Method for measuring relative fluorescence intensity

Abstract

The present invention is a method for measuring the relative fluorescence intensity of a test sample, wherein: a plate-like or film-like compact of a resin composition formed by melt-kneading a raw material mixture that includes a near-infrared fluorescent dye and an amorphous resin is used as a reference plate; a plate-like or film-like compact of a resin composition that, with the exception of not including the near-infrared fluorescent dye, has the same physical makeup as the reference plate is used as a blank plate; the test sample is a compact of a resin composition that includes the near-infrared fluorescent dye; a compact that excludes the near-infrared fluorescent dye from the test sample is used as a test sample blank; and (F1 − F1B) / (Fs − FSB) (where F1 is the fluorescence intensity of the test sample at wavelengths in the near-infrared region, F1B is the fluorescence intensity of the test sample blank at wavelengths in the near-infrared region, FS is the fluorescence intensity of the reference plate at wavelengths in the near-infrared region, and FSB is the fluorescence intensity of the blank plate at wavelengths in the near-infrared region) is the relative fluorescence intensity of the test sample.

Description

[Technical Field]

[0001] This invention relates to a method for determining the relative fluorescence intensity of a test sample that emits near-infrared fluorescence. This application claims priority based on Japanese Patent Application No. 2023-033836, filed in Japan on March 6, 2023, and the contents of that application are incorporated herein by reference. [Background technology]

[0002] Near-infrared fluorescent dyes are used in industrial products, primarily for product identification and anti-counterfeiting. In recent years, they have also been used in medical applications such as bioimaging probes and diagnostic reagents. The near-infrared wavelength range is known to be invisible to the naked eye, has minimal impact on living organisms, and has high penetration into skin and other biological tissues. These characteristics can be utilized by incorporating near-infrared fluorescent dyes into medical devices themselves. For example, by incorporating near-infrared fluorescent dyes into medical devices such as shunt tubes, the location of implanted medical devices can be confirmed by irradiating them with near-infrared light from outside the body.

[0003] If near-infrared fluorescent dyes can be mixed and dispersed in a resin, various molded articles that emit near-infrared fluorescence can be manufactured using that resin as a raw material. However, if the dispersibility of the near-infrared fluorescent dye in the resin is low, the near-infrared fluorescent dye may be unevenly distributed in the resin composition, and aggregates of the near-infrared fluorescent dye may form. Molded articles made from such resin compositions are prone to spot-like or streak-like surface defects. Therefore, it is desirable that the near-infrared fluorescent dye be uniformly dispersed in the resin.

[0004] Melt kneading is a commonly used method for uniformly dispersing additive components in resin because it is suitable for actual production. However, even when melt kneading is performed at a temperature below the decomposition point of the dye, depending on the type of resin and dye and the kneading conditions, dispersion failure may occur or the dye may decompose, resulting in no fluorescence emission. For this reason, unless the near-infrared fluorescent dye has sufficient heat resistance and durability, it is difficult to uniformly disperse it in the resin by melt kneading. For example, Patent Document 1 discloses that by mixing and dispersing a BODIPY dye or DPP-based boron complex, which has excellent heat resistance and emission quantum yield and emits near-infrared fluorescence, in a resin, a near-infrared fluorescent resin composition with strong emission intensity and a molded article made by processing the composition can be obtained.

[0005] On the other hand, products made from molded resin compositions containing near-infrared fluorescent dyes, like molded products containing other fluorescent dyes, must meet a predetermined fluorescence intensity value set in the product design for quality control purposes. Here, fluorescence intensity is easily affected by the measuring device and measurement conditions, and therefore, a standard sample is generally established, and the fluorescence intensity of the sample is evaluated as a relative value to the fluorescence intensity of the standard sample. For fluorescence intensity measurements including the visible light region, rhodamine-based fluorescent dyes such as rhodamine B (CAS No.: 81-88-9) are often used as standard samples. Rhodamine-based fluorescent dyes have low heat resistance and cannot be melt-mixed into resin, and their fluorescence intensity may decrease over time (Patent Document 2). For this reason, a solution diluted to an appropriate concentration at the time of measurement is usually used as the standard sample. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2015 / 056779 [Patent Document 2] Japanese Patent Publication No. 2010-223782 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] On the other hand, there are no known standard samples or measurement methods for measuring the relative fluorescence intensity of test samples that emit near-infrared fluorescence. Standard samples using rhodamine B have a fluorescence peak wavelength in the visible light region and a shoulder in the near-infrared region above 700 nm, so they can also be used for measuring near-infrared emission. However, with this method, there is variability in the preparation of the rhodamine-based fluorescent dye solution itself for each measurement, and the near-infrared fluorescence intensity of the rhodamine-based fluorescent dye solution is also affected by the time elapsed between preparation and measurement. Thus, because there is a large variability in the near-infrared fluorescence intensity value of the standard sample itself, the reliability of the obtained relative fluorescence intensity is insufficient when a rhodamine-based fluorescent dye solution is used as a standard sample for near-infrared emission measurement. In addition, rhodamine B does not have sufficient fluorescence intensity in the near-infrared region, and from this point of view, it is difficult to say that the relative fluorescence intensity of near-infrared fluorescence is being measured appropriately.

[0008] The object of the present invention is to provide a more reliable method for measuring the relative fluorescence intensity of a test sample that emits near-infrared fluorescence, and a kit including a standard plate which is a standard sample used in said method. [Means for solving the problem]

[0009] The present invention is as follows: [1] A method for measuring the relative fluorescence intensity of a test sample, The maximum fluorescence wavelength of the test sample is within the range of 650 nm to 1000 nm. A plate-shaped or film-shaped molded body of a resin composition obtained by melt-kneading a raw material mixture containing a near-infrared fluorescent dye and an amorphous resin is used as a standard plate. A plate-shaped or film-shaped molded body of a resin composition obtained by melt-kneading a raw material mixture having the same composition as the raw material mixture except that it does not contain the aforementioned near-infrared fluorescent dye is used as a blank plate. The test sample is a molded body of a resin composition containing the same or different near-infrared fluorescent dye as the near-infrared fluorescent dye in the standard plate. A molded body having the same composition as the test sample except that it does not contain the near-infrared fluorescent dye contained in the test sample is used as a test sample blank. The fluorescence intensity F1 of the test sample at wavelength λ1, the wavelength λ of the test sample blank 1B of fluorescence intensity F 1B The fluorescence intensity F of the standard plate at wavelength λ S of S The fluorescence intensity F of the blank plate at wavelength λ SB of SB are measured, where the wavelength λ1 is within the range of 650 to 1000 nm, the difference between the wavelength λ1 and the wavelength λ 1B is within 10 nm, the wavelength λ S is within the range of 650 to 1000 nm, the difference between the wavelength λ S and the wavelength λ SB is within 10 nm, and (F1 - F 1B ) / (Fs - F SB ) is taken as the relative fluorescence intensity of the test sample. A method for measuring relative fluorescence intensity. [2] A method for measuring the relative fluorescence intensity according to [1], wherein the fluorescence intensities of the test sample, the test sample blank, the standard plate, and the blank plate are measured using a spectrofluorometer. [3] A method for measuring the relative fluorescence intensity according to [1] or [2], wherein the amorphous resin is a transparent resin. [4] A method for measuring the relative fluorescence intensity according to any one of [1] to [3], wherein the amorphous resin is one or more selected from the group consisting of polycarbonate resins, polystyrene resins, acrylic resins, polyoxymethylene resins, polyester resins, and vinyl chloride resins. [5] A method for measuring the relative fluorescence intensity according to any one of [1] to [4], wherein the standard plate is a plate having a thickness of 1 μm to 15 mm. [6] A method for measuring the relative fluorescence intensity according to any one of [1] to [5], wherein the maximum fluorescence wavelength of the test sample is 700 nm or more. [7] A method for measuring the relative fluorescence intensity according to any one of [1] to [6], wherein the test sample is a molded body obtained by melt-molding a resin composition obtained by melt-kneading a mixture containing a near-infrared fluorescent dye as a raw material. [8] A method for measuring relative fluorescence intensity according to any of [1] to [7] above, wherein the test sample is a molded body used as a medical device. [9] The method for measuring relative fluorescence intensity according to [8], wherein the test sample is at least part a medical device used in the body of a patient.

[10] The near-infrared fluorescent dye is The following general formula (I1)

[0010] [ka]

[0011] [In formula (I1), R a and R b R a The nitrogen atom and R to which it is bonded b Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R c and R d R c The nitrogen atom and R to which it is bonded d Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R e and R f represents a halogen atom or an oxygen atom; R g This represents a hydrogen atom or an electron-withdrawing group. However, R e and R f If it is an oxygen atom, R e , R e The boron atom that bonds with R a , and R a The nitrogen atoms to which it is bonded may together form a ring, R f , R f The boron atom that bonds with R c , and R c The nitrogen atoms to which it is bonded may together form a ring. eIf it is an oxygen atom and does not form a ring, then R e R is an oxygen atom having a substituent, f If it is an oxygen atom and does not form a ring, then R f is an oxygen atom having a substituent. [The compound represented by ] The following general formula (I2)

[0012] [ka]

[0013] [In formula (I2), R a ~R f This is the same as formula (I1) above. ] Compounds represented by the following general formula (I3)

[0014] [ka]

[0015] [In formula (I3), R h and R i R h The nitrogen atom and R to which it is bonded i Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R j and R k R j The nitrogen atom and R to which it is bonded k Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R l , R m , R n , and R o These are, independently of each other, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group; R p and R qThese are, independently of each other, hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. R r and R s These represent, independently of each other, a hydrogen atom or an electron-withdrawing group. ] Compounds represented by ] and the following general formula (I4)

[0016] [ka]

[0017] [In formula (I4), R h ~R q This is the same as formula (I3) above. It is one or more compounds selected from the group consisting of compounds represented by ] The method for measuring the relative fluorescence intensity described in [1] above.

[11] The near-infrared fluorescent dye is defined by the following general formula (I1-0)

[0018] [ka]

[0019] [In formula (I1-0), R 1 , R 2 , and R 3 teeth, (p1) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. (p2)R 1 and R 2 Both form an aromatic 5-membered ring or an aromatic 6-membered ring, R 3 is a hydrogen atom, halogen atom, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (p3)R 2 and R 3together form an aromatic 5-membered ring or an aromatic 6-membered ring, and R 1 represents a hydrogen atom, a halogen atom, C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, or heteroaryl group. R 4 、R 5 、and R 6 are (q1) independently of each other, a hydrogen atom, a halogen atom, C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, or heteroaryl group, (q2) R 4 and R 5 together form an aromatic 5-membered ring or an aromatic 6-membered ring, and R 6 represents a hydrogen atom, a halogen atom, C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, or heteroaryl group, or (q3) R 5 and R 6 together form an aromatic 5-membered ring or an aromatic 6-membered ring, and R 4 represents a hydrogen atom, a halogen atom, C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, or heteroaryl group. R 7 and R 8 represent a halogen atom or an oxygen atom; R 9 represents a hydrogen atom or an electron-withdrawing group. However, when R 7 and R 8 are oxygen atoms, R 7 、R 7 the boron atom to which it is attached, the nitrogen atom to which the boron atom is attached, R 1 、and R 1 the carbon atom to which it is attached may together form a ring, and R 8 、R 8 the boron atom to which it is attached, the nitrogen atom to which the boron atom is attached, R 4 、and R 4 the carbon atom to which it is attached may together form a ring. R 7If it is an oxygen atom and does not form a ring, then R 7 R is an oxygen atom having a substituent, 8 If it is an oxygen atom and does not form a ring, then R 8 is an oxygen atom having a substituent. Compounds represented by ] and the following general formula (I2-0)

[0020] [ka]

[0021] [In formula (I2-0), R 1 ~R 8 The formula is the same as formula (I1-0) above. A method for measuring the relative fluorescence intensity of

[10] , wherein the compound is one or more compounds selected from the group consisting of compounds represented by

[10] .

[12] In the above general formula (I1-0) or the above general formula (I2-0), R 1 and R 2 They form a ring, R 4 and R 5 R forms a ring, or 2 and R 3 They form a ring, R 5 and R 6 They form a ring. The aforementioned ring is given by the following general formulas (C-1) to (C-9)

[0022] [ka]

[0023] [In formulas (C-1) to (C-9), Y 1 ~Y 8 Each of these independently represents a sulfur atom, oxygen atom, nitrogen atom, or phosphorus atom, and R 11 ~R 22 A method for measuring the relative fluorescence intensity of

[11] , which is represented by either a hydrogen atom or any group that does not inhibit the fluorescence of the compound, independently of each other.

[13] The near-infrared fluorescent dye is one of the following general formulas (I3-1) to (I3-6)

[0024] [ka]

[0025] [In formula (I3-1), R 23 , R 24 , R 25 , and R 26 These are, independently of each other, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group; R 27 and R 28 These are, independently of each other, hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group; R 29 and R 30 These independently represent a hydrogen atom or an electron-withdrawing group; Y 9 and Y 10 These represent, independently of each other, a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom; R 31 and R 32 teeth, (p4) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (p5)R 31 and R 32 Both form an optionally substituted aromatic five-membered ring or an optionally substituted aromatic six-membered ring; R 33 and R 34 teeth, (q4) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (q5)R 33 and R 34Both form an aromatic five-membered ring or an aromatic six-membered ring, which may have substituents.

