TWI735726B - Dye-containing alumite treated plasma indicator - Google Patents

Abstract

An object of the present invention is to avoid contamination derived from an ink composition in a chamber. A dye-containing alumite-treated plasma indicator containing a dye in pores formed by anodic oxidation treatment is provided as the solution.

Description

Plasma indicator containing pigment and treated with aluminum oxide skin

The present invention relates to a plasma indicator.

Various equipment and instruments used in hospitals, research institutes, etc., are sterilized for disinfection and sterilization. One of the sterilization treatments is known as plasma sterilization treatment.

Specifically, the plasma sterilization process generates plasma in a plasma-generating gas environment, and sterilization of various equipment, appliances, etc. by low-temperature gas plasma is advantageous in terms of low-temperature sterilization.

In addition, the plasma treatment is not only used for sterilization treatment, but also used for plasma dry etching in the manufacturing steps of semiconductor devices and plasma cleaning of the surface of processed objects such as electronic parts.

In general, plasma dry etching is to apply high-frequency power to electrodes arranged in a reaction chamber of a vacuum vessel, and plasma-generate the plasma introduced into the reaction chamber with gas to etch semiconductor wafers with high precision. In addition, plasma cleaning is to remove metal oxides, organic matter, burrs, etc. that have precipitated or adhered to the surface of the processed objects of electronic parts, etc., to improve adhesion or solder wettability, increase bonding strength, or improve The adhesion or wettability of the sealing resin.

As for the method of detecting the end point of these plasma treatments, it is known that as described in Patent Document 1, an ink composition containing a pigment, a specific surfactant, and a nonionic surfactant is coated on a substrate. Technology placed in a reaction chamber, etc.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2015-013982

The above method is excellent in that the plasma irradiation in the reaction chamber where the plasma treatment is performed can be detected simply and reliably, and the progress of the plasma treatment can be visually confirmed.

However, in the plasma treatment chamber, when the film formed by the ink composition is present, the pigment, surfactant, and optionally the color vehicle will also be treated by the plasma due to the conditions of the plasma treatment. , It is impossible to deny the possibility of some gasification.

Due to partial gasification, pollutants may be produced in the chamber where plasma processing is performed. Therefore, the articles to be processed must be protected from pollution caused by such pollutants.

In order to solve the above-mentioned problems, the inventors of the present invention conducted intensive research and found that a plasma indicator with a specific structure can solve the above-mentioned problems, and thus completed the present invention.

The details are as follows.

1. A plasma indicator that contains pigment and is treated with oxidized aluminum, which is formed by containing pigment in the pores formed by anodic oxidation treatment.

2. The plasma indicator containing pigment and treated with aluminum oxide as described in item 1, wherein the pigment is selected from the group consisting of anthraquinone pigments, methine pigments, azo pigments, phthalocyanine pigments, At least one of the group consisting of triphenylmethane-based coloring, food coloring, and dibenzopyran-based coloring.

3. The pigment-containing plasma indicator treated with aluminum oxide as described in item 1 or 2, wherein the pores are formed by sealing.

According to the present invention, by placing the indicator in the plasma environment in the plasma processing chamber, the indicator can be reliably changed or decolorized, so that it can correctly indicate that the plasma processing has been performed.

At this time, the discoloration/discoloration conditions of the indicator can be adjusted by the size of the pores or the degree of sealing treatment.

In addition, components other than pigments such as surfactants, especially organic compounds, do not exist, and the pigments do not exist on the surface of the substrate but in the pores. Therefore, the plasma treatment does not cause other than pigments. The gasification of the components, etc., can further reduce the probability of contamination of the plasma treatment object caused by this.

1‧‧‧Aluminum forming body

2‧‧‧Anodic oxidation treatment film

3‧‧‧Small holes

4‧‧‧Pigment

Figure 1 is a schematic diagram of the step of containing pigments in pores on the surface of an aluminum molded body.

The plasma indicator of the present invention is obtained by subjecting an aluminum substrate to an aluminizing process, forming pores in advance, and then including pigments in the pores, and then not performing or performing a sealing treatment.

Hereinafter, the manufacturing method of the plasma indicator of the present invention will be described.

