JPH09254304A - Laminated steel plate excellent in press moldability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an excellent corrosion resistance and press moldability by a method wherein the coverage of a Fe-Ni-O-based film and its oxygen content are set to be specified values under the condition that the Fe-Ni-O-based film is formed on a zinc-based plated layer, which is formed on the surface of one side of one steel plate not contacting with a polymer resin layer pinched between two or an upper and a lower steel plates. SOLUTION: This laminated steel plate is produced by pinching polymer resin between two or a front and a rear steel plates, between which at least one steel plate or a zinc-based plated steel plate with a zinc plated layer and a predeterminedly constituted Fe-Ni-O-based film formed in the order named is used as one surfacing steel plate. The coverage of the Fe-Ni-O-based film formed on the zinc-based plated layer is set in total within the range from 10mg/m<2> or more to 1,500mg/m<2> or less in metal equivalent. At the same time, the oxygen content in the Fe-Ni-O-based film is set to be from 0.5-30wt.%. Since the Fe-Ni-O-based film is rigid and has high melting point, the sliding resistance between the surface of the zinc plated layer and a press mold at press molding lowers and the laminated steel plate easily slides on the press mold, resulting in improving the press moldability of the laminated steel plate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated steel sheet having a zinc-based plating layer formed by sandwiching a polymer resin layer between upper and lower two steel sheets and having corrosion resistance and press formability. The present invention relates to an excellent laminated steel plate.

[0002]

2. Description of the Related Art A laminated steel sheet is one in which a polymer resin layer is sandwiched between two upper and lower steel sheets (skin sheets), and the characteristics such as lightness and vibration damping of the polymer resin are imparted to the steel sheet. It is a thing. In recent years, particularly, a vibration-damping steel plate provided with a vibration-damping property has been actively used for the purpose of noise reduction of automobiles and quietness of building materials.

In order to use the laminated steel sheet for the above-mentioned applications, for example, the rustproof steel sheet for automobiles, etc.,
In addition to corrosion resistance, it is necessary that the performance required in the vehicle body manufacturing process is appropriately excellent in press moldability and adhesiveness with an adhesive.

A laminated steel sheet in which a zinc-based plated steel sheet is used as a skin steel sheet sandwiching a polymer resin layer in order to impart corrosion resistance to the laminated steel sheet is disclosed in Japanese Patent Publication No. 27145/1990.
It is disclosed in Japanese Patent Publication No. 94928 and the like (hereinafter collectively referred to as Prior Art 1).

[0005]

However, in general, zinc-based plated steel sheets have a drawback that they are inferior in press formability to cold-rolled steel sheets. This is because when the zinc-based plated steel sheet is press-molded, the sliding resistance between the zinc-based plated steel sheet and the press die is large compared to the case of the cold-rolled steel sheet.
This is because during press forming, it becomes difficult for the steel sheet to flow into the die, particularly at the portion where the sliding resistance between the zinc-based plating layer and the press die is large, and the steel sheet is likely to break.

Various adhesives are applied for the purpose of rust prevention of vehicle bodies and joining of parts, but it is clear that the adhesiveness of zinc-based plated steel sheets is inferior to that of cold-rolled steel sheets in recent years. It's coming.

The performance of the laminated steel sheet is often influenced by the performance of the skin steel sheet, and in the case of the laminated steel sheet described in the prior art 1 in which a zinc-based plated steel sheet is used as the skin steel sheet, the zinc-based plating as described above is used. Although the properties of the steel sheet are directly expressed as the performance of the laminated steel sheet and the corrosion resistance is improved, the press formability and the adhesiveness are inferior.

By the way, as a method for improving the press formability, which is a drawback of zinc-based plated steel sheets, Japanese Patent Laid-Open No. 4-88196 discloses that the surface of zinc-based plated steel sheets contains 50 to 60 g / l of sodium phosphate. By immersing the plated steel sheet in an aqueous solution of pH 2 to 6, electrolytic treatment, or spraying the above aqueous solution, an oxide film mainly composed of P oxide is formed,
A technique for improving press formability is disclosed (hereinafter referred to as Prior Art 2).

Further, in Japanese Patent Laid-Open No. 3-191093, the press formability is improved by producing Ni oxide on the surface of a zinc-based plated steel sheet by electrolytic treatment, dipping treatment, coating oxidation treatment or heat treatment. The technology is disclosed (hereinafter referred to as Prior Art 3).

However, in the techniques disclosed in Prior Art 2 and Prior Art 3, the press formability is improved but the adhesiveness is poor. Therefore, when this zinc-based plated steel sheet is used as the skin steel sheet of the laminated steel sheet, in the laminated steel sheet,
Press formability is improved, but adhesion is not.

Therefore, there is no laminated steel sheet having a zinc-based plating layer which has corrosion resistance, excellent press formability, and, if necessary, excellent adhesiveness.

In order to solve the above-mentioned problems, the present invention provides a laminated steel sheet having a zinc-based plating layer having excellent corrosion resistance and press formability and, if necessary, excellent adhesiveness. The purpose is to do.

