KR20160077126A - Black coated metal plate - Google Patents

Abstract

Provided is a black coated metal plate which is sufficiently thin in total coating film, exhibits good blackness, has no appearance defects, and is excellent in durability. The black coating metal sheet of the present invention is characterized in that a first black layer formed of a water based black resin composition having a water-dispersed polyester resin as a base and having a thickness of 0.8 to 1.6 m is laminated on at least one surface of a metal sheet, And a second black layer having a thickness of 5 to 9 占 퐉, which is formed of a solvent-based black paint, is laminated on the surface of the second black layer, and the aqueous black resin composition contains surface-treated carbon black whose surface is coated with an aqueous resin.

Description

Black paint metal plate {BLACK COATED METAL PLATE}

The present invention relates to a black coated metal plate having good blackness.

Background Art [0002] Conventionally, black plastic has been used as a back cover of a thin television such as a liquid crystal television or a plasma television. In recent years, a steel plate coated with a black coating (PCM: precoated metal ) Is underway.

In the coated steel sheet (PCM) so far, a black pigment such as carbon black is contained in order to hide the appearance and gloss of the original plate (electro-galvanized steel sheet, hot-dip galvanized steel sheet, galvannealed steel sheet, etc.) (Coating amount: about 12 g / m < ² >), and further, under the black coating layer (top coating layer), a primer coating layer (Deposition amount: about 5 g / m < ² >). Thus, in the conventional PCM, the total thickness of the top coating layer and the primer coating layer is usually set to be as large as about 11 to 20 m. However, if the thickness of the coating film is large, the amount of the coating material used increases, and the time for coating and baking becomes long, so that the manufacturing cost increases. For this reason, especially in recent years, as the competition in the thin television market has intensified, demand for compression / reduction of manufacturing costs has increased, and thinning of the coating film in PCM has been demanded.

As a coated steel sheet PCM aiming at thinning, for example, there is a method in which a coating film of undercoat is formed on one side of a steel sheet, and on top of this undercoat film is coated an organic coating film, Has a total thickness of not more than 10 mu m (Patent Document 1).

And a lower layer coating film comprising porous silica as a coloring pigment and a rustproof pigment, wherein the thickness of the outermost layer coating film is 2 占 퐉 or more, the thickness of the lower layer coating film is 2 占 퐉 or more, A coated steel sheet having a film thickness of 10 탆 or less has been proposed (Patent Document 2).

Furthermore, it is also possible to form a lower coating film on a surface of at least one side of the steel sheet using a component of an organic or organic-inorganic composite system as a binder, and to form an upper coating film with an organic component as a binder on the lower coating film, And a coloring pigment is contained in both layers (Patent Document 3).

However, in general, as the thickness of the coating film of the PCM is made thinner, the degree of blackness is lowered, and the appearance of stronger blackish brown color (large b value) or stronger grayish black color (larger L value) tends to appear. Even in the case of the coated steel sheets described in the above Patent Documents 1 to 3, it has been devised to improve the blackness through the inclusion of flaky substances. However, the blackness which is still sufficiently satisfactory (for example, the L value is not more than 20 ).

Thus, the present inventors have found that a coated steel sheet capable of exhibiting good blackness even when the thickness of a black coating film is thin, is a coated steel sheet formed by a black composition containing a surface-treated carbon black having a surface coated with a water-soluble resin and having a film thickness of about 0.3 to 1.5 (see Patent Document 4). This coated steel sheet is capable of realizing a black level of excellent level such that the L value is not more than 20, and is very advantageous from the viewpoint of manufacturing cost reduction because the coating film is very thin, about 0.3 to 1.5 m. On the other hand, on the other hand, in actual production, the black coating is too thin to some extent, resulting in uneven coating or coating film defects due to dust on the production line, which is liable to cause appearance defects, There was work. Particularly, in Patent Document 4, a clear coating is provided on the black coating to develop characteristics such as corrosion resistance and scratch resistance. However, when such a clear coating is present, coating defects such as coating unevenness and dust are promoted, As shown in FIG.

Japanese Patent Application Laid-Open No. 2008-55774 Japanese Patent Application Laid-Open No. 2010-115902 Japanese Patent Laid-Open Publication No. 2013-18192 Japanese Patent Application Laid-Open No. 2011-224972

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a black coating film which is sufficiently thin, exhibits good blackness, has no appearance defects and is excellent in various durability such as scratch resistance, And to provide a coated metal plate.

The black coated metal sheet of the present invention capable of solving the above problems is characterized in that a first black layer formed of a water based black resin composition based on a water dispersed polyester resin and having a thickness of 0.8 to 1.6 m is laminated on at least one side of a metal sheet And a second black layer having a thickness of 5 to 9 m formed on the first black layer by a solvent-based black paint, wherein the water-based black resin composition contains a surface-treated carbon black having a surface coated with an aqueous resin .

It is preferable that the content of the surface-treated carbon black (solid content) is 5 to 15% by mass in 100% by mass of the total solid content of the aqueous black resin composition.

It is preferable that the blackness (L value) of the surface of the second black layer laminated on the first black layer is 20 or less and the value of b is 1.5 or less.

Wherein the resin-based black paint contains resin particles and the particle diameter of the resin particles is 14 占 퐉 or less and the film thickness of the second black layer is t (占 퐉) And is preferably 2 t (μm) or less.

Wherein the content of the water-dispersed polyester resin (solid content) in the water-based black resin composition is 50% by mass or more in the total solid content of 100% by mass, the water- The polyester resin constituting the resin preferably has a Tg of 40 to 70 캜 and a number average molecular weight of 10,000 to 20,000.

It is preferable that the weight of the polyester resin constituting the water-dispersed polyester resin after holding the film at 230 占 폚 for 20 minutes is 96% or more of the mass before the holding.

It is preferable that the aqueous black resin composition includes the water-dispersed polyester resin, the surface-treated carbon black, the colloidal silica, the silane coupling agent, and the metavanadate.

