JP2016078331A - Plasma treatment detection indicator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plasma treatment detection indicator where the generation of fine fiber pieces and colored pigments in a powdery shape from a base material during plasma treatment is evaded (or prevented), and also, at color measurement after plasma treatment, the influence by the chromaticity of measurement places is not received.SOLUTION: Provided is a plasma treatment detection indicator in which a color changing layer whose color is changed in a plasma treatment atmosphere is at least laminated on a part or the whole of the surface of a base material, and is characterized in that: (1) the base material is made of a transparent synthetic resin base material; and (2) the back face of the base material is provided with a colored layer.SELECTED DRAWING: None

Description

  The present invention relates to a plasma processing detection indicator. Note that the plasma treatment in this specification means plasma treatment using plasma generated by applying an AC voltage, a pulse voltage, a high frequency, a microwave, or the like to a plasma generating gas.

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

  Plasma treatment is used not only for sterilization treatment but also for plasma dry etching and plasma cleaning of the surface of an object to be processed such as an electronic component in the manufacture of semiconductor elements.

  In plasma dry etching, a semiconductor wafer is etched with high accuracy by applying high-frequency power to an electrode disposed in a reaction chamber, which is generally a vacuum vessel, and converting plasma generating gas introduced into the reaction chamber into plasma. Plasma cleaning also improves the bond strength and solder wettability by removing metal oxides, organic substances, burrs, etc. deposited or adhered to the surface of the workpiece such as electronic components. Or improve the adhesion and wettability with the sealing resin.

  As a method for detecting the completion of these plasma treatments, a method using a plasma treatment detection indicator in which a discoloration layer changes color in a plasma treatment atmosphere is known.

  For example, Patent Document 1 discloses a plasma processing detection containing 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. An ink composition, wherein the plasma generating gas used for the plasma treatment contains at least one of oxygen and nitrogen, and a discoloration layer comprising the ink composition as a base material A plasma processing detection indicator formed thereon is disclosed.

  Patent Document 2 discloses an inert gas plasma containing 1) at least one of anthraquinone dye, azo dye and methine dye, and 2) at least one of binder resin, cationic surfactant and extender. An ink composition for detecting processing, wherein the inert gas contains at least one selected from the group consisting of helium, neon, argon, krypton and xenon, and the ink composition, A plasma processing detection indicator is disclosed in which a discoloration layer comprising an ink composition is formed on a substrate.

  These plasma processing detection indicators are useful because the completion of the plasma processing can be determined by the color change of the color changing layer. The base material includes a fibrous base material capable of concealing the base color or a colored pigment (concealment pigment) such as titanium dioxide so that the discoloration behavior of the discoloration layer can be determined more reliably. Synthetic resin base materials are generally used.

JP 2013-98196 A JP 2013-95764 A

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

  However, when using a fibrous base material or a synthetic resin base material containing a color pigment, the surface of these base materials is affected by the plasma during the plasma treatment, and fine fiber pieces and color pigments are blown away. When such fine fiber pieces or colored pigments adhere to the discoloration layer, there is a concern of affecting the accurate determination of discoloration of the discoloration layer after the plasma treatment.

  On the other hand, in order to eliminate the concern, it is conceivable to use a transparent synthetic resin substrate as the substrate instead of the above-described fibrous substrate or a synthetic resin substrate containing a color pigment.

  However, when a transparent synthetic resin base material is used, when measuring the color of the indicator after plasma processing, the result depends on the chromaticity of the measurement location of the indicator (eg, the color of the base (base) on which the indicator is placed). (Colorimetric value) is greatly affected. Therefore, there is a concern of affecting the accurate determination of the color change of the color change layer after the plasma treatment.

  Therefore, it is avoided (or prevented) that fine fiber pieces and colored pigments are generated from the base material during the plasma treatment, and the influence of the chromaticity of the measurement location during the color measurement after the plasma treatment. The development of a plasma processing detection indicator that is not affected is desired.

