WO2010114135A1 - プレコート金属板及びその製造方法 - Google Patents

プレコート金属板及びその製造方法 Download PDF

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Publication number
WO2010114135A1
WO2010114135A1 PCT/JP2010/056106 JP2010056106W WO2010114135A1 WO 2010114135 A1 WO2010114135 A1 WO 2010114135A1 JP 2010056106 W JP2010056106 W JP 2010056106W WO 2010114135 A1 WO2010114135 A1 WO 2010114135A1
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Prior art keywords
coating layer
coating
layer
metal sheet
coating film
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PCT/JP2010/056106
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English (en)
French (fr)
Japanese (ja)
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細川智明
植田浩平
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新日本製鐵株式会社
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Application filed by 新日本製鐵株式会社 filed Critical 新日本製鐵株式会社
Priority to KR1020117020158A priority Critical patent/KR101403151B1/ko
Priority to CN201080015519.7A priority patent/CN102369069B/zh
Priority to JP2010525953A priority patent/JP4695725B2/ja
Publication of WO2010114135A1 publication Critical patent/WO2010114135A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2502/00—Acrylic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2508/00—Polyesters

Definitions

  • the present invention relates to a pre-coated metal plate and a method for producing the same, and in particular for various uses such as for home appliances, building materials, civil engineering, machinery, automobiles, furniture, containers, etc.
  • the present invention relates to a pre-coated metal sheet having excellent scratch resistance and a method for producing the same.
  • pre-coated metal that is processed in a state of coating a pre-colored coating film instead of post-coating products that have been painted after processing a conventional metal plate on the outer plate in the home appliance field, building material field, automobile field, etc. Boards are starting to be used.
  • Patent Document 1 As a technique for increasing the gloss of a coating film, for example, as described in Patent Document 1, a technique for reducing the surface roughness of a metal plate as a base material, for example, as described in Patent Document 2, the molecular weight is low.
  • a technique for coating a coating film using a resin for example, a technique for coating a clear coating film on a colored coating layer as disclosed in Patent Document 3, is disclosed.
  • Non-Patent Document 1 When industrially producing a pre-coated metal plate, it is generally manufactured by a continuous coating line called a coil coating line as described in Non-Patent Document 1, for example.
  • a primer coating with a rust prevention function is applied onto a metal plate with a coating device called a roll coater or curtain coater, baked in a hot air oven, etc., and then again colored with a coating device.
  • Two times of coating and baking (typically called a two-coat two-bake method) are generally performed. Therefore, if you try to paint a clear paint film with excellent clarity on the colored layer, the number of paintings will be more than 3 times. Or, it was necessary to take measures such as coating the coil coating line twice.
  • Patent Documents 4 to 12 there is known a wet-on-wet coating method in which a coating is applied repeatedly in an undried state.
  • the precoated metal plate since the precoated metal plate is used after being molded, it is required to have scratch resistance during molding. It is also important to prevent wrinkles that occur during transportation and manual assembly.
  • a polyester resin having a glass transition point of 5 to 40 ° C. and a number average molecular weight of 15,000 to 30,000 and a hexamethoxymethylolated melamine resin are adjusted to a mass ratio of 75/25 to 55/45.
  • a coating material obtained by blending 1 to 2 parts by mass of an amine block of dodecylbenzenesulfonic acid with 100 parts by mass of the blended polyester-melamine resin has high coating film hardness, excellent scratch resistance, and excellent workability.
  • a coating composition for a painted metal sheet is disclosed.
  • Patent Documents 14 and 15 disclose a technique for increasing the hardness and improving the scratch resistance by adding glass fibers or glass beads to the coating film.
  • Patent Documents 16 and 17 disclose techniques for improving the lubricity and improving the scratch resistance by adding resin beads or wax to the coating film.
  • the method of obtaining a pre-coated metal plate with high gloss by applying a paint using a resin having a low molecular weight is relatively simple compared to the method of controlling the surface roughness of the metal plate as the base material. Although it is possible to manufacture, it is difficult to impart other coating film performances such as workability because a specific resin must be used for the paint.
  • Patent Document 13 As a method of obtaining a precoated metal plate having a high gloss relatively easily without using a resin having a performance restriction, there is a method of applying a transparent clear coating on the colored coating layer of Patent Document 13. .
  • the manufacturing problem when this method is applied to an existing 2-coating 2-bake coil coating line can be solved by applying wet-on-wet coating as described above. Patent Document 13), although excellent gloss can be obtained, sufficient scratch resistance cannot be obtained.
  • the technique of adding glass beads to the clear coating film on the colored coating film disclosed in Patent Documents 14 and 15 is effective in improving the coating film hardness, but satisfies the scratch resistance. Has not reached.
  • the addition of wax to the clear coating film on the colored coating film disclosed in Patent Documents 16 and 17 improves the lubricity, but still does not provide sufficient scratch resistance.
  • the addition of glass beads and wax to these films is not suitable for applications that require a glossy appearance because it reduces the gloss of the coating film.
  • an object of the present invention is to provide a precoated metal sheet having high gloss and sharpness and excellent scratch resistance, and a method for producing the same.
  • the top coating is a clear layer containing a silicone-grafted acrylic resin. It has been found that the coating film layer contains a melamine-curing or isocyanate-curing polyester resin, so that it is possible to achieve an improvement in the hardness of the coating film and a reduction in the coefficient of friction while ensuring high gloss.
  • the present inventors have found that a precoated metal sheet having excellent design properties such as sharpness and scratch resistance and excellent workability can be obtained.
