JP2006192595A - Aluminum sheet for aerosol can cap and aerosol can cap - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated film for an aerosol can cap coated with the laminated film excellent in corrosion resistance, moldability and the adhesiveness with a fluoroplastic resin. <P>SOLUTION: This aluminum sheet for the aerosol can cap is constituted by coating at least one side of the aluminum sheet with the layer of mainly a polyamide resin of the laminated film having at least the layer mainly comprising the polyamide resin and the layer, consisting mainly of an adhesive fluoroplastic resin, thereon. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is an aerosol can cap excellent in corrosion resistance that is used by being fitted to the upper part of an aerosol can that is sprayed with dimethyl ether (DME) or liquefied petroleum gas (LPG) as a propellant in the form of a mist or mousse. The present invention also relates to an aluminum plate for an aerosol can cap forming the same.

  Conventionally, as a propellant for aerosol cans, chlorofluorocarbon has been mainly used, but the use of chlorofluorocarbon is restricted from the viewpoint of environmental protection, and DME and LPG have come to be used as an alternative propellant.

  In Patent Document 1, a polyamide resin layer and an ethylene-vinyl alcohol copolymer are provided on at least one surface of an aluminum plate via a heat-modified film obtained by heat-treating a thin film made of an epoxy resin, a fatty acid or a hydroxy-substituted phenol at a temperature of 350 ° C. or higher. A laminate formed by sequentially coating resin layers and an aerosol can cap formed by drawing so that the ethylene-vinyl alcohol copolymer resin layer is the innermost surface are described.

  In Patent Document 2, an ethylene-vinyl alcohol copolymer resin film is laminated on one side or both sides of a metal plate, and then the laminated ethylene-vinyl alcohol copolymer resin layer is added to the glass transition temperature ( Tg) A method for producing an ethylene-vinyl alcohol copolymer-coated metal laminate is disclosed in which heat treatment is performed in a range of ± 30 ° C. and then cold working such as drawing or bending is performed.

  Patent Document 3 describes an aerosol can cap formed by drawing a laminate in which a fluororesin layer is coated on at least one surface of an aluminum plate so that the resin layer becomes an inner surface.

Patent Document 4 discloses an aerosol can obtained by drawing a metal laminate in which at least one surface of aluminum or a steel plate is coated with a fluororesin layer via a copolymer of glycidyl methacrylate and polyolefin so that the resin layer becomes the inner surface. Caps are described.
JP-A-5-305980 Japanese Patent Laid-Open No. 10-24523 JP-A-6-293370 Japanese Patent Laid-Open No. 10-24974

  However, in the aerosol can cap of Patent Document 1, it is required to further improve the moldability of the ethylene-vinyl alcohol copolymer of the laminate on the aluminum plate. Moreover, in the aerosol can cap produced by the coating metal laminated body by the manufacturing method of patent document 2, even if it is a case where a highly corrosive thing, such as an acidic hair dye, is used as the content, the content penetrates the resin layer. Therefore, aluminum is required not to be corroded, and is required to have better corrosion resistance. Moreover, in order to provide a moldability, it is calculated | required to reduce the lubricant added to a covering metal laminated body. Moreover, in the cap for aerosol cans of patent document 3, in order to prevent problems, such as peeling of a film at the time of shaping | molding, it is requested | required that adhesiveness with a fluororesin should be improved more. Further, in the aerosol can cap of Patent Document 4, since the fluororesin is laminated, the corrosion resistance is excellent, but the adhesion between the aluminum plate and the film is poor and the workability is inferior. .

  Then, this invention makes it a subject to provide the laminated | multilayer film for aerosol can caps which was coat | covered with the laminated | multilayer film excellent in corrosion resistance and a moldability, and excellent in adhesiveness with a fluororesin.

  The present invention will be described below. In order to facilitate understanding of the present invention, reference numerals in the accompanying drawings are appended in parentheses, but the present invention is not limited to the illustrated embodiment.

  The first aspect of the present invention mainly comprises a polyamide resin in a laminated film (100a) having at least a layer (20a) mainly comprising a polyamide resin and a layer (40a) mainly comprising an adhesive fluororesin thereon. An aluminum plate (110a) for an aerosol can cap formed by covering at least one surface of an aluminum plate (10a) with a layer (20a) side as a component.

  The second aspect of the present invention is a laminated film (100b) having at least a layer (30b) mainly comprising an ethylene-vinyl alcohol copolymer resin and a layer (40b) mainly comprising an adhesive fluororesin thereon. The aluminum plate (110b) for an aerosol can cap, in which at least one surface of the aluminum plate (10b) is covered with the layer (30b) side mainly composed of an ethylene-vinyl alcohol copolymer resin.

