KR101755963B1 - Metal sheet laminated with water-based resin coating film - Google Patents
Metal sheet laminated with water-based resin coating film Download PDFInfo
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- KR101755963B1 KR101755963B1 KR1020157022630A KR20157022630A KR101755963B1 KR 101755963 B1 KR101755963 B1 KR 101755963B1 KR 1020157022630 A KR1020157022630 A KR 1020157022630A KR 20157022630 A KR20157022630 A KR 20157022630A KR 101755963 B1 KR101755963 B1 KR 101755963B1
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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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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
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- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
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- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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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
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Abstract
A water-based resin film laminated metal sheet which is beautiful and exhibits high blackness is provided. A first water based resin coating film layer containing a black pigment is laminated on at least one side of a metal plate and a second water based resin film layer containing a black pigment is laminated on the second water based resin film layer side and at least one of a colloidal silica, Based resin laminate film laminated with a water-based resin laminate film layer.
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black water-based resin film laminated metal plate used for an outer plate material or building material of a housing, an internal or external part of an automobile or a home electric appliance, The present invention relates to an excellent water based resin film laminated metal plate.
As an external component of electronic and electric devices such as a liquid crystal television, a plasma display, and a DVD player, a black display is required from the viewpoint of designability and the like. Conventionally, a metal plate (PCM: precoated metal) previously coated with a solvent-based black coat is used as the black metal plate. A PCM coated with a black coating film is laminated with a primer coating layer (film thickness of about 3 m) for imparting processability and corrosion resistance, and a top coating layer (film thickness of about 10 m), which is a black layer containing black pigment such as carbon black, And the total film thickness of the primer coating layer and the top coating layer is generally set to be about 10 to 20 mu m thick. However, if the film thickness is increased, the manufacturing cost is considerably increased due to the increase in the amount of the paint used, the large energy consumption due to the long-time conversation of the baking process, and the large-scale use of the thinner which is expensive and environmental load substance. From this background, studies have been made to reduce the coating thickness of the coating film as much as possible so as to reduce the amount of the coating material used. However, there has been a limit to the reduction of the manufacturing cost,
As the coated metal plate which does not use the expensive solvent-based paint, an aqueous resin paint may be used. Since the solvent of the water-based resin paint is water, it does not consume much energy in a long burning process and does not use a thinner which is a high-cost and environmental load substance, so that the manufacturing cost can be greatly reduced. BACKGROUND ART [0002] Conventionally, as a built-in and external component of an electronic or electric appliance using a water-based resin paint, a special chemical treatment in which only a water-based resin coating layer is provided is known, and a metal plate is painted with a water- , It is necessary to contain a large amount of black pigment in the aqueous resin coating film in order to conceal the surface of the metal plate. However, since the black pigment is a component which inhibits the film-forming property of the water-based resin coating layer, it has a problem that the corrosion resistance is remarkably reduced, the water-based resin coating layer is brittle and the scratch resistance is remarkably decreased, Wrinkles, and boiling (coating defects that occur when the solvent in the coating material volatilizes on the surface of the metal plate or on the surface layer of the coating film), and the like. In addition, the waterborne resin coating layer It was difficult to do. Thus, when an aqueous resin paint containing a black pigment is used, it is difficult to achieve both improvement in blackness and improvement in various durability such as corrosion resistance and scratch resistance.
As means for avoiding the deterioration of various durability such as corrosion resistance and scratch resistance, a method of increasing the film thickness of the water based resin coating film layer is conceivable. For example, there is simply a method of increasing the film thickness per layer or a method of further laminating a water based resin coating film. In the method of simply increasing the film thickness per layer, specifically, there is a method of increasing the amount of resin to be coated on the metal plate by increasing the solid content concentration of the composition for forming a water-based resin coating film, As a result, cyclability is lowered, so that it is difficult to manufacture in a high-speed line, resulting in an increase in cost. As a means for avoiding the deterioration of the scratch resistance, there is a method of adjusting the silver color so that scratches are less noticeable. However, in this method, since a beautiful black appearance with a depth is not obtained, the degree of freedom of designability is impaired.
On the other hand, the technique relating to the aqueous resin film laminated metal plate in which a plurality of water based resin coating films are laminated is not only black, but also about other colors, even in the prior art documents and conventional chemical treatment techniques. When the composition for forming a water-based resin coating film is coated on the water-based resin coating layer, it is painted on a water-repellent organic resin, and since the viscosity of the composition for forming an aqueous resin coating film is low, It has been thought that it is difficult to finely finish. Furthermore, lamination of a water-based resin coating film has been avoided in the production of PCM (coil coating) because the solvent-based resin coating film can be laminated by using a solvent-based coating material without sacrificing manufacturing cost.
Patent Literatures 1 to 3 disclose a coated film laminated metal plate in which a second layer which is a coated film cleared on the first layer which is a black coating film is laminated. However, these documents do not disclose a laminated metal film coating layer which is an aqueous resin coating layer in all two layers.
Patent Document 4 discloses a water-based resin film laminated metal plate in which a plurality of water-based resin coating film layers are laminated on a metal plate. However, this document does not mention the above-mentioned problem, nor the solution thereof.
SUMMARY OF THE INVENTION It is an object of the present invention to provide a water-based resin film laminated metal sheet that is beautiful and exhibits high blackness. Another object of the present invention is to provide a water-based resin film laminated metal sheet excellent in scratch resistance, which is particularly important in black which is prone to scratches.
The first waterborne resin coating film laminated metal sheet of the present invention is characterized in that a first waterborne resin coating film layer containing a black pigment is laminated on at least one side of a metal plate and a 3% And a second water-based resin coating film layer which is a clear coating film layer containing silica this month.
The second water-based resin film laminated metal sheet of the present invention is characterized in that a first water-based resin coating film layer containing a black pigment is laminated on at least one surface of a metal sheet, and a blue pigment or a green pigment And a second aqueous resin coating layer containing a polyimide-based thixotropic agent, wherein the total content of the blue pigment and the green pigment in the second aqueous resin coating layer is 3 mass% Or more.
The third water-based resin film laminated metal sheet of the present invention is characterized in that a first water-based resin coating film layer containing a black pigment is laminated on at least one surface of a metal sheet, and a blue pigment or a green pigment And a second water-based resin coating film layer comprising a polyamide-based thixotropic agent, wherein the total content of the blue pigment and the green pigment in the second water-based resin coating film layer is 3 By mass or more, and the content of the colloidal silica in the second water-based resin coating layer is 3% by mass or more.
In any of the water-based resin film laminated metal sheets, it is preferable that the sum of the film thicknesses of the first water-based resin film layer and the second water-based resin film layer is 0.9 to 8.0 탆.
It is preferable that the lightness L * in the L * a * b * color system of the water-based resin film laminated metal sheet is less than 23.
It is preferable that the black pigment contained in the first water based resin coating film layer is 16 mass% or more and 50 mass% or less, and the black pigment is at least one of an ink and a carbon black.
It is preferable that the first water-based resin coating layer contains a polyurethane resin in an amount of 25 mass% or more.
It is preferable that the first water-based resin coating film layer is obtained from a composition for forming a first water-based resin coating film containing at least 1% by mass of a crosslinking agent.
It is preferable that the second water based resin coating film layer does not contain a black pigment.
It is preferable that the second water-based resin coating film layer contains 25 mass% or more of a polyethylene resin and that the film thickness of the first water-based resin coating film layer is 4 times or less the film thickness of the second water-based resin coating film layer.
The metal plate is preferably an electrogalvanized metal plate.
According to the present invention, it is possible to provide a water-based resin coating film laminated metal sheet which is beautiful and exhibits high blackness. The water-based resin film laminated metal sheet according to the present invention can be manufactured without using a solvent-based resin requiring energy for a thinner or a thinner portion having a high environmental load, so that the manufacturing cost can be greatly reduced. Accordingly, the beautiful and black, water-based resin coating laminated metal sheet manufactured at a low cost according to the present invention can be used for exterior materials and building materials such as housings of automobiles and household electric appliances, interior / exterior parts, and forced furniture.
Fig. 1 shows the relationship between the black pigment concentration of the first water-based resin coating layer and the L * of the water-based resin film laminated metal sheet when the second water-based resin coating film layer is a clear coating layer.
As a method for imparting a high blackness to a metal plate, for example, a two-layer water-based resin coating film layer is laminated on a metal plate, and a water-based resin coating film layer (hereinafter referred to as a first water- Based resin film layer on the first water-based resin film layer (hereinafter, referred to as a second water-based resin film layer) on the other hand while appropriately adjusting the concentration of the pigment. In order to increase the blackness by adjusting the concentration of the black pigment in the first water-based resin coating layer, it is necessary to absorb light as much as possible with the black pigment in the water-based resin coating film so as not to reflect the light. When the concentration of the black pigment is too low, light transmitted through and reflected from the clearance between the black pigments is increased, and sufficient blackness is not obtained. On the other hand, the aqueous resin coating layer is a coating layer obtained from an aqueous dispersion in which the resin is dispersed in a water medium, a coating layer in which the surfactant remains in the coating layer for dispersing the resin with the surfactant, Refers to a coating film layer formed of a water-dispersible resin containing carboxylic acid or sulfonic acid having high hydrophilicity in the skeleton, or a coating film layer in which these films coexist.
On the other hand, when the concentration of the black pigment in the first water-based resin coating film layer is appropriately adjusted, for example, the surface of the black pigment is coated with a resin or a surfactant so that the black pigment hardly aggregates, There is a method in which the average is adjusted to be about 0.2 탆. However, even if the above method is employed, it is difficult to avoid agglomeration when the distance between the black pigments is too high because of the high concentration in the water-based resin coating film. As a result, The amount of light becomes large, and it becomes difficult to absorb light with a black pigment. When the first water-based resin film layer containing water or carbon black is formed to a film thickness of 1 m and the second water-based resin film layer which is a water-based resin film layer that has been cleared is formed to have a film thickness of 1 m, The relationship between the pigment concentration and the water-based resin film laminated metal sheet L * (the lower the L * value is, the higher the degree of blackness) is shown in Fig. L * is the lowest (L * = 23) and the blackness is the maximum at a concentration of about 30 mass% in both the feed and carbon black. However, in the water-based resin film laminated metal plate of L *? 23, the original plate can not be completely concealed, and it is difficult to say that it is a beautiful black in the naked eye appearance.
When it is desired to enhance the blackness to exhibit excellent designability, it is conceivable to add black pigment to not only the first water based resin coating film layer but also the second water based resin coating film layer. However, when a second water-based resin coating film layer of black is further laminated on the first water-based resin coating film layer whose blackness is maximized to the maximum (L * is minimized), L * increases and the blackness is lowered I could see that it was discarded. It is considered that the light absorption in the first water-based resin coating layer is disturbed by the black pigment of the second water-based resin coating layer.
From these results, the inventors of the present invention have found that when light is reflected from the surface of a colloidal silica or a colored pigment having a refractive index different from that of the resin component of the second water-based resin coating film layer and can not be completely absorbed into the black pigment of the first water- The light is again returned to the first water based resin coating film layer and the black pigment is absorbed by the black pigment of the first water based resin coating film layer so that the blackness can be improved. That is, the present invention is also contemplated by adding an additive for improving blackness such as colloidal silica, cyan blue, and cyan green to the second water-based resin coating layer.