[0013]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made extensive studies on various characteristics as a laminated steel sheet.

First, the concept of the present invention, which is premised on achieving both corrosion resistance and press formability, will be described below. (1) Regarding the corrosion resistance, since it is affected by the corrosion resistance of the skin steel sheet itself, it is assumed that a steel sheet having a zinc-based plating layer is used as the skin steel sheet.

(2) In the case of press forming, there is a forming problem that leads to press cracking of the laminated steel plate and a forming peculiar to the laminated steel plate that leads to separation between the sandwiched polymer resin layer and the skin steel plate. There is a problem above.

The former largely depends on the characteristics of the laminated steel sheets, and it is effective to reduce the sliding resistance between the surface layers of the laminated steel sheets, that is, the skin steel sheet and the press die.

In the latter case, when the laminated steel sheets pass through the bead of the press die or the die shoulder R, a displacement occurs between the two skin steel plates, and the displacement causes a gap between the polymer resin layer and the skin steel plate. It causes peeling. When this peeling occurs, fatigue cracking may occur in the skin steel sheet of the press-formed laminated steel sheet in use, or the performance as the laminated steel sheet, for example, excellent vibration damping property may not be sufficiently exhibited. The occurrence of this peeling can be improved by increasing the adhesive strength between the sandwiched polymer resin layer and the surface steel plate.

(3) Further, since various adhesives are applied for the purpose of rust prevention of vehicle bodies and joining of parts, in addition to the above-mentioned corrosion resistance and press formability, appropriate adhesiveness is required depending on the application. Become. Since this adhesion depends on the properties of the skin steel sheet,
It is desirable that the skin steel sheet also has adhesiveness.

Further, the improvement of the adhesiveness also leads to the improvement of the peeling (work peeling resistance) between the polymer resin layer and the skin steel sheet described in (2) above.

In the present specification, the former formability, which is closely related to the press cracking observed in cold-rolled steel sheets and galvanized steel sheets, is referred to as press formability, and is unique to laminated steel sheets. Formability related to peeling between the polymer resin layer and the skin steel sheet of the latter laminated steel sheet, which is a problem, is called work peeling resistance or adhesiveness to distinguish between the two.

Based on the above idea, it is important to pay attention to the skin steel sheet to be used and to optimize it. Therefore, a laminated steel sheet which has corrosion resistance by a plating layer and is excellent in press formability and adhesiveness As a result of examination for the purpose of providing the present invention, the present invention has been found out.

Based on the above-mentioned concept, the inventors of the present invention impart corrosion resistance to a zinc-based plating layer in a skin steel sheet constituting a laminated steel sheet, and form an appropriate Fe-Ni-O-based film on the surface thereof. It was found that the press formability and the adhesiveness can be further improved by the above.

That is, the laminated steel sheet using the zinc-based plated steel sheet as the conventional skin steel sheet is inferior in press formability to the case of using the cold rolled steel sheet. The cause is that the sliding resistance between the zinc-based plated steel sheet, which is a skin steel sheet, and the press die is large, so that the zinc having a low melting point and the die cause the adhesion phenomenon under high surface pressure. To prevent this, it is effective to form a film that is harder than the zinc or zinc alloy plating layer and has a high melting point on the surface of the zinc-based plated steel sheet.
The film formed on the zinc-based plating layer in the present invention includes at least Ni and Fe metals and Ni.
And a mixed film containing Fe oxide (hereinafter referred to as Fe-Ni-O based film), which is hard and has a high melting point, so that the sliding resistance between the plating layer surface and the press die during press molding decreases. , The laminated steel sheets will easily slip into the press die,
Press moldability is improved.

Further, the conventional laminated steel sheet having a zinc-based plating layer has a higher adhesiveness with the sandwiched polymer resin layer and an adhesive agent used in the component assembly process, etc. However, the cause was not clear.

As a result of investigations by the inventors of the present invention, it was revealed that the adhesiveness is governed by the composition of the oxide film on the surface. That is, in the case of cold-rolled steel sheet, the oxide film on the surface is mainly Fe oxide, whereas in the case of zinc-based plated steel sheet, Zn oxide is mainly. The adhesiveness differs depending on the composition of this oxide.
The oxide was inferior in adhesiveness to the Fe oxide. Therefore, it is possible to improve the adhesiveness by forming a film containing Fe oxide on the surface layer of the skin steel sheet as in the present invention.

The present invention was made based on the above findings. The means of the present invention will be described below.

A first invention is a laminated steel sheet in which a polymer resin layer is sandwiched between upper and lower two steel sheets, and at least one of the steel sheets is provided on a surface not in contact with the polymer resin layer. , Which has a zinc-based plating layer and an Fe-Ni-O-based coating formed on the zinc-based plating layer, and the total amount of the Fe-Ni-O-based coating deposited is 10 or more 1500mg / The laminated steel sheet is in the range of m ² or less, and the oxygen content of the Fe—Ni—O-based coating is in the range of 0.5 or more and less than 30 wt%.

