JP4593684B1 - Drawing die, method for producing the same and drawing method - Google Patents

Abstract

The present invention provides a production method capable of producing a drawing die having improved slipping properties with respect to a drawing object such as a tube while maintaining the excellent performance of a titanium-based sintered body.
A method for producing a drawing die according to the present invention includes a cermet composed of a sintered body containing at least one titanium compound as a main component of a hard phase among titanium carbide, titanium nitride, and titanium carbonitride. A step of applying a treatment liquid containing a metal salt that reacts with the titanium compound on the surface of the cermet substrate to form a composite oxide on the surface of the substrate; and a step of forming an oxidation resistant film after the application. It is characterized by that.
[Selection] Figure 3

Description

  The present invention relates to a method for manufacturing a drawing die excellent in slipperiness with respect to a drawing object such as a tubular body, and a drawing method using a drawing die obtained by the manufacturing method.

  A titanium carbonitride-based sintered body (titanium carbonitride-based cermet) having titanium carbonitride (TiCN) as the main component of the hard phase and iron group metal as the main component of the binder phase has high hardness and strength, It possesses excellent characteristics such as being difficult to react with the alloy, good slipperiness with various metals, and low coefficient of friction, and metal such as metal pipe expansion dies, contraction dies, cutting tips, etc. It is suitably used as a processed product.

  However, when TiCN-based cermets are exposed to an atmosphere in which oxygen is present at high temperatures, the constituent element titanium is oxidized and titanium oxide is generated on the cermet surface. Since this titanium oxide is brittle, when the metal is processed with a cermet tool on which the titanium oxide film is formed, the titanium oxide film falls off, the surface becomes rough, and the processing performance deteriorates. Furthermore, since the titanium oxide layer wears quickly, durability is also lowered.

  Therefore, conventionally, in order to improve the oxidation resistance of the titanium-based cermet, a method of adding another element to the component constituting the cermet has been proposed.

  For example, the cermet shown in Patent Document 1 is composed of a composite compound of chromium (Cr) and titanium (Ti) as a main component by containing chromium in a titanium-based sintered material, and improves oxidation resistance. I am doing so.

  On the other hand, many surface-coated cermet members in which a hard film is formed on a titanium-based sintered body have been proposed, although not intended to improve oxidation resistance.

  For example, the surface-covered cermet member disclosed in Patent Document 2 is such that a hard film containing titanium is formed on the surface of a cermet as a base material by CVD (chemical vapor deposition), PVD (physical vapor deposition), or the like.

  Furthermore, the surface-coated cermet member shown in Patent Document 3 has a hard film formed on the surface of the cermet base material, and in order to improve the adhesion of the hard film at the interface between the cermet base material surface and the hard film, An element containing layer is formed.

JP 2006-213977 A JP-A-2005-111623 JP 2000-355777 A

  However, as shown in Patent Document 1, a cermet (sintered body) formed by adding another component to a component of a titanium-based sintered material has a component different from that of the titanium-based sintered body and is altered. Therefore, there is a problem that the excellent performance of the titanium-based sintered body is impaired.

  The surface-coated cermet member shown in Patent Document 2 simply forms a hard film by diffusion, but the diffusion amount differs between the binder phase (Co) of the cermet base material and the hard phase (TiC), for example, Since the diffusion hardly progresses on the hard phase, there is a problem that the adhesion of the hard film is lowered and it is difficult to ensure sufficient oxidation resistance by peeling.

  The surface-covered cermet member shown in Patent Document 3 has a problem that the structure is complicated and difficult to manufacture because a diffusion element-containing layer is further formed at the interface between the hard film and the cermet base material. was there.

  Furthermore, when the cermet member described in Patent Documents 1 to 3 is arranged on the inner peripheral surface to form a drawing die, and the pipe body is drawn using the drawing die, the tube on the inner peripheral surface of the drawing die There is a problem that the surface state of the manufactured drawn tube is not so good because the sliding property against the body is insufficient.

  The present invention has been made in view of the above-mentioned problems, and a manufacturing method capable of manufacturing a drawing die having improved slipping properties with respect to a drawing object such as a tube while maintaining the excellent performance of the titanium-based sintered body. Another object of the present invention is to provide a drawing method using a drawing die obtained by the manufacturing method.