[Oxygen skin aluminum treatment of substrate]

The substrate used in the present invention may be a material composed only of aluminum, but may also be a material generally called aluminum alloy (for example, Al-Mn series alloy, Al-Mg series alloy, Al-Mg-Si series alloy Etc.), as long as it is a material that forms pores by anodizing. In addition, the aluminum material itself may be alloyed with other metals and have been colored. Hereinafter, it is referred to as an aluminum molded body.

The shape of the substrate can be plate, rod, wire, foil, etc., and can also be a composite material with other materials (metal, plastic, adhesive, etc.). For example, it may be formed by forming an adhesive layer via a resin film layer on the back side of a plate-shaped or foil-shaped substrate. At this time, when using, the indicator can be fixed at any position. In addition, the aluminum forming system can be subjected to pre-treatments such as grinding, etching, and stain finish/gloss finish.

Before the anodizing treatment, the aluminum molded body is immersed in a sodium hydroxide aqueous solution for a predetermined period of time by a known means, for example, and washed with water for degreasing.

The aluminizing treatment is generally the same as the treatment for imparting corrosion resistance and decoration to the surface of the aluminum formed body (aluminum material), and it must be a treatment that can form pores on the anodized film.

The aluminum molded body is in electrical contact with the anode of the anodizing treatment device, and the anode and the cathode are immersed in the electrolyte together with the anode and the cathode, and an anodic oxidation coating film is formed on the aluminum molded body by energizing the anode and the cathode. . The energization is not limited to direct current, and may be other conventionally known methods such as alternating current or pulse waveform current.

The electrolyte used at this time is preferably a 3 to 30% by weight solution of an electrolyte containing at least any one of sulfuric acid, maleic acid, malonic acid, and oxalic acid. Although not particularly limited to these, in the case of silver that reflects the color of aluminum, sulfuric acid is preferred, and in the case of gold, oxalic acid is preferred. In addition, the electrolysis temperature is set to 0 to 40°C, the current density is set to 0.5 to 3.0 A/dm ² , and anodizing treatment is performed for 5 minutes to 1 hour.

In addition, at this time, by adding metal ions to the electrolyte, a silver colored oxide-coated aluminum treatment surface that does not reflect the color of aluminum can be obtained. For example, when copper ions are added, a green-colored aluminum oxide film is obtained.

The generated pores are, for example, as shown in Fig. 1(a), and are formed as pores 3. The pores 3 are long columnar spaces extending in the depth direction of the anodized film 2 formed on the surface of the aluminum molded body 1 . However, with respect to the surface of the aluminum molded body, it is not limited to those formed at right angles as shown in the figure, and may actually show irregular shapes such as bends and divergence. The diameter of the opening of the pore 3 can be arbitrarily adjusted by the anodizing treatment conditions, but in the present invention, the diameter of the opening of the anodized film formed according to the procedure is 5 to 300 nm. Preferably it is from 5 nm to 50 nm, more preferably from 8 to 50 nm. If it is larger than 300 nm, it is difficult to make the anodic oxidation treatment film into a uniform film, and it is difficult to obtain a porous film of less than 5 nm.

In addition, the length of the pores 3 is not particularly limited, but it is sufficient as long as it is the length necessary for the amount of pigment required for coloring to be sufficiently placed in the pores. Therefore, it is a length of 2 to 50 μm from the aluminum surface toward the thickness direction. It is preferably 3 to 40 μm, more preferably 3 to 20 μm.

After the colored oxide aluminum treatment or the uncolored oxide aluminum treatment, for the purpose of further forming a colored film, a secondary electrolytic treatment can be applied. The secondary electrolytic treatment is performed by immersing the aluminum formed body treated with corrugated aluminum in an aqueous solution containing metal ions to perform electrolytic treatment. For example, an aqueous solution containing nickel, silver, and copper plasma can be used, and coloring can be performed with a color derived from the metal reduced by the plasma.

Through the secondary electrolytic treatment, metal precipitation is generated from the bottom surface to the inner surface of the pores 3 formed on the surface of the colored or uncolored oxide-coated aluminum, and a colored film derived from the metal is formed.

