Technical field
[0001]The present invention relates to an organic resin-coated plated steel sheet.
BACKGROUND
[0002]For home appliances, building materials, etc. for automobiles, in place of conventional post coating product which has been painted after the molding process, also referred to as an organic resin-coated plated steel sheet (precoated steel sheet and the organic resin film coated on the surface of the galvanized steel sheet ) it has come to be used. The organic resin coating coated steel sheet, after being press working, household appliances without such further coating is applied, building materials, often used as a material for automobiles or the like. Therefore, such an organic resin-coated plated steel sheet, so as not to lose the beautiful is during machining, is required to have excellent 耐疵 with resistance.
[0003]
　For example, Patent Document 1, the beads contained a in the organic coating, by specifying the particle size and glass transition temperature of the beads, not easily generated in the film damage due to press working, that is excellent organic resin 耐疵 with properties the coated plated steel sheet discloses.
[0004]
　Further, Patent Document 2, an organic resin-coated plated steel sheet for the drive case such as an optical disc, excellent anti-scratching with respect to the optical disc, and having conductivity, discloses an organic resin-coated plated steel sheet. Specifically, in Patent Document 2, to ensure the conductivity by limiting the thickness of the resin coating, it has secured 耐疵 with resistance by including a bead in the organic resin film.
[0005]
　Patent Document 3 also, as the organic resin coating coated steel sheet having improved anti-damage to the optical disc, discloses an organic resin-coated plated steel sheet containing the beads. In Patent Document 3, the average particle diameter and amount of the beads, and to identify the type of resin and the glass transition temperature and the like, thereby improving the 耐疵 with resistance.
CITATION
Patent Document
[0006]
Patent Document 1: Japanese Patent No. 5644983
Patent Document 2: JP 2008-94085 JP
Patent Document 3: JP 2008-161735 JP
Summary of the Invention
Problems that the Invention is to Solve
[0007]
　Incidentally, an organic resin-coated plated steel sheet at the time of press working, first, applying a press oil on the surface of the organic resin-coated plated steel sheet. Then, it performs the press working. The organic the surface of the resin-coated plated steel sheet is formed unevenness with a bead, hardly scratches the surface of the organic resin coating coated steel sheet during press working. Furthermore, easy press oil by such irregularities are held on the surface of the organic resin-coated plated steel sheet. Therefore, the organic resin coating coated steel sheet is excellent in workability. Then, treating the surface of the organic resin coated plated steel sheet with a degreasing agent. Thus, press oil is removed from the surface of the organic resin-coated plated steel sheet. Here, the degreasing agent remaining on the surface of the organic resin-coated plated steel sheet, causing the problem of a disfiguring of the surface of the organic resin-coated plated steel sheet. Therefore, after the treatment with degreasing agent, a degreasing agent to remove from the surface of the organic resin-coated plated steel sheet by washing with water.
[0008]
　However, the surface of the organic resin-coated plated steel sheet since it is formed irregularities by the beads, degreaser after the uneven washing was a problem that tends to remain. When the degreasing agent remaining in the irregularities, degreasers mark is formed on the surface of the organic resin-coated plated steel sheet. Such degreasing agents marks, so to generate color unevenness on the surface of the organic resin-coated plated steel sheet, thus impairing the appearance of the organic resin-coated plated steel sheet. Therefore, degreasing agent mark hardly occurs, i.e., the organic resin coating coated steel sheet having excellent degreasing properties has been strongly desired. On the other hand, the organic resin coating coated steel sheet, is also required properties such 耐疵 with properties described above.
[0009]
　The present invention has been made in view of the above problems, it is an object of the present invention has the characteristics required for the organic resin coated plated steel sheet while maintaining a low cost, to improve the degreasing, to provide a new and improved organic resin-coated plated steel sheet.
Means for Solving the Problems
[0010]
　In order to solve the above problems, according to an aspect of the present invention, a plated steel sheet, and the organic resin coating covering the coated steel sheet, there an organic resin-coated plated steel sheet having a beads dispersed in an organic resin film, the Te, the organic resin film has a glass transition temperature of 0 ~ 20 ° C. of the polyester resin, and comprises a melamine resin, beads, glass transition temperature of -60 ° C. ~ 50 ° C. of the urethane resin beads, the total organic resin coating It included in the organic resin film in an amount of 1 to 15% by weight, based on the weight, and 5 to 1000 / mm in the organic resin film 2 is dispersed in a surface density of, among organic resin coating, no beads the average thickness of the portion T ([mu] m), an average particle diameter of the beads phi ([mu] m), of an organic resin film, an average thickness of bead coating portion covering the bead t ([mu] m), the glass transition temperature of the polyester resin the gp (° C.), when the glass transition temperature of the beads was Tgb (° C.), and satisfies the relation of the following equation (1) to (3), the organic resin coating coated steel sheet is provided.
　≦ T ≦ 5 15 [mu] m · · · ·
　(1) 1.1 ≦ phi / T ≦ 10 · · · ·
　(2) 13 ≦ (phi / t) × {(Tgb + 273) / (Tgp + 273)} ≦ 140 · · · - (3)
[0011]
　According to another aspect of the present invention, a plated steel sheet, and the organic resin coating covering the coated steel sheet, an organic resin-coated plated steel sheet having a beads dispersed in an organic resin film, an organic resin coating, includes a polyester resin, and a melamine resin, a glass transition temperature of the organic resin film is 0 ~ 35 ° C., beads, glass transition temperature of -60 ° C. ~ 50 ° C. of the urethane resin beads, the total organic resin coating It included in the organic resin film in an amount of 1 to 15% by weight, based on the weight, and 5 to 1000 / mm in the organic resin film 2 is dispersed in a surface density of, among organic resin coating, no beads the average thickness of the portion T ([mu] m), an average particle diameter of the beads phi ([mu] m), of an organic resin film, an average thickness of bead coating portion covering the bead t ([mu] m), the glass transition of the organic resin coating the temperature Tgf ( ), When the glass transition temperature of the beads was Tgb (° C.), and satisfies the relation of the following equation (1) to (3 '), an organic resin-coated plated steel sheet is provided.
　≦ T ≦ 5 15 [mu] m · · · ·
　(1) 1.1 ≦ phi / T ≦ 10 · · · ·
　(2) 10 ≦ (phi / t) × {(Tgb + 273) / (Tgf + 273)} ≦ 115 · · · - (3 ')
[0012]
　Among the organic resin coating film, the average thickness of the bead coating portion covering the bead may be 0.3 ~ 1.0 .mu.m.
[0013]
　It may also have a chemical conversion film formed between the plated steel sheet and the organic resin film.
[0014]
　Further, the organic resin coating is further 3-15% by weight of carbon black, 1 to 10% by weight of the calcium modified silica, of from 0.5 to 5% by weight of the epoxy resin, also contain at least one or more good.
[0015]
　Furthermore, plated steel sheet may be a galvanized steel sheet.
The invention's effect
[0016]
　According to the present invention described above, when pressing an organic resin-coated plated steel sheet by the beads is deformed, the surface of the organic resin film is planarized. Therefore, it is possible to apply the degreaser planarized surface of the organic resin coating. Incidentally, the surface of the organic resin coating until flattening, since there remain irregularities on the surface of the organic resin coating, 耐疵 with resistance in pressing is maintained. Further, since the press oil remains in the unevenness and improved press workability. Then, the organic resin coating is maintained flatness even when removing the degreasing agent, it is possible to more reliably remove the degreaser. In other words, to improve the degreasing. Thereafter, the beads are recovered, the characteristics of 耐疵 with, etc. in a step after an organic resin-coated plated steel sheet (for example, the assembly process, etc.) is ensured. Further, since the above effect can be obtained by thinning the organic resin film, the above effect can be obtained at low cost.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017]
FIG. 1 is a sectional view showing a structure of an organic resin-coated plated steel sheet according to the embodiment of the present invention.
It is a cross-sectional view showing the behavior during the press working of the organic resin film according to [2] The present embodiment.
