Composition for detecting ultraviolet or plasma treatment

Abstract

To provide a novel detection composition that has sufficient reactivity to ultraviolet light or atmospheric pressure plasma. [Solution] A composition for detecting ultraviolet treatment or plasma treatment, comprising at least one selected from the group consisting of organic fluorescent whitening agents, organic light-emitting materials, and inorganic fluorescent materials.

Description

[Technical Field]

[0001] The present invention relates to a composition for detecting ultraviolet treatment or plasma treatment. [Background technology]

[0002] Plasma is utilized in various industrial fields, including welding, cutting and thermal spraying, microfabrication, thin film synthesis, surface modification, and sterilization, disinfection, and sterilization, by utilizing its thermal energy. It is expected that the scope of its applications will continue to expand in the future.

[0003] Furthermore, ultraviolet light (hereinafter also referred to as UV in this specification) is also used primarily for sterilization purposes.

[0004] Plasma or UV treatments are generally not easily observable by visual inspection, making it difficult to determine whether such treatments are in progress or have been completed. Therefore, there is a strong need for a reliable means of determining whether such treatments have been performed or are in progress.

[0005] Several plasma processing detection compositions have been proposed to date as means of confirming plasma processing (see, for example, Patent Document 1).

[0006] Furthermore, in recent years, atmospheric pressure plasma, which can be used under normal pressure, has attracted particular attention from the perspective of improving productivity. On the other hand, depending on the discharge method or structure of the device, ozone may inevitably be generated during atmospheric pressure plasma treatment due to the discharge of gases in the atmosphere.

[0007] Conventional plasma processing detection compositions are generally reactive to ozone, and therefore lack sufficient processing detection capability for pure atmospheric pressure plasma (which is not ozone). In other words, there is a problem in that the possibility of reacting only to ozone and not atmospheric pressure plasma cannot be ruled out. Novel ultraviolet or plasma processing detection compositions are needed. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2019-210468 [Overview of the project] [Problems that the invention aims to solve]

[0009] In view of the above circumstances, the object of the present invention is to provide a novel detection composition that has sufficient reactivity to ultraviolet light or atmospheric pressure plasma. [Means for solving the problem]

[0010] The inventors of this invention conducted extensive research to solve the above problems and found that by including a predetermined substance in the detection material for processing, a detection composition that has low reactivity to ozone and sufficient reactivity to atmospheric pressure plasma can be obtained. Based on this finding, the inventors conducted further research and completed the present invention.

[0011] In other words, the present invention provides the following compositions for detecting ultraviolet treatment or plasma treatment. Section 1. A composition for detecting ultraviolet treatment or plasma treatment, comprising at least one selected from the group consisting of organic fluorescent materials and inorganic fluorescent materials. Section 2. The aforementioned organic fluorescent material is an organic fluorescent whitening agent. The plasma treatment detection composition according to item 1, wherein the organic fluorescent whitening agent is at least one selected from the group consisting of coumarin-type organic fluorescent whitening agents, thiophene-type organic fluorescent whitening agents, naphthalene-type organic fluorescent whitening agents, bisbenzoxazole-type organic fluorescent whitening agents, bis(styryl)biphenyl-type organic fluorescent whitening agents, stilbene-type organic fluorescent whitening agents, and azole-type organic fluorescent whitening agents. Section 3. The plasma treatment detection composition according to item 1 or 2, further comprising a non-coloring dye. Section 4. The composition for detecting plasma treatment according to item 3, which is for detecting atmospheric pressure plasma treatment. Item 5. The composition for detecting plasma treatment according to item 1 or 2, further comprising at least one organic dye selected from the group consisting of methine dyes, anthraquinone dyes, oxazine dyes, azo dyes, thiazine dyes, and triarylmethane dyes. Item 6. A plasma indicator having a plasma treatment detection layer made of the composition according to item 1. Item 7. A real-time analysis method for plasma treatment, comprising the step of irradiating a test substance containing the composition for detecting plasma treatment according to item 1 with plasma. Item 8. A real-time analysis method for ultraviolet treatment, comprising the step of irradiating a test substance containing the composition for detecting ultraviolet treatment according to item 1 with ultraviolet light.

Advantages of the Invention

[0012] The composition for detecting ultraviolet treatment or plasma treatment according to the present invention thus formed has sufficient reactivity with ultraviolet light or atmospheric pressure plasma.

Modes for Carrying Out the Invention

[0013] In this specification, "containing" is a concept encompassing any of "comprise", "consist essentially of", and "consist of". Also, in this specification, when a numerical range is indicated as "A to B", it means A or more and B or less.

[0014] (1. Composition for Detecting Ultraviolet Treatment or Plasma Treatment) The composition for detecting ultraviolet treatment or plasma treatment of the present invention (hereinafter, also simply referred to as "the detection composition of the present invention" or "the composition of the present invention") contains at least one selected from the group consisting of organic fluorescent materials and inorganic fluorescent materials.

[0015] The composition for detecting ultraviolet treatment or plasma treatment of the present invention emits light or changes color by performing ultraviolet treatment or plasma treatment together with an article to be subjected to ultraviolet treatment or plasma treatment. Thereby, it can be suitably utilized for the purpose of confirming in real time that the treatment is being performed or confirming that the treatment has been performed.

[0016] There is no particular limitation on the wavelength of ultraviolet rays to be detected for treatment detection. For example, ultraviolet rays with a wavelength of 10 to 400 nm can be suitably detected. Among these, preferably, UV-C, UV-B or UV-A with a wavelength of 100 to 400 nm, more preferably, ultraviolet rays with a wavelength of 150 to 300 nm by a vacuum ultraviolet laser, xenon lamp, deuterium lamp, mercury lamp and UV-LED which are practical in the industry can be suitably detected.

[0017] Examples of the plasma to be detected for treatment include plasma treatment using plasma generated by applying an alternating voltage, pulse voltage, high frequency or microwave, etc. using a gas for plasma generation, and there is no particular limitation. More specifically, reduced-pressure plasma and atmospheric-pressure plasma can be mentioned.

[0018] Specific examples of atmospheric-pressure plasma treatment include, for example, applications such as cleaning and surface modification of flat panel displays (such as liquid crystal displays); applications such as cleaning and surface modification of mounting substrates or printed wiring boards; applications for surface modification of automotive and aircraft parts, and applications such as disinfection, sterilization and treatment in the medical field (dental or surgical).

[0019] The gas used for generating reduced-pressure plasma is not limited to any gas that can generate plasma by applying AC voltage, pulse voltage, high frequency, microwave, etc., under reduced pressure. Examples include oxygen, nitrogen, hydrogen, chlorine, hydrogen peroxide, helium, argon, silane, ammonia, sulfur bromide, water vapor, nitrous oxide, tetraethoxylan, carbon tetrafluoride, trifluoromethane, carbon tetrachloride, silicon tetrachloride, sulfur hexafluoride, titanium tetrachloride, dichlorosilane, trimethylgallium, trimethylindium, and trimethylaluminum. These reduced-pressure plasma generating gases can be used individually or in mixtures of two or more.