The secondary electrolysis treatment is to immerse the aluminum oxide-treated aluminum in an electrolytic bath containing metal ions, use the oxide-layer aluminum-treated film as an electrode, and also impregnate another electrode, where the electrode makes an alternating current or pulse waveform The person who conducts electricity by energizing the current, etc.

By arbitrarily performing these treatments, you can choose from colored aluminum oxide-treated aluminum and uncolored aluminum oxide-treated aluminum, and you can choose whether to have secondary electrolysis treatment, so you can choose from a total of 4 types of oxygen The aluminum-coated substrate is selected and adopted as the aluminum-coated aluminum substrate before being colored with a pigment in the present invention.

By performing the colored oxide aluminum treatment and/or the secondary electrolysis treatment, the surface color of the treated aluminum substrate can be set to other colors such as green, yellow, and red, instead of silver reflecting the color of aluminum. As a result, the plasma treatment can be confirmed visually more easily than the color of the pigment.

[Pigment]

The pigment used in the present invention must be capable of dyeing aluminum anodized coating film, and be decolorized or discolored by plasma irradiation. Such pigments are selected from the group consisting of anthraquinone pigments, methine pigments, azo pigments, phthalocyanine pigments, triphenylmethane pigments, dibenzopyran pigments, and food colorings. At least one of them.

The anthraquinone-based dye is not limited as long as it uses anthraquinone as a basic skeleton, and well-known anthraquinone-based disperse dyes and the like can also be used. Among them, particularly preferred is an anthraquinone-based dye having an amino group. More preferably, it is an anthraquinone dye having at least one of a first amino group and a second amino group. In this case, each amine group may have two or more, and these may be the same kind or different from each other.

More specifically, for example, 1,4-diaminoanthraquinone (CIDisperse Violet 1), 1-amino-4-hydroxy-2-methylaminoanthraquinone (CIDisperse Red 4), 1- Amino-4-methylaminoanthraquinone (CIDisperse Violet 4), 1,4-diamino-2-methoxyanthraquinone (CIDisperse Red 11), 1-amino-2-methylanthracene Quinone (CIDisperse Orange 11), 1-amino-4-hydroxyanthraquinone (CIDisperse Red 15), 1,4,5,8-tetraaminoanthraquinone (CIDisperse Blue 1), 1,4-bis Amino-5-nitroanthraquinone (CIDisperse Violet 8), CIDisperse Blue 7, etc. (color index names in parentheses).

In addition, the well-known CISolvent Blue 14, CISolvent Blue 35, CISolvent Blue 63, CISolvent Violet 13, CISolvent Violet 14, CISolvent Red 52, CISolvent Red 114, CIVat Blue 21, CIVat Blue 30, CIVat Violet 15, CIVat Violet 17, CIVat Red 19, CIVat Red 28, CIacid Blue 23, CIacid Blue 80, CIacid Violet 43, CIacid Violet 48, CIacid Red 81, CIAcid Red 83, CIReactive Blue 4, CIReactive Blue 19, CIDisperse Blue 7, Sanodye Blue 2LW, Sanodye Blue G and other pigments.

These anthraquinone dyes can be used alone or in combination of two or more kinds. Furthermore, in the present invention, the detection sensitivity can also be controlled by changing the type (molecular structure, etc.) of these anthraquinone-based dyes.

The methine-based dye may be a dye having a methine group. Therefore, in the present invention, polymethine dyes, cyanine dyes, and the like are also included in methine dyes. These can be suitably adopted from known or commercially available methine-based dyes. Specifically, for example: CIBasic Red 12, CIB asic Red 13, CIBasic Red 14, CIBasic Red 15, CIBasic Red 27, CIBasic Red 35, CIBasic Red 36, CIBasic Red 37, CIBasic Red 45, CIBasic Red 48, CIBasic Yellow 11, CIBasic Yellow 12, CIBasic Yellow 13, CIBasic Yellow 14, CIBasic Yellow 21, CIBasic Yellow 22, CIBasic Yellow 23, CIBasic Yellow 24, CIBasic Violet 7, CIBasic Violet 15, CIBasic Violet 16, CIB asic Violet 20, CIBasic Violet 21, CIBasic Violet 39, CIBasic Blue 62, CIBasic Blue 63, Sanodye Yellow 3GL, etc. These may be one type or two or more types may be used in combination.