  The present invention avoids (or prevents) fine fiber pieces and colored pigments from being blown out from the substrate during plasma processing, and depends on the chromaticity of the measurement location during color measurement after plasma processing. The main objective is to provide an unaffected plasma treatment detection indicator.

  As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved when a specific layer is provided on the back surface of the base material after using the specific base material. It came to complete.

That is, the present invention relates to the following plasma processing detection indicator.
1. A plasma processing detection indicator in which at least a discoloration layer that changes color in a plasma processing atmosphere is laminated on a part or all of the surface of a substrate,
(1) The base material is a transparent synthetic resin base material,
(2) having a colored layer on the back surface of the substrate;
An indicator characterized by that.
2. Item 2. The indicator according to Item 1, wherein the indicator has a non-discoloring layer between the substrate and the discoloring layer.
3. Item 3. The indicator according to Item 1 or 2, wherein the indicator has a non-discoloring layer between the substrate and the colored layer.
4). The package for plasma processing by which the indicator in any one of said claim | item 1-3 is provided inside the gas-permeable package.
5. The package according to Item 4, wherein a transparent window portion is provided in a part of the package so that the indicator can be confirmed from the outside.
6). 6. A plasma processing method comprising a step of loading an object to be processed into the package according to Item 4 or 5, a step of sealing the package loaded with the object to be processed, and a step of placing the package in a plasma processing atmosphere. .
7). The processing method according to Item 6, wherein the package is placed in the plasma processing atmosphere until the discoloration layer of the indicator changes color.

  Hereinafter, the plasma processing detection indicator of the present invention and the plasma processing packaging body of the present invention provided with the indicator will be described in detail.

<< 1. Plasma treatment detection indicator >>
The plasma processing detection indicator of the present invention (hereinafter abbreviated as “indicator”) is a plasma processing detection indicator in which at least a discoloration layer that changes color in a plasma processing atmosphere is laminated on part or all of the surface of a substrate. ,
(1) The base material is a transparent synthetic resin base material,
(2) having a colored layer on the back surface of the substrate;
It is characterized by that.

  The indicator of the present invention having the above-described characteristics is that (a) by using a transparent synthetic resin base material as a base material, fine fiber pieces and colored pigments are generated in a powder-like form from the base material during the plasma treatment. Avoided. Further, the indicator of the present invention has (b) a colored layer protected by the base material on the back surface of the base material. Not affected by chromaticity (background color). Due to the effects (a) and (b), it is possible to more accurately determine the discoloration of the discoloration layer after the plasma treatment.

[Base material]
The indicator of the present invention uses a transparent synthetic resin substrate as a substrate. In other words, the indicator of the present invention does not use a synthetic resin substrate containing a fibrous substrate or a colored pigment (a concealing pigment) as the substrate. As described above, the indicator of the present invention uses a transparent synthetic resin base material as a base material, so that the surface of the base material is affected by plasma during the plasma treatment, and fine fiber pieces and colored pigments are powdered. Can be avoided. Therefore, it is possible to avoid a phenomenon in which the fine fiber pieces or the colored pigments adhere to the color changing layer and affect the accurate determination of the color changing of the color changing layer after the plasma treatment. Moreover, the base material in this invention also has a function which protects the direct influence (etching effect | action) to the colored layer by plasma. Although the shape of a base material is not limited, Usually, it is a sheet form or a film form.

  Examples of the resin used for the transparent synthetic resin substrate include polypropylene, polyvinyl chloride, polyethylene terephthalate, polyethylene naphthalate, polyester, polystyrene, polyethylene, polyimide, polyamide, polypropylene, polyvinyl chloride, polycarbonate, and polyacrylonitrile. Synthetic resins are mentioned. These synthetic resins can be used alone or in admixture of two or more. Among these synthetic resins, at least one of polyethylene terephthalate, polyethylene naphthalate, polyethylene, polyimide, and polypropylene is particularly preferable.

  Although the thickness of a base material is not limited, It is preferable that it is about 0.01-0.5 mm.