  In order to achieve the above object, the present invention provides the following means.

[1] Of the surface of the cermet base material, the surface of the cermet base material formed of a sintered body containing at least one titanium compound as a main component of the hard phase among titanium carbide, titanium nitride, and titanium carbonitride. Applying a treatment liquid containing a metal salt that reacts with a titanium compound to form a composite oxide;
And a step of forming an oxidation-resistant film after the coating.

  [2] The method for manufacturing a drawing die according to [1], wherein, in the oxidation resistant film forming step, the oxidation resistant film is formed by heating after the coating.

  [3] The method for producing a drawing die according to the above item 1 or 2, further comprising a step of oxidizing the cermet base material before the coating step.

  [4] The method for producing a drawing die according to any one of items 1 to 3, wherein the titanium compound is titanium carbonitride.

  [5] The drawing die manufacturing method according to any one of [1] to [4], wherein the oxidation resistant film is made of a perovskite complex oxide.

  [6] The method for producing a drawing die as described in 5 above, wherein a treatment liquid containing an alkaline earth metal compound is used as the treatment liquid.

  [7] The drawing die manufacturing method according to any one of [1] to [4], wherein the oxidation-resistant film is made of an ilmenite complex oxide.

  [8] The method for producing a drawing die as described in [7], wherein a treatment liquid containing a transition metal compound of an iron group divalent ion is used as the treatment liquid.

  [9] The drawing die manufacturing method according to any one of [1] to [4], wherein the oxidation resistant film is formed of a spinel complex oxide.

  [10] The method for producing a drawing die as described in 9 above, wherein a treatment liquid containing a magnesium compound or a cobalt compound is used as the treatment liquid.

  [11] The method for manufacturing a drawing die according to any one of items 1 to 10, wherein the oxidation-resistant film has a thickness of 0.5 μm or less.

  [12] The method for manufacturing a drawing die according to any one of [1] to [11], wherein the complex oxide has a crystal structure in which oxygen ions are closely packed.

[13] In a drawing method in which the tube is drawn through a gap between the drawing die and the drawing plug,
A drawing method using the drawing die manufactured by the manufacturing method according to any one of items 1 to 12 as the drawing die.

  [14] A drawing die manufactured by the manufacturing method according to any one of items 1 to 12.

  According to the invention of [1], it is possible to manufacture a drawing die that improves the slipperiness with respect to a drawing object such as a tube while maintaining the excellent performance of the titanium-based sintered body. Further, in this manufacturing method, a drawing die can be easily manufactured simply by forming an oxidation resistant film on the cermet base material.

  In the invention of [2], the oxidation resistant film can be formed more efficiently.

  In the invention of [3], an oxidation resistant film can be sufficiently formed.

  In the invention of [4], a drawing die capable of obtaining the excellent performance of the titanium carbonitride sintered body can be produced.

  In the inventions [5] to [11], it is possible to manufacture a drawing die that further improves the slipperiness with respect to a drawing object such as a tubular body.

  In the invention of [12], the composite oxide containing titanium has a crystal structure in which oxygen ions are closely packed, so that it has a stable structure in which oxygen ions are difficult to move and has excellent oxidation resistance. An oxidation resistant film (passive film) can be formed.

  According to the drawing method of [13], since drawing is performed using a drawing die having a good sliding property with respect to a drawing object such as a tubular body, a drawn product having a smooth surface without roughening can be manufactured.

  According to the invention of [14], there is provided a drawing die having improved slipperiness with respect to a drawing object such as a tube while maintaining the excellent performance of the titanium-based sintered body.

It is sectional drawing which shows typically the surface covering cermet member which comprises at least one part of the drawing die | dye which concerns on this invention. It is a block diagram which shows an example of the manufacturing process of a surface covering cermet member. It is a block diagram which shows the other example of the manufacturing process of a surface covering cermet member. It is sectional drawing which shows roughly the drawing processing method using the drawing die of this invention.

