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WO2001076865A1 - Feuille de metal couverte d'une resine et procede de fabrication de ladite feuille - Google Patents

Feuille de metal couverte d'une resine et procede de fabrication de ladite feuille Download PDF

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Publication number
WO2001076865A1
WO2001076865A1 PCT/JP2001/003137 JP0103137W WO0176865A1 WO 2001076865 A1 WO2001076865 A1 WO 2001076865A1 JP 0103137 W JP0103137 W JP 0103137W WO 0176865 A1 WO0176865 A1 WO 0176865A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
thin film
metal plate
coupling agent
silane coupling
Prior art date
Application number
PCT/JP2001/003137
Other languages
English (en)
Japanese (ja)
Inventor
Yoshio Wakayama
Original Assignee
Mitsubishi Plastics, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Plastics, Inc. filed Critical Mitsubishi Plastics, Inc.
Priority to JP2001574361A priority Critical patent/JP4065693B2/ja
Priority to KR1020027013745A priority patent/KR100663762B1/ko
Publication of WO2001076865A1 publication Critical patent/WO2001076865A1/fr

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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
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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

Definitions

  • the present invention relates to a resin-coated metal plate and a method for producing the same, and a container for a capacitor exterior using the resin-coated metal plate.
  • a resin-coated metal plate in which the surface of a metal plate such as an aluminum plate is coated with a thermoplastic resin coating film has excellent corrosion resistance, electrical insulation, and design, and is used in various fields.
  • an aluminum electrolytic capacitor stores a capacitor element impregnated with an electrolyte in a cylindrical container formed by drawing an aluminum plate, and seals the opening of the container with rubber, etc., and electrically insulates the outer peripheral surface. It is covered with a heat-shrinkable tube made of vinyl chloride resin or olefin resin for the purpose of displaying contents.
  • a metal-coated plate such as an aluminum plate is coated with an insulating resin to form a resin-coated plate.
  • This resin-coated plate is drawn or ironed to form an outer container or cap.
  • There has been proposed a technique for omitting the step of covering with a heat-shrinkable tube and at the same time achieving an insulating property for example, Japanese Patent Laid-Open No. 1-17522, Japanese Utility Model Application Laid-Open No. 3-799974). No., etc.).
  • Techniques for coating the surface of an aluminum plate with an insulating resin to form a resin-coated plate include a method of applying an epoxy resin, a vinyl chloride resin, or a polyester resin to the surface of an aluminum plate, and a method of coating the surface of the aluminum plate. There is a method of laminating a resin film on the substrate.
  • the resin-coated metal sheet with the coating film formed by these conventionally known methods has the disadvantage that the interface between the aluminum plate and the coating film is peeled off in secondary processing steps such as drawing and ironing. was there.
  • the present invention provides excellent adhesion (adhesion or adhesive strength), and even when drawing or ironing is performed, delamination occurs at the interface between the aluminum plate and the thermoplastic resin coating film, and the thermoplastic resin is removed.
  • An object of the present invention is to provide a resin-coated metal plate that does not cause breakage or cracks of a coating film produced, hardly causes delamination over time, and that can be efficiently manufactured. Disclosure of the invention
  • the present invention forms a chemical conversion thin film on the surface of a metal plate, forms a thin film of a silane coupling agent on the surface of the chemical conversion thin film, and forms a thin film of a thermoplastic resin on the surface of the thin film.
  • the above problem was solved by forming a coating film.
  • the corrosion resistance of the metal plate can be improved, and the adhesion between the metal plate and the coating film made of a thermoplastic resin can be improved.
  • the organic functional group of the silane coupling agent reacts with the thermoplastic resin to form a strong bond, thereby forming an interface between the metal plate or the chemical conversion-treated thin film and the coating film made of the thermoplastic resin.
  • the silane coupling agent are firmly bound via the silane coupling agent. For this reason, peeling between eyebrows between the metal plate and the thermoplastic resin coating film, breakage of the thermoplastic resin coating film, and the like can be prevented.
  • a chemical conversion treatment thin film is formed on the surface of the metal plate, and a thin film of a silane coupling agent is formed on the surface of the chemical conversion treatment thin film (hereinafter, referred to as a “silane coupling agent thin film”).
  • a coating film made of a thermoplastic resin hereinafter, referred to as a “thermoplastic resin coating film” formed on the surface of the thin film.
  • the above-mentioned metal plate refers to a plate made of various metals such as iron, various stainless steels, copper, copper alloy, aluminum, aluminum alloy, tin alloy, steel plate, nickel, and zinc. Among these, an aluminum plate is more preferable.
  • the aluminum constituting the aluminum plate means pure A1 and A1 alloy. More specifically, pure A1, JISA1500, A1100, A1200 JIS 1000 series alloys such as 0, Al-Mn series JIS 300-series alloys such as JISA300, A3004, etc. Al-Mg JIS 50,000 series Alloys, etc., but aluminum is not limited to those exemplified.
  • the thickness of the aluminum plate is preferably from 0.1 mm to 0.5 mm, and more preferably from 0.2 mm to 0.5 mm.
  • the chemical conversion treated thin film improves the corrosion resistance and adhesion of the metal plate.
