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

Abstract

The present invention provides a standard sample film, a standard sample, a method for manufacturing the standard sample film, a sample set, a quantitative analysis method, and a transfer film. The standard sample film is used in laser ablation inductively coupled plasma mass spectrometry, contains organic matter, and exhibits low deviation in signal intensity of metal element ions at the measurement position. The standard sample film of the present invention is used in laser ablation inductively coupled plasma mass spectrometry, contains a polymer and a metal element, and has a maximum height difference of 0.50 μm or less in film thickness.

Description

Technical Field

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

[0002] Laser ablation inductively coupled plasma mass spectrometry (hereinafter also referred to as "LA-ICP-MS") is a method for quantitatively analyzing the elements contained in a sample by analyzing the microparticles or vapors produced by explosively peeling off a portion of the sample by irradiating the sample with laser light using inductively coupled plasma mass spectrometry.

[0003] In recent years, femtosecond laser has been used in LA-ICP-MS (Patent Document 1).

[0004] Previous technical literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2018-136190 Summary of the Invention

[0007] Technical issues to be solved by the invention

[0008] Generally, in order to determine the concentration of a metal element in a solid sample in the LA-ICP-MS method, it is necessary to draw a calibration curve using a solid standard sample having a known concentration of the metal element to be measured.

[0009] On the other hand, conventional solid standard samples corresponding to standard samples in the LA-ICP-MS method are mainly inorganic substances such as glass and metal, and organic standard samples (standard samples mainly composed of organic substances) are very rare.

[0010] Furthermore, when using a standard sample to create a calibration curve for the target metal element in LA-ICP-MS, if the signal intensity of the target metal element ions varies depending on the location 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 decreases. Therefore, it is desirable to minimize the difference in signal intensity based on the location where the laser light is irradiated on the standard sample. In other words, it is desirable to minimize the variation in signal intensity based on the measurement location.

[0011] Furthermore, if standard samples can be attached to various materials (inorganic and organic substances), thin film standard substances capable of standardizing substances requiring analysis can be easily produced.

[0012] In view of the above, a first embodiment of the present invention aims to provide a standard sample film for laser ablation inductively coupled plasma mass spectrometry, the standard sample film containing an organic substance and having small variations in signal intensity of ions of a metal element at a measurement position.

[0013] In view of the above circumstances, a second embodiment of the present invention aims to provide a standard sample for laser ablation inductively coupled plasma mass spectrometry, the standard sample containing an organic substance and having small variations in signal intensity of ions of a metal element at a measurement position.

[0014] Furthermore, another object of the present invention is to provide a method for producing a standard sample film, a sample set, a quantitative analysis method, and a transfer film.

[0015] Means for solving technical problems

[0016] The present inventors have conducted intensive studies on the problems of the conventional technology and have found that the above-mentioned problems can be solved by the following configuration.

[0017] (1) A standard sample film for use in laser ablation inductively coupled plasma mass spectrometry, wherein:

[0018] The standard sample film contains polymer and metal elements.

[0019] The maximum height difference of the film thickness of the standard sample film is 0.50 μm or less.

[0020] (2) The standard sample film according to (1), wherein the element concentration deviation of the standard sample film determined by the method X described below is 30% or less.

[0021] (3) The standard sample film according to (1) or (2), wherein the average film thickness of the standard sample film is 3.5 μm or less.

[0022] (4) The standard sample film according to any one of (1) to (3), wherein the metal element is derived from an organic acid metal salt or an inorganic acid metal salt.

[0023] (5) The standard sample film according to any one of (1) to (4), comprising two or more metal elements.

[0024] (6) The standard sample film according to any one of (1) to (5), wherein the polymer is a (meth)acrylic polymer.

[0025] (7) A method for producing a standard sample film, comprising the step of forming a standard sample film by coating a standard sample film-forming composition, wherein the standard sample film-forming composition contains a hydrocarbon, an organic acid metal salt, and an absolute value of a difference in SP value between the hydrocarbon and the standard sample film.1 / 2 Polymers and solvents within .

[0026] (8) The method for producing a standard sample film according to (7), wherein the organic acid has a hydrocarbon group,

[0027] 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 Within.

[0028] (9) A sample set comprising a plurality of standard sample films according to any one of (1) to (6), wherein:

[0029] Multiple standard sample films contain the same type of metal elements.

[0030] The concentrations of the metal elements in the plurality of standard sample films are different from each other.

[0031] (10) A quantitative analysis method based on laser ablation inductively coupled plasma mass spectrometry, comprising: step A, using a plurality of standard sample films according to any one of (1) to (6) having different concentrations of metal elements, and measuring the signal intensity of ions of the metal elements obtained from each standard sample film by laser ablation inductively coupled plasma mass spectrometry;

[0032] Step B: plotting a calibration curve based on the concentration of the metal elements in the plurality of standard sample films and the signal intensity of the ions of the metal elements in the plurality of standard sample films obtained in Step A; and

[0033] In step C, a measurement sample containing the same type of metal element as the metal element in the standard sample film is used to measure the signal intensity of the ion of the metal element in the measurement sample by laser ablation inductively coupled plasma mass spectrometry, and the concentration of the metal element in the measurement sample is calculated based on the calibration curve.

[0034] (11) A transfer film comprising: a temporary support; and

[0035] The standard sample film according to any one of (1) to (6) is placed on a temporary support.

[0036] (12) A standard sample for laser ablation inductively coupled plasma mass spectrometry, the standard sample comprising:

[0037] hydrocarbon;

[0038] Metal salts of organic acids; and

[0039] The absolute value of the difference between the SP value of hydrocarbons is 3.5 MPa 1 / 2 Polymers within.

[0040] (13) The standard sample according to (12), wherein the absolute value of the difference from the SP value of hydrocarbon is less than 2.5 MPa. 1 / 2 Within.

[0041] (14) The standard sample according to (12) or (13), wherein the polymer is a (meth)acrylic polymer.

[0042] (15) The standard sample according to any one of (12) to (14), wherein the hydrocarbon includes an aliphatic saturated hydrocarbon having 10 or more carbon atoms.

[0043] (16) The standard sample according to any one of (12) to (15), wherein the hydrocarbon includes paraffin.

[0044] (17) The standard sample according to any one of (12) to (16), wherein the organic acid has a sulfonic acid group.

[0045] (18) The standard sample according to any one of (12) to (17), wherein the organic acid has a hydrocarbon group.

[0046] (19) The standard sample according to any one of (12) to (18), which contains two or more organic acid metal salts of different metal elements.

[0047] (20) A sample set comprising a plurality of standard samples according to any one of (12) to (19), wherein:

[0048] Multiple standard samples contain the same type of organic acid metal salt.

[0049] The concentrations of the metal elements derived from the same type of organic acid metal salt are different from each other in the plurality of standard samples.

[0050] (21) A quantitative analysis method based on laser ablation inductively coupled plasma mass spectrometry, comprising: step 1, using a plurality of standard samples according to any one of (12) to (19) having different concentrations of metal elements derived from organic acid metal salts, and measuring the signal intensity of ions of the metal elements obtained from each standard sample by laser ablation inductively coupled plasma mass spectrometry;

[0051] Step 2: creating a calibration curve based on the concentration of the metal element derived from the organic acid metal salt in the plurality of standard samples and the signal intensity of the ion of each metal element in the plurality of standard samples obtained in Step 1; and

[0052] In step 3, a measurement sample containing the same type of metal element as the metal element derived from the organic acid metal salt in the standard sample is used to measure the signal intensity of the metal element ion by laser ablation inductively coupled plasma mass spectrometry, and the concentration of the metal element in the measurement sample is calculated based on the calibration curve.

[0053] (22) A transfer film comprising: a temporary support; and

[0054] The sample film is composed of the standard sample described in any one of (12) to (19) arranged on a temporary support.

[0055] Effects of the Invention

[0056] According to the first embodiment of the present invention, a standard sample film for laser ablation inductively coupled plasma mass spectrometry can be provided, the standard sample film containing an organic substance and having small variations in signal intensity of ions of a metal element at a measurement position.

[0057] According to the second embodiment of the present invention, a standard sample for laser ablation inductively coupled plasma mass spectrometry can be provided, the standard sample containing an organic substance and having small variations in signal intensity of ions of a metal element at a measurement position.

[0058] Furthermore, according to the present invention, a method for producing a standard sample film, a sample set, a quantitative analysis method, and a transfer film can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 This is a schematic diagram for explaining a depth profile of secondary ion intensities of metal elements detected by analyzing the depth-direction components of a standard sample film using time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0060] Figure 2 Yes Figure 1 Schematic diagram of an example of a standard sample film to be measured.

[0061] Figure 3 This is a schematic diagram for explaining the procedure when irradiating a standard sample film with laser light.

[0062] Figure 4 This is a schematic diagram of a calibration curve based on metal element concentration and signal intensity.

[0063] Figure 5 This is a schematic diagram for explaining the procedure when irradiating a standard sample with laser light.

[0064] Figure 6 This is a schematic diagram of a calibration curve based on metal element concentration and signal intensity.

[0065] Figure 7 It is for 43 Graph of the calibration curve for Ca. DETAILED DESCRIPTION

[0066] Hereinafter, the present invention will be described in detail. In addition, in this specification, the numerical range represented by "to" means a range including the numerical values ​​recorded before and after "to" as the lower limit and the upper limit. First, the terms used in this specification will be described.

[0067] [First embodiment]

[0068] The characteristics of the standard sample film according to the first embodiment of the present invention include that it contains a polymer as an organic substance and that the maximum height difference of the film thickness of the standard sample film is 0.50 μm or less.

[0069] The present inventors discovered that the variation in signal intensity of metal element ions at the measurement location is primarily related to the thickness of the standard sample film. Specifically, they discovered that when the maximum height difference in the standard sample film is large, the signal intensity of the metal element ions is higher in the thicker portions of the film, while it is lower in the thinner portions, resulting in signal intensity variation. Therefore, the present inventors discovered that adjusting the maximum height difference in the film thickness to a predetermined range can resolve this problem.

[0070] In addition, as methods for reducing the maximum height difference of the film thickness, for example, there can be cited a method using a predetermined binder (a specific polymer and hydrocarbon described later) as described in the second embodiment, a method using a water-soluble polymer and an inorganic acid metal salt, and a method using a surfactant.

[0071] Hereinafter, the standard sample film of the present invention will be described in detail, followed by a detailed description of the method for producing the standard sample film, a sample set, a transfer film, and a quantitative analysis method.