[Colored layer]
The indicator of the present invention has a colored layer on the back surface of the substrate (the colored layer is an opaque layer). Since the coloring layer is protected from direct influence (etching action) by the plasma by the base material, it is possible to conceal the influence of the chromaticity (background color) of the measurement place at the time of color measurement after the plasma treatment. . Therefore, the indicator of the present invention can more accurately determine the color change of the color change layer after the plasma treatment.

  The colored layer can be usually formed with a commercially available normal color ink. For example, water-based ink, oil-based ink, solventless ink, and the like can be used. The ink used for forming the colored layer may contain components blended in known inks, such as resin binders, extenders and solvents.

  The formation of the colored layer is not particularly limited. For example, a colored layer can be formed using ordinary color ink according to a known printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, flexographic printing and the like.

  The thickness of the colored layer is not limited, but is preferably about 0.1 to 10 μm.

[Discoloration layer]
The indicator of the present invention has a discoloration layer on the substrate that changes color in a plasma processing atmosphere using a plasma generating gas. The region where the discoloration layer is formed may be a part or the whole of the substrate surface. The aspect currently formed in part with respect to the base-material surface is illustrated by FIGS. 1-3. In addition, although a discoloration layer can be laminated | stacked on the single side | surface or both surfaces of a base material, it is normally laminated | stacked on the single side | surface of a base material as FIG. 1-3 shows.

  As a color change mode of the color change layer in the present invention, a mode in which the color changes from colored to colorless (or a mode in which the color fades or decolors), a mode in which the color changes from colorless to colored, a certain color changes to another color The aspect which changes is mentioned. In addition, the method for confirming the completion of the plasma treatment by the change of the color change layer is not limited to the case of judging by the color change of the color change layer, and the color change layer is gradually thinned by the etching action by the plasma and finally the color change layer disappears. A method for confirming the completion of the plasma processing is also included. In this case, after the disappearance of the discoloration layer, in a manner that is synchronized with the discoloration layer so that it can be accurately determined where the discoloration layer was formed (so that the discoloration layer and the non-discoloration layer overlap in the same shape). An embodiment in which a non-discoloring layer is formed under the discoloring layer is useful (FIG. 2).

  The discoloration layer that changes color in a plasma treatment atmosphere using the plasma generating gas is coated with an ink composition containing a colorant that changes color in the plasma treatment atmosphere (referred to herein as a “color change pigment”) and dried. Can be formed. As the ink composition, known ones can be widely used. For example, an ink composition containing the following colorant, binder resin, surfactant, and other additives can be suitably used. . Hereinafter, typical components contained in the ink composition will be exemplarily described.

The color changing layer for detecting the colorant plasma is an ink composition containing at least one colorant (color changing dye) selected from the group consisting of anthraquinone dyes, azo dyes, methine dyes, and phthalocyanine dyes. Is preferably formed. The said pigment | dye (a dye is also included) is a discoloration pigment | dye discolored in a plasma processing atmosphere, and can be used 1 type or in mixture of 2 or more types.

  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, CI Disperse Red 167: 1, and the like. These can be used alone or in combination of two or more.

  The methine 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 the methine dyes. These can be appropriately employed from known or commercially available methine dyes. Specifically, CIBasic Red 12, CIBasic 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, CIBasic Violet 20, CIBasic Violet 21, CIBasic Violet 39, CIBasic Blue 62, CIBasic Blue 63, 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.

  In addition to the above general phthalocyanine dyes, the central metal has at least one of zinc, iron, cobalt, nickel, lead, tin, manganese, magnesium, silicon, titanium, vanadium, aluminum, iridium, platinum and ruthenium, A compound in which these central metals are coordinated to phthalocyanine, and a compound coordinated to phthalocyanine in a state where oxygen or chlorine is bonded to the central metal can also be used.

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

  In the present invention, dyes or pigments other than the colorant may coexist. For example, a non-discolored or hardly discolorable dye may be contained in a plasma treatment atmosphere. Examples of the non-discoloring or hardly discoloring colorant include organic pigments and titanium oxide. Thereby, the change of the color tone at the time of color change of a coloring agent can be raised, and the visual recognition effect of a color change can be improved further. Note that the dye that hardly changes color in the plasma processing atmosphere may include a case where the color is slightly changed by a physical etching action in the plasma processing atmosphere.

