TW202121559A - Layered body and indicator - Google Patents

Abstract

To provide a layered body and an indicator, wherein the sensitivity of a detection layer can be adjusted readily, the detection of the progression and end of processing is ensured, the detection that processing is being performed uniformly over the entirety of an object to be processed is straightforward, and the contamination by a contaminant arising concomitantly to these processings may be avoided. The layered body includes a base material layer and a detection layer that changes in color tone by detecting at least one selected from the group consisting of plasma, ozone, UV ray, and a radical-containing gas. The detection layer is provided with a structure body having an interior space communicating with an open hole section on the surface thereof. Contained inside the interior space is a detection agent containing at least one species of detection component that changes in color tone by detecting at least one selected from the group consisting of plasma, ozone, UV ray, and radical-containing gas. In the layered body, the content of each metal atom is less than 5.0 ppm by mass, or, the detection component contains a dye compound containing no atoms other than carbon, hydrogen, oxygen, and nitrogen.

Description

Multilayer body and indicator

The present invention relates to a laminated body and an indicator.

As a processing method for various articles, a method using at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas (hereinafter, sometimes referred to as "plasma, etc.") is widely known. For example, plasma is generated in a gas atmosphere for plasma generation, and various articles or substrates are irradiated with the plasma to perform plasma treatment. Plasma processing is also used to manufacture electronic components (semiconductor chips, light-emitting diodes (Light Emitting Diode, LED), solar cells, liquid crystal displays, organic electro-luminescence (EL) displays, semiconductor lasers , Power components, etc.). For example, in the manufacture of semiconductor wafers, film formation (chemical vapor deposition (CVD) or sputtering, etc.) and resist pattern formation ( Plasma dry etching, ion beam etching, etc.), film etching using a resist pattern, resist pattern removal, cleaning, and other steps are processed by plasma or the like.

When manufacturing electronic components, treatment with plasma or the like must be uniformly performed. For example, regarding the treatment by plasma or the like in the previous step of semiconductor wafer manufacturing, it is important that it is uniformly performed in the wafer surface and has in-plane uniformity. When the in-plane uniformity is impaired, the performance of each semiconductor wafer formed on the semiconductor wafer varies, which affects the yield. Therefore, confirmation of the uniformity of processing by plasma or the like is indispensable for the design of each electronic component manufacturing device and the management of the manufacturing steps using the device.

The confirmation of the uniformity of the processing can be performed using a method of measuring the film characteristics, processing accuracy, etc. of the manufactured electronic component, or a method of separately performing each of the processings and evaluating the uniformity in the plane, or the like. For example, as a method for evaluating the uniformity of the plasma itself, a method of measuring the physical constants of the plasma by a Langmuir probe installed in a manufacturing device, and a method for measuring the physical constant of the plasma by a spectroscopic device are known. The method of luminescence analysis and evaluation of spatial distribution. However, the method of using the Langmuir probe sometimes requires operations such as air release of the manufacturing device or probe disassembly during manufacturing operations, which requires a lot of labor and time. The method of using a spectrometer may not be able to measure the entire plasma in the device because the measurement range is limited. In addition, the method of using a Langmuir probe or a spectrometer does not directly indicate the in-plane distribution of each process, but is accompanied by an analysis operation based on the measurement result.

Patent Document 1 and Patent Document 2 describe indicators that detect the presence or absence of ozone or the like. Patent Document 3 describes that an ink containing a pigment, a specific surfactant, and a nonionic surfactant is applied to a substrate, and it is placed as an indicator in a reaction chamber or the like to detect the end point of the plasma treatment. . Patent Document 4 describes the use of an indicator for detecting plasma or the like that has the same shape as the substrate used in the electronic component manufacturing apparatus to confirm the uniformity of the plasma or the like processing. The indicator includes a color-changing layer formed of ink that changes color or decolors by reacting with plasma or the like. Patent Document 5 describes the use of a plasma indicator containing a pigment in the pores formed by anodizing treatment to prevent contamination by an ink composition or the like.

The indicators described in Patent Document 3 to Patent Document 5 can visually confirm the progress of plasma processing and the like in the reaction chamber, but sensitivity and the like must be adjusted appropriately. In addition, depending on processing conditions and the like, a part of the constituent components of the indicator placed in the chamber may be vaporized, which may cause contamination to the processed object such as plasma processing or the chamber. For example, most inks contain substances containing metal atoms or halogen atoms, and it is also assumed that contamination (contamination) of components containing metal atoms caused by a dispersion medium or the like occurs during preparation. In particular, the presence of metal atoms is undesirable in the previous step of the manufacturing step of a semiconductor device, and an indicator that avoids contamination is sought. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4382816 [Patent Document 2] Japanese Patent Publication No. 2013-537978 [Patent Document 3] Japanese Patent Laid-Open No. 2015-013982 [Patent Document 4] International Publication No. 2015/025699 [Patent Document 5] International Publication No. 2018/128123

[The problem to be solved by the invention]

The object of the present invention is to provide a laminate and an indicator that can easily adjust and detect at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and free radical-containing gases with a color tone The sensitivity of the detection layer is changed, and the progress or the end point of the treatment by at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas can be reliably detected. The object of the present invention is to provide a laminate and an indicator that can easily detect whether the entire object to be processed is uniformly performed by selecting from plasma, ozone, ultraviolet rays, and free radical-containing gases. At least one of the treatments in the group constituted, and can avoid the pollution of the treated object or the chamber caused by the pollutants generated with the treatment. [Means to solve the problem]

The inventors of the present invention conducted studies to solve the above-mentioned problems, and as a result, found that the above-mentioned problems can be solved by forming a laminate of a specific structure and using it as an indicator. Specifically, it is as follows. 1: A laminate having: a detection layer that detects at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and free radical-containing gases and changes in color tone; and a substrate layer, and The detection layer includes a structure having an internal space communicating with an opening portion of the surface, A detection agent is included in the internal space, the detection agent includes at least one detection component, and the detection component detection is selected from at least one of the group consisting of plasma, ozone, ultraviolet rays, and free radical-containing gases. The hue changes, The content of each metal atom in the laminate is less than 5.0 mass ppm. 2: A laminated body having: a detection layer that detects at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas and the color tone is changed; and a substrate layer, and The detection layer includes a structure having an internal space communicating with an opening portion of the surface, A detection agent is included in the internal space, the detection agent includes at least one detection component, and the detection component detection is selected from at least one of the group consisting of plasma, ozone, ultraviolet rays, and free radical-containing gases. The hue changes, The detection agent includes a dye compound that does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen. 3: The layered product described in Item 1, wherein the detection component includes a dye compound that does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen. 4: The laminate according to any one of items 1 to 3, wherein the structure comprises a polyimide resin, a polyimide resin, and a polyimide resin , A structure of at least one resin from the group consisting of polyolefin resin, polyurethane resin, melamine resin, polyester resin, and polycarbonate resin. 5: The laminate according to any one of items 1 to 4, wherein the detection agent includes a resin and/or a resin precursor, and the resin and/or a resin precursor does not contain carbon, hydrogen, or oxygen And atoms other than nitrogen atoms. 6: The laminate according to any one of items 1 to 5, wherein the content of each halogen atom in the laminate is less than 30 mass ppm. 7: An indicator comprising the laminate according to any one of items 1 to 6. [Effects of the invention]

According to the present invention, there is provided a laminated body and an indicator which can easily adjust and detect at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas, and the color tone is generated. The sensitivity of the detection layer is changed, and the progress or the end point of the treatment by at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas can be reliably detected. According to the present invention, there is provided a laminated body and an indicator which can easily detect whether the treatment is uniformly performed on the entire object by being selected from plasma, ozone, ultraviolet rays, and free radical-containing gases. At least one of the treatments in the group, and can avoid the pollution of the treated object or the chamber caused by the pollutants generated with these treatments.

[Layered body] The laminate of the present invention has a detection layer whose color tone changes due to detection of plasma, etc., and a substrate layer. The detection layer includes a structure having an internal space communicating with an opening on the surface, and the internal space contains The detection agent includes at least one detection component that changes the color tone by detecting plasma or the like.

＜Detection layer＞ The change in the color tone of the detection layer occurs when the detection component comes into contact with plasma or the like to cause any one or more of color changes, decolorization, or color development. Here, as described above, plasma or the like is at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas. The detection layer of the present invention does not simply detect plasma or the like, but can easily detect the in-plane uniformity during processing by the plasma or the like by visual observation. In the present invention, the detection agent can be uniformly present in the plane in the detection layer, so it is considered that the detection of in-plane uniformity can be performed. The thickness of the detection layer is not particularly limited as long as it exhibits a detection function, and can be appropriately optimized according to the application, required characteristics, and the like. In order to reliably grasp the change in color tone, it may be 10 μm or more, preferably 15 μm to 100 μm.

(Plasma) Plasma refers to plasma generated by using plasma generating gas and applying AC voltage, DC voltage, pulse voltage, high frequency, microwave, etc., and both pressure-reduced plasma and atmospheric piezoelectric plasma are compatible. The gas for plasma generation is not particularly limited as long as plasma is generated by applying AC voltage, DC voltage, pulse voltage, high frequency, microwave, etc. For example, it can be selected from oxygen, nitrogen, hydrogen, fluorine, chlorine, helium, neon, argon, silane, ammonia, sulfur bromide, water vapor, nitrous oxide, tetraethoxysilane, carbon tetrafluoride, three Group consisting of fluoromethane, carbon tetrachloride, silicon tetrachloride, sulfur hexafluoride, titanium tetrachloride, dichlorosilane, trimethylgallium, trimethylindium, trimethylaluminum, air, and carbon dioxide At least one of them.

