JPH0825559A - Lubricating organic coated composite metallic sheet - Google Patents

Abstract

PURPOSE:To provide a lubricous organic coated metallic sheet which is not only superior in lubricating properties at the time of press processing, blocking resistance at the time of storage conveyance, post processing degreasing and washing properties of organic film but also provided sufficiently with excellent corrosion-proof properties. CONSTITUTION:A lubricous organic coated composite metallic sheet is constituted by possessing a corrosionproof plated layer comprised of a composite zinc electroplated layer wherein at least 0.5g/m<2> of a surface layer part is formed of 'electroplating bath containing an inhibitor' and has C density: 0.001-10% and an acrylic resin film which contains a 1-10% lubricating component as its upper layer and has a thickness of 0. 1-10mum on at least one side of the metallic sheet. In other words, it is constituted by possessing an acrylic resin film which contains a 0.05-20% inhibitor and 1-10% lubricating component on a plated layer of the metallic sheet possessing an ordinary corrosionproof plated layer or a plated layer containing the inhibit or and has a thickness: 0.1 10mum.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to corrosion resistance (primary rust resistance until plastic working and corrosion resistance after film removal), formability, and resin suitable for materials for automobiles, home appliances, civil engineering construction materials, etc. The present invention relates to a lubricious organic coated composite metal plate having excellent film cleaning and removing properties.

[0002]

2. Description of the Related Art Conventionally, the use of lubricating oil has been indispensable when press-working thin metal plates such as steel plates. "Lubricated metal thin plate" is widely used in which an "organic film containing various lubricating components" is formed on the surface of the metal thin plate at the stage of manufacturing the metal plate or at an appropriate stage before reaching the customer, instead of applying the lubricating oil. It has come to be used.
In particular, in the plate materials used for automobile parts, home appliance parts, building materials, etc., the surface of the steel plate that has been subjected to anticorrosion plating such as zinc-based electroplating or hot dip galvanizing has an "organic film containing a lubricating component". "Lubricating organic coated composite steel sheet" was occupying an important position.

As a paint for forming the above organic film, a conventionally known dry or bake-curable coating film containing acrylic resin, epoxy resin, melamine resin, phenol resin, etc. as main components. Although the component of the forming component is applied, in order to impart lubrication performance to the formed organic film, fatty acid, fatty acid ester, fatty acid soap, alcohol
It has been reported that it is preferable to blend one or more lubricating components such as polyethylene, fine powder of polyethylene, graphite, molybdenum disulfide, fine powder of fluororesin, etc. (JP-A-54-40259).
Japanese Patent Laid-Open No. 62-84193, Japanese Patent Publication No. 52-22948, etc.).

However, the above-mentioned lubricative organic coated metal plate has a) lubricity at the time of press working, b) protection from the production of the lubricious organic coated metal plate to the degreasing cleaning of the organic film after the press working. Various properties such as rusting property, c) property that does not stick to each other even if they are stored by stacking lubricious organic coated metal plates (blocking resistance), d) degreasing and cleaning property of organic film after pressing are required. However, the conventional lubricious organic coated metal plate is focused on "lubricity" and has rust prevention (primary rust prevention before plastic working and corrosion resistance after film removal).
There were many drawbacks to the current situation.

Therefore, the object of the present invention is not only excellent in lubricity at the time of press working, blocking resistance at the time of storage / transportation, and degreasing and cleaning property of the organic film after the press working, but also sufficiently excellent. It is an object of the present invention to provide a lubricative organic coated metal plate having anticorrosive properties (primary anticorrosive properties until plastic working and corrosion resistance after film removal).

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors were able to obtain the following knowledge. (a) A zinc-based or aluminum-based anticorrosive plating, on which a lubricative organic coated metal plate having an acrylic resin film containing a lubricating component formed thereon, is placed between the plating layer and the organic film layer. "A thin plating layer obtained from a zinc-based plating bath containing a corrosion-inhibiting organic compound known as an inhibitor (so-called flash plating, a small amount of plating layer)" is interposed or the entire rust-preventive plating layer is formed. Assuming that the plating layer is electrodeposited from the "inhibitor-containing zinc-based plating bath", the plating layer formed from this "inhibitor-containing zinc-based plating bath" is It is a composite zinc-based plating layer ". Therefore, even if the lubricious organic coating metal plate is placed in a corrosive environment, the corrosion inhibiting effect of the inhibitors present in the plating layer is high. Due to the fruit, the corrosion resistance is further improved, and since a part of the organic matter is incorporated into the metal matrix as C (carbon), mechanical properties are improved and good workability is obtained.