[0020] The atmospheric pressure plasma generating gas is not limited to any gas that can generate plasma by applying an AC voltage, pulse voltage, high frequency, microwave, etc., under atmospheric pressure. Examples include oxygen, nitrogen, hydrogen, argon, helium, and air. These atmospheric pressure plasma generating gases can be used individually or in mixtures of two or more.

[0021] (1.1. Organic fluorescent materials) The organic fluorescent material used in the detection composition of the present invention can be a wide range of known materials and is not particularly limited. For example, an organic fluorescent whitening agent can be used.

[0022] The above-mentioned organic fluorescent whitening agent can be any known organic fluorescent whitening agent, and is not particularly limited. For example, coumarin-type organic fluorescent whitening agents, thiophene-type organic fluorescent whitening agents, naphthalene-type organic fluorescent whitening agents, bisbenzoxazole-type organic fluorescent whitening agents, bis(styryl)biphenyl-type organic fluorescent whitening agents, stilbene-type organic fluorescent whitening agents, and azole-type organic fluorescent whitening agents can be used. Among these, it is more preferable to use coumarin-type, thiophene-type, or naphthalene-type organic fluorescent whitening agents.

[0023] The composition of the present invention contains an organic fluorescent whitening agent, which causes it to emit fluorescence when subjected to ultraviolet light treatment or plasma treatment. Furthermore, the composition of the present invention changes color when subjected to plasma treatment.

[0024] The composition of the present invention, by containing an organic fluorescent whitening agent, can be particularly suitably used as a plasma processing detection composition. The plasma processing detection composition of the present invention containing an organic fluorescent whitening agent exhibits good reactivity to atmospheric pressure plasma while having extremely low reactivity to ozone, and can therefore be particularly suitably used as an atmospheric pressure plasma processing detection composition.

[0025] As coumarin-type organic fluorescent whitening agents, a wide range of known agents can be used, and there are no particular limitations. More specifically, 4-methyl-7-hydroxycoumarin, 4-methyl-7-diethylaminocoumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-(2-benzimidazolyl)-7-(diethylamino)coumarin, 4-methyl-7-aminocoumarin, 4-methyl-7-pyrrolinidylcoumarin, 4-methyl-7-(3',5'-diphenyl-4',5'-hydropyrazolyl)coumarin, 4-methyl-3-(4'-cyanophenyl)-7-(3',5'-dimethylpyrazolyl)coumarin, 4-methyl-3-(4'-ethoxycarbonylphenyl)-7-(3 Examples include ',5'-dimethylpyrazolyl)coumarin, 3-(4'-carbonylphenyl)-4-methyl-7-diethylaminocoumarin, 3-(4'-acetylaminophenyl)-4-methyl-7-diethylaminocoumarin, 3-phenyl-7-(3'-methylpyrazolyl)coumarin, 3-(4'-acetylaminophenyl)-7-acetylaminocoumarin, 7-amino-3,4-benzocoumarin, 7-acetylamino-3,4-benzocoumarin, and 2-(3-phenylcoumarin-7-ylamino)-4-chloro-6-dithielamino-1,3,5-triazine, trade name Nikkafluor MCT (manufactured by Nippon Chemical Industries, Ltd.), etc.

[0026] A wide range of known thiophene-type organic fluorescent whitening agents can be used, and there are no particular limitations. More specifically, examples include 2,5-bis(5-t-butyl-2-benzoxazolyl)thiophene, 2,5-bis(benzoxazole-2-yl)thiophene, 2,5-bis(benzoxazole-2-yl)thiophene, and 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole).

[0027] A wide range of known naphthalene-type organic fluorescent whitening agents can be used, and there are no particular limitations. More specifically, examples include 1,4-bis(2-benzoxazolyl)naphthalene, trade name Nikkafluor SC200 (manufactured by Nippon Chemical Industries, Ltd.).

[0028] A wide range of known bisbenzoxazole-type organic fluorescent whitening agents can be used, and there are no particular limitations. More specifically, examples include 2,5-thiophenidiylbis(5-tert-butyl-1,3-benzoxazole), 2,2'-(vinylenedi-p-phenylene)bisbenzoxazole, 2,2'-(naphthalene-1,4-diyl)bis(benzoxazole), 2-[4-[2-[4-(benzoxazole-2-yl)phenyl]vinyl]phenyl]-5-methylbenzoxazole, stilbene-benzoxazoline, and 2,2'-(1,2-ethendiyl)bis(4,1-phenylene)bisbenzoxazole.

[0029] A wide range of known bis(styryl)biphenyl-type organic fluorescent whitening agents can be used, and there are no particular limitations. More specifically, 4,4'-bis(2-methoxystyryl)biphenyl can be given as an example.

[0030] A wide range of known stilbene-type organic fluorescent whitening agents can be used, and there are no particular limitations. More specifically, examples include stilbene derivatives, such as hexanodium-2,2'-[vinylbis[3-sulfonato-4,-phenylene]imino[6-(diethylamino)-1,3,5-triazine-4,2-diyl]imino]]bis(benzene-1,4-disulfonic acid), stilbene-benzoxazoline, 2,2'-(1,2-ethendiyl)bis(4,1-phenylene)bisbenzoxazole, biphenyl-stilbene, and benzenesulfonic acid.

[0031] The above-mentioned organic fluorescent whitening agents may be used individually or in combination of multiple types.

[0032] From the viewpoint that a higher concentration results in a wider detection range, the amount of organic fluorescent material contained in the ultraviolet treatment or plasma treatment detection composition of the present invention is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 10% by mass or more, per 100% by mass of the composition. Furthermore, in order to prevent the occurrence of concentration quenching, the content of organic fluorescent material contained in 100% by mass of the composition is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0033] In addition to organic fluorescent whitening agents, other suitable organic fluorescent materials include rhodamine-based dyes, ABPX (aminobenzopyranoxanthene-based dyes), rare earth fluorescent complexes such as europium / samarium / terbium / dysprosium, and fluorescent proteins such as GFP / sirius / aequorin. These may be used individually or in combination. They may also be used together with the organic fluorescent whitening agents mentioned above, or they may be used alone.

[0034] (1.2. Inorganic fluorescent materials) As the inorganic fluorescent material, known inorganic fluorescent materials can be used, and there is no particular limitation. For example, metal oxides, metal nitrides, and metal fluorides having fluorescence, and perovskite crystals can be exemplified.

[0035] When the composition of the present invention contains an inorganic fluorescent material, it emits fluorescence when subjected to ultraviolet treatment or plasma treatment.

[0036] More specifically, as such a metal oxide, the general composition (Lu,Y) 3-x (AlGa)5O 12 :Ce x or Y3(Al,Ga)5O 12 :Ce can be exemplified by a cerium-activated garnet phosphor.

