WO2018008586A1 - Composition for plasma processing detection and indicator for plasma processing detection - Google Patents

Composition for plasma processing detection and indicator for plasma processing detection Download PDF

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Publication number
WO2018008586A1
WO2018008586A1 PCT/JP2017/024314 JP2017024314W WO2018008586A1 WO 2018008586 A1 WO2018008586 A1 WO 2018008586A1 JP 2017024314 W JP2017024314 W JP 2017024314W WO 2018008586 A1 WO2018008586 A1 WO 2018008586A1
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Prior art keywords
composition
plasma processing
plasma
plasma treatment
color
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PCT/JP2017/024314
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French (fr)
Japanese (ja)
Inventor
武志 作村
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株式会社サクラクレパス
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Application filed by 株式会社サクラクレパス filed Critical 株式会社サクラクレパス
Priority to JP2018526361A priority Critical patent/JP6951765B2/en
Priority to CN201780028056.XA priority patent/CN109154589B/en
Priority to KR1020187030439A priority patent/KR102199265B1/en
Publication of WO2018008586A1 publication Critical patent/WO2018008586A1/en

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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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/226—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating the degree of sterilisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching

Definitions

  • the present invention relates to a plasma processing detection composition and a plasma processing detection indicator.
  • 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.
  • an end point detection method requires a large-scale apparatus such as an emission spectrum analysis apparatus and an arithmetic output apparatus, and it is difficult to individually detect each of the plasma processed objects.
  • an object of the present invention is to provide a highly sensitive plasma processing detection composition and a plasma processing detection indicator.
  • the present inventors have found that the presence or absence of plasma treatment can be detected with high sensitivity by using a combination of a predetermined dye and a color change accelerator, and the present invention is completed. It came to.
  • the present invention [1] Contains one or more first dyes selected from the group consisting of azo, anthraquinone, methine, and xanthene, and a discoloration accelerator for promoting discoloration of the first dye in a plasma treatment atmosphere
  • the discoloration promoter comprises one or more compounds represented by a chemical structural formula including a chemical structure in which two benzene rings are linked by a single bond or a linking group,
  • the linking group is a composition for detecting plasma treatment, characterized in that two or three single bonds are connected in series to connect two benzene rings,
  • the plasma treatment detection composition according to [1] wherein the discoloration accelerator includes one or more compounds represented by general formulas (1) to (3),
  • R 1 to R 10 may be the same or different and each may have a hydrogen atom or an arbitrary substituent.
  • L 1 and L 2 each independently represent a linking group represented by —CH 2 —, —O—, or —S—, and —CH 2 — is a substituent instead of a hydrogen atom. You may have.
  • the presence or absence of plasma processing can be detected with high sensitivity.
  • composition for plasma treatment detection of the present invention comprises one or more first dyes selected from the group consisting of azo, anthraquinone, methine, and xanthene, and a plasma treatment atmosphere of the first dye.
  • a composition for plasma treatment detection comprising a color change accelerator for promoting discoloration below, wherein the color change accelerator includes a chemical structure in which two benzene rings are linked by a single bond or a linking group.
  • the color change accelerator includes a chemical structure in which two benzene rings are linked by a single bond or a linking group.
  • One or more compounds represented by a chemical structural formula are included, and the linking group connects two benzene rings by connecting two or three single bonds in series.
  • the plasma atmosphere in the present invention means an environment of plasma treatment using plasma generated by applying a plasma generating gas and applying an AC voltage, a pulse voltage, a high frequency, a microwave, or the like.
  • the plasma treatment detection composition of the present invention uses one or more dyes selected from the group consisting of azo, anthraquinone, methine, and xanthene as the first dye.
  • 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, CI Disperse Red 167: 1 and the like. These can be used alone or in combination of two or more.
  • 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 (CIDisperseViolet 1), 1-amino-4-hydroxy-2-methylaminoanthraquinone (CIDisperseRed 4), 1-amino-4-methylaminoanthraquinone (CIDisperse Violet 4), 1,4-diamino-2-methoxyanthraquinone (CIDisperse Red 11), 1-amino-2-methylanthraquinone (CIDisperseOrange 11), 1-amino-4-hydroxyanthraquinone (CIDisperse Red 15), 1,4,5,8-tetraaminoanthraquinone (CIDispersepersBlue 1), 1,4-diamino-5-nitroanthraquinone (CIDisperseViolet 8) and the like (color index names in parentheses).
  • 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, CIBasicRed 36, CIBasic Red 37, CIBasic Red 45, CIBasic Red 48, CIBasic Yellow 11, CIBasic Yellow 12, CIBasic Yellow 13, CIBasic Yellow 14, CIBasicYellow 21, CIBasic Yellow 22, CIBasicYellow 23, CIBasic Yellow 24, CIBasicViolet 7, CIBasic Violet 15, CIBasicViolet 16, CIBasic Violet 20, CIBasicViolet 21, CIBasic Violet 39, CIBasicBlue 62, CIBasic Blue 63 and the like. These 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 first dye can be appropriately determined according to the type, desired hue, and the like, but generally it is preferably 0.05 to 5% by mass in the plasma processing detection composition of the present invention. More preferably, the content is 0.1 to 1% by mass.
  • the discoloration accelerator of the present invention includes one or more compounds represented by a chemical structural formula including a chemical structure in which two benzene rings are linked by a single bond or a linking group, and the linking group includes two linking groups. Alternatively, two benzene rings are connected by connecting three single bonds in series.
  • a single bond is a bond that shares a pair of shared electrons between adjacent molecules.
  • a single bond that connects two benzene rings is on two different benzene rings. It is formed by sharing a pair of shared electrons of each one existing carbon atom.
  • the linking group is a chemical structure that connects two benzene rings in the color change accelerator according to the present invention, and the two benzene rings are connected by a structure in which two or three single bonds are connected in series.
  • the linking group may be formed by any atom as long as the two benzene rings are linked by two or three single bonds, and may have an arbitrary substituent.
  • At least one discoloration accelerator represented by the following general formulas (1) to (3).
  • R 1 to R 10 may be the same or different and each may have a hydrogen atom or an arbitrary substituent.
  • the color change accelerator represented by is a biphenyl derivative.
  • R 1 to R 10 may be the same or different and each may have a hydrogen atom or an arbitrary substituent.
  • L 1 represents a linking group represented by —CH 2 —, —O—, or —S—, and —CH 2 — may have a substituent instead of a hydrogen atom. . ] Is a diphenylmethane derivative.
  • R 1 to R 10 may be the same or different and each may have a hydrogen atom or an arbitrary substituent.
  • L1 represents a linking group represented by —CH 2 —, —O—, or —S—, and —CH 2 — may have a substituent instead of a hydrogen atom.
  • color change accelerator corresponding to the general formula (1) examples include biphenyl.
  • color change accelerator corresponding to the above general formula (2) examples include diphenylmethane, diphenyl ether, 2,2bis (4-methylphenyl) -hexafluoropropane, diphenyl sulfide and the like.
  • color change accelerator corresponding to the general formula (3) examples include dibenzyl, benzylphenyl ether, benzylphenyl sulfide, and diphenyl disulfide.
  • the discoloration accelerator can be appropriately determined according to the type and the type of the first dye to be used, and is included in 0.5 to 10 parts by mass in 100 parts by mass of the plasma processing detection composition. Preferably, 2 to 8 parts by mass are contained, more preferably 4 to 6 parts by mass. If the amount of the color change accelerator in 100 parts by mass of the plasma treatment detection composition is less than 0.5 parts by mass, the color change sensitivity of the plasma treatment detection composition in the plasma treatment atmosphere may be lowered. On the other hand, even if the amount exceeds 10 parts by mass, the discoloration sensitivity does not improve further, and from the viewpoint of cost effectiveness, the amount is preferably 10 parts by mass or less.
  • dye and the composition for plasma processing detection which concerns on this invention may also contain the 2nd pigment
  • the second dye a known dye can be widely used as long as it is a dye that does not change color in the plasma treatment atmosphere.
  • plasma is used in the plasma treatment atmosphere as described above. What has the color which can clarify the change of the color tone of the composition for process detection more is preferable. What is necessary is just to set content of a 2nd pigment
  • the binder resin or the plasma processing detection composition of the present invention may contain a binder resin.