  The third aspect of the present invention is a layer (20c) having a polyamide resin as a main component, a layer (30c) having an ethylene-vinyl alcohol copolymer resin as a main component thereon, and an adhesive fluorine on the layer (30c). For an aerosol can cap formed by coating at least one surface of an aluminum plate (10c) with a layer (20c) side mainly comprising a polyamide resin in a laminated film (100c) having at least a layer (40c) mainly comprising a resin It is an aluminum plate (110c).

  The adhesive fluororesin preferably contains a carbonate group, a maleic acid group, or both a carbonate group and a maleic acid group.

  The aluminum plate (10a, 10b, 10c) preferably has a silicon (Si) element content of 5 to 12 atomic% measured on the surface thereof by X-ray photoelectron spectroscopy.

  Moreover, in the aluminum plate (110a, 110b, 110c) for the aerosol can cap of the first to third inventions, a fluorine resin is further formed on the layer (40a, 40b, 40c) containing the adhesive fluororesin as a main component. You may have the layer which consists of.

  In a fourth aspect of the present invention, the aluminum plate for an aerosol can cap (110a, 110b, 110c) according to any one of the above is drawn so that the laminated film (100a, 110b, 100c) surface is inside the cap. This is an aerosol can cap.

  The aluminum plates 110a, 110b, 110c for aerosol cans of the present invention (hereinafter, “110a, 110b, 110c” may be abbreviated as “110”) have adhesive fluororesin or fluororesin on the surface layer. By doing so, it is excellent in moldability to an aerosol can cap and excellent in corrosion resistance as an aerosol can cap.

  Hereinafter, the present invention will be described based on embodiments shown in the drawings.

  FIG. 1 conceptually shows the structure of an aluminum plate for an aerosol can cap of the present invention. The aluminum plates 10a, 10b, and 10c used in the present invention (hereinafter, “10a, 10b, and 10c” may be abbreviated as “10”) are not particularly limited, and various types can be used. From the viewpoint of workability and strength, it is preferable to use an alloy of aluminum and magnesium (5000 series according to JIS H0001).

  Moreover, in order to improve the adhesiveness of a laminated film, it is preferable to give a chemical conversion treatment to the aluminum plate 10 surface. The chemical conversion treatment is not particularly limited, and a treatment usually applied to an aluminum plate can be employed. Specific examples of the chemical conversion treatment include immersion chromic acid treatment, phosphoric acid chromic acid treatment (chromate treatment), etching treatment with an alkali solution or acid solution, or anodization treatment.

  The thickness of the aluminum plate 10 is not specifically limited, Preferably it is 0.2-0.7 mm, More preferably, it is 0.3-0.6 mm.

  In the aluminum plate 10 used in the present invention, the elemental amount of silicon (Si) measured by X-ray photoelectron spectroscopy (ESCA method) on the surface of the aluminum plate 10 is preferably 5 atomic% or more. More preferably, it is at least atomic percent. This is because if the element amount of silicon is too low, the variation in adhesion with the film becomes large, and peeling of the film may occur when drawing or ironing.

  Moreover, it is difficult to obtain a silicon element having an excessive amount of element technically, and the adhesiveness of the film is saturated.

Here, the X-ray photoelectron spectroscopy (ESCA method) is a method of analyzing from the type and chemical bonding state of elements in the vicinity of the surface of the sample knocked out from the atoms on the surface of the sample by irradiation with soft X-rays. The measurement conditions of the ESCA may be normal measurement conditions. For example, the X-ray source is MgKα, the output is 15 kv × 33 mA, and the degree of vacuum is 6.7 × 10 ⁻⁶ Pa (5 × 10 ⁻⁸ torr). ). The amount of element is measured from the spectral intensity distribution of each element.

  By treating the aluminum plate 10 with a silane coupling agent, the amount of Si element on the surface of the aluminum plate 10 can be set within the predetermined range. A silane coupling agent is an organosilicon monomer having two or more different reactive groups in its molecule. One of the two reactive groups is a reactive group that chemically bonds to inorganic substances (glass, metal, etc.), and the other reactive group is a reactive group that chemically bonds to an organic material (various synthetic resins). . Although the reactive group couple | bonded with the aluminum plate 10 is not specifically limited, For example, there exist a methoxy group, an ethoxy group, a silanol group, etc.

  The aluminum plate 10 and the silane coupling agent form an Al—O—Si bond and are firmly bonded. The polyamide resin and ethylene-vinyl alcohol copolymer described below and the silane coupling agent are silane cups. The organic functional group in the ring agent reacts with the organic resin to give a strong bonding force. Thereby, the aluminum plate 10 and the layer mainly composed of polyamide resin and the layer mainly composed of ethylene-vinyl alcohol copolymer are firmly bonded.

  The method for applying the silane coupling agent to the aluminum plate 10 is not particularly limited, and a predetermined amount by a known technique such as a dipping method, a gravure roll method, a reverse roll method, a kiss roll method, an air knife coating method or the like. Can be painted.

