阅读说明：本技术 层叠体以及指示器 (Laminate and indicator ) 是由 西雅之 山川裕 竹冈拓昭 目见田裕一 于 2020-04-14 设计创作，主要内容包括：提供一种层叠体以及指示器,能够容易地调整检测层的灵敏度,可确实地检测处理的进行或终点,可简便地检测均匀地对被处理物整体进行了处理,且可避免伴随这些处理而产生的污染物质所导致的污染。(解决手段)层叠体,具有：检测层,检测选自由等离子体、臭氧、紫外线及含自由基的气体所组成的群组中的至少一种而色调发生变化；及基材层,且所述检测层包括具有与表面的开孔部连通的内部空间的结构体,在所述内部空间内包含检测剂,所述检测剂包含检测选自由等离子体、臭氧、紫外线及含自由基的气体所组成的群组中的至少一种而色调发生变化的检测成分的至少一种,层叠体中的各金属原子的含量未满5.0质量ppm,或所述检测成分包含不含碳、氢、氧及氮以外的原子的色素化合物。(Provided are a laminate and an indicator, which can easily adjust the sensitivity of a detection layer, can reliably detect the progress or end point of a treatment, can easily detect that the entire object to be treated has been uniformly treated, and can avoid contamination caused by a contaminant generated in association with the treatment. A laminate comprising: a detection layer for detecting at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas to change the color tone; and a base material layer, wherein the detection layer includes a structure having an internal space communicating with the opening portion of the surface, the internal space contains a detection agent, the detection agent contains at least one of detection components which detect at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gases and change in color tone, the content of each metal atom in the laminate is less than 5.0 mass ppm, or the detection component contains a dye compound containing no atoms other than carbon, hydrogen, oxygen, and nitrogen.)

1. A laminate having: a detection layer for detecting at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas to change the color tone; and a substrate layer, and

the detection layer includes a structure body having an internal space communicating with the opening portion of the surface,

a detection agent containing at least one detection component that detects at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas to change a color tone is contained in the internal space,

the content of each metal atom in the laminate is less than 5.0 mass ppm.

2. A laminate having: a detection layer for detecting at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas to change the color tone; and a substrate layer, and

the detection layer includes a structure body having an internal space communicating with the opening portion of the surface,

a detection agent containing at least one detection component that detects at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas to change a color tone is contained in the internal space,

the detection agent contains a dye compound containing no atoms other than carbon, hydrogen, oxygen, and nitrogen.

3. The laminate according to claim 1, wherein the detection component comprises a dye compound containing no atom other than carbon, hydrogen, oxygen, and nitrogen.

4. The laminate according to any one of claims 1 to 3, wherein the structure is a structure comprising at least one resin selected from the group consisting of a polyimide-based resin, a polyamideimide-based resin, a polyamide-based resin, a polyolefin-based resin, a polyurethane-based resin, a melamine-based resin, a polyester-based resin, and a polycarbonate-based resin.

5. The laminate of any one of claims 1 to 4, wherein the detection agent comprises a resin and/or a resin precursor that is free of atoms other than carbon, hydrogen, oxygen, and nitrogen atoms.

6. 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.

7. An indicator comprising the laminate according to any one of claims 1 to 6.

Technical Field

The present invention relates to a laminate and an indicator.

Background

As a method for treating 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 or the like") is widely known. For example, plasma is generated in a plasma generating gas atmosphere, and plasma processing is performed by irradiating various articles, substrates, and the like with the plasma.

The treatment with plasma or the like is also performed when manufacturing electronic components (semiconductor chips, Light Emitting Diodes (LEDs), solar cells, liquid crystal displays, organic-Electroluminescence (EL) displays, semiconductor lasers, power elements, and the like).

For example, in the manufacture of semiconductor chips, processes using plasma or the like are performed in each step of film formation (chemical vapor deposition (CVD), sputtering, or the like) on a semiconductor wafer (wafer) in a preceding step, resist pattern formation (plasma dry etching, ion beam etching, or the like), film etching using a resist pattern, resist pattern removal, cleaning, or the like.

In the manufacture of electronic components, it is necessary to perform a uniform treatment by plasma or the like.

For example, regarding a process using plasma or the like in a preceding step of semiconductor chip manufacturing, it is important to perform uniformly in a wafer plane and have in-plane uniformity. If the in-plane uniformity is impaired, the performance of each semiconductor chip formed on the semiconductor wafer varies, and the yield is affected.

Therefore, it is essential to confirm the uniformity of the processing by the plasma or the like in designing each electronic component manufacturing apparatus and managing in the manufacturing steps using the apparatus.

The uniformity of the treatment can be confirmed by a method of measuring the film characteristics, the processing accuracy, and the like of the manufactured electronic component, a method of evaluating the in-plane uniformity by performing the above treatments individually, or the like.

For example, as a method for evaluating the uniformity of plasma itself, a method of measuring a physical constant of plasma by a Langmuir probe (Langmuir probe) provided in a manufacturing apparatus, and a method of evaluating a spatial distribution by analyzing light emission of plasma by a spectroscopic apparatus are known.

However, the method using the langmuir probe may require a lot of labor and time because it requires an operation such as air release from the manufacturing apparatus or probe removal during the manufacturing operation. In the method using the spectroscopic apparatus, the measurement range is limited, and therefore the entire plasma in the apparatus may not be measured. The method using a langmuir probe or a spectroscopic device does not directly show the in-plane distribution of each treatment, but involves an analysis operation based on the measurement result.

Patent documents 1 and 2 describe indicators for detecting the presence or absence of ozone or the like.

Patent document 3 describes that an ink containing a coloring matter, a specific surfactant, and a nonionic surfactant is applied to a substrate, and the ink is placed in a reaction chamber or the like as an indicator to detect the end point of plasma processing.

Patent document 4 describes that the uniformity of processing of plasma or the like is checked by using an indicator for detecting plasma or the like, which has the same shape as a substrate used in an electronic component manufacturing apparatus. A color-changing layer formed of an ink that changes or loses color by reacting with plasma or the like is included in the indicator.

Patent document 5 describes that contamination caused by an ink composition or the like is prevented by using a plasma indicator containing a coloring matter in pores formed by anodic oxidation treatment.

The indicators described in patent documents 3 to 5 can visually confirm the progress of plasma treatment in the reaction chamber, but it is necessary to appropriately adjust the sensitivity and the like.

In addition, a part of the components of the indicator placed in the chamber may be vaporized depending on the process conditions and the like, and the object to be processed such as plasma processing or the chamber may be contaminated. For example, it is assumed that a substance containing a metal atom or a halogen atom is often contained in the ink, and contamination of a component containing a metal atom (contamination) by a dispersion medium or the like occurs during production.

In particular, the presence of metal atoms is undesirable in a step preceding the manufacturing steps of a semiconductor device, and contamination is avoided.

[ Prior art documents ]

[ patent document ]

Patent document 1: japanese patent No. 4382816

Patent document 2: japanese patent laid-open 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

Disclosure of Invention

[ problems to be solved by the invention ]

The present invention has an object to provide a laminate and an indicator that can easily adjust the sensitivity of a detection layer that detects at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas and changes in color tone, and can reliably detect the progress or end point of a process using at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas.

The present invention has an object to provide a laminate and an indicator that can easily detect whether or not a treatment with at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas is uniformly applied to the entire object to be treated, and that can prevent contamination of the object to be treated or the inside of a chamber due to a contaminant generated by the treatment.

[ means for solving problems ]

The present inventors have studied to solve the above problems and found that the problems can be solved by constituting a laminate having a specific structure and using the laminate as an indicator.

Specifically, the following is described.

1: a laminate having: a detection layer for detecting at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas to change the color tone; and a substrate layer, and

the detection layer includes a structure body having an internal space communicating with the opening portion of the surface,

a detection agent containing at least one detection component that detects at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas to change a color tone is contained in the internal space,

the content of each metal atom in the laminate is less than 5.0 mass ppm.

2: a laminate having: a detection layer for detecting at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas to change the color tone; and a substrate layer, and

the detection layer includes a structure body having an internal space communicating with the opening portion of the surface,

a detection agent containing at least one detection component that detects at least one selected from the group consisting of plasma, ozone, ultraviolet light, and a radical-containing gas to change a color tone is contained in the internal space,

the detection agent contains a dye compound containing no atoms other than carbon, hydrogen, oxygen, and nitrogen.

3: the laminate according to item 1, wherein the detection component comprises a dye compound containing no atom other than carbon, hydrogen, oxygen, and nitrogen.

4: the laminate according to any one of the items 1 to 3, wherein the structure is a structure including at least one resin selected from the group consisting of a polyimide-based resin, a polyamideimide-based resin, a polyamide-based resin, a polyolefin-based resin, a polyurethane-based resin, a melamine-based resin, a polyester-based resin, and a polycarbonate-based resin.

5: the laminate according to any one of claims 1 to 4, wherein the detection agent comprises a resin and/or a resin precursor that does not contain atoms other than carbon, hydrogen, oxygen, and nitrogen atoms.