[0037] Also, as the above metal nitride, the general composition CaAlSiN3:Eu 2+ , Ca(Se,S):Eu 2+ , or (Ba,Sr)3SiO5:Eu 2+ can be exemplified by a nitride-based phosphor.

[0038] Furthermore, as the above metal fluoride, manganese-activated fluoride photoluminescence materials such as K2SiF6:Mn 4+ , K2TiF6:Mn 4+ , and K2GeF6:Mn 4+ can be exemplified.

[0039] In this specification, a perovskite crystal is defined as a crystalline compound having a perovskite structure. Such perovskite structures are known in themselves and are described as cubic, pseudocubic, tetragonal, or orthorhombic crystals of the general formula M1M2X3, where M1 is a cation with coordination number 12 (cuboctahedron), M2 is a cation with coordination number 6 (octahedron), and X is an anion in a cubic, pseudocubic, tetragonal, or orthorhombic position in the lattice. In these structures, a selected cation or anion may be replaced by other ions (up to a maximum of several percent of 30 atoms, stochastically or normally), thereby resulting in doped or non-stoichiometric perovskites that still maintain their original crystal structure. Such luminescent perovskite crystals can be obtained, for example, by the method described in International Publication No. 2018 / 028869.

[0040] Such inorganic fluorescent materials may be used individually or in combination of multiple types.

[0041] The amount of inorganic fluorescent material contained in the ultraviolet treatment or plasma treatment detection composition of the present invention is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 10% by mass or more, because a higher concentration results in a larger detection range. Furthermore, in order to prevent the occurrence of concentration quenching, the content of inorganic fluorescent material contained in 100% by mass of the composition is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0042] (1.3. Non-discoloring pigments) The ultraviolet treatment or plasma treatment detection composition of the present invention preferably further contains a non-discoloring dye. In this specification, a non-discoloring dye is defined as a dye that does not fade, become colorless, or undergo any or almost no change in hue or brightness due to ultraviolet treatment or plasma treatment. By containing a non-discoloring dye, the ultraviolet treatment or plasma treatment detection composition of the present invention exhibits more pronounced discoloration in response to atmospheric pressure plasma treatment, making it possible to detect atmospheric pressure plasma treatment with higher sensitivity.

[0043] Such non-color-changing dyes are not particularly limited, and examples include pigments having the above-mentioned properties. Examples of such pigments include azo, phthalocyanine, perylene, and quinacridone pigments. These non-color-changing dyes can be used individually or in combination of two or more types.

[0044] The content of the non-discoloring dye in the ultraviolet treatment or plasma treatment detection composition of the present invention is preferably 0.03% by mass or more, more preferably 0.1% by mass or more, per 100% by mass of the composition. Furthermore, the content of the non-discoloring dye is preferably 2.5% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.6% by mass or less. By setting the content of the non-discoloring dye to 0.03% by mass or more and 1.5% by mass or less, the discoloration of the composition in response to atmospheric pressure plasma treatment becomes more pronounced, and atmospheric pressure plasma treatment can be detected with higher sensitivity.

[0045] (1.4.Organic dye) The ultraviolet or plasma treatment detection composition of the present invention may further preferably contain at least one organic dye selected from the group consisting of methine dyes, anthraquinone dyes, oxazine dyes, azo dyes, thiazine dyes, and triarylmethane dyes. Such organic dyes are dyes that undergo changes in hue or lightness, or fade or become colorless upon ultraviolet treatment or plasma treatment.

[0046] Any dye containing a methine group can be used as a methine-based dye. Therefore, in this invention, polymethine-based dyes, cyanine-based dyes, and the like are also included as methine-based dyes. These can be appropriately selected from known or commercially available methine-based dyes. Specifically, examples include CIBasic Red 12, CIBasic Red 13, CIBasic Red 14, CIBasic Red 15, CIBasic Red 27, CIBasic Red 35, CIBasic Red 36, CIBasic Red 37, CIBasic Red 45, CIBasic Red 48, CIBasic Yellow 11, CIBasic Yellow 12, CIBasic Yellow 13, CIBasic Yellow 14, CIBasic Yellow 21, CIBasic Yellow 22, CIBasic Yellow 23, CIBasic Yellow 24, CIBasic Violet 7, CIBasic Violet 15, CIBasic Violet 16, CIBasic Violet 20, CIBasic Violet 21, CIBasic Violet 39, CIBasic Blue 62, CIBasic Blue 63, etc. These can be used individually or in combination of two or more types.

[0047] The anthraquinone-based dye is not limited to those with an anthraquinone as their basic structure, and known anthraquinone-based disperse dyes can also be used. Anthraquinone-based dyes having amino groups are particularly preferred. More preferably, the anthraquinone-based dye has at least one amino group, a primary amino group and a secondary amino group. In this case, there may be two or more amino groups, and these may be the same or different from each other.

[0048] More specifically, examples include 1,4-diaminoanthraquinone (CIDisperse Violet 1), 1-amino-4-hydroxy-2-methylaminoanthraquinone (CIDisperse Red 4), 1-amino-4-methylaminoanthraquinone (CIDisperse Violet 4), 1,4-diamino-2-methoxyanthraquinone (CIDisperse Red 11), 1-amino-2-methylanthraquinone (CIDisperse Orange 11), 1-amino-4-hydroxyanthraquinone (CIDisperse Red 15), 1,4,5,8-tetraaminoanthraquinone (CIDisperse Blue 1), 1,4-diamino-5-nitroanthraquinone (CIDisperse Violet 8), and 1,4-bis(2-ethylhexylamino)anthraquinone (CISolvent Blue 58) (the names in parentheses are the color index names).

[0049] Other dyes known as CISolvent Blue 14, CISolvent Blue 35, CISolvent Blue 63, CISolvent Violet 13, CISolvent Violet 14, CISolvent Red 52, CISolvent Red 114, CIVat Blue 21, CIVat Blue 30, CIVat Violet 15, CIVat Violet 17, CIVat Red 19, CIVat Red 28, CIAcid Blue 23, CIAcid Blue 80, CIAcid Violet 43, CIAcid Violet 48, CIAcid Red 81, CIAcid Red 83, CIReactive Blue 4, CIReactive Blue 19, CIDisperse Blue 7, CISolvent Blue 90, CISolvent Green 3, CISolvent Blue 36, CIAcid Blue 40, etc., can also be used.

[0050] The oxazine-based dyes are not particularly limited as long as they have at least one oxazine ring from any of the following formulas (A) to (C). For example, monooxazine-based dyes having one oxazine ring, and dioxazine-based dyes having two oxazine rings are also included.

[0051] [ka]

[0052] Furthermore, any of the following can be used as the oxazine-based dye: a basic dye having at least one substituted or unsubstituted amino group as a chromatophore, or a chromium mordant having an OH group, COOH group, or the like as a substituent.

