TW575643B - Surface treated steel sheet and method for producing the same - Google Patents

Description

575643 V. Description of the invention (1) Technical field ^ * Α20 ^ 95 f ^ „method. The surface treatment steel plate which is used as the first layer steel plate and its manufacturing method The background technology coating contains right 9η ^ ^ Bitgong Zhao 46-7161 ^ Due to the nature of money, the 41% -211 series of hot-dip galvanized steel plates have been expanded in recent years, mainly in the field of Jian / Λxuanrong ore steel plates, which show excellent resistance to flat and building materials. The hot-rolled steel plates with acid-eluting scale or cold rolled are processed as follows. Xia Fang, Lian ^ type molten coating equipment, Lian, and L type melting equipment are Bahansi ^ ± ^ ㈢ and 7 The first layer of steel is annealed while maintaining the reducing atmosphere on the surface, and the steel plate is removed at the same time. After the reduction and removal of the oxide film, it passes through the lower end.

: In the immersed coil of Erzhong, the steel plate impregnated in the valley containing the specified concentration is pulled up to the top of the second cold through the synchronous proton, and then the person in friction with the gas arranged on the plating bath contacts the steel surface. Pressurized gas is sprayed to adjust the coating direction: the device is cooled to obtain the heat treatment conditions of the annealing furnace in the continuous melting coating equipment for the two corpses forming the specified forged film, the composition of the plating bath, and the cooling speed after plating, etc. Operation d ensures the desired coating quality and material, and is managed with the specified accuracy. t Wai Yiliang

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Page 6575643 V. Description of the invention (2) Yes: The coatings of the coated steel plate produced by the Zn treatment are mainly composed of the supersaturated part: the part that is dendritic solidified and the remaining tree-like gap special steam Ϊ , 'Dendrite is laminated in the film thickness direction of the plating film. The corrosion resistance 2 due to this. 4. Coating structure, hot-dip coating of 4 1 _Zη series steel sheet is excellent. Usually, about 1.5% by mass of Si is added to the plating bath, and through this, the two Si coatings are melt-plated. In addition, the dryness of the alloy phase plant is about 1 to ^ left. ☆ This alloy phase is less, and the thinner and heavier the part of the characteristic coating structure showing the corrosion resistance is changed, so inhibiting the growth of the alloy phase is helpful to improve Corrosion resistance. In addition, because the two-phase effect becomes the starting point of cracks during harder processing than the coating, it inhibits the growth and reduces the occurrence of cracks, which also results in the improvement of workability. Also, the cracks are for the first layer steel sheet. It is exposed and has poor corrosion resistance, so reducing the occurrence of seams can also improve the corrosion resistance of the processing section. ^, ^ L contains unavoidable impurities in the plating bath, Fe and rhenium dissolved in the steel plate and the machine in the plating bath to suppress the alloy Phase Si, but may also add any other elements, in the alloy phase and the coating, this exists as an alloy or a monomer type. It is often the case that the hot-dip A 1-Zn series steel plate is used for practical purposes , Rarely used as is Generally, the type of surface-treated steel plate that is chemically treated and spray-coated on the surface of the coated steel plate is for use. If the AHn steel plate of soil melting ore is subjected to processing such as bending, cracks will occur on the coating of the processed part according to the degree of processing. This plated steel sheet is based on the existence of the coating / head layer steel sheet interface, which is about 2 to 2 "m thick, and the alloy phase is cracked. Page 7 C: \ 2D-CODE \ 91-04 \ 91101646.ptd 575643

V. Description of the invention (4) Manufacturing method of steel plate. The method for manufacturing the surface-treated steel sheet is a step having the coating film and imparting heat history. ^ The step of imparting heat history is the _thirth of the heat history including the heat experience of imparting an average cold-part velocity of less than 1 ° C / sec for i seconds after the steel sheet is out of the molten plating bath, and The second thermal history is given by a temperature T in the range 130 ~ 30 (TC range T (.0 to 100) 'with an average cooling rate of 0.5x (T-100) (° C / hr) or less) Steps ...... The second heat history imparting step is preferably the following steps: (1) The temperature of the temperature range T (° C) to 1 0 0 ° C after the solidification of the molten bond layer metal plating ranges from 1 0 to 3 0 0 The average cooling rate up to ° C is 0.5 X (T- 1 00) (° c / hr) or less. (2) After the metal plating of the molten plating layer is solidified, the temperature is in the range of 1 3 to 3 0 0 ° C. Heating at T (° C), and thereafter, the average cooling rate from the temperature T (° C) to 100 ° C is 0.5 × (T-100) (° C / hr) or less. This second heat history The application step is preferably performed by applying an average cooling rate from the temperature T (° C) to 100 ° C in the range of 130 to 200 ° C. 0.5 X (τ-1 00) (° C / hr) is constituted by the following thermal history. This second thermal history imparting step is expected from the following (丨~ (4) at least one stage. (1) Before the formation of the chemical conversion coating film (2) In the drying step of the chemical conversion coating film (3) After the chemical conversion coating film is formed (4) The metal plating of the molten coating is solidified In the subsequent cooling process, the step of forming a chemical treatment film is preferably a chromate treatment.

575643 5. Description of the invention (5) Cr s is converted into metallic chromium as L f ^ " "# 〇 ^ SM〇7 After the cloth, the chemical conversion treatment film formed by the dryness of / L degree in the slab coating film. The chemical conversion ratio (a " (B) is more than 1 mass (, A) and the amount of metal chromium conversion (B)) And less than 200. The organic resin in the chemical conversion treatment film is preferably a thermo-hard pure organic resin. Qian T's mechanical tree is coated on the surface of the coating and is treated with chromate, followed by coating with a treatment solution containing organic resin. And at a plate temperature of 80 ~ 3, it contains a chemical conversion treatment film of organic resin. 彳 ，, the secret of the formation of dryness is the amount of mass ratio ⑻ / ⑻ as the chemical conversion organic resin is a good organic in the film Resin is hot hard: In the manufacturing method of the surface-treated steel sheet, the composition treatment is composed of 1 layer and 5 layers, and the film adhesion amount is 0 · ig / m2 or more, and the chemical conversion treatment film is composed of organic resin, And dish_ Γ Preparation: Ϊ :, Shi Xiishi, silane coupling agent, Ca, Ca-based compounds, Μη, Μη 糸, and Mg, Mg-based Compound, Ni, Nl • Prepared by at least one selected from the group of ρ-based compounds, Fe, and Fe-based compounds, Co ^, Co »shanghai rding. The manufacturing method of the surface-treated steel sheet is even better. At least one kind of spraying step above the coating layer.; ::: 5 'The film surface is chemically transformed into a coating surface, and a primer coating is applied and: soil:: 2 The coating film thickness is formed by baking the coating and

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C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 10575643 V. Description of the invention (6) 2 // m above the base is coated with amine and baked to form a coating film thickness of two; and Applying the top coat of the film The top coat is composed of the steps of order two :: f film. The glass transition temperature is 0 ~ 3 (rc / l thousand average knife I is 1 400 0 ~ 26000, glass should be obtained, and the reaction between the ester resin (A) and the epoxy resin (B) is as follows: Contrast with hardening_k = [Wbx (Ma + 2xMb)] / [(Wa + Wb) x2xMb] (M solid 3 formation = tree resin /) + epoxy resin ⑻] Polyvinyl resin W b · [ Polyester resin (a) The weight ratio of the solid content of the polymer and the "polyester resin" (2) 0 2 0 0 polyester resin (E) M a: the number average of the polyester resin (a) Molecular weight Mb: Number average molecular weight of epoxy resin (B) ^ The topcoat is a resin with a number average molecular weight of 50 0 0 and a hardener as the main component. Coating for the base coating film φ% person ΛΑ $ ^ ft y The hardener (D) contained in ^ 枓 is preferably at least one selected from the group consisting of an amine resin and a compound. In the production and production of the surface-treated steel handle, it is expected that the Yakisumi clothes & method In the case where the spraying step is applied, the process has been performed before at least one of the following (1) to (8), (2) the drying step of the chemical conversion treatment, (3) chemical conversion f, / Bottom coating ° Before coating, (4) bottom Spray drying step, the final coating ® binary working, before paint spraying, (6) drying the top coating step " After the completion of finish Α shell coating, (8) plated coating of molten metal after solidification

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575643 V. Description of the invention (8) '------- The chemical conversion treatment film formed is preferably the following two. (2) After coating the treatment liquid containing water-based organic resin and chromic acid and / or order-parts at a temperature of ~ on the surface, apply a chemical conversion treatment film formed by it ^ ^ ^ 1 kg. The chemical conversion ratio UV (B) aV (A) is converted to metallic chromium. The mass r is above the limit and less than 200. The organic tree in the chemical conversion coating is preferably a thermosetting organic resin. The surface of the mine is treated with chromate, followed by coating with water containing ΐΐ 二 ΐΐ: and at a plate temperature of 80 ~ 300. . The mass ratio (A) / (β) of the amount (β) formed by drying at a temperature of not more than 200 rabbits is 1 and the chemical organic material P is more preferable. The organic resin in the chemical conversion treatment film is preferably a hardened organic resin. Q ”、、 Fork less :: ί :: The chemical conversion coating in the steel sheet is best not to contain chromium. In the second chemical conversion, the coating adhesion amount is more than 0 · lg / m2 and less than 5g / m2 is Shi Xi The film is composed of organic resin, phosphoric acid, phosphate, M / 70 stone agent, Ca, Ca-based compound, Mn, Mn-based compound, g, "compound, Ni, Ni-based compound, and c. , C〇: 物

Fe: /; at least one species selected from the group of rhenium compounds. The coating above the coating layer is expected to have at least one coating material on the surface of the chemical conversion treatment, and the coating film is formed by coating the surface of the chemical conversion treatment film with a 'coating base coating'. Film; coated with this base. & and forming a topcoat coating film with a coating film thickness of 5 to 3 0 // m

575643 V. Description of the invention (9) The primer coating is a polyester resin (A) and an epoxy resin (B) with a molecular weight average molecular weight of 丨 40 00 ~ 26 0 0 0 and a glass state = temperature of 0 ~ 30. ) The reaction obtained 'and a modified polyester resin (C) having a k value of 0.7 to 2.5 as shown in the following formula and a hardener (D) were used as the main component resin. k- [Wbx (Ma + 2x Mb)] / [(Wa + Wb) x 2x Mb] but 'Wa: [Polymeric resin (A) + epoxy resin (B)] is the opposite of polyester resin (A Solid content weight ratio

Wb. Solid content ratio of polyester resin (b) to [polyester resin (a) + epoxy resin (b)]

Ma: Number average molecular weight of polyester resin (A)

The number average molecular weight / surface area of Mb ·· epoxy resin (B) is a polyester resin and a hardener having a number average molecular weight of M⑽ ~ 2000 as the main component resin. The coating for the base coating film ^^ + ^ a / π, & i Isocyanate compound hardener (W is made of amine resin and ^, and at least ^ is selected from the group. The surface is preferably In the treatment of Takuya μ v μ π, the coating film contains A120 ~ 95 mass%, and

Mg, V, and at least one selected from the group consisting of 01 to 10. It is preferable to plate an Al-Zn-based coating. Tian Youzhu ^ υ · υ 1〇 The actual use of ^ Ming ^ 1 of the first embodiment: " In the first embodiment of the surface test% A1 of the hot-melt Al-Zn plating plating, but the coating film contains 20 ~ From the viewpoint of 95 mass, d is the first layer steel sheet. In addition, from the corrosion resistance and the like, a particularly good ratio of the shovel film is 1 = a more preferable range is 45 to 65% by mass. And a knife, and A1: 45 to 65 mass%, Si: 〇.7 to

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(10) 2.0% by mass, Fe: underfilled, and the remaining portion is substantially Zn containing unavoidable impurities. In such a composition, excellent surname properties can be exhibited. However, this Xuanrong ore A1-Z η 糸 steel plate is only composed of this bell layer, and it is difficult to obtain the corrosion resistance of the high processing section. The excellent processing section can be obtained only through the thermal experience described below and the formation of a chemical treatment film on the upper layer. Money resistance: There is no particular limitation on the amount of the bell layer attached to the steel plate A 1-Zn η. However, it is generally appropriate to use about 30 ~ 200g / m2 per side. In addition, the coating film of this molten Al-Zn steel sheet must be a coating film obtained after undergoing at least the following thermal history (a) and (b). (a) The average cooling rate of the first 10 seconds immediately after the hot-dip plating of the steel sheet is less than 11 ° C / sec. Heat history (b) After the metal plating of the hot-dip coating is solidified, the temperature ranges from 1 0 to 30 The temperature T (° C) in the 0 ° C range is heated and heated, and thereafter, the temperature T (° C) to 100 ° C is flat ^ The cooling rate is less than or equal to C (° C / hr) shown in (1) below The thermal history, and / or the average cooling rate from 1 300 to 300 ° C after the solidification of the metallized metal plated layer to a temperature of 100 ° C to 100 ° C is as follows: — The thermal history below C (° C / hr) is not C = (T-100) / 2. In the thermal history of (b) above, the better range of temperature τ (it) is 130 ~ 200. . . Here, the above formula is a detailed review of the effects of the inventors and others on the coating based on the temperature increase of the experimental film and the conditions of the cold section and the coldness of the metal after the molten coating is solidified. The result is an experimental formula. $ M guide

575643

575643 V. Description of the invention (12) The solid state of (12) is closer to the equilibrium state, so the two-phase separation of% ΐ ΐΑΐ and Y through the semi-melted state causes the coating to soften. Immediately after the steel sheet has been melted out, the average cooling rate of the first 10 seconds immediately after the negotiation is ut / sec. Because the solidification speed is too fast, the solidification of the molten coating is advanced into an unbalanced L, and it is semi-melted. The time of the state is short, so the phase separation of A1 and Zn cannot be promoted sufficiently, and it is not possible to recombine with the heat history of (b) above and to sufficiently soften the broken film. * Figure 1 is the result of investigating the average cooling rate of the first 10 seconds of the steel sheet immediately after it leaves the molten plating bath. The average cooling rate has a significant effect on the surface protection of the steel sheet. The result is the coating of the test material obtained. In order to form the surface-treated steel sheet satisfying the conditions of the present invention for the steel sheet manufactured through the heat history described above, the surface-treated steel sheet is formed. The evaluation of workability in this test was performed based on the evaluation of workability of the examples described later. As shown in Fig. 1, the average cooling rate of the first 10% of the steel sheet immediately after it leaves the molten plating bath is m / sec or more, and the workability scoring point at 0Tf curve is 2 or less. If the average cooling speed of the coating is less than 11 ° c / sec, the processability score point is 4 or more, and the processing is judged to be particularly improved. The thermal history of the coating must be continuously melted by the above-mentioned (a). A temperature adjustment device is provided between the molten plating bath surface of the equipment and the first time the steel plate from the molten plating bath contacts the roller, and the cooling speed of the dream is controlled by this temperature adjustment device. The temperature adjustment device is preferably provided with a heating or heat preservation device, And if necessary, a cooling means is provided. This cooling means is that the coated steel sheet that controls the cooling rate of the coating through this or heat preservation means contacts the initial roll (top ,,,,

C: \ 2D-C0DE \ 91-04 \ 91101646a.ptd Page 17 575643 V. Description of the invention (13), etc.) It should be cooled before it can be prevented from picking up on the roller surface. As the heating or heat-retaining means of the temperature adjusting device, for example, an induction heater and a gas heating furnace can be used, and as the cooling means, a gas blowing device can be used. However, there are no particular restrictions on the method, shape, scale, etc. of the heating or heating means and cooling means of the temperature adjustment device, and the coating film may be mainly provided with the heat history of (a) above. Secondly, regarding the thermal history of (b) above, the coating film (plating film after the metallization of the molten plating layer is solidified) subjected to the thermal history of (a) above is from 13 to 300 t, preferably from 130 to 20 (The temperature rises and rises in the temperature range TC T (t), and then the average cooling rate from the temperature T (C) to 100 c is to satisfy c (t: / h0 or less as shown in the above formula (1)) Cool it, or make the metallized coating that has been melt-plated to solidify, and the average cooling rate from the cooling process to the maximum temperature is to meet the above two limits: C (t; / hr) shown below to cool, such as The above makes the distortion accumulated in the coating film open, and solid diffusion occurs in the bond film, and the two-phase separation of the sulfide in the coating film generated by the above (a) thermal history is more effectively promoted. After the compound effect of the thermal experience of (a) above, the hafnium coating is significantly softened, and its processability is significantly improved. Here, the above (b) track experience is as follows: w, lon 0 '; ... L If the heating temperature T of the coating of the former is less than 1 3 0 C, the heating temperature as described above cannot be obtained sufficiently. If it exceeds 300t :, the heating of the ϋΎΠ surface promotes the growth of the :: phase at the interface between the first layer steel plate and the coating, which adversely affects the processability. X, from this type: For improvement, For processability, the upper limit of the heating and heating temperature T is 200 ° c. 575643 V. Description of the invention (14) The ash cover is also closed, and J: Gu Rong plating 30 ° C range temperature T The cooling process after spinning is 13 ° ~ When cooling, the temperature τ is 'not full) and the thermal effect is given by the conditions given above. Full ° C' cannot be fully obtained as shown in Figure 2 (a ) In order to investigate the effect of plating and heat treatment on the temperature of the coated film when it is melt-plated: the solidification of the plated steel plate and the effect of the heating temperature on the workability, the result is the obtained supply. The average cooling temperature of the coating film from the heating temperature to loot is within the conditions of the heating and heating experience, and the coating film is formed on the steel plate manufactured by the sister A in the above (b), which meets the requirements of the present invention = (, a) The heat-treated surface-treated steel sheet. @, The workability of the table examples of t in this test The evaluation is carried out. The sweat is estimated to be based on the solid plate described later d) ί 5 weeks to check the average cooling rate of the second coating film of the coated steel after the molten coating is solidified (the heating temperature is raised to ^ Gan uniform cold material) Degree) For the workability of surface-treated steel sheet, the test materials obtained are all the heating and adding of the coating film. The degree is within the conditions of the thermal history of (b) above, and the coating film The steel sheet produced by the thermal process is formed into a surface-treated steel sheet having a chemical treatment film. The evaluation of the workability in this test is based on the workability evaluation of the examples described later. As shown in Fig. 2 (a), (b) As shown, the heating and heating temperature of the mineral film is in the range of 丨 3 ～ 3 ～ 00C, the processability scoring point of 〇τ bending is 4 or more, and square; the preferred condition is 1 3 0 ～ 2 0 0 ° In the range of C, the processability score points are 4 to 5 points. In contrast, the range of heating temperature is from 3 ° to 3 ° c. C: \ 2D-C0DE \ 9l.04 \ 91101646.ptd Page 19575643 5. In addition to the description of the invention (15), the processability The rating point is only 3 points. In addition, in the case where the difference between the average cooling rate from the heating and heating rate to 100 ° C and the "(;" in the above-mentioned formula (1) is 0 to negative (within the scope of the present invention), the workability scoring point of 0 Ding bending It is 4 to 5 points. In contrast, in the case where the difference is positive (outside the scope of the present invention), the processability score point is only 3 points. Let the coating pass through the thermal history of (b) above and continuously melt. Inside or outside the coating equipment, heat treatment or heat preservation is provided for the coating to be heat-treated or heat-retained to perform the specified heat treatment or heat preservation. For example, a heating mechanism (for example, induction heater, gas Heating furnace, hot blast stove, etc.) and continuous heating can be carried out online, and it can also be performed by offline batch heating after winding in the coil. It can also be used in continuous processing equipment outside the ore streamline. Heating mechanism (for example, induction heating X heater; 1 ah gas heating furnace, hot air heating, etc.) may be continuously heated. Furthermore, the coated steel plate is continuously heated in the key laminar flow line and the continuous processing equipment. , In the coil It is also possible to perform appropriate heat preservation or heating after middle winding. In addition, a heat preservation device that can keep the key film hot and cold can be provided during the cooling process after the solidified mineral metal of the Kariya melt coating layer. However, there is no particular limitation on the method, shape, scale, etc. of the heating or heat-preserving device ', and the bell film may mainly be imparted with the thermal history of (b) above. By passing through the above-mentioned (a) and (b) The formation of a specific chemical conversion coating on the surface of the key film subjected to the thermal history can make this surface-treated steel sheet show excellent processability and resistance to insects. The chemical conversion coating formed on the coating surface contains chromium. The conversion of Cr from acid treatment to metallic chromium is preferably img / m2 or more and less than 0.00 mg / m2.

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The surface of a specific coating film that is difficult to cause cracks as described above, and the formation of such a chemical conversion coating film can significantly improve the corrosion resistance of the processed portion. The chemical conversion treatment film may be composed of a multi-layer film, and in this case, it is sufficient if the entire film contains the above-mentioned Cr. Therefore, the above-mentioned cr may be contained only in one layer of the multilayer film, and may also be contained in two or more layers of the film. In the chemical conversion coating, the amount of Cr converted to metallic chromium is less than img / m2, and the corrosion resistance of the processed portion cannot be sufficiently improved. On the other hand, if the amount of Cr is not less than 0.00 mg / m2, the corrosion resistance of the processed portion is improved. The effect is saturated, and on the one hand, the Cr fixation rate is reduced due to the increase in the number of c plants, which harms the environmental harmony. In addition, a more preferable chemical conversion treatment film is a chromate treatment solution containing an aqueous organic resin and chromic acid and / or a chromic acid compound that reduces a part of chromic acid, and is then coated at a plate temperature of 80 to 3 00 ° C. The film obtained by drying under temperature and the weight ratio (A) / (B) of the amount of organic resin (A) contained in the film and the amount of chromium (B) converted into metallic chromium is 1 or more and less than 200 Handle the film. In this way, if the chemical conversion treatment film contains Cr and an organic resin, the corrosion resistance of the processing section can be made better. Moreover, in such a chemical conversion treatment film, if the mass ratio (A) / (B) of the amount of organic resin (A) to the amount of Cr (B) converted into metallic chromium is less than 1, the organic fat cannot be fully improved. The effect of the financial and silver nature of the processing department. On the other hand, if the mass ratio (A) / (B) is more than 200, it is not possible to fully obtain the improvement effect of processing surplus caused by Cr. In addition, when forming a chemical treatment film, the drying temperature after coating the chromate treatment solution is less than 80 ° C ', the appropriate chemical treatment film cannot be formed due to the low temperature. 0 (TC is higher because of higher coating

575643 5. Description of the invention (17) The heat 'promotes the alloying reaction, which may reduce the workability. Moreover, the chemical conversion treatment film is preferably composed of a chromate treatment film and a specific film formed thereon. This upper film is a coating film obtained by coating a treatment solution containing water, resin and drying at a plate temperature of 80 to 300 ° C. The chromate-treated film and its upper layer are processed by chemical conversion treatment of the film and its upper layer. With the film, it is possible to obtain more excellent corrosion resistance in the processed portion. . When the upper layer film is formed, the drying temperature after coating with the treatment liquid is less than 80 ° C, the temperature cannot be used to form a suitable chemical treatment film. On the other hand, if it exceeds 300 ° C. (3, because the coating film is heated higher and the alloying reaction is promoted, the workability may be reduced. This chemical conversion treatment film (chromate treatment film + upper film) contains Cr that is changed to metal chromium. The amount is 0.1 mg / m2 or more and less than 100 mg / m2, and the reasons for limitation are as described above. The upper layer film can be arbitrarily contained or not, but the inclusion of (: ιΊ-shaped towels makes the recording resistance even higher. The upper layer The film thickness of the film is preferably about 0 · 1 5 # m. If the film thickness is less than 0 · 1 # m, the money endurance of the processing department will be improved. When the roll of the surface-treated steel sheet is formed, there is a fear of hooking on the roll. Furthermore, the chemical conversion treatment coating is based on the total organic resin content (A) contained in the coating and the total Crt (B) converted into metallic chromium. The mass ratio (Α) / (β) is 1 or more and less than the best. The ratio λ (A) / (B) of the total organic resin amount (A) and the total ^ s B) converted into metallic chromium is less than}, The effect of the organic resin on improving the corrosion resistance of the processed portion is small. On the other hand, if the mass ratio (a) / (b) is 2000 or more, the effect of improving the corrosion resistance of the processed portion is small. Ci 'on the surface of the embodiment described! The process for producing a steel sheet

XLU C: \ 2D-00DE \ 91-04 \ 91101646.ptd Page 22 575643 V. Description of the invention (18) Method 0 The manufacturing method of Embodiment 1 is A1 in the mineral film manufactured by continuous melting coating equipment, etc. A manufacturing method of a surface-treated steel sheet having a content of 20 to 95% by mass as a head steel sheet and forming a chemical treatment film on the surface thereof. The following steps are performed with the heat of (a) and (b) below, and a step of forming a specific chemical conversion treatment film on the surface of the ore layer steel sheet. (a) The average cooling rate of the first 10 seconds immediately after the steel plate is out of the molten plating bath is a thermal history of less than 1 1 it / sec. (b) After the metal plating of the molten coating is solidified, The temperature T (C) in the range of 3 0 0 ° C is heated and heated, and thereafter, the average cooling rate from the temperature τ (yi) to 〖〇〇 艽 is equal to or lower than c (t / hr) shown in (1) below The average cooling rate from the thermal history, and / or the temperature T (C) to 100 C in the range of 130 to 300 t after the metallization of the molten plating layer is solidified is to satisfy C (° C / hr) The following thermal experience 〇 (Τ-100) / 2

In the thermal history of (a) and (b) given to the coating film, ((1) The calendar is obtained by controlling the cooling conditions of the coating film immediately after the ore layer. ) In terms of thermal history, as mentioned above, it must be on the surface of the melting equipment to reach the touch of the molten bond bath; the temperature adjustment device is set between the formulas and the temperature adjustment = the cooling rate of the pancreas. ° & odd heat preservation means, and if necessary; the name / X is the way and shape with the supplementary section and cooling means ^ t I, f There are no special restrictions on the heating or insurance regulations. "

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5. Description of the invention (19) It is only necessary to impart the thermal experience of (a) above to the mineral film. As the heating or heat-retaining means of the temperature adjustment device, for example, an induction heater and a gas heating furnace can be used, and as the cooling means, a gas blowing device can be used. In addition, the above-mentioned (b) heat history is performed by applying a specific heat treatment to the plated steel plate after the molten metal plating is solidified, or by controlling the cooling of the key film after the solidified mineral metal of the i-plating layer to maintain heat, etc. . The manufacturing method of the present invention is to form a specific chemical conversion coating film on the coating surface of the coated steel sheet. The heat treatment for applying the heat of (b) to the coating film may be performed before the formation of the chemical conversion coating film and in the drying step of the chemical conversion coating film. (3) Any stage after the formation of the chemical conversion treatment film (the application of the treatment liquid and the formation of the film in the drying step). In addition, it may be performed in two or more of these stages. Therefore, the thermal history of the coating film imparting (b) can be performed in at least one of the following stages (1) to (4). (1) Before the formation of the chemical treatment film (2) In the drying step of the chemical treatment film (3) After the chemical treatment film is formed (4) The cooling process after the solidified metal plating of the molten bell layer is solidified, the above method of heat treatment is performed Among them, the method of ① has the advantage of independently optimizing each condition of the heat treatment step and the chemical conversion treatment step, and the methods of ② and ③ are suitable for performing all the processing in the continuous molten plating equipment. Further, since the method of (2) is performed by heating in the drying step of the chemical conversion treatment, it is particularly economical. The heat treatment or heat retention used to impart the heat history of (b) above is a heating or heat preservation device installed inside or outside the continuous melting coating equipment, etc.

