Standard sample film, method for manufacturing standard sample film, standard sample, sample set, quantitative analysis method, transfer film

Abstract

The present invention provides: a standard sample film or a standard sample, which is used for laser ablation inductively coupled plasma mass spectrometry, the standard sample film or the standard sample containing an organic material and having a small variation in the signal intensity of ions of a metal element according to the measurement positions; a method for producing a standard sample film; a sample set; a quantitative analysis method; and a transfer film. A standard sample film according to the present invention is used for laser ablation inductively coupled plasma mass spectrometry; and this standard sample film contains a polymer, a metal element and an internal standard, while having a maximum height difference in the film thickness of the standard sample film of 0.50 μm or less.

Description

[Technical Field]

[0001] The present invention relates to a standard sample film, a method for producing a standard sample film, a standard sample, a sample set, a quantitative analysis method, and a transfer film. [Background technology]

[0002] Laser ablation inductively coupled plasma mass spectrometry (hereinafter referred to as "LA-ICP-MS") is a method for quantitatively analyzing the elements contained in a sample by irradiating the sample with laser light, causing part of the sample to explode and then analyzing the resulting fine particles or gases using inductively coupled plasma mass spectrometry.

[0003] In recent years, femtosecond lasers have been used in the LA-ICP-MS method (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-136190 Summary of the Invention [Problem to be solved by the invention]

[0005] In the LA-ICP-MS method, in order to determine the concentration of metal elements in a solid sample, it is usually necessary to create a calibration curve using a solid standard sample with a known concentration of the metal element to be measured. On the other hand, conventionally, inorganic materials such as glass and metals have been the mainstream of solid standard samples corresponding to standard samples in the LA-ICP-MS method, and organic standard samples (standard samples composed primarily of organic materials) have been limited.

[0006] Furthermore, when creating a calibration curve for the metal element being measured using a standard sample with the LA-ICP-MS method, if the signal intensity of the ions of the metal element being measured varies depending on the position where the laser light is irradiated on the standard sample, an appropriate calibration curve cannot be created, and the accuracy and precision of the quantitative analysis will decrease. For this reason, it is desirable for the difference in signal intensity depending on the position where the laser light is irradiated on the standard sample to be small. In other words, it is desirable for there to be little variation in signal intensity depending on the measurement position. Furthermore, in the LA-ICP-MS method, when measurements are performed over a long period of time, the signal strength from the measurement target may fluctuate (particularly when the signal strength decreases), and it is desirable to be able to detect such fluctuations in sensitivity. Furthermore, if standard samples can be attached to various materials (inorganic and organic), it will be easy to create thin film standard materials that can be used to standardize substances that require analysis.

[0007] In view of the above-mentioned circumstances, an object of the present invention is to provide a standard sample film for use in laser ablation inductively coupled plasma mass spectrometry, which contains organic matter, has small variations in signal intensity of metal element ions depending on the measurement position, and is capable of detecting fluctuations in sensitivity during measurement by laser ablation inductively coupled plasma mass spectrometry. Another object of the present invention is to provide a standard sample for use in laser ablation inductively coupled plasma mass spectrometry, which contains organic matter, has small variations in signal intensity of metal element ions depending on the measurement position, and allows for detection of fluctuations in sensitivity during measurement by laser ablation inductively coupled plasma mass spectrometry. Another object of the present invention is to provide a method for producing a standard sample membrane, a sample set, a quantitative analysis method, and a transfer film. [Means for solving the problem]

[0008] The present inventors have conducted extensive research into the problems of the prior art and have found that the above problems can be solved by the following configuration.

[0009] (1) A standard sample film used in laser ablation inductively coupled plasma mass spectrometry, polymers, metal elements, and internal standards; A standard sample film in which the maximum height difference of the film thickness is 0.50 μm or less. (2) The standard sample film according to (1), wherein the element concentration variation of the standard sample film determined by the method X described below is 30% or less. (3) A standard sample film according to (1) or (2), in which the average thickness of the standard sample film is 3.5 μm or less. (4) The standard sample film according to any one of (1) to (3), wherein the metal element is derived from a metal salt of an organic acid or a metal salt of an inorganic acid. (5) The standard sample film according to any one of (1) to (4), which contains two or more metal elements. (6) The standard sample film according to any one of (1) to (5), wherein the polymer is a (meth)acrylic polymer. (7) The absolute value of the difference between the SP values ​​of hydrocarbons, metal salts of organic acids, and hydrocarbons is 3.5 MPa. 1 / 2 A method for producing a standard sample film, comprising the step of applying a composition for forming a standard sample film, the composition comprising a polymer having a molecular weight of 1000 or less, an internal standard, and a solvent, to form a standard sample film. (8) The organic acid has a hydrocarbon group; The absolute value of the difference between the SP value of the hydrocarbon group and the SP value of the hydrocarbon is 3.5 MPa 1 / 2 (7) The method for producing a standard sample membrane according to (7), (9) A sample set comprising a plurality of standard sample films according to any one of (1) to (6), Multiple standard sample films contain the same type of metal elements, A sample set in which the concentrations of metal elements in multiple standard sample films are different from each other. (10) A step A of measuring the signal intensity of ions of metal elements obtained from each of the standard sample films according to any one of (1) to (6) above, each having a different concentration of metal element, by laser ablation inductively coupled plasma mass spectrometry; Step B of preparing a calibration curve based on the concentrations of metal elements in the plurality of standard sample films and the signal intensities of the ions of the metal elements in each of the plurality of standard sample films obtained in Step A; A quantitative analysis method using laser ablation inductively coupled plasma mass spectrometry, comprising: a step C of measuring the signal intensity of the ions of the metal element in the measurement sample by laser ablation inductively coupled plasma mass spectrometry using a measurement sample containing the same type of metal element as the metal element in the standard sample film, and determining the concentration of the metal element in the measurement sample based on a calibration curve. (11) a temporary support; A transfer film having a standard sample membrane according to any one of (1) to (6) placed on a temporary support. (12) A standard sample used in laser ablation inductively coupled plasma mass spectrometry, Hydrocarbons, a metal salt of an organic acid; The absolute value of the difference with the SP value of hydrocarbons is 3.5 MPa 1 / 2 a polymer within and an internal standard. (13) The absolute value of the difference from the SP value of hydrocarbons is 2.5 MPa. 1 / 2 The standard sample according to (12), wherein the standard sample is within the range of 0.01 to 0.01. (14) The standard sample according to (12) or (13), wherein the polymer is a (meth)acrylic polymer. (15) The standard sample according to any one of (12) to (14), wherein the hydrocarbons include saturated aliphatic hydrocarbons having 10 or more carbon atoms. (16) The standard sample according to any one of (12) to (15), wherein the hydrocarbon contains paraffin. (17) The standard sample according to any one of (12) to (16), wherein the organic acid has a sulfonic acid group. (18) The standard sample according to any one of (12) to (17), wherein the organic acid has a hydrocarbon group. (19) The standard sample according to any one of (12) to (18), which contains metal salts of two or more organic acids with different metal elements. (20) A sample set comprising a plurality of standard samples according to any one of (12) to (19), Multiple standard samples contain metal salts of the same type of organic acid, A sample set in which the concentrations of metal elements derived from metal salts of the same type of organic acid in multiple standard samples are different from each other. (21) A step 1 of measuring the signal intensity of the ion of the metal element obtained from each of the standard samples according to any one of (12) to (19), each having a different concentration of the metal element derived from the metal salt of an organic acid, by laser ablation inductively coupled plasma mass spectrometry; Step 2: creating a calibration curve based on the concentrations of metal elements derived from metal salts of organic acids in the plurality of standard samples and the signal intensities of the ions of the metal elements in each of the plurality of standard samples obtained in step 1; and (3) using a measurement sample containing the same type of metal element as the metal element derived from the metal salt of an organic acid in the standard sample, measuring the signal intensity of the metal element ion by laser ablation inductively coupled plasma mass spectrometry, and determining the concentration of the metal element in the measurement sample based on a calibration curve. (22) a temporary support; A transfer film having a sample film made of the standard sample according to any one of (12) to (19) placed on a temporary support. [Effects of the Invention]

[0010] According to the present invention, there is provided a standard sample film for use in laser ablation inductively coupled plasma mass spectrometry, which contains organic matter, has small variations in signal intensity of metal element ions depending on the measurement position, and can detect fluctuations in sensitivity during measurement by laser ablation inductively coupled plasma mass spectrometry. Furthermore, the present invention can provide a standard sample for use in laser ablation inductively coupled plasma mass spectrometry, which contains an organic substance, has small variations in signal intensity of metal element ions depending on the measurement position, and allows for detection of fluctuations in sensitivity during measurement by laser ablation inductively coupled plasma mass spectrometry. The present invention also provides a method for producing a standard sample film, a sample set, a quantitative analysis method, and a transfer film. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic diagram for explaining the depth profile of secondary ion intensity of metal elements detected by analyzing the components in the depth direction of a standard sample film by time-of-flight secondary ion mass spectrometry (TOF-SIMS). [Figure 2] FIG. 2 is a schematic diagram showing an example of a standard sample film to be measured in FIG. 1. [Figure 3] FIG. 1 is a schematic diagram for explaining the procedure for irradiating a standard sample film with laser light. [Figure 4] FIG. 1 is a schematic diagram of a calibration curve based on the concentration of metal elements and signal intensity. [Figure 5] FIG. 1 is a schematic diagram for explaining a procedure for irradiating a standard sample with laser light. [Figure 6] FIG. 1 is a schematic diagram of a calibration curve based on the concentration of metal elements and signal intensity. [Figure 7] This is a diagram of the calibration curve for 43Ca. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be described in detail below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. First, the terms used in this specification will be explained.

[0013] [First embodiment] The standard sample membrane according to the first embodiment of the present invention is characterized in that it contains a polymer as an organic substance, that the maximum height difference of the film thickness of the standard sample membrane is 0.50 μm or less, and that it contains an internal standard. The present inventors have found that the variation in signal intensity of metal element ions depending on the measurement position is mainly related to the film thickness of the standard sample film. That is, when the maximum height difference of the film thickness of the standard sample film is large, the signal intensity of metal element ions tends to be large in the thick part of the film thickness and small in the thin part of the film thickness, resulting in variation in signal intensity. Therefore, the present inventors have found that the above problem can be solved by adjusting the maximum height difference of the film thickness within a predetermined range. Methods for reducing the maximum difference in film thickness include, for example, a method using a predetermined binder (specific polymers and hydrocarbons described later) as explained in the second embodiment, a method using a water-soluble polymer and a metal salt of an inorganic acid, and a method using a surfactant. Furthermore, by including an internal standard in the standard sample film, fluctuations in sensitivity during measurement by laser ablation inductively coupled plasma mass spectrometry can be detected.

[0014] In the following, the standard sample membrane of the present invention will first be described in detail, followed by a detailed description of the method for producing the standard sample membrane, the sample set, the transfer film, and the quantitative analysis method.

[0015] <Standard sample film> The standard sample film of the first embodiment of the present invention is a standard sample film used in laser ablation inductively coupled plasma mass spectrometry, which contains a polymer, a metal element, and an internal standard, and the maximum height difference of the film thickness of the standard sample film is 0.50 μm or less. Below, we first provide a detailed description of each component contained in the standard sample film.

