JP2023064733A - Ink composition for plasma treatment detection, plasma treatment detection indicator and plasma treatment method - Google Patents

Abstract

To provide a plasma treatment detection indicator that enables checking with increased sensitivity than in the conventional art, regardless of the type of decompressed plasma and atmospheric-pressure plasma and the magnitude of plasma intensity, particularly even in the case of small plasma intensity in atmospheric-pressure plasma treatment, and an ink composition for plasma treatment detection that is used to form a color-changing layer of the indicator.SOLUTION: An ink composition for plasma treatment detection contains 1) an organic dye, 2) a thiol compound, and 3) at least one of silica and hydrophobic alumina.SELECTED DRAWING: None

Description

The present invention relates to an ink composition for plasma treatment detection and a plasma treatment detection indicator using the same. In addition, the plasma treatment in this specification means a plasma treatment using a plasma generated by applying an AC voltage, a pulse voltage, a high frequency, a microwave, etc., using a gas for plasma generation, and includes low pressure plasma and large plasma. Both atmospheric pressure plasmas are applicable.

Various instruments and instruments used in hospitals, laboratories, etc. are sterilized for disinfection and sterilization. Plasma treatment is known as one of these sterilization treatments (eg, "3.3.1 Sterilization experiment using low-pressure discharge plasma" in Non-Patent Document 1).

Plasma treatment is used not only for sterilization but also for plasma dry etching in the manufacture of semiconductor devices and plasma cleaning of the surfaces of objects to be treated such as electronic components.

Plasma dry etching is a means of applying high-frequency power to electrodes placed in a reaction chamber, which is generally a vacuum vessel, and converting a plasma-generating gas introduced into the reaction chamber into plasma to etch a semiconductor wafer with high precision. is. Plasma cleaning is a means of removing metal oxides, organic substances, burrs, etc. deposited or adhered to the surface of objects to be processed, such as electronic components. can be improved, and the adhesion and wettability with the sealing resin can be improved.

As a method for detecting the completion of these plasma processes, there is known a method using a plasma process detection indicator whose discoloration layer changes color in a plasma process atmosphere.

For example, Patent Document 1 discloses an ink composition for plasma treatment detection, which is characterized by containing an organic dye and at least one selected from the group consisting of a photopolymerization initiator, silica, and hydrophobic alumina, and A plasma-treated detection indicator is disclosed in which a color-changing layer of an ink composition is formed on a substrate.

The plasma processing detection indicator of Patent Document 1 can determine the completion of plasma processing even when the plasma intensity is set to be small even in low-pressure plasma, and even when it is used in atmospheric pressure plasma, which generally has a lower plasma intensity than low-pressure plasma. can.

However, due to the increasing demand for higher performance of the plasma processing detection indicator, there is room for improvement in the discoloration behavior of the discoloration layer even in the plasma processing detection indicator described in Patent Document 1, especially when used in atmospheric pressure plasma. There is a demand for higher detection sensitivity.

Therefore, in view of the above problems, regardless of the type of low-pressure plasma and atmospheric pressure plasma and the magnitude of the plasma intensity, even if the plasma intensity is small as in atmospheric pressure plasma processing, it can be confirmed with higher sensitivity than conventional products. It is desired to develop a plasma treatment detection indicator capable of forming the discoloration layer and an ink composition for plasma treatment detection for forming the discoloration layer.

JP 2016-065204 A

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

The present invention is a plasma processing that can be confirmed with higher sensitivity than conventional products, regardless of the type of low pressure plasma and atmospheric pressure plasma and the magnitude of the plasma intensity, especially when the plasma intensity is small like atmospheric pressure plasma processing. It is an object of the present invention to provide a detection indicator and a plasma-treated detection ink composition for forming a color change layer of the indicator. Another object of the present invention is to provide a plasma processing method using the indicator.

As a result of intensive studies aimed at achieving the above object, the inventors of the present invention have found that the above object can be achieved by employing an ink composition having a specific composition, and have completed the present invention. The present invention relates to an ink composition for plasma treatment detection, a plasma treatment detection indicator, and a plasma treatment method described below.

Item 1. An ink composition for plasma processing detection, comprising 1) an organic dye, 2) a thiol compound, and 3) at least one of silica and hydrophobic alumina.

Item 2 The organic dyes include nitroso dyes, nitro dyes, monoazo dyes, diazo dyes, triazo dyes, polyazo dyes, azoic dyes (diazo components), azoic dyes (coupling components), and stilbene dyes. Dyes, carotenoid dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine dyes, thiazole dyes, indamine dyes, indophenol dyes, azine dyes, selected from the group consisting of oxazine dyes, thiazine dyes, sulfur dyes, lactone dyes, hydroxyketone dyes, aminoketone dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, natural dyes and oxidation dyes; Item 1. The ink composition according to item 1, which is at least one of

Item 3 The thiol compound includes a monofunctional thiol compound, a bifunctional primary thiol compound, a trifunctional primary thiol compound, a tetrafunctional primary thiol compound, a bifunctional secondary thiol compound, a trifunctional secondary thiol compound, and a tetrafunctional Item 3. The ink composition according to Item 1 or Item 2, which is at least one selected from the group consisting of secondary thiol compounds.

Item 4. The ink composition according to any one of Items 1 to 3, further comprising a nonionic surfactant.

Item 5. The ink composition according to any one of Items 1 to 4, further comprising a binder resin.

Item 6. A plasma treatment detection indicator having a discoloration layer comprising the ink composition according to any one of Items 1 to 5 above.

Item 7. The plasma treatment detection indicator of Item 6, further comprising a non-discoloring layer.

Item 8. The plasma processing detection indicator according to the above item 6 or 7, which is used for plasma processing detection in atmospheric pressure plasma.

Item 9. A plasma processing method, comprising the step of placing the plasma processing detection indicator according to any one of Items 6 to 8 above and the object to be processed in a plasma processing atmosphere.

The ink composition for plasma processing detection of the present invention uses an organic dye as a discoloring component that changes color in a plasma processing atmosphere, and further contains a thiol compound and silica and / or hydrophobic alumina, so that the ink composition The discoloration performance (discoloration speed, degree of discoloration, change in color difference, etc.) of the discoloration layer composed of is improved in a plasma treatment atmosphere, especially in an atmospheric pressure plasma treatment atmosphere, compared to conventional products. Therefore, the plasma processing detection indicator having the discoloration layer can detect the completion of plasma processing with higher sensitivity than conventional products, regardless of the type of low-pressure plasma or atmospheric pressure plasma and the magnitude of the plasma intensity. Especially in atmospheric pressure plasma, it is highly useful in that it can detect the completion of plasma processing with higher sensitivity than conventional products.