575643 V. Description of Invention (20). It is also possible to install a heating mechanism (for example, an induction heater, a gas heating furnace, a hot air furnace, etc.) in a continuous melting coating equipment and perform continuous heating in an on-line mode. Alternatively, after winding in a coil, the batch heating is performed offline You can do it. In addition, continuous heating equipment (e.g., induction force, heater, gas heating furnace, hot air furnace, etc.) may be used for continuous heating in the continuous processing equipment outside the coating streamline. Furthermore, the ore-layer steel sheet which is continuously heated in the coating streamline and continuously by the above-mentioned continuous processing equipment is wound in a coil and then appropriately maintained or kept heated. In addition, a heat-retaining device that can heat the coating film and cool it slowly can be provided during the cooling process after the solidified mineral metal is cooled. However, there are no particular restrictions on the method, shape, scale, etc. of the heating or heat-preserving device, and it is only necessary to impart the thermal history (b) to the plating film. Still, the preferred composition of the bell layer, the coating adhesion amount, the reasons for limiting the thermal history of (a) and (b) above, and the obtained effects are as described above. . The manufacturing method of Embodiment I is to process at least one or two or more chromates on the coating surface of the coated steel sheet to form Cr containing 0.1 to 1 mg / m2 and less than 1 0 0. mg / m2 of chemical treatment coating. The pre- and post-relationships between the step of forming the chemical conversion treatment film and the heat-experience step imparted to the above (b) are as described above. The above chromate treatment is a method in which a chromate treatment liquid is applied to the surface of a coated steel sheet, and is usually not washed with water and dried at 80 to 300 t. As described above, the chemical conversion treatment film may also be composed of a multi-layer film, and in this case, plural treatments are sequentially performed. In addition, in the case of a multi-layer coating, it is sufficient if the entire coating contains the above-mentioned Cr. Therefore, this Cr may be used only in the multi-layer coating.

C: \ 2D-CODE \ 91-04 \ 91I01646a.ptd page 25 575643 5. Description of the invention (21) It is contained in one layer of the film, and it can also be contained in two or more layers of the film. That is also special: The preferred composition and processing conditions of i ί ΐ film are as described above. / 10% of the treated film will contain water-based organic resin and chromic acid. After coating the chromate of the chromic acid compound reduced by trowel chromic acid, the film obtained by drying at a plate temperature of 80 to 30 (rc) = the amount of organic resin (A) contained in f and the amount converted into metal chromium A chemical treatment film having a chromium content ratio (A) / (B) of 1 or more and less than 200. In addition, after the chromate treatment as described above, a specific upper layer can be formed on the upper layer. In this case, the chemical conversion treatment film is a composite film of chromate treatment and the upper layer film. The total Cr content converted to metallic chromium contained in this chemical conversion treatment film (chromate treatment film + upper layer film) is 0 · img / m2 is above, and less than 100mg / m2. The upper layer film can be arbitrarily contained or not, but when Cr is contained, the corrosion resistance is further improved. The film thickness of the upper layer film is about 0.1 to 5 / zm In this chemical conversion treatment film, the mass ratio (A) / (B) of the total organic resin content (A) contained in the film to the total Cr content (8) converted into metallic chromium is 1 or more and less than 200 is preferable. The upper film is, for example, a coating liquid containing an aqueous organic resin and is applied at a plate temperature of 80 to 300 t. It can be formed by drying. However, the reasons and functions of the above constitutions are limited as follows: Example 1 -1 The cold-rolled steel plate (plate thickness 0.5 mm) manufactured by the 4 method is continuous Melt and melt the plate in the plating equipment, and use 55% A1, 1.5% Si-Zn plating bath (No. 1 ~ 1 ^ 〇.11 in Table 1) '40% person 1-1.0% 8b 211 plating bath (1 ^ 〇.12 of Table 1) and 70% -1.8% Si-Zn plating bath (No. 13 of Table 1) for melt coating. Working line speed

575643 5. Description of the invention (22) ^-The degree is 160m / min, and the amount of coating on one side is to stabilize the deviation between steel plates in the range of 75 ~ 90g / m2. In the manufacturing step of this key layer steel sheet, the coating film is given the heat history (I), (I I) 'shown in Table 1, and the coating surface is subjected to chemical conversion treatment. The chemical conversion treatment condition is a treatment solution in which acrylic latex resin and chromic acid are mixed at a ratio of solid content of resin · C r = 1: 00: 1 (mass ratio), and the surface of the coated steel plate is converted into C r The adhesion amount was 20 mg / m2, and the coating was dried at 120 ° C. However, with regard to N o · 1 1 in Table 1, since the heat history prescribed in the present invention is imparted in the drying step of the chemical conversion treatment, the drying temperature is set to 4 °. 〇.

For the surface-treated steel sheet manufactured in this way, the workability and the corrosion resistance of the machined portion were evaluated according to the following methods. The results are shown in Table 1. (1) Workability The surface-treated steel sheet was bent at 0 T, and a crack at the front end of the 0 τ bend was observed, and evaluated according to the following criteria. 5: No crack was observed even when observed with a magnifying glass of 20 times. 4: No cracks were observed when visually observed, but cracks were observed when viewed with a magnifying glass of 20 times. 3: A crack was observed by visual observation.

2: The crack of the large opening is observed by visual observation. 1: Cracks are generated with peeling. (2) Corrosion resistance of the processed part After the surface-treated steel sheet is bent at 3T, it is installed in a 50t, 98% RH or higher wet test machine, and the scale formation state of the bent part after 1000 hours is observed, and The following benchmarks were evaluated.

575643 V. Description of the invention (23) 5: No abnormality 4: Some mild white money and black records occurred All mild white rust and black rust occurred All significant white rust and black rust occurred Red rust occurred

C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 28 575643 V. Description of Invention (24) Table 1

No Coating composition Thermal history (I) * 1 Average cooling rate (° C / sec) Thermal history shell) * 2 Processability (0T) Corrosion resistance of processed part (3T) Differentiating heating temperature (° 0 * 3 Average cooling rate ( ° C / hr) * 4 Implementation stage of heat treatment * 5 1 55% Al-1.5 ° / 〇Si 15 180 19 (2) 2 1 Comparative Example 2 55% Al-1.5% Si 8 330 50 (2) 3 3 Comparison Example 3 55% Al-1.5% Si 8 105 20 (2) 3 3 Comparative Example 4 55% Al-1.5% Si 8 265 85 (2) 3 3 Comparative Example 5 55% Al-1.5% Si 8 165 45 (2 ) 3 3 Comparative Example 6 55% AM.5% Si 10 280 52 (2) 4 4 The present invention is imitated 7 55% Al-1.5% Si 10 180 23 (2) 5 4 Inventive Example 8 55% Al-1.5 ° / 〇Si 4 145 18 (2) 5 4 Inventive Example J 9 55% Al-1.5% Si 4 240 58 (2) 4 4 Inventive Example 10 55% Al-1.5% Si 8 185 15 ⑴ 5 5 Invention Example 11 55% Al-1.5% Si 8 170 22 (3) 4 4 Invention Example J 12 40% Al-1.0% Si 9 140 15 (2) 4 4 Invention Example 13 70% Al-1.8% Si 7 230 60 (2) 4 4 Example of the invention Page 29 C: \ 2D-CODE \ 91-04 \ 91101646a.ptd 575643

* 1 The average cooling rate of the coating in 10 seconds immediately after the steel plate is out of the molten plating bath. * 2 The heat history imparted by the heat treatment performed after the coating of the molten coating is solidified. 3 The heating temperature of the coating during the heat treatment. The average cold heading of the coated film at a moderate heating temperature to 100 ° C but at a speed of 5 (1): before chemical conversion treatment (2): drying step after chemical conversion treatment (3):% of chemical conversion treatment The value with a bottom line is Examples 1-2 outside the scope of the present invention The cold-rolled steel plate (plate thickness 0.5 mm) manufactured by the conventional method was passed through a continuous melting shovel layer equipment, and was melted by using 55 ^ -1.5% 8b 211 plating bath. ; | Layer. The working linear speed is 160 m / min, and the amount of coating on one surface is such that the deviation between steel plates is stabilized in the range of 75 to 90 g / m2. In the manufacturing steps of this ore-layer steel sheet, the coating films are given the heat history (I) and (I I) shown in Table 2, and the key film surface is subjected to chemical treatment. The formation place is provided that the surface of the coated steel plate is subjected to chromate treatment so that the amount of cr attached to metal converted is 20 mg / m2, dried at 80 t, and the upper layer is coated with amino amino ester latex. Resin treatment solution and dried at 120. For the surface-treated steel sheet manufactured in this way, the workability and the corrosion resistance of the processed portion were evaluated in the same manner as in Example 1. The results are shown in the table

575643 V. Description of Invention (26) Table 2

No Coating composition Thermal history (i) * ι Average cooling rate (° C / sec) Thermal history (π) * 2 Machinability (0T) Corrosion resistance of machined part (3T) Differentiated heating temperature (° 〇 * 3 Average cooling rate (° C / hr) * 4 Implementation stage of heat treatment% 1 55% Al-1.5% Si 10 250 55 (2) 4 4 Example of the present invention 2 55% Al-1.5% Si 10 170 27 (2) 5 4 The present invention Example Page 31 C: \ 2D-CODE \ 91-04 \ 91101646a.ptd 575643 V. Description of the invention (27) Heat imparted by heat treatment of the average cooling rate of the coating film 1 Immediately after the steel sheet is out of the k melting bath 1 Second degree * 2 After the coating of the molten coating is solidified, it undergoes * 3 The heating temperature of the coating during the heat treatment * 4 The average cooling rate of the coating during the heat treatment to i 〇00 * 5): Before the chemical conversion treatment (2): After chemical conversion treatment (3): Drying step of chemical conversion treatment

Form 2: The spray-painted steel sheet of ~ Form 2 is a molten A 1-Zn-based plated steel sheet containing 2—95.5% by mass a 1 in the coating film as the head layer steel plate, and the coating surface is the lower layer. The formation of the chemical conversion treatment film, the primer coating film, and the top coat in this order will be described in detail below. ≫! (1) Melting and melting A 1-Zn η-based coated steel sheet contains 20 to 95% by mass of molten Al to Zn of A1, which has excellent corrosion resistance, and therefore, the viewpoint of corrosion resistance, etc. A more preferable range of the A1 amount is 45 to 65% by mass. In addition, in terms of hafnium plating, the hafnium plating composition is A1: 45 to 65% by mass, Si ·· 〇 · 7 to 2 · 〇, an extremely good quality product, 8% by mass, and the remainder contains unavoidable impurities He ··· In the case of such a composition, two dozens of excellent corrosion-resistant I grades are particularly exhibited, and a molten Al-Zn steel sheet is composed of only this plating layer, which is difficult to obtain. However, this corrosiveness can be obtained through the thermal history described below and the combination of the upper layer and the upper part, such as the film in the industrial department, to obtain excellent corrosion resistance in the machined section. Combined processing

575643 5. Description of the invention (28) There is no particular limitation on the coating adhesion amount of this hot-dip A1-Zn-based steel sheet, but it is generally appropriate to use about 30 to 20 Og / m2 per one side. In addition, the coating film of the molten A 1 -Zn-based steel sheet must be a coating film obtained after undergoing at least the following (a) and (b) thermal history. (a) The average cooling rate of the first 10 seconds immediately after the steel plate is out of the molten plating bath is a thermal history of less than 11 ° C / sec. (b) After the metallization of the molten coating is solidified, ~ 3 0 0 ° C range temperature T (° C) heating and heating, and then, the temperature (. 0 to 10 (TC average cooling rate is to meet the C (° C / hr) shown in (1) below) The following thermal history, and / or, the range of temperature T (. (:) to 100 ° C) after the metallization of the molten plating layer is solidified is to satisfy the following formula: Thermal history below c (° c / hr), 〇 (T-100) / 2 temperature τ (. The more preferable range is again, in the thermal history of (b) above 1 3 0 ~ 2 0 〇0c By making the melting record A 1 good. The so-called properties significantly change the melting bath after the plating bath, so that the melting is close to equilibrium, and a phase separation coating film is taken to return to the U) and (b). The thermal history can be -Zn series.者, and its workability (crack resistance, etc.) is significantly changed through the thermal experience of the above (a) and (b) to improve the processing of the film, the following reasons are considered. T first, steel plate after That is, the thermal history of red (a) above, that is, 10 seconds after it is just out == the cooling rate is sufficiently delayed. The solidification of the coating is more solidified than the normal cooling process, so it is diffused through the semi-melted state. Promote force, and as a result, soften the coating. After that, after this kind of Ϊ:

C: \ 2D-CODE \ 91.04 \ 91101646a.ptd Page 33 575643

V. Description of the invention (29) The ore film of the calendar passes through the thermal history of (b) above, that is, in the temperature range of 130 ~ 300c (preferably 130 ~ 200 ° C). After the heating and heating, the heat is slowly cooled under specific conditions, and / or after the coating is solidified, and the temperature range is 30 ° C to 300 ° C, and the temperature range is slowly cooled under specific conditions. Through the phonon, the distortions accumulated in the coating film during the solidification are opened, and solid diffusion occurs in the ore ^, and the two-phase separation of A 1 and Zn in the coating film generated by the thermal experience of (a) above is more effective. promote. As a result, the coated collar is softened and its workability is significantly improved. 'β Therefore, the softening of such coatings and the significant improvement in processability that accompany them are based on the combined effects of the thermal experience of (a) and (b) above, and it is difficult to achieve only with the thermal experience of either one . Hereinafter, the thermal history of (a) and (b) will be described in detail. First, regarding the thermal history of (a) above, the average cooling rate of the key film in the first 10 seconds immediately after the steel sheet is taken out of the molten ore bath is less than 11 ° C / sec. It is closer to the equilibrium state than the solidification caused by the normal cooling process. Therefore, the two-phase separation of A1 and Zn is promoted through the diffusion in the semi-molten state, resulting in softening of the coating. Immediately after the steel plate is out of the hot melt plating bath, the average cooling rate in the first 10 seconds is 11 ° C / sec or more. Because the solidification rate is too fast, the solidification of the molten coating is performed in an unbalanced state and in a semi-warm state. The time is short, so the two phase separation of A 1 and Zn cannot be fully promoted, and the thermal history of (b) above can not be compounded and the softness of the film can be fully achieved. Figure 3 Influence of the average cooling ambiguity of the silver film in the first 10 seconds on the workability of the surface-treated steel sheet

C: \ 2D-C0DE \ 91-04 \ 91101646a.pt ^ Page 34 575643 Description of the invention (30) The result is the obtained test (b) The steel plate-shaped film made by the thermal history of The sprayed steel that passes through the above-mentioned physical coating-primer coating film_topcoat film is sufficient for the formation of the conditions of the present invention: The evaluation of the raw materials is based on the examples described below. The melting bath sweat was estimated. The average cooling rate of the coating is llt / sec, that is, the workability of the first 10-second buckle processing is estimated to be "A", and then it is 180. The degree of curvature is not, X. " In contrast, the average cooling rate and workability of the plated film are greatly improved. If the weight is equal to or higher than "0", it can be judged that the equipment :: (1) The thermal history of the above (a) must be from continuous melting to the first contact of the steel plate from the molten plating bath to the roller. There is also a coffee degree adjustment device, and the temperature of the film is cooled by this temperature adjustment device: speed. It is preferable that the device for heating and cooling should be provided with heating or heating, and if necessary, cooling means. However, this cooling means is that the coated steel plate that controls the cooling rate of the coating through the heating or f-heating means contacts the initial stick (top pro etc.) It has been previously cooled to prevent picking (up, etc.) from occurring on the surface of the roller. The heating or heat retaining means of the temperature adjustment device can be, for example, an induction heater or a gas heating furnace, and the cooling means can be gas. Blowing device, etc. However, there are no particular restrictions on the method, shape, scale, etc. of the heating or heat-retaining means and cooling means of the temperature adjustment device, and the coating film may be mainly provided with the heat history of (a) above. Secondly, regarding the thermal history of (b) above, the coating film (plating film after the metallization of the molten plating layer is solidified) subjected to the thermal history of (a) is 130 to "ο C, preferably 1 3 0 to 2 0 0 ° C temperature T (C)

575643 V. Description of the invention (31) = cooling at a temperature below c (C / hr), which is not satisfied by the above formula, or the average cooling rate until the temperature is exceeded, or the molten J-plating and J-plating are solidification. " The cooling process of the coating film is 13Q ~ 3Q (rc range temperature \ rr 〇 ° C is the average cooling rate to meet the above formula and will be cooled below. As described above, the accumulation of the mineral film-the oblique is opened. Solid diffusion occurs in the coating, and the Al_ two-phase separation in the hot (?) Hot toilet is further improved. Through such thermal experience and the above (3), the mineral film is significantly softened, and its The processability is significantly affected by the heating effect of the film in the thermal history: 130 ° C, the effect as described above cannot be fully achieved. The other side,?: = More than 30 (TC, because Promote head layer steel ^ Metallographic master: Therefore, it adversely affects workability. From this point of view, for improving workability, the limit is 20 (TC. &Amp; better heating temperature T Up 3 0 0 ^ | " ™ (Τ; Γ ^ ^ ^ ^ 30-^ Λ; 0Γ ^ J ΐ bj-^ ^ ^ ^ ^ on The effect described below is less than 130. 'It is not possible to fully obtain the results shown in Figure 4 (a) for the investigation of the coating of the molten coating when it is heat-treated, and the heat treatment of the plated steel plate. The influence of the temperature on the processability of the sprayed steel sheet, and the heat produced by "为 ^^: 卩 ^ 上 m 的 ⑻" is described by C. \ 2D- CODE \ 9】 -04 \ 91101646.ptd P.365755643 V. Description of the invention (32) The steel plate made of 'forms a chemical-treated coating film—primer coating film—top coating film that meets the conditions of the present invention. Still, The evaluation of the workability in this test was performed based on the workability evaluation of Examples described later.

Fig. 4 (b) is a survey of the average cooling rate (average cooling rate from heating up to 100 ° C.) of the ore film when the ore layer steel plate that has been solidified by the molten metal layer is heat-treated. The effect of the processability of the processed steel sheet 'The test materials obtained as a result are the heating and heating temperature of the coating film within the conditions of the thermal history of (b) above, and the coating films are all for the thermal history of (a) above The manufactured steel sheet is formed into a spray-painted steel sheet that is chemically treated with a film-primer coating film-topcoat film. The evaluation of the workability in this test was performed based on the workability evaluation of the examples described later. As shown in FIGS. 4 (a) and (b), the heating temperature of the plated film is in the range of 3 ° C. to 3 ° C., 1 8 °. The evaluation of the workability of the bending process is "0" or more, and 130 to 20 (the range of the TC in the preferable condition, the evaluation of the workability is "◎". On the other hand, outside the range of heating and heating temperature is 130 to 300 ° c Then, the evaluation of the workability is only "△". Moreover, the difference between the average cooling rate between the heating and heating temperature up to 100 C and the "c" of the above formula is zero two negative (within the scope of the present invention). .Processability in bending

T estimates that the heating temperature of the plated film is 130 to 300 1 in a range of y0 "or more, and" 1300 "in a range of 13 to 200c in a preferable condition. In contrast, in the case where the difference is positive (outside the scope of the present invention), the evaluation of the workability only obtains "△". The coating film is subjected to the thermal history of (b) above, and the coating film is heat-treated or heat-preserved in the continuous molten coating equipment or outside the same equipment.

575643 V. Description of the invention (33) Heat setting, perform specified heat treatment or heat preservation. For example, a heating mechanism is installed in the coating equipment (for example, salted ^ ° 'in a continuous melting furnace, hot air furnace, etc.) and continuous heating is performed online. After being wound in the heating loop of the lice, the batch heating is performed offline. It can also be continuously heated in a continuous processing equipment outside the line via a heating mechanism (for example, 'in a key laminar flow line gas heating furnace, hot air furnace, etc.) ^ 加热 \ Induction heater, coating It can also be used in the stream line and in the continuous processing equipment mentioned above. What's more, after the metallization of the molten plating layer is solidified, ": ,,, and so on. A heat-retaining device that can heat and cool the coating film. However, it is set in the process, but it has restrictions on the method, shape, and regulation of the heating or heat preservation device, and it can mainly impart the thermal history of (b) above to the mineral film. (A) and (b), the surface of the bell film has a stable chemical conversion treatment film, so that this surface-treated steel sheet can exhibit the workability of the = and the insect resistance of the processed part. (2) Chemical treatment film The type of chemical treatment film used for this spray head layer is not special. The chemical treatment can be performed with chromate treatment, zinc phosphate treatment, or treatment with ^ as the main component. Generally speaking, for rice that value the environment: $ Use organic resin as the main ingredient for processing, and for corrosion resistance, use chromate. However, the zinc phosphate treatment has complicated steps. In the case of ^-^ coated steel sheet containing 20 to 70% by mass of A1 in ^, the reactivity of phosphoric acid is sometimes insufficient, so it is considered for use. This.必须 Y must

l_F i m I!

IH C: \ 2D-CODE \ 91-04 \ 91101646a.ptd Page 38 575643 5. Description of the invention (34) (3) Primer coating film The thickness of the primer coating film is 2 ~ 15 // m. The coating film thickness is less than 2 to ΙΪ1. It is not good to obtain sufficient rust resistance. On the other hand, if it exceeds 5 # m, the properties will be reduced, and the manufacturing cost will also increase, so it is not good. In addition, the main agent resin of the wound primer coating film is preferably a polyester-based resin and / or an epoxy-based resin in terms of processability and money resistance of the processing section. This polyester-based resin can also use bisphenol A addition polyester resin, etc., and ▲ epoxy-based resin can also be partially modified by amino resin, stupid resin, amino resin, etc. By. 77 & The desired average molecular weight of the polyester-based resin is from 100 to 300, and more preferably from 300 to 2000. If the number average molecular weight is less than 1,000, the film cannot be sufficiently stretched due to insufficient extension of the coating film, and the film film properties may sometimes be sufficient. On the other hand, if the number average molecular weight exceeds 3,000 The main agent lipid becomes high viscosity, so an excessive dilution solvent must be used, and the ratio of the resin in the coating is reduced, and a proper coating film cannot be obtained, and the compatibility of the toilet composite component is also reduced. In addition, in the case of using a bisphenol A addition polyester resin as the main resin, the content of the bisphenol a in the bisphenol A addition polyester resin is 1 to 70% by mass based on the solid content of the resin, preferably It is appropriate that it is 3 to 60% by mass, and particularly preferably 5 to 5 Bu. The lower limit of this content range is to ensure the strength of the coating film: it is better, and the upper limit is from the viewpoint of ensuring the elongation of the coating film. In view of the polyols used to obtain the polyester resin, ethylene glycol diethylene glycol can be listed. , Dipropylene glycol, polypropylene glycol, neopentyl glycol, diJ, 1 '5-glutarionase, 1' 6-hexanediol, and the like. Also, you can use l 4_ 环 已 = _

C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 39 575643 V. Description of the invention (35) Methanol, polytetramethylene ether glycol, polycaprolactone polyol, glycerol, sorbitol, Mannitol, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol, dipentaerythritol, and the like. These polyols may be used in combination of two or more kinds. In addition, polyvalent bases used to obtain polyester resins include phthalic acid, phthalic anhydride, tetrahydro S macro acid, tetrahydrophthalic anhydride, hexahydrofuric acid, hydrogen Si; acid anhydride, heming acid anhydride, trimellitic acid, etc . Furthermore, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, isophthalic anhydride, terephthalic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, adipic acid can also be used. Acids, azelaic acid, sebacic acid, succinic acid, succinic anhydride, 1,4-cyclohexanedicarboxylic acid, and the like. These polyvalent alkaline acid components may be used in combination of two or more. Examples of the epoxy resin include epoxy compounds composed of bisphenols such as bisphenol A, bisphenol F, and bisphenol S, and epihalohydrin or / 5-methylepihalohydrin, or copolymers thereof. In addition, the mono- or di-acid modifiers, mono-, di- or polyol modifiers, mono- or diamine modifiers, mono-, di- or polyphenol modifiers of these epoxy compounds can also be used as epoxy compounds. Resin. In addition, as the hardener of the above-mentioned base resin, a polyisocyanate compound and / or an amine resin can be used. The polyisocyanate compound may be an isocyanate compound obtained by a general manufacturing method, and is particularly suitable for sealing of benzene, benzene, aromatic diamine, tertiary alcohol, lactam, oxime, etc., which can be used as a one-liquid coating. Polyisocyanate compounds which are blocked by a resist are preferred. By using this blocked polyisocyanate compound, it can be stored in one liquid and can be easily used as a coating

C: \ 2D-CODE \ 91-04 \ 91101646a.ptd Page 40 575643 V. Description of the invention (36). In addition, as the more preferable polyisocyanate hexanoic acid adipate (hereinafter, HDI) and its D substance, non-yellowing diisocyanate (TDI) and its derivatives, 4,4, di-, and di Dimethyl isocyanate (hereinafter, MD I) and its derivatives, diphenyl diphenylmethane diisocyanate (and its derivatives, di cyanic acid; dimethyl xylide (hereinafter, other I)) , Triisocyanate diisocyanate, below), and its derivatized TDI and its biological, hydrogenated under the TMDI) and its derivatives, hydrogen biological and so on. 8〜1 2 、 更 更 I and its derivatives, hydrogenated XDI and its derivatives using a polyisocyanate compound as the isocyanate group and the main agent tree two = dagger, polyisocyanate compound Morr ratio 0. 8 ~ 1 2, better The blending ratio [NC0 / 0H], which is a fluorene group of Wn, is II: Bu, and δ is in a range of 0.990 to L10. The ratio of [NCO / OH] is less than 0 · 8, the coating gland is less ^ ^ < ^^. ^ ^ The film is not hardened enough to obtain the desired coating ΓΓ: Λ square, [_ / 〇 11] The molar ratio exceeds the side reaction of Fupan jr, its former office, and the remaining isocyanate groups, or the side reaction of isocyanate groups and radicals, and the processability of the coating film is reduced. Wait! As the resin, urea, benzoguanamine, and melamine can be used as the resin for the six-year-old reaction, as well as substances that have been burned and tested with alcohols such as methanol and butanol., Specific examples include fluorinated urea. Resin, n-butylated benzoguanamine resin, methylated melamine resin, n-butylated melamine resin, isobutylated melamine resin, etc. When using amine-based resins as hardeners, amine-based resins and Mixing ratio (weight ratio of solid content) of the main resin: main resin: amine resin = 95: 5 ~ 6〇:

575643 V. Description of the invention (37) 4 0, preferably 8 5] 5 to 7 5: 2 5 The blending amount of the hardener is preferably 9 to 50% by mass based on the solid content of the resin. If the blending amount of the hardener is less than 9% by mass, the hardness of the coating film is insufficient. On the other hand, if it exceeds 50% by mass, the processability is insufficient. In addition, hardening catalysts such as p-toluenesulfonic acid, tin octoate, dibutyltin dilaurate, calcium carbonate, kaolin, clay, and oxidation can be added to the resin composition for primer coating film depending on the purpose and application. Various additives such as titanium, red iron oxide, mica, carbon black, aluminum powder, rust preventive pigments such as chromate, aluminum tripolyphosphate, etc. From the viewpoint of corrosion resistance, the rust preventive pigment is preferably chromate. Examples of the chromate include lutetium chromate, potassium chromate, zinc chromate, calcium chromate, and barium chromate. Among them, lanthanide 4 is the most preferred. The content of chromate is 1 to 50% by mass, and more preferably 10 to 45% by mass, in the solid content of the coating film. If the content of chromate is less than 1% by mass, a sufficient rust-preventive effect cannot be obtained. On the other hand, if it exceeds 50% by mass, the adhesion to the topcoat film decreases. (4) Topcoat film The topcoat film has a thickness of 5 ~ 3 0 // m. If the thickness of the coating film is less than 5 / z m, sufficient processability and corrosion resistance of the processed portion cannot be obtained. On the other hand, if it exceeds 30 0 m, the processability decreases and the manufacturing cost increases, which is not good. The glass transition temperature of the topcoat film is 30 to 90 ° C. If the glass transition temperature of the topcoat film is less than 30 ° C, the scratch resistance will be reduced. On the other hand, if it exceeds 90 ° C, the workability of the coating film will be reduced. As mentioned earlier, even the processability of the ore layer steel sheet itself The improvement also lowers the workability of the entire sprayed steel sheet. nil

C: \ 2D-CODE \ 91-04 \ 91101646a.ptd Page 42 575643 V. Description of the invention (38) The main resin of the topcoat film can be made of resin, vinylidene fluoride resin (polyvinylidene fluoride resin) And then 4 ± χ 'τ ♦ /, 丨 ”smart resin's warm man line day &, etc., and the polyacetate resin is in addition to the polyresin resin. Two? Modified polyester resin, acrylic modified polyester resin From the water-based silicone emulsion, among these main agent resins, the processability of the fluorene-based resin and the polyvinylidene fluoride-based resin is preferred, and in particular, the polyvinyl acetate-based resin is the best. The cost is that if the polyester resin has at least two compounds with a sub-quantity of 1 0 0 ~ 200,000 in one molecule, and it is soiled, and the number average fraction average molecular weight is 2_ ~ 2_〇 is ^ There is no particular limitation, but the number average molecular weight of the polyester resin is less than 2000, and decreases. On the other hand, if the number average molecular weight exceeds 20,4, it will decrease and become high viscosity, so excess care must be taken. However, the rate of weathering resin Γ decreases, so it is not possible to obtain a suitable coating 7 and the compatibility of synthesis is sometimes reduced. Here, the amount of polyamidine is calculated by GPG and converted to the average score of the number of females, and the hydroxyl group in the polyester resin molecule can be divided into any one of ^ /. Or the co-chain of the side chain = vinegar resin is obtained by heating the polyacid and the polyhydric alcohol according to the usual method. For example, acetic anhydride, meta-acid, p-acid, mandelic anhydride, maleic acid, hexamethylene Diacid, fumaric acid, etc. Partial propylene

As the polyhydric alcohol, for example, ethylene glycol,., J diol, dipropylene glycol, hydrazine, hydrazine, propylene glycol, butanediol, and 1,6-hexanediol can be used.

