル、スチレン等、が例示できるが、これらには限定されない。
また、アクリル樹脂にエポキシ基を導入する場合、グリシジル(メタ)アクリレート、3,4−エポキシシクロヘキシルメチル(メタ)アクリレート等、と共重合することができる。
Further, the acid value of the polyester resin contained in the adhesive layer 3 of the present embodiment is 7 to 15 mgKOH / g, more preferably 8 to 14 mgKOH / g.
Further, an acrylic resin may be added to the adhesive layer 3 of the present embodiment. Such an acrylic resin has an adhesive ratio of 0.015 to 0.06, more preferably 0.02 to 0.04, as a ratio of acrylic resin / (total of polyester resin and phenol resin). Preferably, it is added to layer 3.
The acid value of the acrylic resin is preferably from 0 to 500 (mgKOH / g). If it is 500 or more, the acrylic resin tends to gel. Further, the hydroxyl value is preferably from 0 to 300 (mgKOH / g).
In addition, the acrylic resin used in the present embodiment may be modified with an epoxy group in order to improve mechanical properties, chemical resistance, adhesiveness, and the like.
Monomers that can constitute the acrylic resin include acrylic acid and methacrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate Alkyl (meth) acrylates such as isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate; Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Monoesters of polyhydric alcohols such as acrylate and polyethylene glycol mono (meth) acrylate with acrylic acid or methacrylic acid; ε-caprolactone adducts of the monoesters; maleic acid, fumaric acid, acrylamide, acrylonitrile, vinyl acetate, Styrene and the like can be exemplified, but not limited thereto.
When an epoxy group is introduced into the acrylic resin, it can be copolymerized with glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, or the like.
<接着剤層に添加される添加剤>
なお接着剤層3は、例えば隠ぺい性や耐食性を向上させる目的として種々の添加剤を含んでいてもよい。かような添加剤として、例えば酸化チタン、アルミペースト、酸化亜鉛、有機顔料、シリカの少なくとも1つを接着剤層3に添加することができる。
なお、添加剤として酸化チタンを用いる場合には、酸化チタンの粒径は0.2 〜 0.5μm程度のものを用いることが好ましい。
また、添加剤としてアルミペーストを用いる場合には、アルミペーストの粒径が3.0〜15.0μm程度のものを用いることが好ましい。
また、添加剤として酸化亜鉛を用いる場合には、酸化亜鉛の粒径が0.3 〜 1.0μmのものを用いることが好ましい。
<Additives added to adhesive layer>
The adhesive layer 3 may contain various additives for the purpose of improving the concealing property and the corrosion resistance, for example. As such an additive, for example, at least one of titanium oxide, aluminum paste, zinc oxide, organic pigment, and silica can be added to the adhesive layer 3.
In addition, when using titanium oxide as an additive, it is preferable to use a titanium oxide having a particle size of about 0.2 to 0.5 μm.
When an aluminum paste is used as an additive, it is preferable to use an aluminum paste having a particle size of about 3.0 to 15.0 μm.
When zinc oxide is used as an additive, it is preferable to use zinc oxide having a particle size of 0.3 to 1.0 μm.
また、添加剤として有機顔料を用いる場合には、有機顔料の粒径が0.1 〜 1.0μmのものを用いることが好ましい。
また、添加剤としてシリカを用いる場合には、シリカの粒径が1.0〜10.0μm程度のものを用いることが好ましい。
上記した具体的な添加剤それぞれの添加量は用途に応じて適宜調整・設定すればよい。なお添加量が少なすぎる場合には隠ぺい性、耐食性向上の効果が不十分となってしまう。また、添加量が多すぎる場合には、接着剤層と熱可塑性樹脂との間での界面剥離や、接着剤層内での剥離を生じる恐れがある。
When an organic pigment is used as an additive, it is preferable to use an organic pigment having a particle size of 0.1 to 1.0 μm.
When silica is used as an additive, it is preferable to use silica having a particle size of about 1.0 to 10.0 μm.
The amount of each of the above specific additives may be appropriately adjusted and set according to the application. If the addition amount is too small, the effect of improving concealing properties and corrosion resistance will be insufficient. If the addition amount is too large, there is a possibility that interfacial peeling between the adhesive layer and the thermoplastic resin and peeling within the adhesive layer may occur.
また、添加剤として、ワックスを添加してもよい。かようなワックスとしては、添加量0.1〜3.0%、融点100〜130℃のものが好ましい。ワックスの具体例としては、例えばポリエチレンワックスなどがあげられる。
以上で説明した添加剤の一覧を表1に示す。
Further, a wax may be added as an additive. As such a wax, a wax having an addition amount of 0.1 to 3.0% and a melting point of 100 to 130 ° C is preferable. Specific examples of the wax include, for example, polyethylene wax.
Table 1 shows a list of the additives described above.
なお、上記添加剤として上記のうち複数の材料を添加する場合には、表1に示される添加量または粒径の比率に応じて複数の添加剤を添加することが望ましい。すなわち、例えばシリカと有機顔料を添加剤として接着剤層3に添加する場合には、シリカと有機顔料の添加量の重量%比は、表1から、[シリカ/有機顔料]が[1/100]〜[1/5]の範囲内となるようにそれぞれ接着剤層3に添加することになる。また、粒径に関して言えば、例えば酸化チタンの粒径に対して表1に示した粒径のシリカを添加するとよい。
このように、表1に示す複数の添加剤のうちから任意の添加剤を複数選択した場合には、添加量または粒径の比に従って接着剤層3に添加されることになる。
When a plurality of the above-mentioned materials are added as the above-mentioned additives, it is desirable to add the plurality of additives according to the amount of addition or the ratio of the particle size shown in Table 1. That is, for example, when silica and an organic pigment are added to the adhesive layer 3 as additives, the weight% ratio of the added amount of the silica and the organic pigment is as shown in Table 1, where [silica / organic pigment] is [1/100]. ] To [1/5], respectively. As for the particle size, for example, silica having a particle size shown in Table 1 with respect to the particle size of titanium oxide may be added.
As described above, when a plurality of optional additives are selected from the plurality of additives shown in Table 1, the additives are added to the adhesive layer 3 in accordance with the added amount or the particle size ratio.