  In the first embodiment of the present invention, the layer 20a mainly composed of polyamide resin and the layer 40a mainly composed of adhesive fluororesin are laminated in this order on the aluminum plate 10a. In the second embodiment of the present invention, a layer 30b mainly composed of an ethylene-vinyl alcohol copolymer and a layer 40b mainly composed of an adhesive fluororesin are arranged in this order on the aluminum plate 10b. Laminated. In the third aspect of the present invention, the layer 20c mainly composed of polyamide resin, the layer 30c mainly composed of ethylene-vinyl alcohol copolymer, and the adhesive fluororesin are mainly formed on the aluminum plate 10c. The component layer 40c is laminated in this order.

  In the layers 20a and 20c containing polyamide resin as the main component (hereinafter, “20a and 20c” may be abbreviated as “20”), the main component itself is 50 mass with respect to the mass of the entire resin layer. %, Preferably 70% by mass or more, more preferably 90% by mass or more, and may contain other substances as appropriate. As other substances, for example, polyolefin resins, acrylic resins, and the like can be used. The “main component” in each layer described below has the same meaning.

  Various additives can be added to the layer 20 mainly composed of polyamide resin. Examples of additives include various antioxidants such as phosphorus and phenol, heat stabilizers, ultraviolet absorbers, light stabilizers, nucleating agents, metal deactivators, residual polymerization catalyst deactivators, nucleating agents, Examples of the antibacterial / antifungal agent, antistatic agent, lubricant, flame retardant, filler, and the like that are commonly used for resin materials can be given.

  The polyamide resin is not particularly limited, and various polyamide resins can be used. Specifically, nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612, a copolymer of nylon 6 and nylon 66, and the like can be suitably used. Can also be used. Of these, nylon 6 and nylon 66 are particularly preferred.

  The weight average molecular weight in terms of styrene measured by gel permeation chromatography of polyamide resin is not particularly limited, but is preferably 3000 to 80000 from the viewpoint of film forming property, mechanical properties of the film, and the like. More preferably, it is ˜50000.

  The thickness of the layer 20 containing the polyamide resin as a main component is not particularly limited, but is preferably 20 to 150 μm, and preferably 30 to 100 μm from the viewpoint of sufficient thickness to give strength to the laminated film. Is more preferable.

  The layer 20 having a polyamide resin as a main component imparts mechanical strength to the laminated film, and imparts impact resistance and the like to the aluminum plate for an aerosol can cap of the present invention.

  The ethylene content of the ethylene-vinyl alcohol copolymer in the layers 30b, 30c (hereinafter, “30b, 30c” may be abbreviated as “30”) mainly composed of the ethylene-vinyl alcohol copolymer is as follows: From the viewpoint of enhancing the corrosion resistance, it is preferably 20 to 60 mol%, and more preferably 30 to 50 mol%.

  Various additives can be added to the layer 30 containing ethylene-vinyl alcohol copolymer as a main component. As the additive, the various additives described above that can be added to the layer 20 containing a polyamide resin as a main component can be used.

  The thickness of the layer 30 containing the ethylene-vinyl alcohol copolymer as a main component is not particularly limited, but is preferably 10 to 50 μm from the viewpoint of improving workability and corrosion resistance and reducing costs, and is 10 to 30 μm. More preferably it is.

  Layers 40a, 40b, and 40c (hereinafter, “40a, 40b, and 40c” may be abbreviated as “40”) mainly composed of an adhesive fluororesin described below are used for the aerosol can cap of the present invention. Although it has the role which gives corrosion resistance to the aluminum plate 110, this corrosion resistance can be made still more favorable by having the layer 30 which has an ethylene-vinyl alcohol copolymer as a main component.

The adhesive fluororesin constituting the layer 40 mainly composed of an adhesive fluororesin has a melting point of 150 ° C. to 250 ° C. and is a kind of modified polyolefin resin, Lexpearl RA3150 (manufactured by Nippon Polyethylene Co., Ltd.) and fluorine A sample obtained by pressing a resin with a sample pressure of 4 × 10 ^{5 to} 5 × 10 ⁵ Pa at 240 ° C. for 10 minutes to produce a laminated sheet, cut into a width of 2.5 cm and a length of 25 cm Refers to a fluororesin having a 180 degree peel strength of 4 N / cm or more when a 180 degree peel strength is measured at a peel rate of 5 mm / min and a temperature of 23 ° C. in accordance with JIS Z0237. .

