JP2013098196A - Ink composition for detection of plasma processing, and indicator for detection of plasma processing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink composition which eliminates the need for a large-scale device, and which allows the detection of completion of plasma processing on each object to be processed, and to provide an indicator with the ink composition.SOLUTION: The ink composition for detection of plasma processing comprises 1) at least one of an anthraquinone-based pigment, an azo-based pigment and a phthalocyanine-based pigment, and 2) at least one of a binder resin, a cation-based surfactant and an extender. A gas for plasma generation which is used for the plasma processing contains at least one of oxygen and nitrogen.

Description

  The present invention relates to an ink composition for plasma processing detection and a plasma processing detection indicator, and more particularly to an ink composition and an indicator for detecting plasma processing using a plasma generating gas containing at least one of oxygen and nitrogen.

  Therefore, the plasma treatment in this specification uses a plasma generating gas containing at least one of oxygen and nitrogen, and uses plasma generated by applying an alternating voltage, a pulse voltage, a high frequency, a microwave, or the like. Means.

  Various equipment and instruments used in hospitals, laboratories and the like are sterilized for disinfection and sterilization. Plasma sterilization is known as one of the sterilization processes (for example, “3.3.1 Sterilization experiment using low-pressure discharge plasma” in Non-Patent Document 1).

  Specifically, the plasma sterilization treatment is a method in which plasma is generated in a plasma generating gas atmosphere containing at least one of oxygen and nitrogen, and equipment, instruments, etc. are sterilized by low temperature gas plasma, and can be subjected to low temperature sterilization treatment. This is advantageous.

  A plasma generating gas containing at least one of oxygen and nitrogen is used not only for sterilization but also for plasma dry etching and plasma cleaning of the surface of an object such as an electronic component in a semiconductor device manufacturing process. Yes.

  Plasma dry etching generally etches semiconductor wafers with high accuracy by applying high-frequency power to electrodes placed in a reaction chamber, which is a vacuum vessel, and converting the plasma generating gas introduced into the reaction chamber into plasma. To do. Plasma cleaning improves the bondability and solder wettability by reducing metal oxides deposited on the surface of electronic parts and other objects to be processed, and improves adhesion strength and adhesion with sealing resin. Improve wettability.

  As a method for detecting the end point of these plasma treatments, for example, Patent Document 1 discloses that “the emission spectrum from the gas plasma is received in the wavelength band of the photomultiplier having a wavelength range of 300 to 650 nm. The method for detecting the end point of plasma dry etching, characterized in that the obtained emission spectrum intensity curve is used.

  Patent Document 2 discloses that a transmission step of changing a transmission wavelength using an incident angle changing unit that changes an incident angle from a plasma light source that is monitored by a bandpass filter that selectively transmits only a specific wavelength region. The detection step of detecting the spectrum transmitted in the transmission step with a detector, the detection output from the detector of the detection step, and the angle output of the incident angle changing means of the transmission step are input, so that the incident angle is Even if it changes, the wavelength conversion means that makes the transmission wavelength detection output become a value that can be obtained without changing the incident angle, the calculation output device equipped with the output correction means is compared and calculated during the reaction and before the reaction, to the output device And a calculation output step of outputting an end point of the plasma processing.

  These conventional end point detection methods require devices such as an emission spectrum analysis device and an arithmetic output device, and it is difficult to individually detect each of the plasma processed objects. Therefore, it is desired to develop a technique that is a simple method that does not require a large-scale apparatus and that can individually detect the completion of plasma processing for each object to be processed.

Japanese Patent Application Laid-Open No. 6-069165 JP 2004-146738 A

Journal of Plasma and Fusion Research Vol.83, No.7 July 2007

  The main object of the present invention is to provide an ink composition capable of individually detecting the completion of plasma processing for each object to be processed and an indicator using the ink composition without requiring a large-scale apparatus.

  As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved by employing an ink composition having a specific composition, and has completed the present invention.