  The ink composition preferably contains at least one of a binder resin, a nonionic surfactant, a cationic surfactant, and an extender in addition to the colorant.

The binder resin may be appropriately selected according to the type of the application surface (base material or non-discoloring layer) of the ink composition. For example, known binder materials used for writing, printing, etc. The resin component can be used as it is. Specific examples include maleic acid resins, ketone resins, rosin modified resins, polyvinyl butyral resins, cellulose resins, polyester resins, styrene maleic resins, styrene acrylic resins, acrylic resins, and the like. The said binder resin can be used by 1 type (s) or 2 or more types.

  In the present invention, a cellulose resin can be particularly preferably used. By using a cellulosic resin, excellent fixability can be obtained even if the ink composition contains a filler (such as silica), and the ink composition can be applied on the substrate (or on the non-discoloring layer). After the film is formed, it is possible to effectively prevent the base material or the non-discoloring layer from falling off or peeling off. Further, it is considered that the effect of facilitating discoloration is exerted by effectively generating a plurality of cracks on the surface of the coating film of the ink composition, thereby creating an environment in which plasma is easily hit.

  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.

  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 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.

  In the present invention, the heat resistance of the ink composition and the coating film (discoloration layer) of the ink composition according to the present invention is improved by using a phenolic resin in addition to the resins listed above as part or all of the binder resin. Can be made.

  The phenolic resin is not limited as long as it is a pigment having a phenol structure. For example, at least one selected from the group consisting of alkylphenol resins, terpene phenol resins, and rosin-modified phenol resins can be suitably used. These phenolic resins can be used alone or in combination of two or more.

  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.

Nonionic surfactant The nonionic surfactant acts as a color change accelerator and can be used in combination with a colorant to obtain better detection sensitivity.

  As the nonionic surfactant, at least one nonionic surfactant represented by the general formulas (I) to (V) is used.

  The following general formula (I)

Shown [However, in the formula, R ₁ and R ₂ are each independently hydrogen, a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms. X represents an oxygen or ester bond. AO represents a repeating unit derived from alkylene oxide. n represents an integer of 1 to 200. ]
The nonionic surfactant represented by these is an alkylene glycol derivative.

  In addition, the following general formula (II)

[However, it is shown in the general formula, R _1, R ₂ and R ₃ are each independently hydrogen, a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms. X represents an oxygen or ester bond. n represents an integer of 1 to 200. ]
Is a polyglycerin derivative.

  In the above general formula (I), examples of AO (monomer) include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, styrene oxide, and the like. , Homopolymers, block copolymers composed of two or more types of AO, or random copolymers. Moreover, in general formula (I) and (II), C1-C30 has preferable C1-C22, C10-C18 is more preferable, X is oxygen, n is 1- An integer of 100 is preferred.

  Specific examples of the nonionic surfactant corresponding to the above general formula (I) or (II) include polyethylene glycol (such as “PEG2000” as a commercial product) (manufactured by Sanyo Chemical Industries, Ltd.), glycerin, polyethylene glycol -Polypropylene glycol copolymer ("Epan 710" etc. as a commercial product) (Daiichi Kogyo Seiyaku Co., Ltd.) etc. are mentioned.

Moreover, in the above, the polymer by which at least _one of R <1> and R < ₂ > was substituted by the C1-C30 linear or branched aliphatic hydrocarbon group is also mentioned as a preferable thing.