  FIG. 4 is a sectional view schematically showing a drawing method using the drawing die (2) of the present invention. The drawing die (2) of the present invention has a surface-coated cermet member (1) in which an oxidation resistant film (12) composed of a composite oxide containing titanium is formed on at least a part of the surface of a cermet base material (11). ) (See FIG. 1). As shown in FIG. 4, only a part of the drawing die (2) may be formed by the surface-covered cermet member (1), or the entire die of the drawing die (2) may be the surface-covered cermet. The structure formed with the member (1) may be sufficient.

  The drawing apparatus shown in FIG. 4 includes a drawing die (2) and a drawing plug (3) disposed in a die hole (21) of the drawing die (2), and the die hole (21) (described above) An annular forming gap is formed between the inner peripheral surface of the drawing die 2) and the drawing plug (3). A pipe body (aluminum pipe or the like) (W) as a work is drawn by being drawn through the forming gap.

  The drawing die (2) includes a substantially short cylindrical die body (20) formed of a metal material (steel material or the like) and a surface coating integrally formed on the inner peripheral surface of the die body (20). A cermet member 1. The surface-covered cermet member (1) is a cermet base material (11) composed of a sintered body containing at least one titanium compound as a main component of a hard phase among titanium carbide, titanium nitride, and titanium carbonitride. Further, the cermet base material (11) is in contact with the inner peripheral surface of the die body (20) in an integrated manner. The oxidation resistant film (12) is formed and exposed on the inner peripheral surface of the drawing die (2) (see FIG. 4).

  The extraction plug (3) disposed in the die hole (21) is supported by a plug rod (5). That is, the plug rod (5) is disposed along the transport path of the tube (W), the base end is fixed to the plug frame (6), and the pull plug (5) is attached to the tip of the plug rod (5). 3) is fixed (see FIG. 4). A chuck (4) is attached to the distal end of the tubular body (W), and the distal end of the tubular body (W) is gripped by the chuck (4) so that the tubular body (W) is moved to the right in the drawing. Can be transported.

  In the present invention, the cermet base material (11) is composed of a sintered body of titanium carbonitride (TiCN). This TiCN-based sintered body (TiCN-based cermet) is composed of a hard phase mainly composed of titanium carbonitride (a component having a hard phase content of 50% by weight or more), nickel (Ni), cobalt (Co), etc. And a binder phase containing as a main component (a component whose content in the binder phase is 50% by weight or more).

  In the present invention, the main component of the hard phase in the cermet base material (11) is not limited to titanium carbonitride, and if it is at least one titanium compound of titanium carbide, titanium nitride, and titanium carbonitride, It can be employed as the main component of the hard phase. For example, a multi-component titanium compound such as TiCN-WC-TaC or TiC-WC-TaC can also be employed as the main component of the hard phase of the cermet base material (11). it can.

  The cermet base material (11) is not particularly limited to those composed only of cermet. For example, a titanium-based cermet layer is provided on the surface of a material other than cermet such as die steel and ceramics. It may be a thing. Although the method of providing a cermet layer on the surface of materials other than cermets, such as die steel and ceramics, is not specifically limited, For example, a thermal spraying method and PVD method are suitable.

  The oxidation resistant film (12) is composed of a complex oxide containing titanium. The composite oxide containing titanium preferably has a crystal structure in which oxygen ions are closely packed. When the composite oxide has a crystal structure in which oxygen ions are closely packed, the oxide oxide film (passive film) has a stable structure in which oxygen ions are difficult to move and has excellent oxidation resistance. ) Can be formed.

Preferred examples of the composite oxide include perovskite (CaTiO ₃ ) type composite oxides, ilmenite (FeTiO ₃ ) type composite oxides, and spinel (MgAl ₂ O ₄ ) type composite oxides.

  Among them, the perovskite complex oxide and the ilmenite complex oxide have very high symmetry and stability in the crystal structure, can more reliably prevent the movement of oxygen ions, and are further excellent in oxidation resistance. An oxidation resistant film can be formed.

Examples of the perovskite complex oxide include oxides having a chemical composition such as CaTiO ₃ , SrTiO ₃ , and BaTiO ₃ .

This perovskite type complex oxide has a structure in which oxygen ions are close-packed in a face-centered cubic type, and cations having a large ion radius such as Ca ²⁺ , Sr ²⁺ , Ba ^2+, etc. It has a structure in which Ti ⁴⁺ ions having a small ion radius enter the gap between oxygen ions and cations, which are replaced with oxygen ions. In other words, it has a structure in which small Ti ⁴⁺ ions enter a gap between large divalent cations and oxygen ions packed in a close-packed state. This crystal structure is very stable, and as described above, oxygen ions are difficult to move.

