JP4925670B2 - Method for manufacturing titanium metal products - Google Patents

Description

  The present invention relates to an electrolytic etching solution for titanium-based metal materials such as titanium and titanium alloys, and a method for producing a titanium-based metal product having a recess and / or a through-hole using the electrolytic etching solution.

  Titanium-based metal materials such as titanium and titanium alloys are excellent in corrosion resistance and specific strength (strength / specific gravity), and thus are used in a wide range of fields such as electronic devices such as semiconductor devices, optical devices, and chemical devices. Furthermore, from the viewpoint of biocompatibility in addition to the above characteristics, it has attracted attention as an implant (embedding) device material for treatment and biological information measurement.

In general, titanium-based metal materials are known as materials that have poor processability and are difficult to process finely. Conventionally, dry etching and chemical etching have been used as processing methods for titanium-based metal materials, which are difficult to process materials (see Patent Documents 1 and 2).
JP 2002-146562 A JP 2005-320608 A

  However, dry etching using a laser, an electron beam, plasma, or the like has a problem that the processed surface may be denatured by heat and is expensive.

  On the other hand, hydrofluoric acid-based etching solutions widely used in chemical etching of titanium-based metal materials are not easy to handle and have safety problems. Also, in chemical etching, it is not easy to control processing conditions such as etching amount.

  Accordingly, an object of the present invention is to provide means capable of processing a titanium-based metal material with high accuracy and high safety.

Means for achieving the object is as follows.
[1] A step of applying a resist to the surface of the titanium-based metal material;
Exposing the resist through a photomask to form a pattern portion; and
Removing a part of the titanium-based metal material surface by removing the pattern portion or the resist other than the pattern portion; and
Forming a recess and / or a through hole by corroding the exposed surface;
A method for producing a titanium-based metal product having a recess and / or a through-hole, including a step of removing a resist on the surface of the titanium-based metal material,
Corrosion of the exposed surface with the titanium-based metal material as an anode, (a) a compound represented by the following general formula (I) , (b) alkali metal chloride and / or alkaline earth metal chloride , and (C) It consists only of a solvent not corresponding to the following general formula (I), which is optionally included, and when component (c) is included, 60% by mass of the total of 100% by mass of component (a) and component (c) The said manufacturing method characterized by performing the above by carrying out the electrolytic process by using the electrolytic etching liquid which a component (a) occupies as an electrolytic solution.
(In the formula, R is a hydrogen atom or a methyl group, and n is an integer in the range of 1 to 3).
[2] The production method according to [1], wherein the component (a) is at least one selected from the group consisting of ethylene glycol, diethylene glycol, and propylene glycol.
[3] The component (b) is sodium chloride, the production method according to [1] or [2] which contains at least one selected from the group consisting of lithium chloride and potassium chloride.
[4] The component (b), process according to any one of at least one comprising a [1] to [3] selected from the group consisting of calcium chloride and strontium chloride.
[5] The method according to any one of [1] to [4], wherein the electrolytic treatment includes stirring the electrolytic etching solution and / or vibrating the etching solution and / or the metal material.
[6] The production method according to [5], wherein the stirring and / or vibration is performed while the electrolysis is temporarily stopped.
[7] In the electrolytic treatment, a two-stage electrolytic process including a first electrolytic treatment and a second electrolytic treatment performed at an interelectrode voltage different from the interelectrode voltage in the first electrolytic treatment is performed at least once. [1] The production method according to any one of [6].
[8] The manufacturing method according to [7], wherein the second electrolytic treatment is performed at an electrode voltage lower than an electrode voltage in the first electrolytic treatment.
[9] The manufacturing method according to [8], wherein the first electrolytic treatment is performed at an electrode voltage in a range of 15 to 40V.
[10] The manufacturing method according to [8] or [9], wherein the second electrolytic treatment is performed at an electrode voltage in a range of 3 to 15V.

ADVANTAGE OF THE INVENTION According to this invention, the titanium metal material which is a difficult-to-work material can be processed with high precision, and the titanium metal product which has a recessed part and / or a through-hole can be manufactured.
Furthermore, the electrolytic etching solution of the present invention is excellent in safety without containing toxic substances and without flammability.