  Specifically, polyoxyethylene (hereinafter referred to as POE) lauryl ether (such as “Emulgen 109P” as a commercial product), POE cetyl ether (such as “Emulgen 220” as a commercial product), POE oleyl ether (“Emulgen 404” as a commercial product) POE stearyl ether (such as “Emulgen 306” as a commercial product), POE alkyl ether (“Emulgen LS-110” as a commercial product) (above, manufactured by Kao Corporation), POE tridecyl ether (“Fine as a commercial product”) Serve TD-150 ", polyethylene glycol monostearate (commercially available" Brownon S-400A "etc.) (above, manufactured by Aoki Yushi Kogyo Co., Ltd.), polyethylene glycol monooleate (" Nonion O-4 "commercially available) "), Tetramethi Glycol derivatives (commercially available products such as “Polycene DC-1100”), polybutylene glycol derivatives (commercially available products such as “Uniol PB-500”), alkylene glycol derivatives (commercially available products such as “Unilube 50MB-5”) (above) POE (20) octyldodecyl ether (such as “Emalex OD-20” as a commercial product), POE (25) octyldodecyl ether (such as “Emalex OD-25” as a commercial product), etc. ) (Nippon Emulsion Co., Ltd.).

  The following general formulas (III) and (IV)

[However, it is shown in the general formula, R _1, R ₂ and R ₃ are each independently hydrogen, a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms. AO represents a repeating unit derived from alkylene oxide. a + b + c represents an integer of 3 to 200. ]
Is a alkylene glycol glyceryl derivative.

  In both the above general formulas, examples of AO (monomer) include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, styrene oxide, and the like. Examples thereof include a polymer, a block copolymer composed of two or more kinds of AO, and a random copolymer. Moreover, in both general formulas, having 1-30 carbon atoms is preferably 1-22 carbon atoms, more preferably 10-18 carbon atoms, and a + b + c is preferably an integer of 3-50.

Examples of the nonionic surfactant corresponding to the general formula (III) include compounds in which R ₁ is an isostearic acid residue, R ₂ and R ₃ are hydrogen, and AO (monomer) is ethylene oxide. Specifically, POE glyceryl isostearate (such as “UNIOX GM-30IS” as a commercial product) (manufactured by NOF Corporation) can be mentioned.

Examples of the nonionic surfactant corresponding to the general formula (IV) include compounds in which R _{1 to} R ₃ are isostearic acid residues and AO (monomer) is ethylene oxide. And POE glyceryl triisostearate (commercially available product such as “UNIOX GT-30IS”) (manufactured by NOF Corporation).

  The following general formula (V)

[However, it is shown in the general _{formula, R 1, R 2, R} 3 and _{R 4} are each independently hydrogen, a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms. X represents an oxygen or ester bond. AO represents a repeating unit derived from alkylene oxide. p + q represents an integer of 0 to 20. ]
A nonionic surfactant represented by the formula is an acetylene glycol derivative.

  In the general formula (V), examples of AO (monomer) include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, styrene oxide, and the like. , Homopolymers, block copolymers composed of two or more types of AO, or random copolymers. Moreover, in general formula (I) and (II), C1-C30 has preferable C1-C22, X is preferable oxygen, and p + q is an integer of 0-10.

As a nonionic surfactant corresponding to the general formula (V), for example, R ₁ and R ₄ are hydrogen, and R ₂ and R ₃ are> C (CH ₃ ) (i-C ₄ H ₉ ). A compound in which X is oxygen and p + q = 0, specifically, 2,4,7,9-tetramethyl-5-decyne-4,7-diol (as a commercially available product, “Surfinol 104H”). Etc.) (made by Air Products Japan Co., Ltd.).

  These nonionic surfactants represented by the general formulas (I) to (V) can be used alone or in admixture of two or more.

  The content of the nonionic surfactant can be appropriately determined according to the type and the type of the colorant to be used, but generally in the ink composition in consideration of the storage stability in the composition and the effect of promoting discoloration. It is desirable that the content be about 0.2 to 10% by weight, particularly 0.5 to 5% 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. The said cationic surfactant can be used by 1 type (s) or 2 or more types.

  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. It is desirable that the content be 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 above extenders can be used alone or in combination of two or more.

  When silica is used as the extender, the type of silica is not particularly limited, but for example, hydrophobic silica is preferable. The silica may be silica that has been surface-treated to impart hydrophobicity.

  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 additive ink compositions can be appropriately blended with components used in known inks such as a solvent, a leveling agent, an antifoaming agent, an ultraviolet absorber, and a surface conditioner, if 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 if appropriate selected according to the dye used, the solubility of the binder resin, etc. good. The said solvent can be used by 1 type (s) or 2 or more types.