[0026] [ka]

[0027] [In formulas (I3-2) to (I3-6), R 23 ~R 30 This is the same as equation (I3-1) above; X 1 and X 2 These represent a nitrogen atom or a phosphorus atom independently of each other; R 35 , R 36 , R 37 , and R 38 teeth, (p6) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. (p7)R 35 and R 36 Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R 37 and R 38 These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. (p8)R 36 and R 37 Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R 35 and R 38 These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (p9)R 37 and R 38 Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R35 and R 36 These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group; R 39 , R 40 , R 41 , and R 42 teeth, (q6) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. (q7)R 39 and R 40 Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R 41 and R 42 These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. (q8)R 40 and R 41 Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R 39 and R 42 These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (q9)R 41 and R 42 Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R 39 and R 40 These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 Compounds represented by any of the following general formulas (I4-1) to (I4-6): [represents an alkoxy group, an aryl group, or a heteroaryl group]

[0028] [ka]

[0029] [In formulas (I4-1) to (I4-6), R 23 ~R 28 This is the same as equation (I3-1) above. In equation (I4-1), R 31 ~R 34 , Y 9 , and Y 10 This is the same as equation (I3-1) above, and in equations (I4-2) to (I4-6), R 35 ~R 42 This is the same as equation (I3-2) above, and in equations (I4-3) to (I4-6), X 1 , and X 2 The formula is the same as formula (I3-3) above. A method for measuring the relative fluorescence intensity of

[10] , wherein the compound is one or more compounds selected from the group consisting of compounds represented by any of the formulas

[10] .

[14] The near-infrared fluorescent dyes are those of the following general formulas: (I1-1-1)~(I1-1-6), (I1-2-1)~(I1-2-12), (I2-1-1)~(I2-1-6), and (I2-2-1)~(I2-2-12)

[0030] [ka]

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] [In the formula, Y 11 and Y 12 These represent, independently of each other, an oxygen atom or a sulfur atom; Y 21 and Y 22 Each represents a carbon atom or a nitrogen atom independently of the other; Q 11 represents a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group; X consists of halogen atoms and C, which are independent of each other. 1-20 Represents an alkoxy group, aryloxy group, or acyloxy group; P 11 ~P 14 and P 17 These are, independently of each other, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 This represents alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups; A 11 ~A 14 These are, independently of each other, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 A phenyl group having 1 to 3 substituents selected from the group consisting of alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups, or a halogen atom, C 1-20 Alkyl alkyl group, C 1-20 Represents a heteroaryl group which may have 1 to 3 substituents selected from the group consisting of alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups; n11~n14 and n17 represent integers from 0 to 3, independently of each other; m1 represents either 0 or 1. A method for measuring the relative fluorescence intensity of

[10] , wherein the compound is one or more compounds selected from the group consisting of compounds represented by any of the above.

[15] The near-infrared fluorescent dye is one of the following general formulas (I3-7)~(I3-9) and (I4-7)~(I4-9)

[0037] [ka]

[0038] [In the formula, Y 23 and Y 24 Each represents a carbon atom or a nitrogen atom independently of the other; Y 13 and Y 14 These represent, independently of each other, an oxygen atom or a sulfur atom; Y 25 and Y 26 Each represents a carbon atom or a nitrogen atom independently of the other; R 47 and R 48 These represent, independently of each other, a hydrogen atom or an electron-withdrawing group; R 43 , R 44 , R 45 , and R 46 represents a halogen atom or an aryl group which may have a substituent; P 15 and P 16 These are, independently of each other, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 This represents alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups; n15 and n16 represent integers between 0 and 3, independently of each other; A 15 and A 16 These are, independently of each other, hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 This represents a phenyl group which may have 1 to 3 substituents selected from the group consisting of alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups. A method for measuring the relative fluorescence intensity of

[10] , wherein the compound is one or more compounds selected from the group consisting of compounds represented by any of the above.

[16] A standard plate comprising a plate-shaped or film-shaped molded body of a resin composition obtained by melt-kneading a raw material mixture containing a near-infrared fluorescent dye and an amorphous resin, A standard plate set for measuring relative fluorescence intensity, comprising a standard plate and a blank plate made of a molded body having the same shape and thickness as the standard plate, which is a resin composition obtained by melt-kneading a raw material mixture having the same composition as the raw material mixture except that it does not contain the aforementioned near-infrared fluorescent dye.

[17] The near-infrared fluorescent dye is The following general formula (I1)

[0039] [ka] [In formula (I1), R a and R b R a The nitrogen atom and R to which it is bonded b Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R c and R d R c The nitrogen atom and R to which it is bonded d Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R e and R f represents a halogen atom or an oxygen atom; R g This represents a hydrogen atom or an electron-withdrawing group. However, R e and R f If it is an oxygen atom, R e , R e The boron atom that bonds with R a , and R a The nitrogen atoms to which it is bonded may together form a ring, R f , R f The boron atom that bonds with R c , and R c The nitrogen atoms to which it is bonded may together form a ring. eIf it is an oxygen atom and does not form a ring, then R e R is an oxygen atom having a substituent, f If it is an oxygen atom and does not form a ring, then R f is an oxygen atom having a substituent. [The compound represented by ] The following general formula (I2)

[0040] [ka]

[0041] [In formula (I2), R a ~R f This is the same as formula (I1) above. ] Compounds represented by the following general formula (I3)

[0042] [ka]

[0043] [In formula (I3), R h and R i R h The nitrogen atom and R to which it is bonded i Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R j and R k R j The nitrogen atom and R to which it is bonded k Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R l , R m , R n , and R o These are, independently of each other, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group; R p and R qThese are, independently of each other, hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. R r and R s These represent, independently of each other, a hydrogen atom or an electron-withdrawing group. ] Compounds represented by ] and the following general formula (I4)

[0044] [ka]

[0045] [In formula (I4), R h ~R q The formula is the same as formula (I3) above. The standard plate set for measuring relative fluorescence intensity of

[16] is one or more compounds selected from the group consisting of compounds represented by

[16] .

[18] The standard plate set for relative fluorescence intensity measurement according to

[16] or

[17] , wherein the standard plate is a plate with a thickness of 1 μm to 15 mm.

[19] A standard plate set for measuring relative fluorescence intensity according to any of the above

[16] to

[18] , wherein the amorphous resin is one or more selected from the group consisting of polycarbonate resins, polystyrene resins, acrylic resins, polyoxymethylene resins, polyester resins, and vinyl chloride resins. [Effects of the Invention]

[0046] The relative fluorescence intensity measurement method according to the present invention is a method for investigating the relative fluorescence intensity of a test sample that emits near-infrared fluorescence, and uses a plate molded from a resin composition obtained by melt-kneading a near-infrared fluorescent dye as a standard sample. Therefore, compared to measurements using a rhodamine-based fluorescent dye solution prepared as in the conventional method as a standard sample, the relative fluorescence intensity of the near-infrared fluorescence of the molded body can be determined with higher accuracy. Furthermore, by using a standard plate set for relative fluorescence intensity measurement that includes the plate, the relative fluorescence intensity measurement method can be carried out more simply. [Modes for carrying out the invention]

[0047] The relative fluorescence intensity measurement method according to the present invention is a method for measuring the relative fluorescence intensity of a test sample that emits near-infrared fluorescence, characterized in that a plate-shaped or film-shaped molded body of a resin composition obtained by melt-kneading a raw material mixture containing a near-infrared fluorescent dye and an amorphous resin is used as a standard plate during fluorescence measurement. In this standard plate, since the near-infrared fluorescent dye is present in the molded body of the resin composition, it is more stable than in a solution state, and the fluorescence intensity of the standard plate is stable over time. For this reason, the same standard plate can be used in common for measurements with long intervals between measurements, eliminating the need for preparation each time and suppressing variability between measurements.

[0048] In the method for measuring relative fluorescence intensity according to the present invention, the relative value of the fluorescence intensity of the test sample at a wavelength substantially the same as wavelength λ1 of the standard plate in the near-infrared region is measured as the relative fluorescence intensity of the test sample. In the present invention and this specification, "substantially the same wavelength as a specific wavelength" means that the difference from that wavelength is within 10 nm, that is, a wavelength substantially the same as wavelength λ means a wavelength of λ ± 10 nm.

[0049] The method for measuring relative fluorescence intensity according to the present invention specifically uses a plate-shaped or film-shaped molded body of a resin composition obtained by melt-kneading a raw material mixture containing a near-infrared fluorescent dye and an amorphous resin as a standard plate, and a plate-shaped or film-shaped molded body of a resin composition obtained by melt-kneading a raw material mixture having the same composition as the raw material mixture except that it does not contain the near-infrared fluorescent dye as a blank plate. The fluorescence intensity F1 of the test sample at wavelength λ1, and wavelength λ that is substantially the same as wavelength λ1. 1B Fluorescence intensity F of the test sample blank in 1B , the wavelength λ of the standard plate S Fluorescence intensity F S , the wavelength λ S wavelength λ is essentially the same wavelength. SB The fluorescence intensity F of the blank plate in the above-mentioned case SBMeasure (F1-F 1B ) / (F S -F SB The relative fluorescence intensity of the test sample is defined as λ1 and λ1. S Both wavelengths are in the near-infrared region, i.e., within the range of 650-1000 nm, and wavelength λ1 and wavelength λ S These wavelengths are essentially the same. By determining the relative fluorescence intensity of the test sample with respect to a standard plate at wavelengths in the near-infrared region, it becomes possible to quantify the fluorescence intensity.

[0050] In this invention, the wavelength λ1 used to measure the fluorescence intensity of the test sample is the same as the wavelength λ used to measure the fluorescence intensity of the standard plate. S The wavelengths may be substantially different, substantially the same, or even identical. For example, if the near-infrared fluorescent dye contained in the test sample and the near-infrared fluorescent dye contained in the standard plate are of the same type, then wavelength λ1 and wavelength λ S Although different wavelengths are acceptable, wavelengths λ1 and λ are preferred for more reliable results. S It is preferable that the wavelengths are substantially the same, and more preferably the same. On the other hand, if the near-infrared fluorescent dye contained in the test sample and the near-infrared fluorescent dye contained in the standard plate are different dyes, then wavelength λ1 and wavelength λ S This may be defined as substantially the same wavelength that shows sufficient fluorescence intensity in both the test sample and the standard plate, with wavelengths λ1 and λ S These may be substantially different wavelengths.

[0051] In this invention, the wavelength λ1 is used to measure the fluorescence intensity of the test sample, and the wavelength λ is used to measure the fluorescence intensity of the standard plate. S The wavelengths are not particularly limited as long as each exhibits sufficient fluorescence intensity. In order to obtain more reliable results, in this invention, wavelength λ1 is set as the maximum fluorescence wavelength of the test sample, and wavelength λ SIt is preferable to use this as the maximum fluorescence wavelength of the standard plate. If the near-infrared fluorescent dye contained in the test sample and the near-infrared fluorescent dye contained in the standard plate are of the same type, the maximum fluorescence wavelength of the test sample and the maximum fluorescence wavelength of the standard plate are substantially the same wavelength.

[0052] In the following, unless otherwise specified, "fluorescence wavelength of the standard plate" refers to "wavelength λ". S This means that "fluorescence intensity of the standard plate" is "wavelength λ of the standard plate" S Fluorescence intensity F S This means that "the fluorescence wavelength of the blank plate" is "wavelength λ SB This means that "the fluorescence intensity of the blank plate" is "the wavelength λ of the blank plate" SB Fluorescence intensity F SB This means "fluorescence wavelength of the test sample" means "wavelength λ1", "fluorescence intensity of the test sample" means "fluorescence intensity F1 at wavelength λ1 of the test sample", and "fluorescence wavelength of the test sample blank" means "wavelength λ 1B This means that "fluorescence intensity of the test sample blank" is "wavelength λ of the test sample blank" 1B Fluorescence intensity F 1B It means "...".

[0053] <Standard Plate> The standard plate used in the present invention is a plate-shaped or film-shaped molded body of a resin composition obtained by melt-kneading a raw material mixture containing a near-infrared fluorescent dye and an amorphous resin. That is, after melt-kneading a raw material mixture containing a near-infrared fluorescent dye and an amorphous resin, the resulting resin composition is molded into a plate-shaped or film-shaped form. Since it is a melt-molded body of a resin composition containing a near-infrared fluorescent dye and an amorphous resin, the standard plate has the near-infrared fluorescent dye uniformly dispersed throughout the entire plate.

[0054] <Near-infrared fluorescent dyes> The near-infrared fluorescent dye contained in the standard plate used in the present invention is a near-infrared fluorescent dye that can be melt-kneaded with resin and has sufficient heat resistance and durability to stably emit near-infrared fluorescence in the resulting mixture. The near-infrared fluorescent dye contained in the standard plate is not particularly limited, as long as it has sufficient heat resistance and durability suitable for melt-kneading.

[0055] The near-infrared fluorescent dyes contained in the standard plates used in the present invention include, specifically, compounds represented by the following general formulas (I1), (I2), (I3), or (I4). These compounds may hereinafter be referred to as "the near-infrared fluorescent dyes according to the present invention."