Hereinafter, the present invention will be described in more detail.
[Electrolytic etchant for titanium metal materials]
The electrolytic etching solution used in the method for producing a titanium-based metal product of the present invention includes (a) a compound represented by the following general formula (I) , (b) an alkali metal chloride and / or an alkaline earth metal chloride. And (c) a solvent that does not correspond to the following general formula (I) optionally included, and when component (c) is included, 60% of the total 100% by mass of component (a) and component (c) Component (a) occupies at least mass% .
(In the formula, R is a hydrogen atom or a methyl group, and n is an integer in the range of 1 to 3).

(In the formula, R is a hydrogen atom or a methyl group, and n is an integer in the range of 1 to 3).

  Since the electrolytic etching solution of the present invention contains highly safe alkali metal chloride and / or alkaline earth metal as a solute and a non-flammable glycol compound as a solvent, it is extremely safe and easy to handle. It has the advantage of being easy.

  In general formula (I), R is a hydrogen atom or a methyl group, and is preferably a hydrogen atom. Moreover, in general formula (I), n is an integer of 1-3, Preferably it is the range of 1-2.

The mechanism by which the metal material is etched by electrolytic treatment using the electrolytic etching solution of the present invention will be described below.
When electrolytic treatment is performed using the electrolytic etching solution of the present invention, a solid film and a liquid mucus (mucus film) are generated on the processed surface. The formation of the solid film inhibits etching (metal removal), and the mucus is considered to have an action of suppressing the oxidation of the processed surface (generation of the solid film) while contributing to the etching. Oxidation of the processed surface hinders etching, but if mucus is held on the processed surface for a predetermined period, it is considered that oxidation of the processed surface is suppressed and etching proceeds well. Therefore, it is preferable that the compound represented by the general formula (I) has an appropriate viscosity and specific gravity such that the mucus is retained on the processed surface for a predetermined period. Furthermore, it is preferable that the compound represented by the general formula (I) can dissolve the solute used (alkali metal chloride and / or alkaline earth metal chloride) well. From the above viewpoint, the compound represented by the general formula (I) is preferably ethylene glycol, diethylene glycol, or propylene glycol, and most preferably ethylene glycol. In the present invention, two or more compounds represented by the general formula (I) can be used in combination.

  The alkali metal chloride is preferably at least one selected from the group consisting of sodium chloride, lithium chloride, and potassium chloride, and sodium chloride is most preferable in view of safety, availability, and the like. The alkaline earth metal chloride is preferably at least one selected from the group consisting of calcium chloride and strontium chloride. In the present invention, two or more alkali metal chlorides and alkaline earth metal chlorides can be used in combination.

  The concentration of the alkali metal chloride and alkaline earth metal chloride in the electrolytic etching solution of the present invention is preferably set in consideration of the solubility of the chloride used and the viscosity of the solution. When ethylene glycol is used as the compound represented by the general formula (I), the concentration of sodium chloride and potassium chloride is, for example, 20 g to 75 g, preferably 40 g to 75 g, most preferably 60 g to 75 g, relative to 1 L of ethylene glycol. It can be. On the other hand, in the case of lithium chloride, for example, 20 g to 150 g, preferably 40 g to 150 g, and most preferably 60 g to 130 g can be used for 1 L of ethylene glycol. In the case of calcium chloride, for example, 20 g to 150 g, preferably 40 g to 150 g, most preferably 60 g to 110 g, and in the case of strontium chloride, 20 g to 1 g of ethylene glycol. ˜180 g, preferably 40 g to 180 g, most preferably 60 g to 160 g. In addition, when a compound other than ethylene glycol is used as the compound represented by the general formula (I), the concentration of the chloride is preferably close to saturation.

The electrolytic etching solution of the present invention can be an anhydrous electrolytic etching solution. The electrolytic etching solution of the present invention may contain a solvent other than the compound represented by the general formula (I), for example, for viscosity adjustment. Examples of the miscible solvent include low-viscosity alcohols, specifically, ethanol and propanol. However, in this case, Ru compound der more than 60 wt% of the solvent represented by general formula (I). From the viewpoint of safety, the electrolytic etching solution of the present invention is preferably composed of the compound represented by the general formula (I) and an alkali metal chloride and / or an alkaline earth metal chloride.