[0016] (polymer) The type of polymer contained in the standard sample membrane is not particularly limited, but examples include water-insoluble and water-soluble polymers. A water-soluble polymer is a polymer that dissolves in an amount of 1 g or more when dried at 105°C for 2 hours and then dissolved in 100 g of water at 25°C. A water-insoluble polymer refers to a polymer other than the water-soluble polymers mentioned above. As will be described later, when preparing a standard sample membrane, it is preferable to use a water-soluble polymer when water is used, and it is preferable to use a water-insoluble polymer when an organic solvent is used.

[0017] Examples of the polymer include (meth)acrylic polymers, styrene polymers, olefin polymers, polyester polymers, polyamide polymers, and cellulose polymers. The (meth)acrylic polymer is a general term for acrylic polymers and methacrylic polymers. The (meth)acrylic polymers, styrene polymers, olefin polymers, polyester polymers, and polyamide polymers exemplified above are often water-insoluble polymers.

[0018] A styrene-based polymer is a polymer that contains repeating units derived from styrene in the largest amount by mass ratio among all repeating units. The content of repeating units derived from styrene in the styrene-based polymer is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total repeating units contained in the styrene-based polymer, in order to further suppress the variation in signal intensity depending on the measurement position of the standard sample film (hereinafter simply referred to as "the point where the effect of the present invention is better"). There is no particular upper limit, but it can be 100% by mass.

[0019] A (meth)acrylic polymer is a polymer containing repeating units derived from an alkyl acrylate and / or an alkyl methacrylate in the largest mass ratio among all repeating units. The (meth)acrylic polymer preferably contains a repeating unit derived from a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms, in terms of achieving better effects of the present invention. The number of carbon atoms in the alkyl group in the (meth)acrylic acid alkyl ester is preferably 2 to 14, more preferably 3 to 10, and even more preferably 3 to 8, in terms of better effects of the present invention. The (meth)acrylic acid alkyl ester is a general term for acrylic acid alkyl ester and methacrylic acid alkyl ester.

[0020] Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, 1,3-dimethylbutyl acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, and n-tetradecyl (meth)acrylate.

[0021] The content of repeating units derived from a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms in the (meth)acrylic polymer is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total repeating units contained in the (meth)acrylic polymer, in order to achieve better effects of the present invention. There is no particular upper limit, but it can be 100% by mass.

[0022] An olefin polymer is a polymer that contains repeating units derived from olefins in the largest amount by mass among all repeating units. Examples of olefins include ethylene and propylene. A polyester polymer is a polymer synthesized by dehydration condensation of a polycarboxylic acid (dicarboxylic acid) and a polyalcohol (diol) to form an ester bond. Examples of polyester polymers include polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. Polyamide polymers are polymers made of many monomers linked together by amide bonds. Examples of polyamide polymers include nylon 6 and nylon 6,6. Cellulosic polymers are polymers that have a cellulose backbone, and examples of such polymers include diacetyl cellulose and triacetyl cellulose.

[0023] The water-soluble polymer is preferably a polymer containing a repeating unit having at least one structure selected from the group consisting of a structure containing a hydroxy group, a structure containing a pyrrolidone ring, and a structure containing an oxyalkylene group.

[0024] Examples of water-soluble polymers containing hydroxy groups include gum arabic, soy gum, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyhydroxyethylated cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, glyoxalated hydroxypropyl methylcellulose, hydroxypropyl methylcellulose phthalate, methylcellulose, and polyvinyl alcohol.

[0025] Examples of water-soluble polymers containing a pyrrolidone ring include polyvinylpyrrolidone and copolymers of vinylpyrrolidone and vinyl acetate. Examples of water-soluble polymers containing an oxyalkylene group include polyalkylene glycols such as polyethylene glycol and polyoxyethylene polyoxypropylene glycol (also called polyoxyethylene-polyoxypropylene condensates), and polyoxyalkylene monoalkyl or aryl ethers such as poly(ethylene glycol) methyl ether and poly(ethylene glycol) phenyl ether.

[0026] Among these, the water-soluble polymer is preferably a water-soluble polymer containing a pyrrolidone ring or a polysaccharide, more preferably a water-soluble polymer containing a pyrrolidone ring, and even more preferably polyvinylpyrrolidone. The polysaccharides include polysaccharides, polysaccharide derivatives, and alkali metal salts thereof. The cellulose-based polymer is preferably a compound in which at least a portion of the hydroxyl groups of cellulose has been substituted with at least one selected from the group consisting of alkyl groups and hydroxyalkyl groups.

[0027] The polymer content in the standard sample membrane is not particularly limited, but in terms of achieving better effects of the present invention, it is preferably 40% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the standard sample membrane. The upper limit is not particularly limited, but it is often less than 99% by mass, and is preferably 98% by mass or less, more preferably 97% by mass or less. The polymers may be used singly or in combination of two or more. When two or more polymers are used in combination, the total content of the polymers is preferably within the above range.

[0028] (metallic element) The metal element is not particularly limited, and examples thereof include known metal elements. Examples of metal elements include metal elements in Groups 1 to 12 of the periodic table excluding hydrogen, and metal elements in Groups 13 to 16 of the periodic table. Metal elements in Group 13 of the periodic table include aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). Metal elements in Group 14 of the periodic table include germanium (Ge), tin (Sn), and lead (Pb). Metal elements in Group 15 of the periodic table include antimony (Sb) and bismuth (Bi). Metal elements in Group 16 of the periodic table include polonium (Po). As the metal element, aluminum, sodium (Na), magnesium (Mg), barium (Ba), calcium (Ca), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), molybdenum (Mo), cadmium (Cd), and lead (Pb) are preferred in terms of providing a better effect of the present invention. In the standard sample film, the metal elements may be ionized.

[0029] The metal elements may be used alone or in combination of two or more. When a standard sample film contains two or more different metal elements, the signal intensities of the two or more metal elements can be obtained using laser ablation inductively coupled plasma mass spectrometry, and a calibration curve for multiple metal elements can be created using a single standard sample film. The number of types of metal elements contained in the standard sample film is not particularly limited, but is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. There is no particular upper limit, but it is often 40 or less.

[0030] The content of metal elements in the standard sample film is not particularly limited, but is preferably 0.1 to 1000 ppm by mass, more preferably 0.1 to 300 ppm by mass, relative to the total mass of the standard sample, in order to obtain a better effect of the present invention. When two or more different metal elements are used in combination, the concentration of each metal element is preferably within the above range.

[0031] The metal elements in the standard sample film are preferably derived from metal salts of organic acids or metal salts of inorganic acids. In other words, by using a metal salt of an organic acid when producing a standard sample membrane, the standard sample membrane contains a metal element derived from the metal salt of the organic acid. In other words, in this case, the standard sample membrane contains a metal salt of an organic acid. Note that the metal salt of the organic acid may be separated into an anion and a cation in the standard sample membrane. Furthermore, by using a metal salt of an inorganic acid when producing the standard sample membrane, the standard sample membrane contains a metal element derived from the metal salt of the inorganic acid. In other words, in this case, the standard sample membrane contains a metal salt of the inorganic acid. Note that the metal salt of the inorganic acid may be separated into anions and cations in the standard sample membrane.

[0032] The metal salt of an organic acid is a salt containing an organic acid and a metal element. Examples of the metal element contained in the metal salt of an organic acid include the metal elements described above. Examples of organic acids include compounds having an acid group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phenolic hydroxyl group, and a thiol group. Of these, compounds having a sulfonic acid group are preferred. The organic acid preferably has a hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group), more preferably has an aliphatic hydrocarbon group, and even more preferably has an alkyl group. The number of carbon atoms in the hydrocarbon group (aliphatic hydrocarbon group, alkyl group) is not particularly limited, but is preferably 5 or more. The organic acid may have both an aliphatic hydrocarbon group and an aromatic hydrocarbon group. As the organic acid, the hydrocarbons having the above acid groups are preferred, and alkylarylsulfonic acids are more preferred, in that the effects of the present invention are more excellent.

[0033] A metal salt of an inorganic acid is a salt containing an inorganic acid and a metal element. Examples of the metal element contained in the metal salt of an inorganic acid include the metal elements described above. Inorganic acids include, for example, hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.

[0034] (internal standard) The internal standard is not particularly limited, and may be any component that can function as an internal standard in the LA-ICP-MS method. As the internal standard, various elements or compounds may be used. The internal standard is preferably an element that is not the target of analysis, that is, an element that is not contained in the measurement sample and is not the target of analysis. Furthermore, the internal standard is preferably an element that does not have spectral interference and behaves in the same manner as the element to be analyzed in plasma. The internal standard is preferably an element of a different kind from the metal elements contained in the standard sample film described above. Specific examples of elements preferred as internal standards include Bi (bismuth), Ho (holmium), In (indium), Rh (rhodium), Sc (scandium), Tb (terbium), and Y (yttrium). If the internal standard is an element, it may be ionized.

[0035] When preparing the standard sample film described below, a commercially available standard solution (e.g., a metal standard solution) may be used as a raw material for preparing the standard sample film-forming composition. For example, the metal standard solution contains a metal that can function as an internal standard.

[0036] The content of the internal standard in the standard sample film is not particularly limited, but is preferably 0.01 to 100 ppm by mass, more preferably 0.1 to 10 ppm by mass, relative to the total mass of the standard sample film. For example, when the internal standard is a specific metal element, the content of the metal element is preferably within the above range.

[0037] As will be described later, in a sample set consisting of a combination of multiple standard sample films, it is preferable that the content of the internal standard in the included standard sample films is similar among the standard sample films. Specifically, it is preferable that the absolute value of the difference in the content of the internal standard among the standard sample films is within 0.01 mass ppm. The lower limit of the absolute value of the difference in content is not particularly limited, but can be 0 mass ppm.

[0038] (Other ingredients) The standard sample film may contain components other than the above-mentioned polymer, metal element, and internal standard, as long as the effects of the present invention are not impaired. The other components include, for example, hydrocarbons. The type of hydrocarbon is not particularly limited, and examples include known hydrocarbons. The hydrocarbon may be a saturated hydrocarbon or an unsaturated hydrocarbon, with saturated hydrocarbons being preferred in that the effects of the present invention are more excellent. The hydrocarbon may be an aliphatic hydrocarbon or an aromatic hydrocarbon, with aliphatic hydrocarbons being preferred in that the effects of the present invention are more excellent. The hydrocarbon may be linear or branched, or may have a cyclic structure. The number of carbon atoms in the hydrocarbon is not particularly limited, and from the viewpoint of achieving superior effects of the present invention, it is preferably 5 or more, more preferably 10 or more, even more preferably 15 or more, and particularly preferably 20 or more. There is no particular upper limit, but it is often 40 or less, and more often 30 or less.

[0039] As the hydrocarbon, aliphatic saturated hydrocarbons are preferred, aliphatic saturated hydrocarbons having 10 or more carbon atoms are more preferred, and paraffin is even more preferred, in terms of achieving better effects of the present invention. In this specification, paraffin means an aliphatic saturated hydrocarbon having 15 or more carbon atoms.

[0040] The SP (Solubility Parameter) value of the hydrocarbon is not particularly limited, but in order to obtain a more excellent effect of the present invention, it is preferably 14 to 18 MPa. 1 / 2is preferable, and 15 to 17 MPa 1 / 2 is more preferred. The SP value is calculated as follows: Using a calculation program (HSPiP, ver. 4.1.07), the molecular structure of each material is input, and the HSP value (δ D , δ P , δ H ) is calculated. Next, calculate the SP value using the following formula. Formula SP value = (δ D 2 +δ P 2 +δ H 2 ) 1 / 2

[0041] The hydrocarbons may be used alone or in combination of two or more.