  • the thickness of the chemical conversion thin film is not particularly limited, but is preferably 1 to 300 A (0.1 to 300 nm). If the thickness of the chemical conversion thin film is less than 50 A (5 nm), the workability may be inferior, for example, when the resin-coated metal plate is drawn, the coating resin may be peeled off. If it exceeds 300 nm), it may be difficult to form a thin film.
  • the range of 500 to 200 A (0, 05 to 2 m) is preferable, and the range of 100 to 200 A is preferable. (0.1 to 2 m) is more preferable. In the case of other thin films, the range of 50 to 300 A (5 to 300 nm) is preferable. If the thickness of the anodic oxide coating is less than 0.05 m, it may not be possible to improve the adhesion, while if it exceeds 2, a long oxidation treatment may be required and the productivity may be poor. .
  • the thickness of the anodic oxide film can be adjusted to the above range by adjusting the processing conditions, in particular, the energizing conditions and the energizing time.
  • the anodized thin film may be an alumite-treated thin film that has been treated with at least an electrolyte containing phosphoric acid.
  • an alumite-treated thin film using phosphoric acid as an electrolyte An alumite-treated thin film using phosphoric acid and sulfuric acid, an alumite-treated thin film using phosphoric acid and oxalic acid as the electrolyte, and an electrolyte And alumite-treated thin films using phosphoric acid and chromic acid.
  • the treatment with phosphoric acid alumite is preferred.
  • electrolytic treatment was performed in a silane coupling addition bath, followed by film lamination.
  • electrolytic treatment was performed in an epoxy mulsion bath. After laminating the film, forming alumite phosphate, electrolytic treatment in a mixed bath of silane coupling agent and epoxy emulsion, and then film laminating. Silane capping treatment or epoxy treatment After emulsion coating, film lamination can also be used.
  • anodic oxide film By forming an anodic oxide film on the surface of the aluminum plate, it is possible to improve the adhesion (adhesion or adhesive strength) between the aluminum plate and the interface of the thermoplastic resin-coated resin film.
  • the surface of the metal plate is composed of a single layer film of chromium hydrated oxide, or a metal chromium layer (lower layer) and a chromium hydrated oxide layer (upper layer).
  • the amount of chromium is 2 to 200 mg / m 2 and the amount of chromium in the upper layer is about 5 to 3 O mg / m 2 .
  • the silane coupling agent thin film is formed by applying the silane coupling agent on the metal plate or the chemical conversion thin film and drying. This thin film functions to improve the adhesion between the metal plate and the thermoplastic resin coating film.
  • the silane coupling agent is an organic silicon compound having two or more different reactive groups in its molecule.
  • One of the two reactive groups is a reactive group that chemically bonds to an inorganic material such as glass or metal, and the other is a reactive group that chemically bonds to an organic material such as various synthetic resins.
  • the reactive group bonded to the metal plate or the chemical conversion thin film, which is an inorganic material is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, and a silanol group.
  • examples of the reactive group chemically bonded to the organic material include an epoxy group, an amino group, a vinyl group, a methacryl group, and a mercapto group.
  • Typical silane coupling agents include ⁇ -glycoxydoxypropyl ethoxylate. Examples thereof include silane, araminopropyltriethoxysilane, and 3-methacryloxypropyltrimethoxysilane.
  • the aluminum plate and the silane coupling agent form a bond of A1-0-Si to form a strong bond, and the thermoplastic resin and the silane coupling agent form an organic functional group of the silane coupling agent. Reacts with thermoplastic resin to form a strong bond. For this reason, the interface between the aluminum plate and the thermoplastic resin coating film is firmly bonded via the silane coupling agent.
  • silane capping agents examples include vinyltrimethoxysilane, clopropylproprimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-aminopropyltriethoxysilane.
  • a silane force Dzupuri ring agent 0. 0 1 ⁇ 1 0 0 O mg / m 2 laid is preferred to apply to form, 0. More preferably, it is formed by applying 5 to 500 mg / m 2 .
  • the coating amount of Shiranka Dzupuri ring agent is zero.
  • a silane coupling agent onto a metal plate or anodized film dilute the silane coupling agent with alcohol or water to uniformly dissolve or disperse the silane coupling agent in order to increase the surface wettability, and reduce the surface tension. It is preferable to lower and apply evenly.
  • a method for lowering the surface tension there is a method of adding an organic compound such as an organic solvent or a surfactant.
  • the concentration of the silane coupling agent aqueous solution is not particularly limited, but the silane coupling agent is added to 100 parts by weight of water. It is preferred that the content be contained in a proportion of 0.01 to 10 parts by weight. If the amount of the silane coupling agent is less than 0.01 part by weight, the above-mentioned adhesive function may not be sufficiently achieved. Meanwhile, 10 parts by weight If the ratio exceeds the above range, the silane coupling agent tends to agglomerate, and similarly, the adhesive function may not be sufficiently performed.
  • the aqueous solution of the silane coupling agent so that the contact angle when applied to the surface of the metal plate or the chemical conversion thin film is 55 ° or less.
