WO2014196440A1 - プラズマ処理検知用インキ組成物及びプラズマ処理検知インジケーター - Google Patents
プラズマ処理検知用インキ組成物及びプラズマ処理検知インジケーター Download PDFInfo
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- WO2014196440A1 WO2014196440A1 PCT/JP2014/064209 JP2014064209W WO2014196440A1 WO 2014196440 A1 WO2014196440 A1 WO 2014196440A1 JP 2014064209 W JP2014064209 W JP 2014064209W WO 2014196440 A1 WO2014196440 A1 WO 2014196440A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32917—Plasma diagnostics
- H01J37/32935—Monitoring and controlling tubes by information coming from the object and/or discharge
- H01J37/32963—End-point detection
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K1/00—Nibs; Writing-points
- B43K1/08—Nibs; Writing-points with ball points; Balls or ball beds
- B43K1/082—Balls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K7/00—Ball-point pens
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K7/00—Ball-point pens
- B43K7/01—Ball-point pens for low viscosity liquid ink
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K8/00—Pens with writing-points other than nibs or balls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D5/00—Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper
- B65D5/42—Details of containers or of foldable or erectable container blanks
- B65D5/4212—Information or decoration elements, e.g. content indicators, or for mailing
- B65D5/4216—Cards, coupons or the like formed integrally with, or printed directly on, the container or lid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
- B65D75/52—Details
- B65D75/522—Inspection openings or windows
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/18—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents providing specific environment for contents, e.g. temperature above or below ambient
- B65D81/20—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents providing specific environment for contents, e.g. temperature above or below ambient under vacuum or superatmospheric pressure, or in a special atmosphere, e.g. of inert gas
- B65D81/2069—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents providing specific environment for contents, e.g. temperature above or below ambient under vacuum or superatmospheric pressure, or in a special atmosphere, e.g. of inert gas in a special atmosphere
- B65D81/2084—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents providing specific environment for contents, e.g. temperature above or below ambient under vacuum or superatmospheric pressure, or in a special atmosphere, e.g. of inert gas in a special atmosphere in a flexible container
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/23—Azo-compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
- G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
- G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
- G06K19/06009—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with optically detectable marking
- G06K19/06018—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with optically detectable marking one-dimensional coding
- G06K19/06028—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with optically detectable marking one-dimensional coding using bar codes
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
- G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
- G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
- G06K19/06009—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with optically detectable marking
- G06K19/06046—Constructional details
- G06K19/0614—Constructional details the marking being selective to wavelength, e.g. color barcode or barcodes only visible under UV or IR
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32917—Plasma diagnostics
- H01J37/32935—Monitoring and controlling tubes by information coming from the object and/or discharge
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32917—Plasma diagnostics
- H01J37/32935—Monitoring and controlling tubes by information coming from the object and/or discharge
- H01J37/32972—Spectral analysis
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/0006—Investigating plasma, e.g. measuring the degree of ionisation or the electron temperature
- H05H1/0012—Investigating plasma, e.g. measuring the degree of ionisation or the electron temperature using electromagnetic or particle radiation, e.g. interferometry
- H05H1/0018—Details
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/0006—Investigating plasma, e.g. measuring the degree of ionisation or the electron temperature
- H05H1/0068—Investigating plasma, e.g. measuring the degree of ionisation or the electron temperature by thermal means
Definitions
- the present invention relates to a plasma treatment detection ink composition and a plasma treatment detection indicator using the same.
- the plasma treatment in this specification means a plasma treatment using plasma generated by applying a plasma generation gas and applying an alternating voltage, a pulse voltage, a high frequency, a microwave, etc. Both plasmas are applicable.
- 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).
- the plasma sterilization treatment is advantageous in that it generates plasma in a plasma generating gas atmosphere and sterilizes equipment, instruments and the like with low temperature gas plasma, and can be subjected to low temperature sterilization treatment.
- the 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 a semiconductor element manufacturing process.
- 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 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.
- Patent Document 1 discloses that “a light emission spectrum from a gas plasma is obtained by receiving all light in a wavelength band of a 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.
- 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.
- the present inventor has found that the above object can be achieved by employing an ink composition having a specific composition, and the present invention has been completed.
- the present invention relates to the following plasma treatment detection ink composition and plasma treatment detection indicator.
- An ink composition for plasma treatment detection containing a dye and a nonionic surfactant, (1) The dye is at least one selected from the group consisting of anthraquinone dyes, methine dyes, azo dyes, phthalocyanine dyes, triphenylmethane dyes, and xanthene dyes, (2)
- the nonionic surfactant is at least one nonionic surfactant represented by the general formulas (I) to (V).
- R 1 , R 2 , R 3 and R 4 each independently represent 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.
- a + b + c represents an integer of 3 to 200.
- p + q represents an integer of 0 to 20.
- An ink composition characterized by that. 2.
- Item 2 The ink composition according to Item 1, further comprising at least one binder resin and extender. 3.
- Item 3 The ink composition according to Item 2, wherein a part or all of the binder resin is a nitrogen-containing polymer. 4).
- Item 4 The ink composition according to Item 3, wherein a part or all of the nitrogen-containing polymer is a polyamide resin. 5.
- Item 3. The ink composition according to Item 2, wherein a part or all of the binder resin is a phenol resin. 6).