Further, when the ink composition for plasma treatment detection of the present invention further contains a nonionic surfactant, the discoloration performance exhibited by the ink composition (especially the degree of discoloration, change in color difference, etc.) is further improved. do.

The ink composition for plasma treatment detection, the plasma treatment detection indicator and the plasma treatment method of the present invention will be described in detail below. In the following, the notation "-" indicating a numerical range indicates "more than or equal to" unless otherwise specified that it means "less than" or "exceeding". That is, "A to B" means "A or more and B or less."

In this specification, the expression "include" or "contain" a certain component means that the component is included and may further contain other components, and that the component is included as an essential component. The concepts "consisting essentially of" or "consisting only of" are also included.

1. Ink Composition for Plasma Treatment Detection The ink composition for plasma treatment detection of the present invention (hereinafter also simply referred to as "ink composition") comprises 1) an organic dye, 2) a thiol compound, and 3) silica and hydrophobic alumina. It is characterized by containing at least one kind.

The ink composition for plasma processing detection of the present invention having the above characteristics uses an organic dye as a discoloring component that changes color in a plasma processing atmosphere, and further contains a thiol compound, silica and/or hydrophobic alumina, The discoloration layer made of the ink composition has improved discoloration performance such as discoloration speed, degree of discoloration, change in color difference, etc. under a plasma treatment atmosphere, particularly in atmospheric pressure plasma, as compared with conventional products. Therefore, the plasma processing detection indicator having the discoloration layer can be confirmed with higher sensitivity than conventional products, regardless of the type of low-pressure plasma or atmospheric pressure plasma and the magnitude of the plasma intensity. In particular, even in atmospheric pressure plasma, the completion of plasma processing can be detected with higher sensitivity than conventional products, which is highly useful.

Each component of the ink composition will be described below.

Color changing component under plasma treatment atmosphere The ink composition of the present invention uses an organic dye as a color changing component for detecting plasma in a plasma treatment atmosphere. Organic dyes exhibit discoloration behavior due to structural changes (partial decomposition, bond breakage, etc.) of organic dyes due to the action of plasma in a plasma treatment atmosphere. Generally, organic dyes change from colored to colorless by the action of plasma.

The organic dye contained in the ink composition is not particularly limited as long as it exhibits the above behavior. For example, it can be appropriately selected from direct dyes, acid dyes, basic dyes, mordant dyes, vat dyes, disperse dyes, reactive dyes and fluorescent brightening dyes. Specific examples of such organic dyes include nitroso dyes (10000-10299), nitro dyes (10300-10999), monoazo dyes (11000-19999), diazo dyes (20000-29999), triazo dyes. Dyes (30000-34999), polyazo dyes (35000-36999), azoic dyes (diazo component) (37000-37275), azoic dyes (coupling component) (37500-37625), stilbene dyes (40000-40799) ), carotenoid dyes (40800-40999), diarylmethane dyes (41000-41999), triarylmethane dyes (42000-44999), xanthene dyes (45000-45999), acridine dyes (46000-46999), Quinoline dyes (47000-47999), methine dyes (48000-48999), thiazole dyes (49000-49399), indamine dyes (49400-49699), indophenol dyes (49700-49999), azine dyes ( 50000-50999), oxazine dyes (51000-51999), thiazine dyes (52000-52999), sulfur dyes (53000-53999), lactone dyes (54000-54999), hydroxyketone dyes (55000-55999) , aminoketone dyes (56000-56999), anthraquinone dyes (58000-72999), indigoid dyes (73000-73999), phthalocyanine dyes (74000-74999), natural dyes (75000-75999) and oxidation dyes ( 76000-76999) (color index (CI) numbers are shown in parentheses). Among the above organic dyes, anthraquinone-based dyes and triarylmethane-based dyes are preferred, and anthraquinone-based dyes are preferred from the viewpoint of susceptibility to discoloration in a plasma treatment atmosphere.

The anthraquinone-based dye is not limited as long as it has an anthraquinone as a basic skeleton, and anthraquinone-based disperse dyes can also be used. In particular, it is preferable to use an anthraquinone dye having an amino group. More preferred are anthraquinone dyes having at least one amino group selected from a primary amino group and a secondary amino group. In this case, the anthraquinone dye may contain two or more of each of the above amino groups, and these amino groups may be the same or different.

Specific anthraquinone dyes include 1,4-diaminoanthraquinone (C.I. Disperse Violet 1), 1-amino-4-hydroxy-2-methylaminoanthraquinone (C.I. Disperse Red 4), and 1-amino-4-methylaminoanthraquinone. (C.I.Disperse Violet 4), 1,4-diamino-2-methoxyanthraquinone (C.I.Disperse Red 11), 1-amino-2-methylanthraquinone (C.I.Disperse Orange 11), 1-amino-4-hydroxyanthraquinone (C.I.Disperse Red 15), 1,4,5,8-tetraaminoanthraquinone (C.I. Disperse Blue 1), 1,4-diamino-5-nitroanthraquinone (C.I. Disperse Violet 8) 1,4-bis(2-ethylhexylamino)anthraquinone (C.I.Solvent Blue 58), etc. (color index names in parentheses).

In addition, C.I.Solvent Blue 14, C.I.Solvent Blue 35, C.I.SOLVENT BLUE 63, C.I.SOLVENT VIOLET 13, C.I.SOLVENT VIOLET 14, C.I.SOLVENT RED 52, C.I.SOL Vent Red 114, C.I.Vat Blue 21, C.I.Vat Blue 30, C.I.vat Violet 15, C.I.Vat Violet 17, C.I.Vat Red 19, C.I.Vat Red 28, C.I.Acid Blue 23, C.I.Acid Blue 80, C.I.Acid Violet 43, C.I.Acid Violet 48, C.I.Acid Red 81, C.I.Acid Red 83, C.I.Reactive Blue Anthraquinone dyes known as C.I. Reactive Blue 19, C.I. Disperse Blue 7, C.I. Solvent Blue 90, C.I. Solvent Green 3, C.I. Solvent Blue 36, C.I. Acid Blue 40, etc. can also be used. Among these anthraquinone dyes, C.I Disperse Blue 7, C.I Disperse Violet 1, C.I. Solvent Blue 58 and the like are preferable.