6: the laminate according to any one of the items 1 to 5, wherein a content of each halogen atom in the laminate is less than 30 mass ppm.

7: an indicator comprising the laminate of any one of items 1 to 6.

[ Effect of the invention ]

According to the present invention, there are provided a laminate and an indicator which can easily adjust the sensitivity of a detection layer for detecting at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and a radical-containing gas, and which changes in color tone, and which can reliably detect the progress or end point of a process using at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and a radical-containing gas.

According to the present invention, there are provided a laminate and an indicator which can easily detect whether or not a treatment with at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and a radical-containing gas is uniformly applied to the entire object to be treated, and which can prevent contamination of the object to be treated or the inside of a chamber due to a contaminant generated by the treatment.

Drawings

FIG. 1 is a view showing a laminate of the present invention

FIG. 2 is an electron micrograph of a cross section of a laminate of the present invention

Detailed Description

[ laminate ]

The laminate of the present invention has a detection layer for detecting plasma or the like to change a color tone, and a base material layer, wherein the detection layer includes a structure having an internal space communicating with an opening portion on a surface, and the internal space contains a detection agent containing at least one of detection components for detecting plasma or the like to change a color tone.

< detection layer >

The change in color tone of the detection layer is caused by a change in color tone of at least one of discoloration, color loss, and color development caused by the contact of the detection component with plasma or the like. Here, the plasma is at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas, as described above.

The detection layer of the present invention can easily detect the in-plane uniformity in the process of plasma or the like by visual observation, without simply detecting plasma or the like. In the present invention, since the detection agent can be uniformly present in the detection layer in the plane, it is considered that the detection of the 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 ensure that the change in color tone can be grasped, the thickness is 10 μm or more, preferably 15 to 100. mu.m.

(plasma)

The plasma refers to a plasma generated by applying an alternating voltage, a direct voltage, a pulse voltage, a high frequency, a microwave, or the like using a plasma generating gas, and both of the reduced pressure plasma and the atmospheric pressure plasma are suitable.

The plasma generating gas is not particularly limited as long as plasma is generated by applying an ac voltage, a dc voltage, a pulse voltage, a high frequency, a microwave, or the like. For example, at least one selected from the group consisting of oxygen, nitrogen, hydrogen, fluorine, chlorine, helium, neon, argon, silane, ammonia, sulfur bromide, water vapor, nitrous oxide, tetraethoxysilane, carbon tetrafluoride, trifluoromethane, carbon tetrachloride, silicon tetrachloride, sulfur hexafluoride, titanium tetrachloride, dichlorosilane, trimethylgallium, trimethylindium, trimethylaluminum, air, and carbon dioxide may be used.

Examples of the plasma include plasma generated in a plasma processing apparatus (an apparatus for performing plasma processing by applying plasma generated by applying an alternating voltage, a direct voltage, a pulse voltage, a high frequency, a microwave, or the like in an atmosphere contained as a plasma generating gas) used in a film forming step, an etching step, an ashing (ashing) step, an impurity adding step, a cleaning step, or the like in the production of an electronic component.

(ozone)

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

(ultraviolet ray)

Ultraviolet rays are electromagnetic waves having a wavelength of about 1nm to 400nm, and include near ultraviolet rays, far ultraviolet rays, or vacuum ultraviolet rays, and extreme ultraviolet rays or extreme ultraviolet rays. Examples thereof include: ultraviolet rays generated from an ultraviolet irradiation device including a mercury lamp or an LED; or ultraviolet rays generated in an ultraviolet treatment apparatus used in a photolithography (photolithography) step, an ashing step, a cleaning step, or the like in the production of electronic components.

(gas containing free radical)

The gas containing the radical is generated by imparting energy to the gas. For example, hydrogen can be generated by passing hydrogen through a thin tube made of Ta heated to 2100K by electron beam impact. In an environment using such a radical-containing gas, it is preferable to control the flow rate of hydrogen and maintain the degree of vacuum at 1.0X 10^-4Torr～1.0×10^-6About Torr. Examples of the gas include a gas containing radicals generated in a gas processing apparatus containing radicals used in a film formation step, an etching step, an ashing step, a cleaning step, and the like in the production of electronic devices.

(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 open pore portion of the surface. The color tone of the detection component may be any color tone as long as the change in color tone of the detection component can be grasped, and is preferably transparent, colored transparent, white, pale, or the like.

As the structure, for example, there can be used: a porous body having an internal space communicating with the opening portion of the surface; a structure in which one or more of a hole, a concave portion, a convex portion, and a crack are provided by a known appropriate means to form a portion corresponding to an internal space communicating with the opening portion of the surface; a composition having a porous material disposed on the surface thereof, and the like. Among them, a porous body having an internal space communicating with the opening portion of the surface is preferably used.

The organic material, inorganic material, and organic-inorganic composite material that constitute the structure include at least one compound. If necessary, an extender and the like may be contained. When the content of each metal atom in the laminate is less than 5.0 mass ppm, it is preferable to use a structure containing no metal atom as the structure.

In the present invention, the structure has a function of masking the color of the wafer, and can increase the change in color tone. Further, by using the structure, the detection agent can change color tone with time according to the degree of penetration of plasma or the like, or change color tone in proportion to the amount or intensity of exposure to plasma or the like.

The porous body having an internal space communicating with the open pore portion of the surface may be any of an inorganic porous body, an organic porous body, and an organic-inorganic composite porous body, for example.

Examples of the inorganic porous material include those selected from the group consisting of metal porous materials; a silica-based porous body (silica gel, aerosol, silica gel, etc.); alumina-based porous bodies (activated alumina and the like); zeolite-based porous bodies (aluminosilicate zeolite, metallosilicate zeolite, aluminophosphate zeolite, etc.); silicate-based porous bodies (kaolinite, montmorillonite, mica, and the like); mesoporous porous bodies (e.g., mesoporous silica); a glass porous body; a ceramic porous body; pumice stone; at least one member selected from the group consisting of porous bodies such as metal oxides and metal hydroxides (e.g., alumite, hydroxyapatite, hydrotalcite, layered zirconium phosphate, heteropolyacid salts, and porous manganese oxide), and the like, but is not particularly limited.

Examples of the organic porous material include at least one selected from the group consisting of a resin porous material (such as a porous film or porous polymer beads), a nonwoven fabric, a woven fabric, paper, wood, leather, activated carbon, fullerene, and carbon nanotubes, but are not particularly limited thereto.

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

Among these resins, polyimide-based resins, polyamideimide-based resins, polyamide-based resins, polyolefin-based resins, polyurethane-based resins, melamine-based resins, polyester-based resins, and polycarbonate-based resins can be preferably used. In particular, it is possible to use,

when a heat-resistant polymer such as a polyamide-imide resin, a polyimide resin, or a polyamide resin is used as a structural body, a laminate having excellent heat resistance is formed, and thus an indicator that can be used under high-temperature conditions and has resistance to a strong plasma treatment can be configured.

Examples of the organic-inorganic composite porous material include at least one selected from the group consisting of a porous material of a resin composition containing an inorganic component, an organic metal structure (metal-organic framework, MOF), and the like, but are not particularly limited.

As the organic component constituting the organic-inorganic composite porous body, an organic component constituting an organic porous body; as the inorganic component constituting the organic-inorganic composite porous body, an inorganic component constituting an organic porous body or a well-known inorganic filler can be used.

Among the above-described structures, as a structure having a portion corresponding to an internal space by providing one or more of a hole, a concave portion, a convex portion, and a crack by a known appropriate means, there can be used: a structure in which a hole is provided by punching with a needle, a laser, or the like; a structure provided with a hole or a recess by chemical treatment or the like; a structure in which a concave portion is provided by embossing (emboss), grinding, or the like; a structure body having a projection formed by blowing a projection forming substance; a structure having cracks formed by preparation using a resin composition or a coating material containing a crack forming agent such as an inorganic filler for forming fine cracks on the surface; a structure or the like in which a porous filler or the like is blended with a binder such as a resin.

In the present invention, when the content of each metal atom in the laminate is less than 5.0 mass ppm, it is preferable to use an organic porous material, particularly a resin porous material, as the structure constituting the detection layer.

In order to prevent contamination of the inside of the electronic device manufacturing apparatus by metal atoms, it is preferable to use an organic porous material, particularly a resin porous material, as a structure constituting the detection layer.

As the resin porous body, a resin porous body prepared by a known method can be used, and examples thereof include the following methods (1) to (4).

(1) Porosification by chemical means using a pore-forming agent or the like (for example, porosification by a blowing agent, porosification using a gas generated at the time of polymerization, modification or molding, porosification (removal or sublimation of a component) by removing a porosification-forming agent after molding (after film formation), porosification by phase separation (use of a mixed solvent having different solubilities or the like), or the like)

(2) Porosification by extension

(3) Porosification by fusion of powder particles

(4) Making holes by mechanical means, e.g. punching

In the present invention, the resin porous body obtained by the method (1) is preferable. In particular, a porous coating film obtained by applying a resin solution containing two or more solvents having different solubilities or boiling points is preferable as the resin porous body.