[0056] [ka]

[0057] [ka]

[0058] In general formula (I1) or general formula (I2), R a and R b R a The nitrogen atom and R to which it is bonded b It forms an aromatic ring consisting of 1 to 3 rings together with the carbon atom to which it is bonded. Similarly, in general formula (I1) or general formula (I2), R c and R d R c The nitrogen atom and R to which it is bonded d It forms an aromatic ring consisting of 1 to 3 rings together with the carbon atom to which it is bonded. a and R b The aromatic ring formed by, and R c and R d Each ring in the aromatic ring formed is either a 5-membered or 6-membered ring. Compounds represented by general formula (I1) or general formula (I2) are R a and R b The aromatic ring and R that are formed c and R dThe aromatic ring formed by this compound has a fused ring structure in which a ring containing a boron atom bonded to two nitrogen atoms is attached. In other words, the compound represented by general formula (I1) or general formula (I2) has a robust fused ring structure consisting of a broad conjugated plane.

[0059] In general formula (I3) or general formula (I4), R h and R i R h The nitrogen atom and R to which it is bonded i It forms an aromatic ring consisting of 1 to 3 rings together with the carbon atom to which it is bonded. Similarly, in general formula (I3) or general formula (I4), R j and R k R j The nitrogen atom and R to which it is bonded k It forms an aromatic ring consisting of 1 to 3 rings together with the carbon atom to which it is bonded. h and R i The aromatic ring formed by, and R j and R k Each ring in the aromatic ring formed is either a 5-membered or 6-membered ring. Compounds represented by general formula (I3) or general formula (I4) are R h and R i A triring is formed by the condensation of an aromatic ring, a ring containing a boron atom bonded to two nitrogen atoms, and a five-membered heteroring containing one nitrogen atom, and R j and R k The compound has a ring structure in which at least six rings are fused together, i.e., a ring containing a boron atom bonded to two nitrogen atoms and a five-membered heteroring containing one nitrogen atom, which are fused together. Thus, the compound represented by general formula (I3) or general formula (I4) has a robust fused ring structure consisting of a very broad conjugated plane.

[0060] R a and R b The aromatic ring formed by, R c and R d The aromatic ring formed by, R h and R i The aromatic ring formed by, and R j and R kThe aromatic ring formed is not particularly limited as long as it has an aromatic property. Examples of such aromatic rings include pyrrole rings, imidazole rings, pyrazole rings, oxazole rings, thiazole rings, pyridine rings, pyrimidine rings, pyridazine rings, isoindole rings, indole rings, indazole rings, purine rings, perimidine rings, thienopyrrole rings, phlopyrrole rings, pyrrolothiazole rings, and pyrrolooxazole rings. Since the maximum fluorescence wavelength is extended to the near-infrared region, in particular, in the case of general formula (I1) or general formula (I3), the aromatic ring preferably has 2 or 3 ring fusions, and more preferably 2 from the standpoint of complexity in synthesis. However, even when the aromatic ring has 1 ring fusion, it is possible to extend the wavelength by devising substituents on the ring or on the boron. Furthermore, in particular, in the case of general formula (I2) or general formula (I4), the wavelength can be extended to the near-infrared region simply by attaching a substituted aryl group or heteroaryl group.

[0061] R a and R b The aromatic ring formed by, R c and R d The aromatic ring formed by, R h and R i The aromatic ring formed by, and R j and R k The aromatic ring formed may be unsubstituted, or it may have one or more substituents. The substituents on the aromatic ring may be "any group that does not inhibit the fluorescence of the compound."

[0062] The near-infrared fluorescent dye according to the present invention is preferably one that does not exhibit mutagenicity, cytotoxicity, sensitization, or skin irritation in necessary biological safety tests. Furthermore, from a safety viewpoint, it is preferable that the near-infrared fluorescent dye according to the present invention does not leach out from molded articles obtained by processing a resin composition containing the near-infrared fluorescent dye when exposed to bodily fluids such as blood or tissue fluid. For this reason, it is preferable that the near-infrared fluorescent dye according to the present invention has low solubility in biological components such as blood. Considering these factors, it is preferable that the substituent is selected to be one that is less likely to exhibit mutagenicity or to reduce water solubility.

[0063] Examples of such substituents include halogen atoms, nitro groups, cyano groups, hydroxyl groups, carboxyl groups, aldehyde groups, sulfonic acid groups, alkylsulfonyl groups, halogenosulfonyl groups, thiol groups, alkylthio groups, isocyanate groups, thioisocyanate groups, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkoxycarbonyl groups, alkylamidecarbonyl groups, alkylcarbonylamide groups, acyl groups, amino groups, monoalkylamino groups, dialkylamino groups, silyl groups, monoalkylsilyl groups, dialkylsilyl groups, trialkylsilyl groups, monoalkoxysilyl groups, dialkoxysilyl groups, trialkoxysilyl groups, aryl groups, and heteroaryl groups. a and R b The aromatic ring formed by, R c and R d The aromatic ring formed by, R h and R i The aromatic ring formed by, and R j and R k The substituents on the aromatic ring formed are preferably cyano groups, hydroxyl groups, carboxyl groups, alkylthio groups, alkyl groups, alkoxy groups, alkoxycarbonyl groups, amide groups, alkylsulfonyl groups, fluorine, chlorine, aryl groups, or heteroaryl groups, from the viewpoint of safety for living organisms, and these substituents may have further substituents. However, safety can be improved by introducing other substituents as well, so the material is not limited to these substituents.

[0064] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms, chlorine atoms, and bromine atoms being preferred, and fluorine atoms being more preferred.

[0065] Alkyl groups, alkenyl groups, and alkynyl groups may be linear, branched, or cyclic (aliphatic ring groups). The number of carbon atoms in these groups is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl (tert-butyl), pentyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups. Examples of alkenyl groups include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, and 2-hexenyl groups. Examples of alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, isopropynyl group, 1-butynyl group, and isobutynyl group.

[0066] Examples of alkyl groups include alkylsulfonyl groups, alkylthio groups, alkoxy groups, alkoxycarbonyl groups, alkylamidecarbonyl groups, alkylcarbonylamide groups, monoalkylamino groups, dialkylamino groups, monoalkylsilyl groups, dialkylsilyl groups, trialkylsilyl groups, monoalkoxysilyl groups, dialkoxysilyl groups, and trialkoxysilyl groups. The alkyl group portion of these groups is the same as that of the alkyl groups mentioned above. For example, examples of alkoxy groups include methoxy groups, ethoxy groups, propyloxy groups, isopropyloxy groups, n-butyloxy groups, isobutyloxy groups, t-butyloxy groups, pentyloxy groups, isoamyloxy groups, hexyloxy groups, heptyloxy groups, octyloxy groups, nonyloxy groups, decyloxy groups, undecyloxy groups, and dodecyloxy groups. Furthermore, examples of monoalkylamino groups include methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, t-butylamino group, pentylamino group, hexylamino group, etc., and examples of dialkylamino groups include dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, dipentylamino group, dihexylamino group, ethylmethylamino group, methylpropylamino group, butylmethylamino group, ethylpropylamino group, butylethylamino group, etc.

[0067] Examples of aryl groups include phenyl, naphthyl, indenyl, and biphenyl groups. Phenyl groups are preferred. Examples of heteroaryl groups include five-membered ring heteroaryl groups such as pyrrolyl, imidazolyl, pyrazolyl, thienyl, furanyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, and thiadiazole groups; six-membered ring heteroaryl groups such as pyridinyl, pyrazinyl, pyrimidinyl, and pyridadinyl groups; and condensed heteroaryl groups such as indolyl, isoindolyl, indazolyl, quinolidinyl, quinolinyl, isoquinolinyl, benzofuranyl, isobenzofuranyl, clomenyl, benzoxazolyl, benzoisoxazolyl, benzothiazolyl, and benzoisothiazolyl groups.

[0068] Alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and heteroaryl groups may be unsubstituted or may have one or more hydrogen atoms substituted by substituents. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, nitro groups, cyano groups, hydroxyl groups, amino groups, thiol groups, carboxyl groups, aldehyde groups, sulfonic acid groups, isocyanate groups, thioisocyanate groups, aryl groups, and heteroaryl groups.

[0069] The absorption and emission wavelengths of fluorescent dyes depend on the surrounding environment. Therefore, the absorption wavelength of a fluorescent dye in a resin may be shorter or longer compared to when it is in solution. When the absorption wavelength of the near-infrared fluorescent dye itself is lengthened according to the present invention, it is preferable because the maximum absorption wavelength will be in the near-infrared region even in various resins. The maximum absorption wavelength of a fluorescent dye can be lengthened by introducing electron-donating groups and electron-withdrawing groups at appropriate positions within the molecule, thereby narrowing the band gap between the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO).

[0070] For example, among the compounds represented by general formula (I1), R a and R b The aromatic ring and R that are formed c and R d An electron-donating group is introduced into the aromatic ring formed by R gBy introducing an electron-withdrawing group, the maximum absorption wavelength and maximum fluorescence wavelength of the compound can be made longer. Similarly, among the compounds represented by general formula (I3), R h and R i The aromatic ring and R that are formed j and R k Introducing an electron-donating group into the aromatic ring formed by R p and R q If it is an aromatic ring, an electron-donating group is introduced into the aromatic ring, or R r and R s By introducing electron-withdrawing groups, the maximum absorption and fluorescence wavelengths of the compound can be extended to longer wavelengths. By combining these designs, it is possible to adjust the wavelength to the desired value.

[0071] Compounds represented by general formula (I2) having an aza-BODIPY skeleton are R a and R b The aromatic ring and R that are formed c and R d The aromatic ring formed by this has a skeleton that absorbs at relatively long wavelengths even when unsubstituted. Unlike the compound represented by general formula (I1), in this skeleton, the bridging portion of the pyrrole is a nitrogen atom, so substituents cannot be introduced on the nitrogen, but the pyrrole portion (R a and R b The aromatic ring and R that are formed c and R d By introducing an electron-donating group to the aromatic ring formed by the compound, the maximum absorption wavelength and maximum fluorescence wavelength of the compound can be extended to longer wavelengths. Similarly, in the case of a compound represented by general formula (I4), the pyrrole moiety (R h and R i The aromatic ring and R that are formed j and R k Introducing an electron-donating group to the aromatic ring formed by, or R p and R q If the compound is an aromatic ring, introducing an electron-donating group to the aromatic ring can extend the maximum absorption wavelength and maximum fluorescence wavelength of the compound to longer wavelengths.

[0072] Therefore, Ra and R b The aromatic ring formed by, R c and R d The aromatic ring formed by, R h and R i The aromatic ring formed by, and R j and R k The substituents on the aromatic ring formed are preferably groups that function as electron-donating groups for the aromatic ring, among "any group that does not inhibit the fluorescence of the compound". The introduction of an electron-donating group to the aromatic ring causes the fluorescence of the compound represented by general formula (I1), general formula (I2), general formula (I3), or general formula (I4) to be shifted to longer wavelengths. Examples of groups that function as electron-donating groups include alkyl groups; alkoxy groups such as methoxy groups; aryl groups (aromatic ring groups) such as phenyl groups, p-alkoxyphenyl groups, p-dialkylaminophenyl groups, and dialkoxyphenyl groups; and heteroaryl groups (heteroaromatic ring groups) such as 2-thienyl groups and 2-furanyl groups. For alkyl groups, alkyl groups in substituents of phenyl groups, and alkyl groups in alkoxy groups, linear or branched alkyl groups having 1 to 10 carbon atoms are preferred. The number of carbon atoms and whether or not the alkyl group is branched may be appropriately selected in consideration of the various physical properties of the dye. From the viewpoint of solubility and compatibility, it is sometimes preferable to have 6 or more carbon atoms, or that the element is branched. a and R b The aromatic ring formed by, R c and R d The aromatic ring formed by, R h and R i The aromatic ring formed by, and R j and R k The substituents on the aromatic ring formed by are C 1-6 Alkyl alkyl group, C 1-6An alkoxy group, aryl group, or heteroaryl group is preferred, a methyl group, ethyl group, methoxy group, phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-dimethylaminophenyl group, dimethoxyphenyl group, thienyl group, or furanyl group is more preferred, and a methyl group, ethyl group, methoxy group, phenyl group, or p-methoxyphenyl group is even more preferred. Because the BODIPY skeleton has high planarity, molecules tend to aggregate by π-π stacking. By introducing an aryl group or heteroaryl group with a bulky substituent into the BODIPY skeleton, molecular aggregation can be suppressed, and the emission quantum yield of a standard plate containing the near-infrared fluorescent dye can be increased.

[0073] In general formula (I1) or general formula (I2), R a and R b The aromatic ring formed by and R c and R d The aromatic ring formed by may be different from or the same as the one formed by R. In general formula (I3) or general formula (I4), h and R i The aromatic ring formed by and R j and R k The aromatic ring formed may be different from or the same as the one formed. The near-infrared fluorescent dye according to the present invention is easy to synthesize and tends to have a higher emission quantum yield, a and R b The aromatic ring and R that are formed c and R d The aromatic ring formed by, or R h and R i The aromatic ring and R that are formed j and R k The aromatic rings formed are preferably of the same type.

