JP3457298B2 - Stripping-type resin-coated titanium material excellent in processability, method for producing the same, and method for stripping the film - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-removable resin-coated titanium material excellent in workability, particularly galling resistance, a method for producing the same, and a method for removing film.

[0002]

2. Description of the Prior Art Titanium materials are generally lightweight.
Due to its high specific strength and excellent corrosion resistance,
It is used in the housing of electronic devices. However, titanium has poor workability, and when deep drawing is performed with oil lubrication that applies high-viscosity press oil, which is generally used to impart lubricity in press working, etc. There was a problem of galling with the mold. In order to deal with such a problem, as a means for improving the workability of a titanium material, JP-A-6-1988 discloses that the surface of the material to be processed is coated with a specific metal such as In to improve the lubricity and A technique for removing the coating metal later is also disclosed in JP-A-9-1085.
Japanese Patent Publication No. 6 discloses a technique in which a plurality of drawing processes are performed on a β-type titanium alloy, a solution heat treatment is performed as a pretreatment for each drawing process, and a technique of performing an aging treatment after the working.

By the way, regarding deep drawing of metal,
In particular, in the field of manufacturing cans for beverages, a technique is generally known in which a polyester resin film, for example, polyethylene terephthalate (hereinafter referred to as PET) is attached to the surface of a metal material to be processed, but such a resin film is processed. It is not supposed to be removed later. That is, the metal material used for applications such as beverage cans has a thickness of 0.1 mm.
The front and rear steel plates and aluminum plates are difficult to process due to their thinness, and PET and other films are attached even after processing so as not to impair the taste, aroma, flavor, etc. of the beverage filled in the can Used as is. JP-A-61-14
9340 discloses PE for the purpose of improving workability.
Although a metal plate coated with a T film is disclosed, the coated metal plate is used in a state where the adhesion with the PET film is maintained even after plastic working, and the PET film is not removed.

On the other hand, in the field of metal processing other than can bodies for beverages and the like, film-removal type coated metal materials are known, for example, as disclosed in JP-A-9-156029 and JP-A-51-6826. A film removal type resin-coated metal material is disclosed.
In these, by forming a coating containing an acrylic resin, metal soap, etc. on the surface of the metal material to be processed,
Improves workability.

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
In the technique of coating the surface of the material with a specific metal disclosed in Japanese Patent Laid-Open No. 8, an increase in cost is inevitable because an expensive metal such as In is used, and the coating metal is removed after processing, but it is pickled. Therefore, there are problems such as environmental pollution due to acid-containing cleaning wastewater, and the inability to maintain the surface skin due to temper rolling due to acid cleaning. In the technique disclosed in JP-A-9-10856, solution heat treatment is performed as a pretreatment for each of a plurality of drawing steps,
Since the aging treatment is performed after processing, it is inefficient, and since each press step requires an annealing step, the work efficiency is significantly reduced due to the complexity of the steps. Further, since a dedicated heat treatment furnace for semi-finished products is required, cost increase cannot be avoided, and there is a problem that energy consumption is high.

Further, titanium is particularly difficult to process among difficult-to-process materials, and due to an increase in deformation resistance due to temper rolling and surface roughness, even a relatively thin material of 1 mm or less is disclosed in JP-A-9-156029. Gazette and Japanese Patent Laid-Open Sho 5
The lubricating coating by the film-removing type coating as disclosed in Japanese Patent Publication No. 1-6826 is not much different from the oil lubrication by the usual oil application, and the galling with the die in the press occurs and it cannot be used as a product. For wood, the application of these technologies is not practical.

On the other hand, in the method of sticking a PET film represented by the above-mentioned JP-A-61-149340 ,
Since the adhesion between the metal material and the resin film such as the PET film is maintained even after the plastic working and the film is not removed, the technique disclosed in the publication is used as a lubricating film (de-filming type) only for processing. Resin coating). That is, it is difficult to peel off the resin coating film that has been once adhered by the technique disclosed in the publication, and therefore it is necessary to coat after processing, and the workability of the metal material to be processed when metal skin is used. It cannot be used as a means of improvement.

As described above, among the difficult-to-work metals, titanium materials that are particularly difficult to work have not yet been developed with satisfactory workability at a practical level, and in order to impart lubricity during working. In the case where a film-removing type resin coating is used for the above, the fact is that a technique for peeling the resin coating has not yet been provided.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a film-removable resin-coated titanium material excellent in workability, particularly galling resistance, and a method for producing the same. It is another object of the present invention to provide a method for removing a resin-coated titanium material, which removes the resin film formed on the surface of the titanium material without performing pickling treatment.