なお本実施形態で用いる接着剤層3には有機溶剤が含有されていてもよい。
かような有機溶剤としては、例えば、エタノール、n−プロパノール、イソプロパノール、n−ブタノール、イソブタノール、sec−ブタノール、tert−ブタノール、イソアミルアルコール、sec−アミルアルコール、tert−アミルアルコール、n−ヘキサノール、シクロヘキサノール、などのアルコール類、メチルエチルケトン、メチルイソブチルケトン、エチルブチルケトンなどのケトン類、テトラヒドロフラン、ジオキサン、1,3−ジオキソラン、などの環状エーテル類、エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールエチルエーテルアセテート、プロピレングリコール、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、プロピレングリコールメチルエーテルアセテート等のグリコール誘導体、3−メトキシ−3−メチルブタノール、3−メトキシブタノール、アセトニトリル、ジメチルホルムアミド、ジメチルアセトアミド、ジアセトンアルコール、アセト酢酸エチル、シクロヘキサノン、トルエン等を挙げることができる。
Note that the adhesive layer 3 used in the present embodiment may contain an organic solvent.
Such organic solvents include, for example, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, n-hexanol, Alcohols such as cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclic ethers such as tetrahydrofuran, dioxane, 1,3-dioxolane, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol Glycol derivatives such as monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate; 3-methoxy-3-methylbutanol; -Methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate, cyclohexanone, toluene and the like.
<有機樹脂被覆鋼板の製造方法>
図2に本実施形態の有機樹脂被覆鋼板10の製造フローを示す。
まずステップ1では、上述した基材を必要に応じて脱脂や洗浄処理を施して準備する。
次いでステップ2では、基材に対して上述した表面処理層2を形成する。なお、このステップ2は適宜省略が可能である。
そしてステップ3では、有機樹脂層4(熱可塑性樹脂)表面に対して上記した接着剤を乾燥膜厚が2〜10μm程度、より好ましくは2〜4μmになるように塗布して接着剤層3を形成する。その後、例えば80〜150℃の温度で乾燥させる。なおステップ3では有機樹脂層4(熱可塑性樹脂)表面に対して上記した接着剤を塗布したが、これに限られず基材1(又は表面処理層2)上に接着剤を塗布する形態でもよいし、有機樹脂層4側と基材1側の双方に接着剤を塗布する形態でもよい。
<Production method of organic resin coated steel sheet>
FIG. 2 shows a manufacturing flow of the organic resin-coated steel sheet 10 of the present embodiment.
First, in step 1, the above-described base material is prepared by performing degreasing and / or cleaning treatment as necessary.
Next, in step 2, the above-mentioned surface treatment layer 2 is formed on the base material. Step 2 can be omitted as appropriate.
In step 3, the adhesive is applied to the surface of the organic resin layer 4 (thermoplastic resin) so that the dry film thickness is about 2 to 10 μm, more preferably 2 to 4 μm. Form. Thereafter, drying is performed at a temperature of, for example, 80 to 150 ° C. In step 3, the above-described adhesive was applied to the surface of the organic resin layer 4 (thermoplastic resin). However, the present invention is not limited to this, and the adhesive may be applied to the base material 1 (or the surface treatment layer 2). Then, an adhesive may be applied to both the organic resin layer 4 side and the substrate 1 side.
次いで、ステップ4では、上記ステップ3で接着剤層3が形成された有機樹脂層4(熱可塑性樹脂)を基材1にラミネートすることにより、本実施形態の有機樹脂被覆鋼板10が作製される。なお、このとき基材1上には表面処理層2が形成されていてもよい。また、前加熱としてのラミネート時における基材1の温度は、180〜280℃であることが好ましい。 Next, in step 4, by laminating the organic resin layer 4 (thermoplastic resin) on which the adhesive layer 3 is formed in step 3 to the substrate 1, the organic resin-coated steel sheet 10 of the present embodiment is produced. . At this time, the surface treatment layer 2 may be formed on the substrate 1. The temperature of the substrate 1 during lamination as preheating is preferably 180 to 280 ° C.
また、ステップ4では、ラミネートして得られた有機樹脂被覆金属板に対して熱処理(後加熱)を行うことにより、基材1と有機樹脂層4(熱可塑性樹脂)との密着性を更に引き上げることができる。かような後加熱としての熱処理の方法は、特に限定されない。また、この後加熱にかかる熱処理温度は、基材1の温度として160〜240℃、より好ましくは170〜210℃である。 In Step 4, the adhesion between the substrate 1 and the organic resin layer 4 (thermoplastic resin) is further raised by performing a heat treatment (post-heating) on the organic resin-coated metal plate obtained by lamination. be able to. The method of the heat treatment as such post-heating is not particularly limited. Further, the heat treatment temperature for the subsequent heating is 160 to 240 ° C., more preferably 170 to 210 ° C., as the temperature of the substrate 1.
後加熱による温度が160℃未満では、3〜30分間の熱処理時間内で、十分は密着性を得ることができない。一方で後加熱による温度が240℃を超えると、二軸延伸ポリエステルフィルムの熱収縮が大きくなり、熱処理後に有機樹脂被覆金属板の端部でフィルム剥離が生じやすくなるからである。
なお、後加熱にかかる熱処理時間は、3〜30分間、より好ましくは5〜20分間である。熱処理時間が3分間未満では、十分な密着性を得ることができない。一方で熱処理時間が30分間を超えると、製缶時など加工の際に接着剤層3が割れやすくなるからである。
If the temperature by post-heating is lower than 160 ° C., sufficient adhesion cannot be obtained within the heat treatment time of 3 to 30 minutes. On the other hand, when the temperature due to the post-heating exceeds 240 ° C., the heat shrinkage of the biaxially stretched polyester film becomes large, and the film tends to peel off at the end of the organic resin-coated metal plate after the heat treatment.
The heat treatment time required for the post-heating is 3 to 30 minutes, more preferably 5 to 20 minutes. If the heat treatment time is less than 3 minutes, sufficient adhesion cannot be obtained. On the other hand, if the heat treatment time exceeds 30 minutes, the adhesive layer 3 is easily broken at the time of processing such as can making.