As the plasma, for example, the following plasma processing equipment (by means of the film forming step, etching step, ashing step, impurity adding step, cleaning step, etc.) used in the manufacture of electronic components can be cited Plasma generated in an apparatus that generates plasma by applying AC voltage, DC voltage, pulse voltage, high frequency, microwave, etc., to perform plasma treatment under an atmosphere contained as a gas for plasma generation.

(ozone) Examples of ozone include ozone generated by oxygen irradiated with ultraviolet rays, ozone generated by discharging oxygen-containing gas such as dry air or oxygen, ozone generated by electrolysis of dilute sulfuric acid, and the like. For example, it may be ozone generated in an ozone treatment device used in a film formation step, an ashing step, a cleaning step, etc., or ozone generated when photochemical smog (smog) is generated when manufacturing electronic components.

(Ultraviolet) Ultraviolet rays refer to electromagnetic waves with a wavelength of about 1 nm to 400 nm, including near ultraviolet rays, far ultraviolet rays or vacuum ultraviolet rays, and extreme ultraviolet rays or extreme ultraviolet rays. Examples include: ultraviolet rays generated from ultraviolet irradiation devices containing mercury lamps or LEDs; or ultraviolet rays generated in ultraviolet treatment devices used in photolithography steps, ashing steps, and cleaning steps when manufacturing electronic components Ultraviolet rays, etc.

(Gas containing radicals) Gas containing radicals is generated by applying energy to the gas. For example, it can be generated by using electron beam impact to pass hydrogen through a thin tube made of Ta heated to 2100 K. In an environment where such a radical-containing gas is used, it is preferable to control the flow rate of hydrogen and maintain the degree of vacuum at about 1.0×10 ^-4 Torr to 1.0×10 ^-6 Torr. For example, a radical-containing gas generated in a radical-containing gas treatment device used in a film forming step, an etching step, an ashing step, a cleaning step, etc., when manufacturing an electronic component, etc. can be cited.

(Structure) The structure constituting the detection layer of the present invention includes at least one selected from the group consisting of an organic material, an inorganic material, and an organic-inorganic composite material, and has an internal space communicating with the opening on the surface. The color tone should just be able to grasp the change of the color tone of the detection component, and it is preferably transparent, colored transparent, white, light color, or the like. As the structure, for example, a porous body having an internal space communicating with the open pores on the surface can be used; one or more of holes, recesses, protrusions, and cracks are provided by a well-known appropriate means to form an opening corresponding to the surface. The structure of the part of the internal space that the pores communicate with; the composition of a porous substance, etc., is arranged on the surface. Among them, it is preferable to use a porous body having an internal space communicating with the open pores on the surface. The organic material, the inorganic material, and the organic-inorganic composite material constituting the structure contain at least one compound. If necessary, ingredients such as extenders may also be included. In addition, when the content of each metal atom in the layered body is less than 5.0 mass ppm, it is preferable to use a structure that does not contain metal atoms as the structure. In the present invention, the structure has a function of covering the color of the wafer, which can increase the color change. In addition, by using the structure, the detection agent can undergo a time-dependent hue change corresponding to the permeability of the plasma or the like, or a hue change proportional to the amount or intensity of exposure to the plasma or the like.

The porous body having an internal space communicating with the open pores on the surface may be any one of an inorganic porous body, an organic porous body, and an organic-inorganic composite porous body, for example. Examples of inorganic porous bodies include metal porous bodies; silica-based porous bodies (silica gel, aerosol, silica gel, etc.); alumina-based porous bodies (activated alumina, etc.); zeolite Porous bodies (aluminosilicate zeolite, metalosilicate zeolite, phosphoaluminate zeolite, etc.); silicate porous bodies (kaolinite, montmorillonite, mica, etc.); mesopores Porous bodies (mesoporous silica, etc.); glass porous bodies; ceramic porous bodies; pumice; porous bodies such as metal oxides or metal hydroxides (alumite, hydroxyapatite, etc.) At least one of the group consisting of hydrotalcite, layered zirconium phosphate, heteropoly acid salt, porous manganese oxide, etc.), but is not particularly limited.

Examples of organic porous bodies include resin porous bodies (porous membranes, porous polymer beads, etc.), non-woven fabrics, knitted fabrics, fabrics, paper, wood, leather, activated carbon, fullerenes, At least one of the group consisting of carbon nanotubes, etc., but is not particularly limited.

As the resin constituting the resin porous body, for example, a known or commercially available resin can be used, for example, at least one selected from the group consisting of the following resins, namely, polyamide resin, polyamide imide resin Resin, polyimide-based resin, amino-based resin (melamine-based resin-benzoguanamine-based resin, urea-based resin, etc.), acrylic resin ((meth)acrylic resin, poly(meth)acrylonitrile) Resins, poly(meth)acrylamide resins, etc.), polyvinylpyrrolidone resins, polyvinylimidazole resins, polyolefin resins (polyethylene resins, polypropylene resins, etc.), fluorine-based resins Resin, chlorinated vinyl resin, vinyl acetate resin, polyvinyl acetal resin (polyvinyl butyral resin, etc.), polyvinyl alcohol resin, polystyrene resin (polystyrene resin, Styrene-maleic acid resin, styrene-acrylic resin, etc.), polyester resin (polyester resin, unsaturated polyester resin, alkyd resin, etc.), phenol resin (phenol resin, Alkylphenol resins, terpene phenol resins, rosin-modified phenol resins, etc.), polyether resins, epoxy resins, maleic acid resins, polyketone resins, polyethyleneimine resins, poly Urethane resins, polysiloxane resins, acetal resins, block polymerization system resins, graft polymerization system resins, cellulose resins, rosin resins (rosin resins, rosin ester resins, etc.) ), rubber-based resins (natural rubber, diene-based rubber, styrene-butadiene (SB) rubber, etc.), but are not particularly limited.

Among these resins, polyimide-based resins, polyimide-based resins, polyamide-based resins, polyolefin-based resins, polyurethane-based resins, melamine-based resins, Polyester resin and polycarbonate resin. in particular, As the structure, if polyimide-based resin, polyimide-based resin, or heat-resistant polymer such as polyimide-based resin is used, a laminated body with excellent heat resistance is formed, so it can be constructed to be able to work under high temperature conditions. It is an indicator that is used under the environment and is resistant to strong plasma processing.

As the organic-inorganic composite porous body, for example, a porous body selected from a resin composition containing an inorganic component, an organometallic structure (metal-organic framework (MOF)), etc. can be cited At least one type, but not particularly limited. As the organic component constituting the organic-inorganic composite porous body, the organic component constituting the organic porous body can be used; as the inorganic component constituting the organic-inorganic composite porous body, the inorganic component constituting the organic porous body can be used. Ingredients or well-known inorganic fillers.

In the structure, as a structure having a portion corresponding to the internal space by providing one or more of holes, recesses, protrusions, and cracks by using a known appropriate means, it is possible to use: by using a needle or a laser, etc. A structure in which holes or recesses are provided by perforation; a structure in which holes or recesses are provided by chemical treatment; a structure in which recesses are provided by embossing or grinding; and a structure in which protrusions are provided by blowing a protruding part-forming substance Structure; a structure with cracks prepared by using a resin composition or paint containing a crack-forming agent such as an inorganic filler that forms fine cracks on the surface; a porous resin is blended with a binder such as resin Structures such as fillers, etc.

In the present invention, when the content of each metal atom in the layered body is less than 5.0 mass ppm, it is preferable to use an organic porous body, particularly a resin porous body, as the structure constituting the detection layer. In addition, in order to prevent contamination in the electronic device manufacturing device caused by metal atoms, it is preferable to use an organic porous body, particularly a resin porous body, as a structure constituting the detection layer.

As a resin porous body, the resin porous body prepared by a well-known method can be used, for example, the following methods (1)-(4) are mentioned. (1) Porosity by chemical means such as the use of pore forming agents (for example, porosity by foaming agent, porosity of gas generated during polymerization or modification or molding, forming (film formation) After) Porosity by removing the porosity forming agent (removal of components or sublimation, etc.), porosity by phase separation (use of mixed solvents with different solubility, etc.), etc.) (2) By extending the porosity (3) Porosity by welding of powder and granular material (4) Porosity by mechanical means such as perforation

In the present invention, the porous resin body obtained by the method (1) described above is preferable. In particular, a porous coating film obtained by coating a resin solution containing two or more solvents having different solubility or boiling point is preferable as the resin porous body. For example, by using a resin solution containing polyimide resins or polyimide imide resins, good solvents for these resins, and poor solvents for these resins, polyimide resins can be obtained Porous body or polyamide resin porous body. As a good solvent for polyimide-based resins or polyimide-based resins, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N,N-dimethylformamide, tetramethylurea, dimethylethylene urea, 1,3-dimethyl-2-imidazolidinone, etc. At least one solvent in the group. As a poor solvent for polyimide-based resins or polyimide-based resins, solvents with a solubility of less than 1% by mass can be used. For example, solvents selected from ether-based solvents (tetraethylene glycol dimethyl ether, Triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc.); hydrocarbon solvents (n-hexane, cyclohexane, etc.) , Benzene, toluene, xylene, petroleum ether, etc.); ester solvents (ethyl carbitol acetate, butyl carbitol acetate, dimethyl succinate, diethyl succinate, glutaric acid Dimethyl, diethyl glutarate, dimethyl adipate, diethyl adipate, etc.); alcohol solvents (triethylene glycol, diethylene glycol, ethylene glycol, methanol, ethanol, etc.) At least one solvent in the group consisting of. Preferable examples include: polyamidoimide resin obtained from a resin solution containing polyamidoimide resin, N-methyl-2-pyrrolidone, and tetraethylene glycol dimethyl ether Resin porous body; a polyimide resin porous body obtained from a resin solution containing polyimide resin, N,N-dimethylacetamide, and tetraethylene glycol dimethyl ether.