On the other hand, in the present specification, the "aqueous resin" is an aqueous dispersion in which the resin is dispersed in an aqueous medium, and the "water-dispersed polyester resin" is an aqueous dispersion in which a polyester resin is dispersed in an aqueous medium. The term "total solid content in the aqueous black resin composition" means the total solid content of the water-dispersed polyester resin, the surface-treated carbon black, and the colloidal silica.

According to the present invention, a first black layer formed of a water-based black resin composition containing a surface-treated carbon black whose surface is coated with an aqueous resin and a second black layer formed of a solvent-based black paint are formed on at least one surface of a metal sheet It is possible to provide a black coated metal plate having good appearance due to the fact that a good blackness is exhibited even if the total coating film is sufficiently thin and coating defects such as coating unevenness and dust are also less noticeable. Further, since the first black layer is formed of the water-based black resin composition based on the water-dispersed polyester resin, it is possible to provide a black-coated metal plate having excellent durability.

The black paint metal sheet (hereinafter sometimes simply referred to as a "black metal plate") of the present invention is a metal plate made of a water-based black resin composition containing at least one surface of a metal sheet, One black layer is laminated on the first black layer and a second black layer formed by solvent-based black coating is laminated on the first black layer. Hereinafter, the black metal of the present invention will be described in detail.

(plate)

The metal plate used in the present invention is not particularly limited as long as it is used as a precoated metal plate. For example, an aluminum plate, a titanium plate, and the like can be used in addition to steel sheets such as a non-plated cold-rolled steel sheet, a hot-dip galvanized steel sheet (GI), a galvannealed galvanized steel sheet (GA), and an electrogalvanized steel sheet (EG). Among them, a hot-dip galvanized steel sheet (GI), an electrogalvanized steel sheet (EG), an aluminum sheet and a titanium sheet are preferable.

It is preferable that the metal plate has a base layer formed on at least one surface by a base treatment in advance. For example, if a chemical conversion coating layer (base layer) formed by a base treatment is provided on the surface of the metal plate on the side forming the first black layer to be described later, adhesion between the metal plate and the first black 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. Of these, an organic coating layer, an inorganic coating layer and a phosphate coating layer are preferable. 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 is added to the organic film for the purpose of improving the corrosion resistance or a small amount of various wax components is added for the purpose of improving the workability after application of the coating film, An phosphorus coupling agent may be added. As the inorganic coating layer, for example, a silicate coating layer and the like may be mentioned, and phosphoric acid or fluoride may be added to the silicate coating 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, for example, 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 production cost rises.

As a particularly preferable embodiment of the metal plate on which the undercoat layer is formed, for example, a ground treatment composition comprising aluminum oxide, colloidal silica and polyacrylic acid (hereinafter sometimes referred to as " Coated on one metal plate and dried. When such a specific under-treatment composition is applied to a galvanized metal sheet, the surface of the metal sheet 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, It is possible to form an insoluble film having excellent adhesion with the black layer. As a result, the film adhesion after bending or press working (after elongation / reduction deformation) is improved and the corrosion resistance and the tape peeling resistance are greatly improved can do.

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 45:55 to 65:35). When the amount of colloidal silica is larger than the above ratio, the film-forming property is lowered, so that the undercoat layer is hardly formed and the effect of improving the corrosion resistance and the adhesion with the top coat is hardly obtained, and the adhesion to the metal plate is also lowered, . 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 composition increases, so that the proportion of the aluminum remaining in the solution which does not react (etch) with the metal plate increases in water, May be lowered.

Among the above specific undercoat compositions, polyacrylic acid is preferably contained in an amount of 0.1 to 5 parts by mass (more preferably 0.2 parts by mass or more and 3 parts by mass or less) based on 100 parts by mass of the total solid content of aluminum oxide and colloidal silica in the process Do. Polyacrylic acid is believed to function to appropriately control the reaction (etching) between the metal plate surface (zinc plating) and aluminum aluminum undergoing galvanization or 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 other hand, the etching becomes insufficient and an insoluble film formed by the aluminum aluminum and the colloidal silica is not sufficiently formed, thereby making it difficult to obtain an effect of improving adhesion and corrosion resistance.

The silane coupling agent is further added to the specific under-treatment composition in an amount of 3 to 15 parts by mass (more preferably 5 parts by mass or more and 12.5 parts by mass or less) based on 100 parts by mass of the total solid content of aluminum oxide and colloidal silica in the composition, It is also preferable to contain them. 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, and in some cases, the coating may peel off under severe processing conditions. On the contrary, , There is a possibility that the corrosion resistance and the adhesion are also lowered.

(First black layer)

Wherein the first black layer laminated on at least one side of the metal plate is formed of a water based black resin composition based on a water dispersed polyester resin and the aqueous black resin composition contains a surface treated carbon black whose surface is coated with an aqueous resin do.

<Surface-treated carbon black>

The water-based black resin composition contains surface-treated carbon black whose surface is coated with an aqueous resin as a black pigment. In ordinary carbon black whose surface is not coated with a water-based resin, secondary aggregation tends to occur due to changes in pH or compatibility with a binder resin when mixed with a binder resin described later, and as a result, The surface-treated carbon black having a surface coated with an aqueous resin exhibits excellent dispersibility when mixed with the binder resin and is hardly secondary aggregated. Therefore, the first black layer formed of the aqueous black resin composition is thin And exhibits a blackness sufficiently high even in the film thickness.

In the present specification, the term "surface-treated carbon black coated with a water-based resin" includes not only a surface in which the entire surface of the carbon black is coated with an aqueous resin but also a part in which the surface is covered.