The azo dye system is not limited as long as it has an azo group -N=N- as a chromophore. For example, monoazo dyes, polyazo dyes, metal complex salt azo dyes, stilbene azo dyes, thiazole azo dyes, and the like can be mentioned. More specifically, if it is expressed by the color index name, for example: CISolvent Red 1, CISolvent Red 3, CISolvent Red 23, CIDisperse Red 13, CIDisperse Red 52, CIDisperse Violet 24, CIDisperse Blue 44 , CIDisperse Red 58, CIDisperse Red 88, CIDisperse Yellow 23, CIDisperse Orange 1, CIDisperse Orange 5, CIDisperse Red 167:1, CIacid Red 18, CIacid Yellow 23, Sanodure Fast Gold L, Sanodure Orange G, Sanodye Red GLW, Sanodal Red B3LW, Sanodure Bordeaux RL, Sanodure Violet CLW, Sanodure Green LWN, Sanodye Brown R, Sanodure Bronze 2LW, Sanodure Fast Bronze L, Sanodure Brown GSL, Sanodure Grey NL liquid, Sanodal Black 2LW, Sanodure Deep Black MLW, Sanodal Black GL Paste, Sanodure Fiery Red ML, Sanodye Golden Orange RLW, Sanodye Red RLW, etc. These may be one type or two or more types may be used in combination.

The phthalocyanine dye system is not limited as long as it is a dye having a phthalocyanine structure. For example, blue copper phthalocyanine, metal-free phthalocyanine showing more blue-green, green highly chlorinated phthalocyanine, low-chlorinated phthalocyanine showing more yellow-green (bromochlorinated copper phthalocyanine), and the like.

Specifically, for example, C.I.Direct Blue 86, C.I.Direct Blue 87, C.I.Basic Blue 140, C.I.Solvent Blue 70, Sanodal Turquoise PLW Liquid, etc. can be mentioned.

In addition to the above-mentioned general phthalocyanine pigments, at least one of zinc, iron, cobalt, nickel, lead, tin, manganese, magnesium, silicon, titanium, palladium, aluminum, iridium, platinum, and ruthenium can also be used as the central metal And these central metal coordinated with phthalocyanine compound, and the above-mentioned central metal is further bound with oxygen or chlorine in the state where it is coordinated with phthalocyanine compound, etc.

The triphenylmethane dye system is not limited as long as it is a dye having a triphenylmethane structure. Examples include: CIacid Blue 90, CIacid Green 16, CIacid Violet 49, CIBasic Red 9, CIBasic Blue 7, CIacid Violet 1, CIDirect Blue 41, CIMordant Blue 1, CIMordant Violet 1, CI Acid Blue 9 and so on. These triphenylmethane-based pigments may be used alone or in combination of two or more.

The dibenzopyran-based pigment system is not limited as long as it is a pigment having a dibenzopyran structure. For example, C.I.Acid Yellow 74, C.I.Acid Red 52, C.I.Acid Violet 30, C.I.Basic Red 1, C.I.Basic Violet 10, C.I.Mordant Red 27, C.I.Mordant Violet 25, etc. can be mentioned. These dibenzopyran-based dyes may be used singly or in combination of two or more.

Food coloring can be used in combination with Edible Red No. 2, Edible Red No. 3, Edible Red No. 102, Edible Red No. 104, Edible Red No. 105, Edible Red No. 106, Edible Yellow No. 4, Edible Yellow No. 5, Edible Green No. 3, Edible Blue No. 1, Edible Blue No. 2, etc.

In the present invention, dyes or pigments other than the above-mentioned dyes may be used in combination. In addition, it is also possible to use pigments (ALFAST RED MF-301B, TAC RED BRL (any of them are trade names)) that are not sure whether they are contained in any of the above. In particular, it may also contain pigment components that do not change color in a plasma environment (referred to as "non-color changing pigments"). In this way, the hue change from a certain color to other colors can be more clarified, and the recognition effect of the color change can be improved. The non-color changing pigments can use well-known pigments, such as the dyes shown under the trade names TAC BLACK-HG and Sanodal Gold 4N. The content of the non-color-changing pigment at this time can be appropriately set according to the type of the non-color-changing pigment and the like.