[0053] These oxazine dyes can be used individually or in combination of two or more. These can be publicly known or commercially available. More specifically, it is desirable to use oxazine dyes such as CI Basic Blue 3, CI Basic Blue 12, CI Basic Blue 6, CI Basic Blue 10, and CI Basic Blue 96, indicated by their color index names. CI Basic Blue 3 is particularly preferable.

[0054] Azo dyes are not limited to those having an azo group -N=N- as a chromophore. Examples include monoazo dyes, polyazo dyes, metal complex azo dyes, stilbene azo dyes, and thiazole azo dyes. More specifically, examples using color index names include CISolvent Red 1, CISolvent Red 3, CISolvent Red 23, CDisperse Red 13, CDisperse Red 52, CDisperse Violet 24, CDisperse Blue 44, CDisperse Red 58, CDisperse Red 88, CDisperse Yellow 23, CDisperse Orange 1, CDisperse Orange 5, and CISolvent Red 167:1. These can be used individually or in combination of two or more.

[0055] The thiazine-based dyes are not particularly limited and can be selected from publicly known or commercially available options. Examples include CIBasic Blue 9, CIBasic Blue 25, CIBasic Blue 24, CIBasic Blue 17, CIBasic Green 5, and CISolvent Blue 8. These can be used individually or in combination of two or more.

[0056] The triarylmethane dyes are not particularly limited, and known or commercially available dyes can be used. For example, CIBasic Blue 1, CIBasic Blue 26, CIBasic Blue 5, CIBasic Blue 8, CIBasic Green 1, CIBasic Red 9, CIBasic Violet 12, CIBasic Violet 14, CIBasic Violet 3, CISolvent Green 15, CISolvent Violet 8, etc. These can be used individually or in combination of two or more. Among these triarylmethane dyes, CISolvent Violet 8, CIBasic Green 1, CIBasic Red 9, CIBasic Blue 1, etc. can be suitably used.

[0057] The content of the above-mentioned organic dye can be appropriately determined depending on the type of organic dye, the desired hue, etc. Generally, it is desirable to have an organic dye content of 0.05 to 20% by mass, particularly 0.1 to 10% by mass, in the composition of the present invention. By setting the organic dye content to 20% by mass or less, there is an advantage that the solubility or dispersibility in the solvent does not decrease when preparing the composition of the present invention, and it is not difficult to form a uniform coating film of the composition of the present invention when forming the discoloration layer. There is also an advantage that when an indicator using the composition of the present invention as the discoloration layer is made, the color of the discoloration layer (the color before discoloration) does not become too dark. On the other hand, by setting the organic dye content to 0.05% by mass or more, when an indicator using the composition of the present invention as the discoloration layer is made, there is an advantage that the color of the discoloration layer (the color before discoloration) does not become too light, and in particular, the hue change of the discoloration layer does not become large and its gradation does not decrease. Furthermore, if the content of the organic dye in the composition of the present invention is too high or too low, it may become difficult to visually confirm the color change before and after discoloration.

[0058] (1.5. Binder resin) The ultraviolet treatment or plasma treatment detection composition of the present invention preferably contains a binder resin. A wide range of known resins that function as binders can be used as such a binder resin. Specifically, one or more selected from the group consisting of polyurethane resins, polyvinyl butyral resins, cellulose resins, styrene acrylic acid resins, polyester resins, polyamide resins, polyacrylonitrile resins, polyimide resins, polyvinylpyrrolidone resins, polyacrylamide resins, polyvinylimidazole resins, ketone resins, phenolic resins, carbolic acid resins, rosin ester resins, maleic acid resins, styrene maleic acid resins, polyol resins, alkylphenol resins, aliphatic saturated hydrocarbon resins, and acrylic resins can be used.

[0059] The amount of binder resin contained in the ultraviolet treatment or plasma treatment detection composition of the present invention is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, per 100% by mass of the composition, in order to ensure practical mechanical and physical strength. Furthermore, in order to obtain sufficient detection sensitivity, the amount of binder resin contained in the composition is preferably 90% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less, per 100% by mass of the composition.

[0060] (1.6. Discoloration Accelerator) The ultraviolet treatment or plasma treatment detection composition of the present invention may further preferably contain a discoloration accelerator for the purpose of further improving detection sensitivity. Such discoloration accelerators can be any conventionally known agents used in the art, and are not particularly limited.

[0061] Examples of such discoloration accelerators include polyethylene glycol, nonionic surfactants, cationic surfactants, and thiol compounds.

[0062] Nonionic surfactants are not particularly limited, and examples include nonionic surfactants represented by the following formulas (I) to (V).

[0063] [ka]

[0064] In the above formula (I), R1 and R2 each independently represent hydrogen, a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 22, and more preferably 10 to 18 carbon atoms. X represents an oxygen atom or an ester bond, preferably an oxygen atom.

[0065] In formula (I) above, AO represents a repeating unit (monomer) derived from alkylene oxide. Such repeating units are not particularly limited and include, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, styrene oxide, etc. The polymerization form of AO is not particularly limited and includes, for example, a homopolymer, a block copolymer or random copolymer composed of two or more types of AO.

[0066] In the above formula (I), n represents an integer from 1 to 200, preferably from 1 to 100. The nonionic surfactant represented by the above formula (I) is an alkylene glycol derivative.

[0067] [ka]

[0068] In the above formula (II), R1, R2, and R3 each independently represent hydrogen, a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 22, and more preferably 10 to 18 carbon atoms.

[0069] In formula (II) above, X represents an oxygen atom or an ester bond, preferably an oxygen atom, and n represents an integer from 1 to 200, more preferably from 1 to 100. The nonionic surfactant represented by formula (II) above is a polyglycerin derivative.

[0070] Examples of specific nonionic surfactants represented by formula (I) or (II) above include polyethylene glycol (such as "PEG2000" as a commercially available product; manufactured by Sanyo Chemical Industries, Ltd.), glycerin, and polyethylene glycol-polypropylene glycol copolymer (such as "Epan 710" as a commercially available product; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[0071] Furthermore, polymers in which at least one of R1 or R2 in the above formula (I) or (II) is substituted with a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms can be cited as preferred nonionic surfactants.

[0072] Examples of such nonionic surfactants include polyoxyethylene (hereinafter referred to as "POE") lauryl ether (commercially available as "Emulgen 109P," etc.), POE cetyl ether (commercially available as "Emulgen 220," etc.), POE oleyl ether (commercially available as "Emulgen 404," etc.), POE stearyl ether (commercially available as "Emulgen 306," etc.), POE alkyl ether (commercially available as "Emulgen LS-110") (all manufactured by Kao Corporation), POE isodecyl ether, POE tridecyl ether (commercially available as "Fineserve TD-150," etc.), polyethylene glycol monostearate (commercially available as "Brownon S Examples include polyethylene glycol monooleate (such as "Nonion O-4" as a commercially available product), tetramethylene glycol derivatives (such as "Polycene DC-1100" as a commercially available product), polybutylene glycol derivatives (such as "Uniol PB-500" as a commercially available product), alkylene glycol derivatives (such as "Unilube 50MB-5" as a commercially available product) (all manufactured by NOF Corporation), POE(20) octyldodecyl ether (such as "Emarex OD-20" as a commercially available product), POE(25) octyldodecyl ether (such as "Emarex OD-25" as a commercially available product) (all manufactured by Nippon Emulsion Co., Ltd.).

