KR101839281B1 - Precoated metal plate - Google Patents
Precoated metal plate Download PDFInfo
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- KR101839281B1 KR101839281B1 KR1020177030919A KR20177030919A KR101839281B1 KR 101839281 B1 KR101839281 B1 KR 101839281B1 KR 1020177030919 A KR1020177030919 A KR 1020177030919A KR 20177030919 A KR20177030919 A KR 20177030919A KR 101839281 B1 KR101839281 B1 KR 101839281B1
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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
- 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
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- 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
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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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
- B05D2301/00—Inorganic additives or organic salts thereof
- B05D2301/10—Phosphates, phosphoric acid or organic salts thereof
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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
- B05D2508/00—Polyesters
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
This precoated metal plate comprises a metal plate, a base coat layer formed on the metal plate and containing no chromate, a primer coat layer formed on the base coat layer and containing no chromate, Wherein the coating film layer including the primer coating layer and the top coating layer has a breaking elongation at break of 10% or more and 25% or less, and the glass transition temperature of the primer coating layer is 50 占 폚 Wherein the top coat layer comprises a resin component and the resin component comprises an acrylic resin or a polyester-modified acrylic resin, wherein when the precoated metal sheet is subjected to 2T tight bending, A total of 5 cracks having a width of 0.1 mm or less were formed in the top coat layer in a range of 1 mm in the direction perpendicular to the bending direction Occur 30 or fewer.
Description
TECHNICAL FIELD [0001] The present invention relates to a precoated metal sheet used for automobiles, household appliances, building materials, civil engineering, machinery, furniture, containers, and the like. The precoated metal sheet has excellent stain resistance, .
A precoated metal plate coated with a colored coating film has been used instead of the post-painted product that has been painted after conventional processing, such as for household appliances, building materials, automobiles, and the like. This precoated metal sheet is obtained by coating a metal plate pretreated with metal with a paint, and is generally used after being painted, cut, and press-molded.
Since the precoated metal sheet is used after forming, it is usually coated with a flexible coating film having a high elongation percentage. On the other hand, such a resin often has a contaminant penetrating or physically adhering to the coating film, It was a drawback. Particularly, in the case of being used outdoors, pollutants such as exhaust gas contained in the air adhere to the surface and are wetted with rain, thereby generating a non-stripe pattern.
Generally, the occurrence of a non-striped pattern is referred to as contamination of the water. The cause of the contamination of the lacquer is said to be the relationship between the water contact angle of the lacquer and the contamination of the lacquer, and the higher the hydrophilicity of the lacquer is, the better. However, if contaminants adhere to a coating film deteriorated (deteriorated by weather) due to the effects of sunlight, wind, rain, etc. under outdoor conditions, the contaminants are physically deeply embedded in the coating film. Therefore, even if the coating film has hydrophilicity, it is difficult to remove such contaminants, and there is a problem that even in the case of a coating film having high hydrophilicity, deterioration in weathering resistance due to weathering deteriorates. Therefore, in order to improve the contamination resistance of the precoated metal sheet for a long period of time, it is necessary not only to impart hydrophilicity to the coating film but also to provide a stain resistant coating film having excellent weatherability over a long period of time, As shown in FIG.
On the other hand, however, since such a contamination-resistant coating film is hard, there is a problem that the processability of the coating film itself is low and the coating film adhesion of the processed portion is low. Therefore, such a precoated metal sheet tends to cause peeling of the coating film in the vicinity of the cut end face portion during shearing. The peeled coating film adheres to the surface of the product, so that, when the press working is performed, a scratch on the coating film, which is a cause of the film fragments peeled off from the end face portion, is formed on the coated film. As described above, there is a problem that when the antifouling coating film is used, the peelability of the coating on the end surface is deteriorated.
Some precoated metal sheets having excellent stain resistance have been reported so far. For example, Patent Document 1 discloses a precoated steel sheet excellent in stain resistance, comprising 100 parts by weight of a polyester resin having a number average molecular weight of 10,000 to 35,000 and a hydroxyl value of 50 to 5, and a methyl etherified hexamethylol melamine resin of 20 to 50 By weight of a steel sheet is formed on a surface treated film on the surface of the steel sheet. However, since the disclosed coating film contains melamine, it has been disadvantageous in that it is decomposed into heat or acid to cause the coating film to be torn, and the contaminants are physically deeply stuck, thereby deteriorating the long-term stain resistance.
As described above, in the techniques described heretofore, there is not disclosed a technique for obtaining a precoated metal sheet excellent in resistance to stains, peeling off of the surface of the coating film and corrosion resistance.
SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a precoated metal sheet having excellent long-term stain resistance, peeling off performance on a side surface, and corrosion resistance.
As a result of intensive studies by the present inventors, it has been contrived that long-term stain resistance can be ensured by applying a hard acrylic resin or a polyester-modified acrylic resin to the resin of the top coat film. Further, the use of an epoxy-modified polyester resin as the resin of the primer coat layer improves the adhesion of the coat to the steel sheet.
Further, by setting the elongation at break of the coating film layer including the primer coat layer and the top coat layer to 10% or more and 25% or less and setting the glass transition point temperature of the primer coat layer to 50 ° C or more and 100 ° C or less, And that the primer coat layer and the top coat layer are slightly cracked when the mold is elongated, so that stress is relieved. As a result, the adhesion between the hard top coating film and the steel sheet is maintained, and the coating film itself is not peeled off and the coating film peelability on the end surface is improved. Further, when any of magnesium phosphate, calcium phosphate, aluminum phosphate and zinc phosphate is used as the anticorrosive pigment in the primer coating layer, the occurrence of zinc oxide (white rust) from cracks is suppressed even when cracks occur, and the organ corrosion resistance is improved . It is presumed that this is because a compound with zinc is formed by elution of a rust inhibitive pigment component containing a phosphorus component to inhibit the elution of zinc.