  • the magnitude of the contact angle is determined by the surface tension between the metal plate and the aqueous solution of the silane coupling agent, and this surface tension is easily determined by the type and amount of the organic solvent and the surfactant added to the aqueous solution of the silane coupling agent.
  • the organic solvent include ethanol, isopropanol, and the like.
  • the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. be able to. These organic solvents and surfactants are appropriately selected from those which do not impair the stability of the aqueous solution of the silane coupling agent, and are added in appropriate amounts.
  • the contact angle is greater than 55 °, the surface tension between the metal plate and the aqueous solution of the silane coupling agent increases, making it difficult to form a uniform coating film on the surface of the metal plate. In some cases, this cannot be achieved sufficiently.
  • a kind and amount of a thickener or an antiseptic that maintains a contact angle of 55 ° or less can be added to the aqueous solution of the silane coupling agent.
  • the contact angle is measured by a so-called droplet method in which the contact angle of a droplet of the aqueous solution of the silane coupling agent attached to the surface of the metal plate is measured by various measuring instruments.
  • a method of applying the silane coupling agent aqueous solution to the surface of the metal plate a commonly used method, for example, a dip method, a spray method, a roll coating method, a gravure roll method, a reverse roll method, or an air knife is used.
  • Method, kiss roll method, spray coat method, bar coat method, date coating method, gravure orifice method, reverse roll method, air-nife coat method and the like can be employed.
  • organic and inorganic additives such as a viscosity modifier, an antifoaming agent, a coloring agent such as a pigment and a dye, a stabilizer, and a solvent for adjusting the solubility can also be added to the silane coupling agent. .
  • the temperature is raised from room temperature to 150 ° C. at a rate of 5 to 50 ° C./s.
  • the coating film formed by applying and drying the above silane coupling agent aqueous solution has a Si element amount of 5 to 1 when its surface is measured by X-ray photoelectron spectroscopy (hereinafter referred to as “ESCA method”). Preferably, it is 5 atomic%. If the content of the Si element is lower than 5 atomic%, it is not preferable because the adhesive function of the aqueous solution of the silane coupling agent cannot be sufficiently obtained. Further, even if the amount of the Si element exceeds 15 atomic%, the adhesive function of the aqueous solution of the silane coupling agent is not further improved.
  • the ESCA method is a solid surface analysis method using electron spectroscopy, and irradiates soft X-rays under high vacuum to the surface of solid samples such as metals, ceramics, inorganic compounds, and polymer materials.
  • the photoelectrons emitted from the surface of the solid sample are detected by an electrostatic energy analyzer, and the type, oxidation state, bonding state, and the like of elements on the surface of the solid sample are analyzed.
  • the measurement conditions of this ESCA method can use ordinary measurement conditions without limitation. For example, MgK, A1K, etc. can be used as the X-ray source, and the output is 15 kvx3. 3 mA, it is possible to set the degree of vacuum such as 5 x 1 0- 8 T orr a.
  • thermoplastic resin coating film improves the electrical insulation and chemical resistance of the resin-coated metal plate, and is used as a printing surface for identification display.
  • thermoplastic resin coating film examples include a film made of a thermoplastic resin.
  • thermoplastic resin examples include a polyester resin and a polyamide resin.
  • polyester resin examples include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexadimethylene terephthalate, and copolyesters thereof, and polyester resins described above.
  • Polyolefin resins such as poly (ethylene / polypropylene), ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, copolymers of ethylene and acrylic acid derivatives, and polyesters of these Examples of the mixture include a resin mixture.
  • polyamide resin examples include polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 46- Aromatic polyamides such as copolymerized polyamides, mixed polyamides, polymethaxylenediene adipamides containing at least 90 mol% of structural units formed by the polycondensation reaction of metaxylylenediamine and adipic acid, and amorphous polyamides And polyamide-based elastomers, impact-resistant polyamides, and mixtures of these polyamide-based resins.
  • Aromatic polyamides such as copolymerized polyamides, mixed polyamides, polymethaxylenediene adipamides containing at least 90 mol% of structural units formed by the polycondensation reaction of metaxylylenediamine and adipic acid, and amorphous polyamides And polyamide-based elastomers, impact-resistant polyamides, and mixtures of these polyamide-based resins.
  • polyamide-based resin with a melting point of 180 ° C or more is used to manufacture a capacitor exterior container from a resin laminate. It can be suitably used when performing.
  • thermoplastic land resin coating film is not particularly limited, and may be extrusion molding using a coat hanger die, a T-die, an I-die, an inflation die, or a calender. It can be manufactured by a conventionally known method such as a molding method.
  • This thermoplastic land resin coating film may be unstretched or biaxially stretched.
  • thermoplastic resin coating film may be laminated on the silane coupling agent thin film using the film formed above, and the thermoplastic resin may be coated on a die such as a T die or an I die. It may be laminated on the silane coupling agent thin film while extruding it into a thin film by an extruder equipped with a silane coupling agent.
  • Resin additives can be added to the thermoplastic resin as needed before forming the film.
  • Resin additives include colorants such as dyes and pigments, lubricants, antiblocking agents, heat stabilizers, antistatic agents, light stabilizers, antioxidants, ultraviolet absorbers, impact modifiers, and antioxidants. Agents, antistatic agents and the like. These resin additives can be blended within a range that does not adversely affect the thermoplastic resin coating film.
