JP2000087238A - Formation of multicolor film and wear resistant and corrosion resistant multicolor member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide non-polluting surface treating technology imparting performance such as wear resistance, corrosion resistance equal to or above the conventional ones and the high visibility of the division in the case of being used for measuring instrument such as calipers. SOLUTION: As to this multicolor film forming method, films different in colors are piles to coat by >=2 layers by an ion plating method, and a part of the film as the upper layer is removed by an etching method or a laser marking method. Namely, from developable colors, the base color and top color are selected to form films of the upper and lower two layers, then, the upper layer film is removed by an optional pattern, and, a member having multicolor of the color in the lower layer film and the color in the upper layer film is formed. Particularly, the base material is subjected to Cr metal bombard treatment, the coated one is piled with a TiAlN film by an ion plating method with a TiAl sintered target in a gaseous N2 atmosphere, it is coated with a CrN film by an ion plating method with a Cr metallic target in a gaseous N2, atmosphere, and a part of the CrN film in the upper layer is removed by an etching or laser marking method. The film thickness of the CrN film is preferably controlled to 1 to 10 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment technique, and more particularly to a wear-resistant and corrosion-resistant member having a multicolor coating formed on a member used for a measuring instrument such as a caliper and having high visibility of a scale. The present invention relates to a method for producing a multicolored film to be obtained.

[0002]

2. Description of the Related Art Generally, a member constituting a caliper used as a measuring instrument is formed of SUS420J2 as a base material, and has a thickness of 10 μm in order to improve abrasion resistance and corrosion resistance. And wet chrome plating. Furthermore, the scale for indicating the measured value is obtained by applying heat by a laser marking method, vaporizing and removing a part of the chromium plating film, and oxidizing a part of the chromium plating film to change it to chromium oxide. Color black,
It has been processed into a member having a high visibility scale.

However, as a recent trend, a low-pollution surface treatment technique in consideration of the natural environment is desired, and a wet chromium plating treatment, which frequently uses harmful chemicals, is contrary thereto.

[0004] Therefore, there has been a demand for a surface treatment technique which can replace wet chromium plating, has low pollution, has excellent abrasion resistance, has excellent corrosion resistance to chemicals, and has high visibility of a developed color.

[0005]

SUMMARY OF THE INVENTION The present invention replaces the wet chromium plating, which has been widely used in the past, in the case where it is used in a measuring instrument such as a vernier caliper with the same or better performance in wear resistance and corrosion resistance. It is an object of the present invention to provide a pollution-free surface treatment technology with high visibility of the scale.

[0006]

According to the present invention, there is provided a method for forming a multicolored film, comprising coating two or more layers of different colors by ion plating, and partially etching the upper layer by etching or laser marking. Is removed.

[0007] In particular, the Cr metal bombardment to the substrate, on top coated with TiAlN coating by ion plating method according TiAl sintered target of N ₂ gas atmosphere, ions by Cr metal target of N ₂ gas atmosphere A CrN film is coated by a plating method, and a part of the upper CrN film is removed by an etching method or a laser marking method. The thickness of the CrN coating is preferably 1 to 10 μm.

[0008] Alternatively, the Ti metal bombardment to the substrate, on top coated with TiAlN coating by ion plating method according TiAl sintered target of N ₂ gas atmosphere, ions by Ti metal target of N ₂ gas atmosphere A TiN film is coated by a plating method, and a part of the upper TiN film is removed by an etching method or a laser marking method. The TiN film preferably has a thickness of 1 to 10 μm.

In the ion plating method using these TiAl sintered targets, the target ratio is 5%.
It is preferable that the bias voltage is 0 to 50 V and the thickness of the TiAlN film is 1 to 6 μm using a TiAl sintered target of 0:50 to 30:70.

[0010] Further, as a method of producing a multicolored film for forming a similar color by using a film having a composition different from that described above or a film having a different combination of upper and lower layers, TiCN, TiAl
N, LaN, or MnN is coated with a black ceramic coating on top of which TiN, ZrN,
A gold ceramic coating made of any of YC ₂ is coated, and a part of the upper gold ceramic coating is removed by an etching method or a laser marking method.

