JP2011038138A - Painted metal material and housing made by using the same - Google Patents

Abstract

The present invention provides a coated metal material having a flat surface coating film corrosion resistance and post-processing adhesion, and capable of high-speed operation, and a processed product using the same.
A metal substrate, a Zn-Ni alloy plating layer provided on the metal substrate, a chromium-free conversion coating provided on the Zn-Ni alloy plating layer, and the conversion coating on the conversion coating Provided with a resin film having a thickness of 2 to 15 μm, and the Zn-Ni alloy plating layer has a Ni content of 10 to 15% by mass or less and an adhesion amount of ² to 25 g / m ² or less. Yes, the Zn-Ni alloy plating layer has a crack at the interface with the chemical conversion film, and the surface of the member provided with at least the metal substrate and the Zn-Ni alloy plating layer obtained by removing the resin film is a scanning electron When observed with a microscope, the number of regions surrounded by cracks seen in the observed image is 2000 to 150,000 pieces / mm ² .
[Selection] Figure 1

Description

  The present invention relates to a coated metal material excellent in adhesion after processing and corrosion resistance on a flat surface. The coated metal material of the present invention can be suitably used as a casing or material for home appliances such as flat panel panels, refrigerators, fan heaters, and air conditioner outdoor units, building materials, and automobile parts. In the present invention, the “casing” means a box-shaped body that accommodates a product or its internal components.

  Usually, a coated metal plate (in the following description, a zinc-based plated steel sheet that is a coated steel sheet in which a coating film is formed on a zinc-based plated steel sheet that is a steel sheet having a zinc-containing plating layer is taken as a specific example). Then, the outer surface coating film to be the design surface is formed from a plurality of coating films such as an undercoat coating film, a top coating film, or an undercoat coating film, an intermediate coating film, and a top coating film. In such a coating film, there is a role for each layer, the undercoat film plays a role as ensuring adhesion and corrosion resistance with the underlying steel sheet, and the overcoat film is designed and resistant to contamination. Responsible for performance, weather resistance, scratch resistance, and chemical resistance. As for the intermediate coating film, it is often used to supplement the role of each of the undercoat and topcoat films.

  Moreover, in order to ensure adhesion between the zinc-coated steel sheet and the undercoat film, the undercoat film usually has a thin film (formation treatment caused by bringing a chemical conversion solution into contact with a substrate such as a steel sheet). In general, when the formation / drying process of the chemical conversion film is included, a coated steel sheet is formed through at least a single-side three-coating three-baking process.

  Such a coated steel sheet has a large number of processes during painting and baking, and requires a long time for production. Therefore, an improvement means for reducing the number of processes is desired from the viewpoint of rationalization of painting work and resource saving. Also, lines that can only be coated with 2 coats and 2 bake processes, including chemical conversion coatings, for example, in-line coater equipment after hot-dip galvanizing or electrogalvanizing lines, and only 2 coats and 2 bakes due to space requirements. Such a coated steel sheet cannot be manufactured in a possible coating line or the like.

  Therefore, it has the same performance as a coated steel sheet with 3 coats and 3 bakes including a conventional chemical coating, and has a structure in which a single layer film is formed on the upper layer of the chemical conversion film, and can be manufactured in a 2 coat 2 bake process. Painted steel sheets are desired. Hereinafter, this chemical conversion film and the film thereon are collectively referred to as a coating layer.

On the other hand, it is desired to use a water-based paint for a paint composition used for producing a coated steel sheet. The water-based paint can reduce the burden on the insulator used to burn the organic solvent generated at the time of paint baking as compared with the solvent-based paint, and the CO ₂ discharged therefrom. It is possible to reduce the amount. In addition, if a completely water-based paint is used, it is not necessary to use the incinerator itself.

  That is, by using a water-based coating composition corresponding to a total of two coating layers including a chemical conversion coating layer, it is possible to alleviate the environmental load imposed by the coating process and rationalize the coating operation. .

  However, when the conventional paint for coated steel sheet is used as it is as a single coating film, the undercoat paint alone is insufficient in processability and chemical resistance, and the topcoat paint alone has adhesion to the underlying steel sheet. Corrosion resistance becomes insufficient. Although it is conceivable to use a powder paint instead of the liquid paint, the powder paint has a thick film thickness and takes time to be cured. Therefore, when considering the rationalization of painting work and resource saving, it is necessary to design a single color coating that has the functions of both the undercoat layer and the overcoat layer of the coated steel sheet and can be cured in a short time. Become.

  By the way, the pre-coated steel sheet (refers to a coated steel sheet in which a painting process is performed in the primary processing stage. In the present invention, the “coated metal material” means a pre-coated metal material including a pre-coated steel sheet). Many performances are required, such as high hardness, excellent stain resistance, excellent chemical resistance, excellent water resistance, and excellent corrosion resistance.

  Here, as the corrosion resistance of the conventional precoated steel sheet, a characteristic that suppresses the occurrence of white rust and / or red rust mainly at the edge of the coating layer and the heel portion of the coating film (hereinafter referred to as “corrosion resistance at the edge”). Has been evaluated. However, the thickness of the entire coating layer (total film thickness) tends to be thin from the viewpoint of environmental considerations and cost reduction (for example, 15 μm or less on the surface (front surface) used on the exterior side). In the field of pre-coated steel sheets, a characteristic that suppresses the occurrence of white rust in a steel plate flat portion, which has not been considered as a problem in the past (hereinafter referred to as “planar portion corrosion resistance” to distinguish it from end portion corrosion resistance), has been regarded as important. Yes.

  In addition, since the coated steel sheet is subjected to secondary processing such as press working in a state having a coating film, if the adhesion between the coating film and the steel sheet forming the substrate is not high, the coating layer is Peeling occurs and the corrosion resistance in this part is significantly reduced.

  With respect to the required characteristics of such a coated steel sheet, for example, in Patent Document 1, a specific polyester resin, melamine resin (curing agent) is used for the purpose of obtaining a coating film excellent in hardness, stain resistance and weather resistance. There have been proposed coating compositions containing the above and coated steel sheets using the same.