  • surface treatment such as corona treatment or flame treatment can be performed for the purpose of improving adhesion (the thickness of the thermoplastic resin coating film is preferably 5 to 200 m, and 5 to 100 m.
  • the thickness of the coating film is less than 5 zm, pinholes are likely to occur, and the corrosion resistance and electrical insulation properties of the aluminum plate, etc. In some cases, it may be difficult to improve the heat resistance, and it may be extremely difficult to laminate the thermoplastic resin coating film on the metal plate. Not only is it too thick, cracks and the like tend to occur during drawing and ironing, and it is not economically favorable.
  • a coating film made of a thermoplastic resin is formed on the silane coupling agent thin film,
  • the layering method includes a continuous method and a patch method.
  • the silane coupling agent is applied on the metal plate or the chemical conversion thin film.
  • the liquid component in which the silane coupling agent is dispersed is scattered by heating to a temperature of 250 to 350 ° C.
  • the thermoplastic resin is extruded into a thin film by an extruder equipped with a die such as a T-die or an I-die, and is laminated while extruding the thermoplastic resin.
  • Pressure lamination is performed using a heated nip roll or the like. After stacking, it is immediately cooled by air cooling or water cooling.
  • the temperature at the time of lamination is lower than 250 ° C, the adhesion between the aluminum plate and the coating film made of thermoplastic resin may not be sufficient, and if the temperature is higher than 350 ° C, Thermal degradation of the film progresses, and the coating film may be damaged or cracked during drawing or ironing.
  • the above-mentioned patch method means that a metal plate on which a silane coupling agent thin film is formed is heated to a melting point of up to 350 ° C. (preferably, at 200 ° C. to 350 ° C.). It is a NIPPRO that extrudes it into a thin film by using an extruder equipped with a die such as a T-die or an I-die, stacks it, or heats an already formed thermoplastic resin coating film below the melting point of the thermoplastic resin. This is a method of cooling by air cooling or water cooling immediately after lamination.
  • the thermoplastic land thermoplastic resin coating film does not adhere sufficiently, and when the resin-coated metal plate is processed, the thermoplastic resin coating film becomes inconsistent.
  • the resin-coated metal sheet may be peeled off, and the thermoplastic resin coating film of the resin-coated metal plate may be too hard, resulting in poor moldability.
  • the temperature is higher than 350 ° C, the metal of the resin-coated metal plate becomes too soft and its strength is remarkably reduced, and dents and the like may easily occur. It may deteriorate.
  • the above melting point refers to the peak temperature of the crystal melting temperature when the temperature is raised at 10 ° C./min by a differential scanning calorimeter (DSC).
  • the hardness of the resin measured from the outer surface of the thermoplastic resin coating film constituting the resin-coated metal sheet is in the range of 25 to 60. . If the Vickers hardness of the resin-coated surface of the aluminum thin plate is less than 25, the resin-coated metal plate may be too soft and formability may be deteriorated.On the other hand, if the Vickers hardness exceeds 60, the resin Coated metal plate is too hard There are cases.
  • the above-mentioned “Pitka hardness” refers to hardness measured in accordance with JISZ2244 “Beakers hardness test-one test method”.
  • an anodic oxide film having a thickness of 0.05 to 2 ⁇ m is formed on the surface of an aluminum plate, and a silane printing agent is applied to the anodic oxide film in a thickness of 0.5 to 500 ⁇ m. was applied at a rate of mg / m 2, further thickness on the thin film of the Shirankappuri ring agent 5 - 2 0 0 a thermoplastic resin covering layer of m, the 2 5 0 ⁇ 3 5 0 ° C
  • a method of producing a resin-coated metal plate by melt-coating in a temperature range is exemplified.
  • a chemical conversion thin film is formed on one side of an aluminum plate having a thickness of 0.1 to 0.5 mm, and then a silane coupling agent is applied on this thin film in a thickness of 0.01 to 10 mm. 0 0 mg / m 2 coating to form a thin film, further, heating the Aruminiumu plate film was laminated in the chemical conversion treatment film ⁇ beauty Shirankatsupuri ring agent in a temperature range of 2 0 0 ⁇ 3 5 0 ° C , the A thermoplastic resin film with a thickness of 5 to 200 mz is coated and pressed from above the thin film of the silane coupling agent, and the Vickers hardness of the thermoplastic resin coating film is in the range of 25 to 60.
  • a silane coupling agent is added in a proportion of 0.01 to 10 parts by weight with respect to 100 parts by weight of water, and the contact angle when applied to the surface of the metal plate is 55 to 50 parts by weight. ° C or less is applied to the surface of the metal plate, and dried at a heating rate of 50 ° C / s or less to form a coating film.
  • a resin-coated metal plate is produced by heating in a temperature range of 50 ° C. and laminating a coating film made of a thermoplastic resin on the surface of the coating film.