That is, the present invention relates to the following plasma treatment detection ink composition and plasma treatment detection indicator.
1.1) An ink composition for detecting plasma treatment, comprising at least one of an anthraquinone dye, azo dye and phthalocyanine dye, and 2) at least one of a binder resin, a cationic surfactant and an extender. The ink composition is characterized in that the plasma generating gas used for the plasma treatment contains at least one of oxygen and nitrogen.
2. Item 2. The ink composition according to Item 1, wherein a part or all of the binder resin is a nitrogen-containing polymer.
3. Item 3. The ink composition according to Item 2, wherein a part or all of the nitrogen-containing polymer is a polyamide resin.
4). Item 4. The ink composition according to Item 3, wherein the polyamide resin is a reaction product of a dimer of linoleic acid and a diamine or polyamine.
5. Item 5. The ink composition according to any one of Items 1 to 4, wherein the cationic surfactant is at least one selected from the group consisting of a tetraalkylammonium salt, an isoquinolinium salt, an imidazolinium salt, and a pyridinium salt. .
6). Item 6. The ink composition according to any one of Items 1 to 5, wherein a part or all of the extender is silica.
7). Item 7. The ink composition according to any one of Items 2 to 6, wherein the content of the nitrogen-containing polymer is 1 to 20% by weight in the ink composition.
8). Item 8. The ink composition according to any one of Items 1 to 7, further comprising at least one pigment component that does not change color in the plasma treatment atmosphere.
9. The plasma processing detection indicator containing the discoloration layer which consists of an ink composition in any one of said claim | item 1 -8.
10. Item 10. The indicator according to Item 9, which has a plurality of cracks on the surface of the discoloration layer.
11. Item 11. The indicator according to Item 9 or 10, further comprising a non-color-changing layer that does not change color in the plasma treatment atmosphere.
12 The package for plasma processing by which the indicator in any one of said item 9-11 is provided in the inner surface of the gas-permeable package.
13. Item 13. The package according to Item 12, wherein a transparent window is provided in a part of the package so that the indicator can be confirmed from the outside.
14 Item 14. The package according to Item 12 or 13, wherein the gas permeable package is formed of polyethylene fibers.
15. 15. A step of loading a workpiece into the package according to any one of Items 12 to 14, a step of sealing the package loaded with the workpiece, and a step of placing the package in the plasma treatment atmosphere. A plasma processing method.
16. Item 16. The processing method according to Item 15, wherein the package is placed in the plasma processing atmosphere until the discoloration layer of the indicator changes color.

  Hereinafter, the ink composition for plasma processing detection and the plasma processing detection indicator of the present invention will be described in detail.

1. Ink composition for detecting plasma treatment The ink composition for detecting plasma treatment of the present invention comprises 1) at least one of anthraquinone dye, azo dye and phthalocyanine dye, and 2) binder resin, cationic surfactant and extender. An ink composition for plasma treatment detection containing at least one of the above, wherein the plasma generating gas used for the plasma treatment contains at least one of oxygen and nitrogen.

Colorant In the composition of the present invention, at least one of an anthraquinone dye, azo dye, and phthalocyanine dye is used as a colorant (discoloration dye).

  The anthraquinone colorant is not limited as long as it has anthraquinone as a basic skeleton, and known anthraquinone type disperse dyes can also be used. An anthraquinone dye having an amino group is particularly preferable. More preferred are anthraquinone dyes having at least one amino group of a primary amino group and a secondary amino group. In this case, each amino group may have two or more, and these may be the same 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-methylanthraquinone (CIDisperse Orange 11), 1-amino-4-hydroxyanthraquinone (CIDisperse Red) 15), 1,4,5,8-tetraaminoanthraquinone (CIDisperse Blue 1), 1,4-diamino-5-nitroanthraquinone (CIDisperse Violet 8) and the like (color index names in parentheses) ).

  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 Dyes known as Blue 4, CI Reactive Blue 19, CI Disperse Blue 7, etc. can also be used.

  These anthraquinone dyes can be used alone or in combination of two or more. Among these anthraquinone dyes, C.I Disperse Blue 7, C.I Disperse Violet 1 and the like are preferable. In the present invention, the detection sensitivity can be controlled by changing the type (molecular structure, etc.) of these anthraquinone dyes.

  The azo dye is not limited as long as it has an azo group —N═N— as a chromophore. Examples thereof include monoazo dyes, polyazo dyes, metal complex azo dyes, stilbene azo dyes, thiazole azo dyes, and the like. More specifically, the color index names are CISolvent Red 1, CISolvent Red 3, CISolvent Red 23, CIDisperse Red 13, CIDisperse Red 52, CIDisperse Violet 24, CIDisperse Blue 44, CIDisperse Red 58, CI Disperse Red 88, CI Disperse Yellow 23, CI Disperse Orange 1, CI Disperse Orange 5, CISolvent Red 167: 1, and the like. These can be used alone or in combination of two or more.