- Item 6. The ink composition according to any one of Items 2 to 5, wherein a part or all of the extender is silica. 7).
- Item 7. The ink composition according to any one of Items 1 to 6, further comprising at least one dye component that does not change color in the plasma treatment atmosphere. 8).
- a plasma processing detection indicator comprising a discoloration layer comprising the ink composition according to any one of items 1 to 7. 9.
- the indicator according to Item 8 further comprising a non-color-changing layer that does not change color in the plasma treatment atmosphere.
- Item 10 The indicator according to Item 8 or 9, wherein the discoloration layer has a barcode shape.
- Item 11 The indicator according to Item 10, wherein the discoloration layer is discolored in a plasma processing environment and can be read by a barcode reader so that plasma processing can be managed.
- 12 A package for plasma processing, wherein the indicator according to any one of Items 8 to 11 is provided on the inner surface of the gas permeable package.
- 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 14.
- a plasma treatment comprising the steps of: loading a workpiece into the package according to item 12 or 13; sealing the package loaded with the workpiece; and placing the package in the plasma treatment atmosphere.
- Method. 15. Item 15. The processing method according to Item 14, wherein the package is placed in the plasma processing atmosphere until the discoloration layer of the indicator changes color. 16.
- the ink composition for detecting plasma treatment of the present invention contains a pigment and a nonionic surfactant, (1)
- the dye is at least one selected from the group consisting of anthraquinone dyes, methine dyes, azo dyes, and phthalocyanine dyes, (2)
- the nonionic surfactant is at least one nonionic surfactant represented by the general formulas (I) to (V).
- R 1 , R 2 , R 3 and R 4 each independently represent 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.
- a + b + c represents an integer of 3 to 200.
- p + q represents an integer of 0 to 20.
- the ink composition of the present invention uses at least one selected from the group consisting of anthraquinone dyes, methine dyes, azo dyes, and phthalocyanine dyes as colorants (also referred to as dyes and discoloration dyes).
- the anthraquinone dye is not limited as long as it has anthraquinone as a basic skeleton, and a known anthraquinone disperse dye or the like 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.
- 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), etc. ).
- 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, CIReactive Blue 19, CI Disperse Blue 7 etc. can also be used.
- anthraquinone dyes can be used alone or in combination of two or more.
- these anthraquinone dyes C.I.Disperse Blue 7, C.I Disperse Violet 1 and the like are preferable.
- the detection sensitivity can be controlled by changing the type (molecular structure, etc.) of these anthraquinone dyes.
- 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.
- 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 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 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.
- 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, CIDisperse Red 88, CIDisperse Yellow 23, CIDisperse Orange 1, CIDisperse 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.
- 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. .
- 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 triphenylmethane dye is not limited as long as it has a triphenylmethane structure.
- CIAcid Blue 90 CIAcid Green 16, CIAcid Violet 49, CIBasic Red 9, CIBasic Blue 7, CIAcid Violet 1, CIDirect Blue 41, CIMordnt Blue 1, CIMordnt Violet 1 .
- These triphenylmethane dyes can be used alone or in combination of two or more.
- the xanthene dye is not limited as long as it is a dye having a xanthene structure. Examples include 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.Mordnt Red 27, C.I.Mordnt Violet 25, and the like. These xanthene dyes 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 5% by weight in the ink composition of the present invention. It is desirable to be 1% by weight.
- dyes or pigments other than the colorant may coexist.
- a pigment component that does not change color in a plasma treatment atmosphere referred to as “non-color-change pigment”
- non-color-change pigment may be included.
- a known ink ordinary color ink
- the ink composition of the present invention contains at least one nonionic surfactant represented by the general formulas (I) to (V) as a color change accelerator in addition to the colorant, and further includes a binder resin as an optional component. Contains bulking agents and the like.
- the nonionic surfactant acts as a color change accelerator and can be used in combination with a colorant to obtain better detection sensitivity.
- nonionic surfactant at least one nonionic surfactant represented by the general formulas (I) to (V) is used.
- R 1 and R 2 each independently represent 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.
- R 1 , R 2 and R 3 each independently represent hydrogen or 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.
- examples of AO 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.
- the number of carbon atoms of 1 to 30 is preferably 1 to 22, more preferably 10 to 18, X is preferably oxygen, and n is 1 to 22. An integer of 100 is preferred.
- 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.
- a polymer in which at least one of R 1 and R 2 is substituted with a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms is also preferable.
- 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 (such as” Brownon S-400A "as a commercial product) (Aoki Yushi Kogyo Co., Ltd.), polyethylene glycol monooleate (“ Nonion O-4 "as a commercial product) "), Tetrame Lenglycol derivatives (such as “Polycene DC-1100” as
- R 1 , R 2 and R 3 each independently represent hydrogen or 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.
- examples of AO 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.
- the number of carbon atoms of 1 to 30 is preferably 1 to 22, more preferably 10 to 18, and a + b + c is preferably an integer of 3 to 50.
- nonionic surfactant corresponding to the general formula (III) examples include compounds in which R 1 is an isostearic acid residue, R 2 and R 3 are hydrogen, and AO (monomer) is ethylene oxide.
- AO monomer
- POE glyceryl isostearate such as “UNIOX GM-30IS” as a commercial product) (manufactured by NOF Corporation) can be mentioned.