A second aspect of the invention is a laminated steel sheet in which a polymer resin layer is sandwiched between two upper and lower steel sheets, wherein the one steel sheet has a zinc-based plating layer on both sides thereof and the zinc-based plating layer. Has a Fe-Ni-O-based coating formed on the other steel plate, and the other steel plate is formed on the zinc-based plating layer and the zinc-based plating layer at least on the surface in contact with the polymer resin layer. Fe-Ni-O based coatings
The adhesion amount of the system coating is within the range of 10 or more and 1500 mg / m ² or less in terms of metal, and the oxygen content of the Fe-Ni-O system coating is 0.
5 or more and less than 30 wt%, and the above Fe-Ni-O
The laminated steel sheet is such that the ratio of the Fe content (wt%) to the sum of the Fe content (wt%) and the Ni content (wt%) in the system coating is in the range of 0.05 or more and less than 1.0.

A third invention is the same as the first or second invention, wherein the polymer resin is a loss tangent based on a glass transition.
The maximum value of (tanδ) is 0.3 or more, and the temperature at which this maximum value is reached is
The laminated steel sheet is in the range of −40 to 80 ° C., the maximum value of the loss coefficient (η) as a laminated steel sheet is 0.1 or more, and the temperature at which this maximum value is shown is in the range of 0 to 120 ° C.

The reasons for limiting the above invention will be described below. <Amount of Fe-Ni-O based coating> By forming the Fe-Ni-O based coating, press formability and adhesiveness are improved. But Fe
If the amount of the -Ni-O-based coating adhered is less than 10 mg / m ^{2 in} terms of metal in the coating, the effect of improving press formability and adhesiveness cannot be obtained. If this adhesion amount exceeds 1500 mg / m ² , the above-mentioned effect is saturated. Therefore, the adhesion amount of Fe-Ni-O system coating is
It should be 10 mg / m ² or more and 1500 mg / m ² or less.

<Oxygen Content of Fe-Ni-O Type Coating> By containing an appropriate amount of oxygen in the Fe-Ni-O type coating, press formability and adhesiveness are improved. However, if the oxygen content in the Fe-Ni-O-based coating is less than 0.5 wt%, the effect of improving press formability is not achieved because the metallic properties of the coating become stronger, and the metal ratio is It becomes large and the wettability is poor and the adhesiveness is poor. On the other hand, if this amount exceeds 30 wt%, the entire film is composed of oxides and the metal simple substance does not exist, which does not satisfy the requirements of the present invention, so that the effect of the present invention cannot be exhibited. Therefore, the oxygen content of the Fe-Ni-O coating is
It must be 0.5 or more and less than 30 wt%.

<Ratio of the Fe content (wt%) to the sum of the Fe content (wt%) and the Ni content (wt%) in the Fe-Ni-O-based coating> Fe-
The ratio of the Fe content (wt%) to the sum of the Fe content (wt%) and the Ni content (wt%) in the Ni-O-based coating (hereinafter, Fe / Fe in the coating
By specifying (+ Ni), it is possible to obtain excellent adhesiveness in addition to press formability. If this ratio is less than 0.05, the effect of improving the adhesiveness cannot be obtained. Further, when this ratio is 1.0, Ni does not exist in the film, and the constituent requirements of the present invention are not satisfied, and when Ni is not present, oil retention is poor and press formability is poor. Therefore, in order to obtain excellent adhesion in addition to excellent press formability,
Fe / Fe + Ni must be 0.05 or more and less than 1.0.

Further, the polymer resin used for the above-mentioned laminated steel sheet has a maximum value of loss tangent (tan δ) based on glass transition of 0.3 or more, and a temperature showing this maximum value is in a range of -40 to 80 ° C. Thus, the polymer resin is sandwiched between steel sheets to form a laminated steel sheet, and the maximum value of the loss coefficient (η) of the laminated steel sheet is 0.1 or more, and the temperature at which the maximum value is 0 to 120 ° C.
When it is within the range, excellent vibration damping properties can be imparted to the laminated steel sheet in addition to the above-mentioned performance.

The effects of the present invention are as follows. The first invention is excellent in press formability.

The second invention is excellent in press formability, adhesiveness with an adhesive material and adhesiveness with a polymer resin layer.

In addition to the effect of the first invention or the second invention described above, the third invention is further excellent in vibration damping property.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, it is preferable to manufacture a laminated steel sheet by using a zinc-based plated steel sheet on which a zinc-based plated layer and a Fe-Ni-O 2 -based coating are formed in advance as a skin steel sheet. is there. However, if possible, it may be one in which a zinc-based plating layer or a Fe—Ni—O 2 -based coating is formed after forming a laminated steel sheet.

An embodiment of the invention in which a zinc-based plated steel sheet is used as the skin steel sheet will be described below.

Here, the zinc-based plated steel sheet means that a zinc-based plated layer is formed on a steel sheet as a base material by one or more methods such as a hot dipping method, an electroplating method, or a vapor phase plating method. It is a steel plate.

