JP4791219B2 - Resin-coated metal plate and method for producing the same - Google Patents

Description

  The present invention relates to a resin-coated metal plate used for can end materials, can body materials, electrical and electronic equipment members, automobile body materials, building materials, and the like, and in particular, a resin-coated metal plate formed by high-speed continuous pressing. About.

  In forming the resin-coated metal plate, lubricity is imparted to the surface of the metal plate in order to facilitate the forming process. This is usually performed by applying a lubricant to a metal plate, but this method is not easy to handle because the lubricant scatters, and it is necessary to remove the lubricant after the molding process. The cost was increased. In addition, a method of applying a paint to a metal plate and applying wax after baking has been proposed, but there is a problem that wax stains occur during molding.

Various proposals have been made for such problems. For example, various methods have been proposed to improve the lubricity of the metal plate surface itself by applying a paint containing a solid lubricant (wax) to form a resin coating layer on the metal surface when coating the metal plate. ing. These include those that specify the particle size of the wax (Patent Documents 1 to 3 below), those that use two types of wax having a large particle size and a small particle size (Patent Documents 4 and 5 below), and wax on the coating surface. There are those that define the area ratio of the particles (Patent Documents 6 to 8 below), and those that define the baking conditions when applying a paint containing wax and then baking (Patent Document 9 below).
JP-A-6-305074 JP 2000-265111 A Japanese Patent No. 3133607 JP-A-5-237449 JP-A-8-1858 Japanese Patent No. 3314228 JP-A-10-29266 Japanese Patent Laid-Open No. 10-52881 JP-A-11-244778

  Patent Document 1 discloses an automobile panel containing 5 to 25% by volume of lubricant fine particles having an average particle diameter of 1.3 μm or less and having a water-soluble polymer film having a film thickness of 0.7 to 10 μm formed on the outermost surface. A surface-treated Al or Al alloy material is described. In this Al or Al alloy material, by restricting the average particle size of the lubricant fine particles to 1.3 μm or less, the particles are relatively distributed on the surface, so that the workability is improved, but the wear resistance is improved. It cannot be secured. In addition, it is difficult to obtain good wear resistance because only the average particle size is defined and the particle size distribution is not defined.

  Patent Document 2 discloses an aqueous surface treating agent for metal materials containing polyethylene wax having an average particle size of 0.01 to 0.2 μm. In this document, the particle size of polyethylene wax is set to 0.2 μm or less from the viewpoint of slidability, but even with this, sufficient slidability is not obtained.

  Patent Document 3 discloses that the resin-coated aluminum plate has an average wax particle size of 10 μm or less and a range of 1 to 10 times the dry film thickness of the resin layer. In this document, the average particle diameter of the wax is specified as described above from the viewpoint of lubricity during press working, but even with this, sufficient lubricity is not obtained.

  In Patent Document 4, as a lubricating resin-treated steel sheet, a large particle size polyolefin wax (average particle size 3 to 5 μm, particle size range 1 to 7 μm) and a small particle size polyolefin wax (average particle size 1 μm or less, maximum particle size 3 μm or less). ) Is coated with a resin containing a wax in a ratio of 5:95 to 95: 5 (weight ratio). However, the above-mentioned large particle size wax has a problem that the particle size is too large and the number of wax particles decreases, resulting in a decrease in wear resistance. Furthermore, one of the two types of waxes having a large particle size and a small particle size has a blending ratio of 5% or more. However, when the blending ratio is close to 5%, the effect of one of the waxes is not fully exhibited. Good moldability and wear resistance cannot be obtained.

  In Patent Document 5, as a surface-treated steel sheet on which an organic resin film is formed, the organic resin film contains 3 to 40% by weight of a solid lubricant, and the solid lubricant has a large particle size (50 of the film thickness of the organic resin film). Described as a mixture of 3 to 50% by weight of a lubricant (˜110%) and 97 to 50% by weight of a lubricant having a small particle size (5% or more and less than 50% of the film thickness of the organic resin film). Has been. However, when the particle diameter of the lubricant is defined based on the film thickness of the resin film as described above, the lubricant particles do not always exhibit a desired uniform distribution, and sufficient lubricity and wear resistance are obtained. It is not possible.

  Patent Documents 7 and 8 describe resin-coated metal plates in which a solid lubricant is fixed on a resin film, and the area ratio occupied by the solid lubricant in a plan view and the protruding height from the resin film surface are within a predetermined range. Has been. However, in these resin-coated metal plates, only the dispersion state of the lubricant on the surface of the resin coating is defined, and the dispersion state of the lubricant inside the resin coating is not taken into consideration, so that sufficient molding can be achieved in press processing with a large amount of deformation. There was a problem that processability was not obtained and the wear resistance of the resin coating layer was inferior.

  In Patent Document 9, in a method for producing an aluminum coated plate for a can lid, a paint containing a wax is applied to a metal strip, and the baking is performed. When baking is performed, the temperature of the metal strip is 5 seconds after the start of baking. It is described that the temperature is controlled to 110 ° C. or lower and 180 ° C. or lower after 10 seconds. However, since the composition of the wax added under the baking conditions is not taken into consideration, the wax is not properly distributed in the resin coating layer, and the moldability and wear resistance of the aluminum coated plate cannot be sufficiently obtained.