(B) The inhibitor content (eutectoid content) in the zinc-based electroplating layer formed by using the "inhibitor-containing zinc-based plating bath" is large in the performance of the lubricating organic coated metal sheet. Although having an influence, this inhibitor content corresponds to the C (carbon) content (eutectoid content) in the plating film, and can be accurately grasped by the C content.

(C) On the other hand, in the case of a lubricating organic coating metal plate having an anticorrosive plating layer and an acrylic resin coating layer containing a lubricating component, when the inhibitor is contained in the acrylic resin coating layer Also, the remarkable effect of improving the corrosion resistance of the lubricious organic coated metal plate can be secured. And
Furthermore, in the case of combining the inhibitor-containing anticorrosion plating layer and the inhibitor-containing acrylic resin film layer,
The effect is further improved. (d) Moreover, even if the inhibitor is contained in the rust-preventive plating layer or the acrylic resin film layer containing a lubricating component, the lubricating property of the organic coated metal plate, the blocking resistance, or the degreasing and cleaning property of the organic film are obtained. There is no adverse effect on.

The present invention has been completed on the basis of the above findings and the like, and is characterized by being constituted by the following matters. (1) On at least one side of the metal plate, at least the surface layer
0.5 g / m ² is “alkynes, alkynols, amines or salts thereof, thio compounds, heterocyclic compounds, polycarboxylic acid compounds or salts thereof, aromatic carboxylic acid compounds or salts thereof, ligninsulfonic acid compounds or An anticorrosion plating layer composed of a composite zinc-based electroplating layer having a C concentration of 0.001 to 10% by weight, which is formed from an electroplating bath containing at least one organic inhibitor selected from the salt thereof;
A lubricious organic coating composite metal plate, characterized by comprising an acrylic resin film having a thickness of 0.1 to 10 μm as an upper layer and containing 1 to 10% by weight of a lubricating component.

(2) The anticorrosion plating layer is a zinc-based or aluminum-based undercoating layer, and "alkynes, alkynols, amines or salts thereof, thio compounds, heterocyclic compounds, polycarboxylic acid compounds or their Adhesion at a C concentration of 0.001 to 10 wt% formed from an electroplating bath containing at least one organic inhibitor selected from salts, aromatic carboxylic acid compounds or salts thereof, lignin sulfonic acid compounds or salts thereof The lubricous organic coating composite metal plate according to the item (1), which is composed of a composite zinc-based electroplating upper layer having an amount of 0.5 to 20 g / m ² .

(3) The total amount of acrylic resin coating is 0.05
To 20% by weight of alkynes, alkynols, amines or salts thereof, thio compounds, heterocyclic compounds, polycarboxylic acid compounds or salts thereof, aromatic carboxylic acid compounds or salts thereof, ligninsulfonic acid compounds or salts thereof 1 to 10 kinds of organic inhibitors selected from
The lubricating organic-coated composite metal sheet according to item (1) or (2) above, which contains a lubricating component in a weight percentage.

(4) On at least one side of the metal plate, an anticorrosion plating layer and an upper layer of "a total amount of 0.05 to 20% by weight of alkynes, alkynols, amines or salts thereof, thio compounds, and complex compounds. One or more organic inhibitors selected from a ring compound, a polycarboxylic acid compound or a salt thereof, an aromatic carboxylic acid compound or a salt thereof, a ligninsulfonic acid compound or a salt thereof, and "1 to 10% by weight of a lubricating component" And a thickness of 0.1 to 10 μm of an acrylic resin film.