C: \ 2D-00DE \ 91-04 \ 91101646.ptd Page 43 575643 5. Description of the invention (39) neopentyl glycol, triethylene glycol, glycerol, pentaerythritol, trimethylolpropane, trimethylolethane Wait. When this polyvinylidene fluoride resin is blended as a component of a topcoat film, it is used in a mixed resin type in which an acrylic resin is mixed with a polyvinylidene fluoride resin. The polyvinylidene fluoride resin preferably has a weight average molecular weight of 3 0 0 0 0 to 7 0 0 0 0 0 and a melting point of 150 to 18 0 ° C. For example, the product name "Kiner 500 (weight average molecular weight: 350,000, dazzle point: 1 60 to 16 ° C)" made by Japan PEN WALT (stock) can be exemplified. The acrylic resin mixed with the polyvinylidene resin is used to The number average molecular weight is preferably from 1000 to 2000. In addition, the propylene resin can be obtained by polymerizing (or copolymerizing) at least one monomer (but containing at least one propylene monomer) by an ordinary method. ① ( Ethylenic monomers having a hydroxyl group, such as hydroxymethyl acrylate, hydroxyethyl (fluorenyl) acrylate, hydroxypropyl (fluorenyl) acrylate, hydroxybutyl (fluorenyl) acrylate, etc. ② (meth) acrylic acid, Vinyl monomers having a carboxyl group, such as butenoic acid, itaconic acid, fumaric acid, maleic acid, and the like ③ (fluorenyl) fluorenyl acrylate, (fluorenyl) ethyl acrylate, (fluorenyl) acrylic Acrylic esters such as propyl ester, butyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, alkyl (meth) acrylate, etc. ① and ② copolymerized ethylene monomer ④ Styrene derivatives such as styrene, α-fluorenylstyrene, o-fluorenylstyrene, m-fluorenylstyrene, and p-fluorenylstyrene. These monomers have functions such as hydroxyl and carboxyl groups through use. Basis

1¾ C: \ 2D-CODE \ 91-04 \ 91101646a.ptd Page 44 575643 V. Description of the invention (40) The body can be cross-linked with other reactive components. The propylene resin used in the present invention does not require self-crosslinking properties, but in the case of the self-crosslinking type, it includes a so-called crosslinkable monomer having two or more radical polymerizable unsaturated bonds in the molecule. Examples of the radically polymerizable monomer include ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, and dimethacrylate 1, 3 -Butanediol ester, trihydroxymethylpropane triacrylate, trihydroxymethylpropane triacrylate, 1,4 diacrylate-butanediol ester, neopentyl glycol diacrylate, 1,6 diacrylate -Ethylene glycol ester, pentaerythritol diacrylate g, pentaerythritol triacrylate, pentaerythritol tetramethylacrylate, glycerol dimethacrylate, glycerol diacrylate, glyceryl diacrylate, propylene glycol diacetate Polymerizable unsaturated compounds such as S purpose, S too acid diallyl S purpose, acrylic glycidyl vinegar, methyl acrylic acid glycidol S purpose. The crosslinkable monomer may be added up to 20% by mass of the propylene resin. The compounding ratio of polyvinylidene fluoride resin and acrylic resin (weight ratio of solid content of resin) is preferably [polyvinylidene fluoride :) Greek resin]: [propylene resin] = 9 0: 1 0 to 5 0: 50. If the weight ratio of acrylic resin to polyvinylidene fluoride resin exceeds 90:10, the thixotropy is high and it is difficult to spray with a roll coater, so it becomes a coating film with uneven surface coating, and the appearance of the coating film is poor. On the other hand, if it is less than 50:50, the adhesion of the coating film over time deteriorates significantly, and the weather resistance is greatly reduced, which is not good. The blending amount of the mixed resin of polyvinylidene fluoride resin and acrylic resin is preferably 40% by mass or more in the solid content of the coating film, and if the blending amount is less than 40% by mass, the intended coating film cannot be obtained sufficiently. performance.

C: \ 2D-CODE \ 91-04 \ 91101646a.ptd Page 45

575643 Description of the invention (42) grease, methylated melamine resin, n-butylated melamine resin, isobutylated melamine resin, and the like. When using an amine-based resin as a hardener, the mixing ratio of the amine-based resin to the main resin (weight ratio of solid content) is the main resin: amine-based resin = 95: 5 to 60: 40, preferably 85: 15 to 75:25. The blending amount of the curing agent is preferably 9 to 50% by mass based on the solid content of the resin. If the blending amount of the hardener is less than 9% by mass, the hardness of the coating film is insufficient, and if it exceeds 50% by mass, the workability is insufficient. "Similar to the resin composition for primer coating film, it can be added to the tree month composition for topcoat film". Para-toluenesulfonic acid, tin octoate, dibutyltin dilaurate can be added depending on the purpose and application. Ester and other hardening catalysts, calcium carbonate, kaolin, clay, titanium oxide, red iron oxide, mica, carbon black, aluminum powder and other pigments, chromate, aluminum tripolyphosphate, and other antifoaming agents , Only> various additives for melon search. Next, the manufacturing method of the sprayed steel plate of Embodiment 2 is demonstrated. The manufacturing method of the second embodiment is a method for manufacturing a spray-coated steel sheet with a molten Al-Zn-based plated steel sheet having an A1 content of 20 to 95% by mass in a money film manufactured by a continuous molten plating equipment or the like, The key film for the steel plate out of the molten forging bath is provided with at least the following steps (3) and (1)), and sequentially forms a chemical conversion treatment film, a primer coating film, and a surface on the surface of the mineral layer steel plate. Steps of paint film. (a) The average cooling rate of the first 10 seconds immediately after the hot-dip plating of the steel sheet is a thermal history of less than 11 ° C / sec. (b) After the metal plating of the hot-dip coating is solidified, 0 0 ° C range temperature

C: \ 2D-C0DE \ 91-04 \ 91101646.ptd P.475755643 V. Description of the invention (43) Degrees D (C) Heating and temperature increase, 1 饴 cooling rate is //, D ^ temperature T (c) to 10 (average up to rc / heat history below C (° C / hr) shown by (丨), coffee) The average cooling rate satisfies the following formula C = (T-100) / 2 ^ In the thermal history of the above (and ") given by the coating film, the heat of (a) is stopped by controlling the cooling conditions of the coating film immediately after coating. In order to solve this (a) thermal history, as mentioned above, it must be from the continuous dazzling ^ ¥, 嘁 plating contact to the first contact of the steel plate out of the molten plating bath = an intermediate temperature adjustment device, and controlled by this temperature adjustment equipment Plating only = depletion speed. As mentioned above, the temperature adjustment equipment is preferably equipped with heating or heating means, and with cooling means as required. There are no particular restrictions on the method, shape, scale, etc. of the heating or holding means and cooling means, and it can mainly The film may be provided with the thermal history of (a). As the heating or heat retaining means of the temperature adjustment device, for example, an induction heater and gas heating can be used, and as the cooling means, a gas blowing device can be used. The thermal history of (b) above is performed by applying a specific heat treatment to the gold-plated steel sheet that has been solidified after being melt-plated, or by controlling the cooling of the plating film after the key metal of the melt-plating is solidified to maintain heat. This manufacturing method is to make a specific chemical treatment film, a primer coating film and a top coat film on the ore film surface of the ore layer steel plate in order. The heat treatment that imparts the heat of the above (b) to the film can be formed in ① Before the treatment, ② The drying step of the chemical conversion treatment, ③ After the chemical conversion treatment is completed (after the application and drying of the treatment liquid), before the primer coating,

C: \ 2D-00DE \ 91-04 \ 9ll01646.ptd Page 48 575643 V. Description of the invention (44) ④ In the drying step of primer coating spraying, + + ^ 7 ^ only soil w ^ ^ τ ⑤ primer后 After the coating is finished (after the coating is dried), before the topcoat is sprayed, ⑥ ^ The topcoat must be completely sprayed out, and the step is not completed. 后 After the topcoat is sprayed (the coating is applied to you) After washing and drying out). It is also possible to carry out one or more of these stages. This can be performed in at least one of the following steps (1) to (8). (1) Before chemical treatment (2) (3) (4) (5) (6) (7) (8) Remaining treatment, after chemical treatment in the drying step of chemical treatment, before primer spraying In the drying step, after the primer coating is finished, the topcoat is sprayed and the front paint is sprayed. In the drying step, after the topcoat is sprayed, the cooling process after the solidification of the metallized layer of the fused layer is solidified: in the above method of heat treatment , ②, ④, and ⑥ are heating or heat-preserving devices provided outside the heat treatment or maintenance provided by the above-mentioned (b) thermal history using chemical formations, and heating mechanisms are installed in the molten coating equipment (for example, induction heating;,: (Body = ten hot blast stoves, etc.) and continuous in-line: line :: two Γ 卷绕 after winding in offline batch heating can also be 'outside the ore streamline π such as induction heating crying, Α even The Bin process equipment is continuously heated by the heating mechanism (such as "gas heating furnace, hot blast furnace, etc.), and the heating in the drying step of the primer coating and topcoat spraying is particularly economical.

C: \ 2D-C0DE \ 91-04 \ 91101646.ptd Page 49 575643 V. Description of the Invention (45), V. Undertaking and ‘into the ore laminar streamline and ^ may also be included. In addition, the coating layer continuously heated by the above-mentioned continuous processing equipment ^, a ”may be appropriately heat-preserved after being wound or kept heated: " Second, a cooling boat is installed during the cooling process after the metallization of the layer is solidified to maintain heat Xu Lengzhi's protection F 埶. Regarding the method of heating or heat-preserving device, # 此 "1 offender, shape of eight blades, size, etc. are not restricted, and the coating can be applied to the above (b ). … ,,,,,,,,,,,,,,,,,, The composition of, the preferred coating composition, the coating adhesion amount, the limited reasons for the thermal history of (a) and (b), and the obtained effects, etc. The foregoing. As mentioned above, the type of chemical conversion treatment applied to the surface of the plated steel sheet as the coating bottom layer is particularly limited, and chromate treatment, zinc treatment, and treatment with organic resin as the main component can be performed. In addition, the drying step of the whole process is the heating and drying of the coating with a hot blast stove, an induction heater, and the like. Therefore, as described above, it is also possible to use this heating and drying to heat the plating. … "F This coating is used to coat the top layer of the coating film, preferably the resin as described above is used as the main sword tree ship, and if necessary, the f material is coated and baked, and then the surface is coated on the upper layer. Lacquer coating; = If the resin described in the above is the main one, shake this, a catty% from the * λ side, and paint the oblique as early as π grease, and if necessary, add a hardener ^ " soil, And bake to form a base coat film and a top coat film. The structure of these primer coating films and topcoat films is as described above. Shiji this = 1 coating for forming soil film (primer coating film and mask) There is no special requirement, but it is better to spray, spray, spray and curtain spray. After the coating has been painted, it is heated by hot air, infrared heating, induction heating, etc. I · »_ 看 __ C: UD'®® ^ l-〇4 \ 91101646a.ptd ^ 50 Page 50575643 V. Description of the invention (46 ) — ^ ~-The coating film is baked to form a coating film. The baking treatment of the heat-hardened coating film is performed in the primer coating spraying, for baking, the mouth (the temperature of the plate reaching the southmost) is 1 50 ~ 2 7 0 ° C, preferably 18 0 ~ 2 5 0 ^ For, Gao Dang. If the baking temperature is less than 150 ° C, the hardening reaction of the coating film is not sufficient, and the resistance of the spray coating of "" 'sprayed steel plate is liable to decrease. On the other hand, if it exceeds 2 7 0, it will overwhelm the excess, and sometimes it is with the topcoat The adhesiveness of the film is reduced. ^ In the topcoat spraying, the baking temperature (the highest plate temperature reached) is 150. to 280. (:, preferably 180 to 260 ° C is appropriate. If the baking temperature is less than 150 ° C, the polymerization reaction of the resin is insufficient, and the corrosion resistance and scratch resistance of the sprayed steel sheet are liable to decrease. On the other hand, if it exceeds 28.0 ° C, the reaction is excessive and the processability may be reduced in some cases. There is no particular limitation on the baking time for primer spraying and topcoat spraying, but usually 20 to 120 seconds is appropriate. Still, as mentioned above, these coating films can also be used. The baking process imparts the thermal history of (b) to the coating film. Example 2 The / v rolled steel plate (plate thickness 0.35 mm) manufactured by the # method is passed through a continuous melting bell layer equipment, using 55 % Al ~ h5% Si-Zn plating bath (Example A1 of the present invention, 1.0% Si-Zη ore bath C, Example of the present invention ~ 0.7) and 70% A1—Si-Zn plating cold example of the present invention No · /) For hot-melt plating. The working linear speed is 16 [[11 / min. The early surface coating adhesion amount is to stabilize the deviation between steel plates in the range of 75 ~ 90 g / m2. Still, comparative examples are also produced ~ .14 of A molten-plated steel sheet with a molten 5% A1-Zn-based coating (single-sided coating adhesion amount: 13 g / m2).

C: \ 2D-CODE \ 91-04 \ 91101646a.ptd Page 51 575643 V. Description of the invention (47) In the manufacturing steps of these ore-layer steel plates, the coatings are given in Tables 3, 5, and 7. The thermal history (I) and (II), and the conditions of the base coat film and the top coat film were changed in various ways, and the following sprayed steel sheets were manufactured. In addition, the paint for the base coat film is shown in Table 9, and the paint for the top coat film is shown in Table 0. [Inventive Example 1] A 55% Aj-Zri-based coated steel sheet having a thermally-treated coating that meets the conditions of the present invention was subjected to a normal chromate treatment (the chromium adhesion amount converted to metallic chromium was 40mg / m2) Then, the following spray-painted steel plate was applied with the primer and top coat. Primer spraying: 125 parts by weight of the stomach, which is converted into a solid content of the main component resin segmented amino group Sa Sa negative epoxy resin (brand name "Ep〇xy 83〇", manufactured by Mitsui Chemicals Co., Ltd.) 75 parts by weight of anti-rust pigment rhenium chromate, 25 parts by weight of pigment titanium oxide and 25 parts by weight of clay, stirred with a sand mill for 1 hour and adjusted to a coating composition, and coated with a bar coater to a dry coating film thickness of 4 "M, and bake it under the conditions of reaching a board temperature of 220 ° C and a baking time of 38 seconds. The topcoat is sprayed with the main resin polymer resin (trade name" ALMATEX P645 ", 100 parts by weight of Mitsui Chemicals Co., Ltd., 25 parts by weight of hardening agent methylated melamine (trade name "Cymel 303", manufactured by Mitsui Chemicals Co., Ltd.), hardening catalyst p-toluenesulfonic acid. 2 parts by weight, 100 parts by weight of titanium oxide, stirred with a sand mill} hours and adjusted to a coating composition, applied with a bar coater to a dry coating film thickness of 3 # m, and baked at 231TC, It was baked under the condition of 53 seconds. In addition, apply polyacetate resin inside paint on the coated steel sheet, and apply rod C: \ 2D-C0DE \ 91-04 \ 91101646.ptd Page 52 ^ 75643 Ⅴ. Description of the invention (48) The thickness of the dry coating film is 38 seconds, and the work temperature is 220 ° C, and the baking [invention example 2 ~ 1Q] pieces are baked. Invention examples 2 ~ 4 are ordered The change of fish feeding conditions is the same as the other conditions. The thermal history conditions of the film are relative to the invention example 1. Invention example 5 ~ β is to make the envy ^ 1 For the invention example 1 change, 1 # ， is the stage (period) of the specified heat history. Inventive Example 7 ~ Γ is to make the plated parts the same as the inventive examples and the conditions are the same as Inventive Example i. The composition is changed relative to Inventive Example 1, and other Inventive Examples 9, 10 are orders; §; ~ 化, 1 # & π also. The coating film thickness of the main main film is different from that of Invention Example 1. The other conditions are the same as the Invention Example. [Invention Examples 11, 12] 1 Use a primer coating different from that of Invention Example 1. The other conditions are the same as those of Invention Example r. : XL: AT: Second base, material is polyester resin (trade name: LMATEX HMP 27 ", manufactured by Mitsui Chemicals Co., Ltd.) with 100 parts by weight = methylated θ melamine Tradename "Cymel 3〇3", manufactured by Mitsui Chemicals (shares) Ltd.) 25 parts by weight, of curing accelerator - Yue acid · 2 billion parts by weight, and the amount of points = the same as in Example 1 invention. '、 The primer coating of Invention Example 1 2 is a two-component resin made of urethane-modified epoxy resin ("Epoxy 802-30CX", manufactured by Mitsui Chemicals Co., Ltd.), and other components and The compounding amount is the same as that of Invention Example 1. [Inventive Example 1, 3, 1 4] The coating film thickness of the top coat film was changed from that of Invention Example 1. The other conditions were the same.

C: \ 2D-Gode \ 91_〇4 \ 91101646. 575643 5. Description of the invention (49) Invention example 1. [Inventive Example 1 5 to 17] An undercoat coating different from that of Inventive Example 1 was used, and the other conditions were the same as that of Inventive Example 15. The topcoat coating was acrylic resin (trade name "ALMATEX 7 4 5-5 Μ" And Mitsui Chemicals Co., Ltd.) as the main resin. Other components and blending amounts are the same as in Example 1. The topcoat paint of Invention Example 16 uses a main resin, polyvinylidene fluoride resin (trade name "Kiner 5000", manufactured by PEN WALT (Japan)), and acrylic resin (trade name "PAROLITE", Rohm & Haas). Manufactured by the company) ^ solid decibel ratio 1 ^ vinylidene fluoride resin · acrylic resin 2 70: 30 ratio, the other components and blending amounts are the same as in Example 1. Inventive Example 7 The topcoat paint of 7 is made of polyester resin (trade name "ΑίΜΑΤΕχ P647 BC", manufactured by Nitsui Chemicals Co., Ltd.) as the main resin, and the other components and blends are the same as Inventive Example 1. [Invention Example 1] The hardener blending amount, and the hard weight part is 40 weights. With respect to the invention example 1, changing the blending amount of the chemical agent in the topcoat coating with respect to the main resin 100. Other conditions are the same as the invention. example 1. [Comparative Examples 1 to 1] These ^ 1 to 5 are heat treatment conditions for the plating layer, Comparative Examples 6 and 7 are primer coatings 1 ;: Ξ: J of: Comparative Examples 8 and 9 are coating film thicknesses of topcoat films, Comparative Example 10 :, Comparative Example 1, Dota I = Tempering temperature, respectively, and those that do not satisfy the conditions of the present invention are the same as those of Inventive Example 1.

575643

Comparative Example 12 is a comparative example in which the key film is not provided with the prescribed experience of the present invention. Comparative Example 13 is a comparative example in which the primer coating is omitted. A comparative example of a Zn ore steel sheet (which is also not provided with the thermal history of the present invention), and other conditions are the same as those of the inventive example 1. *, 疋 For each of the above sprayed steel sheets, the following methods are used. Part bifurcation, corrosion resistance of the processed part, coating film hardness, glass transition temperature. Results and the composition of the sprayed steel plate: ^ 々, film. ^ The knife is not in Table 3 ~ Table 8 0 ① Workability and Bend the sample in a room 30 times 20 ° C. Add the plate: The number (T) is evaluated as follows: ◎: No cracking occurs with 6T bending. 0: Cracking occurs with 6T bending, but with 7T. Δ: A crack occurred with 7T bending, but with 8T X: A crack occurred with 8T bending. ② Adhesiveness of the processed part. The sample was 180 ° C in a room at 20 ° C. After 5T bending, the bent part was bonded with adhesive tape. , Peeling, and measurement of film peeling rate (area Rate%) and evaluated as follows: Bow P Middle Master ◎: Coating film peeling rate 0% 〇: Coating film peeling rate exceeding 0% and less than 10% X: Coating film peeling rate 1 Q% or more ③ Resistance of processed part

C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 55 575643 V. Description of the invention (51) Make the spray-painted steel plate cut into a size of 160mm X 7 Omm and set it at 20mm. (: After 3 to 180 ° bending process, test pieces sealed with tar epoxy coating on the ends of the four sides shall be tested by accelerating the wet and dry repeating conditions specified in JIS κ 562 1 ( Hereinafter, the CCT test) is performed 300 times, and then the expansion ratio (area ratio) of the coating film is measured. This expansion ratio is that the coating film swells in a bending process section with a width of 50-50, which excludes the rain end of the test piece. The total length of the part in the width direction is expressed in% (for example, when there are 2 expansions at 5 and 5 of the width, the expansion rate is 20%). 5% saline spray, 30 ° C, hour-dry 20 "% RH, 50 hours" is 1 time (6 hours), 0. ° C, 2 hours—dry 20% R Η, 3 0 t :, so it repeats until the set number of times J IS K 5 6 The CCT test conditions of 21 are hour-moisture 95% R Η, 30. (3,1 expansion rate is less than 10% 〇: expansion rate is 10% or more, less than 30% Δ: expansion rate is 30% or more 、 Less than 50% X: Expansion rate is more than 50% ④ The hardness of the coating film is according to JIS K 540 0-8 · 4, using the gold l-sign; — A # ， κ π oyster 聿 hardness pencil It was evaluated whether or not a flaw occurred in the topcoat film according to the following. ○: Flaw occurred X: No flaw / defect occurred ⑤: The glass transition temperature of the coating film was measured by TMA ("SS61〇〇" by Seiko Instruments) from 〇〇 (: To 15〇

c: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 56

575643 V. Description of the invention The glass transition temperature of the topcoat film is measured at a temperature increase rate of 10 ° C / m η and a load of 10 grams up to (52) ° C. According to Tables 3 to 8, the sprayed steel sheet of the example of the present invention has good properties in terms of workability, adhesion of the processed portion, corrosion resistance of the processed portion, and coating film hardness. In contrast, the comparative example was inferior to the examples of the present invention in any of the characteristics.