3 is a sectional view showing the behavior during the press working of the organic resin film according to the present embodiment.
4 is a sectional view showing the behavior during the press working of the organic resin film according to the present embodiment.
5 is a sectional view showing the behavior during the press working of the organic resin film according to the present embodiment.
6 is a sectional view showing the behavior during pressing of a conventional organic resin film.
7 is a sectional view showing the behavior during pressing of a conventional organic resin film.
8 is a sectional view showing the behavior during pressing of a conventional organic resin film.
9 is a sectional view showing the behavior during pressing of a conventional organic resin film.
It is a cross-sectional view showing the behavior during pressing of [10] conventional organic resin film.
DESCRIPTION OF THE INVENTION
[0018]
　Reference will now be described in detail preferred embodiments of the present invention. In the specification and the drawings, components having substantially the same function and structure are a repeated explanation thereof by referring to the figures.
[0019]
　<1. Summary of the organic resin-coated plated steel sheet>
　First, with reference to FIG. 1, an outline of an organic resin-coated plated steel sheet 10 according to this embodiment. An organic resin-coated plated steel sheet 10 is provided with a plated steel sheet 20, the organic resin film 30, a bead 40, and a chemical conversion coating 50. Beads 40 are dispersed in the organic resin film 30 to form the uneven surface of the organic resin film 30.
[0020]
　In the present embodiment, when pressing the organic resin-coated plated steel sheet 10, by the bead 40 is deformed, the surface of the organic resin film 30 is planarized. Therefore, it is possible to apply the degreaser planarized surface of the organic resin film 30. Then, the organic resin film 30 to maintain the flatness even when removing the degreasing agent, it is possible to more reliably remove the degreaser. In other words, to improve the degreasing. Then, since the beads 40 is restored, 耐疵 with, etc. is ensured.
[0021]
　<2. Behavior of the organic resin film>
　Next, the behavior of the organic resin film 30 according to the present embodiment at the time of press working will be described in comparison with the behavior of the conventional organic resin film.
[0022]
　First, based on FIGS. 6 to 10, illustrating the behavior of a conventional organic resin film 300. Figure 6 shows the structure of a conventional organic resin-coated plated steel sheet 100. An organic resin-coated plated steel sheet 100 is provided with a plated steel sheet 200, the organic resin film 300, and a bead 400. Sometimes chemical conversion coating between organic resin film 300 and the plated steel plate 200 is formed, but not shown here. Beads 400 are dispersed in the organic resin film 300, to form the uneven surface of the organic resin film 300.
[0023]
　First, as shown in FIG. 7, the press oil 60 is applied to the surface of the organic resin film 300. Then, pressing is made. Beads 400, since hardly deformed at the time of press working, the surface of the organic resin film 300, still uneven by the beads 400 are formed. Therefore, after pressing, as shown in FIG. 8, the press oil 60 remains in the uneven.
[0024]
　Then, as shown in FIG. 9, degreasers 70 is applied to the surface of the organic resin film 300. Then, degreasing agent is removed by washing with water. However, as shown in FIG. 10, since the surface of the organic resin film 300 is formed with irregularities by the beads 400, degreasing agent 70 remains in the washing after the irregularities. Accordingly, the conventional organic resin-coated plated steel sheet 100 when you press working, degreasers mark is formed on the surface of the organic resin-coated plated steel sheet 100 easily.
[0025]
　Next, with reference to FIGS. 2 to 5 show the behavior of the organic resin film 30 according to the present embodiment. In the present embodiment, it is possible to suppress the occurrence of such a degreasing agent marks. First, as shown in FIG. 2, the press oil 60 is applied to the surface of the organic resin film 30. Then, pressing is made. As shown in FIG. 3, the bead 40 is so deformed during press working, the surface of the organic resin film 30 is flattened. The surface of the organic resin film 30 until the flattened, since there remain irregularities on the surface of the organic resin film 30, 耐疵 with resistance in pressing is maintained. Further, since the press oil 60 remains in the uneven, also improved press workability. After pressing, press oil 60 remains on the organic resin film 30.
[0026]
　Then, as shown in FIG. 4, degreasers 70 is applied to the surface of the organic resin film 30. Then, as shown in FIG. 5, the degreasing agent is removed by washing with water. Here, the surface of the organic resin coating 30 maintains the flatness until the washing of at least degreaser 70 is completed. Therefore, it is possible to more reliably remove the degreaser 70. In other words, to improve the degreasing. As a result, hardly degreaser mark is formed on the surface of the organic resin-coated plated steel sheet 10. An organic resin-coated plated steel sheet 10, washed with water and dried. Then, since the beads 40 is restored, the characteristics of 耐疵 with, etc. in a step after an organic resin-coated plated steel sheet 10 (e.g., assembly process, etc.) is ensured.
[0027]
　<3. Detailed configuration of the organic resin-coated plated steel sheet>
　Next, with reference to FIG. 1, a detailed configuration of the organic resin-coated plated steel sheet 10. An organic resin-coated plated steel sheet 10 is provided with a plated steel sheet 20, the organic resin film 30, a bead 40, and a chemical conversion coating 50.
[0028]
　Plated steel sheet 20 is a portion serving as a base material to be coated by the organic resin film 30. Plated steel sheet 20 is preferably a zinc-plated steel sheet. Types of galvanized steel sheet used in this embodiment is not particularly limited. Zinc-plated steel sheet, for example, galvanized steel sheets (GI), electro-galvanized steel sheet (EG), zinc - nickel alloy plated steel sheet, galvannealed steel sheet (GA), aluminum - zinc alloy plated steel sheet, zinc - aluminum - magnesium alloy plated steel sheet, zinc - vanadium composite plated steel sheets, zinc - zirconium composite plated steel plate or the like, generally may be a known galvanized steel sheet. Plated steel sheet 20, other types of plated steel sheets may be, for example, aluminum-based plated steel sheet.
[0029]
　The organic resin film 30 covers the coated steel sheet 20. The organic resin film 30 is formed on one surface of the plated steel sheet 20 may be formed on both surfaces. Further, the organic resin film 30 is formed on one surface of the plated steel sheet 20 may be formed another kind of the resin coating on the other surface.
[0030]
　The organic resin film 30 comprises a glass transition temperature of 0 ° C. ~ 20 ° C. of the polyester resin, and a melamine resin. Polyester resin is a resin as a main component of the organic resin film 30. In other words, the content ratio of the polyester resin is preferably at least 50 wt% based on the total weight of polyester resin and melamine resin. Thus, in this embodiment, it is defined with the polyester resin at least 50 wt% based on the total weight of polyester resin and melamine resin, an organic resin film 30 a coating comprising a melamine resin.
[0031]
　The glass transition temperature of the polyester resin is 0 ~ 20 ° C.. If the glass transition temperature is lower than 0 ° C., the organic resin film 30 is very soft. Therefore, even if the beads 40 are dispersed in the organic resin film 30, it tends to contain the defect in the organic resin film 30 at the time of press working of an organic resin-coated plated steel sheet. That can not be obtained with conditioned superior 耐疵. Further, since the bead 40 is easily restored after pressing, it is difficult to maintain the flatness of the organic resin film 30 for a long time, therefore, degreasing is lowered.
[0032]
　On the other hand, if the glass transition temperature is 20 ° C. greater than the organic resin film 30 becomes very hard. As a result, at the time of press working of an organic resin-coated plated steel sheet, and a crack is generated in the organic resin film 30 appear white-through plating layer underlying phenomenon, i.e. it is possible that whitening occurs. In addition, the beads 40 is also likely to fall off during the press working. Therefore, workability of the organic resin-coated plated steel sheet 10 is reduced.