  In view of the above, an object of the present invention is to obtain a resin-coated metal plate that has sufficient formability that can withstand even when continuously formed by a high-speed press and good wear resistance.

The present invention relates to claim 1,
In a resin-coated metal plate in which a paint containing a wax and a base resin is coated on at least one side of the metal plate to form a resin coating layer,
The resin coating layer is composed of a single type of wax-based resin and the total weight _{W A} weight _{W B,} the wax has an average particle size 0.3~1.0μm be in particle size 1.5μm or less includes a small particle size wax weight _{W S,} and a large particle size wax weight _{W L} which a particle size 2.0~5.0μm having an average particle size 2.5~3.0μm having, 0. 006 ≦ W _A / W _B ≦ 0.2, (W _S + W _L ) / W _A ≧ 0.98, 0.1 ≦ W _S / W _A ≦ 0.9,
The surface occupancy of the wax particles appearing on the surface of the resin coating layer is 20 to 90%,
The cross-sectional occupancy ratio of the wax particles appearing in an arbitrary cross section along the thickness direction of the resin coating layer is 0.5% or more and less than 10%, and in an arbitrary 500 μm length range in the arbitrary cross section. The resin-coated metal plate is characterized in that one or more wax particles are present.
The present invention is as set forth in claim 2.
In a resin-coated metal plate in which a paint containing a wax and a base resin is coated on at least one side of the metal plate to form a resin coating layer,
The resin coating layer is composed of a wax-based resin and the total weight W _A weight W _B, it is those the wax consisting of mutually different at least two kinds of wax of the surface energy, the surface energy of the base resin When the value is E _B and the surface energy values of the minimum and maximum surface energy of the at least two types of waxes are E _L and E _H , 0.006 ≦ W _A / W _B ≦ 0. 2, the relationship of E _H −E _L ≧ 3 mJ / m ² , E _B ≧ E _L +12 mJ / m ² is satisfied,
Wherein the at least two types of surface energy of the wax is minimum is a small particle size wax weight W _S where there is a particle size 1.5μm or less with an average particle size 0.3 to 1.0 [mu] m, the surface energy there is the largest and includes a large diameter wax weight _{W L} which a particle size 2.0~5.0μm having an average particle size _{2.5~3.0μm, (W S + W L} ) / W The relationship _A ≧ 0.98, 0.1 ≦ W _S / W _A ≦ 0.9 is satisfied,
The surface occupancy of the wax particles appearing on the surface of the resin coating layer is 20 to 90%,
The cross-sectional occupancy ratio of the wax particles appearing in an arbitrary cross section along the thickness direction of the resin coating layer is 0.5% or more and less than 10%, and in an arbitrary 500 μm length range in the arbitrary cross section. The resin-coated metal plate is characterized in that one or more wax particles are present.

The present invention according to claim 3 ,
A method for producing a resin-coated metal sheet according to claim 2 ,
The base resin of the baking temperature _{T B} is the _{220 ℃ ≦ T B ≦ 300 ℃} , when the time from baking the start until the temperature of the metal plate reaches 100 ° C. and 200 ° C. was _{t 100} and _{t 200} Baking was performed so that 2 seconds ≦ t ₁₀₀ ≦ 20 seconds, 5 seconds ≦ t ₂₀₀ ≦ 60 seconds .
The present invention according to claim 4,
A method for producing a resin-coated metal sheet according to claim 2,
Wherein at least two kinds of one polyethylene wax of wax, the base resin of the baking temperature T _B is _{220 ℃ ≦ T B ≦ 300 ℃} , 100 ℃ temperature of the metal plate from the baking start, and 200 ° C. Resin-coated metal sheet, wherein baking is performed such that 5 seconds ≦ t ₁₀₀ ≦ 20 seconds, 10 seconds ≦ t ₂₀₀ ≦ 60 seconds , when the time to reach is set to t ₁₀₀ and t ₂₀₀ It was set as the manufacturing method of this.

The present invention according to claim 5 is the invention according to claim 1 or 2 ,
The base resin was one or more thermosetting resins selected from acrylic-modified epoxy resins, epoxy resins, epoxy-urea resins, epoxy-phenol resins, vinyl chloride resins, and polyester resins.
The present invention according to claim 6 is any one of claims 1, 2, and 5,
An undercoat film selected from zirconium phosphate treatment, titanium phosphate treatment, and phosphate chromate treatment was formed on the surface of the metal plate.
The present invention according to claim 7 is any one of claims 1, 2, 5 and 6,
The coating amount of the resin coating layer was 0.5 to 20 g / m ² .

The present invention according to claim 8 is the invention according to claim 3 or 4 ,
The base resin was one or more thermosetting resins selected from acrylic-modified epoxy resins, epoxy resins, epoxy-urea resins, epoxy-phenol resins, vinyl chloride resins, and polyester resins.
In the ninth aspect of the present invention, in any one of the third, fourth and eighth aspects,
An undercoat film selected from zirconium phosphate treatment, titanium phosphate treatment, and phosphate chromate treatment was formed on the surface of the metal plate.
In the tenth aspect of the present invention, in any one of the third, fourth, eighth, and ninth aspects,
The coating amount of the resin coating layer was 0.5 to 20 g / m ² .