  • 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 used as they are.
  • nitrocellulose can be suitably used particularly for part or all of it.
  • the discoloration of the plasma treatment detection composition of the present invention in a plasma treatment atmosphere can be detected with higher sensitivity.
  • the content of the binder resin can be appropriately determined according to the type of the binder resin, the type of the dye to be used, etc., but in general, the content is preferably 50% by mass or less in the plasma treatment detection composition, and 5 to 35% by mass. % Is more preferable.
  • the bulking agent or the plasma processing detection composition of the present invention may contain a bulking agent.
  • the 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.
  • silica is preferable. By using silica in part or all of the extender, 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 and colorant to be used, but generally it is preferably about 1 to 30% by mass in the plasma treatment detection composition. It is more preferable to set it as the mass%.
  • composition for plasma treatment detection of the present invention appropriately contains components used in known inks such as a solvent, a leveling agent, an antifoaming agent, an ultraviolet absorber, and a surface conditioner as necessary. be able to.
  • 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 solvent it is necessary to use what can be finally removed from a coating film by normal temperature or heat drying.
  • 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 is generally about 40 to 95% by mass, particularly 60 to 90% by mass in the plasma processing detection composition. desirable.
  • Viscosity can be adjusted by adjusting the content of the solvent, and a plasma treatment detection composition having a viscosity suitable for various printing methods can be provided.
  • the viscosity of the plasma treatment detection composition is preferably less than 12000 mPa ⁇ s, particularly about 500 to 8000 mPa ⁇ s as a viscosity suitable for silk screen printing, and as a viscosity suitable for gravure printing. It is about 10 to 500 mPa ⁇ s.
  • the components of the plasma processing detection 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.
  • first, at least one of the first pigment, the binder resin, the color change accelerator, and the extender (other additives as necessary) may be blended in the solvent in order, and mixed and stirred with a stirrer.
  • Plasma treatment detection indicator The indicator of the present invention includes a discoloration layer made of the plasma treatment detection composition of the present invention.
  • a discoloration layer can be formed by applying or printing the composition for detecting plasma treatment of the present invention on a substrate.
  • 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 plasma processing detection composition of the present invention. It can also be formed by methods other than printing. For example, a discoloration layer can also be formed by immersing a base material in the composition for plasma processing detection. It is particularly suitable for a material that easily penetrates liquid, 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 present invention indicator 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.
  • Examples 1 to 7 and Comparative Example 1 A red azo dye (CI Disperse Red 167: 1) was used as the first dye in the present invention, and a green phthalocyanine pigment (CI Pigment Green 7) was used as the second dye. After preparing a plasma treatment detection composition based on the composition of Table 1, silk-screen printing on a Toyobo PET base material (trade name: Krisper, product number: K2323), and drying in an 80 ° C. environment for 20 minutes, The indicators of Examples 1 to 7 and Comparative Example 1 were obtained.
  • CI Disperse Red 167: 1 red azo dye
  • CI Pigment Green 7 green phthalocyanine pigment
  • Examples 8-14 As shown in Table 2, plasma treatment detection compositions were prepared by varying the dibenzyl content in Example 1 above, and indicators of Examples 8 to 14 were obtained. (Discoloration test) The indicators of the examples and comparative examples were measured using a handy color meter (product number: NR-11A) manufactured by Nippon Denshoku Industries Co., Ltd. After that, each example and comparative example were installed in a parallel plate high-frequency plasma apparatus (manufactured by Samco, product number: BP-1), oxygen was prepared as a plasma generating gas, oxygen flow rate 10 mL / min, power 15 W, pressure Oxygen plasma treatment was performed under the condition of 10 Pa for (3) minutes. After the oxygen plasma treatment, color measurement was performed again for each of the examples and comparative examples.
  • Example 1 using dibenzyl, benzylphenyl ether, benzylphenyl sulfide, 2,2 bis (4-methylphenyl) -hexafluoropropene, biphenyl, diphenyl ether, diphenylmethane, respectively, as the color change accelerator.
  • the indicators 2, 3, 4, 5, 6, and 7 had a large ⁇ E * ab value as compared with the indicator of Comparative Example 1 that did not use these discoloration accelerators. Therefore, it was confirmed that the sensitivity of the indicator was increased by using the color change accelerator of the present invention for the indicators of Examples 1 to 7. Further, as shown in Table 2, from the results of Examples 1 and 8 to 14, it was confirmed that the sensitivity of the indicator was increased by setting the color change accelerator to a predetermined concentration.

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Abstract

[Problem] To provide a composition for plasma processing detection and an indicator for plasma processing detection, which have high sensitivity. [Solution] A composition for plasma processing detection, which contains one or more first dyes selected from the group consisting of azo, anthraquinone, methine and xanthene and a discoloration accelerator that accelerates discoloration of the first dyes in a plasma processing atmosphere. This composition for plasma processing detection is characterized in that: the discoloration accelerator contains one or more compounds represented by a chemical structural formula that comprises a chemical structure wherein two benzene rings are linked by a single bond or a linking group; and the linking group links the two benzene rings by having two or three single bonds connected in series.

Description

プラズマ処理検知用組成物及びプラズマ処理検知用インジケーターPlasma treatment detection composition and plasma treatment detection indicator
　本発明は、プラズマ処理検知用組成物及びプラズマ処理検知用インジケーターに関する。なお、本明細書におけるプラズマ処理は、プラズマ発生用ガスを用い、交流電圧、パルス電圧、高周波、マイクロ波等を印加することにより発生するプラズマを利用したプラズマ処理を意味し、減圧プラズマ及び大気圧プラズマの両方が該当する。 The present invention relates to a plasma processing detection composition and a plasma processing detection indicator. 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.
　病院、研究所等において使用される各種の器材、器具等は、消毒及び殺菌のために滅菌処理が施される。この滅菌処理の一つとしてプラズマ滅菌処理が知られている（例えば、非特許文献１の「3.3.1低圧力放電プラズマを用いた滅菌実験」欄）。 Various equipment and instruments used in hospitals and laboratories are sterilized for disinfection and sterilization. Plasma sterilization is known as one of the sterilization processes (for example, “3.3.1 Sterilization experiment using low-pressure discharge plasma” in Non-Patent Document 1).
　詳細には、プラズマ滅菌処理は、プラズマ発生用ガス雰囲気下でプラズマを発生させ、低温ガスプラズマにより器材、器具等を滅菌するものであり、低温滅菌処理できる点で有利である。 In detail, 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.
　また、プラズマ処理は、滅菌処理だけでなく半導体素子の製造工程におけるプラズマドライエッチング及び電子部品などの被処理物の表面のプラズマ洗浄にも用いられている。 Further, 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.
　プラズマドライエッチングは、一般的には、真空容器である反応チャンバー内に配置された電極に高周波電力を印加し、反応チャンバー内に導入したプラズマ発生用ガスをプラズマ化して半導体ウェハーを高精度にエッチングする。また、プラズマ洗浄は、電子部品などの被処理物の表面に析出又は付着した金属酸化物、有機物、バリ等を除去することにより、ボンディング性や半田の濡れ性を改善して接着強度を向上させたり、封止樹脂との密着性や濡れ性を改善させたりする。 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.
　これらのプラズマ処理の終点を検知する方法としては、例えば、特許文献１には、「ガスプラズマ中からの発光スペクトルを波長範囲３００～６５０ｎｍのフォトマルチプライアがもつ波長帯域で全て受光することにより得られる発光スペクトル強度曲線を用いたことを特徴とするプラズマドライエッチングの終点検知方法。」が記載されている。 As a method for detecting the end point of these plasma treatments, for example, 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.
　また、特許文献２には、「ある特定波長領域のみを選択的に透過させるバンドパスフィルタに監視するプラズマ光源からの入射角度が変化する入射角変化手段を用いて透過波長を変化させる透過工程と、この透過工程で透過した分光を検知器で検知する検知工程と、この検知工程の検知器からの検知出力および前記透過工程の入射角変化手段の角度出力が入力されることにより、入射角度が変化しても透過波長の検知出力が入射角度を変化させないで得られる値になるようにする波長変換手段、出力補正手段を備える演算出力装置で反応中と反応前を比較演算し、出力装置にプラズマ処理の終点を出力する演算出力工程とを含むことを特徴とするプラズマ処理の終点検知方法。」が記載されている。しかしこのような終点検知方法は、発光スペクトルの解析装置、演算出力装置等の大がかりな装置が必要である上、プラズマ処理された被処理物のそれぞれについて個別検知することは困難である。 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. However, such an end point detection method requires a large-scale apparatus such as an emission spectrum analysis apparatus and an arithmetic output apparatus, and it is difficult to individually detect each of the plasma processed objects.