For example, a polyimide resin porous body or a polyamide resin porous body can be obtained by using a resin solution containing a polyimide resin or a polyamide resin, a good solvent for the resins, and a poor solvent for the resins.

As the good solvent for the polyimide-based resin or the polyamideimide-based resin, for example, at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, tetramethylurea, dimethylethyleneurea, 1, 3-dimethyl-2-imidazolidinone, and the like can be used.

As the poor solvent for the polyimide-based resin or the polyamideimide-based resin, a solvent having a solubility of less than 1 mass% can be used, and for example, a solvent 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, and the like); hydrocarbon solvents (n-hexane, cyclohexane, benzene, toluene, xylene, petroleum ether, etc.); ester-based solvents (ethyl carbitol acetate, butyl carbitol acetate, dimethyl succinate, diethyl succinate, dimethyl glutarate, diethyl glutarate, dimethyl adipate, diethyl adipate, and the like); alcohol solvents (such as triethylene glycol, diethylene glycol, ethylene glycol, methanol, and ethanol).

Preference is given to the following: a polyamide imide resin porous body obtained from a resin solution containing a polyamide imide resin, N-methyl-2-pyrrolidone, and tetraethylene glycol dimethyl ether; a porous polyimide resin body obtained from a resin solution containing a polyimide resin, N-dimethylacetamide, and tetraethylene glycol dimethyl ether.

(detection agent)

The detection agent in the present invention contains at least one of detection components that change in color tone upon detection of plasma or the like.

The detection agent may contain various components as necessary for the purpose of adjusting sensitivity or improving visibility of color difference before and after detection, within a range not impairing the effect of color change due to the detection component.

Examples of such components include a dye (a dye whose color tone does not change when exposed to a detection target) that does not function as the detection component, a resin and/or a resin precursor, a reaction accelerator, a reaction retarder, a filler, and an additive such as a surfactant.

In the present invention, it is preferable that the detecting agent containing the detecting component does not contain a metal atom so that the content of each metal atom in the laminate is less than 5.0 mass ppm. Thus, in the case where the laminate is used as an indicator for detecting plasma or the like in the manufacturing apparatus for electronic components, contamination by metal atoms in the manufacturing apparatus for electronic components can be effectively prevented.

In the present invention, it is preferable to use a detection agent containing a dye compound containing no atom other than carbon, hydrogen, oxygen, and nitrogen. Thus, when the laminate is used as an indicator for detecting plasma or the like, contamination in the manufacturing apparatus of electronic components, particularly contamination by metal atoms or halogen atoms, can be effectively prevented.

The detection agent is preferably prepared by sufficiently purifying the constituent components thereof or by using no metal instrument or the like so as not to mix in impurities such as metal atoms or halogen atoms.

Detection of components-

The compound that is used as a detection component in the present invention and that changes color tone when plasma or the like is detected is not particularly limited as long as it shows a behavior that changes color tone when exposed to plasma or the like.

Examples of such a compound include pigments known as colorants, preferably those of dyes and pigments, which change their color tone upon detection of plasma or the like.

The pigment may be a known or commercially available pigment. Examples of the coloring agent include at least one selected from the group consisting of anthraquinone-based coloring agents; a quinone-based pigment; a perylene pigment; a methine dye; azo dyes (monoazo dyes, disazo dyes, trisazo dyes, polyazo dyes, azo (azo) dyes (disazo components, coupling components), and the like); a phthalocyanine-based coloring matter; a diarylmethane-based pigment; a triarylmethane-based pigment; a xanthene-based dye; an oxazine-based pigment; edible pigment; a perinone-based pigment; diketopyrrolopyrrole-based pigments; quinacridone pigments; anthanthrone-based pigments; a perinone-based pigment; isoindolinone pigments; isoindoline-based pigments; indanthrene (indanthrene) based pigments; coumarin series pigment; quinacridone pigments; pyranthrene-based coloring matter; flavochrome (flavanthrone) series pigments; a nitroso-based pigment; nitro pigments; a distyrene pigment; a carotenoid-based pigment; acridine-based pigments; a quinoline-based pigment; a thiazole-based coloring matter; naphthoquinone-based pigments; indamine (indamine) based pigments; indophenol (indophenol) based pigments; azine-based pigments; a thiazine-based pigment; a vulcanization-based coloring matter; a lactone-based pigment; a hydroxy ketone pigment; an amino ketone-based pigment; indigoid (indigo) based pigments; thioindigo (thioindigo) based pigments; a cationic pigment; a cyanine dye; cyanine (squarylium) based pigments; croconium (croconium) based pigments; a merocyanine-based dye; fluoran-based coloring matter; a spiropyran-based pigment; fulgide (fulgide) -based pigments; an azulene-based pigment; a natural pigment; an oxidation-based pigment; metal complex pigments, etc., but are not limited thereto.

Among the above-mentioned pigments, the pigment for detecting plasma or the like is preferably at least one selected from the group consisting of anthraquinone-based pigments, perylene-based pigments, methine-based pigments, azo-based pigments, phthalocyanine-based pigments, triarylmethane-based pigments, xanthene-based pigments, indanthrene-based pigments, and food pigments.

Among the above pigments, the pigment for detecting ozone is preferably at least one selected from the group consisting of oxazine-based pigments, azo-based pigments, methine-based pigments, indanthrene-based pigments, and anthraquinone-based pigments.

Among the above-mentioned coloring matters, the coloring matter for detecting ultraviolet rays is preferably at least one selected from the group consisting of azo-based coloring matter, anthraquinone-based coloring matter, triarylmethane-based coloring matter, phthalocyanine-based coloring matter, indigo (indigo) based coloring matter, diarylmethane-based coloring matter, triarylamine-based coloring matter, and cyanine-based coloring matter.

More preferably, the following compounds are used together with a dye for detecting the ultraviolet light: the compound is a compound which imparts a change to the color mechanism of the dye by ultraviolet irradiation, and is a compound which becomes a compound which itself imparts a change to the color mechanism of the dye by ultraviolet irradiation and/or a compound which generates a radical which imparts a change to the color mechanism by ultraviolet irradiation.

Examples of the compound for imparting a change in the color development mechanism of the dye by ultraviolet irradiation include at least one compound selected from the group consisting of acetophenone (acetophenone) type compounds, benzophenone type compounds, michael ketone type compounds, benzil (benzil) type compounds, benzoin ether type compounds, benzyl dimethyl ketal type compounds, benzoin benzoate type compounds, α -oxime hydrate type compounds (alpha aquo oxime ester compounds), tetramethylthiuram monosulfide type compounds, thioxanthone type compounds, and acylphosphine oxide type compounds, but are not limited thereto.

In particular, it is preferable to use a compound that generates a radical that changes the color-developing mechanism by irradiation with ultraviolet light, and it is preferable to use at least one selected from compounds that have a maximum absorption at a wavelength of about 150nm to 450nm (more preferably 200nm to 400 nm).

The amount of the compound to be added to the color mechanism of the dye by ultraviolet irradiation may be determined depending on the type of the dye used. The amount of the coloring agent is not particularly limited as long as a sufficient color change effect that can be visually recognized is obtained and the solubility in a solvent or the like does not cause a problem, and examples thereof include about 0.1 to 20 moles, preferably about 0.5 to 15 moles, based on 1 mole of the coloring agent.

When a benzophenone-type compound, a michigan-type compound, a benzil-type compound, a thioxanthone-type compound or the like is used as a compound for changing the color development mechanism of the dye by ultraviolet irradiation, it is preferable to use an amine-based reaction accelerator (amine-based radical accelerator) such as ethanolamine in combination. In this case, the amount of the amine-based reaction accelerator to be blended may be appropriately determined depending on the compound, the pigment, and the like.

Examples of the combination of a dye and a compound which changes the color development mechanism of the dye by ultraviolet irradiation include (1) a combination of an anthraquinone dye and a benzoin ether-type compound, a benzyl dimethyl ketal-type compound, or an acyl phosphine oxide-type compound, (2) a combination of a disazo dye and a benzoin ether-type compound or an acyl phosphine oxide-type compound, (3) a combination of a phthalocyanine dye and a benzoin ether-type compound or an acyl phosphine oxide-type compound, (4) a combination of a cyanine dye and a benzophenone-type compound, and (5) a combination of an azo dye and a benzophenone-type compound or an acyl phosphine oxide-type compound.

Among the above pigments, at least one selected from the group consisting of anthraquinone pigments, azo pigments, and triarylmethane pigments is preferably used for detecting a gas containing a radical.

In the present invention, the coloring matter is preferably selected from anthraquinone-based coloring matters; a perylene pigment; a methine dye; azo dyes (monoazo dyes, disazo dyes, trisazo dyes, polyazo dyes, azo dyes (disazo components), azo dyes (azo components), etc.); a phthalocyanine-based coloring matter; a triarylmethane-based pigment; a xanthene-based dye; an oxazine-based pigment; indanthrene based pigments; at least one of food coloring matters and perinone coloring matters. Particularly preferably at least one selected from the group consisting of anthraquinone-based pigments, perinone-based pigments, methine-based pigments, indanthrene-based pigments, and azo-based pigments.

