TWI325366B - Pre-coated metal plate - Google Patents

Description

(1) 1325366 r'. EMBODIMENT OF THE INVENTION [Technical Field] The present invention relates to an outer sheet or structural member used for household electrical products or steam parts, and a precoated metal which is further used for building materials and the like. board. [Prior Art] The steel sheet or the sheet metal sheet represented by the aluminum sheet or the aluminum alloy sheet has high strength and workability, and is used for various applications such as household electrical products, automotive parts, and other suitable applications. . The surface treatment of the metal sheet used for these applications is carried out for the purpose of improving the appearance, corrosion resistance, etc., and the surface treatment is conventionally performed by processing a metal sheet into a predetermined shape and then applying a post-coat method. Recently, for the purpose of simplification and cost reduction of the job improvement or processing, the pre-coating method using the surface of the pre-coated metal sheet after the surface treatment of the metal sheet has continued to make the recent years. This pre-coated metal plate has been developed to impart various functions such as fingerprint resistance, anti-scratched property, ground connection, heat insulation, antibacterial property, and lubricity in response to the advancement of products and equipment. Functional pre-coated gold is widely used. In the pre-coated metal sheet, it is required to be formed into a surface-coated surface. Therefore, it is required to have excellent automotive-made vehicles and roofing materials (metal sheets for coating materials). The situation of the post-production environment will be pre-determined for use in advance. Moreover, diversification and prevention of scratches and heat dissipation are performed on the plate, and the shape processing property is -4-(2) 1325366 r- ', and The appearance after press forming is directly the appearance of the product, and therefore it is required to have an excellent surface appearance, properties, etc. For example, Patent Document 1 proposes that an aluminum alloy sheet will be epoxy resin, urethane resin, and acrylic resin. A coating material of SiO 2 having a particle diameter of 0.1 // m or less and a lubricant of 5 to 60%, which is a base resin alone or in a mixture thereof, is coated at a thickness of 〇5 to 10 μm. A precoated type metal plate having excellent moldability and scratch resistance is controlled to have a coefficient of friction of 0.15 or less. The precoated metal plate described in Patent Document 1 is composed of an aluminum alloy plate, but In general, A pre-coated metal sheet as a material is evaluated for its use in applications requiring light weight. For example, it is also used in a cover for an optical disk drive for a notebook computer, a frame for a liquid crystal display device, and a back cover. ECU (Electronic Control Unit) for car-mounted electrical equipment, or cover or structural member for car audio, car navigation system, optical disc changer, etc. Among these, it is used in CD-ROM or CD-ROM automatic φ converter In the case of a CD-ROM or a DVD, the CD-ROM and the DVD have been installed. Recently, the CD-ROM has been compiled and the number of CD-ROMs has been increased. There is a problem in that the adhesive such as the identification label for identification is adhered to the surface of the optical disc. However, there is a new problem in the use of such an identification label. It is necessary to pay attention to, for example, a device. The heat, etc., causes a part of the identification label to peel off, and the exposed adhesive portion is attached to the various parts of the rear device. -5- (3) (3) 1325366 Again, as shown in Figure 4. In the conventional optical disk drive 20, the optical disk drive 20 is attached to the tray 21, and the tray 21 is loaded into the cover 22. However, although not shown, recently, it has been developed that the tray on which the optical disk is mounted does not enter and exit, only a slot-in disc drive that inserts a disc into the opening of the disc player and feeds it in. In this slot-type disc player, the disc is in and out of the inner surface of the cover of the disc player. Therefore, there will be When the optical disc enters and exits, the surface of the optical disc rubs against the inner surface of the cover of the disc player, and the problem of sliding scratches is likely to occur. In order to prevent the occurrence of the scratch, it is necessary to prevent the scratch from entering the surface of the optical disc. The pre-coated metal sheet is required for the use of the adhesive together, and the adhesive material is not easily attached, and the dirt or the oil is not easily adhered, and the surface of the optical disc is not easily scratched. In order to solve such a problem, the present inventors have developed a pre-coated metal sheet in which a fluorine-based resin is used as a matrix layer or a urethane bead to prepare a predetermined blending ratio, and the ratio of the film thickness is predetermined. The resin film having the particle diameter within the range is formed on the surface of the metal plate, and the pre-coated metal plate is used for the forming process to have basic and excellent formability and appearance, and the adhesive is not easy to use in combination with the adhesive. Adhesive, dirty, or oil is not easily attached, and it is difficult to cause scratches on the surface of a disc even if it is in contact with a disc (Japanese Patent Application No. 2005-294109). Further, Patent Document 2 discloses a precoated aluminum alloy sheet having a film composed of a base resin layer containing resin beads. However, since the resin beads disclosed in Patent Document 2 are harder materials of acrylic or fluororesin, it is possible to prevent the pre-coated aluminum alloy sheet from being damaged, but it is connected to a disc or the like (-6-f 0017) ( 4) 1325366 In the case of the touch, there is a problem that the surface of the optical disk or the like is damaged. [Patent Document 1] Japanese Patent No. 3338156 (Paragraph No. 8~ [Patent Document 2] Japanese Patent Laid-Open No. 2004-98624 Bulletin [Summary of the Invention] [Problems to be Solved by the Invention] The invention relates to the problem that the adhesive adheres to the double-sided adhesive scratch, and the height of the object is easy to stick to the gold, and the characteristics are scattered as described above, but the user may have even In the case of the