The water-based resin film laminated metal sheet according to the present invention is characterized in that a first water-based resin coating film layer containing a black pigment is laminated on at least one side of a metal plate, and colloidal silica, a blue pigment , And a green pigment are laminated on the second water-base resin film layer.
Hereinafter, constituent materials and manufacturing methods of the water based resin film laminated metal sheet in the present invention will be described.
〔plate〕
The metal plate on which the coating film is laminated is not particularly limited as long as it is used as a disk of a precoated metal. For example, an aluminum plate, a titanium plate, and the like are listed in addition to a metal plate such as an electrogalvanized metal plate (EG), a non-plated cold-rolled metal plate, a hot-dip galvanized metal plate (GI), and a galvannealed hot dip galvanized metal plate (GA). Among these, an electrogalvanized metal sheet (EG), a hot-dip galvanized metal sheet (GI), an aluminum sheet and a titanium sheet are preferable, and an electrogalvanized metal sheet (EG) is more preferable. This is because the electrogalvanized metal sheet (EG) is suitable for external parts of electronic and electric devices such as a back cover of a thin television.
It is preferable that the metal plate has at least one base layer formed in advance by a base treatment. For example, if a chemical conversion coating layer (base layer) formed by a ground treatment is provided on the surface of the metal plate on the side where the first water based resin coating film layer is formed, adhesion between the metal plate and the first water based resin coating film layer is improved.
Examples of the chemical conversion coating layer (base layer) include an organic coating layer, an inorganic coating layer, a phosphate coating layer, and a chromate coating layer. As the organic coating layer, for example, a polyethylene resin, an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a fluorine resin, a mixture thereof, a copolymer and a modified resin may be appropriately selected and used. Silica gel, colloidal silica or the like may be added to the organic film for the purpose of improving corrosion resistance, or a small amount of various wax components may be added for the purpose of improving workability after application of the coating film, An phosphorus coupling agent may be added. Examples of the inorganic coating layer include a silicate coating layer, and phosphoric acid or fluoride may be added to the silicate coating. The phosphate coating layer is a coating layer composed mainly of phosphate consisting of one or more metals selected from Mg, Al, Co, Mn and Ca.
For the purpose of improving the adhesion with the resin film or the corrosion resistance, it is preferable to coat the metal plate with a phosphate coating layer as a base layer.
The adhesion amount of the chemical conversion coating layer (base layer) is not particularly specified, but it is preferably 50 mg / m 2 or more in terms of dry mass from the viewpoint of corrosion resistance if it is an organic coating layer or an inorganic coating layer. However, if it exceeds 150 mg / m 2 , the effect of improving the corrosion resistance is saturated and the manufacturing cost is increased.
A particularly preferable embodiment of the metal plate on which the undercoat layer is formed is a method for manufacturing a metal plate (hereinafter sometimes referred to as a " specific undercoat composition ") comprising a zinc-plated metal plate And dried. When the specific under-treatment composition is applied to a galvanized metal plate, the surface of the metal plate is etched by the hydrogen ions derived from the aluminum acid in the process, and the interaction between the aluminum ion derived from the aluminum acid and the colloidal silica in the first water- It is possible to form an insoluble film having excellent adhesion with the coating film layer, and as a result, the film adhesion of the film after bending or press working (elongation / shrinkage deformation) is improved and the corrosion resistance and the tape peeling resistance are greatly improved .
The content ratio of the aluminum acid and the colloidal silica in the specific under-treatment composition is preferably in the range of 30:70 to 70:30 (more preferably 35:65 to 65:50) in terms of the solid content ratio of aluminum aluminum: colloidal silica (weight ratio) : 35, more preferably 40:50 to 60:50). If the amount of the colloidal silica is larger than the above ratio, the film-forming property is lowered to make it difficult for the undercoat layer to be formed, thereby making it difficult to obtain the effect of improving the corrosion resistance and adhesion with the upper coating, There is a possibility that the film peeling may occur later. On the other hand, if the ratio of the colloidal silica is less than the above ratio, the proportion of the aluminum acid in the solution is increased, so that the proportion of the aluminum remaining in the solution which does not react (etch) with the metal plate is dissolved in water is increased, The corrosion resistance may be lowered.
In the specific under-treatment composition, the polyacrylic acid is preferably contained in an amount of 1.0 to 10.0 parts by mass (more preferably 3.0 parts by mass or more and 6.0 parts by mass or less) based on 100 parts by mass of the total solid content of the aluminum acid and colloidal silica in the process . Polyacrylic acid is considered to have a function of appropriately controlling the reaction (etching) between the metal plate surface (galvanized) and aluminum aluminum undergone galvanizing and the like, and when it is less than the above range, excessive etching occurs, If the amount is larger than the above range, on the contrary, the etching becomes insufficient, and the insoluble film formed by the aluminum aluminum and the colloidal silica being formed is not sufficiently formed, thereby making it difficult to obtain the effect of improving the adhesion and corrosion resistance.
The specific undercoating composition preferably further contains a silane coupling agent in an amount of 3 to 15 parts by mass (more preferably 5 to 12.5 parts by mass) based on 100 parts by mass of the total solid content of aluminum oxide and colloidal silica in the composition . When the silane coupling agent is less than the above range, the effect of improving the adhesion and corrosion resistance to the top coat and the metal sheet tends to become insufficient, resulting in peeling of the coating film under more severe processing conditions. On the contrary, There is a possibility that the corrosion resistance and the adhesion property are also deteriorated.
[First waterborne resin coating layer]
<Carbon black>
The first water-based resin coating film layer contains a black pigment. It is preferable that the black pigment is at least one of an ink and carbon black.
As the carbon black, for example, "SA Black DY-6" manufactured by Mikuni Color Co., Ltd., "# 4000B", "# 4350B", "MHIB # B239M", and "MHIB # B240M" manufactured by Mitsubishi Chemical Corporation are recommended.
Treated carbon black whose surface is coated with a water-based resin to be used. For example, it is preferable to use a high-concentration mink (ink) used in calligraphy. The first water-based resin coating layer can exhibit a sufficiently high blackness even if the first water-based resin coating layer has a thin film thickness because it exhibits excellent dispersibility when mixed with the used binder resin and is hardly secondary aggregated. The surface of the indefinite furnace black produced by the furnace method in which the oil of the petroleum or coal system is incompletely burnt in a high temperature gas is coated with a water based resin, and if necessary, the glycol Based antifreezing agents and antiseptics, followed by mixing and slurrying. For example, commercially available inks (e.g., " Super concentrate BA-8 " manufactured by Kuratake Co., Ltd.) may be used as the template. On the other hand, the surface-treated carbon black or an aqueous dispersion thereof may be prepared on the basis of a known method (for example, Japanese Patent Application Laid-Open No. 7-188597 or Japanese Patent Application Laid-Open No. 6-234946). The surface-treated carbon black (or an aqueous dispersion thereof) may be used alone or in combination of two or more kinds.
The black pigment is preferably contained in an amount of 16 mass% or more and 50 mass% or less, more preferably 25 mass% or more, and 45 mass% or less in 100 mass% of the total solid content of the composition for forming a first aqueous resin coating layer to be. When the content of the black pigment is less than 16 mass%, the black pigment is not contained in a sufficient amount, so that the L * value of the water-based resin film laminated metal sheet becomes high, and sufficient blackness may not be exhibited. On the other hand, when the content of the black pigment is more than 50% by mass, the resin component to be a binder contained in the composition relatively decreases, so that the adhesion between the first waterborne resin film layer and the second waterborne resin film layer becomes low , The composition tends to gel, which may lower the liquid stability of the composition for forming a first aqueous resin coating layer. If the content of the black pigment is 16 mass% or more and 50 mass% or less, it is difficult for the black pigment to be secondary aggregated even when mixed with the binder resin, and high dispersion stability can be maintained.
<Binder Resin>
The composition for forming a water-based resin coating film used for coating the first water-based resin coating film layer (hereinafter referred to as a composition for forming a first water-based resin coating film) usually contains a black pigment in the first water- And a binder resin for fixation. The binder resin is not particularly limited as long as it can fix the black pigment, and examples thereof include acrylic resin, urethane resin, polyolefin resin, polyester resin, fluorine resin, silicone resin, Resin or the like can be suitably used. Among them, a polyethylene resin and a polyurethane resin are preferable because they can effectively suppress the secondary agglomeration of the black pigment in the composition and obtain excellent liquid stability. The binder resins may be used alone or in combination of two or more.
The binder resin is preferably contained in an amount of 30 mass% or more (more preferably 35 mass% or more), and preferably 70 mass% or less (more preferably 30 mass% or more) of 100 mass% of the total solid content of the composition for forming a water- 65% by mass or less). If the content of the binder resin is less than 30 mass%, the film-forming property of the first water-based resin coating film layer is lowered and the fixing of the black pigment in the first water-based resin coating film layer becomes insufficient, or coating unevenness occurs, There is a risk of causing or causing it. On the other hand, when the content of the binder resin exceeds 70% by mass, the content of the black pigment relatively decreases, so that a sufficient blackness may not be obtained.
In order to make the first water based resin coating layer strong, it is preferable that the polyurethane resin contains 25 mass% or more (more preferably 35 mass% or more), and the polyurethane resin is preferably a carboxyl group- More preferably a terpene resin. By containing a polyurethane resin, the first water-based resin coating layer can be made strong. By including the polyurethane resin in the first water-based resin coating layer in an amount of 25 mass% or more, the water- A film laminated metal plate can be obtained.
The carboxyl group-containing polyurethane resin is obtained by subjecting a urethane prepolymer to chain extension reaction with a chain extender. The urethane prepolymer is obtained by reacting a polyisocyanate component and a polyol component, which will be described later. Examples of the polyisocyanate component constituting the urethane prepolymer include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and dicyclohexylmethane diisocyanate ( And hydrogenated MDI) is preferably used as the at least one polyisocyanate. This is because by using such a polyisocyanate, a resin film excellent in corrosion resistance and stability of reaction control can be obtained. Other polyisocyanates can be used as long as they do not deteriorate the corrosion resistance and the stability of the reaction control in addition to the above-mentioned suitable polyisocyanates. However, the content of the suitable polyisocyanate component is preferably It is preferable to set it to 70% by mass or more. If the content of the suitable polyisocyanate component is less than 70% by mass, the stability of the corrosion resistance and reaction control tends to be lowered. Examples of the polyisocyanate other than the above-mentioned suitable polyisocyanate component include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecane methylene diisocyanate, isophorone diisocyanate Xylylene diisocyanate, phenylene diisocyanate, and the like. These polyisocyanates may be used alone or in combination of two or more.
As the polyol component constituting the urethane prepolymer, it is preferable to suitably use all three polyols such as 1,4-cyclohexane dimethanol, polyether polyol and polyol having a carboxyl group, To be a diol. This is because a resin film excellent in corrosion resistance and sliding property can be obtained by using such a polyol component. Further, by using 1,4-cyclohexane dimethanol as the polyol component, the rust-preventive effect of the obtained polyurethane resin can be enhanced.
The polyether polyol is not particularly limited as long as it has at least two hydroxyl groups in the molecular chain and the main skeleton is composed of an alkylene oxide unit. Examples thereof include polyoxyethylene glycol (simply referred to as " polyethylene glycol (Sometimes simply referred to as "polypropylene glycol"), polyoxytetramethylene glycol (simply referred to as "polytetramethylene glycol" or "polytetramethylene ether glycol" Quot;), and a commercially available product can be used. Among the above polyether polyols, polyoxypropylene glycol or polytetramethylene ether glycol is preferably used. The number of functional groups of the polyether polyol is not particularly limited as long as it is at least two, and may be multifunctional, for example, trifunctional or tetrafunctional.