  The phthalocyanine dye is not limited as long as it has a phthalocyanine structure. For example, blue copper phthalocyanine, metal-free phthalocyanine exhibiting a greener blue color, green highly chlorinated phthalocyanine, low chlorinated phthalocyanine exhibiting a yellowish green color (brominated chlorinated copper phthalocyanine) and the like can be mentioned. . Specifically, CI Pigment Green 7, CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 16, CI Pigment Green 36, CI Direct Blue 86 CI Basic Blue 140, CI Solvent Blue 70 and the like. These can be used alone or in combination of two or more.

  The content of the colorant can be appropriately determined according to the type of colorant, desired hue, etc., but is generally about 0.05 to 5% by weight, particularly 0.1 to 1% by weight in the composition of the present invention. % Is desirable.

  In the present invention, a dye or pigment other than the colorant may coexist. In particular, a pigment component that does not change color in a plasma treatment atmosphere (referred to as “non-color-change pigment”) may be included. Thereby, the visual recognition effect can be further enhanced by a change in color tone from one color to another. A known ink (ordinary color ink) can be used as the non-color-changing dye. What is necessary is just to set suitably content of the non-color-change pigment | dye in this case according to the kind etc. of the non-color-change pigment | dye.

  The ink composition for detecting plasma treatment of the present invention contains at least one of a binder resin, a cationic surfactant and an extender in addition to the colorant.

The binder resin may be appropriately selected depending on the type of the substrate, and for example, known resin components used in ink compositions for writing and printing can be employed as they are. Specific examples include maleic acid resins, ketone resins, alkylphenol resins, rosin-modified resins, polyvinyl butyral, cellulose resins, polyester resins, styrene maleic resins, styrene acrylic resins, acrylic resins, and the like. .

  In the present invention, a cellulose resin can be particularly preferably used. By using a cellulosic resin, excellent fixability can be obtained even if a bulking agent (silica or the like) is contained in the ink composition, and it is possible to effectively prevent dropping or peeling from the substrate. it can. Moreover, it can contribute to the sensitivity improvement of an indicator by producing a some crack effectively in the coating-film surface of an ink composition.

  In the present invention, as part or all of the binder resin, a nitrogen-containing polymer may be used in addition to the resins listed above. The nitrogen-containing polymer serves as a sensitivity enhancer in addition to serving as a binder. That is, the accuracy (sensitivity) of plasma processing detection can be further increased by using a sensitivity enhancer. Thereby, since it discolors reliably also in the package for a plasma processing detection, it is very advantageous as an indicator used for a package.

  As the nitrogen-containing polymer, for example, a synthetic resin such as polyamide resin, polyimide resin, polyacrylonitrile resin, amino resin, polyacrylamide, polyvinyl pyrrolidone, polyvinyl imidazole, or polyethyleneimine can be suitably used. These can be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a polyamide resin. The kind of polyamide resin, molecular weight, etc. are not specifically limited, A well-known or commercially available polyamide resin can be used. Among these, a polyamide resin which is a reaction product (long chain linear polymer) of a dimer of linoleic acid and diamine or polyamine can be preferably used. The polyamide resin is a thermoplastic resin having a molecular weight of 4000 to 7000. A commercially available product can also be used for such a resin.

  The content of the binder resin can be appropriately determined according to the type of the binder resin, the type of the colorant to be used, etc., but is generally about 50% by weight or less, particularly 5 to 35% by weight in the ink composition. desirable. When a nitrogen-containing polymer is used as the binder resin, the content of the nitrogen-containing polymer in the ink composition is preferably about 0.1 to 50% by weight, particularly 1 to 20% by weight.

Cationic surfactant The cationic surfactant is not particularly limited, but it is particularly desirable to use at least one of a tetraalkylammonium salt, an isoquinolinium salt, an imidazolinium salt, and a pyridinium salt. A commercial item can also be used for these. By using a cationic surfactant in combination with the colorant, better detection sensitivity can be obtained.

  Of the tetraalkylammonium salts, alkyltrimethylammonium salts and dialkyldimethylammonium salts are preferred. Specifically, palm alkyltrimethylammonium chloride, tallow alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyltrimethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium chloride, tetrapropylammonium chloride, tetramethylammonium bromide, bromide Tetrabutylammonium, tetrapropylammonium bromide, trimethyl-2-hydroxyethylammonium chloride, cetyltrimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, dioctyldimethylammonium chloride, distearyldimethylammonium chloride, alkylbenzyldimethylammonium chloride Etc. In particular, behenyltrimethylammonium chloride, lauryltrimethylammonium chloride and the like are preferable.