[0042] In addition, when the standard sample film contains a metal salt of an organic acid having a hydrocarbon group (when the standard sample film contains a metal element derived from a metal salt of an organic acid), the absolute value of the difference between the SP value of the hydrocarbon group of the organic acid and the SP value of the hydrocarbon is 3.5 MPa, which is a point where the effect of the present invention is more excellent. 1 / 2 It is preferable that the pressure is within 2.0 MPa. 1 / 2 It is more preferable that the pressure is within 1.0 MPa. 1 / 2 The lower limit of the absolute value of the difference is not particularly limited, but it is more preferably within 0 MPa. 1 / 2 Examples include:

[0043] The standard sample film may contain a surfactant. When the standard sample film contains a surfactant, the type of surfactant is not particularly limited, and examples include known surfactants, such as hydrocarbon-based surfactants, fluorine-based and / or silicon-based surfactants (specifically, fluorine-based surfactants, silicon-based surfactants, and surfactants having both fluorine atoms and silicon atoms), with fluorine-based and / or silicon-based surfactants (specifically, fluorine-based surfactants, silicon-based surfactants, and surfactants having both fluorine atoms and silicon atoms) being preferred. By including a surfactant in the standard sample film, coating defects (cracking, coating streaks, surface unevenness) can be suppressed when the film is coated over a large area. Examples of hydrocarbon surfactants include acetylene surfactants such as Olfine D-10A, D-10PG, E1004, E1010, E1020, E1030W, PD-001, PD-002W, PD-004, PD-005, EXP.4001, EXP.4200, EXP.4123, EXP.4300, WE-001, WE-002, and WE-003 (manufactured by Nissin Chemical Industry Co., Ltd.). Examples of the fluorine-based and / or silicone-based surfactant include the surfactants described in paragraph

[0276] of the specification of US Patent Application Publication No. 2008 / 0248425. Furthermore, surfactants other than fluorine-based and / or silicon-based surfactants described in paragraph

[0280] of US Patent Application Publication No. 2008 / 0248425 can also be used. Further, for example, Megafac F-251, F-253, F-410, F-477, F-551, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-565, F-568, F-569, F-570, F-572, F-575, F-576, R-40, R-40-LM, R-41 (manufactured by DIC Corporation), FC4432 (manufactured by Sumitomo 3M Limited), Surflon S-221, S-231, S-232, S-233, S Also usable are S-241, S-242, S-243, S-420, S-431, S-386, S-611, S-647, S-651, S-653, S-656, and S-693 (manufactured by AGC Seimi Chemical Co., Ltd.), PF-136A, PF-156A, and PF-151N (manufactured by OMNOVA), and Futergent 100, 100C, 150, 150CH, 251, 212M, 215M, 250, 222F, 245F, 208G, DFX-18, 710FL, 710FM, 710FS, 610FM, and 683 (manufactured by Neos Corporation). These surfactants may be used alone or in combination of two or more. When the standard sample film contains a surfactant, the content of the surfactant is preferably 0.0001 to 2 mass %, more preferably 0.0005 to 1 mass %, relative to the standard sample film.

[0044] (Standard sample film shape) The maximum difference in film thickness of the standard sample film is 0.50 μm or less, and from the viewpoint of obtaining a more excellent effect of the present invention, it is preferably 0.30 μm or less, more preferably 0.20 μm or less, and even more preferably 0.10 μm or less. There is no particular lower limit, but it is often 0.001 μm or more. The maximum height difference of the film thickness of the standard sample film is measured by the following method. The film thickness of the standard sample film is calculated using a stylus step gauge. The measurement distance is 3 mm, and the scanning speed is 0.02 mm / sec. The 3 mm straight line where the first measurement was made is designated as scan line 1, and the second measurement is made at a location 0.2 mm or more away in a direction perpendicular to scan line 1. Similar measurements are then repeated for a total of 10 measurements. Ten measurements (scans) are made, and the maximum and minimum film thickness values ​​for each scan are found. The difference (value A - value B) between the largest value A of the 10 maximum values ​​obtained from the 10 scans and the smallest value B of the 10 minimum values ​​obtained from the 10 scans is taken as the maximum film thickness difference.

[0045] The average thickness of the standard sample film is not particularly limited, but is preferably 3.5 μm or less, more preferably 2.5 μm or less, and even more preferably 2.0 μm or less, from the viewpoint of the effect of the present invention being more excellent. The lower limit of the average thickness is not particularly limited, but is preferably 0.05 μm or more, more preferably 0.1 μm or more, from the viewpoint of measurement accuracy. The average film thickness is determined by measuring the thickness at any 20 points with a stylus-type step gauge and calculating the arithmetic average.

[0046] In order to obtain a more excellent effect of the present invention, the standard sample film preferably has an element concentration variation of 30% or less, more preferably 20% or less, as determined by the following method X. The lower limit is not particularly limited, but may be 0%. Method X: Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is performed at 10 points on the surface of the standard film, from one surface to the other, to obtain a depth profile of the secondary ion intensity of the metal element. The first position is defined as a position 20% of the total thickness of the standard film, from one surface to the other, and the second position is defined as a position 80% of the total thickness of the standard film, from one surface to the other. The sum of the secondary ion intensities of the metal element from the first position to the second position at each point is calculated, and the relative standard deviation of the resulting 10 secondary ion intensities is calculated to represent the element concentration variation. The above requirements will be explained in detail below with reference to the drawings. Note that the drawings shown below are drawn to a different scale from the actual data in order to make the invention easier to understand.

[0047] Fig. 1 shows an example of a profile (depth profile of secondary ion intensity of metal element) obtained by performing TOF-SIMS from one surface of a standard sample film to the other surface and analyzing the secondary ion intensity of metal element in the depth direction of the standard sample film. Note that in this specification, the depth direction refers to the direction (thickness direction) from one main surface of a standard sample film having two main surfaces to the other main surface.

[0048] More specifically, the profile in FIG. 1 corresponds to the result of analyzing the components in the depth direction of the standard sample film 12 by TOF-SIMS while ion sputtering from one surface 12A (the surface of the standard sample film 12 opposite the substrate 10) of the standard sample film 12 placed on the substrate 10 to the other surface 12B (the surface of the standard sample film 12 facing the substrate 10), as shown in FIG. In the depth profile shown in Figure 1, the horizontal axis (the axis extending left and right on the paper in Figure 1) represents the depth relative to one surface of the standard sample film, and the vertical axis (the axis extending up and down on the paper in Figure 1) represents the secondary ion intensity of the metal element. The TOF-SIMS method is specifically described in "Surface Analysis Technology Selection: Secondary Ion Mass Spectroscopy" edited by the Surface Science Society of Japan, published by Maruzen Co., Ltd. (1999).

[0049] 1, the position 0 on the horizontal axis corresponds to the surface 12A of the standard sample film 12, and the position E on the horizontal axis corresponds to the surface 12B of the standard sample film 12. In other words, the range from 0 to E on the horizontal axis corresponds to one surface of the standard sample film 12 to the other surface.

[0050] It is preferable to perform the TOF-SIMS method while irradiating the standard sample film with an ion beam. When analyzing the components of the standard sample film in the depth direction by TOF-SIMS while irradiating it with an ion beam, a series of operations is repeated: first, component analysis is performed in a surface depth region of 1 to 2 nm, then the sample is excavated further in the depth direction by 1 to several hundred nm, and component analysis is performed in the next surface depth region of 1 to 2 nm.

[0051] As shown in Figures 1 and 2, the first position P1 is a position that is 20% of the total thickness of the standard sample film from one surface to the other surface of the standard sample film, and the second position P2 is a position that is 80% of the total thickness of the standard sample film from one surface to the other surface of the standard sample film. More specifically, as shown by the white arrow in Fig. 2, a first position P1 is a position that is 20% of the total thickness T of the standard sample film from the surface 12A toward the other surface 12B of the standard sample film 12, with the surface 12A as the reference. Also, as shown by the black arrow in Fig. 2, a second position P2 is a position that is 80% of the total thickness T of the standard sample film from the surface 12A toward the other surface 12B of the standard sample film 12, with the surface 12A as the reference. Next, the total value of the secondary ion intensity of the metal element from the first position P1 to the second position P2 is calculated. Specifically, the total value of the secondary ion intensity of the metal element from the first position P1 to the second position P2 shown in FIG. 1 is calculated. As shown in Figure 1, the magnitude of the secondary ion intensity near the surface (surface 12A and surface 12B) of the standard sample film may not be stable due to the influence of surface contamination, etc., so the calculation is performed excluding the secondary ion intensity in the region from one surface of the standard sample film to the first position P1 and the region from the other surface of the standard sample film to the second position P2.

[0052] The above calculation of the total secondary ion intensity of the metal elements is performed at 10 points on the surface of the standard sample film, and the total secondary ion intensity of the metal elements at each measurement point (10 points) is determined. The relative standard deviation of the resulting total secondary ion intensity of the 10 metal elements is calculated to determine the element concentration variation (%). The size of each measurement point is 100 μm long x 100 μm wide. When calculating the relative standard deviation, first, the standard deviation calculated from the total value of the secondary ion intensities of the obtained 10 metal elements and the arithmetic mean value of the total value of the secondary ion intensities of the obtained 10 metal elements are calculated. The ratio (%) of the standard deviation to the obtained arithmetic mean value [(standard deviation / arithmetic mean value) × 100] is calculated and used as the element concentration variation.

[0053] When the standard sample film contains multiple types of metal elements, it is preferable that the variation in the element concentration of at least one of the metal elements is within a predetermined range, and it is more preferable that the variation in the element concentration of each of the metal elements is within a predetermined range. In other words, it is more preferable that the variation in the element concentration of all types of metal elements contained in the standard sample film is within a predetermined range.

[0054] (Method of manufacturing standard sample membrane) The method for producing a standard sample film is not particularly limited as long as it can produce a standard sample film exhibiting the above-mentioned characteristics. For example, when a metal salt of an organic acid is used, a method can be used that includes preparing a standard sample film-forming composition containing a polymer (especially a water-insoluble polymer), a metal salt of an organic acid, an internal standard, other components (e.g., hydrocarbons and surfactants) that are used as needed, and an organic solvent, and then applying the resulting standard sample film-forming composition to a substrate to form a standard sample film. When a metal salt of an inorganic acid is used, a method can be used that includes preparing a standard sample film-forming composition containing a polymer (especially a water-soluble polymer), a metal salt of an inorganic acid, an internal standard, other components (e.g., surfactants) that are used as needed, and water or an aqueous solution containing an inorganic acid, and then applying the resulting standard sample film-forming composition to a substrate to form a standard sample film. That is, a method can be used that includes applying a standard sample film-forming composition containing at least a polymer, a source of a metal element, an internal standard, and a solvent to a substrate to form a standard sample film.

[0055] In particular, the absolute value of the difference between the SP values ​​of a hydrocarbon, a metal salt of an organic acid, and the hydrocarbon is 3.5 MPa, which allows for the production of a standard sample membrane with excellent effects of the present invention with good productivity. 1 / 2 Preferably, the method for producing a standard sample film comprises a step of forming a standard sample film by applying a composition for forming a standard sample film containing a polymer having a molecular weight of 100 or less, an internal standard, and a solvent. The metal salts of hydrocarbons and organic acids, and the internal standards are as described above.