  • the resin-coated metal plate according to the present invention When the resin-coated metal plate according to the present invention is processed by the ironing method, cracks are not easily generated in the thermoplastic resin coating film, and the thermoplastic resin coating film is easily peeled off from the metal plate. Since there is no such material, the tree-covered metal plate can be suitably used as a material for a container manufactured through a plurality of secondary processes such as a bending process, a drawing process, and an ironing process. In addition, this resin-coated metal plate was manufactured using this resin-coated metal plate because the thermoplastic resin coating film does not easily peel off from the metal plate even when heated after processing by various processing methods. The container can withstand heating.
  • the resin-coated metal plate is excellent in pre-processability such as drawing, and can be suitably used for production of a container for an aluminum electrolytic capacitor exterior.
  • resin coating If the Vickers hardness of the cover is in the range of 25 to 60, even if the containers come into contact with each other during press working, or even if the product containers come into contact with each other, dents will occur on the top and side surfaces of the container. This makes it harder to cause such problems, improves the pressure resistance, and makes it possible to provide a beautiful identification printed indication on the top surface of the container.
  • the above resin-coated metal plate can be suitably used as a material for a wall of a building, a partition plate, a design material, a material for manufacturing various cans, and particularly, a container for a capacitor.
  • a resin-coated metal plate on which a coating film made of thermoplastic thermoplastic resin with excellent heat resistance is laminated. It is also preferable to process the coating so that the coating film made of thermoplastic thermoplastic resin is on the outside.
  • the outer container for the capacitor include an outer container for an electrolytic capacitor, an electrolytic capacitor cap, and the like.
  • the resin-coated metal sheet obtained in the test example described below was evaluated by the following method.
  • ⁇ (1) Drawability The resin-coated metal sheet obtained in the test example was Sent to a lance progressive drawing machine and manufactured 100 cylindrical containers (ironing rate 20%) of l O mm 0 x 2 O mm with the thermoplastic resin coating film on the outer surface of the container, and the surface of the aluminum plate The interface between the coating and the coating film was visually observed, and if no delamination was observed at the interface, it was regarded as a non-defective product and indicated as a non-defective product rate (%) or “ ⁇ ”.
  • Diaminosilane N— 2-aminoethyl-3-aminopropyl trimethoxysilane
  • Anodized phosphoric acid-treated coatings with a thickness of 0.05 to 2 / m are excellent in drawing and caulking, and are suitable for each process. No delamination was observed at the interface, and no change over time (deterioration) was observed (see Test Examples 2, 4, and 5).
  • the one coated with silane coupling agent is excellent in drawability and caulking, no delamination is observed at the interface in each process, and no change over time (deterioration) is observed.
  • Both surfaces of a 0.3 mm thick aluminum plate (JISA1500 H22) are anodized with a 20% phosphoric acid solution to form a 0.5 m thick aluminum phosphate.
  • a treated film was formed.
  • a silane coupling agent having a peridode group was applied at 20 mg / m 2 on the coating, and the coated surface was heated to 250 ° C.
  • a film having a thickness of 15 m separately manufactured using the resin shown in Table 3 was overlaid on the heated application surface, and laminated by pressing with a pair of pressure rolls to obtain a resin-coated metal plate. With respect to the obtained resin-coated metal plate, an evaluation test of the above items was performed. Table 3 shows the evaluation test results. Table 3
  • the coating film of the aluminum plate is a polyester resin or polyamide resin, it has excellent drawability and caulking workability, no delamination is observed at the interface in each process, and there is a change with time (deterioration). Not recognized (see Test Examples 13 and 14).
  • a resin-coated metal plate was obtained according to the method of Test Example 13 except that the anodizing treatment was performed as described below. With respect to the obtained resin-coated metal plate, an evaluation test of the above items was performed. Table 5 shows the evaluation test results.
  • Anodizing treatment was performed according to the methods of electrolyte numbers 1 to 4 shown in Table 4.
  • the organic acids used in electrolyte No. 4 are dicarboxylic acid (maleic acid, malonic acid), aromatic sulfonic acid (sulfosalicylic acid, sulfofuric acid), carboxylic acid sulfonate (sulfomaleic acid), and sulfonic acid. (Sulfamic acid) and the like.
  • the treatment conditions are as follows: phosphoric acid concentration: 0.1 to 500 g / l, sulfuric acid 'oxalic acid' chromic acid, concentration of any of the above organic acids: 0.1 to 500 gZl, voltage : 1 to: L00 vA C,:! ⁇ L OO vD C alone or superimposed, time ::! ⁇ 60 min, Thin film Thickness: 50 A ⁇ 50 ⁇ m, Phosphate anion content::! 5500 ppm. Table 4
  • 'Other condition number 2 After forming alumite phosphate, perform AC or DC electrolysis (substrate is negative electrode) in an epoxy emulsion bath, and then perform film lamination.
  • condition number 3 After forming the alumite phosphate, perform AC electrolysis or DC electrolysis (substrate is negative electrode) in a mixed bath of silane capping agent and Epoxy marjon, and then perform film lamination.
  • condition number 4 After electrolytic treatment of other condition numbers 1 to 3 above, perform silane coupling treatment or epoxy emulsion coating, and then perform film lamination.
  • test Examples 20 to 33 shown below The evaluation method will be described.