[0074] In general formula (I1) or general formula (I2), R e and R f These represent, independently of each other, a halogen atom or an oxygen atom. e and R fWhen the atom is a halogen atom, fluorine, chlorine, bromine, or iodine atoms are preferred, fluorine or chlorine atoms are more preferred, and fluorine atoms are particularly preferred because they have a strong bond with boron atoms. e and R f Compounds containing fluorine atoms have high heat resistance, making them advantageous when melt-mixed with resins at high temperatures. Note that compounds represented by general formula (I1) or general formula (I2) include R e and R f Even if the substituent is not a halogen atom or an oxygen atom, but contains an atom that can bond with a boron atom, it can be included in the resin in the same way as the near-infrared fluorescent dye according to the present invention. Such substituents are acceptable as long as they do not inhibit fluorescence.

[0075] In general formula (I1) or general formula (I2), R e and R f If R is an oxygen atom, e , R e The boron atom that bonds with R a , and R a The nitrogen atoms to which it is bonded may together form a ring, R f , R f The boron atom that bonds with R c , and R c The nitrogen atoms to which it is bonded may together form a ring. In other words, when a ring structure is formed, R e , R e The boron atom that bonds with R a , and R a The ring formed by the nitrogen atom to which it is bonded is R a and R b It condenses with the aromatic ring formed by R f , R f The boron atom that bonds with R c , and R c The ring formed by the nitrogen atom to which it is bonded is R c and R d It condenses with the aromatic ring that it forms. e Rings and R formed by the above f The ring formed by these is preferably a 6-membered ring.

[0076] In general formula (I1) or general formula (I2), R e If it is an oxygen atom and does not form a ring, then R e C is an oxygen atom having a substituent (an oxygen atom bonded to a substituent). The substituent may be C 1-20 Examples include alkyl groups, aryl groups, heteroaryl groups, alkylcarbonyl groups, arylcarbonyl groups, or heteroarylcarbonyl groups. Similarly, in general formula (I1) or general formula (I2), R f If it is an oxygen atom and does not form a ring, then R f C is an oxygen atom having a substituent (an oxygen atom bonded to a substituent). The substituent may be C 1-20 Examples include alkyl groups, aryl groups, heteroaryl groups, alkylcarbonyl groups, arylcarbonyl groups, or heteroarylcarbonyl groups. e and R f If both are oxygen atoms with substituents, R e The substituents and R f The substituents that it possesses may be of the same type or different types.

[0077] In general formula (I1) or general formula (I2), R e and R f If R is an oxygen atom, e , R f , and R e and R f The boron atoms bonded to it may together form a ring. For example, the ring structure may be R e and R f Structures in which the same aryl ring or heteroaryl ring is linked, R e and R f One example is a structure in which these groups are linked by alkylene groups.

[0078] In general formula (I3) or general formula (I4), R l , R m , R n , and R o These are, independently of each other, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20Represents an alkoxy group, aryl group, or heteroaryl group. l , R m , R n , or R o When the atom is a halogen atom, fluorine, chlorine, bromine, or iodine atoms are preferred, fluorine or chlorine atoms are more preferred, and fluorine atoms are particularly preferred because they have a strong bond with boron atoms. l , R m , R n , and R o However, compounds containing fluorine atoms have high heat resistance, which is advantageous when melt-mixing them with resins at high temperatures.

[0079] Furthermore, in the present invention and specification, "C 1-20 "Alkyl alkyl" refers to an alkyl group with 1 to 20 carbon atoms, and "C 1-20 The term "alkoxy group" refers to an alkoxy group having 1 to 20 carbon atoms.

[0080] R l , R m , R n , or R o C 1-20 In the case of alkyl groups, the alkyl group may be linear, branched, or cyclic (aliphatic ring group). Examples of such alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, and the like.

[0081] R l , R m , R n , or R o C 1-20In the case of an alkoxy group, the alkyl group portion of the alkoxy group may be linear, branched, or cyclic (aliphatic ring group). Examples of such alkoxy groups include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, t-butyloxy group, pentyloxy group, isoamyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, and dodecyloxy group.

[0082] R l , R m , R n , or R o If the group is an aryl group, examples of such aryl groups include phenyl, naphthyl, indenyl, and biphenyl groups. R l , R m , R n , or R o When the group is a heteroaryl group, examples of such heteroaryl groups include five-membered ring heteroaryl groups such as pyrrolyl, imidazolyl, pyrazolyl, thienyl, furanyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, and thiadiazole groups; six-membered ring heteroaryl groups such as pyridinyl, pyrazinyl, pyrimidinyl, and pyridadinyl groups; and condensed heteroaryl groups such as indolyl, isoindolyl, indazolyl, quinolidinyl, quinolinyl, isoquinolinyl, benzofuranyl, isobenzofuranyl, clomenyl, benzoxazolyl, benzoisoxazolyl, benzothiazolyl, and benzoisothiazolyl groups.

[0083] R l , R m , R n , or R o C represented by 1-20 Alkyl alkyl group, C 1-20The alkoxy group, aryl group, and heteroaryl group may be unsubstituted, or one or more hydrogen atoms may be substituted by substituents. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, nitro groups, cyano groups, hydroxyl groups, amino groups, thiol groups, carboxyl groups, aldehyde groups, sulfonic acid groups, isocyanate groups, thioisocyanate groups, aryl groups, and heteroaryl groups.

[0084] Compounds represented by general formula (I3) or general formula (I4) include R l , R m , R n , and R o Preferably, the element is a halogen atom, an unsubstituted aryl group, or a substituted aryl group, and may be a fluorine atom, a chlorine atom, a bromine atom, an unsubstituted phenyl group, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group is preferred, and may be a fluorine atom, a chlorine atom, an unsubstituted phenyl group, or C 1-10 Alkyl or C 1-10 Phenyl groups substituted with alkoxy groups are more preferred, and fluorine atoms or unsubstituted phenyl groups are particularly preferred.

[0085] In general formula (I3) or general formula (I4), R p and R q These are, independently of each other, hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, aryl group, or heteroaryl group. p and R q The halogen atom represented by C 1-20 Alkyl alkyl group, C 1-20 The alkoxy group, aryl group, and heteroaryl group are R of the general formula (I3) mentioned above. l , R m , R n , or R o Similar examples include the above.

[0086] Compounds represented by general formula (I3) or general formula (I4) include R p and Rq Preferably, it is a hydrogen atom or an aryl group, an unsubstituted phenyl group, or C 1-20 Alkyl or C 1-20 Preferably, the phenyl group is substituted with an alkoxy group, but an unsubstituted phenyl group or C 1-20 A phenyl group substituted with an alkoxy group is more preferable, but an unsubstituted phenyl group or C 1-10 Phenyl groups substituted with alkoxy groups are particularly preferred.

[0087] In general formula (I1), R g R represents a hydrogen atom or an electron-withdrawing group. Also, in general formula (I3), R r and R s These groups independently represent a hydrogen atom or an electron-withdrawing group. Examples of such electron-withdrawing groups include methyl halides such as trifluoromethyl; nitro; cyano; aryl; heteroaryl; alkynyl; alkenyl; substituents having a carbonyl group such as carboxyl, acyl, carbonyloxy, amide, and aldehyde groups; sulfoxide; sulfonyl; alkoxymethyl; and aminomethyl. Aryl and heteroaryl groups having these electron-withdrawing groups as substituents can also be used. Among these electron-withdrawing groups, trifluoromethyl, nitro, cyano, phenyl, and sulfonyl groups are preferred because they can function as strong electron-withdrawing groups, resulting in a longer maximum fluorescence wavelength.

[0088] As the near-infrared fluorescent dye according to the present invention, compounds represented by the following general formula (I1-0) or general formula (I2-0) are preferred. Compounds having a borondipyrromethene skeleton are preferred because their maximum fluorescence wavelength is longer, and in particular, compounds satisfying the following (p2), (p3), (q2), or (q3), in which a pyrrole ring is fused with an aromatic ring or a heteroaromatic ring, are preferred as near-infrared fluorescent dyes because their maximum fluorescence wavelength is even longer.

[0089] [ka]

[0090] In general formula (I1-0) or general formula (I2-0), R 1 , R 2 , and R 3 It satisfies one of the following conditions (p1) to (p3). (p1) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. (p2)R 1 and R 2 Both form an aromatic 5-membered ring or an aromatic 6-membered ring, R 3 is a hydrogen atom, halogen atom, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (p3)R 2 and R 3 Both form an aromatic 5-membered ring or an aromatic 6-membered ring, R 1 is a hydrogen atom, halogen atom, C 1-20 Alkyl alkyl group, C 1-20 This represents an alkoxy group, an aryl group, or a heteroaryl group.

[0091] In general formula (I1-0) or general formula (I2-0), R 4 , R 5 , and R 6 It satisfies any of the following conditions (q1) to (q3). (q1) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. (q2)R 4 and R 5 Both form an aromatic 5-membered ring or an aromatic 6-membered ring, R 6 is a hydrogen atom, halogen atom, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (q3)R 5 and R 6Both form an aromatic 5-membered ring or an aromatic 6-membered ring, R 4 is a hydrogen atom, halogen atom, C 1-20 Alkyl alkyl group, C 1-20 This represents an alkoxy group, an aryl group, or a heteroaryl group.

[0092] The halogen atoms in (p1)~(p3) or (q1)~(q3) above, C 1-20 Alkyl alkyl group, C 1-20 The alkoxy group, aryl group, and heteroaryl group are, respectively, R a and R b Any group exemplified as "any group that does not inhibit the fluorescence of the compound" can be used.

[0093] In the above (p2)~(p3) or (q2)~(q3), R 1 and R 2 A five-membered aromatic ring or a six-membered aromatic ring formed together by R 4 and R 5 A five-membered aromatic ring or a six-membered aromatic ring formed together by R 2 and R 3 A five-membered aromatic ring or a six-membered aromatic ring formed together by R 5 and R 6 The aromatic five-membered ring or aromatic six-membered ring formed by these is preferably represented by any of the following general formulas (C-1) to (C-9), and more preferably by any of the following general formulas (C-1), (C-2), or (C-9). In the following general formulas (C-1) to (C-9), the parts marked with an asterisk are the parts that bond with the borondipyrromethene skeleton in general formula (I1-0) or general formula (I2-0).

[0094] [ka]

[0095] In the general formulas (C-1) to (C-8), Y 1 ~Y 8 These elements independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom. 1 ~Y 8Preferably, these atoms are sulfur atoms, oxygen atoms, or nitrogen atoms, and more preferably, sulfur atoms or oxygen atoms, independently of each other.

[0096] In the general formulas (C-1) to (C-9), R 11 ~R 22 R represents a hydrogen atom or any group that does not inhibit the fluorescence of the compound, independently of each other. Examples of "any group that does not inhibit the fluorescence of the compound" include R. a and R b Any group that does not inhibit the fluorescence of the compound, as exemplified in R, can be used. 11 ~R 22 Preferably, the substituents are independently a hydrogen atom, an unsubstituted aryl group, a substituted aryl group, an unsubstituted heteroaryl group, or a substituted heteroaryl group; more preferably a hydrogen atom, an (unsubstituted) phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group; and even more preferably a hydrogen atom, an (unsubstituted) phenyl group, or a p-methoxyphenyl group. It is particularly preferable that the compound is substituted with at least one of the above unsubstituted aryl groups, substituted aryl groups, unsubstituted heteroaryl groups, or substituted heteroaryl groups, in order to enhance electron-donating properties and to suppress aggregation of the BODIPY skeleton by the bulky substituents.

[0097] As for compounds of general formula (I1-0) or general formula (I2-0), R 1 and R 4 , R 2 and R 5 , and R 3 and R 6 These may be different from each other, but it is preferable that they be of the same type. That is, R 1 , R 2 , and R 3 If the above (p1) is satisfied, R 4 , R 5 , and R 6 It is preferable that the above (q1) is satisfied, and R 1 , R2 , and R 3 If the above (p2) is satisfied, R 4 , R 5 , and R 6 It is preferable that the above (q2) is satisfied, R 1 , R 2 , and R 3 If the above (p3) is satisfied, R 4 , R 5 , and R 6 It is preferable that the above (q3) is satisfied.

[0098] As for compounds of general formula (I1-0) or general formula (I2-0), R 1 and R 2 They form a ring, R 4 and R 5 R forms a ring, or 2 and R 3 They form a ring, R 5 and R 6 It is preferable that the rings form a ring. That is, R 1 , R 2 , and R 3 The above (p2) or (p3) is satisfied, R 4 , R 5 , and R 6 It is preferable that the above-mentioned (q2) or (q3) is satisfied. This is because the condensation of an aromatic ring or heteroaromatic ring with the borondipyrrometene skeleton results in a longer wavelength for the maximum fluorescence.

[0099] In general formula (I1-0) or general formula (I2-0), R 7 and R 8 R represents a halogen atom or an oxygen atom. 7 and R 8 If it is an oxygen atom, R 7 , R 7 A boron atom bonded to it, a nitrogen atom bonded to the boron atom, R 1 , and R 1 The carbon atoms bonded to it may together form a ring, R 8 , R 8 A boron atom bonded to it, a nitrogen atom bonded to the boron atom, R 4, and R 4 The carbon atoms bonded to it may together form a ring. That is, R 7 and boron atoms and R 1 The ring formed by the etc., and R 8 and boron atoms and R 4 The rings formed by these structures all condense with the borondipyrromethene skeleton. 7 and boron atoms and R 1 The ring formed by the etc., and R 8 and boron atoms and R 4 The ring formed by these is preferably a 6-membered ring.