[0056] The absolute value of the difference with the SP value of hydrocarbons is 3.5 MPa 1 / 2 A polymer that is within this range (hereinafter also simply referred to as a "specific polymer") has good compatibility with hydrocarbons. The absolute value of the difference between the SP value of the specific polymer and the SP value of the hydrocarbon is 2.5 MPa, which is a point where the effect of the present invention is more excellent. 1 / 2 Preferably within 2.0 MPa 1 / 2 Within 1.5 MPa is more preferable. 1 / 2 Within 1.0 MPa is particularly preferable. 1 / 2 The lower limit of the absolute value of the difference is not particularly limited, but is preferably 0. The SP value of the specific polymer may be within the above range of the absolute value of the difference, but in order to obtain a more excellent effect of the present invention, it is preferable that the SP value is within the range of 15 to 19 MPa. 1 / 2 is preferably 16 to 17 MPa 1 / 2 is more preferred. In addition, when the specific polymer contains a plurality of repeating units, the SP value of each repeating unit is multiplied by the molar ratio of that repeating unit to all repeating units, and the SP value of the specific polymer is calculated by summing the obtained values. A The repeating unit A and the SP value are SP B and repeating unit B, the molar ratio of repeating unit A to all repeating units is 0.2, and the molar ratio of repeating unit B to all repeating units is 0.8, the SP value of the specific polymer is calculated as follows: SP value of a specific polymer = (SP A ×0.2)+(SP B ×0.8)

[0057] The type of the specific polymer is not particularly limited as long as the absolute value of the difference falls within the above range. The specific polymers include (meth)acrylic polymers, styrene polymers, olefin polymers, polyester polymers, and polyamide polymers, with (meth)acrylic polymers and styrene polymers being preferred, and (meth)acrylic polymers being more preferred. Details of each polymer are as explained in the section on polymers contained in the standard sample membrane.

[0058] The content of the specific polymer contained in the standard sample film-forming composition is preferably adjusted to the same content of the polymer as in the standard sample film described above. The content of the metal salt of an organic acid contained in the standard sample film-forming composition is preferably adjusted to the same content of the metal element as in the standard sample film described above. The content of the internal standard contained in the composition for forming the standard sample film is preferably adjusted to the same content of the internal standard as in the standard sample film described above. The content of hydrocarbons contained in the above-mentioned standard sample film-forming composition is preferably 1 to 60 mass %, more preferably 1 to 40 mass %, even more preferably 1 to 20 mass %, and particularly preferably 1 to 10 mass %, relative to the total amount of the specific polymer, the metal salt of the organic acid, and the hydrocarbon, in order to obtain better effects of the present invention.

[0059] The solvent contained in the standard sample film-forming composition may be any solvent capable of dissolving the various components described above. Examples of the solvent include organic solvents and water, with organic solvents being preferred. Examples of the organic solvent include ketone solvents, alcohol solvents, ether solvents, hydrocarbon solvents, and ester solvents, with ketone solvents or ester solvents being preferred. Specific examples of the solvent include methyl ethyl ketone, butyl acetate, toluene, hexane, acetone, and chloroform. The concentration of the solvent in the composition for forming the standard sample film is not particularly limited, but in order to obtain a film with a highly uniform thickness, the content of the solvent relative to the total mass of the composition is preferably 60 to 99 mass%, more preferably 70 to 99 mass%.

[0060] The method for applying the standard sample film-forming composition onto the substrate is not particularly limited, and includes known methods (for example, spin coating, dip coating, inkjet method, etc.). The type of substrate is not particularly limited, and examples thereof include quartz, glass substrates, and silicon wafers, which have excellent flatness. After the standard sample film-forming composition is applied to the substrate, a drying treatment may be carried out to remove the solvent in the coating film, if necessary. For example, a heating treatment may be used as the drying method. During the drying treatment, hydrocarbons may be removed by volatilization.

[0061] The substrate may be a temporary support. When the substrate is a temporary support, a transfer film is formed having the temporary support and the standard sample film placed on the temporary support. The standard sample film can be placed on the object to be transferred by contacting the standard sample film on the temporary support of this transfer film with the object to be transferred and then peeling off the temporary support. Using such a transfer film, the standard sample film can be placed on objects to be transferred of various shapes.

[0062] Examples of temporary supports include supports whose surfaces are treated with a release agent (such as a silicone-based release agent) and supports that themselves have releasability. The temporary support is preferably a polymer substrate. Examples of materials that can be used to form the temporary support include cellulose-based polymers, (meth)acrylic-based polymers, styrene-based polymers, olefin-based polymers, polyester-based polymers, and polyamide-based polymers. There are no particular restrictions on the water contact angle of the temporary support on the side where the standard sample film is placed, but it is preferably 100 degrees or more in terms of better transferability of the standard sample film. The water contact angle can be measured by the sessile drop method described in JIS R 3257:1999. Specifically, the water contact angle is measured using a contact angle meter FTA1000 (software Fta32) (manufactured by First Ten Angstroms) at a room temperature of 25°C and a humidity of 50%. More specifically, 1.5 μl of pure water is dropped onto the surface of a horizontal temporary support, and the radius r and height h of the pure water droplet on the surface of the temporary support are determined after 30 seconds have passed. The water contact angle θ is then calculated using the formula θ=2arctan(h / r).

[0063] <Sample set> The sample set according to the first embodiment of the present invention is a set of a combination of multiple standard sample films, each containing the same type of metal element, but with different concentrations of the same type of metal element. In laser ablation inductively coupled plasma mass spectrometry, a calibration curve showing the relationship between the concentration of a specific metal element to be measured and the signal intensity is usually created using multiple standard sample films containing the same metal element at different concentrations. In other words, the calibration curve can be easily created by using the above sample set. The number of standard sample films in a sample set is not particularly limited, but preferably includes two or more, more preferably five or more, standard sample films with different metal element concentrations. There is no particular upper limit, but the number is often 10 or less.

[0064] <Quantitative analysis method> By using the standard sample film according to the first embodiment of the present invention, it is possible to analyze the content of metal elements contained in a measurement sample whose content of metal elements is unknown. In the quantitative analysis method of the first embodiment of the present invention, a known laser ablation inductively coupled plasma mass spectrometer can be used. Among them, it is preferable to use a femtosecond laser ablation inductively coupled plasma mass spectrometer. An example of such a spectrometer is the Jupiter solid nebulizer (manufactured by ST Japan). The laser ablation inductively coupled plasma mass spectrometer used in the first embodiment is the same as the laser ablation inductively coupled plasma mass spectrometer used in the second embodiment described later. Details of the apparatus will be explained in the second embodiment.

[0065] The quantitative analysis method includes steps A to C described below. Step A: Using a plurality of standard sample films of the present invention having different concentrations of metal elements, the signal intensity of the ions of the metal elements obtained from each standard sample film is measured by laser ablation inductively coupled plasma mass spectrometry. Step B: A step of creating a calibration curve based on the concentrations of metal elements in the plurality of standard sample films and the signal intensities of the ions of the respective metal elements in the plurality of standard sample films obtained in Step A. Step C: Using a measurement sample containing the same type of metal element as the metal element in the standard sample film, the signal intensity of the metal element ion in the measurement sample is measured by laser ablation inductively coupled plasma mass spectrometry, and the concentration of the metal element in the measurement sample is determined based on the calibration curve. The procedure for each step will be described in detail below.

[0066] (Process A) Step A is a step of measuring the signal intensity of the ions of the metal elements obtained from each of the standard sample films of the present invention, which have different concentrations of the metal elements, by laser ablation inductively coupled plasma mass spectrometry. In this step, a standard sample film with a known concentration of the metal element is used, and the signal intensity obtained from the standard sample film is measured. As described above, in this step A, the signal intensity is measured using a known laser ablation inductively coupled plasma mass spectrometer.

[0067] In step A, laser light may be irradiated onto multiple positions (locations) on the standard sample film, the signal intensity of the metal element ions at each position may be measured, the signal intensities obtained may be arithmetically averaged, and the average signal intensity obtained may be used as the signal intensity obtained from the standard sample film. More specifically, as shown in Fig. 3, a laser beam is irradiated onto each of a plurality of regions 14 in the standard sample film 12. In Fig. 3, the number of regions 14 is nine, but there is no particular limit to this number. Usually, there are five to twenty regions. The size of the region 14 is not particularly limited, but is often 0.1 to 1.0 mm in length and 0.1 to 1.0 mm in width. The distance between the regions 14 is not particularly limited, but is usually about the length of one side of the regions 14 .

[0068] There are no particular limitations on the method of irradiating the standard sample film with laser light. The wavelength of the laser light to be irradiated is not particularly limited, but is preferably 200 to 300 nm, more preferably 230 to 260 nm, in terms of providing a better effect of the present invention. The intensity of the irradiated laser light is not particularly limited, but in order to obtain a more excellent effect of the present invention, it is preferably 1.0 to 2.0 J / cm 2 is preferable, and 1.2 to 1.8 J / cm 2 is more preferred. The pulse width of the irradiated laser light is not particularly limited, but is preferably 200 to 300 fs, more preferably 230 to 250 fs, in terms of providing a better effect of the present invention. The frequency of the laser light to be irradiated is not particularly limited, but is preferably 5000 to 20000 Hz, more preferably 8000 to 12000 Hz, in terms of providing a better effect of the present invention. The irradiation time of the laser light is not particularly limited, but is preferably 0.5 to 3.0 seconds, more preferably 1.5 to 2.5 seconds, in terms of achieving better effects of the present invention.

[0069] The number of standard sample films having different concentrations of metal elements to be used in step A is not particularly limited, and the number required to measure the calibration curve is appropriately selected. To further improve the accuracy of quantitative analysis, the number of standard sample films having different concentrations of metal elements is preferably 2 or more, more preferably 5 to 20, and even more preferably 5 to 10. In other words, it is preferable to obtain at least two or more sets of data (preferably 5 to 20, more preferably 5 to 10) on the concentration of metal elements in the standard sample films and the signal intensity at that concentration.

[0070] By carrying out step A, it is possible to obtain signal intensity data for the ions of the metal element to be measured based on the concentration from multiple standard sample films with different concentrations of the metal element. In other words, it is possible to obtain signal intensity data corresponding to the concentration of the metal element for each concentration of the metal element. In addition, if the standard sample film contains multiple types of metal elements (if it contains metal salts of multiple organic acids with different types of metal elements), in this step A, the signal intensity of ions corresponding to the concentration of each type of metal element may be obtained.

[0071] (Process B) Step B is a step of preparing a calibration curve based on the concentrations of metal elements in a plurality of standard sample films and the signal intensities of the ions of the metal elements in each of the plurality of standard sample films obtained in step A. As described above, in step A, signal intensity data based on the concentration of metal elements can be obtained from multiple standard sample films with different concentrations of the metal elements. In step B, a calibration curve is created using the concentration of the metal elements and the signal intensity of the metal element ions based on the concentration. More specifically, as shown in FIG. 4, for example, points corresponding to the concentration of the metal elements and the signal intensity of the metal element ions in each standard sample film are plotted on an orthogonal coordinate system with the concentration of the metal elements on the horizontal axis and the signal intensity of the metal element ions on the vertical axis (corresponding to the black dots in FIG. 4), and a calibration curve (dashed line in FIG. 4) passing through the plotted points is created. When drawing the calibration curve, for example, a method of drawing a calibration curve (regression line) based on the least squares method can be used. Although five plot points are shown in FIG. 4, the number of plot points is not limited to that shown in FIG.