  According to the present invention, by controlling the dispersion state of the wax on the surface and inside of the resin coating layer in a well-balanced manner, the resin-coated metal exhibiting excellent moldability while maintaining good wax accumulation and wear resistance. A board is obtained.

Hereinafter, embodiments of the present invention will be described in detail.
A feature of the present invention is that in a resin-coated metal plate in which a coating containing a base resin blended with granular wax is coated on at least one side to form a resin coating layer, the wax particles are balanced between the surface and the inside of the resin coating layer. By dispersing well, a resin-coated metal plate having both excellent formability and wear resistance is obtained.

A. Metal plate As the metal plate used in the present invention, an aluminum plate, an aluminum alloy plate, a galvanized steel plate, an aluminum-plated steel plate, a zinc-aluminum alloy-plated steel plate, a stainless steel plate, etc. are preferably used, but are not limited thereto. It is not something.

B. Resin coating layer In the present invention, a resin coating layer is formed on at least one surface of the metal plate. The resin coating layer is formed by coating a base plate and a wax mixed with a paint dissolved or dispersed in a solvent such as an organic solvent or water, and baked after drying.

B-1. As the base resin of the base resin resin coating layer, thermosetting resins such as acrylic-modified epoxy resins, epoxy resins, epoxy-urea resins, epoxy-phenol resins, vinyl chloride resins, and polyester resins are preferably used.
Note that, by applying a base treatment to the surface of the metal plate before the resin is coated on the metal plate to form a base film, the adhesion of the resin coating layer becomes good and contributes to an improvement in molding processability. By using a chromate treatment such as a non-chromate treatment such as a zirconium phosphate treatment or a titanium phosphate treatment, or a chromate treatment such as a phosphoric acid chromate treatment, the undercoat is formed. Furthermore, it is preferable to subject the metal plate to an alkaline degreasing treatment before the base treatment.

B-2. Wax The wax used in the present invention is granular such as polyethylene wax, carnauba wax, lanolin, microcrystalline wax, paraffin wax, polytetrafluoroethylene, etc., and these can be used alone or in combination of two or more.

B-3. Wax grain surface occupancy ratio In the present invention, in order to achieve excellent moldability and wear resistance of the resin-coated metal plate, the surface occupancy ratio of the wax grains appearing on the surface of the resin coating layer needs to be 20 to 90%. There is. If the surface occupancy ratio of the wax particles is less than 20%, sufficient lubricity due to the wax particles cannot be obtained, and molding processability is deteriorated. On the other hand, if the surface occupancy exceeds 90%, a problem that wax particles are deposited on the mold during molding is likely to occur. The surface occupation ratio is more preferably 40 to 80%.

  The surface occupancy ratio of the wax particles on the resin coating surface is defined as the ratio of the area occupied by the wax particles appearing on the surface of the resin coating layer to the total surface area of the resin coating layer when the resin coating layer is viewed from above. Is done. The surface occupancy ratio of the wax particles is obtained by coating the surface of the resin coating layer with a material that imparts conductivity, such as gold, by vapor deposition or sputtering, and analyzing the image observed with an SEM (scanning electron microscope). Can do. For example, at an observation magnification of 500 to 2000 times, five or more fields of view of 100 μm × 100 μm or more are measured, and the average value is used as the occupation ratio.

B-4. In order to achieve excellent formability and wear resistance of the resin-coated metal sheet, the cross-section of the wax particles appearing in an arbitrary cross-section along the thickness direction of the resin-coated layer. The occupation ratio needs to be 0.5% or more and less than 10%. If the cross-sectional occupancy is less than 0.5%, sufficient wear resistance of the resin coating layer cannot be obtained. On the other hand, if it exceeds 10%, the adhesion between the metal plate and the resin coating layer is lowered, and the molding processability and corrosion resistance of the resin-coated metal plate are deteriorated. The cross-sectional occupancy is more preferably 1 to 5%.

  The cross-sectional occupancy ratio of the wax existing inside the resin coating layer is defined as the ratio of the area occupied by the wax grains appearing in this cross section to the total cross-sectional area when an arbitrary cross section perpendicular to the coating surface of the resin coating layer is viewed. The The wax particles appearing in the cross section are a plurality of wax particles that exist independently without being continuous in the resin coating layer. This cross-sectional occupancy ratio is obtained by processing an image obtained by processing a resin coating layer into ultra-thin pieces having a thickness of about 100 nm parallel to the cross-section, staining with a stain such as ruthenic acid, and observing with a TEM (transmission electron microscope). It can be obtained by image analysis. For example, five or more fields of view having a length of 100 μm or more are measured at an observation magnification of 10,000 times, and the average value is used as the cross-sectional occupation ratio.

B-5. In order to achieve excellent moldability and wear resistance of the resin-coated metal sheet, the present invention further includes an arbitrary 500 μm length in an arbitrary cross section in the thickness direction of the resin coating layer. One or more wax grains must be present. Thereby, the excellent moldability and wear resistance of the resin-coated metal plate are achieved. If one or more wax particles are not present in an arbitrary 500 μm length range in the cross section of the resin coating layer, the dispersion uniformity of the wax particles is insufficient, and sufficient wear resistance of the resin coating layer cannot be obtained. The number of such wax particles can be obtained by image analysis of an image observed with a TEM. For example, 10 or more fields having a length of 500 μm were measured at an observation magnification of 10,000 times, and the number of wax particles present in each field was determined.