absence of the resin film surface of the precoated metal sheet, it is desired to attach a member such as a resistance to the resin film surface of the precoated metal sheet with a belt or the like. Therefore, the present invention is In view of the above problems, the object of the development is to provide a pre-coated metal sheet which is adhered to the surface of the resin film by preventing scratches on the optical disk and maintaining the peeling strength of the adhesive to the resin film. Means for Solving the Problem] In order to solve the above problems, the precoated metal plate of the present invention and the precoated metal plate of the resin film formed on the surface thereof are provided. The resin film is provided with an epoxy resin matrix layer; In the oxygen resin matrix layer, the soft bead having a compressive strength of 10% or less at 10% deformation of the single bead of the micro compression test is (5) 1325366 r. The content of the soft bead is 5 for the epoxy resin matrix layer. The mass% or more is 50% by mass or less, and the average particle diameter of the soft beads is 1.1 times or more and 5 times or less the average thickness of the epoxy resin matrix layer. • According to this configuration, it is dispersed by control. The content and the average particle diameter of the soft beads in the epoxy resin matrix-resin layer (resin film) make it possible to act as a cushioning material even if the optical disk is in contact with the optical disk. Therefore, the resin film can be used. It is easy to cause scratches on the surface of a disc or the like. Further, by using a matrix layer which is a main component of the film as an epoxy resin, the peel strength of the adhesive to the resin film can be highly maintained. Therefore, when the parts are adhered to the surface of the film by an adhesive tape or the like, the adhesion is good. In the precoated metal sheet, the urethane beads can be used as the soft beads to form a precoated metal sheet. In the beads, the urethane beads are particularly difficult to be used, so that the use of such urethane beads improves the function of the beads as a buffer material, and further prevents the scratch on the surface of the disc. In the above-mentioned pre-coated metal sheet, the epoxy resin matrix layer may be composed of a main component composed of a bisphenol A type epoxy resin and a urea compound or a phenol compound by heat. The epoxy resin which is crosslinked by the curing agent is formed. The epoxy resin thus combined is not only easy to be coated in an organic solvent, but also has a long life at a normal temperature, and when heat is applied, it can be used in a short time. Easy to harden the reaction 'soft beads or other *.»···· -8- 1325366 tf (6) The dispersibility of the additive is also good, and further has excellent coating properties, so it is easy to carry out the metal plate Coated surface of the film. Further, the hardening reaction by heat forms a three-dimensional mesh structure necessary for securing the strength of the film, and the adhesion between the resin film and the metal plate is made stronger. In the precoated metal sheet, as an additive for imparting lubricity, the epoxy resin matrix layer described above may be configured to contain a fluorine-based lubricant. According to this configuration, by selecting a soft fluorine-based one as a lubricant, the scratch-producing property against the optical disk is not lowered, and the smoothness can be improved. As a result, the operation of the optical disk itself or the operation of the optical disk drive when the optical disk is moved in and out can be smoothly performed. In the aforementioned precoated metal sheet, the fluorine-based lubricant is tetrafluoroethylene. According to this configuration, by using tetrafluoroethylene having a high fluorine content, the improvement in lubricity can be maximized. In the precoated metal sheet, when the amount of the fluorine-based lubricant added is calculated by the following formula (1), the ratio of the fluorine concentration of the outermost surface of the film of the resin film is 10% or less. Within the range A ( % ) = { F / ( F + C + 0 + N ) ) X 1 00 ··· ( 1 ) (wherein A is the ratio of fluorine concentration, F is the mass % of fluorine, and C is carbon Mass%, 0 is oxygen mass%, and N is nitrogen mass%). According to this configuration, by controlling the ratio of the fluorine component in the film to a certain level or less, the peeling strength of the adhesive to the resin film can be highly maintained, so that it is possible to avoid sticking the component to the surface of the dough film with an adhesive tape or the like. The connection (7) (7) 1325366 is reduced. It is preferable that the average particle diameter of the soft beads is 1.5 times or more and 4 times or less the average thickness of the epoxy resin matrix layer. According to this configuration, the soft beads can be used as a cushioning material, and the resin film can further prevent scratches on the surface of the optical disk or the like. In the precoated metal sheet, the content of the soft beads is 10% by mass or more and 40% by mass or less based on the epoxy resin matrix layer. According to this configuration, the soft beads can be used as a cushioning material, and the resin film can further prevent scratches on the surface of the optical disk or the like. Further, when an epoxy-based paint which disperses the soft beads on the surface of the metal plate is applied in order to form a resin film, the viscosity of the epoxy-based paint is adjusted to a predetermined range, so that the paintability is improved. In the precoated metal sheet, a corrosion-resistant film is provided between the metal sheet and the resin film. According to this configuration, the corrosion resistance of the precoated metal sheet can be improved, and the resin film and the metal sheet can be more firmly adhered. In the precoated metal sheet, the metal sheet is made of an aluminum sheet or an aluminum alloy sheet. · According to this configuration, it is possible to reduce the weight compared to the case of using other metal plates. [Effects of the Invention] -10- (8) (8) 1325366 A precoated metal sheet used for forming processing by a resin film formed on the surface of a metal sheet according to the precoated metal sheet of the present invention. Not only basic and excellent formability and appearance, but also the most suitable content of the soft beads dispersed in the resin film (epoxy resin matrix layer) can be made even on the surface of the resin film. The sliding of the surface of the disc also prevents scratches on the disc. Further, the peeling strength of the adhesive to the resin film can be highly maintained, and the adhesion of the component to the surface of the film by a double-sided adhesive tape or the like can be maintained. Therefore, it is possible to provide a precoat which has the property that the adhesive adheres to the surface of the resin film. Metal plate. [Embodiment] Hereinafter, an embodiment of the present invention will be described in detail. 