  Moreover, in patent document 2, by coating the coating composition which mix | blended polyester resin, a melamine resin (curing agent), a rust preventive pigment, organic polymer fine particles, etc., workability, corrosion resistance, adhesiveness, and resistance to one coat. Coated steel sheets that satisfy impact, scratch resistance, and design have been proposed.

  Furthermore, in Patent Document 3, a conversion coating not containing a zinc-based plating layer and chromium is sequentially formed on both surfaces of a steel plate, and a polyester-based resin cured with a crosslinking agent on the conversion coating on one surface of the steel plate; A single coating film containing resin particles having an average particle diameter of 3 to 40 μm, a glass transition temperature of 70 to 200 ° C. and higher hardness than the polyester resin has been proposed.

Japanese Unexamined Patent Publication No. 63-7878 JP 63-114635 A JP 2007-269010 A Japanese Patent Laid-Open No. 9-324282

  However, all of the coated steel sheets described in Patent Documents 1 and 2 are assumed to use a chromate-based film containing chromium as a chemical conversion film, which is environmentally undesirable. In addition, since the polyester resin used is not designed to provide a thin coating film with a strength sufficient to withstand the stress during severe press processing such as drawing, sufficient press workability is achieved. I can't get it.

  Moreover, about the coated steel plate described in patent document 3, although chromium is not contained and a coating film is 1 layer, it is not described at all about ensuring corrosion resistance of the coating-film plane part concerned in that case. .

  Accordingly, an object of the present invention is to solve the above-described problems of the prior art, and a conventional two-layer coating film (a coating film having an undercoat layer and an overcoat layer formed on a metal material on which a chemical conversion film is formed). The present invention provides a coated metal material having a coating film corrosion resistance and post-processing adhesion equivalent to those of a layer) and capable of high-speed operation during manufacturing, and a processed product (for example, a casing) using the same. is there.

  As a result of repeated studies to solve the above-mentioned problems and obtain a coated metal plate having excellent performance while the coating film other than the chemical conversion film in the coating layer has a single layer structure, the substrate The coating layer interposed between the metal material forming the coating layer and the coating layer has a specific composition and a specific surface property, so that a coated metal material having excellent flat surface corrosion resistance and adhesion after processing can be obtained. I found it. The present invention has been made based on such findings, and the gist of the present invention is as follows.

(1) A metal base, a zinc-nickel alloy plating layer provided on the metal base, a chromium-free chemical film provided on the zinc-nickel alloy plating layer, and provided on the chemical film The zinc-nickel alloy plating layer has a nickel content of 10% by mass to 15% by mass and an adhesion amount of 2 g / m ² or more. 25 g / m ² or less, the zinc-nickel alloy plating layer has a crack at the interface with the chemical conversion film, and is obtained by removing the resin film, at least the metal substrate and the zinc-nickel alloy plating When the surface of the member including the layer is observed with a scanning electron microscope, the number of regions surrounded by cracks seen in the observation image is 2000 / mm ² or more and 150,000 / mm ² or less. Painted metal material characterized by that.

  (2) The coated metal material according to (1), wherein the chemical conversion film is formed from a chemical conversion treatment liquid containing a silane coupling agent and / or silica fine particles.

(3) The coated steel material as described in (1) or (2) above, wherein the amount of the chemical conversion coating is 20 mg / m ² or more and 1000 mg / m ² or less.

  (4) The painted metal material according to any one of (1) to (3), wherein the resin film contains a urethane resin and / or a polyester resin.

  (5) A housing characterized by using the painted metal material according to any one of (1) to (4) so that the surface on which the resin film is formed is on the outside.

  Since the plating layer according to the present invention contains nickel in a predetermined content range, the function of suppressing corrosion of a metal substrate, for example, a flat portion of a steel plate, is higher than a plating layer made of galvanizing. Moreover, since the surface of the plating layer has cracks at a predetermined density, the adhesion with the chemical conversion film is improved.

  Therefore, the coated metal material according to the present invention is superior in the corrosion resistance of the flat portion and the adhesion after processing as compared with the coated metal material having a conventional galvanized layer.

(A) It is a figure which shows an example of the surface SEM image of a zinc-nickel zinc plating steel plate, and (b) the measuring method of the number of crack areas. It is another example of the surface SEM image of a zinc- nickel galvanized steel plate. It is another example of the surface SEM image of a zinc- nickel galvanized steel plate. It is another example of the surface SEM image of a zinc- nickel galvanized steel plate. It is another example of the surface SEM image of a zinc- nickel galvanized steel plate.

Hereinafter, the coated metal material according to the present invention and a casing using the same will be described in detail.
The coated metal material according to the present invention includes a metal material, a zinc-nickel alloy plating layer provided on the metal material, a chromium-free chemical conversion film provided on the zinc-nickel alloy plating layer, and this chemical conversion. And a resin film having a thickness of 2 to 15 μm provided on the film. Here, the zinc-nickel alloy plating layer has a nickel content of 10% by mass or more and 15% by mass or less, and an adhesion amount thereof is 2 g / m ² or more and 25 g / m ² or less. In addition, the interface between the zinc-nickel alloy plating layer and the chemical conversion film has cracks, and when the surface obtained by removing at least the resin film from the coated metal material is observed with a scanning electron microscope, the region is surrounded by cracks. The number is 2000 pieces / mm ² or more and 150,000 pieces / mm ² or less.

1. Metal Base Material The material of the metal base material that forms the base material of the coated metal material according to the present invention is not particularly limited as long as it can obtain a sacrificial anticorrosive effect by a zinc-nickel plating layer described later. A typical metal substrate is a steel material mainly composed of iron. The shape of the metal substrate is not particularly limited, but the coated metal material according to the present invention is typically plate-shaped because secondary processing such as press processing is performed in a state having a coating film layer. The thickness (plate thickness) in the case of a board | plate material is not specifically limited. Considering the ease of secondary processing, particularly press working, it is preferable to set the upper limit to about 2 mm.