[0010]

Means for Solving the Problems The inventors of the present invention have made earnest studies to solve the above problems, and as a result, formed fine irregularities on at least one surface of a titanium plate, and then applied the adhesive to the surface on which the irregularities were formed. By coating with a resin film through
The present invention has led to the production of a film-removable resin-coated titanium material which is free from galling even when deep drawing is performed, has no unevenness even in a right-angled bent portion, and is excellent in design.
Further, the film-removing type resin-coated titanium material was subjected to cathodic electrolysis in a neutral salt solution at a predetermined temperature to easily and completely remove the resin coating together with the adhesive.

That is, the above object was achieved by the present invention having the following constitution.

(1) At least one surface of titanium material
An uneven pattern having a roughness Ra of 0.5 to 20.0 μm is provided, and a thickness of 10 to 10 is formed on the surface of the titanium material provided with the uneven pattern.
A film - removable resin-coated titanium material excellent in workability, which is characterized in that a 35 μm polyester film is attached.

[0013]

(2) The surface of at least one surface of the titanium material
A step of providing an uneven pattern having a roughness Ra of 0.5 to 20.0 μm , and a thickness of 10 to 10 on the surface of the titanium material provided with the uneven pattern.
And a step of adhering a 35 μm polyester film via an adhesive, the method for producing a film - removable resin-coated titanium material having excellent processability.

[0015] (3) means for applying at least one surface uneven pattern of the titanium material is by rolling the titanium material at a rolling rate of 3% to 10% by using a roll which uneven pattern is applied, in (2) A method for producing a film-removable resin-coated titanium material having excellent processability as described above.

[0016]

(4) The ultimate plate temperature of the titanium material at the time of sticking the polyester film is 120 to 260 ° C., the film-removing resin having excellent processability according to (2) or (3). Manufacturing method of coated titanium material.

(5) An adhesive used for sticking a polyester film is a polyester adhesive, which is excellent in workability according to any one of (2) to (5). Method for producing a titanium resin-coated titanium material.

(6) The method for removing a film-removing resin-coated titanium material according to (2) , wherein the liquid temperature is room temperature to 80 ° C. after the film-removing resin-coated titanium material is subjected to plastic working. The method for removing a film is characterized in that the polyester film is peeled off by cathodic electrolysis in a neutral salt solution.

(7) The film removal method according to (6) , wherein the neutral salt is sodium sulfate.

(8) A method of removing a film-removing resin-coated titanium material produced by the method according to any one of (2) to (5) , wherein the film-removing resin-coated titanium material is A method for removing a film, which comprises subjecting a resin film to peeling by performing cathodic electrolysis in a neutral salt solution having a liquid temperature of room temperature to 80 ° C. after performing plastic working.

(9) The film removal method according to (8) , wherein the neutral salt is sodium sulfate.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

In the film-removable resin-coated titanium material according to the present invention, "titanium material" includes industrial pure titanium (a commercially available product such as JIS having a predetermined type) and its alloy. The thickness of the titanium material is not particularly limited and can be appropriately selected according to the application. Further, in the present invention, "film removal type" means that the resin film attached on the surface of the titanium material on which irregularities are formed is
This means that at least until the plastic working is completed, peeling does not occur, and after the plastic working, peeling is possible under specific conditions.

In the resin-coated titanium material according to the present invention, minute unevenness is formed on at least one surface of the titanium plate. In the present invention, “fine irregularities” means a surface roughness Ra 0.5.
It is a non-directional irregularity of ˜20.0 μm or a regular irregularity, and by having the irregularities, the titanium material of the present invention has anti-fingerprint property and anti-glare property, and is also excellent in design.

As a method for forming irregularities on the surface of the titanium material, a work roll for cold rolling on which minute irregularities are formed is used, and it is preferably formed by rolling at a rolling rate of about 3 to 10%. it can. If the rolling rate is less than 3%, it is difficult to obtain the desired unevenness because the transfer rate is insufficient (see FIG. 1). On the other hand, if the rolling rate is more than 10%, the work hardening deteriorates the secondary workability. I will end up. More preferably, the rolling rate is 3 to 5%.

The resin-coated titanium material of the present invention is formed by sticking a resin film via an adhesive onto the surface of the titanium material on which minute irregularities have been formed by the above method. By sticking a suitable resin film on the surface of a titanium material having irregularities under predetermined conditions, the resin film effectively functions as a lubricating coating, and the deformation resistance caused by the irregularity of the surface of the titanium material is increased. It is possible to suppress deterioration of workability due to the above and perform good working. The film-removal type resin-coated titanium material, which is excellent in fingerprint resistance, anti-glare property and designability, and is also excellent in processability, is the first time according to the present invention that a resin film is pasted on the surface of a material having minute irregularities. It was provided.

The method of attaching the resin film will be described below.