The present invention will be described in more detail below along with its operation. As described above, according to the present invention, in the conventional lubricious organic coated metal plate, the entire rust-preventive plating layer or at least the surface layer portion of 0.5 g / m ² or more is made into the “inhibitor-containing zinc-based electroplating layer”. Or apply an "acrylic resin film containing a lubricating component" as an organic film,
In the conventional lubricious organic coated metal plate, the organic film is “acrylic resin film containing lubricating component and inhibitor”, or in the conventional lubricious organic coated metal plate, at least the surface layer part of the rust preventive plating layer is formed. Excellent corrosion resistance, lubricity, blocking resistance, and degreasing of organic film by using "inhibitor-containing zinc electroplating layer" and organic film "acrylic resin film containing lubricant and inhibitor" It is characterized in that it also has cleanability, but the base metal plate is not particularly limited. That is, a normal steel plate is generally applied as the base metal plate, but a metal plate can be selected according to the application and use site, for example, using an aluminum plate for weight reduction. .

Further, in the lubricious organic coating composite metal plate according to the present invention, when the "lubricant-containing acrylic resin film" contains an inhibitor, there is no particular limitation on the type or amount of the rust-preventive plating. However, if the "lubricant-containing acrylic resin film" does not contain an inhibitor,
At least 0.5 g / m ^{2 of the} surface layer contains an inhibitor C
Concentration: 0.001 to 10% by weight (same as inhibitor content) It is necessary to provide an anticorrosion plating layer which is a composite zinc-based electroplating part. Here, if the amount of adhesion (thickness) of the inhibitor-containing composite zinc-based electroplated portion is less than 0.5 g / m ² , a sufficient corrosion resistance improving effect cannot be obtained.

The inhibitors applicable to the present invention include alkynes, alkynols, amines or salts thereof, thio compounds, heterocyclic compounds, polycarboxylic acid compounds or salts thereof, aromatic carboxylic acid compounds or salts thereof. , And at least one compound selected from the group consisting of lignin sulfonic acid compounds and salts thereof, more specifically as follows.

That is, the alkynes among the inhibitors are organic compounds containing a carbon-carbon triple bond, and examples thereof include pentin, hexyne, heptin, octyne and the like. The alkynols are organic compounds having one or more hydroxyl groups in the above alkynes, and include propargyl alcohol, 1-hexyne-3-ol,
1-heptin-3-ol and the like can be mentioned.

The amines (or salts thereof) mean 1 in the molecule.
An organic compound (or salt thereof) containing at least one nitrogen atom, which includes both aliphatic and aromatic compounds, and is exemplified by octylamine, nonylamine, decylamine, laurylamine tridecylamine, cetylamine, etc. It A thio compound is an organic compound containing at least one sulfur atom in its molecule, such as decyl mercaptan,
Examples include cetyl mercaptan and thiourea.

The heterocyclic compound is an organic compound containing an atom other than carbon as a ring-constituting atom in a cyclic molecule, such as pyridine and benzothiazo-.
And benzyltriazole, quinoline, indole and the like. In addition, a polycarboxylic acid compound (or a salt thereof)
Is a compound (or salt thereof) containing two or more carboxyl groups in the molecule, and examples thereof include citric acid, succinic acid, malonic acid, adipic acid, sebacic acid and the like.

The aromatic carboxylic acid compound (or salt thereof) is a compound having a carboxyl group linked to an aromatic ring (benzene ring, naphthalene ring, etc.) in its molecule, and includes benzoic acid, cinnamic acid, salicylic acid, Examples include toluic acid and naphthalenecarboxylic acid.

As is clear from the above description, it is also possible to use salts of amines and carboxylic acids. That is, in the case of amines, its acid addition salt (sulfate, hydrochloride, etc.), and in the case of polycarboxylic acid and aromatic carboxylic acid, its metal salt (alkali metal salt,
It is also possible to use a zinc salt or the like) or an ammonium salt.
The ligninsulfonic acid compound or its salt is also as effective as or more effective than the above compound.