  Examples of the isoquinolinium salt include lauryl isoquinolinium bromide, cetyl isoquinolinium bromide, cetyl isoquinolinium chloride, lauryl isoquinolinium chloride and the like. Among these, lauryl isoquinolinium bromide is particularly preferable.

  Examples of the imidazolinium salt include 1-hydroxyethyl-2-oleylimidazolinium chloride and 2-chloro-1,3-dimethylimidazolinium chloride. Among these, 2-chloro-1,3-dimethylimidazolinium chloride is particularly preferable.

  Examples of the pyridinium salt include pyridinium chloride, 1-ethylpyridinium bromide, hexadecylpyridinium chloride, cetylpyridinium chloride, 1-butylpyridinium chloride, Nn-butylpyridinium chloride, hexadecylpyridinium bromide, N-hexadecylpyridinium bromide, 1-dodecylpyridinium chloride, 3-methylhexylpyridinium chloride, 4-methylhexylpyridinium chloride, 3-methyloctylpyridinium chloride, 2-chloro-1-methylpyridinium iodide, 3,4-dimethylbutylpyridinium chloride, pyridinium-n -Hexadecyl chloride-hydrate, N- (cyanomethyl) pyridinium chloride, N-acetonyl pyridi Umbromide, 1- (aminoformylmethyl) pyridinium chloride, 2-amidinopyridinium chloride, 2-aminopyridinium chloride, N-aminopyridinium iodide, 1-aminopyridinium iodide, 1-acetonylpyridinium chloride, N-acetonyl Examples include pyridinium bromide. Among these, hexadecylpyridinium chloride is particularly preferable.

  The content of the cationic surfactant can be appropriately determined according to the type of the surfactant, the type of the colorant to be used, and the like, but is generally about 0.2 to 10% by weight, particularly 0 in the ink composition. Desirably, 5 to 5% by weight.

The extender extender is not particularly limited, and examples thereof include inorganic materials such as bentonite, activated clay, aluminum oxide, silica, silica gel and the like. In addition, materials known as known extender pigments can be used. Among these, at least one of silica, silica gel and alumina is preferable. In particular, silica is more preferable. When silica or the like is used, a plurality of cracks can be effectively generated particularly on the surface of the color changing layer. As a result, the detection sensitivity of the indicator can be further increased.

  The content of the extender can be appropriately determined according to the type of the extender or colorant used, but is generally about 1 to 30% by weight, particularly 2 to 20% by weight in the ink composition. .

Other additives In the ink composition of the present invention, components used in known inks such as a solvent, a leveling agent, an antifoaming agent, an ultraviolet absorber, and a surface conditioner can be appropriately blended as necessary. .

  As the solvent that can be used in the present invention, any solvent that is usually used in ink compositions for printing, writing, etc. can be used. For example, various solvents such as alcohols or polyhydric alcohols, esters, ethers, ketones, hydrocarbons, glycol ethers, etc. can be used, and they are appropriately selected depending on the solubility of the dye used and the resin binder. It ’s fine.

  The content of the solvent can be appropriately determined according to the type of the solvent used and the colorant, but generally it is preferably about 40 to 95% by weight, particularly 60 to 90% by weight in the ink composition.

  The components of the ink composition of the present invention may be blended simultaneously or sequentially and mixed uniformly using a known stirrer such as a homogenizer or a dissolver. For example, first, the colorant, and at least one of a binder resin, a cationic surfactant, and an extender (other additives as necessary) may be blended in the solvent in order, and mixed and stirred with a stirrer.

2. Plasma sterilization detection indicator The indicator of the present invention includes a discoloration layer comprising the above-described ink composition of the present invention. Generally, a discoloration layer can be formed by apply | coating or printing the ink composition of this invention on a base material. The substrate in this case is not particularly limited as long as it can form a discoloration layer. For example, metal or alloy, ceramics, glass, concrete, plastics (polyethylene terephthalate (PET), polypropylene, nylon, polystyrene, polysulfone, polycarbonate, polyimide, etc.), fibers (nonwoven fabric, woven fabric, other fiber sheets), these A composite material or the like can be used. Moreover, synthetic resin fiber paper (synthetic paper) such as polypropylene synthetic paper and polyethylene synthetic paper can also be suitably used.