  The electrolytic etching solution of the present invention is used for electrolytic etching of a titanium metal material. The titanium-based metal material can be pure titanium or a titanium alloy. Specific examples of titanium-based metals include pure titanium; Ti-15Mo, Ti-5Al-2.5Sn, Ti-6Al-4V ELI, Ti-6Al-4V, Ti-6Al-7Nb, Ti-15Mo-5Zr, Ti -5Al-3Mo-4Zr, Ti-13Nb-13Ta, Ti-12Mo-6Zr-2Fe, Ti-15Zr-4Nb-2Ta-0.2Pd, Ti-35.3Nb-5.1Ta-4.6Zr, Ti-29Nb -13Ta-4.6Zr, Ti-15Sn-4Nb-2Ta-0.2Pd, and other alloys containing a large amount of Ti.

[Production method of titanium metal products]
Furthermore, the present invention provides
A step of applying a resist to the surface of the titanium-based metal material (hereinafter referred to as “first step”);
A step of exposing the resist through a photomask to form a pattern portion (hereinafter referred to as “second step”);
A step of exposing a part of the titanium-based metal material surface by removing the pattern portion or the resist other than the pattern portion (hereinafter referred to as “third step”);
A step of forming recesses and / or through holes by corroding the exposed surface (hereinafter referred to as “fourth step”);
A process for removing a resist on the surface of the titanium-based metal material (hereinafter referred to as “fifth process”), and a method for producing a titanium-based metal product having a recess and / or a through-hole,
The present invention relates to the manufacturing method, wherein the corrosion of the exposed surface is performed by electrolytic treatment using the titanium-based metal material as an anode and the electrolytic etching solution of the present invention as an electrolytic solution. In the method for producing a titanium-based metal product of the present invention, the recesses and / or the through holes are formed by performing electrolytic etching using the electrolytic etching solution of the present invention.
Hereinafter, the manufacturing method of the titanium metal product of this invention is demonstrated based on FIG.

FIG. 1 is an explanatory view showing an outline of a method for producing a titanium-based metal product of the present invention.
First, a resist is applied to the surface of the titanium-based metal material (first step: FIG. 1A). Next, by exposing the resist through a photomask, the pattern of the photomask is transferred onto the resist (second step: FIG. 1B). Thereafter, a part of the resist to which the pattern has been transferred is removed to expose a part of the surface of the titanium-based metal material (third step: FIG. 1C).
The first step, the second step, and the third step can be performed using a known photolithography technique that is widely used in electrolytic etching.

  In the present invention, a known resist can be used as the resist. In particular, it is preferable to use a material having good adhesion to a titanium-based metal material. The resist may be applied to only one surface of the metal material, but when forming the through hole, it is preferable to apply the resist to both surfaces of the metal material and form the same pattern on the upper and lower surfaces. In electrolytic etching, the diameter tends to decrease as the etching progresses inside. Therefore, in order to form a through hole having a uniform diameter, it is preferable to form the same pattern on the upper and lower surfaces and perform etching from both surfaces of the metal material. In addition, when applying a resist only to one side, what is necessary is just to perform well-known nonelectroconductive processes, such as nonconductive masking, so that the other surface may not be etched in an electrolytic process.

  In the second step, as the light source, a light source corresponding to the resist used, such as ultraviolet rays, can be used. In the second step, the pattern of the photomask is transferred onto the resist to form a pattern portion. Note that an unexposed portion where exposure is blocked by the photomask becomes a pattern portion.

Thereafter, the resist in the pattern portion (unexposed portion) or other than the pattern portion (exposed portion) is removed to expose a part of the surface of the metal material. The resist can be removed by a known development method. The developer may be appropriately selected according to the resist to be used. When a positive resist is used as the resist, the exposed portion of the resist is removed by development, and when a negative resist is used, the unexposed portion of the resist is removed by development.
Through the above steps, the surface of the metal material can be exposed at a position where the recess and / or the through hole is desired to be formed.

Next, the fourth step will be described.
The fourth step is a step of forming a recess and / or a through hole by corroding the exposed surface (FIG. 1 (d)). In this step, the exposed surface is corroded by electrolytic treatment using the titanium-based metal material as an anode and the electrolytic etching solution of the present invention as an electrolytic solution. Specifically, in the third step, the metal material with a part of the surface exposed can be used as an anode, and the electrolytic etching solution of the present invention can be placed between the anode and the cathode to perform the electrolytic treatment. More specifically, the electrolytic treatment can be performed by immersing the anode and the cathode in an electrolytic etching solution. In this step, the exposed surface is corroded and the metal is removed in the depth direction, whereby a recess and further a through hole can be formed.