[0033]
　In the present embodiment, by making the glass transition temperature of the polyester resin to 0 ° C. ~ 20 ° C., it is possible to increase 耐疵 with organic resin-coated plated steel sheet 10, degreasing, and processability. Here, if the time of producing the organic resin-coated plated steel sheet 10, it is possible to select a desired polyester resin, it is possible to identify the polyester resin sources (e.g. product name). Therefore, in this case, it is possible to use the catalog values ​​as a glass transition temperature of the polyester resin. In other words, the catalog value of the glass transition temperature may be selected polyester resin is 0 ~ 20 ° C.. On the other hand, if the organic resin coating plated steel sheet prefabricated needs to verify it meets the requirements of the present embodiment, it is not easy to identify what parts of such polyesters resins in an organic resin film 30 . Therefore, in this case, it may be measured glass transition temperature of the organic resin film 30. Even if the catalog value of the polyester resin is not may be used a glass transition temperature of the organic resin film 30. If the glass transition temperature of 0 ~ 35 ° C. of the organic resin film 30 may be considered to include the glass transition temperature of 0 ~ 20 ° C. of the polyester resin in an organic resin film 30. The glass transition temperature of the organic resin film 30 can be measured by the following method. In Examples described later were measured glass transition temperature of the organic resin film 30 by the needle penetration method.
[0034]
　As a method for measuring the glass transition temperature of the organic resin film 30 may be a known method. For example, thermomechanical analysis; and needle penetration method (Thermomechanical Analysis TMA), the micro-thermal analysis test device combined scanning probe microscopes, can be from the surface or cross-sectional direction to measure the glass transition temperature of the organic resin film 30 directly. Further, the organic resin film 30 scraped, differential scanning calorimetry (Differential scanning calorimetry; DSC) can also be measured glass transition temperature of the organic resin film 30 by.
[0035]
　The polyester resins usable in the present embodiment, for example, alkyd resins, unsaturated polyester resins, and modified alkyd resins. Alkyd resins are those which the condensate of a polyhydric alcohol such as polybasic acids and glycerol, such as phthalic anhydride as a skeleton, which was modified with oils of fatty acids. Alkyd resins, depending on the type and content of the oil used, the short oil alkyd resin, medium-oil alkyd resins are classified into long oil alkyd resin and very long oil alkyd resin. Unsaturated polyester resin is synthesized by esterifying an unsaturated polybasic acid or a saturated polybasic acid and glycol. Examples of the polybasic acids, e.g., phthalic anhydride, isophthalic acid, terephthalic acid and adipic acid is used, as the glycols, e.g., propylene glycol is often used. The modified alkyd resins, for example, natural resins, those which are modified with polymerizable monomers such as phenol resin or styrene is used. Of course, the glass transition temperature is within the above range, it may be used known polyester resins other than these.
[0036]
　It may be a commercially available product as the polyester resin. Examples of such a commercially available product, for example, manufactured by Toyobo Co., Ltd. of "Byron TM " (Toyobo Co., Ltd. registered trademark) and, Sumika Bayer Urethane Co., Ltd. "Desmophen TM (registered trademark of Sumika Bayer Urethane Co., Ltd.)" and the like cited It is.
[0037]
　Melamine resin is a resin acting as a curing agent. In other words, melamine resin, crosslinking the polyester resin. Therefore, the polyester resin of the organic resin film 30 in the present independent state as the crosslinking reaction is crosslinked to each other by a melamine resin, or non-crosslinked.
[0038]
　Here, by adjusting the degree of crosslinking of the polyester resin, it is possible to adjust the hardness of the organic resin film 30. When the organic resin film 30 is too soft, even beads 40 are dispersed in the organic resin film 30, can become easy combing contains the defect in the organic resin film 30 at the time of press working of an organic resin-coated plated steel sheet. On the other hand, when the organic resin film 30 is too hard, it is possible that whitening occurs during press working of the organic resin-coated plated steel sheet. In addition, there is also a possibility that the beads 40 to fall off. Therefore, workability of the organic resin-coated plated steel sheet 10 is reduced. Specific hardness of the organic resin film 30, it may be adjusted appropriately according to the application of the organic resin-coated plated steel sheet 10.
[0039]
　Melamine resin, it is easy to paint by dissolving in an organic solvent. That is, the organic resin coated plated steel sheet 10, the coating containing a material and bead 40 constituting the organic resin film 30 is applied onto the plated steel sheet 20, it is formed on the plated steel plate 20 by drying. Moreover, melamine resin, at room temperature yet long life in the paint, can be advanced readily crosslinking reaction in a short time when the application of heat. Further, in the melamine resin, the dispersibility of the beads 40 is also good, yet also has excellent paintability. Therefore, it is easy to application of paint to the coated steel sheet 20 surface.
[0040]
　Melamine resins which can be used in the present embodiment is not particularly limited and may be a known melamine resin. The melamine resin which can be used in the present embodiment, for example, complete alkyl type methylated melamine, imino type methylated melamine, methylol melamine, methylol group type methylated melamine, complete alkyl type mixed etherified melamine, methylol group type mixed etherified melamine, melamine resin such as an imino group type mixed ether melamine and the like. As a more specific example, commercially available, for example, CYTEC Co., Ltd. Amino resin "CYMEL TM Series" and "MYCOAT TM Series", manufactured by Mitsui Chemicals, Inc. of amino resin "U-VAN TM Series", manufactured by DIC Corporation "Super BECKAMIN of TM , such as the series" and the like.
[0041]
　Beads 40 are added to the organic resin film 30 in order to increase the 耐疵 with properties of the organic resin-coated plated steel sheet 10. The glass transition temperature of the beads 40 is -60 ℃ ~ 50 ℃. The glass transition temperature of the beads 40 is preferably -40 ℃ ~ 0 ℃. If the (sometimes referred to as a later Tg) The glass transition temperature of the beads 40 is a value within these ranges, the resulting superior and degreasing properties with scratch.
[0042]
　If the glass transition temperature of the beads 40 is less than -60 ° C., too high elastic bead 40, bead 40 is easily restored after pressing. Therefore, it is difficult to maintain the flatness of the organic resin film 30 for a long time, therefore, degreasing is lowered. Further, it deteriorated solvent resistance of the beads 40 themselves easily occurs swelling of the beads 40 with an organic solvent in the paint. In this case, there is a case where the storage stability of the paint becomes insufficient over time. To enhance the stability over time of the degreasing and paint, the glass transition temperature of the beads 40 may be -40 ℃ or higher.
[0043]
　On the other hand, if the glass transition temperature of the beads 40 is greater than 50 ° C., the elasticity of the bead 40 is very low. Therefore, since the bead 40 is less likely to restore during press working, the flatness of the organic resin film 30 is maintained. However, since the time the organic resin film 30 to maintain the flatness becomes extremely long, 耐疵 with resistance decreases. To increase the 耐疵 with organic resin-coated plated steel sheet 10, a glass transition temperature of the beads 40 may be 0 ℃ less. Here, if the time of producing the organic resin-coated plated steel sheet 10, it is possible to select a desired bead 40, it is possible to identify the source of the bead 40 (e.g. product name). Therefore, in this case, it is possible to use the catalog values ​​as a glass transition temperature of the beads 40. On the other hand, if the organic resin coating plated steel sheet prefabricated needs to verify it meets the requirements of the present embodiment, is often the source of the bead 40 is unknown. (If or catalog value does not exist) when the source of the bead 40 is not known, it may be measured glass transition temperature of the beads 40 in the following manner.
[0044]
　As a method for measuring the glass transition temperature of the beads 40 may be a known method similar to the glass transition temperature of the organic resin film 30. For example, a needle penetration method TMA, the micro thermal analysis test device combined scanning probe microscopes, can be directly measured glass transition temperature of the beads 40 from the surface or cross-sectional direction.
[0045]
　The surface tension of the beads 40 is preferably 80 ~ 100mN / m. In this case, it can be applied in the desired thickness of the coating on the plated steel sheet 20. Surface tension organic resin film 30 tends to become thick to cover the bead 40 is less than 80 mN / m beads 40. Therefore, the bead 40 is less likely to restore at the time of press working, 耐疵 with resistance decreases. Meanwhile, it is not preferable because it may become too thin an organic resin film 30 to the surface tension of the beads 40 covers the bead 40 exceeds 100 mN / m, the beads 40 are exposed from the organic resin film 30.