(Detection agent) The detection agent in the present invention contains at least one detection component that changes the color tone by detecting plasma or the like. In addition, the detection agent may contain various components as needed for the purpose of adjusting sensitivity or improving the visibility of color difference before and after detection, within a range that does not impair the effect of the color change caused by the detection component. Such components include, for example, pigments that do not function as the detection components (colorants that do not change color when exposed to the detection target), resins and/or resin precursors, reaction accelerators, reaction delay agents, and fillers , Surfactant and other additives.

In the present invention, in order that the content of each metal atom in the laminate is less than 5.0 mass ppm, it is preferable that the detection agent containing the detection component does not contain metal atoms. With this, when the laminate is used as an indicator for detecting plasma or the like in the manufacturing apparatus of electronic components, it is possible to effectively prevent contamination by metal atoms in the manufacturing apparatus of electronic components. In the present invention, it is preferable to use a detection agent containing a dye compound that does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen. With this, when the laminate is used as an indicator for detecting plasma or the like, it is possible to effectively prevent contamination in the manufacturing equipment of electronic components, particularly contamination caused by metal atoms or halogen atoms. It is preferable that the detection agent is sufficiently purified of its constituent components, or a metal instrument is not used during preparation, so that impurities such as metal atoms or halogen atoms are not mixed in.

-Detection component- As a compound used as a detection component in the present invention that changes the color tone of the detection plasma or the like, it is not particularly limited as long as it exhibits a behavior that changes the color tone when exposed to the plasma or the like. Examples of such compounds include pigments known as colorants, preferably dyes or pigments, and those whose hue is changed by detecting plasma or the like.

Examples of the pigment include known or commercially available pigments. For example, at least one selected from the group consisting of the following pigments, namely, anthraquinone pigments; benzoquinone pigments; perylene pigments; methine pigments; azo pigments (monoazo pigments, double Azo pigments, trisazo pigments, polyazo pigments, azoic pigments (bisazo components, coupling components, etc.); phthalocyanine pigments; diarylmethane series Pigments; Triarylmethane-based pigments; Xanthene-based pigments; Oxazine-based pigments; Food pigments; Pericone-based pigments; Diketopyrrolopyrrole-based pigments; Quinacridone-based pigments; Anthraquinone-based pigments; Violet Cyclic ketone pigments; isoindolinone pigments; isoindoline pigments; indanthrene pigments; coumarin pigments; quinacridone pigments; pyranthrene pigments ; Flavanthrone pigments; nitroso pigments; nitro pigments; stilbene pigments; carotenoid pigments; acridine pigments; quinoline pigments; thiazole pigments; naphthoquinones Pigments; indamine pigments; indophenol pigments; azine pigments; thiazide pigments; sulfur pigments; lactone pigments; hydroxyketone pigments; aminoketone pigments; indigo (Indigoid) pigments; thioindigo pigments; cationic pigments; cyanine pigments; squarylium pigments; croconium pigments; merocyanine pigments; fluoran ( fluoran)-based pigments; spiropyran-based pigments; fulgide-based pigments; azulene-based pigments; natural-based pigments; oxidation-based pigments; metal complex-based pigments, etc., but are not limited to these.

As the pigment for detecting plasma and the like among the pigments, it is preferable to use pigments selected from the group consisting of anthraquinone-based pigments, perylene-based pigments, methine-based pigments, azo-based pigments, phthalocyanine-based pigments, and triarylmethane-based pigments. At least one of the group consisting of xanthene-based pigments, indanthrene-based pigments, and food colorings. As the pigment for detecting ozone among the pigments, it is preferable to use the group selected from the group consisting of oxazine-based pigments, azo-based pigments, methine-based pigments, indanthrene-based pigments, and anthraquinone-based pigments. At least one of them.

As the pigment for detecting ultraviolet rays among the pigments, it is preferable to use selected from the group consisting of azo-based pigments, anthraquinone-based pigments, triarylmethane-based pigments, phthalocyanine-based pigments, indigo-based pigments, and diarylmethane. At least one of the group consisting of a triarylamine-based dye, a triarylamine-based dye, and an cyanine-based dye. It is further preferred to use the following compound together with the dye for detecting the ultraviolet light: the compound is a compound that imparts a change to the color development mechanism of the dye by ultraviolet irradiation, and is converted into the compound itself by ultraviolet irradiation A compound that imparts a change to the color development mechanism of a pigment and/or a compound that generates a radical that imparts a change to the color development mechanism by ultraviolet irradiation. As the compound that imparts a change to the color development mechanism of the pigment by ultraviolet irradiation, at least one selected from the group consisting of the following compounds, namely, acetophenone type compound and benzophenone type compound can be cited , Michelone type compound, benzil type compound, benzoin type compound, benzoin ether type compound, benzyl dimethyl ketal type compound, benzoin benzoate type compound, α-hydrated oxime Alpha compounds (alpha compounds aquo oxime ester), tetramethylthiuram monosulfide type compounds, thioxanthone type compounds, and phosphine oxide type compounds, but are not limited to these. In particular, it is preferable to use a compound that generates radicals that impart a change to the color development mechanism by ultraviolet irradiation, and is preferably selected from a wavelength of about 150 nm to 450 nm (more preferably 200 nm to 400 nm). ) At least one of the compounds with great absorption. The compounding amount of the compound that imparts a change to the color development mechanism of the pigment by ultraviolet irradiation can be determined according to the type of the pigment used and the like. It is sufficient as long as a sufficient discoloration effect that can be recognized by visual observation is obtained and the solubility in a solvent or the like does not cause problems. For example, it may be an amount that is usually 0.1 mol to 20 mol relative to 1 mol of the dye. Around the ear, preferably 0.5 mol to 15 mol.

As a compound that imparts changes to the color development mechanism of the pigment by ultraviolet irradiation, when using a benzophenone type compound, a Michelone type compound, a benzophenone type compound, a thioxanthone type compound, etc. Next, it is preferable to use an amine-based reaction accelerator (amine-based radical accelerator) such as ethanolamine in combination. In this case, the compounding amount of the amine-based reaction accelerator can be appropriately determined according to the compound, pigment, and the like. As a combination of a pigment and a compound that imparts a change to the color development mechanism of the pigment by ultraviolet irradiation, for example, (1) an anthraquinone-based pigment and a benzoin ether-type compound, a benzyl dimethyl ketal-type compound, or an acyl group Combination of phosphine oxide type compound, (2) combination of bisazo pigment and benzoin ether type compound or oxyphosphine oxide type compound, (3) combination of phthalocyanine type pigment and benzoin ether type compound or phosphonium oxide type compound Combinations, (4) a combination of a cyanine-based dye and a benzophenone-type compound, (5) a combination of an azo-based dye and a benzophenone-type compound or an phosphine oxide-type compound, etc.

As a dye for detecting a radical-containing gas among the dyes, it is preferable to use at least one selected from the group consisting of anthraquinone dyes, azo dyes, and triarylmethane dyes.

In the present invention, the pigments are preferably selected from the group consisting of anthraquinone pigments; perylene pigments; methine pigments; azo pigments (monoazo pigments, bisazo pigments, trisazo pigments) Pigments, polyazo pigments, azoic pigments (bisazo components), azoic pigments (coupled components), etc.); phthalocyanine pigments; triarylmethane pigments; xanthenes Pigment; oxazine-based pigment; indanthrene-based pigment; at least one of the group consisting of food coloring and percyclic ketone-based pigment. Particularly preferably, it is at least one selected from the group consisting of anthraquinone-based pigments, percyclic ketone-based pigments, methine-based pigments, indanthrene-based pigments, and azo-based pigments.