[0072] <Standard sample film>

[0073] The standard sample film of the present invention is used for laser ablation inductively coupled plasma mass spectrometry. The standard sample film contains a polymer and a metal element, and the maximum height difference of the film thickness of the standard sample film is less than 0.50 μm.

[0074] First, the components contained in the standard sample film will be described in detail below.

[0075] (polymer)

[0076] The type of polymer contained in the standard sample film is not particularly limited; examples include water-insoluble polymers and water-soluble polymers. A water-soluble polymer is one that dissolves 1 g or more in 100 g of water at 25°C after drying at 105°C for 2 hours. A water-insoluble polymer is a polymer other than the aforementioned water-soluble polymers.

[0077] As described later, when preparing a standard sample film, when water is used, it is preferable to use a water-soluble polymer, and when an organic solvent is used, it is preferable to use a water-insoluble polymer.

[0078] Examples of the polymer include (meth)acrylic polymers, styrene polymers, olefin polymers, polyester polymers, polyamide polymers, and cellulose polymers.

[0079] (Meth)acrylic polymer is a general name for acrylic polymers and methacrylic polymers.

[0080] Many of the (meth)acrylic polymers, styrene polymers, olefin polymers, polyester polymers, and polyamide polymers exemplified above are water-insoluble polymers.

[0081] The styrene-based polymer refers to a polymer containing the largest number of repeating units derived from styrene among all repeating units in terms of mass ratio.

[0082] From the perspective of further suppressing the deviation of the signal intensity at the measurement position based on the standard sample film (hereinafter also referred to as "the perspective of the present invention having a more excellent effect"), the content of the 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, relative to all the repeating units contained in the styrene-based polymer. The upper limit is not particularly limited, and 100% by mass is an example.

[0083] The (meth)acrylic polymer refers to a polymer containing the largest number of repeating units derived from an alkyl acrylate and / or an alkyl methacrylate among all repeating units in terms of mass ratio.

[0084] From the viewpoint of achieving more excellent effects of the present invention, the (meth)acrylic polymer preferably contains a repeating unit derived from an alkyl (meth)acrylate having an alkyl group having 1 to 14 carbon atoms.

[0085] From the viewpoint of achieving more excellent effects of the present invention, the number of carbon atoms in the alkyl (meth)acrylate is preferably 2 to 14, more preferably 3 to 10, and even more preferably 3 to 8.

[0086] Alkyl (meth)acrylate is a general name for alkyl acrylate and alkyl methacrylate.

[0087] Examples of the alkyl (meth)acrylate 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.

[0088] From the perspective of achieving even greater effects of the present invention, the content of repeating units derived from an alkyl (meth)acrylate having an alkyl group having 1 to 14 carbon atoms in the (meth)acrylic polymer is preferably 50% by mass or greater, more preferably 70% by mass or greater, and even more preferably 90% by mass or greater, relative to all repeating units contained in the (meth)acrylic polymer. The upper limit is not particularly limited, but may be 100% by mass.

[0089] An olefin polymer is a polymer containing, in terms of mass ratio, a repeating unit derived from an olefin as the largest component among all repeating units. Examples of the olefin include ethylene and propylene.

[0090] Polyester polymers are polymers synthesized by forming ester bonds by dehydration condensation of polycarboxylic acids (dicarboxylic acids) and polyols (diols). Examples of polyester polymers include polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate.

[0091] A polyamide polymer is a polymer formed by bonding a plurality of monomers via an amide bond. Examples of the polyamide polymer include nylon 6 and nylon 6,6.

[0092] The cellulose polymer refers to a polymer having a cellulose skeleton. Examples of the cellulose polymer include diacetyl cellulose and triacetyl cellulose.

[0093] 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 hydroxyl group, a structure containing a pyrrolidone ring, and a structure containing an oxyalkylene group.

[0094] Examples of the hydroxyl group-containing water-soluble polymer include gum arabic, soybean gum, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethylated cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, glyoxalated hydroxypropyl ethyl cellulose, hydroxypropyl methyl cellulose phthalate, methyl cellulose, and polyvinyl alcohol.

[0095] Examples of the water-soluble polymer containing a pyrrolidone ring include polyvinyl pyrrolidone and a copolymer of vinyl pyrrolidone and vinyl acetate.

[0096] Examples of the water-soluble polymer containing an oxyalkylene group include polyalkylene glycols such as polyethylene glycol and polyoxyethylene polyoxypropylene glycol (also referred to as polyoxyethylene-polyoxypropylene condensate), and polyoxyalkylene monoalkyl ethers or aryl ethers such as poly(ethylene glycol) methyl ether and poly(ethylene glycol) phenylene ether.

[0097] Among them, as the water-soluble polymer, a water-soluble polymer or polysaccharide containing a pyrrolidone ring is preferred, a water-soluble polymer containing a pyrrolidone ring is more preferred, and polyvinyl pyrrolidone is further preferred.

[0098] Examples of the polysaccharides include polysaccharides, polysaccharide derivatives, and alkali metal salts thereof.

[0099] As the cellulose-based polymer, a compound in which at least a part of the hydroxyl groups of cellulose are substituted with at least one selected from the group consisting of an alkyl group and a hydroxyalkyl group is preferred.

[0100] The polymer content in the standard sample film is not particularly limited. From the perspective of achieving even greater effects of the present invention, the polymer content is preferably 40% by mass or greater, more preferably 60% by mass or greater, even more preferably 80% by mass or greater, and particularly preferably 90% by mass or greater, relative to the total mass of the standard sample film. The upper limit is not particularly limited, but is generally less than 99% by mass, preferably 98% by mass or less, and more preferably 97% by mass or less.

[0101] The polymer may be used alone 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.

[0102] (metal element)

[0103] The metal element is not particularly limited, and known metal elements may be mentioned.

[0104] 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. Examples of metal elements belonging to Group 13 of the periodic table include aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). Examples of metal elements belonging to Group 14 of the periodic table include germanium (Ge), tin (Sn), and lead (Pb). Examples of metal elements belonging to Group 15 of the periodic table include antimony (Sb) and bismuth (Bi). Examples of metal elements belonging to Group 16 of the periodic table include polonium (Po).

[0105] As metal elements, from the viewpoint of more excellent effects of the present invention, preferred are 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).

[0106] In addition, metal elements in the standard sample film can be ionized.

[0107] The metal elements may be used alone or in combination of two or more.

[0108] When the standard sample film contains two or more different metal elements, the signal intensities of the two or more metal elements can be obtained in laser ablation inductively coupled plasma mass spectrometry, so that a calibration curve related to multiple metal elements can be drawn using one standard sample film.

[0109] 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. The upper limit is not particularly limited, but is often 40 or less.

[0110] The content of the metal element 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, from the viewpoint of achieving more excellent effects of the present invention.

[0111] When two or more metal elements of different types are used in combination, the concentration of each metal element is preferably within the above range.

[0112] The metal element in the standard sample film is preferably derived from an organic acid metal salt or an inorganic acid metal salt.

[0113] In other words, the standard sample film contains the metal element derived from the organic acid metal salt when the standard sample film is produced. Furthermore, the organic acid metal salt can be separated into anions and cations within the standard sample film.

[0114] Furthermore, when the standard sample film is manufactured, an inorganic acid metal salt is used, so the standard sample film contains a metal element derived from the inorganic acid metal salt. In other words, in this case, the standard sample film contains the inorganic acid metal salt. Furthermore, the inorganic acid metal salt can be separated into anions and cations within the standard sample film.

[0115] The organic acid metal salt refers to a salt containing an organic acid and a metal element.

[0116] Examples of the metal element contained in the organic acid metal salt include the metal elements listed above.

[0117] Examples of the organic acid 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. Among them, compounds having a sulfonic acid group are preferred.

[0118] The organic acid preferably has a hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group), more preferably an aliphatic hydrocarbon group, and even more preferably 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.

[0119] In addition, the organic acid may have both an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

[0120] As the organic acid, from the viewpoint of achieving more excellent effects of the present invention, hydrocarbons having the above-mentioned acid groups are preferred, and alkyl allyl sulfonic acid is more preferred.

[0121] The inorganic acid metal salt refers to a salt containing an inorganic acid and a metal element.

[0122] Examples of the metal element contained in the inorganic acid metal salt include the metal elements listed above.

[0123] Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.

[0124] (Other ingredients)

[0125] The standard sample film may contain other components in addition to the above-mentioned polymer and metal element within a range that does not impair the effects of the present invention.

[0126] As other components, for example, hydrocarbons can be mentioned.

[0127] The type of hydrocarbon is not particularly limited, and known hydrocarbons may be used.

[0128] The hydrocarbon may be a saturated hydrocarbon or an unsaturated hydrocarbon, but is preferably a saturated hydrocarbon from the viewpoint of achieving more excellent effects of the present invention.

[0129] The hydrocarbon may be an aliphatic hydrocarbon or an aromatic hydrocarbon, but is preferably an aliphatic hydrocarbon from the viewpoint of achieving more excellent effects of the present invention.

[0130] The hydrocarbon may be linear or branched, and may have a cyclic structure.

[0131] The number of carbon atoms in the hydrocarbon is not particularly limited, but from the viewpoint of achieving better effects of the present invention, it is preferably 5 or more, more preferably 10 or more, further preferably 15 or more, and particularly preferably 20 or more. The upper limit is not particularly limited, but is often 40 or less, and more often 30 or less.

[0132] As the hydrocarbon, from the viewpoint of further improving the effects of the present invention, an aliphatic saturated hydrocarbon is preferred, an aliphatic saturated hydrocarbon having 10 or more carbon atoms is more preferred, and paraffin is further preferred.

[0133] In this specification, paraffin wax refers to an aliphatic saturated hydrocarbon having 15 or more carbon atoms.

[0134] The SP (Solubility Parameter) value of the hydrocarbon is not particularly limited, but is preferably 14 to 18 MPa from the viewpoint of achieving a more excellent effect of the present invention. 1 / 2 , more preferably 15 to 17 MPa 1 / 2 .

[0135] The calculation method of the SP value is as follows.

[0136] Using the calculation program (HSPiP, ver.4.1.07), the molecular structure of each material was input, and the HSP value (Hansen Solubility Parameter) calculation function included in the program was used to calculate the HSP value (δ D , δ P , δ H ). Then, the SP value is calculated according to the following formula.

[0137] Formula SP value = (δ D 2 +δ P 2 +δ H 2 ) 1 / 2

[0138] The hydrocarbons may be used alone or in combination of two or more.