[0072] (Process C) Step C is a step of measuring the signal intensity of the ions of the metal element by laser ablation inductively coupled plasma mass spectrometry using a measurement sample containing the same type of metal element as the metal element in the standard sample film, and determining the concentration of the metal element in the measurement sample based on the calibration curve. In this step C, laser ablation inductively coupled plasma mass spectrometry is applied to a measurement sample whose concentration of the metal element is unknown, measuring the signal intensity of the ions of the metal element, reading the concentration of the metal element corresponding to the signal intensity of the ions of the metal element in the measurement sample from the calibration curve, and determining the concentration of the detected metal element in the measurement sample.

[0073] More specifically, as shown in Figure 4, if the signal intensity of the ion of a metal element obtained in step C in a measurement sample with an unknown concentration of the metal element is S1, the concentration of the metal element in the measurement sample can be determined as M1 by reading the concentration M1 of the metal element corresponding to the signal intensity S1 from the calibration curve.

[0074] When the measurement sample contains a plurality of metal elements, the concentration of each metal element in the measurement sample can be quantified based on a calibration curve corresponding to each metal element.

[0075] [Second embodiment] A feature of the standard sample according to the second embodiment of the present invention is that it uses a metal salt of an organic acid, a predetermined binder (a hydrocarbon and a predetermined polymer), and an internal standard. The variation in signal intensity of metal element ions depending on the measurement position is mainly related to the uniformity of the distribution of the metal element in the standard sample. In other words, if the metal salt of an organic acid is unevenly distributed in the standard sample, the signal intensity will differ significantly between positions where the metal salt of the organic acid is present and positions where it is not. The inventors have found that by using a specific binder, the metal salt of an organic acid can be uniformly dispersed in the standard sample, resulting in the desired effect. The reference standard of the present invention can be used for a variety of materials, i.e., it can be used for elemental analysis in a wide range of materials, including inorganic and organic substances. Furthermore, by including an internal standard in the standard sample, fluctuations in sensitivity during measurement by laser ablation inductively coupled plasma mass spectrometry can be detected.

[0076] In the following, the standard sample of the present invention will first be described in detail, and then the sample set, transfer film, and quantitative analysis method will be described in detail.

[0077] <Standard sample> The standard sample according to the second embodiment of the present invention is a standard sample used in laser ablation inductively coupled plasma mass spectrometry, and has an absolute difference in SP (Solubility Parameter) between the hydrocarbon, the metal salt of an organic acid, and the hydrocarbon of 3.5 MPa. 1 / 2 The polymers are within the range of 1000 to 10 ... Below, each component contained in the standard sample will be described in detail.

[0078] (hydrocarbons) The type of hydrocarbon is not particularly limited, and examples include known hydrocarbons. The hydrocarbon may be a saturated hydrocarbon or an unsaturated hydrocarbon, with saturated hydrocarbons being preferred in that the effects of the present invention are more excellent. The hydrocarbon may be an aliphatic hydrocarbon or an aromatic hydrocarbon, with aliphatic hydrocarbons being preferred in that the effects of the present invention are more excellent. The hydrocarbon may be linear or branched, or may have a cyclic structure. The number of carbon atoms in the hydrocarbon is not particularly limited, and from the viewpoint of achieving superior effects of the present invention, it is preferably 5 or more, more preferably 10 or more, even more preferably 15 or more, and particularly preferably 20 or more. There is no particular upper limit, but it is often 40 or less, and more often 30 or less.

[0079] As the hydrocarbon, aliphatic saturated hydrocarbons are preferred, aliphatic saturated hydrocarbons having 10 or more carbon atoms are more preferred, and paraffin is even more preferred, in terms of achieving better effects of the present invention. In this specification, paraffin means an aliphatic saturated hydrocarbon having 15 or more carbon atoms.

[0080] The SP value of the hydrocarbon is not particularly limited, but in order to enhance the effects of the present invention, it is preferred that the SP value be 14 to 18 MPa. 1 / 2 is preferable, and 15 to 17 MPa 1 / 2 is more preferred. The SP value is calculated as follows: Using a calculation program (HSPiP, ver. 4.1.07), the molecular structure of each material is input, and the HSP value (δ D , δ P , δ H ) is calculated. Next, calculate the SP value using the following formula. Formula SP value = (δ D 2 +δ P 2 +δ H 2 ) 1 / 2

[0081] The hydrocarbon content in the standard sample is not particularly limited, but in terms of better effects of the present invention, it is preferably 1 to 60 mass % relative to the total mass of the standard sample, more preferably 1 to 40 mass %, even more preferably 1 to 20 mass %, and particularly preferably 1 to 10 mass %. The hydrocarbons may be used alone or in combination of two or more. When two or more hydrocarbons are used in combination, the total content of the hydrocarbons is preferably within the above range.

[0082] (Metal salts of organic acids) The metal salt of an organic acid is a salt containing an organic acid and a metal element. Examples of organic acids include compounds having an acid group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phenolic hydroxyl group, and a thiol group. Of these, compounds having a sulfonic acid group are preferred. The organic acid preferably has a hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group), more preferably has an aliphatic hydrocarbon group, and even more preferably has an alkyl group. The number of carbon atoms in the hydrocarbon group (aliphatic hydrocarbon group, alkyl group) is not particularly limited, but is preferably 5 or more. The organic acid may have both an aliphatic hydrocarbon group and an aromatic hydrocarbon group. As the organic acid, the hydrocarbons having the above acid groups are preferred, and alkylarylsulfonic acids are more preferred, in that the effects of the present invention are more excellent. In addition, the absolute value of the difference between the SP value of the hydrocarbon group of the organic acid and the SP value of the hydrocarbon is 3.5 MPa, which is a value that is more effective in the present invention. 1 / 2 It is preferable that the pressure is within 2.0 MPa. 1 / 2 It is more preferable that the pressure is within 1.0 MPa. 1 / 2 The lower limit of the absolute value of the difference is not particularly limited, but it is more preferably within 0 MPa. 1 / 2 Examples include:

[0083] The metal element of the metal salt is not particularly limited, and examples thereof include known metal elements. Examples of metal elements include metal elements of Groups 1 to 12 of the periodic table excluding hydrogen, and metal elements of Groups 13 to 16 of the periodic table. Metal elements belonging to Group 13 of the periodic table include aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). Metal elements belonging to Group 14 of the periodic table include germanium (Ge), tin (Sn), and lead (Pb). Metal elements belonging to Group 15 of the periodic table include antimony (Sb) and bismuth (Bi). Metal elements belonging to Group 16 of the periodic table include polonium (Po). As the metal element, aluminum (Al), sodium (Na), magnesium (Mg), barium (Ba), calcium (Ca), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), molybdenum (Mo), cadmium (Cd), and lead (Pb) are preferred in terms of providing a more excellent effect of the present invention.

[0084] The content of the metal salt of an organic acid in the standard sample is not particularly limited, but in terms of better effects of the present invention, the concentration of the metal element derived from the metal salt of an organic acid is preferably 0.1 to 1000 ppm by mass, and more preferably 0.1 to 300 ppm by mass, relative to the total mass of the standard sample. The concentration of a metal element derived from a metal salt of an organic acid in a standard sample means the concentration of a metal element contained in a metal salt of an organic acid in the standard sample. The metal salt of an organic acid may be used alone or in combination of two or more. When two or more metal salts of organic acids having different metal elements are used in combination, it is preferable that the concentration of the metal element derived from each metal salt of the organic acid is within the above range.

[0085] As described above, when two or more metal salts of organic acids are used, it is preferable to use metal salts of two or more organic acids having different types of metal elements. When a standard sample contains metal salts of two or more organic acids with different metal elements, the signal intensities of two or more metal elements can be obtained using laser ablation inductively coupled plasma mass spectrometry, and calibration curves for multiple metal elements can be created using a single standard sample. The number of types of metal salts of organic acids containing different types of metal elements in a standard sample is not particularly limited, and is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. There is no particular upper limit, but it is often 40 or less.

[0086] (The absolute value of the difference with the SP value of hydrocarbons is 3.5 MPa. 1 / 2 (polymers within The absolute value of the difference with the SP value of hydrocarbons is 3.5 MPa 1 / 2 A polymer that is within this range (hereinafter also simply referred to as a "specific polymer") has good compatibility with hydrocarbons. The absolute value of the difference between the SP value of the specific polymer and the SP value of the hydrocarbon is 2.5 MPa, which is a point where the effect of the present invention is more excellent. 1 / 2 Preferably within 2.0 MPa 1 / 2 Within 1.5 MPa is more preferable. 1 / 2Within 1.0 MPa is particularly preferable. 1 / 2 The lower limit of the absolute value of the difference is not particularly limited, but is preferably 0. The SP value of the specific polymer may be within the above range of the absolute value of the difference, but in order to obtain a more excellent effect of the present invention, it is preferable that the SP value is within the range of 15 to 19 MPa. 1 / 2 is preferably 16 to 17 MPa 1 / 2 is more preferred. The SP value is calculated as follows: Using a calculation program (HSPiP, ver. 4.1.07), the molecular structure of each material (the structure of the repeating unit in a specific polymer) is input, and the HSP value (Hansen Solubility Parameter) calculation function attached to the program is used to calculate the HSP value (δ D , δ P , δ H ) is calculated. Next, calculate the SP value using the following formula. Formula SP value = (δ D 2 +δ P 2 +δ H 2 ) 1 / 2 When the specific polymer contains a plurality of repeating units, the SP value of the specific polymer is calculated by multiplying the SP value of each repeating unit by the molar ratio of that repeating unit to all repeating units, and the sum of these products is used to calculate the SP value of the specific polymer. A Repeating unit A and SP B and repeating unit B, the molar ratio of repeating unit A to all repeating units is 0.2, and the molar ratio of repeating unit B to all repeating units is 0.8, the SP value of the specific polymer is calculated as follows: SP value of a specific polymer = (SP A ×0.2)+(SP B ×0.8)

[0087] The type of the specific polymer is not particularly limited as long as the absolute value of the difference falls within the above range. The specific polymers include (meth)acrylic polymers, styrene polymers, olefin polymers, polyester polymers, and polyamide polymers, with (meth)acrylic polymers and styrene polymers being preferred, and (meth)acrylic polymers being more preferred. The (meth)acrylic polymer is a general term for acrylic polymers and methacrylic polymers.

[0088] A styrene-based polymer is a polymer that contains repeating units derived from styrene in the largest amount by mass ratio among all repeating units. The content of repeating units derived from styrene in the styrene-based polymer is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total repeating units contained in the styrene-based polymer, in order to obtain a more excellent effect of the present invention. The upper limit is not particularly limited, but may be 100% by mass.

[0089] A (meth)acrylic polymer is a polymer containing repeating units derived from an alkyl acrylate and / or an alkyl methacrylate in the largest mass ratio among all repeating units. The (meth)acrylic polymer preferably contains a repeating unit derived from a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms, in terms of achieving better effects of the present invention. The number of carbon atoms in the alkyl group in the (meth)acrylic acid alkyl ester is preferably 2 to 14, more preferably 3 to 10, and even more preferably 3 to 8, in terms of better effects of the present invention. The (meth)acrylic acid alkyl ester is a general term for acrylic acid alkyl ester and methacrylic acid alkyl ester.

[0090] Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, 1,3-dimethylbutyl acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, and n-tetradecyl (meth)acrylate.