1. A precoated metal sheet is shown in Fig. 1. The precoated metal sheet 1 of the present invention is provided with a metal sheet 2 as a base material; The resin film 3 on the surface of the metal plate 2. In these members, the resin film 3 is composed of an epoxy resin matrix layer 4 and soft beads 5 dispersed in the epoxy resin matrix layer 4, and is controlled so that the content and average of the soft beads 5 are average. The particle size becomes a predetermined enthalpy. Here, the surface means at least one surface of the metal plate 2. Second, explain the structure of each structure. (1) Sheet metal 2 used in the present invention is not particularly limited. In addition to the most -11 - (9) (9) 1325366 times of cold-rolled steel sheet, it is also applicable to molten zinc-plated steel sheets and electric zinc. Various graded steel sheets such as plated steel sheets, alloyed zinc-plated steel sheets, copper-plated steel sheets, and tin-plated steel sheets, alloy steel sheets such as stainless steel, or non-ferrous materials such as aluminum or aluminum alloy sheets, copper or copper alloy sheets All steel plates such as metal plates. Here, the cover of the optical disk drive for the pen gg type computer, the frame of the liquid crystal display device, the cover for the vehicle electrical device, and the like are required to be lightweight, and aluminum or alloy plate is preferred. In particular, the A1-Mg alloy represented by 5052 or 5182 specified by JIS is particularly preferable. (2) Resin film The resin film 3 is composed of an epoxy resin matrix layer 4 and soft beads 5 dispersed in the epoxy resin matrix layer 4, and is formed on the surface of the metal plate 2. (2-1) Epoxy Resin Matrix Layer The epoxy resin matrix layer 4 is a hardened main component composed of a bisphenol a type epoxy resin and a urea compound or a phenol compound by heat. Agent crosslinkers are preferred. The epoxy resin of this combination is not only easy to be coated in an organic solvent, but also has a long life of the coating at normal temperature and can easily undergo a hardening reaction in a short time when heat is applied, a soft bead or a lubricant. The dispersibility is also good, and the coating property is excellent, so that the coating of the film on the surface of the metal plate 2 is easy. Further, it is easy to form a three-dimensional mesh structure required for securing the strength of the film by the hardening reaction of heat, and it is easier to connect the resin film 3 to the metal plate 2.

-12- < S (10) 1325366 1 Focus on making it stronger. Further, when a urea-based compound is used as the curing agent, it is more preferable because it can suppress discoloration caused by heat during the curing reaction. Further, the epoxy resin matrix layer 4 may contain a fluorine-based lubricant represented by a predetermined amount of tetrafluoroethylene. (2-2) Soft Beads In order to apply the pre-coated metal sheet 1 to a portion where the disc or the like is directly slid during the entrance and exit of the optical disc or the like, it is necessary to suppress the occurrence of scratches on the optical disc or the like due to the sliding. Here, in order to prevent scratches on the optical disk or the like, it is indispensable to make the resin film 3 soft. In general, as a method of softening the resin film 3, there is a method of lowering the glass transition temperature of the resin or a method of inhibiting the crosslinking reaction between the resin and the curing agent. In order to effectively soften the resin film 3, it is most effective to soften the matrix resin of the main component of the resin film 3, and the resin film 3 can be softened by actually using these methods for the matrix resin. However, 'in these methods, the softening of the resin film 3 continues to carry out the stone', and there is a side effect of tacking on the resin film 3, so that the following problem occurs. That is, the lubricity of the resin film 3 is remarkable. Lowering, detracting from the action of the disc itself when the disc is taken out or the action of the disc player. On the other hand, when the matrix resin of the resin film 3 is not softened, the soft microparticles are added, that is, when the soft beads 5 are added to the resin film 3 (epoxy resin matrix layer 4), the matrix resin is not required to be lowered. The glass transition temperature or the crosslinking reaction is suppressed, and the entire resin film 3 can be made soft. Therefore, -13-(11) 1325366 does not hinder the lubricity of the resin film 3, and it is possible to ensure scratch resistance against a disk or the like. The softness of the soft beads 5 of the present invention refers to a single bead which is subjected to a micro compression test, and when the deformation is 10% (when a single bead is deformed by 10%), the compressive strength is about 10 MPa or less. As a test machine for performing a micro-compression test, for example, a micro-compression tester MCT-W500 or the like manufactured by Shimadzu Corporation can be used to perform a compression test on a single bead B having a particle diameter of about lym to about 100 μm by using the tester. . More specifically, a single bead having a particle diameter of 5 to 10/im and a desired left and right is attached to the lower pressure plate of the testing machine, and while compressing the single bead while reducing the upper pressing pressure, the load is measured. The load at the time point when the bead diameter is reduced by 1% is taken as the 10% compression load 値. When the 10% compression load 値 is P(N) and the measured particle diameter of the beads is d (mm), the compression at 1% deformation can be calculated according to the following formula (2). Strength St ( MPa ) (refer to Japan Mine φ Industry Association, 8 1 .1 0.24 (1 965 )). Further, the smaller the compressive strength St (MPa) at the time of 10% deformation, the softer the beads become. In the present invention, the compressive strength St (MPa) at the time of 10% deformation needs to be 10 MPa or less, and more desirably 5 MPa or less.

