WO2001076865A1

WO2001076865A1 - Metal sheet coated with resin and method for its production

Info

Publication number: WO2001076865A1
Application number: PCT/JP2001/003137
Authority: WO
Inventors: Yoshio Wakayama
Original assignee: Mitsubishi Plastics, Inc.
Priority date: 2000-04-12
Filing date: 2001-04-11
Publication date: 2001-10-18
Also published as: JP4065693B2; CN1216736C; MY129078A; KR100663762B1; CN1436122A; TW590883B; KR20030001419A

Abstract

A resin-coated metal sheet which comprises a metal sheet, a thin chemical conversion coating film formed on the surface of the metal sheet, a thin film of a silane coupling agent formed on the surface of the coating film, and a coating film of a thermoplastic resin formed on the surface of the thin film. The resin-coated metal sheet is excellent in adhesiveness (adhesive property or adhesion strength), and is free from the occurrence of delamination at the interface of an aluminum sheet and a thermoplastic resin coating film and the damage or cracks of the thermoplastic resin coating film and is less prone to delamination for a long period of time, even when it is subjected to deep drawing or ironing, and further, can be produced with good efficiency.

Description

Description Resin-coated metal sheet and manufacturing method

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. Background art

Conventionally, 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. Have been. For example, 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.

In recent years, the size of electronic components has been reduced, and aluminum electrolytic capacitors have also tended to be miniaturized.In addition, the development of chip-type electrolytic capacitors that eliminate lead wires for surface mounting is underway. . In such an aluminum electrolytic capacitor, it becomes extremely difficult to cover with a heat-shrinkable tube due to the small outer container, and the capacitor element contained in the outer container comes into contact with the inner surface of the outer container to achieve insulation. There was a disadvantage that there was no.

In order to eliminate the above drawbacks, 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. However, 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.

Therefore, 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

In order to solve the above problems, 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.

Since the chemical conversion thin film is provided, 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.

Furthermore, since a thin film of the silane coupling agent is interposed, 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. 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.

Hereinafter, the present invention will be described in detail.

In the resin-coated metal plate according to the present invention, 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”). And 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. As a chemical conversion thin film on a thin aluminum plate,

(a) Phosphoric acid chromate conversion thin film obtained by phosphoric acid chromate conversion treatment,

(b) a thin film composed of an organic thermoplastic resin coating film and chromium,

(c) a chemical conversion treated thin film containing zirconium by the chemical conversion treatment,

(d) a chemical conversion thin film containing titanium by chemical conversion; and

(e) Anodized thin film obtained by anodizing

And the like.

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.

Further, when the chemical conversion treated thin film is an anodized 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.For example, 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. Of these, the treatment with phosphoric acid alumite is preferred.

In addition to the methods described above, after the formation of alumite phosphate, electrolytic treatment was performed in a silane coupling addition bath, followed by film lamination.After the formation of alumite phosphate, 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.

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.

By the way, as a treatment of the metal surface, other than forming a chemical conversion thin film, there is a method of performing single-layer plating, multiple-layer plating or alloy plating, immersion chromic acid treatment, and phosphoric acid chromic acid treatment. Can be In addition, by performing electrolytic chromic acid treatment, 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). it is possible to form a two-layer film, when forming a single-layer coating rather then preferable for it to the 3~ 3 O mg Z m ² about chromium content, lower in the case of forming a two-layer film It is preferable that 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. On the other hand, 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 α-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.

Examples of the above silane capping agents that can be used include vinyltrimethoxysilane, clopropylproprimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-aminopropyltriethoxysilane. — 2—aminoethyl-1 3—aminopropyltrimethoxysilane, 3—mercaptopropyltrimethoxysilane, 3— (N—styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride, ureidoaminopropyldiethoxysilane, etc. Can be

Shirankappuri ring agent layer of the thin film on the metal plate or the chemical conversion treatment film, 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 . When the coating amount of Shiranka Dzupuri ring agent is zero. Less than 0 1 mg / m ^2, when the interface adhesion (adhesiveness) is not sufficient there is, more than 1 0 0 0 mg / m ² and the adhesive When the strength reaches saturation, the increase in adhesive strength is not proportional to the amount of application, and the silane coupling agent tends to agglomerate, making it difficult to apply uniformly.