  • a pre-coated metal plate having a coating layer on one side or both sides of a metal plate The coating layer has at least a top coating layer that is a coating formed on the outermost surface, and an intermediate coating layer that is a lower layer coating in contact with the top coating layer,
  • the top coating layer contains a silicone graft acrylic resin and is a clear coating containing no pigment
  • the intermediate coating layer contains a melamine curable or isocyanate curable polyester resin
  • a coating film containing a coloring pigment Furthermore, the average friction coefficient of the coating layer surface of the coating layer is 0.08 or less, and the hardness of the coating layer surface at 23 ° C.
  • the precoated metal sheet is 75 to 200 N / mm 2 in terms of universal hardness under a load of 5 mN,
  • the precoated metal sheet is characterized in that the specular gloss on the surface of the coating layer is 50% or more when measured under conditions of an incident angle and a light receiving angle of 20 °, respectively.
  • a pre-coated metal plate having a coating layer on one or both sides of the metal plate The coating layer has at least a top coating layer that is a coating formed on the outermost surface, and an intermediate coating layer that is a lower layer coating in contact with the top coating layer,
  • the top coating layer contains a silicone-grafted acrylic resin and a clear coating containing a pigment;
  • the intermediate coating layer contains a melamine-curable or isocyanate-curable polyester resin; and
  • a coating film containing a coloring pigment Furthermore, the average friction coefficient of the coating layer surface of the coating layer is 0.08 or less, and the hardness of the coating layer surface at 23 ° C.
  • the precoated metal sheet is 75 to 200 N / mm 2 in terms of universal hardness under a load of 5 mN,
  • the precoated metal sheet is characterized in that the specular gloss on the surface of the coating layer is 50% or more when measured under conditions of an incident angle and a light receiving angle of 20 °, respectively.
  • the top coating layer is a melamine curable type.
  • the glass transition temperature of the top coating film is 30 to 67 ° C., the ratio of the silicone resin in the silicone graft acrylic resin contained in the top coating film is 3 to 20% by mass,
  • a pre-coated metal plate having a coating layer on one side or both sides of the metal plate The coating layer is at least a top coating layer that is a coating formed on the outermost surface, an intermediate layer that is in contact with the top coating layer, and an intermediate coating that is a lower layer coating that is in contact with the intermediate coating layer And having a layer
  • the top coating layer contains a silicone graft acrylic resin and is a clear coating containing no pigment
  • the intermediate coating layer contains a melamine curable or isocyanate curable polyester resin
  • a coating film containing a coloring pigment Furthermore, the average friction coefficient of the coating layer surface of the coating layer is 0.08 or less, and the hardness of the coating layer surface at 23 ° C.
  • the precoated metal sheet is 75 to 200 N / mm 2 in terms of universal hardness under a load of 5 mN,
  • the precoated metal sheet is characterized in that the specular gloss on the surface of the coating layer is 50% or more when measured under conditions of an incident angle and a light receiving angle of 20 °, respectively.
  • a method for producing a precoated metal sheet according to any one of [1] to [17], A method for producing a pre-coated metal sheet, characterized in that the intermediate coating layer and the top coating layer are baked after being applied by multi-layer simultaneous application or wet-on-wet method, respectively.
  • the present invention it is possible to provide a pre-coated metal plate that has high gloss and sharpness, and has excellent scratch resistance and workability, a manufacturing method thereof, and a coated metal molded product.
  • the pre-coated metal sheet of the present invention has two or more coating layers, and the top coating is a clear coating, so that the surface is smooth, and the incident angle and the light receiving angle are each measured at 20 °. High gloss with a specular gloss of 50% or more is obtained.
  • the clear coating film refers to a coating film having a low pigment concentration in the coating film, a low hiding power of the base, and a transparent feeling.
  • the average friction coefficient is 0.08 or less, and the hardness at 23 ° C. is 75 to 200 N / mm 2 or more in terms of universal hardness under a load of 5 mN. High lubricity and high hardness can be obtained, and both scratch resistance and high gloss can be achieved.
  • the average friction coefficient In order to ensure the scratch resistance of the pre-coated metal plate of the present invention, the average friction coefficient needs to be 0.08 or less.
  • the average friction coefficient is a load of 100 g of stainless steel balls (10 mm ⁇ ), 150 mm / min. The force F applied when moving on the precoated metal plate 110 mm in parallel under the above conditions was measured, and the average of the measured values of the force F at a plurality of locations in the remaining 100 mm range excluding the first 10 mm was calculated.
  • the average coefficient of friction exceeds 0.08, the frictional force when foreign matter comes into contact with the surface of the pre-coated metal sheet and rubs against the mold during molding is increased, and the surface of the film is destroyed, resulting in poor scratch resistance.
  • the average friction coefficient is more preferably 0.05 or less.
  • universal hardness refers to the coating hardness measurement method described in DIN 50359-1 in Germany, and is a square pyramid made of diamond with a face angle of 136 ° (Vickers hardness described in JIS-Z-2244). The same as the indenter used in the test) is pressed against the material surface, and the hardness is calculated from the indentation depth under the applied load conditions.
  • the universal hardness in the present invention is measured under the conditions of a temperature of 23 ° C. and an indentation load of 5 mN and using a micro hardness meter described in this DIN standard.
  • the universal hardness is less than 75 N / mm 2 , even if the average friction coefficient is 0.08 or less, the coating film hardness is low, so that the scratch resistance is poor. If the universal hardness exceeds 200 N / mm 2 , the coating film becomes too hard and it is difficult to ensure processability, which is not suitable.