  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 in the 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.

Formation method of discoloration layer The discoloration layer is formed by using the ink composition, and known printing methods such as spin coating, slit coating, dip coating, spraying, silk screen printing, gravure printing, offset printing, letterpress printing, flexographic printing, etc. It can be carried out according to a known coating method or the like.

  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 arranged inside the plasma processing detection indicator. The crack can be effectively formed by using a cellulosic resin as the binder resin of the ink composition in the present invention. That is, the use of a cellulose resin can form the above cracks while maintaining good fixability.

  The thickness of the color changing layer is not limited, but is generally about 1 to 10 μm.

  In the present invention, in order to further enhance the visual effect when the color-changing layer changes color, for example, (1) a non-color-changing layer is formed between the substrate and the color-changing layer as shown in FIG. Alternatively, (2) as shown in FIG. 3 of the present specification, a non-discoloring layer may be formed between the substrate and the colored 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 a known ink, for example, a resin binder, an extender, a solvent, and the like.

  The non-color-changing layer may be formed in the same manner as the color-changing 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 thickness of the non-discoloring layer is not limited, but is preferably about 1 to 20 μm.

  The indicator of the present invention can be applied to any plasma processing using a plasma generating gas. That is, the present invention can be applied to both low-pressure plasma processing and atmospheric pressure plasma processing.

  Specific examples of low-pressure plasma treatment include film formation, ashing, cleaning, surface modification, etc. for flat panel displays (liquid crystal displays, etc.); film formation, ashing, cleaning, surface modification in semiconductor manufacturing processes Applications such as cleaning of mounting substrates or printed wiring boards, surface modification, etc .; sterilization applications of medical instruments, etc .; applications such as cleaning of mounting parts, surface modification, etc.

  Specific examples of atmospheric pressure plasma treatment include, for example, cleaning of flat panel displays (liquid crystal displays, etc.), surface modification, etc .; usage of mounting boards or printed wiring boards, surface modification, etc .; automobile, Examples include surface modification applications such as aircraft parts, and disinfection, sterilization, and treatment in the medical field (dental or surgical).

  The gas for generating reduced pressure plasma is not limited as long as the gas can generate plasma by applying an alternating voltage, pulse voltage, high frequency, microwave, etc. under reduced pressure. For example, oxygen, nitrogen, hydrogen, Chlorine, hydrogen peroxide, helium, argon, silane, ammonia, sulfur bromide, water vapor, nitrous oxide, tetraethoxylane, carbon tetrafluoride, trifluoromethane, carbon tetrachloride, silicon tetrachloride, sulfur hexafluoride, four Examples thereof include titanium chloride, dichlorosilane, trimethyl gallium, trimethyl indium, and trimethyl aluminum. These gases for generating reduced-pressure plasma can be used alone or in admixture of two or more.

  The atmospheric pressure plasma generating gas is not limited as long as it can generate plasma by applying an alternating voltage, a pulse voltage, a high frequency, a microwave, or the like under atmospheric pressure. For example, oxygen, nitrogen, Examples thereof include hydrogen, argon, helium, air (atmosphere) and the like. These atmospheric pressure plasma generating gases can be used alone or in admixture of two or more.

  When using the indicator of the present invention, specifically, a plasma processing apparatus using a plasma generating gas (specifically, an AC voltage, a pulse voltage, a high frequency, a microwave in an atmosphere containing the plasma generating gas). The indicator of the present invention may be placed inside a device that performs plasma processing by generating plasma by applying plasma or the like to 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.

  The indicator of the present invention can be used as an indicator card as it is. At this time, if the shape of the discoloration layer is a known barcode shape and is set to a condition that allows reading by a barcode reader when the predetermined plasma processing is completed (degree of discoloration), the plasma processing is completed. Subsequent distribution management of plasma processed products can be centrally managed by a bar code. The present invention also includes an invention of an indicator, a plasma processing management method, and a physical distribution management method used for such applications.