However, in order to be used as an indicator in the present invention, it must not be discolored or bleached during the normal period after being colored by the above-mentioned pigment to before use. However, according to the above-mentioned pigment, it is not discolored or bleached, and the coloring is stable over time. The sex is good.

[Application of pigments on the surface of colored or non-colored aluminum formed bodies after anodizing treatment, or on the surface of aluminum formed bodies further subjected to secondary electrolysis treatment]

After pores are formed on the surface of the aluminum molded body by the above-mentioned means, the pigment is embedded in the pores.

For this purpose, the pigment solution is prepared by dissolving the pigment in water or an organic solvent, and an aluminum molded body formed by forming pores by the means described above is immersed in the pigment solution.

The immersion conditions can be set to 2 to 30 minutes, the temperature is 30 to 70°C, and the pigment concentration in the pigment solution is set to 1g/1L to 20g/1L. Water washing/drying is performed after immersion.

With this treatment, as shown in Figure 1(b), the pigment 4 is introduced into the pores. The pigment tends to be fixed as it is closer to the opening of the pore, and a smaller amount is fixed toward the bottom of the pore. Depending on the situation thereafter, a plugging process may be performed to narrow the hole opening on the upper part of the pore.

[The structure of the indicator]

The indicator of the present invention has, for example, a plate-like or foil-like appearance of any size. At least a part of one surface of the plate-like shape forms a part colored by a dye. For example, it can be set as the following surface: the central part of one surface of the rectangular plate-shaped substrate is colored with a dye into a circle, and the surrounding area is not colored with a dye, and then colored or non-colored oxide skin aluminum treatment, and further secondary as needed Surface formed by electrolytic treatment.

However, for example, when dyeing into a circle, it is necessary to provide a masking member that only leaves the circle part and hides other parts on the surface of the substrate before the dyeing step.

The masking member can be removed after the dyeing step, or it can be used as a part of the indicator without removing the remaining state. When used in a residual state, use a resin layer with plasma resistance that does not decompose even in the plasma processing environment in a way that does not contaminate the plasma processing device as much as possible, or use another metal The film is concealed. Moreover, when using it as an indicator without removing the masking member, in order to confirm the degree of discoloration, it may be necessary to remove the dye adhering to the surface of the masking member as the case may be.

When used as an indicator without removing the masking member, in order to improve the visibility of the indicator, it is preferable to use both the color relative to the state after dyeing and the color of the substrate after the dye is decomposed and removed. The color of the color difference can be fully confirmed, and the masking member is colored with a material that does not change color due to plasma.

[Use of indicator]

The indicator of the present invention can be applied to any treatment as long as it is a plasma treatment using a gas for plasma generation. That is, it can be applied to both the reduced pressure plasma treatment and the atmospheric pressure plasma treatment.

Specific examples of reduced-pressure plasma treatment include, for example, the use of cleaning and surface modification of flat panel displays such as liquid crystal displays; and the use of film formation, ashing, cleaning, and surface modification in the semiconductor manufacturing process. ; Uses for cleaning and surface modification of packaging substrates or printed circuit boards; sterilization for medical devices, etc.; cleaning and surface modification for packaging parts, etc.

In addition, specific examples of atmospheric piezoelectric paste treatment include, for example, applications such as film formation, ashing, cleaning, and surface modification of flat panel displays such as liquid crystal displays; cleaning and surface modification of packaging substrates or printed circuit boards, etc. Uses; surface modification of automobile, aircraft parts, etc., disinfection, sterilization, sterilization, treatment, etc. in the medical field (dental or surgical).

The gas for generating plasma under reduced pressure is not limited as long as it can generate plasma by applying AC voltage, pulse voltage, high frequency, microwave, etc. under reduced pressure. Examples include oxygen, nitrogen, hydrogen, chlorine, Hydrogen peroxide, helium, argon, silane, ammonia, sulfur bromide, water vapor, nitrous oxide, tetraethoxysilane, carbon tetrafluoride, trifluoromethane, carbon tetrachloride, silicon tetrachloride, hexafluoride Sulfur, titanium tetrachloride, dichlorosilane, trimethylgallium, trimethylindium, trimethylaluminum, etc. These reduced-pressure plasma generation gases can be used alone or in a mixture of two or more kinds.