[0073] [ka]

[0074] [ka]

[0075] In the above formulas (III) and (IV), R1, R2, and R3 each independently represent hydrogen, a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 22, and more preferably 10 to 18 carbon atoms.

[0076] In formulas (III) and (IV) above, AO represents a repeating unit (monomer) derived from alkylene oxide. Such repeating units are not particularly limited and include, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, styrene oxide, etc. The polymerization form of AO is not particularly limited and includes, for example, a homopolymer, a block copolymer or random copolymer composed of two or more types of AO.

[0077] In formulas (III) and (IV) above, a+b+c represents an integer between 3 and 200, more preferably between 3 and 50. The nonionic surfactants represented by formulas (III) and (IV) above are alkylene glycol glyceryl derivatives.

[0078] Specific nonionic surfactants represented by formula (III) above include compounds in which R1 is an isostearic acid residue, R2 and R3 are hydrogen atoms, and AO (monomer) is ethylene oxide. More specifically, POE glyceryl isostearate (commercially available products such as "Uniox GM-30IS"; manufactured by NOF Corporation) can be cited.

[0079] Specific nonionic surfactants represented by formula (IV) above include compounds in which R1 to R3 are isostearic acid residues and AO (monomer) is ethylene oxide. More specifically, POE glyceryl triisostearate (commercially available as "Uniox GT-30IS," etc.; manufactured by NOF Corporation) can be cited.

[0080] [ka]

[0081] In the above formula (V), R1, R2, R3, or R4 each independently represents hydrogen, a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 22, and more preferably 10 to 18 carbon atoms.

[0082] In formula (V) above, X represents an oxygen atom or an ester bond, preferably an oxygen atom. In formula (V) above, p+q represents an integer from 0 to 200, more preferably from 0 to 10. The nonionic surfactant represented by formula (V) above is an acetylene glycol derivative.

[0083] Specific nonionic surfactants represented by the above formula (V) include compounds in which R1 and R4 are hydrogen atoms, R2 and R3 are C(CH3)(i-C4H9), X is an oxygen atom, and p+q=0. More specifically, 2,4,7,9-tetramethyl-5-decine-4,7-diol (commercially available as "Surfinol 104H," etc.; manufactured by Air Products Japan Co., Ltd.) can be cited.

[0084] Among the nonionic surfactants represented by the above formulas (I) to (V), the nonionic surfactant represented by (I) or (IV) is preferred, and the nonionic surfactant represented by (I) is more preferred.

[0085] The nonionic surfactant contained in the detection composition of the present invention may be one type or two or more types in appropriate combination. The content of such nonionic surfactant is not particularly limited as long as it does not hinder the effect exhibited by the detection composition of the present invention. For example, the content of the nonionic surfactant can be about 0.001 to 20% by mass, preferably about 0.01 to 15% by mass, relative to the detection composition of the present invention, and most preferably about 0.1 to 10% by mass. For example, when using a thiol compound as described later, odor may be a problem if the amount used is large. Therefore, by setting the content of the thiol compound low, to about 0.01 to 5% by mass relative to the detection composition, and combining it with a nonionic surfactant in the range of 0.1 to 10% by mass relative to the detection composition, it is possible to improve the color change performance while suppressing the odor problem of the thiol compound.

[0086] By incorporating a nonionic surfactant into the detection composition of the present invention, the dispersibility of the dye to be discolored in the coating film applied to the indicator with the detection composition is improved, and the discoloration performance exhibited by the detection composition after plasma treatment can be further enhanced. Furthermore, when a nonionic surfactant is included, the vividness of the color of the discolored layer (the color after discoloration) can also be improved.

[0087] The cationic surfactant is not particularly limited, but it is especially desirable to use at least one of tetraalkylammonium salts, isoquinolinium salts, imidazolinium salts, and pyridinium salts. Commercially available products of these can also be used. By using a cationic surfactant in combination with the above-mentioned colorant, better detection sensitivity can be obtained. The above-mentioned cationic surfactant can be used individually or in combination of two or more types.

[0088] Among tetraalkylammonium salts, alkyltrimethylammonium salts and dialkyldimethylammonium salts are preferred. Specifically, examples include coconut alkyltrimethylammonium chloride, beef tallow alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyltrimethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium chloride, tetrapropylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetrapropylammonium bromide, trimethyl-2-hydroxyethylammonium chloride, cetyltrimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, dioctyldimethylammonium chloride, distearyldimethylammonium chloride, and alkylbenzyldimethylammonium chloride. In particular, behenyltrimethylammonium chloride and lauryltrimethylammonium chloride are preferred.

[0089] Examples of isoquinolinium salts include lauryl isoquinolinium bromide, cetyl isoquinolinium bromide, cetyl isoquinolinium chloride, and lauryl isoquinolinium chloride. Among these, lauryl isoquinolinium bromide is particularly preferred.

[0090] Examples of imidazolinium salts include 1-hydroxyethyl-2-oleylimidazolinium chloride and 2-chloro-1,3-dimethylimidazolinium chloride. Among these, 2-chloro-1,3-dimethylimidazolinium chloride is particularly preferred.

[0091] Examples of pyridinium salts include pyridinium chloride, 1-ethylpyridinium bromide, hexadecylpyridinium chloride, cetylpyridinium chloride, 1-butylpyridinium chloride, Nn-butylpyridinium chloride, hexadecylpyridinium bromide, N-hexadecylpyridinium bromide, 1-dodecylpyridinium chloride, 3-methylhexylpyridinium chloride, 4-methylhexylpyridinium chloride, 3-methyloctylpyridinium chloride, and 2-chloro-1-methyl Examples include lupyridinium iodide, 3,4-dimethylbutylpyridinium chloride, pyridinium-n-hexadecylchloride hydrate, N-(cyanomethyl)pyridinium chloride, N-acetonylpyridinium bromide, 1-(aminoformylmethyl)pyridinium chloride, 2-amidinopyridinium chloride, 2-aminopyridinium chloride, N-aminopyridinium iodide, 1-aminopyridinium iodide, 1-acetonylpyridinium chloride, and N-acetonylpyridinium bromide. Among these, hexadecylpyridinium chloride is particularly preferred.

[0092] The content of cationic surfactant can be appropriately determined depending on the type of surfactant and the type of colorant used, but it is generally desirable to have a content of about 0.2 to 10% by mass, and particularly 0.5 to 6% by mass, in the detection composition.

[0093] There are no particular limitations on the thiol compounds; for example, thiol compounds having 1 to 4 thiol groups can be mentioned.