  The material of the cathode can be appropriately selected according to the composition of the electrolytic etching solution. Examples of the material for the cathode include titanium, platinum, stainless steel, and copper. Titanium is preferable in order to prevent the adverse effect of precipitation at the anode. Moreover, there is no restriction | limiting in particular about the shape of a cathode, According to the shape of the metal material to process, it is preferable to set it as the shape where an electric current flows uniformly, for example, it can be set as flat form.

The electrolytic treatment can be performed by a known method, and the electrolysis conditions can be appropriately set according to the metal material to be processed and the shape (diameter, depth, etc.) of the desired recess and through hole. For example, the electrode voltage can be 3 to 40 V, and the current density can be 5 to 800 mA / cm ² . What is necessary is just to set the electrolytic treatment time according to the thickness of a metal material, a desired recessed part, the shape of a through-hole, etc., for example, can be 5-120 minutes. Further, if the etching rate is excessively high, the etching surface becomes rough and the surface property may be deteriorated. Further, if the etching rate is increased, the time required for forming the through hole is shortened, but the roundness of the obtained through hole may be decreased or the hole diameter may vary. Therefore, in the present invention, it is preferable to set the electrolysis conditions so that the etching rate is 2 μm / min or less (more preferably 0.5 to 1 μm / min) in consideration of surface properties, roundness, and the like.

  The temperature of the electrolytic etching solution when performing the electrolytic treatment can be, for example, about room temperature (room temperature). If the liquid temperature is raised, the etching rate can be increased. However, if the etching rate is excessively high, surface properties, roundness deterioration, and pore diameter variation may occur. Moreover, since the viscosity of a liquid falls, so that liquid temperature becomes high, when the liquid temperature is too high, there exists a possibility that the above-mentioned mucus may not be hold | maintained on a processed surface but etching may not advance favorably. Therefore, in the present invention, it is preferable that the temperature of the electrolytic etching solution is in the range of 0 to 35 ° C. More preferably, it is the range of 20-30 degreeC.

In the electrolytic etching, a recess is formed in the processed surface, and the etching progresses as the depth becomes deeper, thereby forming a recess and a through hole. During the electrolytic treatment, the mucus described above accumulates in the recess. However, since the mucus has a high resistance, if the mucus becomes too thick, it becomes difficult for electricity to flow, and the electrolytic treatment may not proceed well.
Therefore, in the present invention, in the electrolytic treatment, it is preferable to diffuse the mucus accumulated in the depression into the etching solution by stirring the solution or vibrating the solution and / or the metal material. This can prevent the mucus from becoming too thick and hindering the electrolytic treatment. The stirring of the liquid and the vibration of the liquid and the metal material can be performed by a known method such as a magnetic stirrer or ultrasonic treatment. The conditions of stirring and vibration (number of times, time, etc.) may be appropriately set in consideration of the viscosity of the liquid, the volume, the size of the dent, etc. so that the mucus can be diffused.

  In the present invention, all steps can be performed continuously without suspending electrolysis, but in order to efficiently remove mucus, it is preferable that the stirring and vibration be performed after suspending electrolysis.

In electrolytic etching, the higher the voltage between the electrodes, the faster the etching (metal removal) speed, and the etching can be performed in a short time. However, when etching is performed by electrolytic treatment at a high voltage and high current density, heat, temperature, the solid film described above, and the like are likely to be uneven, and bubbles are also generated. Such non-uniformity of heat generation, temperature, film, etc. and generation of bubbles destroys the mucus layer covering the etched surface, preventing the antioxidation effect, and the surface properties (smoothness, glossiness) of the etched surface. Degree). In addition, if the bubbles stay in the recess, the portion is not electrolyzed, so that etching (metal removal) proceeds non-uniformly, which may deteriorate the shape accuracy.
On the other hand, when electrolytic treatment is performed at a relatively low voltage and low current density, concave portions and / or through-holes having excellent surface properties and shape accuracy can be formed, but a long time is required. Further, even when electrolytic treatment is performed at a relatively low voltage and low current density, a solid film is once formed on the surface. This solid film usually peels naturally, but may stay on the etched surface. Such retention of the solid film hinders the progress of etching, which causes the etching surface to be non-uniform.
Therefore, in order to perform an etching process having excellent surface properties and shape accuracy, it is necessary to perform a film removal process such as ultrasonic treatment and stirring of an electrolytic etching solution.