2. Zinc-Nickel Alloy Plating Layer As described above, the zinc-nickel alloy plating layer included in the painted metal material according to the present invention has the following characteristics regarding the composition and surface properties.

(1) Composition Nickel content in a plating layer is 10 mass% or more and 15 mass% or less. When the nickel content is less than 10% by mass, the effect of improving the corrosion resistance of the flat surface due to the inclusion of nickel cannot be stably obtained, and white rust is likely to be generated from the flat surface portion. When the nickel content exceeds 15% by mass, the sacrificial anticorrosive effect is hardly obtained, and red rust is likely to be generated from the flat portion. Moreover, since the plating hardness becomes excessively high, problems such as powdering are likely to occur. The range of more preferable nickel content is 11.5 mass% or more and 13.5 mass% or less.

(2) Surface properties The plating layer according to the present invention has cracks at the interface with the chemical conversion film. It is presumed that an anchor effect in which the coating layer is firmly fixed on the plating layer is obtained and adhesion is improved by entering the coating layer, particularly the component forming the chemical conversion layer, into the crack.

  When the crack density at the interface is excessively low, this anchor effect cannot be obtained, and it becomes difficult to obtain an improvement in adhesion. On the other hand, when the crack density at the interface is excessively high, the adhesion between the plating layer and the metal substrate is reduced, and as a result, the coating layer containing the plating layer is easily peeled off. Therefore, the crack density at the interface has an appropriate range.

In the present invention, the resin film is removed from the coated metal material according to the present invention, and the surface of a member including at least a metal base and a zinc-nickel alloy plating layer can be observed with a scanning electron microscope (SEM). The number of regions surrounded by cracks seen in the surface observation image is obtained, and the crack density at this interface is evaluated by the number of the regions per unit area (1 mm ² ). Here, the “region surrounded by cracks” is a region partitioned in an island shape by cracks as seen in an observation image by SEM.

Specifically, the crack density is evaluated as follows.
First, the resin film is removed from the painted metal material. By removing the resin film, the surface of the member including at least the metal base material and the zinc-nickel alloy plating layer can be exposed. Here, the chemical conversion film between the resin film and the plating layer may not necessarily be removed. The chemical conversion film is generally extremely thin, and as described later, when it is made of a silane coupling agent, it may be present as a single layer film, and does not hinder subsequent crack observation by SEM. Of course, when the chemical conversion film is thick and the conductivity is low, it becomes an obstacle to the observation of cracks, so it is preferable to remove it.

  The method for removing the resin film is not particularly limited. It may be heated to melt or volatilize, or may be chemically dissolved. Or you may physically remove by carrying out the blast process of the grade which does not affect a plating layer. The blast treatment is preferable because the chemical conversion film is also removed in many cases, so that the crack can be observed stably.

  The surface thus obtained is observed with a scanning electron microscope (SEM). The type of SEM, acceleration voltage, and the like are not particularly limited, but it is preferable to use a microscope that can achieve high resolution such as FE-SEM.

The surface is observed by SEM, and the number of regions surrounded by cracks is measured. The field of view at this time is not particularly limited, but if it is excessively wide, that is, if the magnification is low, the resolution tends to be low, so the number of areas tends to be measured lower. If it is excessively narrow, that is, if the magnification is high However, although the resolution is high, the variation at each measurement point tends to increase, and the reliability of the number of regions tends to decrease. Therefore, it is preferable to measure by the following method. That is, surface observation is performed at a magnification of 1000 with respect to 30 arbitrary locations on the surface of the plating layer of the sample. The number of regions surrounded by cracks (the number of cracks) in a field of 0.1 mm × 0.05 mm arbitrarily set for the obtained 30 observation images is counted. The counting method is not particularly limited, and an appropriate image analysis means may be used. An average value of the number of cracks obtained from 30 observation images is calculated, and a value obtained by multiplying the average by 200 is defined as a crack density (the number of crack regions per 1 mm ² ).

When the crack density thus determined is 2000 pieces / mm ² or more and 150,000 pieces / mm ² or less, a coated metal material having excellent adhesion can be obtained. The preferable range of the crack density is 3000 pieces / mm ² or more and 100000 pieces / mm ² or less, and 3000 pieces / mm ² or more and 50000 pieces / mm ² or less is particularly preferable.

  Strictly speaking, the influence on the apparatus such as the SEM acceleration voltage when the observation image is obtained, and the influence on the sample such as the concentration of the non-conductive material (for example, the material constituting the chemical conversion film) remaining on the observed surface. For example, the crack density measured may vary. However, even if such a variation factor is considered within a normally conceivable range, if the crack density is within the above range, a coated metal material having excellent adhesion can be stably obtained.

(3) Amount of adhesion The amount of adhesion in the plating layer according to the present invention is 2 g / m ² or more and 25 g / m ² or less. When the adhesion amount is excessively small, the plating layer is not formed uniformly, and it becomes difficult to achieve high corrosion resistance over the entire surface of the metal material. On the other hand, when the amount of adhesion is excessively large, there is a concern that the manufacturing cost becomes high and powdering is likely to occur and problems such as deterioration of workability occur. From the viewpoint of highly combining productivity, workability and corrosion resistance, it is preferably 5 g / m ² or more and 20 g / m ² or less.

(4) Crack formation method The crack formation method in the plating layer which concerns on this invention is not specifically limited. Cracks may be formed by chemical treatment, or may be formed by thermal or physical treatment.

  From the viewpoint of easy formation of cracks and high controllability of the crack density of the cracks to be formed, it is preferable to form the cracks by chemical treatment. In chemical treatment, stress accumulated in the plating layer as zinc dissolves by contacting the plating layer with a material that constitutes the plating layer, such as acid and alkali, especially the treatment solution that dissolves zinc. Is relaxed and cracks are formed.

  The plating layer according to the present invention is composed of zinc-nickel alloy plating, and this plating is generally processed using an acidic bath. In such a process, as described in Patent Document 4, equipment composed of a plurality of types of plating cells is often used. Therefore, when the final cell 1 or 2 is not energized and immersed in the plating solution without energization, the acid contained in the plating solution dissolves zinc from the surface of the plating layer and causes cracks on the surface of the plating layer. be able to.