To apply 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. As a method for lowering the surface tension, there is a method of adding an organic compound such as an organic solvent or a surfactant.

When the silane coupling agent is applied as an aqueous solution to the surface of a metal plate or a chemical conversion treated thin film, 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.

Further, it is preferable to adjust 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. Can be adjusted. Examples of the organic solvent include ethanol, isopropanol, and the like. Examples of 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.

If 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.

In addition to the organic solvent and the surfactant, 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.

As 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.

Various 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. .

After application, it is preferable to dry by evaporating and scattering the solvent and the like. When drying, it is preferable to raise the temperature at a heating rate of 50 ° C / s or less. If the temperature is increased at a rate exceeding 50 ° C / s, the applied silane coupling agent aqueous solution may be denatured. In short, the adhesive function of the coating film formed by the silane coupling agent aqueous solution may be reduced. It is particularly preferable that 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. In this method, 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.

A coating film made of a thermoplastic resin is formed on the silane coupling agent layer. This 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.

Examples of the thermoplastic resin coating film include a film made of a thermoplastic resin. Examples of the thermoplastic resin include a polyester resin and a polyamide resin. Examples of the polyester resin 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.

Examples of the polyamide resin 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.

Among these, from the viewpoint of heat resistance, especially from the viewpoint of heat resistance in one step of solder reflow, 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.

The method for forming the above-mentioned 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.

Moreover, the 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.

Various kinds of 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. Furthermore, 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. zm is preferred, and the range of 10 Atm to 50 m is more preferred If 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.

In the continuous method, first, the silane coupling agent is applied on the metal plate or the chemical conversion thin film. Next, the liquid component in which the silane coupling agent is dispersed is scattered by heating to a temperature of 250 to 350 ° C. Immediately, 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.

In this case, if 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.

On the other hand, 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.

In this case, if the melting point is lower than the melting point of the thermoplastic resin, 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. On the other hand, if 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).

In the resin-coated metal sheet according to the present invention, it is preferable that 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. In addition, the above-mentioned “Pitka hardness” refers to hardness measured in accordance with JISZ2244 “Beakers hardness test-one test method”.

Next, several specific examples of the method for producing the resin-coated metal sheet according to the present invention will be described.

As a first example, an anodic oxide film having a thickness of 0.05 to 2 μm 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 μm. 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.

As a second example, 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及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. There is a method for producing a resin-coated metal plate.

Further, as a third example, 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. There is a method in which 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.

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.

Further, 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. In addition, 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.

Further, 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. In addition, when manufacturing this container for an exterior of a capacitor, it is necessary to go through a solder reflow process, so use 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. Examples of the outer container for the capacitor include an outer container for an electrolytic capacitor, an electrolytic capacitor cap, and the like. Example

Hereinafter, the present invention will be described in more detail based on test examples, but the present invention is not limited to the following description examples without departing from the gist thereof. 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 “〇”.

(2) Caulking workability: Manufacture 100 cylindrical containers of 10 mm ø X 20 mm, rotate them at 100 rpm, and make a disk-shaped caulking sesame with a thickness of 3 mm. R = l, 5 mm semi-circular shape) and caulking so that the diameter becomes 7.5 mm (diameter change rate = 25%), and the interface between the aluminum plate surface and the coating film Was visually observed, and a sample without delamination at the interface was regarded as a non-defective product and indicated as a non-defective product rate (%) or “または”.

(3) Temporal change: 100 containers subjected to the caulking workability evaluation test described in (2) above were allowed to stand at room temperature for 10 days, and then visually observed again at the interface between the aluminum plate surface and the coating film. The product with no delamination at the interface was regarded as a non-defective product, and was regarded as a non-defective product ratio (%) Displayed.