  • the universal hardness is preferably 75 to 200 N / mm 2 .
  • the universal hardness is preferably controlled to 150 to 200 N / mm 2 .
  • the specular gloss of the precoated metal sheet coating surface of the present invention can be measured according to JIS Z 8741, and it is necessary to be 50% or more when the incident angle and the light receiving angle are each measured at 20 °. If it is less than 50%, the appearance quality is poor.
  • the top coating layer of the precoated metal sheet of the present invention is characterized by containing a silicone graft acrylic resin.
  • the silicone graft acrylic resin is obtained by graft polymerization of a silicone resin on an acrylic resin main chain. Excellent lubricity can be effectively obtained by the excellent strength and transparency of the acrylic resin of the main chain and the property that the silicone resin hanging from the main chain is easily coordinated to the surface of the coating film. Further, since the silicone resin has relatively high strength in addition to high lubricity, it is possible to form a coating film excellent in gloss, hardness and lubricity by containing a silicone graft acrylic resin in the top coating layer.
  • the design can be further improved.
  • the top coating layer of the pre-coated metal plate of the present invention a clear coating film containing a bright pigment, in addition to improving the design properties, the wrinkle resistance becomes less noticeable, and the anti-glare property can also be improved.
  • the content of the silicone graft acrylic resin in the top coating film is preferably 2 to 20% by mass in terms of silicone resin.
  • the content of the silicone graft acrylic resin in the coating film is less than 2% by mass, the lubricity is not sufficient and it is difficult to ensure scratch resistance. If it exceeds 20% by mass, the storage stability of the paint may be lowered, and stable production becomes difficult.
  • "silicone resin conversion" here means expressing content of a silicone graft acrylic resin using content of the total amount of the silicone monomer contained in a top coating film.
  • Resins other than silicone-grafted acrylic contained in the top coating can be used without problems as long as they are compatible with silicone-grafted acrylic resin, but have excellent compatibility with silicone-grafted acrylic resin, and excellent strength. Acrylic resin having transparency is most suitable.
  • the crosslinking agent for the top coating film is preferably a melamine resin or an isocyanate compound.
  • the melamine resin has higher hardness than the isocyanate compound, and it is easy to obtain a predetermined coating film hardness. However, if the melamine resin is concentrated on the surface of the coating film by using an amine block of dodecylbenzenesulfonic acid, etc., the silicone resin becomes difficult to coordinate on the surface of the coating film, which may reduce the lubricity.
  • the blending amount when the melamine resin is used as a crosslinking agent is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the silicone graft acrylic resin from the viewpoint of ensuring the hardness and lubricity of the top coating film. .
  • the melamine resin is used as a crosslinking agent and left at high temperature, the reaction with the silicone-grafted acrylic resin tends to proceed and the storage stability of the paint may be inferior. Is more preferable than melamine resin.
  • the molar ratio of NCO / OH is 0.9 / 1.0 or more. This is because it is considered that when the NCO / OH molar ratio is lower than 0.9 / 1.0, crosslinking is insufficient and the coating becomes too soft.
  • the NCO / OH molar ratio is usually optimal when a silicone-grafted acrylic resin is used as the main resin. It has been found that the hardness and workability can be balanced at a higher order when the NCO / OH molar ratio is 0.05 / 1.0 to 0.5 / 1.0, which is lower than the previously stated value.
  • the silicone graft acrylic resin is harder than the isocyanate compound, so the NCO / OH molar ratio is low, that is, the amount of the isocyanate compound is small, so that a hard coating film is obtained and the crosslink density is low, so that high workability is achieved. It is estimated that However, when the molar ratio of NCO / OH is lower than 0.05 / 1.0, the crosslinking density is too low, and the coating film hardness may not be obtained. When isophorone diisocyanate is used as the isocyanate compound, it is easy to obtain a high coating film hardness. This is because isophorone diisocyanate has a hard skeleton.
  • the NCO / OH molar ratio When an isocyanate compound is used as a coating film curing agent, it is usually necessary to set the NCO / OH molar ratio to 0.9 / 1.0 or more. This is because when the molar ratio of NCO / OH is less than 0.9 / 1.0, the amount of isocyanate groups contributing to the crosslinking reaction becomes too small, and the effect of improving the film hardness by the crosslinking reaction is insufficient and the coating film becomes too soft. it is conceivable that. However, in the case of the present invention using a silicone graft acrylic resin as the main resin, if the NCO / OH molar ratio is 0.9 / 1.0 or more, the NCO / OH molar ratio is less than 0.9 / 1.0.
  • the coating film hardness was lower than that of the product.
  • the present inventors have considered that the molar ratio of NCO / OH is usually optimum. It was found that the hardness and workability can be balanced in a high order by setting the value to 0.05 / 1.0 to 0.5 / 1.0, which is lower than the value.
  • the glass transition temperature of the top layer is preferably 30 to 67 ° C.
  • the coating film hardness is lowered and the scratch resistance may be inferior.
  • the glass transition temperature is higher than 67 ° C., the coating film hardness is excessively increased and becomes brittle, and the workability may be lowered.
  • the ratio of the silicone resin in the silicone graft acrylic resin is preferably 3 to 20% by mass.
  • the ratio of the silicone resin in the silicone graft acrylic resin is lower than 3% by mass, the coordination of the silicone resin to the surface of the top coating layer becomes insufficient, the lubricity becomes low, and the scratch resistance may be inferior.