- nonionic surfactant corresponding to the general formula (IV) examples include compounds in which R 1 to R 3 are isostearic acid residues and AO (monomer) is ethylene oxide.
- AO monomer
- POE glyceryl triisostearate commercially available product such as “Uniox GT-30IS”) (manufactured by NOF Corporation).
- R 1 , R 2 , R 3 and R 4 each independently represent 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.
- examples of AO 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.
- those having 1 to 30 carbon atoms are preferably 1 to 22 carbon atoms
- X is preferably oxygen
- p + q is preferably an integer of 0 to 10.
- 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 (the commercially available product “Surfinol 104H”). Etc.) (made by Air Products Japan Co., Ltd.).
- 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.
- the binder resin may be appropriately selected according to 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.
- a cellulose resin can be particularly preferably used.
- a cellulosic resin 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.
- 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.
- 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.
- a polyamide resin 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.
- 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 heat resistance of the ink composition and the color changing layer made of the ink composition can be improved by using a phenolic resin in addition to the above-mentioned resins as a part or all of the binder resin.
- the phenolic resin is not limited as long as it is a pigment having a phenol structure.
- 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 used, etc., but is generally about 50% by weight or less, particularly 5 to 35% by weight in the ink composition. desirable.
- 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.
- the extender extender is not particularly limited, and examples thereof include inorganic materials such as bentonite, activated clay, aluminum oxide, silica, and silica gel.
- materials known as known extender pigments can be used.
- at least one of silica, silica gel and alumina is preferable, and silica is more preferable.
- 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 extender or colorant used, but generally it is preferably about 1 to 30% by weight, particularly 2 to 20% by weight in the ink composition. .
- 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. .
- any solvent that is usually used in ink compositions for printing, writing, etc. can be used.
- 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. That's fine.
- a fast-drying solvent having a relative evaporation rate of 1.0 or more when the evaporation rate of n-butyl acetate is 1.0 is suitable for gravure printing, and the relative evaporation rate is 0.01.
- Those having a mixing speed of 1.0 to 1.0 mixed appropriately are suitable for screen printing.
- 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 viscosity can be adjusted by adjusting the content of the solvent, and an ink composition having a viscosity suitable for various printing methods can be provided.
- the viscosity of the ink composition is preferably less than 12000 mPa ⁇ s.
- the viscosity suitable for silk screen printing is about 500 to 8000 mPa ⁇ s, and the viscosity suitable for gravure printing is 10 to 500 mPa ⁇ s. ⁇ It is about s.
- 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.
- a known stirrer such as a homogenizer or a dissolver.
- 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.
- the indicator of the present invention includes a discoloration layer comprising the ink composition of the present invention.
- a discoloration layer can be formed by apply
- the substrate in this case is not particularly limited as long as it can form a discoloration layer.
- the base material examples include metals or alloys, ceramics, glass, concrete, plastics (polyethylene terephthalate (PET), polypropylene, nylon, polystyrene, polysulfone, polycarbonate, polyimide, etc.), fibers (nonwoven fabrics, woven fabrics, other Fiber sheet), composite materials of these, and the like can be used.
- synthetic resin fiber paper synthetic paper
- synthetic paper such as polypropylene synthetic paper and polyethylene synthetic paper can also be suitably used.
- the discoloration 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 according to a known printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, flexographic printing, etc., using the ink composition of the present invention. It can also be formed by methods other than printing.
- 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 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.
- the 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.
- 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.
- 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, such as a resin binder, an extender, and a solvent.
- the formation of the non-discoloring layer may be the same as in the case of the discoloring layer.
- 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.
- one color changing layer and one non-color changing layer may be formed, or a plurality of layers may be formed. Further, the discoloration layers or the 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.
- the discoloration layer and the non-discoloration layer may be formed on the entire surface of the substrate or each layer, or may be partially formed.
- 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.
- 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.
- the color-changing layer and the 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 changes, or the color difference between the color-changing layer and the non-color-changing layer disappears only after the color changing. It can also be formed.
- the color-changing layer and the non-color-changing layer may be formed so that at least one of characters, designs, and symbols appears only when the color-changing layer changes color.
- 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.
- the color changing layer and the non-color changing layer before the color change may be different from each other.
- 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.
- 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. Thereby, the amount of ink to be used can be saved.
- 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.
- 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 between the color changing layer and the non-color changing layer in the color changing-non-color changing layer can be made substantially indistinguishable, it is possible to achieve better design.
- 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.
- the low-pressure plasma treatment include, for example, applications such as cleaning and surface modification of flat panel displays (liquid crystal displays, etc.); applications such as film formation, ashing, cleaning and surface modification in semiconductor manufacturing processes; Or uses such as cleaning of printed wiring boards and surface modification; sterilization applications such as medical instruments; uses such as cleaning of mounted parts and surface modification.
- atmospheric pressure plasma processing include, for example, film formation, ashing, cleaning, surface modification, etc. of flat panel displays (liquid crystal displays, etc.); cleaning of mounting substrates or printed wiring boards, surface modification Applications such as surface modification for automobiles, aircraft parts, etc., and applications such as disinfection, sterilization, and treatment in the medical field (dental or surgery).
- 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.
- 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.
- oxygen, nitrogen examples thereof include hydrogen, argon, helium, and air.