[Experimental example 1]

(Test Examples 1 to 5)

Both sides of a 0.3 mm thick aluminum plate (JISA1500H22) were anodized with a 20% phosphoric acid solution, and phosphoric acid with the thickness shown in Table 1 was obtained. A lumite-treated film was formed. Next, the silane capping agent shown in Table 11 was applied to the anodic oxide coating at a rate of 5 Omg / m ² , and the coated surface was heated to 280 ° C. A film of polyimide 6 (melting point: 222 ° C), separately manufactured and having a thickness of 15 μm, was stacked on the heated application surface, and laminated by pressing with a pair of pressure rolls. Obtained. The obtained resin-coated metal sheet was subjected to the above-described evaluation tests. Table 1 shows the evaluation test results.

(Test Examples 6 to 7)

In the example described in Test Example 1, in place of the anodizing treatment with a 20% phosphoric acid solution, treatment with phosphoric acid chromate (chromium amount 1 O mg / m ² , Test Example 6) or treatment with alumite oxalate ( Test Example 7) was performed to form respective coatings. An evaluation test of the above items was performed on the obtained resin-coated metal plate. Table 1 shows the evaluation test results.

[* 1] The abbreviation of the coupling agent has the following meaning.

* Aminosilane = 3-aminopropyltriethoxysilane

氺 Glycidoxy = 3-glycidoxypropyltrimethoxysilane

* Diaminosilane = N— 2-aminoethyl-3-aminopropyl trimethoxysilane

(Yuto) From Table 1, the following becomes clear.

(1) 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).

(2) On the other hand, when the alumite-treated film was formed but the film was less than 0.1 lm thick (see Test Example 1), the interface was delaminated at the interface in the caulking process. Is observed, and remarkable changes with time are observed. However, some squeezing is possible.

(3) Even with the same anodic oxide coating, a phosphoric acid chromate-treated coating was formed, but although there was no problem with drawing, it was inferior in crimpability and markedly changed with time.

(Deterioration) is observed (see Test Example 6).

(4) Furthermore, even if the same anodic oxide coating was formed with the oxalic acid alumite-treated coating, both the caulking workability and the change over time were remarkably inferior (see Test Example 7).

(5) Even if the alumite-treated coating film was formed and the silane coupling agent was not applied thereto, the caulking processability was inferior and remarkable aging (deterioration) was observed (Test Example 3). See).

(Test Example 8: L 2)

Both sides of a 0.3 m thick aluminum plate (JISA1500 H22) are anodized with a 20% phosphoric acid solution to form a 0.6 zm thick aluminum phosphate. An it-treated film was formed. A silane coupling agent having a functional group shown in Table 2 was applied to the coating at ²⁰ mg / m ^2, and the coated surface was heated to 280 ° C. A 15 mm thick polyimide 6 (melting point: 22 ° C) film was separately laminated on the heated coating surface, and laminated by pressing with a pair of pressure rolls. I got With respect to the obtained resin-coated metal plate, an evaluation test of the above items was performed. Table 2 shows the evaluation test results. Table 2

[* 2] The coupling agent having each active group has the following meaning.

* Amino group = 3-aminopropyltriethoxysilane

* Dimini group = N— 2-aminoethyl-3-aminopropyltrimethoxysilane

* Glycidoxy group = 3—Glycidoxypropyltrimethoxysilane

* Methacryloxy group = 3—Methacryloxypropyl trimethoxysilane

* ゥ laid group = uretaminobutyral pyrtriethoxysilane

(Result)

From Table 2, the following becomes clear.

(1) 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.

(See Test Examples 8 to 12).

(Test Examples 13 to: 15)

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

(Result)

Table 3 reveals the following.

(1) When 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).

(2) On the other hand, when the coating film is polypropylene, delamination is observed on the surface during the drawing process, and the drawing process is poor (see Test Example 15).

(Test example 16-: 19)

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 method)

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

Furthermore, the following conditions were used as accompanying conditions.

• Other condition No. 1: After the formation of alumite phosphate, perform AC or DC electrolysis (substrate is negative electrode) in a silane coupling addition bath, and then perform film luminescence.

'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.

Other 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.

Other 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.

Table 5

[Experimental example 2]

Next, a test example based on another evaluation is shown. Used in Test Examples 20 to 33 shown below The evaluation method will be described.