The present invention has been completed on the basis of these findings, and the gist of the present invention is as follows.
(1) A method of manufacturing a semiconductor device, comprising the steps of: (1) a metal plate, a ground coating layer formed on the metal plate and containing no chromate, a primer coating layer formed on the ground coating layer and containing no chromate, Wherein the primer coating layer comprises a primer coating layer and a top coating layer, wherein the primer coating layer has a breaking elongation at break of 10% or more and 25% or less and a glass transition temperature of the primer coating layer is more than 50 DEG C Or less, and the top coat layer comprises a resin component, wherein the resin component comprises an acrylic resin or a polyester-modified acrylic resin, and when the precoated metal sheet is subjected to 2T tight bending, a bending head A total of 5 to 30 cracks having a width of 0.1 mm or less are formed in the top coat layer in a range of 1 mm in the direction perpendicular to the direction , Precoated metal plate.
(2) The precoated metal sheet according to (1), wherein the primer coating layer has a breaking elongation at break of at least 40% and at most 50%, and a breaking elongation at break of the top coating layer is at least 5% Wherein the coating layer comprises at least one of magnesium oxide, calcium phosphate, aluminum phosphate or zinc phosphate, and the resin component in the primer coat layer comprises an epoxy-modified polyester resin .
(3) The precoated metal sheet according to (1) or (2) above, wherein the primer coat layer comprises a rust preventive pigment, and the concentration of the rust preventive pigment is from 10 parts by mass to 160 parts by mass Or less.
(4) In the precoated metal sheet according to any one of (1) to (3), the top coat layer may not contain a melamine resin.
(5) In the precoated metal sheet according to any one of (1) to (4), the coefficient of dynamic friction of the surface of the top coat layer may be 0.06 or more and 0.25 or less.
(6) The precoated metal sheet according to any one of (1) to (5) above may have a water contact angle of 60 degrees or less on the surface of the top coat layer after being left in a humidified environment at 50 DEG C and 95% RH for 72 hours .
(7) In the precoated metal sheet according to any one of (1) to (6), the top coat layer may contain an organosilicate.
(8) In the precoated metal sheet according to (7), the content of the organosilicate in the top coat layer may be 0.1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the resin solid content of the top coat film.
(9) In the precoated metal sheet according to any one of (1) to (8), the base coat layer may contain at least one of fine silica, a silane coupling agent and tannic acid.
(10) The precoated metal sheet according to any one of (1) to (9), wherein the primer coat layer has a thickness of 3 to 10 탆 and the top coat layer has a thickness of 5 to 25 탆 .
According to the present invention, it is possible to provide a precoated metal sheet having excellent stain resistance, excellent peel resistance on the end face after machining, and corrosion resistance.
Brief Description of the Drawings Fig. 1 schematically shows a state of a crack when a pre-coated metal sheet according to an embodiment of the present invention is subjected to 2T tight bending, then cut perpendicularly to the bending direction about the top of the bending head, Fig.
FIG. 2 is a view schematically showing a state in which the precoated metal sheet according to the embodiment of the present invention is subjected to 2T tight bending process, and FIG. 2 schematically shows the state of cracks Fig.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.
A precoated metal sheet according to an embodiment of the present invention comprises a metal plate, a base coat layer formed on the metal sheet and containing no chromate, a primer coat layer formed on the base coat layer and containing no chromate, And a top coat layer formed on the coat layer.
The undercoating layer and primer coating layer do not contain chromate. When the undercoat layer and the primer coat layer do not contain chromates or phosphates, they are excellent in that they do not use materials that adversely affect the environment or human body.
The breaking limit elongation at break of the coating film layer including the primer coat layer and the top coat layer is 10% or more and 25% or less. If it is less than 10%, cracks of the coating film layer are large, so that the corrosion resistance of the processed portion is deteriorated or the coating film peeling occurs. On the other hand, if it exceeds 25%, the stain resistance is deteriorated.
The glass transition point temperature of the primer coat layer is more than 50 ° C and not more than 100 ° C. Further, it is preferably higher than 60 deg. C and lower than 80 deg.
The glass transition point temperature can be obtained in accordance with the differential scanning calorimetry (DSC method) of the transition temperature measurement method of plastics (JIS K7121 1987) using a coated or peeled coating film.
It is preferable that the elongation at break of the primer coating layer is 40% or more and 50% or less. Thereby, the effect of relaxing the stress of the top coating film, generating a suitable crack, and further suppressing peeling of the coating film can be obtained.
The breaking limit elongation of the top coat layer is preferably 5% or more and 10% or less. As a result, the top coating film is made harder and the stain resistance of the precoated metal plate is excellent.
The elongation at break of each coating layer can be measured by, for example, performing a tensile test on a coated film obtained by slicing a thin piece with a microtome or the like parallel to the surface and isolating each layer, using a small table tester.
The breaking elongation at break of the primer coat layer and the top coat layer is not determined solely by the elongation at break of the primer coat layer and the top coat layer alone but affects the adhesion of the interface between the primer coat layer and the top coat layer. The breaking elongation at break of the primer coat layer and the top coat layer can be adjusted, for example, by the concentration of the anticorrosive pigment. When the concentration of the anticorrosive pigment is 10 parts by mass or more based on 100 parts by mass of the resin solid content, adhesion between the primer coat layer and the top coat layer is improved, and the elongation at break of the primer coat layer is 40% to 50% The elongation at break of the coating film layer including the primer coat layer and the top coat layer is 10% or more and 25% or less by setting the elongation at break to 5% or more and 10% or less.
It is a structural feature of the coating film of the present invention that the elongation at break of the coating film layer including the primer coat layer and the top coat layer is 10% or more and 25% or less, The elongation percentage, the concentration of the anticorrosive pigment, and the like.