In the present invention, the titanium material having a surface with fine irregularities is heated to a predetermined temperature after degreasing. Then, a sheet-shaped resin film coated with an adhesive in advance is placed on the uneven titanium surface, and the resin film is adhered to the uneven titanium surface by pressing with a roll. .

The resin-coated titanium material of the present invention is of the film-removing type as described above, and the titanium material temperature at the time of attaching the resin film,
Since the kind and thickness of the resin film, the kind of the adhesive, and the pressurizing condition have a great influence on the ease of peeling the resin film after processing, setting of these conditions is important in the present invention. That is, the present invention, the conditions for attaching the resin coating to the titanium material, do not peel off at least during plastic working,
The workability of the titanium material is improved by applying the film under the condition that it is preliminarily assumed to be removed by cathodic electrolysis in a neutral salt solution after the plastic working.

As the resin film in the present invention, a polyester film can be preferably used, and a PET film is particularly preferable. The thickness of the resin film is 1
0 to 35 μm is preferable. If the thickness is less than 10 μm, sufficient slip in the mold cannot be obtained and galling may occur during deep drawing. On the other hand, if the thickness exceeds 35 μm, not only waste of resources but also peeling during processing may be caused. As the adhesive, for example, a hot melt type polyester type adhesive can be used, and a polyethylene type adhesive is particularly preferable.

The preferred ultimate temperature of the titanium material can be appropriately selected depending on the melting point of the adhesive applied to the resin film, but is preferably 120 to 260 ° C.
When the reached plate temperature of the titanium material is less than 120 ° C., the unmelted portion may become a nest on the pasting surface and serve as a peeling starting point during processing,
On the other hand, when the temperature exceeds 260 ° C., when the PET film is used as the resin film, the melting point of the film becomes higher than that of the film,
It becomes difficult to obtain a good attachment surface.

After the resin coating is formed, the resin-coated titanium material of the present invention is forcedly cooled or naturally cooled. afterwards,
The titanium material may be provided to the processor in a coiled state. Alternatively, after being wound into a coil, it may be provided as a cut plate by a slitter, a leveler, or the like.

The resin-coated titanium material of the present invention, which can be provided in the shape of a coil or a cut plate, is subjected to plastic working by a press, a bender or the like. Generally, when used in the housing of electronic equipment, deep drawing with high workability is required, but the resin coated titanium material of the present invention has sufficient deep drawing resistance and galling resistance.

The resin-coated titanium material of the present invention is a film-removing type, and the present invention is also characterized by the film-removing method. The method for removing the resin film in the present invention will be described below.

That is, the resin-coated titanium material of the present invention
After the plastic processing, the oil film is the cathode in a neutral salt solution at a specified temperature.
The whole adhesive is removed by electrolysis. Say here
As the "neutral salt", sodium sulfate, potassium sulfate,
Examples include sodium nitrate and potassium nitrate.
However, sodium sulfate is preferred from the viewpoint of safety and economy.
Can be used. The concentration of the neutral salt solution is preferably
1 to 15% by mass, more preferably 2 to 5% by mass
Is. Even if the concentration exceeds 15% by mass, no further effect
If not, on the other hand, if it is less than 1% by mass, the electrolyte concentration is too low.
Can be powered because of. Also, a neutral salt solution
Is preferably room temperature (about 20 ° C) to 90 ° C,
More preferably, it is 40-80 degreeC. Below room temperature
In this case, it takes a long time to peel off and the efficiency is poor, while it exceeds 90 ° C.
This can cause safety issues. Current value for electrolysis
Affects the peeling speed at the adhesive interface, 125 mA / c
m ^TwoThe above is desirable. 125 mA / cm^TwoIs less than
It's done. The energization time is set appropriately according to the temperature of the neutral salt solution.
Can be set. For example, if it is 80 ° C, peel it off in a few minutes.
Can be separated, but at 40 ° C it takes a dozen minutes
It This film removal process is a process after processing such as pressing.
So, for example, punch out continuously with the tie rod left
Even if the film is removed in the continuous film removal tank attached to the press
Good. After removing the film, the titanium material is washed with water and used as a component.
It can be sent to the assembly process.

According to the film removing method of the present invention, the resin film can be easily and completely removed without performing the pickling treatment, so that it is necessary to apply the paint after processing or use the metal skin. It is especially effective when

[0038]

EXAMPLE A pure titanium JIS type 1 material is subjected to temper rolling with a rolling rate of 5% by using a roll having fine irregularities with a surface roughness Ra of 3.0 μm by electric discharge machining, and fine irregularities are formed on the titanium surface. Formed. The workability was lowered by 5% temper rolling, and was about 60% of the material as shown in FIG. After that, the surface was alkali degreased, and a PET film having a film thickness of 35 μm was adhered to both surfaces of the base material heated to 140 ° C. with a polyethylene adhesive at an application pressure of 12 kg / cm ² .