  • a polyimide resin-coated metal plate was obtained in the same manner as in Test Example 21 except that the chemical conversion-treated thin film was replaced with a thin film formed by alumite phosphate chemical conversion treatment. .
  • Table 6 shows the results of the evaluation of the obtained polyamide resin-coated metal sheet by the above evaluation method.
  • Example 20 In the example described in Test Example 20, the same procedure as in Example 2 was repeated except that the coupling agent was changed to methacryloxypropyl methoxysilane and the temperature of the aluminum plate was changed to 380 ° C. Thus, a polyimide resin-coated metal plate was obtained.
  • Table 7 shows the results of the evaluation of the obtained polyamide resin-coated metal sheet by the above evaluation method.
  • silane coupling agents are as follows. The same applies to the following table.
  • Epoxysilane type ⁇ -glycidoxypropyltriethoxysilane
  • Aminosilane type y-aminopropyltriethoxysilane
  • Acrylic silanes 3-methacryloxypropyl trimethoxysilane Table 7
  • a chemical conversion thin film is provided on the surface of an aluminum thin plate, a layer of a silane-based coupling agent is provided thereon, and the temperature of the aluminum thin plate is heated to a temperature in the range of 200 to 350 ° C to form a resin film.
  • a chemical conversion thin film and a silane-based coupling agent layer are provided on the surface of the aluminum sheet, and the temperature of the aluminum sheet is coated at 200 ° C.
  • the hardness of the resin-coated surface exceeds 60 in Vickers hardness, the aluminum thin plate of the substrate is damaged during the press working (see Test Example 28).
  • Example 23 the procedure was the same as in Example 2, except that the coating amount of the capping agent was changed to 500 mg / m 2 and the temperature of the aluminum plate was changed to 290 ° C. Thus, a polyimide resin-coated metal plate was obtained.
  • Table 8 shows the results of the evaluation of the obtained polyamide resin-coated metal plate by the above evaluation method.
  • Test Example 3 1 In the example described in Test Example 3 0, except for changing the coating amount of Katsupuri ring agent 1 0 0 0 m gZm 2, to obtain a made of Polyamide resin-coated metal sheet by the same procedure as in the Example.
  • Table 8 shows the results of the evaluation of the obtained polyamide resin-coated metal sheet by the above evaluation method.
  • Table 8 reveals the following.
  • a thin film is provided on the surface of an aluminum thin plate, a layer of a silane coupling agent is provided thereon, and the coating amount of the silane coupling agent is 0.01 to 100 mg / m 2.
  • the press workability is excellent, and even if the containers come into contact with each other, the wall surface is unlikely to be dented (see Test Examples 29 to 31).
  • the application amount of the silane-based coupling agent was 0.05 mg / m 2 In the case of a small amount, the adhesion between the aluminum thin plate and the coating film was poor, and the coating film was peeled off during pressing (see Test Example 32).
  • test Examples 34 to 52 shown below are shown.
  • the evaluation method of the silane coupling agent aqueous solution was based on the method described in the following (1) and (2).
  • the evaluation method of the resin laminate is based on the following methods (3) to (6).
  • An aluminum plate (same type as that prepared in Test Example 38) was continuously transferred as a long strip, and 100 g of water was added to the surface of this aluminum plate with a silane coupling agent (alumino). Propylene triethoxysilane) 0.1 lg and nonionic surfactant (Same type as used in Test Example 34) An aqueous solution of a silane coupling agent in which 0.4 g was blended and the contact angle was adjusted to 50 ° when applied to the surface of the aluminum plate.
  • silane coupling agent alumino
  • Propylene triethoxysilane 0.1 lg
  • nonionic surfactant (Same type as used in Test Example 34)
  • Resin laminates were prepared by laminating boriamid 6 thin films having a melting point of 220 ° C and a thickness of 20 m. In the step of preparing the resin laminate, the measurement (3) was performed, and the obtained resin laminate was subjected to the evaluation tests (4) to (6). Table 11 shows the results.
  • the specific range of the amount of the silane coupling agent, the contact angle of the aqueous solution of the silane coupling agent, the rate of temperature rise during drying after applying the aqueous solution of the silane coupling agent, and the heating temperature of the coating film are all within a specific range.
  • the resin laminate prepared as the inside had a Si element content on the surface of the coating film within the range of 5 to 15 atomic%, and was excellent in workability and adhesion after processing (Test Examples 46 to 60). See 48).
  • a resin laminate prepared using a silane coupling agent aqueous solution containing a silane coupling agent in an amount of 0.01 part by weight or less has a coating element surface with an elemental Si content of less than 5 parts. % And lower adhesion after processing (see Test Example 49).
  • a resin laminate prepared by heating the coating film at a temperature higher than 350 ° C has poor workability such as cracks in the polyethylene terephthalate thin film during processing, and also has poor adhesion after processing. Was inferior. (See Test Example 52). Industrial applicability
  • the present invention has the following particularly advantageous effects, and its industrial utility value is extremely large.
  • the surface of the aluminum plate and the aluminum plate can be removed. Excellent adhesiveness (adhesion or adhesive strength) at the interface of the coating film. Even if drawn or ironed, the coating film made of thermoplastic resin will not be damaged or cracked. Peeling is unlikely to occur.