(a) Picker hardness: Vickers hardness was measured on the resin-coated surface of the prepared thin aluminum sheet of the resin-coated metal plate in accordance with JISZ2244 "Vikars hardness test-one test method". The load at the time of hardness measurement was 0.9987 N ₍

() Workability: Using the prepared resin-coated metal plate, perform 7-step drawing with a lance progressive drawing machine, and use a resin-coated layer as the outer surface of the container to create a cylindrical container with a l O mm 0 x 2 O mm height. 20%), and the state of delamination between layers was visually observed. "〇" indicates no interlaminar peeling, and "を" indicates

Displayed as "X".

(c) Concavity: A cylindrical container with a height of 10 m øX20 mm was filled with a capacitor element, rubber was sealed, and a sample container was prepared by caulking. The 100 sample containers were placed in a 200 mm × 200 mm × 200 mm paper container, and longitudinal vibration was applied at a vibration speed of 10 cm / sec for 1 hour. One hour later, the sample container was taken out, and the appearance of the top surface was observed. At this time, samples with dents on the bottom and side walls of the sample container were marked with “X” and those without dents were marked with “〇”.

(d) Comprehensive evaluation: In all of the above evaluation items (a) to (c), those with acceptable quality were judged as “〇”, and those with one evaluation item failed were judged as “X”.

[Test Example 20]

The surface of a 0.3 mm thick aluminum (JISA 110) plate was etched with a 10% aqueous sodium hydroxide solution at 50 ° C for 30 seconds and then with a 10% aqueous nitric acid solution. A neutralization treatment was performed, followed by washing with water for 10 seconds. Next, a phosphoric acid chromate chemical conversion thin film (Cr = 20 mg / m ² ) was formed on one surface of the aluminum plate. On this chemical conversion treatment film, a § one Aminopuropiruto Li et Tokishishiran as Kadzupuringu agent after drying and SO m gZm ² coating, heating the aluminum plate to a temperature of 2 1 0 ° C, was applied to Katsupuri ing agent A polyamide 6 film having a thickness of 15 m was pressure-bonded to the surface to obtain a polyamide resin-coated metal plate. Table 6 shows the results of the evaluation of the obtained polyamide resin-coated metal sheet by the above evaluation method.

[Test Example 2 1]

In the example described in Test Example 20, the chemical conversion-treated thin film was replaced with a thin film having a thickness of 1000 A formed by oxalic acid alumite chemical conversion treatment, and the coupling agent was replaced with α-glycidoxyprovir triethoxysilane. Temperature to 250 ° C Other than that, a polyamide resin-coated metal plate was obtained in the same procedure as in the same example. Table 6 shows the results of the evaluation of the obtained polyamide resin-coated metal sheet by the above evaluation method.

[Test Example 2 2]

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.

[Test Example 2 3]

In the example described in Test Example 21, except that the chemical conversion treated thin film was replaced with a thin film formed by phosphoric acid chromate treatment, a polyamide resin-coated metal plate was formed in the same procedure as in the same example. Obtained. Table 6 shows the results of the evaluation of the obtained polyamide resin-coated metal sheet by the above evaluation method.

[Test Example 2 4]

In the example described in Test Example 23, a polyamide resin-coated metal plate was obtained in the same procedure as in Example 2, except that the capping agent was changed to y-aminoprovir triethoxysilane. Table 6 shows the results of the evaluation of the obtained polyamide resin-coated metal sheet by the above evaluation method.

[Test Example 25]

In the example described in Test Example 20, except that the coupling agent was not applied, a polyamide resin-coated metal plate was obtained in the same procedure as in the same example. Table 7 shows the results of the evaluation of the obtained polyimide resin-coated metal sheet by the above evaluation method.

[Test Example 26]

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.

[Test Example 2 7]

In the example described in Test Example 23, a polyamide resin-coated metal plate was obtained in the same procedure as in the example except that the temperature of the aluminum plate was changed to 38O 0 C. Got Table 7 shows the results of the evaluation performed on the polyamide resin-coated metal plate by the above evaluation method.