　その他、これまでに多くのプラズマ処理検知用インキ組成物やプラズマ処理検知用インジケーターが提案されてきたが、感度の高さという点では不十分なものが多くあり、いまだ改善の余地が残されていた。 In addition, many ink compositions for plasma processing detection and indicators for plasma processing detection have been proposed so far, but many of them are insufficient in terms of sensitivity, and there is still room for improvement. It was.
特開平６－０６９１６５号公報Japanese Patent Application Laid-Open No. 6-069165 特開２００４－１４６７３８号公報JP 2004-146738 A
　上記のような事情に鑑み、本発明の目的とするところは、感度の高いプラズマ処理検知用組成物及びプラズマ処理検知用インジケーターを提供することにある。 In view of the circumstances as described above, an object of the present invention is to provide a highly sensitive plasma processing detection composition and a plasma processing detection indicator.
　本発明者は上記課題を解決すべく鋭意研究を重ねた結果、所定の色素と変色促進剤との組み合わせを利用することで、プラズマ処理の有無を感度よく検知できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the presence or absence of plasma treatment can be detected with high sensitivity by using a combination of a predetermined dye and a color change accelerator, and the present invention is completed. It came to.
　即ち、本発明は、
　〔１〕アゾ、アントラキノン、メチン、及びキサンテンからなる群から選択される１種以上の第１の色素及び該第１の色素のプラズマ処理雰囲気下での変色を促進するための変色促進剤を含有するプラズマ処理検知用組成物であって、前記変色促進剤は、２つのベンゼン環が単結合又は連結基により連結された化学構造を包含する化学構造式により表わされる化合物を１種以上含み、前記連結基は、２つ又は３つの単結合が直列につながることにより２つのベンゼン環を連結することを特徴とする、プラズマ処理検知用組成物、
　〔２〕前記変色促進剤は、一般式（１）～（３）により表わされる化合物を１種以上含む、前記〔１〕に記載のプラズマ処理検知用組成物、 That is, the present invention
[1] Contains one or more first dyes selected from the group consisting of azo, anthraquinone, methine, and xanthene, and a discoloration accelerator for promoting discoloration of the first dye in a plasma treatment atmosphere The discoloration promoter comprises one or more compounds represented by a chemical structural formula including a chemical structure in which two benzene rings are linked by a single bond or a linking group, The linking group is a composition for detecting plasma treatment, characterized in that two or three single bonds are connected in series to connect two benzene rings,
[2] The plasma treatment detection composition according to [1], wherein the discoloration accelerator includes one or more compounds represented by general formulas (1) to (3),
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
〔但し、上記一般式中、Ｒ１～Ｒ１０は、同一又は異なって、水素原子または任意の置換基を有していてもよい。また、上記一般式中、Ｌ１、Ｌ２は、それぞれ独立に－ＣＨ２－、－Ｏ－、又は－Ｓ－で表わされる連結基を表し、－ＣＨ２－は水素原子に替えて置換基を有していてもよい。〕
　〔３〕プラズマ処理検知用組成物１００質量部中に前記変色促進剤が０．５～１０質量部含まれる、前記〔１〕又は〔２〕に記載のプラズマ処理検知用組成物、
　〔４〕さらにプラズマ処理雰囲気下で変色しない第２の色素を含む、前記〔１〕～〔３〕のいずれかに記載のプラズマ処理検知用組成物、
　〔５〕さらにバインダー樹脂として、該バインダー樹脂の一部又は全部にニトロセルロースを含有する、前記〔１〕～〔４〕のいずれかに記載のプラズマ処理検知用組成物、
　〔６〕さらに増量剤として、該増量剤の一部又は全部にシリカを含有する、前記〔１〕～〔５〕のいずれかに記載のプラズマ処理検知用組成物、
　〔７〕前記〔１〕～〔６〕のいずれかに記載のプラズマ処理検知用組成物を用いて形成された変色層を有するプラズマ処理検知インジケーター、
　に関する。 [However, in the above general formula, R 1 to R 10 may be the same or different and each may have a hydrogen atom or an arbitrary substituent. In the above general formula, L 1 and L 2 each independently represent a linking group represented by —CH 2 —, —O—, or —S—, and —CH 2 — is a substituent instead of a hydrogen atom. You may have. ]
[3] The plasma treatment detection composition according to [1] or [2], wherein 0.5 to 10 parts by weight of the discoloration accelerator is contained in 100 parts by weight of the plasma treatment detection composition,
[4] The plasma treatment detection composition according to any one of [1] to [3], further comprising a second dye that does not change color in a plasma treatment atmosphere,
[5] The composition for detecting plasma treatment according to any one of [1] to [4], further comprising nitrocellulose as a binder resin in part or all of the binder resin;
[6] The composition for detecting plasma treatment according to any one of [1] to [5], further comprising silica as part of or all of the extender as an extender;
[7] A plasma processing detection indicator having a discoloration layer formed using the plasma processing detection composition according to any one of [1] to [6],
About.
　以上にしてなる本発明に係るプラズマ処理検知用組成物及びプラズマ処理検知用インジケーターによれば、プラズマ処理の有無を感度良く検知することができる。 According to the plasma processing detection composition and the plasma processing detection indicator according to the present invention as described above, the presence or absence of plasma processing can be detected with high sensitivity.
　以下、本発明のプラズマ処理検知用組成物及びプラズマ処理検知インジケーターについて詳細に説明する。
１．プラズマ処理検知用組成物
　本発明のプラズマ処理検知用組成物は、アゾ、アントラキノン、メチン、及びキサンテンからなる群から選択される１種以上の第１の色素及び該第１の色素のプラズマ処理雰囲気下での変色を促進するための変色促進剤を含有するプラズマ処理検知用組成物であって、前記変色促進剤は、２つのベンゼン環が単結合又は連結基により連結された化学構造を包含する化学構造式により表わされる化合物を１種以上含み、前記連結基は、２つ又は３つの単結合が直列につながることにより２つのベンゼン環を連結することを特徴とする。 Hereinafter, the composition for plasma processing detection and the plasma processing detection indicator of the present invention will be described in detail.
1. Composition for Plasma Treatment Detection The composition for plasma treatment detection of the present invention comprises one or more first dyes selected from the group consisting of azo, anthraquinone, methine, and xanthene, and a plasma treatment atmosphere of the first dye. A composition for plasma treatment detection comprising a color change accelerator for promoting discoloration below, wherein the color change accelerator includes a chemical structure in which two benzene rings are linked by a single bond or a linking group. One or more compounds represented by a chemical structural formula are included, and the linking group connects two benzene rings by connecting two or three single bonds in series.
　本発明におけるプラズマ雰囲気下とは、プラズマ発生用ガスを用い、交流電圧、パルス電圧、高周波、マイクロ波等を印加することにより発生するプラズマを利用したプラズマ処理の環境下を意味するものである。 The plasma atmosphere in the present invention means an environment of plasma treatment using plasma generated by applying a plasma generating gas and applying an AC voltage, a pulse voltage, a high frequency, a microwave, or the like.
　第１の色素
　本発明のプラズマ処理検知用組成物は、第１の色素として、アゾ、アントラキノン、メチン、及びキサンテンからなる群から選択される１種以上の色素を使用する。 First Dye The plasma treatment detection composition of the present invention uses one or more dyes selected from the group consisting of azo, anthraquinone, methine, and xanthene as the first dye.