The carbon black constituting the surface-treated carbon black is not particularly limited and includes, for example, oil smoke, pine smoke, commercially available coloring carbon black, and carbon black for rubber. The water-based resin covering the surface of the carbon black is not particularly limited as long as it can prevent secondary aggregation of carbon black, and examples thereof include gelatin, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble acrylic resin, poly Acrylamide, polyvinylpyridine, polyacrylic acid, and the like. The amount (coating amount) of the water-based resin is preferably 5 parts by mass or more and 380 parts by mass or less based on 100 parts by mass of the carbon black. The surface-treated carbon black may further have a surfactant attached thereto. This makes it possible to further suppress secondary agglomeration of the surface-treated carbon black in the binder resin. Examples of such a surfactant include known anionic, nonionic, and cationic surfactants.

As the surface-treated carbon black, for example, it is preferable to use a high-concentration mink (ink) used in a calligraphy. The siloxane is an aqueous dispersion containing surface-treated carbon black. For example, the surface of the irregular purifier black prepared by the furnace method such as incomplete combustion of petroleum or coal-based oil in a high-temperature gas is coated with a water-based resin , A glycol-based cryoprotectant and a preservative, if necessary, and mixing and slurrying the mixture. For example, commercially available inks (for example, &quot; Super Mackerel Ba-8 made by Kuretake Co., Ltd. &quot;, etc.) can be used as an example. 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, JP-A 7-188597 or JP-A 6-234946). The surface-treated carbon black (or an aqueous dispersion thereof) may be used alone or in combination of two or more.

The surface-treated carbon black (solid content thereof when the aqueous dispersion of surface-treated carbon black is used) is preferably 5 mass% or more (more preferably 8 mass% or more) of 100 mass% , Preferably not more than 15 mass% (more preferably not more than 12 mass%). By laminating the first black layer, the L value and the b value of the metal plate can be lowered. However, when the content of the surface-treated carbon black is less than 5 mass%, the L value and the b value As a result, the L value and the b value of the black metal plate obtained by laminating the second black layers are increased, and dark brown color is exhibited, and sufficient blackness can not be expressed. On the other hand, when the content of the surface-treated carbon black is more than 15% by mass, since the resin component to be a binder contained in the composition is relatively decreased, adhesion between the first black layer and the second black layer is lowered, Gelation tends to occur, and the liquid stability of the aqueous black resin composition may be deteriorated or the workability may be deteriorated. When the content of the surface-treated carbon black is within the above range, the surface-treated carbon black is hardly secondary agglomerated even when mixed with the binder resin, and high dispersion stability can be maintained. Further, even when the second black layer is laminated on the first black layer, sufficient blackness can be exhibited. The glossiness (G60), L value, and b value can be measured by the method described in the following examples.

<Water-dispersed polyester resin>

The water-based black resin composition usually contains a binder resin for fixing the surface-treated carbon black in the first black layer formed of the composition, and water-dispersed polyester resin is used as the binder resin. By using the water-dispersed polyester resin, the secondary aggregation of the surface-treated carbon black in the composition can be effectively inhibited, and excellent liquid stability can be obtained. The water-dispersed polyester resin may be used alone or in combination of two or more.

The water-dispersed polyester resin is an aqueous dispersion wherein a polyester resin is dispersed in an aqueous medium. The polyester resin constituting the water-dispersed polyester resin is obtained by polycondensation of a polycarboxylic acid and glycol.

As the polyvalent carboxylic acid component constituting the polyester resin, an aromatic, aliphatic or alicyclic dicarboxylic acid, a trivalent or higher polyvalent carboxylic acid, or an ester derivative thereof may be used.

Examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6- Ethane-p, p'-dicarboxylic acid, phenyl indene dicarboxylic acid, and the like.

Examples of aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimeric acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexane Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like, and ester-forming derivatives thereof.

Examples of the glycol component constituting the polyester resin include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonenediol, 1 2-ethylhexane-1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2 -Ethyl-2-isobutyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, 2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4 , 4'-thiodiphenol, bisphenol A, 4,4'-methylene diphenol, 4,4'- (2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzenes, 4,4'-isopropylidene phenol, 4,4'-isopropylidene diol, cyclopentane-1,2-diol, cyclohexane- , 2-diol, cyclohexane-1,4-diol, and the like.

Further, in order to facilitate the water oxidation of the polyester resin, a compound containing a carboxylic acid (salt) group, a compound containing a sulfonic acid (salt) group, a compound containing a phosphonic acid (salt) group and the like may be copolymerized.

In the present invention, as the polyester resin, for example, a modified polyester copolymer such as a block copolymer or a graft copolymer modified with acrylic, urethane, epoxy or the like can be used.

Preferable examples of the polyester resin include polyester resins selected from terephthalic acid, isophthalic acid, sebacic acid, 5-sodium sulfoisophthalic acid as an acid component, ethylene glycol, diethylene glycol, 1,4-butanediol and neopentyl glycol as glycol components , And the like.

The above-mentioned polyester resin can be produced by the following production method. For example, when a dicarboxylic acid component is composed of terephthalic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid and the glycol component is composed of ethylene glycol and neopentyl glycol, these monomers are directly esterified Or a ester exchange reaction, and a second step in which the reaction product of the first step is subjected to a polycondensation reaction. At this time, as the reaction catalyst, for example, alkali metal, alkaline earth metal, manganese, cobalt, zinc, antimony, germanium, titanium compound and the like can be used.

The number average molecular weight (Mn) of the polyester resin in terms of polystyrene is preferably 10,000 to 20,000, more preferably 15,000 to 20,000, and still more preferably 15,000 to 18,000.

The glass transition temperature (Tg) of the polyester resin is preferably 40 to 70 占 폚, and more preferably 40 to 67 占 폚.

In the simultaneous differential thermal thermal mass simultaneous measurement apparatus, the film made of the polyester resin is held at 230 占 폚 for 20 minutes and then the mass thereof is measured. The mass after the holding for 20 minutes is set to the simultaneous thermal thermal mass mass spectrometer Is preferably 96% or more (the amount of decrease in thermal mass is 4 mass% or less). Since the second black layer is baked on the first black layer at about 230 ° C, if the base resin of the first black layer is pyrolyzed at 230 ° C (the thermal mass reduction amount exceeds 4% by mass) The adhesion between the first black layer and the second black layer is lowered, and the bending workability and the corrosion resistance after processing are significantly deteriorated. For example, EXSTAR6000 TG / DTA 6200 manufactured by Nippon High-Tech Science Co., Ltd. can be used as the simultaneous thermal thermal mass simultaneous measuring device. A specific method of measuring the reduction amount of heat mass will be described later.