C. First production condition for achieving a dispersed state of wax particles
C-1. The blending ratio of the wax particles to the base resin The surface occupancy, the cross-sectional occupancy, and the number of existing wax particles in the resin coating layer are achieved by satisfying the following first manufacturing condition. That is, wax particles having a large particle size (large particle size wax) and wax particles having a small particle size (small particle size wax) are blended at a predetermined ratio, and the blending ratio of the total wax to the base resin is 0. It is achieved by setting it to 6 to 20% by weight. When the blending ratio is less than 0.6% by weight, the amount of wax is insufficient, and the moldability and wear resistance of the resin-coated metal plate cannot be obtained. It is particularly effective to make it 1% by weight or more. If the amount exceeds 5% by weight, the increase in the effect becomes dull with respect to the added amount, but a certain effect can be obtained. On the other hand, if it exceeds 20% by weight, wax accumulates on the mold during the press forming process and normal press molding cannot be performed, and there are also problems such as adhesion of dirt.

C-2. Particle size distribution of the granular wax The particle size distribution of the large particle size wax and the small particle size wax needs to be 1.5 μm or less for the small particle size wax and 2.0 to 5.0 μm for the large particle size wax. Further, it is necessary that the average particle size of the small particle size wax is 0.3 to 1.0 μm and the average particle size of the large particle size wax is 2.5 to 3.0 μm.

  The reason why the compounding ratio between the base resin and the wax particles and the particle size of the wax are specified as described above is as follows. The inventors of the present invention have measured the surface energy of a coating layer to which a small particle size wax was added, and found that the surface energy was smaller than that of a coating layer to which no wax was added or a coating layer to which only a large particle size wax was added. Thus, it was found that a small particle size wax tends to exist in a large amount on the surface of the coating layer. This is presumably because wax particles having a smaller particle size are more likely to be raised on the surface when the coating layer is baked. The wax particles present on the surface can contribute to the moldability of the resin-coated metal plate.

  Thus, in order to exhibit the property of being easily raised on the surface of the coating layer, the particle size of the small particle size wax needs to be 1.5 μm or less. If the thickness exceeds 1.5 μm, the distribution amount of the wax particles on the surface of the coating layer becomes insufficient, and the moldability of the resin-coated metal plate is deteriorated. The average particle size of the small particle size wax needs to be 0.3 to 1.0 μm. When the average particle size is less than 0.3 μm, the required number of small particle size waxes becomes too large, which is not preferable for production. When the average particle size exceeds 1.0 μm, the distribution amount of wax particles on the surface of the coating layer is small. This is because it becomes insufficient and the formability of the resin-coated metal plate is deteriorated.

In addition, from the knowledge about the surface energy of the coating layer to which the small particle size wax is added, the present inventors have found that the coating layer to which the large particle size wax has been added has a higher surface energy of the coating layer, It was found that there is a tendency to stay inside the coating layer rather than to float on the surface. Since many wax grains are present in the coating layer, even if the coating layer is worn, the wax is appropriately exposed from the coating layer, so that it is possible to always maintain a low friction coefficient and difficult to wear state. For this purpose, the large particle size wax needs to have a particle size of 2.0 μm or more. However, if the wax particle size exceeds 5.0 μm, the number of existing wax particles is inevitably small, and the number of existing wax particles is inevitably reduced. Become.
The average particle size of the large particle size wax needs to be 2.5 to 3.0 μm. This is because if the average particle size is less than 2.5 μm or more than 3.0 μm, the effect that the wax particles stay inside the coating layer is not sufficiently exhibited.

C-3. Weight ratio of large and small granular wax In order to obtain the effects of the present invention by exerting the actions of the large particle size wax and the small particle size wax as described above, it is necessary to define the compounding ratio of the wax as follows: . That is, relative to the total weight _{W A} wax particle, the weight of the small particle size wax particles _{W S,} the weight of large particle size wax particles is taken as _{W L, (W S + W} L) / W A ≧ 0. 98 and 0.1 ≦ W _S / W _A ≦ 0.9. Outside these ranges, the effects of both waxes cannot be exerted together, and either or both of moldability and wear resistance cannot be sufficiently obtained. More preferably, 0.2 ≦ W _S / W _A ≦ 0.6. In the case of (W _S + W _L ) / W _A = 1.0, W _S : W _L = 10: 90 to 90:10.
The types of the large particle size wax and the small particle size wax may be the same or different.

D. Second manufacturing conditions for achieving a dispersed state of wax particles The surface occupancy, the cross-sectional occupancy and the number of existing wax particles in the resin coating layer are the following second instead of the first manufacturing conditions. This is also achieved by satisfying the manufacturing conditions of That is,
-The blending ratio of the total wax particles to the base resin is 0.6 to 20% by weight,
- surface energy using at least two different wax particles from each other, said at least two kinds of wax grains, the surface energy value of the base resin and E _B, of at least two kinds of surface energy of the wax particles is smallest And the maximum surface energy values of E _L and E _H are E _H −E _L ≧ 3 mJ / m ² , E _B ≧ E _L +12 mJ / m ² , and the baking temperature of the base resin (Plate arrival temperature “PMT”) is 220 to 300 ° C.,
The time from the start of baking until the temperature of the metal plate reaches 100 ° C. is 2 to 20 seconds, and the time from the start of baking until the temperature of the metal plate reaches 200 ° C. is 5 to 60 seconds. Manufacturing conditions are adopted.