<容器>
図3に有機樹脂被覆鋼板10を用いて製造した容器Cを示す。
本実施形態の容器Cは、接着剤層3を介して基材1に有機樹脂2を被覆して有機樹脂被覆鋼板10を得た後、これを絞り成形、絞り再絞り成形、ストレッチドロー成形、ストレッチアイアニング成形、絞りしごき成形等の各種成形を施すことで作製することが出来る。
なお図3では本実施形態の有機樹脂被覆金属板を用いたシームレス缶を示している。同図においては、シームレス缶の内面側に上記した表面処理層2や接着剤層3、有機樹脂層(熱可塑性樹脂)4が被覆された例を示しているが、このシームレス缶の外側にも公知の種々の皮膜が形成されていてもよい。あるいは、シームレス缶の外面側に上記した表面処理層2や接着剤層3、有機樹脂層(熱可塑性樹脂)4が被覆されていてもよい。また、本発明の有機樹脂被覆金属板は、シームレス缶以外にも溶接缶といった3ピース缶にも適用することができる。
また、本実施形態により得られる有機樹脂被覆鋼板10は、図3に示される缶蓋Cpとしても利用可能であり、上述した「容器」には、容器の一部として機能する缶蓋も含まれるものとする。なお缶蓋の構造は特に限定されないが、例えば平蓋、イージーオープン缶蓋などが挙げられる。
<Container>
FIG. 3 shows a container C manufactured using the organic resin-coated steel sheet 10.
The container C of the present embodiment is obtained by coating the base material 1 with the organic resin 2 via the adhesive layer 3 to obtain the organic resin-coated steel sheet 10, and then drawing, drawing and redrawing, stretching draw forming, It can be produced by performing various moldings such as stretch ironing molding and drawing and ironing molding.
FIG. 3 shows a seamless can using the organic resin-coated metal plate of the present embodiment. FIG. 1 shows an example in which the surface treatment layer 2, the adhesive layer 3, and the organic resin layer (thermoplastic resin) 4 are coated on the inner surface side of the seamless can. Various known films may be formed. Alternatively, the outer surface side of the seamless can may be coated with the above-described surface treatment layer 2, adhesive layer 3, and organic resin layer (thermoplastic resin) 4. Further, the organic resin-coated metal plate of the present invention can be applied to a three-piece can such as a welded can in addition to a seamless can.
Further, the organic resin-coated steel sheet 10 obtained according to the present embodiment can also be used as the can lid Cp shown in FIG. 3, and the above-mentioned “container” includes a can lid that functions as a part of the container. Shall be. The structure of the can lid is not particularly limited, and examples thereof include a flat lid and an easy-open can lid.
また、本実施形態を適用する缶蓋の場合において、有機樹脂層4としては、上述した熱可塑性樹脂の他、塗膜であることが好ましい。かような塗膜としては、熱硬化性樹脂塗料、例えば、フェノール−ホルムアルデヒド樹脂、フラン−ホルムアルデヒド樹脂、キシレン−ホルムアルデヒド樹脂、ケトン−ホルムアルデヒド樹脂、尿素ホルムアルデヒド樹脂、メラミン−ホルムアルデヒド樹脂、アルキド樹脂、不飽和ポリエステル樹脂、エポキシ樹脂、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、或いは熱可塑性樹脂塗料、例えば塩化ビニル−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、エポキシアクリル系塗料、エポキシフェノール系塗料、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が好適である。
なお、本発明の有機樹脂被覆鋼板の接着剤層はビスフェノール類に由来する成分を含まないので、有機樹脂層4を塗膜で構成する場合も、ビスフェノール類に由来する成分を含まない塗料を選択するのが好ましい。
In the case of a can lid to which the present embodiment is applied, the organic resin layer 4 is preferably a coating film in addition to the above-described thermoplastic resin. Examples of such coatings include thermosetting resin paints such as phenol-formaldehyde resins, furan-formaldehyde resins, xylene-formaldehyde resins, ketone-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, alkyd resins, and unsaturated resins. Polyester resin, epoxy resin, bismaleimide resin, triallyl cyanurate resin, thermosetting acrylic resin, silicone resin, oily resin, or thermoplastic resin paint such as vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate Partially saponified polymers, vinyl chloride-maleic acid copolymers, vinyl chloride-maleic acid-vinyl acetate copolymers, acrylic polymers, saturated polyester resins and the like can be mentioned. These resin coatings may be used alone or in combination of two or more. Among these, epoxy acrylic paints, epoxy phenol paints, polyester paints, epoxy urea paints, vinyl organosol paints and the like are preferred.
In addition, since the adhesive layer of the organic resin-coated steel sheet of the present invention does not contain a component derived from bisphenols, even when the organic resin layer 4 is formed of a coating film, a paint containing no component derived from bisphenols is selected. Is preferred.
<実施例>
以下に実施例を挙げて本発明について具体的に説明するが、本発明はこれら実施例に限定されるものではない。
まず初めに後述する実施例、比較例および参考例における各特性の評価あるいは測定態様について説明する。
<Example>
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.
First, evaluation or measurement modes of each characteristic in Examples, Comparative Examples, and Reference Examples described later will be described.
<接着剤層3における厚み(膜厚)の測定方法>
有機樹脂被覆金属板の基材1を硫酸で溶解させ、有機樹脂層(熱可塑性樹脂)4と接着剤層3のみに単離した。その後、樹脂に埋め込んで包埋処理を行い、次いでミクロトームで厚み方向にスライスし、厚み3μmのサンプルを作製した。サンプルを透過型光学顕微鏡にセットし、偏光を加えることにより、有機樹脂層(熱可塑性樹脂)4と接着剤層3を区別し、接着剤層3における厚みを測定した。
<Method of measuring thickness (film thickness) of adhesive layer 3>
The substrate 1 of the organic resin-coated metal plate was dissolved with sulfuric acid, and isolated into only the organic resin layer (thermoplastic resin) 4 and the adhesive layer 3. Thereafter, the sample was embedded in a resin to perform an embedding process, and then sliced in a thickness direction with a microtome to prepare a sample having a thickness of 3 μm. The sample was set on a transmission optical microscope, and polarized light was applied to distinguish the organic resin layer (thermoplastic resin) 4 from the adhesive layer 3 and measure the thickness of the adhesive layer 3.