The water-dispersed polyester resin is preferably contained in an amount of 50 mass% or more (more preferably 60 mass% or more), preferably 85 mass% or less (more preferably, 80% by mass or less). If the content of the water-dispersed polyester resin is less than 50% by mass, the film-forming property of the film is lowered, the fixing of the surface-treated carbon black becomes insufficient, or coating unevenness occurs, which may cause appearance problems. On the other hand, when the content of the water-dispersed polyester resin exceeds 85% by mass, the content of the surface-treated carbon black relatively decreases, so that sufficient blackness may not be obtained.

The water-dispersed polyester resin may be a commercially available product. Examples of the water-dispersed polyester resin include Bayern (registered trademark) MD-1100, Bayeral (registered trademark) MD-1200, (Registered trademark) MD-1245 &quot;, and the like. These resins may be used alone or in combination of two or more.

<Cross-linking agent>

The water-based black resin composition may contain a crosslinking agent, but it is preferable that the crosslinking agent is not included. Specifically, the crosslinking agent is preferably contained in an amount of 5 parts by mass or less, more preferably 2 parts by mass or less, further preferably 0 parts by mass (based on 100 parts by mass of the total solid content in the aqueous black resin composition And the black resin composition does not contain a crosslinking agent). When the cross-linking agent is included, the hardness of the film increases, but micro-cracks are generated in the bent portion due to lowering of the bending workability, so that the corrosion resistance of the first black layer and the metal plate after the SST cycle test (salt spray test) There is a possibility that the adhesion is lowered. Examples of the crosslinking agent include oxazoline group-containing polymers such as zirconium carbonate ammonium, Epochros (registered trademark) K series manufactured by Nippon Catalysts.

<Colloidal silica>

The water-based black resin composition preferably further contains colloidal silica. As a result, the surface-treated carbon black can be favorably fixed to the first black layer, and the corrosion resistance and hardness of the resulting black metal plate can be improved. Although the details of this mechanism are not clear, it is presumed that the colloidal silica dissolves and elutes under the corrosive environment, resulting in a buffering action of pH and a passive film forming action. Moreover, when the colloidal silica is contained, the effect is also confirmed in preventing the aggregation of the aqueous black resin composition during coating and drying.

The colloidal silica is not particularly limited, but colloidal silica having a particle diameter of 4 to 20 nm is preferable from the viewpoints of improvement in dispersibility and corrosion resistance in the aqueous black resin composition, and specifically, colloidal silica having a particle diameter of 4 to 6 nm (Trade name, "SNOWTEX (registered trademark) XS" available from Nissan Chemical Industries, Ltd.) and colloidal silica having a particle diameter of 8 to 11 nm ("Snowtex (registered trademark)" available from Nissan Chemical Industries, ), And colloidal silica having a particle diameter of 10 to 20 nm ("Snowtex (registered trademark) 40" manufactured by Nissan Chemical Industries Co., Ltd. as a commercial product). Among them, "SNOWTEX (registered trademark) XS" .

The colloidal silica (solid content) is preferably 10 mass% or more (more preferably 12 mass% or more), and preferably 20 mass% or less (more preferably 20 mass% or less) of 100 mass% 17% by mass or less). If the content of the colloidal silica is less than 10% by mass, corrosion resistance may be deteriorated. On the other hand, if the content of the colloidal silica is more than 20% by mass, the hardness of the coating film is increased, and the workability may be lowered.

<Silane coupling agent>

The aqueous black resin composition may further contain a silane coupling agent. When the silane coupling agent is contained, adhesion between the first black 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 for example,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane, Vinyltris (? -Methoxyethoxy) silane, and the like. On the other hand, a silane coupling agent may be a commercially available product, and for example,? -Glycidoxypropyl trimethoxysilane "KBM403" (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be used.

The content of the silane coupling agent is preferably not less than 5 parts by mass (more preferably not less than 10 parts by mass) and not more than 20 parts by mass (more preferably not more than 20 parts by mass, 15 parts by mass or less). When the content of the silane coupling agent is less than 5 parts by mass, the adhesion between the first black layer and the metal plate may be lowered. On the other hand, when the content of the silane coupling agent exceeds 20 parts by mass, the effect of improving the adhesion between the first black layer and the metal sheet tends to be saturated.

&Lt; Metavanadate &gt;

The aqueous black resin composition preferably further contains a metavanadate. The metavanadate salt also dissolves in the same manner as the colloidal silica, thereby inhibiting the dissolution and dissolution of the metal plate, thereby improving the corrosion resistance. In order to effectively exhibit this effect, 1 to 3 parts by mass of the metavanadate may be used relative to 100 parts by mass of the total solid content in the aqueous black resin composition. When the amount is less than 1 part by mass, the effect of improving the corrosion resistance becomes insufficient. When the amount is more than 3 parts by mass, the effect of improving the corrosion resistance tends to become saturated. For example, in the case where the water-based black resin composition has a glycidoxime-containing silane coupling agent, the excess metavanadate inhibits the hydrolysis reaction of the silane coupling agent containing glycidoxy group, It is presumed that the corrosion resistance is degraded because it affects the bonding force of the resin component. The amount of the metavanadate salt is more preferably from 1 to 4 parts by mass. On the other hand, a suitable amount of the metavanadate is the V element converted amount.

Examples of the metavanadate include sodium metavanadate (NaVO ₃ ), ammonium metavanadate (NH ₄ VO ₃ ), potassium metavanadate (KVO ₃ ) and the like. These may be used alone or in combination of two or more.