- These atmospheric pressure plasma generating gases can be used alone or in admixture of two or more.
- 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, or on an object to be processed housed therein 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.
- 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 includes inventions of indicators, plasma processing management methods, and physical distribution management methods used for such applications. 3.
- 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.
- a known or commercially available product used as a plasma processing package can be used.
- a package formed of polyethylene fibers polyethylene synthetic paper
- 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.
- the indicator of the present invention may be disposed on the inner surface of the 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.
- an indicator can be formed at the manufacturing stage of the package.
- 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.
- 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.
- the present invention 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 a to-be-processed object in a package, it seals in accordance with well-known methods, such as heat sealing. Next, the whole package is placed in a plasma treatment atmosphere. For example, it arrange
- Drawing Tool Furthermore, the present invention also includes an invention of a drawing tool filled with the ink composition of the present invention.
- the drawing tool includes a writing tool (marker, ballpoint pen, brushed container, stamp, etc.) or applicator, and there is no space for placing an indicator around the plasma processing object due to the size of the plasma processing apparatus. For example, it is possible to confirm that a predetermined plasma treatment is completed by discoloring the mark by marking a part of the workpiece to be subjected to the plasma treatment with the drawing tool.
- a writing tool marker, ballpoint pen, brushed container, stamp, etc.
- applicator there is no space for placing an indicator around the plasma processing object due to the size of the plasma processing apparatus. For example, it is possible to confirm that a predetermined plasma treatment is completed by discoloring the mark by marking a part of the workpiece to be subjected to the plasma treatment with the drawing tool.
- a core-type writing instrument such as a sign pen, or a ballpoint pen.
- a ballpoint pen is a writing instrument in which an ink containing tube loaded with an ink composition is provided in a shaft and the ink composition is leached from a pen tip on which a small sphere is mounted.
- the center-type writing instrument has a center core in which the fiber bundle is converged as an ink containing portion, and a pen tip (tip) that flows out the ink composition stored in the center core.
- a writing instrument provided with a plastic core, a brush-like object, or a brush-like object.
- Writing instruments can be assembled using known members.
- a ballpoint pen is assembled by a known assembling method together with a ballpoint pen tip having a known structure made of a known material by loading the ink composition of the present invention into an ink containing tube formed of a known material and having a known size.
- the ink storage tube is, for example, a synthetic resin pipe such as polyethylene and polypropylene, or a metal pipe.
- the ballpoint pen tip may be a normal one, and a difference between the ball diameter and the ball house inner diameter of, for example, 0.01 mm or more can be used.
- the viscosity of the ink composition of the present invention can be adjusted according to the characteristics and handling properties of each drawing tool.
- the ink composition of the present invention contains a pigment and a nonionic surfactant, (1)
- the dye is at least one of an anthraquinone dye, a methine dye, an azo dye, and a phthalocyanine dye, (2)
- the nonionic surfactant is at least one of the nonionic surfactants represented by the general formulas (I) to (V), so that a plasma treatment detection including a discolored layer made of the ink composition is performed.
- the indicator does not require a large-scale device and can individually detect the completion of the plasma processing using the plasma generating gas for each object to be processed.
- Example 1 Reference example 1, and Comparative example 1, it is a figure which shows the relationship between the processing time and discoloration color difference ((DELTA) E * ab) when nitrogen plasma processing is changed to 10, 20, 30, 40 minutes. is there.
- each ink composition was screen-printed and dried on a white PET film “Toyobo Crisper K2323” to obtain purple indicators.
- Test example 1 Each indicator was subjected to a heat resistance test and a discoloration test. Each test method and evaluation criteria are as follows. ⁇ Heat resistance test ⁇ First, the chromaticity L * a * b * of the color changing layer (before heat treatment) of each indicator was measured with a handy color meter NR-11A manufactured by Nippon Denshoku Industries Co., Ltd.
- each indicator was left to stand in a thermostat at 170 ° C. for 10 minutes for heat treatment. This condition reproduces the situation in which the plasma generating gas is not correctly supplied due to some trouble in the plasma processing apparatus and unintentional overheating occurs.
- the chromaticity before heat treatment is L * 1 , a * 1 , b * 1
- the chromaticity after heat treatment is L * 2 , a * 2 , b * 2
- the chromaticity difference (color difference) is Expressed as E * ab.
- the discoloration color difference ⁇ E * ab 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 Table 1.
- Each indicator is set in a microwave plasma processing device “Toshiba TMP-0063A”, oxygen is prepared as a plasma generating gas, and the condition “oxygen flow rate 0.5 L / min, vacuum degree 1.7 Torr”, frequency 2 Oxygen plasma treatment was performed by applying a microwave of .45 GHz and an output of 0.5 kW for 3 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 Table 1. (Discussion) All indicators turned green by nitrogen plasma treatment and turned pink by oxygen plasma.
- Reference Examples 1 and 2 are the results when the cationic surfactant “Nikkor CA2580”, which has been used as a color change accelerator in the ink composition for detecting plasma treatment, is used, and does not contain a color change accelerator. Compared with Examples 1 and 2, it can be seen that there is a discoloration promoting effect.