The oxidation resistant film (12) made of this perovskite complex oxide reacts an alkaline earth metal such as Ca, Sr or Ba with a titanium oxide such as titanium oxide (TiO ₂ ) produced on the surface of the cermet substrate. It is formed by making it.

The ilmenite-type complex _oxide, can be cited _{FeTiO 3, NiTiO 3, CoTiO 3} , MnTiO 3, MgTiO 3, oxide having a chemical composition such as a ZnTiO _3.

This ilmenite-type complex oxide has a crystal structure similar to corundum, and has a structure in which cations enter oxygen gas gap positions (6-coordinates) in a structure in which oxygen ions are closely packed in hexagonal form. ing. In other words, Fe ²⁺ , Ni ²⁺ , Co ²⁺ , Mn ²⁺ , Mg ²⁺ , Zn ²⁺ ions, etc. with small ionic radii, and Ti ^{4 in} the gaps between the oxygen ions packed in the close-packed state. ^It has a structure with ⁺ ions. This crystal structure is also very stable and has a structure in which oxygen ions are difficult to move as described above.

  The oxidation resistant film (12) made of this ilmenite type complex oxide is composed of a transition metal of iron group divalent ions such as Fe, Ni, Co, Mn, Mg, Zn, and titanium oxide produced on the surface of the cermet substrate. It is formed by reacting.

Examples of the spinel complex oxide include oxides having chemical compositions such as MgTi ₂ O ₄ , Mg ₂ TiO ₄ , CoTi ₂ O ₄ , and Co ₂ TiO ₄ .

This spinel type complex oxide has a structure in which oxygen ions are close-packed in a face-centered cubic type. Spinel-type complex oxides containing Ti are crystals that are slightly inferior in stability due to differences in the charge of Ti ions. However, in practice, Ti ³⁺ ions are not observed, and even in the case of a complex oxide of the same element, Ti is a tetravalent Mg ₂ TiO ₄ spinel rather than a trivalent MgTi ₂ O _4. It is considered that it has a mold structure and has a structure in which Mg enters a so-called A site and Mg and Ti ⁴⁺ enter a B site.

  In the present invention, anatase type, rutile type, brookite type titanium oxide formed on the cermet base material (11) is not employed as the oxidation resistant film (12).

  In the present invention, the thickness (T) of the oxidation resistant film (12) formed on the cermet base material (11) is adjusted to 0.5 μm or less, preferably 0.4 μm or less, more preferably 0.1 μm or more. Is good. That is, when this film thickness (T) is too thick, the surface of the oxidation resistant film (12) may become rough. Moreover, when the film thickness (T) is too thin, there is a possibility that it is difficult to sufficiently obtain the effect of improving the slip property.

  Next, a process for forming the oxidation resistant film (12) on the cermet base material (11) will be described.

  As shown in FIG. 2, in this embodiment, first, the cermet base material (11) is heated and oxidized, and then a treatment liquid containing a predetermined metal salt is applied to the surface of the cermet base material (11). (Processing liquid application process). Thereafter, after drying, the cermet base material (11) is heated to cause the metal salt in the treatment liquid to react with titanium oxide (titanium oxide) on the surface of the cermet base material, thereby providing an oxidation resistant film (12). As a result, a composite oxide is produced.

  Here, the metal salt that reacts with titanium oxide to form a perovskite-type composite oxide is an alkaline earth metal such as Ca, Sr, or Ba, and this alkaline earth metal compound is contained in the treatment liquid. . Examples of the alkaline earth metal compound include calcium acetate (such as calcium acetate monohydrate).

  The metal salt that forms the ilmenite type complex oxide is a transition metal of an iron group divalent ion such as Fe, Ni, Co, Mn, Mg, Zn, and the transition metal compound is contained in the treatment liquid. Examples of the transition metal compound include nickel acetate (for example, Ni (II) acetate tetrahydrate).