Further, TiCN, TiAlN, La
N, superimposed over coated with black ceramic coating consisting of either _{MnN, CrN, Cr 2 N,} Ti
A chrome ceramic coating made of either C or ZrC is coated, and a part of the upper chrome ceramic coating is removed by etching or laser marking.

A scale is provided on a member which is a measuring instrument by these multicolor coating forming methods to obtain a wear-resistant and corrosion-resistant member. Further, the wear-resistant and corrosion-resistant member of the present invention can be widely applied as various parts.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The ion plating method used in the present invention has a performance alternative to the wet chrome plating method,
As a surface treatment technology (surface modification technology) with low pollution and high mass productivity in consideration of the natural environment, it belongs to a ceramic hard coating generation technology by a dry method. Ceramic hard coatings produced by the dry method are excellent in improving surface hardness, abrasion resistance and corrosion resistance, and are used in various fields such as cutting tools, dies, cutting tools, decorative parts, mechanical parts and electric parts. Widely applied.

An ion plating method is one of the methods that can produce the ceramic hard coating at a relatively low temperature (200 to 500 ° C.). In the ion plating method,
For example, a black ceramic coating is formed on the first layer on the base side of a member constituting a caliper, and a ceramic coating of the same color as the color formed by wet chrome plating is formed on the first layer as a second layer. Once formed, a portion of the chrome-colored ceramic coating of the second layer is evaporated or removed by laser marking or etching. By making the black ceramic coating of the first layer visible in this way, the invention of a pollution-free multicolor coating generation method replacing the conventional wet chrome plating method has been reached.

The ion plating method is a method of increasing kinetic energy by ionizing evaporated particles when forming a film in a vacuum, and is extremely excellent in that the characteristics, adhesion and reactivity of the film can be enhanced.

The ion plating method includes a DC discharge method, a high-frequency excitation method, an activated reactive vapor deposition method, a hollow cathode method, a cathode arc method, and the like, depending on the ionization method.

In the present invention, the cathodic arc ion plating method is particularly preferred. In this method, a metal target, which is an evaporation source, is used as a cathode, and a chamber is used as an anode. An arc discharge is generated between the two, ionizing the metal vapor, and the reaction gas is also ionized by collision with the ions. A film is formed by laminating on the surface of the member. For example, when a nitride film is formed, a reaction gas containing nitrogen atoms is introduced into the chamber. The cathodic arc ion plating method has a high ionization rate of metal vapor and multiple evaporation sources can be installed at the top, bottom, left and right inside the chamber. Suitable for forming a film having a uniform thickness, particularly for forming a hard film.

As the substrate in the present invention, a substrate of almost any material can be used if the heat treatment temperature of the substrate is 200 ° C. or higher. In the case of a member whose tempering temperature is as low as 200 ° C. or less, such as SUS420J2, it is necessary to keep the coating temperature from exceeding 200 ° C. for that reason,
It is desirable to control the film forming conditions while measuring the temperature of the member with an infrared radiation thermometer.

Further, for example, the material of the member used for the caliper is SUS420J2 and the tempering temperature is around 200 ° C., so that it is necessary to coat at a low temperature. In order to perform such low-temperature coating, it is preferable to perform metal bombarding for a certain period of time, adjust the current, and monitor the temperature of the member being coated with an infrared thermometer.

In order to form a ceramic coating having a different color, a known ion plating method is used. For example, in the case of two colors, two different targets are set, and a gas is selected according to a compound to be produced. What is necessary is just to flow into a vacuum chamber.

As colors that can be formed, for example, films having different compositions can be considered for forming the following colors, and the formation of each film is different from the target used in the evaporation source and the atmosphere.

For a chromium or gray color, a CrN film which forms the target as Cr and the atmosphere as N ₂ ,
The target is Cr, the atmosphere is N ₂ , the Cr ₂ N film is formed under the same conditions as above, and the target is Ti.
TiC film generated as C ₂ H ₂ + Ar or CH ₄ + Ar as an atmosphere, Zr as a target, and Z generated as an atmosphere as C ₂ H ₂ + Ar or CH ₄ + Ar
Select one of the rC coatings.