<熱可塑性樹脂との密着性評価方法>
有機樹脂被覆金属板の密着性は、平板、絞り缶の缶側壁部でそれぞれ評価を行った。また、レトルト処理後にも同様な方法で行った。レトルト処理は、試験片を水中に浸漬させた状態で、125℃で30分間の条件で行い、室温で冷却した後に評価に供した。
具体的な評価としては、有機樹脂被覆金属板について、5mm間隔で金属板に達する深さの碁盤目を入れ、テープで剥離し、剥離の程度を目視にて観察して評価した。
<Method of evaluating adhesion to thermoplastic resin>
The adhesion of the organic resin-coated metal plate was evaluated on a flat plate and a can side wall portion of a drawn can, respectively. Further, the same method was used after the retort treatment. The retort treatment was performed at 125 ° C. for 30 minutes in a state where the test piece was immersed in water.
As a specific evaluation, a checkerboard having a depth reaching the metal plate at an interval of 5 mm was inserted into the organic resin-coated metal plate, peeled off with a tape, and the degree of peeling was visually observed and evaluated.
なお密着性の評価は以下の基準で行った。なお、密着性評価は、後述する全ての実施例及び比較例について行った。
[密着性の評価基準]
◎:目視で判定した結果、熱可塑性樹脂の剥離が認められなかった。
○:目視で判定した結果、実用には供せるが熱可塑性樹脂の剥離がわずかながら認められた。
△:目視で判定した結果、熱可塑性樹脂の剥離が1/5以下の面積率で認められた。
×:目視で判定した結果、熱可塑性樹脂の剥離が1/5を超える面積率で認められた。
なお、密着性評価においては、上記基準で評価が◎もしくは○である場合に、飲食缶用途として用いた際に十分な密着性を有するものであると判断した。
The evaluation of adhesion was performed according to the following criteria. The evaluation of adhesion was performed for all Examples and Comparative Examples described later.
[Evaluation criteria for adhesion]
A: No peeling of the thermoplastic resin was observed as a result of the visual judgment.
:: As a result of visual judgment, slight peeling of the thermoplastic resin was recognized although it could be put to practical use.
B: As a result of visual judgment, peeling of the thermoplastic resin was recognized at an area ratio of 1/5 or less.
X: As a result of visual judgment, peeling of the thermoplastic resin was observed at an area ratio exceeding 1/5.
In the evaluation of adhesiveness, when the evaluation was ◎ or で according to the above criteria, it was determined that the film had sufficient adhesiveness when used for food and drink cans.
<缶側壁部での評価方法>
有機樹脂被覆金属板にパラフィンワックスを塗布した後、直径160mmのブランクに打ち抜いた後、絞り加工を2回行い、絞り比1.8、高さ50mm、直径90mm成形缶を得た。
そしてこの絞り成形缶の缶側壁部を50mm×60mmの大きさに切出し、湾曲を強制した後、5mm間隔で金属板に達する深さの碁盤目を入れ、テープで剥離し、剥離の程度を目視にて観察して評価した。
<Evaluation method on the side wall of the can>
After the paraffin wax was applied to the organic resin-coated metal plate, the blank was punched into a blank having a diameter of 160 mm, and then subjected to drawing twice, to obtain a molded can having a drawing ratio of 1.8, a height of 50 mm, and a diameter of 90 mm.
Then, the side wall portion of the draw-formed can is cut out to a size of 50 mm × 60 mm, and a curve is forcibly applied. Then, grids having a depth reaching the metal plate are inserted at intervals of 5 mm, peeled off with a tape, and the degree of peeling is visually observed. Observed and evaluated.
なお缶側壁部での密着性の評価は以下の基準で行った。この密着性評価は、後述する全ての実施例及び比較例について行った。
[缶側壁部での密着性の評価基準]
◎:目視で判定した結果、熱可塑性樹脂の剥離が認められなかった。
○:目視で判定した結果、実用には供せるが熱可塑性樹脂の剥離がわずかながら認められた。
△:目視で判定した結果、熱可塑性樹脂の剥離が1/5以下の面積率で認められた。
×:目視で判定した結果、熱可塑性樹脂の剥離が1/5を超える面積率で認められた。
なお、密着性評価においては、上記基準で評価が◎もしくは○である場合に、飲食缶用途として用いた際に十分な密着性を有するものであると判断した。
The evaluation of the adhesion at the side wall of the can was performed according to the following criteria. This adhesion evaluation was performed for all Examples and Comparative Examples described later.
[Evaluation criteria for adhesion on the side wall of the can]
A: No peeling of the thermoplastic resin was observed as a result of the visual judgment.
:: As a result of visual judgment, slight peeling of the thermoplastic resin was recognized although it could be put to practical use.
B: As a result of visual judgment, peeling of the thermoplastic resin was recognized at an area ratio of 1/5 or less.
X: As a result of visual judgment, peeling of the thermoplastic resin was observed at an area ratio exceeding 1/5.
In the evaluation of adhesiveness, when the evaluation was ◎ or で according to the above criteria, it was determined that the film had sufficient adhesiveness when used for food and drink cans.
<内容物充填評価(パックテスト)>
有機樹脂被覆金属板を円形ブランクに打ち抜いた後、絞り加工を2回行い、底部パネル加工、ビード加工、トリミング加工を行い、缶内径83.2mm 、缶高さ44.1mm 、内容積213mlの再絞り缶を成形した。
得られた絞り缶に、内容物を充填後、アルミニウム製イージーオープン蓋を二重巻締めした後、レトルト処理を行った。
なお内容物は、ツナ油漬け、ツナ水煮、鮪醤油煮にて行い、37℃3カ月経時後の内容物の品質保持性(外観、pH、味)を評価した。
<Evaluation of content filling (pack test)>
After punching an organic resin-coated metal plate into a circular blank, drawing is performed twice, bottom panel processing, bead processing, and trimming processing are performed. The inner diameter of the can is 83.2 mm, the height of the can is 44.1 mm, and the inner volume is 213 ml. A drawn can was formed.
After filling the obtained squeezed can with the contents, the aluminum easy-open lid was double-tightened and then retorted.
The contents were pickled in tuna oil, boiled in tuna water, and boiled in tuna soy sauce, and the quality retention (appearance, pH, taste) of the contents after 3 months at 37 ° C. was evaluated.
なおパックテストの評価は以下の基準で行った。
[パックテストの評価基準]
○:参考例1と同等である
△:参考例1に比べ、若干内容物が変色、あるいは味が変化していた。
×:参考例1に比べ、内容物が変色、あるいは味が変化していた。
なお品質保持性が参考例1と同等である場合に実用適性があると判断した。
The pack test was evaluated based on the following criteria.