The chemical composition of the zinc-based plating layer is not only pure zinc but also Fe, Ni, Co, Mn, Cr, Mo, Al, Ti, Sn, W, Si and P.
Any metal or oxide such as b, Nb and Ta, or a single layer or a plurality of plating layers containing a predetermined amount of one or more of organic substances may be used. Further, the plating layer may contain fine particles such as SiO ₂ and Al ₂ O ₃ , and the component elements of the plating layer are the same and the constituent elements of the plating layer are the same, which are composed of a plurality of layers having different composition. It may be a functionally graded plating layer in which the composition is continuously changed in the thickness direction.

The above-mentioned zinc-based plating layer is made of Fe-N described later.
Although it is formed on the surface of the steel sheet which is the lower layer of the iO-based coating, it may be formed on the surface of the steel sheet on which the coating is not formed, depending on the usage of the laminated steel sheet.

On the zinc-based plating layer described above, the first
Of a predetermined structure as described in the second invention or the second invention
-Form a Ni-O based coating. The Fe-Ni-O-based coating is not limited by the forming method thereof, and the forming method includes a displacement plating method, a method of dipping in an aqueous solution containing an oxidizing agent, and a cathode in an aqueous solution containing an oxidizing agent. Electrolytic treatment, anodic electrolytic treatment, spraying method of predetermined solution, roll coating method, various CVD
Method, a vacuum deposition method, a vapor deposition method such as a sputter deposition method, or the like can be adopted.

In the Fe-Ni-O type coating film of the present invention, Zn, Co, Mn, Mo, Al, which are contained in the lower zinc type plating layer,
Even if an oxide, a hydroxide, or a simple substance of metal, in which an element such as Ti, Sn, W, Si, Pb and Ta is incorporated, is contained, the above-mentioned effect is obtained.

The Fe-Ni-O-based coating described above is formed on at least one zinc-based plating layer of at least one steel sheet used as a skin steel sheet of a laminated steel sheet. For the film-forming surface, one-sided or double-sided film formation can be appropriately selected depending on, for example, the necessity in the component manufacturing process.

If necessary, a chromate treatment, a resin film or the like may be provided on the surface of the surface steel sheet in contact with the resin in order to improve the adhesiveness, as long as the effects of the present invention are not impaired.

A zinc-based plated steel sheet having a predetermined composition formed on the zinc-based plated layer obtained above was used as at least one of the skin steel sheets. The laminated steel sheet of the present invention can be obtained by sandwiching the molecular resin layer by a conventional method.

As the above-mentioned sandwiching method, a method of laminating a polymer resin film on one steel plate and then thermocompression bonding of the other steel plate, or applying a liquid polymer resin to one steel plate and then the other steel plate A method of stacking and curing by heating can be exemplified, but the method is not limited to this method.

As the polymer resin, a thermoplastic resin such as a modified polyethylene resin, a modified polypropylene resin, a vinyl acetate resin, a polyester resin, an acrylic resin, an epoxy resin,
Thermosetting resins such as urethane-based and polyester-based, and polymers of these with rubbers such as styrene-butadiene rubber or polymer alloys can be used. Further, the end surface corrosion resistance, the work peeling resistance, and the adhesiveness of the bonding surface may be improved by improving the physical properties of the resin based on these resins or compounding the resin.

The thickness of the polymer resin layer sandwiched between the two skin steel sheets is not particularly limited and may be a commonly used thickness.
Generally, the thickness is often about 30 to 100 μm, which is easy to manufacture, but the thickness is not limited to this.

[0050] The adhesive strength of a laminated steel sheets in terms of resistance to processing peelability (shear adhesion) is normal temperature at 90 kgf / cm ² or more, more preferably 110 kgf / cm ² or more, as measured by a viscoelastic spectrometer Dynamic modulus at 0.5 Hz is 1 × 10 ⁷ dyne / cm ²
It is desirable that this is the case.

Surface of steel sheet (flat portion) Even if the corrosion resistance is excellent, depending on the environment in which the laminated steel sheet is used, the plating composition itself may easily elute at the end surface of the polymer sheet side of the steel sheet, In some cases, a part of the plating composition for alloy plating tends to be preferentially eluted, and as a result, peeling may occur between the polymer resin layer and the skin steel plate, and corrosion resistance may be reduced. In this case, the occurrence of peeling is suppressed by a known method for improving the end face corrosion resistance and the adhesiveness, such as using a polymer resin (thermosetting resin) that is cross-linked as necessary to improve the adhesiveness. You can

When the molding conditions are strict and good work peeling resistance is required, the elastic modulus is increased and the balance of the elastic modulus and the elongation of the polymer resin is taken into consideration to increase the elastic modulus of the press die. The work peel resistance can be further improved by suppressing the amount of displacement between the two skin steel plates when passing the bead or the die shoulder R, improving the elongation property, and increasing the adhesive strength.