The triarylmethane-based dye is not particularly limited as long as it has a triarylmethane structure. For example, CI Acid Blue 90, CI Acid Green 16, CI Acid Violet 49, CI Basic Red 9, CI Basic Blue 7, CI Acid Violet 1, CI Direct Blue 41, CI Mordnt Blue 1, CI Mordnt Violet 1, etc. .

The organic dyes contained in the ink composition can be used alone or in combination of two or more. By changing the types of dyes and the combination of mixtures, the color (type and density) in the discolored state can be changed. And the detection sensitivity can be arbitrarily adjusted.

The content of the organic dye can be appropriately determined according to the type of organic dye, the desired hue, and the like. Generally, the content of the organic dye in the ink composition is desirably about 0.05 to 20% by weight, particularly about 0.1 to 10% by weight. By setting the content of the organic dye to about 20% by weight or less, the solubility or dispersibility in a solvent during preparation of the ink composition does not decrease, and a uniform coating film of the ink composition is formed during the formation of the discoloration layer. There is an advantage that it is difficult to form. There is also an advantage that the color of the discoloration layer (color before discoloration) does not become too dark when an indicator having the ink composition as the discoloration layer is produced. On the other hand, when the content of the organic dye is about 0.05% by weight or more, the color of the color change layer (the color before color change) becomes lighter when an indicator having the ink composition as the color change layer is produced. In particular, there is an advantage that the hue change of the discoloration layer is increased and the gradation is not deteriorated. Also, when the content of the organic dye in the ink composition is excessive or insufficient, it may be difficult to visually confirm the color change before and after the discoloration.

The ink composition may contain a dye or a pigment together with the organic dye. For example, it is possible to contain a dye that does not discolor or hardly discolors in a plasma treatment atmosphere. Examples of such non-discoloring or non-discoloring dyes include organic pigments and titanium oxide. By incorporating such a dye or pigment, it is possible to enhance the change in color tone when the organic dye is discolored, thereby further enhancing the effect of visually recognizing the discoloration. In addition, the above-described dyes that are difficult to discolor in the plasma treatment atmosphere may contain those that undergo a slight discoloration under the physical etching action in the plasma treatment atmosphere.

Thiol compound The thiol compound contained in the ink composition is not particularly limited as long as the effects of the present invention are exhibited. Examples include thiol compounds having 1 to 4 thiol groups.

The specific thiol compound described above is not particularly limited as long as the effects of the present invention are exhibited. Examples include monofunctional thiol compounds, bifunctional thiol compounds, trifunctional thiol compounds, and tetrafunctional thiol compounds. Among these thiol compounds, bifunctional thiol compounds, trifunctional thiol compounds, and tetrafunctional thiol compounds can each include a compound having a primary thiol or a compound having a secondary thiol.

The specific monofunctional thiol compound described above is not particularly limited as long as the effects of the present invention are exhibited. For example, 1-pentanethiol, 1-hexanethiol, 1-heptanethiol, 1-octanethiol, 1-decanethiol, 1-dodecanethiol, 1-hexadecanethiol, 1-octadecanethiol, cyclohexanethiol, eicosanethiol, doco Santhiol, tetracosanethiol, hexacosanethiol, octacosanethiol, t-dodecylmercaptan, methylthioglycolate, β-mercaptopropionic acid, methyl-3-mercaptopropionate, ethylthioglycolate, butylthioglycolate, butyl -3-mercaptopropionate, isooctylthioglycolate, isooctyl-3-mercaptopropionate, isodecylthioglycolate, isodecyl-3-mercaptopropionate, dodecylthioglycolate, dodecyl-3-mercaptopropionate thioglycolate, octadecyl thioglycolate, octadecyl-3-mercaptopropionate, thioglycolic acid, and the like.

The specific bifunctional primary thiol compound described above is not particularly limited as long as the effects of the present invention are exhibited. Examples include 2,2'-(ethylenedioxy)diethanethiol, ethylene glycol bis-mercaptoacetate and the like.

The specific trifunctional primary thiol compound described above is not particularly limited as long as the effects of the present invention are exhibited. Examples include trimethylolpropane tris(3-mercaptopropionate).

The specific tetrafunctional primary thiol compound described above is not particularly limited as long as the effects of the present invention are exhibited. Examples include pentaerythritol tetrakis(3-mercaptopropionate).

The specific bifunctional secondary thiol compound described above is not particularly limited as long as the effects of the present invention are exhibited. 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), 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), butanediolbis(3-mercaptovalerate), octanediolbis(3-mercaptovalerate), and the like.

The specific trifunctional secondary thiol compound described above is not particularly limited as long as the effects of the present invention are exhibited. For example, trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (2-mercaptopropionate), trimethylolpropane tris (4-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate) , 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and the like.

The specific tetrafunctional secondary thiol compound described above is not particularly limited as long as the effects of the present invention are exhibited. For example, pentaerythritol tetrakis (3-mercapto-2-propionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), pentaerythritol tetrakis (4-mercaptovalerate), penta Erythritol tetrakis, 2,2'-(ethylenedioxy)diethanethiol, ethylene glycol bis-mercaptoacetate, pentaerythritol tetrakis(3-mercaptopropionate) and the like can be mentioned.

Among these thiol compounds, 1-octanethiol, β-mercaptopropionic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritol tetrakis (3- mercaptobutyrate) is preferred, pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), and β-mercaptopropionic acid are more preferred, pentaerythritol tetrakis(3-mercaptobutyrate) ), and trimethylolpropane tris(3-mercaptopropionate) are more preferred, and trimethylolpropane tris(3-mercaptopropionate) is most preferred.

The trimethylolpropane tris(3-mercaptopropionate) is a compound containing three thiol groups called TMMP, and pentaerythritol tetrakis(3-mercaptopropionate) is a compound containing four thiols called PEMP. Pentaerythritol tetrakis(3-mercaptobutyrate) is a compound containing four thiol groups called Karenz MT® PE1.

The content of the thiol compound contained in the ink composition can be appropriately determined according to the type thereof and the type of organic dye used. Generally, the content of the thiol compound in the ink composition can be about 0.005 to 30% by weight. It is preferably about 0.01 to 20% by weight, more preferably about 0.03 to 15% by weight. If the content of the thiol compound exceeds about 30% by weight, the offensive odor peculiar to the thiol compound is generated. Depending on the mode of use of the ink composition for plasma treatment detection, generation of offensive odor may not be desirable. Further, by setting the content of the thiol compound to about 0.005% by weight or more, a sufficient improvement in discoloration performance exhibited by the ink composition after plasma treatment can be expected.