The polyether polyol is obtained, for example, by adding an alkylene oxide such as ethylene oxide or propylene oxide with an initiator as a starting material. Examples of the compound having an active hydrogen include diols such as propylene glycol and ethylene glycol, triols such as glycerin, trimethylol propane, hexyl lauryl and triethanol amine, tetra compounds such as diglycerin and pentaerythritol, Olive, other sorbitol, sucrose, phosphoric acid, and the like. At this time, if a diol is used as an initiator to be used, a bifunctional polyether polyol is obtained, and when a triol is used, a trifunctional polyether polyol is obtained.
Further, polyoxytetramethylene glycol is obtained, for example, by ring-opening polymerization of tetrahydrofuran.
As the polyether polyol, for example, a commercially available product having an average molecular weight of about 400 to about 4000 is preferably used. When the average molecular weight is less than about 400, the resin coating is hard and when it is more than 4000, the resin becomes excessively flexible. On the other hand, the average molecular weight is obtained from OH of the polyol (hydroxyl group).
In the present invention, it is also preferable that the mass ratio of 1,4-cyclohexane dimethanol and polyether polyol is 1,4-cyclohexane dimethanol: polyether polyol = 1: 1 to 1: 19 to be. This is because by using a certain proportion of 1,4-cyclohexane dimethanol having an anti-corrosive effect, the anti-corrosive effect of the obtained polyurethane resin can be further enhanced.
The polyol having a carboxyl group used in the present invention is not particularly limited as long as it has at least one carboxyl group and at least two hydroxyl groups and includes, for example, dimethylol propionic acid, dimethylol butanoic acid, dihydroxypropionic acid, ≪ / RTI >
In addition to the above-mentioned suitable polyol component, other polyols may be used within a range not lowering the corrosion resistance. The content of the suitable polyol component is preferably 70 mass% or more of the total polyol component. If the content of the compatible polyol component is less than 70% by mass, the corrosion resistance tends to decrease. The polyol other than the above-mentioned suitable polyol component is not particularly limited as long as it has a plurality of hydroxyl groups, and examples thereof include a low molecular weight polyol and a high molecular weight polyol. The low molecular weight polyol is a polyol having a molecular weight of about 500 or less. Examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, Diols such as 6-hexanediol; And triols such as glycerin, trimethylol propane and hexyl lauryl.
The high molecular weight polyol is a polyol having a molecular weight of more than about 500, and examples thereof include condensation polyester polyols such as polyethylene adipate (PEA), polybutylene adipate (PBA) and polyhexamethylene adipate (PHMA); Lactone-based polyester polyols such as poly-epsilon -caprolactone (PCL); Polycarbonate polyols such as polyhexamethylene carbonate and the like; And acrylic polyol.
The chain extender for chain extension reaction of the above-mentioned urethane prepolymer is not particularly limited, and examples thereof include polyamines, low molecular weight polyols, alkanolamines and the like. As the polyol having a low molecular weight, the same polyols as those described above can be used. Examples of the polyamine include aliphatic polyamines such as ethylene diamine, propylene diamine and hexamethylene diamine; Aromatic polyamines such as tolylene diamine, xylylenediamine, and diaminodiphenylmethane; Alicyclic polyamines such as diaminocyclohexyl methane, piperazine and isophoronediamine; And hydrazine such as hydrazine, succinic acid dihydrazide, adipic acid dihydrazide, and phthalic acid dihydrazide. Among them, it is preferable to use ethylenediamine and / or hydrazine as a chain extender component. Examples of the alkanolamine include diethanolamine, monoethanolamine, and the like.
In the present invention, it is preferable to use an aqueous dispersion of the carboxyl group-containing polyurethane resin. The aqueous dispersion of the carboxyl group-containing polyurethane resin can be prepared by a known method, for example, a method in which a carboxyl group of a carboxyl group-containing urethane prepolymer is neutralized with a base and emulsified and dispersed in water to effect a chain extension reaction, A method in which a polyurethane resin is subjected to chain extension reaction by emulsifying and dispersing the polyurethane resin in the presence of an emulsifier at a high shear force, or the like, or may be produced based on a known method (for example, Japanese Patent Application Laid-Open No. 2005-199673). On the other hand, the case where the second water based resin coating film layer contains a polyurethane resin can also be adjusted in the same manner as described above.
<Colloidal silica>
The first water-based resin coating film layer preferably contains 5 mass% or more of colloidal silica, more preferably 7 mass% or more and 40 mass% or less, and further preferably 10 mass% or more and 30 mass% or less. By containing colloidal silica, corrosion resistance can be imparted, and since it is a hard particle, scratch resistance of the first waterborne resin coating film layer at the time of processing can be improved. If the content of the colloidal silica is less than 5% by mass, corrosion resistance may be deteriorated. When the content of the colloidal silica exceeds 40% by mass, the film-formability of the water-based resin coating film is lowered, and the corrosion resistance is lowered or the film is brittle and the workability is sometimes deteriorated.
The colloidal silica is not particularly limited, but colloidal silica having a particle diameter of 1 to 20 nm is preferable from the viewpoints of improvement in dispersibility and corrosion resistance in a composition for forming a first water-based resin coating film, and specifically, (Commercially available as "Snowtex (registered trademark) XS" manufactured by Nissan Chemical Industries, Ltd.) and colloidal silica having a particle diameter of 8 to 11 nm (commercially available products include "Snowtex Colloidal silica having a particle diameter of 10 to 20 nm (commercially available product "Snowtex (registered trademark) 40" manufactured by Nissan Chemical Industries, Ltd.) XS " is preferable.
In order to maximize the effect of the colloidal silica, the average particle diameter of the colloidal silica is preferably in the range of 3 to 15 nm. As the average particle size of the colloidal silica becomes smaller, the corrosion resistance of the water based resin coating film is improved. However, when the average particle diameter is less than about 3 nm, the effect of improving the corrosion resistance tends to be saturated. The stability is lowered and gelation tends to occur. On the other hand, when the average particle size of the colloidal silica exceeds 15 nm, the film-forming property of the first water-based resin coating film is lowered and the corrosion resistance tends to deteriorate.
On the other hand, the average particle diameter of the colloidal silica and other powder can be determined from the value of the specific surface area measured by the BET adsorption method in accordance with JIS Z8830-2013. A method of calculating the particle diameter from the specific surface area of the fine particles will be described below.
The specific surface area S (m 2 / g) of the fine particles is the sum of the surface areas of the fine particles of 1 g. That is, the specific surface area S (m 2 / g) of the fine particles is a value obtained by dividing the surface area of one fine particle by the mass of one fine particle. The surface area of one particle is 4? (D / 2) 2 =? D 2 (nm 2 ), and the mass of one particle is ρ · {4π / 3 × (d / 2) 3} = ρ · a is πd 3/6 (nm 3 × g / cm 3) ( and in the particle size of the fine particles d (nm), the ρ (g / cm 3) density). The specific surface area S (m 2 / g) of the fine particles can be expressed by the following formula.
S (m 2 / g) = πd 2 (nm 2) / (ρ · πd 3/6) (nm 3 × g / cm 3) = 6 / d · ρ ((nm 2) / (nm 3 × g / cm 3 )) = 6,000 / d · ρ (m 2 / g)
Therefore, since d (nm) = 6,000 / S · rho, the particle diameter can be obtained from the specific surface area.
<Silane coupling agent>
The composition for forming the first water-based resin coating film may further contain a silane coupling agent. When the silane coupling agent is contained, the adhesion between the first water-based resin coating layer and the metal sheet can be enhanced.
As the silane coupling agent, a silane coupling agent having a glycidoxy group at the terminal is preferable, and examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, vinyltris (? -methoxyethoxy) silane, and the like.
The content of the silane coupling agent is preferably 5 parts by mass or more (more preferably 10 parts by mass or more) relative to 100 parts by mass of the total solid content of the black pigment, the binder resin and the colloidal silica, By mass or less (more preferably 15 parts by mass or less). When the content of the silane coupling agent is less than 5 parts by mass, the effect obtained by adding the silane coupling agent may not be sufficiently obtained. On the other hand, when the content of the silane coupling agent exceeds 25 parts by mass, a large amount of unreacted silane coupling agent remains in the water based resin film laminated metal sheet, and the corrosion resistance tends to decrease.
<Cross-linking agent>
The composition for forming the first water-based resin coating film preferably contains a crosslinking agent in an amount of 1% by mass or more. When the crosslinking agent is contained in an amount of 1% by mass or more, the first water-based resin coating layer becomes strong, and the scratch resistance can be further improved. Examples of the crosslinking agent include an epoxy compound, a melamine compound, and an isocyanate compound.
≪ Thickness &
The film thickness (dry film thickness) of the first water-based resin film layer is 0.6 μm or more (more preferably 0.9 μm or more, and more preferably 1.1 μm or more), and 7.0 μm or less (more preferably 6.0 μm or less Preferably not more than 5.0 mu m). When the thickness of the first water-based resin coating film layer is less than 0.6 탆, when the polyurethane resin is contained in the first water-based resin coating film layer, although a strong coating film is obtained by containing a polyurethane resin, There is a possibility that sex is not obtained. On the other hand, if the film thickness of the first water-based resin coating film layer exceeds 7.0 탆, wrinkles tend to occur in the first water-based resin film layer, resulting in defective appearance. Further, the time required for coating and drying becomes longer, and the manufacturing cost is increased.
<Others>
The first water-based resin coating film layer preferably contains a polyamide-based thixotropic agent. Details will be described later.
[Second waterborne resin coating layer]
<Pigment>
The second water-based resin coating film layer contains one or more kinds selected from colloidal silica, blue pigment, and green pigment. The second water-based resin coating film layer may include colloidal silica and may contain no blue pigment or green pigment, or may include at least one of a blue pigment and a green pigment, and may not include colloidal silica. Colloidal silica is transparent and hardly absorbs light, and blue pigments and green pigments absorb specific light but do not have as high a water absorbency as black pigments, so that a blackness improving effect is easily obtained.
From the viewpoint of the blackness improving effect, the colloidal silica is preferably a fine particle having an average particle diameter of 1 to 100 nm. Further, a more preferable upper limit of the average particle diameter of the colloidal silica is 50 nm, a more preferable upper limit is 25 nm, and a more preferable lower limit is 4 nm.
Examples of the method for measuring the average particle diameter of the colloidal silica include the Sears method and the dynamic light scattering method in addition to the BET method described above. For example, when the average particle diameter is 4 to 6 nm, the Sears method is used. It is preferable to employ the BET method, and in the case of using chain silica, dynamic light scattering method is preferably employed.
On the other hand, the content of the black pigment in the second water-based resin coating film layer is preferably 10 mass% or less, and more preferably, it is not contained. Since the black pigment is a component to embrittle the water-based resin coating layer, adding black pigment to the second water-based resin coating layer may lower the scratch resistance of the second water-based resin coating layer.
<Colloidal silica>
By containing colloidal silica in the second water-based resin coating film layer, corrosion resistance and hardness of the resulting water-based resin coating film laminated metal sheet can be improved. The details of the mechanism for improving the corrosion resistance are unclear, but it is presumed that the silica is dissolved and eluted under the corrosive environment, resulting in a buffering action of pH or a passive film forming action.