As specific examples of these pigments, for example, at least one of the following pigments can be cited, that is, dye index (Color Index, CI) acid black (Acid Black) 123; CI acid blue (Acid Blue) 1, 3 , 5, 7, 9, 11, 15, 17, 19, 22, 23, 24, 38, 48, 75, 80, 83, 86, 88, 90, 91, 93, 93:1, 100, 103, 104 , 108, 109, 110, 119, 123, 147, 213, 269; CI Acid Green 16; CI Acid Red 52, 81, 83; CI Acid Violet 1, 3, 7, 10, 12, 14, 15, 16, 17, 19, 20, 21, 23, 25, 30, 38, 39, 43, 48, 49, 72; CI Acid Yellow (Acid Yellow) 11, 12, 13 , 14, 21, 22, 23, 24, 74; CI Azoic Coupling Component 2, 3, 4, 5, 7, 11, 14, 16, 17, 18, 19, 20, 29, 36 ; CI Azoic Diazo Component 1, 5, 8, 12, 13, 20, 24, 34, 41, 48, 109; CI Azoic Brown 11; CI Basic Blue (Basic Blue) 1, 5, 7, 8, 26, 62, 63, 140; CI Basic Green (Basic Green) 1, 4; CI Basic Red (Basic Red) 1, 9, 12, 13, 14, 15, 27, 35, 36, 37, 45, 48; CI Developer (Developer) 8, 18, 20, 21, 22; CI Direct Blue (Direct Blue) 41, 86, 87; CI Disperse Black (Disperse Black) 1, 2, 29; CI Disperse Blue 1, 3, 5, 6, 7, 26, 27, 44; CI Disperse Orange 1, 3, 5, 11, 13; CI Disperse Red ) 1, 4, 9, 11, 13, 15, 17, 52, 58, 88, 167:1; CI Disperse Violet 1, 4, 8; CI Disperse Yellow 1, 3, 4 , 5, 7, 8, 23, 31, 60, 61; CI medium blue (Mordant Blue) 1; CI medium red (mordant red) 11 , 15, 27; CI Mordant Violet 1, 25; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 16; CI Pigment Green 7, 36; CI Reactive Blue 4, 19; CI Solvent Black 3; CI Solvent Brown 3, 5; CI Solvent Blue 11, 14, 35, 63, 70; CI solvent Green (Solvent Green) 3, 5, 15; CI Solvent Orange (Solvent Orange) 1, 2, 14, 55, 60, 78, 90; CI Solvent Red (Solvent Red) 1, 3, 18, 23, 24, 25 , 27, 49, 52, 114, 135, 162, 179; CI Solvent Violet 8, 13, 14, 29; CI Solvent Yellow 2, 6, 14, 16, 21, 29, 33 , 56; CI Vat Black (Vat Black) 8, 9, 25, 27, 29; CI Vat Brown (Vat Brown) 1, 3, 25, 44; CI Vat Blue (Vat Blue) 1, 4, 12, 20, 21, 30; CI Vat Green 1, 3, 8, 9; CI Vat Orange 7, 9, 13, 15; CI Vat Red 10, 13, 15, 19, 28 , 29; CI Vat Violet 13, 15, 17; CI Vat Yellow 4, 10, 20; Lumogen F IR 788; Lumogen F Orange (Orange) 240; Lumogen F powder (Pink) 285; Lumogen F red (Red) 300, 305, 339; Lumogen F purple (Violet) 570; Lumogen ) F Yellow (Yellow) 083, 170; Iketon Violet extra (Iketon Violet extra); Oil Peacock Blue (Oil Peacock Blue); Oil Brown BG extra (Oil Brown BG extra); Edible Red No. 1; Edible Red No. 3 Edible red 102; edible red 104; edible red 105; edible red 106; edible yellow 4; edible yellow 5; edible green 3; edible blue 1; edible blue 2 and so on.

For example, it is preferable to use at least one selected from the group consisting of the following pigments: Acid Black 123; CI Azoic Brown 11; CI Azoic Coupling Component 2 , 3, 4, 5, 7, 11, 14, 16, 17, 18, 19, 20, 29, 36; CI Azoic Diazo Component 1, 5, 8, 12, 13, 20, 24, 34, 41, 48, 109; CI Basic Green (Basic Green) 4; CI Developer (Developer) 8, 18, 20, 21, 22; CI Disperse Black (Disperse Black) 1, 2, 29; CI Disperse Blue 1, 3, 5, 6, 7, 26, 27; CI Disperse Orange 1, 3, 11, 13; CI Disperse Red 1, 4, 9, 11, 15, 17; CI Disperse Violet 1, 4, 8; CI Disperse Yellow 1, 3, 4, 5, 7, 8, 23, 31, 60, 61; CI media red (mordant red ) 11, 15, 27; CI Solvent Black 3; CI Solvent Blue 11, 35; CI Solvent Brown 3, 5; CI Solvent Green 3; CI Solvent Orange (Solvent Orange) 1, 2, 14; CI solvent red (Solvent Red) 1, 3, 18, 23, 24, 25, 27, 49, 52; CI solvent violet (Solvent Violet) 13, 14; CI solvent yellow ( Solvent Yellow 2, 6, 14, 16, 21, 29, 33, 56; CI Vat Black 8, 9, 25, 27, 29; CI Vat Blue 1, 4, 12, 20 ; CI Vat Brown 1, 3, 25, 44; CI Vat Green 1, 3, 8, 9; CI Vat Orange 7, 9, 13, 15; CI Vat Red ( Vat Red 10, 13, 15; CI Vat Violet 13; CI Vat Yellow 4, 10, 20; Lumogen F IR 788; Lumogen ogen) F orange (Orange) 240; Luma near (Lumogen) F powder (Pink) 285; Luma near (Lumogen) F red (Red) 300, 305, 339; Luma near (Lumogen) F purple (Violet) 570; Lumogen F Yellow (Yellow) 083, 170; Iketon Violet extra (Iketon Violet extra); Oil Peacock Blue (Oil Peacock Blue); Oil Brown BG extra (Oil Brown BG extra), etc.

More preferably, at least one selected from the group consisting of the following pigments, namely, CI Azoic Coupling Component 3, 16; CI Basic Green 4; CI Mordant Red 27 ; CI solvent black (Solvent Black) 3; CI solvent blue (Solvent Blue) 35; CI solvent red (Solvent Red) 18, 24, 27, 49, 52; CI solvent violet (Solvent Violet) 14; CI solvent yellow (Solvent Yellow 29; CI Vat Black 8, 9, 25, 27, 29; CI Vat Brown 1, 3, 25, 44; CI Vat Green 8; CI Vat Black Orange 13, 15; CI Vat Red 10, 13, 15; CI Vat Yellow 10, 20; Lumogen F IR 788; Lumogen F Orange ) 240; Luma near (Lumogen) F powder (Pink) 285; Luma near (Lumogen) F red (Red) 300, 305, 339; Luma near (Lumogen) F purple (Violet) 570; Luma near ( Lumogen F Yellow (Yellow) 083, 170; Iketon Violet extra (Iketon Violet extra); Oil Peacock Blue (Oil Peacock Blue); Oil Brown BG extra (Oil Brown BG extra).

In the present invention, by changing the types of these pigments (molecular structure, etc.), mixing multiple pigments, etc., the detection sensitivity or the color development and hue changes of the detection layer can be controlled. The content of these pigments may be appropriately determined according to the type of pigment, the desired discoloration (detection sensitivity), the product form, the characteristics of the structure, and the like. For example, the detection layer may contain 0.01% by mass to 20% by mass, preferably 0.1% by mass to 10% by mass of dye. In addition, for example, the detection agent may contain 0.01% by mass to 100% by mass, preferably 0.1% by mass to 100% by mass of dye.

-Dye that does not function as the detection component- In the present invention, a dye that does not function as the detection component may be included in the detection agent. By including such a pigment that does not function as the detection component, the visual recognition effect can be further improved by changing the hue of a certain color to another. As such a pigment that does not function as the detection component, at least one selected from the group consisting of pigments that do not cause a change in color tone when exposed to a detection target, but is not particularly limited. For example, at least one selected from the group consisting of pigments can be used, that is, pigments that do not cause a change in hue even when plasma is detected, and those that do not cause a change in hue even when plasma is detected. Pigments that change the hue due to the detection target. When the detection agent contains a pigment that does not function as the detection component, the content of the pigment that does not function as the detection component can be appropriately determined according to the type, the visibility of the detection layer, the desired hue, etc., generally In particular, it is preferable to set it to about 0% by mass to 99.99% by mass in the detection agent, particularly 0% by mass to 99.9% by mass.

-Resin and/or resin precursor- In the present invention, a resin and/or resin precursor that can function as a binder may be included in the detection agent. As the resin, any one of natural resin and synthetic resin may be used, and may be a commercially available resin. In addition, any one can be used with regard to the molecular weight or molecular weight distribution of the resin. As the resin precursor, any resin precursor can be used as long as it can become a resin by reaction. For example, at least one selected from the group consisting of (meth)acrylate-based compounds, polyamide acid, polyurethane prepolymers, and the like can be cited, but it is not particularly limited. The resin and/or resin precursor are appropriately selected according to the components constituting the detection agent and the like. Since the detection agent contains resin and/or resin precursors, for example, the fixation of the detection agent can be adjusted, the detection component can be prevented from detaching or peeling from the detection agent or the detection layer, and the contact between the detection component and the detection object can be controlled. > Carry out sensitivity adjustment, detection agent protection, etc.

As such resins, known or commercially available resins can be used. For example, at least one selected from the group consisting of polyamide resins, polyimide resins, and polyamide resins can be cited. Amine resins, amino resins (melamine resins, benzoguanamine resins, urea resins, etc.), acrylic resins ((meth)acrylic resins, poly(meth)acrylonitrile resins, etc.) (Meth)acrylamide resins, etc.), polyvinylpyrrolidone resins, polyvinylimidazole resins, polyolefin resins (polyethylene resins, polypropylene resins, etc.), fluorine resins, vinyl chloride resins Resin, vinyl acetate resin, polyvinyl acetal resin (polyvinyl butyral resin, etc.), polyvinyl alcohol resin, polystyrene resin (polystyrene resin, styrene-maleic acid Resins, styrene-acrylic resins, etc.), polyester resins (polyester resins, unsaturated polyester resins, alkyd resins, etc.), phenol resins (phenol resins, alkylphenol resins, etc.) Terpene phenol resin, rosin modified phenol resin, etc.), polyether resin, epoxy resin, maleic acid resin, polyketone resin, polyethyleneimine resin, polyurethane resin Resins, silicone resins, acetal resins, block polymerization system resins, graft polymerization system resins, cellulose resins, rosin resins (rosin resins, rosin ester resins, etc.), rubber resins ( Natural rubber, diene rubber, SB rubber, etc.). When the detection agent contains a resin and/or resin precursor, the content of the resin and/or resin precursor can be appropriately determined according to the type of resin and/or resin precursor, the type of detection component used, and the like. For example, in general, it can be used in a detection agent in an amount of about 50% by mass or less, preferably 5% to 35% by mass.

-Surfactant- In the present invention, a surfactant may be included in the detection agent. The surfactant includes at least one selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants, but is not particularly limited. Among these, it is preferable to use at least one selected from the group consisting of nonionic surfactants and cationic surfactants, particularly when detecting plasma or the like. Thereby, the discoloration of the detection component can be promoted and the detection sensitivity of the detection component can be improved.