St = 2.8P / (nd2)... Mathematical formula (2) (where 'in the mathematical formula' Π indicates the pi.) Again, as such a soft bead 5, ideally used, such as urethane beads, ethylene one Methyl methacrylate copolymer (EMMA) beads, -14-3 (12) 1325366 low density polyethylene (LDPE) beads, and the like. In addition, as a uric acid, it is preferable to use EMMA such as MELTEX® (Deng) manufactured by Sanyo Chemical Co., Ltd., and DAIMIC BEADS® manufactured by Daisei Seiki Co., Ltd. (registered at Yardpar (registered trademark) manufactured by Sekisho Industrial Co., Ltd.) Beads can be ideally used, such as soft beads A and soft bead LDPE beads manufactured by Sumitomo Chemicals Co., Ltd., and can be ideally used by Sumitomo Semin Chemical Co., Ltd. Beads® (registered trademark). (The content of the soft beads: 5% by mass or more and 50% by mass or less) In order to improve the scratch resistance of the optical disk or the like, the soft bead ratio is preferably as large as the epoxy resin matrix layer 4. When the content ratio of 5 is less than 5% by mass, the amount of the soft beads 5 fixed in the epoxy resin moment is small, and the action as a cushioning material is lowered, and the production resistance is poor. Further, when the content of the soft beads 5 is gradually increased, φ increases the viscosity of the coating material in which the soft beads 5 are dispersed, so that when the coating material is applied to the metal plate 2 by rolling or the like, the uniform film thickness is lowered. . For the above reasons, the content of the soft beads 5 is 5% by mass or more and 50% by mass or less based on the epoxy resin matrix layer 4. In order to ensure the performance of the soft beads 5 at a high level, the content of the soft beads 5 is preferably 10% by mass or more, and in order to secure a more stable content of the coated beads 5, it is preferably 4% by mass or less. (Average particle size of soft beads: average of epoxy resin matrix layers

Ethyl vinegar beads recorded trademarks), . Also, DEIKA B, etc. (FLOW 5 contains a soft bead layer 4 to scratch, and the coated oxygen-coated tree is coated by the wheel, for the rate, sex, soft thickness of I -MM.· κ h - 15- (13) 1325366 « 1 -1 times or more and 5 times or less) In order to ensure the scratch resistance of the optical disk or the like with the soft beads 5, the average particle diameter of the soft beads 5 is larger than the average thickness of the epoxy resin matrix layer 4. Big is extremely important. As a result, as shown in FIG. 1, the cross-sectional shape of the resin film 3 is such that the portion where the soft bead 5 is present has a convex fine uneven shape, so that the optical disk or the like and the epoxy resin matrix layer 4 can be greatly reduced. The contact area and the soft soft beads 5 function as a cushioning material at the contact portion, so that the scratch prevention property against the optical disk or the like can be ensured. When the average particle diameter of the soft beads 5 is more than 5 times the average thickness of the epoxy resin matrix layer 4, most of the soft beads 5 are less likely to be fixed to the epoxy resin matrix layer 4, Therefore, the effect of preventing sliding scratches on a disc or the like is reduced. In addition, when the average particle diameter of the soft beads 5 is less than 1 _1 times the average thickness of the epoxy resin matrix layer 4, the soft beads 5 having a small particle diameter are easily buried in the epoxy resin matrix. The layer 4 thus causes a reduction in the effect of preventing sliding scratches on a disc or the like. Therefore, the average particle diameter of the soft φ beads 5 is set to be 1. 1 time or more and 5 times or less the average thickness of the epoxy resin matrix layer. Further, it is more preferably 1.5 times or more and 4 times or less the average thickness of the epoxy resin matrix layer 4. When the average particle diameter of the soft beads 5 and the average thickness of the epoxy resin matrix layer 4 are maintained in such a relationship, it is possible to prevent sliding scratches on the optical disk or the like, but even if the above relationship is maintained, it is necessary to use the above. In the case of the soft bead 5 of the particle size, the average thickness of the epoxy resin matrix layer 4 must be increased. Therefore, the thickness of the resin film 3 is more than necessary, and it is not economical. On the contrary, it is less than necessary. In the case of the soft beads 5, -16 (14) (14) 1325366, it is industrially difficult to control the relationship between the average particle diameter of the soft beads 5 and the average thickness of the epoxy resin matrix layer 4. Therefore, the average particle diameter of the soft beads 5 is desirably about 5 to 30/zm, and the average thickness of the epoxy resin matrix layer 4 is preferably 3 #m or more and 10/zm or less. In addition, the average thickness of the epoxy resin matrix layer 4 is measured by measuring the weight of the resin film 3 per unit area and converting the specific gravity to 1. In the particle size of the soft beads 5, there is actually a distribution. For example, the volume distribution of beads with a volume of 50% particle diameter and about 8/m is distributed from a minimum of about 1/m to a maximum of 20#m (refer to D AIMIC BEADS® of Dajing Refined). (Login trademark) particle size distribution (same meaning as particle size distribution)). Therefore, in the present invention, as the index of the particle diameter of the soft beads 5, the average particle diameter is employed. In addition, the average particle diameter is an integrated volume of 50% particle diameter measured by a laser-retracted particle size distribution measuring instrument or the like in a state where the soft beads 5 are dispersed in water. (The ratio of the fluorine concentration of the resin film) The resin film 3 is a fluorine-containing additive in the epoxy resin matrix layer 4, and the ratio of the fluorine concentration of the outermost surface of the film of the resin film 3 is calculated by the following formula (1). When the ratio of the fluorine concentration is 10% or less, more preferably 7% or less: AC % ) ={F/ ( F + C + 0+N ) } X1〇〇· · · (1) In the above, A is the ratio of the fluorine concentration, F is the fluorine mass%, C is the carbon mass%, 〇 is the oxygen mass%, and N is the nitrogen mass%). * j 。 。 。 。 。 。 。 。 