<Other components>

The water-based black resin composition may further contain various additives if necessary insofar as the effect of the present invention is not impaired. For example, in the field of consumer electronics such as a thin television, complicated press processing and the like are often performed on a black metal plate, and workability is required as a required performance for a black metal plate. In such a case, by adding an aqueous wax to the aqueous black resin composition, lubricity can be imparted to the first black layer to improve workability. Examples of the water-based wax include polyethylene waxes such as &quot; Chemipear (registered trademark) W700 &quot;, &quot; Chemipear (registered trademark) W950 &quot;, and Chemipear (registered trademark) W900 available from Mitsui Chemicals.

The first black layer in the present invention can be formed by applying the above-described aqueous black resin composition to a predetermined dry film thickness on one side or both sides of the above-mentioned metal plate, followed by drying.

The film thickness (dry film thickness) of the first black layer is 0.8 μm or more (preferably 0.9 μm or more, more preferably 1.0 μm or more), 1.6 μm or less (preferably 1.5 μm or less, 1.3 μm or less). If the film thickness of the first black layer is less than 0.8 탆, the blackness of the first black layer, and thus the obtained black metal plate, becomes insufficient, resulting in a dark brown color. On the other hand, if the film thickness of the first black layer exceeds 1.6 탆, the blackness is excellent, but the effect of further improving the blackness is hardly obtained, while the time required for coating and drying becomes long, and the manufacturing cost becomes high. In addition, if the thickness of the first black layer is excessively large, for example, the conductivity required when used in the field of consumer electronics such as a thin television can not be achieved.

In the preferred embodiment of the present invention, the blackness (L value) of the surface of the first black layer is 40 or less (more preferably 38 or less, more preferably 35 or less) , And the b value is 3 or less (more preferably 2.6 or less, further preferably 2.1 or less). In the present invention, the L value and the b value are brightness indices of measured values measured by the method specified in JIS Z 8722, and can be measured by the methods described in the following examples. In addition, regarding the L * value and the b * value converted based on the following formula, the preferable upper limit thereof is a range calculated from the upper limit value of the L value and the b value described above.

L * = 1.3632L-3.5904

b * = 1.5744b-0.0380

The glossiness (G value) of the black metal sheet measured at an angle of 60 DEG is preferably 30 or less, more preferably 27 or less, in the black metal sheet provided with only the first black layer .

The water-based black resin composition can be prepared by mixing the respective components described above at a predetermined ratio, and the order of mixing is not particularly limited. The water-based black resin composition preferably contains a water-dispersed polyester resin, a surface-treated carbon black, a colloidal silica, a silane coupling agent, and a metavanadate.

The method of applying and drying the aqueous black resin composition when forming the first black 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 curtain flow coater method, a roll coater method, a spraying method and a spraying method. Among them, from the viewpoint of cost and the like, a bar coater method, The sprayer method is preferred. The drying temperature is not particularly limited as long as the black layer is not deteriorated by heat. For example, the drying temperature is preferably about 130 to 180 캜, and more preferably about 150 to 170 캜.

(Second black layer)

The second black layer to be laminated on the first black layer can be formed by applying solvent-based black paint to a predetermined dry film thickness, followed by drying and baking. With such a second black layer, the film thickness of the first black layer formed by the aqueous black resin composition is as thin as the above range, and coating defects due to coating unevenness, dust on the production line, Even if discarded, the black metal plate can maintain a good appearance.

The solvent-based black paint is not particularly limited and those conventionally used for a black metal plate can be used. The solvent-based black paint can be obtained, for example, by mixing a base resin (e.g., a high-molecular polyester resin having a number average molecular weight of 10,000 to 20,000 or the like), a curing agent (e.g., melamine curing agent) Therefore, a known method (for example, a method of adding an anticorrosive pigment (for example, an aluminum-based anticorrosive pigment, a magnesium phosphate-based anticorrosive pigment, a calcium silicate-based anticorrosive pigment and the like), an extender pigment, . &Lt; / RTI &gt; As the solvent type black paint, commercially available products can be used. For example, "FLC495 Black", "FLC6000 Black", "FLC6070 Black", "FLC6080 Black", "FLC6090 Black", "FLC6100 Black &quot;, and &quot; HF1600 Black &quot; manufactured by BASF Coatings Japan. The solvent-based black paint may be used alone, or two or more thereof may be used in combination. On the other hand, from the viewpoints of workability, scratch resistance and abrasion resistance, the Tg of the base resin (for example, polyester resin) of the solvent-based black paint is preferably 15 to 30 占 폚.

The solvent-based black paint preferably contains resin particles. As a result, a black metal plate having a high blackness and a good uneven appearance and feel is obtained.

The resin particles may be organic particles (for example, acrylic beads, styrene acrylic beads, urethane beads, etc.), or inorganic particles (for example, glass beads, silica beads, etc.). In particular, acrylic beads are preferable because they are difficult to aggregate in solvent-based black paint and are easily available. The resin particles may be of only one type, or two or more types may be used in combination.

The particle diameter of the resin particles is preferably 14 占 퐉 or less, more preferably 12 占 퐉 or less, and even more preferably 10 占 퐉 or less, from the viewpoint of coatability when a paint is applied by a roll coater or the like. If the particle diameter of the resin particles exceeds 14 μm, there is a possibility that streaks [streaking] or the like may occur at the time of coating.

Particularly, the particle diameter of the resin particle is preferably not less than t (μm) and not more than 2t (μm), where t (μm) is the thickness of the second black layer. For example, when the coat of the second black layer is about 15 mu m thick, when the solvent in the coating material is volatilized, vortex convection accompanying the volatilization occurs in the wet state and the resin particles move to the surface of the coating film, A coating film is formed. However, in the present invention, since the film thickness of the second black layer is thin as described later, the occurrence of eddy convection can not be expected. If the film thickness of the second black layer and the particle diameter of the resin particle satisfy the above-described relationship, even if the film thickness of the second black layer is thin, good unevenness can be expressed.