[0100] In general formula (I1-0) or general formula (I2-0), R 7 If it is an oxygen atom and does not form a ring, then R 7 C is an oxygen atom having a substituent (an oxygen atom bonded to a substituent). The substituent may be C 1-20 Examples include alkyl groups, aryl groups, or heteroaryl groups. Similarly, in general formula (I1-0) or general formula (I2-0), R 8 If it is an oxygen atom and does not form a ring, then R 8 C is an oxygen atom having a substituent (an oxygen atom bonded to a substituent). The substituent may be C 1-20 Examples include alkyl groups, aryl groups, or heteroaryl groups. 7 and R 8 If both are oxygen atoms with substituents, R 7 The substituents and R 8 The substituents that it possesses may be of the same type or different types.

[0101] In general formula (I1-0), R 9 R represents a hydrogen atom or an electron-withdrawing group. As an electron-withdrawing group, R gSimilar groups to those listed above can be cited. Among these, fluoroalkyl groups, nitro groups, cyano groups, aryl groups, and sulfonyl groups are preferred from the viewpoint of extending the maximum fluorescence wavelength, as they can function as strong electron-withdrawing groups. Trifluoromethyl groups, nitro groups, cyano groups, phenyl groups, and sulfonyl groups are more preferred, and trifluoromethyl groups, cyano groups, phenyl groups, and sulfonyl groups are even more preferred from the viewpoint of safety for living organisms. However, the substituents are not limited to these.

[0102] The near-infrared fluorescent dye according to the present invention is a compound represented by general formula (I1-0) or general formula (I2-0), and R 1 and R 2 Both are rings represented by the above general formula (C-1), R 11 and R 12 One of them is a hydrogen atom, and the other is a halogen atom with 1 to 3 hydrogen atoms, C 1-20 Alkyl alkyl group, or C 1-20 A ring is formed which is a phenyl group, thienyl group, or furanyl group, which may be substituted with an alkoxy group, R 4 and R 5 Both are R 1 and R 2 It forms a ring of the same kind as the ring formed by R 3 and R 6 is a hydrogen atom, and R 7 and R 8 Compounds in which the atom is a halogen atom; R 1 and R 2 Both are rings represented by the above general formula (C-2), R 13 and R 14 One of them is a hydrogen atom, and the other is a halogen atom with 1 to 3 hydrogen atoms, C 1-20 Alkyl alkyl group, or C 1-20 A ring is formed which is a phenyl group, thienyl group, or furanyl group, which may be substituted with an alkoxy group, R 4 and R 5 Both are R 1 and R 2 It forms a ring of the same kind as the ring formed by R 3 and R 6 is a hydrogen atom, and R 7and R 8 Compounds in which the atom is a halogen atom; R 2 and R 3 Both are rings represented by the above general formula (C-1), R 11 and R 12 One of them is a hydrogen atom, and the other is a halogen atom with 1 to 3 hydrogen atoms, C 1-20 Alkyl alkyl group, or C 1-20 A ring is formed which is a phenyl group, thienyl group, or furanyl group, which may be substituted with an alkoxy group, R 5 and R 6 Both are R 2 and R 3 It forms a ring of the same kind as the ring formed by R 1 and R 4 is a hydrogen atom, and R 7 and R 8 Compounds in which the atom is a halogen atom; R 2 and R 3 Both are rings represented by the following general formula (C-2), R 13 and R 14 One of them is a hydrogen atom, and the other is a halogen atom with 1 to 3 hydrogen atoms, C 1-20 Alkyl alkyl group, or C 1-20 A ring is formed which is a phenyl group, thienyl group, or furanyl group, which may be substituted with an alkoxy group, R 5 and R 6 Both are R 2 and R 3 It forms a ring of the same kind as the ring formed by R 1 and R 4 is a hydrogen atom, and R 7 and R 8 Compounds in which the atom is a halogen atom; R 2 and R 3 Both are rings represented by the following general formula (C-9), R 19 ~R 22 One of the following is a halogen atom, C 1-20 Alkyl alkyl group, or C 1-20 A phenyl group, thienyl group, or furanyl group which may be substituted with an alkoxy group, and the remaining three atoms form a ring with hydrogen atoms, R 5 and R 6Both are R 2 and R 3 It forms a ring of the same kind as the ring formed by R 1 and R 4 hydrogen atoms, halogen atoms, C 1-20 Alkyl alkyl group, or C 1-20 A phenyl group, thienyl group, or furanyl group which may be substituted with an alkoxy group, R 7 and R 8 Compounds in which is a halogen atom; preferred. If these compounds are compounds represented by the general formula (I1-0), R 9 It is more preferable that the group is a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group, and it is particularly preferable that the group is a trifluoromethyl group or a phenyl group.

[0103] Preferred compounds for the near-infrared fluorescent dye according to the present invention include the following general compounds (I1-1), (I1-2), (I1-3), (I2-1), (I2-2), and (I2-3). Among the following general compounds (I1-1), etc., R 1 , R 3 , R 4 , and R 6 ~R 8 The above is synonymous, ED represents an electron-donating group, EW represents an electron-withdrawing group, and Z 1 ~Z 4 Each ring independently represents a five-membered or six-membered aryl group, or a five-membered or six-membered heteroaryl group.

[0104] [ka]

[0105] For the general formula (I1-1), compounds represented by the general formulas (I1-1-1) to (I1-1-6) are preferred; for the general formula (I1-2), compounds represented by the general formulas (I1-2-1) to (I1-2-12) are preferred; for the general formula (I2-1), compounds represented by the general formulas (I2-1-1) to (I2-1-6) are preferred; and for the general formula (I2-2), compounds represented by the general formulas (I2-2-1) to (I2-2-12) are preferred.

[0106] [ka]

[0107] [ka]

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[0112] In the general formulas (I1-1-1)~(I1-1-6), (I1-2-1)~(I1-2-4), (I1-2-7)~(I1-2-10), (I2-1-1)~(I2-1-6), (I2-2-1)~(I2-2-4), and (I2-2-7)~(I2-2-10), Y 11 and Y 12 These represent, independently of each other, an oxygen atom or a sulfur atom, and Y 21 and Y22 These represent a carbon atom or a nitrogen atom independently of each other. Compounds represented by general formula (I1-1-1), etc., include Y 11 and Y 12 Preferably, the atoms are of the same type, Y 21 and Y 22 It is preferable that these atoms are of the same type.

[0113] In general formulas (I1-1-1)~(I1-1-6), (I1-2-1)~(I1-2-12), Q 11 R represents a hydrogen atom or an electron-withdrawing group. As an electron-withdrawing group, R g Similar groups to those listed above can be cited. Compounds represented by general formula (I1-1-1), etc., include Q 11 Compounds in which the group is a trifluoromethyl group, a cyano group, a nitro group, or an optionally substituted phenyl group are preferred, and compounds in which the group is a trifluoromethyl group or an optionally substituted phenyl group are more preferred.

[0114] In the general formulas (I1-1-1)~(I1-1-2), (I1-2-1)~(I1-2-2), (I1-2-6), (I2-1-1)~(I2-1-2), and (I2-2-1)~(I2-2-2), (I2-2-6), X is a halogen atom, C, and X are independent of each other. 1-20 This represents an alkoxy group, an aryloxy group, or an acyloxy group.

[0115] X is C 1-20 In the case of an alkoxy group, the alkyl group portion of the alkoxy group may be linear, branched, or cyclic (aliphatic ring group). Examples of such alkoxy groups include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, t-butyloxy group, pentyloxy group, isoamyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, and dodecyloxy group.

[0116] When X is an aryloxy group, examples of such aryloxy groups include phenyloxy group, naphthyloxy group, indenyloxy group, biphenyloxy group, etc.

[0117] When X is an acyloxy group, an alkylcarbonyloxy group or an arylcarbonyloxy group is preferred as the acyloxy group. Examples of the alkylcarbonyloxy group include methylcarbonyloxy group (acetoxy group), ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, isobutylcarbonyloxy group, t-butylcarbonyloxy group, pentylcarbonyloxy group, isoamylcarbonyloxy group, hexylcarbonyloxy group, heptylcarbonyloxy group, octylcarbonyloxy group, nonylcarbonyloxy group, decylcarbonyloxy group, undecylcarbonyloxy group, dodecylcarbonyloxy group, etc. Examples of the arylcarbonyloxy group include phenylcarbonyloxy group (benzoyloxy group), naphthylcarbonyloxy group, indenylcarbonyloxy group, biphenylcarbonyloxy group, etc.

[0118] Compounds represented by any of the general formulas (I1-1-1)~(I1-1-2), (I1-2-1)~(I1-2-2), (I1-2-6), (I2-1-1)~(I2-1-2), (I2-2-1)~(I2-2-2), and (I2-2-6) are preferably those in which X is a halogen atom, and are particularly preferably those in which X is a fluorine atom.

[0119] In the general formulas (I1-1-3)~(I1-1-4), (I1-2-7), (I1-2-9), (I1-2-11), (I2-1-3)~(I2-1-4), (I2-2-7), (I2-2-9), and (I2-2-11), m1 represents either 0 or 1.

[0120] In the general formulas (I1-1-5)~(I1-1-6), (I1-2-3)~(I1-2-6), (I1-2-8), (I1-2-10)~(I1-2-12), (I2-1-5)~(I2-1-6), (I2-2-3)~(I1-2-6), (I2-2-8), and (I2-2-10)~(I2-2-12), P 11 ~P 14 and P 17 These are, independently of each other, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 This represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group. 11 ~P 14 C in 1-20 Alkyl alkyl group, C 1-20 The alkoxy group, monoalkylamino group, or dialkylamino group are, respectively, the R g The same items listed in (p1)~(p3) and (q1)~(q3) can be listed. 11 ~P 14 and P 17 C 1-20 Alkyl alkyl group, C 1-20 It is preferable that the group is an alkoxy group, an (unsubstituted) phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group, and from the viewpoint of biosafety, C 1-20 Alkyl alkyl group, C 1-20 More preferably, the substituent is an alkoxy group, a phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group, and these substituents may have further substituents. However, safety can be improved by introducing other substituents as well, so the substituents are not limited to these.

[0121] In the general formulas (I1-1-5)~(I1-1-6), (I1-2-3)~(I1-2-6), (I1-2-8), (I1-2-10)~(I1-2-12), (I2-1-5)~(I2-1-6), (I2-2-3)~(I1-2-6), (I2-2-8), and (I2-2-10)~(I2-2-12), n11~n14 and n17 independently represent integers from 0 to 3. In one numerator, P 11 If there are multiple instances of (i.e., n11 is 2 or 3), multiple P 11 These may all be the same type of functional group, or they may be different types of functional groups. 12 ~P 14 and P 17 The same applies to this matter.

[0122] In the general formulas (I1-1-1)~(I1-1-6), (I1-2-1)~(I1-2-4), (I1-2-6)~(I1-2-12), (I2-1-1)~(I2-1-6), (I2-2-1)~(I2-2-4), and (I2-2-6)~(I2-2-12), A 11 ~A 14 These are, independently of each other, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 A phenyl group having 1 to 3 substituents selected from the group consisting of alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups, or a halogen atom, C 1-20 Alkyl alkyl group, C 1-20 This represents a heteroaryl group which may have 1 to 3 substituents selected from the group consisting of alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups. The R in the general formula (I3) above represents the heteroaryl group. l , R m , R n , or R o Similar examples include a thienyl group or a furanyl group, which is preferred. C in the substituent that the phenyl group or heteroaryl group may have. 1-20 Alkyl alkyl group, C 1-20 The alkoxy group, monoalkylamino group, or dialkylamino group are, respectively, the R gThe same items listed in (p1)~(p3) and (q1)~(q3) are listed. A 11 ~A 14 These include an unsubstituted phenyl group and one or two carbon atoms. 1-20 A phenyl group having an alkoxy group as a substituent, or a heteroaryl group, is preferred, as is an unsubstituted phenyl group or one carbon atom. 1-20 A phenyl group having an alkoxy group as a substituent is more preferable, as is an unsubstituted phenyl group or a single carbon atom. 1-10 A phenyl group having an alkoxy group as a substituent is more preferable, as is an unsubstituted phenyl group or a single carbon atom. 1-6 A phenyl group having an alkoxy group as a substituent is even more preferred. Also, as a compound represented by general formula (I1-1-1), etc., A 11 ~A 14 Preferably, all of them are of the same type of functional group.

[0123] As the near-infrared fluorescent dye according to the present invention, compounds represented by any of the following general formulas (1-1) to (1-37), (2-1) to (2-7), (3-1) to (3-37), (4-1) to (4-7), and (5-1) to (5-2) are particularly preferred, compounds represented by any of the following general formulas (1-1) to (1-12), (1-25) to (1-31), (2-1) to (2-7), and (3-25) to (3-31) are more preferred, and compounds represented by any of the following general formulas (1-1), (1-3), (1-4), (1-6), (1-25), (1-27), (2-1), (3-1), (3-3), (3-4), (3-6), (3-25), (3-27), and (4-1) are even more preferred.