Further, IR spectrum of the adhesive fluorocarbon resin in the present invention ^has an absorption peak between 1780cm ^-1 ~1880cm -1. Preferably, IR spectrum of the adhesive ^fluororesin, 1790 cm -1 between between and ^{1845cm -1 ~1855cm} -1 of ～1800Cm ^-1, has an absorption peak due to anhydride such as maleic anhydride groups, ^{Alternatively,} 1800 cm -1 has an absorption peak due to end carbonate groups during ～1815Cm ^{-1, or} between 1790cm ^-1 ~1800cm ^-1, and between 1800 cm ^-1 ~ of 1845cm ^-1 ~1855cm -1 Between 1815 cm ⁻¹ , it has an absorption peak due to a mixture of anhydrides such as maleic anhydride groups and terminal carbonate groups.

More preferably, IR spectrum of the adhesive ^fluororesin, 1790 cm -1 between between and ^{1845cm -1 ~1855cm} -1 of ~1800cm ^-1, has an absorption peak due to anhydride such as maleic anhydride groups Alternatively, it has an absorption peak due to the terminal carbonate group between 1800 cm ^{−1 and} 1815 cm ⁻¹ .

Further, the main chain due to the CH ₂ groups of the absorption peak near 2881cm ^-1 to the height of the absorption peaks between ^{1790cm -1 ~1800cm} -1 attributed to anhydride such as maleic anhydride groups of height The ratio is 0.5 to 1.5, preferably 0.7 to 1.2, and more preferably 0.8 to 1.0.

Moreover, the ratio of the height of the absorption peak between 1800 cm ⁻¹ to 1815 cm ⁻¹ due to the terminal carbonate group to the height of the absorption peak near 2881 cm ⁻¹ due to the CH ₂ group of the main chain is 1. It is 0-2.0, Preferably it is 1.2-1.8, More preferably, it is 1.5-1.7.

  As such a fluororesin having adhesive strength, for example, a homopolymer or copolymer having a tetrafluoroethylene unit, such as a carbonate group, a carboxylic acid halide group, a hydroxyl group, a carboxyl group, or an epoxy group at the terminal or side chain A resin having a functional group of A plurality of resins may be mixed as long as the melting point and the adhesive strength are expressed. Examples of commercially available fluororesins having adhesive strength as described above include Neoflon EFEP (manufactured by Daikin Industries) and Fullon LM-ETFE AH2000 (manufactured by Asahi Glass Co., Ltd.).

  Various additives can be added to the layer 40 mainly composed of an adhesive fluororesin. As the additive, the various additives described above that can be added to the layer mainly composed of polyamide resin can be used.

  The thickness of the layer 40 containing the adhesive fluororesin as a main component is preferably 1 μm or more, and more preferably 5 μm or more from the viewpoint of improving the strength and corrosion resistance of the layer 40 containing the adhesive fluororesin as a main component. preferable. Moreover, from the film forming property and economical viewpoint of a laminated film, it is preferable that it is 100 micrometers or less, and it is further more preferable that it is 50 micrometers or less.

  By laminating the layer 40 having an adhesive fluororesin as a main component on the layer 30 having an ethylene-vinyl alcohol copolymer resin as a main component, the drawability to an aerosol can cap is improved. In the layer 30 mainly composed of ethylene-vinyl alcohol copolymer resin, molding defects such as cracks do not occur. Moreover, the corrosion resistance of the aerosol can cap of the present invention is excellent by making the surface layer the layer 40 mainly composed of an adhesive fluororesin. Furthermore, since the layer 40 having an adhesive fluororesin as a main component is excellent in adhesiveness with an ethylene-vinyl alcohol copolymer resin and a polyamide resin, a laminated film having a good adhesive force between the layers can be obtained. .

  Moreover, in the aluminum plate for aerosol can caps of this invention, you may have a layer which consists of a fluororesin further on the layer which consists of said adhesive fluororesin.

  As the fluororesin, it is preferable to use ethylene-tetrafluoroethylene copolymer (ETFE) from the viewpoint of adhesiveness.

  Various additives can be added to the layer made of the fluororesin. As the additive, the various additives described above that can be added to the layer mainly composed of polyamide resin can be used.

  The thickness of the layer made of the fluororesin is preferably 1 μm or more, and more preferably 3 μm or more, from the viewpoint of increasing the strength and corrosion resistance of the layer made of the fluororesin. Moreover, from the film forming property of a laminated film and an economical viewpoint, it is preferable that it is 10 micrometers or less, and it is more preferable that it is 5 micrometers or less.

  By providing a layer made of a fluororesin on the layer 40 containing an adhesive fluororesin as a main component, the corrosion resistance of the aerosol can cap of the present invention can be further improved.

  In the present invention, “having at least” means that the laminated film 100a, 100b, 100c (hereinafter, “100a, 100b, 100c” may be abbreviated as “100”) is a layer 20 containing a polyamide resin as a main component. In addition, the layer 30 containing ethylene-vinyl alcohol copolymer as a main component, the layer 40 containing an adhesive fluororesin as a main component, and other layers other than the layer consisting of a fluororesin are within the range not impairing the effects of the present invention. It means that you may have. Examples of other layers include layers made of olefins such as polyethylene and polypropylene.