Specific examples of these pigments include at least one of the group consisting of Color Index (c.i.) Acid Black (Acid Black) 123; c.i. 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: 1. 100, 103, 104, 108, 109, 110, 119, 123, 147, 213, 269; c.i. Acid Green (Acid Green) 16; c.i. Acid Red (Acid Red)52, 81, 83; c.i. Acid Violet (Acid Violet)1, 3, 7, 10, 12, 14, 15, 16, 17, 19, 20, 21, 23, 25, 30, 38, 39, 43, 48, 49, 72; c.i. Acid Yellow 11, 12, 13, 14, 21, 22, 23, 24, 74; c.i. azo Coupling Component (azo Coupling Component)2, 3, 4, 5, 7, 11, 14, 16, 17, 18, 19, 20, 29, 36; c.i. ice-dyed Diazo components (azo Diazo components) 1, 5, 8, 12, 13, 20, 24, 34, 41, 48, 109; azo Brown (Azoic Brown) 11; c.i. Basic Blue (Basic Blue)1, 5, 7, 8, 26, 62, 63, 140; c.i. Basic Green (Basic Green)1, 4; c.i. Basic Red (Basic Red)1, 9, 12, 13, 14, 15, 27, 35, 36, 37, 45, 48; c.i. developers (developers) 8, 18, 20, 21, 22; c.i. Direct Blue (Direct Blue)41, 86, 87; c.i. Disperse Black (Disperse Black)1, 2, 29; c.i. Disperse Blue (Disperse Blue)1, 3, 5, 6, 7, 26, 27, 44; c.i. Disperse Orange (Disperse Orange)1, 3, 5, 11, 13; c.i. Disperse Red (Disperse Red)1, 4, 9, 11, 13, 15, 17, 52, 58, 88, 167: 1; c.i. Disperse Violet (Disperse Violet)1, 4, 8; c.i. disperse yellow (disperse) 1,3, 4, 5, 7, 8, 23, 31, 60, 61; c.i. media Blue (Mordant Blue) 1; c.i. mordant red (mordant red)11, 15, 27; c.i. Mordant Violet (Mordant Violet)1, 25; c.i. Pigment Blue (Pigment Blue)15, 15: 3. 15: 4. 15: 6. 16; c.i. Pigment Green (Pigment Green)7, 36; c.i. Reactive Blue (Reactive Blue)4, 19; c.i. Solvent Black (Solvent Black) 3; c.i. Solvent Brown (Solvent Brown)3, 5; c.i. Solvent Blue (Solvent Blue)11, 14, 35, 63, 70; c.i. Solvent Green 3, 5, 15; c.i. Solvent Orange (Solvent Orange)1, 2, 14, 55, 60, 78, 90; c.i. Solvent Red (Solvent Red)1, 3, 18, 23, 24, 25, 27, 49, 52, 114, 135, 162, 179; c.i. Solvent Violet (Solvent Violet)8, 13, 14, 29; c.i. Solvent Yellow 2, 6, 14, 16, 21, 29, 33, 56; c.i. Vat Black (Vat Black)8, 9, 25, 27, 29; c.i. Vat Brown (Vat Brown)1, 3, 25, 44; c.i. Vat Blue (Vat Blue)1, 4, 12, 20, 21, 30; c.i. Vat Green 1,3, 8, 9; c.i. Vat Orange (Vat Orange)7, 9, 13, 15; c.i. Vat Red (Vat Red)10, 13, 15, 19, 28, 29; c.i. Vat Violet (Vat Violet)13, 15, 17; c.i. Vat Yellow 4, 10, 20; ramus juba (Lumogen) F IR 788; ramus juana (Lumogen) F Orange (Orange) 240; leimei (Lumogen) F powder (Pink) 285; road horse near (Lumogen) F Red (Red)300, 305, 339; lomaton (Lumogen) F Violet (Violet) 570; ramus juba (Lumogen) F Yellow (Yellow)083, 170; akton Violet extra (Iketon Violet extra); malachite Blue (Oil peach Blue); oil palm BG extra (Oil Brown BG extra); edible red No. 1; edible red No. 3; edible red No. 102; edible red No. 104; edible red No. 105; edible red 106; edible yellow No. 4; edible yellow No. 5; edible No. 3; edible blue No. 1; edible blue No. 2, etc.

For example, it is preferable to use at least one selected from the group consisting of Acid Black (Acid Black) 123; azo Brown (Azoic Brown) 11; c.i. azo coupling Component (azo coupling Component)2, 3, 4, 5, 7, 11, 14, 16, 17, 18, 19, 20, 29, 36; c.i. ice-dyed Diazo components (azo Diazo components) 1, 5, 8, 12, 13, 20, 24, 34, 41, 48, 109; c.i. Basic Green (Basic Green) 4; c.i. developers (developers) 8, 18, 20, 21, 22; c.i. Disperse Black (Disperse Black)1, 2, 29; c.i. Disperse Blue (Disperse Blue)1, 3, 5, 6, 7, 26, 27; c.i. Disperse Orange (Disperse Orange)1, 3, 11, 13; c.i. Disperse Red (Disperse Red)1, 4, 9, 11, 15, 17; c.i. Disperse Violet (Disperse Violet)1, 4, 8; c.i. Disperse Yellow (Disperse Yellow)1, 3, 4, 5, 7, 8, 23, 31, 60, 61; c.i. mordant red (mordant red)11, 15, 27; c.i. Solvent Black (Solvent Black) 3; c.i. Solvent Blue (Solvent Blue)11, 35; c.i. Solvent Brown (Solvent Brown)3, 5; c.i. Solvent Green (Solvent Green) 3; c.i. Solvent Orange (Solvent Orange)1, 2, 14; c.i. Solvent Red (Solvent Red)1, 3, 18, 23, 24, 25, 27, 49, 52; c.i. Solvent Violet (Solvent Violet)13, 14; c.i. Solvent Yellow 2, 6, 14, 16, 21, 29, 33, 56; c.i. Vat Black (Vat Black)8, 9, 25, 27, 29; c.i. Vat Blue (Vat Blue)1, 4, 12, 20; c.i. Vat Brown (Vat Brown)1, 3, 25, 44; c.i. Vat Green 1,3, 8, 9; c.i. Vat Orange (Vat Orange)7, 9, 13, 15; c.i. Vat Red (Vat Red)10, 13, 15; c.i. Vat Violet (Vat Violet) 13; c.i. Vat Yellow 4, 10, 20; ramus juba (Lumogen) F IR 788; ramus juana (Lumogen) F Orange (Orange) 240; leimei (Lumogen) F powder (Pink) 285; road horse near (Lumogen) F Red (Red)300, 305, 339; lomaton (Lumogen) F Violet (Violet) 570; ramus juba (Lumogen) F Yellow (Yellow)083, 170; akton Violet extra (Iketon Violet extra); malachite Blue (Oil peach Blue); oil palm BG extra (Oil Brown BG extra), etc.

More preferably at least one selected from the group consisting of c.i. azo Coupling components (azo Coupling components) 3, 16; c.i. Basic Green (Basic Green) 4; c.i. mordant red (mordant red) 27; c.i. Solvent Black (Solvent Black) 3; c.i. Solvent Blue (Solvent Blue) 35; c.i. Solvent Red (Solvent Red)18, 24, 27, 49, 52; c.i. Solvent Violet (Solvent Violet) 14; c.i. Solvent Yellow (Solvent Yellow) 29; c.i. Vat Black (Vat Black)8, 9, 25, 27, 29; c.i. Vat Brown (Vat Brown)1, 3, 25, 44; c.i. Vat Green (Vat Green) 8; c.i. Vat Orange (Vat Orange)13, 15; c.i. Vat Red (Vat Red)10, 13, 15; c.i. Vat Yellow 10, 20; ramus juba (Lumogen) F IR 788; ramus juana (Lumogen) F Orange (Orange) 240; leimei (Lumogen) F powder (Pink) 285; road horse near (Lumogen) F Red (Red)300, 305, 339; lomaton (Lumogen) F Violet (Violet) 570; ramus juba (Lumogen) F Yellow (Yellow)083, 170; akton Violet extra (Iketon Violet extra); malachite Blue (Oil peach Blue); oil palm BG extra (Oil Brown BG extra).

In the present invention, the detection sensitivity can be controlled or the color development and color tone of the detection layer can be controlled by changing the type (molecular structure, etc.) of these dyes or by mixing a plurality of dyes.

The content of these dyes may be determined as appropriate depending on the type of dye, desired discoloration (detection sensitivity), product form, characteristics of the structure, and the like.

For example, the dye may be contained in the detection layer in an amount of 0.01 to 20% by mass, preferably 0.1 to 10% by mass. For example, the detection agent may contain 0.01 to 100% by mass, preferably 0.1 to 100% by mass of a dye.