[Evaluation criteria for pack test]
:: equivalent to Reference Example 1 △: Compared to Reference Example 1, the contents were slightly discolored or the taste was changed.
×: The content was discolored or the taste was changed as compared with Reference Example 1.
In addition, when the quality retention was equivalent to that of Reference Example 1, it was determined that there was practicality.
<実施例1>
厚さ12μmの熱可塑性樹脂(二軸延伸ポリエステルフィルム)に表2に示す接着剤Aをグラビアコーターにて塗装し100℃で乾燥させた。その際、接着剤の塗布量は20mg/dm2であり、乾燥後の厚みが2μmとした。このとき、接着剤の厚み/熱可塑性樹脂の厚みは17%であった。
基材は、厚さ0.16mmの低炭素アルミキルド鋼の冷延鋼板を用い、この金属板をアルカリ水溶液中で電解脱脂して水洗いを行い、更に硫酸酸洗と水洗いを行った後に、電解処理により金属クロム量100mg/m2、クロム水酸化物15mg/m2からなるクロムめっき層を形成させ、TFSを作製した。
<Example 1>
The adhesive A shown in Table 2 was applied to a thermoplastic resin (biaxially stretched polyester film) having a thickness of 12 μm using a gravure coater and dried at 100 ° C. At that time, the applied amount of the adhesive was 20 mg / dm 2 , and the thickness after drying was 2 μm. At this time, the thickness of the adhesive / the thickness of the thermoplastic resin was 17%.
The base material is a cold-rolled steel sheet of low carbon aluminum killed steel with a thickness of 0.16 mm. This metal sheet is electrolytically degreased in an alkaline aqueous solution, washed with water, further washed with sulfuric acid and water, and then subjected to electrolytic treatment. the metallic chromium amount 100 mg / m 2, to form a chromium plating layer of chromium hydroxide 15 mg / m 2, to prepare a TFS.
次いで、表面処理金属板を240℃に加熱し、表面処理金属板の両面に、ラミネートロールを用いて、上記熱可塑性樹脂を熱圧着し、直ちに水冷することにより、有機樹脂被覆金属板を形成した。
得られた、有機樹脂被覆金属板は180℃で5分間加熱を行った後、上述した方法にしたがって、密着性の評価を行った。結果を表3に示す。
Next, the surface-treated metal plate was heated to 240 ° C., and the thermoplastic resin was thermocompression-bonded to both sides of the surface-treated metal plate using a laminating roll, and immediately cooled with water to form an organic resin-coated metal plate. .
The obtained organic resin-coated metal plate was heated at 180 ° C. for 5 minutes, and then the adhesion was evaluated according to the method described above. Table 3 shows the results.
<実施例2>
有機樹脂被覆金属板の熱処理温度を10分間とした以外は実施例1と同様に行った。結果を表3に示す。
<Example 2>
The procedure was performed in the same manner as in Example 1 except that the heat treatment temperature of the organic resin-coated metal plate was changed to 10 minutes. Table 3 shows the results.
<実施例3>
接着剤の厚みを3μmとした以外は実施例1と同様に行った。結果を表3に示す。
<Example 3>
The same operation as in Example 1 was performed except that the thickness of the adhesive was 3 μm. Table 3 shows the results.
<実施例4>
有機樹脂被覆金属板の熱処理温度を10分間とした以外は実施例3と同様に行った。結果を表3に示す。
<Example 4>
The procedure was performed in the same manner as in Example 3, except that the heat treatment temperature of the organic resin-coated metal plate was changed to 10 minutes. Table 3 shows the results.
<実施例5>
接着剤の厚みを4μmとした以外は実施例1と同様に行った。結果を表3に示す。
<Example 5>
The procedure was performed in the same manner as in Example 1 except that the thickness of the adhesive was changed to 4 μm. Table 3 shows the results.
<実施例6>
有機樹脂被覆金属板の熱処理温度を10分間とした以外は実施例5と同様に行った。結果を表3に示す。
<Example 6>
The procedure was performed in the same manner as in Example 5, except that the heat treatment temperature of the organic resin-coated metal plate was changed to 10 minutes. Table 3 shows the results.
<実施例7>
熱可塑性樹脂の厚みを19μmとし、表面処理金属板を260℃に加熱して、熱可塑性樹脂を熱圧着した以外は実施例4と同様に行った。結果を表3に示す。
<Example 7>
Example 4 was carried out in the same manner as in Example 4 except that the thickness of the thermoplastic resin was 19 µm, the surface-treated metal plate was heated to 260 ° C, and the thermoplastic resin was thermocompressed. Table 3 shows the results.
<実施例8>
接着剤の厚みを4μmとした以外は実施例7と同様に行った。結果を表3に示す。
<Example 8>
The same operation as in Example 7 was performed except that the thickness of the adhesive was 4 μm. Table 3 shows the results.
<実施例9>
基材は、厚さ0.16mmの低炭素アルミキルド鋼の冷延鋼板を用い、この金属板をアルカリ水溶液中で電解脱脂して水洗いを行い、更に硫酸酸洗と水洗いを行った後に、電解処理によりSn量2.8g/m2からなるSnめっき層を形成させ、リフロー処理(溶融溶錫処理)を行った後、電解処理によりCr量5mg/m2からなるCr酸素化合物層を形成したぶりきを用いた。また、接着剤の成分を表2に示す接着剤Bとし、表面処理金属板を220℃に加熱して、熱可塑性樹脂を熱圧着した。それ以外は実施例6と同様に行った。結果を表3に示す。
<Example 9>
The base material is a cold-rolled steel sheet of low carbon aluminum killed steel with a thickness of 0.16 mm. This metal sheet is electrolytically degreased in an alkaline aqueous solution, washed with water, further washed with sulfuric acid and water, and then subjected to electrolytic treatment. To form a Sn plating layer having an Sn amount of 2.8 g / m 2 , performing a reflow treatment (fused molten tin treatment), and then forming a Cr oxygen compound layer having a Cr amount of 5 mg / m 2 by electrolytic treatment. Was used. The components of the adhesive were adhesive B shown in Table 2, the surface-treated metal plate was heated to 220 ° C., and the thermoplastic resin was thermocompressed. Other than that, it carried out similarly to Example 6. Table 3 shows the results.