[0139] In addition, when the standard sample film contains an organic acid metal salt having a hydrocarbon group (when the standard sample film contains a metal element derived from the organic acid metal salt), 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 preferably within 3.5 MPa from the viewpoint of further improving the effect of the present invention. 1 / 2 Within, more preferably within 2.0MPa 1 / 2 Within, more preferably within 1.0 MPa 1 / 2 The lower limit of the absolute value of the above difference is not particularly limited, and can be 0 MPa. 1 / 2 .

[0140] The standard sample film may contain a surfactant.

[0141] When the standard sample film contains a surfactant, the type of surfactant is not particularly limited, and known surfactants may be listed, for example, hydrocarbon surfactants, fluorine and / or silicon surfactants (specifically, fluorine surfactants, silicon surfactants or surfactants having both fluorine atoms and silicon atoms), preferably fluorine and / or silicon surfactants (specifically, fluorine surfactants, silicon surfactants or surfactants having both fluorine atoms and silicon atoms).

[0142] The standard sample film contains a surfactant, and thus coating defects (shrinkage, coating streaks, and surface irregularities) can be suppressed when the film is formed by coating over a large area.

[0143] Examples of the hydrocarbon surfactant include acetylene surfactants OLFIN 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.).

[0144] Examples of the fluorine-based and / or silicon-based surfactants include the surfactants described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425.

[0145] Furthermore, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph

[0280] of the specification of U.S. Patent Application Publication No. 2008 / 0248425 can also be used.

[0146] Furthermore, 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-241, S-242, S-243, S-420, S-431, S-386, S-611, S-647, S-651, S-653, S-656, S-693 (manufactured by AGC Seimi Chemical Co., Ltd.), PF-136A, PF-156A, PF-151N (manufactured by OMNOVA Solutions Inc.), FTERGENT 100, 100C, 150, 150CH, 251, 212M, 215M, 250, 222F, 245F, 208G, DFX-18, 710FL, 710FM, 710FS, 610FM, 683 (manufactured by NEOS Co., Ltd.).

[0147] These surfactants may be used alone or in combination of two or more.

[0148] 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 %, based on the total solid content of the standard sample film.

[0149] (Shape of standard sample film)

[0150] The maximum height difference of the standard sample film thickness is 0.50 μm or less, preferably 0.30 μm or less, more preferably 0.20 μm or less, and even more preferably 0.10 μm or less from the viewpoint of achieving better effects of the present invention. The lower limit is not particularly limited, but is often 0.001 μm or more.

[0151] The maximum height difference of the film thickness of the above-mentioned standard sample film is measured by the following method.

[0152] Use a probe-type film thickness measuring machine to calculate the film thickness of the standard sample film. The measuring distance is 3mm and the scanning speed is 0.02mm / sec. The 3mm straight line measured for the first time is used as scanning line 1, and the second measurement is performed at a position separated by a distance of more than 0.2mm in the direction perpendicular to the scanning line 1. In the following, the same measurement is repeated for a total of 10 measurements. Perform 10 measurements (scans) to find the maximum and minimum values ​​of the film thickness in each scan, and take the difference between the maximum value A among the 10 maximum values ​​obtained by 10 scans and the minimum value B among the 10 minimum values ​​obtained by 10 scans (value A-value B) as the maximum height difference of the film thickness.

[0153] The average film thickness of the standard sample film is not particularly limited. From the perspective of achieving the best effects of the present invention, it is preferably 3.5 μm or less, more preferably 2.5 μm or less, and even more preferably 2.0 μm or less. The lower limit of the average film thickness is not particularly limited. From the perspective of measurement accuracy, it is preferably 0.05 μm or more, and more preferably 0.1 μm or more.

[0154] The average film thickness was determined by measuring the thickness at 20 arbitrary locations using a probe-type film thickness measuring device and taking the arithmetic average.

[0155] In order to achieve more excellent effects of the present invention, the element concentration deviation of the standard sample film determined by the following method X is preferably 30% or less, more preferably 20% or less. The lower limit is not particularly limited, but may be 0%.

[0156] Method X: Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is performed at 10 locations on the surface of the standard sample film from one surface of the standard sample film to the other surface to obtain a depth profile of the secondary ion intensity of the metal element. The position at 20% of the total thickness of the standard sample film from one surface of the standard sample film to the other surface side is taken as the first position, and the position at 80% of the total thickness of the standard sample film from one surface of the standard sample film to the other surface side is taken as the second position. The total value of the secondary ion intensity of the metal element from the first position to the second position at each location is calculated, and the relative standard deviation of the total value of the 10 secondary ion intensities obtained is calculated as the element concentration deviation.

[0157] The above elements will be described in detail below using the accompanying drawings. In addition, in order to facilitate understanding of the contents of the invention, the following drawings are described in a manner different from actual data and scale.

[0158] Figure 1An example of a profile (depth-direction profile of secondary ion intensity of metal elements) obtained by analyzing the secondary ion intensity of metal elements in the depth direction of a standard sample film from one surface toward the other surface using the TOF-SIMS method is shown in FIG. 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 toward the other main surface.

[0159] More specifically, Figure 1 The analysis diagram in is equivalent to Figure 2 The results show that one surface 12A (the surface on the opposite side of the substrate 10 of the standard sample film 12) of the standard sample film 12 arranged on the substrate 10 is facing the other surface 12B (the surface on the substrate 10 side of the standard sample film 12), and the components in the depth direction of the standard sample film are analyzed by the TOF-SIMS method while ion sputtering is performed.

[0160] Figure 1 In the depth-direction profile diagram described in Figure 1 In the figure, the axis extending to the left and right of the paper) represents the depth based on one surface of the standard sample film, and the vertical axis ( Figure 1 In the figure, the axis extending in the vertical direction of the paper represents the secondary ion strength of the metal element.

[0161] The TOF-SIMS method is specifically described in "Surface Analysis Technology Series: Secondary Ion Mass Spectrometry" compiled by the Surface Science Society of Japan, published by Maruzen Co., Ltd. in 1999.

[0162] Figure 1 The horizontal axis 0 corresponds to surface 12A of standard sample film 12 , and the horizontal axis E corresponds to surface 12B of standard sample film 12 . That is, the horizontal axis 0 to E corresponds to one surface of standard sample film 12 to the other surface.

[0163] Furthermore, TOF-SIMS is preferably performed while irradiating the standard sample film with an ion beam. When analyzing the composition of the standard sample film in the depth direction using TOF-SIMS while irradiating the film with an ion beam, the following sequence of steps is repeated: analyzing the composition of a region 1 to 2 nm deep from the surface, then drilling deeper by 1 nm to several hundred nm, and analyzing the composition of the next region 1 to 2 nm deep from the surface.

[0164] like Figure 1 and 2As shown, the position at 20% of the total thickness of the standard sample film from one surface toward the other surface is defined as the first position P1, and the position at 80% of the total thickness of the standard sample film from one surface toward the other surface is defined as the second position P2.

[0165] More specifically, if Figure 2 As shown by the hollow arrow, the first position P1 is a position that is 20% of the total thickness T of the standard sample film from one surface 12A toward the other surface 12B of the standard sample film 12 with respect to the surface 12A. Figure 2 As indicated by the black arrow in the middle, a position that is 80% of the total thickness T of the standard sample film from one surface 12A toward the other surface 12B of the standard sample film 12 is defined as the second position P2 .

[0166] 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, Figure 1 The total value of the secondary ion intensity of the metal element from the first position P1 to the second position P2 shown in .

[0167] like Figure 1 As shown, near the surface of the standard sample film (surface 12A and surface 12B), the secondary ion intensity is sometimes unstable due to the influence of surface contamination, etc. Therefore, the secondary ion intensity in the area from one surface of the standard sample film to the first position P1 and the area from the other surface of the standard sample film to the second position P2 are excluded from the calculation.

[0168] The sum of the secondary ion intensities of the metal elements is calculated at 10 locations on the surface of the standard sample film. The sum of the secondary ion intensities of the metal elements at each measurement location (10 locations) is then calculated. The relative standard deviation of the sum of the secondary ion intensities of the 10 metal elements is calculated as the element concentration deviation (%).

[0169] The size of each measurement site was set to a range of 100 μm in length×100 μm in width.

[0170] To calculate the relative standard deviation, first determine the standard deviation calculated from the sum of the secondary ion intensities of the ten metal elements and the arithmetic mean of the sum of the secondary ion intensities of the ten metal elements. The ratio (%) of the standard deviation to the arithmetic mean is calculated as [(standard deviation / arithmetic mean) × 100] to obtain the element concentration deviation.

[0171] Furthermore, when the standard sample film contains multiple metal elements, it is preferred that the concentration variation of at least one of the metal elements be within a predetermined range, and it is more preferred that the concentration variation of each of the metal elements be within a predetermined range. In other words, it is more preferred that the concentration variation of all metal elements contained in the standard sample film be within a predetermined range.

[0172] (Method for producing standard sample film)

[0173] The method for manufacturing the standard sample film is not particularly limited as long as a standard sample film showing the above-mentioned characteristics can be manufactured. For example, when an organic acid metal salt is used, a method having the following steps can be cited: a standard sample film-forming composition containing a polymer (especially a water-insoluble polymer), an organic acid metal salt, other components used as needed (for example, hydrocarbons and surfactants), and an organic solvent is prepared, and the obtained standard sample film-forming composition is applied to a substrate to form a standard sample film. Furthermore, when an inorganic acid metal salt is used, a method having the following steps can be cited: a standard sample film-forming composition containing a polymer (especially a water-soluble polymer), an inorganic acid metal salt, other components used as needed (for example, surfactants), and an aqueous solution containing water or an inorganic acid is prepared, and the obtained standard sample film-forming composition is applied to a substrate to form a standard sample film. That is, a method having the following steps can be cited: a standard sample film-forming composition containing at least a polymer, a source of metal element, and a solvent is applied to a substrate to form a standard sample film.

[0174] Among them, from the viewpoint of being able to produce a standard sample film with excellent effects of the present invention with high yield, a method for producing a standard sample film comprising the following steps is preferred: coating a film containing a hydrocarbon and an organic acid metal salt, the absolute value of the difference in SP value between the hydrocarbon and the film is less than 3.5 MPa. 1 / 2 A standard sample film is formed by preparing a standard sample film-forming composition containing a polymer and a solvent in an amount of 1:1 to 1:1.

[0175] The hydrocarbon and the organic acid metal salt are as described above.