　アゾ系色素は、発色団としてアゾ基－Ｎ＝Ｎ－を有するものであれば限定されない。例えば、モノアゾ色素、ポリアゾ色素、金属錯塩アゾ色素、スチルベンアゾ色素、チアゾールアゾ色素等が挙げられる。より具体的にカラーインデックス名で表記すれば、C.I.Solvent Red 1、C.I.Solvent Red 3、C.I.Solvent Red 23、C.I.Disperse Red 13、C.I.Disperse Red 52、C.I.Disperse Violet 24、C.I.Disperse Blue 44、C.I.Disperse Red 58、C.I.Disperse Red 88、C.I.Disperse Yellow 23、C.I.Disperse Orange 1、C.I.Disperse Orange 5、C.I. Disperse Red 167:1等を挙げることができる。これらは、１種又は２種以上で用いることができる。 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, CIDisperse Red 88, CIDisperse Yellow 23, CIDisperse Orange 1, CIDisperse Orange 5, CI Disperse Red 167: 1 and the like. These can be used alone or in combination of two or more.
　アントラキノン系色素はアントラキノンを基本骨格とするものであれば限定的でなく、公知のアントラキノン系分散染料等も使用できる。特にアミノ基を有するアントラキノン系色素が好ましい。より好ましくは、第一アミノ基及び第二アミノ基の少なくとも１種のアミノ基を有するアントラキノン系色素である。この場合、各アミノ基は、２以上有していてもよく、これらは互いに同種又は相異なってもよい。 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.
　より具体的には、例えば１，４－ジアミノアントラキノン（C.I.DisperseViolet 1）、１－アミノ－４－ヒドロキシ－２－メチルアミノアントラキノン（C.I.DisperseRed 4）、１－アミノ－４－メチルアミノアントラキノン（C.I.Disperse Violet 4）、１，４－ジアミノ－２－メトキシアントラキノン（C.I.Disperse Red 11）、１－アミノ－２－メチルアントラキノン（C.I.DisperseOrange 11）、１－アミノ－４－ヒドロキシアントラキノン（C.I.Disperse Red 15）、１，４，５，８－テトラアミノアントラキノン（C.I.Disperse Blue 1）、１，４－ジアミノ－５－ニトロアントラキノン（C.I.DisperseViolet 8）等を挙げることができる（カッコ内はカラーインデックス名）。 More specifically, for example, 1,4-diaminoanthraquinone (CIDisperseViolet 1), 1-amino-4-hydroxy-2-methylaminoanthraquinone (CIDisperseRed 4), 1-amino-4-methylaminoanthraquinone (CIDisperse Violet 4), 1,4-diamino-2-methoxyanthraquinone (CIDisperse Red 11), 1-amino-2-methylanthraquinone (CIDisperseOrange 11), 1-amino-4-hydroxyanthraquinone (CIDisperse Red 15), 1,4,5,8-tetraaminoanthraquinone (CIDispersepersBlue 1), 1,4-diamino-5-nitroanthraquinone (CIDisperseViolet 8) and the like (color index names in parentheses).
　その他にも C.I.Solvent Blue 14、C.I.Solvent Blue 35、C.I.Solvent Blue 63、C.I.Solvent Violet 13、C.I.SolventViolet 14、C.I.Solvent Red 52、C.I.SolventRed 114、C.I.Vat Blue 21、C.I.VatBlue 30、C.I.Vat Violet 15、C.I.VatViolet 17、C.I.Vat Red 19、C.I.VatRed 28、C.I.Acid Blue 23、C.I.AcidBlue 80、C.I.Acid Violet 43、C.I.AcidViolet 48、C.I.Acid Red 81、C.I.AcidRed 83、C.I.Reactive Blue 4、C.I.Reactive Blue 19、C.I.Disperse Blue 7 等として知られている色素も使用することができる。 In addition, CISolventolBlue 14, CISolvent Blue 35, CISolvent Blue 63, CISolvent Violet 13, CISolventViolet 14, CISolvent Red 52, CISolventRedvent114, CIVat Blue 21, CIVatBlue 30, CIVat Violet 15, CIVatViolet 17, CIVat Red 19, CIVatRed 28, CIAcid Blue 23, CIAcidBlue 80, CIAcid Violet 43, CIAcidViolet 48, CIAcid Red 81, CIAcidRed 83, CIReactive Blue 4, CIReactive Blue 19, A dye known as CIDisperse Blue 7 etc. can also be used.
　これらのアントラキノン系色素は、単独又は２種以上を併用することができる。これらのアントラキノン系色素の中でも、C.I Disperse Blue 7、C.I Disperse Violet 1 等が好ましい。また、本発明では、これらのアントラキノン系色素の種類（分子構造等）を変えることによって検知感度の制御を行うこともできる。 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.
　メチン系色素としては、メチン基を有する色素であればよい。従って、本発明において、ポリメチン系色素、シアニン系色素等もメチン系色素に包含される。これらは、公知又は市販のメチン系色素から適宜採用することができる。具体的には、C.I.Basic Red 12、C.I.Basic Red 13、C.I.Basic Red 14、C.I.Basic Red 15、C.I.Basic Red 27、C.I.Basic Red 35、C.I.BasicRed 36、C.I.Basic Red 37、C.I.BasicRed 45、C.I.Basic Red 48、C.I.Basic Yellow 11、C.I.Basic Yellow 12、C.I.Basic Yellow 13、C.I.Basic Yellow 14、C.I.BasicYellow 21、C.I.Basic Yellow 22、C.I.BasicYellow 23、C.I.Basic Yellow 24、C.I.BasicViolet 7、C.I.Basic Violet 15、C.I.BasicViolet 16、C.I.Basic Violet 20、C.I.BasicViolet 21、C.I.Basic Violet 39、C.I.BasicBlue 62、C.I.Basic Blue 63等を挙げることができる。これらは、１種又は２種以上で用いることができる。 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, CIBasicRed 36, CIBasic Red 37, CIBasic Red 45, CIBasic Red 48, CIBasic Yellow 11, CIBasic Yellow 12, CIBasic Yellow 13, CIBasic Yellow 14, CIBasicYellow 21, CIBasic Yellow 22, CIBasicYellow 23, CIBasic Yellow 24, CIBasicViolet 7, CIBasic Violet 15, CIBasicViolet 16, CIBasic Violet 20, CIBasicViolet 21, CIBasic Violet 39, CIBasicBlue 62, CIBasic Blue 63 and the like. These can be used alone or in combination of two or more.
　キサンテン系色素としては、キサンテン構造を有する色素であれば限定されない。例えば、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等が挙げられる。これらのキサンテン系染料は、１種又は２種以上で使用することができる。 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.
　第１の色素の含有量は、その種類や所望の色相等に応じて適宜決定できるが、一般的には本発明のプラズマ処理検知用組成物中０．０５～５質量％とするのが好ましく、０．１～１質量％とするのがより好ましい。 The content of the first dye can be appropriately determined according to the type, desired hue, and the like, but generally it is preferably 0.05 to 5% by mass in the plasma processing detection composition of the present invention. More preferably, the content is 0.1 to 1% by mass.
　変色促進剤
　本発明の変色促進剤は、２つのベンゼン環が単結合又は連結基により連結された化学構造を包含する化学構造式により表わされる化合物を１種以上含み、前記連結基は、２つ又は３つの単結合が直列につながることにより２つのベンゼン環を連結することを特徴とする。 Discoloration accelerator The discoloration accelerator of the present invention includes one or more compounds represented by a chemical structural formula including a chemical structure in which two benzene rings are linked by a single bond or a linking group, and the linking group includes two linking groups. Alternatively, two benzene rings are connected by connecting three single bonds in series.
　単結合は、隣接する分子間で共有電子対一組を共有する結合のことであり、本発明に係る変色促進剤において、２つのベンゼン環を連結する単結合は、２つの異なるベンゼン環上に存在する各１つの炭素原子の共有電子対一組を共有して形成される。 A single bond is a bond that shares a pair of shared electrons between adjacent molecules. In the color change accelerator according to the present invention, a single bond that connects two benzene rings is on two different benzene rings. It is formed by sharing a pair of shared electrons of each one existing carbon atom.
　連結基は、本発明に係る変色促進剤において、２つのベンゼン環を連結する化学構造であり、２つ又は３つの単結合が直列につながった構造により、前記２つのベンゼン環が連結される。連結基は、２つ又は３つの単結合により前記２つのベンゼン環が連結されていれば任意の原子により形成されてよく、また任意の置換基を有していてもよい。 The linking group is a chemical structure that connects two benzene rings in the color change accelerator according to the present invention, and the two benzene rings are connected by a structure in which two or three single bonds are connected in series. The linking group may be formed by any atom as long as the two benzene rings are linked by two or three single bonds, and may have an arbitrary substituent.