- Examples 1, 2 and 4 to 7 were the same as or more than Reference Example 1, and Examples 8 and 10 to 13 had a color change difference of Reference Example 2 or more, and a color change promoting effect was observed. These are examples of imparting the effect of promoting discoloration of both nitrogen plasma and oxygen plasma by the addition of a nonionic surfactant.
- Example 3 and Example 9 are larger than that of Reference Example 1 (comparison with Example 3) and Reference Example 2 (comparison with Example 9) only with respect to nitrogen plasma. No discoloration promoting effect was observed. That is, these are examples in which the discoloration promoting effect is selectively imparted to nitrogen plasma by the addition of a nonionic surfactant.
- FIG. 1 shows the relationship between the treatment time and the color change ( ⁇ E * ab) when the nitrogen plasma treatment was changed to 10, 20, 30, and 40 minutes for Examples 1, 2, Reference Example 1, and Comparative Example 1. Show.
- the plasma processing detection indicator using the ink composition of the present invention can provide a detection sensitivity superior to that of the conventional product.
- the discoloration layers of the indicators of Examples 1 to 7, 9, 10, 13 and Comparative Example 1 containing a phenolic resin as part or all of the binder resin are those in which the binder resin does not contain a phenolic resin. 2, it can be seen that the discoloration color difference ( ⁇ E * ab) in the heat resistance test is small as compared with the discoloration layer of the indicator of Comparative Example 2 and Examples 11 and 12. This result has shown that the heat resistance of a discoloration layer improves by containing a phenol-type resin in binder resin. Therefore, when a phenolic resin is contained in the binder resin, the plasma generation gas is not correctly supplied due to some trouble in the plasma processing apparatus, and the discoloration due to heat alone is suppressed even under unintentional overheating. can do.
- Test example 2 ⁇ Discoloration test ⁇ The discoloration layer (before the plasma treatment) of the indicator of Example 1 produced using the ink composition of Example 1 was subjected to various plasma treatments shown below.
- the discoloration color difference ⁇ E * ab before and after plasma treatment was measured using a handy color difference meter “CR-300 manufactured by Konica Minolta”.
- Plasma treatment (1) Water vapor, hydrogen peroxide plasma , Equipment: High-frequency plasma treatment equipment BP-1 (Samco) ⁇ Vapor: 2mmol / min, power: 75W, pressure: 40Pa, distance between electrodes: 50mm, processing time: 20min
- Test example 4 A discoloration test similar to that of Test Example 2 was performed on the discoloration layer of the indicator of Example 3 prepared using the ink composition of Example 3, and any of plasma treatments (1) to (7) was performed. It was also confirmed that the discoloration color difference ⁇ E * ab before and after the treatment was 5 or more under the above conditions. That is, it was demonstrated that the completion of the plasma treatment can be confirmed.
- Test Example 5 When the same discoloration test as in Test Example 2 was performed on the discoloration layer of the indicator of Example 4 produced using the ink composition of Example 4, any of the plasma treatments (1) to (7) was performed. It was also confirmed that the discoloration color difference ⁇ E * ab before and after the treatment was 5 or more under the above conditions. That is, it was demonstrated that the completion of the plasma treatment can be confirmed.
- Examples 14-17 To 1 part by weight of the ink composition obtained in Examples 1 to 4, 1 part by weight of propylene glycol monomethyl ether was added and stirred for 15 minutes with a stirrer to prepare an oil-based ink composition for ballpoint pens.
- One end of a polypropylene tube is press-fitted with a pen body equipped with a 0.7 mm ⁇ diameter hard ball and a white ballpoint pen socket, filled with the oil-based ink composition for the ballpoint pen, and further centrifuged to remove the ink. A free ink ballpoint pen was produced by removing the bubbles.
- Examples 18-20 To 1 part by weight of the ink composition obtained in Examples 5 to 7, 2 parts by weight of propylene glycol monomethyl ether was added and stirred for 15 minutes with a stirrer to prepare an oil-based ink composition for a marking pen.
- the oil-based ink composition for marking pens was filled in a writing instrument (Oil marker made by Sakura Crepas, trade name “Pen Touch”) using felt as a pen tip.
- Examples 21-27 To 1 part by weight of the ink composition obtained in Examples 8 to 13, 2 parts by weight of propylene glycol monomethyl ether was added and stirred for 15 minutes with a stirrer to prepare an oil-based ink composition for marking pens. An oil-based ink composition for marking pens was filled into a core-type marking pen.