  • the ratio of the silicone resin in the silicone graft acrylic resin is higher than 20% by mass, the storage stability of the paint may be lowered.
  • the film thickness of the top coating layer is preferably 1 to 10 ⁇ m. If the film thickness of the top coating layer is less than 1 ⁇ m, the intermediate coating layer cannot be completely covered, and gloss and lubricity may be lowered. If the film thickness of the top coating layer exceeds 10 ⁇ m, the workability may be reduced. Moreover, it is not preferable also in terms of cost.
  • the intermediate coating layer contains a melamine curable or isocyanate curable polyester resin and also contains a color pigment. Further, the glass transition temperature of the intermediate coating layer is preferably 25 to 50 ° C.
  • the reason why the main resin of the intermediate coating layer is limited to the polyester resin is to ensure workability by using a polyester resin having excellent ductility and adhesion as the intermediate coating layer. Furthermore, the reason for limiting the glass transition temperature of the intermediate coating film layer is to make the hardness and workability compatible. If the glass transition temperature of the intermediate coating film layer is less than 25 ° C., the hardness may be insufficient. If it exceeds ° C., the workability may be insufficient, so the glass transition temperature of the intermediate coating layer is set to 25 to 50 ° C.
  • the intermediate coating film can be used in combination with a resin other than the polyester resin of the main resin, but in order to ensure the ductility and adhesion that are the characteristics of the polyester resin described above, the polyester to be included in the intermediate coating
  • the concentration of the resin is preferably 70% by mass or more.
  • the type of resin other than the polyester resin that can be used for the intermediate coating film is not particularly limited, and a resin that does not adversely affect the performance and paintability of the coating film can be appropriately selected and used as necessary.
  • the thickness of the intermediate coating layer is preferably 5 to 20 ⁇ m. Since the precoat metal plate of the present invention has a configuration in which the top coating layer is harder than the intermediate coating layer, as the thickness of the intermediate coating layer increases, the hardness of the entire coating layer of the intermediate coating layer increases. When the film thickness of the intermediate coating layer exceeds 20 ⁇ m, the universal hardness may be 75 N / mm 2 or less. Therefore, the thickness is preferably 20 ⁇ m or less. Further, if the film thickness of the intermediate coating film layer is less than 5 ⁇ m, the concealment ratio by the pigment may be lowered and it may be difficult to produce a color, so the film thickness of the intermediate coating film is preferably 5 ⁇ m or more. Further, from the viewpoint of securing the ductility of the film, the film thickness of the intermediate coating film is preferably 5 ⁇ m or more.
  • the glass transition temperature of the coating film in the precoat metal plate of this invention is a glass transition temperature as a bulk of the coating film after adding these in the case of the coating film containing a pigment and a hardening
  • the glass transition temperature of the coating film may be measured using a differential scanning calorimeter (generally called DSC) after peeling the coating film applied to the precoated metal plate, or coated as a precoated metal plate. Measurement may be performed using a thermomechanical analyzer (generally called TMA). Moreover, you may measure by a generally well-known method. It is known that the glass transition temperature of the coating film has some errors depending on the measuring equipment and measurement conditions.
  • the glass transition temperature of the coating film when measured by any one of a plurality of generally known glass transition temperature measurement methods, that is, a method using DSC or a method using TMA, the glass transition temperature of the coating film is measured. Is included within the scope of the present invention. Since the glass transition temperature of the coating film is mainly governed by the glass transition temperature of the base resin, the glass transition temperature of the coating film can be adjusted by controlling the glass transition temperature of the base resin.
  • the Ra (centerline average roughness) at the interface between the top coating layer and the intermediate coating layer of the present invention is more preferably 0.3 to 0.8 ⁇ m. If Ra at the interface of the coating film is less than 0.3 ⁇ m, the adhesion at the coating film interface may be lowered.
  • the adhesion of the coating films is maintained by physical bonds such as chemical bonds, hydrogen bonds and van der Waals forces between the coating films.
  • physical bonds such as chemical bonds, hydrogen bonds and van der Waals forces between the coating films.
  • the adhesion force by an anchor effect is provided.
  • the Ra of the interface of each coating film exceeds 0.8 ⁇ m, the appearance may be affected and the gloss may be lowered.
  • the interface Ra can be measured by the following method (basically, a method according to JIS-B-0601-1982).
  • the pre-coated metal plate of the present invention coats a transparent clear coating on the colored coating layer. Therefore, when manufacturing with the existing two-coat two-bake specification equipment, an additional coating device and oven, or coil It is necessary to pass the coating line twice.
  • the pre-coated metal sheet of the present invention can be manufactured with existing two-coat two-bake specification equipment. Further, the above-mentioned Ra of the interface can be achieved by multilayer simultaneous application or wet-on-wet, and a good processed part appearance can be obtained by applying the multilayer simultaneous application or wet-on-wet as described later. Therefore, it is preferable also from these points.
  • the multilayer simultaneous application in the present invention is a method in which a plurality of coating liquids such as a slot die coater or a slide hopper type curtain coater are simultaneously applied to a substrate and then dried and baked in multiple layers simultaneously.
  • a plurality of coating liquids such as a slot die coater or a slide hopper type curtain coater are simultaneously applied to a substrate and then dried and baked in multiple layers simultaneously.
  • wet-on-wet coating means that after coating the coating liquid on the substrate once, another coating liquid is further coated on it in the wet state before the coating liquid dries.
  • the multi-layer coating liquid is simultaneously dried and baked.