<実施例10>
基材は、厚さ0.16mmの低炭素アルミキルド鋼の冷延鋼板を用い、この金属板をアルカリ水溶液中で電解脱脂して水洗いを行い、更に硫酸酸洗と水洗いを行った後に、電解処理によりZr量100mg/m2からなるZr酸素化合物層を形成させたものを用いた以外は実施例2と同様に行った。電解処理には、フッ化ジルコニウムアンモニウムを主成分とするpH3.0の処理液を用いた。結果を表3に示す。
<Example 10>
The base material is a cold-rolled steel sheet of low carbon aluminum killed steel having a thickness of 0.16 mm. This metal sheet is electrolytically degreased in an aqueous alkaline solution, washed with water, and further washed with sulfuric acid and water, followed by electrolytic treatment. Example 2 was carried out in the same manner as in Example 2 except that a Zr oxygen compound layer having a Zr amount of 100 mg / m 2 was formed. For the electrolytic treatment, a treatment solution having a pH of 3.0 containing zirconium ammonium fluoride as a main component was used. Table 3 shows the results.
<実施例11>
基材は、厚さ0.16mmの低炭素アルミキルド鋼の冷延鋼板を用い、この金属板をアルカリ水溶液中で電解脱脂して水洗いを行い、更に硫酸酸洗と水洗いを行った後に、電解処理によりSn量2.8g/m2からなるSnめっき層を形成させ、リフロー処理(溶融溶錫処理)を行った後、電解処理によりAl量5mg/m2からなるAl水酸化物層を形成したぶりきを用いた。それ以外は実施例2と同様に行った。結果を表3に示す。
<Example 11>
The base material is a cold-rolled steel sheet of low carbon aluminum killed steel with a thickness of 0.16 mm. This metal sheet is electrolytically degreased in an alkaline aqueous solution, washed with water, further washed with sulfuric acid and water, and then subjected to electrolytic treatment. To form an Sn plating layer having an Sn amount of 2.8 g / m 2 , performing a reflow treatment (fused tin treatment), and then forming an Al hydroxide layer having an Al amount of 5 mg / m 2 by electrolytic treatment. Tinplate was used. Other than that, it carried out similarly to Example 2. Table 3 shows the results.
<実施例12>
接着剤の成分を表2に示す接着剤Cとした以外は実施例2と同様に行った。結果を表3に示す。
<Example 12>
The procedure was performed in the same manner as in Example 2 except that the components of the adhesive were changed to Adhesive C shown in Table 2. Table 3 shows the results.
<実施例13>
接着剤の成分を表2に示す接着剤Dとした以外は実施例2と同様に行った。結果を表3に示す。
<Example 13>
The procedure was performed in the same manner as in Example 2 except that the components of the adhesive were changed to Adhesive D shown in Table 2. Table 3 shows the results.
なお、表3に示されるように、接着剤の成分がビスフェノール類に由来する成分をそれぞれ含まないポリエステル樹脂とレゾール型フェノール樹脂が、前記ポリエステル樹脂/前記レゾール型フェノール樹脂の比として5.7〜19の割合で含有されており、接着剤と熱可塑性樹脂の厚みの比(接着剤の厚み/熱可塑性樹脂の厚み)が14%〜50%のものは、缶側壁部においても有機樹脂被覆金属板の密着性が十分であり、レトルト処理後も十分な密着性を有することが示された。また、金属板の表面には表面処理層を有し、表面処理層はジルコニウム、アルミニウム、チタンのいずれかの酸素化合物から成る場合でも、良好な結果が得られた。 As shown in Table 3, the ratio of the polyester resin and the resol-type phenol resin in which the components of the adhesive do not include the components derived from bisphenols is 5.7 to 19%, and the ratio of the thickness of the adhesive to the thickness of the thermoplastic resin (thickness of the adhesive / thickness of the thermoplastic resin) is 14% to 50%. It was shown that the plate had sufficient adhesiveness and had sufficient adhesiveness even after retort treatment. Further, good results were obtained even when the surface of the metal plate had a surface treatment layer, and the surface treatment layer was made of any one of oxygen compounds of zirconium, aluminum and titanium.
<実施例14>
接着剤の成分を表2に示す接着剤F、表面処理金属板を260℃に加熱して、熱可塑性樹脂を熱圧着した以外は実施例4と同様に行った。結果を表3に示す。
<Example 14>
The procedure of Example 4 was repeated except that the components of the adhesive were as shown in Table 2, and the surface-treated metal plate was heated to 260 ° C. and the thermoplastic resin was thermocompressed. Table 3 shows the results.
<実施例15>
接着剤の成分を表2に示す接着剤Gとした以外は実施例14と同様に行った。結果を表3に示す。
<Example 15>
Example 14 was carried out in the same manner as in Example 14 except that the components of the adhesive were changed to the adhesive G shown in Table 2. Table 3 shows the results.
<実施例16>
接着剤の成分を表2に示す接着剤Hとした以外は実施例14と同様に行った。結果を表3に示す。
<Example 16>
Example 14 was carried out in the same manner as in Example 14, except that the components of the adhesive were adhesive H shown in Table 2. Table 3 shows the results.
<実施例17>
厚さ12μmの熱可塑性樹脂(二軸延伸ポリエステルフィルム)に表2に示す接着剤Aをグラビアコーターにて塗装し100℃で乾燥させた。その際、接着剤の塗布量は30mg/dm2であり、乾燥後の厚みが3μmとした。このとき、接着剤の厚み/熱可塑性樹脂の厚みは25%であった。
基材は、厚さ0.16mmの低炭素アルミキルド鋼の冷延金属板を用い、この金属板をアルカリ水溶液中で電解脱脂して水洗いを行い、更に硫酸酸洗と水洗いを行った後に、電解処理により金属クロム量100mg/m2、クロム水酸化物15mg/m2からなるクロムめっき層を形成させ、TFSを作製した。
<Example 17>
The adhesive A shown in Table 2 was applied to a thermoplastic resin (biaxially stretched polyester film) having a thickness of 12 μm using a gravure coater and dried at 100 ° C. At that time, the applied amount of the adhesive was 30 mg / dm 2 , and the thickness after drying was 3 μm. At this time, the thickness of the adhesive / the thickness of the thermoplastic resin was 25%.