Examples of nonionic surfactants include at least one selected from the group consisting of (1) to (4) below: (1) alkanediol derivatives (for example, polyethylene glycol (for example, The trade name "PEG2000" manufactured by Sanyo Chemical Industry Co., Ltd.), polyethylene glycol-polypropylene glycol copolymer (for example, the trade name "EPAN (EPAN) 710" manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., etc.), polyoxyethylene Alkyl ether (for example, the trade name "EMULGEN 109P" manufactured by Kao Corporation, etc.), polyolefin glycol monofatty acid ester, etc.); (2) polyglycerol derivatives; (3) alkanediol Glycerin derivatives (for example, fatty acid polyoxyalkylene glycerol (for example, the trade name "UNIOX GM-30IS" manufactured by NOF Corporation, etc.)), and (4) acetylene glycol derivatives (for example, "SURFYNOL 104H" manufactured by AIR PRODUCTS JAPAN, etc.), but there are no special restrictions. When a nonionic surfactant is included in the detection agent, the content of the nonionic surfactant can be appropriately determined according to the type of nonionic surfactant, the type of detection component used, and the like. For example, considering the preservability in the detection agent and the effect of promoting discoloration, the detection agent can be set to about 0.1% by mass to 10% by mass, preferably 0.5% by mass to 5% by mass.

Examples of cationic surfactants include at least one selected from the group consisting of (1) to (4) below: (1) tetraalkylammonium salt (for example, alkyltrimethylammonium salt ( For example, behenyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, etc.), dialkyl dimethyl ammonium salt, etc.); (2) isoquinolinium salt (for example, lauryl isoquinoline Bromide, etc.); (3) imidazolium salt (for example, 2-chloro-1,3-dimethylimidazolium chloride, etc.); and (4) pyridinium salt (for example, cetylpyridinium chloride) Etc.), but not particularly limited. When the detection agent contains a cationic surfactant, the content of the cationic surfactant can be appropriately determined according to the type of cationic surfactant, the type of detection component used, and the like. For example, in consideration of the preservability and discoloration promotion effect in the detection agent, the detection agent can be set to about 0.1% by mass to 10% by mass, preferably 0.5% by mass to 5% by mass.

-Filling agent- In the present invention, a filler may also be included in the detection agent. As the filler, known or commercially available fillers can be used, for example, those selected from bentonite, clay, activated clay, talc, alumina, silica, silica gel, calcium carbonate, barium sulfate, resin beads, etc. At least one of the groups, but not particularly limited. For example, when the detection agent contains resin, if silicon dioxide or the like is included, many fine cracks are generated on the surface of the detection agent, so the detection sensitivity can be improved. The content of the filler can be appropriately determined according to the type of filler and the type of detection component used, etc., within a range that does not greatly impair the effect of the color change caused by the detection component. For example, in consideration of the preservability and discoloration promotion effect in the detection agent, the detection agent can be set to about 0.1% by mass to 10% by mass, preferably 0.5% by mass to 5% by mass.

-Color change retarder- In the present invention, in order to delay the color tone change of the detection agent, a color tone change retarder may be included in the detection agent. As the color change retarder, for example, a color change retarder having a function of blocking the contact of plasma or the like with the detection component can be used. As the color change retarder, for example, absorbents selected from absorbing plasma and the like (for example, known or commercially available ion absorbents, radical absorbents, ozone absorbents, ultraviolet absorbents, etc.); self-plasma and other shielding agents At least one of the group consisting of the shielding agent (for example, the resin or filler, etc.) of the detection component, but is not particularly limited. The content of the color tone change retarder can be appropriately determined according to the desired retardation effect of the color tone change, the composition of the detection agent, and the like, within a range that does not greatly impair the effect of the color tone change by the detection component. For example, it can be set to about 0% by mass to 10% by mass in the detection agent.

-Color change accelerator- In the present invention, in order to promote the hue change of the detection agent, a known or commercially available hue change promoter may be included in the detection agent. Examples of such hue change promoters include resins selected from resins having a function of enhancing the detection accuracy (sensitivity) of plasmas and the like (for example, nitrogen-containing resins effective for enhancing plasma detections), and the interface At least one of the active agent, the filler, etc., but is not particularly limited. The content of the color tone change retarder can be appropriately determined in a range that does not greatly impair the effect of the color tone change caused by the detection component according to the desired acceleration effect of the color tone change, the composition of the detection agent, and the like. For example, it can be set to about 0% by mass to 10% by mass in the detection agent.

-Solvent- In the present invention, a known or commercially available solvent may also be included in the detection agent. The solvent is used to introduce and hold the detection component in the internal space of the structure having the internal space with the opening on the surface in the detection layer. The solvent is usually removed by means such as drying, but it can also be present in a small amount in the detection reagent. As the solvent, for example, at least one selected from the group consisting of the following solvents, namely water; hydrocarbon solvents (for example, hexane, cyclohexane, toluene, xylene, benzene, tetralin, mineral spirits) Etc.); Alcohol solvents (for example, methanol, ethanol, propanol, butanol, furfuryl alcohol, octanol, stearyl alcohol, oleyl alcohol, benzyl alcohol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene two Alcohol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, glycerin, trimethylolethane, trimethylolpropane, etc.); ether solvents (for example, dimethyl ether, diethyl ether, phenyl ether, Benzyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tetrahydrofuran, dioxane, morpholine, etc. ); Ester solvents (for example, methyl acetate, ethyl acetate, butyl acetate, pentyl acetate, ethyl lactate, glycol diacetate, dimethyl carbonate, vegetable oil, γ-butyrolactone, ε- Caprolactone, etc.); ketone solvents (for example, acetone, methyl ethyl ketone, cyclohexanone, diacetone alcohol, isophorone, acetophenone, etc.); phenolic solvents (for example, phenol, cresol, etc.) ); fatty acid solvents (for example, palmitic acid, isopalmitic acid, oleic acid, isostearic acid, etc.); carbonate solvents (for example, dimethyl carbonate, diethyl carbonate, propylene carbonate, carbonic acid Ethylene ethylene, etc.); amine solvents (triethanolamine, tripropanolamine, tributanolamine, N,N-dimethyl-2-aminoethanol, N,N-diethyl-2-aminoethanol Etc.), amide-based solvents (for example, acetamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.); halogen Substituted hydrocarbon solvents (for example, carbon tetrachloride, chloroform, trichloroethane, fluorine-containing solvents), etc., but are not particularly limited.

The solvent only needs to be capable of dissolving or dispersing the detection component. Preferably, a solvent that can dissolve the detection component is used. Furthermore, the solvent is preferably highly refined to reduce the content of metal atoms or halogen atoms. This reduces the content of metal atoms or the content of halogen atoms in the laminate. When the detection component is introduced and held in the internal space, the amount of solvent used can be appropriately determined according to the type of solvent, the composition of the detection agent, and the like. It is preferably an amount to the extent that the detection component does not precipitate when a solution or dispersion of the detection component is formed. For example, in the case of using a solvent that can dissolve the detection component, the concentration of the detection component is preferably 0.1% by mass to 30% by mass, but it is not particularly limited. In the case where the solvent is included after the detection component is held in the internal space, the content of the solvent is set to a range where the detection agent does not flow easily and does not impair the effect of the color change caused by the detection component. It also depends on the composition of the detection agent. For example, the detection agent may contain about 0% to 1% by mass of a solvent.

-Other additives- In the present invention, other additives other than the above-mentioned components may be included in the detection agent as necessary. In the present invention, as other additives that may be included in the detection agent, at least one selected from the group consisting of a leveling agent, a defoaming agent, and a surface regulator can be cited, but it is not particularly limited. The content of other additives can be appropriately determined according to the composition of the detection agent, etc., within a range that does not impair the effect of the color change caused by the detection component. For example, in the detection agent, it can be set to about 0 mass% to 5 mass%.

＜Substrate layer＞ The base material layer only needs to support the detection layer. In consideration of the required characteristics, use, etc. of the laminate, at least one selected from the group consisting of inorganic materials, organic materials, and composites of these can be cited, but it is not particularly limited. In addition, the thickness of the substrate layer is not particularly limited as long as it can reliably support the detection layer, and it can be 0.01 mm to 10 mm, preferably 0.01 mm to 1 mm. As the inorganic material, for example, at least one selected from the group consisting of metals or alloys, semiconductor materials, ceramics, glass, quartz, sapphire, and concrete can be cited, but is not particularly limited. Examples of organic materials include at least one selected from the group consisting of resin, paper, synthetic paper, wood, fibers (non-woven fabrics, woven fabrics, fabrics, and other fiber sheets), leather, etc., but there is no particular limited. As the composite, for example, a laminate or a composition obtained by using at least one material selected from the group consisting of the inorganic material and the organic material can be cited, but it is not particularly limited. As the substrate layer, among these, it is preferable to use at least one selected from the group consisting of semiconductor materials, glass, sapphire, resin, and paper.

Examples of the semiconductor material include those selected from silicon (Si), germanium (Ge), tellurium (Te), zinc oxide (ZnO), gallium arsenide (GaAs), gallium nitride (GaN), gallium oxide (Ga ₂ O ₃ ), aluminum nitride (AlN), indium nitride (InN), silicon carbide (SiC), aluminum gallium nitride (AlGaN), indium gallium nitride (InGaN), indium aluminum gallium nitride (InAlGaN), At least one of diamond, silicide material (β-FeSi ₂ , MgSi ₂ , NiSi ₂ , BaSi ₂ , CrSi ₂ , CoSi ₂ , TaSi, etc.), metal oxide or metal oxynitride, etc., but It is not particularly limited.