[0124] [ka]

[0125] [ka]

[0126] [ka]

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[0129] [ka]

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[0135] In general formulas (1-1) to (1-37), (2-1) to (2-7), (3-1) to (3-37), (4-1) to (4-7), (5-1) to (5-2), P 1 ~P 4 and P 18 These are, independently of each other, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20This represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group. 1 ~P 4 C in 1-20 Alkyl alkyl group, C 1-20 The alkoxy group, monoalkylamino group, or dialkylamino group are, respectively, the R g The same items listed in (p1)~(p3) and (q1)~(q3) can be listed. 1 ~P 4 and P 18 C 1-20 Alkyl alkyl group, C 1-20 It is preferable that the group is an alkoxy group, an (unsubstituted) phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group, and from the viewpoint of biosafety, C 1-20 Alkyl alkyl group, C 1-20 More preferably, the substituent is an alkoxy group, a phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group, and these substituents may have further substituents. However, safety can be improved by introducing other substituents as well, so the substituents are not limited to these.

[0136] In the general formulas (1-1)~(1-37), (2-1)~(2-7), (3-1)~(3-37), (4-1)~(4-7), and (5-1)~(5-2), n1~n4 and n18 represent integers from 0 to 3, independently of each other. In one numerator, P 1 If there are multiple instances of (i.e., when n1 is 2 or 3), multiple P 1 These may all be the same type of functional group, or they may be different types of functional groups. 2 ~P 4 and P 18 The same applies to this matter.

[0137] In general formulas (1-1) to (1-37), (2-1) to (2-7), and (5-1), Q represents a trifluoromethyl group, a cyano group, a nitro group, or an optionally substituted phenyl group, preferably a trifluoromethyl group or an optionally substituted phenyl group, and more preferably a trifluoromethyl group or an unsubstituted phenyl group. Optional substituents on the phenyl group include halogen atoms and C 1-20 Alkyl alkyl group, C 1-20 Examples include alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups.

[0138] In general formulas (1-1) to (1-31) and (3-1) to (3-31), X is the same as in general formula (1-1-1), etc. For compounds represented by general formula (1-1), etc., X is preferably a halogen atom, and particularly preferably a fluorine atom.

[0139] In general formulas (1-32) to (1-34) and (3-32) to (3-34), m2 is either 0 or 1. For compounds represented by general formula (1-32), etc., it is preferable that m2 is 1.

[0140] Compounds represented by general formulas (1-1) to (1-37), (2-1) to (2-7), and (5-1) include P 1 ~P 4 and P 18 They are independent of each other, C 1-20 Alkyl alkyl group, C 1-20 The group is preferably an alkoxy group, an (unsubstituted) phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group, where n1 to n4 and n18 are independently 0 to 2, and Q is a trifluoromethyl group or a phenyl group. Similarly, compounds represented by the general formulas (3-1) to (3-37), (4-1) to (4-7), and (5-2) include P 1 ~P 4 and P 18 They are independent of each other, C 1-20 Alkyl alkyl group, C 1-20The group is preferably an alkoxy group, an (unsubstituted) phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group, where n1 to n4 and n18 are independently 0 to 2.

[0141] As the near-infrared fluorescent dye according to the present invention, compounds represented by any of the following general formulas (I3-1) to (I3-6), or compounds represented by any of the general formulas (I4-1) to (I4-6), are also preferred because their maximum fluorescence wavelength is longer.

[0142] [ka]

[0143] [ka]

[0144] In general formulas (I3-1) to (I3-6) and general formulas (I4-1) to (I4-6), R 23 , R 24 , R 25 , and R 26 These are, independently of each other, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, aryl group, or heteroaryl group. 23 , R 24 , R 25 , or R 26 The halogen atom represented by C 1-20 Alkyl alkyl group, C 1-20 The alkoxy group, aryl group, and heteroaryl group are R of the general formula (I3) mentioned above. l , R m , R n , or R o Similar compounds can be cited. Compounds represented by any of the general formulas (I3-1) to (I3-6) or any of the general formulas (I4-1) to (I4-6) are considered to have high thermal stability, R 23 , R 24 , R25 , and R 26 Preferably, the element is a halogen atom, an unsubstituted aryl group, or a substituted aryl group, specifically a fluorine atom, a chlorine atom, a bromine atom, an unsubstituted phenyl group, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group is preferred, and may be a fluorine atom, a chlorine atom, an unsubstituted phenyl group, or C 1-10 Alkyl or C 1-10 Phenyl groups substituted with alkoxy groups are more preferable, as they yield compounds that combine high luminescence efficiency and thermal stability; therefore, fluorine atoms or unsubstituted phenyl groups are particularly preferred.

[0145] In general formulas (I3-1) to (I3-6) and general formulas (I4-1) to (I4-6), R 27 and R 28 These are, independently of each other, hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, aryl group, or heteroaryl group. 27 or R 28 The halogen atom represented by C 1-20 Alkyl alkyl group, C 1-20 The alkoxy group, aryl group, and heteroaryl group are R of the general formula (I3) mentioned above. p or R q Similar compounds can be cited. Compounds represented by any of the general formulas (I3-1) to (I3-6) or any of the general formulas (I4-1) to (I4-6) include R 27 and R 28 It is preferable that the atom is a hydrogen atom or an aryl group, as this yields compounds with high luminescence efficiency. Therefore, hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl or C 1-20 Preferably, the phenyl group is substituted with an alkoxy group, and may be a hydrogen atom, an unsubstituted phenyl group, or a linear or branched C group. 1-20 A phenyl group substituted with an alkoxy group is more preferable, as it yields a compound with high luminescence efficiency and excellent compatibility with resins. Therefore, an unsubstituted phenyl group or a linear or branched C group is preferable.1-10 Particularly preferred is a phenyl group substituted with an alkoxy group.

[0146] In General Formulas (I3-1) to (I3-6), R 29 and R 30 each independently represent a hydrogen atom or an electron-withdrawing group. As the electron-withdrawing group represented by R 29 or R 30 , those similar to R r or R s in the general formula (I3) can be mentioned. As the compound represented by any of the general formulas (I3-1) to (I3-6), since a compound with a longer fluorescence wavelength and high luminous efficiency can be obtained, R 29 and R 30 are preferably a fluoroalkyl group, nitro group, cyano group, or aryl group that can function as a strong electron-withdrawing group, more preferably a trifluoromethyl group, nitro group, cyano group, or phenyl group that may have a substituent, and even more preferably a trifluoromethyl group or a cyano group because a compound with high luminous efficiency and excellent compatibility with a resin can be obtained.

[0147] In General Formulas (I3-1) and (I4-1), Y 9 and Y 10 each independently represent a sulfur atom, oxygen atom, nitrogen atom, or phosphorus atom. As the compound represented by the general formula (I3-1) or (I4-1), since a compound with high luminous efficiency can be obtained, Y 9 and Y 10 are preferably each independently a sulfur atom, oxygen atom, or nitrogen atom, more preferably each independently a sulfur atom or an oxygen atom, and even more preferably both sulfur atoms or both oxygen atoms because a compound having both high luminous efficiency and thermal stability can be obtained.

[0148] In General Formulas (I3-3) to (I3-6) and (I4-3) to (I4-6), X 1 and X 2These represent a nitrogen atom or a phosphorus atom independently of each other. Compounds represented by general formulas (I3-3) to (I3-6) or general formulas (I4-3) to (I4-6) include X 1 and X 2 However, compounds with high luminescence efficiency are preferable if both atoms are nitrogen atoms or phosphorus atoms, and compounds with both atoms being nitrogen atoms are even preferable if both atoms are nitrogen atoms, as this allows for the acquisition of compounds that combine high luminescence efficiency and thermal stability.

[0149] In general formula (I3-1) and general formula (I4-1), R 31 and R 32 The following conditions (p4) or (p5) are met: (p4) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 This represents an alkoxy group, an aryl group, or a heteroaryl group. (p5)R 31 and R 32 Both form an aromatic five-membered ring or an aromatic six-membered ring, which may have substituents.

[0150] In general formula (I3-1) and general formula (I4-1), R 33 and R 34 The following conditions (q4) or (q5) are met. (q4) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (q5)R 33 and R 34 Both form an aromatic five-membered ring or an aromatic six-membered ring, which may have substituents.

[0151] In general formulas (I3-2) to (I3-6) and general formulas (I4-2) to (I4-6), R 35 , R 36 , R 37 , and R 38 It satisfies one of the following conditions (p6) to (p9). (p6) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 This represents an alkoxy group, an aryl group, or a heteroaryl group. (p7)R 35 and R 36 Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R 37 and R 38 These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 This represents an alkoxy group, an aryl group, or a heteroaryl group. (p8)R 36 and R 37 Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R 35 and R 38 These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 This represents an alkoxy group, an aryl group, or a heteroaryl group. (p9)R 37 and R 38 Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R 35 and R 36 These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 This represents an alkoxy group, an aryl group, or a heteroaryl group.

[0152] In general formulas (I3-2) to (I3-6) and general formulas (I4-2) to (I4-6), R 39 , R 40 , R 41 , and R 42 It satisfies any of the following conditions (q6) to (q9). (q6) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 This represents an alkoxy group, an aryl group, or a heteroaryl group. (q7)R 39 and R40 both form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, and R 41 and R 42 each independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group. (q8)R 40 and R 41 both form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, and R 39 and R 42 each independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group. (q9)R 41 and R 42 both form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, and R 39 and R 40 each independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group.

[0153] For the halogen atom, C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, and heteroaryl group in (p4), (p6) to (p9) and (q4), (q6) to (q9), respectively, those exemplified as "any group that does not inhibit the fluorescence of the compound" in R a and R b can be used.

[0154] In (p5), (p7) to (p9), (q5), (q7) to (q9), the aromatic 5-membered ring or aromatic 6-membered ring formed by both R 31 and R 32 , the aromatic 5-membered ring or aromatic 6-membered ring formed by both R 33 and R 34 , the aromatic 5-membered ring or aromatic 6-membered ring formed by both R 35 and R36 A five-membered aromatic ring or a six-membered aromatic ring formed together by R 36 and R 37 A five-membered aromatic ring or a six-membered aromatic ring formed together by R 37 and R 38 A five-membered aromatic ring or a six-membered aromatic ring formed together by R 39 and R 40 A five-membered aromatic ring or a six-membered aromatic ring formed together by R 40 and R 41 A five-membered aromatic ring or a six-membered aromatic ring formed together by R 41 and R 42 The aromatic five-membered ring or aromatic six-membered ring formed by these is preferably one represented by any of the general formulas (C-1) to (C-9), and is more preferably represented by the general formula (C-9) because it yields a compound with high thermal stability.

[0155] The compound represented by (I3-1) above is R 23 , R 24 , R 25 , and R 26 Both are halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl or C 1-10 A phenyl group substituted with an alkoxy group; R 27 and R 28 Both are hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group; R 29 and R 30 Both are trifluoromethyl, nitro, cyano, or phenyl groups; Y 9 and Y 10 Both are sulfur atoms or oxygen atoms; R 31 and R 32 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 31 and R 32 They both form a phenyl group which may have substituents; R 33 and R 34 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R33 and R 34 A compound that forms a phenyl group which may both have substituents is preferred, R 23 , R 24 , R 25 , and R 26 Both are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 Both are unsubstituted phenyl groups, or linear or branched C groups. 1-20 A phenyl group substituted with an alkoxy group; R 29 and R 30 Both are trifluoromethyl groups, nitro groups, or cyano groups; Y 9 and Y 10 Both are sulfur atoms or oxygen atoms; R 31 and R 32 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 31 and R 32 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group; R 33 and R 34 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 33 and R 34 Both are unsubstituted phenyl groups or C 1-10 Compounds that form phenyl groups substituted with alkyl groups are more preferable because they have high luminescence efficiency and excellent compatibility with resins.

[0156] The compound represented by (I3-2) above is R 23 , R 24 , R 25 , and R 26 Both are halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl or C 1-10 A phenyl group substituted with an alkoxy group; R 27 and R 28 Both are hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group; R29 and R 30 Both are trifluoromethyl groups, nitro groups, cyano groups, or phenyl groups; R 35 , R 36 , R 37 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 35 and R 36 They form a phenyl group which may both have substituents, R 37 and R 38 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 36 and R 37 They form a phenyl group which may both have substituents, R 35 and R 38 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 37 and R 38 They form a phenyl group which may both have substituents, R 35 and R 36 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group; R 39 , R 40 , R 41 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 39 and R 40 They form a phenyl group which may both have substituents, R 41 and R 42 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 40 and R 41 They form a phenyl group which may both have substituents, R 39 and R 42 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 41 and R 42 They form a phenyl group which may both have substituents, R 39 and R 40 These are hydrogen atoms or C, independently of each other. 1-20Compounds that are alkyl groups are preferred, R 23 , R 24 , R 25 , and R 26 Both are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 Both are unsubstituted phenyl groups, or linear or branched C groups. 1-20 A phenyl group substituted with an alkoxy group; R 29 and R 30 Both are trifluoromethyl groups, nitro groups, or cyano groups; R 35 , R 36 , R 37 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 35 and R 36 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 37 and R 38 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 36 and R 37 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 35 and R 38 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 37 and R 38 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 35 and R 36 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group; R 39 , R 40 , R 41 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 39 and R 40 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 41and R 42 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 40 and R 41 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 39 and R 42 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 41 and R 42 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 39 and R 40 These are hydrogen atoms or C, independently of each other. 1-20 Compounds that are alkyl groups are more preferable because they have high luminescence efficiency and excellent compatibility with resins.