3. Chemical conversion coating The coated metal material according to the present invention has a chemical conversion coating (a coating formed by chemical conversion treatment) on the plating layer. In the present invention, the chemical conversion film is a so-called chromium-free chemical conversion film containing no chromium at all from the viewpoint of the environment.

  The composition and film thickness of this chemical conversion film are not limited. Any composition may be used as long as the adhesion between the plating layer and the coating film is ensured, but those that improve the corrosion resistance in addition to the adhesion are more preferable.

  From the viewpoint of improving both adhesion and corrosion resistance, an inorganic chemical conversion film or an inorganic-organic composite chemical conversion film may be appropriately set as the chemical conversion film. Such a chemical conversion film is obtained by performing chemical conversion treatment using a chemical conversion treatment solution having the following components.

  In the case of an inorganic chemical conversion film, a chemical conversion treatment solution containing one or more inorganic materials selected from silane coupling agents, silica fine particles, vanadium compounds, titanium compounds, zirconium compounds, phosphate compounds and the like may be used. Among these, a chemical conversion film obtained by using a chemical conversion treatment containing one or two inorganic materials selected from silane coupling agents and silica fine particles is particularly preferable.

  On the other hand, in the case of an inorganic-organic composite chemical conversion film, in addition to the inorganic materials contained in the chemical conversion treatment liquid for the inorganic chemical conversion film, a water-soluble or water-dispersed urethane resin, phenol resin, acrylic resin, polyester resin What is necessary is just to use the chemical conversion liquid containing 1 or more types of organic type materials chosen from these.

The silane coupling agent forms a film having a crosslinked siloxane bond as a skeleton by hydrolyzing an alkoxy group into hydroxyl groups and condensing the hydroxyl groups. When there are few alkoxy groups, a crosslinking reaction may be delayed and adhesiveness with a plating layer may fall. On the other hand, when there are few organic functional groups, adhesiveness with a coating film may fall. From these points, the silane coupling agent is preferably a trialkoxyl type. Specific examples of silane coupling agents suitable for use in the present invention include, but are not limited to, the following compounds (including common names):
Vinylethoxysilane, vinylmethoxysilane, N- (2-aminomethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminomethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, Tetraethoxysilane, and tetramethoxysilane.

  There are two types of silica fine particles, liquid phase silica and gas phase silica, but any of these may be used. It is to be noted that the finer the silica particles, the smaller the particle size in the state of being dispersed in the chemical conversion treatment liquid for forming the chemical conversion film, which is preferable because the interaction between the silica fine particles and the plating layer is more likely to occur.

Examples of vanadium compounds include, but are not limited to, ammonium vanadate, ammonium metavanadate, and the like.
Titanium compounds include Ti alkoxide, basic Ti carbonate, Ti fluoride, Ti-containing organic chelate, Ti-containing coupling agent (Ti alkoxide has an organic functional group such as epoxy group, vinyl group, amino group, methacryloxy group, etc. Examples of such compounds are not limited to these.

  Examples of the zirconium compound include Zr alkoxide, basic Zr carbonate, Zr fluoride, Zr-containing organic chelate and the like, but are not limited thereto.

Examples of the phosphoric acid compound include orthophosphoric acid, pyrophosphoric acid, and polyphosphoric acid, but are not limited thereto.
If the adhesion amount of the chemical conversion film is 20 mg / m ² or more and 1000 mg / m ² or less, good adhesion and corrosion resistance can be stably secured. When the amount of adhesion is excessively small, the chemical conversion film on the plating layer does not exist sufficiently, and it becomes difficult to express excellent adhesion. On the other hand, when the adhesion amount is excessively large, the chemical conversion film itself may be coherently broken and the cost becomes high.
The manufacturing method of a chemical conversion film is not limited. What is necessary is just to implement suitably the processing method suitable for the chemical conversion liquid which forms a chemical conversion film.

4). Resin Film The coated metal material according to the present invention includes a resin film as a film provided on the chemical conversion film. Here, the “resin film” means that a binder component which is one of the components constituting a coating composition for forming a film is mainly composed of a resin.

  The coating composition for forming the resin film has, in addition to the binder component, other components such as a pigment and resin particles as necessary, and these are dissolved and / or dispersed in a medium. The components constituting the coating composition will be described below.

(1) Binder component The binder component is composed of a binder resin, which is a resin as a main component of the binder component, a curing agent, and other components. Each component will be described in detail below.

A) Binder resin The binder resin is preferably a resin whose main resin is at least one of water-dispersed polyester and urethane resin, or a blend of these, and specifically includes the following three aspects.

i) Polyester resin alone A water-dispersed polyester resin may be used alone as a binder resin. The molecular weight is preferably 10,000 to 30,000. If the molecular weight is 10,000 or less, there is a concern that it is difficult to ensure sufficient processability. On the other hand, when the molecular weight exceeds 30000, the bonding site of the resin itself is lowered, so that it is difficult to ensure excellent adhesion with the chemical conversion film, and the crosslinking reaction with a curing agent such as melamine is not sufficiently performed. There is a concern about performance deterioration (for example, hardness reduction) as a resin film constituting the layer. A single type of polyester resin may be used, or a plurality of types may be blended.

ii) Urethane resin alone A water-dispersed urethane resin may be used alone as the binder resin. The emulsion particle diameter of the urethane resin is 10 nm or more and 100 nm or less, and more preferably 20 nm or more and 60 nm or less. If the particle size is excessively small, there is a concern that the cost will increase. On the other hand, when the particle size is excessively large, the gap between the emulsions becomes large when a coating is formed, and the barrier property as a coating (corrosive substance penetrates from the surface of the coating layer to the metal substrate. There is a concern that the property of suppression will be reduced. As the type of urethane resin, there are an ether type, a polycarbonate type, an ester type, an acrylic graphite type, etc., but these may be used alone or in combination. From another viewpoint, binder resins having different Tg may be blended and used. In this case, it is possible to obtain a resin film that has both excellent barrier properties provided by a resin having a high Tg and excellent processability provided by a resin having a low Tg.
iii) Blend resin You may use it as resin which blended the said polyester resin and urethane resin. The blend ratio is not particularly limited. What is necessary is just to set an appropriate blend ratio according to a use. Of course, also in this case, each of the polyester resin and the urethane resin may be composed of a plurality of types of resins.