  Therefore, in the present invention, an electrolytic etching solution is disposed between the titanium-based metal material (anode) and the cathode in order to simultaneously shorten the etching time, improve the surface properties of the etched surface, and improve the etching processing shape accuracy (for example, both of them). Dipping the electrode in an electrolytic etching solution), and performing at least one two-step electrolysis process including a first electrolysis process and a second electrolysis process performed at an interelectrode voltage different from the interelectrode voltage in the first electrolysis process Preferably it is done. Furthermore, it is preferable that the second electrolytic treatment is performed at an interelectrode voltage lower than the interelectrode voltage in the first electrolytic treatment. Specifically, a high voltage electrolysis treatment is performed at an interelectrode voltage in the range of 15 to 40 V, and then an interelectrode voltage lower than the interelectrode voltage in the high voltage electrolysis treatment, and an electrode in the range of 3 to 15 V It is preferable to perform low voltage electrolysis with an inter-voltage. Here, the “interelectrode voltage” refers to the voltage between the anode (workpiece) and the cathode (electrode).

As described above, an etching surface excellent in surface property and shape accuracy can be obtained in a short time by combining electrolytic treatment at different interelectrode voltages. This point will be described in more detail.
In the electrolytic treatment of the titanium-based metal material in the present invention, it is considered that a reaction for forming a solid film (oxide film) and a reaction for eluting titanium into the electrolytic etching solution to generate mucus are proceeding. When a voltage is applied to the cathode and anode (workpiece), a mucus film is formed on the anode surface. Immediately after the voltage is applied (initial stage), this mucus film is thin, so that the antioxidant effect of the mucus functions sufficiently. First, the formation of a solid film (oxide film) proceeds. On the other hand, when the mucus film becomes thick enough over time, the anti-oxidation effect of mucus effectively functions, the formation of a solid film (oxide film) is suppressed, and the elution reaction (mucus production) of titanium proceeds predominantly. Etching (metal removal) effect appears. Further, this elution reaction also has an effect of peeling off the previously generated solid film. That is, it is considered that the electrolytic etching of the titanium-based metal material effectively proceeds inside the mucous film.
In high-voltage electrolysis treatment, a mucus film is generated and the solid film is peeled off in a short time, and before the phenomenon that the mucus film is destroyed due to heat generation, etc., switching to low-voltage electrolysis treatment makes it possible to peel off the high-voltage electrolysis treatment The solid film that could not be removed can be peeled off and a uniform titanium elution reaction can proceed in the mucus film. In low-voltage electrolysis treatment, the reaction with the effect of etching (metal removal) proceeds only moderately, but the heat generation and heat dissipation on the etched surface are balanced, and a uniform electrolytic reaction is maintained over time. It is possible to obtain an etched surface having excellent properties and shape accuracy. As described above, by combining the high voltage electrolysis treatment and the low voltage electrolysis treatment, it is possible to form a recess and / or a through-hole having excellent surface properties and shape accuracy in a short time.

  As described above, bubbles may be generated in the high voltage electrolysis treatment, and bubbles may be partially generated in the low voltage electrolysis treatment. As described above, bubbles may hinder etching. As described above, stirring the liquid or vibrating the liquid and / or the metal material is also effective for removing bubbles and favorably performing etching. Further, it is considered that the agitation and vibration also have an effect of releasing heat near the processed surface generated by the electrolytic treatment.

  The interelectrode voltage in the high-voltage electrolysis treatment can be in the range of 15 to 40V, preferably 20 to 35V, and particularly preferably 20 to 25V. If the voltage between the electrodes is 40 V or less, the surface properties and shape accuracy of the etched surface can be kept good. On the other hand, if the interelectrode voltage is 15 V or more, the machining time can be shortened.

  The interelectrode voltage in the low-voltage electrolysis treatment is an inter-electrode voltage lower than the interelectrode voltage in the high-voltage electrolysis treatment, and can be in the range of 3 to 15 V, preferably 6 to 10 V, particularly preferably 6 It is in the range of ~ 8V. If the interelectrode voltage in the low-voltage electrolytic treatment is within the above range, good etching can be performed.