　中でも、下記一般式（１）～（３）で示される変色促進剤の少なくとも１種以上を用いることが好ましい。 Among these, it is preferable to use at least one discoloration accelerator represented by the following general formulas (1) to (3).
　下記一般式（１） The following general formula (1)
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
〔但し、上記一般式中、Ｒ１～Ｒ１０は、同一又は異なって、水素原子または任意の置換基を有していてもよい。〕
で表わされる変色促進剤は、ビフェニル誘導体である。 [However, in the above general formula, R 1 to R 10 may be the same or different and each may have a hydrogen atom or an arbitrary substituent. ]
The color change accelerator represented by is a biphenyl derivative.
　また、下記一般式（２） Also, the following general formula (2)
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
〔但し、上記一般式中、Ｒ１～Ｒ１０は、同一又は異なって、水素原子または任意の置換基を有していてもよい。また、上記一般式中Ｌ１は、－ＣＨ２－、－Ｏ－、又は－Ｓ－で表わされる連結基を表し、－ＣＨ２－は水素原子に替えて置換基を有していてもよい。〕
で表わされる変色促進剤は、ジフェニルメタン誘導体である。 [However, in the above general formula, R 1 to R 10 may be the same or different and each may have a hydrogen atom or an arbitrary substituent. In the general formula, L 1 represents a linking group represented by —CH 2 —, —O—, or —S—, and —CH 2 — may have a substituent instead of a hydrogen atom. . ]
Is a diphenylmethane derivative.
　また、下記一般式（３） Also, the following general formula (3)
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
〔但し、上記一般式中、Ｒ１～Ｒ１０は、同一又は異なって、水素原子または任意の置換基を有していてもよい。また、上記一般式中Ｌ１は、－ＣＨ２－、－Ｏ－、又は－Ｓ－で表わされる連結基を表し、－ＣＨ２－は水素原子に替えて置換基を有していてもよい。〕
で表わされる変色促進剤は、ジベンジル誘導体である。 [However, in the above general formula, R 1 to R 10 may be the same or different and each may have a hydrogen atom or an arbitrary substituent. In the general formula, L1 represents a linking group represented by —CH 2 —, —O—, or —S—, and —CH 2 — may have a substituent instead of a hydrogen atom. ]
Is a dibenzyl derivative.
　上記一般式（１）に該当する変色促進剤として、具体的にはビフェニル等を挙げることができる。 Specific examples of the color change accelerator corresponding to the general formula (1) include biphenyl.
　上記一般式（２）に該当する変色促進剤として、具体的にはジフェニルメタン、ジフェニルエーテル、２，２ビス（４－メチルフェニル）－ヘキサフルオロプロパン、ジフェニルスルフィド等を挙げることができる。 Specific examples of the color change accelerator corresponding to the above general formula (2) include diphenylmethane, diphenyl ether, 2,2bis (4-methylphenyl) -hexafluoropropane, diphenyl sulfide and the like.
　上記一般式（３）に該当する変色促進剤として、具体的にはジベンジル、ベンジルフェニルエーテル、ベンジルフェニルスルフィド、ジフェニルジスルフィド等を挙げることができる。 Specific examples of the color change accelerator corresponding to the general formula (3) include dibenzyl, benzylphenyl ether, benzylphenyl sulfide, and diphenyl disulfide.
　変色促進剤は、その種類及び使用する第１の色素の種類等に応じて適宜決定できるが、プラズマ処理検知用組成物１００質量部中に、０．５～１０質量部含まれるようにするのが好ましく、２～８質量部含まれるようにするのがより好ましく、４～６質量部含まれるようにするのがさらに好ましい。プラズマ処理検知用組成物１００質量部中の変色促進剤の量が０．５質量部未満であると、プラズマ処理雰囲気化におけるプラズマ処理検知用組成物の変色の感度が低下するおそれがある。逆に１０質量部より多くなってもそれ以上に変色の感度が向上するわけでもなく、費用対効果の観点から、１０質量部以下とするのが好ましい。 The discoloration accelerator can be appropriately determined according to the type and the type of the first dye to be used, and is included in 0.5 to 10 parts by mass in 100 parts by mass of the plasma processing detection composition. Preferably, 2 to 8 parts by mass are contained, more preferably 4 to 6 parts by mass. If the amount of the color change accelerator in 100 parts by mass of the plasma treatment detection composition is less than 0.5 parts by mass, the color change sensitivity of the plasma treatment detection composition in the plasma treatment atmosphere may be lowered. On the other hand, even if the amount exceeds 10 parts by mass, the discoloration sensitivity does not improve further, and from the viewpoint of cost effectiveness, the amount is preferably 10 parts by mass or less.
　第２の色素
　また本発明に係るプラズマ処理検知用組成物は、上述した第１の色素以外に、プラズマ処理雰囲気下で変色しない第２の色素を含んでもよい。これによって、プラズマ処理検知用組成物のある色から他の色への色調の変化をより明確化でき、変色の視認効果をいっそう高めることができる。第２の色素としては、プラズマ処理雰囲気下で変色しない色素であれば、公知の色素を広く採用することができるが、第１の色素の色調に応じて、上述のごとくプラズマ処理雰囲気下でプラズマ処理検知用組成物の色調の変化をより明確化できるような色を有するものが好ましい。第２の色素の含有量は、第１の色素の種類等に応じて適宜設定すればよい。 The 2nd pigment | dye and the composition for plasma processing detection which concerns on this invention may also contain the 2nd pigment | dye which does not discolor in a plasma processing atmosphere other than the 1st pigment | dye mentioned above. As a result, the change in color tone from one color of the plasma treatment detection composition to another color can be clarified, and the visual effect of discoloration can be further enhanced. As the second dye, a known dye can be widely used as long as it is a dye that does not change color in the plasma treatment atmosphere. However, depending on the color tone of the first dye, plasma is used in the plasma treatment atmosphere as described above. What has the color which can clarify the change of the color tone of the composition for process detection more is preferable. What is necessary is just to set content of a 2nd pigment | dye suitably according to the kind etc. of a 1st pigment | dye.
　バインダー樹脂
　また本発明のプラズマ処理検知用組成物には、バインダー樹脂を含有させてもよい。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。 The binder resin or the plasma processing detection composition of the present invention may contain a binder resin. 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 used as they are. For example, maleic acid resin, ketone resin, polyvinyl butyral resin, cellulose resin, acrylic resin, styrene maleic acid resin, styrene acrylic acid resin, polyester resin, polyamide resin, polyacrylonitrile resin, polyimide resin, polyvinyl pyrrolidone resin, poly Examples include acrylamide resin, polyvinyl imidazole resin, polyethyleneimine resin, amino resin, and the like.
　本発明におけるバインダー樹脂としては、特にその一部又は全部にニトロセルロースを好適に用いることができる。ニトロセルロース樹脂を使用することにより、プラズマ処理雰囲気下における本発明のプラズマ処理検知用組成物の変色を、より感度高く検知することができる。 As the binder resin in the present invention, nitrocellulose can be suitably used particularly for part or all of it. By using the nitrocellulose resin, the discoloration of the plasma treatment detection composition of the present invention in a plasma treatment atmosphere can be detected with higher sensitivity.
　バインダー樹脂の含有量は、バインダー樹脂の種類、用いる色素の種類等に応じて適宜決定できるが、一般的にはプラズマ処理検知用組成物中５０質量％以下とするのが好ましく、５～３５質量％とするのがより好ましい。 The content of the binder resin can be appropriately determined according to the type of the binder resin, the type of the dye to be used, etc., but in general, the content is preferably 50% by mass or less in the plasma treatment detection composition, and 5 to 35% by mass. % Is more preferable.
　増量剤
　また本発明のプラズマ処理検知用組成物は、増量剤を含有していてもよい。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、シリカが好ましい。シリカを増量剤の一部又は全部に使用することにより、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。 The bulking agent or the plasma processing detection composition of the present invention may contain a bulking agent. The extender is not particularly limited, and examples thereof include inorganic materials such as bentonite, activated clay, aluminum oxide, silica, and silica gel. In addition, materials known as known extender pigments can be used. Among these, silica is preferable. By using silica in part or all of the extender, 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.