[Test Example 28]

In the example described in Test Example 24, except that the temperature of the aluminum plate was changed to 200 ° C., a polyamide resin-coated metal plate was obtained in the same procedure as in the same example. Table 7 shows the results of the evaluation of the obtained polyamide resin-coated metal sheet by the above evaluation method.

Table 6

[Note] The silane coupling agents are as follows. The same applies to the following table.

Epoxysilane type: α-glycidoxypropyltriethoxysilane

Aminosilane type: y-aminopropyltriethoxysilane

Acrylic silanes: 3-methacryloxypropyl trimethoxysilane Table 7

(result) Tables 6 and 7 reveal the following.

(1) 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. Coating and crimping resin-coated metal plates with a Vickers hardness of 25 to 60 in terms of the hardness of the resin-coated surface of the aluminum sheet when pressed with excellent adhesion between the aluminum sheet and the coating film. Even when the coating film does not peel off and the containers come into contact with each other, dents do not easily occur on the wall surface (see Test Examples 20 to 24).

(2) On the other hand, even if a chemical conversion thin film is provided on the surface of an aluminum thin plate, a layer of a silane-based capping agent is not provided and a resin film is coated and pressed, the coated film peels off during press working ( See Test Example 25).

(3) Even if a chemical conversion treatment thin film is provided on the surface of an aluminum thin plate and a silane-based coupling agent layer is provided thereon, the temperature of the aluminum thin plate is raised above 350 ° C to cover and crimp. In this case, the surface hardness of the resin-coated metal plate is lower than 25 in terms of Vickers hardness, and when the containers come into contact with each other, dents easily occur on the wall surface (see Test Examples 26 to 27).

(4) Further, 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. In the case where 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).

[Test Example 2 9]

In the example described in Test Example 2 0, changing the coating amount of Kadzupuri ring agent 1 0 0 mg / m ^2, except that a temperature of the aluminum plate 2 9 0 ° C is the same as in the example procedure 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 30]

In the example described in Test 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.

[Test Example 3 2]

In the example described in Test Example 29, a polyamide resin-coated metal plate was obtained in the same procedure as in the example described above, except that the coating amount of the capping agent was changed to 0.05 mg / m ² . Table 8 shows the results of the evaluation of the obtained polyamide resin-coated metal sheet by the above evaluation method.

[Test Example 3 3]

In the example described in Test Example 31, a polyamide resin-coated metal plate was obtained in the same procedure as in the example described above, except that the amount of the coating agent applied was changed to 1300 mg / m ² . Table 8 shows the results of the evaluation of the obtained polyamide resin-coated metal sheet by the above evaluation method.

Table 8

(Result)

Table 8 reveals the following.

(1) 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. In the range of, 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).

(2) On the other hand, 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).

(3) When it is more the coating amount of Thin type couplings agent ^{1 3 0 0 mg / m 2} , poor stability of the couplings agent solution, uniformly be coated cloth to the surface of the aluminum sheet (See Test Example 33).

[Experiment 3];

Next, a test example based on another evaluation is shown. The evaluation methods used in 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).

(1) Measurement of contact angle: At a temperature of 23 ° C and a humidity of 50%, a required amount of silane coupling agent aqueous solution was dropped on the surface of the prepared metal plate, and a contact angle meter (Kyowa Interface Science Co., Ltd.) The contact angle is measured using a product name: CA-A).

(2) Evaluation of wettability: The prepared metal plate was cut into A4 size, and an aqueous solution of a silane capping agent was applied to the surface using a barco 10g / m ² to check the state of the coating film. Observe visually. Observation results were evaluated as 〇 if a uniform coating film was formed without repelling, and X if the coating film was repelled and had a spotted shape.

(3) Measurement of Si element content: In the process of preparing a resin laminate, an aqueous solution of a silane coupling agent is applied to the surface of a metal plate and dried to form a coating film, and then the ESCA method (X-ray source: M g K a, output: 1 5 kv X 3 3 mA , vacuum: by ^{5 x 1 0- 8 T orr)} , measured S i element of the surface of the coating film (atomic%).