D-1. Mixing ratio of wax particles to base resin The mixing ratio of wax particles to base resin is as shown in C-1.
D-2. The lower the surface energy of the surface energy wax resin is, the more easily the wax is exposed on the surface of the resin coating layer. As described above, when the wax is composed of mutually different at least two kinds of wax of the surface energy, the value is less than 12 mJ / m ² of E _B -E _L, hardly wax exposed on the resin coating layer surface, the resin-coated The surface occupancy ratio of the wax in the layer is less than 20%, the lubricity is lowered, and sufficient moldability cannot be obtained.
Further, as described above, when the value of E _H -E _L is less than 3 mJ / m ² , the wax is not distributed in a well-balanced manner on the surface and inside of the resin coating layer, and both the moldability and wear resistance are satisfied. I can't.

The surface energy is calculated by the following equation by measuring the contact angle with water and the contact angle with methylene iodide using a contact angle meter.
γ = 6.281 cos θ _W +1.132 cos θ _m −0.1541, where γ is the surface energy (mJ / m ² ), θ _W is the water contact angle (rad), and θ _m is the methylene iodide contact angle ( rad).

D-3. Baking conditions The baking conditions need to be as follows. The time t ₁₀₀ from the start of baking until the temperature of the metal plate reaches 100 ° C. is 2 to 20 seconds, and the time t ₂₀₀ until the temperature reaches 200 ° C. is also 5 to 60 seconds. When the temperature of the metal plate reaches 100 ° C. in less than 2 seconds from the start of baking or reaches 200 ° C. in less than 5 seconds, the wax is difficult to be exposed on the surface of the resin coating layer, and the wax is placed on the resin coating layer surface and inside. This is because they cannot be distributed in a well-balanced manner and cannot satisfy both molding processability and wear resistance.

When at least polyethylene wax is contained in the wax, the time t ₁₀₀ until the temperature of the metal plate reaches 100 ° C. from the start of baking is set to 5 to 20 seconds, and the time t until the temperature reaches 200 ° C. ₂₀₀ is 10 to 60 seconds. This is because polyethylene wax is difficult to be exposed on the surface of the resin coating layer, and thus it is necessary to slow the temperature increase rate. When the temperature of the metal plate reaches 100 ° C. in less than 5 seconds from the start of baking or reaches 200 ° C. in less than 10 seconds, the wax is difficult to be exposed on the surface of the resin coating layer. This is because they cannot be distributed in a well-balanced manner inside and cannot satisfy both molding processability and wear resistance.

  In addition, if the time for the temperature of the metal plate to reach 100 ° C. or 200 ° C. is equal to or longer than the lower limit time defined above, the wax can be distributed in the resin coating layer in a well-balanced manner. However, since the effect is saturated even if it takes more time, the time to reach 100 ° C. is practically within 20 seconds, and the time to reach 200 ° C. is preferably within 60 seconds. The total baking time is preferably set within 100 seconds.

E. Resin coating amount The resin coating layer has good moldability and other characteristics when the coating amount is 0.5 to 20 g / m ² . If it is less than 0.5 g / m ² , even if the wax distribution state is defined as described above, the molding processability is lowered and the corrosion resistance is also poor. When the coating amount exceeds 20 g / m ² , molding processability is lowered due to a decrease in adhesion of the resin coating layer, and the cost is further increased, which is not economical. The resin coating amount is preferably 1 to 15 g / m ² . In addition, the coating amount of the resin coating layer is measured using a film mass test method by sulfuric acid film removal.

Examples 1 to 23 and Comparative Examples 1 to 25
As the metal plate, an aluminum alloy plate (JIS A5182-O) having a thickness of 0.8 mm was used. After degreasing both surfaces of the above alloy plate using a commercially available alkaline degreasing liquid (manufactured by Nippon Paint Co., Ltd., Surf Cleaner 420N-2), a commercially available phosphoric acid chromate solution (manufactured by Nippon Paint Co., Ltd.) is used as a base treatment. Then, a chemical conversion treatment of 20 mg / m ^{2 in} terms of Cr amount was performed as the adhesion amount using Al Surf Surf 45/405). Next, an epoxy-based paint in which a wax and an epoxy resin as a base resin are dispersed in a mixed solution of water as a solvent and an organic solvent is applied to both surfaces of the alloy plate by a roll coater in a continuous coating line, and the baking time is 60. Second, a baking treatment was performed at a baking temperature of 260 ° C. to form a resin coating layer, and a resin-coated metal plate was produced. The wax used was a mixture of a small particle size and a large particle size polyethylene wax. The resin coating amount was 50 g / m ² . The resin coating amount was measured by a film mass test method using sulfuric acid film removal. That is, a resin coating plate of 100 mm × 100 mm was immersed in concentrated sulfuric acid to dissolve the resin coating layer, and the weight before and after the resin coating layer was measured to obtain the resin coating amount.