The base material is a cold-rolled metal sheet of low carbon aluminum killed steel with a thickness of 0.16 mm. This metal sheet is electrolytically degreased in an aqueous alkaline solution, washed with water, further washed with sulfuric acid and water, and then subjected to electrolytic treatment. metallic chromium amount 100 mg / m 2 by the processing, to form a chromium plating layer of chromium hydroxide 15 mg / m 2, to prepare a TFS.
次いで、表面処理金属板を240℃に加熱し、表面処理金属板の両面に、ラミネートロールを用いて、上記熱可塑性樹脂を熱圧着し、直ちに水冷することにより、有機樹脂被覆金属板を形成した。
得られた、有機樹脂被覆金属板は180℃で10分間加熱を行った後、上述した方法にしたがって、絞り缶を作製した。その後、内容物を充填し、経時後、品質保持性の評価を行った。結果を表4に示す。
Next, the surface-treated metal plate was heated to 240 ° C., and the thermoplastic resin was thermocompression-bonded to both sides of the surface-treated metal plate using a laminating roll, and immediately cooled with water to form an organic resin-coated metal plate. .
The obtained organic resin-coated metal plate was heated at 180 ° C. for 10 minutes, and then a drawn can was manufactured according to the method described above. Thereafter, the contents were filled, and after a lapse of time, the quality retention was evaluated. Table 4 shows the results.
<実施例18>
熱可塑性樹脂の厚みを19μmとした以外は実施例14と同様に行った。結果を表4に示す。
<Example 18>
The same operation as in Example 14 was performed except that the thickness of the thermoplastic resin was changed to 19 μm. Table 4 shows the results.
以下で示す実施例19〜23においては、主に缶蓋への適用を想定して平板の評価のみ行った。
<実施例19>
接着剤の成分を表2に示す接着剤Jとし、塗布量を10mg/dm2とした以外は実施例2と同様に行った。結果を表5に示す。
In Examples 19 to 23 shown below, only the evaluation of a flat plate was performed mainly assuming application to a can lid.
<Example 19>
The same procedure as in Example 2 was carried out except that the components of the adhesive were adhesive J shown in Table 2 and the application amount was 10 mg / dm 2 . Table 5 shows the results.
<実施例20>
接着剤の塗布量を10mg/dm2とした以外は実施例2と同様に行った。結果を表5に示す。
<Example 20>
The same operation as in Example 2 was performed except that the amount of the adhesive applied was 10 mg / dm 2 . Table 5 shows the results.
<実施例21>
接着剤の塗布量を50mg/dm2とした以外は実施例2と同様に行った。結果を表5に示す。
<Example 21>
The same procedure as in Example 2 was performed except that the amount of the adhesive applied was 50 mg / dm 2 . Table 5 shows the results.
<実施例22>
接着剤の塗布量を3mg/dm2とした以外は実施例2と同様に行った。結果を表5に示す。
<Example 22>
The same procedure as in Example 2 was performed except that the amount of the adhesive applied was 3 mg / dm 2 . Table 5 shows the results.
<実施例23>
接着剤の塗布量を70mg/dm2とした以外は実施例2と同様に行った。結果を表5に示す。
<Example 23>
Example 2 was repeated except that the amount of the adhesive applied was 70 mg / dm 2 . Table 5 shows the results.
<比較例1>
接着剤の成分を表2に示す接着剤I、接着剤の厚みを1.5μmとし、表面処理金属板を260℃に加熱して、熱可塑性樹脂を熱圧着した。それ以外は実施例1と同様に行った。結果を表3に示す。
<Comparative Example 1>
The components of the adhesive were adhesive I shown in Table 2, the thickness of the adhesive was 1.5 μm, the surface-treated metal plate was heated to 260 ° C., and the thermoplastic resin was thermocompressed. Other than that, it carried out similarly to Example 1. Table 3 shows the results.
<比較例2>
熱可塑性樹脂の厚みを19μm、接着剤の厚みを2μmとし、有機樹脂被覆金属板の熱処理温度を5分間とした以外は比較例1と同様に行った。結果を表3に示す。
<Comparative Example 2>
The procedure was performed in the same manner as in Comparative Example 1 except that the thickness of the thermoplastic resin was 19 μm, the thickness of the adhesive was 2 μm, and the heat treatment temperature of the organic resin-coated metal plate was 5 minutes. Table 3 shows the results.
<比較例3>
有機樹脂被覆金属板の熱処理温度を10分間とした以外は比較例2と同様に行った。結果を表3に示す。
<Comparative Example 3>
The procedure was performed in the same manner as in Comparative Example 2 except that the heat treatment temperature of the organic resin-coated metal plate was changed to 10 minutes. Table 3 shows the results.
<比較例4>
熱可塑性樹脂の厚みを19μm、接着剤の厚みを2.5μmとした以外は比較例1と同様に行った。結果を表3に示す。
<Comparative Example 4>
The procedure was performed in the same manner as in Comparative Example 1 except that the thickness of the thermoplastic resin was 19 μm and the thickness of the adhesive was 2.5 μm. Table 3 shows the results.
<比較例5>
接着剤の成分を表2に示す接着剤E、接着剤の厚みを3μmとした以外は実施例11と同様に行った。結果を表3に示す。
<Comparative Example 5>
The same procedures as in Example 11 were carried out except that the components of the adhesive were adhesive E shown in Table 2 and the thickness of the adhesive was 3 μm. Table 3 shows the results.
<比較例6>
接着剤の組成をエポキシフェノールとし、接着剤の厚みを1μmとした以外は実施例14と同様に行った。結果を表4に示す。
<Comparative Example 6>
Example 14 was repeated except that the composition of the adhesive was epoxy phenol and the thickness of the adhesive was 1 μm. Table 4 shows the results.