  • the hardness of the resin-coated surface of the aluminum sheet is in the range of 25 to 60 in terms of Vickers hardness. Excellent, and even if the containers obtained by processing are in contact with each other, dents do not easily occur on the wall surface.
  • the outer container for an aluminum electrolytic capacitor according to the present invention does not require a step of coating with a heat-shrinkable tube unlike the conventional case, and the manufacturing process is simple.
  • the resin-coated metal plate of the present invention forms a coating film by applying an aqueous solution of a specific silane coupling agent to the surface of the metal plate and drying it at a specific heating rate, and forming the coating film at a specific temperature.
  • a specific silane coupling agent a specific silane coupling agent
  • the thermoplastic resin thin film is prepared by laminating the thermoplastic resin thin film by heating in the above process, when the resin-coated metal plate is processed by the ironing method, the thermoplastic resin thin film is hardly cracked, and the thermoplastic resin thin film is hardened. It does not easily peel off from the metal plate.
  • the resin-coated metal plate according to the present invention forms a coating film by applying a specific aqueous solution of a silane coupling agent to the surface of the metal plate and drying it at a specific heating rate.
  • a specific aqueous solution of a silane coupling agent to the surface of the metal plate and drying it at a specific heating rate.
  • the resin-coated metal plate according to the present invention heats the coating film formed on the surface of the metal plate in a temperature range of 350 ° C. from the melting point of the thermoplastic resin thin film to form the thermoplastic resin thin film.
  • the strength of the metal plate does not decrease, and the thermoplastic resin thin film does not deteriorate.
  • the resin-coated metal plate according to the present invention heats the coating film formed on the surface of the metal plate in a temperature range of 350 ° C. from the melting point of the thermoplastic resin thin film to form the thermoplastic resin thin film.
  • the economic disadvantages of conventional high-temperature heat treatment are eliminated.
  • the external container for a capacitor according to the present invention is prepared by squeezing or ironing the resin-coated metal plate, so that even if it is heated after being commercialized,
  • the thermoplastic resin thin film that constitutes the outer packaging container for the capacitor does not peel off from the metal plate, and has high commercial value.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Feuille de métal couverte de résine qui est constituée d'une feuille de métal, d'un film mince de revêtement de conversion chimique formé sur la surface de la feuille de métal, d'un film mince d'un agent de pontage de silane formé sur la surface du film de revêtement, et d'un film de revêtement constitué d'une résine thermoplastique formé sur la surface du film mince. Ladite feuille de métal couverte d'une résine possède une excellente adhésivité (pouvoir adhésif ou force d'adhésion), ne présente pas de dommages ou de fissures dans le film de résine thermoplastique et est moins sujette, pendant une longue période, à la séparation au niveau de l'interface entre une feuille d'aluminium et un film de résine thermoplastique, même quand elle est soumise à un fort étirage. Cette feuille peut en outre être produite avec un haut rendement.
PCT/JP2001/003137 2000-04-12 2001-04-11 Feuille de metal couverte d'une resine et procede de fabrication de ladite feuille WO2001076865A1 (fr)

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Cited By (15)

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JP2003286581A (ja) * 2002-03-29 2003-10-10 Sumitomo Metal Ind Ltd 表面処理ステンレス鋼板とその製造方法
WO2005041226A1 (fr) * 2003-10-29 2005-05-06 Showa Denko K. K. Condensateur electrolytique