In addition, the colloidal silica has an effect of improving blackness comparable to that of a blue pigment to be described later, and has a greater effect of increasing blackness than the green pigment described later. Although the refractive index of the colloidal silica and the blue pigment and the green pigment is not about 1.5, the average particle diameter of the colloidal silica is generally smaller than that of the blue pigment and the green pigment, It is considered that by adding colloidal silica to the second water based resin coating film layer, a blackness improving effect comparable to that of a blue pigment can be obtained.
The colloidal silica is not particularly limited and may be the same as the colloidal silica used in the above-mentioned composition for forming a water-based resin coating film.
The colloidal silica (solid content) is preferably selected from the group consisting of 100 mass% of the total solids of the composition for forming a water-based resin coating film used for coating the second water-based resin coating film layer (hereinafter referred to as a composition for forming a second water- (More preferably 10 mass% or more), and preferably 70 mass% or less (more preferably 60 mass% or less). If the content of the colloidal silica is less than 3% by mass, the blackness (L * value) of the water-based resin film laminated metal sheet becomes 23 or more, which is difficult to be said to be black beautifully in the naked eye appearance, and the corrosion resistance is also lowered. On the other hand, when the content of the colloidal silica exceeds 70% by mass, the stability of the composition deteriorates and the viscosity of the composition increases with elapsed time, and the effect of further improving the corrosion resistance is not obtained, which is economically disadvantageous.
<Blue pigment, green pigment>
When colloidal silica is not contained in the second water-based resin coating film layer, at least one of a blue pigment and a green pigment and a polyamide-based thixotropic agent must be contained in the second water-based resin coating film layer. The total content of the blue pigment and the green pigment in the second water based resin coating film layer is 3% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass or more. If the total content of the blue pigment and the green pigment is less than 3% by mass, it becomes difficult to obtain sufficient blackness in the water based resin film laminated metal sheet. On the other hand, the coloring pigment is a component which inhibits the film-forming property, which may cause a decrease in adhesion. Therefore, in order to ensure sufficient adhesion between the second water-based resin film layer and the first water-based resin film layer, the total content of the blue pigment and the green pigment in the second water-based resin film layer is preferably 80% More preferably 70% by mass or less, and even more preferably 50% by mass or less.
On the other hand, the second water-based resin coating film layer may contain at least one of a blue pigment and a green pigment and a polyamide thixotropic agent in a state in which colloidal silica is contained. Details of the polyamide-based thixotropic agent will be described later.
Examples of commercially available blue pigments include "AF Blue E-2B" (manufactured by Dainichi Seika Kogyo K.K.) comprising a phthalocyanine-based coloring matter and a water-soluble acrylic resin, a " Quot; SA Blue DY-12 " (manufactured by Mikuni Color), and " PSM Blue HB " (made by Mikuni Color) comprising a cyanine dye and a nonionic surfactant. .
As a green pigment, commercially available products include "AF Green E-1" (manufactured by Dainichi Seika Kogyo K.K.) comprising a phthalocyanine-based coloring matter and a water-soluble acrylic resin, a " SA Green DY-4 " (manufactured by Mikuni Color), and among these, " SA Green DY-4 " is particularly preferable.
The blue pigment and the green pigment are preferably phthalocyanine pigments. Further, the black pigment can be more enhanced by the blue pigment than by the green pigment. The blue color is darker than the green color, and it is considered that the effect of increasing the blackness is increased.
≪ Polyamide-based thixotropic agent >
As described above, in the present invention, when a blue pigment or a green pigment is contained in the second water-based resin coating film layer, a polyamide-based thixotropic agent is added to the second water-based resin film-forming composition. When the second water-based resin coating film layer containing a blue pigment, a green pigment and the like is laminated on the first water-based resin coating film layer, the blackness of the water-based resin film laminated metal sheet is improved, There is a possibility that it will become noticeable. Specifically, in the coating of the water-based resin coating film, components such as pigment are unevenly distributed on the surface of the wet film, resulting in unevenness in wettability and unevenness on the surface of the water-based resin coating film. When the second water based resin coating film layer does not contain a blue pigment or a green pigment and only colloidal silica is contained, the colloidal silica is fine and transparent, so that the second water based resin coating film layer is not colored, Even if irregularities are formed on the surface of the second water-based resin coating layer, uneven application is not noticeable. However, when at least one of the blue pigment and the green pigment is contained, since these pigments are colored pigments, unevenness in application becomes conspicuous. In order to suppress the uneven application of the second water-based resin coating layer, a polyamide-based thixotropic agent is added to the second water-based resin coating layer. On the other hand, when the second water-based resin coating film layer does not contain a blue pigment or a green pigment and only colloidal silica is contained, a polyamide-based thixotropic agent may be added.
When at least one of the blue pigment and the green pigment is contained in the second water based resin coating film layer, the polyamide thixotropic agent is contained in an amount of 0.05 mass% or more, more preferably 0.1 mass% or more, and 5 mass% % Or less. The viscosity of the low-shear rate region of the composition for forming a second water-based resin film can be sufficiently increased even if the amount of the polyamide-based thixotropic agent is as small as about 0.05% by mass, and a uniform wet film It is possible to maintain the uniform state until after drying, so that it is possible to effectively prevent occurrence of uneven application. Thus, even if the second water-based resin coating layer containing at least one of the blue pigment and the green pigment is applied uniformly on the first water-based resin coating layer as the black layer, a water-based resin coating film laminated metal sheet having an elegant appearance have. When the polyamide-based thixotropic agent is less than 0.05% by mass, the viscosity of the low-shear rate region of the composition for forming a second water-based resin coating film does not become sufficiently high, so that a uniform wet film is uniformly maintained It becomes difficult.
The polyamide-based thixotropic agent is obtained by reacting a dicarboxylic acid and a diamine, but is not particularly limited as far as it is a polyamide-based thixotropic agent capable of being dispersed in a composition for forming a second water-based resin coating film. The polyamide-based thixotropic agent is available, for example, as Disperson (registered trademark) AQ series from Kusumoto Chemical Co., Ltd. In the AQ series, polyamide represented by the following formula (R, R 'is an alkyl group) is used as a main component, and the molecular weight of the polyamide in the AQ series is 3000 or less.
The polyamide-based thixotropic agent forms a three-dimensional network structure in the paint to cause steric hindrance with polyimide-based thixotropic agents, extender pigments such as resin and silica particles in paints, colored pigments and the like, Or adsorption of the particles to increase the steric hindrance between the particles, thereby exhibiting an effect of suppressing fluidity of the composition for forming a second water-based resin coating film. Since the network structure is formed by a weak bond such as Van der Waals force or hydrogen bond, it is easily cut at a certain shear rate, but when it is restrained, the network structure is restored again. Therefore, thixotropic property (thixotropic property) is expressed by adding a polyamic thixotropic agent to the composition for forming a second water-based resin coating film, the mesh structure is cut in the high shear rate region and the viscosity is lowered, When it becomes a zone of low-speed interruption, the network structure is restored and the viscosity becomes high.
In addition, as described above, it is preferable to add a polyamic thixotropic agent to the first water-based resin coating film layer. In the first waterborne resin film layer, the amount of the polyamide-based thixotropic agent is preferably 0.05 to 5 mass%, more preferably 0.1 mass% or more and 2 mass% or less. By increasing the viscosity of the composition for forming a first water-based resin coating film in the low-shear rate region, the first water-based resin coating layer can be more reliably maintained in a uniform state until after drying. Further, by preventing the pigment from segregating as a result of the movement of the pigment in the first water-based resin coating layer, irregularities appearing on the surface of the first water-based resin coating layer (the surface in contact with the second water-based resin coating layer) By reducing the film thickness difference as much as possible, the influence on the second water-based resin coating film layer is reduced, and occurrence of uneven application can be suppressed.
<Lubricant>
It is preferable that the second water-based resin coating film layer contains a lubricant. By including the lubricant, friction on the surface of the second water-based resin coating layer is reduced, and scratches are less likely to occur. The lubricant is preferably contained in an amount of 1.5 mass% or more, more preferably 3.0 mass% or more and 20 mass% or less. When the content of the lubricant is less than 1.5% by mass, the improvement in the lubricity of the obtained second waterborne resin coating layer is not sufficient and the friction reducing effect may not be sufficiently obtained. Even when the lubricant is added in an amount exceeding 20% by mass, the effect of lowering the coefficient of dynamic friction is saturated, so that it is useless.
Examples of the lubricant include polyolefin waxes such as polyethylene, oxidized polyethylene and polypropylene; Fluorinated resins such as polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, and tetrafluoroethylene; Organic modified polysiloxanes; Paraffin wax and the like can be used. Among these, polyethylene wax or organic modified polysiloxane is preferable.
The polyethylene wax is present in the form of a sphere in the second water-based resin coating film layer, so that friction on the surface of the second water-based resin coating film layer can be effectively reduced, which is effective in suppressing occurrence of scratches and the like. Examples of the polyethylene wax include "Chemipear (registered trademark) W700", "Chemipear (registered trademark) W950" and "Chemipear (registered trademark) W900" manufactured by Mitsui Chemicals. The addition amount of the polyethylene wax is preferably 1.5 mass% or more, and more preferably 3.0 mass% or more. When the content of the polyethylene wax is less than 1.5% by mass, the improvement in the lubricity of the obtained second water-based resin coating layer is not sufficient and the effect of reducing friction may not be sufficiently obtained. However, when the content of the polyethylene wax is more than 20% by mass, the film-forming property of the second water-based resin coating film layer is lowered, and the corrosion resistance may be lowered.
As the polyethylene wax particles, those having a spherical shape and an average particle diameter of 0.1 to 3 m are preferably used. When the average particle diameter exceeds 3 탆, it is difficult to uniformly disperse in the composition for forming a second water-based resin coating film, and the corrosion resistance tends to be deteriorated because it inhibits the film formability. On the other hand, when the average particle diameter of the polyethylene wax particles is smaller than 0.1 占 퐉, the lubricity of the second aqueous resin coating layer may not be improved. On the other hand, the average particle diameter of the polyethylene wax particles can be measured by the Coulter counter method.
Since the organic modified polysiloxane floats on the surface of the second water-based resin coating layer, the friction on the surface of the second water-based resin coating layer can be effectively reduced. Examples of the organically modified polysiloxane include polyester-modified, polyether-modified, and aralkyl-modified ones. Among these, polyether-modified polysiloxanes are particularly preferable. The addition amount of the organic modified polysiloxane is preferably 1% by mass or more, and more preferably 3% by mass or more. When the content of the organic modified polysiloxane is less than 1% by mass, the improvement in the lubricity of the obtained second water-based resin coating layer is not sufficient and the effect of reducing friction is not sufficiently obtained. When the content of the organic modified polysiloxane exceeds 20% by mass, the ratio to the second water-based resin coating layer becomes too high, and the properties such as corrosion resistance may be adversely affected.
<Binder Resin>
The composition for forming the second water-based resin coating film generally includes a binder resin for fixing the colloidal silica or the colored pigment in the second water-based resin coating film layer formed from the composition. The kind of the binder resin is not particularly limited as long as it can fix the colloidal silica or the colored pigment, and the binder resin is not particularly limited, and examples thereof include acrylic resin, uretene resin, polyolefin resin, polyester resin, fluorine resin, Mixed or modified resin may be suitably used. Among them, polyethylene resin and polyurethane resin are preferable because they can effectively suppress the secondary agglomeration of the black pigment in the composition and obtain excellent liquid stability. The binder resins may be used alone or in combination of two or more.