C: \ 2D-CODE \ 91-04 \ 91101646a.ptd Page 57 575643 V. Description of the invention (53) Table 3

No. Thermal history of coating composition (I ”l Average cooling rate (° C / sec) Thermal history I) * 2 Primer coating film Topcoat film Topcoat film Tg (° 〇 * 8 Differentiating heating temperature (.〇 * 3 Average cooling rate (° C / hr) * 4 Implementation stage of heat treatment "Type * 6 Coating film thickness Um) Type * 7 Coating film thickness (// m) 1 55% Al-1.5% Si 10 180 23 1 B 4 E 13 60 This pay 2 55% AM.5% Si 10 280 52 1 B 4 E 13 60 This pay 3 35% 5% Al-1.5% Si 4 145 18 1 B 4 E 13 60 Inventive example 4 55% AM .5% Si; 4 240 58 1 B 4 E 13 60 This pay 5 55% AM.5% Si 8 185 15 2 B 4 E 13 60 This example 6 55% Al-1.5% Si 8 170 22 3 B 4 E 13 60 Example of the invention 7 40% AH.0% Si 10 180 23 1 B 4 E 13 60 This example 8 70% Al-1.8% Si 10 180 23 1 B 4 E 13 60 Example 9 of the invention 55% Al-1.5% Si 10 180 23 1 B 2 E 13 60

C: \ 2D-C0DE \ 91-04 \ 91101646a.ptd P.585755643 V. Description of the invention (54) * 1 The average cooling rate of the coating film for 10 seconds immediately after the steel plate is out of the molten plating bath * 2 Heat history due to the heat treatment performed after the coating is solidified * 3 The heating temperature of the coating during the heat treatment * 4 The average cooling rate of the coating until the heating temperature reaches 100 ° C during the heat treatment * 5 (1): Before the chemical conversion treatment (2): After chemical conversion treatment and before primer spraying (3): After topcoat spraying * 6 Primer coating film composition symbols shown in Table 9 * 7 Table 10 Primer film composition symbols shown in Table 0 Glass transition temperature of topcoat film 4

No. Performance classification Processability Processing section Adhesive processing section Corrosion resistance coating film hardness 1 ◎ ◎ ◎ 〇 Inventive Example 2 ○ ◎ ◎ 〇 Inventive Example 3 ◎ ◎ ◎ 〇 Inventive Example 4 ○ ◎ ○ Inventive Example 5 ◎ ◎ ◎ Inventive Example 6 ◎ ◎ ◎ 〇 Inventive Example 7 ◎ ◎ 〇 Inventive Example 8 ◎ ◎ 〇 Inventive Example 9 ◎ ◎ ◎ 〇 Inventive Example

C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 59 575643 V. Description of Invention (55) Table 5

No. Coating composition Thermal history * 1 Average cooling vine (Usee) Thermal history (π) * 2 Base coat film Topcoat film Topcoat film Tg (° 〇 * 8 Differentiated heating temperature (t) * 3 Average cooling rate (° C / hr) * 4 Implementation stage of heat treatment "Type * 6 Coating film thickness (m) Type * 7 Coating film thickness (/ zm) 10 55% AH.5% Si 10 180 23 1 B 10 E 13 60 copies Inventive Example 11 55% AM.5% Si 10 180 23 1 A 4 E 13 60 Inventive Example 12 55% AM.5% Si 10 180 23 1 C 4 E 13 60 Present pay 13 55% Al-1.5% Si 10 180 23 1 B 4 E 5 60 Inventive Example 14 55% AM.5% Si 10 180 23 2 B 4 E 20 60 Inventive Example 15 55% Al-1.5% Si 10 180 23 3 B 4 i 13 60 Invention Example 16 40% AM.5% Si 10 180 23 1 B 4 J 13 55 Invention Example 17 70% AM.5% Si 10 180 23 1 B 4 D 13 30 Present Pay 18 55% Al-1.5% Si 10 180 23 1 B 4 F 13 80 Example of the invention C: \ 2D-C0DE \ 91-04 \ 91101646a.ptd Page 60 575643 V. Description of the invention (56) * 1 Immediately 10 seconds after the steel plate is out of the molten plating bath The average cooling rate of the coating film * 2 The heat history imparted by the heat treatment performed after the coating film of the molten coating layer is solidified * 3 The heating temperature of the coating film during the heat treatment * 4 Average cooling rate of the coating during heating up to 100 ° C * 5 (1): before chemical conversion treatment (2): after chemical conversion treatment, before primer coating (3): after spray coating * 6 Base coating film composition symbols shown in Table 9 * 7 Table 10 Top coating film composition symbols shown in Table 0 * 8 Glass transition temperature of top coating film Table 6

No. Performance classification Processability Processing part Adhesiveness processing part Corrosion resistance coating film hardness 10 ◎ ◎ ◎ 〇 Example 11 of the present invention ◎ ◎ ◎ ○ Example 12 of the present invention ◎ ◎ ◎ 〇 Example 13 of the present invention ◎ ◎ ○ 〇 Example of the present invention 14 ◎ ◎ ◎ 〇Inventive Example 15 ○ ◎ ◎ 〇Inventive Example 16 ◎ ◎ ◎ 〇Inventive Example 17 ◎ ◎ ◎ 〇Inventive Example 18 ○ ◎ ◎ Inventive Example

C: \ 2D-C0DE \ 91-04 \ 91101646a.ptd page 61 575643 V. Description of invention (57) Table 7

No. Coating composition Thermal history (I) * l Average cold leg (° C / sec) Thermal history (II) * 2 Primer coating film Topcoat film Topcoat film Tg (° 〇 * 8 Differentiating heating temperature (° C) * 3 Average cold cage degree (° C / hr) * 4 Implementation stage of hot surface "Type * 6 Type of coating film thickness * 7 && film thickness 1 55% Al-1.5% Si 15 180 19 1 B 4 E 13 60 Comparative Example 2 55% Al-1.5% Si 8 330 50 1 B 4 E 13 60 Comparative Example 3 55% AM.5% Si 8 105 20 1 B 4 E 13 60 Comparative Example 4 55% AM .5% Si 8 265 85 1 B 4 E 13 60 Comparative Example 5 55% AM. 5% Si 8 165 45 2 B 4 E 13 60 Comparative Example 6 55% Al-1.5% Si 10 180 23 3 B 1 E 13 60 Specific pay 7 55% AM.5% Si 10 180 23 1 B 19 E 13 60 Comparative Example 8 55% Al-1.5% Si 10 180 23 1 B 4 E 3 60 Comparative Example 9 55% Al-1.5% Si 10 180 23 1 B 4 E 35 60 Comparative Example 10 55% Al-1.5% Si 10 180 23 1 B 4 G 13 20 Comparative Example 11 55% AH.5% Si 10 180 23 1 B 4 Η 13 95 Comparative Example 12 55 % AH.5% Si---B 4 Ε 13 60 Comparative Example 13 55% AH.5% Si 10 180 23 1--Ε 13 60 Comparative Example 14 5% A1---B 4 Ε 13 60 Comparative Example No. Page 62 C: \ 2D-CODE \ 91-04 \ 91101646a.ptd 575643 5. Description of the invention ( 58) * 1 The average cooling rate of the coating film in 10 seconds immediately after the steel plate is out of the molten plating bath * 2 The heat history imparted by the heat treatment performed after the coating of the molten coating is solidified * 3 The heating temperature of the coating film during the heat treatment * 4 Average cooling rate of the coating during heating up to 100 ° C * 5 (1): before chemical conversion treatment (2): after chemical conversion treatment, before primer coating (3): after spray coating * 6 Base coating film composition symbol shown in Table 9 * 7 Top coating film composition symbol shown in Table 0 * 8 Glass transition temperature of top coating film ※ The values with underline are outside the scope of the present invention

Properties Mb. Processing by adding X-shaped processing parts: Guo coating film distinguishes adhesion corrosion resistance hardness 1 Δ 〇Δ 〇 Comparative Example 2 X 〇X 〇 Comparative Example 3 Δ 0 Δ 〇 Comparative Example 4 △ 〇Δ 〇 Comparison M 5 △ 〇Δ 〇 Comparative Example 6 ◎ △ 〇 Comparison 洌 7 △ 〇〇X Comparative Example 8 X ◎ X 〇 Ratio Example 9 Δ X △ 〇 Comparative Example 10 ◎ 〇X Comparative Example 11 X 〇X: 0 Comparative Example 12 X 〇X 0 Comparative Example 13 ◎ XXX Comparative Example 14 ◎ ◎. X 〇Hinge Example Page 63 C: \ 2D-CODE \ 91-04 \ 91101646.ptd 575643 5. Description of Invention (59) Table 9 [Under the bottom Composition of coating film] Marker base resin resin hardener type blending amount kind blending amount A Polyester resin: Mitsui Chemicals [ALMATEX HMP27] 100 Methylated melamine: Mitsui Chemicals [Cymel 303] 25 B Segmented Urethane Modified Epoxy Resin: Made by Mitsui Chemicals [Epoxy 830] 125-0 C Urethane Modified Epoxy Resin: Made by Mitsui Chemicals (Epoxy 802-30CX) ] 125-0 * 1 "Mixed amount" is the weight part converted into solid content * 2 0.2-weight of p-toluenesulfonic acid is mixed in the coating film component A * 3 In coating film ingredients A to C, 75 parts by weight of chromic gill, 25 parts by weight of titanium oxide, and 24.5 parts by weight of clay are shown in Table 10. [Topcoat coating film components] Marking amount of the main component resin hardener Kind blending amount D Polyester resin: Mitsui Chemicals Co., Ltd. [ALMATEX P647BC] 100 Methylated melamine: Mitsui Chemicals Co., Ltd. [Cymel 303] 25 E Polyester resin: Mitsui Chemicals Co., Ltd. [ALMATEX P645] 100 methylated melamine: Mitsui Chemicals [Cymel 303] 25 F polyester resin: Mitsui Chemicals [ALMATEX P645] 100 methylated melamine: Mitsui Chemicals [Cymel] 303] 40 G polyester resin: Mitsui Chemicals Co., Ltd. [ALMATEX P647BC] 100 methylated melamine: Mitsui Chemicals Co., Ltd. [Cymd 303] 10 Η Polyester resin: Mitsui Chemicals Co., Ltd. [ALMATEX P645 ] 100 Methylated melamine: Mitsui Chemicals Co., Ltd. [Cymel 303] 80 I Propylene resin: Mitsui Chemicals Co., Ltd. [ALMATEX 745-5M] 100 Methylated melamine: Mitsui Chemicals Co., Ltd. [Cymd 303] 25 J Polyvinylidene fluoride resin + acrylic resin * 1 100 Methylated melamine: made by Mitsui Chemicals [Cymel 303]-* 1 "Kiner 500" and Rohm & made by PEN WALT (Japan) Ha "Parol ite" manufactured by the company is mixed with a solid content weight ratio of 70/30. ※ "Mixed amount" is a weight part converted into solid content. ※ In the coating film components D ~ J, p-toluenesulfonic acid is added separately. 2 Parts by weight, 25 parts by weight of titanium oxide

Page 64 C: \ 2D-C0DE \ 91-04 \ 91101646.ptd 575643 V. Description of the invention (60) ''

Implementation of disc state I The sprayed steel plate of Embodiment 3 is made of a fused A1 Z η-based ore layer steel plate containing 20 to 95% by mass of the coating film as the head layer steel plate. Formation of chemical treatment film, primer coating film and topcoat film in sequence. Hereinafter, these configurations will be described in detail. (1) A molten Al-Zn plated steel sheet containing 20 to 95% by mass of A1 in a Wei film. A molten Al-Zn plated steel sheet has excellent corrosion resistance. From the viewpoint of corrosion resistance, etc., A1 in the coating film A more preferable range is 45 to 65% by mass. In addition, the particularly preferred composition of the plating film is 8:45 to 65% by mass, and 81: 0.7 to 2.0% by mass.卩 6: Less than 10% by mass, and the remaining portion is substantial Zn containing unavoidable impurities, and particularly exhibits excellent corrosion resistance in the case of such a composition. However, the hot-dip A1-Zn steel sheet is only composed of this coating layer, and it is difficult to obtain high processing portion corrosion resistance. The excellent corrosion resistance of the processed portion can be obtained only through the thermal history described later and the combination of the upper chemical conversion coating. In addition, the coating adhesion amount of this hot-dip A1-Zn-based steel sheet is not particularly limited, but it is generally appropriate to be about 30 to 200 g / m2 per one side. In addition, the coating film of the molten A 1 -Zn series steel plate must be a ship film obtained through at least the following thermal experience of (a) and (b). (a) The average cooling rate of the first 10 seconds immediately after the hot-dip plating of the steel sheet is a thermal history of less than ll ° C / sec. (b) After the metal plating of the hot-dip coating is solidified, the temperature ranges from 1 0 to 3 0 0. 〇Range temperature T (° C) is raised and heated, and thereafter, the temperature T (° C) to 100 ° C is flat ^ The cooling rate is a heat that satisfies c (° C / hr) or less as shown in (1) below experience,

575643 5. Description of the invention (61) and / or, after the solidification of the metal plated by the molten plating layer is solidified, the average cooling rate from the temperature T (C) to 100 ° C is satisfied. The thermal history of C (° C / hr) below C (° C / hr) is shown in the following formula: (丁 -100) / 2 In the thermal history of (b) above, the better range of the temperature T (t :) is 1 3 0 to 2 0 0. . . The key film becomes a molten Al to Zn-based plating layer through the heat history of (a) and (b), and the workability (crack resistance, etc.) is significantly improved. (2) Chemical treatment film The type of chemical treatment film used for the spray head layer is not particularly limited, and chemical treatment can be performed with chromate treatment, phosphate treatment, or organic resin-based treatment. In general, organic resins are used as the main component when the environment is important, and chromate is used when the corrosion resistance is important. However, zinc phosphate treatment has complicated steps. In the case of a molten A1-Zn-based coated steel sheet containing 20 to 70% by mass of A 丨 in the plating, the reactivity of phosphoric acid is sometimes insufficient, so it is used in the case of use. This must be considered. (3) Primer coating film The primer coating film has a number average molecular weight of 1400 () to 2600G and a glass transition temperature of 0 to 30. (: The polyester resin (A) and the epoxy resin (should be obtained, and the k value shown in the following formula is 0.7 ~ 2 · 5 与, and the hardener ⑻ is the main component resin.) ... = [Wbx (Ma + 2x Mb)] / [(Wa + Wb) x 2x Mb] However, Wa: [Polyester Resin (A) + Epoxy Resin (B)] as opposed to Polyester Resin, page 66575643 V. Description of the invention (62) (A) Solid content ratio by weight

Wb: Solid content of the polyester resin (B) relative to [polyester resin (A) + cyclofluorene resin (B)] 39 M a: Number average molecular weight of polyester resin (a) M b: Epoxy The number average molecular weight of the resin (B) is used to obtain the modified polyester resin (c). The polyester resin (A) is mainly an ester compound of a polybasic acid and a polyol. Dibasic acid, meta-anhydride, hexamellitic anhydride can be used for polyacid test Polyvalent acids and the like having trivalent or higher valences, and these polyvalent alkaline acid components may be used in combination of two or more kinds. Polyols are mainly ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 3-pentylpentanediol, neopentyl glycol, i, 4-butanediol, 1,5- Aliphatic or cycloaliphatic diols such as pentanediol, 1,4-hexanediol, 1,6-hexanediol, 1,4-cyclohexane, and methanol, and glycerol may be used in combination if necessary , Trihydroxymethylethane, trihydroxymethylpropane, trihydroxymethylbutane, hexanetriol, pentaerythritol, tripentaerythritol, etc. 0 Polyester resins (A) must have a number average molecular weight of 1 400 0 ~ 260 0 0, glass transition temperature is 0 ~ 30 ° C. In addition, poly (S) resin (a) is more preferably a number-average molecule $ 18 0 0 to 2 1 0 0, and a glass transition temperature of 5 to 25 ° C. If the number average molecular weight of the polyg resin (A) is less than 4000, the extension of the coating film is insufficient, and the processability is reduced. On the other hand, if the number average molecular weight exceeds 2600 0 0 ′, the adhesion between the coating film and the head layer is insufficient, and the scratch resistance is lowered, and more

C: \ 2D-C0DE \ 91-04 \ 91101646.ptd P.675755643 V. Description of the invention (63) And 'Because the coating composition becomes high viscosity, it must be adjusted by spraying workability and environment with excess dilution solvent In terms of sex, it is not good. In addition, if the glass transition temperature of the polyS resin (A) exceeds 30 °. 〇, the elongation of the coating film is insufficient, and the workability is reduced. On the other hand, if it is less than 0. 〇, the strength and toughness of the coating film are insufficient, and sufficient scratch resistance cannot be obtained. The epoxy resin (b) which reacts with the polyester resin (A) is used to improve the adhesion with the head layer. Examples of the epoxy resin to which the third embodiment is applicable include bisphenol A and bisphenol. The bisphenols such as phenol F, bisphenol S, etc. react with epi-alcohol or perylene epi-alcohol, or bisphenol ring resins of copolymers thereof. < The epoxy resin (B) is preferably one having a number average molecular weight of 5000 to 2000. If the number average molecular weight of the epoxy resin is less than 5,000, the scratch resistance is insufficient. On the other hand, if it is 2 ^ 00 or more, the compatibility with the polyester resin decreases. The method of modifying the polyester resin (A) through the epoxy resin (B) may be a method of adding an epoxy resin during the synthesis of the resin, and a method of reacting the amine catalyst resin with the epoxy resin. Among these modification methods, from the viewpoint of unfavorable film processability and the necessary adhesion can be obtained, "", after resin synthesis, the method of reacting with epoxy resin in the presence of amine catalyst is For the oxygen resin (C), the value shown in the above formula (1) must be 0 7 b. If this k value is less than 0.7, the epoxy resin is small, and sufficient scratch resistance is obtained. On the other hand, there is no%. On the other hand, if the k value exceeds 2.5, the epoxy tree u is %%, and the rigidity of the tree is known to be strong, so sufficient processability cannot be obtained. H yu

575643 5. Description of the invention (64) --- The side hardener (D) can use amine resin and / or polyisocyanate compound. The amine-based resin used as the hardener is a part or all of the product obtained by the condensation reaction of urea, benzguanamine, melamine and the like, and the resin is alkyl etherified with alcohols such as methanol and ethanol. Specific examples include fluorinated urea resins, n-butylated benzoguanidine amine resins, fluorinated melamine resins, n-butylated melamine resins, and isobutyl resins. Food and cosmetic polyisocyanate compounds can use isocyanated characters obtained by general production methods, and especially can be used as one-liquid coatings of phenol, cresol, aromatic diamine, tertiary alcohol, lactam, oxime, etc. The blocking agent is preferably a polyisocyanate compound. By using this blocked polyisocyanate compound, it can be stored in one liquid form and can be easily used as a coating. In addition, more preferable polyisocyanate compounds include non-yellowing adipate diisocyanate (hereinafter, HD I) and derivatives thereof, cresyl diisocyanate (hereinafter, TDI) and derivatives thereof. , 4,4, -diphenylmethane diisocyanate (hereinafter 'MD I') and its derivatives, xylene diisocyanate (hereinafter, XD f) and its derivatives, isophoric monoisocyanate Ester (hereinafter, I p J) I) and its derivatives, trimethylhexyl diisocyanate (hereinafter, TMD 0 and its derivatives, hydrogenated TDI and its derivatives, hydrogenated MDI and its derivatives, hydrogenated And its derivatives, etc. The proportion of the modified polyester resin (c) and the hardener (D) in the primer coating film (coating for the primer coating film) is the solid content and the weight ratio is the modified polyester resin ( c) / Hardener (D) = 90/10 ~ 6 5/35 is preferred. If the ratio of modified polyester resin (C) exceeds 9 0/1 0 ', sufficient hardenability cannot be obtained, which can cause financial damage. Cai Rong

C: \ 2D-0QDE \ 91-04 \ 91101646.ptd p. 69575643, description of the invention (65) lowering of the agent properties' On the other hand, if the ratio of the modified polyester resin (c) is less than 65/35, there is an excess The hardeners react with each other or between the hardeners and the modified polyester resin (c), and the workability and adhesion of the processed parts are reduced. In the coating for primer coating film, in addition to the above-mentioned main agent resin modified polymer resin (C) and hardener (D), if necessary, hardening catalysts, pigments, other antifoaming agents, stoppers, etc. can be added. Various additives. The hardening catalyst is used as needed to promote the hardening reaction of the resin component (main resin and hardener). Examples of the hardening catalyst that can be used include acids or neutralized products. ^ Examples include p-toluenesulfonic acid, twelve Hardened catalysts such as alkyl benzylsulfonic acid, di / nonylcaine, acid 'dinonylnaphthalene disulfonic acid and its amine neutralizer, tin octoate, dibutyltin dilaurate, etc. are representative examples. The above pigments are anti-rust pigments such as strontium chromate, potassium chromate, chromate, calcium chromate, chromic acid, etc., inorganic pigments such as titanium dioxide, carbon black, iron oxide, talc, silica, etc. The constitution pigment can be matched according to the purpose. The above organic solvents used in coatings can be dimethylbenzene, toluene, methyl ethyl ketone, n-butyl acetate, ethyl acetate, methanol, ethanol, cyclohexane stone / solvent-based solvents, solvent oil (minera In organic solvents such as 1 spirit), one or two or more kinds are used in combination according to the type of resin to be applied. The pigment blending amount of 8 2 f coating is based on the solid t weight ratio of the resin component contained in the coating film [Yan Yue material / resin] is 0.6 ~ L 〇, more preferably 0 · 65 ~ 0 · 8 is Shida When the weight ratio is less than 0 · 6, sufficient scratch resistance cannot be obtained, and on the other hand, when it exceeds 1 · 0, sufficient processability cannot be obtained. In addition, the thickness of the primer coating film is 2 or more, and sufficient rust prevention properties cannot be obtained. Film thickness is less than 2 // mth

V. Description of the invention (66) (4) Topcoat film The topcoat film is a coating where the polyester tree and hardener with a number average molecular weight of 5000-2000 are used as the main component resin. The dried film formed was a coating film of 5-30 / ζιη. Wood,. Hai ♦ Shu Yue Yue (E) is mainly an ester compound of polyacid and polyhydric alcohol, and the polyacid and polyhydric alcohol described in the primer coating film are used. The polyester resin (E) of the main resin must have a number average molecular weight of ˜2 ^ 00, preferably 50,000 ~ 150,000. The number of polyester resins (E) is less than 500, and the stretch of the coating film is insufficient, and the processability is reduced. Another: Surface ^^^ 20 0 〇〇 is not good because it imparts damage resistance and weather resistance. Poly ϊ ::: tincture is not particularly limited, and can be used generally as a top coat and / or a polyisocyanate compound. Ester compounds, amine-based resins, and polyisocyanates are the same as those described in the topcoat paint. ; Agents and so on:; :::? Hardening catalysts, pigments, other defoamers, antifoams 2 :::: ^ =: ^ (main resin and hardener) hardylnaphthalenesulfonic acid's-nonylnaphthalene eicosyl-alkylhydrazone, dinon Base ... hardened contact, tin octoate, di-tau, the above-mentioned pigments are the organic heart of titanium dioxide, cyan blue, cyanine, etc ... inorganic pigments such as di-emulsified iron, such as flower-family, alpha stone, silica, etc. 575643 V. Description of the invention (67) Metal powders such as aluminum powder and nickel powder can be matched according to the purpose. The organic solvents used in the coatings can be xylene, methylbenzyl, methyl ethyl ketone, n-butyl acetate, ethyl acetate, methanol, ethanol, cyclohexane, petroleum-based solvents, and solvent oils. In organic solvents such as irit), one or two or more kinds are used in combination according to the type of resin to be applied. The thickness of the topcoat film is 5 ~ 3 0 // m. If the thickness of the coating film is less than 5 // m, sufficient workability and corrosion resistance in the processed portion cannot be obtained. On the other hand, if it exceeds 3 0 // m, the workability is reduced and the cost is increased, which is not preferable. Next, the manufacturing method of the sprayed steel plate of Embodiment 3 is demonstrated. The manufacturing method of Embodiment 3 is a method for manufacturing a spray-coated steel sheet with a molten Al-Zn-based coated steel sheet having an A1 content of 20 to 95% by mass in a mineral film manufactured by a continuous molten plating equipment, etc., The ore film of the steel plate out of the molten ore bath is provided with at least the following steps (a) & (b) thermal history, and a chemical treatment film, a primer coating film and a surface are sequentially formed on the surface of the ore layer steel plate. Steps of paint film. (a) The average cooling rate of the first 10 seconds immediately after the steel plate is out of the molten plating bath is less than 11 ° C / sec. Heat history (b) After the plating metal is solidified, it is heated at 1 3 0 ~ The temperature T (° C) in the range of 3 0 0 ° C is heated up, and thereafter, the average cooling rate from the temperature τ (it) to 100 π is a heat satisfying c (t / hr) or less as shown in (1) below Experience: and / or, the average cooling rate from the range of temperature 3 (C) to 100 C after the solidification of the metallized metal plated by the molten plating layer is C ( ° C / hr) The thermal history below (T-100) / 2

575643

In the thermal history of (a) & (b) given to the arsine plating, the track of (a) is performed by controlling the cooling conditions of the coating immediately after the coating. '' For the mineral film and the thermal history of this (a), as mentioned above, a temperature adjustment device must be installed between the molten plating bath surface of the continuous melting equipment and the time when the steel plate from the molten plating bath first contacts the roll, and the temperature is passed through this temperature. Adjust the equipment to control the speed of the cold section of the plating. As described above, the temperature adjustment device is preferably equipped with heating or = ..., hand #, and is considered to have cooling means, and there are no particular restrictions on the method, shape, scale, etc. of the heating or heat keeping means and cooling means, and mainly The money film may be given the thermal experience of (a) above. As the heating or heat retaining means of the temperature adjusting device, for example, an induction heater and a gas heating furnace can be used, and as the cooling means, a gas blowing device can be used. / Furthermore, the thermal history of (b) above is performed by applying specific heat treatment to the steel plate of the fused layer after the solidification of the bond metal, or by controlling the cooling of the coating after the fused metal of the ore layer is solidified to maintain the heat. . The manufacturing method of the present invention is to sequentially form a specific chemical conversion coating film, a primer coating film and a topcoat film on the coating surface of a coated steel plate, and the heat treatment for applying the heat of the above (b) to the coating film may be performed before the chemical conversion treatment, ② During the drying step of chemical conversion treatment, ③ After the chemical conversion treatment is completed (after the treatment liquid is applied and dried), before the primer coating is sprayed, ④ During the primer coating drying step, ⑤ after the primer coating is completed (the coating After coating and drying), before topcoat spraying, during the drying step of ⑥ topcoat spraying, and at any stage after the topcoat spraying is finished (after coating and drying). In addition, it may be performed in two or more of these stages. Therefore, the thermal history of the coating film imparting (b) can be performed in at least one of the following stages (!) To (8).

575643 V. Description of the invention (69) (1) (2) (3) (4) (5) (6) (7) (8) Remaining treatment, in the drying step of the formation treatment before the formation treatment, after the formation treatment, the bottom The drying step of the primer coating before the spray coating is completed. After the primer coating is finished, the topcoat is sprayed and the front coating is sprayed. In the drying step, the topcoat is sprayed after the topcoat is sprayed. Among the above methods of heat treatment, ②, ④, and ⑥ are particularly economical because of the μ treatment of the towel using chemical conversion, primer coating, and top coat. The heat treatment or heat retention given to the above (b) thermal history is performed by a heating or heat retention device installed inside or outside the continuous coating equipment. Also, the manufactured hot-dip plating ^ —211 series steel plate The preferred J-layer adhesion amount, U), and the reasons for the limitation of the thermal history of the plutonium are as follows. "As for the type of mouth chemical treatment, there is no particular limitation." Organic resin is used as the main component. Yet! General: The processing step is to heat and dry the pancreas with a hot blast stove, induction heater, etc., so the heating and drying of the coating film can be used as described above. /; The primer coating is applied and baked on the upper layer of the chemically treated broken film, and then the top paint is applied and baked on the upper layer to form the primer, coating film and

Page 74 575643 V. Description of the invention (70) Topcoat film. The structure of these primer coating films and topcoat films is as described above. The primer coating and topcoat coating can be prepared by using a disperser and agitator such as ball mill, sand mill, and I-kun mill. The spraying method of the coating material used to form the coating film (primer coating film and topcoat film) is not particularly limited, but roller coating, curtain spraying, etc. are preferred. After the coating is spray-coated, the coating film is baked by a heating hand 4 such as hot air heating, infrared heating, induction heating, etc., and the resin is hardened to obtain the coating film. The baking process when the coating film is heated and hardened is to make the base coating paint reach a maximum plate temperature of 180 ° C ~ 270 ° C, and bake in this temperature range for about 30 seconds to i 2 seconds. grilled. When the board temperature is less than 80 t, the curing reaction of the resin is insufficient, and the damage resistance and financial performance are reduced. On the other hand, when the plate temperature exceeds 27 ° C., the reaction is excessive and the adhesion to the topcoat coating is reduced. And the top coat coating has a maximum plate temperature of 180 ° to 2700 ° C, and at. In this degree range, baking is performed for about 30 seconds to 120 seconds. When the plate temperature is lower than 180 ° C, the resin hardening reaction is insufficient, and the solubility and damage resistance to solvents and chemicals are reduced. When the plate temperature reached 2700 r, the reaction was excessive and workability was reduced. It is also possible to impart the thermal history of (b) to the plating film by using the baking treatment of these coating films as described above. Example 3 A cold-rolled steel plate (thickness: 0.35 mm) manufactured by the ¥ method was prepared in a continuous fusion bond layer δ and a through plate was used. A 55% A1-1.5% Si-Zn bond bath and 40% A1 -1 · were used. 〇% Si-Zn plating bath and 70% A1-1 · 8% Si-Zn plating bath were used for melt coating. The working linear speed is 160m / min, and the amount of coating on one side is equal to that between the steel plates.