[0046]
　In addition, the beads 40, is a urethane resin beads. This can increase the 耐疵 with organic resin-coated plated steel sheet 10. Further, it can be a value within the aforementioned range of the surface tension of the bead 40.
[0047]
　As the urethane resin beads which can be used in the present embodiment, for example, those obtained by polyaddition reaction of a compound having a diisocyanate and a hydroxyl group, by the action of Bisukurorugi acid esters of glycol diamine in the presence of a dehydrochlorination agent those obtained, those obtained by the reaction of a diamine with ethylene carbonate, those obtained by ω- amino alcohols by condensation of this changed to chloroformate ester or carbamic acid ester, those obtained by the reaction of a bis-urethane and a diamine etc. the. Of the urethane resin beads listed above, it is often used those obtained by polyaddition reaction of a compound having a diisocyanate and a hydroxyl group. Here, as the diisocyanate, tolylene diisocyanate (2,4- and mixtures of 2,6-) is often used. Further, as a compound having a hydroxyl group, polyoxypropylene glycol, polyoxypropylene - ether compounds such as polyoxyethylene glycol, a compound of polyester obtained by condensation of adipic acid and ethylene glycol is often used.
[0048]
　Examples of commercially available products of the urethane resin beads, for example, Negami Industries, Ltd. "Art Pearl" (Negami Industrial Co., registered trademark), manufactured by Sanyo Chemical Industries, Ltd. of Meltex (registered trademark), Dainichiseika Color & Chemicals Mfg. Co., Ltd. of Daimikku beads (registered trademark), and the like.
[0049]
　Further, the beads 40 are included in the organic resin film 30 at a rate of 1 to 15 wt% based on the total weight of the organic resin film 30. If the content of the beads 40 is less than 1 wt%, 耐疵 with organic resin-coated plated steel sheet 10 becomes insufficient. If the content of the bead 40 is more than 15 wt%, the corrosion resistance of the organic resin-coated plated steel sheet 10 becomes insufficient. Incidentally, if the time of producing the organic resin-coated plated steel sheet 10, it is possible to select a mass% of the beads 40, the weight percent of the beads 40 can be a value within the above range. On the other hand, if the organic resin coating plated steel sheet prefabricated needs to verify it meets the requirements of the present embodiment, the weight percent of the beads 40 can be measured by the following method. That is, observed in the thickness direction parallel cross section of the organic resin film 30 (the cross section perpendicular to the surface of the organic resin film 30) FE-SEM (field emission scanning electron microscope). Then, measuring the area ratio of the beads 40 in the cross-section (area ratio of the beads 40 to the total area of ​​the cross section). Area ratio of the beads 40 corresponds to the volume ratio of the beads 40 to the total volume of the organic resin film 30. The specific gravity of the beads 40 and other resin parts and (these are determined by actual measurement), based on the volume ratio of the beads 40, measuring the mass% of the beads 40. Incidentally, the measurement method similar dispersion ratio of the beads 40 to be described later to observe the surface of the organic resin-coated plated steel sheet 10, may identify the volume ratio of the beads 40. Portion surface protrudes becomes existence region of the beads.
[0050]
　The mass% of the beads 40 may be determined by the following method. First, the total weight W of the organic resin film 30 p to measure (g) Then, the dispersion ratio of the beads 40 [rho S [pieces / mm 2 Request] in the manner described below. Then, the total weight W of the bead 40 b seek the following equation.
　W b = (4 [pi] / 3) × (phi / 2) 3 × S × [rho s × [rho b
　in the above formula, phi is the average particle diameter of the beads 40, [rho b is the bead 40 density [g / cm 3 it is a. The specific gravity of the beads 40, for example 1.2 [g / cm 3 a] degree. S is (area of the release portion) a measurement area when calculated on the total weight of the organic resin film 30 [mm 2 is. Then, determine the weight percent of the beads 40 by the following equation.
　Mass% of the beads 100 × W = b / W p [wt%]
[0051]
　Further, the beads 40 is 5 to 1,000 / mm in the organic resin film 2 is dispersed in areal density of. In the present embodiment, shown in areal density rather than volume density dispersion ratio of the beads. The particle size of the beads 40 in this embodiment is larger than the thickness of the organic resin film 30, a plurality of beads 40 with each other do not overlap in the thickness direction of the organic resin film 30. Therefore, the dispersion ratio of the beads 40 can be expressed by "surface density". To obtain excellent scratch with resistance, better dispersion ratio of the beads 40 is high is preferable. Dispersion ratio 5 / mm beads 40 2 is less than, less the amount of the beads 40 are dispersed in the organic resin film 30, sufficient scratch with resistance can not be obtained. As variance ratio of the beads 40 increases, increasing the amount of beads 40, resistance with scratch is improved. However, the dispersion ratio of the beads 40 is too high, the organic resin coating amount for adhering the beads 40 is relatively lowered, the adhesion between the resin and the beads 40 may be insufficient. As a result, the beads 40 are dropped out of the organic resin film 30 may not be obtained with with excellent scratch. Therefore, the dispersion rate of the beads A is 1000 / mm 2 or less.
[0052]
　Dispersion ratio of the beads 40, that is, the surface density can be measured by the following method. In other words, to observe the surface of the organic resin-coated plated steel sheet 10 by an optical microscope or scanning electron microscope, 1 mm 2 was measured and the number of the beads 40 in the field of view, the measured value and the dispersion ratio. Note 1 beads are fully seated in the visual field of the frame, for beads only part is within the framework of the field of view is counted as 0.5 pieces. Note that the display method of the dispersion ratio, the integer portion of the dispersion ratio is rounded to the nearest whole if a 1 digit, if the integer part of the dispersion ratio is 2 or three orders of magnitude are rounded to one place following , integer part of the dispersion ratio may then rounding the 10 following in the case of more than four digits. Beads 40 in this embodiment protrudes from the surface of the organic resin film 30. Therefore, it is possible to easily count the beads 40 by observation from the surface. In the embodiment described below, to measure the dispersion ratio of the beads 40 by this method.
[0053]
　Also, of the organic resin film 30, wherein the beads 40 are not present the average film thickness (hereinafter, also referred to as a flat portion 32) T ([mu] m), an average particle diameter of the beads 40 phi ([mu] m), the organic resin film 30 of the average thickness of the bead covering part 31 covering the beads 40 t (μm), Tgp ( ℃) a glass transition temperature of the polyester resin, when the glass transition temperature of the beads 40 was Tgb (° C.), the following the relationship of equation (1) to (3) are met.
　≦ T ≦ 5 15 [mu] m · · · ·
　(1) 1.1 ≦ phi / T ≦ 10 · · · ·
　(2) 13 ≦ (phi / t) × {(Tgb + 273) / (Tgp + 273)} ≦ 140 · · · - (3)
[0054]
　If the average thickness of the flat portion 32 is less than 5 [mu] m, the corrosion resistance becomes insufficient. If the average thickness of the flat portion 32 is more than 15 [mu] m, the cost of the organic resin-coated plated steel sheet 10 becomes very high.
[0055]
　If phi / T is less than 1.1, 耐疵 with organic resin-coated plated steel sheet 10 is reduced. In this case, because the amount of protrusion of the flat portion 32 of the bead 40 is reduced. If phi / T is more than 10, the bead 40 is easily restored after pressing. Therefore, it is difficult to maintain the flatness of the organic resin film 30 for a long time, therefore, degreasing is lowered. Further, since the bead 40 is likely to fall off during press working, workability decreases. Here, phi / T is preferably 1.1-5. If phi / T is more than 5, the organic resin film 30 after the press working may not become completely flat. However, as shown in Examples below, the effect of the present embodiment even when the phi / T is more than 5 is obtained.