[0176] The absolute value of the difference between the SP value of hydrocarbons is 3.5 MPa 1 / 2 Polymers with a molecular weight of 1000 Å or less (hereinafter also referred to as "specific polymers") have good compatibility with hydrocarbons.

[0177] From the viewpoint of further improving the effects of the present invention, the absolute value of the difference between the SP value of the specific polymer and the SP value of the hydrocarbon is preferably 2.5 MPa. 1 / 2 Within, more preferably 2.0MPa 1 / 2 Within, especially preferably 1.5MPa 1 / 2 Within, most preferably 1.0MPa1 / 2 The lower limit of the absolute value of the difference is not particularly limited, but is preferably 0.

[0178] The SP value of the specific polymer may satisfy the above-mentioned range of the absolute value of the difference, but is preferably 15 to 19 MPa from the viewpoint of achieving a more excellent effect of the present invention. 1 / 2 , more preferably 16 to 17 MPa 1 / 2 .

[0179] When the specific polymer contains a plurality of repeating units, the product of the SP value of each repeating unit and the molar ratio of the repeating unit to all repeating units is calculated, and the SP value of the specific polymer is calculated in total. A Repeating units A and SP B When the repeating unit B is 100%, and the molar ratio of the repeating unit A relative to all the repeating units is 0.2 and the molar ratio of the repeating unit B relative to all the repeating units is 0.8, the SP value of the specific polymer is calculated as follows.

[0180] SP value of a specific polymer = (SP A ×0.2)+(SP B ×0.8)

[0181] The type of the specific polymer is not particularly limited as long as it satisfies the above range of the absolute value of the difference.

[0182] Examples of the specific polymer include (meth)acrylic polymers, styrene polymers, olefin polymers, polyester polymers, and polyamide polymers. A (meth)acrylic polymer or a styrene polymer is preferred, and a (meth)acrylic polymer is more preferred.

[0183] The details of each polymer are as described in the polymer contained in the standard sample film.

[0184] The content of the specific polymer contained in the standard sample film-forming composition is preferably adjusted to the content of the polymer in the standard sample film.

[0185] The content of the organic acid metal salt contained in the standard sample film-forming composition is preferably adjusted to the content of the metal element in the standard sample film.

[0186] From the viewpoint of achieving a more excellent effect of the present invention, the content of the hydrocarbon contained in the standard sample film-forming composition is preferably 1 to 60 mass %, more preferably 1 to 40 mass %, further preferably 1 to 20 mass %, and particularly preferably 1 to 10 mass % relative to the total amount of the specific polymer, the organic acid metal salt, and the hydrocarbon.

[0187] 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 and ester solvents being preferred.

[0188] Specific examples of the solvent include methyl ethyl ketone, butyl acetate, toluene, hexane, acetone, and chloroform.

[0189] The concentration of the solvent in the standard sample film-forming composition is not particularly limited. From the perspective of obtaining a film with 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%.

[0190] The method for coating the standard sample film-forming composition on the substrate is not particularly limited, and examples thereof include known methods (for example, spin coating, dip coating, inkjet coating, etc.).

[0191] The type of substrate is not particularly limited, and examples thereof include quartz, glass substrates, and silicon wafers from the viewpoint of excellent flatness.

[0192] After applying the standard sample film-forming composition to the substrate, a drying treatment may be performed as needed to remove the solvent from the coating. Examples of drying methods include heating. The drying treatment volatilizes and removes hydrocarbons.

[0193] The substrate may be a temporary support.

[0194] When the substrate serves as a temporary support, a transfer film is formed comprising the temporary support and the standard sample film disposed on the temporary support. The standard sample film on the temporary support of the transfer film is brought into contact with the object to be transferred, and the temporary support is peeled off, thereby allowing the standard sample film to be disposed on the object to be transferred. Using this transfer film, the standard sample film can be disposed on objects of various shapes.

[0195] Examples of the temporary support include a support whose surface is treated with a release agent (eg, a silicone-based release agent) and a support having a release property per se.

[0196] As the temporary support, a polymer substrate is preferred.

[0197] Examples of the material constituting the temporary support include cellulose-based polymers, (meth)acrylic polymers, styrene-based polymers, olefin-based polymers, polyester-based polymers, and polyamide-based polymers.

[0198] The water contact angle on the side of the temporary support where the standard sample film is placed is not particularly limited, but is preferably 100 degrees or more from the viewpoint of better transferability of the standard sample film.

[0199] The water contact angle can be measured using the non-wetting drop method described in JIS R 3257:1999. Specifically, the water contact angle is measured using a contact angle meter FTA1000 (softwear FTA32) (manufactured by First Ten Angstroms, Inc.) at 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. The radius r and height h of the pure water droplet on the temporary support surface after 30 seconds are determined. The water contact angle θ is then calculated using the formula θ = 2arctan(h / r).

[0200] <Sample Group>

[0201] The sample set according to the first embodiment of the present invention is a combination of a plurality of standard sample films. The plurality of standard sample films contain the same type of metal element, and the concentrations of the same type of metal element in the plurality of standard sample films are different from each other.

[0202] In laser ablation inductively coupled plasma mass spectrometry, multiple standard sample films containing the same metal element but varying concentrations are typically used to create a calibration curve representing the relationship between the concentration of a given metal element being measured and its signal intensity. Specifically, using this sample set allows for easy creation of a calibration curve.

[0203] The number of standard sample films in the sample set is not particularly limited, but preferably includes two or more standard sample films having different metal element concentrations, more preferably includes 5 or more. The upper limit is not particularly limited, but is usually 10 or less.

[0204] <Quantitative Analysis Method>

[0205] By using the standard sample film of the present invention, it is possible to analyze the content of a metal element contained in a measurement sample whose content of the metal element is unknown.

[0206] 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, a femtosecond laser ablation inductively coupled plasma mass spectrometer is preferably used. Examples of such a device include the Jupiter solid nebulizer (manufactured by ST Japan INC.).

[0207] 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 below. The device will be described in detail in the second embodiment.

[0208] The quantitative analysis method includes steps A to C described below.

[0209] Step A: Using a plurality of standard sample films of the present invention having different concentrations of metal elements, and measuring the signal intensity of metal element ions obtained from each standard sample film by laser ablation inductively coupled plasma mass spectrometry

[0210] Step B: Creating a calibration curve based on the concentration of metal elements in the plurality of standard sample films and the signal intensity of ions of the metal elements in the plurality of standard sample films obtained in step A

[0211] Step C: Using a measurement sample containing the same metal element as the metal element in the standard sample film, measuring the signal intensity of the metal element ion in the measurement sample 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

[0212] The order of each step is described in detail below.

[0213] (Process A)

[0214] Step A involves using multiple standard sample films of the present invention having different metal element concentrations and measuring the signal intensity of metal element ions obtained from each standard sample film by laser ablation inductively coupled plasma mass spectrometry. In this step, a standard sample film having a known metal element concentration is used to measure the signal intensity obtained from the standard sample film.

[0215] As described above, in this step A, a known laser ablation inductively coupled plasma mass spectrometer is used to measure the signal intensity.

[0216] In process A, laser light can be irradiated on multiple positions (locations) of the standard sample film to measure the signal intensity of the metal element ions at each position, and the obtained signal intensities are arithmetic averaged, so that the obtained average signal intensity is used as the signal intensity obtained from the standard sample film.

[0217] More specifically, if Figure 3 As shown, a plurality of regions 14 in the standard sample film 12 are irradiated with laser light respectively. Figure 3 In the embodiment, the number of regions 14 is 9, but the number is not particularly limited. Usually, the number is 5 to 20.

[0218] The size of the region 14 is not particularly limited, but is generally 0.1 to 1.0 mm in length and 0.1 to 1.0 mm in width.

[0219] The interval between the regions 14 is not particularly limited, and is usually approximately the length of one side of the region 14 .

[0220] There is no particular limitation on the method of irradiating the standard sample film with laser light.

[0221] 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, from the viewpoint of achieving more excellent effects of the present invention.

[0222] The intensity of the irradiated laser light is not particularly limited, but is preferably 1.0 to 2.0 J / cm2 from the viewpoint of achieving the best effect of the present invention. 2 , more preferably 1.2 to 1.8 J / cm 2 .

[0223] 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, from the viewpoint of achieving more excellent effects of the present invention.

[0224] 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, from the viewpoint of achieving more excellent effects of the present invention.

[0225] 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, from the viewpoint of achieving more excellent effects of the present invention.

[0226] The number of standard sample films having different metal element concentrations used in step A is not particularly limited, and the number required for measuring the calibration curve can be appropriately selected.

[0227] From the perspective of further improving the accuracy of quantitative analysis, the number of standard sample films having different metal element concentrations is preferably 2 or more, more preferably 5 to 20, and even more preferably 5 to 10. In other words, it is desirable to obtain data on the concentrations of metal elements in at least 2 (preferably 5 to 20, more preferably 5 to 10) standard sample films and the signal intensities at those concentrations.

[0228] By performing step A, data on the signal intensity of ions of the metal element to be measured based on the concentration of the metal element can be obtained from multiple standard sample films having different metal element concentrations. In other words, data on the signal intensity corresponding to the metal element concentration can be obtained for each metal element concentration.

[0229] When the standard sample film contains multiple metal elements (when it contains multiple organic acid metal salts of different metal elements), in this step A, the signal intensity of ions corresponding to the concentration of each metal element can be obtained.

[0230] (Process B)

[0231] Step B is a step of creating a calibration curve based on the concentration of the metal element in the plurality of standard sample films and the signal intensity of the ion of each metal element in the plurality of standard sample films obtained in step A.

[0232] As described above, in step A, data on the signal intensity based on the concentration of the metal element can be obtained from a plurality of standard sample films having different concentrations of the metal element. In this step B, a calibration curve is drawn using the concentration of the metal element and the signal intensity of the metal element ion based on the concentration. More specifically, for example, Figure 4 As shown in the figure, points corresponding to the concentration of metal elements and the signal intensity of metal element ions in each standard sample film are plotted on a rectangular coordinate with the concentration of metal elements as the horizontal axis and the signal intensity of metal element ions as the vertical axis (equivalent to Figure 4 ), and draw a calibration curve through the plotted points ( Figure 4 When drawing a calibration curve, for example, a method of drawing a calibration curve (regression line) according to the least squares method can be cited.

[0233] Figure 4 In the table, there are 5 plot points, but the number of plot points is not limited to Figure 4 .