[0094] The specific thiol compounds described above are not particularly limited within the scope in which the effects of the present invention are exhibited. For example, monofunctional thiol compounds, difunctional thiol compounds, trifunctional thiol compounds, tetrafunctional thiol compounds, etc., can be mentioned. Among these thiol compounds, difunctional thiol compounds, trifunctional thiol compounds, and tetrafunctional thiol compounds can each include compounds having a primary thiol or compounds having a secondary thiol.

[0095] The specific monofunctional thiol compounds described above are not particularly limited within the scope of the effects of the present invention. For example, 1-pentanethiol, 1-hexanethiol, 1-heptanethiol, 1-octanthiol, 1-decanethiol, 1-dodecanethiol, 1-hexadecanethiol, 1-octadecanethiol, cyclohexanethiol, eicosanthiol, docosanthiol, tetracosanthiol, hexacosanthiol, octacosanthiol, t-dodecyl mercaptan, methyl thioglycolate, β-mercaptopropionic acid, methyl-3-mercaptopropionic acid Examples include thioglycolate, ethyl thioglycolate, butyl thioglycolate, butyl-3-mercaptopropionate, isooctyl thioglycolate, isooctyl-3-mercaptopropionate, isodecyl thioglycolate, isodecyl-3-mercaptopropionate, dodecyl thioglycolate, dodecyl-3-mercaptopropionate, octadecyl thioglycolate, octadecyl-3-mercaptopropionate, thioglycolic acid, and the like.

[0096] The specific difunctional primary thiol compounds described above are not particularly limited within the scope of the effects of the present invention. For example, 2,2'-(ethylenedioxy)diethanethiol, ethylene glycol bis-mercaptoacetate, and the like can be cited.

[0097] The specific trifunctional primary thiol compounds described above are not particularly limited within the scope of the effects of the present invention. For example, trimethylolpropanetris(3-mercaptopropionate) can be cited.

[0098] The specific tetrafunctional primary thiol compounds described above are not particularly limited within the scope of the effects of the present invention. For example, pentaerythritol tetrakis(3-mercaptopropionate) can be cited.

[0099] The specific bifunctional secondary thiol compounds described above are not particularly limited within the scope of the effects of the present invention. For example, 1,4-bis(3-mercaptobutyryloxy)butane, bis(1-mercaptoethyl)phthalate, bis(2-mercaptopropyl)phthalate, bis(3-mercaptobutyl)phthalate, ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate), ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate) Examples include octanediol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), ethylene glycol bis(4-mercaptovalerate), propylene glycol bis(4-mercaptoisovalerate), diethylene glycol bis(4-mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol bis(4-mercaptovalerate), ethylene glycol bis(3-mercaptovalerate), propylene glycol bis(3-mercaptovalerate), diethylene glycol bis(3-mercaptovalerate), butanediol bis(3-mercaptovalerate), octanediol bis(3-mercaptovalerate), etc.

[0100] The specific trifunctional secondary thiol compounds described above are not particularly limited within the scope of the effects of the present invention. Examples include trimethylolpropanetris(3-mercaptobutyrate), trimethylolpropanetris(2-mercaptopropionate), trimethylolpropanetris(4-mercaptovalerate), trimethylolpropanetris(3-mercaptovalerate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0101] The specific tetrafunctional secondary thiol compounds described above are not particularly limited within the scope of the effects of the present invention. For example, pentaerythritol tetrakis(3-mercapto-2-propionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(2-mercaptoisobutyrate), pentaerythritol tetrakis(4-mercaptovalerate), pentaerythritol tetrakis, 2,2'-(ethylenedioxy)diethanethiol, ethylene glycol bis-mercaptoacetate, pentaerythritol tetrakis(3-mercaptopropionate), and the like can be cited.

[0102] Among these thiol compounds, 1-octanthiol, β-mercaptopropionic acid, trimethylolpropantris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptobutyrate) are preferred, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropantris (3-mercaptopropionate), and β-mercaptopropionic acid are more preferred, pentaerythritol tetrakis (3-mercaptobutyrate) and trimethylolpropantris (3-mercaptopropionate) are even more preferred, and trimethylolpropantris (3-mercaptopropionate) is the most preferred.

[0103] The above trimethylolpropanetris (3-mercaptopropionate) is a compound containing three thiol groups called TMMP, pentaerythritol tetrakis (3-mercaptopropionate) is a compound containing four thiol groups called PEMP, and pentaerythritol tetrakis (3-mercaptobutyrate) is a compound containing four thiol groups called Karenz MT(registered trademark)PE1.

[0104] The content of the thiol compound contained in the composition of the present invention can be appropriately determined depending on the type of thiol compound and the type of organic dye used. Generally, the content of the thiol compound in the composition of the present invention can be set to about 0.005 to 30% by mass. Preferably, it is about 0.01 to 20% by mass, and more preferably, about 0.03 to 15% by mass. If the content of the thiol compound exceeds about 30% by mass, an unpleasant odor characteristic of thiol compounds will be generated. Depending on how the composition of the present invention is used, the generation of an unpleasant odor may be undesirable. Furthermore, by setting the content of the thiol compound to about 0.005% by mass or more, a sufficient improvement in the color change performance exhibited by the composition of the present invention after plasma treatment can be expected.

[0105] (1.7. Volume expander) The detection composition of the present invention may optionally contain an extender. The extender is not particularly limited and can be an inorganic material such as bentonite, activated clay, aluminum oxide, silica, or silica gel. Other known extender pigments can also be used. Among these, at least one of silica, silica gel, and alumina is preferred. Silica is particularly preferred. When silica or the like is used, multiple cracks can be effectively generated on the surface of the discolored layer. As a result, the detection sensitivity of the indicator can be further increased. The extender may be used alone or in combination of multiple types.

[0106] The amount of bulking agent can be appropriately determined depending on the type of bulking agent and coloring agent used. Generally, it is preferable to have about 1 to 30% by mass, and more preferably 2 to 20% by mass, in 100% by mass of the detection composition of the present invention.

[0107] (1.8. Other Additives) The detection composition of the present invention may optionally contain known components used in inks, such as solvents, leveling agents, defoaming agents, ultraviolet absorbers, and surface modifiers.

[0108] As a solvent, any solvent commonly 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, and glycol ethers can be used, and should be appropriately selected depending on the solubility of the dye and binder resin used. One or more of the above solvents can be used.

[0109] The solvent content can be appropriately determined depending on the type of solvent and dye used, but generally, it is desirable to have approximately 40-95% by mass, and particularly 60-90% by mass, of the detection composition.

[0110] Each component of the detection composition of the present invention can be added simultaneously or sequentially and mixed uniformly using a known stirrer such as a homogenizer or dissolver. For example, the dye, along with at least one of the polyurethane resin, color change accelerator, and bulking agent (and other additives as needed), can be added to the solvent in order and then mixed and stirred with a stirrer.