  The color changing layer in the present invention includes not only the color changing to another color but also the color fading or erasing.

  The discoloration layer can be formed by using the ink composition of the present invention according to a known printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, flexographic printing and the like. It can also be formed by methods other than printing. For example, the discoloration layer can be formed by immersing the substrate in the ink composition. It is particularly suitable for a material into which ink penetrates, such as a nonwoven fabric.

  The discoloration layer desirably has a plurality of cracks on its surface. That is, it is desirable that open pores are formed on the surface of the discoloration layer to make it porous. With this configuration, the sensitivity of plasma processing detection can be further increased. In this case, a desired color change effect can be obtained even if the color change layer is disposed inside the plasma processing detection package. A crack can be effectively formed by using a cellulose resin as a binder of the ink composition of the present invention. That is, the use of a cellulose resin can form the above cracks while maintaining good fixability.

  In the present invention, a non-discoloring layer that does not change color in a plasma treatment atmosphere may be formed on the substrate and / or the discoloring layer. The non-discoloring layer can be usually formed with a commercially available ordinary color ink. For example, water-based ink, oil-based ink, solventless ink, and the like can be used. The ink used for forming the non-discoloring layer may contain components blended in known inks, such as resin binders, extenders, solvents, and the like.

  The non-discoloring layer may be formed in the same manner as in the discoloring layer. For example, normal color ink can be used according to a known printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, or flexographic printing. The order of printing of the color changing layer and the non-color changing layer is not particularly limited, and may be appropriately selected according to the design to be printed.

  In the indicator of the present invention, one color changing layer and one non-color changing layer may be formed, or a plurality of layers may be formed. Further, discoloration layers or non-discoloration layers may be laminated. In this case, the discoloration layers may have the same composition or different compositions. Similarly, the non-discoloring layers may have the same composition or different compositions.

  Furthermore, the color-changing layer and the non-color-changing layer may be formed on the entire surface of the substrate or each layer, or may be partially formed. In these cases, in particular, in order to ensure the color change of the color change layer, the color change layer and the non-color change layer may be formed so that a part or all of at least one color change layer is exposed to the plasma treatment atmosphere.

  In the present invention, the discoloration layer and the non-discoloration layer may be combined in any way as long as the completion of the plasma treatment can be confirmed. For example, a color-changing layer and a non-color-changing layer are formed so that the color difference between the color-changing layer and the non-color-changing layer can be discriminated only after the color-changing layer is changed, or a color difference between the color-changing layer and the non-color-changing layer disappears only after the color change. It can also be formed. In the present invention, it is particularly preferable to form the color-changing layer and the non-color-changing layer so that the color difference between the color-changing layer and the non-color-changing layer can be discriminated only by the color change.

  In order to identify the color difference, for example, the color-changing layer and the non-color-changing layer may be formed so that at least one of a character, a pattern, and a symbol appears only when the color-changing layer changes. In the present invention, characters, designs, and symbols include all information that informs discoloration. What is necessary is just to design these characters etc. suitably according to the purpose of use.

  Further, the color changing layer and the non-color changing layer before the color change may be different from each other. For example, they may be substantially the same color so that the color difference (contrast) between the color-change layer and the non-color-change layer can be identified only after the color change.

  In the indicator of the present invention, the color changing layer and the non-color changing layer can be formed so that the color changing layer and the non-color changing layer do not overlap. As a result, the amount of ink used can be saved.

  Furthermore, in the present invention, a color changing layer or a non-color changing layer may be further formed on at least one of the color changing layer and the non-color changing layer. For example, if a color-changing layer having a different design is formed on a layer in which the color-changing layer and the non-color-changing layer are formed so as not to overlap the color-changing layer and the non-color-changing layer (referred to as “color-changing-non-color-changing layer”), Since the boundary line between the color changing layer and the non-color changing layer in the color changing-non-color changing layer can be made substantially indistinguishable, a more excellent design can be achieved.

  The indicator of the present invention can be applied to any plasma treatment using a plasma generating gas containing at least one of oxygen and nitrogen. Accordingly, a plasma processing apparatus using a plasma generating gas containing at least one of oxygen and nitrogen (specifically, an alternating voltage, a pulse voltage in an atmosphere containing at least one of oxygen and nitrogen as a plasma generating gas) It is useful as an indicator in an apparatus that performs plasma processing by generating plasma by applying high frequency, microwave, or the like. For example, when the indicator is used, the indicator of the present invention may be placed in the plasma processing apparatus or the object to be processed and exposed to the plasma processing atmosphere. In this case, it is possible to detect that a predetermined plasma process has been performed by changing the color of an indicator placed in the apparatus.