The binder resin is preferably contained in an amount of 15 mass% or more (more preferably 25 mass% or more), preferably 85 mass% or less (more preferably 20 mass% or more) of 100 mass% of the total solid content of the composition for forming a water- 75% by mass or less). If the content of the binder resin is less than 15 mass%, the film-forming property of the second water-based resin coating film layer is lowered and the fixing of the colloidal silica or the colored pigment in the second water-based resin coating film layer becomes insufficient, There is a fear of causing or causing appearance problems. On the other hand, when the content of the binder resin exceeds 85% by mass, the content of the colloidal silica and the color pigment is relatively decreased. Therefore, the light which has not been sufficiently absorbed by the black pigment of the first water- It is difficult to return to the coating film layer, and there is a possibility that sufficient blackness is not obtained.
In view of the tape peeling property in the 2T bending cellophane tape peeling test described later, it is preferable that the second water based resin coating film layer contains 25 mass% or more of the polyethylene resin, more preferably 30 mass% It is preferably at least 35 mass%. Since the adhesiveness to the olefin resin-specific tape is low, peeling of the tape wrapped up to the first water-based resin coating film layer is suppressed, so that the tape peeling property is improved.
The polyethylene resin may be an olefin-α, β-unsaturated carboxylic acid copolymer (hereinafter sometimes referred to as "olefin-acid copolymer"), an α, β-unsaturated carboxylic acid polymer (hereinafter sometimes referred to as "carboxylic acid polymer" , And an oxazoline group-containing polymer. Since the olefin-acid copolymer and the carboxylic acid polymer do not impair the dispersion stability of the colloidal silica or the colored pigment in the composition for forming the second water-based resin coating film and are excellent in barrier properties, the penetration of water into the first water- To improve the corrosion resistance.
On the other hand, the "olefin-acid copolymer" in the present invention is a copolymer of an olefin and an α, β-unsaturated carboxylic acid, and the constituent unit derived from an olefin is contained in the copolymer in an amount of 50% And the constituent unit derived from the carboxylic acid is 50 mass% or less). "Carboxylic acid polymer" means a polymer (including a copolymer) obtained by polymerization using an α, β-unsaturated carboxylic acid as a monomer, and means that the constituent unit derived from an α, β-unsaturated carboxylic acid is 90 mass% or more in the polymer do.
The olefin-acid copolymer can be produced by copolymerizing an olefin with an?,? - unsaturated carboxylic acid by a known method, and is also commercially available. The olefin-acid copolymers may be used alone or in combination of two or more.
The olefins usable for the production of the olefin-acid copolymer are not particularly limited, but ethylene, propylene and the like are preferable, and ethylene is more preferable. In the olefin-acid copolymer, the olefin constituent unit may be derived from only one kind of olefin, or may be derived from two or more kinds of olefins.
The?,? - unsaturated carboxylic acid which can be used in the production of the olefin-acid copolymer is not particularly limited, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and isocrotonic acid; And dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. Of these, acrylic acid is preferred. In the olefin-acid copolymer, the constituent unit of the?,? - unsaturated carboxylic acid may be derived from only one?,? - unsaturated carboxylic acid, or may be derived from two or more?,? - unsaturated carboxylic acids.
The?,? - unsaturated carboxylic acid unit in the olefin-acid copolymer acts to improve the adhesion between the first waterborne resin film layer and the second waterborne resin film layer. In order to effectively exhibit such action, The amount of the? -unsaturated carboxylic acid unit is preferably 5% by mass or more, and more preferably 10% by mass or more. On the other hand, the upper limit of the amount of the?,? - unsaturated carboxylic acid unit in the copolymer is 50 mass% as described above, but is preferably 30 mass% or less, more preferably 25 mass% or less, from the viewpoint of corrosion resistance.
The olefin-acid copolymer may have a constitutional unit derived from other monomers as long as it does not adversely affect the secondary aggregation inhibition of the colloidal silica or the colored pigment. In the olefin-acid copolymer, the amount of the constituent unit derived from the other monomer is preferably 10% by mass or less, more preferably 5% by mass or less, and the most preferred olefin-acid copolymer is olefin- Unsaturated carboxylic acid. Preferred olefin-acid copolymers include ethylene-acrylic acid copolymers.
The weight average molecular weight (Mw) of the olefin-acid copolymer in terms of polystyrene is preferably 1,000 to 100,000, more preferably 3,000 to 70,000, and still more preferably 5,000 to 3,000. This Mw can be measured by GPC using polystyrene as a standard.
Examples of the carboxylic acid polymer include homopolymers or copolymers of one or more?,? - unsaturated carboxylic acids, or copolymers obtained by further copolymerizing other monomers (excluding olefins). Such a carboxylic acid polymer can be produced by a known method and is also commercially available. The carboxylic acid polymer may be used alone or in combination of two or more.
As the?,? - unsaturated carboxylic acid which can be used for the production of the carboxylic acid polymer, any of the?,? - unsaturated carboxylic acids exemplified for use in the synthesis of the olefin-acid copolymer can be used. Of these, acrylic acid and maleic acid are preferable, and maleic acid is more preferable.
The carboxylic acid polymer may contain a constituent unit derived from a monomer other than the?,? - unsaturated carboxylic acid, but the amount of the constituent unit derived from the other monomer is 10 mass% or less, preferably 5 mass% or less, , a carboxylic acid polymer composed solely of? -unsaturated carboxylic acid is more preferable.
Examples of preferred carboxylic acid polymers include polyacrylic acid, polymethacrylic acid, acrylic acid-maleic acid copolymer, and polymaleic acid. Of these, from the viewpoint of adhesion with the first water-based resin coating film layer, desirable. Since the amount of the carboxyl group is large in the polymaleic acid, the adhesion between the first waterborne resin film layer and the second waterborne resin film layer is further improved.
The weight average molecular weight (Mw) of the carboxylic acid polymer is preferably 500 to 30,000, more preferably 800 to 10,000, more preferably 900 to 3,000, and most preferably 1,000 to 2,000 in terms of polystyrene. This Mw can be measured by GPC using polystyrene as a standard.
The content (mass ratio) of the olefin-acid copolymer and the carboxylic acid polymer in the polyethylene resin is preferably 1,000: 1 to 10: 1, more preferably 200: 1 to 20: 1, 25: 1. If the content of the carboxylic acid polymer is too low, the effect of combining the olefin-acid copolymer and the carboxylic acid polymer may not be sufficiently exhibited. Conversely, if the content of the carboxylic acid polymer is excessive, the content of the olefin- The polymer is phase-separated and there is a fear that the second water-based resin coating film layer is not uniformly formed.
The oxazoline group-containing polymer has an oxazoline group, and the oxazoline group is cross-linked with the carboxyl group of the olefin-acid copolymer or the carboxylic acid polymer, whereby the resins are crosslinked to form a dense network structure. As a result, the barrier property of the second water-based resin coating film layer is improved, and penetration of water into the first water-based resin coating film layer is suppressed, so that the corrosion resistance is improved.
As the oxazoline group-containing polymer, it is preferable that the main chain is made of styrene / acrylic. For example, "Epochros (registered trademark)" manufactured by Nippon Shokubai Co., Ltd. is suitably used as a commercially available product. K-2010E (Tg: -50 ° C) and K-2020E (Tg: 0 ° C) are preferable as the "Epochros (registered trademark) ) And K-2030E (Tg: 50 DEG C). Among them, "Epochros (registered trademark) K-2030E" is most preferable in that a harder film can be obtained.
(More preferably 2 parts by mass or more, and more preferably 3 parts by mass or more) based on the total 100 parts by mass (solid content) of the olefin-acid copolymer and the carboxylic acid polymer And more preferably 8 parts by mass or less (more preferably 7 parts by mass or less, further preferably 6 parts by mass or less, particularly preferably 4 parts by mass or less). If the content of the oxazoline group-containing polymer is less than the above-mentioned range, the crosslinking reaction becomes insufficient and the denseness of the formed second water-based resin coating film layer can not be obtained, and the resultant corrosion resistance of the water- have. On the other hand, when the content of the oxazoline group-containing polymer is larger than the above-mentioned range, the functional group (carboxyl group) of the second waterborne resin coating layer decreases due to excessive crosslinking reaction and the adhesion of the first waterborne resin coating layer is lowered have.
On the other hand, the case where the first water based resin coating film layer contains a polyethylene resin can also be adjusted in the same manner as described above.
≪ Thickness &
The second water-based resin coating film layer in the present invention can be formed by applying the composition for forming a second water-based resin coating film to a predetermined dry film thickness on one side or both sides of the above-mentioned metal plate and drying it.
The film thickness (dry film thickness) of the second water-based resin film layer is 0.3 μm or more (preferably 0.5 μm or more, more preferably 0.9 μm or more), and 7.0 μm or less (preferably 6.0 μm or less, Is 5.0 占 퐉 or less). If the film thickness of the second water-based resin coating film layer is less than 0.3 탆, light which is not sufficiently absorbed by the black pigment of the first water-based resin coating film layer is reflected from the surface of the colloidal silica or colored pigment in the second water- It is not possible to sufficiently return the light to the first water-based resin coating layer again, so that it is difficult to sufficiently improve the blackness. On the other hand, if the film thickness of the second water-based resin coating film layer exceeds 7.0 m, boiling tends to occur in the second water-based resin coating film layer, resulting in defective appearance. Further, the time required for coating and drying becomes longer, and the manufacturing cost is increased.
[Total Film Thickness and Ratio of First Waterborne Resin Coating Layer and Second Waterborne Resin Coating Layer]
The total thickness of the first water-based resin coating film layer and the second water-based resin coating film layer is 0.9 탆 or more (preferably 1.0 탆 or more, and more preferably 1.3 탆 or more), 8.0 탆 or less (preferably 7.0 탆 or less, More preferably 6.0 m or less). If the total film thickness is less than 0.9 占 퐉, the blackness of the first waterborne resin coating film layer, and furthermore the obtained waterborne resin coating film laminate metal sheet becomes insufficient. Further, when the total film thickness is 1.0 占 퐉 or more, sufficient blackness and scratch resistance can be more easily satisfied. On the other hand, if the total film thickness exceeds 8.0 탆, the blackness is excellent, but the effect of improving the blackness of the further layer is hardly obtained. On the other hand, wrinkles may occur in the first water- Boiling occurs in the coating film layer, resulting in poor appearance. Further, the time required for coating and drying becomes longer, and the manufacturing cost is increased.
The film thickness of the first water-based resin coating film layer is preferably 4 times or less the film thickness of the second water-based resin coating film layer. As the film thickness of the first water-based resin coating layer becomes thicker, the peeling resistance of the inner tape deteriorates, and as the film thickness of the second water-based resin coating film layer becomes thinner, the peeling resistance of the inner tape deteriorates. Further, as the adhesiveness between the second water-based resin film layer and the tape becomes higher (as the concentration of the polyurethane resin with higher tape adhesiveness becomes higher in the second water-based resin film layer), a 2T bending cellophane tape peeling test , It tends to peel off to the first water-based resin coating film layer, and the black outer appearance after peeling is damaged. If the total film thickness of the first water-based resin coating film layer and the second water-based resin coating film layer is within the above-mentioned predetermined range, if the film thickness ratio is within the above range regardless of the film thickness, peeling of the first water- .