The fluorine mass %, the carbon mass %, the oxygen mass %, and the nitrogen mass % are calculated by the above mathematical formula (1). Further, the outermost surface of the film referred to herein means the surface on the adhesive side of the adhesive tape, i.e., the outermost surface of the precoated metal sheet 1, and the interface between the non-resin film 3 and the metal sheet 2. Specifically, the ratio of the fluorine concentration on the outermost surface of the film means that the surface of the precoated metal plate 1 is internally drilled by an argon splashing shovel or the like, and each is performed by ESCA. In the elemental analysis, the mass % of each element obtained in the state where the argon sputtering time is zero. That is, since all surfaces are not controlled by argon sputtering or the like, they are defined as the outermost surface. In the case where the fluorine-based additive is contained in the epoxy resin matrix layer 4, the ratio of the fluorine concentration on the outermost surface of the film may exceed 10%. In this case, the ratio of fluorine which is present on the outermost surface of the film of the resin film 3 and which has an influence on the peeling property of the adhesive becomes too high, so that the peeling strength at the time of attaching the component or the like with the double-sided adhesive tape becomes It is too big to become a stable force. (Corrosion-Resistant Film) Next, the pre-coated metal sheet 1 of the present invention may be provided with a corrosion-resistant film (not shown) between the metal sheet 2 and the epoxy-based resin matrix layer 4 including the soft beads 5. . By forming the corrosion-resistant film, the pre-coated metal plate 1 can be imparted with corrosion resistance, and the adhesion between the metal plate 2 and the resin film 3 < 5 -18-(16) 1325366 can be improved. The structure of the corrosion resistant film is as follows. As the corrosion-resistant film, a chromium phosphate film, a chromic acid film, a chromium phosphate film, an acidified lanthanide film, a coated chromic acid film, or a conventional chromic acid film including a conventional corrosion-resistant film containing Cr or Zr as a component can be suitably used. Or a coated zirconium film or the like. Further, the adhesion amount of the corrosion-resistant film is preferably 0 to 50 m g/m 2 in terms of Cr or Zr. When the adhesion amount of the corrosion-resistant film is less than 10 mg/m2, the entire surface of the metal plate 2 cannot be uniformly covered, and it is difficult to ensure corrosion resistance, and it cannot be used for a long period of time. In addition, when the amount of adhesion exceeds 50 mg/m2, cracking (peeling) occurs in the corrosion-resistant film itself by press forming or the like, and high corrosion resistance cannot be maintained for a long period of time. 2. Method for Producing Precoated Metal Sheet The method for producing a precoated metal sheet of the present invention is known in the art of combining the following processes, that is, coating the surface of a metal sheet with epoxy dispersed with soft beads. The process of coating the coating; and the process of forming the resin film by baking the epoxy coating which has been applied. The following describes each process. The initial process is a process for coating the surface of a metal plate with an epoxy-based coating in which soft beads are dispersed. The epoxy-based coating used is a main component composed of bisphenol A-type epoxy resin and urea. It is preferred that the curing agent composed of the compound or the phenolic compound is dissolved in an organic solvent. Further, in the epoxy-based paint, it is desirable to add a lubricant such as a natural wax, a petroleum wax, a synthetic wax or a mixture of these waxes in addition to the soft beads of the essential component, wherein a fluorine-based compound represented by tetrafluoroethylene is used. Lubricant, when the following mathematical formula (1)

<S -19- (17) 1325366 Calculating the ratio of the fluorine concentration on the outermost surface of the film of the resin film The ratio of the concentration is not more than 10%, and more preferably, it is used without being used. A ( % ) ={F / ( F + C + O + N) } x 1 〇〇... (wherein, Α is the ratio of the fluorine concentration, F is the fluoromass mass%, Ο is the oxygen mass %, N is a nitrogen mass%) and an additive for various dyes or pigments for coloring, various inorganic chelating agents for improving the degree of tree or preventing scratch generation, and the like, does not exceed the requirements of the present invention. The dispersion of the urethane beads of the epoxy-based paint may be an ultrasonic treatment, a magnet stirrer or an impeller mixer: a homogenizer, a mixing and pulverizing device, a ball mill, a bead mill treatment, or the like. The application of the oxygen coating material may be carried out by various methods such as a brushing machine, a roller coating machine, a roll coater, an electrostatic coating machine, and a knife coating coater, but the coating amount is used. Further, it is preferable to apply a roller which is simple in operation, and the coating amount is set to a conveyance speed of the sheet, a rotation direction of the roller coating, and a rotation speed, and an epoxy resin matrix layer having an average thickness of 3 is formed on the surface of the metal plate. It is also possible to degrease the surface before applying the epoxy coating. Degreasing process. For example, when the rate of the metal plate is t, the fluorine is over 7%, the C is a hardening additive of the carbon grease film, and the stirring cloth of the stirring processor or the like Machine, curtain curtain, die-casting mold can be equal to the metal degree, etc., suitable for ~1 0 // m to spray the surface of the metal plate with alkali-20- < ε (18) (18) 1325366 aqueous solution Wash with water to degrease the surface of the metal plate. Further, as described above, when a corrosion-resistant film is provided between the metal plate and the epoxy resin film, the chemical treatment liquid containing chromium ions or the like can be sprayed on the surface of the metal plate to form a corrosion resistance. Sex film. Next, the next process of the process of applying the epoxy-based coating to the metal plate is a process of forming a resin film (a matrix layer of an epoxy-based resin containing soft beads) from the epoxy-based coating to be applied, and coating the coating. The epoxy-based paint on the metal plate is subjected to a barbecue treatment to harden (crosslink) the epoxy-based paint. Then, the resin film is strongly adhered to the metal plate by curing (crosslinking) with an epoxy-based paint. Further, the soft beads are fixed to the fluorine resin matrix