3. Package The present invention includes a plasma processing package in which the indicator of the present invention is provided on the inner surface of a gas permeable package.

  The gas permeable packaging body is preferably a packaging body that can be plasma-treated while the object to be treated is sealed therein. For this, a known or commercially available product used as a plasma processing package (pouch) can be used. For example, a package formed of polyethylene fibers (polyethylene synthetic paper) can be suitably used. An object to be processed is put in this package and the opening is sealed by heat sealing or the like, and then the entire package can be processed in a plasma processing apparatus.

  What is necessary is just to arrange | position this invention indicator to the inner surface of the said package. The arrangement method is not limited, and the indicator can also be constituted by applying or printing the ink composition of the present invention directly on the inner surface of the package, in addition to a method using an adhesive, heat sealing, or the like. Moreover, in the case of the application or printing, an indicator can be formed at the manufacturing stage of the package.

  In the package of the present invention, it is desirable that a transparent window is provided in a part of the package so that the indicator can be confirmed from the outside. For example, the package may be made of a transparent sheet and the polyethylene synthetic paper, and the indicator may be formed on the inner surface of the package at a position where it can be visually recognized through the transparent sheet.

  When plasma treatment is performed using the package of the present invention, for example, a step of loading a workpiece into the package, a step of sealing the package loaded with the workpiece, and placing the package in a plasma treatment atmosphere A method having a process may be used. More specifically, after putting an object to be processed into a package, it is sealed according to a known method such as heat sealing. Next, the whole package is placed in a plasma treatment atmosphere. For example, it arrange | positions in the processing chamber of a well-known or commercially available plasma processing apparatus, and processes. After the treatment is completed, the whole package can be taken out and stored in the package until it is used. In this case, it is preferable that the package is placed in the plasma treatment atmosphere until the discoloration layer of the indicator is discolored.

  The ink composition of the present invention contains 1) at least one of an anthraquinone dye, azo dye, and phthalocyanine dye, and 2) at least one of a binder resin, a cationic surfactant, and an extender. The plasma processing detection indicator including the discolored layer made of the composition can individually detect the completion of the plasma processing for each object to be processed without requiring a large-scale apparatus.

It is a figure which shows the relationship between the time of the plasma processing of Example 1, and a discoloration color difference. It is a figure which shows the relationship between the time of the plasma processing of Example 2, and a discoloration color difference.

  Examples and comparative examples are shown below to further clarify the features of the present invention. In addition, this invention is not restrict | limited to the aspect of an Example.

Preparation Example 1 (Preparation of ink composition A)
CI Solvent Red 167: 1 (azo dye) 1.0 part, CI Pigment Green 7 (phthalocyanine dye) 3.0 part, Versamide 756 (polyamide resin from Cognis Japan) 5.0 part, RS1 / 2 (S Nitrocellulose (NP Japan) 5.0 parts, NIKKOL CA-2150 (quaternary ammonium salt surfactant made by Nikko Chemicals) 4.0 parts, Aerosil R-972 (Nippon Aerosil silica gel) 5. Ink composition A was prepared by mixing 0 parts, 52.5 parts butyl cellosolve and 24.5 parts cyclohexanone.

Comparative Preparation Example 1 (Preparation of ink composition B)
CI Basic Red 14 (methine dye) 0.5 parts, CI Pigment Green 7 (phthalocyanine dye) 2.0 parts, Jonkrill 690 (BASF styrene acrylic resin) 2 parts, MOWITAL PVB-B20H (Kuraray) Ink composition B was prepared by mixing 10.0 parts of vinyl butyral resin), 1.0 part of NIKKOL CA-2150 (quaternary ammonium salt surfactant made by Nikko Chemicals) and 53.5 parts of butyl cellosolve.

Example 1
The ink composition A prepared in Preparation Example 1 was screen-printed and dried on white PET to obtain a light purple indicator A. Indicator A is set in TMP-0063, a microwave plasma processing apparatus manufactured by Toshiba, condition 1 “nitrogen flow rate 0.5 L / min, vacuum degree 1.7 Torr” and condition 2 “nitrogen flow rate 1.0 L / min, vacuum degree 3. Under the condition of “0 Torr”, plasma treatment was performed by applying a microwave of frequency 2.45 GHz and output 1 kW for 1 to 60 minutes.