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Abstract
Description
1.色素及びノニオン系界面活性剤を含有するプラズマ処理検知用インキ組成物であって、
(1)前記色素は、アントラキノン系色素、メチン系色素、アゾ系色素、フタロシアニン系色素、トリフェニルメタン系色素及びキサンテン系色素からなる群から選択される少なくとも1種であり、
(2)前記ノニオン系界面活性剤は、一般式(I)~(V)で示されるノニオン系界面活性剤の少なくとも1種である、
ことを特徴とするインキ組成物。
2.更に、バインダー樹脂及び増量剤の少なくとも1種を含有する、上記項1に記載のインキ組成物。
3.前記バインダー樹脂の一部又は全部が、窒素含有高分子である、上記項2に記載のインキ組成物。
4.前記窒素含有高分子の一部又は全部が、ポリアミド樹脂である、上記項3に記載のインキ組成物。
5.前記バインダー樹脂の一部又は全部が、フェノール系樹脂である、上記項2に記載のインキ組成物。
6.前記増量剤の一部又は全部が、シリカである、上記項2~5のいずれかに記載のインキ組成物。
7.更に、前記プラズマ処理雰囲気下で変色しない色素成分の少なくとも1種を含有する、上記項1~6のいずれかに記載のインキ組成物。
8.上記項1~7のいずれかに記載のインキ組成物からなる変色層を含むプラズマ処理検知インジケーター。
9.更に、前記プラズマ処理雰囲気下で変色しない非変色層を含む、上記項8に記載のインジケーター。
10.前記変色層の形状がバーコードの形状である、上記項8又は9に記載のインジケーター。
11.プラズマ処理環境下で前記変色層が変色してバーコードリーダーによる読み取りが可能となることによりプラズマ処理管理が行える、上記項10に記載のインジケーター。
12.気体透過性包装体の内面に上記項8~11のいずれかに記載のインジケーターが設けられているプラズマ処理用包装体。
13.前記インジケーターを外部から確認できるように、包装体の一部に透明窓部が設けられている、上記項12に記載の包装体。
14.上記項12又は13に記載の包装体に被処理物を装填する工程、被処理物が装填された包装体を密封する工程、及び当該包装体を前記プラズマ処理雰囲気下に置く工程を有するプラズマ処理方法。
15.前記インジケーターの変色層が変色するまで前記プラズマ処理雰囲気下に包装体を置く、上記項14に記載の処理方法。
16.上記項1~7のいずれかに記載のインキ組成物を充填した描画具。
1.プラズマ処理検知用インキ組成物
本発明のプラズマ処理検知用インキ組成物(以下、単に「インキ組成物」とも言う)は、色素及びノニオン系界面活性剤を含有し、
(1)前記色素は、アントラキノン系色素、メチン系色素、アゾ系色素及びフタロシアニン系色素からなる群から選択される少なくとも1種であり、
(2)前記ノニオン系界面活性剤は、一般式(I)~(V)で示されるノニオン系界面活性剤の少なくとも1種である、
ことを特徴とする。
本発明のインキ組成物は、着色剤(色素、変色色素とも言う)として、アントラキノン系色素、メチン色素、アゾ系色素及びフタロシアニン系色素からなる群から選択される少なくとも1種を用いる。
本発明のインキ組成物では、ノニオン系界面活性剤は変色促進剤として作用し、着色剤と併用することによって、より優れた検知感度を得ることができる。
で表されるノニオン系界面活性剤は、アルキレングリコール誘導体である。
で表されるノニオン系界面活性剤は、ポリグリセリン誘導体である。
で表されるノニオン系界面活性剤は、アルキレングリコールグリセリル誘導体である。
で表されるノニオン系界面活性剤はアセチレングリコール誘導体である。
バインダー樹脂としては、基材の種類等に応じて適宜選択すればよく、例えば筆記用、印刷用等のインキ組成物に用いられている公知の樹脂成分をそのまま採用できる。例えば、マレイン酸樹脂、ケトン樹脂、ポリビニルブチラール樹脂、セルロース系樹脂、アクリル系樹脂、スチレンマレイン酸樹脂、スチレンアクリル酸樹脂、ポリエステル系樹脂、ポリアミド樹脂、ポリアクリロニトリル樹脂、ポリイミド樹脂、ポリビニルピロリドン樹脂、ポリアクリルアミド樹脂、ポリビニルイミダゾール樹脂、ポリエチレンイミン樹脂、アミノ樹脂等を挙げることができる。
ポリアミド樹脂の種類、分子量等は特に限定されず、公知又は市販のポリアミド樹脂を用いることができる。この中でも、リノール酸の二量体とジアミン又はポリアミンとの反応生成物(長鎖線状重合物)であるポリアミド樹脂を好適に用いることができる。ポリアミド樹脂は、分子量4000~7000の熱可塑性樹脂である。このような樹脂も市販品を用いることができる。
増量剤としては、特に制限されず、例えば、ベントナイト、活性白土、酸化アルミニウム、シリカ、シリカゲル等の無機材料を挙げることができる。その他にも公知の体質顔料として知られている材料を用いることができる。この中でも、シリカ、シリカゲル及びアルミナの少なくもと1種が好ましく、特にシリカがより好ましい。シリカ等を使用する場合には、特に変色層表面に複数のクラックを効果的に生じさせることができる。その結果、インジケーターの検知感度をより高めることができる。
本発明のインキ組成物は、必要に応じて溶剤、レベリング剤、消泡剤、紫外線吸収剤、表面調整剤等の公知のインキに用いられている成分を適宜配合することができる。
2.プラズマ処理検知インジケーター
本発明のインジケーターは、本発明のインキ組成物からなる変色層を含む。一般的には、基材上に本発明のインキ組成物を塗布又は印刷することによって変色層を形成することができる。この場合の基材としては、変色層を形成できるものであれば特に制限されない。
3.包装体
本発明は、気体透過性包装体の内面に本発明のインジケーターが設けられているプラズマ処理用包装体を包含する。
4.描画具
更に、本発明は本発明のインキ組成物を充填した描画具の発明も包含している。
(1)前記色素は、アントラキノン系色素、メチン系色素、アゾ系色素及びフタロシアニン系色素の少なくとも1種であり、
(2)前記ノニオン系界面活性剤は、一般式(I)~(V)で示されるノニオン系界面活性剤の少なくとも1種であることにより、当該インキ組成物からなる変色層を含むプラズマ処理検知インジケーターは、大掛かりな装置を必要とせず、被処理物のそれぞれについて、プラズマ発生用ガスを用いたプラズマ処理の完了を個別検知することができる。