When the laminated steel sheet is required to have a damping property, the loss tangent (tan
The maximum value of δ) is 0.3 or more, and the temperature at which this maximum value is -40
The maximum value of the loss factor (η) of the laminated steel sheet is 0.1 or more, and the temperature at which the maximum value is in the range of 0 to 120 ° C.

Zinc-based plating layer of skin steel sheet and Fe-N on it
The treatment of the surface on which the iO-based coating is not formed is not particularly limited. It can be appropriately selected according to the usage state of the laminated steel sheet. It may be a single or composite coating such as zinc-based plating, non-zinc-based plating, chemical conversion coating, organic resin coating or the like, or may be untreated bare steel sheet without any special treatment coating.

As the steel plate used above, a steel plate such as a cold rolled steel plate manufactured by a conventional method can be used. The plate thickness is generally 0.2 to 1.0 mm. But,
The plate thickness is not limited to this, and the plate thickness can be appropriately selected according to the application. Further, in the case of severe press working, a known method of improving formability such as increasing the r value of the steel sheet and increasing the crack limit drawing ratio can be used in combination.

[0056]

【Example】

<Example 1> Fe-Ni-O-based coatings were formed on the surfaces of various plated steel sheets, and laminated steel sheets were produced using these. Next, the press formability, adhesiveness, and vibration damping of the laminated steel sheets were evaluated. The manufacturing conditions and test conditions are shown below.

(1) Used galvanized steel sheet GA: hot-dip galvanized steel sheet (10 wt% Fe, balance Zn),
The adhesion amount is 60g / m ² on both sides, and the plate thickness is 0.4mm. GI: Hot-dip galvanized steel sheet with an adhesion of 90g / m ^{2 on} both sides,
Plate thickness 0.4 mm. EG: Electrogalvanized steel sheet, the adhesion amount is 40g / m ^{2 on} both sides,
Plate thickness 0.4 mm. Zn-Fe: Electric Zn-Fe alloy plated steel sheet (15wt% Fe), the adhesion amount is 40g / m ^{2 on} both sides, and the plate thickness is 0.4mm. Zn-Ni: Electric Zn-Ni alloy plated steel sheet (12 wt% Ni), the adhesion amount is 30 g / m ^{2 on} both sides, and the plate thickness is 0.4 mm. Zn-Cr: Electric Zn-Cr alloy-plated steel sheet (4wt% Cr), with an adhesion of 20g / m ^{2 on} both sides and a plate thickness of 0.4mm. Zn-Al: Hot-dip Zn-Al alloy-plated steel sheet (5 wt% Al) with an adhesion of 60 g / m ^{2 on} both sides and a sheet thickness of 0.4 mm.

(2) Method for forming Fe-Ni-O based coating An Fe-Ni-O based coating was formed on the surface of the above plated steel sheet by any of the following three methods.

<Formation Method A> A predetermined Fe-Ni-O-based film is formed on the surface of the original plate by subjecting the original plate to cathodic electrolysis in a mixed solution of iron sulfate and nickel sulfate containing an oxidizing agent. It was Here, the nickel sulfate concentration is constant at 100 g / l,
The iron sulfate concentration was changed to various predetermined values, and the pH was 2.5.
, The bath temperature was constant at 50 ° C., and hydrogen peroxide was used as an oxidizer to adjust the oxygen content of the film by changing the concentration to various predetermined values.

<Forming Method B> An aqueous solution containing nickel chloride at a concentration of 120 g / l and various predetermined concentrations of iron chloride was sprayed onto the original plate, and oxygen in the Fe-Ni-O-based film was mixed in a mixed atmosphere of air and ozone. By drying while adjusting the content, a predetermined Fe-Ni-O-based film was formed on the surface of the original plate.

<Forming Method C> The original plate was immersed in an aqueous solution containing nickel chloride at a concentration of 120 g / l and various concentrations of iron chloride at a pH of 2.5 to 3.5 and a bath temperature of 50 ° C. By adjusting the immersion time, the amount of the Fe-Ni-O-based coating adhered was changed to various predetermined values. Further, the oxygen content of the Fe-Ni-O-based coating was changed to various predetermined values by adjusting the pH. Further, in order to adjust the oxygen content, a predetermined oxidant is added to the aqueous solution, and by a method such as heat treatment in a predetermined oxidizing atmosphere, a predetermined Fe-Ni- on the surface of the original plate. An O-based film was formed.

(3) Method of measuring Fe-Ni-O type coating amount, oxygen content, Fe / Fe + Ni <deposition amount and Fe / Fe + Ni> Plating species are GI, EG, Zn-Cr, Zn-
For Al, the coating was dissolved and exfoliated with dilute hydrochloric acid together with the plating surface layer of the lower layer, and Fe, Ni and metal were quantitatively analyzed by the ICP method for measurement.