[0234] (Process C)

[0235] Step C involves measuring the signal intensity of the metal element ions using laser ablation inductively coupled plasma mass spectrometry (LAICP-MS) using a measurement sample containing the same 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. In Step C, LAICP-MS is applied to a measurement sample whose metal element concentration is unknown to determine the signal intensity of the metal element ions. The concentration of the metal element corresponding to the signal intensity of the metal element ions in the measurement sample is read from the calibration curve to determine the concentration of the detection metal element in the measurement sample.

[0236] More specifically, if Figure 4As shown, when the concentration of the metal element obtained in process C is unknown, the signal intensity of the metal element ion of the measurement sample is S1, the concentration M1 of the metal element corresponding to the signal intensity S1 is read from the calibration curve, thereby being able to quantify the concentration of the metal element in the measurement sample as M1.

[0237] Furthermore, 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.

[0238] [Second embodiment]

[0239] The characteristic feature of the standard sample according to the second embodiment of the present invention is the use of an organic acid metal salt and a predetermined binder (hydrocarbon and a predetermined polymer).

[0240] The deviation of the signal intensity of the ion of the metal element based on the determination position is mainly relevant to the uniformity of the distribution of the metal element in the standard sample. That is, in the standard sample, when the organic acid metal salt is unevenly distributed, the signal intensity of the position where the metal acid of the organic acid is located is greatly different from that at the position where it is not. The present inventors have found that by using a predetermined adhesive, the organic acid metal salt can be uniformly dispersed in the standard sample, and the result can obtain the desired effect.

[0241] Furthermore, the reference material of the present invention can be used for various materials. In other words, the reference material of the present invention can be used for elemental analysis in a wide range of materials including inorganic and organic substances.

[0242] Hereinafter, the standard sample of the present invention will be described in detail, and then the sample set, transfer film, and quantitative analysis method will be described in detail.

[0243] <Standard Sample>

[0244] The standard sample of the present invention is used for laser ablation inductively coupled plasma mass spectrometry. The standard sample contains hydrocarbons, organic acid metal salts and the absolute value of the difference between the SP (Solubility Parameter) value of the standard sample and the hydrocarbon is 3.5 MPa. 1 / 2 Polymers within.

[0245] The following describes in detail the components contained in the standard sample.

[0246] (hydrocarbon)

[0247] The type of hydrocarbon is not particularly limited, and known hydrocarbons may be used.

[0248] The hydrocarbon may be a saturated hydrocarbon or an unsaturated hydrocarbon, but is preferably a saturated hydrocarbon from the viewpoint of achieving more excellent effects of the present invention.

[0249] The hydrocarbon may be an aliphatic hydrocarbon or an aromatic hydrocarbon, but is preferably an aliphatic hydrocarbon from the viewpoint of achieving more excellent effects of the present invention.

[0250] The hydrocarbon may be linear or branched, and may have a cyclic structure.

[0251] The number of carbon atoms in the hydrocarbon is not particularly limited, but from the viewpoint of achieving better effects of the present invention, it is preferably 5 or more, more preferably 10 or more, further preferably 15 or more, and particularly preferably 20 or more. The upper limit is not particularly limited, but is often 40 or less, and more often 30 or less.

[0252] As the hydrocarbon, from the viewpoint of further improving the effects of the present invention, an aliphatic saturated hydrocarbon is preferred, an aliphatic saturated hydrocarbon having 10 or more carbon atoms is more preferred, and paraffin is further preferred.

[0253] In this specification, paraffin wax refers to an aliphatic saturated hydrocarbon having 15 or more carbon atoms.

[0254] The SP value of the hydrocarbon is not particularly limited, but is preferably 14 to 18 MPa from the viewpoint of achieving a more excellent effect of the present invention. 1 / 2 , more preferably 15 to 17 MPa 1 / 2 .

[0255] The calculation method of the SP value is as follows.

[0256] Using the calculation program (HSPiP, ver.4.1.07), the molecular structure of each material was input, and the HSP value (Hansen Solubility Parameter) calculation function included in the program was used to calculate the HSP value (δ D , δ P , δ H ). Then, the SP value is calculated according to the following formula.

[0257] Formula SP value = (δ D 2 +δ P 2 +δ H 2 ) 1 / 2

[0258] The content of hydrocarbons in the standard sample is not particularly limited. From the viewpoint of achieving the best effects of the present invention, it is preferably 1 to 60 mass %, more preferably 1 to 40 mass %, further preferably 1 to 20 mass %, and particularly preferably 1 to 10 mass % relative to the total mass of the standard sample.

[0259] 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.

[0260] (Organic acid metal salt)

[0261] The organic acid metal salt refers to a salt containing an organic acid and a metal element.

[0262] Examples of the organic acid 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. Among them, compounds having a sulfonic acid group are preferred.

[0263] The organic acid preferably has a hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group), more preferably an aliphatic hydrocarbon group, and even more preferably 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.

[0264] In addition, the organic acid may have both an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

[0265] As the organic acid, from the viewpoint of achieving more excellent effects of the present invention, hydrocarbons having the above-mentioned acid groups are preferred, and alkyl allyl sulfonic acid is more preferred.

[0266] Furthermore, from the viewpoint of achieving a more excellent effect of the present invention, 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 preferably within 3.5 MPa. 1 / 2 Within, more preferably 2.0MPa 1 / 2 Within, more preferably 1.0 MPa 1 / 2 The lower limit of the absolute value of the above difference is not particularly limited, and can be 0 MPa. 1 / 2 .

[0267] The metal element of the metal salt is not particularly limited, and known metal elements can be listed. As the metal element, for example, metal elements of the 1st to 12th group of the periodic table and metal elements of the 13th to 16th groups of the periodic table can be listed except hydrogen. As metal elements belonging to the 13th group of the periodic table, aluminum (Al), gallium (Ga), indium (In) and thallium (Tl) can be listed. As metal elements belonging to the 14th group of the periodic table, germanium (Ge), tin (Sn) and lead (Pb) can be listed. As metal elements belonging to the 15th group of the periodic table, antimony (Sb) and bismuth (Bi) can be listed. As metal elements belonging to the 16th group of the periodic table, polonium (Po) can be listed.

[0268] As metal elements, from the viewpoint of more excellent effects of the present invention, preferred are 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).

[0269] The content of the organic acid metal salt in the standard sample is not particularly limited. From the viewpoint of achieving better effects of the present invention, the concentration of the metal element derived from the organic acid metal salt 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.

[0270] The concentration of the metal element derived from the organic acid metal salt in the standard sample refers to the concentration of the metal element contained in the organic acid metal salt in the standard sample.

[0271] The organic acid metal salt may be used alone or in combination of two or more. When two or more organic acid metal salts containing different metal elements are used in combination, the concentration of the metal element derived from each organic acid metal salt is preferably within the above range.

[0272] As described above, when two or more organic acid metal salts are used, it is preferable to use two or more organic acid metal salts having different kinds of metal elements.

[0273] When the standard sample contains two or more organic acid metal salts of different metal elements, the signal intensities of the two or more metal elements can be obtained in laser ablation inductively coupled plasma mass spectrometry, thereby enabling a calibration curve related to multiple metal elements to be drawn using one standard sample.

[0274] The number of organic acid metal salts containing different metal elements in the standard sample is not particularly limited, but is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. The upper limit is not particularly limited, but is often 40 or less.

[0275] (The absolute value of the difference from the SP value of hydrocarbons is 3.5MPa 1 / 2 polymers within

[0276] The absolute value of the difference between the SP value of hydrocarbons is 3.5 MPa 1 / 2 Polymers with a molecular weight of 1000 Å or less (hereinafter also referred to as "specific polymers") have good compatibility with hydrocarbons.

[0277] From the viewpoint of further improving the effects of the present invention, the absolute value of the difference between the SP value of the specific polymer and the SP value of the hydrocarbon is preferably 2.5 MPa. 1 / 2 Within, more preferably 2.0MPa 1 / 2 Within, especially preferably 1.5MPa 1 / 2 Within, most preferably 1.0MPa 1 / 2 The lower limit of the absolute value of the difference is not particularly limited, but is preferably 0.

[0278] The SP value of the specific polymer may satisfy the above-mentioned range of the absolute value of the difference, but is preferably 15 to 19 MPa from the viewpoint of achieving a more excellent effect of the present invention. 1 / 2 , more preferably 16 to 17 MPa 1 / 2 .

[0279] The calculation method of the SP value is as follows.

[0280] Using the calculation program (HSPiP, ver.4.1.07), the molecular structure of each material (the structure of the repeating unit in a specific polymer) was input, and the HSP value (Hansen Solubility Parameter) calculation function included in the program was used to calculate the HSP value (δ D , δ P , δ H ). Then, the SP value is calculated according to the following formula.

[0281] Formula SP value = (δ D 2 +δ P 2 +δ H 2 ) 1 / 2

[0282] When the specific polymer contains a plurality of repeating units, the product of the SP value of each repeating unit and the molar ratio of the repeating unit to all repeating units is calculated, and the SP value of the specific polymer is calculated in total. A Repeating units A and SP B When the repeating unit B is 100%, and the molar ratio of the repeating unit A relative to all the repeating units is 0.2 and the molar ratio of the repeating unit B relative to all the repeating units is 0.8, the SP value of the specific polymer is calculated as follows.

[0283] SP value of a specific polymer = (SP A ×0.2)+(SP B ×0.8)

[0284] The type of the specific polymer is not particularly limited as long as it satisfies the above range of the absolute value of the difference.

[0285] Examples of the specific polymer include (meth)acrylic polymers, styrene polymers, olefin polymers, polyester polymers, and polyamide polymers. A (meth)acrylic polymer or a styrene polymer is preferred, and a (meth)acrylic polymer is more preferred.

[0286] (Meth)acrylic polymer is a general name for acrylic polymers and methacrylic polymers.

[0287] The styrene-based polymer refers to a polymer containing the largest number of repeating units derived from styrene among all repeating units in terms of mass ratio.

[0288] From the viewpoint of being more excellent in the effect of the present invention, the content of the 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 still more preferably 90% by mass or more relative to all the repeating units contained in the styrene-based polymer. The upper limit is not particularly limited, and 100% by mass can be cited.

[0289] The (meth)acrylic polymer refers to a polymer containing the largest number of repeating units derived from an alkyl acrylate and / or an alkyl methacrylate among all repeating units in terms of mass ratio.

[0290] From the viewpoint of achieving more excellent effects of the present invention, the (meth)acrylic polymer preferably contains a repeating unit derived from an alkyl (meth)acrylate having an alkyl group having 1 to 14 carbon atoms.