A pigment that does not function as the detection component

In the present invention, the detection agent may contain a dye that does not function as the detection component.

By including such a dye that does not function as the detection component, the visual recognition effect can be further improved by changing the color tone from one color to another.

The dye that does not function as the detection component includes at least one dye selected from the group consisting of dyes 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 a dye that does not cause a change in color tone even when plasma or the like is detected, and the like can be used.

When the dye that does not exhibit the function as the detection component is contained in the detection agent, the content of the dye that does not exhibit the function as the detection component may be appropriately determined depending on the type, the visibility of the detection layer, the desired color tone, and the like, and is generally preferably about 0% by mass to 99.99% by mass, and particularly preferably about 0% by mass to 99.9% by mass in the detection agent.

Resins and/or resin precursors

In the present invention, the detection agent may contain a resin and/or a resin precursor that can function as a binder.

As the resin, either a natural resin or a synthetic resin may be used, or a commercially available resin may be used. In addition, any of the molecular weight and the molecular weight distribution of the resin may be used.

As the resin precursor, any resin precursor can be used as long as it can be made into a resin by a reaction. Examples of the solvent include, but are not particularly limited to, at least one selected from the group consisting of (meth) acrylate compounds, polyamic acids, and polyurethane prepolymers.

The resin and/or the resin precursor are appropriately selected depending on the components constituting the detection agent and the like.

By including a resin and/or a resin precursor in the detection agent, for example, the fixing property of the detection agent, the prevention of separation or peeling of the detection component from the detection agent or the detection layer, the adjustment of sensitivity by BR > such as the control of contact between the detection component and the detection object, the protection of the detection agent, and the like can be adjusted.

As such a resin, a known or commercially available resin may be used, and examples thereof include at least one selected from the group consisting of a polyamide resin, a polyamideimide resin, a polyimide resin, an amino resin (a melamine resin-benzoguanamine resin, a urea resin, and the like), an acrylic resin ((meth) acrylic resin, a poly (meth) acrylonitrile resin, a poly (meth) acrylamide resin, and the like), a polyvinylpyrrolidone resin, a polyvinylimidazole resin, a polyolefin resin (a polyethylene resin, a polypropylene resin, and the like), a fluorine resin, a vinyl chloride resin, a vinyl acetate resin, a polyvinyl acetal resin (a polyvinyl butyral resin, and the like), a polyvinyl alcohol resin, a polystyrene resin (a polystyrene resin, a polyamide resin, an amino resin (a melamine resin-benzoguanamine resin, a urea resin, and the like), an acrylic resin, a polyvinyl pyrrolidone resin, a polyvinyl imidazole resin, a polyvinyl acetal resin, a polyvinyl butyral resin, and the like, Styrene-maleic acid-based resin, styrene-acrylic acid-based resin, etc.), polyester-based resin (polyester-based resin, unsaturated polyester-based resin, alkyd-based resin, etc.), phenol-based resin (phenol-based resin, alkylphenol-based resin, terpene-phenol-based resin, rosin-modified phenol-based resin, etc.), polyether-based resin, epoxy-based resin, maleic acid-based resin, polyketone-based resin, polyethyleneimine-based resin, polyurethane-based resin, polysiloxane-based resin, acetal-based resin, block polymerization-based resin, graft polymerization-based resin, cellulose-based resin, rosin-based resin (rosin-based resin, etc.), rubber-based resin (natural rubber, diene-based rubber, SB rubber, etc.).

When the detection agent contains a resin and/or a resin precursor, the content of the resin and/or the resin precursor can be appropriately determined depending on the kind of the resin and/or the resin precursor, the kind of the detection component used, and the like. For example, the detection agent is generally used in an amount of about 50% by mass or less, preferably 5% by mass to 35% by mass.

Surfactants-

In the present invention, the detection agent may contain a surfactant.

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, in particular, in the detection of plasma or the like, it is preferable to use at least one selected from the group consisting of nonionic surfactants and cationic surfactants.

This promotes the discoloration of the detection component and improves the detection sensitivity of the detection component.

Examples of the nonionic surfactant include at least one selected from the group consisting of the following (1) to (4): (1) alkylene glycol derivatives (for example, polyethylene glycol (for example, trade name "PEG 2000" manufactured by sanyo chemical industry corporation), polyethylene glycol-polypropylene glycol copolymers (for example, trade name "Epa (EPAN) 710" manufactured by first industrial pharmaceutical industry corporation), polyoxyalkylene alkyl ethers (for example, trade name "emargine (EMULGEN) 109P" manufactured by kaowang corporation), polyolefin glycol monofatty acid esters, and the like); (2) a polyglycerol derivative; (3) examples of the alkylene glycol glycerol derivative include, but are not particularly limited to, fatty acid polyoxyalkylene glycerol derivatives (for example, "UNIOX GM-30 IS" trade name manufactured by japanese oil corporation), and (4) acetylene glycol derivatives (for example, "sarfenal 104H" manufactured by AIR PRODUCTS JAPAN).

When the detection agent contains a nonionic surfactant, the content of the nonionic surfactant can be appropriately determined depending on the type of the nonionic surfactant, the type of the detection component used, and the like. For example, the content of the detection agent may be about 0.1 to 10% by mass, preferably about 0.5 to 5% by mass, in consideration of the storage stability and the discoloration-promoting effect of the detection agent.

Examples of the cationic surfactant include at least one selected from the group consisting of the following (1) to (4): (1) tetraalkylammonium salts (e.g., alkyltrimethylammonium salts (e.g., behenyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.), dialkyldimethylammonium salts, etc.); (2) isoquinolinium salts (e.g., lauryl isoquinoline bromide, etc.); (3) imidazolium salts (e.g., 2-chloro-1, 3-dimethylimidazolium chloride, etc.); and (4) pyridinium salts (e.g., cetyl pyridinium chloride), and the like, but are not particularly limited.

When the detection agent contains a cationic surfactant, the content of the cationic surfactant can be appropriately determined depending on the kind of the cationic surfactant, the kind of the detection component used, and the like. For example, the content of the detection agent may be about 0.1 to 10% by mass, preferably about 0.5 to 5% by mass, in consideration of the storage stability and the discoloration-promoting effect of the detection agent.

Fillers-

In the present invention, the detection agent may contain a filler. As the filler, a known or commercially available filler can be used, and examples thereof include at least one selected from the group consisting of bentonite, clay, activated clay, talc, alumina, silica gel, calcium carbonate, barium sulfate, resin beads, and the like, but are not particularly limited.

For example, when the detection agent contains a resin, if the detection agent contains silica or the like, a large number of fine cracks are generated on the surface of the detection agent, and thus the detection sensitivity can be improved.

The content of the filler may be appropriately determined within a range not largely impairing the effect of the color tone change by the detection component, depending on the type of the filler and the type of the detection component used. For example, the content of the detection agent may be about 0.1 to 10% by mass, preferably about 0.5 to 5% by mass, in consideration of the storage stability and the discoloration-promoting effect of the detection agent.

Colour change retarders

In the present invention, a color change retarder may be contained in the detection agent in order to retard the color change of the detection agent. As the color tone change retarder, for example, a color tone change retarder having a function of inhibiting contact between plasma or the like and the detection component can be used.

Examples of the color change retarder include an absorber selected from the group consisting of known or commercially available ion absorbers, radical absorbers, ozone absorbers, and ultraviolet absorbers which absorb plasma and the like; at least one member selected from the group consisting of a shielding agent (for example, the resin, the filler, and the like) for shielding a component to be detected from plasma, but is not particularly limited.

The content of the color tone change retarder may be appropriately determined within a range not largely impairing the effect of color tone change by the detection component, depending on the retardation effect of desired color tone change, the composition of the detection agent, and the like. For example, the content of the detection agent may be about 0% by mass to about 10% by mass.

Color tone change promoters

In the present invention, a known or commercially available color tone change promoter may be included in the detection agent in order to promote the color tone change of the detection agent.

Examples of such a color tone change accelerator include at least one selected from the group consisting of a resin having a function of enhancing the detection accuracy (sensitivity) of plasma or the like (for example, a nitrogen-containing resin effective for enhancing the detection of plasma or the like), the surfactant, the filler, and the like, but are not particularly limited.

The content of the color-tone change retarder may be appropriately determined within a range not largely impairing the effect of color-tone change by the detection component, depending on the desired effect of promoting color-tone change, the composition of the detection agent, and the like. For example, the content of the detection agent may be about 0% by mass to about 10% by mass.

-solvent-

In the present invention, the detection reagent may contain a known or commercially available solvent.

The solvent is used to introduce and hold the detection component into the internal space of the structure having the internal space with the opening portion on the surface in the detection layer. The solvent is usually removed by drying or the like, but may be present in a small amount in the detection agent.