By the way, in the lubricating organic coating composite metal plate of the present invention provided with an anticorrosion plating layer containing an inhibitor,
Control the plating bath so that the entire corrosion-preventive plating layer is the "inhibitor-containing zinc-based electroplating layer" or that the surface layer portion of 0.5g / m ² or more is the "inhibitor-containing zinc-based electroplating layer". It goes without saying that the plating layer may be electrodeposited, but a conventional anticorrosion-plated metal plate is used, and "inhibitor-containing zinc-based electroplating" is flash-plated as a second layer on the plating layer. Can be said to be practical.

In this case, the type of the first layer plating is not particularly limited, but it can be said that zinc-based or aluminum-based plating, which has excellent corrosion resistance as well as the conventional organic coated metal plate, is preferable as the plating type. For example, pure Zn, Zn-X
(X = Fe, Co, Ni, Mn, Cr, Mg, Al), pure Al, Al-Mn and the like can be exemplified, and the plating method may be any of electroplating, hot dipping, vapor deposition plating and the like. However, either single-sided plating or double-sided plating may be used. Further, the coating amount is not particularly limited, but it is preferably in the range of 10 to 60 g / m ² per side from the viewpoint of balance between workability and corrosion resistance.

Then, on the first layer plating, an adhesion-producing amount of 0.5 g / m ² or more and a C concentration (carbon content) of 0.001 to 10 generated from an electroplating bath containing an inhibitor.
A second layer flash plating film, which is a wt% composite zinc-based electroplating, is provided. Regarding the amount of the second-layer flash plating film deposited, if it is less than 0.5 g / m ² , sufficient corrosion resistance improving effect cannot be obtained, while if it exceeds 20 g / m ² , workability is deteriorated. It is also disadvantageous in terms of cost. At this time, in the case where the plating layer immediately below is formed by the electroplating method, the electroplating is performed only by washing with water without a drying step. In order to activate the surface of the plating layer formed immediately below by the hot dip plating method or the vapor phase plating method, 40
It is immersed in an aqueous solution of 60 to 80 ° C. containing NaOH of 120 g / L and washed with water to remove the alkali, and then electroplating is performed.

By the way, in order to form the inhibitor-containing composite zinc-based electroplating layer, a known pure zinc electroplating bath, or an alloying element such as sulfate, acetate, carbonate, molybdate, or hypophosphorus is used. Acid salts, organometallic salts, or electroplating baths that have been adjusted in advance to obtain the desired composition in the state where the metals related to the alloy components are dissolved are used as basic baths, with inhibitors added to them. And deposit it.

For example, in the case of pure zinc electroplating in which an inhibitor is codeposited, the following conditions are recommended. (A) plating bath composition _{ZnSO 4 · 7H 2 O: 20~35wt} %, Na 2 SO 4 + (NH 4) 2 SO 4: 5~10wt%, inhibitor -: 0.001 ~10wt%, pH: 1~4. (B) Electrolysis conditions Bath temperature: 40 to 65 ° C., current density: 40 to 150 A / dm ² , liquid flow rate: 0.5 to 3 m / sec. Then, in the case of zinc alloy electroplating in which an inhibitor is co-deposited, for example, in a similar plating bath, the alloy element is sulfated,
It may be added in the form of an acetate, a carbonate, a molybdate, a hypophosphite, an organometallic salt, or a plating bath containing a solution of these alloying elements may be used for electrodeposition.

Here, the content ratio of the inhibitor in the zinc-based composite electroplating layer obtained from the plating bath to which the inhibitor is added is in good agreement with the C concentration in the plating coating layer. The content of the eutectoid inhibitor can be estimated by the C concentration of. The C concentration in the plating coating layer can be quantified by mechanically peeling only the plating film from the base metal plate and applying a combustion method (gas analysis).

C in the zinc-based composite electroplating coating layer obtained from the plating bath containing the inhibitor.
If the concentration is less than 0.001 wt%, the inhibitor amount in the plating coating layer is insufficient and the effect of improving corrosion resistance and workability (formability) is not sufficient, while the C concentration in the plating coating layer is 10 wt%.
If it exceeds, the properties of the plating surface deteriorate and the workability also tends to decrease. The C concentration in the plating layer is 0.001 ~
In order to achieve 10 wt%, the amount of inhibitor added to the plating solution may be adjusted.