C. \ 2D-C0DE \ 91-04 \ 91101646.ptd Page 75 575643 5. Description of the invention (71) The deviation is stable in the range of 75 ~ 90g / m2. Also, a fused aluminum alloy steel sheet of a molten 5% Al-Zn series ore layer of a comparative example (single-side bell layer adhesion amount: 13 g / m2) was also produced. In the manufacturing steps of these plated steel sheets, the coatings are given the thermal history (I) and (II) that are not shown in Tables 丨 to Table 14, and the conditions of the primer coating film and the topcoat film are changed in various ways, and manufactured as follows The sprayed steel plate. The following coating materials are used for the base coating film and the top coating film. (1.1) Preparation of Resin Composition for Primer Coatings • Synthesis Example of Poly Resin Resin 1 p-phthalic acid 2 15 · 8 parts by weight (1.3 mol), isophthalic acid 182.6 parts by weight (1.1 mol ), 189.8 parts by weight of adipic acid (1.3 moles), 124 wounds of ethylene glycol (2.0 moles), neopentyl glycol 1664 weight (ι · 6 moles), "Epic lone 850" (trade name, large Nihon Ink Co., Ltd.) was 3.4 parts by weight, and dioctyltin oxide was 0.1 parts by weight, and the nitrogen gas flow was 240. The reaction was carried out for 2 hours at 0 ° C. Thereafter, the pressure was reduced to 1 mmHg over 1 hour, and the reaction was performed at 260 ° C for 1 hour, and dissolved in sobeso 150 to obtain 35% of a non-volatile component, an average molecular weight of 2000, and glassy state. It is a polyester resin (A1) at a temperature of 10 °. • t S resin synthesis example 2 p-acetic acid 2 15 · 8 parts by weight (1.3 moles), isophthalic acid 182.6 parts by weight (1.1 moles), adipic acid 189.8 parts by weight (1.3 moles), 124 parts by weight of ethylene glycol (2.0 moles), 166.4 parts by weight of neopentyl glycol (1.6 moles), "Epiclone 850" (trade name, manufactured by Dainippon Ink Co., Ltd.) 30.4 weight injury, and oxidation 0.1 parts by weight of dioctyltin under a nitrogen stream at a temperature of 2.4

C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 76 575643 V. Description of the invention (72) 2 hours S reaction. Thereafter, the pressure was reduced to 1 mmHg for 1 hour, and the reaction was further performed at 260 ° C for 20 minutes. The solution was dissolved in solbes 0150 to obtain 35% of a nonvolatile component, an average molecular weight of 16,000, and a glassy state. Temperature 15. 〇。 Polyester resin (A 2). (1.2) Preparation of primer coatings The primer coatings corresponding to the components (p 丨) to (p 7) of the primer coatings in Table 15 are based on the above-mentioned polystyrene resin (A1) or (A2) (not Epoxy resin (rEpiclone 4〇5 () manufactured by Dainippon Ink Co., Ltd.) was blended in the ratio shown in Table 5 and 0.5 parts by weight of triethylamine was added in a nitrogen stream. The reaction was performed at 40 ° C for 2 hours to obtain a resin composition for primer coating. In addition, as for the undercoat paint corresponding to the undercoat film component (p9) in Table 5, epoxy resin (Epic 1 made by Daikoku Ink Co., Ltd.) was used in the polyester resin (A1). 0 5 0 ″) are blended at room temperature in the ratio shown in Table 5. It should be noted that the base coating material corresponding to the base coating film component (P8) in Table 15 was used as it was without reacting the above-mentioned polyester resin (A1) with the epoxy resin. For each of the above-mentioned resin compositions for primer coating, 100 parts by weight, 34 parts by weight of chromic acid, 2.5 parts by weight of aluminum tripolyphosphate, 6 parts by weight of titanium oxide, and "Di spa lone # 1" were added. 83 0 "(trade name, manufactured by Kusumoto Chemicals Co., Ltd.) 〇 · 1 part by weight, and the pigment is dispersed for 4 hours by a glass bead-type high-speed shaker, and the hardener is shown in Table 3 in parts by weight and silane coupling. 3 parts by weight of the mixture was added to the primer coating (p 1) to (p 9) for the purpose of stirring. (2.1) Preparation of resin composition for topcoat coatings • Resin Synthesis Example 3 332 parts by weight of ugly acid (2.0 mol) and 83 parts by weight of isophthalic acid (0.5 mol)

575643 V. Description of the invention (73) '-Ear), 160.6 parts by weight of adipic acid (1 ear), _ Lili 仞 ui ear), 1 36 4 parts by weight of ethylene glycol (2.2 Moore) , 145.6 parts by weight of neopentyl glycol (1.4 moles), and 1 part by weight of dioctyltin oxide G 'under a nitrogen flow t23 (rc for 2 hours under acetic acid. Thereafter, calendar 1 The pressure was reduced to 1 mmHg for one hour, and the reaction was further performed at 26 ° C for 30 minutes, and dissolved in a cyclohexanone / s0lbes 0150 mixed solvent (weight ratio 50/50) to obtain a non-volatile content of 40%, an average Polyimide resin (£ 1) with a molecular weight of 150 () and a glass transition temperature of 18 C. • Resin Synthesis Example 4 332 parts by weight of terephthalic acid (2.0 mol) and 83 parts by weight of isophthalic acid (0.5 mole), 160.6 parts by weight of adipic acid (ι · ιmol), 1364 parts by weight of ethylene glycol (2.2 mole), 145.6 parts by weight of neopentyl glycol (1 · 4 mol), and 0.1 parts by weight of dioctyltin oxide, and subjected to an esterification reaction under a nitrogen stream at 230 for 2 hours. Thereafter, the pressure was reduced to 1 mmHg over 1 hour, and then performed at 260 ° C. 1. 5 hours reaction and dissolve in cyclohexanone / SOBeso 15 0 mixed solvent to obtain polyester resin (E2) with non-volatile content of 35%, average molecular weight of 220 0 0, and glass transition temperature of 10 ° C. (2.2) Preparation of topcoat coating Polyester resin (E1) for topcoat coating ) 4 2 5 parts by weight, inorganic pigments 1 3 3 parts by weight, "Dispalone # 2150" (trade name, manufactured by Kusumoto Chemical Co., Ltd.) 0 · 3 parts by weight The pigment is dispersed in a glass bead type high-speed shaker for 2 hours And added "Banox D55 0" (trade name, made by Dainippon Ink Co., Ltd.) 54.5 parts by weight, and "p〇1 yf 1 ow S" (trade name, made by Kyoeisha Oil Chemical Industry Co., Ltd.) 0. 6 parts by weight, 5 parts by weight of matting agent, and 0.5 parts by weight of polyethylene wax. 'Stirring to obtain the top paint (T1) for the purpose. In addition, the same treatment uses poly

C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 78 575643 5. Description of the invention (74) " " Ester resin (E2), obtain the topcoat paint (T2) shown in Table 16. In each example, after applying a common chromate treatment to each plated steel plate, the primer coating was applied with a bar coater, and the steel plate was baked at a temperature of 2 2 0 and a baking time of 38 seconds, followed by The topcoat paint was applied with a bar coater, and baked at a steel plate reaching 230 ° C and a baking time of 53 seconds. For each of the above spray-painted steel sheets, the workability, the corrosion resistance of the machined portion, and the coating film hardness were evaluated by the following methods. The results and the composition of the sprayed steel sheet are shown in Tables 1 to 14. (1) Workability The inside surface of the sprayed steel plate is sandwiched with a steel plate with a different diameter in a room at 20 ° C, and then it is clamped for 180 °. It was bent, and the coating film of the bent portion was observed with a 30-times magnifying glass, and evaluated on the basis of the following. :: 1 § 〇 was sandwiched between steel plates with a thickness of 0.5 mm. There was no cracking of the coating film during bending. ○: It was sandwiched between steel plates with a thickness of 0 · 7 mm for 1800. No cracking of the coating film occurred during bending. Δ: 180 ° was sandwiched between steel plates having a thickness of 1.0 mm. No cracking of the coating film occurred during the bending X: It was sandwiched by a steel plate with a thickness of 1.0 mm for 180 °. Coating cracks did not occur during bending. (2) Coating hardness Using Mitsubishi Pencil "Uni" and testing in accordance with JIS K 540 0-8 · 4, observe the peeling state of the coating film. In a test using a pencil with a hardness of 3Η, those with little peeling between the coated steel sheet and the coating film on the top layer are regarded as "0".

C: \ 2D-00DE \ 91-04 \ 91101646.ptd Page 79575643 V. Description of the invention (75) In the test using hardness 2 Η wrong pen, there is almost no peeling between the coated steel sheet and the coating film on the head layer It was regarded as "△", and in the test using a pencil with a hardness of 2Η, the case where peeling occurred between the plated steel sheet of the head layer and the coating film was regarded as "χ". (3) Money-resistance of the processing section Cut the sprayed steel plate to 150mm x 70mm, and bend the inner side of the sprayed steel plate with a steel rod with a diameter of 0.75 mm in a 20 ° C room to perform bending processing. After that, the cut end surface and the inside are sealed with a tar epoxy paint to prepare a sample for the resistance test of the processed part. The test was performed under dry and wet repeated conditions according to JIS κ 5 62 1, and after a total of 4,000 cycles in the following cycles, the swelling rate of the coating film was measured. Follow the conditions ... [5% saline spray, 30, 0.5 hours-95% wet, 30 C, 1.5 hours-dry 20% RH, 50, 2 hours-dry 20% RH, 30 ° C, 2 hours "for} times, and repeat the specified number of times. Estimation method: In the bending processing portion except for the width of 50 mm across both ends, the total length in the width direction of the part where the coating film is inflated is expressed in% (for example, there are 2 locations where the 5 mm width of 50 mm is expanded. , Its expansion rate is 20%). The evaluation is as follows. Ma ◎: Expansion rate is less than 10% 〇 · Expansion rate is 10% or more and less than 30% △: Expansion rate is 30% or more and less than 70% X: Expansion rate is 70% or more Right according to Table 1 1 ~ Table 14 shows that the sprayed steel sheet of the example of the present invention has good properties in terms of addition, corrosion resistance of the processed part, and hardness of the coating film. The comparative example is inferior to the examples of the present invention in any of the characteristics. .

C: \ 2D-C0DE \ 91-04 \ 91101646.ptd P.805755643 V. Description of the invention (76) Distinguish 1_ Examples of the present invention Examples of the present invention Examples of the present invention Examples of the present invention Examples of the present invention Examples of the present invention | Examples Invention Example • 4ΠΠ Pencil hardness 〇〇〇〇〇〇〇〇 Corrosion resistance of the processed part ◎ ◎ ◎ ◎ ◎ 〇〇 Workability ○ ◎ ◎ ◎ ◎ ◎ ◎ Coating thickness of sprayed steel plate topcoat film (// m) cn mmmmr〇m Junbu tlmlj pu jygn rH tH rH rH — TH rH rH Primer coating film thickness (// m) Inch inch Inch inch Inch inch Μ rH 1—H 1-H T- ^ Type * 6 1_ s S 5 : S s P: s S Thermal history (II) * 2 Heat treatment practice | application stage "T— (tH t—H (N tH average cooling rate (° C / hr) * 4 (N m 〇0000 m CN m CN (N heating temperature (° 〇 * 3 280 § TH 240 iT) oo rH 〇rH S TH g T—H —M _ 8 oo inch 00 00 〇〇 coating composition 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5% Si 40% Al-1.0% Si 70% Al-1.8% Si No. rH m inch 00 C: \ 2D-C0DE \ 91-04 \ 91101646.pt d p. 81 1111 575643 V. Description of the invention (77) * 1 The average cooling rate of the coating in 10 seconds immediately after the steel plate is out of the molten plating bath * 2 The heat imparted by the heat treatment performed after the coating of the molten coating is solidified After * 3 heating and heating temperature of the coating during heat treatment * 4 Average cooling rate of the coating during heating and heating up to 100 ° C * 5 (1): before chemical conversion treatment (2): after chemical conversion treatment, primer coating spraying Front (3): After spraying the topcoat * 6 Table 1 5 shows the composition of the base coating film composition mark * 7 Table 1 6 shows the composition of the top coating film composition mark

C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 82 575643 V. Description of the invention (78)

Distinguish the present invention examples Inventive examples Inventive examples Inventive examples Inventive examples Inventive examples Inventive examples A3U # 1 Pencil hardness 〇〇〇〇〇〇〇 Processing part corrosion resistance ◎ ◎ 〇 ◎ ◎ ○ Processability ◎ 〇 ◎ ◎ ◎ 〇 Coating thickness of sprayed steel plate topcoat film (/ zm) Γ〇m rn Type * 7 ^ rH i—Η rH pj iH rH Base coating film thickness (" m) inch inch inch inch inch 0 inch 00 〇 < N T * H τ— < rH r * H Type * 6 CS Pm cn Oh 2 Oh S 5: 5: Thermal history (Π) * 2 Implementation stage of heat treatment * 5 r " H fH ▼ -H Average cooling rate (° C / hr) * 4 m CO CN cn CN CN m CN < N m CN Heating temperature (° 〇 * 3 180 ggr * H 180 gg § τ · Η —m * s |? 1 | δ o 〇〇o 〇o 〇 Coating composition 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5 % Si 55% Al-1.0% Si No. 〇 \ o τ-Ή rH m inch rH C: \ 2D-C0DE \ 91-04 \ 91101646.ptd page 83 575643 5. Description of the invention (79) * 1 The average cooling rate of the coating in 10 seconds immediately after exiting the molten plating bath * 2 Heat history due to the heat treatment performed after the coating of the molten coating is solidified * 3 The heating temperature of the coating during the heat treatment * 4 The average cooling rate of the coating during the heat treatment up to 100 ° C * 5 (1) : Before chemical conversion treatment (2): After chemical conversion treatment, before primer spraying (3): After topcoat spraying * 6 Table 15 Primer coating film composition symbols shown in Table 5 * 7 Table 16 Topcoat Coating composition mark

C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 84 575643 V. Description of the invention (80) Distinguish comparative examples, comparative examples, comparative examples, comparative examples, comparative examples, comparative examples | Performance. Pencil hardness 〇〇〇 〇〇X 〇X Corrosion resistance of the machined part <] X < X <] < <] X 丨 Workability < XXX < ◎ X ◎ Coating thickness of sprayed steel plate top coat film ro 2 2 2 type * 7 rH 1-4 i-Η TH a τ—Η, thickness of base coat film (// m) inch inch inch inch inch inch f '4 fH τ-Η 〇 1 type * 6 S s 5: S sv〇Oh £ οο Ρη Thermal history (Π) * 2 Implementation stage of heat treatment * 5 tH r—Η An average cooling rate (° C / hr) * 4 2 00 m CN CN m CN Heating temperature (° 〇 * 3 § 330 s 1-* ^ 265 1 " < § 180 § -_ h Μ-® f §] mb ki 〇0000 00 〇〇〇oo Coating composition i 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5% Si 55% Al-1.5% Si d τ— (CN m inch 卜 00 C: \ 2D-CODE \ 91-04 \ 91101646.ptd page 85__1 575643 five Description of the invention (81) * 1 The average cooling rate of the coating film in 10 seconds immediately after the steel plate is out of the molten plating bath * 2 The heat history imparted by the heat treatment performed after the coating of the molten plating layer is solidified * 3 The temperature of the coating is increased during the heat treatment Heating temperature * 4 Average cooling rate of the coating during heating up to 100 ° C * 5 (1): before chemical conversion treatment (2): after chemical conversion treatment, before primer coating (3): topcoat spray After coating * 6 Table 1 5 shows the base coating film composition symbols * 7 Table 1 6 shows the top coating film composition symbols

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C: \ 2D-CODE \ 91-04 \ 91101646.ptd P.875755643 V. Description of the invention (83) * 1 The average cooling rate of the coating film for 10 seconds immediately after the steel plate is out of the molten plating bath * 2 Heat history due to the heat treatment performed after the coating is solidified * 3 The heating temperature of the coating during the heat treatment * 4 The average cooling rate of the coating during the heat treatment to 100 ° C * 5 (1): Chemical conversion treatment Before (2): After chemical conversion treatment, before primer spraying (3): After topcoat spraying * 6 Primer coating film composition symbol shown in Table 1 5 * 7 Table 16 Topcoat coating film composition shown in Table 6 mark

C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 88 575643 V. Description of the invention (84) Table 15 [Bottom coating film composition] Marker base resin resin hardener polyester resin modified resin type * 1 number Compound amount in the average molecular type Compound amount P1 Polyester resin (A1) 20000 251 Epoxy resin * 2 12 Melamine resin * 3 26 P2 Polyester resin (A1) 20000 257 Epoxy resin * 2 10 Melamine resin * 3 26 P3 polyester resin (A1) 20000 214 epoxy resin * 2 25 melamine resin * 3 26 P4 polyester resin (A2) 16000 243 epoxy resin * 2 15 melamine resin * 3 26 P5 polyester (A1) 20000 251 epoxy resin * 2 12 polyisocyanate compound * 4 33 P6 polyester resin (A1) 20000 269 epoxy resin * 2 6 melamine resin * 3 26 P7 polyester resin (A1) 20000 180 epoxy resin * 2 37 Melamine resin * 3 26 P8 Polyester resin (A1) 20000 286--Melamine resin * 3 26 P9 Polyester resin (A1) 20000 251 Epoxy resin * 5 12 Melamine resin * 3 26 Page 89 C: \ 2D-CODE \ 91-04 \ 91101646.ptd '575643 5. Description of the invention (85) The polyester resins (Al) and (A2) described in Synthesis Examples 1 and 2 of Wood 1 polyester resin. "Epic lone 40 50" (manufactured by Dainippon Ink Co., Ltd.) was allowed to react with polyester resin at 140 ° C for 2 hours under the presence of triethylamine. Factory Super Becamine L117 "(made by Daiyoshi Ink (stock) Co., Ltd., does not emit 60%). "Banox D5 50" (made by Dainippon Ink Co., Ltd., non-volatile content 55%). "Epic lone 405 0" (manufactured by Dainippon Ink Co., Ltd.) was mixed with polyester resin at room temperature. In the coating materials (P1) to (P9), 34 parts by weight of chromic acid, 2.5 parts by weight of aluminum phosphate, 6 parts by weight of titanium oxide, and "D1Spal〇ne" are added with respect to the main agent resin. # 1 830 "(made by Kasei Kasei Co., Ltd.) 0 · 1 part by weight and 3 parts by weight of the dream-fired coupling agent. The "mixing amount" described in the table is a weight part including a volatile component. In addition, the blending amount of the hardener is 氺 2 * 3 氺 4 * 5 parts by weight based on 100 parts by weight of the main resin. Table 1 6 [Topcoat film component] Mark the main agent resin hardener type * 1 Number average Molecular weight τι Polyester (E1) 15000 T2 Polyester (E2) 22000 C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 90 575643 V. Description of the invention (86) * 2 * 1 Resin synthesis examples 3 and 4 The polyester resins (E1) and (E2) described in the above. "Banox · D550" (manufactured by Dainippon Ink Co., Ltd., non-volatile content 55%) ※ 133 parts by weight of titanium dioxide and "DiSpal〇ne # 2150" (Nanmoto Chemicals ( 3 parts by weight), 0.6 parts by weight of "Poly flow S" (manufactured by Kyoeisha Oil Chemical Industry Co., Ltd.), and 0.5 parts by weight of polyethylene wax. ※ The "combination amount" is a weight part including volatile components in the fourth embodiment. The surface-treated steel sheet in the fourth embodiment is a hot-dip plated A 1-Zη-based steel plate containing 20 to 95 mass% A1 in the coating film as a head layer. Steel plate. From the standpoint of remanence, etc., the more preferable range of the amount of A1 in the plating film is 45 to 65% by mass. The most preferable composition of the coating is Al: 45 to 65% by mass, Si: 07 to 2.0% by mass, Fe: less than 10% by mass, and the remaining portion is substantially Zn containing unavoidable impurities. Particularly in the case of such a composition, excellent residual resistance can be exerted. However, this molten bell A 1 -Zn steel sheet is only composed of this bond layer, and it is difficult to obtain high machining part residual resistance. The excellent processed part corrosion resistance can be obtained only through the thermal history described below and the combination of the upper layer and the compound treatment film. Sex. Also, there is no particular limitation on the amount of ore deposits on this smelting ore A 1-Zn 糸 steel plate, but generally it is appropriate to use about 30 to 2000 g / m2 per side. In the surface-treated steel sheet of the fourth embodiment, the chemical conversion treatment film formed on the forged film surface is selected from one or more chromic acid compounds containing complex acid, complex salt compound, and a part of chromic acid, and is thermosetting. After applying the chromate treatment solution of organic resin, it is dried at a plate temperature of 1 3 to 3 0 ° C.

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= For the obtained film, the mass ratio (A) / (B) of the amount of organic resin (A) contained in the film to the amount of Cr converted into the metal complex ") must be 1 or more and less than 200 ' It is preferably 50 or more and 150 or less, and a conversion treatment film converted into metallic chromium having a Cr content of 0.00 / m or more and less than 100 mg / m2, and preferably 5 mg / m2 or more and below. If the amount of Cr converted to metallic chromium is less than 0.1 mg / m2, the corrosion resistance of the processed portion cannot be sufficiently improved. On the other hand, if the amount of Cr is 100 mg / f2 or more, the effect of improving the corrosion resistance of the processed portion is saturated, and On the one hand, the Cr fixation rate decreases due to the increase in ^ $, which impairs the environmental compatibility. In addition, Embodiment 4 mixes an organic resin in the chemical conversion treatment film for the purpose of improving the corrosion resistance of the processed part, but the organic resin must be thermally hardened. 1 ± Organic tree knowing. When continuous roll forming is performed on the surface-treated steel sheet, the roll temperature is greatly increased. When the organic resin contained in the chemical conversion treatment film is a common thermoplastic resin and a general latex resin, The rise of the roller temperature causes damage to the film, which causes processing The appearance is deteriorated. Therefore, in order to solve such problems, it was reviewed that the use of thermosetting resin as the resin blended in the film can greatly improve the damage resistance at high temperatures. As a result, even in continuous roll molding During processing, there will be no problems after processing. Here, the term “crosslinking reaction grease, polyester resin, polymerizable resin, etc., such as the addition or condensation polymerization of organic polymers that generate thermosetting materials” refers to The resins through the shape-functional side chains react with each other, or use the main chain or the resin, the thermosetting amino resin, the heating during the formation of the film, or the radical of the double bond between the organic polymer and the hard side chain Resin can use alkyd resin, epoxy resin

575643 5. Description of the invention (88) One or more of grease, styrene resin, or their modified resin. Among them, polyester resins, polyurethane resins, and acrylic resins are particularly preferred from the viewpoint of processability. The thermosetting resin described above includes a water dispersion system and a solvent system, and both of them can be used. Moreover, in such a chemical conversion treatment film, if the mass ratio (A) / (B) of the amount of organic resin (A) to the amount of C r (B) converted into metallic chromium is less than 1, the organic resin cannot be sufficiently improved. The effect of the processing department on the resistance to I insects. On the other hand, if the mass ratio (A) / (B) is 200 or more, the effect of improving the corrosion resistance of the processed portion due to Cr cannot be sufficiently obtained. When forming a chemical treatment film, the drying temperature after coating the chromate treatment solution is less than 130 ° C, the temperature cannot be used to form a suitable chemical treatment film. On the other hand, if it exceeds 3, 〇〇 It is because the coating film is heated more hot, and promotes the alloying reaction, which may reduce the workability. The surface-treated steel sheet of Embodiment 4 is formed with a general chromate film on the coating surface, and the above-mentioned specific chemical treatment film may be formed on the upper layer. In this case, the chemical treatment film is composed of a two-layer film. It is expected that More improved corrosion resistance. At this time, the composition and the like of the chromate film formed on the lower layer side are not particularly limited, and a known composition may be applied to a generally plated steel sheet. An organic resin can be arbitrarily added to the chromate film, but it does not generally contain an organic resin. : Be: In the surface-treated steel sheet of Form 4, in order to give specificity to the coating film: T is contained in the chemical conversion treatment film after the formation of the chemical treatment film, and the characteristics of the organic resin 1 5 < Lattice i is effective for adding inorganic additives (fine particles) to the chemical conversion coating and to the moon / middle glands. i machine page 93C: \ 2D-CODE \ 91-04 \ 91101646.ptd 575643 5. Description of the invention (89) ---- Additives can be mixed with silica, phosphoric acid-based compounds, silicic acid compounds (such as Ca salt ' Mg salt) and the like. In the surface-treated steel sheet according to the fourth embodiment, it is preferable that the molten A 1-Zn-based coated steel sheet ore film is subjected to at least the following (a) and (b) thermal history and is subjected to such (a) and (b) ) Forming the above-mentioned specific, chemically-treated coating on the surface of the plated film subjected to heat, particularly excellent processability and processing properties can be obtained. σ Insect (a) The average cooling rate of the first 10 seconds immediately after the hot-dip plating of the steel plate is less than 11 / sec. Heat history Ύ (b) After the metal plating of the molten plating layer is solidified, the temperature ranges from 1 to 3 to 3 〇 0 ° C range temperature T (° C) heating and heating, and thereafter, the temperature T (. 0 to 100) and the flat $ cold section speed is to satisfy C (. (3 / hr) The following thermal history, and / or the temperature range from 130 to 300 after the solidification of the bond metal of the molten ore layer, from the temperature T (° C) to 100, the average cooling rate so far is to satisfy the following formula The thermal history below C (° C / hr) is shown as 〇 (T-1 00) / 2. In the thermal history of (b) above, the better range of temperature D (.0) is 1 3 0 ~ 2 0 0 ℃. ", And the grade is made by making the film through the thermal experience of (a) and (b) above, then it can become a Xuanrongzhong A 1 -Zn series coating, and its processability (crack resistance, etc.) ) Significant improvement. Next, 'the manufacturing method of the surface-treated steel sheet according to the fourth embodiment will be described. The manufacturing method of the fourth embodiment is produced by a continuous molten plating equipment or the like.