[0111] (2. Plasma Indicator) The plasma indicator of the present invention (hereinafter also simply referred to as "the indicator of the present invention") includes, for example, a color-changing layer made of the detection composition of the present invention. Specifically, the color-changing layer can be formed by coating or printing the detection composition of the present invention onto a substrate and then drying it, and this can be used as the indicator of the present invention. The substrate is not particularly limited as long as it can form a color-changing layer. The content of each component in the color-changing layer will be described below, but since the color-changing layer has undergone a drying process, it is substantially free of solvents, although a small or unavoidable residue may remain depending on the drying conditions, etc.

[0112] The organic fluorescent material and inorganic fluorescent material contained in the indicator of the present invention can be the same as those in the detection composition described above. The content of such organic and inorganic fluorescent materials is not particularly limited as long as it is within the range that the effects of the present invention are achieved. For example, the content in the color-changing layer can usually be about 0.1 to 35% by mass. Preferably, it can be about 0.2 to 20% by mass. Setting the content to about 35% by mass or less has the advantage that the color of the color-changing layer (the color before color change) does not become too dark when the color-changing layer is formed. Setting the content to about 0.1% by mass or more has the advantage that when the color-changing layer is formed, the color of the color-changing layer (the color before color change) does not become too light, and in particular, the change in the color-changing layer does not become large and its gradation does not decrease. Furthermore, if the content of organic and inorganic fluorescent materials in the color-changing layer is too high or too low, it may become difficult to visually confirm the color change before and after color change.

[0113] The pigment contained in the indicator of the present invention can be the same as that of the detection composition described above. The pigment content is not particularly limited as long as it is within the range that the effects of the present invention are achieved. For example, the pigment content in the discoloration layer can usually be about 0.01 to 10% by mass. Preferably, the pigment content can be about 0.02 to 5% by mass. By setting the pigment content to 0.01% by mass or more, when the discoloration layer is formed, the color of the discoloration layer (the color before discoloration) does not become too light, and in particular, there is the advantage that the hue change of the discoloration layer becomes larger. Also, by setting the pigment content to 10% by mass or less, when the discoloration layer is formed, the color of the discoloration layer (the color before discoloration) does not become too dark, and there is the advantage that the hue change before and after discoloration can be easily confirmed by visual observation.

[0114] The thiol compound contained in the indicator of the present invention can be the same as that used in the detection composition described above. The content of such thiol compounds is not particularly limited as long as it does not affect the effects of the present invention. For example, the thiol compound content in the discoloration layer can typically be 0.03 to 60% by mass. Preferably, the thiol compound content can be 0.06 to 55% by mass. If the thiol compound content is 60% by mass or more, an unpleasant odor characteristic of thiol compounds will be generated, which is undesirable. If the thiol compound content is 0.03% by mass or less, a sufficient improvement in the discoloration performance exhibited by the discoloration layer after plasma treatment cannot be expected.

[0115] The silica contained in the indicator of the present invention can be the same as that in the detection composition described above. The silica content is not particularly limited as long as it is within the range that the effects of the present invention are achieved. For example, the silica content in the discoloration layer can typically be about 3 to 85% by mass. Preferably, the silica content can be about 5 to 70% by mass. By setting the silica content to 3% by mass or more, a sufficient improvement in the discoloration performance exhibited by the discoloration layer after plasma treatment can be expected. Similarly, by setting the silica content to 85% by mass or less, a sufficient improvement in discoloration performance can also be expected.

[0116] The binder resin contained in the indicator of the present invention can be the same as that of the detection composition described above. The content of such binder resin is not particularly limited as long as it is within the range that the effects of the present invention are achieved. For example, the binder resin content in the discoloration layer can usually be about 0.3 to 80% by mass. Preferably, the binder resin content can be about 3 to 60% by mass. By setting the binder resin content to about 0.3% by mass or more, there is the advantage of improved fixation. Also, by setting the binder resin content to about 80% by mass or less, there is the advantage of a faster discoloration rate.

[0117] The nonionic surfactant contained in the indicator of the present invention can be the same as that in the detection composition described above. The content of such a nonionic surfactant is not particularly limited as long as it is within the range that the effects of the present invention are achieved. For example, it can usually be about 0.003 to 60% by mass in the discoloration layer. Preferably, it can be about 3 to 50% by mass. By setting the content of the nonionic surfactant to 0.003% by mass or more, there is a significant advantage in significantly improving the discoloration performance exhibited by the discoloration layer after plasma treatment. Furthermore, by setting the content of the nonionic surfactant to 60% by mass or less, there is an advantage in improving the fixation properties.

[0118] Specific examples of substrates include metals or alloys, ceramics, glass, concrete, plastics (polyethylene terephthalate (PET), polypropylene, nylon, polystyrene, polysulfone, polycarbonate, polyimide, etc.), fibers (nonwoven fabrics, woven fabrics, paper, other fiber sheets), and composite materials thereof. Synthetic resin fiber paper (synthetic paper) such as polypropylene synthetic paper and polyethylene synthetic paper can also be suitably used as the above substrate. Among these substrates, when the detection composition of the present invention does not contain a resin binder or contains a small amount of resin binder, a permeable substrate such as fibers that can be impregnated with the detection composition is preferred from the viewpoint of the fixation of the detection composition.

[0119] Examples of the discoloration patterns of the discoloration layer in the present invention include patterns in which the color changes from colorless to colored, patterns in which the color changes from colored to colorless, and patterns in which one color changes to another.

[0120] The discoloration layer can be formed using the detection composition of the present invention, according to known printing methods such as screen printing, gravure printing, offset printing, letterpress printing, and flexographic printing. It can also be formed by methods other than printing. For example, the discoloration layer can be formed on a substrate by immersing it in the detection composition.

[0121] The discolored layer should preferably have multiple cracks on its surface. That is, it is desirable that open pores are formed on the surface of the discolored layer, making it porous. By creating these cracks, the sensitivity of plasma processing detection can be further improved.

[0122] To further enhance the visibility effect when the discoloration layer changes color, a non-discoloration layer (undercoat layer) can be formed between the substrate and the discoloration layer, for example. Such a non-discoloration layer can usually be formed using commercially available ordinary color inks. For example, water-based inks, oil-based inks, solvent-free inks, etc., can be used. The ink used to form the non-discoloration layer may contain components that are blended in known inks, such as resin binders, fillers, solvents, etc. Furthermore, the composition of the non-discoloration layer can include components that do not contain the discoloration components included in the indicator. For example, the composition can include at least one of the following: thiol compounds, binder resins, silica, hydrophobic alumina, pigments, fillers, cationic surfactants, nonionic surfactants, leveling agents, defoamers, ultraviolet absorbers, surface modifiers, organic crosslinking agents, antioxidants, ozone degradation inhibitors, antistatic agents, lubricants, tackifiers, flame retardants, etc.

[0123] The formation of the non-discolored layer can be done in the same way as the formation of the discolored layer. For example, it can be done using ordinary colored inks and known printing methods such as screen printing, gravure printing, offset printing, letterpress printing, and flexographic printing.