  Moreover, the metal salt which produces | generates a spinel type complex oxide is a salt of Mg and Co, and these metal compounds are contained in the treatment liquid. Examples of the metal compound include cobalt acetate (for example, Co (II) acetate tetrahydrate).

  On the other hand, the treatment liquid containing a metal salt uses an aqueous or non-aqueous solvent depending on various additives to be added.

  Furthermore, the treatment liquid for film formation has a problem of “wetability” with the surface of the cermet base material (11). When this “wetting property” is poor, when the treatment liquid is applied to the surface of the cermet base material, it is repelled on the surface of the cermet base material, and a desired oxidation-resistant film (12) is formed due to insufficient application amount. May be difficult. Therefore, when the “wetting property” is poor, it is necessary to solve the problem. As this solution, the surface of the cermet base material (11) is oxidized with hydrogen peroxide water or heated in the atmosphere to oxidize, thereby forming an extremely thin oxide layer on the surface of the base material. The method can be suitably employed. Further, “wetting” can be improved by adding an appropriate additive such as a surfactant to the treatment liquid.

  Further, when applying the treatment liquid to the cermet base material (11), there is a problem of “sagging” of the treatment liquid depending on the viscosity of the treatment liquid. When this “sag” occurs, it becomes difficult to form a desired oxidation-resistant film (12) due to a shortage of processing liquid. In particular, since a three-dimensional shape always has a rising portion, “sag” is likely to occur at the rising portion. Therefore, in the case of a processing solution using an aqueous solvent, a water-soluble paste (thickening agent) is added to the processing solution in order to eliminate the “sag” problem, and an appropriate viscosity is given. Thus, it is preferable to perform subsequent steps such as a drying process and a heating process in a state in which occurrence of “sag” is reliably prevented.

  Depending on the type and concentration of the paste, the coating film after moisture drying may peel off due to shrinkage or the like. The problem of shrinkage peeling can be solved by adding a water-soluble polyhydric alcohol having a relatively high boiling point as a plasticizer. By this addition, the film can maintain flexibility even after moisture drying.

  Further, when the solubility of the metal salt in the treatment liquid is small, precipitation of the metal salt may occur. This solubility problem can be solved by adding an organic acid such as formic acid, acetic acid, or citric acid to the treatment solution.

  When it is desired to keep the production temperature of the complex oxide low (for example, when it is desired to make it 500 ° C. or lower), a sodium salt (for example, sodium hydrogen carbonate) for producing the complex oxide at a low temperature is used as a reaction aid. What is necessary is just to add.

  As described above, the aqueous processing liquid includes a paste, a surfactant, a plasticizer, an organic acid, a reaction aid and the like in addition to the metal salt and the solvent, and is composed of a slurry or a paste having viscosity. Yes.

  Moreover, as a method of apply | coating a process liquid to the surface of a cermet base material (11), the process liquid is apply | coated with a brush etc., sprayed by spray etc., the method of immersing a cermet base material (11) in a process liquid, etc. Can be adopted.

  In this embodiment, the treatment liquid is applied to the cermet base material (11) and dried, and then the oxidation-resistant film (12) is generated by heating. The heating condition during the film formation is sodium salt. In the case of not adding, it is good to set in air at 380 to 700 ° C. for 1 to 60 minutes, preferably at 570 to 620 ° C. for 2 to 20 minutes. That is, if the heating temperature is too high, the progress of oxidation may be superior to the formation of the oxidation resistant film (12). If the heating temperature is too low or the heating time is too short, the oxidation resistant film (12 ) May be insufficient, or the film thickness may be too thin, making it difficult to obtain a sufficient slip improvement effect.

  In the above example, oxidation treatment by heating is performed before the treatment liquid is applied to the cermet base material (11). As described above, it is preferable to promote the oxidation of titanium by heating before application of the treatment liquid, but this heat oxidation treatment is not always necessary and can be omitted. That is, as shown in FIG. 3, the treatment liquid is immediately applied to the cermet base material (11) without performing the heat oxidation treatment (treatment liquid application treatment), and then dried, and the oxidation resistant film formation treatment by heating. May be performed. Thus, even if oxidation treatment is not performed in advance, a titanium oxide film is generated on the surface of the cermet base material (11) to some extent during the formation of the oxidation resistant film, so that this titanium oxide reacts with the treatment liquid. Thus, a desired oxidation resistant film (12) is formed.