B) Curing agent It is preferable to use a water-soluble curing agent, and specifically, melamine is preferably used. The addition amount of the curing agent is preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin solid content. Here, the “resin solid content” refers to a solid content derived from the binder component among the solid content (resin film) when the coating composition is baked. Therefore, “mass% with respect to the resin solid content” substantially means a mass ratio when the weight measurement value when only the binder component is cured is 100%.

  When the addition amount is less than 5 parts by mass, particularly when the main resin is a polyester resin, a sufficient crosslinking reaction between the resin and the curing agent cannot be expected, and there is a concern that the performance as a resin film becomes insufficient. The On the other hand, when the addition amount is more than 30 parts by mass, the crosslinking reaction proceeds too much, the resin film becomes excessively hard, and there is a concern that the workability is lowered. In addition, as a kind of preferable hardening | curing agent, it is preferable to use the hardening agent with comparatively small surface free energy which is easy to concentrate on the resin film surface from a viewpoint of coexistence with outstanding workability and moderate hardness. Specific examples include methylated melamine and butylated melamine.

C) Curing catalyst The binder component preferably contains a curing catalyst. One of the roles of the curing catalyst is to promote the self-condensation reaction between the curing agents and the crosslinking reaction between the curing agent and the resin. Further, by using methylated melamine or butylated melamine having a small surface free energy, a curing agent is concentrated on the surface of the resin film, and a crosslinking reaction and a self-condensation reaction are promoted. For this reason, the resin film near the surface is particularly improved in solvent resistance and chemical resistance. In addition, when the resin film contains resin particles described later, the hardness near the surface of the resin film is increased by the hardener concentrated on the surface, and the resin particles are less likely to be lost during pressing.

  Further, the concentration of the curing agent on the surface realizes a configuration in which the surface portion of the resin film is hard but the inside of the resin film is relatively soft. For this reason, the defect (resin film of the resin film) that the entire resin film cannot follow the deformation of the metal base material accompanying the press process while suppressing the defect (galling) due to the deformation of the resin film surface part during the press process. (Cracking) can be suppressed. And since the surface part of the resin film is hard, the outstanding barrier property is ensured. Therefore, it is possible to improve the flat portion corrosion resistance and the secondary workability, particularly the press workability in a well-balanced manner while being a single color coating film.

  As the curing catalyst, dodecylbenzenesulfonic acid or paratoluenesulfonic acid is suitable, and among these catalysts, it is particularly preferable to use an amine-blocked catalyst from the viewpoint of further concentrating the curing agent. The addition amount of the curing catalyst is preferably 0.1 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the coating material. When the addition amount is excessively small, there is a concern that the effect as a curing catalyst, that is, the curing is not sufficiently promoted. On the other hand, when the addition amount is excessively large, there is a concern that crosslinking or the like proceeds excessively and a new problem occurs such as a defect in the appearance of the resin film.

(2) Pigment The pigment contained in the resin film according to the present embodiment also contains a color pigment, a rust preventive pigment and a bright pigment as necessary.

A) Colored pigment It is preferable to use an inorganic pigment excellent in cost, safety, water resistance and weather resistance as a color pigment to be added to adjust the resin film to a specific color tone. Further, when either or both of carbon black and titania pigments are contained in addition to the colored pigment, the thermal radiation of the resin film itself is improved. Therefore, when applying to the housing | casing of the electrical / electronic device by which heat radiation is calculated | required, it is preferable to contain these pigments.

Further, in order to ensure the processability of the resin film, the concealability in the thin film, etc., the particle size of these colored pigments is preferably 0.5 μm or less.
Here, the “average particle size” in the pigment refers to the average primary particle size when the pigment present in the resin film is present alone, and when the pigment is present in an aggregated state, It means the average secondary particle size representing the particle size, and is preferably obtained by the following measurement method. First, the coated steel sheet on which the coating layer is formed is cut to expose the cross section, and the cross section is further polished. The cross section thus obtained is observed with an SEM to obtain an observation image of the cross section in the resin film. Select several pigments in the field of view of the observed image, measure the long side length and short side length of each pigment, calculate the average value of these long sides and the average value of the short sides, and The average primary particle size is calculated on average.

  Note that the numerical value of the average primary particle diameter varies slightly depending on the measurement method. For example, it may vary depending on the measurement principle when using a particle size distribution meter, and depending on the image processing method in the case of image analysis. However, the range of the particle size of the pigment defined in the present invention takes such fluctuations into consideration, and any particle size obtained by any method is within the range defined in the present invention. It is possible to stably achieve the effects of the period.

B) Extender The resin film may contain extender. An extender is a pigment used for the purpose of diluting or increasing the amount of other pigments or improving the strength of a resin film, although it does not have coloring power or hiding power. Specifically, barium sulfate, carbonate Examples include calcium, talc and kaolin.

C) Bright pigment When applied to applications that require a design such as a metallic tone, a metallic tone can be developed by adding a bright pigment such as mica or aluminum flakes. The average particle diameter of these bright pigments is preferably about 4 times or less the resin film thickness. In addition, as for the addition amount, in order to ensure processability, particularly press workability, the total amount of the bright pigment and the anticorrosive pigment (pigment having an average average particle size of 0.5 μm or more) is 15 with respect to the solid content of the paint. It is preferable to make it mass% or less.