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575643

In addition, the method of forming the metal after the plating method is suitable for the shape of the film, and any of the methods of the film can be a gas blowing device. The above-mentioned (b) heat history is performed by subjecting the gold-plated steel plate to be melt-plated to specific heat treatment or controlling the cooling of the coating after the mouth is solidified to maintain heat.纟 =

In order to form a special chemical treatment coating on the ore film surface of the ore plate, the heat treatment of the above (b) heat treatment can be performed in ① formation treatment: ② in the drying step of the formation treatment film, ③ formation treatment After the formation (the application of the treatment solution and the formation of the drying step), the process is performed. In addition, it may be performed in two or more of these stages. The thermal history imparted to the coating film (b) can be performed in one of the following stages (1) to (4). (1) Before the formation of the chemical conversion treatment film (2) During the drying step of the chemical conversion treatment film (3) After the chemical conversion treatment film is formed (4) The cooling process after the solidified metal plating of the bond bond layer is solidified

Among the above methods for heat treatment, the method of ① has the advantage of independently optimizing each condition of the heat treatment step and the formation treatment step, and the methods of ② and ③ are suitable for use in continuous molten plating equipment Perform all processing. In addition, since the method of (2) is heat treatment by heating in the drying step of the chemical conversion treatment, it is particularly economical. "Still, the preferred composition of the manufactured hot-dip A1-Zri-based steel sheet, the coating adhesion amount, the reasons for the limitation of the above (a) and (b) thermal history, and the effects obtained are as described above. In the manufacturing method, for the coating surface of the coated steel plate,

575643 V. Description of the invention (92) One or more chromate treatment liquids containing thermochromic organic resin are selected from the group consisting of chromic acid, chromate compounds, and a part of chromic acid compounds to be reduced. Dry at a temperature of 130 ~ 300 ° C, so that the mass ratio (A) / (B) of the amount of organic resin (A) contained in the film to the amount of Cr (B) converted into metallic chromium is 1 or more and When it is over 200, preferably 50 or more and 150 or less, the amount of Cr converted into metallic chromium is 0-1 mg / m2 or more and less than 100 mg / m2, preferably 5 mg / m2 or more and 40 mg / m2 or less. Handle the film. This chromate treatment is a method in which a chromate treatment liquid is applied to the surface of a coated steel sheet, and is usually dried without being washed with water.

In addition, in the manufacturing method of the fourth embodiment, after a general chromate treatment is applied to the plating surface, a film can also be formed on the upper layer through the specific chromate treatment described above. In this case, a two-layer film Of the chemical treatment coating. On this date, the chromate treatment on the lower layer side can be performed according to the well-known processing conditions generally applied to the ore-layer steel sheet. Example 4-1 A cold-rolled steel plate (plate thickness: 0.5 mm) produced by a conventional method was prepared on a continuous hot-melt plating layer 5 and a through-pass plate was used, and the hot-rolled coating was performed using a 55% A1 -1 · 5% Si-Zn plating bath. The working linear speed is 160m / min, and the amount of single-sided coating adhesion is 75g / m2.

In the manufacturing step of the coated steel sheet, the coated film is given a thermal history with an average cooling rate of 15 t / sec immediately after the steel sheet is out of the coating bath, and a chemical conversion treatment is applied to the coated surface. The following materials were used as organic resins for adding a chemical conversion treatment film. [A] Thermosetting resin (main resin, polyester polyester amino latex resin, hardener: isocyanate hardener)

C: \ 2D-CODE \ 91-04 \ 911O1646.ptd P.975755643 V. Description of the Invention (93) (b) > Thermosetting resin (main resin: acrylic latex resin with tertiary amine group and carboxyl group Hardener: epoxy silane compound with both alkoxysilyl group and epoxy group) (c) Thermoplastic resin (MMA-MA type acrylic latex resin) (d) Thermoplastic resin (polyester urethane Latex resin) A treatment liquid in which any of the above-mentioned organic resins and chromic acid are mixed at a specified ratio, the plated steel sheet surface is coated to a specified amount of Cr adhesion, and dried up to a plate temperature of 160 ° C. For the surface-treated steel sheet manufactured in this way, the corrosion resistance, roll formability, and fixation rate of the processed portion were evaluated according to the following methods. The results and chemical conversion treatment conditions are shown in Table 7. (1) The survivability of the machining department is 5T. The surface-treated steel plate is bent to 5T. The test is carried out with salt water spray. The appearance of rust in the bent portion after 500 hours is observed. The benchmark is evaluated. According to the following ◎: no abnormality (the area ratio of rust occurrence is less than 10%) 〇: there is a slight occurrence of white rust and black rust (the area ratio of rust occurrence is less than 25%) and there is white rust, Occurrence of black rust (rust occurrence area rate of 25% to 80%) Heman X: Significant white rust and black rust occurrence (rust occurrence area rate of 80% with (2) roll forming processability; for 30mm X 30 0 Guan Zhi surface-treated steel plate, using a stretching machine at a mold temperature of 80 ° C and a welding load of 100 kg = ^ C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 98575643 Five 2. Description of the invention (94) A folding test, and visually observe the appearance after drawing, and evaluate it as follows: Standard ◎: Blackened area is less than 1 Q%, and no film peeling matter is attached to gold, ,, 衩 /, 〇 ... The blackened area is more than 10% and less than 25%, or the film peeling is slightly attached to the eight molds; 1 △: The blackened area is more than 25% and less than 5 0%, or the film peeling has significant adhesion to the eight molds; * X: the blackened area is more than 50%, or there is a significant "bite mark" on the surface of the coated steel plate ^ (3) Cr Fixation rate The surface-treated steel sheet was immersed in boiling water for 30 minutes, and the amount of Cr adhered thereto was measured by fluorescent X-rays. The residual rate (%) of Cr was determined as the solid rate, and it was determined based on the following criteria. Evaluation.

◎ 〇 △ X C r Survival rate above 95% Cr Survival rate above 85% and under 95% Cr Survival rate above 75% and under 85%

575643 V. Description of Invention (95) Table 17

No. Chemical conversion treatment film performance classification Organic resin Organic resin / Cr * 3 Cr adhesion amount (mg / m2) Corrosion resistance of the roll forming process section Type of Cr fixing rate * 1 Hardening dose "1 ⑷ 10 100 20 ◎ ○ ◎ Examples of the present invention 2 ⑷ 0 100 20 X Δ ◎ Comparative Example 3 (b) 10 100 20 ◎ ○ ◎ Inventive Example 4 (b) 0 100 20 X △ ◎ Comparative Example 5 (a) 10 — 0 Δ X — Comparative Example 6 (a ) 10 50 80 〇〇 Inventive Example 7 (a) 10 50 150 Δ OX Comparative Example 8 — — — 20 XXX Comparative Example 9 (a) 10 150 20 OO Inventive Example 10 (a) 10 300 20 Δ △ 〇 Comparative example 11 (c) — 100 20 Δ X 〇 Comparative example 12 ⑼ — 100 20 Δ Δ 〇 Comparative example drawing! Hidden C: \ 2D-C0DE \ 91-04 \ 91101646.ptd Page 100 575643 Five 2. Description of the invention (96) * 1 (a) to (d) * 2 described in the description of this specification * 2 100 parts by weight of the hardener based on the main resin resin * 3 parts by weight of the organic resin (A) and conversion into The mass ratio (A) / (B) of the cr amount (B) of metallic chromium ※ The underlined symbols or values are outside the scope of the present invention. 〇. 5mm) Pass through the plate in a continuous molten coating equipment, and use 55% A1-1.5% Si-Zn plating bath (No. · 1 ~ No.11, No.14 ~ No. · 25 of Table 2 ~ Table 5 ), 40% A, 1.0% Si-Zn plating bath (No. 13 in Table 18 and Table 19) for melt coating. The working linear speed is 160 m / min, and the coating amount on one side is 75 g / m2. Here In the manufacturing steps of the ore-layer steel plate, the coating film is given the thermal history shown in Tables 8 and 20, and the coating surface is subjected to chemical conversion treatment. The organic resin for adding the chemical conversion treatment film is used and Example 4-丨The same substance. A treatment solution in which the organic resin and chromic acid are mixed at a specified ratio, a specified amount of Cr is applied to the surface of the plated steel sheet, and the plate is dried at a maximum temperature of 600 ° C. For the surface-treated steel sheet, the moldability and cr fixation rate were evaluated in the same manner as in Example 4-1, and the processability and the surplus of the processing department were evaluated according to the following methods. As a result, the thermal history imparted to the plating film, and the chemical conversion treatment The conditions are shown in Tables 2 to 5. 〇 (1) Workability The surface-treated steel sheet was bent at 0T. 0T crack was observed and this curved distal portion

575643 V. Description of the invention (97) and evaluated according to the following criteria. 5: No crack was observed even when observed with a magnifying glass of 20 times. 4: No cracks were observed when visually observed, but cracks were observed when viewed with a magnifying glass of 20 times. Visual inspection revealed cracks. Visual inspection revealed cracks in the large openings. Cracking occurs with peeling. (2) I insect properties in the processing department # After the surface-treated steel plate was bent at 3T, it was installed in a salt water spray tester, and the state of rust occurrence in the bent portion after 500 hours was observed, and evaluated according to the following criteria. No abnormality. Some mild white rust and black rust occurred. All mild white rust and black rust occurred. All significant white rust and black rust occurred. Red recording occurred.

91101646.ptd Page 102 575643 V. Description of Invention (98)

No. Coating composition heat history (I) * 1 Average cooling rate (° C / sec) Thermal history (II) * 2 Differentiated heating temperature (° C) * 3 Average cooling rate (° C / hr) * 4 Implementation stage * 5 1 55% Al-1.5% Si 15 180 19 (2) Comparative example 2 55% AM.5% Si 8 330 50 (2) Comparative example 3 55% Al-1.5% Si 8 105 20 ⑺ Comparative example 4 55% Al-1.5% Si 8 265 85 ⑺ Comparative Example 5 55% Al-1.5% Si 8 165 45 (2) Comparative Example 6 55% Al-1.5% Si 10 280 52 (2) Inventive Example 7 55% Al-1.5 ° / 〇Si 10 180 23 (2) Inventive Example 8 55% Al-1.5% Si 4 145 18 (2) Inventive Example 9 55% Al-1.5% Si 4 240 58 Inventive Example 10 55% Al-1.5% Si 8 185 15 ⑴ Inventive Example 11 55% Al-1.5% Si 8 170 22 (3) Inventive Example 12 40% Al-1.0% Si 9 140 15 (2) Inventive Example 13 70% Al -1.8% Si 7 230 60 (2) Example of the present invention * 1 The average cooling rate of the coating film of 10 seconds immediately after the molten steel plating bath is discharged * 2 The heat treatment performed after the coating of the molten coating is solidified Thermal history * 3 Heated heating temperature of coating during heat treatment * 4 Average of heat-treated heating temperature to 100 ° C during heat treatment Cooling rate * 5 (1): before the chemical conversion treatment (2): (3) chemical conversion treatment: drying step of chemical conversion treatment with the bobbin thread ※ symbols or values outside the range of the present invention

Page 103 C: \ 2D-mDE \ 91 -04 \ 91101646.ptd 575643 V. Description of the invention (99) Table 19

No. Chemical treatment film Processability Processing section Corrosion resistance Moldability Cr Fixation rate Classification Organic resin Organic resin / Cr * 8 & Adhesion (mg / m2) Type * 6 Hardening dose * 7 1 ⑻ 10 100 20 2 1 ◎ ◎ Comparative Example 2 ⑻ 10 100 20 3 3 ◎ 比较 Comparative Example 3 ⑷ 10 100 20 3 3 ◎ 比较 Comparative Example 4 ⑻ 10 100 20 3 3 ◎ 比较 Comparative Example 5 ⑻ 10 100 20 3 3 ◎ ◎ Comparative Example 6 ⑻ 10 100 20 4 4 ◎ ◎ Inventive Example 7 (a) 10 100 20 5 4 ◎ ◎ Inventive Example 8 ⑷ 10 100 20 5 4 ◎ ◎ Inventive Example 9 (a) 10 100 20 4 4 ◎ ◎ Inventive Example 10 ( a) 10 100 20 5 5 ◎ ◎ Inventive Example 11 (a) 10 100 20 4 4 ◎ ◎ Inventive Example 12 (a) 10 100 20 4 4 ◎ ◎ Inventive Example 13 (a) 10 100 20 4 4 ◎ ◎ Examples of the present invention * 6 (a) to (d) * 7 described in the description of the specification * 7 parts by weight of the hardener based on 100 parts by weight of the main resin * 8 the amount of organic resin (A) and the amount converted into metallic chromium Cr content (B) Mass ratio (A) / (B) ※ Underlined symbols or values are outside the scope of the present invention

Page 104 C: \ 2D-CODE \ 91-04 \ 91101646.ptd 575643 V. Description of the invention (100)

No. Coating composition thermal history (I) * 1 Average cooling rate (° C / sec) Thermal history (II) * 2 Differentiated heating temperature (° C) * 3 Average cooling rate (° C / hr) Μ Implementation of heat treatment Stage "14 55% Al-1.5% Si 10 180 23 (2) Example 15 of the present invention 15 55% Al-1.5% Si 10 180 23 (2) Comparative example 16 55% Al-1.5% Si 10 180 23 (2) This Invention Example 17 55% Al-1.5% Si 10 ISO 23 (2) Comparative Example 18 55% Al-1.5% Si 10 180 23 (2) Comparative Example 19 55% Al-1.5% Si 10 180 23 (2) The present invention Example 20 55% AM.5% Si 10 180 23 (2) Comparative Example 21 55% Al-1.5% Si 10 180 23 (2) Comparative Example 22 55% Al-1.5% Si 10 180 23 (2) Example of the present invention 23 55% Al-1.5% Si 10 180 23 ⑺ Comparative Example 24 55% Al-1.5% Si 10 180 23 (2) Comparative Example 25 55% Al-1.5% Si 10 180 23 (2) Comparative Example * 1 The average cooling rate of the coating film in 10 seconds immediately after the hot-melt bath is discharged * 2 The heat history imparted by the heat treatment performed after the coating of the hot-melt coating is solidified * 3 The heating temperature of the coating during heat treatment * 4 Average cooling rate of coatings up to 100 ° C * 5 (1): chemical conversion Before treatment (2): (3) chemical conversion treatment: drying step of chemical conversion treatment with ※ baseline values outside the range of the present invention

C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 105 575643 V. Description of Invention (101) Table 21

No. Chemical treatment coating processability processing section corrosion resistance roll moldability Cr fixation rate classification organic resin organic resin / & * 8 Cr adhesion amount (mg / m2) type * 6 hardening dose * 7 14 ⑻ 10 100 20 5 〇 ◎ ◎ Inventive Example 15 ⑻ 0 100 20 5 XX ◎ Comparative Example 16 (b) 10 100 20 5 ○ ◎ Inventive Example 17 (b) 0 100 20 5 XX ◎ Comparative Example 18 (a) 10 — 0 5 XX- Comparative Example 19 (a) 10 50 80 5 〇00 Inventive Example 20 (a) 10 50 150 5 〇ΔX Comparative Example 21 — —-20 5 XXX Comparative Example 22 (a) 10 150 20 5 〇〇 本Invention Example 23 (a) 10 300 20 5 Δ Δ 〇 Comparative Example 24 (c) — 100 20 5 XX 〇 Comparative Example 25 ⑹ — 100 20 5 Δ △ 〇 Comparative Example * 6 (a) described in the description of this specification (D) * 7 parts by weight with respect to 100 parts by weight of the hardener of the main component resin * 8 mass ratio (A) / (B) of the amount of organic resin (A) to the amount of C r (B) converted into metallic chromium ) ※ The underlined symbols or values are outside the scope of the present invention

Page 106 C: \ 2D-OODE \ 91-O4 \ 91101646.ptd 575643 V. Description of the Invention (102) Example 4-3 The cold-rolled steel plate (sheet thickness: 0.5mm) manufactured by the conventional method was continuously melted. The plating equipment is used to pass through the plate and 55% A1 -1 · 5% si-Zn plating bath is used for melt coating. Working linear speed is 160m / min. The single-sided ore deposit is m2 °

In the step of manufacturing the bell layer steel sheet, the coating film is given the heat history shown in Table 22, and the coating surface is subjected to chemical conversion treatment. The chemical conversion treatment conditions were a combination of the resin (b) used in Example 4-1 (100 parts by weight with respect to the base resin and 10 parts by weight of the hardener) and chromic acid at an organic resin / Cr = 1/1100. The mixing solution of the ratio 'coated on the surface of the ore layer steel plate is coated with Cr: 20 mg / m2, and dried at a maximum temperature of 160 ° C. For the surface-treated steel sheet thus manufactured ', the workability (crack resistance) and the corrosion resistance of the processed portion were evaluated in the same manner as in Example 4-2. As a result, the thermal history imparted to the plating film is shown in Table 22. Table 22

No. Coating composition heat history (I) * 1 average cooling rate (° C / sec) heat history shell) * 2 processability corrosion resistance temperature rise heating temperature (° 〇 * 3 average cooling rate (° C / hr) * 4 Implementation stage of heat treatment * 5 1 55% Al-1.5% Si 10 250 55 (2) 4 4 Inventive Example 2 55% AM.5% Si 10 170 27 (2) 5 4 Inventive Example

C: \ 2D-CODE \ 91-04 \ 9n01646.ptd P.1075755643 V. Description of the Invention (103) * 1 The average cooling rate of the coating film in 10 seconds immediately after the steel plate is out of the molten plating bath * 2 Heat history due to the heat treatment performed after the coating is solidified * 3 The heating temperature of the coating during the heat treatment * 4 The heating temperature during the heating to 10 (the average cooling rate of the coating up to TC * 5 (1)): before the chemical conversion treatment (2): After the chemical conversion treatment (3) ... Drying steps of chemical conversion treatment

C: \ 2D-C0DE \ 91-04 \ 91101646.ptd P.108575643 V. Description of the invention (104) The surface-treated steel sheet of male yoke form 5 is a molten plated A 1 with a coating film containing 20 to 95 mass ^ 4 -Zii series steel plate as the first layer steel plate. From the viewpoint of corrosion resistance and the like, the more preferable range of the amount of A1 in the money film is π to π mass%. The most preferable composition of the coating is A 1 ·· 4 5 to 65% by mass, s i · f) 7% by mass and Fe ·· is less than! . In the case of such a composition, especially the mass%, the residual portion, and the unavoidable Zn η 7: are contained, and Zη can exhibit excellent erosiveness. However, this hot-dip A 1 _Zη-based steel sheet is only composed of this coating layer. [B] = Obtaining the corrosion resistance of the two processed parts, and the excellent corrosion resistance of the processed part can be obtained through the thermal history described below and the compound coating on the upper layer. Second, there is no particular limitation on the coating adhesion amount of this hot-dip AI-Zη-based steel sheet: Generally, it is appropriate to use about 30 to 200 g / m2 per side. In the surface-treated steel sheet of the fifth embodiment, the treatment film formed on the coating surface is converted to metal chrome with the above and less than 100 mg / m2, preferably ⑽ "2 or more and * It is a chromate coating film below m, a coating film formed with the upper layer thereof, and the film thickness of the 82-curable organic resin as the resin for forming the coating film is 0.1 to 5 乂 it is 0.5 to 3 # m of the organic resin The film is composed of salt. In order to improve the corrosion resistance by blunting the surface of the coating by 0.1 mg / m2, the effect of improving the corrosion resistance is not sufficient, and the content is less than 100 mg / m2. Then, not only the combined adhesion amount Γ and the neodymium resistance effect cannot be obtained, but also the appearance quality is lowered due to coloring. &Amp; Poor & In this chromate film, silica can be added to improve the organicness with the upper layer.

I Page 109C: \ 2D-C0DE \ 91-04 \ 91101646.ptd 575643 V. Description of the invention (105) Adhesiveness of the resin film, and obtaining chemical treatment ^ When heat treatment is performed on specific heat, prevent The film performs an imparting effect. The type of added Shi Xi stone, in order to improve the treatment of silver coatings with reduced silver resistance, the effect of dry silica is = the adhesion with the upper resin film is reduced in terms of corrosion resistance, in terms of wetness. 'From the prevention of heat, if you choose the type of silica added ^ "f has a greater effect. Therefore, the ratio of solid content in the coating is 1 to 50. The expected amount of silica added is%. Shell 1, preferably 5 to 30 mass, can be appropriately added to the chromate coating, such as, for example, anti-worming and anti-coloring additives, such as acid, fluoride, phosphoric acid, phosphoric acid In the chemical system, metal salts such as inorganic and Ca can also be added. ', 〇 物, Ni, 〇, Fe, Zn, Mg Chromate treatment for the bond layer steel sheet surface is usually at 80 ~ 250 t: the temperature of the kiln drying furnace main cloth treatment solution is added to the network The "m-acid coating film" is formed on the upper layer of the acid film. The organic resin is used to form the film resin: the film is used to make the thermosetting film. The thickness of the organic resin in the organic resin film must be 0.1 ~ 5 // m. If the surface-treated steel sheet is cured, it is a hardening resin. It rises in the chemical treatment coating; when it is processed by molding, the temperature of the resin and the general latex resin is not normal. Make processing outside after processing: after the roll temperature rise makes the film problem review, the result is through the use of: dagger. So, in order to solve this kind of resin, it can be destroyed at high temperature; ^ = chemical resin as The organic scratch resistance of the film has been greatly improved. As a result, even C: \ 2D-CODE \ 91-04 \ 9U01646.ptd p. 110M 575643 V. Description of the invention (106) is also a problem in continuous light forming processing. After the work, the appearance will not be asked. The so-called hot Addition or condensation reaction of chemical additives when the functional side chain dimorphic film of organic polymer is produced by chemical resin, or resin 2 or side chain of cross-linking reaction of organic polymer and hard polymerization Double bond radical lipids, polyester resins, etc ... This thermosetting resin can be used with alkyd tree moon water water sun tree moon day, polyurethane resin, propylene Jiao II + two: or other -More than one kind of modified resin and so on. Also, the workability viewpoint is better. In addition: = A: vinegar resin, acrylic resin is made of additives and solvents, and can be used. Among the thermosetting resins These trees are dispersed with water to harden by coating with resin solution. The hardening temperature is based on the force: heat generates a cross-linking reaction. In the present invention, the type of hardener and the type of hardening agent is 4 ... ^ ^ ^ i ^ Seeing the limits, the resin solution can also be completely hardened by heating after coating =, but it can also be hardened by coating after heating to a suitable state (via through plate rollers, etc.) (The hardened state in which the film does not fall off during contact), and is completely hardened by subsequent heat treatment. If the film thickness of the organic resin film is less than 0 · 丨 # m, the roll moldability is insufficient. On the other hand, if the film thickness exceeds 5 vm, the adhesion of the resin to the molding roll is increased, which is not good. In the surface-treated steel sheet of the form 5, in order to give a specific thermal history to the plating film, when the heat treatment is performed after the formation of the chemical conversion treatment film, there is a possibility that

C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 111 575643

Damage to the chemical treatment film is effective in adding additives to the chemical treatment film, which can be combined with the properties of one or more organic resins such as silica, acid-filled Ca salt, Mg salt, etc. In this case, there is no branch ^ Additives (fine particles). Inorganic compounds and silicic acid compounds (for example, in the surface-treated steel sheet of the fifth embodiment, the chemical treatment film is under the chromate film, and therefore does not contain cr in the organic resin film. Therefore, the surface-treated steel sheet is special It has excellent resistance to Cr dissolution. Among the surface-treated steel sheets that are subjected to the application of Shape 5, the ore film of the molten m η-type steel layer is preferably a coating film obtained after at least the following (a) and (b) thermal experience. , And forming the above-mentioned specific chemical treatment film on the surface of the coating film subjected to such (a) and (b) thermal experience, can obtain particularly excellent workability and processing department surplus 0 (a) steel plate just out of Kariya Immediately after Jingluo, the average cooling rate in the first 10 seconds is less than 1 ° C / sec. Heat history (b) After the metal plating by the molten coating is solidified, the temperature is in the range of 1 30 to 3 0 ° C The average cooling rate from T (C) to heating and then 'temperature T (° C) to 100 ° C is to satisfy the thermal history below C (t / hr) shown in (1) below, and / or, The temperature range from 1 3 0 ~ 3 0 0 ° C after the solidification of the metal to be melt-plated is from T (° C) to 100 ° C The average cooling rate satisfies the thermal history C = (T-100) / 2 below C (° c / hr) shown in the following formula. In the thermal history of (b) above, the temperature T (° C) A more preferred range is 130 to 200 ° C. By making the mineral film through the thermal experience of (a) and (b) above, it can become

C: \ 2D-00DE \ 9l.04 \ 91101646.ptd Page 112 575643 V. Description of the invention (108) A 1 -Zn-based coating is melt-plated, and its processability (crack resistance, etc.) is significantly improved. Next, a method for manufacturing a surface-treated steel sheet according to the fifth embodiment will be described. The manufacturing method of the perforating shape 5 is to use a hot-melt plated 1-211 series steel plate with an A1 content of 20 to 95% by mass in a coating film manufactured by a continuous molten coating equipment and the like as a head layer steel plate, and form a chemical reaction on the surface thereof. Method for manufacturing a surface-treated steel sheet that processes a film 'has a step of imparting at least the following thermal history to a shovel film of a molten ore bath steel sheet, and forming a specific chemical conversion treatment on the surface of a coated steel sheet Coating step. (a) The average cooling rate of the first 10 seconds immediately after the steel sheet is out of the money melting bath is less than 11 ° C / sec. Heat history (b) After the metal plating of the molten coating is solidified, The temperature T (° C) in the range of 0 0 ° C is heated and heated, and thereafter, the average cooling rate from the temperature t (° c) to 100 ° c is to satisfy C (it / hr) shown in (1) below. The following thermal history, and / or the average cooling rate of the temperature range T (° C) to 100 ° C after the solidification of the molten plated metal is 1 ° to 300 ° C is to satisfy the following formula The thermal history below C (〇C / hr) is shown as C: (T-100) / 2 of the above (a) and (b) thermal history given to the coating, the thermal history of (a) is via It is performed by controlling the cooling conditions of the plating film immediately after the plating. In order to provide the coating film with this (a) thermal history, as described above, a temperature adjustment device must be installed between the molten plating bath surface of the continuous melting equipment and the time when the steel plate from the molten plating bath first contacts the roller, and the temperature is passed through this temperature. Adjust equipment to control ship fiber 1 1 m

II »ίΐ

IS m

Page 113 C: \ 2D-C0DE \ 91-04 \ 91101646.ptd 575643 5. Explanation of the invention (109) Speed. As described above, the temperature adjustment device is preferably provided with a heating or heat keeping hand & 'and a cooling means as required. There is no particular restriction on the method, shape, scale, etc. of the heating or heat keeping means and the cooling means. The money film can impart the thermal experience of (a) above. As the heating or heat-retaining means of the temperature adjustment device, for example, an induction heater and gas heating I can be used, and as the cooling means, a gas blowing device can be used. … Or, the thermal history of (b) above is to apply specific heat treatment to the molten steel plate to be melt-plated, or to control the cooling of the coating after the molten metal plated weight is used to maintain heat, etc. And proceed. According to the invention, the specific chemical conversion coating is formed on the coating surface of the plated steel sheet. ②, in the drying step of the conversion coating, ③ = ^ ^ ^ ρί; 1ΛΤ ^ ^ J "is performed in two or more stages. Therefore, the thermal history of the coating film imparting (b) can be performed in at least one of the following steps (1) to (4). (2) (3) (4) (1) In the drying step of the chemical conversion treatment film before the formation of the chemical conversion treatment film, the cooling process after the solidification of the molten metal plating after the formation of the chemical conversion treatment film is formed. Each of the above-mentioned four processing steps and chemical conversion processing steps + w ^ / ON and step is independently optimized and optimized. The method is suitable to be used in continuous melting coating equipment. Where it is, the method of ② is in the drying step of chemical conversion treatment.