Here, as the metal oxide or metal oxynitride, for example, at least one selected from the group consisting of the following metal oxides or metal oxynitrides, namely, In-Sn-Ga-Zn-O series Oxide, In-Hf-Ga-Zn-O series oxide, In-Al-Ga-Zn-O series oxide, In-Sn-Al-Zn-O series oxide, In-Sn-Hf-Zn- O-based oxide, In-Hf-Al-Zn-O-based oxide, In-Ga-Zn-O-based oxide, In-Sn-Zn-O-based oxide, In-Al-Zn-O-based oxide , Sn-Ga-Zn-O series oxide, Al-Ga-Zn-O series oxide, Sn-Al-Zn-O series oxide, In-Sn-Zn-O series oxide, In-Hf-Zn -O-based oxides, In-La-Zn-O-based oxides, In-Ce-Zn-O-based oxides, In-Pr-Zn-O-based oxides, In-Nd-Zn-O-based oxides, In-Sm-Zn-O series oxide, In-Eu-Zn-O series oxide, In-Gd-Zn-O series oxide, In-Tb-Zn-O series oxide, In-Dy-Zn- O-based oxide, In-Ho-Zn-O-based oxide, In-Er-Zn-O-based oxide, In-Tm-Zn-O-based oxide, In-Yb-Zn-O-based oxide, In -Lu-Zn-O series oxide, In-Zn-O series oxide, Sn-Zn-O series oxide, Al-Zn-O series oxide, Zn-Mg-O series oxide, Sn-Mg- O-based oxides, In-Mg-O-based oxides, In-Ga-O-based oxides, Zn-ON-based oxynitrides, In-O-based oxides (indium oxide), Sn-O-based oxides (oxidized Tin), Zn-O series (zinc oxide), etc., but are not particularly limited. Here, for example, the so-called In-Sn-Ga-Zn-O-based oxide refers to an oxide semiconductor having indium (In), tin (Sn), gallium (Ga), zinc (Zn), and oxygen (O), The composition ratio of each atom is not particularly limited, and atoms such as silicon (Si) may be included in some cases.

As the resin, a known or commercially available resin can be used, for example, at least one selected from the group consisting of the following resins, namely, polyolefin resin (polyethylene, polypropylene, polynorbornene, etc.); Polyvinyl chloride resin; vinylidene chloride resin, fluorine resin, polyester resin (polyethylene terephthalate, polyethylene naphthalate, etc.); polystyrene resin; polyamide Amine resins; polyamide resins; polyamide resins; polysulfide resins; polysulfide resins; polyetherketone resins; polyether resins; polyurethane resins; Polycarbonate resin; acrylic resin; acrylonitrile-butadiene-styrene (acrylonitrile-butadiene-styrene, ABS) resin, etc., but not particularly limited. Preferably, it can be selected from polyethylene terephthalate, polyethylene naphthalate, polyethylene resin, polypropylene resin, polynorbornene resin, polyamide resin, polyamide resin At least one of the group consisting of amide resin, polyimide resin, polycarbonate resin, acrylic resin, and the like.

For example, when the laminate is used as an indicator of a device for manufacturing semiconductors, the base material is preferably silicon, gallium arsenide, or silicon carbide. For example, when the laminate is used as an indicator of a device for manufacturing LEDs, the substrate is preferably sapphire, gallium nitride, gallium arsenide, or the like. For example, when the laminate is used as an indicator of a device for manufacturing semiconductor lasers, the base material is preferably gallium arsenide, gallium nitride, sapphire, or the like. For example, when the laminate is used as an indicator of a device for manufacturing a power element, the substrate is preferably silicon carbide, gallium nitride, silicon, or the like. For example, when the laminate is used as an indicator of a device for manufacturing solar cells, the base material is preferably silicon, glass, germanium, or the like. For example, when the laminate is used as an indicator of a device for manufacturing a liquid crystal display, the substrate is preferably silicon, glass, germanium, or the like. For example, when the laminate is used as an indicator of a device for manufacturing an organic EL display, the substrate is preferably glass or the like. For example, when the laminate is used as an inexpensive or simple indicator, the base material is preferably resin, paper, glass, or the like.

＜Content of each metal atom＞ In the present invention, the content of each metal atom in the laminate can be less than 5.0 mass ppm, for example, less than 1.0 mass ppm. It is preferably less than 0.5 mass ppm, more preferably less than 0.1 mass ppm, more preferably less than 1 mass ppt, and most preferably less than 0.5 mass ppt. Here, "metal atoms" refer to atoms other than hydrogen, carbon, nitrogen, oxygen, silicon, fluorine, chlorine, bromine, iodine, and rare gases. In order that the content of each metal atom in the layered body is less than 5.0 mass ppm, for example, less than 1.0 mass ppm, the detection layer and the base material layer are composed of components that do not contain metal atoms. In addition, all components related to the laminate (including solvents, etc.) do not contain metal atoms, and further, the metal atom-containing substances contained as impurities are removed by purification. Furthermore, in the manufacturing step, it is preferable not to use an appliance or the like that causes mixing (contamination) of metal atoms. In the present invention, the content of each metal atom is measured by ICP-MS (Inductively Coupled Plasma Mass Spectrometry) etc. for each material and substrate layer constituting the detection layer. If the content of each metal atom is less than 5.0 Mass ppm, the content of each metal atom in the laminate is less than 5.0 mass ppm. In addition, the indicator including the laminate of the present invention is introduced into the processing device together with the material to be processed, and processing such as plasma processing is performed. After that, each metal atom located on the surface of the material to be processed introduced in the processing device is recovered with hydrofluoric acid, and the content of each metal atom is measured by ICP-MS. If the content of each metal atom is less than 5.0 mass ppm, each of the laminates The metal atom may be less than 5.0 mass ppm. By making the content of each metal atom in the laminate less than 5.0 mass ppm, for example less than 1.0 mass ppm, when the laminate is used as an indicator used in an electronic component manufacturing device, it is possible to prevent processed objects and The contamination of metal atoms in the manufacturing device is described. Thereby, it is possible to obtain an indicator that can be used particularly in the manufacturing steps of semiconductor electronic devices where the presence of metal atoms is not desired (especially in the etching process step in the first half of the process).

<The content of each halogen atom> In the present invention, the content of each halogen atom in the laminate can be less than 30 mass ppm, for example, less than 5 mass ppm. It is preferably less than 1 mass ppm, more preferably less than 0.5 mass ppm, and most preferably less than 1 ppt. In order that the content of each halogen atom in the laminate is less than 30 ppm by mass, for example, less than 5 ppm by mass, it is preferable that the detection layer and the base layer be composed of a material that does not contain halogen atoms. In addition, for all components related to the laminate (including solvents, etc.), it is preferable to use a substance containing no halogen atom and to remove the halogen atom-containing substance contained as an impurity by purification. Furthermore, it is preferable to use the method etc. which do not use the equipment etc. which generate|occur|produce the mixing (contamination) of a halogen atom in a manufacturing process. In the present invention, the content of each halogen atom is measured by combustion ion chromatography or ICP-MS (Inductively Coupled Plasma Mass Spectrometry) for each material and substrate layer constituting the detection layer. If each is less than 30 mass ppm, the content of each halogen atom in the laminate is less than 30 mass ppm. In addition, the indicator including the laminate of the present invention is introduced into the processing device together with the material to be processed, and processing such as plasma processing is performed. After that, the halogen atoms on the surface of the processed material introduced in the processing device are recovered, and the content of each halogen atom is measured by combustion ion chromatography or ICP-MS. If the content of each halogen atom is less than 30 mass ppm, each of the laminates The content of halogen atoms may be less than 30 mass ppm. By setting the content of each halogen atom in the laminate to less than 30 mass ppm, for example, less than 5 mass ppm, when the laminate is used as an indicator used in an electronic component manufacturing device, it is possible to prevent processed objects and The pollution of halogen atoms in the manufacturing equipment is described. Thereby, it is possible to obtain an indicator that can be used particularly in the manufacturing steps of semiconductor electronic components where the presence of halogen atoms is not desired (especially in the etching process step in the first half of the process).

＜Layer structure＞ The layered product of the present invention has not only a detection layer and a base layer whose hue changes due to detection of plasma or the like, but also a non-detection layer whose hue does not change even if the plasma or the like is detected. The stacking order of the detection layer, the base material layer, and the non-detection layer may be any order. The detection layer and the non-detection layer may be formed into one layer each, or multiple layers may be formed separately. In addition, color-changing layers or non-color-changing layers may be laminated together. In this case, the detection layers may have the same composition or different compositions, and the non-color changing layers may have the same composition or different compositions. The detection layer and the non-detection layer may be formed on the entire surface of the base layer or each layer, or may be partially formed. In these cases, particularly in order to ensure a change in the color tone of the detection layer, the detection layer and the non-detection layer can be formed so that a part or all of at least one detection layer is exposed to plasma or the like.

The layered product of the present invention can be arbitrarily combined with a color-changing layer and a non-color-changing layer as long as the completion of each treatment or the in-plane uniformity can be confirmed. For example, the color tone of the detection layer before the color tone change and the color tone of the non-detection layer can be formed into the same color tone, and the color difference between the detection layer and the non-detection layer can be distinguished by the change in the color tone of the detection layer due to plasma or the like. Ways to form a detection layer and a non-detection layer. In addition, the color tone of the detection layer before the color tone change and the color tone of the non-detection layer can be formed into different colors, and the color difference between the detection layer and the non-detection layer disappears due to the change in the color tone of the detection layer due to plasma or the like. A detection layer and a non-detection layer are formed.