(4) Evaluation of processability: The resin laminate was subjected to 7-step drawing with a lance progressive drawing machine, and the diameter of the resin layer was 10 mm and the height was 2 so that the surface on which the thermoplastic resin thin film was laminated was the outer surface of the container. Prepare a 0 mm cylindrical container and visually observe whether the thermoplastic resin thin film has peeled off from the metal plate. Observation results were evaluated as 〇 when no peeling was observed, and as X when peeling was observed.

(5) Evaluation of adhesion after processing: The cylindrical container prepared for the evaluation of workability described above was placed in a hot air drying oven at 270 ° C and left for 1 minute, and then the cylindrical container was dried with hot air. Take out of the furnace and visually observe whether the thermoplastic resin thin film laminated on the outer surface of the container has peeled off. Observation results were evaluated as 〇 when no peeling was observed, and as X when peeling was observed. (6) Comprehensive evaluation: If both the above processability and post-working adhesion were judged as “〇”, the overall evaluation also judged as “〇”. If both were judged as “X”, and either of them was judged as “X” Those judged were judged as X in the comprehensive evaluation.

[Test Examples 34 to 45]

100 g of water was mixed with a silane coupling agent and a nonionic surfactant (active ingredient: polyoxyethylene alkyl ether, cloud point: 42.1 ° C) in the amounts shown in Table 9 respectively. Four kinds of aqueous solutions of silane coupling agents were prepared. Table 9

0.3 mm thick stainless steel plate (SUS430-2B), 0.3 mm thick aluminum chromate-treated aluminum plate (alloy number: A110) 0 PH 24, chromium content in chromium hydrated oxide: 20 mg / m ² ) and 0.3 mm thick electrolytic cupric acid treated steel sheet (lower layer metal chromium content: 100 mg / m ² , and the amount of chromium in the upper layer hydrated oxide of 18 mg / m ² ) were prepared. <Evaluation of aqueous solution of silane coupling agent>

The four types of silane coupling agent aqueous solutions shown in Table 9 were dropped on the surfaces of the three types of metal plates, respectively, and the above-mentioned (1) was measured. Further, the four types of silane capping agent aqueous solutions shown in Table 9 were applied to the surfaces of the above three types of metal plates, respectively, and the above-described evaluation test (2) was performed. Table 10 shows the results. Table 10

From Table 9 and Table 10, the following becomes clear.

(A) The contact angle was measured by dropping four types of silane coupling agent aqueous solutions on the surfaces of the above three types of metal plates. As a result, the silane coupling agent aqueous solution I or the silane coupling agent aqueous solution III was obtained for all metal plates. Had a contact angle of 55 ° or less (see Test Examples 34 to 36, Test Examples 38 to 40, and Test Examples 42 to 44). On the other hand, the contact angle of the silane coupling agent aqueous solution IV was greater than 55 ° (Test Example).

37, 41, 45). This is because the amount of the nonionic surfactant in the aqueous solution IV of the silane coupling agent is insufficient.

(Mouth) In addition, four types of silane coupling agent aqueous solutions were applied to the surfaces of the three types of metal plates to evaluate the wettability. As a result, the silane coupling agent aqueous solution I to the silane coupling agent aqueous solution III were applied. A uniform coating was formed on the surface of each metal plate, and the wettability was good (Test Examples 34 to 36, Test Examples 38 to 40, Test Examples

4 2-4 4). On the other hand, no uniform coating film was formed on the surface of the metal plate coated with the silane coupling agent aqueous solution IV (the coating film became spot-like and the wettability was poor (Test Example 37, (See 41 and 45.) This is because the contact angle of the silane coupling agent aqueous solution IV is larger than 55 °.

[Test Example 4 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.

10 g / m ² was applied and dried at a heating rate of 5 ° C./s to form a coating film.The coating film was then heated at 250 ° C. 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.

[Test Examples 4 7 to 5 2]

In the example described in Test Example 46, the type and amount of the silane coupling agent, the rate of temperature rise during drying after the application of the aqueous solution of the silane coupling agent (the heating temperature of the coating film, the type of the thermoplastic resin thin film, Resin laminates were prepared in the same manner as in the same example except that they were changed to those described in Table 11. In the process of preparing these resin laminates, measurement was performed in the same manner as in the same example. An evaluation test was performed on the obtained resin laminate in the same manner as in the same example, and the results are shown in Table 11.