Table 1 summarizes the breaking limit elongation and the concentration of the anticorrosive pigment for the top coat layer, the primer coat layer and the coat layer formed by combining the primer coat layer and the top coat layer in the present embodiment. In principle, it is generally considered to use a coating film having a high elongation (soft) on the top coating layer as the upper layer with a large deformation and a coating film having a low elongation (hard) on the primer coating layer as the lower layer having a small deformation. However, the present invention utilizes reverse development, and is characterized by using a coating film having a low elongation (hard) in the top coating layer and a coating film having a high elongation (soft) in the primer coating layer.
That is, when the elongation percentage of the top coat layer and the primer coat layer is set within the above range, the total elongation percentage of the top coat layer and the primer coat layer combined can be set high even if a coat film having a low elongation percentage is used for the top coat layer. At this time, it was found that the contribution of the elongation percentage of the top coat layer to the overall elongation was smaller than usual. As a result, it has been found that the total elongation is ensured and the width of the cracks generated in the processed portion of the top coat layer when the 2T contact bending process is performed after the coating film can be suppressed to 0.1 mm or less.
The
The width 1 of the crack generated in the processed portion of the
The maximum width of the cracks was measured by measuring the crack width (1) of the top coating layer included in the range (A) of 1 mm in the direction perpendicular to the bending direction about the bending head top portion in the above 10 sections, And the maximum value among all of the measured values.
The number of cracks is calculated by summing the number of cracks in the top coat layer included in the range A of 1 mm in the direction perpendicular to the bending direction centering on the top of the bending head in each of the ten cut surfaces, Value of the value.
In the combination of the top coating layer and the primer coating layer in the examples of the present invention described later, the relationship between the respective elongation ratios and the overall elongation ratios was subjected to multiple correlation analysis.
As a result, in the scope of the present invention example, the following formula (1) was obtained, and the contribution of the elongation percentage of Y (top coat layer) to the overall elongation was very small.
Z = -1.7 + 0.46X + 0.03Y (1)
X is the elongation of the primer coat layer
Y is the elongation of the top coat layer
Z is the total elongation
On the other hand, in the range of the comparative example, the following formula (2) was obtained, and the contribution of the elongation percentage of the top coat layer to the overall elongation was great.
Z = -3.5 + 0.61X + 0.32Y (2)
As described above, among the factors of the contribution of the elongation percentage of the top coat layer to the total elongation percentage between the present invention and the comparative example, there is a difference in adhesiveness between the top coat layer and the primer coat layer And the influence of the adhesion between the primer coat layer and the undercoat layer are considered.
When the precoated metal sheet according to the embodiment of the present invention is subjected to the 2T tight bending process, if the total number of cracks of not more than 0.1 mm in width in the top coat layer is 5 or more and 30 or less in total, the stress is appropriately relaxed, Is excellent in adhesion after processing. If the width of the crack is larger than 0.1 mm, the adhesion between the primer coating film and the steel sheet is deteriorated, and the adhesion after processing becomes poor. When the width of the crack is larger than 0.1 mm, the effect of elution of the anticorrosive pigment is not obtained and the corrosion resistance of the processed portion is deteriorated. If the number of cracks is less than 5, the stress is not relaxed and the adhesion after processing is lowered. If the number of cracks is more than 30, the adhesion between the primer coating film and the steel sheet is deteriorated, and adhesion after processing becomes poor.
By controlling the glass transition point temperature of the primer coating layer and the breaking limit elongation of the coating layer combined with the primer coat layer and the top coat layer as described above, the precoated metal sheet has good adhesion and an appropriate elongation, When the coating film is stretched by the mold, fine cracks are generated and the stress is relaxed. Therefore, the coating film peeling property of the end face is excellent.
When the elongation at break of the primer coating layer is increased, the elongation at break of the coating film layer, which is the sum of the primer coat layer and the top coat layer, is increased. As a result, the value is higher than the elongation at break of the top coat layer alone.
The top coat layer includes a resin component, and the resin component includes an acrylic resin or a polyester-modified acrylic resin. Thus, the precoated metal sheet has excellent stain resistance in terms of stain resistance, in particular, weather resistance.
The acrylic resin is a copolymer obtained by heating reaction of an acrylic monomer or methacrylic monomer having a hydroxyl group with an acrylic acid ester or a methacrylic acid ester by a well-known method. As the acrylic monomer or methacrylic monomer having a hydroxyl group, for example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate and the like can be used , And these may be used singly or in combination of plural species. Examples of the acrylic acid esters or methacrylic acid esters include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and the like. These may be used singly or in combination of a plurality of species.
The polyester-modified acrylic resin may be obtained by cross-linking a polyester with an acrylate with a cross-linking agent such as a combination, a copolymerization or the like. When the polyester-modified acrylic resin is obtained by polymerizing a lactone-modified acrylic polyol and a carboxyl group-containing vinyl-based monomer, the stain resistance is excellent and more preferable. The lactone-modified acrylic polyol is obtained by copolymerizing a mixture of a hydroxyl group-containing vinyl monomer, a carboxyl group-containing vinyl monomer and other vinyl monomers in the presence of an ordinary radical polymerization initiator and an acrylic resin And then adding a lactone compound to the reaction mixture to carry out ring-opening addition reaction in the absence of a catalyst. Examples of the carboxyl group-containing vinyl monomers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, adducts of the above-mentioned hydroxyl group-containing vinyl monomers with phthalic anhydride or hexahydrophthalic anhydride .
The primer coating layer preferably contains a rustproof pigment and a resin component. Since the primer coating layer contains the anticorrosive pigment, the breaking extension ratio of the top coating layer and the primer coating layer can be adjusted. In addition, even when cracks are generated, the occurrence of zinc oxide (white rust) from the cracks is suppressed, and the rust-preventive pigment is eluted instead, thereby improving the corrosion resistance. In order to impart long-term corrosion resistance, the anticorrosive pigment preferably contains at least one of magnesium phosphate, calcium phosphate, aluminum phosphate and zinc phosphate. The resin component in the primer coating layer preferably comprises (1) an epoxy resin and / or a polyester resin, or (2) an epoxy-modified polyester resin. The adhesion between the coating film and the steel sheet is determined by the adhesion between the primer coat layer and the under coat layer. In order to improve the adhesion, it is preferable that the resin component in the primer coat layer includes an epoxy-modified polyester resin.