Particle size and average particle size of large and small wax, weight ratio of small diameter wax to total weight of wax, weight ratio of small diameter wax to large diameter wax, weight ratio of total amount of wax to base resin, surface area of wax, cross section of wax The occupation ratio, the number of existing waxes, and the performance evaluation (molding processability, wear resistance, wax depositability) of the produced resin-coated metal sheet are shown in Table 1 for Examples 1 to 23 and Comparative Examples 1 to 25. Are shown in Table 2. Note that since the wax contains only a small-diameter wax and a large-diameter wax, (W _S + W _L ) / W _A = 1.

  Measurement of wax particle size and average particle size, wax surface occupancy, wax cross-sectional occupancy, the number of wax particles present, and performance evaluation of the resin-coated metal sheet produced (moldability, wear resistance, Wax depositability was performed as follows.

The particle size distribution and the average particle size The particle size distribution of the wax particles was measured using a laser diffraction / scattering particle size distribution measuring apparatus LA-920 manufactured by Horiba, Ltd. The average particle size of the wax particles was calculated by an arithmetic average based on volume.

Wax surface occupancy rate The resin coating layer surface of the prepared resin-coated metal plate was coated by depositing gold, and the field of view of 100 μm × 100 μm or more on the coating surface was observed with an observation magnification of 1000 × 5 by SEM (scanning electron microscope). More than one place was observed. By analyzing the observed image, the ratio of the occupied area of the wax to the total area of the observed part was determined for each visual field, and the wax surface occupation ratio was calculated as the average value.

Wax cross-section occupancy The resin-coated metal plate of the resin-coated metal plate was processed into ultra-thin pieces having a thickness of about 100 nm cut by parallel cross-sections along the thickness direction and dyed with ruthenic acid. Using a TEM (transmission electron microscope), a field of view of 100 μm or more in the cross section of the ultrathin piece was observed at five or more places at an observation magnification of 10,000 times. By analyzing the observed image, the ratio of the occupied area of the wax to the total area of the observed part was obtained in each field of view, and the wax cross-sectional occupancy was calculated as the average value.

The cross section along the thickness direction of the resin-coated metal plate of the resin-coated metal plate produced in the presence range of the wax was observed by TEM. By analyzing the observed image, the number of wax particles existing in an arbitrary 500 μm long range in the cross section was obtained.

As an evaluation of the moldability, the cylindrical deep drawing was performed with a molding tester, and the molding breaking height was measured and evaluated. The molding conditions were punch diameter: φ40 mm, shoulder R4.5 mm, drawing die: φ42.5 mm, shoulder R8.0 mm, blank diameter: φ84 mm, wrinkle holding force: 2.0 tonf, molding speed: 20 mm / sec. When the molding break height is 7 mm or more, the workability in actual use is very excellent, and ◎, and when the mold break height is 5 mm or more and less than 7 mm, the workability in actual use is not a problem, so it is marked as ○. When the height was less than 5 mm, cracks and the like occurred in actual use, and normal press molding was not possible. ◎ and ○ were accepted, and x was rejected.

Abrasion resistance was evaluated with a Haydon type frictional wear tester. The same place was repeatedly slid with a contact, and the number of sliding until the friction coefficient exceeded 0.2 was measured. The sliding conditions were: contact: φ3 mm carbide ball, sliding width: 10 mm, load: 500 gf, sliding speed: 10 mm / second. When the number of sliding is 500 times or more, ◎ because the wear resistance in actual use is very excellent, and when the number of sliding is 200 or more and less than 500, there is no problem in the wear resistance in actual use. When the number of sliding times is less than 200 times, the wear resistance in actual use is insufficient, and a part of the coating film is scraped to deteriorate the corrosion resistance and design properties. ◎ and ○ were accepted, and x was rejected.

Wax depositability Wax depositability was evaluated by measuring the amount of wax adhering to the mold after performing continuous pressing of 10,000 sheets using the mold used for moldability. The amount of adhesion was less than 3 mg, ◎, 3 mg or more and less than 7 mg was marked as ◯, and 7 mg or more was marked as x. ◎ and ○ were accepted, and x was rejected.

As shown in Table 1, in Examples 1 to 23, all the requirements specified in claim 1 were satisfied , and as a result, molding processability, wear resistance and wax depositability as the performance of the produced resin-coated metal sheet were obtained. All of these evaluation items passed.

As shown in Table 2, in Comparative Examples 1 to 4, the weight ratio of the small diameter wax to the total weight of the wax did not satisfy the predetermined requirement. In Comparative Examples 5, 6, 10, 11, 15, and 16, the particle diameter and average particle diameter of the large-diameter wax did not satisfy the predetermined requirements. In Comparative Examples 7, 8, 13, and 18, the particle size and average particle size of the small-diameter wax do not satisfy the predetermined requirements, and in Comparative Examples 9, 14, and 19, the particle size and average particle size of the large and small-diameter wax are The prescribed requirements were not met. In Comparative Examples 20 to 23, the weight ratio of the small diameter wax to the total weight of the wax and the weight ratio of the small diameter wax to the large diameter wax did not satisfy the predetermined requirements. In Comparative Examples 24 and 25, the weight ratio of the total wax amount to the base resin did not satisfy the predetermined requirement.
Thus, in Comparative Examples 1 to 25, all the requirements defined in claim 1 are not satisfied, and as a result, molding processability, wear resistance, and wax depositability as the performance of the produced resin-coated metal sheet are obtained. Any of the evaluation items of was rejected.