  • the lower layer coating film is applied with a roll coater or a curtain flow coater
  • the upper layer coating film is applied with a coating method such as a curtain flow coater before baking this.
  • a multilayer coating film of a lower layer coating film and an upper layer coating film is baked simultaneously.
  • the concentration gradient layer in the present invention has a structure in which the top coating film side is hard and gradually becomes softer toward the intermediate coating film layer side. Therefore, even if a crack occurs in the hard top coating layer by bending or the like, the progress of the crack is suppressed by the concentration gradient layer at the interface and does not reach the intermediate coating layer. Since the top coating layer is clear, if the cracks remain only in the top coating layer, the effect on the appearance is minimal and does not cause a problem.
  • the coating liquid of each layer is slightly mixed at the interface, so that excellent adhesion between the intermediate coating film layer and the top coating film layer is obtained. can get.
  • the multi-layer simultaneous coating of the present invention is a commonly known coating baking furnace, for example, a hot air drying furnace, an induction heating furnace, an infrared heating furnace, or a combination thereof.
  • a furnace or the like can be used.
  • the color pigment added to the intermediate coating film layer of the precoated metal plate of the present invention generally known inorganic pigments, organic pigments and metallic pigments can be used. Specific examples include carbon black, titanium oxide, zinc white, naphthol red, disazo yellow, disazopyrazolone orange, aluminum pigment, nickel pigment, and the like.
  • the color when the color is black or dark, it is easy to notice wrinkles and it is difficult to secure the light fastness, but the present invention has no problem even if it is black or dark. It is effective and exhibits good scratch resistance.
  • the metal material may be an alloy material.
  • a steel plate, a stainless steel plate, an aluminum plate, an aluminum alloy plate, a titanium plate, a copper plate, etc. are mentioned.
  • the surface of these materials may be plated.
  • Examples of the type of plating include zinc plating, aluminum plating, copper plating, nickel plating and the like. These alloy platings may be used.
  • steel plates generally known steel plates and plated steel plates such as hot dip galvanized steel plates, electrogalvanized steel plates, zinc-nickel alloy plated steel plates, hot dip galvanized steel plates, aluminum plated steel plates, aluminum-zinc alloyed steel plates, etc. Applicable.
  • the adhesion between the metal plate and the coating layer is improved, which is more preferable.
  • the chemical conversion treatment zinc phosphate chemical conversion treatment, coating chromate treatment, electrolytic chromic acid treatment, reaction chromate treatment, chromate-free chemical conversion treatment, or the like can be used.
  • the chromate-free chemical conversion treatment those treated with an aqueous solution containing a silane coupling agent, a zirconium compound, a titanium compound, tannin or tannic acid, a resin, silica and the like are known, and Japanese Patent Laid-Open No. 53-9238 is known.
  • JP-A-9-241576, JP-A-2001-89868, JP-A-2001-316845, JP-A-2002-60959, JP-A-2002-38280, JP-A-2002-266081 You may use the well-known technique described in Kaikai 2003-253464 etc.
  • These chemical conversion treatments are commercially available, for example, chromate treatment “ZM-1300AN” manufactured by Nihon Parkerizing Co., Ltd., chromate-free chemical conversion treatment “CT-E300N” manufactured by Nihon Parkerizing Co., Ltd., and trivalent chromium-based chemical conversion manufactured by Nippon Paint Co., Ltd.
  • the treatment “Surfcoat (registered trademark) NRC1000” or the like can be used.
  • the pre-coated metal plate of the present invention can be coated with a primer coating film having a rust preventive paint function as required.
  • a primer coating film having a rust preventive paint function As required, the primer coating is applied, the corrosion resistance of the metal plate is improved, which is more preferable.
  • the primer coating film to be applied to the pre-coated metal plate of the present invention generally known primer coating films for pre-coated metal plates, for example, polyester-based primers, epoxy-based primers, urethane-based primers and the like can be used.
  • the curing agent for the primer coating film may be either melamine type or isocyanate type.
  • the primer coating film to be applied to the pre-coated metal plate of the present invention is generally applied by a known coating method such as a roll coater, roller curtain coater, ringer roll coater, spray coating, etc. For example, it can be baked in a hot air drying furnace, an induction heating furnace, an infrared heating furnace, or a furnace using these in combination.
  • a glass reactor equipped with a mechanical stirrer, thermometer, condenser, and dry nitrogen gas inlet is charged with 100 parts by mass of isopropyl alcohol in a flask, heated to 80 ° C. in a dry nitrogen atmosphere, and mixed as shown in Table 1.
  • the liquid was dropped in a dropping funnel over 2 hours, and then kept at the same temperature for 4 hours, after which the reaction was terminated. In this way, a graft copolymer solution was obtained.
  • the graft copolymer solutions obtained from the mixed solutions 1 to 12 are referred to as graft copolymer solutions 1 to 12.
  • a commercially available silicone graft acrylic resin was also used. “Reseda (registered trademark) GS-1015” (glass transition temperature 54 ° C.) manufactured by Toa Gosei Co., Ltd. was used.
  • Byron (registered trademark) GK810 glass transition temperature 46 ° C.
  • Byron registered trademark
  • GK810 glass transition temperature 46 ° C.
  • “Super Becamine (registered trademark) J830” which is a butylated melamine resin (hereinafter referred to as butylated melamine) manufactured by Dainippon Ink and Chemicals, Inc., a fully alkyl methylated melamine resin manufactured by Mitsui Cytec. (Hereinafter referred to as methylated melamine) “Cymel (registered trademark) 303”, an isocyanate compound manufactured by Sumika Bayer Urethane Co., Ltd.