layer. Depending on the temperature of the grilling film, the scratch-proof property of the film on the film or the adhesion of the double-sided adhesive tape is not affected, but when the grilling temperature is less than 200 ° C, the epoxy-based paint is hardened (cross-linked). It is not sufficient, and when the grilling temperature exceeds 300 ° C, the epoxy-based paint is thermally degraded (decomposed). Therefore, it is preferably 200 ° C or more and 30 or less (TC or less. Barbecue processing time, preferably 20 to 60) If the processing time is less than 20 seconds, the grilling tends to be insufficient, and when it exceeds 60 seconds, the grilling processing time is too long, and the productivity at each time is liable to be lowered. Further, the grilling process can be used, for example. The hot air furnace, the induction heating furnace, the near-infrared furnace, the far-infrared furnace, and the energy line hardening furnace are carried out. [Examples] Next, the type and average thickness of the matrix layer of the resin film are changed for the precoated metal sheet of the present invention. The type of beads dispersed in the matrix layer,

-21 - S (19) !325366 When the hardness (compressive strength at 10% deformation), the content ratio, the average particle diameter, and the ratio of the surface fluorine concentration adjusted by the amount of tetrafluoroethylene added are 'confirmed on the disc, etc. Examples and comparative examples for preventing scratch resistance and adhesion peelability and coating properties will be described. (Examples 1 to 1 2)

As Examples 1 to 12, a precoated metal plate was produced in accordance with the above production method. The respective structures of the precoated metal sheets are as follows. (Metal plate) An aluminum alloy plate of 5052-H3 4 having a thickness of 0.5 mm' JIS was used. (Corrosion resistant film) A chromium phosphate film is formed on both sides of the aluminum alloy plate. The amount of adhesion of the chromium phosphate film was 20 mg/m2 in terms of Cr. (Resin film) The outermost surface of the chromium phosphate film is coated with a soft bead having a compressive strength at a deformation of 10% defined by the present invention and an epoxy-based paint in which a tetrafluoroethylene powder is dispersed, at a grilling temperature (metal) The peak temperature of the plate was subjected to a baking treatment at 250 ° C to form a resin film (fluorine-based resin matrix layer). Here, urethane beads were used as soft beads. Further, in Example 1 of which the surface fluorine concentration was 0%, no tetrafluoroethylene powder was added. Here, as the epoxy-based paint, a main component composed of bisphenol A type epoxy tree-22-(20) (20) 1325366 grease and a curing agent composed of a urea-based compound are dissolved in an organic solvent. A liquid epoxy urea paint. In addition, this time, it is a coating made by Otsuka Ink Chemical Industry Co., Ltd., but the coating of the same composition can also be obtained by Kansai Paint Co., Ltd. and Japan Coatings Co., Ltd. (Comparative Examples 1 to 1 2) As a comparison with the above Examples 1 to 2, precoated metal sheets of Comparative Examples 1 to 12 were produced. Comparative Example 1 is an epoxy-based paint containing no soft beads. 'Comparative Examples 2 and 3 are those in which the use rate of the soft beads is not in accordance with the present invention. 'Comparative Examples 4 and 5 are the average particle diameters of the soft beads used. The relationship between the average thickness of the epoxy resin matrix layer is not in accordance with the scope of the patent application of the present invention, and the comparative examples 6 and 7 are the results of increasing the amount of fluorine in the outermost surface of the film using the addition amount of the tetrafluoroethylene powder. In the patent application scope of the invention, 'Comparative Examples 8 and 9 use a resin matrix layer different from the epoxy type. 'Comparative Example 10 is that the type of the resin matrix layer is different from the epoxy type and the ratio of the fluorine concentration does not match. In the patent application scope of the present invention, 'Comparative Examples 11 and 12 are those which use compressive strength beads (i.e., non-soft beads) which do not have a deformation of 10% as defined in the present invention. Next, the ratio of the fluorine concentration of the outermost surface of the film of the resin film was measured in the resin films of the precoated metal sheets of Examples 1 to 12 and Comparative Examples 1 to 12, and the results are shown in Table 1. Further, the measurement method of each characteristic is as follows. (The ratio of the fluorine concentration) -23- (21) 1325366 The outermost surface of the film of the resin film was measured by ESC A (manufactured by Shimadzu Corporation) to obtain atomic % of four elements of fluorine 'carbon, oxygen, and nitrogen. These atomic % are converted into mass % using the atomic weight of each element. Using the fluorine content % (F), carbon mass % (C), oxygen mass % (〇), and nitrogen mass % (N), the ratio (A (%)) of the fluorine concentration was calculated by the following mathematical formula (1). A ( % ) = {F / ( F + C + 0 + N ) ) X 1 00 · (1) Here, the outermost surface of the film refers to the surface of the precoated metal plate produced as described above. In this state, the state in which the argon sputtering time is zero is measured. The resin film composed of the epoxy resin matrix layer and the beads is a film which is observed in micrometers and has an uneven film. Therefore, when the analysis is performed by ESCA, when the area of the analysis surface is too narrow, the information of the portion where the epoxy resin matrix layer is partially concentrated or the portion where the opposite pearl is partially concentrated is not obtained. There is a ratio of fluorine concentration, which produces unevenness at each measurement time point. Therefore, the area of the surface to be analyzed is set to 3 πιηηφ ' to obtain the average information of the resin film. Here, of course, the outermost surface of the film In the inside of the film, the parts which were not contaminated by oil or the like were selected and measured. Next, the scratch-preventing property and adhesion of the pre-coated metal sheets of Examples 1 to 12 and Comparative Examples 1 to 12 were observed. With adhesion, measurement, evaluation, The results are shown in Table 1. Further, adhesion assay prevent generation of scratch resistance and adhesion with the evaluation method are as follows.