[0056]
　In the formula (3), the term (phi / t) is the average thickness t ([mu] m) and the ratio of the average particle diameter of phi ([mu] m) and the bead-coated portion 31 of the bead 40. As this term is large, the average particle diameter of the beads 40 to the average thickness of the bead-coated portion 31 is increased, the beads 40 is easily restored after pressing. Term {(Tgb + 273) / (Tgp + 273)} is the ratio of the absolute temperature conversion value of the glass transition temperature of the absolute temperature conversion value and the polyester resin having a glass transition temperature of the beads 40. As this term is large, the ratio of the hardness of the bead relative to the hardness of the polyester resin is high, the bead 40 is easily restored after pressing. The present inventors, the effect of the value obtained by multiplying these terms gives the organic resin film 30, and a result of intensive studies to productivity and the like of the organic resin film 30, turned out to be preferable that the expression (3) is satisfied did. That, (φ / t) × {(Tgb + 273) / (Tgp + 273)} may be less than 13, since the time the organic resin film 30 to maintain the flatness becomes extremely long, 耐疵 with resistance decreases. (Φ / t) when × {(Tgb + 273) / (Tgp + 273)} is more than 140, the bead 40 is easily restored after pressing. Therefore, it is difficult to maintain the flatness of the organic resin film 30 for a long time, therefore, degreasing is lowered. Here, (φ / t) × {(Tgb + 273) / (Tgp + 273)} is preferably from 15 to 50, and more preferably 20-37. (Φ / t) If the value of × {(Tgb + 273) / (Tgp + 273)} is a value within these ranges, a further improvement in the quality of the organic resin film 30 can be expected. Furthermore, (phi / t) If the value of × {(Tgb + 273) / (Tgp + 273)} is 50 or less, the quality of the organic resin film 30 can be expected to stabilize.
[0057]
　Here, the average thickness of the flat portion 32 is measured by the following method. That is, the observed (thickness direction parallel cross section of the organic resin-coated plated steel sheet 10, i.e. the cross-section shown in FIG. 1) vertical section of the organic resin-coated plated steel sheet 10 with FE-SEM. Then, 10,000 times where no beads 40 in the field of view (i.e., area where the surfaces of the plated steel sheet 20 of the organic resin film 30 becomes substantially parallel) obtains the maximum thickness at and optionally 10-field observation average of the maximum 10 points (arithmetic mean) may be the average thickness of the flat portion 32 Te. In the following examples, it was measured average thickness of the flat portion 32 by this method.
[0058]
　The average particle diameter of the beads 40 may be used to catalog values ​​of the beads 40. In Examples described later, it was used catalog value of the beads 40. If there is no such value may be measured an average particle size in the following manner. That is, the organic polishing the surface of the resin-coated plated steel sheet 10, to observe the cross section formed by the polishing (where a flat cross-section) with FE-SEM. The cross-sectional diameter of the beads 40, gradually increases for each repeated polishing, eventually reaching a maximum value. The maximum value corresponds to a particle size of the beads 40. Continuing the polishing, the cross-sectional diameter decreases. Therefore, to measure the cross-sectional diameter of the beads 40 to be observed in certain field each time the polishing and the maximum measurement value and the particle diameter of the beads 40. Then, the arithmetic mean value of the particle diameter of the beads 40 of the plurality of arbitrarily chosen (e.g. 20) and the average particle diameter of the beads 40. Since if the cross-sectional diameter that is first observed is the maximum value, the cross-sectional diameter that is less likely than the actual particle size excluded from the time of obtaining the average value.
[0059]
　The polishing method is not particularly limited, and may be a known method. For example, it is possible to use a resin embedding polishing or microtome processing. When obtaining the average particle diameter of the beads 40 is particularly high precision, Cryo FIB-SEM as a polishing method (Cryo Scanning Electronscopy combined with Focused Ion Beam) is preferred. The sample temperature was about -100 ° C., for processing a sample with an ion beam, less damage to the coating due to heat generation caused by ion beam irradiation, since it is possible to polishing at the sub-nanometer, even small beads it is possible to determine the particle size.
[0060]
　The average thickness of the bead covering part 31 is measured by the following method. Here, bead coating portion 31 is a portion that covers the protruding portion of the bead 40 (portion projecting from the flat portion 32). In the measurement method similar to an average particle diameter of the beads 40, to measure the bead size while repeating polishing the cross section shown in FIG. 1 little by little. Then, the cross-sectional diameter of the beads 40 is to measure the thickness of the organic resin film that exists at the time of reaching the maximum value, 12 o'clock direction from the center of the bead 40 (upward direction in FIG. 1). The average thickness of the bead covering part 31, and the arithmetic mean value of a plurality of arbitrarily chosen (e.g. 20). In Examples described later were measured average thickness by this method. The average thickness in the range of bead coating portion 31, from the viewpoint of balance between the time for maintaining the flatness of the maintaining and the organic resin film 30 of 耐疵 with resistance, it is preferably 0.3 ~ 1.0 .mu.m. If the average thickness of the bead-coated portion 31 is less than 0.3 [mu] m, bead 40 is easily restored, there is a possibility that the time for maintaining the flatness of the organic resin film 30 is shortened. Further, the bead coated portion 31 there is a possibility to break. On the other hand, if the average thickness of the bead-coated portion 31 is more than 1.0 .mu.m, too long time to maintain the flatness of the organic resin film 30, 耐疵 with resistance may be deteriorated.
[0061]
　Incidentally, in the equation (3) includes a glass transition temperature Tgp of the polyester resin. As described above, when the organic resin coating plated steel sheet prefabricated needs to verify it meets the requirements of the present embodiment, to identify what parts of such polyesters resins in an organic resin film 30 It's not easy. Therefore, in this case, instead of the equation (3), it may be used the following formula (3 '). That is, the organic resin coated plated steel sheet 10 according to this embodiment, equation (1) described above, satisfies the requirements of (2) of the other, the following equation (3 '). In Equation (3 '), Tgf is the glass transition temperature of the organic resin film 30, the meaning of the other symbols are the same as Equation (3).
　10 ≦ (φ / t) × {(Tgb + 273) / (Tgf + 273)} ≦ 115 ···· (3 ')
[0062]
　Technical significance of equation (3 ') is similar to Equation (3). That is, term {(Tgb + 273) / (Tgf + 273)} is the ratio of the absolute temperature conversion value of the glass transition temperature of the absolute temperature conversion value and the organic resin film 30 of the glass transition temperature of the beads 40. As this term is large, the said bead is hardened to the organic resin film 30, the bead 40 is easily restored after pressing. The present inventors, the value obtained by multiplying these terms effect of the organic resin film 30, the result of intensive studies to productivity and the like of the organic resin film 30, it was found that it is preferable that the expression (3 ') is satisfied . That, (φ / t) × {(Tgb + 273) / (Tgf + 273)} may be less than 10, since the time the organic resin film 30 to maintain the flatness becomes extremely long, 耐疵 with resistance decreases. (Φ / t) × If {(Tgb + 273) / (Tgf + 273)} is more than 115, the bead 40 is easily restored after pressing. Therefore, it is difficult to maintain the flatness of the organic resin film 30 for a long time, therefore, degreasing is lowered. Here, (φ / t) × {(Tgb + 273) / (Tgf + 273)} is preferably from 15 to 55, and more preferably 16-32. (Φ / t) If the value of × {(Tgb + 273) / (Tgf + 273)} is a value within these ranges, a further improvement in the quality of the organic resin film 30 can be expected. Furthermore, (phi / t) If the value of × {(Tgb + 273) / (Tgf + 273)} is 55 or less, the quality of the organic resin film 30 can be expected to stabilize.
[0063]
　The organic resin film 30 further, 3-15% by weight of carbon black, 1 to 10% by weight of the calcium modified silica, of from 0.5 to 5% by weight of the epoxy resin may contain at least one or more . Note that these content are all mass% to the total weight of the organic resin film 30.