Examples of the epoxy-modified polyester resin include a reaction product of a carboxyl group of a polyester resin and an epoxy group-containing resin, a reaction product of a hydroxyl group in the polyester resin and a hydroxyl group in the epoxy resin through a polyisocyanate compound, And reaction products obtained by the addition of a resin, condensation, graft, or the like.
Examples of the polyester resin include various polyester resins obtained by a known esterification method from a polyhydric alcohol and a polybasic acid. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, hydrogenated bisphenol, Examples of the polybasic acid include phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride and the like. Examples of the polybasic acid include ethylene oxide adduct or propylene oxide adduct, glycerin, trimethylolethane, trimethylol propane, pentaerythritol, Phthalic anhydride, phthalic anhydride, azelaic acid, sebacic acid, maleic anhydride, fumaric acid, anhydrous trimellitic acid and anhydrous pyromellitic acid, and if necessary, monobasic acids such as benzoic acid and p- Or may be used in combination.
As the epoxy resin, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolak type epoxy resin and the like can be given.
Examples of the polyisocyanate compound include toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, Methane diisocyanate, hydrogenated xylylene diisocyanate and / or their adduct, buret or isocyanurate, and the non-sulfur substitution such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate and the like The adduct, buret or isocyanate of the polyisocyanate compound is particularly preferable. These polyisocyanate compounds may be used singly or in combination of two or more.
As the aluminum phosphate used for the anticorrosive pigment, a generally known one such as a reagent can be used. As the aluminum tripolyphosphate, aluminum triphosphate generally known can be used. For example, " K-WHITE " (registered trademark), which is a tripolyphosphoric acid aluminum hydride aluminum available from TAYKA CO., LTD. Can be used.
As the calcium phosphate, generally known ones such as reagents can be used. Particularly, it is preferable that aluminum dihydrogen tripolyphosphate is treated with calcium, and for example, " K-WHITE / Ca650 " (calcium treatment) manufactured by Teika Corporation can be used.
As the magnesium phosphate, generally known magnesium phosphate can be used. Particularly, aluminum magnesium tripolyphosphate subjected to magnesium treatment is suitable, and for example, " K-WHITE / K-G105 ", which is aluminum aluminum tripolyphosphate subjected to magnesium treatment by Teika, can be used.
As zinc phosphate, generally known ones such as reagents can be used. Particularly, it is suitable that aluminum dihydrogen tripolyphosphate is zinc-treated, and for example, " K-WHITE / # 105 "
The glass transition point temperature of the primer coat layer is more than 50 ° C and not more than 100 ° C. If the glass transition temperature is 50 캜 or less, cracks do not occur when the coating film is stretched by the mold at the time of pressing, and the peelability of the coating film on the end surface is deteriorated. If the glass transition point temperature is higher than 100 占 폚, cracks are excessively large and the fragmented coating film is peeled off, resulting in deterioration of peelability of the coating film on the end face.
The glass transition temperature of the primer coating layer can be controlled by the glass transition temperature of the epoxy-modified polyester resin as the main resin. In particular, the glass transition temperature of the primer coat layer can be controlled by changing the glass transition temperature of the polyester resin portion.
The top coat layer preferably contains no melamine resin. When the top coat layer contains no melamine resin, the weather resistance is more excellent because the deterioration by the acid rain is particularly small. In addition, since it prevents physical adherence of contaminants, it also results in excellent stain resistance.
The coefficient of dynamic friction of the surface of the precoated metal sheet according to the embodiment of the present invention is determined by the coefficient of dynamic friction of the surface of the top coat layer and is preferably 0.06 or more and 0.25 or less and more preferably 0.06 or more and 0.13 or less. If the coefficient of dynamic friction is 0.06 or more, it is preferable that the pre-coated metal plate is made of a coil, so that no breakage of the coil occurs. When the kinetic friction coefficient is 0.25 or less, scratches do not occur on the coating film during pressing, and the pressing property is not deteriorated.
The coefficient of dynamic friction may be adjusted by using a commonly used wax and by adding the wax to the top coat layer.
It is preferable that the water contact angle of the surface of the top coat layer after leaving the precoated metal sheet according to the embodiment of the present invention in a humidified environment of 50 캜 and 95% RH for 72 hours is 60 degrees or less. When the water contact angle under these conditions is 60 degrees or less, the contamination tends to be more easily washed away by the rain. The smaller the water contact angle under these conditions is, the smaller the better, and the lower limit value is not particularly limited. This water contact angle can be measured using a known measuring instrument. As a method of making the water contact angle under such conditions 60 degrees or less, a method of adding organosilicate to the top coating film is considered, but other methods may be used. The top coat layer preferably contains an organosilicate.
The organosilicate is a compound containing a hydrolyzable silicon group and is a compound represented by the following general formula (1) or a partial decomposition condensation product thereof.
(In the formula (1), R 1 to R 4 each represent an organic group which may be the same or different from each other, and n represents an integer of 1 or more)
The content of the organosilicate contained in the top coat layer is preferably 0.1 part by mass or more and 20 parts by mass or less, more preferably 5 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the resin solid content of the top coat layer. When the content of the organosilicate is 0.1 parts by mass or more, the stain resistance is improved, which is preferable. When the content of the organosilicate is more than 20 parts by mass (more than 20 parts by mass), appearance defects tend to occur.
The concentration of the anticorrosive pigment in the primer coating layer is preferably 10 parts by mass or more and 160 parts by mass or less, more preferably 50 parts by mass or more and 160 parts by mass or less, based on 100 parts by mass of the resin solid content. When the concentration of the anticorrosive pigment is 10 parts by mass or more, the anticorrosive property is improved. Therefore, when the concentration of the anticorrosive pigment is more than 160 parts by mass, the amount of the resin component is small.