≪2. Package >>
The present invention includes a plasma processing package in which the indicator of the present invention is provided inside 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. Specifically, after a workpiece is loaded into a package body in which the indicator of the present invention is provided and the opening is sealed by heat sealing or the like, the whole package body can be processed in a plasma processing apparatus. .

  What is necessary is just to arrange | position the indicator of this invention inside 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 on 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 seen 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 It can be performed by a method having steps. 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, the plasma treatment is preferably performed by placing the package in a plasma treatment atmosphere until the discoloration layer of the indicator changes color.

  In the indicator of the present invention, by using a transparent synthetic resin base material as a base material, it is avoided that fine fiber pieces and colored pigments are generated in a powdered form from the base material during the plasma treatment. Moreover, since the indicator of this invention has a colored layer on the back surface of a base material, even if a base material is transparent, it is not influenced by the chromaticity of a measurement place at the time of the color measurement after a plasma process. Therefore, it is possible to more accurately determine the color change of the color change layer after the plasma treatment.

It is a figure which shows the one aspect | mode of the plasma processing detection indicator of this invention. It is a figure which shows the one aspect | mode of the plasma processing detection indicator of this invention. It is a figure which shows the one aspect | mode of the plasma processing detection indicator of this invention.

  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.

Example 1
A transparent PET film (Toyobo Co., Ltd. E5100) with a thickness of 50 μm is prepared as a base material, and non-discoloring layer forming ink (Diatone Eco Pure SOY HP J, high-performance soybean oil ink, manufactured by Sakata Inx Co., Ltd.) To form a non-discoloring layer having a thickness of 10 μm.

  Next, the color layer forming ink (Diatone Eco Pure SOY HP J, high-performance soybean oil ink) is printed on the back side of the base material by offset printing (white back printing) A 1 μm colored layer was formed.

  Next, a color-changing layer having a thickness of 5 μm was formed on the non-color-changing layer using a color-changing layer-forming ink A (manufactured by Sakura Crepas Co., Ltd., containing a color-changing dye but not containing a non-color-changing dye).

The indicator was produced through the above steps.
(Composition of discoloration layer forming ink A)

Example 2
A transparent PET film (Toyobo Co., Ltd. E5100) with a thickness of 50 μm is prepared as a base material, and a color changing layer forming ink B (made by Sakura Crepas Co., Ltd., containing a color changing dye and a non-color changing dye) Was used to form a discoloration layer having a thickness of 5 μm.

  Next, the color layer forming ink (Diatone Eco Pure SOY HP J, high-performance soybean oil ink) is printed on the back side of the base material by offset printing (white back printing) A 1 μm colored layer was formed.

The indicator was produced through the following steps.
(Composition of discoloration layer forming ink B)

Comparative Example 1
In Example 1, an indicator was produced in the same manner as in Example 1 except that no colored layer was formed on the back surface of the substrate.

Comparative Example 2
In Example 2, an indicator was produced in the same manner as in Example 2 except that no colored layer was formed on the back surface of the substrate.

Comparative Example 3
In Example 1, instead of the transparent PET film, a white PET film having a thickness of 188 μm (manufactured by Toyobo Co., Ltd., Crisper K2323) was used as the substrate. Moreover, the colored layer was not formed in the back surface of the said base material. About others, it carried out similarly to Example 1, and produced the indicator.

Comparative Example 4
In Example 2, instead of the transparent PET film, a white PET film having a thickness of 188 μm (manufactured by Toyobo Co., Ltd., Chrispar K2323) was used as the substrate. Moreover, the colored layer was not formed in the back surface of the said base material. About others, it carried out similarly to Example 2, and produced the indicator.

Test example 1 (plasma treatment)
The indicator produced in each Example and Comparative Example was installed in a high-frequency plasma apparatus “Samco, BP-1”, and plasma was generated using “O ₂ gas and CF ₄ gas mixed gas” and “Ar gas”, respectively. The change in the substrate after the plasma treatment was generated was observed with the naked eye.