  • HDI “Desmodur BL3175 (trade name)” (hereinafter referred to as HDI), “Death” “Module BL4265SN (trade name)” (hereinafter referred to as IPDI), “Desmodule BL1265MPA / X (trade name)” (hereinafter referred to as TDI), “Duranate E402-B80T” (hereinafter referred to as HDI ⁇ 2) manufactured by Asahi Kasei Chemicals ⁇ ) was used.
  • aluminum flake “Aluminum paste CR-9800RM (trade name)” (average particle size 8 ⁇ m) manufactured by Asahi Kasei Metals Co., Ltd.
  • aluminum flake “Lupaste 7220NS (trade name)” manufactured by Toyo Aluminum Co., Ltd. (average particle size 25 ⁇ m) was used.
  • a commercially available microcrystalline wax was used as the wax used in the comparative material.
  • the dilution solvent used what was mixed with cyclohexanone: solvesso 150 1: 1 by mass ratio.
  • Byron (registered trademark) GK140 glass transition temperature 20 ° C.
  • Byron (registered trademark) GK360 glass transition temperature 36 ° C.
  • Byron (manufactured by Toyobo Co., Ltd.) (Registered trademark) GK110 "(glass transition temperature 50 ° C) and” Byron (registered trademark) 660 "(glass transition temperature 55 ° C) were used. If necessary, they were mixed to adjust the glass transition temperature of the resin.
  • Super Becamine (registered trademark) J830 which is a butylated melamine resin (hereinafter referred to as butylated melamine) manufactured by Dainippon Ink and Chemicals, Inc. was used.
  • Commercially available aluminum flakes were used, commercially available carbon black was used for black pigments, commercially available titanium oxide was used for white pigments, and commercially available bengara was used for red pigments.
  • Solvesso 150 1: 1 was used.
  • the glass transition temperature of the coating film is a thermomechanical analyzer “SSC5200 series T manufactured by Seiko Electronics Co., Ltd. With “MA / SS120C”, the probe at the time of measurement was measured using a needle probe.
  • a clear paint of FL641EU primer which is a polyester primer for PCM manufactured by Japan Fine Coatings Co., Ltd.
  • K-WHITE # 105 was used with a tripolyaluminum dihydrogen phosphate manufactured by Teika, which is a chromate-free rust preventive pigment.
  • Teika tripolyaluminum dihydrogen phosphate manufactured by Teika
  • the prepared original plate is spray-degreased with a 2% by weight, 50 ° C. aqueous solution of an alkaline degreasing solution “FC-4336” manufactured by Nihon Parkerizing Co., Ltd., washed with water, dried, and then chromate-free formed by Nihon Parkerizing Co., Ltd.
  • the treatment “CT-E300N” was applied with a roll coater and dried in a hot air oven. The drying conditions in the hot air oven were 60 ° C. at the ultimate plate temperature of the steel plate.
  • the coating amount of the chromate-free treatment was applied so that the total solid content was 200 g / m 2 .
  • the primer coating is applied on one side of the chemical-treated metal plate, and the other side is coated with the gray color of “FL100HQ”, which is the back side coating, on a roll coater, and hot air is blown into the induction heating. It was dried and cured in a furnace under the condition that the ultimate temperature of the metal plate was 210 ° C. And after dry baking, water was wiped with a spray to the painted metal plate, and water-cooled.
  • coating method (ii) this coating method is referred to as “coating method (ii)”).
  • coating method (iii) the coating method in this procedure is referred to as “coating method (iii)”.
  • an intermediate coating, an intermediate coating, and a top coating are simultaneously laminated on the primer coating by a slide hopper type curtain coater, and the ultimate temperature of the metal plate is 230 in an induction heating furnace in which hot air is blown.
  • the laminated coating film was simultaneously dried and cured under the condition of ° C.
  • coating method (iv) this coating method is referred to as “coating method (iv)”).
  • coating method (v) only one layer of intermediate coating is applied on the primer coating with a roll coater, baked, and one layer of intermediate coating is applied again on the intermediate coating with a roll coater, baked, and again on the intermediate coating.
  • a four-layer pre-coated metal plate was also prepared by applying a single layer of top coating on a roll coater and baking it (the coating method in this procedure is referred to as “coating method (v)”).
  • Lubricant HEIDON-14 was used and a stainless steel ball (10 mm ⁇ ) was loaded at 100 g, 150 mm / min. Under this condition, the force F applied when the precoated metal plate was moved in parallel by 110 mm was measured, and the average friction coefficient was calculated. In addition, the measurement location was made into five places within the remaining 100mm range except the first 10mm.
  • a processed part adhesion test is also performed, in which the tape is attached to the processed part and peeled off.
  • the adhesiveness after the tape is peeled is visually observed, no clear peeling is observed in the coating film.
  • the case where coating film peeling is observed with a total length of less than half with respect to the total length of the film is evaluated as ⁇ , and the case where coating film peeling is recognized with a total length of more than half with respect to the total length of the bent portion is evaluated as x. did.
  • Color value The L value was measured according to JIS Z 8722 with a spectrocolorimeter (manufactured by Suga Test Instruments, model MSC-45-2B).
  • Anti-thickening resistance of paint 200 g of paint was placed in a paint can (1 liter, outer diameter ⁇ 112 mm, height 130 mm), covered, and stored at 50 ° C. for 1 hour, and the anti-thickening resistance of the paint was investigated.