Silica and Hydrophobic Alumina Silica and hydrophobic alumina can be used either or both.
Although silica is not particularly limited, for example, hydrophobic silica is preferable. The silica may be silica that has been surface treated to impart hydrophobicity. Although the average particle size of silica is not particularly limited, it is preferably about 5 to 100 nm, more preferably about 5 to 50 nm.

The content of silica can be appropriately determined according to its type and the type of organic dye used, etc., but in consideration of the storage stability and discoloration promoting effect in the ink composition, it is generally 1 to 1 About 30% by weight, preferably about 2 to 20% by weight. By setting the content of silica to about 1% by weight or more, a sufficient improvement in discoloration performance exhibited by the ink composition after plasma treatment can be expected. Also, by setting the content of silica to about 30% by weight or less, a sufficient improvement in discoloration performance can be similarly expected.

The hydrophobic alumina is not particularly limited as long as it is surface-treated with a compound having a hydrophobic group. Untreated alumina and hydrophilic alumina can be used as extenders as described later, but they are clearly distinguished from hydrophobic alumina by the presence or absence of surface treatment and the difference in the type of surface treatment. Although the average particle size of the hydrophobic alumina is not particularly limited, it is preferably about 5 to 100 nm, more preferably about 5 to 50 nm.

The content of hydrophobic alumina can be appropriately determined depending on the degree of hydrophobicity and the type of organic dye used. About 0.5 to 50% by weight, preferably about 1 to 30% by weight. By setting the content of the hydrophobic alumina to about 0.5% by weight or more, it can be expected that the discoloration performance of the ink composition after the plasma treatment will be sufficiently improved. Also, by setting the content of the hydrophobic alumina to about 50% by weight or less, a sufficient improvement in discoloration performance can be similarly expected.

The ink composition for plasma treatment detection of the present invention can contain a binder resin in order to impart strength when it is used as a coating film.

Such a binder resin may be appropriately selected according to the type of base material of the plasma treatment detection indicator described later. can be adopted. 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, polyvinylpyrrolidone resin, poly Acrylamide resins, polyvinylimidazole resins, polyethyleneimine resins, amino resins and the like can be mentioned.

In the present invention, a cellulose-based resin can be particularly preferably used as the binder resin. By using a cellulose-based resin, even if the ink composition contains an extender or the like in addition to at least one of silica and hydrophobic alumina, excellent fixability can be obtained, and the ink composition can be applied onto the substrate. It is possible to effectively prevent falling off, peeling, etc. from the substrate after forming the coating film. In addition, by effectively creating a plurality of cracks on the coating film surface of the ink composition, there is an effect of creating an environment that is easy to be exposed to plasma, so that the discoloration performance of the ink composition after plasma treatment is sufficiently improved. It is thought that

In the present invention, a polyvinyl butyral resin can be preferably used as the binder resin. By using a polyvinyl butyral resin, an improvement in discoloration properties is recognized as compared with the case of using other binder resins (especially cellulose resins) or the case of not using a binder resin.

In the present invention, a nitrogen-containing polymer can also be used as part or all of the binder resin in addition to the resins listed above. Such nitrogen-containing polymers serve as sensitivity enhancers in addition to serving as binders. That is, by using the sensitivity enhancer, the precision (sensitivity) of plasma processing detection can be further enhanced.

Synthetic resins such as polyamide resins, polyimide resins, polyacrylonitrile resins, amino resins, polyacrylamides, polyvinylpyrrolidone, polyvinylimidazole, and polyethyleneimine can be suitably used as nitrogen-containing polymers. These can be used alone or in combination of two or more. In the present invention, it is particularly preferred to use a polyamide resin. The type, molecular weight, etc. of the polyamide resin are not particularly limited, and known or commercially available polyamide resins can be used. Among these, a polyamide resin which is a reaction product (long-chain linear polymer) of a dimer of linoleic acid and a diamine or polyamine can be preferably used. A polyamide resin is a thermoplastic resin having a molecular weight of about 4,000 to 7,000. Commercially available products can also be used for such resins.

In the present invention, by using a phenolic resin other than the resins listed above as part or all of the binder resin, the heat resistance of the ink composition and the discoloration layer made of the ink composition can be improved.

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

The content of the binder resin can be appropriately determined according to the type of the binder resin, the type of the organic dye used, etc., but is generally about 50% by weight or less, particularly about 5 to 35% by weight, in the ink composition. is desirable. When a nitrogen-containing polymer is used as the binder resin, the content of the nitrogen-containing polymer in the ink composition is desirably about 0.1 to 50% by weight, particularly about 1 to 20% by weight. The content of the binder resin affects the discoloration performance of the discoloration layer. When the binder resin content is large, the discoloration speed tends to be slow, and when the binder resin content is low, the discoloration speed tends to increase. Therefore, an ink composition that does not contain a binder resin can be used to adjust the discoloration speed to be fast. Here, when the binder resin is not contained or the amount of the binder resin is small, the fixability of the ink composition tends to deteriorate.

Other additives The ink composition may contain solvents, extenders, nonionic surfactants, cationic surfactants, leveling agents, antifoaming agents, UV absorbers, surface conditioners, organic cross-linking agents, oxidizing agents, if necessary. Components used in known inks such as inhibitors, antiozonants, antistatic agents, lubricants, tackifiers, and flame retardants can be blended as appropriate.

The solvent is not particularly limited as long as it is usually used in ink compositions for printing, writing, etc., and can exhibit the effects of the present invention. For example, various solvents such as alcohols, polyhydric alcohols, esters, ethers, ketones, hydrocarbons, and glycol ethers can be used. It can be selected as appropriate. The above solvents can be used alone or in combination of two or more.

The content of the solvent can be appropriately determined according to the type of the solvent and organic dye used, etc., but in general, it can be about 40 to 95% by weight in the ink composition, and about 60 to 90% by weight. preferably.

The bulking agent is not particularly limited as long as the effects of the present invention can be exhibited. Examples thereof include inorganic materials such as bentonite, activated clay, untreated alumina, hydrophilic alumina and silica gel. In addition, materials known as known extender pigments can be used. Among these, silica gel and hydrophilic alumina are preferred. The above bulking agents can be used singly or in combination of two or more. By using such an extender, the extender has the effect of making the surface of the coating film (discoloration layer) itself of the ink composition of the present invention porous, thereby creating an environment where plasma is likely to hit. By containing at least one of silica and hydrophobic alumina, in addition to the effects exhibited by the ink composition of the present invention, it is possible to add a discoloration promoting effect based on the addition of an extender.