  Here, “paint solid content” means the solid content when a coating film made of a paint for forming a resin film is baked, and this “paint” includes a chemical conversion treatment liquid for forming a chemical conversion film. Not included. The mass of the paint solids is measured as follows. That is, a predetermined amount of paint or paint raw material (binder resin or the like) is placed in an oven, and the inside of the oven is heated while measuring its mass to solidify the paint or paint raw material. The mass measurement value of the solidified product when solidified until there is no mass change in the oven is defined as the mass of the solid content of the paint. Therefore, “mass% with respect to the solid content of the paint” refers to a mass ratio when the weight measurement value is 100%. Examples of the component constituting the paint solid content include other components such as a binder component, a pigment, and resin particles.

In order not to impair the heat dissipation, mica having a relatively high heat radiation property than aluminum flakes is suitable. Note that these bright pigments may be used by blending two types of mica and aluminum flakes depending on the type of metallic tone required.
Further, these bright pigments have a particle size larger than 0.5 μm, and there is a concern that the workability and the corrosion resistance of the flat surface portion are reduced by increasing the addition amount. A preferable addition amount is preferably 20% by mass or less based on the solid content of the paint as a whole of a pigment larger than 0.5 μm including the bright pigment, in order to ensure the above performance.

D) Rust preventive pigment As a rust preventive pigment to be added to the resin film, porous silica having an oil absorption of 50 ml / 100 g or more and 1000 ml / 100 g or less and an average particle diameter of 10 μm or less is suitable. When other phosphoric acid type rust preventive pigments and ion exchange silica are used alone, sufficient corrosion resistance improvement effect cannot be obtained when the same amount of addition as porous silica is added, and it is the same as porous silica. If a large amount of rust preventive pigment is added in order to exhibit excellent corrosion resistance, the processability of the resin film itself is impaired, and the design property is also impaired.

  The reason why the oil absorption is 50 ml / 100 g or more and 1000 ml / 100 g or less is that sufficient corrosion resistance cannot be obtained when it is less than 50 ml / 100 g, and the viscosity of the paint is remarkably increased when it exceeds 1000 ml / 100 g. It is. On the other hand, if the average particle size exceeds 10 μm, it is excessively large compared to the thickness of the resin film, so that the possibility of the pigment dropping off increases, and there is a concern that the corrosion resistance may be adversely affected. In addition, the minimum of an average particle diameter is not specifically limited.

  The appropriate addition amount of the porous silica to the coating film is 5% by mass or more and 15% by mass or less with respect to the solid content of the paint, and a more preferable range is 5% by mass or more and less than 10% by mass with respect to the solid content of the paint. It is. If it is less than 5% by mass, sufficient corrosion resistance effect cannot be obtained, and if it exceeds 15% by mass, the processability of the resin film is impaired and the amount of the color pigment that can be added to the resin film is reduced. In particular, the hiding property and the color tone stability are impaired.

  As for the rust preventive pigment, other phosphoric acid rust preventive pigments other than porous silica, ion exchange silica, etc. may be used in combination as long as color tone stability, concealment, press workability, etc. can be secured. Although it is possible, in order to ensure processability, particularly press workability, it is preferable that the total pigment including the anticorrosive pigment is larger than 0.5 μm and has a solid content of 20% by mass or less.

(3) Other components As components contained in the resin film in addition to the binder component and pigment described above, leveling agents, resin particles, conductive powder for improving weldability and electromagnetic wave shielding properties, and weather resistance are improved. Examples include effective ultraviolet absorbers and light stabilizers, waxes effective for improving press workability, and the like, which may be appropriately contained as necessary.

  Among these, the resin film preferably contains resin particles. These resin particles have the role of reducing the contact area between the resin film and the mold during press processing and improving the lubricity, and the role of suppressing damage to the paint film due to direct contact between the resin film and the mold. . Examples of the resin particles include acrylic resin beads and PTFE resin. These resin particles have higher hardness and higher Tg than polyester and urethane resins, which are the main resins, enabling stable lubrication and protection of the resin film even when the mold becomes hot during continuous pressing. is there. The average particle diameter of the resin particles is not particularly limited, but is preferably within twice the thickness of the resin film. If it is twice or more, the resin particles are likely to be lost during press working. For this reason, the possibility of scratching the resin film and the possibility of not passing through the roll gap during coating are increased. In addition, regarding acrylic resin and PTFE resin, although depending on press conditions, it is preferable to add two types to the paint. The addition amount of the resin particles is 0.5% by mass or more and less than 15% by mass with respect to the solid content of the paint, and a more preferable range is 1% by mass or more and less than 10% by mass. Further, as a method for improving the lubricity with the mold, a low Tg wax resin such as polyolefin or microcrystalline may be added in addition to the above resin.

(4) Thickness of resin film The thickness of the resin film is preferably in the range of 2 μm to 15 μm. If the thickness is less than 2 μm, the concealability of the resin film is inferior, and the corrosion resistance of the flat surface portion may be lowered. If the thickness exceeds 15 μm, the cost is disadvantageous. The thickness of the resin film is more preferably 3 μm or more and 10 μm or less, and particularly preferably 4 μm or more and 9 μm or less.

5). Solvent / Dispersion Medium The treatment liquid for forming the chemical conversion film and the medium (solvent / dispersion medium) in the coating composition for forming the resin film contain water as a main component. In order to improve the dissolution / dispersion of the solute / dispersoid, a liquid organic substance having a high solubility in water (polar organic solvent), for example, alcohol, ether, ketone, etc. may be used together with water.

  Here, as will be described later, the baking temperature of the resin film is often sufficiently higher than the boiling point of water. For this reason, when the boiling point of the medium is 100 ° C. or lower, the entire medium including water (boiling point is 100 ° C.), which is the main medium of the paint, is quickly evaporated in the baking process, and the unevenness of the coating film surface generated during coating There is a concern that the paint may solidify before it becomes smooth. At this time, the appearance is not excellent in smoothness, and regions having locally different color tones are formed in spots.