Next, for the plating species of GA, Zn-Fe, and Zn-Ni, since the lower plating layer contains the constituent elements in the Fe-Ni-O-based film, the Fe of the upper layer is measured by the ICP method. It is difficult to completely separate the constituent elements in the -Ni-O based coating from the constituent elements in the lower plated layer. Therefore, by the ICP method, Fe-Ni-
Among the elements in the O 2 -based film, only the elements not contained in the lower plated layer were quantitatively analyzed. Furthermore, after Ar ion sputtering, the composition distribution of each component element in the depth direction of the plating layer was measured by repeating the measurement of each component element in the Fe-Ni-O 2 -based coating from the surface by the XPS method. In this measurement method, Fe not contained in the lower plated layer
-The depth from the surface where the element of the Ni-O system film shows the maximum concentration (x) and the depth from the surface where the element is no longer detected (y) and the surface from the surface which shows the above maximum concentration The depth (x + (y−x) / 2) from the surface to which half the difference (y−x) from the depth (x) is added, that is, the depth (x) from the surface showing the maximum concentration. And the depth (y) from the surface where the element is no longer detected, the average depth from the surface ((x +
y) / 2) was defined as the thickness of the Fe-Ni-O based film. Then, the Fe-Ni-O 2 film deposition amount and composition were determined from the results of the ICP method and the XPS method. Next, Fe / Fe + in the film
Ni was calculated.

<Oxygen Content> The oxygen content was determined from the depth direction analysis result by Auger electron spectroscopy (AES).

(4) Polymer resin used AC: A rubber having a maximum loss tangent (tan δ) of 0.7, a temperature showing this maximum of 5 ° C., and a dynamic elastic modulus of 2 × 10 ⁷ dyne / cm ² . Modified acrylic ester (thermosetting resin) PP: Loss tangent (tan δ) has a maximum value of 0.3, the temperature at which this maximum value is 50 ° C, acrylic acid modification with a dynamic elastic modulus of 5 × 10 ⁹ dyne / cm ² Polypropylene (thermoplastic resin) PE: The maximum value of loss tangent (tan δ) is 0.2, the temperature showing this maximum value is 20 ° C, and the dynamic elastic modulus is 6 × 10 ⁸ dyne / cm ² acrylic acid-modified polyethylene (heat Plastic resin)

The loss tangent (tan δ) of the polymer resin is
50 with an Iwamoto Co., Ltd. viscoelasticity spectrometer (VES-F3)
It was measured in Hz.

(5) Method for producing laminated steel sheet For comparison, a plated steel sheet having no Fe-Ni-O based coating was added to the various plated steel sheets having the Fe-Ni-O based coating formed above. Then, as the upper and lower skin steel sheets, zinc-based plated steel sheets (hereinafter referred to as the same type) having the same plating type and Fe-Ni-O 3 -based coating were used, and laminated steel sheets were prepared by the following method.

For the rubber-modified acrylic ester (AC), a gel-like resin is applied to the surface of a steel sheet by a knife coater, and then the other steel sheet is applied with a pair of resin lining rolls at 10 to 20 / cm ^2. Were laminated by applying the surface pressure of No. 1 and held at 170 ° C. for 5 minutes to be heat-cured to produce a laminated steel sheet having a polymer resin layer thickness of 50 μm.

Regarding acrylic acid-modified polypropylene (PP) and acrylic acid-modified polyethylene (PE), a resin film was pasted on a steel plate surface preheated to 120 ° C. using a laminating roll, and then 180 ° C. (above the melting point of the resin ), The steel plate to which this film is laminated and the other steel plate separately heated to 180 ℃, by a pair of resin lining rolls, by applying a surface pressure of 10 to ²⁰ kgf / cm ² by laminating, A laminated steel sheet having a polymer resin layer thickness of 50 μm was produced.

(6) Evaluation Test Method <Press Formability> Press formability was evaluated by sliding resistance. In order to evaluate the sliding resistance, the friction coefficient was measured by the friction coefficient measuring device shown in FIG. The measurement is performed by fixing the sample 1 to the sample table 2 set on the horizontally movable slide table 3, pressing the bead 6 with a predetermined load (N), and then pulling out the sliding resistance (F) to the load cell. 8
The friction coefficient (μ) was calculated from the formula μ = F / N.

The shape and dimensions of the used beads 6 (type A) are shown in FIG. 2. The contact surface with the sample is wide.
It has a flat surface with a length of 10 mm and a length of 3 mm. Also, in the test, as a lubricating oil, Knox Thrust made by Japan Parkerizing Co., Ltd.
550HN was applied to the sample and used. The pressing load (N) was 400 kgf and the pulling speed was 1 m / min.

<Adhesiveness Test> First, the adhesive strength of the laminated steel sheet with the polymer resin was evaluated by the shear adhesive strength (τ). The measurement conforms to JIS K 6850, using a 25 × 150 mm test piece,
Make a slit so that the lap size is 25 × 12.5 mm,
The pulling speed was 5 mm / min.