[0064]
　Carbon black acts as a black pigment in the organic resin film 30, it is possible to achieve desired aesthetic property (blackness). If the content of carbon black is less than 3 mass%, a sufficient blackness can not be obtained. As a result, there is a possibility that the plated steel sheet 20 is visible. In other words, there is a possibility that the concealing property of the organic resin-coated plated steel sheet 10 is reduced. On the other hand, if the content of carbon black exceeds 15 mass%, there is a possibility that the corrosion resistance decreases.
[0065]
　Types of carbon blacks usable in the present embodiment is not particularly limited, for example, can be used furnace black, Ketjen black, acetylene black, channel black, a known carbon black. In other instances, well-known ozone treatment, plasma treatment, may be used carbon blacks liquid phase oxidation process. Dispersibility and coating quality of the particle size of the carbon black in the coating material used, so long as there is no problem in coatability not particularly limited, for example, be used carbon black 10 ~ 120 nm in primary particle size good. Design of a thin film (coloring, concealing property) Considering and corrosion resistance, it is preferable that the primary particle diameter using a particulate carbon black 10 ~ 50 nm. For these carbon blacks which are agglomerated in the process of dispersing in the coating occurs, it is generally difficult to disperse while the primary particles. That, in fact exist in the paint in the form of secondary particles having a larger particle diameter than the primary particle diameter are present in the same form even black coating that forms from the coating material.
[0066]
　Calcium-modified silica, serves as a rust-preventive pigment in an organic resin film 30 can be maintained for a long time a beautiful organic resin-coated plated steel sheet 10. Furthermore, the calcium-modified silica, since itself is hard, to increase the hardness of the organic resin film 30, thereby improving the 耐疵 with resistance. If the content of calcium-modified silica is less than 1 wt%, there is a possibility that the corrosion resistance decreases. On the other hand, if the content of calcium-modified silica exceeds 10 mass%, the other constituents ratio of the organic resin film 30 is relatively lowered, sufficient performance can not be obtained.
[0067]
　Epoxy resins can enhance the adhesion between the organic resin film 30 and the plated steel plate 20. That is, the epoxy resin can be an organic resin film 30 hardly peeled from plated steel sheet 20 at the time of press working of an organic resin-coated plated steel sheet 10. In other words, processability so as to improve the adhesive property. Further, the epoxy resin, since improved adhesiveness between the organic resin film 30 and the beads 40, which contributes to the improvement of resistance with scratch. Here, if the content of the epoxy resin is less than 0.5 mass%, there is a possibility that processability adhesiveness is lowered. When the content ratio of the epoxy resin exceeds 5 mass%, other components ratio of the organic resin film 30 is relatively reduced, there may not sufficient performance can be obtained. The epoxy resin can be used, for example, bisphenol A type epoxy resins, acryl-modified epoxy resin, and bisphenol F type epoxy resin.
[0068]
　Chemical conversion coating 50 is formed between the organic resin film 30 and the plated steel plate 20. Chemical conversion coating 50 is obtained by chemical conversion treatment of the surface of the plated steel sheet 20. Since adhesion between the organic resin film 30 by the chemical conversion coating 50 and the plated steel plate 20 is increased, processability so as to improve the adhesive property.
[0069]
　Kind of chemical conversion treatment is not particularly limited. Examples of possible chemical conversion in the present embodiment, the chemical conversion treatment for zinc-based plated steel sheet and the like. For example, chemical conversion treatment, a zinc phosphate conversion treatment, coating chromate treatment, electrolytic chromic acid treatment, reaction chromate treatment, it may be a chromate-free-based chemical conversion treatment or the like. The chromate-free chemical conversion treatment, a silane coupling agent, zirconium compound, titanium compound, tannin or tannic acid, resin, and a method of processing a zinc-based plating layer in an aqueous solution containing silica or the like are known. Chemical conversion of the present embodiment, Sho 53-9238, JP-A No. 9-241576, JP-2001-89868, JP 2001-316845, JP 2002-60959, JP open 2002-38280, JP 2002-266081, JP-it may be a known chemical conversion treatment described in JP-2003-253464 Patent Publication. The treatment solution for making these chemical conversion treatment, a commercially available chemical conversion treatment liquid, for example, Nippon Parkerizing Co., Ltd. of chromate treatment solution "ZM-1300AN", Nippon Parkerizing Co., Ltd. of chromate-free chemical conversion treatment solution "CT-E300N" , trivalent chromium-based chemical conversion treatment liquid manufactured by Nippon paint Surf Chemicals Inc. "Surf coat (R) NRC1000", and the like. Incidentally, the chemical conversion treatment coating 50 may be omitted.
[0070]
　<4. The organic resin coating method for producing a plated steel sheet>
　is not a method of manufacturing an organic resin-coated plated steel sheet 10 is not particularly limited, for example, to prepare a coating material containing a material and bead 40 constituting the organic resin film 30, the plated steel sheet 20 This paint composition applied followed by drying.
[0071]
　Here, it is preferable that the surface tension of the coating material is 20 ~ 35 mN / m, it is preferable that the viscosity of the paint is 300 ~ 1000mPa · s. If these conditions are met, it can be applied in the desired thickness of the coating on the plated steel sheet 20. In the case where the surface tension of the coating material is less than 20 mN / m, too thin an organic resin film 30, it beads 40 is easily restored, the degreasing may be reduced. If the surface tension of the coating material is more than 35 mN / m, deviation occurs in the distribution of the beads 40, 耐疵 with property as a result may be lowered. Further, if the viscosity of the coating is less than 300 mPa · s, too thin an organic resin film 30, it beads 40 is easily restored, the degreasing may be reduced. If the viscosity of the paint is more than 1000 mPa · s, deviation occurs in the distribution of the beads 40, 耐疵 with property as a result may be lowered. In other words, the surface tension of the coating material, viscosity, and surface tension of the beads is adjusted to a value within the above range, it is possible to form an organic resin film having the above characteristics.
[0072]
　Coating method is not particularly limited, the applicable coating method to the conventional manufacturing method can be used in the present embodiment. As the coating method, for example, a curtain coating method, a roll coater method, die coater method, doctor blade method and the like. Among these methods, a curtain coating method is preferred. According to a curtain coater method, because it is possible to more uniformly apply the high viscosity of the paint of 300 ~ 1000mPa · s.
[0073]
　The type of organic solvent used in the paint is not particularly limited, the organic solvent is applied to a conventional manufacturing method can be used in the present embodiment. The organic solvent can be used, for example, cyclohexanone, MEK, xylene, a mixture of such Solvesso 150. Depending on the solubility of the resin to be used, it can be used to adjust the formulation of these organic solvents.
Example
[0074]
　<1. Preparation of Varnish coating>
　is amorphous polyester resin manufactured by Toyobo Co., Ltd. "Vylon (TM) 500 (Tg: 4 ℃)", "Byron (registered trademark) 270 (TG50 ° C.)", "Byron (R ) UR-6100 (a Tg-30 ° C.) ", cyclohexanone in an organic solvent (mass ratio: Solvesso 150 (trade name) = 1: was dissolved in use) of a mixture to 1. Here, by adjusting the mixing ratio of these polyester resins were adjusted glass transition temperature Tgp of the total polyester resin. Next, Mitsui Cytec melamine resin "Cymel (trademark) 303" was added to the above solution as a curing agent. The addition amount of the melamine resin, the mass ratio of the solid resin content, a polyester resin solid content: melamine resin solids was adjusted to the ratio shown in Tables 1 to 6. Further, this mixed solution of a polyester resin and a melamine resin, further Mitsui Cytec of an acidic catalyst "Catalyst 600" ( "crosslinking reactions" in Table 1 to Table 6) was added 0.5% by weight. Further, at the time of manufacturing of some of the test materials, and the DIC Co., Ltd. Epoxy resin "EPICLON EXA-123" were added to the mixed solution in the proportions shown in Tables 1 to 6. Then, to obtain a varnish coating by stirring the mixed solution.