  • the viscosity was adjusted to 20 ° C., filled into an Iwata cup, and the number of seconds until the whole amount flowed out was measured using a stopwatch.
  • the value obtained by dividing the number of seconds of the paint after storage (measured by the Iwata cup) by the viscosity of the paint before storage is less than 1.5, the value of 1.5 or more and less than 3 is ⁇ , 3 or more Was marked with x. 9.
  • Measurement of boundary surface Ra Ra of the boundary surface between the intermediate coating layer and the top coating layer is obtained by cutting the coating film of each example in a direction perpendicular to the coating direction, embedding in a resin, and polishing the coating film.
  • the cross section perpendicular to the surface of the film was smoothed and evaluated by a photograph taken with a scanning microscope of 3500 times.
  • measure the area of the vertical line part with an image processing device as the average value Ra was calculated from the equation.
  • l (el) was 3 mm.
  • Tables 4 to 7 show the precoated metal sheets prepared in the present invention and the evaluation results. In addition, although the effect of this invention is demonstrated using the test material which gave the primer coating film, also when not giving a primer coating film, the performance similar to what gave the primer coating film is acquired.
  • the pre-coated metal plates of the present invention had excellent scratch resistance, gloss and workability.
  • the top coating layer is a clear coating that does not contain a pigment, and the silicone graft acrylic resin content in the top coating is 2 ⁇ in terms of silicone resin. 18% by mass, the intermediate coating film layer contains a color pigment, a melamine-curable or isocyanate-curable polyester resin, and the intermediate coating film has a glass transition temperature of 25 to 50 ° C., Contains a silicone graft acrylic resin having a glass transition temperature of 30 to 67 ° C.
  • those containing a melamine curable or isocyanate curable polyester resin and having a glass transition temperature of 25 to 50 ° C. are excellent. It had excellent scratch resistance, gloss, and processability.
  • the content of the silicone graft acrylic resin in the top coating exceeds 18% by mass in terms of silicone resin (Examples-20 and 21), and the ratio of the silicone resin in the silicone graft acrylic resin exceeds 20% by mass.
  • the one (Example-21) tended to have relatively low storage stability of the paint.
  • the glass transition temperature of the top coating layer is less than 30 ° C. (Comparative Example-22) and the glass transition temperature of the intermediate coating film is less than 25 ° C. (Comparative Example-26), the universal hardness tends to decrease. Yes, the scratch resistance is poor, the content of the silicone graft acrylic resin in the top coating is less than 2% by mass in terms of silicone resin (Comparative Example-24, 25), the ratio of the silicone resin in the silicone graft acrylic resin Of less than 3% by mass (Comparative Example -24) had a tendency for the coefficient of dynamic friction to decrease and the scratch resistance was poor.
  • the film thickness of the top coating layer is more preferably 1 to 10 ⁇ m.
  • the film thickness of the intermediate coating film layer was 3 ⁇ m (Example-36), the L value was slightly increased and black color was less likely to be produced.
  • the film thickness of the intermediate coating layer was 22 ⁇ m (Example-43), the hardness slightly decreased and the scratch resistance tended to decrease.
  • the film thickness of the intermediate coating layer is more preferably 5 to 20 ⁇ m.
  • Examples -63 to 77 Those using an isocyanate compound as a cross-linking agent (Examples -63 to 77) tended to have better resistance to thickening of the top paint. It can be seen that when the molar ratio of NCO / OH is 0.05 to 0.3 / 1.0 (Examples -68 to 70), higher scratch resistance is obtained, which is more preferable.
  • Table C shows wear resistance. When the hardness of the coating layer surface at 23 ° C. was 150 to 200 N / mm 2 in terms of universal hardness under a 5 mN load (Examples 80 to 88), there was a tendency that high wear resistance could be imparted.
  • Isophorone diisocyanate (IPDI) was used as the isocyanate compound, and the NCO / OH molar ratio of 0.1 to 0.5 / 1.0 (Examples-82, 85, 86) tended to have excellent wear resistance.
  • Table D shows the influence of the interface Ra between the intermediate coating layer and the top layer.
  • Interfacial Ra between the intermediate coating layer and the top layer is 0.3 to 0.8 (Examples-89, 91, 93, 95, 97, 99, 101, 103, 105, 107), workability and adhesion It can be seen that this is improved and more suitable.