Ϊ75643 V. Description of the invention (110) Heat treatment is performed by heating, so it is particularly economical. The manufacturing method of Embodiment 5 is to apply V Λ to the surface of the plate, and apply chromate treatment to the surface of the steel plate. The shape of the steel plate is changed to a metal network, and the adhesion amount is img / m2 or more. ς 100mg / m 'is preferably 5mg / m2 or more and 4fimrT / 2 " ^, and 40mg / m2 or less chromic acid gs 祜 Ξ film tree Ϊ: ΪΛ layer 5 is formed with a thermosetting organic resin: forming a blanket The version of the amine w-day-thickness is 0 · 1 ~ 5 // m, which is thinner than 盍 η ς 0 丄. Quan Jia Feng Yan · 5 ~ 3 // in organic resin = acid salt treatment In order to add salt treatment liquid such as Shi Xishi, if necessary, coating the surface of the coated steel plate with Yikou 30 (TC heating and drying. Soil The cloth 'is usually not washed with water and formed at 80 ~ on the above-mentioned organic resin coating film in order to form the coating resin, | It needs to be coated with a humanized organic resin as a liquid, and heat-treated to make the resin; the resin of the cloth additive is soluble. The formation of organic resin coatings is as follows: Force mi: The reason for the limitation of the coating composition, the formation and chemical treatment: skin = V step, and the pre- and post-relationships of the steps that impart the above-mentioned heating process are described in the rain. Example 5 -1 JS ί 2 Γ Cold-rolled steel plate (thickness 0.5mm) on a continuous-type melting bell n? Plate, using ㈣ak5% si-zn plating bath for melt coating. Working line speed is 160m / min, single-sided coating The adhesion amount is 75g / m2. In the manufacturing steps of the pure plating layer, the average cooling fan degree of the cooling film of the money film money board 10 seconds immediately after the bath is 15 t / Sec, and for the coating surface; ^ Through chemical conversion treatment. The complex salt treatment is to dry dry Xi Xi stone, dish acid and chromic acid to dry Shi Xi stone: Dish acid : Mix at a ratio of 1: 1: 1: 1,

575643 5. Description of the invention (111) The treatment liquid with the cr reduction ratio adjusted to 40% is applied to the coated steel sheet surface, and dried at a plate temperature of 80 ° C to form a chromate film. For the chromate coating surface, an organic resin coating is formed. The following coating resins are used. (a) Thermosetting resin (main agent resin ·· polyester polyol resin, hardener: diisocyanate-based hardener) (b) Thermosetting resin (main agent resin ·· propylene polyol resin, hardener: honey Amine resin) (c) Thermoplastic resin (MMA-MA type acrylic latex resin)

The solvent-based resin solution containing any of the above-mentioned organic resins is applied to a chromate-treated surface by a roller coating method, and heated and dried at a plate temperature of 600. For the surface-treated steel sheet manufactured in this way, the corrosion resistance and roll formability of the processed portion were evaluated in accordance with the following methods. The results and chemical conversion treatment conditions are shown in Table 2-3. (1) Corrosion resistance of machined part

The surface-treated steel plate was given 5 T wild-curled wire, and after total bowing at λ total Ar 31, I was put into a salt water spray tester. The rust occurrence state of the bent portion after 5,000 hours at the Aya Matsuri Festival, and the benchmark was evaluated. No abnormality (the area ratio of rust occurrence is less than 10%)

〇: Slight white rust and black rust occurred (less than 25% of rust occurred). The above i have the occurrence of black and black recording (the area where the recording occurred is not more than white rust and roll forming processability. Black rust occurs (the area ratio of rust occurrence is 80%).

X: (2)

575643 i, invention description 012) " " '——- For a surface treated steel plate of 30mm x 30 0_, use a tensile welding machine with a mold temperature of 80 ° C, a compression load of 100 kg and The 浐 5mm weld was pressed in a flat plate bending test, and the appearance after drawing was observed with the eye =, and evaluated according to the following criteria. ◎: The blackened area is less than 10%, and there is no film peeling off ... Adhering grapes. The blackened area is 10% or more and less than 25%, or the film is slightly attached to the mold & △ . The blackened area is more than 25% and less than 50%, or the film peeling has significant adhesion to the metal mold. D X: The blackened area is 50% or more, or there is a significant "bite mark" on the surface of the coated steel plate.

575643 V. Description of Invention (113) Table 23

No Chemical-resistance coating film processing section Scum-resistant roll moldability Differentiating coating (mg / m2) Type of organic resin coating * 1 Hardening dose * 2 Film thickness (// m) 1 20 ⑷ 10 2 〇 ◎ This invention 2 (a ) 0 2 Δ] X Comparative Example 3 ZU Jb) 10 2 〇 ◎ Inventive Example] 4 20 (b) 0 2 Δ X Comparative Example 5 (b) 10 2 X △ Comparative Example 6 80 (b) 10 2 〇〇 Inventive Example 7 1 Du (b) 10 2 〇 △ Comparative Example 8 20 ^^ — — — XX Comparative Example 9 20 (b) 10 4 ◎ 〇 Inventive Example 10 20 (b) 10 7 ◎ △ Comparative Example 11 20 (c) 0 2 XX * 1 (a) to (d) * 2 described in the description of the specification. * 2 parts by weight of the hardener based on 100 parts by weight of the resin of the main agent. Out-of-range Example 5-2 The cold-rolled steel plate (plate thickness 0.5 mm) manufactured by the conventional method was passed through a continuous molten plating equipment, and a 55% A1 1.5% Si-Zn plating bath (Table 24 ~ Table 27 ^ No. 1 ~ No. 11, No. 14 ~ No. 24), 40% A 1-1. 0 ° / 〇Si-Zn plating bath (No. 12 in Table 2 and Table 3) and 70% A, 1.8% Si-Zn plating bath (No. 13 in Table 2 and Table 3) Melting. Working linear speed is 160m / min.

C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 118 575643 5. Description of the invention (H4) The weight is 75g / m2. In the manufacturing steps of the ore layer steel plate, the ore film is imparted with a thermal history, and the surface of the ore film is converted into a virtual ^ / dry silica, phosphoric acid, and chromic acid. Dry silica: phosphoric acid: yushishi mixed And the reduction ratio of C r is adjusted to 40%. The coating solution is coated on the surface of the coated steel plate with U / G treatment solution and dried at a plate temperature of 80 ° C to form chromium. S 夂 salt coating. The organic resin that forms the organic resin film on the chromate film surface is the material that makes the film, and will contain any of the above organic ^ ;: shell yoke example 5 -1 same solution, with _ + cry π _ g + 禋 has a stack The solvent-based resin of Shuzhi is dissolved and dried. It is coated on the ground, and the plate temperature is 160 ° C. For the same surface produced by the treatment, the jealous seven-stained steel plate is evaluated according to the methods of Example 5 -1 and U. The moldability of Qin b is evaluated. , And according to the following (crack resistance) and processing department resistance. As a result, heat history was imparted to the plating film ~ Table 27. The chemical conversion treatment conditions are shown in Table 24. (1) Workability The surface-treated steel sheet was bent and scratched at 0T, and evaluated according to the following criteria. < Check for cracks in the front end of the GW curve 5. No cracks were observed even when observed with a 20-fold magnifying glass. 4: No cracks were observed by visual observation on the right, and cracks were observed by employment. T sees clothing marks, but if it is 2. Observation by a magnifying glass A crack was observed by visual observation. Visual inspection revealed cracks in the large openings. Cracking occurs with peeling. x t

Page 119 575643 V. Description of the invention (115) After the surface-treated steel sheet is bent to 5T, it is installed in a compound cycle test machine, and the state of rust occurrence in the bent portion after 50 cycles is observed, and it is evaluated according to the following criteria. Still, one cycle of the compound cycle test is [3 0 ° C, 5% NaC 1 spray, 0.5 hours]-[3 (TC wet, 1.5 hours)-[dry (30 ° C, 2 Hours)]. ◎: No abnormality (rust occurrence area ratio is less than 10%) 〇: Mild white rust and black rust occur (rust occurrence area ratio is 10% or more and less than 25%) △: white Occurrence of rust and black rust (25% or more and less than 80% of rust occurrence area) X: Significant white rust and black rust occur (80% or more of rust occurrence area ratio)

C: \ 2D-C0DE \ 91-04 \ 91101646.ptd Page 120 575643 V. Description of the invention (116) Table 2 4

No. Coating composition thermal history (I) * 1 Average cooling rate (° C / sec) Thermal history (Π) * 2 Differentiated heating temperature (° C) * 3 Average cooling rate (° C / hr) * 4 Implementation stage * 5 1 55% AM.5% Si 15 180 19 (2) Comparative Example 2 55% AM.5% Si 8 330 50 (2) Comparative Example 3 55% Al-1.5% Si 8 105 20 (2) Comparative Example 4 55% Al-1.5% Si 8 265 85 (2) Comparative Example 5 55% Al-1.5% Si 8 165 45 (2) Comparative Example 6 55% Al-1.5% Si 10 280 52 (2) The present invention Example 7 55% Al-1.5% Si 10 180 23 (2) Inventive Example 8 55% Al-1.5% Si 4 145 18 (2) Inventive Example 9 55% AM.5% Si 4 240 58 (2) Present Invention Example 10 55% AM.5% Si 8 185 15 (1) Invention Example 11 55% AM.5% Si 8 170 22 (3) Invention Example 12 40% Al-1.0% Si 9 140 15 (2) Example 13 of the present invention 70% Al-1.8% Si 7 230 60 (2) Example of the present invention * 1 The average cooling rate of the bell film within 10 seconds immediately after the steel sheet is immediately out of the molten ore bath * 2 Heat history due to subsequent heat treatment * 3 Heating temperature of the coating during heat treatment * 4 Average cooling rate of the coating during heating to 100 ° C Degree * 5 (1): before chemical conversion treatment (2): after chemical conversion treatment (3): drying step of chemical conversion treatment ※ The values with underline are outside the scope of the present invention

Page 121 C: \ 2D-CODE \ 91-04 \ 91101646.ptd 575643 V. Description of the invention (117) Table 25

No Chemical conversion treatment Film processing section Processing section Corrosion resistance Roller moldability Differentiate the amount of chromate film 〇 Adhesion (mg / nr) Type of organic resin film * 6 Hardening dose * 7 Film thickness (m) 1 20 (b) 10 2 2 X ◎ Comparative Example 2 20 (b) 10 2 3 X ◎ Comparative Example 3 20 (b) 10 2 3 X ◎ Comparative Example 4 20 (b) 10 2 3 X ◎ Comparative Example 5 20 (b) 10 2 3 X ◎ Comparative Example 6 20 (b) 10 2 4 〇 Inventive Example 7 20 (b) 10 2 5 〇 Inventive Example 8 20 (b) 10 2 5 X ◎ Inventive Example 9 20 (b) 10 2 4 〇 ◎ Inventive Example 10 20 (b) 10 2 5 〇 Inventive Example 11 2Q (b) 10 2 4 〇 Inventive Example 12 20 (b) 10 2 4 〇 Inventive Example 13 20 (b) 10 2 4 〇 ◎ Examples of the present invention * 1 (a) to (c) * 2 described in the description of this specification * 2 parts by weight of the hardener based on 100 parts by weight of the main resin ※ Underlined symbols or values are within the scope of the present invention outer

Page 122 C: \ 2D-mDE \ 91-04 \ 91101646.ptd 575643 V. Description of the invention (118)

No. Thermal history of coating composition (I) * 1 Average cooling rate (° C / sec) Thermal history (II) * 2 Differentiated heating temperature (° C) * 3 Average cooling rate (° C / hr) * 4 Implementation stage * 5 14 55% Al-1.5% Si 10 180 23 (2) Example 15 of the invention 15 55% Al-1.5% Si 10 180 23 (2) Comparative example 16 55% Al-1.5% Si 10 180 23 (2 ) Inventive Example 17 55% Al-1.5% Si 10 180 23 ⑺ Comparative Example. 18 55% Al-1.5% Si 10 180 23 (2) Comparative Example 19 55% Al-1.5% Si 10 180 23 (2) Present Invention Example 20 55% Al-1.5% Si 10 180 23 (2) Comparative Example 21 55% Al-1.5% Si 10 180 23 (2) Comparative Example 22 55% AM. 5% Si 10 180 23 (2) The present invention Example 23 55% Al-1.5% Si 10 180 23 (2) Comparative Example 24 55% Al-1.5% Si 10 180 23 (2) Comparative Example * 1 The average of the coating film in 10 seconds immediately after the steel plate was out of the molten plating bath Cooling rate * 2 Thermal history due to heat treatment performed after the coating of the molten coating is solidified * 3 Temperature rise and heating temperature of the coating during heat treatment * 4 Average cooling rate of the coating during heating up to 100 ° C * 5 (1): before chemical conversion (2): after chemical conversion (3): chemical conversion Drying steps ※ The values with underline are outside the scope of the present invention

Page 123 C: \ 2D-C0DE \ 91-04 \ 91101646.ptd 575643 V. Description of the invention (119) Table 27 Chemical treatment coating ^^ ____ Cr adhesion amount of the salt coating (mg / m2) Organic resin coating main Resin * 6 | Hardening dose_Processing Department ί〇Ξ 部 ^ Type Corrosion Resistance

N〇 ^-(a) ~ (C). 2 parts by weight of the curing agent based on 100 parts by weight of the main component resin ^ Underlined symbols or values are outside the scope of the present invention. The cold-rolled steel plate (plate thickness 0.5mm) manufactured by the method is prepared by continuous hot-dip plating = 2 prepared Zhongtong plates, and is melted by using 55% and 1.5% in a _211 money bath. The working linear speed is 160m / min.

Mg / W. In the manufacturing steps of this plated steel sheet, the coating is given the coatings shown in Table 28, and the coating surface is chemically treated. The chemical treatment conditions were the same as in Example 5-2. After the same chromate treatment and the formation of a chromate film with a Cr adhesion amount (converted to gold) of 2Omg / m2, it was more polymerized than the main resin.

C: \ 2D-C0DE \ 91-04 \ 91101646.ptd 575643

100 parts by weight of the alcohol resin is added with 10 parts by weight of the solvent-based resin solution of the hardener diisocyanate resin, and the complexate-treated surface is coated with an applicator, and dried at a plate temperature of 160 ° C to form a film thickness of 2⑽ of organic resin coating. With respect to the surface-treated steel sheet manufactured in this way, the workability (crack resistance) and the corrosion resistance of the processed portion were evaluated in the same manner as in Example -2. The results and the thermal history imparted to the bell film are shown in Tables 2 to 8. Table 2 8

No. Thermal history ⑴ * 1 Average cooling rate (° C / sec) Thermal history (II) ”Corrosion resistance of processability processing section Differentiated heating temperature (° C) * 3 Average cooling rate (° C / hr) * 4 Heat treatment Implementation stage * 5 1 55% AM.5% Si 10 250 55 (2) 4 〇 Example 2 of the present invention 55% Al-1.5% Si 10 170 27 (2) 5 〇 Example of the present invention * 1 Steel sheet is just hot-melted The average cooling rate of the coating film in 10 seconds immediately after the bath * 2 The heat treatment temperature imparted by the heat treatment performed after the coating of the molten coating is solidified 3 The heating temperature of the bell film during the heat treatment * 4 The heating temperature is increased to 1 during the heat treatment Average cooling rate of the coating film up to 〇 ° C * 5 (1): before chemical conversion treatment (2): after chemical conversion treatment (3): drying step of chemical conversion treatment

C: \ 2D-CODE \ 91-04 \ 9n01646.ptd P.1255755643 V. Description of the Invention (121) Existing_Form 6 ·· The surface-treated steel plate of Embodiment 6 contains 2 〇 ~ 9 5 Once the% A1 is hot-dip plated with 1-211 series steel plate as the first layer steel plate. In addition, from the viewpoint of resistance to 3 miles, the more preferable range of the amount of A1 in the plating film is 45 to 65% by mass. In addition, the particularly good composition of the key film is Al: 45 to 65% by mass, si.Q 2.0% by mass, Fe: less than 10% by mass, and the remainder is essentially a substance containing unavoidable impurities. Zn is particularly effective in the case of such a composition ^ Moreover, if the coating film contains one or more selected one of Mg, V, and Mn in total 0. 〇1 ~ 1 〇 mass%, the corrosion resistance can be further improved And processability. If the total content of these elements is less than 0.01% by mass, the full effect cannot be obtained. On the other hand, if it exceeds 10% by mass, the effect of improving the corrosion resistance is increased. . However, if the above-mentioned A1-Z η steel plate is composed of only this chain layer, it is difficult to obtain the corrosion resistance of the high-processing part. The excellent performance can be achieved only through the thermal history described below and the formation of the upper layer of the chemical treatment film. The processing department is resistant to # 彳 生. In addition, the coating amount of the hot-dip A1-Zη-based steel sheet is not particularly limited, but it is generally suitable to be about 30 to 200 g / m2 per one side. In addition, the coating film of the molten A 1-Zn steel sheet must be a coating film obtained by undergoing at least the following thermal history (a) and (b). (a) The average cooling rate of the first 10 seconds immediately after the steel plate is out of the molten plating bath is less than 11 ° C / sec. Thermal history (b) After the mineral metal of the smelting ore layer is solidified, the temperature ranges from 1 3 0 to The temperature in the range of 300 ° C (° C) is increased by heating, and thereafter, the average temperature T (t :) to 100 ° c

C: \ 2D-OODE \ 91-O4 \ 91101646.ptd P.1265755643 V. Description of the invention (122) '-The cooling rate is to meet the thermal history below c (t / hr) shown in (1) below , And / or, after the metallization of the molten plating layer is solidified, the average cooling rate from the temperature T (t :) to 〇〇0 is to satisfy the following / c (t: / hr) The following thermal history is 0 (T-1 00) / 2. In the thermal history of (b) above, the temperature τ (it) is more preferably in the range of 130 to 2 0 ° C. horse

By making the coating film through the thermal experience of (a) and (b) above, it can be a hot-dip Al-Zn-based coating, and its processability (crack resistance, etc.) is significantly improved. ) And (10) have significantly improved the film processing f, based on the following reasons. First, the steel sheet immediately passes the thermal experience of (a) immediately after the cold-plating, that is, after the hot-plating Immediately after the bath, the average cooling rate of the 10-shift buckle is a sufficiently delayed thermal meridian, so that the solidification of the molten coating is closer to an equilibrium state than that caused by the usual cooling process, so the diffusion of the semi-melted state promotes A1 and the As a result, the coating is softened. After that, the coating is subjected to such thermal treatment [and then the thermal treatment through (b) described above, that is, 130 to 300 ° C (preferably 1 30). ~ 2 0 0 it) in the temperature range after heating up and heating under specific conditions and slowly cooling, and / or 130 ~ 30 (rc (more than 30 ~ 2 0 0 c)) The conditions of Xu Leng's heat experience, The product's skew is opened, and the solid is diffused in the coating film, and the phase separation of 1 and Zn in the coating film generated by the thermal experience of (a) is more effectively promoted. As a result, the coating film is significantly softened and its The workability is significantly improved.

Page 127 557643 V. Description of the invention (123) Because: softening of such ore films and the accompanying $: the complex thermal experience according to the above ⑷ and (b) = which one's thermal experience is Difficult to achieve. Use only the following. The thermal history of (a) & (b) above will be described in detail. The mineral bath ί 立 Z t ί ί thermal experience is to make the steel plate just out of the smelting and melting =: the average cooling rate of the ore film is not full. This solidification is closer to the equilibrium state, so through semi-melting ::: over: Therefore, the two-phase separation of A1 and Zη is promoted into, the expansion of r; ... that is, the first 1. The average cold time in seconds is due to the fact that the solidification of the coating film is to fully promote the softening of the film by the non-sequential two-phase separation method. On the surface of the equipment, it is necessary to control the P speed of the coating film from the melting bath surface of the equipment to the melting spade bath. The I-degree adjustment device is preferably provided with a heating or holding means, but a cooling means. However, this cooling means is to be initially light (top) counted by contacting the ore layer steel plate with the cooling rate of the film, and the cooling rate is prevented, and the purpose of preventing pick up on the roller surface is to find its purpose. . The heating or heat-retaining means of the temperature adjustment device can be, for example, a 'cooling' means, which can be achieved by using a gas tank. However, regarding the heating or protection of the temperature adjustment device: \ 2D-OODE \ 91 * 04 \ 91101646.ptd P.1285755643 V. Description of the invention (124) — The method, shape, and specification of the heat and cooling means Mainly, the thermal history of the above (a) may be given to the plating film. "', Do n’t limit, secondly, regarding the thermal experience of (b) above, the upper coating film (the coating film after the metal plating of the molten plating layer is solidified) is 130 ;: calendar :, preferably 13α ~ 20 { The rc range temperature is 7 (. moderate temperature increase plus 埶 = degree 1 ^) to 100. 〇; average cooling rate so far to meet the above two / C (t / hr) below to cool, or make the melted ❹ ❹ After the solidified coating is cooled, the cooling process is from 13 to 300 °. The average cooling rate up to ° is to satisfy the above formula (C / hr) or less. 'The coating is made as described above. The distortion in the medium is opened, and solid diffusion occurs in the coating, and the warp ^ (a). The thermal & experience of the two-phase separation of A1 and Y in the resulting mineral film is more effectively promoted. The combination of the thermal history and the thermal history (a) described above significantly softens the bond film, and its processability is significantly improved. At this point, the temperature is 130 ° C. (B) The heating temperature of the coating film in the thermal history If T is not full, the method will fully achieve the above-mentioned effect. On the other hand, if the θ 2 temperature T exceeds 300 t, it will promote the first layer steel plate. The growth of the cup phase of the coating interface plate adversely affects the processability. Furthermore, the cooling process after the solidified metal of the molten coating is solidified 丨 30 ~ 300 C 牦 ambient temperature T (C) to When the thermal history of (b) above is to cool by the given strip, and the temperature T is less than 13t, the above effect cannot be fully obtained. Page 129 C: \ 2D-CODE \ 91-04 \ 91101646.ptd 575643 V. Description of the invention (125) The coating film is subjected to the thermal history of (b) above, and the coating film is heat-treated or heat-protected in the continuous melting coating equipment or outside the equipment. Carry out the specified heat treatment or heat preservation. For example, it is possible to install heating mechanisms (such as' induction heaters, gas heating furnaces, ... air furnaces, etc.) in a continuous, melted layer, and perform continuous heating in-line. Also, the coils can be heated by offline batch heating after being wound. Also, continuous heating equipment (such as, gas heating furnace, hot air furnace, etc.) in continuous processing equipment outside Υ is also used for continuous heating. ; More,:, plate, after winding in the coil Proper heat preservation ;; Force heat = Layer steel can be set during the cooling process after heat preservation and cold cooling. However, regarding heating or heat preservation devices ^ ^ Don't restrict it 'and mainly give money film i (b) =? See mold and so on without passing through the heat such as (a) and ⑻bis) above. A fixed non-chromate coating layer. The surface forming steel sheet with excellent processability and corrosion resistance in the processed part is said to have excellent surface treatment. The surface treated steel sheet has a specific coating layer as described above. The coated surface of this cover does not contain Chromium single-layer or multi-layer organic resins and inorganic components and t < & 丄 '/ said <? Reverse film 0 right- ^ properties contained in the coating are all to improve the effect. Processability and corrosion resistance of processed parts For example, acryl-based resin: a driver is not particularly limited, and an epoxy-based resin may be used. Tochigi secret oil, olefin resin,

C: \ 2D-CODE \ 91-04 \ 9110l646.ptd Page 130 575643 V. Description of the invention (126) Overlay machine; it has the effect of improving money tolerance. = Add "ingredients can achieve the desired properties. Inorganic components include: 戈 ... Goate salt ⑷. Zinc Linate, Wu Lu, Magnesium Phosphate, Crossbow Stone Stone, Shixiyan coupling agent (such as' amine 5 basic cuts of the base stone, cyanide isocyanate 氰酸, / m ethylene based system, τ-based propyleneoxy system, etc.), Ca, Mn, Mg, Ni, Co, Fe .. compounds (example =, calcium silicate, calcium carbonate, etc.), M4 compounds (for example, manganese nitrate), Mg compounds (for example, magnesium nitrate, magnesium acetate, etc.), Ni, for example / nickel acetate, nickel nitrate Etc.), co-based compounds (for example, vinegar i 0, cobalt nitrate, etc.), Fe-based compounds (for example, iron nitrate, etc.), etc., and their officials: one or two or more. These inorganic components are formed through Coating = Dissolving or dispersing in mash (about the metal is to dissolve or disperse in the form of metal ions or fine powder), it can be used as the coating component. F The coating can be a single layer or multiple layers (multiple layers), and one Films (layers) (Sound ^ ^ The organic resin and inorganic components described in the soil, and can also be included in each film 8-9. That is, in the coating In the case of a single layer, the organic resin and inorganic components in the film ^ are described above, but when the coating layer is multi-layered = 5 t ', the film in the layer contains the above-mentioned inorganic components (or 9 above ( 'Or 7% of the above-mentioned coatings), the organic resin film in the upper layer of the film ^ 丨, a film made of resin) can also be. Also, multilayer quilts, ^ to J layer containing organic Resin and inorganic components. 〇 · The adhesion amount (the total adhesion amount when the coating layer is multi-layered) is' and less than 5 g / m2, preferably 1 · 0 g / m2 and less than 5 g /

C: \ 2D-CODE \ 91-04 \ 9ll0l646ptd Page 131 575643 ^ ϊ ^ (127)-~ --- m2. When the adhesion amount is less than 0 · lg / m2, sufficient corrosion resistance cannot be obtained. On the other hand, if the adhesion amount is 5 g / m2 or more, the film is easily peeled off by processing. In addition, the processability and the corrosion resistance of the processed part are particularly good. The solid content mass ratio between the organic resin and the inorganic component in the coating layer is [organic tree month]: [inorganic component] = 1 〇〇: 1 ~ 〇0, more preferably 〇〇〇: i〜5〇. If the inorganic component ratio is less than 1 part with respect to 100 parts of the organic resin, sufficient money resistance cannot be obtained. In addition, if the ratio of the inorganic component to 100 parts of the organic resin exceeds 100 parts, it is easy to peel off the film through processing. Next, a method for manufacturing a surface-treated steel sheet according to the embodiment β will be described. The manufacturing method of the shell shape 6 is to use a molten zinc-plated aluminum-zinc-based steel sheet with an A1 content of 20 to 95% by mass in a coating film manufactured by a continuous smelting ore layer equipment, etc. A method for producing a surface-treated steel sheet having a surface-forming chemical-treatment coating film has a step of imparting at least the following heat history to the coating of a steel plate of a molten plating bath, and forming a specific chemical conversion on the surface of the plated steel sheet Steps for processing the film. (a) The average cooling rate of the first 10 seconds immediately after the steel plate is out of the molten plating bath is less than 11 ° C / sec. Heat history (b) After the metal plating by the molten plating is solidified, the temperature ranges from 1 0 to 3 0 The temperature T (° C) in the 0 ° C range is heated and heated, and thereafter, the average cooling rate from the temperature τ (it) to 100 ° C is to satisfy a thermal history below C (/ hr) shown in (1) below. , And / or, the average cooling rate from the temperature between 130 ° C to 100 ° C in the range from 130 to 300 ° C after the metallization of the molten plating layer is solidified is C (° C / hr)

575643

V. Description of the invention (128) C = (T-1〇〇) / 2 For the coating, the cooling and heat preservation means and cooling of the coating are set between the coating and melting equipment. The given control is immediately assigned to this (ak melt forging bath temperature adjustment speed. If 'and depending on the means of the square film given to the heating means can be used to make the above (a) and (b) thermal history, (a The heat of) is performed under the cooling conditions of the plating film after the plating.