[0157] The compound represented by (I3-3) above is R 23 , R 24 , R 25 , and R 26 Both are halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl or C 1-10 A phenyl group substituted with an alkoxy group; R 27 and R 28 Both are hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group; R 29 and R 30 Both are trifluoromethyl, nitro, cyano, or phenyl groups; X 1 and X 2 Both are nitrogen atoms; R 36 , R 37 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 36 and R 37 They form a phenyl group which may both have substituents, R 38 is a hydrogen atom or C 1-20 It is an alkyl group, or R37 and R 38 They form a phenyl group which may both have substituents, R 36 is a hydrogen atom or C 1-20 It is an alkyl group; R 40 , R 41 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 40 and R 41 They form a phenyl group which may both have substituents, R 42 is a hydrogen atom or C 1-20 It is an alkyl group, or R 41 and R 42 They form a phenyl group which may both have substituents, R 40 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are preferred, R 23 , R 24 , R 25 , and R 26 Both are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 Both are unsubstituted phenyl groups, or linear or branched C groups. 1-20 A phenyl group substituted with an alkoxy group; R 29 and R 30 Both are trifluoromethyl groups, nitro groups, or cyano groups; X 1 and X 2 Both are nitrogen atoms; R 36 , R 37 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 36 and R 37 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 38 is a hydrogen atom or C 1-20 It is an alkyl group, or R 37 and R 38 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 36 is a hydrogen atom or C1-20 It is an alkyl group; R 40 , R 41 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 40 and R 41 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 42 is a hydrogen atom or C 1-20 It is an alkyl group, or R 41 and R 42 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 40 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferable because they have high luminescence efficiency and excellent compatibility with resins.

[0158] The compound represented by (I3-4) above is R 23 , R 24 , R 25 , and R 26 Both are halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl or C 1-10 A phenyl group substituted with an alkoxy group; R 27 and R 28 Both are hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group; R 29 and R 30 Both are trifluoromethyl, nitro, cyano, or phenyl groups; X 1 and X 2 Both are nitrogen atoms; R 35 , R 36 , and R 37 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 35 and R 36 They form a phenyl group which may both have substituents, R 37 is a hydrogen atom or C 1-20 It is an alkyl group, or R36 and R 37 They form a phenyl group which may both have substituents, R 35 is a hydrogen atom or C 1-20 It is an alkyl group; R 39 , R 40 , and R 41 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 39 and R 40 They form a phenyl group which may both have substituents, R 41 is a hydrogen atom or C 1-20 It is an alkyl group, or R 40 and R 41 They form a phenyl group which may both have substituents, R 39 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are preferred, R 23 , R 24 , R 25 , and R 26 Both are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 Both are unsubstituted phenyl groups, or linear or branched C groups. 1-20 A phenyl group substituted with an alkoxy group; R 29 and R 30 Both are trifluoromethyl groups, nitro groups, or cyano groups; X 1 and X 2 Both are nitrogen atoms; R 35 , R 36 , and R 37 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 35 and R 36 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 37 is a hydrogen atom or C 1-20 It is an alkyl group, or R 36 and R 37 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 35 is a hydrogen atom or C1-20 It is an alkyl group; R 39 , R 40 , and R 41 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 39 and R 40 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 41 is a hydrogen atom or C 1-20 It is an alkyl group, or R 40 and R 41 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 39 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferable because they have high luminescence efficiency and excellent compatibility with resins.

[0159] The compounds represented by (I3-5) above include R 23 , R 24 , R 25 , and R 26 Both are halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl or C 1-10 A phenyl group substituted with an alkoxy group; R 27 and R 28 Both are hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group; R 29 and R 30 Both are trifluoromethyl, nitro, cyano, or phenyl groups; X 1 and X 2 Both are nitrogen atoms; R 35 , R 36 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 35 and R 36 They form a phenyl group which may both have substituents, R 38 is a hydrogen atom or C 1-20 It is an alkyl group; R39 , R 40 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 39 and R 40 They form a phenyl group which may both have substituents, R 42 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are preferred, R 23 , R 24 , R 25 , and R 26 Both are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 Both are unsubstituted phenyl groups, or linear or branched C groups. 1-20 A phenyl group substituted with an alkoxy group; R 29 and R 30 Both are trifluoromethyl groups, nitro groups, or cyano groups; X 1 and X 2 Both are nitrogen atoms; R 35 , R 36 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 35 and R 36 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 38 is a hydrogen atom or C 1-20 It is an alkyl group; R 39 , R 40 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 39 and R 40 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 42 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferable because they have high luminescence efficiency and excellent compatibility with resins.

[0160] The compound represented by (I3-6) above is R23 , R 24 , R 25 , and R 26 Both are halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl or C 1-10 A phenyl group substituted with an alkoxy group; R 27 and R 28 Both are hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group; R 29 and R 30 Both are trifluoromethyl, nitro, cyano, or phenyl groups; X 1 and X 2 Both are nitrogen atoms; R 35 , R 37 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 37 and R 38 They form a phenyl group which may both have substituents, R 35 is a hydrogen atom or C 1-20 It is an alkyl group; R 39 , R 41 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 41 and R 42 They form a phenyl group which may both have substituents, R 39 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are preferred, R 23 , R 24 , R 25 , and R 26 Both are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 Both are unsubstituted phenyl groups, or linear or branched C groups. 1-20 A phenyl group substituted with an alkoxy group; R 29 and R 30 Both are trifluoromethyl groups, nitro groups, or cyano groups; X 1 and X 2Both are nitrogen atoms; R 35 , R 37 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 37 and R 38 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 35 is a hydrogen atom or C 1-20 It is an alkyl group; R 39 , R 41 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 41 and R 42 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 39 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferable because they have high luminescence efficiency and excellent compatibility with resins.

[0161] The compound represented by (I4-1) above is R 23 , R 24 , R 25 , and R 26 Both are halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl or C 1-10 A phenyl group substituted with an alkoxy group; R 27 and R 28 Both are hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group; Y 9 and Y 10 Both are sulfur atoms or oxygen atoms; R 31 and R 32 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 31 and R 32 They both form a phenyl group which may have substituents; R 33 and R 34These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 33 and R 34 A compound that forms a phenyl group which may both have substituents is preferred, R 23 , R 24 , R 25 , and R 26 Both are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 Both are unsubstituted phenyl groups, or linear or branched C groups. 1-20 A phenyl group substituted with an alkoxy group; Y 9 and Y 10 Both are sulfur atoms or oxygen atoms; R 31 and R 32 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 31 and R 32 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group; R 33 and R 34 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 33 and R 34 Both are unsubstituted phenyl groups or C 1-10 Compounds that form phenyl groups substituted with alkyl groups are more preferable because they have high luminescence efficiency and excellent compatibility with resins.

[0162] The compound represented by (I4-2) above is R 23 , R 24 , R 25 , and R 26 Both are halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl or C 1-10 A phenyl group substituted with an alkoxy group; R 27 and R 28 Both are hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group; R 35 , R36 , R 37 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 35 and R 36 They form a phenyl group which may both have substituents, R 37 and R 38 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 36 and R 37 They form a phenyl group which may both have substituents, R 35 and R 38 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 37 and R 38 They form a phenyl group which may both have substituents, R 35 and R 36 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group; R 39 , R 40 , R 41 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 39 and R 40 They form a phenyl group which may both have substituents, R 41 and R 42 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 40 and R 41 They form a phenyl group which may both have substituents, R 39 and R 42 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 41 and R 42 They form a phenyl group which may both have substituents, R 39 and R 42 These are hydrogen atoms or C, independently of each other. 1-20 Compounds that are alkyl groups are preferred, R 23 , R 24 , R 25 , and R 26Both are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 Both are unsubstituted phenyl groups, or linear or branched C groups. 1-20 A phenyl group substituted with an alkoxy group; R 35 , R 36 , R 37 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 35 and R 36 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 37 and R 38 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 36 and R 37 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 35 and R 38 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 37 and R 38 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 35 and R 36 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group; R 39 , R 40 , R 41 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 39 and R 40 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 41 and R 42 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 40 and R 41 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R39 and R 42 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 41 and R 42 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 39 and R 42 These are hydrogen atoms or C, independently of each other. 1-20 Compounds that are alkyl groups are more preferable because they have high luminescence efficiency and excellent compatibility with resins.

[0163] The compound represented by (I4-3) above is R 23 , R 24 , R 25 , and R 26 Both are halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl or C 1-10 A phenyl group substituted with an alkoxy group; R 27 and R 28 Both are hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 Both are nitrogen atoms; R 36 , R 37 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 36 and R 37 They form a phenyl group which may both have substituents, R 38 is a hydrogen atom or C 1-20 It is an alkyl group, or R 37 and R 38 They form a phenyl group which may both have substituents, R 36 is a hydrogen atom or C 1-20 It is an alkyl group; R 40 , R 41 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 40 and R41 They form a phenyl group which may both have substituents, R 42 is a hydrogen atom or C 1-20 It is an alkyl group, or R 41 and R 42 They form a phenyl group which may both have substituents, R 40 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are preferred, R 23 , R 24 , R 25 , and R 26 Both are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 Both are unsubstituted phenyl groups, or linear or branched C groups. 1-20 A phenyl group substituted with an alkoxy group; R 36 , R 37 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 36 and R 37 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 38 is a hydrogen atom or C 1-20 It is an alkyl group, or R 37 and R 38 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 36 is a hydrogen atom or C 1-20 It is an alkyl group; R 40 , R 41 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 40 and R 41 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 42 is a hydrogen atom or C 1-20 It is an alkyl group, or R 41 and R 42 Both are unsubstituted phenyl groups or C 1-10Forms an alkyl-substituted phenyl group, R 40 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferable because they have high luminescence efficiency and excellent compatibility with resins.

[0164] The compound represented by (I4-4) above is R 23 , R 24 , R 25 , and R 26 Both are halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl or C 1-10 A phenyl group substituted with an alkoxy group; R 27 and R 28 Both are hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 Both are nitrogen atoms; R 35 , R 36 , and R 37 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 35 and R 36 They form a phenyl group which may both have substituents, R 37 is a hydrogen atom or C 1-20 It is an alkyl group, or R 36 and R 37 They form a phenyl group which may both have substituents, R 35 is a hydrogen atom or C 1-20 It is an alkyl group; R 39 , R 40 , and R 41 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 39 and R 40 They form a phenyl group which may both have substituents, R 41 is a hydrogen atom or C 1-20 It is an alkyl group, or R 40 and R 41 They form a phenyl group which may both have substituents, R 39is a hydrogen atom or C 1-20 Compounds that are alkyl groups are preferred, R 23 , R 24 , R 25 , and R 26 Both are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 Both are unsubstituted phenyl groups, or linear or branched C groups. 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 Both are nitrogen atoms; R 35 , R 36 , and R 37 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 35 and R 36 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 37 is a hydrogen atom or C 1-20 It is an alkyl group, or R 36 and R 37 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 35 is a hydrogen atom or C 1-20 It is an alkyl group; R 39 , R 40 , and R 41 These are hydrogen atoms or C, independently of each other. 1-20 R is an alkyl group. 39 and R 40 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 41 is a hydrogen atom or C 1-20 It is an alkyl group, or R 40 and R 41 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 39 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferable because they have high luminescence efficiency and excellent compatibility with resins.

[0165] The compound represented by (I4-5) above is R 23 , R 24 , R 25 , and R 26 Both are halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl or C 1-10 A phenyl group substituted with an alkoxy group; R 27 and R 28 Both are hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 Both are nitrogen atoms; R 35 , R 36 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 35 and R 36 They form a phenyl group which may both have substituents, R 38 is a hydrogen atom or C 1-20 It is an alkyl group; R 39 , R 40 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 39 and R 40 They form a phenyl group which may both have substituents, R 42 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are preferred, R 23 , R 24 , R 25 , and R 26 Both are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 Both are unsubstituted phenyl groups, or linear or branched C groups. 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 Both are nitrogen atoms; R 35 , R 36 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20It is an alkyl group, or R 35 and R 36 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 38 is a hydrogen atom or C 1-20 It is an alkyl group; R 39 , R 40 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 39 and R 40 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 42 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferable because they have high luminescence efficiency and excellent compatibility with resins.

[0166] The compound represented by (I4-6) above is R 23 , R 24 , R 25 , and R 26 Both are halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl or C 1-10 A phenyl group substituted with an alkoxy group; R 27 and R 28 Both are hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl or C 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 Both are nitrogen atoms; R 35 , R 37 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 37 and R 38 They form a phenyl group which may both have substituents, R 35 is a hydrogen atom or C 1-20 It is an alkyl group; R 39 , R 41 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20It is an alkyl group, or R 41 and R 42 They form a phenyl group which may both have substituents, R 39 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are preferred, R 23 , R 24 , R 25 , and R 26 Both are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 Both are unsubstituted phenyl groups, or linear or branched C groups. 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 Both are nitrogen atoms; R 35 , R 37 , and R 38 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 37 and R 38 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 35 is a hydrogen atom or C 1-20 It is an alkyl group; R 39 , R 41 , and R 42 These are hydrogen atoms or C, independently of each other. 1-20 It is an alkyl group, or R 41 and R 42 Both are unsubstituted phenyl groups or C 1-10 Forms an alkyl-substituted phenyl group, R 39 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferable because they have high luminescence efficiency and excellent compatibility with resins.