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  • Paints Or Removers (AREA)
PCT/JP2010/056106 2009-03-30 2010-03-29 プレコート金属板及びその製造方法 WO2010114135A1 (ja)

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JP2012192582A (ja) * 2011-03-16 2012-10-11 Kobe Steel Ltd プレコートアルミニウム板
JP2014131838A (ja) * 2013-01-04 2014-07-17 Nippon Steel & Sumitomo Metal 投影性に優れるとともにマーカー描き性及び拭き取り性に優れるプレコート金属板及びその製造方法
JP5935949B2 (ja) * 2014-02-28 2016-06-15 新日鐵住金株式会社 プレコート金属板、プレコート金属板の製造方法
JPWO2014103906A1 (ja) * 2012-12-28 2017-01-12 関西ペイント株式会社 塗料組成物及び塗膜形成方法
WO2020110753A1 (ja) * 2018-11-30 2020-06-04 株式会社ネオス コーティング剤、コーティング膜ならびにそれを用いた物品、および物品の傷つき防止方法
JP2020528102A (ja) * 2017-07-26 2020-09-17 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ 二重層硬化機構で極性−促進の層間触媒移動により形成される低温硬化コーティング
US10921492B2 (en) 2018-01-09 2021-02-16 Corning Incorporated Coated articles with light-altering features and methods for the production thereof
US20220161293A1 (en) * 2020-11-23 2022-05-26 Lacks Enterprises, Inc. Laser ablated paint over surface treated chrome
WO2022202383A1 (ja) * 2021-03-26 2022-09-29 リンテック株式会社 剥離シート
US11940593B2 (en) 2020-07-09 2024-03-26 Corning Incorporated Display articles with diffractive, antiglare surfaces and methods of making the same
JP7548279B2 (ja) 2022-08-30 2024-09-10 ａｒｔｉｅｎｃｅ株式会社 成形加飾用積層体

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WO2017104762A1 (ja) * 2015-12-18 2017-06-22 旭硝子株式会社 塗装体および建築外装部材
TWI670467B (zh) * 2018-10-15 2019-09-01 立普思股份有限公司 使用深度影像偵測的加工方法

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JP2003154309A (ja) * 2001-11-20 2003-05-27 Nisshin Steel Co Ltd 耐跡残り性，加工性に優れたクリア塗装ステンレス鋼板
WO2006062214A1 (ja) * 2004-12-08 2006-06-15 Nippon Steel Corporation プレコート金属板およびプレコート金属板の製造方法
JP2006175810A (ja) * 2004-12-24 2006-07-06 Nippon Steel Corp 加工性と耐汚染性に優れた塗装金属板及びその製造方法

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JP4579129B2 (ja) * 2005-10-26 2010-11-10 新日鐵住金ステンレス株式会社 フッ素クリヤ塗装ステンレス鋼板およびその製造方法
JP4448511B2 (ja) * 2006-12-26 2010-04-14 株式会社神戸製鋼所 プレコート金属板およびプレコート金属板の製造方法
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JPH10298495A (ja) * 1997-04-22 1998-11-10 Nippon Paint Co Ltd 硬化性一液シリコーン変性アクリルエマルション塗料組成物
JP2001018322A (ja) * 1999-07-05 2001-01-23 Kobe Steel Ltd 耐疵付き性及び耐指紋性に優れた導電性黒色表面処理金属板
JP2002361787A (ja) * 2001-06-04 2002-12-18 Kansai Paint Co Ltd 高意匠性金属サイディング構造
JP2003154309A (ja) * 2001-11-20 2003-05-27 Nisshin Steel Co Ltd 耐跡残り性，加工性に優れたクリア塗装ステンレス鋼板
WO2006062214A1 (ja) * 2004-12-08 2006-06-15 Nippon Steel Corporation プレコート金属板およびプレコート金属板の製造方法
JP2006175810A (ja) * 2004-12-24 2006-07-06 Nippon Steel Corp 加工性と耐汚染性に優れた塗装金属板及びその製造方法

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012192582A (ja) * 2011-03-16 2012-10-11 Kobe Steel Ltd プレコートアルミニウム板
JPWO2014103906A1 (ja) * 2012-12-28 2017-01-12 関西ペイント株式会社 塗料組成物及び塗膜形成方法
JP2014131838A (ja) * 2013-01-04 2014-07-17 Nippon Steel & Sumitomo Metal 投影性に優れるとともにマーカー描き性及び拭き取り性に優れるプレコート金属板及びその製造方法
JP5935949B2 (ja) * 2014-02-28 2016-06-15 新日鐵住金株式会社 プレコート金属板、プレコート金属板の製造方法
JP7333776B2 (ja) 2017-07-26 2023-08-25 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング 二重層硬化機構で極性－促進の層間触媒移動により形成される低温硬化コーティング
JP2020528102A (ja) * 2017-07-26 2020-09-17 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ 二重層硬化機構で極性−促進の層間触媒移動により形成される低温硬化コーティング
US10921492B2 (en) 2018-01-09 2021-02-16 Corning Incorporated Coated articles with light-altering features and methods for the production thereof
US12019209B2 (en) 2018-01-09 2024-06-25 Corning Incorporated Coated articles with light-altering features and methods for the production thereof
WO2020110753A1 (ja) * 2018-11-30 2020-06-04 株式会社ネオス コーティング剤、コーティング膜ならびにそれを用いた物品、および物品の傷つき防止方法
JPWO2020110753A1 (ja) * 2018-11-30 2021-09-02 株式会社ネオス コーティング剤、コーティング膜ならびにそれを用いた物品、および物品の傷つき防止方法
US11971519B2 (en) 2020-07-09 2024-04-30 Corning Incorporated Display articles with antiglare surfaces and thin, durable antireflection coatings
US11940593B2 (en) 2020-07-09 2024-03-26 Corning Incorporated Display articles with diffractive, antiglare surfaces and methods of making the same
US11977206B2 (en) 2020-07-09 2024-05-07 Corning Incorporated Display articles with diffractive, antiglare surfaces and thin, durable antireflection coatings
US20220161293A1 (en) * 2020-11-23 2022-05-26 Lacks Enterprises, Inc. Laser ablated paint over surface treated chrome
WO2022202383A1 (ja) * 2021-03-26 2022-09-29 リンテック株式会社 剥離シート
JP7548279B2 (ja) 2022-08-30 2024-09-10 ａｒｔｉｅｎｃｅ株式会社 成形加飾用積層体

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CN102369069A (zh) 2012-03-07
JPWO2010114135A1 (ja) 2012-10-11
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TW201043457A (en) 2010-12-16

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