〔quite〕
The composition for forming a water-based resin coating film can be prepared by mixing the respective components described above at a predetermined ratio. The mixing order is not particularly limited.
The method of applying and drying the composition for forming an aqueous resin coating film when forming the aqueous resin film layer is not particularly limited and a known method can be suitably employed. Examples of the application method of the composition include a bar coater method, a roll coater method, a curtain flow coater method, a spraying method, a spraying method and the like. Among them, from the viewpoint of cost, The law is preferable. The drying temperature is not particularly limited as long as it does not deteriorate the waterborne resin coating layer by heat. For example, the drying temperature is preferably about 50 to 160 DEG C, and more preferably about 70 to 140 DEG C.
When a non-chromate type chemical conversion coating layer (base layer) is formed on the surface of a metal plate by a ground treatment, a non-chromate type metal film laminate metal plate is obtained by applying a chemical conversion coating layer by a roll coating method, a spraying method, have.
[Measurement of Blackness]
The water-based resin film laminated metal sheet has excellent blackness. In a preferred embodiment of the present invention, the water-based resin film laminated metal sheet has a blackness (L * value) of less than 23, and more preferably less than 21. When the blackness (L * value) is 23 or more, it is difficult to say that the black color is beautiful in the naked eye. On the other hand, in the present invention, the L value is a brightness index of an actual value measured by a method specified in JIS Z8722, and can be measured by the method described in the following examples, and is converted into an L * value based on the following equation .
L * = 1.3632L-3.5904
〔Other〕
It is preferable from the viewpoints of corrosion resistance, workability and the like that the coating film is laminated on the opposite surface (hereinafter referred to as the back surface) of the coating surface according to the present invention (referred to as surface in the specification). When a black appearance is required on the back surface as well as on the surface, it is preferable to appropriately adjust and coat the coating film used in the present invention in accordance with the required degree of blackness.
This application claims the benefit of priority based on Japanese Patent Application No. 2013-033817 filed on February 22, 2013, and Japanese Patent Application No. 2013-204220 filed on September 30, The entire contents of Japanese Patent Application No. 2013-033817 filed on February 22, 2013, and Japanese Patent Application No. 2013-204220 filed on September 30, 2013 are incorporated herein by reference in their entirety.
Example
EXAMPLES The present invention will be described in more detail by the following examples, but the following examples do not limit the present invention, but the scope of the present invention is not limited to these examples. In the following description, "%" represents "mass%" and "part" represents "mass part".
The evaluation methods used for each of the following waterborne resin film laminated metal sheets are as follows.
[Assessment Methods]
(1) Uneven application
The coated sample was cut into 50 x 120 mm so that the direction of coating was long, and the surface was observed with naked eyes to evaluate the state of occurrence of coating unevenness by the following evaluation criteria.
A: No uneven application
B: Uneven application
(2) Color tone (blackness evaluation)
The L value of the sealing material which is a water-based resin film laminated metal sheet was measured using a spectrophotometer ("Spectro Color Meter SQ2000" manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the L value obtained was converted into the L * value The blackness was evaluated.
L * = 1.3632L-3.5904
The evaluation of blackness in the test piece was carried out from the value of L * in accordance with the following evaluation criteria.
A: L * value less than 21
B: L * value is 21 or more and less than 23
C: L * value is 23 or more
(3) wrinkles
The coated sample was cut into 50 x 120 mm so that the coating direction was long, and the surface was visually observed to evaluate the occurrence of wrinkles by the following evaluation criteria.
A: No wrinkles
B: Partially creased wrinkles were observed.
C: The wrinkles of the axial shape are confirmed on the entire surface.
(4) Boiling
After the second aqueous resin coating layer was coated and dried, the presence or absence of boiling was observed using a microscope at a magnification of 175 times at a field of 1.5 x 2.0 mm and evaluated according to the following evaluation criteria.
A: No boiling within the above visual range
B: the number of brews within the above-mentioned visual range is less than 5
C: The number of brews within the above-mentioned visual range is 5 or more
(5) Scratch resistance
A predetermined load was applied to the specimen at room temperature using a scratch needle made of sapphire (tip radius of curvature: 0.075 mm) by a surface tester ("HEIDON-140 DR" After scratching with a load of 100 mm / min and a sliding distance of 20 mm, the surface of the water-based resin film laminated metal plate was evaluated for scratches. The above loads are 10, 15, 20, 25, ... g to 5 g, and the maximum load at which no scratches occurred was measured.
Evaluation of scratch resistance on a blank was performed on the following evaluation criteria from the maximum load at which no scratches were found.
A: 85gf or more
B: 60 gf or more and less than 85 gf
C: less than 60 gf
On the other hand, as a comparative material, black PCM in which a top coating layer having a film thickness of 6.0 mu m was laminated on a primer coating layer having a thickness of 1.0 mu m was subjected to the same measurement as above, and the maximum load without scratches was 60 gf. The black PCM was produced by the following production method. First, a solvent-based primer ("NC66-59 primer" manufactured by Nippon FinePrep Co., Ltd.) was diluted with a thinner (xylene: cyclohexanone = 50:50) so as to have a film thickness of 1.0 μm, , And dried by heating at 205 DEG C for 60 seconds to form a primer coating layer. Next, a solvent-based black top coat ("FLC495 black" manufactured by Nippon Fine Coating Co., Ltd.) was diluted with the above-mentioned thinner so as to have a film thickness of 6.0 μm, and then applied onto a primer coating layer with a bar coater and heated at 250 ° C. for 60 seconds Dried to form a top coating layer, and a black PCM having a total thickness of 7.0 m was formed.
(6) Peelability
A waterborne resin film laminated metal plate was subjected to 2 T bending, a cellophane tape (Nichibanze Cellotape (registered trademark) CT405AP-24) was attached to the processed portion, the cellophane tape was peeled off and the presence or absence of peeling of the first waterborne resin film layer (2T bending cellophane tape peeling test) was carried out, and evaluation was made based on the following evaluation criteria.
A: No peeling
B: In the point shape peeling
[Fabrication of an underfloor metal plate]
First, 26.3 parts of acidic colloidal silica ("SNOWTEX (registered trademark) O";
Next, the treatment composition solution not obtained, electrolytic zinc-coated metal plate having a thickness of 0.45mm (EG; Zn coating weight 20g / m 2) on the top and bottom faces of a manual roll coating device, the coating to be 103mg / m 2 by dry weight And then dried at 220 DEG C for 12 seconds to prepare a metal plate for undercoating. Hereinafter, an electroplated galvanized metal sheet is used as the untreated metal sheet EG.
[Additive for improving blackness]
At least one of the colloidal silica and various pigments listed in Table 1 was contained in the second water-based resin coating layer. "Snowtex (registered trademark) XS" manufactured by Nissan Chemical Industries, Ltd., having a particle diameter of 4 to 6 nm (nominal value) is referred to as colloidal silica A, "Snowtex (registered trademark)" manufactured by Nissan Chemical Industries, 40 " is referred to as colloidal silica B. Details will be described later.
[Production of a polyurethane resin composition for forming a first water-based resin coating film layer and a method for forming a metal plate having a polyurethane-containing first water-based resin coating film layer]
(For Nos. 1 to 11 and Nos. 23 to 24)
60 g of polytetramethylene ether glycol (number average molecular weight 1000, manufactured by Hodogaya Chemical Industry Co., Ltd.) as a polyol component was added to an autoclave (content 1.0 L) having an emulsification facility equipped with a stirrer, a thermometer and a temperature controller, 14 g of dimethanol and 20 g of dimethylolpropionic acid were added, and 30.0 g of N-methylpyrrolidone was further added as a reaction solvent. 104 g of tolylene diisocyanate as an isocyanate component was added, the temperature was raised to 80 to 85 캜, and the reaction was carried out for 5 hours. The NCO content of the obtained prepolymer was 8.9%. Further, 16 g of triethylamine was added to neutralize, and a mixed aqueous solution of 16 g of ethylenediamine and 480 g of water was added and emulsified at 50 ° C for 4 hours. The mixture was subjected to a chain extension reaction to obtain an aqueous dispersion containing a carboxyl group-containing polyurethane resin Nonvolatile resin component: 29.1%, acid value: 41.4 or less, polyurethane resin aqueous solution).
Epiklon (registered trademark) CR75), colloidal silica A, and glycidoxine-containing silane coupling agent ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd.) were added to the aqueous polyurethane resin solution obtained above, (Solid content concentration: 100%), black pigment ("Super Concentrate BA-8" manufactured by Kuratake Co., Ltd. or carbon black 1: "SA Black DY-6" manufactured by Mikuni Color Co., Ltd.) A polyurethane resin composition was prepared. The blending ratio of each component was blended so that 57.5 parts of a polyurethane resin, 2.5 parts of an epoxy crosslinking agent, 10 parts of colloidal silica, and 30 parts of a black pigment were calculated in terms of solid content. The polyurethane resin composition for forming the first water based resin film layer was diluted with pure water and adjusted to a solid content concentration of 10% and agitated at 700 rpm x 10 minutes using a disper stirrer. Then, on the surface of the untreated metal plate EG, And dried by heating at a plate temperature of about 120 to 130 占 폚 (furnace temperature 220 占 폚 for 12 seconds) to form a polyurethane-containing first aqueous resin coating layer on the metal plate.
(For No. 27 to 60)
The above epoxy-based crosslinking agent, colloidal silica A, black pigment (ink or ink and carbon black 1) were sequentially added to the aqueous polyurethane resin solution obtained above to prepare a polyurethane resin for forming a first aqueous resin coating layer To prepare a resin composition. The blending ratio of each component was blended so as to be 45.1 to 63.2 parts of a polyurethane resin, 2.0 to 2.8 parts of an epoxy crosslinking agent, 7.9 to 11 parts of colloidal silica, and 23 to 45 parts of a black pigment in terms of solid content. The polyurethane resin composition for forming the first water based resin film layer was diluted with pure water and adjusted to a solid content concentration of 10% and agitated at 700 rpm x 10 minutes using a disper stirrer. Then, on the surface of the untreated metal plate EG, And dried by heating at a plate temperature of about 120 to 130 占 폚 (furnace temperature 220 占 폚 for 12 seconds) to form a polyurethane-containing first aqueous resin coating layer on the metal plate.
(For No. 69 to 111)
The above epoxy-based crosslinking agent, colloidal silica A, and black pigment (ink and carbon black 1) were sequentially added to the aqueous polyurethane resin solution obtained above to prepare a polyurethane resin composition for forming a first aqueous resin coating layer It was prepared. The blending ratio of each component was blended so as to be 45.1 to 63.2 parts of a polyurethane resin, 2.0 to 2.8 parts of an epoxy crosslinking agent, 7.9 to 11 parts of colloidal silica, and 23 to 45 parts of a black pigment in terms of solid content. The polyurethane resin composition for forming the first water based resin film layer was diluted with pure water to adjust the solid content concentration to 15% and stirred at 700 rpm x 10 minutes using a Disper Mixer. Thereafter, And dried by heating at a plate temperature of about 120 to 130 캜 (furnace temperature of 220 캜 for 12 seconds) to form a polyurethane-containing first aqueous resin coating layer on the metal plate.