  As a matter of course, the oxidation treatment before applying the treatment liquid should be omitted in any case of forming any oxidation resistant film (12) of the perovskite complex compound, the ilmenite complex oxide and the spinel complex oxide. Can do.

  Thus, the oxidation resistant film (12) is formed on the surface of the titanium carbonitride-based cermet base material (11), and the TiCN-based surface-covered cermet member (1) is manufactured (see FIGS. 1 and 4). In this surface-coated cermet member (1), the constituent components of the cermet base material (11) are the same as the constituent components of the TiCN-based sintered body, and the properties of the base material (11) do not change. The excellent performance possessed by the bonded body can be obtained with certainty.

  Furthermore, the surface-coated cermet member (1) of the present embodiment can be easily produced simply by applying a treatment liquid to the cermet base material (11) and heating it.

  In particular, in this embodiment, the titanium oxide film produced on the cermet base material (11) is reacted with the metal salt of the treatment liquid to form the oxidation resistant film (12). The oxidation-resistant film (12) can be reliably formed without being affected by the type of elements contained, and the oxidation-resistant film (12) can be more easily formed. As a result, the surface-coated cermet member ( 1) can be manufactured even more easily.

  Moreover, since the said oxidation-resistant film | membrane (12) is formed in the surface covering cermet member (1) so that it may become clear from the following Example, slip property with respect to a tubular body (W) can be improved.

  Next, a method for manufacturing the drawing die (2) will be described. For example, after the cermet base material (11) is shrink-fitted on the inner peripheral surface of the hot die body (20), the drawing die (2) is oxidized resistant to the cermet base material (11) by the method described above. It can be manufactured by forming a membrane (12).

  Here, when the temperature at which the oxidation resistant film (12) is generated is a temperature exceeding the tempering temperature of the steel material, the hardness of the die body (20) is lowered. It is necessary to carry out at a temperature below the tempering temperature of the steel material. In the case of SKD61 hot die steel, it is desirable to produce composite oxide at 520 ° C or lower. To meet this condition, for example, the temperature is adjusted to around 500 ° C and the heating time is adjusted to about 30 minutes. Accordingly, an oxidation resistant film (12) having a film thickness of about 0.2 μm can be formed.

  Next, a drawing method using the drawing die (2) will be described. First, with the tubular body (W) set, the plug rod (5) is disposed along the axis inside the tubular body (W), and the tip of the tubular body (W) is connected to the drawing die (2) and the drawing. It is inserted into the molding gap between the plugs (3) and gripped by the chuck (4). Next, the chuck (4) is moved rightward in the drawing by driving means (not shown), whereby the tube (W) gripped by the chuck (4) is moved between the drawing die (2) and the drawing plug (3). Drawing is performed through the molding gap (see FIG. 4).

  When the drawing process is started in this way, the pipe body (W) passes through the forming gap between the drawing die (2) and the drawing plug (3). At this time, the drawing die (2) is a TiCN-based sintered body. The cermet base material itself exhibits excellent performance (excellent performance such as being difficult to react with aluminum and its alloys), and the oxidation resistant film (12) of the drawing die (2) has a tubular body ( Exhibits excellent slipperiness against W). For this reason, for example, the dimensional stability, strength, and hardness of the drawing die (2) can be sufficiently secured, the drawing process can be performed smoothly and accurately, and the surface condition and dimensional accuracy are high. A drawn product with quality can be obtained. Moreover, weight reduction of the drawing die (2) can also be realized by using the TiCN sintered body.

  Note that the drawing die (2) of the present invention can be reprocessed (ie, similar to the above) when the oxidation resistant film (12) is worn by performing the drawing process as described above many times. A new oxidation resistant film may be formed by performing the above operation.

  As the drawing die according to the present invention, a drawing die for drawing a solid product, a die for forming the outer surface of a drawn product in a die for drawing a hollow product, and a die for forming an inner surface (hollow inner surface) of a drawn product in a die for drawing a hollow product Any of (plug rods) is included, but not particularly limited thereto.