[0091] The content of repeating units derived from a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms in the (meth)acrylic polymer is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total repeating units contained in the (meth)acrylic polymer, in order to achieve better effects of the present invention. There is no particular upper limit, but it can be 100% by mass.

[0092] An olefin polymer is a polymer that contains repeating units derived from olefins in the largest amount by mass among all repeating units. Examples of olefins include ethylene and propylene. A polyester polymer is a polymer synthesized by dehydration condensation of a polycarboxylic acid (dicarboxylic acid) and a polyalcohol (diol) to form an ester bond. Examples of polyester polymers include polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. Polyamide polymers are polymers made of many monomers linked together by amide bonds. Examples of polyamide polymers include nylon 6 and nylon 6,6.

[0093] The content of the specific polymer in the standard sample is not particularly limited, but in terms of achieving better effects of the present invention, it is preferably 40% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the standard sample. The upper limit is not particularly limited, but it is often less than 99% by mass, and is preferably 98% by mass or less, more preferably 97% by mass or less. The specific polymer may be used alone or in combination of two or more. When two or more specific polymers are used in combination, the total content of the specific polymers is preferably within the above range.

[0094] (internal standard) The internal standard is not particularly limited, and may be any component that can function as an internal standard in the LA-ICP-MS method. As the internal standard, various elements or compounds may be used. The internal standard is preferably an element that is not the target of analysis, that is, an element that is not contained in the measurement sample and is not the target of analysis. Furthermore, the internal standard is preferably an element that does not have spectral interference and behaves in the same manner as the element to be analyzed in plasma. The internal standard is preferably an element (preferably a metal element) different from the metal element contained in the above-mentioned standard sample. Specific examples of elements preferred as internal standards include Bi (bismuth), Ho (holmium), In (indium), Rh (rhodium), Sc (scandium), Tb (terbium), and Y (yttrium). If the internal standard is an element, it may be ionized.

[0095] When preparing the standard sample described below, a commercially available standard solution (e.g., a metal standard solution) may be used as a raw material. For example, a metal standard solution contains a metal element that can function as an internal standard.

[0096] The content of the internal standard in the standard sample is not particularly limited, but is preferably 0.01 to 100 ppm by mass, more preferably 0.1 to 10 ppm by mass, relative to the total mass of the standard sample. For example, when the internal standard is a specific metal element, the content of the metal element is preferably within the above range.

[0097] As will be described later, in a sample set in which multiple standard samples are combined, it is preferable that the content of the internal standard in the included standard samples be similar among the standard samples. Specifically, it is preferable that the absolute value of the difference in the content of the internal standard among the standard samples be within 0.01 ppm by mass. The lower limit of the absolute value of the difference in content is not particularly limited, but can be 0 ppm by mass.

[0098] The standard sample may contain components other than the above-mentioned hydrocarbons, metal salts of organic acids, specific polymers, and internal standards, as long as the effects of the present invention are not impaired. Other components include a solvent. The content of other components in the standard sample is preferably 5% by mass or less, more preferably 1% by mass or less, relative to the total mass of the standard sample. There is no lower limit, but 0% by mass is an example.

[0099] The method for producing the standard sample is not particularly limited, and examples thereof include a method of mixing the various components described above (hydrocarbon, metal salt of organic acid, specific polymer, and internal standard). Examples of the mixing method include a method of adding the various components to a solvent, mixing and stirring, and then removing the solvent.

[0100] The shape of the standard sample is not particularly limited, and may be a film or a block. Among them, a film is preferable in terms of ease of measurement. When the standard sample of the present invention is a film, the surface flatness of the obtained film is excellent. When the standard sample is in the form of a film, the average film thickness of the standard sample is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, and even more preferably 0.5 to 3.5 μm, in terms of better effects of the present invention. The average film thickness is determined by measuring the thickness of any 20 points on the sample film of the standard sample using a stylus profilometer and calculating the arithmetic mean of the measured thicknesses.

[0101] The method for producing a sample film made of a standard sample is not particularly limited, and examples include a method in which a solvent and the various components described above (hydrocarbon, metal salt of organic acid, specific polymer, and internal standard) are mixed to prepare a composition, the resulting composition is applied to a substrate, and a drying process is performed as necessary.

[0102] The type of solvent used is not particularly limited, and any solvent capable of dissolving the various components described above may be used. Examples of the solvent include organic solvents and water, with organic solvents being preferred. Examples of the organic solvent include ketone solvents, alcohol solvents, ether solvents, hydrocarbon solvents, and ester solvents, with ketone solvents or ester solvents being preferred. Specific examples of the solvent include methyl ethyl ketone, butyl acetate, toluene, hexane, acetone, and chloroform. The concentration of the solvent in the composition is not particularly limited, but in order to obtain a film with a highly uniform thickness, the content of the solvent relative to the total mass of the composition is preferably 60 to 99 mass%, more preferably 70 to 99 mass%.

[0103] The method for applying the composition onto the substrate is not particularly limited, and includes known methods (for example, spin coating, dip coating, inkjet method, etc.). The type of substrate is not particularly limited, and examples thereof include quartz, glass substrates, and silicon wafers, which have excellent flatness. After the composition is applied to the substrate, a drying treatment may be carried out, if necessary, to remove the solvent from the coating film. Examples of the drying treatment method include a heat treatment.

[0104] The substrate may be a temporary support. When the substrate is a temporary support, a transfer film is formed having the temporary support and a sample film made of the standard sample placed on the temporary support. The sample film on the temporary support of this transfer film is brought into contact with the object to be transferred, and the temporary support is then peeled off, thereby allowing the sample film to be placed on the object to be transferred. Using such a transfer film, the sample film can be placed on objects of various shapes.

[0105] Examples of temporary supports include supports whose surfaces are treated with a release agent (such as a silicone-based release agent) and supports that themselves have releasability. The temporary support is preferably a polymer substrate. Examples of materials that can be used to form the temporary support include cellulose-based polymers, (meth)acrylic-based polymers, styrene-based polymers, olefin-based polymers, polyester-based polymers, and polyamide-based polymers. There are no particular restrictions on the water contact angle of the temporary support on the side where the sample film made of the standard sample is placed, but it is preferably 100 degrees or more in terms of better transferability of the sample film. The water contact angle can be measured by the sessile drop method described in JIS R 3257:1999. Specifically, the water contact angle is measured using a contact angle meter FTA1000 (software Fta32) (manufactured by First Ten Angstroms) at a room temperature of 25°C and a humidity of 50%. More specifically, 1.5 μl of pure water is dropped onto the surface of a horizontal temporary support, and the radius r and height h of the pure water droplet on the surface of the temporary support are determined after 30 seconds have passed. The water contact angle θ is then calculated using the formula θ=2arctan(h / r).

[0106] <Sample set> The sample set according to the second embodiment of the present invention is a set of a combination of multiple standard samples, each containing a metal salt of the same type of organic acid, with the concentrations of the metal salt of the same type of organic acid in the multiple standard samples being different from one another. In laser ablation inductively coupled plasma mass spectrometry, a calibration curve showing the relationship between the concentration of a specific metal element to be measured and the signal intensity is usually created using multiple standard samples containing metal salts of the same type of organic acid at different concentrations. In other words, the use of the sample set makes it easy to create a calibration curve. The number of standard samples in the sample set is not particularly limited, but preferably includes two or more, more preferably five or more, standard samples with different concentrations of metal salts of organic acids. There is no particular upper limit, but the number is often 10 or less.

[0107] <Quantitative analysis method> By using the standard sample according to the second embodiment of the present invention, it is possible to analyze the content of metal elements contained in a measurement sample whose content of metal elements is unknown. In the quantitative analysis method of the second embodiment of the present invention, a known laser ablation inductively coupled plasma mass spectrometer can be used. Among them, it is preferable to use a femtosecond laser ablation inductively coupled plasma mass spectrometer. An example of such a spectrometer is the Jupiter solid nebulizer (manufactured by ST Japan). A laser ablation inductively coupled plasma mass spectrometer typically has a laser ablation section (hereinafter also simply referred to as "LA section") and an inductively coupled plasma mass spectrometry section (hereinafter also simply referred to as "ICP-MS section").

[0108] The LA unit is a unit that irradiates a laser beam onto a sample to perform laser ablation. The structure of the LA unit is not particularly limited, and a known structure can be adopted, and it usually has a stage for placing the sample and a laser irradiation unit. A carrier gas consisting of rare gases such as helium (He) and argon (Ar) is introduced into the LA unit to transport the fine particles or gaseous matter generated by the laser beam irradiation to the ICP-MS unit. Usually, the LA section and the ICP-MS section are connected via a pipe.

[0109] In the ICP-MS section, the measurement target material transported from the LA section is ionized by high-temperature plasma maintained by high-frequency electromagnetic induction, and the ions are detected by a mass spectrometer to measure the atomic species and their concentrations. The structure of the ICP-MS unit is not particularly limited, and any known structure can be adopted. Typically, the ICP-MS unit comprises a plasma torch that generates plasma to ionize the sample introduced together with the carrier gas, and a mass spectrometer located near the tip of the plasma torch.

[0110] The quantitative analysis method includes steps 1 to 3 described below. Step 1: Using a plurality of standard samples of the present invention having different concentrations of metal elements derived from metal salts of organic acids, the signal intensity of the ions of the metal elements obtained from each standard sample is measured by laser ablation inductively coupled plasma mass spectrometry. Step 2: A step of preparing a calibration curve based on the concentrations of metal elements derived from metal salts of organic acids in the plurality of standard samples and the signal intensities of the ions of the metal elements in each of the plurality of standard samples obtained in step 1. Step 3: Using a measurement sample containing the same type of metal element as the metal element derived from the metal salt of an organic acid in the standard sample, the signal intensity of the metal element ion is measured by laser ablation inductively coupled plasma mass spectrometry, and the concentration of the metal element in the measurement sample is determined based on the calibration curve. The procedure for each step will be described in detail below.

[0111] (Process 1) Step 1 is a step of measuring the signal intensity of the ion of the metal element obtained from each of the standard samples of the present invention, which have different concentrations of the metal element derived from the metal salt of an organic acid, by laser ablation inductively coupled plasma mass spectrometry. In this step, a standard sample having a known concentration of the metal element derived from the metal salt of an organic acid is used, and the signal intensity obtained from the standard sample is measured. As described above, in this step 1, the signal intensity is measured using a known laser ablation inductively coupled plasma mass spectrometer.

[0112] In step 1, laser light may be irradiated onto multiple positions (locations) on the standard sample, the signal intensity of the metal element ions at each position may be measured, the signal intensities obtained may be arithmetically averaged, and the average signal intensity obtained may be used as the signal intensity obtained from the standard sample. More specifically, as shown in Fig. 5, a laser beam is irradiated onto each of a plurality of regions 22 in a standard sample 20. In Fig. 5, the number of regions 22 is nine, but the number is not particularly limited. Usually, there are five to twenty regions. The size of the region 22 is not particularly limited, but is often 0.1 to 1.0 mm in length and 0.1 to 1.0 mm in width. The distance between the regions 22 is not particularly limited, but is usually about the length of one side of the regions 22 .