For purple and black colors, the target is Ti
The atmosphere is C ₂ H ₂ + N ₂ + Ar or CH ₄ + N
TiCN film generated as ₂ + Ar, target is T
TiAlN generated as iAl and atmosphere as N ₂
One of a LaN film that generates a film and a target of La and an atmosphere of N ₂ , and a MnN film that generates a target of Mn and an atmosphere of N ₂ is selected.

[0024] The gold color, a target as Ti, TiN coating film that produces the atmosphere as N _2, a target as Zr, ZrN coatings to generate the atmosphere as N _2, a target as Y, the atmosphere C ₂ H ₂ + Ar or YC ₂ coating generated as CH ₄ + Ar is selected.

In order to increase the visibility and decorativeness of a multicolor, a base color and a top ground color are selected from the colors that can be formed to form upper and lower two-layer coatings. If removed in a pattern, the color of the lower layer film becomes prominent and the color of the upper layer film becomes a multicolored member.

As a method of forming an arbitrary pattern,
An etching method that dissolves the upper layer film with a chemical using a mask,
A laser marking method for removing the upper layer film by vaporizing the outermost surface with a laser is known, but a laser marking method is desirable in consideration of mass productivity.

When a black color is used as the base color and a chrome color is used as the top color, a TiAlN film which is easy to prepare as a black film, has high film hardness, and has high heat resistance is desirable.

That is, the TiAl target is evaporated and reacted with nitrogen gas to form a TiAlN film. The target ratio of TiAl is 50:50 to 30: 7
The bias voltage is 0 to 50 V, with the range of 0 as the film forming condition.
In this case, black with high visibility can be developed. Further, since the internal stress of the TiAlN film is high, if the film is thickened, the film may peel off from the base material. Therefore, the film thickness is preferably 1 to 6 μm in consideration of wear resistance.

As the chromium coating, a CrN coating which is easy to manufacture and has excellent wear resistance and corrosion resistance is desirable.

That is, the Cr metal target is evaporated and reacted with nitrogen gas to form a CrN coating. C
The thickness of the rN coating is preferably 1 to 10 μm. 1μ thickness
If the thickness is less than 10 m, sufficient abrasion resistance and corrosion resistance cannot be obtained and 10
When the thickness is more than μm, the dimensional accuracy is deteriorated and the cost is increased.

When it is desired to give a gold color to the underlayer or the upper layer, a TiN film is desirable from the viewpoint of ease of film formation and high film performance. The Ti metal target is evaporated and reacted with nitrogen gas to produce a TiN coating. The thickness of the TiN film is preferably 1 to 10 μm. If the thickness is less than 1 μm, sufficient abrasion resistance and corrosion resistance cannot be obtained. If the thickness is more than 10 μm, dimensional accuracy deteriorates, coating time becomes longer, mass productivity decreases, and cost increases.

In the present invention, laser processing is suitable in consideration of the high degree of freedom of the production pattern and mass productivity. There are various types of laser oscillators depending on the laser medium and the oscillation method, but a fixed laser using an optical crystal as the laser medium is preferable because of its small size, controllability, and workability. Among solid-state lasers, it is desirable to use a YAG laser that is widely used in the industry and has many products.

The YAG laser is an acronym for yttrium, aluminum and garnet, and is used as a laser medium by doping neodymium into a crystal composed of these, and is called an Nd: YAG laser and has an oscillation wavelength. Is 1.064 μm.

The oscillation mode of the YAG laser is a continuous wave (C
W) Oscillation, pulse oscillation, and oscillation (Q-switch oscillation) in which a continuous wave is pulsed using an ultrasonic modulation element. CW
The oscillation is continuously excited by the light of the arc lamp to emit a continuous wave. The pulse oscillation is excited by a flash lamp filled with xenon gas. The Q-switch oscillation is the A.S. O. An element (Acoustic-Optic Element) is inserted, and CW oscillation is pulsed.