As the anticorrosive pigment of the primer coating layer coated on the precoated metal sheet, known anticorrosive pigments may be used in combination, and examples thereof include calcium ion-exchanged silica, magnesium silicate compounds, non-hexavalent chromium-based anticorrosive agents such as molybdate, Acid / phosphoric acid combined pigments (commonly referred to as VP pigments), and the like. They may use commercially available products. The calcium ion-exchanged silica generally means a type in which calcium is ion-exchanged with a silanol group on the surface of a known silica, and a commercially available one may be used. Commercially available calcium ion exchange silicas include "SHIELDEX" (registered trademark) of GRACE Corporation.
It is more preferable to contain at least one of fine silica, a silane coupling agent, and tannic acid with respect to the base coat layer because the primer coat layer has excellent adhesion with the epoxy-modified polyester resin.
The adhesion amount of the base coat layer is not particularly specified, but it is more preferable that the total solid content is in the range of 10 to 1000 mg / m < 2 >. If the adhesion amount of the base coat layer is less than 10 mg /
It is more preferable that the addition amount of tannic acid is 2 to 80 g / l. If the addition amount of tannic acid is less than 2 g / l, the rust inhibitive effect and the film adhesion can not be sufficiently obtained. On the other hand, if the addition amount of tannic acid exceeds 80 g / l, the rust inhibitive effect and the coating film adhesion are deteriorated or not dissolved in the aqueous solution.
Examples of usable silane coupling agents include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) (2-aminoethyl) aminopropylmethyldiethoxysilane,? - (2-aminoethyl) aminopropylmethyldimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Methacryl Methylpropylmethyldiethoxysilane, N-β- (N-vinylbenzylaminoethyl) - γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, , N -? - (N-vinylbenzylaminoethyl) -? - aminopropylmethyldimethoxysilane, N-? - (N- vinylbenzylaminoethyl) -? - aminopropyltriethoxysilane, N- N-vinylbenzylaminoethyl) -? - aminopropylmethyldiethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxine ? -Mercaptopropyltrimethoxysilane,? -Mercaptopropylmethyldimethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane, Mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane,? -Mercaptopropylmethyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltriacetoxysilane,? -Chloropropyl Γ-chloropropylmethyldimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropylmethyldiethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, γ- Anilinopropyltrimethoxysilane,? -Anilinopropyltriethoxysilane,? -Anilinopropylmethyldiethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxy Silane, octa (Trimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (triethoxysilyl) propyl] ammonium chloride, Octadecyldimethyl [3- (methyldiethoxysilyl) propyl] ammonium chloride,? -Chloropropylmethyldimethoxysilane,? -Mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, .
In view of coating film adhesion and corrosion resistance, the content of the silane coupling agent is more preferably 2 to 80 g / l.
In the present embodiment, the term "fine silica" refers to silica capable of stably maintaining an aqueous dispersion state when dispersed in water to have a fine particle size. Examples of the particulate silica include "Snowtex N", "Snowtex C", "Snowtex UP", "Snowtex PS" (all manufactured by Nissan Kagaku Kogyo), "Adelite AT-20Q" Or silica powder such as Aerosil # 300 (available from Nippon Aerosil Co., Ltd.) or the like can be used. The fine silica may be appropriately selected depending on the performance required.
As a dry baking method in coating, a commonly known dry baking method such as a hot air oven, a flame type oven, a far infrared ray oven, an induction heating type oven and the like can be used.
The primer coating layer and the top coating layer according to the present embodiment each preferably have a thickness of 1 to 30 mu m. When the film thickness is less than 1 mu m, there is a possibility that the function (for example, coloring property) as a coating film layer may not be obtained. When the film thickness exceeds 30 mu m, there is a fear that a coating defect called bubbling have.
As the metal plate used in the precoated metal sheet according to the embodiment of the present invention, generally known metal materials can be used. Such a metal material may be an alloy material. Examples of such a metal material include a steel sheet, a stainless steel sheet, an aluminum sheet, an aluminum alloy sheet, a titanium sheet, and a copper sheet. The surface of these materials may be subjected to various platings.
Examples of the plating include zinc plating, aluminum plating, copper plating, and nickel plating, and they may be alloy plating thereof. In the case of a steel sheet, a commonly known steel sheet and plating such as a hot-dip galvanized steel sheet, an electro-galvanized steel sheet, a zinc-nickel alloy coated steel sheet, a galvannealed galvanized steel sheet, an aluminum coated steel sheet, an aluminum- Steel plate can be applied. In particular, zinc-based plated steel sheet is more suitable because corrosion resistance is further improved. Here, the zinc-based plated steel sheet refers to zinc-plated steel sheets, such as hot-dip galvanized steel sheets and electro-galvanized steel sheets, zinc-plated steel sheets, zinc-nickel alloy plated steel sheets, molten alloyed galvanized steel sheets and zinc- And other metal-plated steel sheets. Of these zinc-plated steel sheets, zinc-plated steel sheets such as hot-dip galvanized steel sheets and electro-galvanized steel sheets are more suitable because they have a large sacrificial effect and excellent corrosion resistance. Further, when the plating amount of these zinc plated steel sheets is 40 to 90 g / m < 2 > per one side, the workability and corrosion resistance are both compatible. If the coating amount per one surface is less than 40 g /
The coating method of each coating layer is not particularly limited and a generally known coating method such as roll coating, ringer roll coating, air spraying, airless spraying, dipping, or the like can be employed. In addition, coating is more preferable because coating efficiency is good and mass production is possible when the application is carried out in a continuous coating line, which is also called a general coil coating line or sheet coating line, in which these coating apparatuses are fully equipped.
Example
The details of the examples will be described below.