The laminate of the present invention is particularly preferred to form the detection layer and the non-detection layer in such a way that the color difference between the detection layer and the non-detection layer can be distinguished by the change in the color tone of the detection layer due to plasma or the like. For example, in the case where the color difference of the color-changing layer can be recognized by the change of the color tone of the detection layer caused by plasma or the like, for example, at least one of characters, patterns, and symbols can be displayed by the color change of the color-changing layer Form a color-changing layer and a non-color-changing layer. The characters, patterns, and signs contain all the information to notify the change of color, and these characters and the like can be appropriately designed according to the purpose of use, etc.

In the laminate of the present invention, the detection layer and the non-detection layer may not overlap, and the detection layer and the non-detection layer may be overlapped. In addition, in the laminate of the present invention, a detection layer or a non-detection layer can be further formed on at least one of the detection layer and the non-detection layer. For example, if the detection layer and the non-detection layer are formed so that the detection layer and the non-detection layer are not overlapped (referred to as "detection-non-detection layer"), a detection layer with another design can be formed. Since the boundary line between the detection layer and the non-detection layer in the detection-non-detection layer is substantially unrecognizable, more excellent design can be achieved. In the layered body of the present invention, as a preferable way of layer structure, the following can be cited: (1) A laminate in which a detection layer is adjacently formed on at least one main surface of a substrate layer; (2) A non-detection layer and a detection layer are sequentially formed on the substrate layer and are on the main surface of the substrate layer The non-detection layer is formed adjacently on top, and the detection layer is formed adjacently on the main surface of the non-detection layer. The layered body of (1) above may be a layered body in which a non-detection layer is formed adjacent to the main surface of the detection layer.

＜Shape＞ The shape of the layered body of the present invention can be formed into any shape according to the use and the like. For example, it may be formed to have the same shape as a substrate used in an electronic component manufacturing apparatus. Thereby, the laminated body can be used as a so-called dummy substrate, and it is possible to easily detect whether or not the above-mentioned processing is uniformly performed on the entire substrate. Here, "the same shape as the substrate used in the electronic component manufacturing apparatus" not only refers to the case where the shape of the substrate used in the electronic component manufacturing apparatus is exactly the same, but may also be any of the following cases, namely The shape of the substrate used in the electronic component manufacturing device is substantially the same as the shape of the substrate used in the electronic component manufacturing device to the extent that it can be placed (embedded) in the installation location of the substrate in each electronic component device to be processed. The so-called substantially the same, for example, as long as the length of the main surface of the laminate relative to the length of the main surface of the substrate (in the case of the main surface shape is circular, it is the diameter, if the main surface shape is square or rectangular, etc., it is vertical And the length in the lateral direction) should be within ±5.0 mm, and the difference between the thickness of the laminate and the thickness of the substrate should be within ±1000 μm.

＜Manufacturing method of laminated body＞ As a manufacturing method of a laminated body, the following methods (1)-(4) are mentioned, for example, but it does not specifically limit. (1) After a structure with an internal space communicating with the openings on the surface is provided on the substrate layer by a known appropriate means, the detection agent or the detection agent solution is coated, impregnated, or sprayed to make the detection agent The method of keeping in the internal space. (2) A structure having an internal space communicating with the surface openings is formed by a well-known appropriate method, and a detection agent or a detection agent solution is coated, impregnated, or sprayed on it to keep the detection agent in place. The method in which the internal space is then fixed on the substrate layer by a well-known appropriate means. (3) The composition including the component forming the structure, the component forming the internal space communicating with the opening on the surface in the structure, and the detection agent is placed on the substrate layer, and then the composition is placed in the structure A treatment method for forming an internal space that communicates with the opening on the surface. (4) Prepare a composition including the components forming the structure, the components forming the internal space in the structure communicating with the openings on the surface, and the detection agent, and forming the structure in the structure communicating with the openings on the surface The method of fixing the detection agent on the substrate layer by a well-known appropriate method after keeping the detection agent in the internal space. In the present invention, the method (1) or (2) is preferred, and the method (1) is more preferred from the viewpoints of ease of production of the layered body, prevention of impurities from being mixed into the layered body, and the like.

In addition, when mixing, dissolving or dispersing, if necessary, a known mixer can be used. At this time, it is preferable not to mix contaminated components originating from the mixer. When mixing, dissolving or dispersing, a known method can be used. For example, a method of putting a detection component into the solvent, a method of putting a solvent into a detection component, a method of putting each component constituting a detection agent into the solvent one by one, etc. can be used. When holding the detection component in the internal space, if necessary, the solvent can be removed by known means such as drying.

When the structure is provided on the substrate layer, there is a possibility that the adhesiveness can be improved by subjecting the substrate layer to surface treatment as necessary. As the surface treatment, at least one selected from the group consisting of well-known primer treatment, chemical conversion treatment, plasma treatment, corona treatment, flame treatment, sandblast treatment, and the like can be cited. As a means for providing a structure on the base layer, for example, the following method (1) or (2) can be used, but it is not particularly limited. (1) A solution for preparing a structure is applied on the substrate layer subjected to the surface treatment. (2) After preparing the structure in advance, use an adhesive or the like to adhere it to the substrate layer. In the present invention, the method (1) described above can be preferably used from the viewpoints of ease of production of the laminate, prevention of impurities derived from the adhesive from being mixed into the laminate, and the like.

＜Use of laminated body＞ The layered product of the present invention can be used not only to detect plasma or the like by measuring the color difference based on the color of the detection layer before processing, but also as an indicator for detecting the uniformity of processing of the plasma or the like. For example, the laminate can be used as an indicator in devices for manufacturing electronic components such as semiconductors, LEDs, semiconductor lasers, power devices, solar cells, liquid crystal displays, organic EL displays, and microelectromechanical systems (MEMS). .

In the present invention, by using a commercially available colorimeter to measure the color tone of the detection layer before and after the detection plasma, etc., the L*a*b* color space can be obtained (in addition, L*a*b* color space It is a color system commonly used when expressing the color of an object, and it is standardized by the Commission Internationale de L'Eclairage (CIE) in 1976 and is based on the Japanese Industrial Standards (JIS) Z 8781-4 Or the color system used in JIS Z 8781-5) L* representing brightness, chromaticity a* and b* representing hue and chroma. Using these values of L*, a*, and b*, the color difference ΔE is calculated ^{by the following formula ΔE*=[(ΔL*) 2} + (Δa*) ² + (Δb*) ² ] ^1/2. Based on the color difference ΔE, not only the detection of plasma and the like by the detection layer can be measured, but also the in-plane uniformity of the plasma and the like in the plane of the detection layer can be quantitatively obtained. In particular, the in-plane distribution of chromatic aberration (the in-plane distribution of the discoloration of the detection layer) has a correlation with the flow of plasma and the like. Therefore, it is possible to form an indicator that grasps the flow of important plasma or the like when manufacturing electronic components by grasping the in-plane distribution of color difference, and evaluates the uniformity in the processing surface in a short time. Regarding the laminate of the present invention, it can be accurately visually judged that ΔE is 0.9 or more, preferably 3.0 or more, when it is processed by plasma or the like for a predetermined time, so it is more preferable. In addition, the change in hue after showing the highest value of ΔE is preferably less than 3.0 within the predetermined processing time. By forming a laminate showing such ΔE, it is possible to accurately grasp the processing by plasma or the like, and it is also easy to grasp the in-plane uniformity and the like.

When using the indicator, it is sufficient to place the indicator of the present invention on the installation site of the substrate in each electronic component manufacturing apparatus that performs the above-mentioned processing when manufacturing electronic components. For example, it can be arranged horizontally (horizontally) relative to the wafer stage, heater, vacuum chuck stage, etc., and it can also be arranged vertically (vertical) using a wafer boat or the like. If the indicator of the present invention and the substrate used in the manufacture of electronic components have the same shape, it can be processed or installed in the same manner as the substrate. In this case, the hue changes by the indicator placed in the device being exposed to the process, so that the in-plane uniformity of the process can be easily detected. [Example]

Hereinafter, examples and comparative examples are given to explain the laminate and indicator of the present invention in more detail. However, the present invention is not limited to these examples.

(Example 1) As the base material layer, a silicon substrate used in the manufacture of semiconductors is used. After surface treatment is performed on the surface of the silicon substrate, the surface treatment surface is coated with a polyamide imide resin solution for forming a porous body and dried, on the surface treatment surface of the silicon substrate A porous polyimide resin (polyimide resin porous film) with a thickness of about 20 μm is formed. Regarding the polyimide-based resin porous body, it was confirmed by electron microscope observation that it had pores having openings on the surface. A solution (concentration 2% by mass (Example 1)) of C.I. Solvent Violet 14 as a pigment that does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen was prepared. The prepared detection agent solution is applied and impregnated in the polyamideimide-based resin porous body, and then dried to produce a laminate. For the produced laminate, the measurement of the content of each metal atom, the measurement of the content of each halogen atom, and the performance evaluation as a plasma indicator were performed as follows. The results are shown in Table 1.

(Determination of the atomic content of each metal) For the silicon substrate, the polyimide imide resin solution for forming porous bodies, and the detection agent solution, the metal atom content was measured by ICP-MS (Inductively Coupled Plasma Mass Spectrometry). The result was The amount of metal atoms detected is less than 0.5 mass ppm, respectively. Therefore, the content of each metal atom in the laminate is less than 0.5 mass ppm.