[0075]
　<2. Production of steel plate coating paint>
　to the above varnish paint, Tokai Carbon Co., Ltd. of carbon black as carbon black "Toka Black # 7300", GRACE Co., Ltd. of calcium-modified silica as anti-rust pigments "SHIELDEX C303", Negami industry as urethane beads Company Ltd. Art Pearl, by dispersing in the proportions shown in Sekisui Chemical Co., Ltd. as acrylic beads "MBX" manufactured by Toray Industries, Inc. as nylon beads "SP" series to each tables 1 to 6, a predetermined steel plate coated paint It was produced. Then, the surface tension and viscosity of the steel sheet coated paint was measured by the following method. In other words, the surface tension of the paint using the DY-300 manufactured by Kyowa Interface Science Co., was measured by the platinum ring method. The viscosity of the paint was determined by A & D Co. tuning-fork vibration type viscometer (SV-10). Both coating temperature was 25 ° C.. The surface tension of the beads using PW-500 manufactured by Kyowa Interface Science Co., to measure the contact angle of the particles was determined based on the contact angle.
[0076]
　<3. Preparation of test material>
　Next, electro-galvanized steel sheet (coating weight 20 g / m per side 2 Prepare) is coated with a steel plate coated paint described above in the double-sided, and dried. Thus, to prepare a test material. Incidentally, in making the part of the test materials is the chemical conversion coating was formed on the surface of the electro-galvanized steel sheet, to form an organic resin coating on the chemical conversion coating. Chemical conversion coating, Nippon Parkerizing Co. chromate-free chemical conversion solution deposition amount after drying "CT-E300N" is 100 mg / m 2It was applied under conditions such that the steel sheet temperature was formed by drying at 60 ° C.. A plurality of types of test materials # 1-52 changing the various parameters were produced. Test materials # 1 to # 5 is obtained by changing the glass transition temperature Tgp of the polyester resin. Test materials # 6 to # 9 is obtained by changing the content of the beads. Test materials # 10 ~ # 13, is obtained by changing the glass transition temperature Tgb of the beads. Test materials # 14 ~ # 17, is obtained by changing the distribution ratio of the beads. Test materials # 18 ~ # 19 is obtained by changing the type of bead (type of resin). Test materials # 20 ~ # 23, is obtained by changing the average thickness of the beads did not exist. Test materials # 24 ~ # 27 is obtained by changing the value of phi / T. Test materials # 28 to # 31 is obtained by changing the value of the equation (3). Test materials # 32 to # 35 is obtained by changing the content of the epoxy resin. Test materials # 36 ~ # 39, is obtained by changing the content of carbon black. Test materials # 40 to # 43 is obtained by changing the content of the calcium modified silica. Test material # 44 is obtained by forming a chemical conversion coating. Test materials # 45 to # 47 is obtained by changing the surface tension of the steel sheet coated paint. Test materials # 48 to # 50 is obtained by changing the viscosity of the steel sheet coated paint. Test materials # 51 ~ # 52 is obtained by changing the surface tension of the beads. Test material # 53 is obtained by a 0.3μm average thickness of the bead-coated portion 31. The test materials # 54 is obtained by a value close to the value of the equation (3) to 37. Test material # 55 is obtained by a value close to 50 the value of the equation (3). Test materials # 56, the # 57 is one manufactured by the same manufacturing conditions as the test material # 30. The physical properties of each sample are summarized in Tables 1 to 6. Numbers underlined in the table indicates a value deviating from this embodiment.
[0077]
　<4. Evaluation Test>
　Next, were subjected to the following evaluation tests. The results are summarized in Tables 1 to 6.
[0078]
　(4-1. Restoring time of the beads)
　using a laser microscope, the height of the beads at any position of the initial design surface (raw test material surface) (h 0 a) were measured. Thereafter, pressurized at a pressure of 10MPa the mirror-polished stainless steel plate. Pressurization time was 5 seconds. The height of the beads after pressurization圧直(h x a) was measured by a laser microscope. H X was measured immediately after the press every 20 minutes. Thereafter, h x / h 0 time is more than 0.8 was defined as recovery time of the beads. The test was conducted in a room air conditioning worked, the steel sheet, the press die and the room temperature was controlled at 25 ± 3 ° C.. 1-5 (hr) was passed level.
[0079]
　(4-2. Degreasing)
　the press oil is applied to the initial design surface was pressurized with mirror-polished stainless steel plate at a pressure of 10 MPa. Pressurization time was 5 seconds. The press oil using the Japan machine tool oil manufactured by PG3080. Thereafter, degreasing by spraying with a spray degreasing liquid on the design surface after pressing. The degreasing solution used was dissolved at a concentration of 20g / L in distilled water Fine Cleaner 4326 manufactured by Nippon Parkerizing Co.. Degreasing solution temperature was 50 ± 5 ° C., the degreasing time was 60 seconds. Thereafter, washing with water and drying the steel sheet surface, a degreasing agent about the rest of the surface was visually evaluated. Pass level was set at 3 or more.
[0080]
　(. 4-2-1 Evaluation Criteria)
　5: Even when viewed from the front, degreasing agent marks even when viewed from an oblique is not visible
　4: degreasing agent marks can not be seen when viewed from the front, slightly degreasing agent when viewed from an oblique marks can be seen
　3: degreasing agent marks appear slightly when viewed from the front, slightly degreasing agent marks when viewed from the oblique is visible
　2: degreasing agent marks appear slightly when viewed from the front, clearly degreasing agent when viewed from an oblique marks can be seen
　1: even when viewed from the front, degreasing agent marks even when viewed from an oblique direction is clearly visible
[0081]
　(4-3.耐疵with resistance)
　of each sample is brought into close contact with the electro-galvanized steel sheet (untreated material), the test material is rotated 90 ° in pressurized state. Pressurization 0.5 kg / cm 2 and the test temperature was 25 ° C.. It was then visually evaluated the appearance of the test material. Pass level was set at 3 or more.
[0082]
　(. 4-3-1 Evaluation Criteria)
　5: scratches are not visible at all
　4: fine crack the case, without exposing the base material
　3: Raw material is slightly exposed (exposed area: relative to the total area of one side of the test material Te less than 5%)
　2: Raw material is exposed (exposed area: 5% or more of the total area of one side of the test material, less than 10%)
　1: Raw material is exposed (exposed area: total area of one side of the test material 10% or more with respect to)
[0083]
　(4-4. Workability)
　in the central portion of the design surface of the test piece, the test piece at Erichsen tester (according to A dimension of JIS Z 2247) was subjected to extrusion to failure. Here, electro-galvanized steel sheet used had a thickness of 0.4 mm, extrusion height was selected material of the electro-galvanized steel sheet as the above 14 mm. Then, the processing unit was visually observed or 10x loupe to evaluate the whitening degree. Here, the whitening is a phenomenon which cracks occur in the coating by the processing unit seen through plating layer underlying. Pass level was set at 3 or more.
[0084]
　(. 4-4-1 Evaluation Criteria)
　5: loupe whitening is not observed in
　4: Whitening is observed only in the vicinity broken part with a loupe, not observed whitening by visual
　3: rupture the vicinity visually only whitening is observed slightly
　(level visible within a distance 10cm between the test piece)
　2: whitening only near fracture portion visually were clearly observed
　(level visible within a distance 50cm between the test piece)
　1: breaking visually whitening is also found in other parts vicinity
[0085]
　(4-5. Processing adhesion)
　bending 0T the test material (bent 180 °) giving the process, after the bent portion outside of the film was peeled off with tape and observed for coating adhesion state to the tape side. Then, to evaluate the processability adhesion according to the following evaluation standard. In such adhesion test, it was evaluated as acceptable levels of 3 or more. Specifically, if the score is 4 or more, excellent adhesion, 3 or more was judged to be acceptable (which is acceptable level).