[0113] There are no particular limitations on the method of irradiating the standard sample with laser light. The wavelength of the laser light to be irradiated is not particularly limited, but is preferably 200 to 300 nm, more preferably 230 to 260 nm, in terms of providing a better effect of the present invention. The intensity of the irradiated laser light is not particularly limited, but in order to obtain a more excellent effect of the present invention, it is preferably 1.0 to 2.0 J / cm 2 is preferable, and 1.2 to 1.8 J / cm 2 is more preferred. The pulse width of the irradiated laser light is not particularly limited, but is preferably 200 to 300 fs, more preferably 230 to 250 fs, in terms of providing a better effect of the present invention. The frequency of the laser light to be irradiated is not particularly limited, but is preferably 5000 to 20000 Hz, more preferably 8000 to 12000 Hz, in terms of providing a better effect of the present invention. The irradiation time of the laser light is not particularly limited, but is preferably 0.5 to 3.0 seconds, more preferably 1.5 to 2.5 seconds, in terms of achieving better effects of the present invention.

[0114] The number of standard samples having different concentrations of metal elements derived from metal salts of organic acids used in step 1 is not particularly limited, and the number required to measure a calibration curve is appropriately selected. In order to further improve the accuracy of quantitative analysis, the number of standard samples having different concentrations of metal elements derived from metal salts of organic acids is preferably 2 or more, more preferably 5 to 20, and even more preferably 5 to 10. In other words, it is preferable to obtain at least 2 or more (preferably 5 to 20, more preferably 5 to 10) data on the concentration of metal elements in the standard samples and the signal intensity at that concentration.

[0115] By carrying out step 1, it is possible to obtain signal intensity data for the ions of the metal element to be measured based on the concentration from multiple standard samples with different concentrations of the metal element. In other words, it is possible to obtain signal intensity data corresponding to the concentration of the metal element for each concentration of the metal element. In addition, when the standard sample contains multiple types of metal elements (when it contains metal salts of multiple organic acids with different types of metal elements), in this step 1, the signal intensities of ions corresponding to the concentrations of each type of metal element may be obtained.

[0116] (Process 2) Step 2 is a step of creating a calibration curve based on the concentrations of metal elements derived from metal salts of organic acids in multiple standard samples and the signal intensities of the ions of each metal element in the multiple standard samples obtained in step 1. As described above, in step 1, signal intensity data based on the concentration of a metal element can be obtained from multiple standard samples with different concentrations of the metal element. In step 2, a calibration curve is created using the concentration of the metal element and the signal intensity of the metal element ion based on that concentration. More specifically, as shown in FIG. 6, for example, points corresponding to the concentration of the metal element and the signal intensity of the metal element ion in each standard sample are plotted on an orthogonal coordinate system with the concentration of the metal element on the horizontal axis and the signal intensity of the metal element ion on the vertical axis (corresponding to the black dots in FIG. 6), and a calibration curve (dashed line in FIG. 6) passing through the plotted points is created. When drawing the calibration curve, for example, a method of drawing a calibration curve (regression line) based on the least squares method can be used. Although five plot points are shown in FIG. 6, the number of plot points is not limited to that shown in FIG.

[0117] (Step 3) Step 3 is a step in which a measurement sample containing the same type of metal element as the metal element derived from the metal salt of an organic acid in the standard sample is used, and the signal intensity of the metal element ion is measured by laser ablation inductively coupled plasma mass spectrometry, and the concentration of the metal element in the measurement sample is determined based on the calibration curve. In this step, laser ablation inductively coupled plasma mass spectrometry is applied to a measurement sample whose concentration of the metal element is unknown, the signal intensity of the metal element ion is measured, and the concentration of the metal element corresponding to the signal intensity of the metal element ion in the measurement sample is read from the calibration curve, and the concentration of the detected metal element in the measurement sample is determined.

[0118] More specifically, as shown in Figure 6, if the signal intensity of the ion of a metal element in the measurement sample obtained in step 3, whose concentration is unknown, is S1, the concentration of the metal element in the measurement sample can be determined as M1 by reading the concentration M1 of the metal element corresponding to the signal intensity S1 from the calibration curve.

[0119] When the measurement sample contains a plurality of metal elements, the concentration of each metal element in the measurement sample can be quantified based on a calibration curve corresponding to each metal element. [Example]

[0120] The features of the present invention will be explained in more detail below with reference to examples and comparative examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[0121] Example 1A Example 1A-1 Polybutyl methacrylate, a metal dispersion liquid (CONOSTAN STD, manufactured by SCP Sciences), and a Y standard solution (CONOSTAN STD, manufactured by SCP Sciences) were added to methyl ethyl ketone and dissolved to obtain a solution. The concentration of polybutyl methacrylate was 10% by mass relative to the total mass of the solution. The metal dispersion liquid also contained a plurality of alkylarylsulfonates of different metal species (SP value of the hydrocarbon group: 16 MPa). 1 / 2 ), and paraffin (SP value: 16 MPa) 1 / 2 ) was contained. The metal dispersion liquid was added so that the concentration of aluminum element in the standard sample described below was 40 ppm by mass. The metal dispersion liquid contained the same amounts of sodium element, magnesium element, aluminum element, calcium element, titanium element, vanadium element, chromium element, manganese element, iron element, nickel element, copper element, zinc element, molybdenum element, cadmium element, barium element, and lead element as aluminum element. The Y standard solution was a raw material liquid for adding Y (yttrium) as an internal standard, and an amount of Y was used so that the Y concentration would be 1 ppm by mass relative to the total mass of the resulting standard sample. In addition, the difference between the SP value of the hydrocarbon group contained in the alkylarylsulfonate and the SP value of paraffin is 0 MPa. 1 / 2 It was.

[0122] The resulting solution was spin-coated (2000 rpm, 20 seconds) onto a synthetic quartz (2.5 cm length x 2.5 cm width x 0.7 mm thickness) to prepare a film-like standard sample on the synthetic quartz. The paraffin content relative to the total mass of the standard sample was 8 mass%, and the polybutyl methacrylate content relative to the total mass of the standard sample was the remainder excluding the paraffin, components derived from the metal dispersion (e.g., alkylarylsulfonium salt), and the internal standard.

[0123] Femtosecond laser ablation inductively coupled plasma mass spectrometry was performed using the obtained film-like standard sample. The femtosecond laser ablation device used was a Jupiter solid nebulizer (manufactured by ST Japan). The various conditions were as follows: Laser conditions Laser device: LPS MultiProbe Laser wavelength: 260nm Laser power (fluence): 0.5~1.5J / cm 2 Laser pulse width: 247fs Laser frequency: 10,000Hz Irradiation time: approx. 2 seconds Carrier gas: He gas 0.6 L / min in the sample chamber, Ar gas 1.1 L / min added immediately after the sample chamber Irradiation area: 1mm x 1mm ICP-MS conditions MS measurement device: iCAP TQ (Thermo Fisher Scientific) RF power: 1550W ·Cooling gas flow rate:14L / min ·Auxiliary gas flow rate:0.8L / min

[0124] Laser ablation was performed on nine regions (each region measuring 1 mm length × 1 mm width) of the film-like standard sample (standard sample film) to vaporize the sample, as shown in Figures 3 and 5. The spacing between each region was 1 mm. After obtaining the signal intensities corresponding to the nine regions, the average value (average signal intensity) and standard deviation of the signal intensities were calculated, and further, the relative standard deviation of the signal intensities was calculated. The relative standard deviation of the signal intensity shown in Table 1 below is the worst value among all the metal elements contained in the standard sample.

[0125] Before measuring the laser ablation, the maximum height difference in the film thickness of the prepared standard sample was calculated using a stylus-type profilometer. The maximum height difference of the film thickness was measured as follows. The film thickness of the standard sample film was calculated using a stylus profilometer. The measurement distance was 3 mm, and the scanning speed was 0.02 mm / sec. The 3 mm straight line where the first measurement was made was designated as scan line 1, and the second measurement was made at a location 0.2 mm or more away in a direction perpendicular to scan line 1. Similar measurements were repeated for a total of 10 measurements. Ten measurements (scans) were made, and the maximum and minimum film thickness values ​​for each scan were determined. The difference (value A - value B) between the largest value A of the 10 maximum values ​​obtained from the 10 scans and the smallest value B of the 10 minimum values ​​obtained from the 10 scans was taken as the maximum film thickness difference.

[0126] (Examples 1A-2 to 1A-3 and Comparative Example 1A-1) The relative standard deviation of the signal intensity was determined in the same manner as in Example 1A-1, except that the type of polymer used was changed as shown in Table 1 below.

[0127] The above-described method X was carried out on the film-like standard samples (standard sample films) obtained in each of the examples and comparative examples, and the element concentration variations (%) of the metal elements contained in the standard sample films were calculated.

[0128] In Table 1, "PBMA" represents polybutyl methacrylate, "PMMA" represents polymethyl methacrylate, "PS" represents polystyrene, and "PVBC" represents polyvinylbenzyl chloride. In Table 1, "Na concentration variation (%)" represents the element concentration variation (%) of the Na element calculated by the above-mentioned method X, and "Mg concentration variation (%)" represents the element concentration variation (%) of the Mg element calculated by the above-mentioned method X.

[0129] [Table 1]

[0130] As shown in Table 1, it was confirmed that the relative standard deviation of signal intensity was small when the standard sample of the present invention was used. In other words, it was confirmed that the variation in signal intensity of metal elements depending on the measurement position was small. Among these, a comparison of Examples 1A-1 to 1A-3 reveals that the absolute value of the difference from hydrocarbon (paraffin) is 2.5 MPa. 1 / 2 Within (preferably, 1.0 MPa 1 / 2 It was confirmed that the effect was superior when the

[0131] Furthermore, the femtosecond laser ablation device was used continuously, and the standard sample of Example 1A-1 was measured 1 hour and 10 hours after the device was first used, and the signal intensity of Y (yttrium), the internal standard in the standard sample, was measured. Comparing the two signal intensities, it was found that the signal intensity measured 10 hours after the device was first used was 10% lower than the signal intensity measured 1 hour after the device was first used. From these results, it was confirmed that the detection sensitivity decreased when the device was used continuously for 10 hours, and it was confirmed that the use of an internal standard can detect fluctuations in sensitivity during measurement. When the standard samples of Examples 1A-2 and 1A-3 were used instead of the standard sample of Example 1A-1, a decrease in the signal intensity of the internal standard Y was confirmed, as described above, and it was confirmed that fluctuations in sensitivity during measurement could be detected.

[0132] Example 2A Polyvinylpyrrolidone (PVP), NaCl standard solution (for atomic absorption, manufactured by Kanto Chemical Co., Inc.), and Y standard solution (for atomic absorption, manufactured by Kanto Chemical Co., Inc.) were added to water and dissolved to obtain a solution. The concentration of polyvinylpyrrolidone was 6% by mass based on the total mass of the solution. The NaCl standard solution was added so that the Na element concentration in the standard sample was 40 ppm by mass. The Y standard solution was a raw material solution for adding Y (yttrium) as an internal standard, and was used in an amount such that the Y concentration would be 1 ppm by mass based on the total mass of the resulting standard sample. The obtained solution was spin-coated (rotation speed: 1000 rpm, time: 20 seconds) onto a quartz substrate (2.5 cm length × 2.5 cm width × 1.0 mm thickness) and baked on a hot plate at 200°C for 5 minutes to prepare a film-like standard sample (standard sample film) on the quartz substrate. Using the obtained standard sample membrane, various evaluations were carried out in the same manner as in Example 1A-1. The results are shown in Table 2. PVP is a water-soluble polymer.