Examples of the solvent include at least one selected from the group consisting of water; hydrocarbon solvents (e.g., hexane, cyclohexane, toluene, xylene, benzene, tetrahydronaphthalene, 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 glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, glycerol, trimethylolethane, trimethylolpropane, etc.); ether solvents (e.g., 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, and the like); ester-based solvents (e.g., methyl acetate, ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, glycol diacetate, dimethyl carbonate, vegetable oils, γ -butyrolactone, ε -caprolactone, etc.); ketone solvents (e.g., acetone, methyl ethyl ketone, cyclohexanone, diacetone alcohol, isophorone, acetophenone, etc.); phenol solvents (e.g., phenol, cresol, etc.); fatty acid-based solvents (e.g., palmitic acid, isopalmitic acid, oleic acid, isostearic acid, etc.); carbonate-based solvents (e.g., dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, etc.); amine-based solvents (triethanolamine, tripropanolamine, tributanolamine, N-dimethyl-2-aminoethanol, N-diethyl-2-aminoethanol, etc.), amide-based solvents (e.g., acetamide, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.); halogenated hydrocarbon solvents (for example, carbon tetrachloride, chloroform, trichloroethane, fluorine-containing solvents) and the like, but are not particularly limited.

The solvent may be one capable of dissolving or dispersing the detection component. Preferably a solvent is used in which the detection component is soluble. The solvent is preferably highly purified to reduce the content of metal atoms or halogen atoms. This reduces the content of metal atoms or halogen atoms in the laminate.

When the detection component is introduced and held in the internal space, the amount of the solvent to be used may be determined as appropriate depending on the kind of the solvent, the composition of the detection agent, and the like. The amount is preferably such that the detection component does not precipitate when a solution or dispersion of the detection component is formed. For example, when a solvent capable of dissolving the detection component is used, the concentration of the detection component is preferably 0.1 to 30% by mass, but is not particularly limited.

When the detection component is held in the internal space and then the solvent is also contained, the content of the solvent is set to a range in which the detection agent does not easily flow and the effect of the change in color tone due to the detection component is not impaired. The solvent may be contained in the detection agent in an amount of about 0 to 1 mass%, for example, depending on the composition of the detection agent.

Other additives

In the present invention, the detection agent may optionally contain other additives than the above-mentioned components. In the present invention, the other additive that may be contained in the detection agent includes at least one selected from the group consisting of a leveling agent, an antifoaming agent, and a surface conditioner, but is not particularly limited.

The content of the other additives may be determined as appropriate depending on the composition of the detection agent, etc., within a range not impairing the effect of the color tone change by the detection component. For example, the content of the detection agent may be about 0% by mass to about 5% by mass.

< substrate layer >

The substrate layer may be any layer as long as it can support the detection layer. In consideration of the properties, applications, and the like required for the laminate, at least one selected from the group consisting of inorganic materials, organic materials, and composites thereof may be used, but the invention is not particularly limited thereto.

The thickness of the base material layer is not particularly limited as long as the detection layer can be supported reliably, and may be 0.01mm to 10mm, preferably 0.01mm to 1 mm.

Examples of the inorganic material include at least one selected from the group consisting of a metal or an alloy, a semiconductor material, a ceramic, a glass, quartz, sapphire, concrete, and the like, but are not particularly limited.

Examples of the organic material include at least one selected from the group consisting of resin, paper, synthetic paper, wood, and fibers (nonwoven fabric, woven fabric, other fibrous sheet), leather, and the like, but are not particularly limited.

Examples of the composite include a laminate and a composition obtained by using at least one material selected from the group consisting of the inorganic material and the organic material, but are not particularly limited.

Of these, at least one selected from the group consisting of semiconductor materials, glass, sapphire, resins, and paper is preferably used as the base layer.

Examples of the semiconductor material include materials selected from the group consisting of silicon (Si), germanium (Ge), tellurium (Te), zinc oxide (ZnO), gallium arsenide (GaAs), gallium nitride (GaN), and gallium oxide (Ga)₂O₃) Aluminum nitride (AlN), indium nitride (InN), silicon carbide (SiC), aluminum gallium nitride (AlGaN), indium gallium nitride (InGaN), indium aluminum gallium nitride (InAlGaN), diamond, silicide material (beta-FeSi)₂、MgSi₂、NiSi₂、BaSi₂、CrSi₂、CoSi₂TaSi, etc.), metal oxidationOr a metal oxynitride, but is not particularly limited.

The metal oxide or metal oxynitride may be at least one selected from the group consisting of In-Sn-Ga-Zn-O-based oxides, In-Hf-Ga-Zn-O-based oxides, In-Al-Ga-Zn-O-based oxides, In-Sn-Al-Zn-O-based oxides, In-Sn-Hf-Zn-O-based oxides, In-Hf-Al-Zn-O-based oxides, In-Ga-Zn-O-based oxides, In-Sn-Zn-O-based oxides, In-Al-Zn-O-based oxides, Sn-Ga-Zn-O-based oxides, and metal oxynitride, Al-Ga-Zn-O-based oxide, Sn-Al-Zn-O-based oxide, In-Sn-Zn-O-based oxide, In-Hf-Zn-O-based oxide, In-La-Zn-O-based oxide, In-Ce-Zn-O-based oxide, In-Pr-Zn-O-based oxide, In-Nd-Zn-O-based oxide, In-Sm-Zn-O-based oxide, In-Eu-Zn-O-based oxide, In-Gd-Zn-O-based oxide, In-Tb-Zn-O-based oxide, In-Dy-Zn-O-based oxide, In-Ho-Zn-O-based oxide, In-Er-Zn-O-based oxide, In-La-Zn-O-based oxide, In-Pr-Zn-O-based oxide, In-Nd-Zn-O-based oxide, In-La-Zn-O-based oxide, In-Fe-element, In-element, In-Tm-Zn-O-based oxide, In-Yb-Zn-O-based oxide, In-Lu-Zn-O-based oxide, In-Zn-O-based oxide, Sn-Zn-O-based oxide, Al-Zn-O-based oxide, Zn-Mg-O-based oxide, Sn-Mg-O-based oxide, In-Ga-O-based oxide, Zn-O-N-based oxynitride, In-O-based oxide (indium oxide), Sn-O-based oxide (tin oxide), Zn-O-based oxide (zinc oxide), etc., but are not particularly limited.

Here, for example, the In-Sn-Ga-Zn-O-based oxide refers to an oxide semiconductor including indium (In), tin (Sn), gallium (Ga), zinc (Zn), and oxygen (O), and the composition ratio of each atom is not particularly limited, and may include atoms such as silicon (Si) In some cases.

As the resin, a known or commercially available resin can be used, and examples thereof include at least one selected from the group consisting of polyolefin-based resins (polyethylene, polypropylene, polynorbornene, and the like); a polyvinyl chloride resin; vinylidene chloride-based resins, fluorine-based resins, polyester-based resins (polyethylene terephthalate, polyethylene naphthalate, etc.); a polystyrene-based resin; a polyimide-based resin; a polyamide resin; a polyamide imide resin; a polysulfone-based resin; a polythioether resin; a polyether ketone resin; a polyether resin; a polyurethane resin; a polycarbonate-based resin; an acrylic resin; an acrylonitrile-butadiene-styrene (ABS) resin, but is not particularly limited.

Preferably, at least one selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polyethylene resins, polypropylene resins, polynorbornene resins, polyamide resins, polyamideimide resins, polyimide resins, polycarbonate resins, acrylic resins, and the like is used.

For example, when the laminate is used as an indicator of an apparatus for manufacturing a semiconductor, the substrate is preferably silicon, gallium arsenide, or silicon carbide.

For example, when the laminate is used as an indicator of an apparatus 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 an apparatus for manufacturing a semiconductor laser, 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 base material is preferably silicon carbide, gallium nitride, silicon, or the like.

For example, when the laminate is used as an indicator of an apparatus for manufacturing a solar cell, the substrate is preferably silicon, glass, germanium, or the like.

For example, in the case where the laminate is used as an indicator for 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 an apparatus 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 substrate 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 may be less than 5.0 mass ppm, for example, less than 1.0 mass ppm. Preferably less than 0.5 mass ppm, more preferably less than 0.1 mass ppm, still more preferably less than 1 mass ppt, and most preferably less than 0.5 mass ppt.

Here, the "metal atom" refers to an atom other than hydrogen, carbon, nitrogen, oxygen, silicon, fluorine, chlorine, bromine, iodine, and a rare gas.

The detection layer and the base material layer are composed of components not containing a metal atom so that the content of each metal atom in the laminate is less than 5.0 mass ppm, for example, less than 1.0 mass ppm. Further, all components (including a solvent and the like) related to the laminate are not allowed to contain a metal atom, and a substance containing a metal atom contained as an impurity is removed by refining. Further, in the production step, it is preferable not to use a tool or the like which causes contamination (contamination) of metal atoms.

In the present invention, the content of each metal atom in each material constituting the detection layer and the base material layer is measured by ICP-MS (high frequency Inductively Coupled Plasma Mass Spectrometry/Inductively Coupled Plasma Mass Spectrometry) or the like, and if the content is less than 5.0 Mass ppm, the content of each metal atom in the laminate is less than 5.0 Mass ppm.