1. Metal disc
(Hereinafter referred to as GI) manufactured by Sinnett Tetsu Sumikin K.K., an electrodeposited galvanized steel sheet " NS ZINCK COAT (registered trademark) " manufactured by Shinnitetsu Sumikin K.K., (Hereinafter referred to as ZL), an aluminum plate " JIS3004 " (hereinafter referred to as " JIS3004 ") (hereinafter referred to as " EG ", trade name, manufactured by Shinnitetsu Sumitomo Chemical Co., (Hereinafter referred to as " GL "), stainless steel plate " SUS430 " (hereinafter referred to as SUS), zinc-aluminum alloy plated steel sheet of Nittetsu Sumikin Kogyo Co., Aluminum-magnesium alloy coated steel sheet "ZAM (registered trademark)" (hereinafter referred to as "SD") manufactured by Nippon Seisakusho Co., Ltd., zinc-aluminum- trademark) (Hereinafter referred to as ZAM) was used as a disc. The plate thickness of the original plate was 0.6 mm.
The plating amount of ZL used in this experiment was 20 g /
2. Paint
In this embodiment, a three-layer coating film of a top coat film layer, a primer coat layer and a back coat film layer on one surface (surface) of the core plate (original plate) ), A precoated metal plate having the same base coat layer as the surface, the same primer coat layer as the surface thereof, and a back coat layer thereon was produced.
(Base coat layer coating)
Paint 1: EC2000 manufactured by Nippon Paint Co., Ltd.
, 5 g / L of a silane coupling agent (? -Glycidoxypropyltrimethoxysilane), 1.0 g / L of an aqueous dispersion colloidal silica ("Snow Tech-N" manufactured by Nissan Kagaku Co., Ltd.) (MD-1100, manufactured by Toyobo Co., Ltd.) in an amount of 25 g / L
(Primer Coating Layer Coating)
The resin shown in Table 2 was dissolved in an organic solvent (Cyclohexanone: Solvesso 150 = 1: 1 mixed in mass ratio) as the main resin so that the resin solid content concentration was 30% by mass. When two kinds of main resins were mixed, the main resin was mixed in an amount of 50 mass%. The glass transition point temperature of the resin shown in Table 2 was measured by differential scanning calorimetry.
Then, as a cross-linking agent, a melamine resin "Cymel (registered trademark) 303" manufactured by Cytec Industries was added to the main resin. The amount of the melamine resin to be added was such that the ratio of the resin solids to the mass of the main resin solids: melamine resin solids was 80: 20. To the mixed solution of the polyester resin and the melamine resin was added 0.5% by mass of an acidic catalyst " Catalyst (registered trademark) 600 " manufactured by Cytec Industries, and the mixture was stirred to obtain a clear paint. K-WHITE G-105 "(hereinafter referred to as" P-Al ") tripolyphosphate dibasic calcium phosphate," Sildex C303 "(hereinafter referred to as" (Hereinafter referred to as " P-Zn "), phosphorus acid dihydrogen phosphate (hereinafter referred to as P-Mg) (Hereinafter referred to as " P-Ca ") was added in an amount required and stirred to obtain a primer coating (see Table 3 below). The glass transition point temperature of the resin shown in Table 3 was measured by differential scanning calorimetry.
Epoxy-Modified Polyester Resin: A copolymer obtained by copolymerizing a bisphenol A type epoxy resin and a polyester (each grade of Byyo Bosa Byron)
Epoxy resin: bisphenol A type epoxy resin
Polyester resin (glass transition temperature: 55 캜): Byron (registered trademark) 660
A tensile test was conducted to measure the elongation at break of the primer coat layer. In the tensile test,
(Top coating layer paint)
<Main resin>
The resin shown in the following Table 4 was used as the main resin. Here, the glass transition point temperature of the resin shown in Table 4 was measured by differential scanning calorimetry.
Acrylic resin (glass transition temperature: 55 占 폚): YU-WOO (registered trademark) S-2818
Polyester resin (glass transition temperature: 55 캜): Byron (registered trademark) 660
Polyester resin (glass transition temperature: 79 占 폚): Byron 占 885
Polyester-modified acrylic resin (glass transition temperature: 21 占 폚 and 55 占 폚): The copolymer
<Cross-linking agent>
Examples of the amino resin crosslinking agent include "Cymel (registered trademark) 303" (referred to as Me), a methylated melamine resin manufactured by Mitsui Cytec, Desmodule BL-3175 (referred to as BI), an isocyanate of Sumitomo Bayer Urethane Of an epoxy resin EX-252 (referred to as EP) was added so that the main resin: crosslinking agent was 80:20 by mass. Quot; Catalyst 602 " manufactured by Mitsui Cytec was used as the catalyst. The addition amount of the catalyst was 0.5 part by mass with respect to 100 parts by mass of the main resin solid fraction.
<Organosilicate>
As the organosilicate, methyl silicate 51 (manufactured by Colcoat) was added.
<Wax>
And those having a melting point of 61 占 폚 manufactured by Nippon Seiro Co., Ltd. were used. The coefficient of dynamic friction was changed by the addition amount of the wax.
<Pigment>
Titanium oxide, iron oxide and carbon black, which are commercially available, were used for coloring. The total pigment concentration was 20 parts by mass based on 100 parts by mass of the solid content.
Table 5 shows the composition of the top coating material obtained by mixing these materials. In Table 5, the addition amount of silicate is a part by mass with respect to 100 parts by mass of resin solid content. These were dissolved in an organic solvent (mixed with cyclohexanone: Solvesso 150 = 1: 1 in a mass ratio) so that the resin solid content concentration was 30 mass%.