The current density in the high-voltage electrolytic treatment can be set in the range of, for example, 80 to 800 mA / cm ² . Preferably 100~500mA / cm ^2, particularly preferably from 150~300mA / cm ^2. On the other hand, the current density in the low-voltage electrolytic treatment can be set in the range of, for example, 5 to 80 mA / cm ² . Preferably it is 10-60 mA / cm < ² >, Most preferably, it is the range of 15-35 mA / cm < ² >. The current density in the electrolytic treatment can be set to a desired value by adjusting the applied voltage. In addition, the said current density shall mean the current density immediately after voltage application.

  In the high-voltage electrolysis treatment, the metal can be removed (etched) in a short time, but if it is performed for an excessively long time, the surface property and the shape accuracy may be deteriorated. Therefore, the voltage electrolysis step is preferably performed for 10 seconds to 5 minutes, and more preferably for 30 seconds to 2 minutes. On the other hand, the low-voltage electrolytic treatment does not adversely affect the etched surface even if it is performed for a long time, but it is performed, for example, for 3 to 30 minutes, preferably 10 to 20 minutes, from the viewpoint of processing in a short time. Can do.

  In the present invention, the number of repetitions of the two-stage electrolysis process may be appropriately set according to the thickness of the metal material to be processed. However, it is preferable to repeat two or more times in order to obtain an etched surface with excellent surface properties and shape accuracy. In the present invention, the cycle of the high voltage electrolysis treatment and the low voltage electrolysis treatment can be performed, for example, twice or more, preferably three times or more. The number of repetitions is preferably set as appropriate in consideration of the balance between the etching rate, surface properties, and shape accuracy.

Next, after the formation of the recesses and / or the through holes in the fourth step, the resist remaining on the surface of the metal material is removed (fifth step: FIG. 1E). The resist removal can be performed by a known method using a resist stripping solution or a solvent such as acetone corresponding to the resist to be used.
Through the above steps, a titanium-based metal product having a recess and / or a through hole can be obtained.

  INDUSTRIAL APPLICABILITY The present invention can be applied to various metal products to which titanium-based metal materials are applied, for example, electronic devices such as semiconductor devices, optical devices, chemical devices, and device materials for implants for treatment and biological information measurement. It is. Specifically, the metal product may be a component in which a groove or a hole is formed in a thin plate, for example, an optical slit for an encoder, an aperture, or the like.

  Hereinafter, the present invention will be further described based on examples. However, this invention is not limited to the aspect shown in the Example.

Electrolytic etching sample A resist (Fuji Hunt Electronics Technology Co., Ltd., SC450, film thickness: 3 μm) was applied to both sides of a pure titanium plate (100 mm × 100 mm, thickness 0.05 mm). Next, after exposure through a photomask, development is performed, and φ0.5 (pitch 1.0 mm), φ0.2 (pitch 0.4 mm), φ0.1 (pitch 0.2 mm), φ0. 10 rows of hole patterns of 08 (pitch 0.16 mm) and φ0.05 (pitch 0.10 mm) were formed and cut one by one, and each was used as an electrolytic etching sample.

Electrolytic etching apparatus The structure of the electrolytic etching apparatus is shown in FIG.
As the power source, a DC power source (A & D, AD-8723, 0 to 30 V) was used. For the electrolytic etching tank, a glass square container (100 mm x 100 mm x 100 mm) is used, and the electrode (the cathode is a pure titanium plate (thickness 0.2 mm) and the anode is the above-mentioned electrolytic etching sample) is placed at the opposite position. Arranged along the side.

Evaluation Method (1) Penetration Confirmation Electrolytic etching was observed with an optical microscope GX71 (Olympus Optical Industry) to confirm the success or failure of penetration.
(2) Surface quality The surface quality of the electrolytically etched surface was observed with an electron microscope SE-2150 (Hitachi, Ltd.).
(3) Etching rate The etching rate (removed amount per unit time; μm / min) was determined from the time required for penetration of the electrolytic etching sample having a thickness of 0.05 mm.

[Example 1]
An electrolytic etching solution was prepared by dissolving 40 g of sodium chloride in 600 ml of ethylene glycol, and the solution temperature was adjusted to 20 ° C. Using this electrolytic etching solution, an etching sample was prepared using the electrolytic etching apparatus shown in FIG. 2, “Electrodeposition between electrodes 20 V, 1 minute electrolysis treatment → interelectrode voltage 7.5 V, 9 minutes electrolysis treatment → electrolysis pause, solution agitation The process of "was repeated and the electrolytic treatment was performed.
After repeating this process seven times, the electrolytic treatment was terminated because the penetration of φ0.5 holes was confirmed visually. When the sample was observed with an optical microscope after removing the resist, penetration of all the holes of φ0.5 to φ0.05 was confirmed. An SEM photograph of the φ0.1 hole after the treatment is shown in FIG. It was confirmed that a through-hole having a high-quality (smooth) processed surface could be electrolytically etched at an etching rate of 0.36 μm / min by the electrolytic etching solution and the electrolytic process.