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

Nonionic Surfactant The nonionic surfactant contained as another additive in the ink composition of the present invention is not particularly limited. agents can be mentioned.

In the above formula (I), R ₁ and R ₂ are each independently hydrogen, a linear or branched aliphatic hydrocarbon having 1 to 30 carbon atoms, preferably 1 to 22 carbon atoms, more preferably 10 to 18 carbon atoms. indicates a group. X represents an oxygen atom or an ester bond, preferably an oxygen atom.

In the above formula (I), AO represents a repeating unit (monomer) derived from alkylene oxide. Such repeating units are not particularly limited, and examples thereof include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, and styrene oxide. The polymerization form of AO is not particularly limited, and examples thereof include homopolymers, block copolymers and random copolymers composed of two or more kinds of AOs.

In the above formula (I), n represents an integer of 1-200, preferably 1-100. The nonionic surfactant represented by formula (I) above is an alkylene glycol derivative.

In the above formula (II), R ₁ , R ₂ and R ₃ are each independently hydrogen, a linear or branched fatty acid having 1 to 30 carbon atoms, preferably 1 to 22 carbon atoms, more preferably 10 to 18 carbon atoms. indicates a group hydrocarbon group.

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

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

In addition, a polymer in which at least one of R ₁ and R ₂ in the above formula (I) or (II) is substituted with a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms is used as a preferred nonionic interface It can be mentioned as an active agent.

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 (“Emulgen 404” etc. as a commercial product), POE stearyl ether (“Emulgen 306” etc. as a commercial product), POE alkyl ether (“Emulgen LS-110” as a commercial product) (above, Kao Co., Ltd.), POE tridecyl ether (commercially available “Fineserve TD-150” etc.), polyethylene glycol monostearate (commercially available “Blaunon S-400A” etc.) (manufactured by Aoki Oil Industry Co., Ltd.) , polyethylene glycol monooleate ("Nonion O-4" etc. as a commercial product), tetramethylene glycol derivatives ("Polycene DC-1100" etc. as a commercial product), polybutylene glycol derivatives ("Uniol PB-500" as a commercial product) etc.), alkylene glycol derivatives (commercially available products such as “Unilube 50MB-5”) (manufactured by NOF Corporation), etc.), POE (20) octyldodecyl ether (commercially available products such as “Emarex OD-20”) .

In formulas (III) and (IV) above, R ₁ , R ₂ and R ₃ are each independently hydrogen, a linear chain having 1 to 30 carbon atoms, preferably 1 to 22 carbon atoms, more preferably 10 to 18 carbon atoms, or Indicates a branched aliphatic hydrocarbon group.

In formulas (III) and (IV) above, AO represents a repeating unit (monomer) derived from alkylene oxide. Such repeating units are not particularly limited, and examples thereof include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, and styrene oxide. The polymerization form of AO is not particularly limited, and examples thereof include homopolymers, block copolymers and random copolymers composed of two or more kinds of AOs.

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

Specific examples of nonionic surfactants represented by the above formula (III) include compounds in which _R1 is an isostearic acid residue, _R2 and _R3 are hydrogen, and AO (monomer) is ethylene oxide. More specifically, POE glyceryl isostearate ("Uniox GM-30IS" etc. as a commercial product; manufactured by NOF Corporation) can be mentioned.

Examples of specific nonionic surfactants represented by formula (IV) include compounds in which R ₁ to R ₃ are isostearic acid residues and AO (monomer) is ethylene oxide. Examples include POE glyceryl triisostearate ("Uniox GT-30IS" etc. as a commercial product; manufactured by NOF Corporation).

In the above formula (V), R ₁ , R ₂ , R ₃ or R ₄ are each independently hydrogen, straight chain having 1 to 30 carbon atoms, preferably 1 to 22 carbon atoms, more preferably 10 to 18 carbon atoms, or Indicates a branched aliphatic hydrocarbon group.

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

As a specific nonionic surfactant represented by the above formula (V), R ₁ and R ₄ are hydrogen atoms, R ₂ and R ₃ are C(CH ₃ )(iC ₄ H ₉ ) , X is an oxygen atom and p+q=0. More specifically, 2,4,7,9-tetramethyl-5-decyne-4,7-diol (commercially available products such as "Surfinol 104H"; manufactured by Air Products Japan Co., Ltd.) can be mentioned. .

Among the nonionic surfactants represented by the above formulas (I) to (V), the nonionic surfactants represented by the above (I) or (IV) are preferable, and the nonionic surfactants represented by the above (I) agents are more preferred.

The nonionic surfactant contained in the ink composition of the present invention may be used singly or in combination of two or more. The content of such a nonionic surfactant is not particularly limited as long as it does not impair the effects exhibited by the ink composition of the present invention. For example, with respect to the ink composition of the present invention, the content of the nonionic surfactant can be about 0.001 to 20% by weight, preferably about 0.01 to 15% by weight. A content of about 10% by weight is most preferable. When the amount of the thiol compound described above is large, odor may become a problem. By combining the content of the surfactant in the range of about 0.1 to 10% by weight with respect to the ink composition, it is possible to improve discoloration performance while suppressing the odor problem of the thiol compound.

By including a nonionic surfactant in the ink composition of the present invention, the dispersibility of the dye to be discolored in the coating film obtained by applying the ink composition to the indicator increases, and the ink composition after plasma treatment exhibits. Discoloration performance can be further improved. Moreover, when a nonionic surfactant is contained, the effect of improving the vividness of the color of the discolored layer (color after discoloration) is also obtained.

Cationic Surfactant The cationic surfactant is not limited, but preferably at least one selected from the group consisting of alkylammonium salts, isoquinolinium salts, imidazolinium salts and pyridinium salts. Known or commercially available products can also be used as these.

Among the above alkylammonium salts, alkyltrimethylammonium salts, dialkyldimethylammonium salts and the like are preferable, and alkyltrimethylammonium salts are particularly preferable from the viewpoint of controlling discoloration in a plasma treatment atmosphere. Specifically, coconut alkyltrimethylammonium chloride, tallow alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, lauryltrimethylammonium chloride, octadecyltrimethylammonium chloride, dioctyldimethylammonium chloride, distearyldimethylammonium chloride, chloride Alkylbenzyldimethylammonium and the like can be mentioned. Cocoalkyltrimethylammonium chloride, lauryltrimethylammonium chloride and the like are particularly preferred.