　増量剤の含有量は、用いる増量剤や着色材の種類等に応じて適宜決定できるが、一般的にはプラズマ処理検知用組成物中１～３０質量％程度とするのが好ましく、２～２０質量％とするのがより好ましい。 The content of the extender can be appropriately determined according to the type of extender and colorant to be used, but generally it is preferably about 1 to 30% by mass in the plasma treatment detection composition. It is more preferable to set it as the mass%.
　その他の添加剤
　本発明のプラズマ処理検知用組成物は、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。 Other Additives The composition for plasma treatment detection of the present invention appropriately contains components used in known inks such as a solvent, a leveling agent, an antifoaming agent, an ultraviolet absorber, and a surface conditioner as necessary. be able to.
　本発明で使用できる溶剤としては、通常、印刷用、筆記用等のインキ組成物に用いられる溶剤であればいずれも使用できる。例えば、アルコール又は多価アルコール系、エステル系、エーテル系、ケトン系、炭化水素系、グリコールエーテル系等の各種溶剤が使用でき、使用する色素、樹脂系バインダーの溶解性等に応じて適宜選択すればよい。なお、溶剤としては、最終的に常温又は加熱乾燥によって塗膜から除去できるものを用いることが必要である。溶剤としては、例えば、酢酸ｎ－ブチルの蒸発速度を１．０としたときの相対蒸発速度が１．０以上である速乾性のものがグラビア印刷に適しており、相対蒸発速度が０．０１～１．０のものを適宜混合して乾燥速度を調節したものはスクリーン印刷に適している。 As the solvent that can be used in the present invention, any solvent that is usually used in ink compositions for printing, writing, etc. can be used. For example, various solvents such as alcohols or polyhydric alcohols, esters, ethers, ketones, hydrocarbons, glycol ethers, etc. can be used, and they are appropriately selected depending on the solubility of the dye used and the resin binder. That's fine. In addition, as a solvent, it is necessary to use what can be finally removed from a coating film by normal temperature or heat drying. As the solvent, for example, 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.
　溶剤の含有量は、用いる溶剤や着色剤の種類等に応じて適宜決定できるが、一般的にはプラズマ処理検知用組成物中４０～９５質量％程度、特に６０～９０質量％とすることが望ましい。 The content of the solvent can be appropriately determined according to the type of the solvent used and the colorant, but is generally about 40 to 95% by mass, particularly 60 to 90% by mass in the plasma processing detection composition. desirable.
　溶剤の含有量の調整により粘度を調整でき、各種印刷手法に適した粘度のプラズマ処理検知用組成物を提供することができる。本発明では、プラズマ処理検知用組成物の粘度は１２０００ｍＰａ・ｓ未満とすることが好ましく、特にシルクスクリーン印刷に適した粘度としては５００～８０００ｍＰａ・ｓ程度であり、グラビア印刷に適した粘度としては１０～５００ｍＰａ・ｓ程度である。 Viscosity can be adjusted by adjusting the content of the solvent, and a plasma treatment detection composition having a viscosity suitable for various printing methods can be provided. In the present invention, the viscosity of the plasma treatment detection composition is preferably less than 12000 mPa · s, particularly about 500 to 8000 mPa · s as a viscosity suitable for silk screen printing, and as a viscosity suitable for gravure printing. It is about 10 to 500 mPa · s.
　本発明のプラズマ処理検知用組成物の各成分は、同時に又は順次に配合し、ホモジナイザー、ディゾルバー等の公知の攪拌機を用いて均一に混合すれば良い。例えば、まず溶剤に前記第１の色素、並びにバインダー樹脂、変色促進剤及び増量剤の少なくとも１種（必要に応じてその他の添加剤）を順に配合し、攪拌機により混合・攪拌すれば良い。
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、本発明のプラズマ処理検知用組成物からなる変色層を含む。一般的には、基材上に本発明のプラズマ処理検知用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。 The components of the plasma processing detection composition of the present invention may be blended simultaneously or sequentially and mixed uniformly using a known stirrer such as a homogenizer or a dissolver. For example, first, at least one of the first pigment, the binder resin, the color change accelerator, and the extender (other additives as necessary) may be blended in the solvent in order, and mixed and stirred with a stirrer.
2. Plasma treatment detection indicator The indicator of the present invention includes a discoloration layer made of the plasma treatment detection composition of the present invention. Generally, a discoloration layer can be formed by applying or printing the composition for detecting plasma treatment of the present invention on a substrate. The substrate in this case is not particularly limited as long as it can form a discoloration layer.
　基材としては、例えば、金属又は合金、セラミックス、ガラス、コンクリート、プラスチックス（ポリエチレンテレフタレート（ＰＥＴ）、ポリプロピレン、ナイロン、ポリスチレン、ポリサルフォン、ポリカーボネート、ポリイミド等）、繊維類（不織布、織布、その他の繊維シート）、これらの複合材料等を用いることができる。また、ポリプロピレン合成紙、ポリエチレン合成紙等の合成樹脂繊維紙（合成紙）も好適に用いることができる。 Examples of the base material 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. Moreover, synthetic resin fiber paper (synthetic paper) such as polypropylene synthetic paper and polyethylene synthetic paper can also be suitably used.
　本発明における変色層は、色が他の色に変化するもののほか、色が退色又は消色するものも包含される。 The discoloration layer in the present invention includes not only the color changing to another color but also the color fading or erasing.
　変色層の形成は、本発明のプラズマ処理検知用組成物を用い、シルクスクリーン印刷、グラビア印刷、オフセット印刷、凸版印刷、フレキソ印刷等の公知の印刷方法に従って行うことができる。また、印刷以外の方法でも形成できる。例えば、基材をプラズマ処理検知用組成物中に浸漬することによって変色層を形成することもできる。不織布等のように液体が浸透しやすい材料には特に好適である。 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 plasma processing detection composition of the present invention. It can also be formed by methods other than printing. For example, a discoloration layer can also be formed by immersing a base material in the composition for plasma processing detection. It is particularly suitable for a material that easily penetrates liquid, such as a nonwoven fabric.
　変色層は、その表面に複数のクラックを有することが望ましい。すなわち、変色層の表面に開放気孔が形成され、多孔質化していることが望ましい。かかる構成により、プラズマ処理検知の感度をより高めることができる。この場合には、プラズマ処理検知包装体の内部に変色層が配置されても、所望の変色効果が得られる。クラックは、特に本発明のインキ組成物のバインダーとしてセルロース系樹脂を用いることによって効果的に形成することができる。すなわち、セルロース系樹脂の使用により、良好な定着性を維持しつつ、上記のようなクラックを形成することができる。 It is desirable that 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.
　本発明では、さらにプラズマ処理雰囲気下で変色しない非変色層が基材上及び／又は変色層上に形成されていても良い。非変色層は、通常は市販の普通色インキにより形成することができる。例えば、水性インキ、油性インキ、無溶剤型インキ等を用いることができる。非変色層の形成に用いるインキには、公知のインキに配合されている成分、例えば樹脂バインダー、増量剤、溶剤等が含まれていてもよい。 In the present invention, a non-discoloring layer that does not change color in a plasma treatment atmosphere may be formed on the substrate and / or the discoloring layer. The non-discoloring layer can be usually formed with a commercially available ordinary color ink. For example, water-based ink, oil-based ink, solventless ink, and the like can be used. The ink used for forming the non-discoloring layer may contain components blended in a known ink, such as a resin binder, an extender, and a solvent.
　非変色層の形成は、変色層の場合と同様にすればよい。例えば、普通色インキを用い、シルクスクリーン印刷、グラビア印刷、オフセット印刷、凸版印刷、フレキソ印刷等の公知の印刷方法に従って行うことができる。なお、変色層・非変色層の印刷の順序は特に制限されず、印刷するデザイン等に応じて適宜選択すればよい。 The formation of the non-discoloring layer may be the same as in the case of the discoloring layer. For example, normal color ink can be used according to a known printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, or flexographic printing. The order of printing of the color changing layer and the non-color changing layer is not particularly limited, and may be appropriately selected according to the design to be printed.