When configuring a die for pulling out the hollow product,
1) Configuration in which only the outer surface forming die is provided with the surface coated cermet member (1) 2) Configuration in which only the inner surface forming die (plug rod) is provided with the surface coated cermet member (1) 3) External surface forming die Any of the configurations provided with the surface-covered cermet member (1) may be employed for both the inner surface forming die and the inner surface forming die, and in particular, the configuration of 3) may be employed.

  Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

<Example 1>
Similar to the above embodiment, a cermet base material composed of a titanium carbonitride-based sintered body is prepared, and Ni (II) acetate tetrahydrate 9.3 is used as a treatment liquid for forming an oxidation resistant film. Parts by weight, 4.7 parts by weight of polyvinylpyrrolidone (paste), 1.9 parts by weight of alkyl glucoside (surfactant), 5.6 parts by weight of glycerin (polyhydric alcohol), 4.9 parts by weight of citric acid, hydrogen carbonate A mixture in which 6.5 parts by mass of sodium (sodium salt) and 67.1 parts by mass of water were mixed was prepared.

After the treatment liquid is applied to the surface of the cermet base material, it is dried, and in the atmosphere (in the air), the temperature is raised to a temperature of 500 ° C. in a hot air circulating high-temperature furnace, and further maintained at 500 ° C. for 30 minutes, On the cermet substrate, an oxidation resistant film composed of an ilmenite complex oxide (NiTiO ₃ layer) was formed to obtain a surface-coated cermet member. In this case, the oxidation resistant film formed on the surface showed a blue interference color.

<Example 2>
As in the above embodiment, a cermet base material composed of a titanium carbonitride-based sintered body was prepared.

In addition, 9.8 parts by mass of calcium acetate monohydrate, 3.9 parts by mass of polyvinylpyrrolidone (glue), 1.4 parts by mass of alkyl glucoside (surfactant), 4.4 parts by mass of glycerin (polyhydric alcohol) Part, acetic acid 24.4 parts by mass, sodium acetate (sodium salt) 4.9 parts by mass, and a mixture of 51.2 parts by mass of water were prepared as a treatment liquid, and this treatment liquid was prepared on the surface of the cermet substrate. And heated to 500 ° C. in a hot-air circulating high temperature furnace (electric furnace) and held at 500 ° C. for 30 minutes. On the cermet substrate, a perovskite complex oxide (CaTiO ₃ layer) The surface-resistant cermet member of Example 2 was obtained. In this case, the oxidation resistant film had a slightly glossy silver gray color.

<Example 3>
Co (II) acetate tetrahydrate 14.7 parts by mass, 6.2 parts by mass of polyvinylpyrrolidone (glue), 1.8 parts by mass of alkyl glucoside (surfactant), 2.1 of glycerin (polyhydric alcohol) A mixture obtained by mixing 7 parts by mass of water and 75.2 parts by mass of water is prepared as a treatment liquid, and the treatment liquid is applied to the surface of a cermet substrate made of the same titanium carbonitride-based sintered body as in Example 1 above. The temperature is raised in a hot air circulation type high temperature furnace (electric furnace) to a temperature of 600 ° C. in the air, and further maintained at 600 ° C. for 30 minutes to form a spinel complex oxide (Co ₂ TiO ₄ layer) on the cermet substrate. Thus, a surface-coated cermet member of Example 3 was obtained. In this case, although it was slightly dull, a glossy oxidation resistant film mainly composed of blue was observed.

  Next, in order to evaluate the slipperiness (surface state of the tubular body) with respect to the tubular body in the actual use of the surface-coated cermet members of Examples 1 to 3 and Comparative Example 1 obtained as described above, the above-mentioned was described. As shown in FIG. 4, the inner peripheral surface portion of the drawing die (2) was constituted by the respective surface-covered cermet members (1), and an aluminum tube (W) was drawn using the drawing die (2).

  The drawing die (2) was manufactured as follows. That is, after the cermet base material (11) is shrink-fitted on the inner peripheral surface of the die body (20) made of a hot steel material, the oxidation-resistant film (12) is applied to the inner peripheral surface of the cermet base material (11). ), The inner peripheral surface portion of the drawing die (2) was constituted by the surface-coated cermet member (1) to obtain a drawing die (2). The heating temperature at the time of forming the oxidation resistant film was set to 500 ° C., and the heating time was set to 30 minutes, thereby forming an oxidation resistant film (12) having a film thickness (T) of 0.2 μm.