[Example 2]
The electrolytic etching solution having the same composition as in Example 1 was adjusted to a liquid temperature of 35 ° C., and the same electrolytic etching apparatus as in Example 1 was used, and “electrolysis treatment between electrodes 20 V, 1 minute → interelectrode voltage 7.5 V, 9 minutes” The electrolytic treatment was performed by repeating the process of “electrolytic treatment → electrolytic pause, liquid stirring”.
After repeating this process four times, the treatment was terminated because the penetration of φ0.5 holes was confirmed visually. When the treated sample was observed with an optical microscope, penetration of holes of φ0.5 to φ0.08 was confirmed. It was confirmed that the through hole could be electrolytically etched at an etching rate of 0.63 μm / min by the above electrolytic process.

[Example 3]
Using the same electrolytic etching solution (liquid temperature 20 ° C.) and electrolytic etching apparatus as in Example 1, the process of “electrode voltage 20 V, 1 minute electrolytic treatment → electrolytic pause, liquid stirring” was repeated to perform electrolytic treatment.
After repeating this process 25 times, since the penetration of a hole of φ0.5 was confirmed visually, the processing was terminated. When the treated sample was observed with an optical microscope, penetration of holes of φ0.5 to φ0.08 was confirmed. It was confirmed that the through hole could be electrolytically etched at an etching rate of 1 μm / min by the above electrolytic process.

[Example 4]
Using the same electrolytic etching solution (20 ° C.) and electrolytic etching apparatus as in Example 1, the process of “interelectrode voltage 20 V, 1 minute electrolysis treatment → solution stirring” was repeated 20 times, and then the interelectrode voltage 20 V for 1 minute. Then, an electrolytic treatment was performed for 14 minutes at an interelectrode voltage of 7.5V.
When the treated sample was observed with an optical microscope, penetration of holes of φ0.5 to φ0.08 was confirmed. Through the electrolytic process, it was confirmed that the through hole could be electrolytically etched at an etching rate of 0.71 μm / min.

[Example 5]
An electrolytic etching solution was prepared by dissolving 25 g of sodium chloride in a liquid obtained by mixing 400 ml of ethylene glycol and 200 ml of ethanol, and adjusted to a liquid temperature of 20 ° C. Using this electrolytic etching solution, using the same electrolytic etching apparatus as in Example 1, the following is performed: “electrode voltage 20 V, 1 minute electrolytic treatment → electrode voltage 7.5 V, 9 minute electrolytic treatment → electrolytic pause, liquid stirring” The process was repeated for electrolytic treatment.
After repeating this process three times, the process was terminated because the penetration of a hole of φ0.5 was visually confirmed. When the treated sample was observed with an optical microscope, penetration of holes of φ0.5 to φ0.08 was confirmed. It was confirmed that a through hole having a relatively high quality (smooth) processed surface could be electrolytically etched at an etching rate of 0.83 μm / min by the electrolytic etching solution and the electrolytic process.

[Example 6]
An electrolytic etching solution having the same composition as in Example 1 was adjusted to a liquid temperature of 50 ° C., and the same electrolytic etching solution and electrolytic etching apparatus as in Example 1 were used. The process of "was repeated and the electrolytic treatment was performed.
After repeating this process 6 times, the penetration of φ0.5 hole was confirmed by visual inspection, and the processing was terminated. When the treated sample was observed with an optical microscope, penetration of holes of φ0.5 to φ0.08 was confirmed. An SEM photograph of the φ0.1 hole after the treatment is shown in FIG. It was confirmed that the through holes could be electrolytically etched at an etching rate of 4.2 μm / min.