(For No. 112 to 150)
The epoxy-based crosslinking agent, colloidal silica A, and black pigment (ink and carbon black 1) were sequentially added to the aqueous polyurethane resin solution obtained above. 112 to 114, a polyurethane resin composition for forming a first aqueous resin coating layer was prepared by adding an aqueous solution of a polyethylene resin described later. The blending ratio of each component is from 28.0 to 67.0 parts of a polyurethane resin, 0.0 to 29.0 parts of a polyethylene resin, 0.0 to 7.5 parts of an epoxy crosslinking agent, 1 to 40 parts of colloidal silica, 30 parts of a black pigment Part, carbon black 1: 10 parts). The polyurethane resin composition for forming the first water based resin film layer was diluted with pure water and adjusted to a solid content concentration of 10% and agitated at 700 rpm x 10 minutes using a disper stirrer. Then, on the surface of the untreated metal plate EG, And dried by heating at a plate temperature of about 120 to 130 占 폚 (furnace temperature 220 占 폚 for 12 seconds) to form a polyurethane-containing first aqueous resin coating layer on the metal plate.
(For Nos. 151 to 191)
The above epoxy-based crosslinking agent, colloidal silica A, and black pigment (ink and carbon black 1) were sequentially added to the aqueous polyurethane resin solution obtained above to prepare a polyurethane resin composition for forming a first aqueous resin coating layer It was prepared. The blending ratio of each component was blended so as to be 57.5 parts of polyurethane resin, 2.5 parts of epoxy crosslinking agent, 10 parts of colloidal silica, 30 parts of black pigment (20 parts of food: 1 part of carbon black) in terms of solid content . The polyurethane resin composition for forming the first water based resin film layer was diluted with pure water to adjust the solid content concentration to 15% and stirred at 700 rpm x 10 minutes using a Disper Mixer. Thereafter, And dried by heating at a plate temperature of about 120 to 130 占 폚 (furnace temperature 220 占 폚 for 12 seconds) to form a polyurethane-containing first aqueous resin coating layer on the metal plate.
(Nos. 192 to 206 and Nos. 209 to 235)
A polyurethane resin composition for forming a first aqueous resin coating layer was prepared by sequentially adding the above epoxy cross-linking agent, colloidal silica A, and black pigment (carbon black 1) to the polyurethane resin aqueous solution obtained above . The blending ratio of each component was blended so that 61.2 to 76.0 parts of a polyurethane resin, 1.0 to 4.0 parts of an epoxy crosslinking agent, 3.0 to 18 parts of colloidal silica, and 17 to 25 parts of a black pigment were calculated in terms of solid content. The polyurethane resin composition for forming the first water based resin film layer was diluted with pure water to adjust the solid content concentration to 15% and stirred at 700 rpm x 10 minutes using a Disper Mixer. Thereafter, And then dried by heating at a plate temperature of about 120 to 130 占 폚 (furnace temperature 220 占 폚 for 12 seconds) to form a polyurethane-containing first aqueous resin coating layer on the metal plate.
(Regarding Nos. 207 to 208)
To the aqueous polyurethane resin solution obtained above was added the above epoxy crosslinking agent, colloidal silica A, black pigment (carbon black 2: SA Black E-1319 manufactured by Mikuni Color Co., Ltd. or carbon black 3: GP Black 1188 ) Were sequentially added to prepare a polyurethane resin composition for forming a first aqueous resin coating layer. The blending ratio of each component was blended so that 71 parts of a polyurethane resin, 5.0 parts of an epoxy crosslinking agent, 5.0 parts of colloidal silica, and 19 parts of a black pigment (carbon black 2 or carbon black 3) in terms of solid content. The polyurethane resin composition for forming the first water based resin film layer was diluted with pure water to adjust the solid content concentration to 15% and stirred at 700 rpm x 10 minutes using a Disper Mixer. Thereafter, And dried by heating at a plate temperature of about 120 to 130 캜 (furnace temperature of 220 캜 for 12 seconds) to form a polyurethane-containing first aqueous resin coating layer on the metal plate.
[Production of polyethylene resin composition forming first aqueous resin coating layer and formation of metal plate having polyethylene-containing first aqueous resin coating layer]
(For Nos. 12 to 22 and Nos. 25 to 26)
(Manufactured by Dow Chemical Co., Ltd .; " Primakore (registered trademark) 5990I ", constituent units derived from acrylic acid: 20%, and a mass average molecular weight (Mw , 8.0 parts of an aqueous solution of polymaleic acid (Nitto (registered trademark) PMA-50W, Mw: about 1100 (in terms of polystyrene), 50% by volume), 200.0 parts of a polymaleic acid aqueous solution , 35.5 parts of triethylamine (0.63 equivalents relative to the carboxyl groups of the ethylene-acrylic acid copolymer), 6.9 parts of a 48% NaOH aqueous solution (1.5 equivalents to the carboxyl groups of the ethylene-acrylic acid copolymer), tall oil fatty acid FA3 ") and 792.6 parts of ion-exchanged water were sealed, and the mixture was stirred at 150 ° C and 5 atmospheric pressure for 3 hours at high speed, followed by cooling to 30 ° C. Subsequently, 10.4 parts of a glycidoxine-containing silane coupling agent ("TSL8350" manufactured by Momentive Performance Materials (formerly GE Toshiba Silicones), γ-glycidoxypropyltrimethoxysilane), 10.4 parts of carbodiimide , 31.2 parts of an organo-containing compound ("CARBODILITE (registered trademark) SV-02" manufactured by Nissinbo Chemicals, polycarbodiimide, Mw: 2,700, solid content 40%) and 72.8 parts of ion-exchanged water were added and stirred for 10 minutes, (Emulsion) of an olefin-acid copolymer and a carboxylic acid polymer (solid content concentration: about 20%, measured according to JIS K6833) to obtain an aqueous dispersion in which a polyethylene resin was dispersed (hereinafter referred to as a polyethylene resin aqueous solution).
A colloidal silica A, a glycidoxime-containing silane coupling agent ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration: 100%), and an oxazoline (Epochros (registered trademark) K-2030E (solid content concentration: 40%) manufactured by Nippon Shokubai Co., Ltd.) were sequentially added to prepare a polyethylene resin composition for forming a first aqueous resin coating layer. The blending ratio of each component was blended so as to be 53.2 parts of polyethylene resin, 30 parts of black pigment, 9.3 parts of colloidal silica, 4.7 parts of silane coupling agent and 2.8 parts of oxazoline group-containing polymer in terms of solid content. The polyethylene resin composition for forming the first water based resin film layer was diluted with pure water and adjusted to a solid content concentration of 10% and agitated at 700 rpm x 10 minutes using a disper stirrer. Then, the surface of the untreated metal plate EG was coated with a film thickness of 1.0 μm and dried by heating at a plate temperature of 120 to 130 ° C. (furnace temperature: 220 ° C. × 12 seconds) to form a polyethylene-containing first aqueous resin coating layer on the undercoated metal plate EG.
(For Nos. 61 to 68)
To the aqueous polyethylene resin solution obtained above, a black pigment (only ink), colloidal silica A, a glycidoxime-containing silane coupling agent, and the oxazoline group-containing polymer were sequentially added to form a first aqueous resin film layer To prepare a polyethylene resin composition. The blending ratio of each component was blended so as to be 53.2 parts of polyethylene resin, 30 parts of black pigment, 9.3 parts of colloidal silica, 4.7 parts of silane coupling agent and 2.8 parts of oxazoline group-containing polymer in terms of solid content. The polyethylene resin composition for forming the first water based resin film layer was diluted with pure water and adjusted to a solid content concentration of 10% and stirred at 700 rpm x 10 minutes using a disper mixer. The surface of the untreated metal plate EG was coated with a film thickness 0.7 And dried by heating at a plate temperature of 120 to 130 占 폚 (furnace temperature of 220 占 폚 for 12 seconds) to form a polyethylene-containing first aqueous resin coating layer on the undercoated metal plate EG.
[Preparation of a polyurethane resin composition for forming a second waterborne resin film layer and a method for forming a metal sheet having a polyurethane-containing second waterborne resin film layer]
(For Nos. 23 to 26)
To the aqueous polyurethane resin solution obtained above was added the above epoxy cross-linking agent, colloidal silica B, polyamide thixotropic agent (Disperson (registered trademark) AQ-607:
(For Nos. 27 to 36, 49 to 50, 56, and 67 to 68)
To the aqueous polyurethane resin solution obtained above, an epoxy cross-linking agent, an additive for improving blackness (a mixture of colloidal silica B, cyan blue, or colloidal silica B, cyan blue, and dioxazine violet) The polyamide was sequentially added to prepare a polyurethane resin composition for forming a second aqueous resin coating layer. The blending ratio of each component was blended in an amount of 68.1 to 87.8 parts of a polyurethane resin, 1.7 to 2.2 parts of an epoxy crosslinking agent, 10 to 30 parts of an additive, 0 part of polyamide or 0.2 part in terms of solid content. The polyurethane resin composition for forming a second waterborne resin film layer was diluted with pure water and adjusted to a solid concentration of 10 to 15% and stirred at 700 rpm x 10 minutes using a Disper Mixer. Then, And dried by heating at a plate temperature of 120 to 130 캜 (furnace temperature: 220 캜 × 12 seconds) to form a second water-based resin coating film containing polyurethene on the first water- Layer laminated metal plate was obtained.
[Production of a polyethylene resin composition forming a second waterborne resin film layer and a method of forming a metal sheet having a polyethylene-containing second waterborne resin film layer]
(For Nos. 1 to 22)
626 parts of water and 160 parts of ethylene-acrylic acid copolymer (
To the emulsion mixture obtained above, a glycidyl group-containing compound A (Epiclon CR5L manufactured by DIC) as an external crosslinking agent, colloidal silica A as an additive for improving the blackness or various coloring pigments (ink, carbon black 1, ), Polyamide-based thixotropic agent (Disperson (registered trademark) AQ-607: solid content concentration of 15% or less, polyamide-based thixotropic agent ) Were sequentially added to prepare a polyethylene resin composition for forming a second aqueous resin film layer. The mixing ratio of each component was adjusted so as to be 64.8 parts or 65 parts of the emulsion mixture, 5 parts of the crosslinking agent, 30 parts of the additive, 0 or 0.2 parts of the polyamide in terms of solid content. The polyethylene resin composition for forming the second water based resin film layer was diluted with pure water and adjusted to a solid content concentration of 10% and stirred with a dispenser at 700 rpm for 10 minutes. Then, a roll coater film Laminated metal sheet on which a polyethylene-containing second water-based resin film layer was formed on the first water-based resin coat layer by drying at a plate temperature of 120 to 130 캜 (furnace temperature: 220 캜 × 12 seconds) .
(Nos. 37 to 48, 51 to 55, and 57 to 66)
The glycidyl group-containing compound A, the additive for improving blackness (a mixture of colloidal silica A, cyan blue, cyanogen green, colloidal silica A and cyan blue), the polyamide Were sequentially added to prepare a polyethylene resin composition for forming a second waterborne resin coating layer. The blending ratio of each component was blended in an amount of 27.1 to 86.4 parts of the emulsion mixture, 2.7 to 8.6 parts of the crosslinking agent, 5 to 70 parts of the additive and 0 or 0.2 parts of the polyamide in terms of solid content. The polyethylene resin composition for forming the second waterborne resin film layer was diluted with pure water and adjusted to a solid concentration of 7 to 15% and stirred with a dispenser at 700 rpm for 10 minutes. Then, on the first waterborne resin film layer, And dried by heating at a plate temperature of 120 to 130 캜 (furnace temperature: 220 캜 × 12 seconds) to form a second water-based resin film layer containing polyethylene on the first water-based resin coating film layer To obtain a laminated metal film.