<参考例1>
基材は、厚さ0.16mmの低炭素アルミキルド鋼の冷延鋼板を用い、この金属板をアルカリ水溶液中で電解脱脂して水洗いを行い、更に硫酸酸洗と水洗いを行った後に、電解処理により金属クロム量100mg/m2、クロム水酸化物15mg/m2からなるクロムめっき層を形成させ、TFSを作製した。
上記表面処理金属板について、温度190℃で10分間の熱処理を行った後に、焼付け乾燥後の塗膜厚が70mg/dm2となるようにエポキシフェノール系塗料を塗装後、温度200℃で10分間の焼付けを行うことで、有機樹脂被覆金属板を得た。次に、実施例13と同内容量の溶接缶を作製した。その後、内容物を充填し、経時後、品質保持性の評価を行った。参考例1は現行市販されている生産品に相当する。結果を表4に示す。
<Reference Example 1>
The base material is a cold-rolled steel sheet of low carbon aluminum killed steel with a thickness of 0.16 mm. This metal sheet is electrolytically degreased in an alkaline aqueous solution, washed with water, further washed with sulfuric acid and water, and then subjected to electrolytic treatment. the metallic chromium amount 100 mg / m 2, to form a chromium plating layer of chromium hydroxide 15 mg / m 2, to prepare a TFS.
After heat-treating the surface-treated metal plate at a temperature of 190 ° C. for 10 minutes, an epoxyphenol-based paint is applied so that the coating thickness after baking and drying is 70 mg / dm 2, and then at a temperature of 200 ° C. for 10 minutes. Was obtained to obtain an organic resin-coated metal plate. Next, a welding can having the same capacity as in Example 13 was produced. Thereafter, the contents were filled, and after a lapse of time, the quality retention was evaluated. Reference Example 1 corresponds to a product currently on the market. Table 4 shows the results.
表4に示されるように本発明によって得られた有機樹脂被覆金属板は、いずれの内容物においても品質保持性が参考例1と同等で良好であった。なお比較例9は現行市販されている生産品に相当するが、ツナ水煮、鮪醤油煮など一部の内容物においては、参考例1よりも特性が劣るため適用されていない。したがって、本発明によって得られた有機樹脂被覆金属板は、従来品よりも実用適性があると判断される。 As shown in Table 4, the organic resin-coated metal plate obtained according to the present invention was as good in quality retention as in Reference Example 1 in all contents. Note that Comparative Example 9 is equivalent to a commercially available product, but is not applied to some contents such as boiled tuna and boiled tuna soy because the properties are inferior to those of Reference Example 1. Therefore, it is judged that the organic resin-coated metal plate obtained by the present invention has more practical suitability than the conventional product.
以上から明らかなとおり、本発明の各実施例では加工密着性、レトルト密着性および品質保持性がすべて良好な結果となった。
なお上記した実施形態と各実施例は、本発明の趣旨を逸脱しない範囲で種々の変形が可能である。
As is clear from the above, in each of the examples of the present invention, the processing adhesion, the retort adhesion and the quality retention were all good.
The above-described embodiment and each example can be variously modified without departing from the spirit of the present invention.
以上説明したように、本発明の有機樹脂被覆鋼板およびそれを用いた缶や缶蓋などの容器は、BPAを用いずに密着性と品質保持性を同時に高い次元で備えており、広い分野の産業への適用が可能である。 As described above, the organic resin-coated steel sheet of the present invention and containers using the same, such as cans and can lids, have high levels of adhesion and quality retention at the same time without using BPA. It can be applied to industry.
1 基材
2 表面処理層
3 接着剤層
4 有機樹脂層
10 有機樹脂被覆鋼板
C 容器
Cp 缶蓋
DESCRIPTION OF SYMBOLS 1 Base material 2 Surface treatment layer 3 Adhesive layer 4 Organic resin layer 10 Organic resin-coated steel plate C Container Cp Can lid
Claims (9)
前記基材に被覆される有機樹脂層と、
前記基材と前記有機樹脂層との間に介在するとともに、ビスフェノール類に由来する成分をそれぞれ含まないポリエステル樹脂とレゾール型フェノール樹脂が、前記ポリエステル樹脂/前記レゾール型フェノール樹脂の比として5.7〜19の割合で含有されてなる接着剤層と、を含み、
前記接着剤層は、
前記ポリエステル樹脂と前記フェノール樹脂との合計の重量に対する重量比が、アクリル樹脂/(ポリエステル樹脂とフェノール樹脂との合計)の比として、0.015〜0.06の重量比であるアクリル樹脂を含むことを特徴とする有機樹脂被覆鋼板。 A substrate,
An organic resin layer coated on the base material,
A polyester resin and a resole-type phenol resin which are interposed between the base material and the organic resin layer and do not contain a component derived from bisphenols respectively have a ratio of the polyester resin / the resole-type phenol resin of 5.7. an adhesive layer formed by a proportion of to 19, only including,
The adhesive layer,
The weight ratio to the total weight of the polyester resin and the phenol resin includes an acrylic resin having a weight ratio of 0.015 to 0.06 as a ratio of acrylic resin / (total of polyester resin and phenol resin). An organic resin-coated steel sheet characterized by the above-mentioned.
前記表面処理層は、クロム、ジルコニウム、アルミニウム及びチタンのいずれかを含む酸素化合物から成る請求項1〜4のいずれか一項に記載の有機樹脂被覆鋼板。 A surface treatment layer is formed on at least a side of the base material that is in contact with the adhesive layer,
The organic resin-coated steel sheet according to any one of claims 1 to 4 , wherein the surface treatment layer is made of an oxygen compound containing any one of chromium, zirconium, aluminum, and titanium.
前記接着剤層が介在するように前記基材上に前記有機樹脂層を形成する工程と、
前記有機樹脂層が形成された基材に対し、180℃〜280℃の温度範囲で前加熱処理を行う工程と、
前記前加熱処理の後で、前記有機樹脂層が形成された基材に対して160℃〜240℃の温度範囲内で後加熱処理を行う工程と、
を含むことを特徴とする有機樹脂被覆鋼板の製造方法。 An adhesive layer containing a polyester resin and a resol-type phenol resin each containing no component derived from bisphenols in a ratio of 5.7 to 19 as the ratio of the polyester resin / the resol-type phenol resin is used as a base material. Or a step of forming on at least one surface of the organic resin layer,
Forming the organic resin layer on the base material such that the adhesive layer is interposed,
Performing a pre-heating treatment on the substrate on which the organic resin layer is formed in a temperature range of 180 ° C to 280 ° C;
After the pre-heating treatment, a step of performing a post-heating treatment on the substrate on which the organic resin layer is formed within a temperature range of 160 ° C to 240 ° C,
A method for producing an organic resin-coated steel sheet, comprising:
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