The gas for generating atmospheric piezoelectric plasma is not limited as long as it can generate plasma by applying AC voltage, pulse voltage, high frequency, microwave, etc. under atmospheric pressure, for example: oxygen, nitrogen, hydrogen, argon, helium, air, etc. . These atmospheric pressure generating gases can be used singly or in mixture of two or more kinds.

When using the indicator of the present invention, specifically, in a plasma processing device using plasma generating gas (specifically, by applying AC voltage, pulse voltage, high frequency in an environment containing plasma generating gas The indicator of the present invention can be placed in the inside of the device (device for plasma processing) or the processed object contained in the microwave, etc. to generate plasma, and exposed to the plasma processing environment. At this time, the predetermined plasma treatment that has been performed can be detected by changing the color of the indicator placed in the device.

The indicator of the present invention can be directly used as an indicator card. At this time, if the shape of the color-changing layer is set to a well-known barcode shape, it is set to be a condition that can be read by a barcode reader at the stage after the predetermined plasma treatment is completed (the degree of color change), then the barcode can be used Unified management of the completion of plasma treatment and the logistics management of subsequent plasma treatments. The present invention can be applied to indicators, plasma processing management methods, and logistics management methods that use such applications.

The indicator of the present invention can be stored in the inner surface of a gas-permeable package.

The gas-permeable package is preferably a package that can be directly plasma-processed in a state where the object to be processed can be enclosed therein. This system can be used as a package (bag) for plasma treatment, which is known or commercially available. For example, a package made of polyethylene-based XVI (polyethylene synthetic paper) can be suitably used. After the object to be processed is placed in the package and the opening is sealed by heat sealing or the like, the entire package can be processed in a plasma processing apparatus.

In addition to these circumstances, it can also be arranged on the inner surface of the above-mentioned package. The method of disposition is not limited. In addition to adhesives, heat sealing and other methods, the indicator of the present invention can also be directly coated or printed on the inner surface of the package to form the indicator. In addition, when the coating or printing is performed as described above, the indicator may be formed in the manufacturing stage of the package.

Next, in order to allow the indicator to be confirmed from the outside, it is preferable to provide a transparent window in a part of the package. For example, as long as the packaging body is made of a transparent sheet and the aforementioned polyethylene synthetic paper, and an indicator can be provided at a position that can be recognized through the transparent sheet.

When plasma processing is performed using the package containing the indicator of the present invention, for example, a method having the following steps can be used: the step of filling the package with the processed object, and the step of sealing the package filled with the processed object , And the step of placing the package in a plasma processing environment. More specifically, after the object to be processed is placed in the package, it is sealed according to a known method such as heat sealing. Then, the entire package together with the package is placed in a plasma processing environment. For example, it is disposed in the processing chamber of a known or commercially available plasma processing device for processing. After the treatment is completed, the entire package is taken out, and it can be stored directly in the package until use. At this time, the plasma treatment is preferably to place the package in the plasma treatment environment until the discoloration layer of the indicator changes color.

[Example]

[Making of indicator]

(Degreasing step)

Prepare JIS A1050 aluminum molded body, immerse this in 50°C, 6.5% sodium hydroxide aqueous solution for 3 minutes, wash with water, and further immerse in 10% nitric acid at room temperature for 3 minutes and neutralize, wash with ion exchange water for degreasing .

(Steps of anodizing treatment)

Prepare 15% sulfuric acid as an electrolyte, immerse the degreased aluminum molded body in the electrolyte, and conduct electrolysis by a DC constant current electrolysis method. A carbon plate is used as the opposite electrode.

During electrolysis, the current density is 1.0A/dm ² , the bath temperature is 20°C, and the electrolysis time is 40 minutes.