On the other hand, the adhesive force between the surface of the laminated steel sheet and the adhesive was evaluated by T-type peel adhesion (TP). In addition, the test piece was prepared by bonding two types of skin steel sheets of the same type of laminated steel sheets of 200 × 300 mm to each other with a vinyl chloride-based hemming adhesive to a thickness of 150 μm, and then holding at 150 ° C. for 10 minutes. It was made. The measurement was carried out in accordance with JIS K 6854 by cutting into 25 × 150 mm test pieces and pulling speed at 50 mm / min.

<Damping property> The damping property of the laminated steel sheet is 25 × 220 mm.
And, a 25 × 280 mm test piece was subjected to central vibration, and the loss coefficient at 1000 Hz was measured and evaluated by the half-width method from the resonance response curve.

Tables 1 to 3 show the contents and test results of the test materials based on Example 1.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

From Tables 1 and 2, the following can be said. Fe-Ni-
The range in which the amount of the O-based coating adhered is 10 or more and 1500 mg / m ² or less and the oxygen content is 0.5 or more and less than 30 wt% (hereinafter, referred to as coating conditions 1
Inventive Example 1 satisfying the above) has a small friction coefficient,
Excellent press formability.

The amount of Fe-Ni-O-based coating adhered is 10 or more 1500 mg / m
² or less, oxygen content of 0.5 to less than 30 wt% Fe / Fe in the film
+ Ni is in the range of 0.05 or more and less than 1.0 (hereinafter, coating conditions of the present invention
Inventive Example 2 satisfying 2) has a small friction coefficient,
Moreover, the adhesive force (TP) with the adhesive and the adhesive force with the polymer resin layer
Good (τ) and excellent press moldability and adhesiveness.

Fe of the Fe-Ni-O-based coating formed on the surface steel plate
The ratio Fe / Fe + Ni is below the range of coating condition 2 of the present invention Table 2
No. 46, the adhesive force (TP) with the adhesive and the adhesive force (τ) with the polymer resin layer were inferior to those of the above-mentioned Inventive Example 2, and the adhesiveness was not improved.

No Fe-Ni-O-based coating is formed on the polymer resin layer side of the skin steel sheet, No. 18 to No. 24 in Table 1 and Table 2
No. 47 to No. 52, the adhesive strength (τ) with the polymer resin layer is lower than that of Inventive Example 2, and the adhesiveness with the polymer resin layer is inferior.

Next, the following can be said from Table 3. Fe-Ni
No. 1 to No. 7 in Table 3 in which -O-based coating is not formed are all the invention examples 1 and the invention examples described above regardless of the type of plating.
The coefficient of friction is larger than that of 2 and the adhesive force (T
P), the adhesive force (τ) with the polymer resin layer is low, and the press moldability and adhesiveness are poor.

No. 8 to No. 10 in Table 3 in which the amount of the Fe-Ni-O-based coating adhered falls below the ranges of the coating condition 1 and the coating condition 2 of the present invention.
, No.12, No.13, No.15 are all the above Table 1,
Inventive Example 1 and Inventive Example 2 listed in Table 2, the friction coefficient is large, the adhesive force with the polymer resin layer (τ), the adhesive force with the adhesive (TP) is low, press moldability, Poor adhesion.

The oxygen content of the Fe-Ni-O-based coating is below the ranges of the coating condition 1 and the coating condition 2 of the present invention.
o.14 has a higher friction coefficient than Invention Example 1 and Invention Example 2, a low adhesive force (TP) with an adhesive, press moldability,
Poor adhesion.

From Tables 1 to 3, the vibration damping properties are
The following can be said. The maximum value of the loss tangent (tan δ) based on the glass transition of the polymer resin is 0.3 or more, and the temperature at which this maximum value is exhibited satisfies the range of -40 to 80 ° C (hereinafter referred to as the polymer resin condition of the present invention). A table in which laminated steel sheets are made using rubber-modified acrylic ester (AC), which is a polymer resin.
No. 1 in No. 1 and No. 29 in Table 2 in which a laminated steel sheet is manufactured using acrylic acid-modified polypropylene (PP) have a maximum loss coefficient (η) of 0.1 or more as a laminated steel sheet. ,
The temperature showing the maximum value is in the range of 0 to 120 ° C., and in addition to the press moldability or the press moldability described above, the vibration damping property is further excellent.

On the other hand, the laminated steel sheet of No. 6 in Table 3 which is manufactured by using acrylic acid-modified polyethylene (PE) which is a polymer resin which is out of the polymer resin conditions of the present invention,
The maximum value of the loss coefficient (η) as a laminated steel sheet is less than 0.1, and the vibration damping property is poor.

<Example 2> The test conditions were in accordance with Example 1, but the press moldability was evaluated by additionally adding the following test method.

In contrast to Example 1, the amount of Fe-Ni-O-based coating and the composition were changed to investigate the detailed effects of these, and the press formability was evaluated under more severe conditions. The effect of reducing the friction coefficient under severe conditions, that is, the effect of improving press formability, has been clarified.

The test conditions were in accordance with Example 1, but the press moldability was evaluated by additionally adding the following test method.