As a result of the observation, the case where powder blowing was not recognized on the substrate surface was evaluated as ◯, and the case where powder blowing was observed on the substrate surface was evaluated as x. The results are shown in Table 3 below.
(Processing conditions when mixed gas is used)
・ Device: Parallel plate high-frequency plasma device BP-1 (Samco)
・ O ₂ gas: 10ml / min, CF ₄ gas: 5ml / min
・ Power: 75W, Pressure: 100Pa, Power distance: 50mm
・ Processing time: 10 min
(Processing conditions when Ar gas is used)
・ Device: Parallel plate high-frequency plasma device BP-1 (Samco)
・ Ar gas: 20ml / min
・ Power: 75W, Pressure: 20Pa, Power distance: 50mm
・ Processing time: 30min

Test example 2 (colorimetry test)
The chromaticity (L ^* a ^* b ^* ) of the region where the color-changing layer (and non-color-changing layer) of each indicator plasma-treated in Test Example 1 is formed is determined as a handy color manufactured by Nippon Denshoku Industries Co., Ltd. Measurement (colorimetry) was performed using a total NR-11A, and chromaticity difference (color difference) ΔE ^* ab was calculated from the measured value.
Specifically, the following (1) and (2):
(1) When each indicator is placed on white drawing paper, and
(2) When each indicator is placed on black drawing paper,
(1) The chromaticity of the area when measured with each indicator placed on the white drawing paper is L ^* 1, a ^* 1, b ^* 1, and (2) on the black drawing paper. The chromaticity of the region when measured with each indicator placed on was L ^* 2, a ^* 2, and b ^* 2. The chromaticity difference ΔE ^* ab is then expressed as:
Difference in chromaticity (color difference) ΔE ^* ab = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2
[In the formula, ΔL ^* = L ^* 2-L ^* 1, Δa ^* = a ^* 2-a ^* 1, and Δb ^* = b ^* 2-b ^* 1. ]
Calculated with The results are shown in Table 3 below.

  As is clear from the results in Table 3, the indicator of the present invention in which a transparent synthetic resin base material was used as the base material and a colored layer was formed on the back surface of the base material was found to have powder blowing on the base material surface after the plasma treatment. In addition, it is hardly affected by the chromaticity of the measurement place at the time of color measurement after the plasma treatment. Therefore, it is possible to more accurately determine the color change of the color change layer after the plasma treatment. On the other hand, the indicator of Comparative Examples 1 and 2 which uses a transparent synthetic resin base material as a base material and does not form a colored layer on the back surface of the base material is a measurement place at the time of color measurement after the plasma treatment. Therefore, it is difficult to accurately determine the discoloration of the discoloration layer after the plasma treatment. In addition, in the indicators of Comparative Examples 3 and 4 using an opaque (white) synthetic resin base material as the base material and forming a colored layer on the back surface of the base material, powder spraying was recognized on the base material surface after the plasma treatment. It was.

1. Indicator 2. 2. Colored layer Base material 4. 4. Discoloration layer Non-discoloring layer

Claims (7)

A plasma processing detection indicator in which at least a discoloration layer that changes color in a plasma processing atmosphere is laminated on a part or all of the surface of a substrate,
(1) The base material is a transparent synthetic resin base material,
(2) having a colored layer on the back surface of the substrate;
An indicator characterized by that.   The indicator of Claim 1 which has a non-discoloring layer between the said base material and the said discoloration layer.   The indicator of Claim 1 or 2 which has a non-discoloring layer between the said base material and the said colored layer.   The plasma processing packaging body in which the indicator in any one of Claims 1-3 is provided in the inside of a gas-permeable packaging body.   The package according to claim 4, wherein a transparent window is provided in a part of the package so that the indicator can be confirmed from the outside.   A plasma processing method comprising a step of loading an object to be processed in the package according to claim 4 or 5, a step of sealing the package loaded with the object to be processed, and a step of placing the package in a plasma processing atmosphere. .   The processing method according to claim 6, wherein the package is placed in the plasma processing atmosphere until the color changing layer of the indicator changes color.

Images