[0086]
　(. 4-5-1 Evaluation Criteria)
　5: No coating adhered to the tape side
　4: in the presence decapsulated at several points on the tape side, flaking length of the steel plate side, the total length of the working portion of one surface of the test piece less than 5% for
　3: in the presence decapsulated at several points on the tape side, flaking length of the steel sheet side, at least 5% relative to the total length of the processing portion of one surface of the test material, less than 10%
　2: tape side to have decapsulated, peeling length of the steel sheet side is 10% or more with respect to total length of the working portion of one surface of the test material, less than 20%
　1: film peeling tape side, flaking length of the steel sheet side, test 20% or more with respect to the total length of one side of the working portion of the timber
[0087]
　(4-6. Corrosion)
　on the central portion of the design surface of the test piece was subjected to 6mm extrusion at Erichsen tester (according to A dimension of JIS Z 2247). It was then carried out for 120 hours salt spray test (SST) in conformity with the end face of the test piece in JIS Z 2371 with sealing tape. Then, by observing the rust occurrence portion subjected to extrusion after completion of the test, it was evaluated corrosion resistance according to the following evaluation criteria. Pass level was set at 3 or more.
　
　5: white rust area is less than 1% of the total area of one side of the sample material
　4: white rust area of 1% or more of the total area of one side of the test material, less than 5%
　3: white rust area is 5% or more with respect to the total area of one side of the test material, less than 10%
　2: White rust occurrence area is more than 10% of the total area of one side of the test material, less than 30%
　1: white rust area over 30% of the total area of one side of the test material
[0088]
　(4-7. Temporal stability of the coating)
　after making the steel sheet coated paint was one month aging deterioration at a temperature 40 ° C.. Applying a time-dependent deterioration paint on the steel sheet was observed coated plate after baking and curing visually and 30-fold loupe. Then, to evaluate the temporal stability of the coating with the following evaluation criteria.
[0089]
　(. 4-7-1 Evaluation Criteria)
　￮: None solids in the paint
　×: There is a solid in the paint, visible with the naked eye
[0090]
　<5. Discussion>
　was underlined in the results that fail in the evaluation test. As apparent from the results shown in Tables 1 to 6, satisfying test materials of the present embodiment, that embodiment, while passing results were obtained in all the evaluation items, in the comparative example, any failure of the results obtained in Kano evaluation items. Incidentally, the test materials # 23, there was the a performance to good, too thick a film thickness of the organic resin film, the manufacturing cost has become very high. Test material # 28, recovery of the beads is very slow, the test materials # 31, recovery of the beads was very fast. Comparing the test pieces # 32-35, when the content of the epoxy resin is a value within the preferred range, it was found that particularly good results are obtained. Comparing the test pieces # 36 ~ # 39, if the content of carbon black is a value within the preferred range, especially good results could be obtained. Comparing the test pieces # 40 to # 43, when the amount of calcium-modified silica is a value within the preferred range, it was found that particularly good results are obtained. According to test materials # 44, by forming a chemical conversion coating, it was found that particularly good results are obtained. Test materials # 1, according to the # 53 to # 55, apparent that when the value of the average thickness or formula beads coated portion 31 (3) has a value in a preferred range Particularly good results are obtained Became. Also, test materials # 30, # 56, according to # 57, if the value of equation (3) exceeds 50, the stability of the quality of the organic resin-coated plated steel sheet 10 was found to be lowered. Incidentally, Equation (3) Similar results verified by replacing the equation (3 ') a was obtained.
[0091]
Replenishment under Rule 26 09.05.2018]　
[Table 1]

[0092]
Replenishment under Rule 26 09.05.2018]　
[Table 2]

[0093]
Replenishment under Rule 26 09.05.2018]　
[Table 3]

[0094]
Replenishment under Rule 26 09.05.2018]　
[Table 4]

[0095]
Replenishment under Rule 26 09.05.2018]　
[Table 5]

[0096]
Replenishment under Rule 26 09.05.2018]　
[Table 6]

[0097]
　Having described in detail preferred embodiments of the present invention with reference to the accompanying drawings, the present invention is not limited to such an example. It would be appreciated by those skilled in the relevant field of technology of the present invention, within the scope of the technical idea described in the claims, it is intended to cover various changes and modifications , also such modifications are intended to fall within the technical scope of the present invention.
DESCRIPTION OF SYMBOLS
[0098]
　10 an organic resin-coated plated steel sheet
　20 plated steel sheets
　30 organic resin film
　31 beads coated portion
　32 flat portion
　40 bead
　50 chemical conversion coating
　60 press oil
　70 degreaser

The scope of the claims
[Requested item 1]And plated steel sheet
　and the organic resin coating covering said plated steel sheet,
　an organic resin-coated plated steel sheet having a beads dispersed in the organic resin film,
　the organic resin film has a glass transition temperature of 0 ~ 20 ° C. includes a polyester resin, and melamine resin,
　the beads, the glass transition temperature of -60 ° C. ~ 50 ° C. of the urethane resin beads, at a ratio of 1 to 15% by weight based on the total weight of the organic resin coating included in the organic resin film and the organic resin film 5 to 1000 / mm 2 is dispersed in a surface density of,
　said one of the organic resin coating film, the average thickness of the beads did not exist T ([mu] m ), an average particle diameter of the beads phi ([mu] m), of the organic resin film, an average thickness of bead coating portion covering said bead t ([mu] m), a glass transition temperature of the polyester resin Tg (° C.), when the glass transition temperature of the beads was Tgb (° C.), and satisfies the relation of the following equation (1) to (3), an organic resin-coated plated steel sheet.
　≦ T ≦ 5 15 [mu] m · · · ·
　(1) 1.1 ≦ phi / T ≦ 10 · · · · (2)
　13 ≦ (phi / t) × {(Tgb + 273) / (Tgp + 273)} ≦ 140 · · · - (3)
[Requested item 2]
　And plated steel sheet
　and the organic resin coating covering said plated steel sheet,
　said an organic resin-coated plated steel sheet having a beads dispersed in an organic resin film in,
　the organic resin coating, a polyester resin, and a melamine resin wherein,
　the glass transition temperature of the organic resin film is 0 ~ 35 ° C.,
　the bead is urethane resin beads having a glass transition temperature of -60 ° C. ~ 50 ° C., based on the total weight of the organic resin coating It included in the organic resin film in an amount of 1 to 15 wt%, and wherein said 5 to 1,000 / mm in the organic resin film in 2 dispersed in a surface density of,
　among the organic resin coating, wherein the beads did not exist the average thickness of the T ([mu] m), an average particle diameter of the beads phi ([mu] m), the out of the organic resin coating film, the average thickness of the bead coating portion covering said bead t ([mu] m), the organic resin coating The glass transition temperature Tgf (° C.), when the glass transition temperature of the beads was Tgb (° C.), and satisfies the relation of the following equation (1) to (3 '), an organic resin-coated plated steel sheet .
　≦ T ≦ 5 15 [mu] m · · · · (1)
　1.1 ≦ phi / T ≦ 10 · · · ·
　(2) 10 ≦ (phi / t) × {(Tgb + 273) / (Tgf + 273)} ≦ 115 · · · - (3 ')
[Requested item 3]
　Among the organic resin film, the average thickness of the bead coating portion covering said bead, characterized in that it is a 0.3 ~ 1.0 .mu.m, an organic resin-coated plated steel sheet according to claim 1 or 2.
[Requested item 4]
　It characterized by having a chemical conversion film formed between the organic resin film and the plated steel sheet, the organic resin coating plated steel sheet according to any one of claims 1-3.
[Requested item 5]
　The organic resin coating is further 3-15% by weight of carbon black, 1 to 10% by weight of the calcium modified silica, of from 0.5 to 5% by weight of the epoxy resin, and characterized in that it contains at least one more to the organic resin coating plated steel sheet according to any one of claims 1-4.
[Requested item 6]Wherein said plated steel sheet is zinc-plated steel sheet, the organic resin coating coated steel sheet according to any one of claims 1 to 5.