  The method of covering the surface of the aluminum plate 10 with the laminated film 100 includes a method of laminating the laminated film 100 previously formed into two or three layers by a known method such as a feed block on the aluminum plate 10, A method of sequentially laminating a film of layers on the aluminum plate 10 is exemplified, but it is not particularly limited to this, and by a method of attaching each layer on the aluminum plate 10 using an adhesive. It can also be laminated.

  An aerosol can in which an aluminum plate is directly laminated with a layer 40 mainly composed of an adhesive fluororesin and at least one surface of the aluminum plate is covered only with the layer 40 mainly composed of an adhesive fluororesin. An aluminum plate for a cap can also be used. In addition, a laminated film having a layer made of a fluororesin and a layer made of a fluororesin, and a layer made of a fluororesin, by laminating a layer made of the fluororesin on the layer 40 made mainly of the adhesive fluororesin The aluminum plate for aerosol can caps can be formed by coating at least one surface of an aluminum plate with the layer 40 side mainly composed of an adhesive fluororesin.

  In the aluminum plate for aerosol can caps or the aerosol can cap in which the layer 40 mainly composed of the adhesive fluororesin is directly bonded to the aluminum plate 10, the aluminum plate 10 and the adhesive fluororesin are mainly used. Neither the layer 20 containing a polyamide resin as a main component nor the layer 30 containing an ethylene-vinyl alcohol copolymer resin as a main component is interposed between the layer 40 as a component. Therefore, in such a form, although it is somewhat inferior in corrosion resistance, while being able to enjoy the lubricity of adhesive fluororesin, it can be set as the aluminum plate for aerosol can caps excellent in economy. In addition, as shown in Reference Example 1, there is an effect that practical adhesive strength can be obtained without special treatment of the aluminum plate.

  The aerosol can cap of the present invention is produced by drawing an aluminum plate 110 for an aerosol can cap so that the surface of the laminated film 100 is inside the cap. The drawing process can be performed by a normal cold working method according to the cap shape. The cap of the present invention is fitted on the upper portion of the aerosol can, and can be used also on the uppermost cap for attaching the injection valve or the shoulder portion in the middle of the main body.

Example 1
An ethanol solution containing 0.5% of 3-aminopropyltriethoxysilane (A1100 manufactured by Nihon Unicar Co., Ltd.) was applied to one side of an aluminum plate (A5052-O, thickness 0.43 mm) whose surface was chromated with a roll coater. Then, it was dried at 150 ° C. for 20 minutes. As a result of surface analysis by the ESCA method (X-ray source: MgKα, output: 15 Kv × 33 mA, degree of vacuum: 6.7 × 10 ⁻⁶ Pa (5 × 10 ⁻⁸ Torr)) of the aluminum plate surface after drying, The Si element abundance was 6.3 atomic%.

  The aluminum plate is heated, and a film made of nylon 6 (Diamilon C, Mitsubishi Plastics Co., Ltd., thickness 20 μm) is laminated at 250 ° C., and further, EVOH having an ethylene content of 32 mol% (Eval manufactured by Kuraray Co., Ltd.) 10 μm thick) and an adhesive fluororesin film (EFEP RP-4020 manufactured by Daikin Industries, Ltd., thickness 10 μm) were sequentially laminated to prepare an aluminum plate for an aerosol can cap of the present invention.

  The obtained aluminum plate was drawn and formed into an aerosol can cap of the final product shape so that the laminated film surface was inside. Next, after attaching a valve to this aerosol can cap, it was fitted on the upper portion of the aerosol can body (40 mm diameter × 96 mm height, molded by impact molding method, inner surface sprayed with polyamideimide paint). The corrosion resistance of this aerosol can was confirmed. The results are shown in Table 1.

Example 2
On one side of an aluminum plate (A5052-O, thickness 0.43 mm) whose surface was chromated, an ethanol solution containing 1.0% of 3-aminopropyltriethoxysilane (A1100 manufactured by Nihon Unicar Company) was applied with a roll coater. Then, it was dried at 150 ° C. for 20 minutes. As a result of surface analysis by the ESCA method (X-ray source: MgKα, output: 15 Kv × 33 mA, degree of vacuum: 6.7 × 10 ⁻⁶ Pa (5 × 10 ⁻⁸ Torr)) of the aluminum plate surface after drying, The Si element abundance was 7.1 atomic%.

  About the said aluminum plate, it carried out similarly to Example 1, and laminated the three types of resin films, and produced the aluminum plate for aerosol can caps of this invention. The obtained aluminum plate for an aerosol can cap was molded in the same manner as in Example 1 to produce an aerosol can, and the corrosion resistance was confirmed. The results are shown in Table 1.