(For No. 69 to 111)
To the emulsion mixture obtained above, the glycidyl group-containing compound A, the additive for improving blackness (a mixture of colloidal silica A, cyan blue, cyanogen, colloidal silica A and cyan blue, colloidal silica A And a mixture of cyano green) and polyamide were sequentially added to prepare a polyethylene resin composition for forming a second aqueous resin coating layer. The blending ratio of each component was blended in an amount of 64.8 to 88.2 parts of the emulsion mixture, 5 to 6.8 parts of the crosslinking agent, 5 to 30 parts of the additive, and 0 or 0.2 parts of the polyamide in terms of solid content. The polyethylene resin composition for forming the second waterborne resin coating layer was diluted with pure water to adjust the solid concentration to 15% and stirred at 700 rpm x 10 minutes using a dispenser. Thereafter, a bar coater And dried by heating at a plate temperature of 120 to 130 占 폚 (furnace temperature of 220 占 폚 for 12 seconds) to obtain a coating film laminated with a polyethylene-containing second water-based resin coating film layer on the first water- A metal plate was obtained.
(For No. 112 to 150)
(Glycidyl group-containing compound B (Epiclon CR75 manufactured by DIC) as an external crosslinking agent, an additive for improving blackness (colloidal silica A, cyan blue, cyanogen green), polyamide , And further a polyethylene wax particle ("Chemipel (registered trademark) W-700" manufactured by Mitsui Chemicals, Ltd., average particle diameter 1 μm, softening point 132 ° C.) or polysiloxane- based lubricant (polyether modified polydimethylsiloxane: BYK-337 "manufactured by Japan Chemical Co., Ltd.," BYK-307 "manufactured by Japan Chemical Industry Co., Ltd., BYK-337 manufactured by Big Chemie Japan, and polydimethylsiloxane containing polyetherester modified hydroxyl group: BYK-375 manufactured by Big Chem Japan Co., And No. 123 to 127, a polyurethane resin aqueous solution was also added to prepare a polyethylene resin composition for forming a second aqueous resin coating layer. The blending ratio of each component is from 0.0 to 79.0 parts of a polyethylene resin, 0.0 to 59.0 parts of a polyurethane resin, 0.0 to 17.5 parts of a crosslinking agent, 10 to 70 parts of an additive, 1.8 to 9.8 parts of polyethylene wax particles or a polysiloxane- 1.8 or 9.8 parts, and polyamide 0.2 parts. The polyethylene resin composition for forming the second water based resin film layer was diluted with pure water and adjusted to a solid content concentration of 10% and stirred with a dispenser at 700 rpm for 10 minutes. Then, a roll coater film Laminated metal sheet on which a polyethylene-containing second water-based resin film layer was formed on the first water-based resin coat layer by drying at a plate temperature of 120 to 130 캜 (furnace temperature: 220 캜 × 12 seconds) .
(For Nos. 151 to 191)
The glycidyl group-containing compound B, the additive for improving the blackness (colloidal silica A, cyan blue, cyanogen green), the polyethylene wax particles, and the polyamide were sequentially added to the aqueous polyethylene resin solution, To prepare a polyethylene resin composition for forming a second aqueous resin coating layer. The blending ratio of each component was blended so that 59.0 parts of a polyethylene resin, 7.5 parts of a crosslinking agent, 30 parts of an additive, 3.3 parts of a polyethylene wax particle and 0.2 parts of a polyamide were obtained in terms of solid content. The polyethylene resin composition for forming the second waterborne resin coating layer was diluted with pure water to adjust the solid concentration to 15% and stirred at 700 rpm x 10 minutes using a dispenser. Thereafter, a bar coater And dried by heating at a plate temperature of 120 to 130 占 폚 (furnace temperature: 220 占 폚 for 12 seconds) to form a coating film laminated with a polyethylene-containing second water-based resin coating film layer on the first water- A metal plate was obtained.
(For Nos. 192 to 235)
The glycidyl group-containing compound B, the additive for improving the blackness (colloidal silica A), the polyethylene wax particles, and the polyamide were sequentially added to the polyethylene resin aqueous solution to form a second water- To prepare a polyethylene resin composition. The blending ratio of each component was blended so that 59.0 parts of a polyethylene resin, 0.0 part of a polyurethane resin, 7.5 parts of a crosslinking agent, 30 parts of an additive, 3.3 parts of polyethylene wax particles and 0.2 parts of polyamide were contained in terms of solid content. The polyethylene resin composition for forming the second water based resin film layer was diluted with pure water and adjusted to a solid content concentration of 10% and stirred with a dispenser at 700 rpm for 10 minutes. Then, a roll coater film And then heated and dried at a plate temperature of 120 to 130 占 폚 (furnace temperature: 220 占 폚 占 12 seconds) to obtain a coating film laminated with a polyethylene-containing second water-based resin coating film layer formed on the first water- A metal plate was obtained.
According to the present invention, it is possible to provide a water-based resin coating film laminated metal sheet excellent in blackness and appearance. Therefore, the beautiful and black, water-based resin film laminated metal sheet manufactured at a low cost according to the present invention can be applied to an outer plate material or building material such as a housing of an automobile or home electrical appliance, interior / exterior parts, and forced furniture.
Claims (12)
Wherein the sum of the film thicknesses of the first water-based resin film layer and the second water-based resin film layer is 0.9 to 8.0 m.
Wherein the L * a * b * color system of the water-based resin film laminated metal sheet has a lightness L * of less than 23.
And the black pigment contained in the first water based resin coating film layer is 16 mass% or more and 50 mass% or less.
Wherein the black pigment contained in the first water-based resin coating layer is at least one of an ink and carbon black.
Wherein the first water based resin coating film layer contains a polyurethane resin in an amount of 25 mass% or more.
Wherein the first water-based resin coating film layer is obtained from a composition for forming a first water-based resin coating film containing at least 1% by mass of a crosslinking agent.
And the second water-based resin coating film layer does not contain a black pigment.
Wherein the second water-based resin coating film layer contains 25 mass% or more of a polyethylene resin and the film thickness of the first water-based resin film layer is 4 times or less the film thickness of the second water- .
Wherein the metal plate is an electro galvanized metal plate.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP-P-2013-033817 | 2013-02-22 | ||
| JP2013033817 | 2013-02-22 | ||
| JPJP-P-2013-204220 | 2013-09-30 | ||
| JP2013204220A JP6140586B2 (en) | 2013-02-22 | 2013-09-30 | Water-based resin coating laminated metal sheet |
| PCT/JP2014/053815 WO2014129475A1 (en) | 2013-02-22 | 2014-02-18 | Metal sheet laminated with water-based resin coating film |
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| Publication Number | Publication Date |
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| KR20150110695A KR20150110695A (en) | 2015-10-02 |
| KR101755963B1 true KR101755963B1 (en) | 2017-07-07 |
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| KR1020157022630A KR101755963B1 (en) | 2013-02-22 | 2014-02-18 | Metal sheet laminated with water-based resin coating film |
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| JP (1) | JP6140586B2 (en) |
| KR (1) | KR101755963B1 (en) |
| CN (1) | CN104995021B (en) |
| TW (1) | TWI537126B (en) |
| WO (1) | WO2014129475A1 (en) |
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| JP6396786B2 (en) * | 2014-12-18 | 2018-09-26 | 株式会社神戸製鋼所 | Aqueous two-layer coated metal plate |
| JP2016175400A (en) * | 2015-03-19 | 2016-10-06 | 株式会社神戸製鋼所 | Resin-coated galvanized metal plate |
| JP2017165026A (en) * | 2016-03-17 | 2017-09-21 | 株式会社神戸製鋼所 | Aqueous resin-coated metal plate |
| CN109563625B (en) * | 2016-08-08 | 2021-06-22 | Dic株式会社 | Laminate, metal mesh, and touch panel |
| EP4177312A1 (en) * | 2020-07-02 | 2023-05-10 | Toyo Aluminium Kabushiki Kaisha | Composite pigment, thermoplastic resin composition containing same, and molded body |
| JP7438078B2 (en) * | 2020-10-20 | 2024-02-26 | 日本ペイント・サーフケミカルズ株式会社 | Water-based coating agent for steel materials, film, coating method for steel materials, and steel materials |
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| JPH0679842B2 (en) * | 1988-06-27 | 1994-10-12 | 新日本製鐵株式会社 | Black surface treated steel plate |
| US4968391A (en) * | 1988-01-29 | 1990-11-06 | Nippon Steel Corporation | Process for the preparation of a black surface-treated steel sheet |
| JPH0681163A (en) * | 1992-08-31 | 1994-03-22 | Nkk Corp | Weldable one-side black steel |
| JP3590656B2 (en) * | 1994-09-09 | 2004-11-17 | 関西ペイント株式会社 | Painted steel plate with good stain resistance |
| JPH08243488A (en) * | 1995-03-14 | 1996-09-24 | Nippon Steel Corp | Organic composite steel panel excellent in chemical forming treatment resistance |
| JPH1148403A (en) * | 1997-08-06 | 1999-02-23 | Toyo Kohan Co Ltd | Surface-treated metallic sheet excellent in perspiration resistance and lubricity and manufacture thereof |
| JP2001009966A (en) * | 1999-06-30 | 2001-01-16 | Kobe Steel Ltd | Weldable black metal sheet |
| JP4667562B2 (en) * | 2000-06-29 | 2011-04-13 | 日新製鋼株式会社 | White painted metal plate with excellent processability, light reflectivity and light reflectivity |
| JP2002047579A (en) * | 2000-07-31 | 2002-02-15 | Kobe Steel Ltd | Surface-treated metallic material excellent in black appearance |
| JP4154189B2 (en) * | 2002-08-27 | 2008-09-24 | 大宝化学工業株式会社 | Silica-containing acrylic resin pre-coated metal painted plate |
| JP2007126904A (en) * | 2005-11-04 | 2007-05-24 | Nisshin Steel Co Ltd | Kitchen sink superior in flaw resistance, staining resistance and hot water resistance |
| JP2008285632A (en) * | 2007-05-21 | 2008-11-27 | Mikuni Color Ltd | High jetness carbon black dispersion, process for producing the same, and coating material composition using the high jetness carbon black dispersion |
| DE102008009481A1 (en) * | 2008-02-15 | 2009-08-20 | Basf Coatings Ag | Aqueous coating composition, process for its preparation and its use |
| JP5527753B2 (en) * | 2009-05-25 | 2014-06-25 | 東洋アルミニウム株式会社 | Surface-coated metallic pigment, water-based paint containing the same, and coated product on which the same is applied |
| CN102448722B (en) * | 2009-05-27 | 2013-11-13 | 新日铁住金株式会社 | Chromate-free black coated metal plate |
| JP5695430B2 (en) * | 2010-03-31 | 2015-04-08 | 株式会社神戸製鋼所 | Black metal plate |
| JP5582109B2 (en) * | 2011-07-21 | 2014-09-03 | 新日鐵住金株式会社 | Clear coat steel plate with excellent red rust resistance |
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| KR20150110695A (en) | 2015-10-02 |
| TWI537126B (en) | 2016-06-11 |
| WO2014129475A1 (en) | 2014-08-28 |
| JP6140586B2 (en) | 2017-05-31 |
| TW201500180A (en) | 2015-01-01 |
| CN104995021B (en) | 2017-11-14 |
| CN104995021A (en) | 2015-10-21 |
| JP2014184709A (en) | 2014-10-02 |
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