The film thickness (dry film thickness) of the second black layer is not less than 5 占 퐉 (preferably not less than 6 占 퐉, more preferably not less than 7 占 퐉) and not more than 9 占 퐉 (preferably not more than 8 占 퐉). If the film thickness of the second black layer is less than 5 占 퐉, the appearance may be deteriorated or the blackness of the obtained black metal plate may become insufficient, and the film tends to be weakened against wear and scratches. On the other hand, if the film thickness of the second black layer exceeds 9 탆, the time required for coating and drying becomes longer, which tends to increase the manufacturing cost and impair the bending workability. On the other hand, when the solvent-based black paint contains resin particles, the film thickness (dry film thickness) of the second black layer is the thickness of the film formed of the solvent-based black paint excluding the resin particles, The thickness shall be measured.

In the preferred embodiment of the present invention, the blackness (L value) of the black metal plate surface of the present invention (the surface of the second black layer laminated on the first black layer) is 20 (More preferably not more than 19, still more preferably not more than 18), and the b value is not more than 1.5 (more preferably not more than 1.2, more preferably not more than 1.0). In the present invention, the L value and the b value are brightness indices of measured values measured by the method specified in JIS Z 8722, and can be measured by the methods described in the following examples. In addition, regarding the L * value and the b * value converted based on the following formula, the preferable upper limit thereof is a range calculated from the upper limit value of the L value and the b value described above.

L * = 1.3632L-3.5904

b * = 1.5744b-0.0380

The glossiness (G60) of the black metal sheet provided with the first black layer and the second black layer is preferably 20 or less, more preferably 17 or less, and still more preferably 15 or less.

The method of applying, drying and baking the solvent-based black paint in forming the second black layer is not particularly limited and a known method can be suitably employed. As a coating method of the paint, there may be mentioned the method described in the first black layer formation, and among these, from the viewpoint of cost, the bar coater method, the roll coater method and the sprayer method are preferable. The drying and baking temperatures are preferably, for example, about 200 to 240 캜.

This application claims the benefit of priority based on Japanese Patent Application No. 2013-224374 filed on October 29, 2013. The entire contents of the specification of Japanese Patent Application No. 2013-224374 filed on October 29, 2013 are incorporated herein by reference.

Example

Hereinafter, the present invention will be described in detail based on examples. It should be noted, however, that the present invention is not limited to the following examples, and all modifications that do not depart from the spirit and scope of the present invention are included in the technical scope of the present invention.

In the following, &quot;% &quot; represents &quot; mass% &quot;.

First, the evaluation method used in the embodiment will be described below.

(Black degree)

(A black metal plate (hereinafter referred to as a "black metal plate (single-layer laminate)") provided only with a first black layer, or a black metal plate having a first black layer provided thereon The L value and b value of a black metal plate provided with a black layer and a second black layer (hereinafter also referred to as "black metal plate (two-layer lamination)") were measured and the blackness was evaluated by the obtained L value and b value In the present invention, with respect to the black metal plate (single-layer laminate), the L value of the first black layer is 40 or less and the b value is 3 or less, and with respect to the black metal plate The L value was 20 or less, and the b value was 1.5 or less.

(Gloss level)

(G value) of the black metal plate was measured at an angle (G60) of 60 degrees using "Gloss Meter VG2000" manufactured by Nippon Denshoku Industries Co., In the present invention, the degree of gloss (G60) of the black metal plate (single-layer laminate) is not more than 30 and the degree of gloss (G60) is not more than 20 for the black metal plate (two-layer laminate).

(Processability (T bending))

(Black metal plate) cut into a size of 50 mm x 50 mm was held in an atmosphere at 0 ° C for 1 hour, and then lightly bent with a vise with the surface (the second black layer forming surface) And the presence or absence of cracks in the bent portion after the processing was visually observed or observed with a magnifying glass of 10 times. In the evaluation method, the number of sheets of the black metal plate to be interposed is 0T, and the number of sheets which is 1T is larger than the number of sheets when the surface is cracked with 1T as 1T. The crack limit (for example, 2T is the crack limit).

(SST cycle test (salt spray test))

After 2T bending at room temperature, the test piece (black metal plate) was subjected to 2 cycles of salt water spray test in which salt water spraying (8 hours of spraying) based on JIS Z 2371 and 16 hours of resting time of 1 hour were carried out. Thereafter, the occurrence of white rust on the bent portion (excluding both ends 10 mm) was observed and evaluated according to the following criteria.

◎: no occurrence of white rust is confirmed at all

○: White rust is extremely rare

△: White rust occurred but less than 5% occurred

X: Rice is present in more than 5%

(Tape peeling test)

A tape peeling test (tape used: Nichia's Reflective Cellotape (registered trademark) No. 405) was applied to a blank (black metal plate) after the above SST cycle test to measure the bending strength The occurrence of film peeling was observed and evaluated according to the following criteria.

&Amp; cir &amp;: Peeling of the coating film is not confirmed at all

&Amp; cir &amp;: There is one paint film peel on the spot

?: Peeling of the coating film on the spot is 2 to 5

X: Peeling of the coating film on the spot is 6 or more

(My sand eraser abrasion)

A sand eraser with a diameter of 6 mm was set on a sliding test apparatus, and a load of 16.5 N was applied to the surface (second black layer forming side) of the blank (black metal plate) Treated metal plate) was visually observed and evaluated according to the following criteria.

◎: no exposure of base metal is confirmed at all

○: Exposure of base metal is extremely slight.

Δ: Exposure of the base metal is confirmed, but the length of the exposed portion is within 2 mm

X: Exposure of the base metal is confirmed, and the length of the exposed portion is more than 2 mm

(Scratch resistance (pencil hardness))

The pencil hardness at which the surface of the second black layer was not scratched by a pencil scratching tester was determined for a blank material (black metal plate) based on JIS K 5400 (1990).