Example 3
After applying an ethanol solution containing 3% of 3-aminopropyltriethoxysilane (A1100 manufactured by Nihon Unicar Co., Ltd.) on one side of an aluminum plate (A5052-O, thickness 0.43 mm) whose surface was chromated, Dry at 150 ° C. for 20 minutes. As a result of surface analysis by the ESCA method (X-ray source: MgKα, output: 15 Kv × 33 mA, degree of vacuum: 6.7 × 10 ⁻⁶ Pa (5 × 10 ⁻⁸ Torr)) of the aluminum plate surface after drying, The amount of Si element present was 10.5 atomic%.

  About the said aluminum plate, it carried out similarly to Example 1, and laminated the three types of resin films, and produced the aluminum plate for aerosol can caps of this invention. The obtained aluminum plate for an aerosol can cap was molded in the same manner as in Example 1 to produce an aerosol can, and the corrosion resistance was confirmed. The results are shown in Table 1.

Example 4
On one side of an aluminum plate (A5052-O, thickness 0.43 mm) whose surface was chromated, an ethanol solution containing 1.0% of 3-aminopropyltriethoxysilane (A1100 manufactured by Nihon Unicar Company) was applied with a roll coater. Then, it was dried at 150 ° C. for 20 minutes. As a result of surface analysis by the ESCA method (X-ray source: MgKα, output: 15 Kv × 33 mA, degree of vacuum: 6.7 × 10 ⁻⁶ Pa (5 × 10 ⁻⁸ Torr)) of the aluminum plate surface after drying, The Si element abundance was 7.1 atomic%.

  The aluminum plate is heated, and a film made of nylon 6 (Mitsubishi Resin Diamilon C, thickness 20 μm) is laminated at 250 ° C., on which an adhesive fluororesin film (Daikin Industries EFEP RP-4020, The aluminum plate for aerosol can caps of the present invention was produced by laminating successively 10 μm thick). The obtained aluminum plate for an aerosol can cap was molded in the same manner as in Example 1 to produce an aerosol can, and the corrosion resistance was confirmed. The results are shown in Table 1.

  The obtained aluminum plate was drawn and formed into an aerosol can cap of the final product shape so that the laminated film was inside. Next, after attaching a valve to this aerosol can cap, it was fitted on the upper portion of the aerosol can body (40 mm diameter × 96 mm height, molded by impact molding method, inner surface sprayed with polyamideimide paint). The corrosion resistance of this aerosol can was confirmed. The results are shown in Table 1.

Example 5
On one side of an aluminum plate (A5052-O, thickness 0.43 mm) whose surface was chromated, an ethanol solution containing 1.0% of 3-aminopropyltriethoxysilane (A1100 manufactured by Nihon Unicar Company) was applied with a roll coater. Then, it was dried at 150 ° C. for 20 minutes. As a result of surface analysis by the ESCA method (X-ray source: MgKα, output: 15 Kv × 33 mA, degree of vacuum: 6.7 × 10 ⁻⁶ Pa (5 × 10 ⁻⁸ Torr)) of the aluminum plate surface after drying, The Si element abundance was 7.1 atomic%.

  The aluminum plate is heated, EVOH having an ethylene content of 32 mol% (Eval, Kuraray, thickness 10 μm) is laminated at 250 ° C., and an adhesive fluororesin film (EFEP RP-4020, manufactured by Daikin Industries, Ltd.) The aluminum plate for aerosol can caps of the present invention was produced by laminating 10 μm thickness). The obtained aluminum plate for an aerosol can cap was molded in the same manner as in Example 1 to produce an aerosol can, and the corrosion resistance was confirmed. The results are shown in Table 1.

Example 6
An ethanol solution containing 0.1% of 3-aminopropyltriethoxysilane (A1100 manufactured by Nihon Unicar Co., Ltd.) was applied to one surface of an aluminum plate (A5052-O, thickness 0.43 mm) whose surface was chromated with a roll coater. Then, it was dried at 150 ° C. for 20 minutes. As a result of surface analysis by the ESCA method (X-ray source: MgKα, output: 15 Kv × 33 mA, degree of vacuum: 6.7 × 10 ⁻⁶ Pa (5 × 10 ⁻⁸ Torr)) of the aluminum plate surface after drying, The amount of Si element present was 4.4 atomic%.

  About the said aluminum plate, it carried out similarly to Example 1, and laminated the three types of resin films, and produced the aluminum plate for aerosol can caps. The obtained aluminum plate for an aerosol can cap was molded in the same manner as in Example 1 to produce an aerosol can, and the corrosion resistance was confirmed. The results are shown in Table 1.