　本発明のインジケーターでは、変色層及び非変色層をそれぞれ１層ずつ形成してもよいし、あるいはそれぞれ複数層形成してもよい。また、変色層どうし又は非変色層どうしを積層してもよい。この場合、変色層どうしが互いに同じ組成であっても又は異なる組成であってもよい。同様に、非変色層どうしが互いに同じ組成であっても又は異なる組成であってもよい。 In the indicator of the present invention, one color changing layer and one non-color changing layer may be formed, or a plurality of layers may be formed. Further, 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.
　さらに、変色層及び非変色層は、基材又は各層の全面に形成しても良く、あるいは部分的に形成してもよい。これらの場合、特に変色層の変色を確保するために、少なくとも１つの変色層の一部又は全部がプラズマ処理雰囲気に晒されるように変色層及び非変色層を形成すればよい。 Furthermore, 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. In these cases, in particular, in order to ensure the color change of the color change layer, the color change layer and the non-color change layer may be formed so that a part or all of at least one color change layer is exposed to the plasma treatment atmosphere.
　本発明では、プラズマ処理の完了が確認できる限り、変色層と非変色層とをどのように組み合わせてもよい。例えば、変色層の変色によりはじめて変色層と非変色層の色差が識別できるように変色層及び非変色層を形成したり、あるいは変色によってはじめて変色層及び非変色層との色差が消滅したりするように形成することもできる。本発明では、特に、変色によってはじめて変色層と非変色層との色差が識別できるように変色層及び非変色層を形成することが好ましい。 In the present invention, the discoloration layer and the non-discoloration layer may be combined in any way as long as the completion of the plasma treatment can be confirmed. For example, 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. In the present invention, it is particularly preferable to form the color-changing layer and the non-color-changing layer so that the color difference between the color-changing layer and the non-color-changing layer can be discriminated only by the color change.
　色差が識別できるようにする場合には、例えば変色層の変色によりはじめて文字、図柄及び記号の少なくとも１種が現れるように変色層及び非変色層を形成すれば良い。本発明では、文字、図柄及び記号は、変色を知らせるすべての情報を包含する。これら文字等は、使用目的等に応じて適宜デザインすればよい。 In order to make it possible to identify the color difference, for example, the color-changing layer and the non-color-changing layer may be formed so that at least one of characters, designs, and symbols appears only when the color-changing layer changes color. In the present invention, characters, designs, and symbols include all information that informs discoloration. What is necessary is just to design these characters etc. suitably according to the purpose of use.
　また、変色前における変色層と非変色層とを互いに異なる色としても良い。例えば、両者を実質的に同じ色とし、変色後にはじめて変色層と非変色層との色差（コントラスト）が識別できるようにしてもよい。 Also, the color changing layer and the non-color changing layer before the color change may be different from each other. For example, they may be substantially the same color so that the color difference (contrast) between the color-change layer and the non-color-change layer can be identified only after the color change.
　本発明のインジケーターでは、変色層と非変色層とが重ならないように変色層及び非変色層を形成することができる。これにより、使用するインキ量を節約することができる。 In the indicator of the present invention, the color changing layer and the non-color changing layer can be formed so that the color changing layer and the non-color changing layer do not overlap. Thereby, the amount of ink to be used can be saved.
　さらに、本発明では、変色層及び非変色層の少なくとも一方の層上にさらに変色層又は非変色層を形成しても良い。例えば、変色層と非変色層とが重ならないように変色層及び非変色層を形成した層（「変色－非変色層」という）の上からさらに別のデザインを有する変色層を形成すれば、変色－非変色層における変色層及び非変色層の境界線が実質的に識別できない状態にすることができるので、より優れた意匠性を達成することができる。 Furthermore, in the present invention, a color changing layer or a non-color changing layer may be further formed on at least one of the color changing layer and the non-color changing layer. For example, if a color-changing layer having a different design is formed on a layer in which the color-changing layer and the non-color-changing layer are formed so as not to overlap the color-changing layer and the non-color-changing layer (referred to as “color-changing-non-color-changing layer”), Since the boundary 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.
　本発明のインジケーターは、プラズマ発生用ガスを用いるプラズマ処理であればいずれにも適用できる。つまり、減圧プラズマ処理及び大気圧プラズマ処理の両方に適用できる。 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.
　減圧プラズマ処理の具体例としては、例えば、フラットパネルディスプレイ（液晶ディスプレイなど）の洗浄、表面改質等の用途；半導体製造工程における製膜、灰化、洗浄、表面改質等の用途；実装基板又はプリント配線基板の洗浄、表面改質等の用途；医療器具などの滅菌用途；実装部品の洗浄、表面改質等の用途等が挙げられる。 Specific examples of 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.
　また、大気圧プラズマ処理の具体例としては、例えば、フラットパネルディスプレイ（液晶ディスプレイなど）の製膜、灰化、洗浄、表面改質等の用途；実装基板又はプリント配線基板の洗浄、表面改質等の用途；自動車、航空機部品等の表面改質用途、医療分野（歯科又は外科）における消毒、殺菌、治療等の用途等が挙げられる。 Specific examples of 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).
　減圧プラズマ発生用ガスとしては、減圧下、交流電圧、パルス電圧、高周波、マイクロ波等を印加することによりプラズマを発生させることができるガスであれば限定されず、例えば、酸素、窒素、水素、塩素、過酸化水素、ヘリウム、アルゴン、シラン、アンモニア、臭化硫黄、水蒸気、亜酸化窒素、テトラエトキシラン、四フッ化炭素、トリフルオロメタン、四塩化炭素、四塩化ケイ素、六フッ化硫黄、四塩化チタン、ジクロロシラン、トリメチルガリウム、トリメチルインジウム、トリメチルアルミニウム等が挙げられる。これらの減圧プラズマ発生用ガスは、単独又は２種以上を混合して使用することができる。 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.
　大気圧プラズマ発生用ガスとしては、大気圧下、交流電圧、パルス電圧、高周波、マイクロ波等を印加することによりプラズマを発生させることができるガスであれば限定されず、例えば、酸素、窒素、水素、アルゴン、ヘリウム、空気等があげられる。これらの大気圧プラズマ発生用ガスは、単独又は２種以上を混合して使用することができる。 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, and air. These atmospheric pressure plasma generating gases can be used alone or in admixture of two or more.
　本発明のインジケーターを使用する際は、具体的には、プラズマ発生用ガスを用いるプラズマ処理装置（具体的には、プラズマ発生用ガスを含有する雰囲気下で交流電圧、パルス電圧、高周波、マイクロ波等を印加してプラズマを発生させることによりプラズマ処理を行う装置）の内部又は当該内部に収容されている被処理物に本発明インジケーターを置き、プラズマ処理雰囲気下に晒せばよい。この場合、装置内に置かれたインジケーターの変色により所定のプラズマ処理が行われたこと検知することができる。 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, 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.
　本発明インジケーターは、そのままインジケーターカードとして使用することができる。このとき、変色層の形状を公知のバーコードの形状とし、所定のプラズマ処理が完了した段階（変色の程度）でバーコードリーダーによる読み取りが可能となる条件に設定すれば、プラズマ処理の完了とその後のプラズマ処理物の物流管理をバーコードにより一元管理することができる。本発明は、かかる用途に用いるインジケーター、プラズマ処理管理方法及び物流管理方法の発明も包含している。 The present invention indicator 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 includes inventions of indicators, plasma processing management methods, and physical distribution management methods used for such applications.
　以上、本発明の実施形態について説明したが、本発明はこうした例に何ら限定されるものではなく、本発明の要旨を逸脱しない範囲において種々なる形態で実施し得ることは勿論である。 The embodiments of the present invention have been described above. However, the present invention is not limited to these examples, and it is needless to say that the present invention can be implemented in various forms without departing from the gist of the present invention.
　以下、実施例に基づき、本発明の実施形態をより具体的に説明するが、本発明がこれらに限定されるものではない。 Hereinafter, the embodiments of the present invention will be described more specifically based on examples, but the present invention is not limited to these.