The secondary workability was determined by the cupping test (punch diameter 33
mm, blank diameter 64-80 mm, wrinkle holding force 900
kgf) and Erichsen test according to JIS Z 2247A method. Regarding the lubrication conditions, the evaluation results of the example of the present invention using a PET film and the comparative example using oil lubrication instead of the PET film are shown in FIGS. 3 and 4. It can be seen from FIGS. 3 and 4 that the secondary workability evaluation shows almost the same characteristics as the material due to the PET film lubrication effect, although the workability was deteriorated by temper rolling (FIG. 2).

In the step of removing the PET film, 8
The peeling was evaluated within 2 minutes at an applied voltage of 1.25 mA / mm ² in a 5% sodium sulfate aqueous solution heated to 0 ° C. Results are shown in FIG.

Regarding the lubrication conditions, FIG. 6 shows the results of comparing the changes in the texture of the cup shoulder after processing when oil lubrication was used as a comparative example and when the PET film of the present invention was used. In the present invention example using the PET film (Fig. B), no change in texture was observed, which is far superior to the comparative example using oil lubrication (Fig. A).

[0042]

As described in detail above, it has been found that the film-removing resin-coated titanium material according to the present invention exhibits the same workability even during the secondary working and is extremely excellent in workability. Further, by using the film removing method according to the present invention, the resin film as the lubricating film could be easily peeled off.

[Brief description of drawings]

FIG. 1 is a graph showing a material surface roughness when a predetermined rolling is performed by a cold rolling roll having a surface roughness Ra of 3.0 μm.

FIG. 2 is a graph showing an SS curve of a pure titanium type 1 material and the same material subjected to temper rolling of 5%.

[Fig. 3] Pure titanium type 1 material (PET lubrication) and the same material subjected to 5% temper rolling (oil lubrication, PET lubrication)
The graph which shows the cupping test result of.

FIG. 4 is a graph showing Erichsen test results of pure titanium type 1 material and the same material subjected to 5% temper rolling under oil and PET lubrication.

FIG. 5 is a graph showing the relationship between the electrolytic treatment temperature and the peeling time in the film removal treatment of a sample attached at an ultimate plate temperature of 140 ° C.

FIG. 6 is a photograph showing the sample surface after the cupping test shown in FIG.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C25F 1/00 C25F 1/00 Z (72) Inventor Toshiyuki Yatsushiro 4-10-1 Funawato, Itabashi-ku, Tokyo (56) References JP-A-10-114013 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 B21B 1/22 B21B 3/00 B21D 22 / 08 B21D 31/00 C25F 1/00

Claims (9)

(57) [Claims] 1. A surface roughness R on at least one surface of a titanium material.
a 0.5 to 20.0 μm unevenness pattern is formed, and the thickness is 10 to 35 μm on the surface of the titanium material on which the unevenness pattern is formed.
A film - removable resin-coated titanium material having excellent processability, characterized in that a polyester film of m is attached. 2. A surface roughness R on at least one surface of a titanium material.
a step of providing an uneven pattern of 0.5 to 20.0 μm , and a thickness of 10 to 35 μm on the surface of the titanium material provided with the uneven pattern
And a step of adhering the polyester-based film of 1) via an adhesive, the method for producing a film - removable resin-coated titanium material having excellent processability. Wherein means for performing at least one surface uneven pattern of the titanium material is by rolling the titanium material at a rolling rate of 3% to 10% by using a roll which uneven pattern is applied, 請
The method for producing a film-removable resin-coated titanium material having excellent processability according to claim 2 . 4. The film-forming resin-coated titanium material excellent in processability according to claim 2 or 3 , characterized in that the reached plate temperature of the titanium material when the polyester film is attached is 120 to 260 ° C. Manufacturing method. 5. The film-forming resin coating having excellent processability according to claim 2 , wherein the adhesive used for sticking the polyester film is a polyester adhesive. Method for manufacturing titanium material. 6. The method for removing a film-removing resin-coated titanium material according to claim 1 , wherein the liquid temperature is room temperature to 80 ° C. after plasticizing the film-removing resin-coated titanium material. A method for removing a film, which comprises peeling a polyester film by cathodic electrolysis in a neutral salt solution. 7. The method for removing film according to claim 6 , wherein the neutral salt is sodium sulfate. 8. A method for removing a film-removing resin-coated titanium material produced by the method according to claim 2 , wherein the film-removing resin-coated titanium material is subjected to plastic working. After the application, a polyester film is peeled off by cathodic electrolysis in a neutral salt solution having a liquid temperature of room temperature to 80 ° C. 9. The method for removing film according to claim 8 , wherein the neutral salt is sodium sulfate.