On the inhibitor-containing single-layer plating layer or the inhibitor-containing second layer flash plating film layer formed as described above, an acrylic resin film containing a lubricating component having a thickness of 0.1 to 10 μm is formed. It is provided in. At this time, the surface of the plating layer may be subjected to chemical conversion treatment (chromate treatment or phosphate treatment) in the usual manner, and then the acrylic resin film may be provided.

The acrylic resin used in the present invention is a generally used thermoplastic acrylic resin for paints, and may be one obtained by any polymerization method. About such acrylic resin and its manufacturing method, "Introduction to synthetic resin for paint" by Kyozo Kitaoka (published by Kobunshi Publishing Co., Ltd.)
And so on.

For example, the acrylic resin is a monomer (mainly monofunctional) selected from vinyl unsaturated carboxylic acid and vinyl unsaturated carboxylic acid ester (ester with alcohol having 1 to 25 carbon atoms). The above) are polymerized. Specific examples of these monomers include acrylic acid or methacrylic acid {hereinafter, these are abbreviated as "(meth) acrylic acid"}, sorbic acid, itaconic acid, maleic acid, fumaric acid, methyl (meth) acrylic acid. -, Ethyl (meth) acrylate, propyl (meth) acrylate-
Butyl (meth) acrylate, isobutyl (meth)
Acrylate, 2-ethyl-hexyl (meth) acrylate
G, hexyl (meth) acrylate, lauryl (meth)
Acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate And the like. The polymerization of the acrylic monomer is
For example, a monomer mixture of two or more components consisting of at least one vinyl unsaturated carboxylic acid and at least one vinyl unsaturated carboxylic acid ester is used, and an ordinary polymerization method such as a solution polymerization method or an emulsification method is used. It may be carried out by a polymerization method or the like. The polymer may be neutralized with ammonia, amine or the like in order to improve the stability of the coating composition.

However, the acrylic resin used in the present invention preferably has an acid value in the range of 10 to 200 and a glass transition temperature in the range of 5 to 110 ° C. Resin acid value is 1
If it is less than 0, the degreasing and detergency is poor, and if it exceeds 200, the rust preventive property of the film itself is deteriorated. If the glass transition temperature is lower than 5 ° C, the film has a high tackiness and is poor in block resistance.
If it exceeds 110 ° C, the corrosion resistance and degreasing and detergency deteriorate.

A lubricating component is added to the acrylic resin coating composition in order to ensure the lubricity of the organic coated composite metal plate. As the lubricating component, known organic waxes such as polyethylene wax and fluororesin wax, or inorganic lubricants such as graphite and molybdenum disulfide can be used. The lubricating component is blended so that the content ratio in the acrylic resin film is 1 to 10% by weight, but if the content ratio in the film is less than 1% by weight, sufficient lubricating performance cannot be obtained, while If the content exceeds 10% by weight, not only the effect of improving lubricity cannot be obtained, but also the primary rust preventive performance deteriorates.

The acrylic resin coating composition containing a lubricating component is applied to a plated metal plate by a conventional means such as a roll coater, and hot air or active energy is applied.
It is dried by irradiation with rays to form a solid film. The baking of this organic film may be carried out in the temperature range of 80 to 250 ° C., but it is preferable to adjust the baking temperature to 80 to 200 ° C. if possible in consideration of economic reasons.

As described above, the thickness of the lubricating component-containing acrylic resin film is adjusted to 0.1 to 10 μm. However, if the film thickness is less than 0.1 μm, sufficient lubricity cannot be obtained, while 10 μm Even if the thickness is made thicker, further lubricating performance cannot be obtained, which is not economically disadvantageous, but also becomes poor in degreasing and cleaning properties after plastic working. The thus-obtained lubricious organic coating composite metal plate of the present invention has a plating layer containing an organic substance (inhibitor) having a corrosion inhibiting effect, and thus exhibits corrosion resistance that is difficult to obtain with conventional lubricating organic coating metal plates. Not only does it show excellent workability, lubricity, blocking resistance, and degreasing and cleaning properties of organic coatings.