JP2005210069A (ja) * 2003-10-29 2005-08-04 Showa Denko Kk 電解コンデンサ
JP2006316834A (ja) * 2005-05-11 2006-11-24 Honda Motor Co Ltd 圧力容器用ライナの製造方法
JP2007258422A (ja) * 2006-03-23 2007-10-04 Sanyo Electric Co Ltd 固体電解コンデンサ及びその製造方法
JP2007266202A (ja) * 2006-03-28 2007-10-11 Saga Sanyo Industries Co Ltd 電解コンデンサの製造方法
US7495888B2 (en) 2003-10-29 2009-02-24 Showa Denko K.K. Electrolytic capacitor
JP2009059287A (ja) * 2007-09-03 2009-03-19 Mitsubishi Electric Corp Ｒｆｉｄタグの製造方法
JP2009212117A (ja) * 2008-02-29 2009-09-17 Nichicon Corp コンデンサ用ケース、該コンデンサ用ケースを備えたコンデンサおよびコンデンサ用ケースの製造方法
JP2013091855A (ja) * 2005-08-31 2013-05-16 Castrol Ltd アルコキシシランコーチング
JP2013150964A (ja) * 2012-01-26 2013-08-08 Mitsubishi Alum Co Ltd 加工性に優れる表面処理アルミニウム板の製造方法
JP2013221210A (ja) * 2012-04-19 2013-10-28 Hitachi Ltd 防食処理アルミニウム材及びその製造方法
WO2015150116A1 (fr) * 2014-03-31 2015-10-08 Volkswagen Ag Pièce hybride métal-plastique et procédé de production
JP2019085459A (ja) * 2017-11-02 2019-06-06 株式会社放電精密加工研究所 アルマイト材の代替材料に用いることができる表面被覆基材、その基板表面にトップコート層を形成するための塗料組成物
CN114799031A (zh) * 2022-04-20 2022-07-29 无锡神意环件法兰有限公司 轮胎模具用锻件的生产工艺及其用途

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CN101900245B (zh) * 2009-05-27 2014-08-13 晟铭电子科技股份有限公司 板件结构及其制造方法
WO2011001862A1 (fr) * 2009-06-30 2011-01-06 関西ペイント株式会社 Procédé de production d'un élément en acier inoxydable ayant un film de revêtement
CN102505134B (zh) * 2011-12-21 2014-11-26 广东生益科技股份有限公司 散热基板用铝板及其处理方法
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JP6066896B2 (ja) 2013-12-17 2017-01-25 日新製鋼株式会社 成形材製造方法
CN104790009B (zh) * 2014-01-16 2017-09-29 深圳富泰宏精密工业有限公司 金属与树脂的复合体的制备方法及由该方法制得的复合体
CN105729717B (zh) * 2014-12-09 2018-05-29 深圳富泰宏精密工业有限公司 金属与树脂的复合体的制备方法及由该方法制得的复合体
TWI727112B (zh) * 2017-10-31 2021-05-11 中國鋼鐵股份有限公司 絕緣鋁材之製造方法及其絕緣鋁材、絕緣鋁殼與電子元件產品
CN108660495A (zh) * 2018-03-30 2018-10-16 江苏三锋汽车饰件有限公司 一种铝合金多彩涂层防腐蚀处理工艺
CN109066503A (zh) * 2018-07-02 2018-12-21 安徽坤和电气有限公司 一种耐腐蚀的高强塑钢电缆桥架
JP6764517B1 (ja) * 2019-11-08 2020-09-30 ドングァン ディーエスピー テクノロジー カンパニー リミテッド アルミニウム表面処理方法

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Cited By (21)

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JP2003286581A (ja) * 2002-03-29 2003-10-10 Sumitomo Metal Ind Ltd 表面処理ステンレス鋼板とその製造方法
JP4532235B2 (ja) * 2003-10-29 2010-08-25 昭和電工株式会社 コンデンサ
WO2005041226A1 (fr) * 2003-10-29 2005-05-06 Showa Denko K. K. Condensateur electrolytique
JP2005210069A (ja) * 2003-10-29 2005-08-04 Showa Denko Kk 電解コンデンサ
US7495888B2 (en) 2003-10-29 2009-02-24 Showa Denko K.K. Electrolytic capacitor
JP2006316834A (ja) * 2005-05-11 2006-11-24 Honda Motor Co Ltd 圧力容器用ライナの製造方法
JP2013091855A (ja) * 2005-08-31 2013-05-16 Castrol Ltd アルコキシシランコーチング
JP2007258422A (ja) * 2006-03-23 2007-10-04 Sanyo Electric Co Ltd 固体電解コンデンサ及びその製造方法
JP4688710B2 (ja) * 2006-03-28 2011-05-25 佐賀三洋工業株式会社 電解コンデンサの製造方法
JP2007266202A (ja) * 2006-03-28 2007-10-11 Saga Sanyo Industries Co Ltd 電解コンデンサの製造方法
JP2009059287A (ja) * 2007-09-03 2009-03-19 Mitsubishi Electric Corp Ｒｆｉｄタグの製造方法
JP4706677B2 (ja) * 2007-09-03 2011-06-22 三菱電機株式会社 Ｒｆｉｄタグの製造方法
JP2009212117A (ja) * 2008-02-29 2009-09-17 Nichicon Corp コンデンサ用ケース、該コンデンサ用ケースを備えたコンデンサおよびコンデンサ用ケースの製造方法
JP2013150964A (ja) * 2012-01-26 2013-08-08 Mitsubishi Alum Co Ltd 加工性に優れる表面処理アルミニウム板の製造方法
JP2013221210A (ja) * 2012-04-19 2013-10-28 Hitachi Ltd 防食処理アルミニウム材及びその製造方法
WO2015150116A1 (fr) * 2014-03-31 2015-10-08 Volkswagen Ag Pièce hybride métal-plastique et procédé de production
US10213961B2 (en) 2014-03-31 2019-02-26 Volkswagen Aktiengesellschaft Plastic-metal hybrid component and method for producing same
JP2019085459A (ja) * 2017-11-02 2019-06-06 株式会社放電精密加工研究所 アルマイト材の代替材料に用いることができる表面被覆基材、その基板表面にトップコート層を形成するための塗料組成物
JP7148237B2 (ja) 2017-11-02 2022-10-05 株式会社放電精密加工研究所 アルマイト材の代替材料に用いることができる表面被覆基材、その基板表面にトップコート層を形成するための塗料組成物
CN114799031A (zh) * 2022-04-20 2022-07-29 无锡神意环件法兰有限公司 轮胎模具用锻件的生产工艺及其用途
CN114799031B (zh) * 2022-04-20 2023-05-26 无锡神意环件法兰有限公司 轮胎模具用锻件的生产工艺及其用途

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TW590883B (en) 2004-06-11
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