  The discoloration color difference before and after the plasma treatment was measured using a handy color difference meter CR-300 manufactured by Konica Minolta. The color difference measurement results are shown in FIG. As is apparent from the results of FIG. 1, the indicator A gradually changed color from light purple to green according to the plasma treatment time.

Example 2
The plasma generating gas is changed to oxygen, and condition 3 “oxygen flow rate 0.5 L / min, vacuum degree 2.0 Torr” and condition 4 “oxygen flow rate 1.0 L / min, vacuum degree 2.7 Torr” are adopted, and further processing Plasma treatment was performed in the same manner as in Example 1 except that the time was 1 to 30 minutes.

  The color difference measurement results are shown in FIG. As is apparent from the results of FIG. 2, the indicator A gradually changed from light purple to white according to the plasma treatment time.

Example 3
Indicator A is set in Toshiba microwave plasma processing equipment TMP-0063, the flow gas is a mixed gas of any ratio of nitrogen and oxygen (see Table 1), the mixed gas flow rate is 1.0 L / min, the degree of vacuum is 2.7 Torr. Under the conditions described above, plasma treatment was performed by applying a microwave of frequency 2.45 GHz and output 1 kW for 5 minutes. Moreover, the plasma treatment was similarly performed when the mixed gas was air.

  As a result, the light purple indicator A was changed to a color difference ΔE * ab = 19.8 to 29.2 as shown in Table 1.

Comparative Example 1
The ink composition B prepared in Comparative Preparation Example 1 was screen-printed and dried on white PET to obtain a red bean color indicator B.

  Plasma treatment was performed in the same manner as in Example 1 except that indicator B was used instead of indicator A. As a result, the color difference before and after the treatment of the indicator B was ΔE * ab = 0.1 to 1.5, and the color was not changed as a red bean color.

Comparative Example 2
Plasma treatment was performed in the same manner as in Example 2 except that indicator B was used instead of indicator A. As a result, the color difference before and after the treatment of the indicator B was ΔE * ab = 1.3 to 7.9, and the color was not changed as it was red beans.

Claims (16)

  1) An ink composition for plasma treatment detection comprising at least one of an anthraquinone dye, azo dye and phthalocyanine dye, and 2) at least one of a binder resin, a cationic surfactant and an extender, An ink composition, wherein the plasma generating gas used for the plasma treatment contains at least one of oxygen and nitrogen.   The ink composition according to claim 1, wherein a part or all of the binder resin is a nitrogen-containing polymer.   The ink composition according to claim 2, wherein a part or all of the nitrogen-containing polymer is a polyamide resin.   The ink composition according to claim 3, wherein the polyamide resin is a reaction product of a dimer of linoleic acid and a diamine or polyamine.   The ink composition according to claim 1, wherein the cationic surfactant is at least one selected from the group consisting of a tetraalkylammonium salt, an isoquinolinium salt, an imidazolinium salt, and a pyridinium salt. .   The ink composition according to any one of claims 1 to 5, wherein a part or all of the extender is silica.   The ink composition according to any one of claims 2 to 6, wherein the content of the nitrogen-containing polymer is 1 to 20% by weight in the ink composition.   Furthermore, the ink composition in any one of Claims 1-7 containing at least 1 sort (s) of the pigment | dye component which does not change color in the said plasma treatment atmosphere.   The plasma processing detection indicator containing the discoloration layer which consists of an ink composition in any one of Claims 1-8.   The indicator according to claim 9 which has a plurality of cracks on the surface of said discoloration layer.   Furthermore, the indicator of Claim 9 or 10 containing the non-discoloring layer which does not discolor in the said plasma processing atmosphere.   The package for plasma processing by which the indicator in any one of Claims 9-11 is provided in the inner surface of the gas-permeable package.   The package according to claim 12, wherein a transparent window portion is provided on a part of the package so that the indicator can be confirmed from the outside.   The package according to claim 12 or 13, wherein the gas permeable package is formed of polyethylene fibers.   A process of loading an object to be processed into the package according to claim 12, a process of sealing the package loaded with the object to be processed, and a process of placing the package in the plasma processing atmosphere. A plasma processing method.   The processing method of Claim 15 which puts a package body in the said plasma processing atmosphere until the discoloration layer of the said indicator discolors.

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