) In terms of thermal history, as mentioned above, it is necessary to initially contact the steel plate from the continuous melting surface to the dazzling melting key bath. The temperature control equipment is preferably equipped with heating or Need to have cooling means' There are no particular restrictions on heating or offering style, shape, scale, etc .: 2 The thermal history of (a) may be sufficient. Examples of the temperature adjusting device include an induction heater and a gas heating furnace, and a gas blowing device.

Also, the above (b) thermal history is performed by subjecting the plated steel plate after the molten metal coating to solidification to a specific heat treatment or controlling the cooling of the coating film after the f-metal solidified by the molten coating is solidified to maintain heat. The manufacturing method of the present invention is to form a specific chemical conversion coating on the film-coated surface of the key-layer steel plate. The heat treatment for applying the heat of (b) to the coating can be performed before the formation of the chemical conversion treatment film and the drying step of the chemical conversion treatment film. Medium and ③ Any stage after the formation of the chemical conversion treatment film (after the coating of the treatment liquid and the film formation in the drying step). In addition, it may be performed in two or more of these stages. Therefore, the thermal history of the coating film imparting (b) can be performed in at least one of the following steps (1) to (4). (1) Before the formation of the chemical conversion treatment film (2) In the drying step of the chemical conversion treatment film

C: \ 2D-CODE \ 9l-04 \ 91101646.ptd Page 133 575643 V. Description of the invention (129) (3) After the formation of the coating film (4) The cooling process after the solidification of the molten metal plating layer is solidified ' The method points of the above-mentioned methods for performing the heat treatment, and the methods of ② and ③ are suitable for independently optimizing each of the conditions of the processing steps: chemical processing steps; all processes are performed in the thermal continuous melting coating equipment. In addition, the Λ of the method A, and + n into W is excellent in economy because it is also heat-treated by heating in the drying step of the chemical conversion treatment. The heat treatment or heat preservation for imparting the heat history of (b) above is performed through a heating or heat preservation device, ~ provided inside or outside the flail-type molten coating equipment. It is also possible to install a heating mechanism (for example, a heater, a gas heating furnace, a hot air furnace, etc.) in the continuous melting coating equipment and perform continuous heating in an on-line mode. After winding in a coil, it can be separated offline. Batch heating is also possible. It is also possible to perform continuous heating in a continuous processing facility outside the ore stream line via a heating mechanism y (e.g., an induction heater, a gas heating furnace, a hot air furnace, etc.). Furthermore, it is also possible to heat the ore-layer steel sheet which is continuously heated in the coating stream line and continuously by the above-mentioned continuous processing equipment in a coil, and keep it heated. In addition, a heat-retaining device that can heat the coating film and cool it down can be provided during the cooling process after the solidified metal plating is solidified. However, there are no particular restrictions on the method, shape, scale, etc. of the heating or heat-preserving device, and the coating film can be mainly provided with the thermal history of (b) above. The preferable coating composition, coating adhesion amount, the reasons for limiting the thermal history of (a) and (b) above, and the obtained effects are as described above for the hot-dip A1 ~ 2η-based steel plates manufactured by Shang. The step of forming a specific coating layer on the surface of the steel sheet is to make the

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5. Description of the invention (130) The t-side is formed as a single layer or layer containing organic resin and inorganic components and not containing chromium, and a coating layer with a coating adhesion amount of at least 0.1 g / m2 and less than 5 g / m2. The relationship between the step of forming this coating layer and the step of imparting the above (b) thermal history is as described above. The types of organic resins and inorganic components are the same as described above. The coating solution can be formed by coating or drying the T liquid on the surface of the plated steel sheet by dissolving or dispersing (the metal is dissolved or decomposed in the form of metal ions or fine powder). . Usually, after the treatment liquid is applied, it is not washed with water and dried at 80 to 300. As mentioned above, the coating layer may be a single layer or a plurality of layers (a plurality of layers). Therefore, a single-layer coating layer containing the above-mentioned organic resin and inorganic component may be formed on the surface of the coating film. In the case where the coating layer is multilayered, a coating film containing the above-mentioned inorganic component (or the above-mentioned inorganic component) may be formed on the surface of the coating film. It is also possible to form a film containing an organic resin (or a film made of the above-mentioned organic resin) on the upper layer. In addition, at least one layer of the multilayer film may contain an organic resin and an inorganic component. = Surface treatment of the surface-treated steel sheet according to the sixth embodiment described above, formation of a coating film of the layer 『I】 can be made into a mouth-coated steel sheet. Its coating: Lipid-based coating film, epoxy resin-based coating film, acrylic '' = other resins modified such as epoxy resin modified polymer catalysts, pigments, Tim 4: in the fat, you can add a hardener μ On the surface-treated steel handle, ^ + ^ Conversely, the coating method of forming a coating film on the surface is parallel, and the mouth coating method can be listed with ^ ^ ^ ^ Industrial Niu Wei applicator spraying, curtain flow spraying special spray nozzle

575643 5. Description of the invention (131) Tu, etc. After the material is sprayed, it is generally heated and dried by means of hot air drying, infrared irradiation, and superheating to form a coating film. … Example 6-1 A cold-rolled steel plate (plate thickness of 0.5 mm) manufactured by a conventional method is used to pass through a plate in a continuous hot-melt plating 2 facility, and has the same cold composition as that of the hafnium-plated composition shown in Tables 29 to 34. A variety of bright A1-Zn based plating baths are used for melt coating. The working linear speed is 160m / min, and the amount of coating on one side is to stabilize the deviation between steel plates in the range of 75 ~ 90g / m2. In the manufacturing steps of the plated steel sheet, the coating films are given the thermal history (I) and (II) shown in Tables 29 to 34, and a coating layer is formed on the coating surface. This coating layer is formed by applying a treatment solution 'for dissolving or dispersing the organic resin and inorganic components on the surface of the plated steel sheet, and drying it by heating at 50 ° C. In addition, for some examples (No. 11, No. 12), a treatment solution for dissolving metal ions is applied to the surface of the plated steel sheet, and after heating and drying at 120 ° C, the upper layer will be dissolved or dispersed. The organic resin and inorganic component treatment liquid is applied and dried at 150 ° C. For the surface-treated steel sheet manufactured in this way, the workability and the corrosion resistance of the machined portion were evaluated according to the following methods. The results are shown in Tables 2 9 to 34. (1) Workability The surface-treated steel sheet was bent at 0T, and a crack at the front end of the 0τ bend was observed, and evaluated according to the following criteria. 5 ·· No cracks were observed even with a magnifying glass of 20 times. 4 ··· No cracks were observed when visually observed, but cracks were observed when observed with a magnifying glass of 20 times.

C: \ 2D-CODE \ 9l-04 \ 91101646.ptd Page 136 575643 V. Description of the invention (132) A crack was observed by visual observation. Visual inspection revealed cracks in the large openings. Cracking occurs with peeling. (2) Corrosion resistance of the processed part After the surface-treated steel sheet is bent at 3T, it is installed in a wet tester at 50 ° C and above 98% RH, and the state of rust occurrence in the bent part after 1000 hours is observed. The following benchmarks were evaluated. No abnormalities Some mild white rust and black rust occurred All mild white and black rust occurred Significant white rust and black rust occurred Red rust occurred

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No. Coating composition heat history⑴M Average cooling rate (° C / sec) Thermal history (π) * 2 Differentiated heating temperature (° 〇 * 3 Average cooling rate (° C / hr) * 4 Implementation stage of heat treatment M 1 55 % Al-1.5% Si 10 180 23 (2) Comparative Example 2 55% Al-1.5% Si 10 180 23 (2) Comparative Example 3 55% Al-1.5% Si 10 180 23 (2) Comparative Example 4 55% Al -1.5% Si 10 180 23 ⑺ Comparative Example 5 55% Al-1.5% Si 10 180 23 ⑺ Inventive Example 6 55% Al-1.5% Si 10 180 23 (2) Inventive Example 7 55% Al-1.5% Si 10 180 23 (2) Inventive Example 8 55% Al-1.5% Si 10 180 23 (2) Inventive Example 9 55% Al-1.5% Si 10 180 23 (2) Inventive Example 10 55% Al-1.5% Si 10 180 23 (2) Inventive Example 11 55% Al-1.5% Si 10 180 23 (2) Inventive Example 12 55% Al-1.5% Si 10 180 23 (2) Inventive Example 13 55% Al-1.5 % Si 10 180 23 (2) Inventive Example 14 55% Al-1.5% Si 10 180 23 (2) Inventive Example Table 29 氺 1 氺 2 * 3 氺 4 氺 5 Speed (1): The average cooling time of the coating film formed within 10 seconds immediately after the molten plating bath is formed. The heating temperature in the heating treatment of the coating in a heating temperature raised to 10 until the average degree of supercooling of the film square ° c layer of the front cover (2) is formed: The cover layer is formed after (3) ·· cover layers the drying step

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No The coating layer processing section distinguishes the upper layer or the single layer of the lower layer of the coating ⑷ / (B) Coating adhesion amount Corrosion-resistant organic resin (A) Inorganic component (B) * 6 (mg / m2) * 7 1 Single layer — — — — — 1 Comparative Example 2 Single Layer —-Phosphoric Acid — 100 1 Comparative Example 3 Single Layer — — Silica — 200 1 Comparative Example 4 Single Layer — Urethane Resin — — 2000 2 Comparative Example 5 Single Layer — Urethane Ester Resin Phosphoric Acid 100/20 2000 4 Inventive Example 6 Monolayer-Urethane Resin Silica 100/20 2000 4 Inventive Example 7 Monolayer-Urethane Resin Phosphoric Acid, Silicone Coupling Agent 100 / 30 (20 + 10) 2000 5 Inventive Example 8 Monolayer-Urethane Resin Phosphoric Acid, Phosphoric Acid Ca 100/30 (20 + 10) 2000 5 Inventive Example 9 Monolayer-Urethane Resin Phosphoric Acid, Phosphoric acid Mη 100/30 (20 + 10) 2000 5 Example 10 of the present invention Monolayer-Urethane resin phosphoric acid, phosphoric acid Mg 100/30 (20 + 10) 2000 5 Example 11 of the present invention-'ItS Nitroamine amine Urethane resin phosphoric acid, silane coupling agent 100/30 (20 + 10) 50 + 2000 5 Example 12 of the present invention Two-layer Co + Fe urethane resin phosphoric acid, Alkane coupling agent 100/30 (20 + 10) 50 + 2000 5 Example 13 of the present invention Single-layer acrylic resin phosphoric acid, silane coupling agent 100/30 (20 + 10) 2000 5 Example 14 of the present invention Single layer—epoxy resin phosphoric acid, Siyuan Coupling Agent 100/30 (20 + 10) 2000 5 Example of the invention * 6 Mass ratio of solid content of organic resin / inorganic component. The ratio of each inorganic component in the left column is in parentheses. * 7 No. 11 and No. 12 are [Amount of coating on lower layer + Amount of coating on upper layer]

Page 139 C: \ 2D-C0DE \ 91-04 \ 91101646.ptd 575643 V. Description of the invention (135) Table 31

No. Thermal history of coating composition (I) * 1 Average cooling rate (° C / sec) Thermal history (II) * 2 Differentiated heating temperature (° C) * 3 Average cooling rate (° C / hr) * 4 Implementation stage M 15 55% Al-1.5% Si 15 180 19 (2) Comparative Example 16 55% Al-1.5% Si 8 330 50 (2) Comparative Example 17 55% Al-1.5% Si 8 105 20 (2) Comparison Example 18 55% Al-1.5 ° / 〇Si 8 265 85 ⑺ Comparative Example 19 55% Al-1.5% Si 8 165 45 (2) Comparative Example 20 55% Al-1.5% Si 10 280 52 (2) Example of the present invention 21 55% Al-1.5% Si 10 180 23 (2) Example of the present invention 22 55% Al-1.5% Si 4 145 18 (2) Example 23 of the present invention 55% Al-1.5% Si 4 240 58 (2) Example of the present invention Example 24 55% Al-1.5% Si 8 185 15 (1) Example 25 of the present invention 25 55% Al-1.5% Si 8 170 22 (3) Example 26 of the present invention 40 40% Al-1.0% Si 9 140 15 (2) Example Inventive Example 27 70% AM.8% Si 7 230 60 (2) Inventive Example 氺 1 氺 2 氺 3 氺 4 氺 5 The average cooling rate of the plating film for 10 seconds immediately after the steel plate is out of the molten plating bath is melt-plated. The heat imparted by the heat treatment performed after the coating is solidified is subjected to the heating temperature of the coating during the heat treatment, and the heating temperature is increased to 100 ° C during the heat treatment. The average cooling speed of the film was (1): the front cover layer (2) is formed: (3) after the coating layer is formed: cover layer dried steps of forming

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No The coating layer processing section distinguishes the upper or lower layer of the coating layer (A) / (B) Coating adhesion amount Corrosion-resistant organic resin (A) Inorganic component (B) * 6 (mg / m2) * 7 15 Monolayer-amine Urethane resin phosphoric acid, silane coupling agent 100/30 (20 + 10) 2000 1 Comparative Example 16 Single layer-Urethane resin phosphoric acid, silane coupling agent 100/30 (20 + 10) 2000 3 Comparative example 17 Single layer-Urethane resin phosphoric acid, silane coupling agent 100/30 (20 + 10) 2000 3 Comparative Example 18 Single layer-Urethane resin: phosphoric acid, silane coupling agent 100/30 (20 + 10) 2000 3 Comparative Example 19 Monolayer-Urethane Resin Phosphoric Acid, Silane Coupling Agent 100/30 (20 + 10) 2000 3 Comparative Example 20 Single Layer-Urethane Resin Phosphoric Acid, Silane Coupling Agent 100/30 ( 20 + 10) 2000 4 Inventive Example 21 Monolayer-Urethane Resin Phosphoric Acid and Silane Coupling Agent 100/30 (20 + 10) 2000 5 Inventive Example 22 Single Layer-Urethane Resin Phosphoric Acid and Silane Coupling agent 100/30 (20 + 10) 2000 4 Example 23 of the present invention Monolayer-Urethane tree moonlight phosphoric acid, silane coupling agent 100/30 (20 + 10) 2000 5 Illustrative Example 24 Monolayer-Urethane resin phosphoric acid, silane coupling agent 100/30 (20 + 10) 2000 4 Example 25 of the present invention Single layer.-Urethane resin phosphoric acid, silane coupling agent 100/30 ( 20 + 10) 2000 4 Inventive Example 26 single layer; — Urethane resin phosphoric acid, silane coupling agent 100/30 (20 + 10) 2000 4 Inventive Example 27 Single layer monourethane resin phosphoric acid, Silane coupling agent 100/30 (20 + 10) 2000 4 Example of the present invention * 6 Mass of solid content of organic resin / inorganic component. The ratio of each inorganic component in the parentheses is the left column

Page 141 C: \ 2D-CODE \ 91-04 \ 91101646.ptd 575643 V. Description of the invention (137) Table 33

No. Coating composition heat history⑴ * 1 Average cooling rate (° C / sec) Thermal history (π) * 2 Differentiated heating temperature (° 〇 * 3 Average cooling rate (° C / hr) * 4 Implementation stage of heat treatment Μ 28 55% A1 -1.5% Si 10 180 20 (2) Example of the present invention 29 55% Al-1.5% Si-3% Mg 10 180 20 (2) Example of the present invention 30 55% Al-1.5% Si-2% V 10 180 20 (2) Example 31 of the present invention 55% Al-1.5% Si-2% Mn 10 180 20 (2) Example 32 of the present invention 55% Al-1.5% Si-3% Mg-2 ° / 〇V 10 180 20 (2) Example 33 of the invention 33 55% Al-1.5% Si-3% Mg-2 ° / 〇Mn 10 180 20 (2) Example 34 of the invention 34 55% Al-1.5% Si-3% Mg-2 ° / 〇V-2 ° / 〇Mn 10 180 20 (2) Example of the present invention * 1 The average cooling rate of the coating film in 10 seconds immediately after the steel plate is out of the molten plating bath * 2 Heat treatment performed after the coating of the molten coating is solidified Heat history provided * 3 Heating temperature of the coating film during heat treatment * 4 Average cooling rate of the coating film during heating process to 100 ° C * 5 (1): Before coating layer formation (2): Coating After layer formation (3): drying step during coating layer formation

C: \ 2D-00DE \ 91-04 \ 91101646.ptd Page 142 575643 V. Description of Invention (138) Table 34

No Corrosion resistance of the processed part of the coating layer Classification of the upper layer or single layer of the film form (A) / (B) * 6 Coating adhesion amount (mg / m2) * 7 Organic resin (A) Inorganic component (B) 28 Single layer-amine Urethane resin phosphoric acid, silane coupling agent 100/30 (20 + 10) 2000 4 Inventive example 29 Single layer-Urethane resin phosphoric acid, silane coupling agent 100/30 (20 + 10) 2000 5 The present invention Example 30 Monolayer-Urethane Resin Phosphoric Acid and Silane Coupling Agent 100/30 (20 + 10) 2000 5 Inventive Example 31 Single Layer-Urethane Resin Phosphoric Acid and Silane Coupling Agent 100/30 (20 +10) 2000 5 Inventive Example 32 Monolayer-Urethane Resin Phosphoric Acid, Silane Coupling Agent 100/30 (20 + 10) 2000 5 Inventive Example 33 Single Layer-Urethane Resin Phosphoric Acid, Silane Coupling Mixture 100/30 (20 + 10) 2000 5 Example of the present invention 34 Monolayer-Urethane resin phosphoric acid, silane coupling agent 100/30 (20 + 10) 2000 5 Example of the present invention

* 6 Mass ratio of solid content of organic resin / inorganic component. The ratio of each inorganic component in the parentheses is left

P.143 C: \ 2D-CODE \ 91-04 \ 91101646.ptd 575643 Brief Description of Drawings Figure 1 is a graph showing the influence of the average cooling rate of the plating film of the first embodiment on the workability of the surface-treated steel sheet. Fig. 2 (a) is a graph showing the influence of the temperature increase heating rate of the plating film of the first embodiment on the workability of the surface-treated steel sheet. Fig. 2 (b) is a graph showing the influence of the average cooling rate of the plated film on the workability of the surface-treated steel sheet in the first embodiment. Fig. 3 is a graph showing the influence of the average cooling rate of the plating film on the workability of the surface-treated steel sheet according to the second embodiment. Fig. 4 (a) is a graph showing the influence of the heating temperature of the plating film of the second embodiment on the workability of the surface-treated steel sheet. Fig. 4 (b) is a graph showing the influence of the average cooling rate of the plated film on the workability of the surface-treated steel sheet in the second embodiment.

91101646.ptd Page 144

Claims (1)

--.......... ^ VI. Application scope ~ 575643 1 · A method for manufacturing a surface-treated steel sheet by immersing the steel sheet in a molten plating bath to form an A1 content of 20 ~ The method for manufacturing a 95% by mass iAl-Zn-based coating film and the surface-treated steel sheet formed by the step of forming a chemical conversion coating film on the coating film has a step of 'giving a thermal history to the bell film', The steps include the first thermal history assignment step of imparting a thermal history with an average cooling rate of less than 1 1 / sgc after the steel sheet is out of the molten plating bath, and the temperature in the range of 130 to 300 ° C. T (° C) to 100. (: The average cooling rate up to now is the second thermal history assigning step of the thermal history below 0.5 × (T100) (° c / hr). 2 • Manufacturing of surface-treated steel sheet as described in item 1 of the scope of patent application The method, wherein the second thermal history imparting step is a temperature ranging from 130 to 300 ° C after the solidification of the plated metal to the molten ore layer is solidified, and the average cooling rate up to 0 to 100 t is 0. · Constructed by a thermal history below 5χ (TlO〇) (^ / hr). 3 · As in the method for manufacturing a surface-treated steel sheet according to item 1 of the scope of patent application, wherein the second thermal history imparting step is to be imparted to After the metallization of the molten plating layer is solidified, it is heated at a temperature τ (.0) in the range of 130 to 300 t. Thereafter, the average cooling rate from the temperature T (C) to 100 C is 0.5 > < (τ — 1 〇〇) (艽 / hr) below the thermal history. 4 · Rushen: the method of manufacturing a surface-treated steel sheet of the patent scope, wherein the second thermal history granting step is from 130 ~ 2 0 (TC Range temperature; (The average cooling rate up to? Is composed of thermal history below 0.5 χ (τ-1 () 〇) (% ~). 5.such as Please surface of patentable scope of the item of the first method for producing a steel sheet processing C: \ 2D-CODE \ 91-04 \ 91101646.ptd Page 145 575643 VI. Application for Patent Scope 2: The step of forming a chemical conversion treatment film is by chromate treatment, and the form of metal chromium is changed to 0. It is composed of a chemical conversion treatment film of 1 mg / m2 or more and less than 1 满 w. 6 According to the method for manufacturing a surface-treated steel sheet as described in item 5 of the scope of the patent application, the second step of forming a chemical treatment film is to reduce the part containing water I = organic resin and chromic acid and / or chromic acid to the coating surface. Chromic acid # 2 = Chromium I salt treatment liquid is applied, and then the temperature of the plate temperature of 80 ~ 300 ° C is used to form the mass ratio (A) of the organic resin contained in the film and converted into metal ( A) A chemical treatment coating made of an organic tree of 1 or less and less than 200. The method for manufacturing a surface-treated steel sheet according to item 5 of the 7 + 2 patent patent. ^ The step of forming a chemical conversion treatment film is to apply chromic acid to the coating surface: the reason is that the human coating contains water-based organic resin. The treatment solution was dried at a plate temperature of 80 MPa to form a chemical conversion treatment film containing an organic resin. 8 According to the method for manufacturing a surface-treated steel sheet as described in item 7 of the scope of patent application, the chemical conversion treatment film in f is the quality of the amount of organic resin (a) contained in the film and the amount of Cr (B) converted to metallic chromium. Ratio 1, Berry ratio U) / (B) is more than 1 and less than ZUU ° 9 Shiru, please refer to the patent scope 6, the manufacturing method of the surface treatment steel is the opposite, /, in the chemical conversion treatment film Organic resins are thermosetting. For example, the method for manufacturing a surface-treated steel sheet under the scope of the patent application item 7, the organic resin in the chemical conversion treatment film is thermally hardened. Η. For the method for the manufacture of the surface-treated steel sheet under the scope of the patent application item i, 575643 6. Scope of patent application Where the chemical conversion coating is made of organic resin and contains at least one option-駄: phosphate, silica, silane coupling agent, qq-based compound, η-a chemical compound, M g, M g-based compound, Ni, ni-based compound. It is composed of at least one layer of Fe, Fe, and Co compounds, and does not contain chromium, and the coating adhesion amount is 0 g / m2 or more and less than 5 g / m2. Λ2 · Λ The method of manufacturing a surface-treated steel sheet under the scope of patent application No. 1 is performed in the paragraph which is at least one of the following steps (1) to (4) (1) before the formation of the coating film (2) In the drying step of the treatment film (3), after the formation of the formation treatment film (4;: skin :: f layer, the metal plating is a cooling process after solidification. There is a manufacturing method for the formation treatment 1 = surface treatment steel plate, coating Step 1. Apply at least one coating on the skin-breaking surface to spray 1 4 · If the scope of the patent application is applied, the coating method of spraying + tracer, surface treatment steel plate is coated and baked, Mi Er = In order to coat the surface of the chemical conversion treatment layer, apply a coating step; and apply a primer coating film having a thickness of 2 # m or more to the primer layer, and a step of 5 to 3 0 // m of the top coat film 2 top coat The material is boxed and baked to form a thick coating film, and the glass transition temperature is set to 0 ~ 30 with 氐 k material as the pass. Take a bow knife $ 140,000 ~ 26000, glass should be Obtained, and the inverse (C) of $ ester resin (A) and epoxy resin (B), and hardener shown by the following formula D) = modified polyester resin 乂 horse main component resin with a value of 0.7 ~ 2.5, 575643 VI. Patent application scope k = [Wbx (Ma + 2x Mb)] / [(Wa + Wb) x 2x Mb ] But "Wa ·· [Polyester resin (Α) + epoxy resin (Α) solid content weight ratio" π relative polyester resin Wb: [polyester resin (Α) + epoxy resin (β)]] The solids content of the phase is greater than the weight ratio of bismuth grease (B) Ma: the number average score of the polyester resin (A) Mb: the number average molecular weight of the epoxy resin (B) = 2 0 0 0 0 polyester resin (E ) The topcoat is a resin with a number average molecular weight ^ and a hardener as the main component. ",, 1 · If the patent application method is adopted, the coating for the primer coating film: the resin for the manufacture of the surface-treated steel sheet and The isocyanate compound and the hardener (D) 4 contained in the compound are made of amine group 16. If the patent application method is adopted, the second heat-treated steel sheet and the surface-treated steel sheet are manufactured in one stage. The person v is in the following steps (1) to (8) to (1) before the chemical conversion treatment (3) (4) (5) (6) ⑺ (8) Chemical conversion treatment end in the drying step of chemical conversion treatment. ^ Ma Tuo, cold I bottom f. Before the coating process, the coating process is finished in the drying step of the primer and the coating is finished. In the drying step of the topcoat and the topcoat spraying, the coating of the main coating is finished. 被 & Cooling process 1 7 · If applying for patent Fan Tuchu] Manufacture method of surface treated steel sheet of item 1 C: \ 2D-C0DE \ 91-04 \ 9H01646.ptd Chapter 148