Silane or soft. Linkability, agent difficult processability Test Heating rate Thermoplastic Si content

Type of heating temperature Total "tl test Resin coating After processing

Compounding amount Evaluation example (° C / s) (° C) Film type

(g / (atomic ¾) adhesion

(100 g of water)

A-Aminoff. Mouth. Le

o

46 (Example) Triethoxysilane 5 250 e. Reamite, 6 7.34 〇

0.1 mm

o

47 (Example) Triethoxysilane 20 330 e. Liami 6 10.52 〇

2.0 Outside the library, kissif. Lohi. Le o

48 (Example) Triethoxysilane 5 280 PET 9.15 〇

0.1 ° Amino 7 ° Lohi. Le

Experiment o

49 (Comparative Example) Triethoxysilane 40 250 Holia 6 4.10 X Example

3 0.009 X

A-Aminoff ° 11 °

ο

50 (Comparative Example) Triethoxysilane 53 280 e. Riamide 6 4.14 X

0.5 X

A-amino. Le

X

51 (Comparative Example) Triethoxysilane 5 200 e. Ramito, 6 12.12 X

3.0 Not implemented a-Aminof. Π ヒ. ) 1 / X

52 (Comparative Example) Triethoxysilane 45 380 PET 8.35 X

1.0 X From Table 10 and Table 11, the following becomes clear.

(C) 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).

(2) 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).

(E) In a resin laminate prepared by increasing the temperature rising rate during drying after applying the silane coupling agent aqueous solution to more than 50 ° C / s, the amount of Si element on the surface of the coating film is less than 5 atomic%. It was low and had poor adhesion after processing (see Test Example 50).

(F) The resin laminate prepared by setting the heating temperature of the coating film lower than the melting point of the thermoplastic resin (220 ° C) was inferior in workability such as the removal of the boronamide 6 thin film during processing. In this case, since the evaluation of adhesion after processing was impossible, it was not carried out (see Test Example 51).

(G) 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

As described in detail above, the present invention has the following particularly advantageous effects, and its industrial utility value is extremely large.

(1) In the case where the resin-coated metal plate according to the present invention has a phosphoric acid alumite-treated film having a thickness of 0.05 to 2 m as an anodized film, 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.

(2) In the resin-coated metal plate according to the present invention, when a silane coupling agent is interposed between the anodized phosphate coating and the resin coating, the adhesion between the aluminum plate surface and the coating film (adhesion Or adhesive strength). Even if drawn or ironed, the thermoplastic resin coating does not break, crack, etc., hardly deteriorates over time, and delamination hardly occurs.

(3) According to the production method according to the present invention, drawing and ironing are performed as in the method described in Japanese Patent Application Laid-Open No. After performing the process, there is no need to heat and re-melt the thermoplastic resin coating film, and a resin-coated metal plate with excellent adhesion (adhesion or adhesive strength) between the aluminum plate surface and the coating film interface can be obtained. , It can be manufactured efficiently.

(4) According to the method for producing a resin-coated metal sheet according to the present invention, a resin-coated metal sheet having excellent press workability such as drawing and hardly peeling off the coating film during processing can be obtained.

(5) According to the method for producing a resin-coated metal plate according to the present invention, since one side of the base aluminum sheet is covered with the resin film, a beautiful printed display for identification can be easily provided. .

(6) According to the method for producing a resin-coated metal sheet according to the present invention, 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.

(7) 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.

(8) 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. When 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.

(9) 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. When prepared by laminating a thermoplastic land resin thin film by heating at a constant temperature, even if this resin-coated metal plate is subjected to heat treatment after processing by various processing methods, the thermoplastic resin thin film can be easily formed from the metal plate. Does not peel off.

(10) 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. When prepared by lamination, the strength of the metal plate does not decrease, and the thermoplastic resin thin film does not deteriorate.

(11) 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. When prepared in layers, the economic disadvantages of conventional high-temperature heat treatment are eliminated.

(12) According to the method for producing a resin-coated metal plate according to the present invention, a resin-coated metal plate having the above-described effects can be produced.