Example 7
A bisphenol-type epoxy resin (weight average molecular weight 380, epoxy equivalent 180-200) dissolved in methyl ethyl ketone on one surface of an aluminum plate (A5052-O, thickness 0.43 mm) whose surface was chromated was applied with a roll coater after drying. It applied so that thickness might be set to 1 micrometer. After the aluminum plate was heat-treated and modified at 400 ° C., a film made of nylon 6 (Mitsubishi Resin Diamilon C, thickness 20 μm) was laminated at 280 ° C., and the ethylene content was further 32 mol%. EVOH (Kuraray Eval, thickness 10 μm) and an adhesive fluororesin film (Daikin Industries EFEP RP-4020, thickness 10 μm) were sequentially laminated to prepare an aluminum plate for an aerosol can cap.
The obtained aluminum plate for an aerosol can cap was molded in the same manner as in Example 1 to produce an aerosol can, and the corrosion resistance was confirmed. The results are shown in Table 1.

Example 8
An ethanol solution containing 0.5% of 3-aminopropyltriethoxysilane (A1100 manufactured by Nihon Unicar Co., Ltd.) was applied to one side of an aluminum plate (A5052-O, thickness 0.43 mm) whose surface was chromated with a roll coater. Then, it was dried at 150 ° C. for 20 minutes. As a result of surface analysis by the ESCA method (X-ray source: MgKα, output: 15 Kv × 33 mA, degree of vacuum: 6.7 × 10 ⁻⁶ Pa (5 × 10 ⁻⁸ Torr)) of the aluminum plate surface after drying, The Si element abundance was 6.3 atomic%.

  The aluminum plate is heated, and a film made of nylon 6 (Diamilon C, Mitsubishi Plastics Co., Ltd., thickness 20 μm) is laminated at 250 ° C., and further, EVOH having an ethylene content of 32 mol% (Eval manufactured by Kuraray Co., Ltd.) An aluminum plate for an aerosol can cap was prepared by sequentially laminating an adhesive fluororesin (EFEP RP-4020, thickness 10 μm, manufactured by Daikin Industries, Ltd.) and a fluororesin film (Aflex ETFE, thickness 12 μm, manufactured by Asahi Glass Co., Ltd.). The obtained aluminum plate for an aerosol can cap was molded in the same manner as in Example 1 to produce an aerosol can, and the corrosion resistance was confirmed. The results are shown in Table 1.

Comparative Example 1
An ethanol solution containing 0.5% of 3-aminopropyltriethoxysilane (A1100 manufactured by Nihon Unicar Co., Ltd.) was applied to one side of an aluminum plate (A5052-O, thickness 0.43 mm) whose surface was chromated with a roll coater. Then, it was dried at 150 ° C. for 20 minutes. As a result of surface analysis by the ESCA method (X-ray source: MgKα, output: 15 Kv × 33 mA, degree of vacuum: 6.7 × 10 ⁻⁶ Pa (5 × 10 ⁻⁸ Torr)) of the aluminum plate surface after drying, The Si element abundance was 6.3 atomic%.

  The aluminum plate is heated, and a film made of nylon 6 (Diamilon C, Mitsubishi Plastics Co., Ltd., thickness 20 μm) is laminated at 250 ° C., and further, EVOH having an ethylene content of 32 mol% (Eval manufactured by Kuraray Co., Ltd.) An aluminum plate for aerosol can caps was prepared by laminating successively 10 μm thick). The obtained aluminum plate for an aerosol can cap was molded in the same manner as in Example 1 to produce an aerosol can, and the corrosion resistance was confirmed. The results are shown in Table 1.

Reference example 1
One surface of a chromate-treated aluminum plate (A5052-O, thickness 0.43 mm) was heated to 200 ° C. without any special treatment, and an adhesive fluororesin film (EFEP RP-4020 manufactured by Daikin Industries, Ltd.) 10 μm) was laminated to prepare an aluminum plate for an aerosol can cap. The obtained aluminum plate for an aerosol can cap was molded in the same manner as in Example 1 to produce an aerosol can, and the corrosion resistance was confirmed. The results are shown in Table 1.

<Evaluation>
(1) Formability When aluminum plate for aerosol can cap is drawn and formed into aerosol can cap, which is the final product shape, ○ that does not cause appearance abnormalities such as film peeling, △ that occurs a little What was generated was evaluated as x.

(2) Corrosion resistance 1
When an aerosol can is filled with LPG hair treatment, which is a commercially available propellant, and stored at 50 ° C for 3 months in an inverted state, there is no abnormality in the inner surface of the aerosol can cap. A case where a little abnormality occurred was evaluated as Δ, and a case where a lot of abnormality occurred was evaluated as ×.

(3) Corrosion resistance 2
When the aerosol can is filled with DME acid solution (PH = 2), a commercially available propellant, and stored in an inverted state at 50 ° C. for 3 months, there is no abnormality in the inner surface of the aerosol can cap. The evaluation was evaluated as ◯ when there was no abnormality, △ when there was a little abnormality, and X when there was a lot of abnormality.

  Table 1 revealed the following.