Further, the indicator including the laminate of the present invention is introduced into a treatment apparatus together with a material to be treated, and is subjected to a treatment such as a plasma treatment. Then, the metal atoms on the surface of the material to be treated introduced into the treatment apparatus are collected by hydrofluoric acid or the like, and the content of the metal atoms is measured by ICP-MS or the like, and if the content is less than 5.0 mass ppm, the content of the metal atoms in the laminate may be less than 5.0 mass ppm.

When the content of each metal atom in the laminate is less than 5.0 mass ppm, for example, less than 1.0 mass ppm, contamination of the object to be treated and the metal atoms in the manufacturing apparatus can be prevented when the laminate is used as an indicator used in the manufacturing apparatus for electronic components.

Thereby, an indicator that can be used particularly in the manufacturing step of a semiconductor electronic component in which the presence of metal atoms is not desired (particularly, the etching treatment step in the first half process) can be obtained.

< content of each halogen atom >

In the present invention, the content of each halogen atom in the laminate may be less than 30 mass ppm, for example, less than 5 mass ppm. Preferably less than 1 ppm by mass, more preferably less than 0.5 ppm by mass, and most preferably less than 1 ppt.

In order to make the content of each halogen atom in the laminate less than 30 mass ppm, for example less than 5 mass ppm, it is preferable that the detection layer and the base material layer are made of a material containing no halogen atom. In addition, as for all components (including a solvent and the like) related to the laminate, it is preferable to use a substance containing no halogen atom and remove a substance containing a halogen atom as an impurity by purification. Further, it is preferable to use a method or the like in which a tool or the like that generates contamination of halogen atoms is not used in the production step.

In the present invention, the halogen atom content of each material and base layer constituting the detection layer is measured by combustion ion chromatography, ICP-MS (high frequency Inductively Coupled Plasma Mass Spectrometry), or the like, and if the halogen atom content is less than 30 Mass ppm, the halogen atom content in the laminate is less than 30 Mass ppm.

Further, the indicator including the laminate of the present invention is introduced into a treatment apparatus together with a material to be treated, and is subjected to a treatment such as a plasma treatment. Then, the halogen atoms on the surface of the material to be treated introduced into the treatment apparatus are collected and the content of each halogen atom is measured by combustion ion chromatography, ICP-MS, or the like, and if each is less than 30 mass ppm, the content of each halogen atom in the laminate may be less than 30 mass ppm.

When the content of each halogen atom in the laminate is less than 30 mass ppm, for example, less than 5 mass ppm, contamination of the object to be treated and the halogen atom in the manufacturing apparatus can be prevented when the laminate is used as an indicator used in the manufacturing apparatus of the electronic component.

Thereby, an indicator that can be used particularly in the manufacturing step of a semiconductor electronic component in which the presence of halogen atoms is not desired (particularly, the etching treatment step in the first half process) can be obtained.

< layer Structure >

The laminate of the present invention may have not only a detection layer and a base layer for detecting plasma or the like to change color tone but also a non-detection layer for detecting plasma or the like to prevent color tone from changing.

The detection layer, the base layer, and the non-detection layer may be laminated in any order.

The detection layer and the non-detection layer may be formed as one layer or as multiple layers, respectively. In addition, the color-changing layers may be laminated with each other or with non-color-changing layers. In this case, the detection layers may be of the same composition as each other or may be of different compositions from each other, and the non-color-changing layers may be of the same composition as each other or may be of different compositions from each other.

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 formed partially. In these cases, in particular, in order to ensure a change in color tone of the detection layer, the detection layer and the non-detection layer may be formed such that a part or all of at least one detection layer is exposed to plasma or the like.

In the laminate of the present invention, the color-changing layer and the non-color-changing layer may be combined as desired 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 may be formed to be the same color tone, and the detection layer and the non-detection layer may be formed so that the color difference between the detection layer and the non-detection layer can be recognized by the change in the color tone of the detection layer due to plasma or the like.

Further, the color tone of the detection layer before the color tone change and the color tone of the non-detection layer may be formed to be different, and the detection layer and the non-detection layer may be formed so that the color tone of the detection layer changes by plasma or the like to eliminate the color difference between the detection layer and the non-detection layer.

In particular, the laminate of the present invention is preferably formed with the detection layer and the non-detection layer so that the color difference between the detection layer and the non-detection layer can be recognized by a change in color tone of the detection layer due to plasma or the like.

For example, when the color difference of the color-changing layer can be recognized by the change in color tone of the detection layer due to plasma or the like, the color-changing layer and the non-color-changing layer can be formed so that at least one of characters, patterns, and symbols appears due to the color change of the color-changing layer.

The characters, patterns, and symbols include all information for notifying color change, and these characters and the like can be designed appropriately according to the purpose of use and the like.

In the laminate of the present invention, the detection layer and the non-detection layer may not overlap each other, or the detection layer and the non-detection layer may overlap each other.

In the laminate of the present invention, a detection layer or a non-detection layer may be formed on at least one of the detection layer and the non-detection layer.

For example, if a detection layer having another design is formed on a layer in which the detection layer and the non-detection layer are formed so as not to overlap with each other (referred to as a "detection-non-detection layer"), the boundary between the detection layer and the non-detection layer in the detection-non-detection layer can be substantially indistinguishable, and therefore, more excellent design can be achieved.

In the laminate of the present invention, preferred embodiments of the layer structure include:

(1) a laminate having a detection layer formed adjacent to at least one main surface of a base material layer;

(2) the laminate is formed by forming a non-detection layer and a detection layer on a base material layer in this order, the non-detection layer being formed adjacent to the main surface of the base material layer, and the detection layer being formed adjacent to the main surface of the non-detection layer.

In the laminate of (1), the non-detection layer may be formed adjacent to the main surface of the detection layer.

< shape >

The shape of the laminate of the present invention may be any shape depending on the application.

For example, the substrate may be formed in the same shape as the substrate used in the electronic component manufacturing apparatus.

This makes it possible to use the laminate as a so-called dummy substrate, and to easily detect whether or not the treatment is uniformly applied to the entire substrate.

Here, "the same shape as the substrate used in the electronic component manufacturing apparatus" means not only a case where the substrate is completely the same shape as the substrate used in the electronic component manufacturing apparatus, but also a case where the substrate is substantially the same shape as the substrate used in the electronic component manufacturing apparatus to the extent that the substrate can be placed (embedded) in each electronic component apparatus in which the above-described processing is performed. The same applies to the case where, for example, the difference between the length of the main surface of the laminate and the length of the main surface of the substrate (diameter in the case where the main surface is circular, length in the longitudinal direction and the lateral direction in the case where the main surface is square, rectangular, or the like) is within ± 5.0mm, and the difference between the thickness of the laminate and the thickness of the substrate is within ± 1000 μm or so.

< method for producing laminate >

Examples of the method for producing the laminate include the following methods (1) to (4), but are not particularly limited.

(1) A method of providing a structure having an internal space communicating with the open pore portion of the surface on the base material layer by a known appropriate means, and then applying, impregnating, spraying, or the like a detection agent or a detection agent solution to hold the detection agent in the internal space.

(2) A method of forming a structure having an internal space communicating with the open pore portion of the surface by a known appropriate means, applying, impregnating, spraying or the like a detection agent or a detection agent solution thereon to hold the detection agent in the internal space, and then fixing the structure to the base material layer by a known appropriate means.

(3) And a method in which a composition containing a component for forming a structure, a component for forming an internal space in the structure, the internal space being in communication with the open pore portion of the surface, and the detection agent is provided on the base material layer, and then a treatment for forming an internal space in the structure, the internal space being in communication with the open pore portion of the surface, is performed.

(4) A method of preparing a composition containing a component for forming a structure, a component for forming an internal space in the structure communicating with the open pore portion of the surface, and the detection agent, forming an internal space in the structure communicating with the open pore portion of the surface and holding the detection agent in the internal space, and then fixing the detection agent to the base material layer by a known appropriate means.

In the present invention, the method (1) or (2) is preferable, and the method (1) is more preferable, from the viewpoints of ease of production of the laminate, prevention of mixing of impurities into the laminate, and the like.

In addition, when mixing, dissolving or dispersing, a known stirrer may be used as necessary. In this case, it is preferable that no contamination component from the stirrer is mixed.

For mixing, dissolving or dispersing, a known method can be used. For example, a method of adding a detection component to the solvent, a method of adding a solvent to a detection component, a method of sequentially adding each component constituting a detection agent to the solvent, and the like can be used.

When the detection component is held in the internal space, the solvent may be removed by a known means such as drying, if necessary.

When the structure is provided on the base material layer, the base material layer may be surface-treated as necessary to improve adhesion. The surface treatment may be at least one selected from the group consisting of primer treatment, chemical conversion treatment, plasma treatment, corona treatment, flame treatment, sand blast (sandblast) treatment, and the like, which are well known.

As a means for providing the structure on the base material layer, for example, the following method (1) or (2) can be used, but is not particularly limited.