  In order to avoid such problems, it is preferable to increase the boiling point of the entire medium by containing a substance having a boiling point higher than that of water as the medium. An example of such a high boiling point medium is butyl cellosolve. The amount of high-boiling medium added to water is the minimum amount of energy required for baking while suppressing the occurrence of poor appearance in consideration of the characteristics of the high-boiling medium added and the content of other components of the coating composition. It is sufficient to set as appropriate. For example, when a substance having a boiling point of 160 ° C. or higher is contained as a medium, a resin film having a good appearance can be stably obtained by setting the content to 3% by mass or more of the amount of water contained in the coating composition. Is achieved.

6). Manufacturing method The manufacturing method of the coating layer which concerns on this embodiment is not specifically limited. First, according to a conventional method, the above-mentioned chemical conversion treatment solution is brought into contact with a metal substrate, and subsequently baked to obtain a metal material having a chemical conversion film formed on the surface. Examples of specific contact methods between the metal substrate and the chemical conversion treatment liquid include dipping, spraying, and roll coating.

  Next, the above-mentioned coating composition is applied on the metal material on which the chemical conversion film is formed at a predetermined thickness by any method to obtain a metal material on which the coating layer is formed on the chemical conversion film. Specific application methods include dipping, spraying, roll coating, coating with a bar coater or a doctor blade.

  Subsequently, when the metal material on which the paint layer is formed is baked to volatilize the medium and the binder component is cured, a metal material having a solid resin film, that is, a painted metal material is obtained.

What is necessary is just to select the optimal temperature suitably for the baking temperature of a chemical conversion film and a resin film according to the composition of a chemical conversion liquid, a coating material, and the characteristic calculated | required.
The baking temperature of the chemical conversion film is not particularly limited. For example, by drying the film, for example, by setting the PMT (maximum temperature of the substrate) to 80 ° C. or higher, a chemical conversion film that generally satisfies the required performance such as sufficient corrosion resistance, conductivity, and film adhesion can be obtained. It is done.

  On the other hand, the baking temperature of the resin film is preferably 170 ° C. or higher in terms of PMT. If it is lower than 170 ° C., the resin film may not be sufficiently cured since the crosslinking start temperature of the resin film is not sufficiently reached.

The baking time of the chemical conversion film and the resin film may be appropriately selected in consideration of the baking temperature.
In addition, you may apply | coat the clear coating material and / or coloring coating material which have an additional function on the coating metal material of this embodiment. By applying such a paint, it is possible to produce a coated metal material having new performance that is not found in a conventional painted metal material at a low cost in a conventional 3-coat 3-bake coating process. Examples of the additional function include, but are not limited to, contamination resistance, deodorization, and deodorization having a photocatalytic function.

7). Housing A housing that is a box-shaped body that accommodates a product or its internal parts by appropriately performing secondary processing, specifically cutting, bending, pressing, etc., on the coated metal material according to the present invention. The body can be formed. In this case, it is preferable that the surface having the above-described plating layer and coating layer is the outside, that is, the front surface.

  In this case, the surface treatment on the surface facing the inner side of the housing, that is, the back surface is not particularly limited. From the viewpoint of corrosion resistance and the like, it is preferable that a plating layer and / or a chemical conversion film, and further a resin film is formed on the surface of the metal substrate also on the back surface. In the case where the back surface is provided with a chemical conversion film, the amount of adhesion may be appropriately set according to the application as shown below.

i) Case of having a single resin film on the chemical conversion film in the same manner as the front surface In this case, by performing the same chemical conversion treatment as the front surface, good adhesion and corrosion resistance can be ensured. That is, the preferable adhesion amount in this case is 20 mg / m ² or more and 1000 mg / m ² or less.

ii) In the case of only chemical conversion treatment It is preferably used when conductivity or the like is required. In this case, the preferable amount of chemical conversion film is 100 mg / m ² or more and 1000 mg / m ² or less, which is good. Conductivity and corrosion resistance can be ensured. When the amount of adhesion is excessively small, the chemical conversion film on the plating surface does not exist sufficiently, and it becomes difficult to express excellent adhesion. On the other hand, when the amount of adhesion is excessively large, the chemical conversion film itself may be coherently broken and the cost becomes high. Further, the chemical conversion treatment liquid itself is preferably a system containing a material having a rust prevention function (corrosion prevention additive: vanadium compound, titanium compound, manganese compound, phosphate compound, etc.) in consideration of corrosion resistance. It is also possible to use a system to which wax or the like is added in order to ensure the properties.

1. Preparation of steel plate samples (1) Plated steel plate Zinc-nickel alloy electroplated steel plate (SZ), electrogalvanized steel plate (EG), hot dip galvanized steel plate (GI) shown in the table below are used as the zinc-based plated steel plate for the base material. did. All the steel plates were 250 × 300 mm in size.

About the zinc-nickel alloy electroplated steel sheet, the surface was cracked by the following method.
That is, cracks were generated by subjecting the final cells 1 and 2 in the electroplating line to a non-energized immersion treatment. Moreover, the crack density was increased or decreased by adjusting the line speed, the plating solution pH, and the number of non-energized cells.

The crack density on the surface of the zinc-nickel alloy electroplated steel sheet having cracks was measured by the following method.
The SEM used for SEM observation was a S-3400N scanning electron microscope manufactured by Hitachi High-Tech Science Systems Co., Ltd., and observed a crack with an SE image with an acceleration voltage of 25.0 kV. The number of regions surrounded by cracks (crack regions), that is, the number of cracks, was measured within a range of 0.1 mm × 0.05 mm randomly selected in each photograph.

  The number of cracks is obtained as follows. Fig.1 (a) is an example of the surface SEM image with the zinc-nickel plating steel plate which has a crack. In the SEM image, when the entire crack region is within a range of 0.1 mm × 0.05 mm (measurement range), the crack surrounding the crack region is represented by a solid line as shown in FIG. . On the other hand, when a part of the crack region is included in the measurement range, the cracks surrounding the crack region are those extending outside the measurement range and those outside the measurement range as shown in FIG. Surround with a dotted line. In this way, after identifying a crack region that is at least partially included in the measurement range, the number of crack regions (first crack number) and a portion that are surrounded by only the solid line, that is, the crack region that is entirely included in the measurement range Is the number of crack regions surrounded by a dotted line, that is, the number of crack regions partially outside the measurement range (second crack number). Then, the number of first cracks + the number of second cracks / 4 is defined as the number of cracks in one measurement range.