(13) 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.

Claims

The scope of the claims

1. A resin coating formed by forming a chemical conversion thin film on the surface of a metal plate, forming a thin film of a silane coupling agent on the surface of the chemical conversion thin film, and forming a coating film made of a thermoplastic resin on the surface of the thin film Metal plate.

2. The above-mentioned chemical conversion thin film is composed of a phosphoric acid chromate chemical conversion thin film, a thin film composed of an organic resin thin film and chromium, a chemical conversion thin film containing zirconium, a chemical conversion thin film containing titanium, and an anodized thin film. 2. The resin-coated metal plate according to claim 1, which is any one selected from the group consisting of:

3. The resin-coated metal plate according to claim 1, wherein the coating film made of a thermoplastic resin is a coating film made of a resin selected from a polyester resin or a polyamide resin.

4. The metal plate is an aluminum plate, the chemical conversion thin film is an anodized thin film having a thickness of 0.05 to 2 m, and the thermoplastic resin coating film has a thickness of 5 to 5 m. 2. The resin-coated metal plate according to claim 1, which is a coating film of 200 m.

5. The resin-coated metal sheet according to claim 4, wherein the anodized thin film is an alumite-treated thin film that has been treated with an electrolyte containing at least phosphoric acid.

6. forming an anodic oxide coating having a thickness of 0. 0 5 ~ 2 m on the surface of the aluminum plate, on the anodic oxide coating in this the Shirankappuri ring agent 0. 5~ 5 0 0 mg / m 2 split The silane coupling agent is then coated with a thermoplastic resin coating film with a thickness of 5 to 200 μm over a thin film of this silane coupling agent in a temperature range of 250 to 350 ° C. Of manufacturing a resin-coated metal sheet.

7.The metal plate is an aluminum plate with a thickness of 0.1 to 0.5 mm, and the thin film of the silane coupling agent is 0.01 to 100 mg / m2 of a silane coupling agent. ⁽² ) The layer formed by coating, the thermoplastic resin coating film is a film having a thickness of 5 to 200 zm, and is formed after the thermoplastic resin coating film is formed. 2. The resin-coated metal plate c according to claim 1, wherein the hardness of the resin is in the range of 25 to 60.

8.A chemical conversion thin film is formed on one side of an aluminum plate with 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 100 mg / m. ^{(2) A} thin film is formed by coating, and the aluminum plate on which the chemical conversion treated thin film and the thin film of the silane coupling agent are laminated is heated in a temperature range of 200 to 350 ° C. The Vickers hardness of the thermoplastic resin coating film surface is 5 to 200 m / m2 from the top of the thin film of the silane coupling agent. A method for producing a resin-coated metal sheet, which is in the range of the above.

9. The thin film of the silane coupling agent was prepared by mixing the silane coupling agent in a proportion of 0.01 to 10 parts by weight with respect to 100 parts by weight of water, and applied to the surface of the metal plate. It is formed by applying an aqueous solution of a silane coupling agent with a contact angle of 55 ° or less to the surface of the metal plate and drying it at a heating rate of 50 ° C / s or less. 2. The resin-coated metal plate according to claim 1, wherein the resin-coated film is laminated on the surface of the silane coupling agent thin film heated in a temperature range of 350 ° C. from its melting point.

10. The resin-coated metal plate according to claim 1, wherein the thin film of the silane coupling agent has an Si element content of 5 to 15 atomic% when its surface is measured by X-ray photoelectron spectroscopy. .

1.1. 100 to 100 parts by weight of water, 0.01 to 10 parts by weight of a silane coupling agent is mixed, and the contact angle when applied to the surface of a metal plate is set to 55 ° or less. The aqueous solution of the silane coupling agent was 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 method for producing a resin-coated metal plate in which a coating film made of a thermoplastic resin is laminated on the surface of this coating film by heating in a temperature range of ° C.

1 2. For the exterior of a capacitor prepared by drawing or ironing the resin-coated metal plate according to any one of claims 1 to 5, claim 7, claim 9 or claim 10. container.

13. The external container for a capacitor according to claim 12, wherein the coating film made of the thermoplastic resin is provided outside.