(1) And coating the solution for preparing the structure on the substrate layer subjected to the surface treatment.

(2) After the structure is prepared in advance, it is bonded to the base material layer using an adhesive or the like.

In the present invention, the method (1) is preferably used from the viewpoints of ease of production of the laminate, prevention of contamination of the laminate with impurities derived from the adhesive, and the like.

< use of laminate >

The laminate of the present invention can be used not only for detecting plasma or the like by measuring a color difference based on the color of the detection layer before treatment, but also as an indicator for detecting the uniformity of treatment of plasma or the like.

For example, the laminate can be used as an indicator in an apparatus for manufacturing an electronic element such as a semiconductor, an LED, a semiconductor laser, a power element, a solar cell, a liquid crystal display, an organic EL display, or a Micro Electro Mechanical System (MEMS).

In the present invention, by measuring the color tone of the detection layer before and after the detection of plasma or the like by using a commercially available colorimeter, L a b color space (further, L a b color space is a color system generally used when representing the color of an object, and is a color system also used in Japanese Industrial Standards (JIS) Z8781-4 or JIS Z8781-5 standardized by the Commission international de L' Eclairage (CIE) in 1976, and is obtained as values of L representing the luminance, and chromaticity a and b representing the hue and the chroma. Using the values of L, a, and b, the following formula Δ E ═ Δ L ═ is given²+(Δa*)²+(Δb*)²]^1/2The color difference Δ E is calculated.

Based on the color difference Δ E, not only the detection of plasma or the like by the detection layer can be measured, but also the in-plane uniformity or the like of plasma or the like in the plane of the detection layer can be quantitatively obtained.

In particular, the in-plane distribution of chromatic aberration (in-plane distribution of discoloration of the detection layer) has a correlation with the flow of plasma or the like. Therefore, it is possible to form an indicator that grasps the in-plane distribution of chromatic aberration, thereby grasping the flow of plasma or the like that is important when manufacturing an electronic component, and evaluating the uniformity in the processing plane in a short time.

The laminate of the present invention is preferably because Δ E can be accurately visually judged to be 0.9 or more, preferably 3.0 or more, when treated with plasma or the like for a predetermined time. The change in color tone after the maximum value of Δ E is shown is preferably less than 3.0 within a predetermined processing time. By forming a laminate body showing such Δ E, it is possible to accurately grasp the treatment by plasma or the like, and it is also easy to grasp the in-plane uniformity or the like.

When the indicator is used, the indicator of the present invention may be placed at a position where the substrate is disposed in each electronic component manufacturing apparatus that performs the above-described processing when manufacturing the electronic component.

For example, the wafer stage, the heater, the vacuum chuck stage, and the like may be horizontally (laterally) disposed, and a wafer boat, and the like may be vertically (vertically) disposed.

If the indicator of the present invention is formed in the same shape as the substrate used in the manufacture of the electronic component, the indicator can be processed or disposed in the same manner as the substrate.

In this case, the indicator placed in the apparatus is exposed to the treatment to change the color tone, and the in-plane uniformity of the treatment can be easily detected.

[ examples ]

The laminate and the indicator of the present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples.

(example 1)

As the base material layer, a silicon substrate used for manufacturing a semiconductor is used.

After the surface treatment of the silicon substrate, a polyamide imide resin solution for forming a porous body was applied to the surface-treated surface and dried, and a polyamide imide resin porous body (a polyamide imide resin porous film) having a thickness of about 20 μm was formed on the surface-treated surface of the silicon substrate. The polyamide imide resin porous body was observed by an electron microscope to have pores having open pores on the surface.

A solution (concentration 2 mass% (example 1)) of c.i. Solvent Violet (Solvent Violet)14 was prepared as a dye containing no carbon, hydrogen, oxygen, and atoms other than nitrogen.

The prepared detection agent solution is applied to and impregnated in the polyamide imide resin porous body, followed by drying, thereby producing a laminate.

The produced laminate was measured for the content of each metal atom, the content of each halogen atom, and the performance as a plasma indicator, as described below.

The results are shown in table 1.

(measurement of the content of each Metal atom)

The contents of metal atoms in the silicon substrate, the polyamide imide resin solution for forming a porous body, and the detection agent solution were measured by ICP-MS (high frequency Inductively Coupled Plasma Mass Spectrometry/Inductively Coupled Plasma Mass Spectrometry), and as a result, the amounts of metal atoms detected were less than 0.5 Mass ppm, respectively.

Therefore, the content of each metal atom in the laminate is less than 0.5 mass ppm.

(measurement of halogen atom content)

The halogen atom content of the silicon substrate, the polyamide imide resin solution for forming a porous body, and the detection agent solution was measured by combustion ion chromatography and ICP-MS (high frequency Inductively Coupled Plasma Mass Spectrometry/Inductively Coupled Plasma Mass Spectrometry), and as a result, the halogen atoms were each detected in an amount of less than 5 Mass ppm.

Therefore, the content of each halogen atom in the laminate is less than 5 mass ppm.

(evaluation of Properties)

The laminate was used as a dummy substrate, a commercial plasma irradiation apparatus was used, and CF was used₄Gas, at gas flow rate: plasma treatment was carried out under conditions of 10cc/min, output 50W, initial pressure 5Pa, and treatment pressure 20 Pa.

For the laminate not subjected to the plasma treatment and the laminate subjected to the plasma treatment for a predetermined time, L, a, and b were measured by a colorimeter, and the color difference Δ E before and after the plasma treatment was obtained. The results are shown in table 1.

(examples 2 to 16)

A laminate was produced in the same manner as in example 1, except that solutions (the concentrations are shown in table 1) of c.i. solvent Red 52, c.i. solvent blue 35, c.i. solvent violet 13, c.i. solvent violet 14, c.i. solvent green 3, and lomagen (Lumogen) F Red (Red)305, which are pigments containing no atoms other than carbon, hydrogen, oxygen, and nitrogen, were used as the detector solutions.

The measurement of the content of each metal atom, the measurement of the content of each halogen atom, and the evaluation of the performance as a plasma indicator were performed on the laminate produced in the same manner as in example 1. The results are shown together in table 1.

Comparative example 1

A laminate was produced in the same manner as in example 1, except that the polyamide imide resin porous body was not coated with or impregnated with the detection agent solution.

The measurement of the content of each metal atom, the measurement of the content of each halogen atom, and the evaluation of the performance as a plasma indicator were performed on the laminate produced in the same manner as in example 1. The results are shown together in table 1.

[ Table 1]

(example 17)

A laminate was produced in the same manner as in example 1, except that a polyimide resin solution for forming a porous body was used instead of the polyimide resin solution for forming a porous body. Thereafter, performance evaluation as a plasma indicator was performed in the same manner as in example 1 except that the treatment time was changed, and the color difference Δ E was obtained. The contents of the metal atom and the halogen atom were measured in the same manner as in example 1. The results are shown in table 2.

(example 18)

A laminate was prepared in the same manner as in example 17, except that ramachot (Lumogen) F Red (Red)305 was used instead of c.i. solvent violet 14. Thereafter, the color difference Δ E was obtained in the same manner as in example 17. The results are shown together in Table 2.

[ Table 2]

(example 19, example 20)

After a surface treatment of a silicon substrate used for manufacturing a semiconductor, a polyimide resin solution for forming a porous body is applied to the surface treated surface and dried. Thus, a porous polyimide resin body (porous polyimide resin coating) having pores with openings on the surface and a thickness of about 20 μm was formed on the surface-treated surface of the silicon substrate.

A 1.0 mass% solution (example 19) and a 0.25 mass% solution (example 20) of ramacho (Lumogen) F Red (Red)305, which are pigments containing no atoms other than carbon, hydrogen, oxygen, and nitrogen, were prepared as the detection agent solutions.

The prepared detection agent solution is applied to and impregnated in the porous polyimide resin body, followed by drying, thereby producing a laminate.

The content of each metal atom, the content of each halogen atom, and the performance of the plasma indicator were measured in the same manner as in example 1 for each of the laminates thus produced.

The results are shown in table 3.

[ Table 3]

As is apparent from tables 1 to 3, depending on the structure having an internal space communicating with the open pore portion of the surface and the type of the dye, it takes time until the color change starts (the amount of plasma irradiation required for the color change is large) when the concentration of the dye in the detector solution is high; if the concentration is low, the discoloration is small.

Further, the indicator including the laminate of the present invention can determine whether or not the treatment is properly performed based on a change in color tone by visual observation. In this case, the sensitivity can be adjusted by adjusting the type and concentration of the dye in the solution of the detection agent, and whether or not the entire treatment object has been uniformly treated can be easily detected by visual inspection.

Further, the indicator including the laminate of the present invention has a small content of metal atoms or halogen atoms. Thus, when performing a process using at least one selected from the group consisting of plasma, ozone, ultraviolet rays, and radical-containing gas, contamination of the object to be processed or the inside of the chamber by the generated contaminant can be avoided.

[ description of symbols ]

1: structural body

2: detection agent

3: substrate layer

4: and (6) detecting the layer.