Examples 24-33 and Comparative Examples 26-36
Except that an aluminum alloy plate (JIS A5182-H19) having a plate thickness of 0.25 mm was used as the metal plate, both surfaces of the alloy plate were subjected to alkali degreasing and ground treatment in the same manner as in Example 1. Next, an epoxy paint in which a wax and an epoxy resin as a base resin are dispersed in a mixed solution of water and an organic solvent as a solvent is applied to both surfaces of the alloy plate by a roll coater in a continuous coating line, and a baking time is 60 seconds. Then, a baking treatment was performed at a baking temperature of 260 ° C. to form a resin coating layer, and a resin-coated metal plate was produced. As baking conditions, total baking time, 100 ° C. arrival time, and 200 ° C. arrival time were variously set. As the wax, one kind or a mixture of two or more kinds of carnauba wax, polyethylene wax, lanolin wax, and paraffin wax were used.

  Wax properties (type, surface energy, weight ratio of wax amount to base resin, difference between maximum surface energy and minimum surface energy of wax, minimum surface energy of wax and base resin Difference in surface energy), baking conditions, resin coating amount, wax surface occupancy, wax cross-sectional occupancy, number of waxes present, performance evaluation (molding process, wear resistance, wax deposit, resin coating layer Adhesiveness) is shown in Table 3 for Examples 24-33 and Table 4 for Comparative Examples 26-36, respectively.

  Resin coating amount, wax surface occupancy, wax cross-section occupancy, number of existing waxes, and performance evaluation (molding property, wear resistance, wax deposit, adhesion of resin coating layer) are as follows: The measurement was performed as described above.

Resin coating amount The coating amount of the resin coating layer was measured in the same manner as in Example 1 by the above-described film mass test method using sulfuric acid film removal.

The surface occupancy of the wax, the cross-sectional occupancy of the wax, and the number of existing waxes were measured in the same manner as in Example 1.

Molding workability The molding break height was measured in the same manner as in Example 1. The measurement conditions were punch diameter: φ33 mm, shoulder R4.5 mm, drawing die: φ33.6 mm, shoulder R4.0 mm, blank diameter: φ68 mm, wrinkle holding force: 1.0 tonf, molding speed: 20 mm / sec. The evaluation was ◎ when the molding break height was 7 mm or more, ◯ when it was 5 mm or more and less than 7 mm, and × when it was less than 5 mm. ◎ and ○ were accepted, and x was rejected.

Abrasion resistance In the same manner as in Example 1, the number of sliding was measured to evaluate the abrasion resistance.

Wax deposition property In the same manner as in Example 1, the amount of wax was measured and evaluated.

Adhesiveness of the resin coating layer The adhesiveness of the resin coating layer was evaluated by primary adhesion and secondary adhesion by the following methods (a) and (b).
(A) Primary adhesion: 100 square grid cuts were made on the surface of the resin coating layer at intervals of 1 mm using a cutter knife in accordance with the method described in JIS K 5400-8-5-2, and tape A peel test was performed.
(B) Secondary adhesion: After being immersed in boiling water for 30 minutes, taken out and allowed to stand for 1 hour, a test was conducted in the same manner as the primary adhesion.
Both primary and secondary were evaluated according to JIS K 5400-8-5-2. The case where no peeling is observed is rated as ◎ with an evaluation score of 10, and the case where the area of the defect is less than 5% of the total square area is evaluated as ○ with the evaluation score of 8, and the area of the defect is 5% or more of the total square area The case was evaluated as x with an evaluation score of 6 or less. ◎ and ○ were accepted, and x was rejected.

As shown in Table 3, in Examples 24-33, all the requirements specified in claim 3 were satisfied , and as a result, molding processability, wear resistance, and wax depositability as the performance of the produced resin-coated metal sheet were obtained. And the evaluation items of adhesion were both acceptable.

As shown in Table 4, since only one type of wax was used in Comparative Examples 26 to 28, the difference between the maximum surface energy and the minimum surface energy of the wax was zero, and the surface energy difference did not satisfy the predetermined requirements. . Furthermore, in Comparative Example 27, the predetermined requirement regarding the difference between the surface energy of the base resin and the minimum surface energy of the wax was not satisfied. In Comparative Example 29, the predetermined requirement regarding the difference between the maximum surface energy and the minimum surface energy of the wax was not satisfied. In Comparative Examples 30 and 32, the weight ratio of the total wax amount to the base resin did not satisfy the predetermined requirement. In Comparative Example 31, the predetermined requirement regarding the difference between the surface energy of the base resin and the minimum surface energy of the wax was not satisfied. The comparative example 33 shows the comparative example of claim 3, and the 100 ° C. arrival time and the 200 ° C. arrival time under the baking conditions did not satisfy the predetermined requirements. Comparative examples 34 to 36 show comparative examples of claim 4. In Comparative Example 34, the arrival time at 100 ° C. under the baking condition did not satisfy the predetermined requirement. In Comparative Example 35, the 200 ° C. arrival time under the baking conditions did not satisfy the predetermined requirements. In Comparative Example 36, the 100 ° C. arrival time and the 200 ° C. arrival time in the baking conditions did not satisfy the predetermined requirements. Thus, in Comparative Examples 26 to 36, all the requirements specified in claim 3 or 4 were satisfied. Orazu a result, moldability as performance of resin-coated metal plate produced, abrasion resistance, one of the evaluation items of the wax deposition and adhesion have failed.