表1に示される組成で各成分を混合することにより各インキ組成物を調製した。
各インジケーターに対して耐熱性試験及び変色性試験を行った。各試験方法及び評価基準は下記の通りである。
≪耐熱性試験≫
先ず、各インジケーターの変色層(熱処理前)の色度L*a*b*を日本電色工業株式会社製ハンディー型色彩計NR-11Aで測色した。
試験結果を表1に示す。
≪変色性試験≫
(窒素プラズマ処理)
各インジケーターをマイクロ波プラズマ処理装置「東芝製TMP-0063A」にセットし、プラズマ発生用ガスとして窒素を用意し、条件「窒素流量0.5L/分、真空度1.7Torr」にて、周波数2.45GHz、出力1kWのマイクロ波を10分印加することで窒素プラズマ処理を行った。
(酸素プラズマ処理)
各インジケーターをマイクロ波プラズマ処理装置「東芝製TMP-0063A」にセットし、プラズマ発生用ガスとして酸素を用意し、条件「酸素流量0.5L/分、真空度1.7Torr」にて、周波数2.45GHz、出力0.5kWのマイクロ波を3分印加することで酸素プラズマ処理を行った。
(考 察)
いずれのインジケーターも、窒素プラズマ処理によって緑色に、酸素プラズマによってピンク色に変色した。参考例1及び2は、従来からプラズマ処理検知用インキ組成物で変色促進剤として用いられているカチオン性界面活性剤「ニッコールCA2580」を使用した時の結果であり、変色促進剤を含まない比較例1及び2と比べると変色促進効果があることが分かる。
≪変色性試験≫
実施例1のインキ組成物を用いて作製した実施例1のインジケーターの変色層(プラズマ処理前)を下記に示す種々のプラズマ処理にそれぞれ供した。
(プラズマ処理条件)
プラズマ処理(1):水蒸気・過酸化水素プラズマ
・装置:高周波プラズマ処理装置BP-1(サムコ製)
・蒸気:2mmol/min,電力:75W, 圧力:40Pa, 極間距離:50mm,処理時間:20min
プラズマ処理(2):四フッ化炭素プラズマ
・装置:高周波プラズマ処理装置BP-1(サムコ製)
・CF4ガス:5ml/min,電力:75W, 圧力:100Pa, 極間距離:50mm,処理時間:10min
プラズマ処理(3):アルゴンプラズマ
・装置:高周波プラズマ処理装置BP-1(サムコ製)
・Arガス:20ml/min,電力:75W, 圧力:20Pa, 極間距離:50mm,処理時間:30min
プラズマ処理(4):大気圧プラズマ
・装置:プラズマトリートシステム(理化精機製)
・ガス:ドライエアー40L/h,照射距離:10mm,処理時間:400m/s×10回
プラズマ処理(5):大気圧プラズマ
・装置:タフプラズマ(富士機械製造製)
・ガス:N229.7L/min+ドライエアー0.3L/min,照射距離:10mm,処理時間:20m/s×10回
プラズマ処理(6):大気圧プラズマ
・装置:Precise300C(イースクエア製)
・ガス:N2125/min+H2O 2L/min,照射距離:1mm,処理時間:1m/s×10回
プラズマ処理(7):大気圧プラズマ
・装置:Precise300C(イースクエア製)
・ガス:N2125/min+H2 3.6L/min,照射距離:1mm,処理時間:1m/s×10回
試験例3
実施例2のインキ組成物を用いて作製した実施例2のインジケーターの変色層に対して、試験例2と同様の変色性試験をそれぞれ実施したところ、プラズマ処理(1)~(7)のいずれの条件においても処理前後の変色色差ΔE*abが5以上であることを確認した。即ち、プラズマ処理の完了を確認できることが実証された。
実施例3のインキ組成物を用いて作製した実施例3のインジケーターの変色層に対して、試験例2と同様の変色性試験をそれぞれ実施したところ、プラズマ処理(1)~(7)のいずれの条件においても処理前後の変色色差ΔE*abが5以上であることを確認した。即ち、プラズマ処理の完了を確認できることが実証された。
実施例4のインキ組成物を用いて作製した実施例4のインジケーターの変色層に対して、試験例2と同様の変色性試験をそれぞれ実施したところ、プラズマ処理(1)~(7)のいずれの条件においても処理前後の変色色差ΔE*abが5以上であることを確認した。即ち、プラズマ処理の完了を確認できることが実証された。
実施例1~4で得られたインキ組成物1重量部に対してプロピレングリコールモノメチルエーテル1重量部を加えて攪拌機で15分撹拌し、ボールペン用油性インキ組成物を調製した。ポリプロピレン製のチューブの一端に、直径0.7mmφの超硬ボールと洋白製ボールペンソケットを装着したペン体を圧入し、前記ボールペン用油性インキ組成物を充填した後、更に遠心分離でインキ中の泡を除去することで、フリーインキ式ボールペンを作製した。
実施例5~7で得られたインキ組成物1重量部に対してプロピレングリコールモノメチルエーテル2重量部を加えて攪拌機で15分撹拌し、マーキングペン用油性インキ組成物を調製した。マーキングペン用油性インキ組成物を、フェルトをペン先として使用した筆記具(サクラクレパス社製油性マーカー、商品名「ペンタッチ」)に充填した。
実施例8~13で得られたインキ組成物1重量部に対してプロピレングリコールモノメチルエーテル2重量部を加えて攪拌機で15分撹拌し、マーキングペン用油性インキ組成物を調製した。マーキングペン用油性インキ組成物を、中芯式マーキングペンに充填した。
Claims (16)
- 色素及びノニオン系界面活性剤を含有するプラズマ処理検知用インキ組成物であって、
(1)前記色素は、アントラキノン系色素、メチン系色素、アゾ系色素、フタロシアニン系色素、トリフェニルメタン系色素及びキサンテン系色素からなる群から選択される少なくとも1種であり、
(2)前記ノニオン系界面活性剤は、一般式(I)~(V)で示されるノニオン系界面活性剤の少なくとも1種である、
ことを特徴とするインキ組成物。 - 更に、バインダー樹脂及び増量剤の少なくとも1種を含有する、請求項1に記載のインキ組成物。
- 前記バインダー樹脂の一部又は全部が、窒素含有高分子である、請求項2に記載のインキ組成物。
- 前記窒素含有高分子の一部又は全部が、ポリアミド樹脂である、請求項3に記載のインキ組成物。