Examples of the isoquinolinium salt include laurylisoquinolinium bromide, cetylisoquinolinium bromide, cetylisoquinolinium chloride, and laurylisoquinolinium chloride. Among these, laurylisoquinolinium bromide is particularly preferred.

Examples of the 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.

Examples of the pyridinium salts include pyridinium chloride, 1-ethylpyridinium bromide, hexadecylpyridinium chloride, cetylpyridinium chloride, 1-butylpyridinium chloride, Nn-butylpyridinium chloride, hexadecylpyridinium bromide, and N-hexadecylpyridinium bromide. , 1-dodecylpyridinium chloride, 3-methylhexylpyridinium chloride, 4-methylhexylpyridinium chloride, 3-methyloctylpyridinium chloride, 2-chloro-1-methylpyridinium iodide, 3,4-dimethylbutylpyridinium chloride, pyridinium- n-hexadecyl chloride-hydrate, N-(cyanomethyl)pyridinium chloride, N-acetonylpyridinium bromide, 1-(aminoformylmethyl)pyridinium chloride, 2-amidinopyridinium chloride, 2-aminopyridinium chloride, N-amino pyridinium iodide, 1-aminopyridinium iodide, 1-acetonylpyridinium chloride, N-acetonylpyridinium bromide and the like. Among these, hexadecylpyridinium chloride is particularly preferred.

The content of the cationic surfactant can be appropriately determined according to its type and the type of organic dye used, etc. Generally, the cationic surfactant content is about 0.2 to 20% by weight in the ink composition. content, particularly the content of the cationic surfactant of about 0.5 to 10% by weight.

Each component of the ink composition of the present invention may be blended simultaneously or sequentially and uniformly mixed using a known stirrer such as a homogenizer or a dissolver. For example, first, 1) the organic dye, 2) a thiol compound, and 3) at least one of silica and hydrophobic alumina, and optionally a binder resin and additives (excluding an extender) are mixed in order with a solvent. Finally, if necessary, an extender may be blended and mixed and stirred with a stirrer.

2. Plasma Treatment Sensitive Indicator The indicator of the present invention comprises a color change layer comprising the ink composition of the present invention. Specifically, the ink composition of the present invention is applied or printed on a substrate and then dried to form a discoloration layer, which can be used as the indicator of the present invention. The substrate is not particularly limited as long as it can form a discolored layer. The content of each component in the discoloration layer is described below. Since the discoloration layer has undergone a drying process, the solvent is not substantially contained, but depending on the drying conditions, etc., a small amount or inevitably remains. is allowed.

The organic dye contained in the indicator of the present invention can be the same as the ink composition for plasma treatment detection described above. The content of such an organic dye is not particularly limited as long as the effects of the present invention are achieved. For example, the content of the organic dye in the discoloration layer can be usually about 0.1 to 35% by weight. Preferably, the content of the organic dye can be about 0.2 to 20% by weight. By setting the content of the organic dye to about 35% by weight or less, there is an advantage that the color of the discolored layer (the color before discolored) does not become too dark when the discolored layer is formed. By setting the content of the organic dye to about 0.1% by weight or more, when the discoloration layer is formed, the color of the discoloration layer (color before discoloration) does not become too light, and in particular, the discoloration layer does not change. There is an advantage that it becomes large and the gradation does not deteriorate. In addition, when the content of the organic dye in the discoloration layer is excessive or insufficient, it may be difficult to visually confirm the color change before and after the discoloration.

The pigment contained in the indicator of the present invention can be the same as the ink composition for plasma treatment detection described above. The content of such pigments is not particularly limited as long as the effects of the present invention are achieved. For example, the content of the pigment in the discoloration layer can be usually about 0.01 to 10% by weight. Preferably, the pigment content can be about 0.02 to 5% by weight. By setting the content of the pigment to 0.01% by weight or more, when the discoloration layer is formed, the color of the discoloration layer (color before discoloration) does not become too light, and in particular, the hue change of the discoloration layer is large. There are advantages. In addition, by setting the content of the pigment to 10% by weight or less, the color of the discoloration layer (color before discoloration) does not become too dark when the discoloration layer is formed, and the hue change before and after discoloration is visually observed. This has the advantage of making it easier to check.

The thiol compound contained in the indicator of the present invention can be the same as the ink composition for plasma treatment detection. The content of such a thiol compound is not particularly limited as long as the effects of the present invention are achieved. For example, the content of the thiol compound in the discoloration layer can be usually 0.03 to 60% by weight. Preferably, the thiol compound content can be from 0.06 to 55% by weight. If the content of the thiol compound is about 60% by weight or more, the offensive odor peculiar to the thiol compound is generated, which is not preferable. If the content of the thiol compound is about 0.03% by weight or less, a sufficient improvement in discoloration performance exhibited by the discoloration layer after plasma treatment cannot be expected.

The silica contained in the indicator of the present invention can be the same as the ink composition for plasma treatment detection described above. The content of such silica is not particularly limited as long as the effects of the present invention are achieved. For example, the content of silica in the discoloration layer can be normally about 3 to 85% by weight. Preferably, the content of silica can be about 5 to 70% by weight. By setting the content of silica to 3% by weight or more, a sufficient improvement in discoloration performance exhibited by the discoloration layer after plasma treatment can be expected. Also, by setting the content of silica to 85% by weight or less, a sufficient improvement in discoloration performance can be similarly expected.

The binder resin contained in the indicator of the present invention can be the same as the ink composition for plasma treatment detection. The content of such a binder resin is not particularly limited as long as the effects of the present invention are achieved. For example, the content of the binder resin in the discoloration layer can be usually about 0.3 to 80% by weight. Preferably, the content of the binder resin can be about 3 to 60% by weight. By setting the content of the binder resin to about 0.3% by weight or more, there is an advantage that the fixability is improved. Also, by setting the content of the binder resin to about 80% by weight or less, there is an advantage that the discoloration speed is increased.

The nonionic surfactant contained in the indicator of the present invention can be the same as the ink composition for plasma treatment detection. The content of such a nonionic surfactant is not particularly limited as long as the effects of the present invention are achieved. For example, it can be usually about 0.003 to 60% by weight in the discoloration layer. Preferably, it can be about 3 to 50% by weight. By setting the content of the nonionic surfactant to 0.003% by weight or more, there is a merit of sufficiently improving the discoloration performance exhibited by the discoloration layer after the plasma treatment. Further, by setting the content of the nonionic surfactant to 60% by weight or less, there is an advantage that the fixability is improved.