According to the above measuring method, the number of cracks in the measurement range shown in FIG. 1B is 15 + 22/4 = 205.
Furthermore, the average value of the number of crack regions in each measurement range of 30 photographs was calculated, and the value obtained by multiplying by 200 was taken as the crack density. The crack density of the steel sheet in the photograph of FIG. 1 was 4000 pieces / mm ² .

For reference, in FIGS. 2 to 5, of the 30 photographs of samples with crack densities of 300 / mm ² , 2000 / mm ² , 3000 / mm ² , and 10000 / mm ² , respectively. A representative surface SEM image is shown.

After performing alkali degreasing and water washing on both surfaces of each substrate-plated steel sheet according to a conventional method, the following steps were performed to prepare a coated steel sheet.
(2) Chemical conversion liquid For the chemical conversion liquid, three types of chemical conversion chemicals containing and not containing the silane coupling agent shown in Table 2 below were prepared.

Silane coupling agent: 3-glycidoxypropyltrimethoxysilane
Chisso Corporation Sila Ace S510
・ Colloidal silica: Snowtex N, manufactured by Nissan Chemical Industries, Ltd.
-Zirconium ammonium carbonate: General reagent-Water-dispersed phenolic resin: Phenolite PE-602 manufactured by DIC Corporation

(3) Colored paint The water-dispersed or water-soluble resin used is as shown in Table 3.

  A base resin is prepared by adding 15% by mass of a melamine-based curing agent (Summar M-50W, manufactured by Sumitomo Chemical Co., Ltd.) to these resins with respect to the solid content of the paint. Was added to prepare a coating composition shown in Table 4. In addition, 0.2 mass% of a curing catalyst (Mitsui Cytec Co., Ltd. Catalyst 4050) was added to the prepared coating composition. The medium (solvent / dispersion medium) was water, and 1.5% by mass was added to the weight of water added to the paint using butyl cellosolve as a medium for improving the appearance.

The base paint described in Table 4 below contained the following pigments.
CB: Carbon black MA100 manufactured by Mitsubishi Chemical Corporation
Silica: Syromask (Ca 0% type) oil absorption 50 ml / 100 g or more, average particle size 1.0 μm or more manufactured by Fuji Silysia Chemical Co., Ltd. Beads: Acrylic resin beads having an average particle size 8 μm Luster pigment: Average particle size 8 μm Mica and aluminum flakes with an average particle size of 10μm blended 1: 1

  In addition, the column of the addition amount and the column of each pigment in Table 4 indicate the content (unit: mass%) of the base resin and each pigment with respect to the solid content of the paint.

(4) Preparation of front surface (design surface) sample The above chemical conversion treatment solution was prepared and applied onto a plated steel plate using a bar coater, and the maximum temperature (PMT) of the plate reached 80 ° C. in 10 seconds. And a chemical conversion treatment film on the front surface was formed.

The amount of chemical conversion treatment adhesion was adjusted with the count of the bar coater, dilution, etc. so that each treatment solution would be 50 mg / m ² .
Next, using the coating composition shown in Table 4, it was applied to a steel plate sample on which a chemical conversion film was formed, using a bar coater, and heated so that the maximum temperature (PMT) of the plate reached 180 ° C. in 50 seconds. Then, a resin film forming the top coat film on the front surface was formed. The film thickness was adjusted by adding a solvent and changing the bar coater count to obtain a film thickness of 7 μm.
Table 5 shows samples prepared by combining the base material, the chemical conversion treatment, and the resin film.

2. Evaluation method (1) Adhesiveness after processing The sample was bent at room temperature, and the bent part was attached with a cellophane tape, left at room temperature for 1 hour, and then peeled off. And the coating film adhering to the adhesive surface of a tape was observed visually, and the following criteria evaluated. ○ Passed above:
◎: No peeling of coating film,
○: Partial coating peeling occurred,
Δ: Coating film generated, substrate exposure,
X: The coating film was peeled off at the entire bent part.

(2) Corrosion resistance Four test sides of 70 mm × 150 mm size were sealed, a salt spray test was performed under the conditions specified in JIS 2371, and the corrosion area ratio of the flat portion of the sample after the test was obtained and evaluated. The judgment criteria are as follows, and ◎ and ○ were accepted:
◎: No white rust after 240 hours,
○: No white rust generated after 120 hours, white rust generated after 240 hours,
Δ: White rust generated after 120 hours (dots),
×: Red rust generated after 120 hours, and white rust generated on the entire surface.

3. Evaluation results Table 5 shows the evaluation results.

Claims (5)

A metal substrate;
A zinc-nickel alloy plating layer provided on the metal substrate;
A chromium-free chemical conversion film provided on the zinc-nickel alloy plating layer;
A resin film having a thickness of 2 to 15 μm provided on the chemical conversion film,
The zinc-nickel alloy plating layer has a nickel content of 10% by mass or more and 15% by mass or less, and an adhesion amount thereof is 2 g / m ² or more and 25 g / m ² or less,
The zinc-nickel alloy plating layer has a crack at the interface with the chemical conversion film, and is obtained by removing the resin film, and has a surface of a member including at least the metal base material and the zinc-nickel alloy plating layer. A painted metal material characterized in that the number of regions surrounded by cracks seen in an observed image when observed with a scanning electron microscope is 2000 / mm ² or more and 150,000 / mm ² or less.   The coated metal material according to claim 1, wherein the chemical conversion film is formed from a chemical conversion treatment liquid containing a silane coupling agent and / or silica fine particles. The coated steel material according to claim 1 or 2, wherein an adhesion amount of the chemical conversion film is 20 mg / m ² or more and 1000 mg / m ² or less.   The painted metal material according to any one of claims 1 to 3, wherein the resin film contains a urethane resin and / or a polyester resin.   A housing comprising the coated metal material according to any one of claims 1 to 4 so that a surface on which the resin film is formed is on an outer side.