[0291] From the viewpoint of achieving more excellent effects of the present invention, the number of carbon atoms in the alkyl (meth)acrylate is preferably 2 to 14, more preferably 3 to 10, and even more preferably 3 to 8.

[0292] Alkyl (meth)acrylate is a general name for alkyl acrylate and alkyl methacrylate.

[0293] Examples of the alkyl (meth)acrylate 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.

[0294] From the perspective of achieving even greater effects of the present invention, the content of repeating units derived from an alkyl (meth)acrylate having an alkyl group having 1 to 14 carbon atoms in the (meth)acrylic polymer is preferably 50% by mass or greater, more preferably 70% by mass or greater, and even more preferably 90% by mass or greater, relative to all repeating units contained in the (meth)acrylic polymer. The upper limit is not particularly limited, but may be 100% by mass.

[0295] An olefin polymer is a polymer containing, in terms of mass ratio, a repeating unit derived from an olefin as the largest component among all repeating units. Examples of the olefin include ethylene and propylene.

[0296] Polyester polymers are polymers synthesized by forming ester bonds by dehydration condensation of polycarboxylic acids (dicarboxylic acids) and polyols (diols). Examples of polyester polymers include polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate.

[0297] A polyamide polymer is a polymer formed by bonding a plurality of monomers via an amide bond. Examples of the polyamide polymer include nylon 6 and nylon 6,6.

[0298] The content of the specific polymer in the standard sample is not particularly limited. From the perspective of achieving the best effects of the present invention, the content is preferably 40% by mass or greater, more preferably 60% by mass or greater, even more preferably 80% by mass or greater, and particularly preferably 90% by mass or greater, relative to the total mass of the standard sample. The upper limit is not particularly limited, but is generally less than 99% by mass, preferably 98% by mass or less, and more preferably 97% by mass or less.

[0299] 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.

[0300] The standard sample may contain other components in addition to the above-mentioned hydrocarbons, organic acid metal salts, and specific polymers within a range that does not impair the effects of the present invention.

[0301] As other components, a solvent can be mentioned.

[0302] 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. The lower limit is not limited, and 0% by mass is an example.

[0303] The method for preparing the standard sample is not particularly limited, and examples include a method of mixing the various components (hydrocarbon, organic acid metal salt, and specific polymer) described above. Examples of the mixing method include a method of adding the various components to a solvent, mixing and stirring, and removing the solvent.

[0304] The shape of the standard sample is not particularly limited and can be film-like or block-like. Wherein, from the viewpoint of easily implementing the measurement, it is preferably film-like. In addition, when the standard sample of the present invention is film-like, the surface flatness of the resulting film is excellent.

[0305] When the standard sample is in a film form, the average thickness of the sample film composed 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 from the viewpoint of achieving better effects of the present invention.

[0306] The average film thickness is determined by measuring the thickness of a sample film composed of a standard sample at 20 arbitrary locations using a probe-type film thickness measuring device and taking the arithmetic average of the measured thicknesses.

[0307] The method for producing the sample film composed of the standard sample is not limited. Examples include a method of mixing a solvent and the above-mentioned various components (hydrocarbon, organic acid metal salt and specific polymer) to prepare a composition, applying the obtained composition on a substrate, and performing a drying treatment as needed.

[0308] The type of solvent used is not particularly limited, as long as it can dissolve the various components mentioned 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 and ester solvents being preferred.

[0309] Specific examples of the solvent include methyl ethyl ketone, butyl acetate, toluene, hexane, acetone, and chloroform.

[0310] The concentration of the solvent in the composition is not particularly limited. From the viewpoint of obtaining a film with 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%.

[0311] The method for applying the composition on the substrate is not particularly limited, and examples thereof include known methods (for example, spin coating, dip coating, inkjet coating, etc.).

[0312] The type of substrate is not particularly limited, and examples thereof include quartz, glass substrates, and silicon wafers from the viewpoint of excellent flatness.

[0313] After the composition is applied to the substrate, a drying treatment may be performed as needed to remove the solvent in the coating film. Examples of the drying treatment method include heating.

[0314] The substrate may be a temporary support.

[0315] When the substrate serves as a temporary support, a transfer film is formed comprising the temporary support and a sample film composed of the standard sample placed on the temporary support. The sample film on the temporary support of the transfer film is brought into contact with the object to be transferred, and the temporary support is peeled off, thereby allowing the sample film to be placed on the object to be transferred. Using this transfer film, the sample film can be placed on objects of various shapes.

[0316] Examples of the temporary support include a support whose surface is treated with a release agent (eg, a silicone-based release agent) and a support having a release property per se.

[0317] As the temporary support, a polymer substrate is preferred.

[0318] Examples of the material constituting the temporary support include cellulose-based polymers, (meth)acrylic polymers, styrene-based polymers, olefin-based polymers, polyester-based polymers, and polyamide-based polymers.

[0319] The water contact angle on the side of the sample film composed of the standard sample on the temporary support is not particularly limited, but is preferably 100 degrees or more from the viewpoint of better transferability of the sample film.

[0320] The water contact angle can be measured using the non-wetting drop method described in JIS R 3257:1999. Specifically, the water contact angle is measured using a contact angle meter FTA1000 (softwear FTA32) (manufactured by First Ten Angstroms, Inc.) at 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. The radius r and height h of the pure water droplet on the temporary support surface after 30 seconds are determined. The water contact angle θ is then calculated using the formula θ = 2arctan(h / r).

[0321] <Sample Group>

[0322] The sample set according to the second embodiment of the present invention is a combination of a plurality of standard samples. The plurality of standard samples contain the same type of organic acid metal salt, and the concentrations of the same type of organic acid metal salt in the plurality of standard samples are different from each other.

[0323] In laser ablation inductively coupled plasma mass spectrometry, multiple standard samples of the same type of organic acid metal salt, each containing different concentrations, are typically used to create a calibration curve representing the relationship between the concentration and signal intensity of a given metal element being measured. Specifically, using this sample set allows for easy creation of a calibration curve.

[0324] The number of standard samples in the sample set is not particularly limited, but preferably includes two or more standard samples having different concentrations of the organic acid metal salt, more preferably includes five or more. The upper limit is not particularly limited, but is usually 10 or less.

[0325] <Quantitative Analysis Method>

[0326] By using the standard sample of the present invention, it is possible to analyze the content of a metal element contained in a measurement sample whose content of the metal element is unknown.

[0327] 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, a femtosecond laser ablation inductively coupled plasma mass spectrometer is preferably used. Examples of such a device include the Jupiter solid nebulizer (manufactured by ST Japan INC.).

[0328] A laser ablation inductively coupled plasma mass spectrometer generally includes a laser ablation section (hereinafter also referred to as "LA section") and an inductively coupled plasma mass spectrometer section (hereinafter also referred to as "ICP-MS section").

[0329] The LA section is where laser ablation is performed by irradiating the sample with laser light. The structure of the LA section is not particularly limited and can employ a known structure. Typically, it comprises a stage for placing the sample and a laser irradiation section. A carrier gas composed of noble gases such as helium (He) and argon (Ar) is introduced into the LA section, and the particles or vapors generated by laser irradiation are transported to the ICP-MS section.

[0330] Typically, the LA section and the ICP-MS section are connected via a pipeline.

[0331] In the ICP-MS section, the measurement target 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 atomic species and their concentrations.

[0332] The structure of the ICP-MS unit is not particularly limited and a known structure may be adopted. Generally, most units include a plasma torch for generating plasma to ionize a sample introduced together with a carrier gas and a mass spectrometer located near the front end of the plasma torch.

[0333] The quantitative analysis method includes steps 1 to 3 described below.

[0334] Step 1: Using a plurality of standard samples of the present invention having different concentrations of metal elements derived from organic acid metal salts, a step of measuring the signal intensity of metal element ions obtained from each standard sample by laser ablation inductively coupled plasma mass spectrometry

[0335] Step 2: Creating a calibration curve based on the concentration of the metal element derived from the organic acid metal salt in the plurality of standard samples and the signal intensity of the ion of each metal element in the plurality of standard samples obtained in Step 1

[0336] Step 3: Using a measurement sample containing the same metal element as the metal element derived from the organic acid metal salt 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.

[0337] The order of each step is described in detail below.

[0338] (Process 1)

[0339] Step 1 involves measuring the signal intensity of the metal element ions obtained from each of the plurality of standard samples of the present invention having different concentrations of the metal element derived from the organic acid metal salt by laser ablation inductively coupled plasma mass spectrometry. In this step, the signal intensity obtained from the standard samples is measured using a known concentration of the metal element derived from the organic acid metal salt.

[0340] As described above, in step 1, a known laser ablation inductively coupled plasma mass spectrometer is used to measure the signal intensity.

[0341] In process 1, laser light can be irradiated on multiple positions (parts) of the standard sample to measure the signal intensity of the metal element ions at each position, and the obtained signal intensities are arithmetic averaged, so that the obtained average signal intensity is used as the signal intensity obtained from the standard sample.

[0342] More specifically, if Figure 5 As shown, a plurality of regions 22 in the standard sample 20 are irradiated with laser light respectively. Figure 5 In the embodiment, the number of regions 22 is 9, but the number is not particularly limited. Usually, the number is 5 to 20.

[0343] The size of the region 22 is not particularly limited, but is generally 0.1 to 1.0 mm in length and 0.1 to 1.0 mm in width.

[0344] The interval between the regions 22 is not particularly limited, and is usually about the length of one side of the region 22 .

[0345] There is no particular limitation on the method of irradiating the standard sample with laser light.

[0346] 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, from the viewpoint of achieving more excellent effects of the present invention.

[0347] The intensity of the irradiated laser light is not particularly limited, but is preferably 1.0 to 2.0 J / cm2 from the viewpoint of achieving the best effect of the present invention. 2 , more preferably 1.2 to 1.8 J / cm 2 .

[0348] 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, from the viewpoint of achieving more excellent effects of the present invention.

[0349] 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, from the viewpoint of achieving more excellent effects of the present invention.

[0350] 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, from the viewpoint of achieving more excellent effects of the present invention.

[0351] The number of standard samples having different concentrations of the metal element derived from the organic acid metal salt used in step 1 is not particularly limited, and the number required for measuring the calibration curve can be appropriately selected.

[0352] From the perspective of further improving the accuracy of quantitative analysis, the number of standard samples having different concentrations of the metal element derived from the organic acid metal salt 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 data on the concentration of the metal element in at least 2 (preferably 5 to 20, more preferably 5 to 10) standard samples and the signal intensity at that concentration.