  By setting the surface occupancy of the wax particles in the resin coating layer, the cross-sectional occupancy, and the number of wax particles in the cross-section within a predetermined range, sufficient moldability that can withstand continuous molding with a high-speed press and good A resin-coated metal plate having wear resistance can be provided.

Claims (10)

In a resin-coated metal plate in which a paint containing a wax and a base resin is coated on at least one side of the metal plate to form a resin coating layer,
The resin coating layer is composed of a single type of wax-based resin and the total weight _{W A} weight _{W B,} the wax has an average particle size 0.3~1.0μm be in particle size 1.5μm or less includes a small particle size wax weight _{W S,} and a large particle size wax weight _{W L} which a particle size 2.0~5.0μm having an average particle size 2.5~3.0μm having, 0. 006 ≦ W _A / W _B ≦ 0.2, (W _S + W _L ) / W _A ≧ 0.98, 0.1 ≦ W _S / W _A ≦ 0.9,
The surface occupancy of the wax particles appearing on the surface of the resin coating layer is 20 to 90%,
The cross-sectional occupancy ratio of the wax particles appearing in an arbitrary cross section along the thickness direction of the resin coating layer is 0.5% or more and less than 10%, and in an arbitrary 500 μm length range in the arbitrary cross section. A resin-coated metal plate, wherein one or more wax particles are present. In a resin-coated metal plate in which a paint containing a wax and a base resin is coated on at least one side of the metal plate to form a resin coating layer,
The resin coating layer has a weight W _B Base resin and total weight W _A The wax is composed of at least two kinds of waxes having different surface energies, and the surface energy value of the base resin is represented by E _B And the surface energy values of the minimum and maximum surface energy of the at least two types of waxes are E _L And E _H 0.006 ≦ W _A / W _B ≦ 0.2, E _H -E _L ≧ 3mJ / m ² , E _B ≧ E _L +12 mJ / m ² The relationship of
Among the at least two kinds of waxes, the one having the smallest surface energy is a weight W having a particle size of 1.5 μm or less and an average particle size of 0.3 to 1.0 μm. _S A small particle size wax having the largest surface energy and having a particle size of 2.0 to 5.0 μm and an average particle size of 2.5 to 3.0 μm. _L (W) _S + W _L ) / W _A ≧ 0.98, 0.1 ≦ W _S / W _A ≦ 0.9 is satisfied,
The surface occupancy of the wax particles appearing on the surface of the resin coating layer is 20 to 90%,
The cross-sectional occupancy ratio of the wax particles appearing in an arbitrary cross section along the thickness direction of the resin coating layer is 0.5% or more and less than 10%, and in an arbitrary 500 μm length range in the arbitrary cross section. A resin-coated metal plate, wherein one or more wax particles are present. A method for producing a resin-coated metal sheet according to claim 2 ,
The base resin of the baking temperature _{T B} is _{220 ℃ ≦ T B ≦ 300 ℃} , when the time from baked with the start until the temperature of the metal plate reaches 100 ° C. and 200 ° C. was _{t 100} and _{t 200} And baking for 2 seconds ≦ t ₁₀₀ ≦ 20 seconds, 5 seconds ≦ t ₂₀₀ ≦ 60 seconds. A method for producing a resin-coated metal sheet according to claim 2 ,
Wherein at least two kinds of one polyethylene wax of wax, the base baking temperature T _B of the resin is 220 ° C. ≦ T _B ≦ 300 ° C., the temperature is 100 ° C. and 200 of the metal plate from baked with the start Resin-coated metal, wherein baking is performed such that 5 seconds ≦ t ₁₀₀ ≦ 20 seconds, 10 seconds ≦ t ₂₀₀ ≦ 60 seconds, when the time to reach ° C. is t ₁₀₀ and t ₂₀₀ A manufacturing method of a board. The base resin is one or more thermosetting resins selected from acrylic-modified epoxy resins, epoxy resins, epoxy-urea resins, epoxy-phenol resins, vinyl chloride resins, and polyester resins. The resin-coated metal plate described. The resin coating according to any one of claims 1, 2, and 5, wherein an undercoat film selected from zirconium phosphate treatment, titanium phosphate treatment, and phosphate chromate treatment is formed on the surface of the metal plate. Metal plate. The coating amount of the resin coating layer is 0.5 to 20 g / m. ² The resin-coated metal plate according to any one of claims 1, 2, 5, and 6. The base resin is one or more thermosetting resins selected from an acrylic-modified epoxy resin, an epoxy resin, an epoxy-urea resin, an epoxy-phenolic resin, a vinyl chloride resin, and a polyester resin. The manufacturing method of the resin-coated metal plate of description. Before forming the resin coating layer, a surface treatment selected from zirconium phosphate treatment, titanium phosphate treatment, and phosphate chromate treatment is applied to the surface of the metal plate. A method for producing a resin-coated metal plate according to Item. The coating amount of the resin coating layer is 0.5 to 20 g / m. ² The method for producing a resin-coated metal plate according to any one of claims 3, 4, 8, and 9.