- 前記バインダー樹脂の一部又は全部が、フェノール系樹脂である、請求項2に記載のインキ組成物。
- 前記増量剤の一部又は全部が、シリカである、請求項2~5のいずれかに記載のインキ組成物。
- 更に、前記プラズマ処理雰囲気下で変色しない色素成分の少なくとも1種を含有する、請求項1~6のいずれかに記載のインキ組成物。
- 請求項1~7のいずれかに記載のインキ組成物からなる変色層を含むプラズマ処理検知インジケーター。
- 更に、前記プラズマ処理雰囲気下で変色しない非変色層を含む、請求項8に記載のインジケーター。
- 前記変色層の形状がバーコードの形状である、請求項8又は9に記載のインジケーター。
- プラズマ処理環境下で前記変色層が変色してバーコードリーダーによる読み取りが可能となることによりプラズマ処理管理が行える、請求項10に記載のインジケーター。
- 気体透過性包装体の内面に請求項8~11のいずれかに記載のインジケーターが設けられているプラズマ処理用包装体。
- 前記インジケーターを外部から確認できるように、包装体の一部に透明窓部が設けられている、請求項12に記載の包装体。
- 請求項12又は13に記載の包装体に被処理物を装填する工程、被処理物が装填された包装体を密封する工程、及び当該包装体を前記プラズマ処理雰囲気下に置く工程を有するプラズマ処理方法。
- 前記インジケーターの変色層が変色するまで前記プラズマ処理雰囲気下に包装体を置く、請求項14に記載の処理方法。
- 請求項1~7のいずれかに記載のインキ組成物を充填した描画具。
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- 2014-05-29 KR KR1020157033730A patent/KR102190811B1/ko active IP Right Grant
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US10181414B2 (en) | 2013-08-22 | 2019-01-15 | Sakura Color Products Corporation | Indicator used in electronic device manufacturing apparatus and method for designing and/or managing the apparatus |
US10401338B2 (en) | 2014-02-14 | 2019-09-03 | Sakura Color Products Corporation | Plasma processing detection indicator |
US20170044389A1 (en) * | 2014-04-21 | 2017-02-16 | Sakura Color Products Corporation | Ink composition for detecting plasma treatment and indicator for detecting plasma treatment |
US10184058B2 (en) * | 2014-04-21 | 2019-01-22 | Sakura Color Products Corporation | Ink composition for detecting plasma treatment and indicator for detecting plasma treatment |
US10180392B2 (en) | 2014-05-09 | 2019-01-15 | Sakura Color Products Corporation | Plasma processing detection indicator using inorganic substance as a color-change layer |
US20170101548A1 (en) * | 2014-09-16 | 2017-04-13 | Sakura Color Products Corporation | Ink composition for plasma treatment detection, and plasma treatment detection indicator |
US10400125B2 (en) * | 2014-09-16 | 2019-09-03 | Sakura Color Products Corporation | Ink composition for plasma treatment detection, and plasma treatment detection indicator |
US10180413B2 (en) | 2014-12-02 | 2019-01-15 | Sakura Color Products Corporation | Ink composition for plasma processing detection, and indicator for plasma processing detection using said ink composition |
Also Published As
Publication number | Publication date |
---|---|
JP6126042B2 (ja) | 2017-05-10 |
US20160133444A1 (en) | 2016-05-12 |
CN105308132A (zh) | 2016-02-03 |
KR20160014611A (ko) | 2016-02-11 |
CN105308132B (zh) | 2017-11-10 |
JP2015013982A (ja) | 2015-01-22 |
TWI628243B (zh) | 2018-07-01 |
TW201905114A (zh) | 2019-02-01 |
KR102190811B1 (ko) | 2020-12-14 |
TW201512321A (zh) | 2015-04-01 |
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