[0124] The indicator of the present invention can be applied to any plasma treatment using a plasma generating gas without any particular limitations. In other words, it can be applied to both reduced-pressure plasma treatment and atmospheric pressure plasma treatment. Furthermore, the indicator of the present invention has a significant advantage in that it can detect the completion of plasma treatment with high sensitivity even in atmospheric pressure plasma, which is considered to have a relatively low plasma intensity.

[0125] (3. Real-time analysis method for plasma processing) This invention encompasses an invention relating to a real-time analysis method for plasma processing.

[0126] The real-time analysis method for plasma processing according to the present invention comprises the step of irradiating a test substance containing the plasma processing detection composition described above with plasma.

[0127] As described above, the composition of the present invention emits fluorescence upon plasma treatment. In the real-time analysis method of plasma treatment of the present invention, a test substance (subject) containing the composition of the present invention is irradiated with plasma, and the fluorescence emitted therefrom is detected.

[0128] In other words, by performing the steps of irradiating a test substance containing the composition of the present invention with plasma, and preferably detecting the fluorescence emitted from the test substance as a result of the plasma irradiation, in parallel, the status of the plasma treatment can be grasped in real time.

[0129] In the embodiment in which the test substance contains the composition of the present invention, for example, it is preferable that the composition of the present invention coats the outer surface of the test substance. More specifically, it is preferable that the composition of the present invention coats the outer surface of the test substance by application, attachment, or other means.

[0130] As a means of detecting fluorescence emitted when a test substance is irradiated with plasma, a wide range of known devices for detecting or capturing fluorescence can be used, and there are no particular limitations. However, if only the generation of fluorescence is detected, it is only possible to confirm whether or not the test substance was irradiated with plasma.

[0131] On the other hand, by using a device that can recognize the location information of fluorescence generation, it is also possible to map the location information of the plasma irradiation.

[0132] Although embodiments of the present invention have been described above, the present invention is not limited in any way to these examples, and can be implemented in various forms without departing from the spirit of the invention. [Examples]

[0133] The embodiments of the present invention will be described in more detail below based on examples, but the present invention is not limited to these.

[0134] (Examples 1-10, Comparative Examples 1-4) Each detection composition was prepared by mixing the components based on the compositions shown in Table 1. Note that blank spaces in Table 1 indicate that the corresponding component was not present.

[0135] (Examples 11-19) Furthermore, based on the compositions shown in Table 2, various detection compositions containing color-changing and / or non-color-changing dyes were prepared. Examples 1 and 2 shown in Table 2 are identical to those described in Table 1.

[0136] Each indicator was obtained by printing the detection composition of each example or comparative example onto a clean paper substrate using a Minomat screen printing machine.

[0137] (Discoloration evaluation test) First, the chromaticity L*a*b* of the discolored layer (before plasma treatment) of each indicator was measured using a Konica Minolta FD-7 fluorescence spectrometer.

[0138] Next, each indicator was installed in an atmospheric pressure plasma processing device (AETP Corporation, device model: AP4000R).

[0139] The chromaticity before plasma treatment was denoted as L*1, a*1, and b*1, and the chromaticity after plasma treatment was denoted as L*2, a*2, and b*2. The difference in chromaticity (color difference) was expressed as △E*ab using the following formula. Table 1 shows the color difference of the discolored layer for each indicator.

[0140] Color difference △E*ab = [(L*2-L*1)2+(a*2-a*1)2+(b*2-b*1)2]¹ / ² (Plasma treatment conditions)

[0141] Atmospheric pressure plasma treatment was performed as follows. • Gas: Compressed air, flow rate 50 SLM • High-frequency power output: 500W ·Irradiation distance: 10mm, • Number of processing times: 1, Processing speed: 100 mm / sec, • Nozzle head: Rotating nozzle (18°)

[0142] Ozone treatment (O3) was carried out as follows. • CT value: 20 ppm·min

[0143] [Table 1]

[0144] [Table 2]

[0145] As shown in Table 1, the indicators prepared using the detection compositions of each example showed good reactivity to plasma treatment. In addition, it was confirmed that their reaction to ozone was suppressed.

[0146] Furthermore, as shown in Table 2, it was confirmed that the detection sensitivity to atmospheric pressure plasma treatment is improved by further including a non-color-changing dye in the detection composition. It was also confirmed that by adopting a composition containing a color-changing dye, the detection sensitivity to ozone treatment can be improved when necessary.

[0147] (Real-time analysis test of plasma treatment) When the room lights were turned off while irradiating the indicators in Examples 1-19 with plasma, it was visually confirmed that in all cases the indicators emitted fluorescence distinct from the emission of the plasma device, only during irradiation. Furthermore, this phenomenon was captured in both images and videos.

[0148] As demonstrated by the fact that the indicators in Examples 1 to 19 were able to identify the location where plasma was being irradiated in real time, it was confirmed that the position of the irradiation location can be adjusted visually and using an image recognition device.

[0149] Next, when the plasma irradiation conditions were changed with the room lights turned off, a change in the fluorescence intensity emitted by the indicator was observed. Furthermore, this change could be captured in both images and videos. Thus, since the indicators in Examples 1 to 19 were able to detect the plasma intensity in real time, it was confirmed that the plasma intensity at the irradiation site can be evaluated visually and using an image recognition device.

[0150] Since the location and intensity of plasma irradiation can be measured in real time, these two types of information can be integrated and calculated by a computer to obtain plasma intensity mapping data for any given time during processing. In other words, real-time mapping data of plasma processing intensity can be reproduced.

Claims

1. A composition for detecting ultraviolet treatment or plasma treatment, comprising at least one selected from the group consisting of organic fluorescent materials and inorganic fluorescent materials.

2. The aforementioned organic fluorescent material is an organic fluorescent whitening agent. The plasma treatment detection composition according to claim 1, wherein the organic fluorescent whitening agent is at least one selected from the group consisting of coumarin-type organic fluorescent whitening agents, thiophene-type organic fluorescent whitening agents, naphthalene-type organic fluorescent whitening agents, bisbenzoxazole-type organic fluorescent whitening agents, bis(styryl)biphenyl-type organic fluorescent whitening agents, stilbene-type organic fluorescent whitening agents, and azole-type organic fluorescent whitening agents.

3. The plasma processing detection composition according to claim 1 or 2, further comprising a non-coloring dye.

4. A plasma processing detection composition according to claim 3, for use in detecting atmospheric pressure plasma processing.

5. The plasma treatment detection composition according to claim 1 or 2, further comprising at least one organic dye selected from the group consisting of methine dyes, anthraquinone dyes, oxazine dyes, azo dyes, thiazine dyes, and triarylmethane dyes.

6. A plasma indicator having a plasma processing detection layer made of the composition described in claim 1.

7. A real-time analysis method for plasma processing, comprising the step of irradiating a test substance containing the plasma processing detection composition described in claim 1 with plasma.

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