　実施例１～７及び比較例１
　本発明における第１の色素として、赤色のアゾ系染料（Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ　Ｒｅｄ　１６７：１）を、第２の色素として緑色のフタロシアニン系顔料（Ｃ．Ｉ．　Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７）を使用した。表１の組成に基づき、プラズマ処理検知用組成物を調製した後、東洋紡製のＰＥＴ基材（商品名：クリスパー、品番：Ｋ２３２３）にシルクスクリーン印刷し、８０℃環境下で２０分乾燥させ、実施例１～７及び比較例１のインジケーターを得た。 Examples 1 to 7 and Comparative Example 1
A red azo dye (CI Disperse Red 167: 1) was used as the first dye in the present invention, and a green phthalocyanine pigment (CI Pigment Green 7) was used as the second dye. After preparing a plasma treatment detection composition based on the composition of Table 1, silk-screen printing on a Toyobo PET base material (trade name: Krisper, product number: K2323), and drying in an 80 ° C. environment for 20 minutes, The indicators of Examples 1 to 7 and Comparative Example 1 were obtained.
　実施例８～１４
　表２にあるように、上記実施例１におけるジベンジルの含有量を振ってプラズマ処理検知用組成物を調製し、実施例８～１４のインジケーターを得た。
（変色性試験）
　各実施例及び比較例のインジケーターを、日本電色工業社製のハンディー型色彩計（品番：ＮＲ－１１Ａ）を用いて測色した。その後各実施例及び比較例を、平行平板高周波プラズマ装置（サムコ社製、品番：ＢＰ－１）に設置の上、プラズマ発生用ガスとして酸素を用意し、酸素流量１０ｍＬ／分、電力１５Ｗ、圧力１０Ｐａの条件で（３）分間、酸素プラズマ処理を行った。酸素プラズマ処理後、各実施例及び比較例について、再度測色を行った。各実施例及び比較例のプラズマ処理に対する感度については、測色により得られたプラズマ処理前の色度Ｌ＊１、ａ＊１、ｂ＊１及びプラズマ処理後のＬ＊２、ａ＊２、ｂ＊２を用いて下記数１に基づいてΔＥ＊ａｂを算出し、評価した。 Examples 8-14
As shown in Table 2, plasma treatment detection compositions were prepared by varying the dibenzyl content in Example 1 above, and indicators of Examples 8 to 14 were obtained.
(Discoloration test)
The indicators of the examples and comparative examples were measured using a handy color meter (product number: NR-11A) manufactured by Nippon Denshoku Industries Co., Ltd. After that, each example and comparative example were installed in a parallel plate high-frequency plasma apparatus (manufactured by Samco, product number: BP-1), oxygen was prepared as a plasma generating gas, oxygen flow rate 10 mL / min, power 15 W, pressure Oxygen plasma treatment was performed under the condition of 10 Pa for (3) minutes. After the oxygen plasma treatment, color measurement was performed again for each of the examples and comparative examples. About the sensitivity with respect to the plasma processing of each Example and a comparative example, chromaticity L * 1, a * 1, b * 1 before plasma processing obtained by color measurement, and L * 2, a * 2, after plasma processing, ΔE * ab was calculated based on the following formula 1 using b * 2 and evaluated.
Figure JPOXMLDOC01-appb-M000006
Figure JPOXMLDOC01-appb-M000006
（変色性試験結果）
　表１に示したように、変色促進剤としてジベンジル、ベンジルフェニルエーテル、ベンジルフェニルスルフィド、２,２ビス（４－メチルフェニル）－ヘキサフルオロプロペン、ビフェニル、ジフェニルエーテル、ジフェニルメタンを使用したそれぞれ実施例１、２、３、４、５、６、７のインジケーターは、これらの変色促進剤を使用しない比較例１のインジケーターと対比してΔＥ＊ａｂ値が大きかった。よって実施例１～７のインジケーターに本発明の変色促進剤を使用したことにより、インジケーターの感度が上がったことが確認された。また、表２に示したように、実施例１及び８～１４の結果から、変色促進剤を所定の濃度とすることにより、インジケーターの感度が上昇することが確認できた。 (Discoloration test results)
As shown in Table 1, Example 1 using dibenzyl, benzylphenyl ether, benzylphenyl sulfide, 2,2 bis (4-methylphenyl) -hexafluoropropene, biphenyl, diphenyl ether, diphenylmethane, respectively, as the color change accelerator. The indicators 2, 3, 4, 5, 6, and 7 had a large ΔE * ab value as compared with the indicator of Comparative Example 1 that did not use these discoloration accelerators. Therefore, it was confirmed that the sensitivity of the indicator was increased by using the color change accelerator of the present invention for the indicators of Examples 1 to 7. Further, as shown in Table 2, from the results of Examples 1 and 8 to 14, it was confirmed that the sensitivity of the indicator was increased by setting the color change accelerator to a predetermined concentration.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008

Claims (7)

  1. 　アゾ、アントラキノン、メチン、及びキサンテンからなる群から選択される１種以上の第１の色素及び該第１の色素のプラズマ処理雰囲気下での変色を促進するための変色促進剤を含有するプラズマ処理検知用組成物であって、
    　前記変色促進剤は、２つのベンゼン環が単結合又は連結基により連結された化学構造を包含する化学構造式により表わされる化合物を１種以上含み、
    　前記連結基は、２つ又は３つの単結合が直列につながることにより２つのベンゼン環を連結することを特徴とする、プラズマ処理検知用組成物。     Plasma treatment containing one or more first dyes selected from the group consisting of azo, anthraquinone, methine, and xanthene and a discoloration accelerator for promoting discoloration of the first dye in a plasma treatment atmosphere A sensing composition comprising:
    The discoloration accelerator includes one or more compounds represented by a chemical structural formula including a chemical structure in which two benzene rings are linked by a single bond or a linking group,
    The composition for plasma treatment detection, wherein the linking group connects two benzene rings by connecting two or three single bonds in series.
  2. 　前記変色促進剤は、一般式（１）～（３）により表わされる化合物を１種以上含む、請求項１に記載のプラズマ処理検知用組成物。
    Figure JPOXMLDOC01-appb-C000001
    〔但し、上記一般式中、Ｒ１～Ｒ１０は、同一又は異なって、水素原子又は任意の置換基を有していてもよい。また、上記一般式中、Ｌ１、Ｌ２は、それぞれ独立に－ＣＨ２－、－Ｏ－、又は－Ｓ－で表わされる連結基を表し、－ＣＨ２－は水素原子に替えて置換基を有していてもよい。〕     The composition for plasma processing detection according to claim 1, wherein the discoloration accelerator contains one or more compounds represented by the general formulas (1) to (3).
    Figure JPOXMLDOC01-appb-C000001
    [However, in the above general formula, R 1 to R 10 may be the same or different and each may have a hydrogen atom or an arbitrary substituent. In the above general formula, L 1 and L 2 each independently represent a linking group represented by —CH 2 —, —O—, or —S—, and —CH 2 — is a substituent instead of a hydrogen atom. You may have. ]
  3. 　プラズマ処理検知用組成物１００質量部中に前記変色促進剤が０．５～１０質量部含まれる、請求項１又は２に記載のプラズマ処理検知用組成物。 The plasma treatment detection composition according to claim 1 or 2, wherein 0.5 to 10 parts by mass of the color change accelerator is contained in 100 parts by mass of the plasma treatment detection composition.
  4. 　さらにプラズマ処理雰囲気下で変色しない第２の色素を含む、請求項１～３のいずれか１項に記載のプラズマ処理検知用組成物。 The plasma processing detection composition according to any one of claims 1 to 3, further comprising a second dye that does not change color in a plasma processing atmosphere.
  5. 　さらにバインダー樹脂として、該バインダー樹脂の一部又は全部にニトロセルロースを含有する、請求項１～４のいずれか１項に記載のプラズマ処理検知用組成物。 The plasma processing detection composition according to any one of claims 1 to 4, further comprising nitrocellulose as a binder resin in a part or all of the binder resin.
  6. 　さらに増量剤として、該増量剤の一部又は全部にシリカを含有する、請求項１～５のいずれか１項に記載のプラズマ処理検知用組成物。 The composition for detecting plasma treatment according to any one of claims 1 to 5, further comprising silica as a bulking agent in part or all of the bulking agent.
  7. 　請求項１～６のいずれか１項に記載のプラズマ処理検知用組成物を用いて形成された変色層を有するプラズマ処理検知インジケーター。 A plasma treatment detection indicator having a discoloration layer formed using the composition for plasma treatment detection according to any one of claims 1 to 6.
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