Specific substrates include, for example, metals or alloys, ceramics, glass, concrete, plastics (polyethylene terephthalate (PET), polypropylene, nylon, polystyrene, polysulfone, polycarbonate, polyimide, etc.), fibers (non-woven fabrics, woven fabrics, paper, other fiber sheets), composite materials thereof, and the like. Synthetic resin fiber paper (synthetic paper) such as polypropylene synthetic paper and polyethylene synthetic paper can also be suitably used as the substrate. Among these base materials, when the ink composition of the present invention does not contain a resin binder or when the content of the resin binder is small, fibers that can be impregnated with the ink composition from the viewpoint of fixability of the ink composition. Permeable substrates such as are preferred.

Examples of the mode of color change of the color change layer in the present invention include a mode in which the color changes from colored to colorless, and a mode in which a certain color changes to another color.

The discoloration layer can be formed using the ink composition of the present invention according to known printing methods such as silk screen printing, gravure printing, offset printing, letterpress printing, and flexographic printing. Moreover, it can be formed by a method other than printing. For example, a color change layer can be formed on the substrate by immersing the substrate in the ink composition.

The discoloration layer desirably has a plurality of cracks on its surface. That is, it is desirable that open pores are formed on the surface of the discoloration layer to make it porous. By providing cracks in this manner, the sensitivity of plasma processing detection can be further enhanced. Cracks can be effectively formed particularly by using a cellulose resin together as the binder resin of the ink composition of the present invention. That is, by using a cellulose resin, it is possible to form cracks as described above while maintaining good fixability.

In the present invention, for example, a non-discoloring layer (undercoat layer) can be formed between the substrate and the discoloration layer in order to further enhance the visual effect when the discoloration layer is discolored. Such a non-discoloring layer can usually be formed with a commercially available normal color ink. For example, water-based ink, oil-based ink, non-solvent ink, etc. can be used. The ink used for forming the non-discoloring layer may contain components blended in known inks, such as resin binders, extenders and solvents. Also, the composition of the non-discoloring layer may contain a component that does not have the discoloring component contained in the indicator. For example, thiol compounds, binder resins, silica, hydrophobic alumina, pigments, extenders, cationic surfactants, nonionic surfactants, leveling agents, antifoaming agents, ultraviolet absorbers, surface conditioners, organic cross-linking agents, oxidation The composition may contain at least one of an inhibitor, an antiozonant, an antistatic agent, a lubricant, a tackifier, a flame retardant, and the like.

The non-discoloring layer may be formed in the same manner as the discoloring layer. For example, using plain color ink, it can be carried out by a known printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, flexographic printing, and the like.

The indicator of the present invention can be applied without particular limitation as long as it is a plasma treatment using a plasma generating gas. That is, it can be applied to both low pressure plasma processing and atmospheric pressure plasma processing. The indicator of the present invention is superior in that the completion of plasma processing can be detected with high sensitivity even in atmospheric pressure plasma, which is said to have a relatively low plasma intensity among these plasma processing.

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

Further, as specific examples of atmospheric pressure plasma treatment, 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; Examples include surface modification applications for aircraft parts and the like, and applications such as disinfection, sterilization, and treatment in the medical field (dental or surgical).

The low-pressure plasma generating gas is not particularly limited as long as it is a gas that can generate plasma by applying AC voltage, pulse voltage, high frequency, microwave, or the like under reduced pressure. For example, oxygen, nitrogen, hydrogen, chlorine, hydrogen peroxide, helium, argon, silane, ammonia, sulfur bromide, water vapor, nitrous oxide, tetraethoxylan, carbon tetrafluoride, trifluoromethane, carbon tetrachloride, tetrachloride Gases such as silicon, sulfur hexafluoride, titanium tetrachloride, dichlorosilane, trimethylgallium, trimethylindium, and trimethylaluminum can be mentioned. These gases for low-pressure plasma generation can be used alone or in combination of two or more.

The gas for generating atmospheric pressure plasma is not particularly limited as long as it is a gas capable of generating plasma by applying AC voltage, pulse voltage, high frequency, microwave or the like under atmospheric pressure. Examples include gases such as oxygen, nitrogen, hydrogen, argon, helium, and air. These atmospheric pressure plasma generating gases can be used alone or in combination of two or more.

When using the indicator of the present invention, specifically, a plasma processing apparatus using a plasma generating gas (specifically, an alternating voltage, a pulse voltage, a high frequency, a microwave in an atmosphere containing a plasma generating gas The indicator of the present invention may be placed in the interior of a plasma processing apparatus or an object to be processed contained therein and exposed to the plasma processing atmosphere. In this case, it can be detected that the predetermined plasma treatment has been performed by the color change of the indicator placed in the apparatus. That is, the present invention includes a plasma processing method having a step of placing a plasma processing detection indicator and an object to be processed in a plasma processing atmosphere.

The indicator of the present invention can be used as an indicator card as it is. At this time, if the shape of the discoloration layer is the shape of a known barcode, and the condition is set so that it can be read by a barcode reader at the stage when a predetermined plasma treatment is completed (degree of discoloration), the plasma treatment is completed. Subsequent physical distribution management of plasma-treated products can be centrally managed by barcodes. The present invention also includes inventions such as indicators, plasma processing control methods, and physical distribution control methods used for such applications.

The contents of the publications and web pages cited herein are hereby incorporated by reference. In addition, various characteristics such as properties, structures, and functions described for each of the embodiments of the present invention described above can be combined as appropriate to specify aspects included in the present invention. That is, the present invention can encompass all inventions of aspects of each characteristic disclosed herein that can be combined.

Examples and comparative examples are shown below to further clarify the features of the present invention. In addition, it cannot be overemphasized that this invention is not restricted to the aspect of an Example.

Examples 1 to 6 and Comparative Example 1
Each ink composition was prepared by mixing each component according to the composition shown in Table 1. A blank part in Table 1 means that the corresponding component is not contained.

Each of these ink compositions was silk-screen printed onto a base material (printing paper made by Sakurai, trade name “Staclean SC175RC”) and forcedly dried in a constant temperature bath (75° C.) for 15 minutes to obtain each indicator. .