In order to measure the breaking limit elongation of the top coat layer, a tensile test was conducted. In the tensile test,
3. Fabrication of Precoated Metal Plate
Various metal plates were degreased by immersion for 10 seconds in an aqueous solution having a concentration of 2 mass% of FC-4336 (Nippon Perkerizing agent) at a temperature of 60 占 폚, washed with water and then dried. Subsequently, the base coat was applied to both sides of the metal plate by a roll coater and dried in a hot air oven. The drying conditions in the hot air oven were 60 DEG C as the reaching plate temperature of the metal plate. The adhesion amount of the chromate-free treatment was coated so as to be 80 g /
Subsequently, the primer coating film prepared as described above was coated on both sides of the undercoating metal plate so as to have a dry film thickness of 5 mu m by a roll coater. In the induction heating furnace in which hot air was blown, 210 < 0 > C. After drying and baking, the painted metal plate was wiped off with water and water-cooled.
The top coat was applied on one side of the primer coating film layer and the gray color of "FL100HQ", the back coat of Nippon Fine Coatings Co., Ltd., on the other side was coated with a roll coater so that the top coat had a dry film thickness of 15 μm, The resultant was dried and baked at the same time in the induction heating furnace in which hot air was blown so that the dry film thickness became 5 占 퐉 and the reaching plate temperature of the metal plate became 230 占 폚 and water-cooled to obtain a precoated steel sheet.
The structure of the surface of the prepared sample is shown in Table 6 below.
The evaluation method of the precoated metal sheet will be described in detail.
1. Water contact angle
The prepared precoated metal sheet was allowed to stand for 72 hours under a humidified atmosphere of 50 캜 and 95% RH, and 2.0 占 퐇 of water droplets were dropped onto the surface of the top coat layer using "DM-501" manufactured by Kyowa Gaimengagakusha, The water contact angle was measured by the? / 2 method after a second. The measurement was performed five times, and the average value thereof was evaluated.
2. Pollution resistance test
The produced samples were subjected to an exposure test for 3 months at an outdoor exposure test site near the coast of Futtsu City, Chiba Prefecture. The samples after the test were visually evaluated for the presence or absence of contaminants. The results were evaluated as A when no contaminants were present, B when a contaminant was slightly observed, and C when contaminants were clearly observed. When the evaluation was C, it was judged that the contamination resistance deteriorated.
3. Contamination test
The prepared samples were subjected to an exposure test for 12 months at an outdoor exposure test site near the coast of Futsu City, Chiba Prefecture. The samples after the test were visually evaluated for presence or absence of contaminants including dirt spots, and when there were no dirt marks or no contaminants, A was observed. In some cases, dirt spots were observed in some cases, B, the part where the dripping water was observed, the part where the whole was also contaminated was C, the case where the dripping water was clearly observed, and the case where the whole was also contaminated was evaluated as D. When the evaluation was D, it was judged that the contamination resistance of the inside water drops.
4. Adhesion peelability
The prepared precoated metal sheet was cut and the lower burr portion was further lowered in the burr direction using a metal mold. The tape was reliably adhered to the coating film on the end face portion, and the peeling of the tape was visually observed. Respectively. A is the case where no peeling is observed at all, C is a case where slight cracking or peeling is observed in the coating film, and C is a case where there is a clear large crack or peeling in the coating film. When the evaluation was C, it was judged that the coating film peelability on the end face after the processing was deteriorated.
5. Evaluation of Work Crack
The test piece cut into a width of 5 cm was subjected to 2 T bending in an atmosphere of 20 캜 by a test method according to JIS G3312. Specifically, two sheets of the same test plates were sandwiched between the inner sides, and the surface with the top coat coated on the outside was subjected to 180 degree contact bending (see Fig. 2). A pressure-sensitive adhesive tape (product name: cellophane tape) was attached to the entire bent portion, the adhesive tape was peeled off, and the peeled test piece was cut parallel to the bending direction so as to divide the width of the test piece into 10 equal parts. Respectively. The width (1) of the crack was measured by measuring the outermost surface layer of the
6. Corrosion resistance test
A sample subjected to 2 T bending under an environment of 20 캜 was subjected to a salt spray test by the method described in JIS K 5400.9.1. The brine was sprayed to the processing part. The test time was 240 hours for the sample using EG and ZL as the original plate, and 500 hours for the sample used for the other original plate. The area ratio of white rust of the processed portion was measured. A was evaluated as A, B as 20% or less, C as 50% or less, and D as 50% or more. When the evaluation was D, it was judged that the corrosion resistance was poor.
7. Kinetic friction coefficient
Using a surface tester HEIDON-14 (manufactured by Shinto Kagaku Co., Ltd.), a load was measured under the conditions of a load of 100 g, a ball indenter of 10 mm, and a moving speed of 150 mm / min.
The evaluation results of the test are summarized in Table 7.
A tensile test was conducted to measure the elongation at break of the coating film layer including the primer coat layer and the top coat layer. In the tensile test, the
The pre-coated metal sheet according to the embodiment of the present invention was subjected to the tensile test until the elongation at break reached 10%, but cracks did not occur.
As apparent from Table 7, the precoated metal sheet of the present invention example shows excellent stain resistance, excellent peelability on the end face after processing, and excellent corrosion resistance.
As is clear from Table 7, the precoated metal sheet of the present invention had a tensile strength at a range (A) in the length of 1 mm in the direction perpendicular to the bending direction centered on the top of the bending head, It can be seen that a total of 5 or more and less than 30 cracks having a width of 0.1 mm or less is generated.
As is apparent from Table 7, when the breakage limit elongation at break of the coating layer combined with the primer coating layer and the top coating layer was set to less than 10% (level 43), cracks in the coating layer were larger than those in Example 1, The peelability of the coating film on the surface is clearly deteriorated. Further, in the case where the breaking limit elongation percentage of the coating layer combined with the primer coat layer and the top coat layer is set to exceed 25% (levels 38, 40 to 42 and 44 to 48), the stain resistance or the end face coat The peelability is deteriorated.
Further, when the breakage limit elongation of the top coat layer is more than 10% and the elongation at break of the primer coat layer is not less than 40% and not more than 50% (level 40 and 45 to 47), the stain resistance is clearly lower than that of the present invention. .