(Determination of the content of each halogen atom) For the silicon substrate, the polyimide imide resin solution for forming porous bodies, and the detection agent solution, it is measured by combustion ion chromatography and ICP-MS (Inductively Coupled Plasma Mass Spectrometry) The content of halogen atoms showed that each of the halogen atoms was less than 5 ppm by mass. Therefore, the content of each halogen atom in the laminate is less than 5 mass ppm.

(Performance evaluation) The laminate is used as a dummy substrate, a commercially available plasma irradiation device is used, and CF ₄ gas is used. The gas flow rate: 10 cc/min, output power 50 W, initial pressure 5 Pa, and processing pressure 20 Pa Under the conditions of plasma treatment. Regarding the layered body not subjected to the plasma treatment and the layered body subjected to the plasma treatment for a predetermined period of time, L*, a*, and b* were measured with a colorimeter to obtain the color difference ΔE before and after the plasma treatment. The results are shown in Table 1.

(Example 2 to Example 16) CI Solvent Red 52, CI Solvent Blue 35, CI Solvent Violet 13, CI Solvent Violet 14, CI Solvent Green 3, Lumogen F, which are all pigments that do not contain atoms other than carbon, hydrogen, oxygen, and nitrogen A layered body was prepared in the same manner as in Example 1 except that a solution of Red 305 (concentrations are described in Table 1) was used as a detection agent solution. For the produced laminate, the measurement of the content of each metal atom, the measurement of the content of each halogen atom, and the performance evaluation as a plasma indicator were performed in the same manner as in Example 1. The results are shown in Table 1 together.

(Comparative example 1) Except that the detection agent solution was not applied and impregnated in the polyimide-based resin porous body, a laminate was prepared in the same manner as in Example 1. For the produced laminate, the measurement of the content of each metal atom, the measurement of the content of each halogen atom, and the performance evaluation as a plasma indicator were performed in the same manner as in Example 1. The results are shown in Table 1 together.

[Table 1] pigment Concentration (wt%) ΔE The content of each metal atom (mass ppm) The content of each halogen atom (mass ppm) Plasma processing time (min) 1 3 6 10 15 Example 1 CI solvent violet 14 2.0 3.8 14.4 26.2 33.1 38.6 Less than 0.5 Less than 5 Example 2 CI solvent violet 14 1.0 20.4 37.1 36.3 35.5 34.0 Less than 0.5 Less than 5 Example 3 CI solvent violet 14 0.5 9.7 19.5 22.4 22.1 21.7 Less than 0.5 Less than 5 Example 4 Luma near (Lumogen) F red (Red) 305 2.0 11.8 27.2 35.5 37.8 41.3 Less than 0.5 Less than 5 Example 5 Luma near (Lumogen) F red (Red) 305 1.0 8.3 17.3 20.9 25.0 29.6 Less than 0.5 Less than 5 Example 6 Luma near (Lumogen) F red (Red) 305 0.5 11.7 20.0 23.3 23.6 24.5 Less than 0.5 Less than 5 Example 7 CI solvent violet 13 2.0 17.1 44.8 46.7 45.5 45.5 Less than 0.5 Less than 5 Example 8 CI solvent violet 13 1.0 10.1 23.5 26.4 25.9 24.8 Less than 0.5 Less than 5 Example 9 CI solvent violet 13 0.5 8.8 13.2 15.4 17.0 15.8 Less than 0.5 Less than 5 Example 10 CI Solvent Red 52 2.0 6.8 10.0 12.2 13.5 14.3 Less than 0.5 Less than 5 Example 11 CI Solvent Red 52 1.0 9.4 11.8 12.9 12.9 13.0 Less than 0.5 Less than 5 Example 12 CI Solvent Red 52 0.5 4.1 5.0 6.2 6.7 6.7 Less than 0.5 Less than 5 Example 13 CI solvent green 3 2.0 20.7 34.9 39.0 37.1 35.6 Less than 0.5 Less than 5 Example 14 CI solvent green 3 1.0 9.9 16.0 18.8 20.5 20.9 Less than 0.5 Less than 5 Example 15 CI solvent green 3 0.5 9.9 12.9 14.1 14.1 13.9 Less than 0.5 Less than 5 Example 16 CI solvent blue 35 0.5 28.5 51.1 50.5 50.5 49.0 Less than 0.5 Less than 5 Comparative example 1 - - 0.8 2.2 4.7 6.3 7.6 Less than 0.5 Less than 5

(Example 17) Except having used the polyimide resin solution for porous body formation instead of the polyimide resin solution for porous body formation, it carried out similarly to Example 1, and prepared the laminated body. After that, except that the treatment time was changed, the performance evaluation as a plasma indicator was performed in the same manner as in Example 1, and the color difference ΔE was determined. In addition, the contents of metal atoms and halogen atoms were measured in the same manner as in Example 1. The results are shown in Table 2.

(Example 18) Except for using Lumogen F red (Red) 305 instead of C.I. Solvent Violet 14, a laminate was prepared in the same manner as in Example 17. Thereafter, in the same manner as in Example 17, the color difference ΔE was determined. The results are shown in Table 2 together.

[Table 2] pigment Concentration (wt%) ΔE Metal atom content (mass ppm) Halogen atom content (mass ppm) Plasma processing time (min) 5 10 20 25 Example 17 CI solvent violet 14 2.0 13.0 22.9 35.7 39.4 Less than 0.5 Less than 5 Example 18 Luma near (Lumogen) F red (Red) 305 2.0 25.4 30.2 43.5 49.4 Less than 0.5 Less than 5

(Example 19, Example 20) After surface-treating the surface of the silicon substrate used in the manufacture of semiconductors, the polyimide-based resin solution for forming a porous body is applied to the surface-treated surface and dried. Thereby, a polyimide-based resin porous body (polyimide-based resin porous film) having a thickness of about 20 μm and having pores with openings on the surface is formed on the surface treatment surface of the silicon substrate. A 1.0% by mass solution (Example 19) and a 0.25% by mass solution (Example 20) of Lumogen F Red (Red) 305 as a pigment containing no atoms other than carbon, hydrogen, oxygen, and nitrogen were produced , As a detection agent solution. The prepared detection agent solution is applied and impregnated in the polyimide-based resin porous body, and then dried to produce a laminate. For the produced laminate, the measurement of the content of each metal atom, the measurement of the content of each halogen atom, and the performance evaluation as a plasma indicator were performed in the same manner as in Example 1. The results are shown in Table 3.

[table 3] pigment concentration ΔE Metal atom content (mass ppm) Halogen atom content (mass ppm) Plasma processing time (min) (Wt%) 5 10 15 20 Na Mg Al Ca Fe Zn Cl Example 19 Luma near (Lumogen) F red (Red) 305 1.0 6.2 10.4 18.3 34.7 2.6 Less than 0.5 2.3 0.6 1.8 0.5 18 Example 20 Luma near (Lumogen) F red (Red) 305 0.25 13.8 26.6 36.5 41.0 3.2 1.0 0.9 1.8 Less than 0.5 Less than 0.5 7

From Tables 1 to 3, it can be seen that although it also depends on the type of structure or pigment that has an internal space communicating with the openings on the surface, if the concentration of the pigment in the detection agent solution is high, it takes time before the discoloration starts (the discoloration The plasma exposure required is large); if the concentration is low, the discoloration is small. Furthermore, the indicator including the layered body of the present invention can determine whether the processing is properly performed based on the change in the color tone by visual observation. At this time, the sensitivity can be adjusted by adjusting the type and concentration of the pigment in the detection agent solution, and it can be easily detected by visual inspection whether the entire object to be processed is uniformly processed. Furthermore, the content of metal atoms or halogen atoms in the indicator including the laminate of the present invention is small. Thereby, when performing treatment by at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and free radical-containing gas, it is possible to avoid the treatment object or the chamber caused by the generated pollutants Pollution.

1: structure 2: Detection agent 3: Substrate layer 4: Detection layer

Fig. 1 is a diagram showing a laminate of the present invention. Fig. 2 is an electron micrograph of the cross section of the laminate of the present invention.

1: structure

2: Detection agent

3: Substrate layer

4: Detection layer

Claims (7)

A laminate having: a detection layer that detects at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and free radical-containing gases and changes in color tone; and a substrate layer, and The detection layer includes a structure having an internal space communicating with an opening portion of the surface, A detection agent is included in the internal space, the detection agent includes at least one detection component, and the detection component detection is selected from at least one of the group consisting of plasma, ozone, ultraviolet rays, and free radical-containing gas. The hue changes, The content of each metal atom in the laminate is less than 5.0 mass ppm. A laminate having: a detection layer that detects at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and free radical-containing gases and changes in color tone; and a substrate layer, and The detection layer includes a structure having an internal space communicating with an opening portion of the surface, A detection agent is included in the internal space, the detection agent includes at least one detection component, and the detection component detection is selected from at least one of the group consisting of plasma, ozone, ultraviolet rays, and free radical-containing gases. The hue changes, The detection agent includes a dye compound that does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen. The layered product according to claim 1, wherein the detection component includes a dye compound that does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen. The laminate according to any one of claims 1 to 3, wherein the structure comprises a polyimide resin, a polyimide resin, a polyimide resin, and a polyimide resin. A structure of at least one resin from the group consisting of olefin resin, polyurethane resin, melamine resin, polyester resin, and polycarbonate resin. The laminate according to any one of claims 1 to 4, wherein the detection agent includes a resin and/or a resin precursor, and the resin and/or a resin precursor does not contain carbon, hydrogen, oxygen, and nitrogen Atoms other than atoms. The laminate according to any one of claims 1 to 5, wherein the content of each halogen atom in the laminate is less than 30 mass ppm. An indicator comprising the layered body according to any one of claim 1 to claim 6.

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