< S -24- (22) (22) 1325366 (Scratch-proofing of the disc) The surface of the disc that is sold on the market is brought into contact with the surface of the resin film of the pre-coated metal sheet, and the finger is gently pressed. After rubbing back and forth 10 times to the left and right, the scratches on the surface of the optical disc were visually evaluated. At this time, in comparison with the disc scratch pattern of Figs. 2 to 3, the scratch scratch pattern with the scratch is selected, and the scratch pattern is judged as the result of the scratch prevention property of the precoated metal sheet. However, the scratches caused by the edge rubbing of the optical disc are not determined by the sliding scratches on the surface of the resin film and the recording surface of the optical disc. It is determined that the scratch-producing property is excellent as "?", the scratch-prone property is good, and the scratch-prone property is set to "△". It is set to "X" to prevent scratches. (Adhesive tape adhesion) Adhesive tape peel strength ' was measured according to the 180 degree peel test specified in JIS K 6 8 54-2. The adhesive tape was a double-sided adhesive tape sold by the market (a double-sided adhesive tape manufactured by SLIONTEC Corporation, model 5460, bandwidth 6 mm). Further, as a measurement condition, a peeling strength of 50 rnm/min was used using a precoated metal plate having a length of 1 00 mm x width of 60 mm and an adhesive tape having a length of 100 mm and a width of 6 mm. In addition, the adhesion evaluation of Table 1 is "〇" when the peeling strength of the adhesive tape is 2_0N/6mm or more, and it has excellent adhesiveness, and when it is less than 2.01^/611^1, it is "><", poor adhesion. -25 - < S' (23)1325366 m ratio? 2 cases of epoxy-based acrylic beads SI in in r· o CM CSJ XN C0 的 hard hardness ratio 酽 ring gas system 〇 f- nylon beads CM ID c \i 〇NN < 〇〇sm ity tHL/ XBU ratio r in urethane phthalate 呀 f* 00 csi 〇CVJ 〇| n] ◎ IA 〇6 X i matrix different comparison example 9 urethane system in Ethyl carbamate beads in CO 〇i 〇CSJ n ◎ m X matrix difference 1 Comparative Example 8 Polyester tn urethane formic acid beads in 00 csi 〇CO ◎ (0 X 1- 1 1 matrix different comparative example 7 epoxy Line in urethane beads to »* CO N 〇SI @ σ> 6 X Fluoride acesulfame too high Comparative Example 6 Epoxy U) Amine I acid B | Ester beads | U) r- CO csi s ◎ CJ produced X Fluoride concentration over 髙 Comparative example i 5 Cyclone in urethane beads (0 Ο « o (D o N CO < η csi 〇Ιϋδ Comparative Example 4 味U mo Γ" urethane Bead tn (0 (0 6 S w X 0) csi 0 : particle size ί is too small compared to film thickness. Comparative Example 3 Steep mm in urethane beads in CO N SI CO ◎ in eg 〇 Painted cheeks Comparative Example 2 Epoxy-based in urethane beads in t-CD csi nl to 0 0) N 〇囤 Comparative Example 1 Epoxy-based in m IIII CO X ri 〇 mm Example 12 Epoxy-based in urethane Ester beads to 00 NON o ◎ o csi 〇 施 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 11 π CO 〇5 揖0» ft ON urethane bead ID 〇η u> 〇eg CO @ 0) csi 〇K Example 8 Oxygen O urethane beads U) 〇η o CO o CM n ◎ 00 cj 〇Example 7 Epoxy type o urethane beads in T· c\io CM (0 @ O CO 〇捶 "K epoxy system o Ψ- frKl 狴 狴 避 avoid mr~ to t - o CNJ n ◎ 卜 csi 〇匡揖 WK epoxy system in urethane beads tn oo oo c \io U) n ◎ if) csi 〇 Example 4 epoxy based in urethane beads in 00 N · o read < 0 ◎ ω csi 〇 Example 3 Epoxy-based IT) urethane beads in T— 00 c\io csi C9 © GO Csj 〇 Example 2 Epoxy-based in urethane beads To » N o CO ◎ 0) csj 〇 Example 1 Cyclonic system in mr~ 00 c\i tn CO 〇 Γ 3 〇 Resin matrix layer type ms ss 驭 Bead type Kg sm 宕缰mm Bead average particle size ( B:ro) B/A bead content rate (mass*%) Ratio of the surface fluorine concentration of the resin film to the surface (%) m & SN铉Adhesive tape peeling strength (N/6mm) Adhesive evaluation 1 Coating property Remarks 黏 Adhesive tape adhesion wake up ms: » ffi N 乡锊<π 伥1长鼷蝈m -26-