On the other hand, in the lubricious organic coating composite metal plate of the present invention provided with an acrylic resin coating containing an inhibitor, the type of the plating layer and the amount of the coating adhered are particularly limited as long as it is so-called "anticorrosion plating". is not. However, like the lower layer plating when performing the two-layer plating described above, a zinc-based or aluminum-based plated steel sheet having excellent corrosion resistance is preferable, and for example, pure Zn, Zn-X (X = Fe, Co, Ni,
Mn, Cr, Mg, Al), pure Al, Al-Mn, etc. are preferably applied. Of course, the plating method is electroplating, hot dipping,
Either vapor deposition plating or the like is possible, and either single-sided plating or double-sided plating may be used. As described above, the coating weight is not particularly limited, but it can be said that it is preferably in the range of 10 to 60 g / m ² per side from the viewpoint of the balance between workability and corrosion resistance.

Further, an upper layer plating generally called flash plating may be further provided on at least one surface of the above zinc-based or aluminum-based plated metal plate. Also in this case, if the plating layer directly below is formed by electroplating, electroplating may be performed only by washing with water without a drying step, and the plating layer directly below is formed by hot dip plating or vapor phase plating. In order to activate the surface, it is preferable to immerse it in an aqueous solution containing 40 to 120 g / L of NaOH at 60 to 80 ° C., wash it with water to remove the alkali, and then perform electroplating.

If necessary, a chemical conversion treatment (chromate treatment or phosphate treatment) is performed on the plating layer of the anticorrosion-plated metal plate, and then an acrylic resin film containing an inhibitor and a lubricating component is formed. Is done. The acrylic resin film can be formed, for example, as follows. The acrylic resin coating composition to be used may be the same as that used in the case where the above-mentioned inhibitor is not blended, to which an inhibitor and a lubricating component for ensuring lubricity are added, and It is applied to a plated metal plate by a conventional means such as a coater and dried and baked by irradiation with hot air or active energy rays. The baking temperature at this time is also 80 to 250 ° C. (preferably 80 to 200).
℃) is good.

By the way, in order to include an inhibitor in the acrylic resin film, for example, a desired inhibitor may be dissolved in advance in a coating composition (resin solution) to be used for coating, and the coating baking may be carried out in the usual manner. Should be done. Also, as the lubricating component blended to ensure lubricity, as described above, an organic wax such as polyethylene wax or fluororesin wax, or an inorganic lubricant such as graphite or molybdenum disulfide is used. Good.

In this case, the inhibitor content of the acrylic resin film was limited to 0.05 to 20% by weight and the lubricating component content was limited to 1 to 10% by weight, for the following reason. That is, if the inhibitor content in the acrylic resin film is less than 0.05% by weight, sufficient primary rust preventive performance cannot be obtained, while if it exceeds 20% by weight, the formability of the acrylic resin film is increased. This is because, as a result, the primary rust preventive performance becomes insufficient, but more preferably 0.5 to 5
It is good to adjust to the weight percent. If the content of the lubricating component in the acrylic resin film is less than 1% by weight, sufficient lubricating performance cannot be obtained, while if it exceeds 10% by weight, the effect of improving lubricity cannot be obtained.

The thickness of the acrylic resin film containing the inhibitor and the lubricating component is adjusted to 0.1 to 10 μm. This is because when the film thickness is less than 0.1 μm, sufficient primary rust preventive performance and lubricity can be obtained. On the other hand, even if the thickness is more than 10 μm, no further lubricating performance can be obtained, which is not economically disadvantageous, but also the degreasing and cleaning property after plastic working is inferior. The resin film thickness is preferably 0.2 to 3
It is better to adjust to μm.

The thus-obtained lubricating organic coating composite metal sheet of the present invention contains an organic substance (inhibitor) having a corrosion inhibiting effect in the acrylic resin film, and therefore the conventional lubricating organic coating metal sheet is used. Not only does it exhibit corrosion resistance that is difficult to obtain, but it also exhibits excellent performance in terms of workability, lubricity, blocking resistance, and degreasing and cleaning properties of organic coatings.

Next, the present invention will be described with reference to examples.