(Heat mass reduction amount)

4.4264 g of a film made of a water-dispersed polyester resin was set in a differential thermal and thermal mass simultaneous measuring device (&quot; EXSTAR6000 TG / DTA 6200 &quot; manufactured by Nippon High Tech Science Co., Ltd.), and under the condition that air flows at an air volume of 50 ml / (230 ° C) for 20 minutes and then compared with the mass (4.4264 g) of the film before holding the apparatus for simultaneous thermal and thermal mass measurement for 20 minutes at 230 ° C And how much the mass was reduced after the maintenance was measured.

[Example 1]

(Fabrication of underfloor metal plate)

First, 26.3 parts by mass of an acidic colloidal silica ("SNOWTEX (registered trademark) O", solid content concentration of 20%) and 95.3 parts by mass of an acid aluminum (manufactured by YONEYAMA CHEMICAL CO. , And 0.075 parts by mass of polyacrylic acid ("JURIMA (registered trademark) AC-10-LP", solid content 100%, manufactured by Nippon Joho Kagaku Co., Ltd.) was further added to the mixture, and a silane coupling agent Ltd., solid content: 100%) was added to prepare an undercoat composition solution (solid content concentration: 1.7%).

Next, the obtained undercoat treatment composition solution was coated on the front and back surfaces of an electrogalvanized steel sheet (EG; Zn adhesion amount 20 g / m ² ) so as to have a dry weight of 103 mg / m ² by a manual roll coating apparatus, And then dried at 120 DEG C for 60 seconds to prepare a metal plate for undercoating. On the other hand, also in the examples and comparative examples to be described later other than Example 1, a metal plate subjected to undercut treatment is similarly formed.

(Formation of first black layer)

&Lt; Preparation of aqueous black resin composition &gt;

75 parts by mass of a water-dispersed polyester resin having a Tg of 61 deg. C and a Mn of 20,000 (Toyobo Co., Ltd. Bayeralt (registered trademark) MD-1245, solid content concentration of 30%) as a base resin was prepared as a base resin, 2 parts by mass of "SA-BLACK DY-6" (trade name, manufactured by Mikuni Color Co., Ltd., solid content concentration: 30.5%)) was added. Next, 15 parts by mass of colloidal silica (SNOWTEX (registered trademark) XS, solid content 100%) was added, and further 15 mass parts of a silane coupling agent (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd., solid content: 100%) And 2 parts by mass of sodium metavanadate (NaVO ₃ , manufactured by Shin Kagaku Kogyo Co., Ltd .; solid content concentration: 65%) were added to prepare a water-based black resin composition.

&Lt; Coating of waterborne black resin composition &gt;

The aqueous black resin composition thus obtained was applied to the surface of the undercoated metal plate so as to have a dry film thickness shown in Table 1 by a bar coating machine and then dried at 160 캜 for 60 seconds to form a first black layer .

Table 1 shows the glossiness (G60), L value, and b value for a black metal plate (single-layer laminate) obtained by changing the film thickness of the first black layer as described above.

(Formation of second black layer)

Acryl beads ("Love Color (registered trademark)" manufactured by Dainichi Seika Co., Ltd.) having a particle size of 10 μm were added to 2 mass parts of 100 parts by mass of the dried solid content of the coating material in a solvent black paint ("FLC495 black" manufactured by Nippon Fine Chemicals Co., And the viscosity was measured by a Ford Cup No. 4 with a thickness of about 50 seconds. The surface of the first black layer was coated on the surface of the first black layer by a bar coating machine so as to have a dry film thickness of 7 탆, and then dried and sintered at 230 캜 for 60 seconds , And a second black layer was formed to obtain a black metal plate (two-layer lamination).

Table 1 shows the glossiness (G60), L value, and b value for the black metal plate (two-layer laminate) obtained by changing the film thickness of the first black layer as described above.

(Formation of the back side layer)

&Lt; Preparation of polyethylene-based resin composition &gt;

25.7 parts by mass of a solid content of a polyethylene resin (S-120 manufactured by Mitsui Chemicals, Inc., solid content concentration of 27%) was prepared as a base resin, and a colloidal silica having a surface area average particle diameter of 4-6 nm (notarized value) 31.5 parts by mass of TEX (registered trademark) XS, solid content 100%) and colloidal silica (SNOWTEX (registered trademark) 40 (solid content concentration 40%)) having a surface area average particle diameter of 10 to 20 nm Mass part was added. , 9.0 parts by mass of a silane coupling agent ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd., solid content: 100%) and 1.0 part by mass of sodium metavanadate (NaVO ₃ , manufactured by Shin Kagaku Kogyo Co., Ltd., solid content concentration: 65% , 1.3 parts by mass of an acrylic-modified epoxy resin ("MODEPIX (registered trademark) 302" (solid content concentration 33.5%) manufactured by Arakawa Chemical Industries Co., Ltd.) was added. Finally, a polyethylene wax (Chemipel (registered trademark) W-700 5.0 parts by mass of a fluorine-based lubricant &quot; PTFE 31-JR &quot; (average particle diameter 0.2 to 0.25 mu m, To prepare a resin composition.

&Lt; Painting of polyethylene-based resin composition &gt;

The polyethylene-based resin composition obtained above was coated on the back surface of the undercoated metal sheet (the surface opposite to the surface on which the first black layer and the second black layer were coated) with a bar coating coating apparatus so as to have a dry film thickness of 0.5 m , And then dried at 160 DEG C for 60 seconds to form a backcoat layer. On the other hand, also in Examples and Comparative Examples other than the following Example 1, a back coating layer is likewise formed.

[Comparative Example 1 ']

(Black primer FP1817, manufactured by KCC Corporation (Korea)) was used in place of the aqueous black resin composition in the formation of the first black layer of Example 1, And then dried at 230 캜 for 60 seconds to form a first black layer in the same manner as in Example 1.