[0353] By performing step 1, data on the signal intensity of ions of the metal element to be measured based on the concentrations of the metal element can be obtained from a plurality of standard samples having different metal element concentrations. In other words, data on the signal intensity corresponding to the metal element concentration can be obtained for each metal element concentration.

[0354] When the standard sample contains multiple metal elements (when it contains multiple organic acid metal salts of different metal elements), in step 1, the signal intensity of ions corresponding to the concentration of each metal element can be obtained.

[0355] (Process 2)

[0356] Step 2 is a step of creating a calibration curve based on the concentration of the metal element derived from the organic acid metal salt in the plurality of standard samples and the signal intensity of the ion of each metal element in the plurality of standard samples obtained in step 1.

[0357] As described above, in step 1, data on the signal intensity based on the concentration of the metal element can be obtained from a plurality of standard samples having different concentrations of the metal element. In this step 2, a calibration curve is drawn using the concentration of the metal element and the signal intensity of the metal element ion based on the concentration. More specifically, for example, Figure 6 As shown in the figure, on a rectangular coordinate with the concentration of the metal element as the horizontal axis and the signal intensity of the ion of the metal element as the vertical axis, points corresponding to the concentration of the metal element in each standard sample and the signal intensity of the ion of the metal element are plotted (equivalent to Figure 6 ), and draw a calibration curve through the plotted points ( Figure 6 When drawing a calibration curve, for example, a method of drawing a calibration curve (regression line) according to the least squares method can be cited.

[0358] Figure 6 In the table, there are 5 plot points, but the number of plot points is not limited to Figure 6 .

[0359] (Process 3)

[0360] Step 3 involves measuring the signal intensity of the metal element ions using laser ablation-inductively coupled plasma-mass spectrometry (LAICP-MS) using a measurement sample containing the same metal element as the metal element derived from the organic acid metal salt in the standard sample, and determining the concentration of the metal element in the measurement sample based on a calibration curve. In this step, LAICP-MS is applied to a measurement sample whose metal element concentration is unknown to measure the signal intensity of the metal element ions. The metal element concentration corresponding to the signal intensity of the metal element ions in the measurement sample is read from the calibration curve to determine the concentration of the detected metal element in the measurement sample.

[0361] More specifically, if Figure 6 As shown, when the concentration of the metal element obtained in process 3 is an unknown measurement sample, the signal intensity of the metal element ion is S1, the concentration M1 of the metal element corresponding to the signal intensity S1 is read from the calibration curve, thereby being able to quantify the concentration of the metal element in the measurement sample as M1.

[0362] Furthermore, 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.

[0363] Example

[0364] The following examples and comparative examples are provided to further illustrate the characteristics of the present invention. The materials, usage amounts, ratios, treatment contents, and treatment steps shown in the following examples can be appropriately modified without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed in a restrictive manner based on the specific examples shown below.

[0365] <Example A>

[0366] (Example A1)

[0367] A solution was prepared by adding polybutyl methacrylate and a metal dispersion (manufactured by CONOSTAN STD and SCP SCIENCE) to methyl ethyl ketone and dissolving them. The concentration of polybutyl methacrylate was 10% by mass relative to the total mass of the solution. The metal dispersion contained a plurality of alkyl allyl sulfonates (SP value of the hydrocarbon group: 16 MPa) of different metal species. 1 / 2 ) and paraffin (SP value: 16MPa 1 / 2 The metal dispersion was added to the standard sample described below to achieve an aluminum concentration of 40 ppm by mass. Furthermore, the metal dispersion contained sodium, magnesium, aluminum, calcium, titanium, vanadium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, cadmium, barium, and lead in amounts equivalent to the aluminum.

[0368] Furthermore, the difference between the SP value of the hydrocarbon group contained in the alkyl allyl sulfonate and the SP value of the paraffin wax is 0 MPa. 1 / 2 .

[0369] The resulting solution was spin-coated (rotation speed: 2000 rpm, time: 20 seconds) onto synthetic quartz (2.5 cm long x 2.5 cm wide x 0.7 mm thick) to form a film-like standard sample on the synthetic quartz. The paraffin wax content relative to the total mass of the standard sample was 8% by mass, and the polybutyl methacrylate content relative to the total mass of the standard sample was the remainder excluding the paraffin wax and components derived from the metal dispersion (e.g., alkyl allyl sulfonium salt).

[0370] Femtosecond laser ablation inductively coupled plasma mass spectrometry was performed using the obtained film-shaped standard sample.

[0371] The femtosecond laser ablation apparatus used was Jupiter solid nebulizer (manufactured by ST Japan INC.).

[0372] The various conditions are as follows.

[0373] Laser conditions

[0374] Laser device: LPS MultiProbe

[0375] Laser wavelength: 260nm

[0376] Laser power (flux): 0.5-1.5 J / cm 2

[0377] Laser pulse width: 247fs

[0378] Laser frequency: 10,000 Hz

[0379] Irradiation time: about 2 seconds

[0380] Carrier gas: He gas is added in the sample chamber at 0.6 L / min, and Ar gas is added directly behind the sample chamber at 1.1 L / min.

[0381] Irradiation range: 1mm vertical × 1mm horizontal

[0382] ICP-MS conditions

[0383] MS measurement device: iCAP TQ (Thermo Fisher Scientific)

[0384] RF power: 1550W

[0385] ·Cooling gas flow rate: 14L / min

[0386] ·Auxiliary gas flow rate: 0.8L / min

[0387] like Figure 3 and 5 As shown, nine regions (each region size: 1 mm in length x 1 mm in width) of a film-like standard sample (standard sample film) were laser ablated to vaporize the sample. The intervals between the regions were 1 mm.

[0388] 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 then the relative standard deviation of the signal intensities was calculated.

[0389] In addition, regarding the relative standard deviation of the signal intensity shown in Table 1 described later, the relative standard deviation of all the metal elements contained in the standard sample was calculated, and the worst value was shown.

[0390] Furthermore, before the laser ablation measurement, the maximum height difference of the film thickness of the prepared standard sample was calculated using a probe-type film thickness measuring device.

[0391] The maximum height difference of the film thickness is measured as follows.

[0392] The film thickness of the standard sample film was calculated using a probe-type film thickness measuring machine. The measuring distance was 3 mm and the scanning speed was 0.02 mm / sec. The 3 mm straight line measured for the first time was used as scanning line 1, and the second measurement was performed at a position at a distance of more than 0.2 mm in the direction perpendicular to scanning line 1. The same measurement was repeated below, and a total of 10 measurements were performed. 10 measurements (scans) were performed to find the maximum and minimum values ​​of the film thickness in each scan, and the difference between the maximum value A among the 10 maximum values ​​obtained by 10 scans and the minimum value B among the 10 minimum values ​​obtained by 10 scans (value A-value B) was used as the maximum height difference of the film thickness.

[0393] (Examples A2 to A3 and Comparative Example A1)

[0394] The relative standard deviation of the signal intensity was determined by the same procedure as in Example A1, except that the type of the polymer used was changed as shown in Table 1 described later.

[0395] The above-described method X was applied to the film-shaped standard samples (standard sample films) obtained in each of the examples and comparative examples, and the element concentration deviation (%) of the metal elements contained in the standard sample films was calculated.

[0396] In Table 1, “PBMA” represents polybutyl methacrylate, “PMMA” represents polymethyl methacrylate, “PS” represents polystyrene, and “PVBC” represents polyvinyl benzyl chloride.

[0397] In Table 1, “Na concentration deviation (%)” indicates the element concentration deviation (%) of the Na element calculated by the above-mentioned method X, and “Mg concentration deviation (%)” indicates the element concentration deviation (%) of the Mg element calculated by the above-mentioned method X.

[0398] [Table 1]

[0399]

[0400] As shown in Table 1, it was confirmed that the relative standard deviation of the signal intensity was small when the standard sample of the present invention was used. In other words, it was confirmed that the variation in the signal intensity of the metal element depending on the measurement position was small.

[0401] Among them, by comparing Examples A1 to A3, it was confirmed that when the absolute value of the difference with hydrocarbons (paraffin) is 2.5 MPa 1 / 2 When within (preferably 1.0 MPa 1 / 2 The effect is more excellent.

[0402] (Example 2A)

[0403] Polyvinyl pyrrolidone (PVP) and a NaCl standard solution (for atomic absorption spectroscopy, manufactured by Kanto Chemical Co., Inc.) were added to water and dissolved to obtain a solution. The concentration of the polyvinyl pyrrolidone was 6% by mass relative to the total mass of the solution. The NaCl standard solution was added to the standard sample to obtain a Na element concentration of 40 ppm by mass.

[0404] The obtained solution was spin-coated (rotation speed: 1000 rpm, time: 20 seconds) on a quartz substrate (2.5 cm long × 2.5 cm wide × 1.0 mm thick) and baked at 200°C for 5 minutes using a hot plate to produce a film-shaped standard sample (standard sample film) on the quartz substrate.

[0405] Using the obtained standard sample film, various evaluations were carried out in the same manner as in Example A1. The results are shown in Table 2.

[0406] In addition, PVP is equivalent to a water-soluble polymer.

[0407] [Table 2]

[0408]

[0409] As shown in Table 2, it was confirmed that the relative standard deviation of the 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 the metal element intensity depending on the measurement position was small.

[0410] (Example 3A)

[0411] Polybutyl methacrylate, a metal dispersion (CONOSTAN STD, manufactured by SCP Science), 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 to the standard sample to obtain an aluminum concentration of 100 ppm by mass.

[0412] The obtained solution was spin-coated on a disk-shaped silicon wafer (4.0 inches in diameter x 0.5 mm in thickness) and baked at 200° C. for 5 minutes using a hot plate to produce a film-shaped standard sample (standard sample film) on the silicon wafer.

[0413] A test piece of the standard sample film having a length of 2.5 cm and a width of 2.5 cm was cut out from an arbitrary position of the silicon wafer, and the obtained test piece was evaluated. The results are shown in Table 3.

[0414] [Table 3]

[0415]

[0416] As shown in Table 3, it was confirmed that the relative standard deviation of the 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 the metal element intensity depending on the measurement position was small.

[0417] <Example B>

[0418] The results of the analysis of the metal elements ( 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 at each concentration of Pb) was calculated. Furthermore, as described in Example A above, in Example B, nine regions of a single standard sample were irradiated with laser light, and the average value of the resulting signal intensities was used as the signal intensities shown in Tables 4 to 6. The results are shown in Tables 4 to 6.