  Next, using the drawing die (2), the drawing apparatus shown in FIG. 4 was constructed, and the drawing tube (W) was drawn through the drawing die (2). The surface state (surface roughness) of the drawn tube thus obtained was evaluated. The results are shown in Table 1. The surface roughness is Rz (maximum height roughness) measured in accordance with JIS B0601-2001.

In addition, the drawing conditions at the time of the said drawing process are as follows.
Drawing conditions: Lubricating oil (Kyoei Yuka Co., Ltd., trade name “Strol ES”)
Lubricating oil supply rate 1000g / min
Drawing speed 30m / min

  As is apparent from Table 1, the drawn tube obtained by drawing using the drawing dies of Examples 1 to 3 of the present invention has no roughness and a smooth surface state.

  On the other hand, the drawn tube manufactured by drawing using the drawing die of Comparative Example 1 in which no oxidation-resistant film (surface coating) is formed has a rough surface, and the surface state is not good. It was.

  The drawing die according to the present invention is not particularly limited. For example, the drawing die is used as a tube-expanding die, a tube-reducing die, and the like, and is particularly preferably used for drawing a photosensitive drum.

DESCRIPTION OF SYMBOLS 1 ... Surface covering cermet member 2 ... Drawing die 11 ... Cermet base material 12 ... Oxidation-resistant film T ... Film thickness W ... Tube

Claims (18)

Among the titanium carbide, titanium nitride and titanium carbonitride, on the surface of the cermet base material composed of a sintered body containing at least one titanium compound as a main component of the hard phase, Applying a treatment liquid containing a metal salt that reacts to form a composite oxide;
Forming an oxidation-resistant film composed of a composite oxide containing titanium on the cermet base material by heating at 380 to 700 ° C. after the coating. Wherein prior to the coating step, the manufacturing method of the drawing die according to claim 1, characterized in that it comprises a step of performing an oxidation processing on the cermet substrate. The titanium compound, method for producing a drawing die according to claim 1 or 2 is titanium carbonitride. The said oxidation-resistant film is a manufacturing method of the drawing die | dye of any one of Claims 1-3 comprised by a perovskite type complex oxide. The method for producing a drawing die according to claim 4 , wherein a treatment liquid containing an alkaline earth metal compound is used as the treatment liquid. The said oxidation-resistant film is a manufacturing method of the drawing die | dye of any one of Claims 1-3 comprised with an ilmenite type complex oxide. The manufacturing method of the drawing die | dye of Claim 6 using the processing liquid containing the transition metal compound of an iron group divalent ion as the said processing liquid. The said oxidation-resistant film is a manufacturing method of the drawing die | dye of any one of Claims 1-3 comprised with a spinel type complex oxide. The method for producing a drawing die according to claim 8 , wherein a treatment liquid containing a magnesium compound or a cobalt compound is used as the treatment liquid. The method for manufacturing a drawing die according to any one of claims 1 to 9 , wherein the oxidation-resistant film has a thickness of 0.5 µm or less. The composite oxide, method for producing a drawing die according to any one of claims 1 to 10 oxygen ions and having a close-packed crystal structure. The method for producing a drawing die according to any one of claims 1 to 11, wherein the treatment liquid contains water as a solvent and contains an organic acid. The method for producing a drawing die according to any one of claims 1 to 12, wherein the treatment liquid contains water as a solvent and contains a sodium salt. The method for producing a drawing die according to any one of claims 1 to 13, wherein the treatment liquid contains water as a solvent and contains a water-soluble thickener. The method for producing a drawing die according to claim 1, wherein the treatment liquid contains water as a solvent and contains a water-soluble polyhydric alcohol. The method for producing a drawing die according to any one of claims 1 to 15, wherein the treatment liquid contains water as a solvent and a surfactant. In the drawing method in which the tube is drawn through the gap between the drawing die and the drawing plug,
Examples drawing die, drawing processing method which comprises using a drawing die manufactured by the method according to any one of claims 1-16. A drawing die manufactured by the manufacturing method according to any one of claims 1 to 16 .

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