(Dyeing step)

The anodized aluminum molded body was immersed in a dye solution with a dye concentration of 5 g/L, a pH of 5.5, and a temperature of 50°C obtained by using the dyes shown in Table 1 for 10 minutes. The density of the color caused by dyeing can be adjusted by changing the dye concentration, pH, temperature and time during immersion.

In addition, the electrolysis conditions in the anodizing step can be changed to adjust the color density due to dyeing.

[High Frequency Plasma Treatment]

The indicator made by the above steps is set in the plasma processing device.

Thereafter, under the following conditions, only O ₂ gas and a _{mixed gas of O 2} gas and CF ₄ gas were used to generate plasma, and the plasma was detected by an indicator.

(High frequency O ₂ plasma treatment conditions)

Using a parallel plate type high-frequency plasma device BP-1 (manufactured by Samco Co., Ltd.), O ₂ gas was supplied at 10ml/min, and the distance between electrodes was set to 50mm under a pressure of 100Pa, and the process was performed at 100W for 30 minutes. Plasma processing.

(Microwave O ₂ Plasma Treatment Conditions)

Using a microwave plasma device (TMP-0063 (manufactured by Toshiba Co., Ltd.)), O ₂ gas was supplied with 1 kW of electricity under a pressure of 2.5 Torr. The initial decompression was 0.95 Torr and the initial temperature was 30 to 33°C. Perform plasma treatment for 30 minutes.

(High frequency O ₂ /CF ₄ plasma treatment conditions)

Using a parallel plate type high-frequency plasma device BP-1 (manufactured by Samco Co., Ltd.), while _{supplying O 2} gas at 10 ml/min and CF ₄ gas at 5 ml/min, the distance between electrodes is set at a pressure of 100 Pa. The diameter is 50mm, and plasma treatment is performed at 100W for 30 minutes.

[Evaluation]

(Color change during plasma detection)

The color before and after the detection plasma was confirmed visually.

(Color changing performance)

Line up the indicators before and after the plasma detection step to visually confirm the degree of discoloration.

Discoloration can be confirmed visually ‧‧‧‧○

Unable to visually confirm the discoloration‧‧‧×

(Changes in color change performance over time)

After leaving the indicator at 50°C for 4 weeks, the above-mentioned discoloration performance was evaluated.

Can confirm the color change performance unchanged from the initial stage‧‧‧‧‧‧‧○

The discoloration performance has decreased since the initial stage, but the discoloration can be confirmed ‧‧‧△

Unable to confirm the change over time‧‧‧‧‧‧‧‧‧‧‧‧-

In Examples 1 to 19, substrates treated with various oxides of aluminum and dyed with various dyes were used for plasma testing.

In Comparative Examples 1 to 5, those that have undergone various aluminizing treatments but are not dyed with dyes or dyed with inorganic salt dyes are used for plasma treatment.

According to Examples 1 to 19 of Table 1 above, when aluminum plates dyed with dyes are used, the discoloration of plasma caused by high frequency and microwave can be detected.

On the other hand, if it is Comparative Examples 1 to 5 after dyeing with no dye or dyeing with an inorganic salt dye, there is no discoloration.

In addition, in the case of Examples 1 to 19, there is no trace of any substance released from the aluminum formed body into the plasma environment.

The substrates of Examples 1 to 19 can be provided with appropriate patterns by using commercially available masking materials before the aluminizing treatment or in the middle of each step of coloring, which can improve the design of the indicator. When Topresist 1000 manufactured by Okuno Pharmaceutical Co., Ltd. is used as a masking material, and if the masking material is not removed and used as a part of the indicator, the adverse effects due to plasma treatment are not seen.

1‧‧‧Aluminum forming body

2‧‧‧Anodic oxidation treatment film

3‧‧‧Small holes

4‧‧‧Pigment

Claims (2)

A plasma indicator that contains pigment and is treated with oxidized aluminum, which contains pigment in the pores formed by anodizing treatment, wherein the pigment is selected from the group consisting of anthraquinone pigments, methine pigments, At least one of the group consisting of metal-free azo dyes, phthalocyanine dyes, triphenylmethane dyes, food dyes, and dibenzopyran dyes. As described in item 1 of the scope of patent application, the pigment-containing plasma indicator treated with aluminum oxide, wherein the pores are formed by sealing.

Images