[0133] [Table 2]

[0134] As shown in Table 2, it was confirmed that the relative standard deviation of signal intensity was small when the standard sample (standard sample film) of the present invention was used. In other words, it was confirmed that the variation in metal element intensity depending on the measurement position was small.

[0135] Furthermore, the femtosecond laser ablation device was used continuously, and the standard sample of Example 2A was measured 1 hour and 10 hours after the device was first used, and the signal intensity of the internal standard Y (yttrium) in the standard sample was measured. Comparing the two signal intensities, it was found that the signal intensity measured 10 hours after the device was first used was 10% lower than the signal intensity measured 1 hour after the device was first used. From these results, it was confirmed that the detection sensitivity decreased when the device was used continuously for 10 hours, and it was confirmed that the use of an internal standard can detect fluctuations in sensitivity during measurement.

[0136] Example 3A Polybutyl methacrylate, a metal dispersion (CONOSTAN STD, manufactured by SCP Sciences), a Y standard solution (CONOSTAN STD, manufactured by SCP Sciences), and a surfactant (MEGAFAC R-41, manufactured by DIC Corporation) were added to butyl acetate and dissolved to obtain a solution. The concentration of polybutyl methacrylate was 6% by mass relative to the total mass of the solution, and the concentration of the surfactant was 0.05% by mass relative to the total mass of the solution. The metal dispersion was added so that the aluminum concentration in the standard sample was 100 ppm by mass. The Y standard solution was a raw material solution for adding the internal standard Y (yttrium), and was used in an amount such that the Y concentration would be 1 ppm by mass relative to the total mass of the resulting standard sample. The obtained solution was spin-coated onto a disk-shaped silicon wafer (4.0 inch diameter x 0.5 mm thickness) and baked on a hot plate at 200°C for 5 minutes to prepare a film-like standard sample (standard sample film) on the silicon wafer. A test piece of the standard sample film measuring 2.5 cm in length and 2.5 cm in width was cut out from an arbitrary position in the silicon wafer, and the obtained test piece was evaluated. The results are shown in Table 3.

[0137] [Table 3]

[0138] As shown in Table 3, it was confirmed that the relative standard deviation of signal intensity was small when the standard sample (standard sample film) of the present invention was used. In other words, it was confirmed that the variation in metal element intensity depending on the measurement position was small.

[0139] Furthermore, the femtosecond laser ablation device was used continuously, and the standard sample of Example 3A was measured 1 hour and 10 hours after the device was first used, and the signal intensity of the internal standard Y (yttrium) in the standard sample was measured. Comparing the two signal intensities, it was found that the signal intensity measured 10 hours after the device was first used was 10% lower than the signal intensity measured 1 hour after the device was first used. From these results, it was confirmed that the detection sensitivity decreased when the device was used continuously for 10 hours, and it was confirmed that the use of an internal standard can detect fluctuations in sensitivity during measurement.

[0140] Example B The same procedure as in Example 1A-1 was followed to adjust the amount of metal dispersion liquid added so that the contents of sodium, magnesium, aluminum, calcium, titanium, vanadium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, cadmium, barium, and lead relative to the total mass of the standard sample were 0 ppm by mass, 23 ppm by mass, 41 ppm by mass, 60 ppm by mass, 76 ppm by mass, 109 ppm by mass, 164 ppm by mass, and 201 ppm by mass, respectively. 23 Na, 25 Mg, 27 Al, 43 Ca, 49 Ti, 51 V, 53 Cr, 55 Mn, 57 Fe, 60 Ni, 65 Cu, 66 Zn, 95 Mo, 111 Cd, 137 Ba, 208 The signal intensity was determined for each concentration of Pb. As described in Example A above, in Example B, nine regions of one standard sample were irradiated with laser light, and the average of the obtained signal intensities was used as the signal intensities shown in Tables 4 to 6. The results are shown in Tables 4 to 6. In addition, points corresponding to the concentration of each metal element and the signal intensity of the ion of the metal element were plotted on an orthogonal coordinate system with the concentration of each metal element on the horizontal axis and the signal intensity of the ion of the metal element on the vertical axis, and a calibration curve passing through the plotted points was created by the least squares method to calculate the coefficient of determination. In Tables 4 to 6, "calibration curve" represents a linear function of the created calibration curve, and "coefficient of determination (R 2 )" represents the coefficient of determination obtained by the least squares method. The closer the coefficient of determination is to 1.000, the better the results. As a representative example, see Figure 7. 43 The results for Ca are shown.

[0141] The metal dispersion (CONOSTAN STD, manufactured by SCP Science) contained sodium alkyl sulfonate, magnesium alkyl aryl sulfonate, aluminum alkyl aryl sulfonate, calcium alkyl aryl sulfonate, titanium alkyl aryl sulfonate, vanadium alkyl aryl sulfonate, chromium alkyl aryl sulfonate, manganese alkyl aryl sulfonate, iron alkyl aryl sulfonate, nickel alkyl aryl sulfonate, copper alkyl aryl sulfonate, zinc alkyl aryl sulfonate, molybdenum amine alkyl aryl sulfonate, cadmium alkyl aryl sulfonate, barium alkyl aryl sulfonate, and lead alkyl aryl sulfonate. The metal dispersion contained 0.01% by mass of the metal salts of the organic acids listed above. For example, magnesium alkyl aryl sulfonate was included so that the amount of magnesium element in the metal dispersion was 0.01% by mass.

[0142] [Table 4]

[0143] [Table 5]

[0144] [Table 6]

[0145] As shown in Tables 4 to 6, the linearity of the calibration curves obtained was excellent for all metal elements, and good results were obtained. By using the above calibration curve, laser ablation inductively coupled plasma mass spectrometry can be performed on a measurement sample with an unknown concentration of a metal element, and the metal element can be quantified from the obtained signal intensity.

[0146] Example C Example C1 As in Example 1A-1, polybutyl methacrylate, a metal dispersion (CONOSTAN STD, manufactured by SCP Sciences), and a Y standard solution (CONOSTAN STD, manufactured by SCP Sciences) were added to methyl ethyl ketone and dissolved to obtain a solution. The metal dispersion was added so that the aluminum element concentration in the standard sample was 40 ppm by mass. The Y standard solution was a raw material solution for adding the internal standard Y (yttrium), and an amount of Y was used such that the Y concentration was 1 ppm by mass relative to the total mass of the resulting standard sample.

[0147] The resulting solution was spin-coated (2000 rpm, 20 seconds) onto a polypropylene film (2.5 cm long x 2.5 cm wide x 0.01 mm thick) to prepare a film-like standard sample (standard sample film) on the polypropylene film (hereinafter referred to as temporary support). The paraffin content relative to the total mass of the standard sample film was 8 mass%, and the polybutyl methacrylate content relative to the total mass of the standard sample film was the remainder excluding the paraffin, components derived from the metal dispersion (e.g., alkylarylsulfonium salt), and components derived from the Y standard solution (e.g., Y (yttrium)).

[0148] The average film thickness of the standard sample film on the resulting temporary support was calculated using a stylus step gauge.

[0149] The surface of the standard sample film on the temporary support was pressed against a silicon wafer and held there for 1 minute. The pressure during pressing was approximately 50 g / cm. 2 The environment was normal temperature and humidity.

[0150] The temporary support was peeled off, and the area ratio of the standard sample film transferred to the silicon wafer side was calculated, with the area of ​​the standard sample film on the temporary support set at 100%. The average film thickness of the standard sample film transferred to the silicon wafer side was also calculated using a stylus profilometer.

[0151] (Example C2) A standard sample film was prepared and pressed onto a silicon wafer in the same manner as in Example C1, except that the type of temporary support onto which the solution was applied was changed as shown in Table 7. The thickness of the polyethylene terephthalate film (Example C2) was 0.01 mm.

[0152] The water contact angle of the temporary support used was measured according to the method described above. In Table 7, "Transfer area (%)" represents the ratio of the area of ​​the standard sample film transferred to the silicon wafer side when the temporary support was peeled off, with the area of ​​the standard sample film on the temporary support being 100%. In Table 7, the column "Average film thickness (nm) of transferred standard sample film" indicates the average film thickness of the standard sample film transferred to the silicon wafer side.

[0153] [Table 7]

[0154] As shown in Table 7, the standard sample film could be transferred onto a silicon wafer using a polypropylene film and a polyethylene terephthalate film as a temporary support. In particular, a comparison of Examples C1 and C2 confirmed that a more excellent effect was achieved when the water contact angle of the temporary support was 100 degrees or more. [Explanation of symbols]

[0155] 10 Substrate 12 Standard sample membrane 14 areas 20 Standard Samples 22 areas

Claims

1. The absolute value of the difference between the SP values ​​of the hydrocarbon, the metal salt of the organic acid, and the hydrocarbon is 3.5 MPa. １／２ A method for producing a standard sample film, comprising the step of applying a composition for forming a standard sample film, the composition comprising a polymer having a molecular weight of 1000 or less, an internal standard, and a solvent, to form a standard sample film.

2. the organic acid has a hydrocarbon group, The absolute value of the difference between the SP value of the hydrocarbon group and the SP value of the hydrocarbon is 3.5 MPa. １／２ The method for producing a standard sample membrane according to claim 1, wherein the production time is within 1000 s.

3. A standard sample used in laser ablation inductively coupled plasma mass spectrometry, comprising: Hydrocarbons, a metal salt of an organic acid; The absolute value of the difference from the SP value of the hydrocarbon is 3.5 MPa １／２ a polymer within and an internal standard.

4. The polymer has an absolute value of the difference between the SP value of the polymer and the SP value of the hydrocarbon of 2.5 MPa. １／２ The standard sample according to claim 3, wherein the standard sample is within the range of 0.1 to 1.0 μm.

5. The standard sample according to claim 3 , wherein the polymer is a (meth)acrylic polymer.

6. 4. The standard sample according to claim 3, wherein the hydrocarbons include saturated aliphatic hydrocarbons having 10 or more carbon atoms.

7. 4. The standard of claim 3, wherein the hydrocarbon comprises paraffin.

8. 4. The standard sample according to claim 3, wherein the organic acid has a sulfonic acid group.

9. 4. The standard sample according to claim 3, wherein the organic acid has a hydrocarbon group.

10. 4. The standard sample according to claim 3, comprising two or more metal salts of said organic acids each having a different type of metal element.

11. A sample set comprising a combination of a plurality of standard samples according to any one of claims 3 to 10, the plurality of standard samples contain metal salts of the same type of organic acid; A sample set in which the concentrations of metal elements derived from the metal salts of the same type of organic acid in the plurality of standard samples are different from each other.

12. a step 1 of measuring a signal intensity of an ion of the metal element obtained from each of the standard samples according to any one of claims 3 to 10, the standard samples having different concentrations of the metal element derived from the metal salt of the organic acid, by laser ablation inductively coupled plasma mass spectrometry; a step 2 of preparing a calibration curve based on the concentrations of the metal elements derived from the metal salts of the organic acids in the plurality of standard samples and the signal intensities of the ions of the metal elements in each of the plurality of standard samples obtained in the step 1; and step 3: using a measurement sample containing the same type of metal element as the metal element derived from the metal salt of an organic acid in the standard sample, measuring the signal intensity of the ion of the metal element by laser ablation inductively coupled plasma mass spectrometry, and determining the concentration of the metal element in the measurement sample based on the calibration curve.

13. A temporary support; A transfer film having a sample film made of the standard sample according to any one of claims 3 to 10, placed on the temporary support.

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