Among them, as a method of oscillating a YAG laser suitable for the present invention, the price of a lamp, low output, high workability, and high scanning performance in order to irradiate a laser beam onto an arbitrary pattern are considered. From, YAG (Q switch oscillation)
It is desirable to use a laser.

In order to form a pattern with two colors, it is necessary to instantaneously vaporize the coating on the outermost surface so that the lower coating does not undergo extreme discoloration due to the heat of the laser. Processing conditions are determined by laser output, oscillation frequency, scanning speed for drawing a pattern, and laser beam diameter. If the laser output is too low or the scanning speed is too high, the pattern cannot be clearly formed, or the color of the underlayer film becomes faint.

The laser conditions include the melting point of the coating, the vaporization temperature,
It is determined by film thickness, work speed, and visibility. 10 μm thick
In the following nitride films, the laser output is set to 90 to 150 W, and the scanning speed is set to 120 to 200 nm / sec.
In the pattern described above, only the upper layer coating can be vaporized, and a pattern with high visibility can be formed.

(Example 1) SUS is used as a member for forming a two-color coating in which the outermost surface is chrome and the scale is black.
A caliper made of 420J2 and having a total length of 230 mm was used. This material has a tempering temperature of 200 ° C and a hardness of HR
C52. For the surface finish, honing processing of # 220 to # 320 is applied for the purpose of preventing reflection. After this member was ultrasonically cleaned with ethanol, it was set in a chamber of a cathode arc ion plating apparatus. For the ion plating device, a Cr metal target and TiAl
(50%: 50%) A sintered target was provided.

The vacuum chamber was evacuated to 2 × 10 ⁻⁵ Torr or less. Subsequently, a -800 V bias voltage was applied, and a chromium metal bombardment treatment was performed so that the base material did not exceed 200 ° C. Next, N ₂ gas is supplied for 30 mTo.
rr, a bias voltage of -50 V
The 1N film was coated to a thickness of 4 μm. The temperature of the coating was measured with an infrared radiation thermometer so that the base material would not be dull, and the current value was adjusted so that a film could be formed at 190 ° C. After the film formation, the N ₂ gas is again supplied with 50 mTorr.
r, and a CrN film was coated to a thickness of 2 μm at a bias voltage of −300 V. Also at this time, the film formation temperature was set not to exceed 190 ° C.

The calipers on which the two-layer coating was formed in this manner were engraved by laser marking. The laser used was a YAG laser marking device.

Laser power 120 W, frequency 44 kHz
Processed under the conditions of z and scanning speed of 200 mm / sec, the outermost surface is a chromium color of CrN, and light black TiA
1N color was obtained. The coating performance after the laser marking was 704 HV in hardness, which exceeded the hardness of 613 HV in the case of wet chrome plating. Abrasion resistance was tested by scratching the scale area with a fingernail and rubbing with a sand eraser, and was equivalent to the wet chrome plating method.

(Example 2) SUS is used as a member for forming a two-color film in which the outermost surface is colored chrome and the scale is black.
A caliper made of 420J2 and having a total length of 230 mm was used. This material has a tempering temperature of 200 ° C and a hardness of HR
C52. For the surface finish, honing processing of # 220 to # 320 is applied for the purpose of preventing reflection. After this member was ultrasonically cleaned with ethanol, it was set in a chamber of a cathode arc ion plating apparatus. For the ion plating device, a Cr metal target and TiAl
(40%: 60%) A sintered target was provided.

The vacuum chamber was evacuated to 2 × 10 ⁻⁵ Torr or less. Subsequently, a -800 V bias voltage was applied, and a chromium metal bombardment treatment was performed so that the base material did not exceed 200 ° C. Next, N ₂ gas is supplied for 30 mTo.
rr, a bias voltage of -50 V
The 1N film was coated to a thickness of 3 μm. The current value was adjusted so that the temperature of the coating did not exceed 190 ° C. while measuring with an infrared radiation thermometer so that the base material would not be dulled. After the film formation is completed, N ₂ gas is again supplied at 50 mTorr.
, And a CrN film was coated to a thickness of 8 μm at a bias voltage of −300 V. Also at this time, the film formation temperature was set not to exceed 190 ° C.