【Example】

<Example 1> First, a cold-rolled steel sheet (0.5 mm thick) was used as a base material, and the lower layer plating shown in Tables 1 and 2 was applied by an ordinary electroplating method, followed by plating bath composition shown in Table 3. (As appropriate, Table 1
And the inhibitor shown in Table 2 was added) and the upper layer flash plating was performed under the plating conditions.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

Then, an acrylic resin film containing a lubricating component was formed on the multi-layer plated steel sheet to prepare a lubricious organic coated composite steel sheet. The acrylic resin film is formed by adding a polyethylene wax (addition ratio: 5% by weight) to an acrylic resin aqueous dispersion having an acid value of 60 and a glass transition temperature of 65 ° C., as in the conventional lubricating resin film. The bar
It was carried out by coating with a coater and baking.
The lubricity, degreasing and detergency, blocking resistance, and corrosion resistance (when stacked and exposed) of the thus obtained lubricious organic coated composite steel sheet were evaluated by the following methods.

[Lubricity] The maximum blank diameter that could be drawn through was measured with a punch diameter of 33.0 mmφ and a pressing force of 1000 kg / cm ² , and the limiting drawing ratio (A) was calculated by the following formula. Limit drawing ratio = maximum blank diameter / punch diameter Further, the limit drawing ratio (B) of the unlubricated steel sheet is similarly obtained, and the ratio of the limit drawing ratio (A / B = test piece limit drawing ratio / unprocessed steel sheet limit drawing) The cylindrical drawability, that is, the lubricity was evaluated by the following three grades. ×: A / B <1.0, Δ: A / B = 1.0 to 1.1, ◯: A / B> 1.1.

[Degreasing and Cleaning Property] Fine Cleaner FC4
An aqueous solution of 326 (trade name: Nippon Parkerizing Co., Ltd.) with a concentration of 2% is used at a temperature of 60 to 70 ° C. and a spray pressure of 1
After degreasing and washing by spraying at 5 kg / cm ² for 5 seconds, the presence or absence of water repellency was examined and evaluated according to the following 3 grades. ×: All surfaces are repelled, △: Partially repelled, ○: Water is not repelled.

[Blocking resistance] 0.8 mm × 70 mm × 1
Two 50 mm lubricious organic coated composite steel plate test pieces were superposed so that the coating surfaces were in close contact with each other, and aged at a temperature of 50 ° C. under a load of 67 kg / cm ² , and then 500 g / m ² Aging is carried out at 40 ° C. for 16 hours under load, and thereafter, it is further aged at room temperature for 50 days under no load. After that, the blocking resistance is evaluated by the following three grades according to the adhesive state when separated. did. ×: Adhesive, △: Slightly adherent, ○: No adhesive.

[Rust Prevention] 1) 0.5 g / m ² of commercially available rust preventive oil was applied to the coating surfaces of two test pieces of a 0.8 mm × 70 mm × 150 mm lubricious organic coated composite steel sheet when stacked.
After the coated surfaces were superposed on each other, a load of 50 kg / cm ² was applied and aged at 50 ° C. for 24 hours. In addition, one drop of water was interposed between the dry coating films. 2) During exposure 0.8mm × 70mm × 150mm Lubricating organic coated composite steel plate test piece After applying 0.5g / m ² of rust preventive oil on the coating surface of two test pieces, this is exposed under the exposure condition in the open air room. It was left for 30 days. Then, the rust preventive property was evaluated by visually observing the rusting condition and evaluated according to the following criteria. ×: Rusted, Δ: Slightly rusted, ◯: No rusted.

The results are also shown in Tables 1 and 2 above. As is clear from the results shown in Tables 1 and 2, it can be seen that all of the lubricious organic coated composite steel sheets according to the present invention exhibit excellent lubricity, degreasing and detergency, blocking resistance, and corrosion resistance.

Example 2 First, a cold-rolled steel sheet (0.5 mm thick) was used as a base material, and the plating shown in Tables 4 to 6 (partially two-layer plating) was applied by an electroplating method in the usual manner. .