[0419] Furthermore, on a rectangular coordinate system with the concentration of each metal element as the horizontal axis and the signal intensity of the metal element ion as the vertical axis, points corresponding to the concentration of each metal element and the signal intensity of the metal element ion were plotted, and a calibration curve passing through the plotted points was drawn using the least squares method to calculate the coefficient of determination. In Tables 4 to 6, "calibration curve" represents the linear function of the drawn 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 result.

[0420] In addition, as a representative example, Figure 7 Shown in 43 The results when Ca.

[0421] The metal dispersion (manufactured by CONOSTAN STD and SCP SCIENCE) contained sodium alkylsulfonate, magnesium alkylallylsulfonate, aluminum alkylallylsulfonate, calcium alkylallylsulfonate, titanium alkylallylsulfonate, vanadium alkylallylsulfonate, chromium alkylallylsulfonate, manganese alkylallylsulfonate, iron alkylallylsulfonate, nickel alkylallylsulfonate, copper alkylallylsulfonate, zinc alkylallylsulfonate, molybdenumamine alkylallylsulfonate, cadmium alkylallylsulfonate, barium alkylallylsulfonate, and lead alkylallylsulfonate. The concentration of each of the organic acid metal salts in the metal dispersion was 0.01% by mass, calculated as the metal element. For example, the content of magnesium alkylallylsulfonate was such that the amount of magnesium in the metal dispersion reached 0.01% by mass.

[0422] [Table 4]

[0423]

[0424] [Table 5]

[0425]

[0426] [Table 6]

[0427]

[0428] As shown in Tables 4 to 6, the obtained calibration curves had excellent linearity for all metal elements, and thus good results were obtained.

[0429] By using the calibration curve, laser ablation inductively coupled plasma mass spectrometry is performed on a measurement sample whose concentration of the metal element is unknown, and the metal element can be quantified from the obtained signal intensity.

[0430] <Example C>

[0431] (Example C1)

[0432] As in Example A1, polybutyl methacrylate and a metal dispersion (manufactured by CONOSTAN STD, SCP SCIENCE) were added to methyl ethyl ketone and dissolved to obtain a solution. The metal dispersion was added to the standard sample to obtain an aluminum element concentration of 40 mass ppm.

[0433] The resulting solution was spin-coated (rotation speed: 2000 rpm, time: 20 seconds) onto a polypropylene film (2.5 cm long x 2.5 cm wide x 0.01 mm thick) to prepare a film-shaped standard sample (standard sample film) on the polypropylene film (hereinafter referred to as a temporary support). The paraffin content relative to the total mass of the standard sample film was 8% by mass, and the polybutyl methacrylate content relative to the total mass of the standard sample film was the remainder excluding the paraffin and components derived from the metal dispersion (e.g., alkyl allyl sulfonium salt).

[0434] The average film thickness of the standard sample film on the obtained temporary support was calculated using a probe-type film thickness measuring instrument.

[0435] The standard sample film surface on the obtained temporary support was pressed against the silicon wafer and held for 1 minute. The pressure during pressing was about 50 g / cm 2 , the environment is normal temperature and humidity.

[0436] The temporary support was peeled off, and the area of ​​the standard sample film on the temporary support was taken as 100%. The ratio of the area of ​​the standard sample film transferred to the silicon wafer was calculated. Furthermore, the average film thickness of the standard sample film transferred to the silicon wafer was calculated using a probe-type film thickness meter.

[0437] (Example C2)

[0438] The standard sample film was prepared and pressed against a silicon wafer in the same manner as in Example C1, except that the type of temporary support for coating the solution was changed to that shown in Table 7. The polyethylene terephthalate film (Example C2) had a thickness of 0.01 mm.

[0439] The water contact angle of the temporary support used was measured according to the above method.

[0440] In Table 7, "Transferred area (%)" indicates the ratio of the area of ​​the standard sample film transferred to the silicon wafer side when the temporary support is peeled off, with the area of ​​the standard sample film on the temporary support being 100%.

[0441] In Table 7, the column "Average film thickness (nm) of transferred standard sample films" shows the average film thickness of the standard sample films transferred to the silicon wafer side.

[0442] [Table 7]

[0443]

[0444] As shown in Table 7, polypropylene film and polyethylene terephthalate film were used as temporary supports, and the standard sample films were transferred onto silicon wafers. Comparison of Examples C1 and C2 confirmed that the effect was more excellent when the water contact angle of the temporary support was 100 degrees or greater.

[0445] Explanation of symbols

[0446] 10-substrate, 12-standard sample film, 14-area, 20-standard sample, 22-area.

Claims

1. A standard sample film for use in laser ablation inductively coupled plasma mass spectrometry, wherein: The standard sample film contains polymer and metal elements. The maximum height difference of the film thickness of the standard sample film is less than 0.50 μm. The maximum height difference of the film thickness of the standard sample film is measured by the following method: The thickness of the standard sample film was calculated using a probe-type film thickness measuring instrument. The measurement distance was 3 mm and the scanning speed was 0.02 mm / sec. The 3 mm straight line used in the first measurement was defined as scan line 1. A second measurement was performed at a location 0.2 mm or more apart in a direction perpendicular to scan line 1. Below, the same measurement is repeated for a total of 10 measurements. The 10 measurements, i.e. scans, are performed to find the maximum and minimum values ​​of the film thickness in each scan. The difference between the largest value A among the 10 maximum values ​​obtained by 10 scans and the smallest value B among the 10 minimum values ​​obtained by 10 scans (value A - value B) is taken as the maximum height difference of the film thickness.

2. The standard sample film according to claim 1, wherein The element concentration deviation of the standard sample film obtained by the following method X is 30% or less. Method X: Time-of-flight secondary ion mass spectrometry is performed at 10 locations on the surface of the standard sample film, from one surface of the standard sample film toward the other surface, to obtain a depth profile of the secondary ion intensity of the metal element. When a position at 20% of the total thickness of the standard sample film from one surface of the standard sample film toward the other surface is taken as the first position, and a position at 80% of the total thickness of the standard sample film from one surface of the standard sample film toward the other surface is taken as the second position, the total value of the secondary ion intensity of the metal element from the first position to the second position at each location is calculated, and the relative standard deviation of the total value of the 10 secondary ion intensities obtained is calculated, and the relative standard deviation is used as the element concentration deviation.

3. The standard sample film according to claim 1 or 2, wherein: The average film thickness of the standard sample film is 3.5 μm or less.

4. The standard sample film according to claim 1 or 2, wherein The metal element is derived from an organic acid metal salt or an inorganic acid metal salt. The standard sample film according to claim 1 or 2, comprising two or more metal elements.

6. The standard sample film according to claim 1 or 2, wherein: The polymer is a (meth)acrylic polymer.

7. A method for producing a standard sample film, comprising the steps of applying a standard sample film-forming composition to form the standard sample film. The standard sample film-forming composition comprises: hydrocarbon, Organic acid metal salts, The absolute value of the difference between the SP value of the hydrocarbon is 3.5 MPa 1 / 2 Polymers within solvent.

8. The method for producing a standard sample film according to claim 7, wherein: 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 within 3.5 MPa 1 / 2 Within.

9. A sample set, which is formed by combining a plurality of standard sample films according to any one of claims 1 to 6, wherein: The plurality of standard sample films contain the same type of metal elements, The concentrations of the metal elements in the plurality of standard sample films are different from each other.

10. A quantitative analysis method based on laser ablation inductively coupled plasma mass spectrometry, comprising: Step A, using a plurality of standard sample films according to any one of claims 1 to 6 having different concentrations of the metal element, and measuring the signal intensity of the ions of the metal element obtained from each of the standard sample films by laser ablation inductively coupled plasma mass spectrometry; Step B: drawing a calibration curve based on the concentration of the metal element in the plurality of standard sample films and the signal intensity of the ion of each metal element in the plurality of standard sample films obtained in Step A; and In step C, a measurement sample containing the same type of metal element as the metal element in the standard sample film is used to measure the signal intensity of the ions of the metal element in the measurement sample by laser ablation inductively coupled plasma mass spectrometry, and the concentration of the metal element in the measurement sample is calculated based on the calibration curve.

11. A transfer film comprising: temporary supports; and The standard sample film according to any one of claims 1 to 6 is disposed on the temporary support.

12. A standard sample for use in laser ablation inductively coupled plasma mass spectrometry, the standard sample comprising: hydrocarbon; Metal salts of organic acids; and The absolute value of the difference between the SP value of the hydrocarbon is 3.5 MPa 1 / 2 Polymers within.

13. The standard sample according to claim 12, wherein: The absolute value of the difference between the SP value of the polymer and the hydrocarbon is less than 2.5 MPa. 1 / 2 Within.

14. The standard sample according to claim 12 or 13, wherein: The polymer is a (meth)acrylic polymer.

15. The standard sample according to claim 12 or 13, wherein: The hydrocarbons include aliphatic saturated hydrocarbons having 10 or more carbon atoms.

16. The standard sample according to claim 12 or 13, wherein: The hydrocarbons include paraffins.

17. The standard sample according to claim 12 or 13, wherein: The organic acid has a sulfonic acid group.

18. The standard sample according to claim 12 or 13, wherein: The organic acid has a hydrocarbon group.

19. The standard sample according to claim 12 or 13, wherein: The standard sample contains two or more organic acid metal salts having different kinds of metal elements.

20. A sample set, which is formed by combining a plurality of standard samples according to any one of claims 12 to 19, wherein: The plurality of standard samples contain the same type of organic acid metal salt, The concentrations of the metal elements derived from the same type of organic acid metal salt in the plurality of standard samples are different from each other.

21. A quantitative analysis method based on laser ablation inductively coupled plasma mass spectrometry, comprising: Step 1, using a plurality of standard samples according to any one of claims 12 to 19 having different concentrations of the metal element derived from the organic acid metal salt, and measuring the signal intensity of the metal element ion obtained from each of the standard samples by laser ablation inductively coupled plasma mass spectrometry; Step 2: plotting a calibration curve based on the concentration of the metal element derived from the organic acid metal salt in the plurality of standard samples and the signal intensity of the ion of each metal element in the plurality of standard samples obtained in Step 1; and In step 3, a measurement sample containing the same type of metal element as the metal element derived from the organic acid metal salt in the standard sample is used to measure the signal intensity of the ion of the metal element by laser ablation inductively coupled plasma mass spectrometry, and the concentration of the metal element in the measurement sample is calculated based on the calibration curve.

22. A transfer film comprising: temporary supports; and The sample film is composed of the standard sample according to any one of claims 12 to 19 arranged on the temporary support.

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