The calipers on which the two-layer coating was formed in this manner were engraved by laser marking. The laser used was a YAG laser marking device.

Laser output: 120 W, frequency: 44 kHz
Processed under the conditions of z and scanning speed of 200 mm / sec, the outermost surface is a chromium color of CrN, and light black TiA
1N color was obtained. The coating performance after the laser marking was 693 HV in hardness, which exceeded the hardness of 613 HV in the wet chrome plating method. Abrasion resistance was tested by scratching the scale area with a fingernail and rubbing with a sand eraser, and was equivalent to the wet chrome plating method.

(Example 3) SUS42 was used as a member for forming a two-color coating in which the outermost surface was gold and the scale was black.
A caliper made of 0J2 and having a total length of 230 mm was used.
This material has a tempering temperature of 200 ° C and a hardness of HRC5
2. Surface finish is for anti-reflection and appearance,
Honing processing of # 220 to # 320 is performed. After this member was ultrasonically cleaned with ethanol, it was set in a chamber of a cathode arc ion plating apparatus. For the ion plating apparatus, a Ti metal target and a TiAl (40
%: 60%) A sintered target was provided.

The vacuum chamber was evacuated to 2 × 10 ⁻⁵ Torr or less. Subsequently, a -800 V bias voltage was applied, and a chromium metal bombardment treatment was performed so that the base material did not exceed 200 ° C. Next, N ₂ gas is supplied for 30 mTo.
rr, a bias voltage of -50 V
The 1N film was coated to a thickness of 4 μm. The current value was adjusted so that the temperature of the coating did not exceed 190 ° C. while measuring with an infrared radiation thermometer so that the base material would not be dulled. After the film formation is completed, N ₂ gas is again supplied at 50 mTorr.
, And a CrN film was coated to a thickness of 2 μm at a bias voltage of −300 V. Also at this time, the film formation temperature was set not to exceed 190 ° C.

The calipers on which the two-layer coating was formed in this manner were engraved with a scale by a laser marking method. The laser used was a YAG laser marking device.

Laser output: 120 W, frequency: 44 kHz
Processed under the conditions of z and scanning speed of 200 mm / sec, the outermost surface is gold of TiN, and the scale is pale black TiAlN
I got the color. Regarding the film performance after the completion of the laser marking, the hardness was 704 HV. Abrasion resistance was tested by scratching the scale with a fingernail and rubbing with a sand eraser, and was equivalent to the wet chrome plating method.

Further, a scale was engraved on the caliper formed with the two-layer coating by a laser marking method having different specifications. The laser used was a YAG laser marking device.

Laser output 100 W, frequency 44 kHz
z, the scanning speed is 180 mm / sec, the outermost surface is gold of TiN, and the scale is pale black TiAlN
I got the color. Regarding the film performance after the completion of the laser marking, the hardness was 804 HV. Abrasion resistance was tested by scratching the scale area with a fingernail and rubbing with a sand eraser, and was equivalent to the wet chrome plating method.

(Example 4) SUS42 was used as a member for forming a two-color film in which the outermost surface was black and the scale was gold.
A caliper made of 0J2 and having a total length of 230 mm was used.
This material has a tempering temperature of 200 ° C and a hardness of HRC5
2. Surface finish is for anti-reflection and appearance,
Honing processing of # 220 to # 320 is performed. After this member was ultrasonically cleaned with ethanol, it was set in a chamber of a cathode arc ion plating apparatus. For the ion plating apparatus, a Ti metal target and a TiAl (40
%: 60%) A sintered target was provided.

The vacuum chamber was evacuated to 2 × 10 ⁻⁵ Torr or less. Subsequently, a bias voltage of -800 V was applied, and titanium metal bombardment was performed so that the base material did not exceed 220 ° C. Next, N ₂ gas is supplied for 30 mTo.
rr, a bias voltage of -50 V
The 1N film was coated to a thickness of 4 μm. The current value was adjusted so that the temperature of the coating did not exceed 190 ° C. while measuring with an infrared radiation thermometer so that the base material would not be dulled. After the film formation is completed, N ₂ gas is again supplied at 50 mTorr.
And a CrN film was coated to a thickness of 2 μm at a bias voltage of −300 V. Also at this time, the film formation temperature was set not to exceed 190 ° C.