Example 2 is an example in which the liquid temperature was raised compared to Example 1. In addition, Example 1 is an example in which electrolytic treatment with high voltage and electrolytic treatment with low voltage are combined, while Example 3 is an example in which electrolytic treatment is performed only with high voltage. In Example 2 and Example 3, the time required for forming the through-hole was shorter than that in Example 1. However, when the surface quality was observed, the through holes formed in Example 1 were higher in smoothness and higher quality than the through holes formed in Examples 2 and 3.
Example 5 is an example in which ethanol was added to reduce the viscosity of the electrolytic etching solution. In Example 5, the etching rate was higher than that in Example 1, but when the surface quality of the formed through hole was observed, the surface quality was lowered as compared with the through hole formed in Example 1.
Moreover, since the liquid temperature of Example 6 was higher than that of Example 1 and the voltage was high, the etching rate was high. However, as can be seen from a comparison between FIG. 4 and FIG. 5, the holes formed in Example 1 had higher roundness and fewer variations in hole diameter than the holes formed in Example 6.
From the above results, it can be seen that the composition temperature of the electrolytic etching solution and the electrolysis conditions should be set in consideration of the desired quality and processing time.
In addition, Example 3 is an example in which electrolytic treatment with high voltage and liquid stirring are repeated, whereas Example 4 is based on electrolytic treatment with high voltage and low voltage after repeating electrolytic treatment and liquid stirring with high voltage. This is an example in which electrolytic treatment was performed. When the surface quality was observed, the through hole formed in Example 4 was higher in smoothness and high quality than the through hole formed in Example 3. From this result, it is understood that the surface quality can be improved by combining “high voltage electrolysis treatment → low voltage electrolysis treatment” after the process of “high voltage electrolysis treatment → liquid stirring”.

  The present invention is applicable to various fields in which titanium-based metal materials such as electronic devices, optical devices, chemical devices, and device materials for implants for treatment and biological information measurement are used.

It is explanatory drawing which shows the outline of the manufacturing method of the titanium metal product of this invention. It is explanatory drawing of an electrolytic etching sample. The structure of an electrolytic etching apparatus is shown. 2 is a SEM photograph of a φ0.1 hole after treatment in Example 1. 7 is a SEM photograph of φ0.1 hole after treatment in Example 6.

Claims (10)

Applying a resist to the surface of the titanium-based metal material;
Exposing the resist through a photomask to form a pattern portion; and
Removing a part of the titanium-based metal material surface by removing the pattern portion or the resist other than the pattern portion; and
Forming a recess and / or a through hole by corroding the exposed surface;
A method for producing a titanium-based metal product having a recess and / or a through-hole, including a step of removing a resist on the surface of the titanium-based metal material,
Corrosion of the exposed surface with the titanium-based metal material as an anode, (a) a compound represented by the following general formula (I) , (b) alkali metal chloride and / or alkaline earth metal chloride , and (C) It consists only of a solvent not corresponding to the following general formula (I), which is optionally included, and when component (c) is included, 60% by mass of the total of 100% by mass of component (a) and component (c) The said manufacturing method characterized by performing the above by carrying out the electrolytic process by using the electrolytic etching liquid which a component (a) occupies as an electrolytic solution.
(In the formula, R is a hydrogen atom or a methyl group, and n is an integer in the range of 1 to 3). The manufacturing method according to claim 1, wherein the component (a) is at least one selected from the group consisting of ethylene glycol, diethylene glycol, and propylene glycol. The said component (b) is a manufacturing method of Claim 1 or 2 containing at least 1 type chosen from the group which consists of sodium chloride, lithium chloride, and potassium chloride. The said component (b) is a manufacturing method of any one of Claims 1-3 containing at least 1 type chosen from the group which consists of calcium chloride and strontium chloride. The said electrolytic treatment is a manufacturing method of any one of Claims 1-4 including stirring an electrolytic etching liquid and / or vibrating the said etching liquid and / or a metal material. The manufacturing method according to claim 5, wherein the agitation and / or vibration is performed while the electrolysis is temporarily stopped. 2. The electrolysis process includes performing a two-stage electrolysis process including a first electrolysis process and a second electrolysis process performed at an interelectrode voltage different from the interelectrode voltage in the first electrolysis process at least once. The manufacturing method of any one of -6. The manufacturing method according to claim 7, wherein the second electrolytic treatment is performed at an electrode voltage lower than an electrode voltage in the first electrolytic treatment. The manufacturing method according to claim 8, wherein the first electrolytic treatment is performed at an electrode voltage in a range of 15 to 40V. 10. The manufacturing method according to claim 8, wherein the second electrolytic treatment is performed at an electrode voltage in a range of 3 to 15V.