<S (24) (24) 1325366 As shown in Table 1, in the precoated metal sheets of Examples 1 to 12, the adhesive tape peeling strength of either of them was higher than 2.0 N/6 mm, showing excellent adhesion of the adhesive tape. Sexuality, and it is good or excellent about the prevention of scratches on the disc. In addition, it is confirmed that the content of the urethane beads is increased, and the scratch-producing property is prevented from increasing. When the content is 5 mass% or more, the content is generally good, and when the content is 10% by mass or more, the content is 10% by mass or more. , it shows excellent scratch resistance. In terms of the precoated metal sheets of Comparative Examples 1, 2, 4, 5, 11, and 12, the peel strength of the adhesive tape is higher than 2.0 N/6 mm, which shows that the adhesive tape is excellent in adhesion, but the scratch prevention of the optical disc is generated. Poor sex. Further, in Comparative Examples 6 to 10, it was shown that the scratch resistance of the optical disk was excellent, but the adhesive tape peeling strength was less than 2.0 N/6 mm, and the adhesive tape peeling property was poor. Further, in Comparative Example 3, the content of the soft beads was 60% by mass, which exceeded the range of the present invention. Therefore, the viscosity of the epoxy-based coating material was remarkably increased, and the coating property was difficult. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing the structure of a precoated metal sheet of the present invention. 2 is a microscope photograph for determining a disc scratch pattern for preventing scratches on an optical disc, (a) a scratch pattern for preventing scratch generation, and (b) a scratch pattern for preventing scratch generation. . Fig. 3 is a view of a microscope for determining a scratch-off pattern of a disc for preventing scratches on a disc, (a) a scratch pattern for preventing scratches from being slightly bad, and (b) a scratch for preventing scratches. Template. -27- (25) (25) 1325366 Fig. 4 is a perspective view schematically showing the structure of the optical disk drive. [Main component symbol description] 1 : Pre-coated metal plate 2 : Metal plate 3 : Resin film 4 : Epoxy resin matrix layer 5 : Soft beads 10 : CD 20 : CD player 21 : Tray 22 : Cover

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Claims (1)

1325366 (1) X. Patent application scope 1. A pre-coated metal plate is a precoated metal plate having a metal plate and a resin film formed on the surface thereof, wherein the resin film has an epoxy resin matrix. And a soft bead which is dispersed in the epoxy resin matrix layer and has a compressive strength of 10 MPa or less when the single bead of the micro compression test is 10% deformed, and the content of the soft bead is the epoxy resin matrix layer. The average particle diameter of the soft bead is 1.1 times or more and 5 times or less the average thickness of the epoxy resin matrix layer, in an amount of 5% by mass or more and 50% by mass or less. 2. The precoated metal sheet of claim 1, wherein the soft bead is a urethane bead. 3. The precoated metal sheet according to claim 1 or 2, wherein the epoxy resin matrix layer is a main component composed of a bisphenol A type epoxy resin by heat, and A film obtained by crosslinking a curing agent composed of a urea compound or a phenol compound. 4. The precoated metal sheet according to claim 1 or 2, wherein the epoxy resin matrix layer contains a fluorine-based lubricant as an additive for imparting lubricity. 5. The precoated metal sheet of claim 4, wherein the fluorine-based lubricant is tetrafluoroethylene. 6. The pre-coated metal sheet according to the fourth aspect of the invention, wherein the amount of the fluorine-based lubricant added is a ratio of a fluorine concentration of the outermost surface of the film of the resin film calculated by the following formula (1). The ratio of the fluorine concentration -29-(2) (2)1325366 is in the range of 10% or less: A ( % ) ={f / ( f+c + o + n) ) x 1 0 〇·· (1) (In the formula, A is a ratio of a fluorine concentration, F is a fluorine mass%, C is a carbon mass%, 0 is an oxygen mass%, and N is a nitrogen mass%). 7. The precoated metal sheet according to claim 1 or 2, wherein the average particle diameter of the soft beads is 1.5 times or more and 4 times or less the average thickness of the epoxy resin matrix layer. 8. The precoated metal sheet according to the first or second aspect of the invention, wherein the content of the soft bead is 10% by mass or more and 40% by mass or less based on the epoxy resin matrix layer. 9. The precoated metal sheet according to claim 1 or 2, wherein a corrosion resistant film is provided between the metal sheet and the resin film. 10. Precoating according to claim 1 or 2 Metal plate, wherein 'the aforementioned metal plate is an aluminum plate or an aluminum alloy plate. r «&* 5 -30-