In this way, the calipers formed with the two-layer coating were marked with laser markings. The laser used was a YAG laser marking device.

Laser output 140 W, frequency 44 kHz
Processing was performed under the conditions of z and a scanning speed of 180 mm / sec, and the outermost surface was black of TiAlN, and golden TiN was able to be displayed on the scale. Regarding the film performance after the completion of the laser marking, the hardness was 630 HV. Abrasion resistance was tested by scratching the scale area with a fingernail and rubbing with a sand eraser, and was equivalent to the wet chrome plating method.

(Comparative Example) As a comparative example, a manufacturing method according to a conventional technique was performed. The caliper member with a total length of 230 mm is S
Made of US420J2, tempering temperature is 200 ℃,
The hardness is HRC52. For the surface finish, honing processing of # 220 to # 320 is applied for the purpose of preventing reflection. A film having a thickness of 10 μm was formed thereon by a wet chrome plating method. The surface hardness was as low as 612 HV.

[0057]

According to the method of the present invention, a non-polluting surface treatment technique which has the same or better performance in surface hardness and the like and high visibility of the scale is used instead of the wet chromium plating method which has been widely used in the past. Can be provided.

Claims (12)

[Claims] 1. A method for producing a multicolored film, comprising coating two or more layers of different colors by ion plating, and removing part of the upper layer by etching or laser marking. 2. The substrate is subjected to a Cr metal bombardment treatment,
On top coated with TiAlN coating by ion plating method according TiAl sintered target of N ₂ gas atmosphere, coating the CrN film by ion plating method using Cr metal target of N ₂ gas atmosphere, etching or laser marking A method for forming a multicolored film by removing a part of the upper CrN film by a method. 3. The film thickness of the CrN film is 1 to 10 μm.
The method according to claim 2, wherein: 4. The substrate is subjected to Ti metal bombardment treatment,
On top coated with TiAlN coating by ion plating method according TiAl sintered target of N ₂ gas atmosphere, coated with TiN coating in an ion plating method using Ti metal target of N ₂ gas atmosphere, etching or laser marking A method of forming a multicolored film by removing a part of an upper TiN film by a method. 5. The TiN film has a thickness of 1 to 10 μm.
The method according to claim 4, wherein: 6. An ion plating method using the TiAl sintered target, wherein the target ratio is 50:50 to
The method for producing a multicolor coating according to any one of claims 2 to 5, wherein a 30:70 TiAl sintered target is used. 7. The method for producing a multicolor film according to claim 2, wherein the ion plating method using the TiAl sintered target has a bias voltage of 0 to 50 V. 8. The TiAlN film has a thickness of 1 to 6 μm.
The method for producing a multicolored film according to any one of claims 2 to 7, wherein m is m. 9. The method according to claim 1, wherein the base material is TiCN, TiAlN, LaN,
On top coated a black ceramic coating consisting of either MnN, TiN, ZrN, coated gold ceramic coating consisting of either YC _2, part of the upper gold ceramic coating by etching or laser marking method A method for producing a multicolored film that removes carbon. 10. A substrate comprising TiCN, TiAlN, La
N, superimposed over coated with black ceramic coating consisting of either _{MnN, CrN, Cr 2 N,} Ti
A method of forming a multicolor film, in which a chromium ceramic film made of either C or ZrC is coated and a part of the upper chromium ceramic film is removed by an etching method or a laser marking method. 11. An abrasion-resistant and corrosion-resistant multicolored member, wherein a multicolored film is formed on a surface by the method for producing a multicolored film according to any one of claims 1 to 10. 12. A wear-resistant and corrosion-resistant multicolored member, wherein a scale is provided on a base material as a measuring device by the method for producing a multicolored film according to any one of claims 1 to 10.