Examples 7-12
Each ink composition was prepared by mixing each component according to the composition shown in Table 1. A blank part in Table 1 means that the corresponding component is not contained.

5.31% by weight of MOWITAL PVB B-30H (polyvinyl butyral resin manufactured by Kuraray), 12.75% of Aerosil R972 (silica manufactured by Nippon Aerosil), After applying an undercoat liquid (non-discoloring layer) composed of 81.94% by weight of butyl cellosolve (solvent), each of the ink compositions shown in Examples 7 to 12 was silk-screen printed and printed in a constant temperature bath (75 ° C.). Each indicator was formed by force drying for 15 minutes.

A color change test was performed on each indicator.

Each test method and evaluation criteria are as follows.
≪Discoloration Test: Atmospheric Pressure Plasma Treatment≫
First, the chromaticity L*a*b* of the color change layer (before plasma treatment) of each indicator was measured with a colorimeter FD-5 manufactured by Konica Minolta.

Next, each indicator was installed in an atmospheric pressure plasma processing apparatus "AP2000 (manufactured by Denshi Giken)".

Chromaticity before plasma treatment is L* ₁ , a* ₁ , b* ₁ , chromaticity after plasma treatment is L* ₂ , a* ₂ , b* ₂ . It is expressed as ΔE*ab. Table 1 shows the color difference of the discolored layer in each indicator.

Color difference △E*ab=[(L* ₂ -L* ₁ ) ² + (a* ₂ -a* ₁ ) ² + (b* ₂ -b* ₁ ) ² ] ^1/2 (plasma treatment conditions)
・Gas: nitrogen gas flow rate 70SLM, dry air flow rate 5SLM,
・High frequency power supply output: 15.0 kV,
・Irradiation distance: 3 mm,
・Processing times: 1 time,
・Processing speed: 600mm/min,

(Consideration)
Various thiol compounds (1-octanethiol, β-mercaptopropionic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), The plasma treatment detection indicators of Examples 1 to 5 containing pentaerythritol tetrakis (3-mercaptobutyrate)) are higher than the plasma treatment detection indicators of Comparative Examples containing photopolymerization initiators instead of various thiol compounds. It can be seen that the color difference (ΔE*ab value) is large and the detection sensitivity is high.

In addition, as shown in the plasma treatment detection indicators of Examples 7 to 12, it was also found that the content of the thiol compound exhibited a high color difference in the range of 0.03 to 20.00% by weight. When the color difference between the plasma processing detection indicator of Example 3 without the undercoat layer and the plasma processing detection indicator of Example 10 with the undercoat layer is compared, the plasma processing detection indicator of Example 10 Since the color difference is higher, it can be seen that the provision of the undercoat layer improves the visibility and makes it easier to accurately confirm the degree of discoloration.

Examples 13-30
Furthermore, ink compositions were prepared by mixing each component according to the compositions shown in Tables 2 and 3 below in the same manner as in the above Examples and Comparative Examples. , and these were subjected to a discoloration test to calculate the ΔE*ab value. The results are also shown in Tables 2 and 3. Blanks in Tables 2 and 3 mean that the corresponding component is not contained.

Sources of the components (nonionic surfactants) listed in Tables 2 and 3 are as follows.
(Nonionic surfactant represented by the above formula (I))
・Nonion S-207 …NOF Corporation ・Nonion S-202 …NOF Corporation ・Nonion S-215 …NOF Corporation ・Nonion K-204 …NOF Corporation ・Nonion ID-206 …NOF Corporation・ Nonionic E-205 ... NOF Corporation ・ Emulgen 408 ... Kao Corporation (nonionic surfactant represented by the above formula (II))
・ Unilube 75DE-2620R ... NOF Corporation (nonionic surfactant represented by the above formula (IV))
・ Uniox GT-20IS ... NOF Corporation (nonionic surfactant represented by the above formula (V))
・ Surfynol 104H … Air Products Japan Co., Ltd.

(Consideration)
From the results shown in Table 2, various nonionic surfactants (Nonion S-207, Nonion S-202, Nonion S-215, Nonion K-204, Nonion ID-206, Nonion E-205, Emulgen 408: nonionic surfactant represented by the above formula (I); Unilube 75DE-2620R: nonionic surfactant represented by the above formula (II); Uniox GT-20IS: nonionic surfactant represented by the above formula (IV) agent; Surfynol 104H: a nonionic surfactant represented by the above formula (V)) was found to further increase the ΔE*ab value.

From the results shown in Table 3, even if the content of the thiol compound (the odor may become a problem when used in large amounts) is reduced, the odor of the thiol compound is reduced by including the nonionic surfactant in the ink composition. It was found that the △E*ab value could be increased while suppressing the problem of .

Moreover, even if the degree of increase in the ΔE*ab value was the same, it was found that the degree of discoloration in the examples containing the nonionic surfactant was more clearly visible.

Claims (9)

An ink composition for plasma processing detection, comprising: 1) an organic dye, 2) a thiol compound, and 3) at least one of silica and hydrophobic alumina. The organic dyes include nitroso dyes, nitro dyes, monoazo dyes, diazo dyes, triazo dyes, polyazo dyes, azoic dyes (diazo component), azoic dyes (coupling component), stilbene dyes, Carotenoid dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine dyes, thiazole dyes, indamine dyes, indophenol dyes, azine dyes, oxazine dyes At least selected from the group consisting of dyes, thiazine dyes, sulfur dyes, lactone dyes, hydroxyketone dyes, aminoketone dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, natural dyes and oxidation dyes 2. The ink composition of claim 1, which is one. The thiol compound includes a monofunctional thiol compound, a bifunctional primary thiol compound, a trifunctional primary thiol compound, a tetrafunctional primary thiol compound, a bifunctional secondary thiol compound, a trifunctional secondary thiol compound, and a tetrafunctional secondary The ink composition according to claim 1 or 2, which is at least one selected from the group consisting of thiol compounds. 3. The ink composition according to claim 1, further comprising a nonionic surfactant. 3. The ink composition according to claim 1, further comprising a binder resin. A plasma treatment detection indicator comprising a discoloration layer comprising the ink composition according to claim 1 or 2. 7. The plasma treatment sensing indicator of claim 6, further comprising a non-color changing layer. 7. The plasma processing detection indicator according to claim 6, for use in plasma processing detection in atmospheric pressure plasma. 7. A plasma processing method comprising the step of placing the plasma processing detection indicator according to claim 6 and an object to be processed in a plasma processing atmosphere.