In addition, when the breakage limit elongation of the top coating layer is 5% or more and 10% or less and the elongation at break of the primer coating layer is less than 40% (Levels 37, 43, and 49), cracks in the coating layer , And the coating film peelability on the end face after processing is clearly lowered.
As is apparent from Table 7, when the resin components of the primer coat layer and the top coat layer were all polyester resins and the elongation at break of the coating layer combined with the primer coat layer and the top coat layer was less than 10% 49), it is found that the stain resistance and the peelability of the coating film on the end face after processing are lower than those of the present invention. When the resin components of the primer coat layer and the top coat layer were all made of polyester resin and the elongation at break of the primer coating layer was set to 50% or more (level 48), the stain resistance and the post- It can be seen that the peelability of the coating film on the surface is clearly deteriorated.
In addition, even when the breakage limit elongation of the top coating layer is made to exceed 10% (levels 45 to 47), it is found that the stain resistance and the coating film peelability on the end face after processing are clearly lower than those of the present invention.
Although the embodiments of the present invention have been described in detail with reference to the drawings, the present invention is not limited to these examples. It will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. It is to be understood that they fall within the technical scope of the invention.
According to the embodiment of the present invention, it is possible to provide a precoated metal sheet excellent in long-term stain resistance, coating film peelability on end face, and corrosion resistance.
1: Width of crack
2: Saw coating layer
3: Primer coating layer
4: Precoated metal plate
A: A range of 1 mm in the direction perpendicular to the bending direction about the top of the bending head
Claims (10)
A base coat layer formed on the metal sheet and containing no chromate,
A primer coat layer formed on the base coat layer and containing no chromate,
A precoated metal plate having a top coating layer formed on the primer coating layer,
A breaking limit elongation at break of the coating layer comprising the primer coat layer and the top coat layer is at least 10% and at most 25%
Wherein the primer coat layer has a glass transition temperature of more than 50 DEG C but not more than 100 DEG C,
Wherein the top coat layer comprises a resin component, the resin component comprises an acrylic resin or a polyester-modified acrylic resin,
When the precoated metal sheet was subjected to 2T tight bending, a total of 5 to 30 cracks having a width of 0.1 mm or less was formed in the top coat in a range of 1 mm in the direction perpendicular to the bending direction centered on the bending head top portion Wherein the pre-coated metal plate is a metal plate.
Wherein the top coat layer has an elongation at break of not less than 5% and not more than 10%
Wherein the primer coating layer comprises at least one of magnesium phosphate, calcium phosphate, aluminum phosphate or zinc phosphate, and the resin component in the primer coat layer is an epoxy-modified polyester Wherein the pre-coated metal sheet comprises a resin.
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| PCT/JP2015/062867 WO2016174746A1 (en) | 2015-04-28 | 2015-04-28 | Pre-coated metal plate |
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| JP7058160B2 (en) * | 2018-03-28 | 2022-04-21 | 三井化学株式会社 | Metal primer, laminate, battery and packaging |
| CN110760916B (en) * | 2019-11-18 | 2022-04-05 | 和县科嘉阀门铸造有限公司 | Method for improving corrosion resistance of magnesium alloy valve |
| JP6898006B2 (en) | 2019-12-23 | 2021-07-07 | テック大洋工業株式会社 | Laminated body and rust prevention method |
| AU2022248122A1 (en) | 2021-03-31 | 2023-09-28 | Nippon Steel Corporation | Precoated plated steel sheet and molded product |
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| JP2001311038A (en) | 2000-04-27 | 2001-11-09 | Nippon Yushi Basf Coatings Kk | Primer coating composition |
| JP2006175810A (en) | 2004-12-24 | 2006-07-06 | Nippon Steel Corp | Coated metal sheet good in processability and antistaining properties, and its manufacturing method |
| JP2008254313A (en) | 2007-04-04 | 2008-10-23 | Nippon Steel Corp | Precoated metal sheet, metal molded body formed by working the same and manufacturing method of precoated metal sheet |
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| JPS5783449A (en) * | 1980-11-13 | 1982-05-25 | Nippon Paint Co Ltd | Precoated metallic plate |
| JPH01194979A (en) * | 1987-09-25 | 1989-08-04 | Kansai Paint Co Ltd | Method of coating aluminum foil |
| JP3144433B2 (en) * | 1991-12-20 | 2001-03-12 | 日立金属株式会社 | Weatherproof coating film and aluminum wheel formed therefrom |
| JPH10314664A (en) * | 1997-05-22 | 1998-12-02 | Nisshin Steel Co Ltd | Precoated steel sheet excellent in resistance to staining |
| JP2000144019A (en) * | 1998-11-06 | 2000-05-26 | Nippon Steel Metal Prod Co Ltd | Coated steel sheet having high hardness and high anticorrosion and excellent in chipping resistance |
| JP4398771B2 (en) * | 2004-04-02 | 2010-01-13 | 株式会社神戸製鋼所 | Resin coated metal plate |
| JP4460441B2 (en) * | 2004-12-24 | 2010-05-12 | 新日本製鐵株式会社 | Painted metal plate |
| JP4808717B2 (en) * | 2005-07-28 | 2011-11-02 | 新日本製鐵株式会社 | Pre-coated metal plate and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001311038A (en) | 2000-04-27 | 2001-11-09 | Nippon Yushi Basf Coatings Kk | Primer coating composition |
| JP2006175810A (en) | 2004-12-24 | 2006-07-06 | Nippon Steel Corp | Coated metal sheet good in processability and antistaining properties, and its manufacturing method |
| JP2008254313A (en) | 2007-04-04 | 2008-10-23 | Nippon Steel Corp | Precoated metal sheet, metal molded body formed by working the same and manufacturing method of precoated metal sheet |
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| JPWO2016174746A1 (en) | 2017-05-18 |
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| CN107531018A (en) | 2018-01-02 |
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