<Press Formability> In the above-mentioned friction coefficient measurement test, as shown in FIG. 3, the contact surface with the sample has a width of 1 mm.
A test using a flat bead (designated as type B) having a length of 0 mm and a length of 60 mm was added.

Tables 4 to 7 show the contents and test results of the test materials based on Example 2.

[0093]

[Table 4]

[0094]

[Table 5]

[0095]

[Table 6]

[0096]

[Table 7]

The following can be said from Tables 4 to 7. Fe
Regarding the effect of the amount of the -Ni-O-based coating adhered, it can be seen that within the range of the present invention, as the amount of the coating adhered increases, the friction coefficient decreases and the press formability improves.

Invention Example 1 Satisfying the Coating Condition 1 of the Present Invention
Are excellent in press formability. Inventive Example 2, which satisfies the coating condition 2 of the present invention, is excellent in press formability and adhesiveness.

On the other hand, the amount of coating adhered depends on the coating conditions of the present invention.
1, under the condition of coating condition 2 Comparative example No. 1001 to N in Table 4
o.1003 has a high friction coefficient and the adhesive strength (T
P), the adhesive force (τ) with the polymer resin layer is low, and the press moldability and adhesiveness are poor.

Fe / Fe + Ni in the film is below the ranges of the film condition 1 and the film condition 2 of the present invention. Comparative example No. 1018 of Table 5 shows the adhesive force (TP) with the adhesive and the polymer resin layer. Has low adhesive strength (τ) and poor adhesiveness.

Fe / Fe + Ni in the coating exceeds the ranges of the coating conditions 1 and 2 of the present invention, Comparative Example No. 1034 in Table 5 has a large friction coefficient and poor press formability.

The oxygen content in the coating depends on the coating condition 1 of the present invention.
, Comparative example No. 1035, No. 1036 in Table 6 below coating condition 2
Has a large friction coefficient, and has a low adhesive force (TP) with an adhesive and a low adhesive force (τ) with a polymer resin layer, resulting in poor press moldability and adhesiveness.

Further, Comparative Examples No. 1052 and No. 1061 in Table 7 in which the Fe-Ni-O type coating is not formed have a large coefficient of friction, and have an adhesive force (TP) with the adhesive and a polymer resin layer. Has a low adhesive strength (τ) and is inferior in press formability and adhesiveness.

[0104]

As described above, according to the present invention, a laminated steel sheet having corrosion resistance and excellent press formability or press formability and adhesiveness can be obtained. It is possible to improve the quality of steel sheet members, expand uses, and bring industrially useful effects.

[Brief description of drawings]

FIG. 1 is a schematic view showing a friction coefficient measuring device.

FIG. 2 is a schematic view showing the shape and size of a bead used for measuring a friction coefficient.

FIG. 3 is a schematic view showing shapes and dimensions of other beads used for measuring a friction coefficient.

[Explanation of symbols]

 1 sample 2 sample table 3 slide table 4 roller 5 slide table support 6 bead 7 load cell for pressing force measurement 8 load cell for sliding resistance measurement 9 rail

Claims (3)

[Claims] 1. A laminated steel sheet comprising a polymer resin layer sandwiched between two upper and lower steel sheets, wherein at least one of the steel sheets has a zinc-based plating on a surface not in contact with the polymer resin layer. Layer and Fe-N formed on the zinc-based plating layer
It has an iO-based coating, the amount of the Fe-Ni-O-based coating deposited is within the range of 10 or more and 1500 mg / m ² or less in terms of metal, and the oxygen content of the Fe-Ni-O-based coating is Content is 0.5 or more 3
Laminated steel sheet with excellent press formability in the range of less than 0 wt%. 2. A laminated steel sheet in which a polymer resin layer is sandwiched between two upper and lower steel sheets, wherein the one steel sheet is formed on both sides of the zinc-based plating layer and on the zinc-based plating layer. Has a Fe-Ni-O-based coating, the other steel sheet, at least on the surface of the side in contact with the polymer resin layer, a zinc-based plating layer, Fe-Ni formed on the zinc-based plating layer -O-based coating, the amount of each Fe-Ni-O-based coating deposited is within the range of 10 or more and 1500 mg / m ² or less in terms of metal, and the Fe-Ni-O-based coating Oxygen content of 0.5 or more and 30 wt%
Fe in the range below and in the Fe-Ni-O-based coating
A laminated steel sheet excellent in press formability and adhesiveness, wherein the ratio of the Fe content (wt%) to the sum of the content (wt%) and the Ni content (wt%) is in the range of 0.05 or more and less than 1.0. 3. The maximum loss tangent (tan δ) based on the glass transition of the polymer resin is 0.3 or more, the temperature at which this maximum is -40 to 80 ° C., and the loss as a laminated steel sheet. The maximum value of the coefficient (η) is 0.1 or more, and the temperature exhibiting this maximum value is in the range of 0 to 120 ° C. The press formability and vibration damping property according to any one of claims 1 to 3. Excellent laminated steel sheet.