[0053]

[Table 4]

[0054]

[Table 5]

[0055]

[Table 6]

Then, on the plated steel sheet, similarly, Table 4
Through the use of the inhibitor and the acrylic resin film containing the lubricating component shown in Table 6, a lubricating organic coated composite steel sheet was prepared. At this time, in some cases, the surface of the plated steel sheet was chromated before the acrylic resin film was formed. The acrylic resin film is formed by adding the inhibitors shown in Tables 4 to 6 and a polyethylene wax (addition ratio: 5% by weight) to an acrylic resin aqueous dispersion having an acid value of 55 and a glass transition temperature of 50 ° C. What you did is bar coater
Was applied and baked.

The lubricity, the degreasing and cleaning property, the blocking resistance, and the corrosion resistance (at the time of stacking and at the time of exposure) of the thus obtained lubricious organic coated composite steel sheet were evaluated in the same manner as in Example 1. The results are also shown in Tables 4 to 6 above. As is clear from the results shown in Tables 4 to 6, it can be seen that all of the lubricious organic coated composite steel sheets according to the present invention exhibit excellent lubricity, degreasing and detergency, blocking resistance, and corrosion resistance.

Separately from these, with respect to the two-layer plated steel sheets according to the test numbers 1 to 24 in Tables 1 and 2 shown in Example 1, the surface thereof has the test numbers 33 to 33 in Table 4 above. It was also confirmed that the corrosion resistance was further improved when various lubricative organic coated composite steel sheets were formed by forming the acrylic resin coating according to 57 in any combination.

[0059]

[Summary of Effects] As described above, according to the present invention, a lubricity exhibiting a high corrosion resistance, which is not present in conventional lubricious organic coated steel sheets, and having excellent performance as a material for automobiles, home electric appliances, civil engineering construction members, etc. Industrially useful effects such as stable provision of an organic coated composite metal plate are provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location // C23C 28/00 A

Claims (4)

[Claims] 1. An alkyne, alkynol, 0.5 g / m ² of at least the surface layer portion on at least one surface of a metal plate.
Amines or salts thereof, thio compounds, heterocyclic compounds,
C concentration formed from an electroplating bath containing at least one organic inhibitor selected from a polycarboxylic acid compound or a salt thereof, an aromatic carboxylic acid compound or a salt thereof, a ligninsulfonic acid compound or a salt thereof: 0.001
It has an anticorrosion plating layer consisting of ~ 10% by weight of a composite zinc-based electroplating layer and an acrylic resin film having a thickness of 0.1-10 µm containing 1-10% by weight of a lubricating component as an upper layer. A lubricious organic coating composite metal plate characterized by the above. 2. An anticorrosion plating layer, a zinc-based or aluminum-based undercoating layer, and "alkynes, alkynols, amines or salts thereof, thio compounds, heterocyclic compounds, polycarboxylic acid compounds or salts thereof. , An electroplating bath containing one or more organic inhibitors selected from aromatic carboxylic acid compounds or salts thereof and lignin sulfonic acid compounds or salts thereof.
The lubricious organic coating composite metal plate according to claim 1, which is composed of a composite zinc-based electroplating upper layer having an amount of 0.001 to 10% by weight and an adhesion amount of 0.5 to 20 g / m ² . 3. The total amount of the acrylic resin film is 0.05 to
From 20% by weight of alkynes, alkynols, amines or salts thereof, thio compounds, heterocyclic compounds, polycarboxylic acid compounds or salts thereof, aromatic carboxylic acid compounds or salts thereof, ligninsulfonic acid compounds or salts thereof The lubricious organic coating composite metal plate according to claim 1 or 2, which comprises one or more selected organic inhibitors and 1 to 10% by weight of a lubricating component. 4. An anticorrosion plating layer on at least one surface of a metal plate, and an alkyne, alkynol, amine or salt thereof in a total amount of 0.05 to 20% by weight as an upper layer.
Thio compounds, heterocyclic compounds, polycarboxylic acid compounds or salts thereof, aromatic carboxylic acid compounds or salts thereof,
Acrylic resin film having a thickness of 0.1 to 10 μm, containing “one or more organic inhibitors selected from lignin sulfonic acid compounds or salts thereof” and “1 to 10% by weight of lubricating component” A lubricious organic coating composite metal plate characterized by being formed.