  (1) An aluminum plate for an aerosol can cap in which nylon 6, EVOH (EVAL), and an adhesive fluororesin film (EFEP) are laminated on the surface of an aluminum plate made of a predetermined silicon (Si) element amount (atomic%) Moreover, it was excellent in the moldability to an aerosol can cap, and was excellent in the corrosion resistance as an aerosol can cap (Examples 1-3).

  (2) An aluminum plate for an aerosol can cap in which nylon 6 and an adhesive fluororesin film (EFEP) are laminated on the surface of an aluminum plate made of a predetermined silicon (Si) element amount (atomic%) is applied to the aerosol can cap. The moldability was excellent, and the corrosion resistance as an aerosol can cap was excellent (Example 4).

  (3) An aluminum plate for an aerosol can cap in which EVOH (Eval) and an adhesive fluororesin film (EFEP) are laminated on the surface of an aluminum plate made of a predetermined amount of silicon (Si) element (atomic%) It was excellent in moldability to a cap and excellent in corrosion resistance as an aerosol can cap (Example 5).

  (4) For aerosol can caps in which nylon 6, EVOH (EVAL), and adhesive fluororesin film (EFEP) are laminated on the surface of an aluminum plate whose elemental amount (atomic%) of silicon (Si) is outside the predetermined range When the aluminum plate was molded into an aerosol can cap, a part of the laminated film was peeled between the nylon 6 and the aluminum plate (Example 6).

  (5) An aluminum plate obtained by applying an epoxy resin to the surface of an aluminum plate and laminating nylon 6, EVOH (eval), and an adhesive fluororesin film (EFEP) is made of EVOH (eval) when forming an aerosol can cap. Cracks occurred on a part of the film surface. In addition, as for the corrosion resistance, there was no problem when the LPG hair treatment, which is a commercially available propellant, was used as the content, but the DME acidic liquid (PH = 2), which was a commercially available propellant, was filled as the content. In this case, corrosion of aluminum was confirmed (Example 7).

  (6) Nylon 6, EVOH (Eval), adhesive fluororesin film (EFEP) and fluororesin film (ETFE) were laminated on the surface of an aluminum plate made of a predetermined silicon (Si) element amount (atomic%). When the aluminum plate was molded into an aerosol can cap, a part of the aluminum plate was peeled off between the nylon 6 film and the EVOH film (Example 8).

  (7) An aluminum plate in which nylon 6 and EVOH (Eval) are laminated on the surface of an aluminum plate made of a predetermined silicon (Si) element amount (atomic%) is inferior in corrosion resistance as an aerosol can cap. (Comparative Example 1).

  While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. However, it can be changed as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification, and an aluminum plate for an aerosol can cap with such a change, and by drawing the aluminum plate Such aerosol can caps should also be understood as being within the scope of the present invention.

It is a conceptual diagram which shows the structure of the aluminum plate for aerosol can caps of this invention.

Explanation of symbols

110a, 110b, 110c Aluminum plate for aerosol can cap 100a, 100b, 100c Laminated film 10a, 10b, 10c Aluminum plate 20a, 20c Layers mainly composed of polyamide resin 30b, 30c Mainly composed of ethylene-vinyl alcohol copolymer Layer 40a, 40b, 40c Layer mainly composed of adhesive fluororesin

Claims (8)

  At least one side of the aluminum plate is covered with a layer side mainly composed of polyamide resin in a laminated film having at least a layer mainly composed of polyamide resin and a layer mainly composed of adhesive fluororesin thereon. An aluminum plate for aerosol can caps.   Layer having ethylene-vinyl alcohol copolymer resin as main component in laminated film having at least layer having ethylene-vinyl alcohol copolymer resin as main component and layer having adhesive fluororesin as main component thereon An aluminum plate for an aerosol can cap formed by covering at least one surface of an aluminum plate with a side.   Polyamide resin in a laminated film having at least a layer mainly comprising a polyamide resin, a layer mainly comprising an ethylene-vinyl alcohol copolymer resin thereon, and a layer mainly comprising an adhesive fluororesin thereon An aluminum plate for aerosol can caps, wherein at least one surface of an aluminum plate is covered with a layer side mainly composed of.   The aluminum plate for aerosol can caps in any one of Claims 1-3 in which the said adhesive fluororesin contains a carbonate group.   The aluminum plate for aerosol can caps in any one of Claims 1-4 in which the said adhesive fluororesin contains a maleic acid group.   The aluminum plate for aerosol can caps in any one of Claims 1-5 whose element amount of the silicon (Si) measured by the X ray photoelectron spectroscopy is 5-12 atomic% in the surface of the said aluminum plate. .   The aluminum plate for aerosol can caps in any one of Claims 1-6 which has a layer which consists of a fluororesin further on the layer which has the said adhesive fluororesin as a main component. An aerosol can cap formed by drawing the aluminum plate for an aerosol can cap according to any one of claims 1 to 7 so that the laminated film surface is inside the cap.

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