Table 2 shows the glossiness (G60), L value, and b value for the black metal plate (single-layer laminate) obtained by changing the film thickness of the first black layer as described above. Comparative Example 1'-8 shows the glossiness (G60), L value, and b value of a metal plate on which no black layer is laminated, and a metal plate on which nothing is laminated.

A second black layer was formed in the same manner as in Example 1 to obtain a black metal plate (two-layer lamination).

Table 2 shows the glossiness (G60), L value, and b value for the black metal plate (two-layer laminate) obtained by changing the film thickness of the first black layer as described above.

[Example 2, Comparative Example 2]

(Formation of first black layer)

&Lt; Preparation of aqueous black resin composition &gt;

69 to 81 parts by mass of a water-dispersed polyester resin having a Tg of 67 占 폚 and a Mn of 15,000 (Toyobo Co., Ltd. Bayeral 占 MD-1200, solid content concentration of 34%) as a base resin was prepared as a base resin, 4 to 16 parts by mass of the surface-treated carbon black was added so that the mass ratio of "INCUBATED BA-8" and "SA BLACK DY-6" was 2: 8. 15 parts by mass of colloidal silica (Snowtex (registered trademark) XS, solid content 100%) was added to obtain a water-dispersed polyester resin (solid content), surface-treated carbon black (solid content), and colloidal silica Was added in an amount of 100 parts by mass. , 15 parts by mass of a silane coupling agent ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%) and 2 parts by mass of sodium metabisulphate (manufactured by Shinco Chemical Co., Ltd., solid content concentration 65% A water-based black resin composition was prepared so as to have a concentration of carbon black.

&Lt; Coating of waterborne black resin composition &gt;

The aqueous black resin composition obtained above was applied to the surface of the undercoated metal sheet so as to have a dry film thickness of 1.2 탆 by a bar coating machine and then dried at 160 캜 for 60 seconds to form a first black layer did.

Table 3 shows the glossiness (G60), L value, and b value for a black metal plate (single-layer laminate) obtained by changing the concentration of the surface-treated carbon black in the first black layer as described above.

(Formation of second black layer)

A second black layer was formed in the same manner as in Example 1 except that the solvent-based black paint was changed to "FLC6080 black" manufactured by Nippon Fine Chemicals Co., Ltd. instead of "FLC495 Black" manufactured by Nippon Fine Chemicals Co., .

The glossiness (G60), the L value, the b value, and the coating film performance such as T-bending workability of the black metal plate (two-layer laminate) obtained by changing the concentration of the surface-treated carbon black in the first black layer Table 3 shows the results.

[Example 3, Comparative Example 3]

(Formation of first black layer)

&Lt; Preparation of aqueous black resin composition &gt;

Except that 75 parts by mass of a solid content of a water-dispersed polyester resin having a Tg of 67 占 폚 and a Mn of 15,000 as a base resin (Toyoda Bosea Bayeral 占 MD-1200, solid content concentration of 34%) was prepared. To prepare a resin composition.

&Lt; Coating of waterborne black resin composition &gt;

The aqueous black resin composition obtained above was applied to the surface of the undercoated metal sheet so as to have a dry film thickness of 1.2 탆 by a bar coating machine and then dried at 160 캜 for 60 seconds to form a first black layer did.

(Formation of second black layer)

A second black layer was formed on the surface of the first black layer in the same manner as in Example 2 except that the coating was applied so as to have a dry film thickness shown in Table 4 with a bar coating coating device to obtain a black metal plate.

Table 4 shows the coating performance such as T-bending workability of the black metal plate obtained by changing the film thickness of the second black layer as described above.

[Example 4, Comparative Example 4]

(Formation of first black layer)

&Lt; Preparation of aqueous black resin composition &gt;

Aqueous black resin composition was prepared in the same manner as in Example 1 except that the base resin was changed to the resins A to G shown in Table 5. [

&Lt; Coating of waterborne black resin composition &gt;

The aqueous black resin composition obtained above was applied to the surface of the undercoated metal sheet so as to have a dry film thickness of 1.2 탆 by a bar coating machine and then dried at 160 캜 for 60 seconds to form a first black layer did.

(Formation of second black layer)

A second black layer was formed in the same manner as in Example 2 to obtain a black metal plate.

Table 6 shows the coating performance such as pencil hardness and T-bendability of the black metal plate obtained by changing the base resin in the first black layer as described above.

Claims (7)

Based black resin composition based on a water-dispersed polyester resin is laminated on at least one surface of a metal sheet and a first black layer having a film thickness of 0.8 to 1.6 m is laminated on the first black layer, A second black layer having a thickness of 5 to 9 m is laminated,
The aqueous black resin composition contains a surface-treated carbon black having a surface coated with an aqueous resin
Wherein the metal plate is a metal plate. The method according to claim 1,
Wherein the content of the surface-treated carbon black (solid content) is 5 to 15 mass% in 100 mass% of the total solid content of the water-based black resin composition. The method according to claim 1,
Wherein the blackness (L value) of the surface of the second black layer laminated on the first black layer is not more than 20 and the b value is not more than 1.5. The method according to claim 1,
Wherein the resin-based black paint contains resin particles and the particle diameter of the resin particles is 14 占 퐉 or less and the film thickness of the second black layer is t (占 퐉) Black painted metal sheet of 2 t (μm) or less. The method according to claim 1,
Wherein the content of the water-dispersed polyester resin (solid content) in the water-based black resin composition is 50% by mass or more and the cross-linking agent is not contained in the aqueous black resin composition,
The polyester resin constituting the water-dispersed polyester resin preferably has a Tg of 40 to 70 캜 and a number average molecular weight of 10,000 to 20,000
Black painted metal plate. The method according to claim 1,
Wherein the film made of the polyester resin constituting the water-dispersed polyester resin has a mass after holding at 230 캜 for 20 minutes of 96% or more of the mass before holding. The method according to claim 1,
Wherein the water-based black resin composition comprises the water-dispersed polyester resin, the surface-treated carbon black, the colloidal silica, the silane coupling agent, and the metavanadate.