[0167] The compound represented by any of (I3-1) to (I3-6) above is preferably a compound represented by any of the following general formulas (I3-7) to (I3-9), and the compound represented by any of (I4-1) to (I4-6) above is preferably a compound represented by any of the following general formulas (I4-7) to (I4-9).

[0168] [ka]

[0169] In general formulas (I3-7) and (I4-7), Y 23 and Y 24 These represent, independently of each other, a carbon atom or a nitrogen atom. In general formulas (I3-7), etc., Y 23 and Y 24 It is preferable that these atoms are of the same type.

[0170] In general formulas (I3-8) and (I4-8), Y 13 and Y 14 These represent, independently of each other, an oxygen atom or a sulfur atom. In general formulas (I3-8), etc., Y 13 and Y 14 It is preferable that these atoms are of the same type.

[0171] In general formulas (I3-9) and (I4-9), Y 25 and Y 26 These represent, independently of each other, a carbon atom or a nitrogen atom. In general formulas (I3-9), etc., Y 25 and Y 26 It is preferable that these atoms are of the same type.

[0172] In general formulas (I3-7) to (I3-9), R 47 and R 48 These groups independently represent a hydrogen atom or an electron-withdrawing group, and are preferably trifluoromethyl, cyano, nitro, sulfonyl, or phenyl groups, with trifluoromethyl or cyano groups being particularly preferred, as they result in high fluorescence intensity. In general formulas (I3-7), etc., R 47 and R 48 It is preferable that these are of the same type of functional group.

[0173] In general formulas (I3-7) to (I3-9) and (I4-7) to (I4-9), R 43 , R 44 , R 45 , and R 46R represents a halogen atom or an aryl group which may have a substituent. a and R b The groups exemplified in the text as "any group that does not inhibit the fluorescence of the compound" can be used. Furthermore, the substituents that the aryl group may have can be "any group that does not inhibit the fluorescence of the compound," for example, C 1-6 Alkyl alkyl group, C 1-6 Examples include alkoxy groups, aryl groups, or heteroaryl groups. In general formulas (I3-7) to (I3-9) and (I4-7) to (I4-9), R 43 ~R 46 These may each be a different group, but it is preferable that they are all of the same type. Compounds represented by any of the general formulas (I3-7)~(I3-9) and (I4-7)~(I4-9) include R 43 ~R 46 However, it is preferable that all are halogen atoms of the same type, or that all are phenyl groups which may have substituents of the same type, more preferably that all are fluorine atoms or unsubstituted phenyl groups, and particularly preferably that all are fluorine atoms.

[0174] In general formulas (I3-7) to (I3-9) and (I4-7) to (I4-9), P 15 ~P 16 These are, independently of each other, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 This represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group. 15 ~P 16 C in 1-20 Alkyl alkyl group, C 1-20 The alkoxy group, monoalkylamino group, or dialkylamino group are, respectively, the R g The same items listed in (p1)~(p3) and (q1)~(q3) can be listed. 15 ~P 16 C 1-20 Alkyl alkyl group, C 1-20It is preferable that the group is an alkoxy group, an (unsubstituted) phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group, and from the viewpoint of biosafety, C 1-20 Alkyl alkyl group, C 1-20 More preferably, the substituent is an alkoxy group, a phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group, and these substituents may have further substituents. However, safety can be improved by introducing other substituents as well, so the substituents are not limited to these.

[0175] In the general formulas (I3-7)~(I3-9) and (I4-7)~(I4-9), n15~n16 represent integers from 0 to 3, independently of each other. In one numerator, P 15 If there are multiple instances of (i.e., n15 is 2 or 3), multiple P 15 These may all be the same type of functional group, or they may be different types of functional groups. 16 The same applies to this matter.

[0176] In general formulas (I3-7) to (I3-9) and (I4-7) to (I4-9), A 15 ~A 16 These are, independently of each other, hydrogen atoms, halogen atoms, and C 1-20 Alkyl alkyl group, C 1-20 This represents a phenyl group which may have 1 to 3 substituents selected from the group consisting of alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups. 1-20 Alkyl alkyl group, C 1-20 The alkoxy group, monoalkylamino group, or dialkylamino group are, respectively, the R g The same items listed in (p1)~(p3) and (q1)~(q3) are listed. A 15 ~A 16 Examples include an unsubstituted phenyl group and one or two C12s. 1-20A phenyl group having an alkoxy group as a substituent is preferred, as is an unsubstituted phenyl group or a single carbon atom. 1-20 A phenyl group having an alkoxy group as a substituent is more preferable, as is an unsubstituted phenyl group or a single carbon atom. 1-10 A phenyl group having an alkoxy group as a substituent is even more preferred. Also, as a compound represented by general formula (I3-7), A 15 ~A 16 Preferably, all of them are of the same type of functional group.

[0177] Compounds represented by any of the above formulas (I3-1) to (I3-6) and (I4-1) to (I4-6) include compounds represented by any of the following general formulas (6-1) to (6-12) and (7-1) to (7-12). In general formulas (6-7) to (6-12) and (7-7) to (7-12), Ph means an unsubstituted phenyl group. Among the compounds represented by any of the above formulas (I3-1) to (I3-6) and (I4-1) to (I4-6), compounds represented by general formulas (6-4), (6-5), (6-7), (6-8), (7-4), (7-5), (7-7), and (7-8) are particularly preferred, and compounds represented by general formulas (6-4), (6-5), (6-7), and (6-8) are more preferred.

[0178] In general formulas (6-1) to (6-12), (7-1) to (7-12), P 5 ~P 8 These are, independently of each other, halogen atoms, C 1-20 Alkyl alkyl group, C 1-20 This represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group. 5 ~P 8 C in 1-20 Alkyl alkyl group, C 1-20 The alkoxy group, monoalkylamino group, or dialkylamino group are, respectively, the R g The same items listed in (p1)~(p3) and (q1)~(q3) can be listed. 5 ~P 8 C 1-20 Alkyl alkyl group, C 1-20It is preferable that the group is an alkoxy group, an (unsubstituted) phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group, and from the viewpoint of biosafety, C 1-20 Alkyl alkyl group, C 1-20 It is more preferably an alkoxy group, a phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group, C 1-20 Alkyl alkyl group or C 1-20 It is even more preferable that it be an alkoxy group, C 1-10 Alkyl alkyl group or C 1-10 It is even more preferable that the substituents be alkoxy groups, and these substituents may have further substituents. However, safety can be improved by introducing other substituents as well, so the substituents are not limited to these.

[0179] In the general formulas (6-1)~(6-12) and (7-1)~(7-12), n5~n8 represent integers from 0 to 3, independently of each other. In one numerator, P 5 If there are multiple instances of (i.e., n5 is 2 or 3), multiple P 5 These may all be the same type of functional group, or they may be different types of functional groups. 6 ~P 8 The same applies to this matter.

[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] Compounds represented by general formulas (6-1) to (6-12) and (7-1) to (7-12) include P 5 ~P 8 C 1-20 Alkyl alkyl group or C 1-20 It is an alkoxy group, and preferably n5 to n8 are independently 0 to 2, P 5 and P 6 C 1-20 It is an alkyl group, and n5 and n6 are independently 0 to 2, P 7 and P 8 C 1-20 It is an alkoxy group, and it is more preferable that n7 and n8 are independently 0 to 1, P 5 and P 6 C 1-20 It is an alkyl group, and n5 and n6 are independently 1 to 2, P 7 and P 8 C 1-20 It is more preferable that the alkoxy group has n7 and n8 equal to 1.

[0185] Compounds represented by general formulas (6-1) to (6-12) specifically include those represented by the following formulas (6-1-1) to (6-12-1). "λ" is the peak wavelength of the absorption spectrum of each compound, and "Em" is the peak wavelength of the fluorescence spectrum.

[0186] [ka]

[0187] [ka]

[0188] The near-infrared fluorescent dye contained in the standard plate used in the present invention only needs to have a maximum fluorescence wavelength of 650 nm to 1000 nm, and may contain only one type of dye or two or more types. The standard plate used in the present invention preferably has a maximum fluorescence wavelength of 700 nm or higher, and more preferably 720 nm or higher. The standard plate used in the present invention may have two or more fluorescence wavelength peaks within the 650 nm to 1000 nm range, but it is preferable to have only one peak at the maximum fluorescence wavelength. Therefore, it is preferable that the near-infrared fluorescent dye contained in the standard plate used in the present invention be of only one type.

[0189] <Amorphous resin> Amorphous resins generally tend to show little change over time and have the advantage of easily uniformizing the pigments in the resin composition. For this reason, near-infrared fluorescence chromaticity can be uniformly present throughout the plate, and it can be used stably for a long period of time. Therefore, amorphous resin is used as the resin constituting the standard plate used in the present invention.

[0190] As for amorphous resins, there are no particular limitations as long as no crystals are present in the molded product, but it is preferable that the molded product made solely from the resin is transparent, a so-called transparent resin. Here, transparency means that the total light transmittance of a 2mm thickness in the visible region (wavelength range of 380 to 650nm) is 70% or more. This is because, with transparent resins, not only does light emitted from inside the resin reach the outside of the resin, but light does not diffuse easily inside the resin, thus reducing the influence of scratches and other factors on fluorescence intensity.

[0191] The amorphous resin constituting the standard plate used in the present invention may be a thermoplastic resin or a thermosetting resin. When used in a molded article, thermosetting resins may harden during melt-kneading, so it is preferable that the resin component contained in the standard plate used in the present invention be a thermoplastic resin. For example, if the standard plate used in the present invention is a thermoplastic resin composition, the resin component as a whole may be a thermoplastic resin, and may contain a small amount of non-thermoplastic resin.

[0192] Specific examples of amorphous resins that constitute the standard plate used in the present invention include polycarbonate resins such as polycarbonate (PC), polystyrene resins such as polystyrene (PS), imide-modified polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, imide-modified ABS resin, styrene-acrylonitrile copolymer (SAN) resin, and acrylonitrile-ethylene-propylene-diene-styrene (AES) resin; acrylic resins such as polyacrylic acid, polymethacrylic acid, polymethyl polyacrylate, polymethyl methacrylate (PMMA), and polyethyl methacrylate; polyoxymethylene resins such as polyoxymethylene (POM); polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate; and vinyl chloride resins such as polyvinyl chloride (PVC) and vinyl chloride-vinyl acetate copolymer resin. The resin component contained in the standard plate used in the present invention may be a single type or a mixture of two or more types. When mixing two or more types, it is preferable to use a combination of resins that have high compatibility. In particular, it is preferable to use one or more amorphous resins selected from the group consisting of PC, PS, PMMA, POM, PET, PVC, and transparent ABS as the amorphous resin constituting the standard plate used in the present invention. PS may be general-purpose transparent polystyrene (GPPS) or high-impact polystyrene (HIPS). In the present invention, PC is particularly preferred as the amorphous resin constituting the standard plate because it has high hardness and is stable against scratches and bending.

[0193] <Molding> The melt-kneading of a raw material mixture containing a near-infrared fluorescent dye and an amorphous resin, and the molding of the resulting resin composition into a plate, can be carried out by conventional methods using commercially available melt-kneaders and molding machines. For example, a powder composition of a near-infrared fluorescent dye and pellets of amorphous resin can be pre-mixed to form the raw material mixture, which is then put into a melt-kneader. The mixture is kneaded in a high-temperature environment above the melting point of the amorphous resin, and the resulting kneaded material (resin composition) is then molded into a plate. The molding method is not particularly limited, but examples include casting, injection molding using a mold, compression molding, extrusion molding using a T-die, blow molding, etc.

[0194] In the present invention, instead of a molded body of a resin composition obtained by melt-kneading a raw material mixture containing a near-infrared fluorescent dye and an amorphous resin, a plate can be used as a standard plate in which a liquid resin composition obtained by dissolving a raw material mixture containing a near-infrared fluorescent dye and an amorphous resin in a solvent is applied to the surface of a glass substrate to form a coating film, or a coating film (film) that has been peeled off the glass substrate after being formed on the glass substrate can be used. The raw material mixture containing the near-infrared fluorescent dye and an amorphous resin can be the same as described above. The solvent used to dissolve the raw material mixture is not particularly limited, but a volatile solvent is preferred. Examples of such solvents include toluene, xylene, naphthalene, hexane, benzene, dichloromethane, tetrachloromethane, methanol, ethanol, propanol, butanol, acetone, formic acid, methyl ethyl ketone, acetonitrile, dimethyl sulfoxide, dimethylformamide, etc., and a mixture of two or more of these solvents may also be used. The method for applying the liquid resin composition to the surface of the transparent plate that serves as the substrate is not particularly limited and includes spray coating, spin coating, slit coating, roll coating, etc. The dry film thickness of the coating film containing the near-infrared fluorescent dye and amorphous resin formed on the surface of the transparent plate is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 50 μm, in order to measure the relative fluorescence intensity of the test sample at a higher concentration.

[0195] The shape of the standard plate is not particularly limited as long as it is plate-shaped, and can be appropriately molded into a shape that can be measured by the measuring instrument used for measuring near-infrared fluorescence intensity. The top surface of the standard plate may be circular, elliptical, a polygon such as a square, pentagon, hexagon, or octagon, or any other shape. If the top surface of the standard plate is square, the rectangle may, for example, have dimensions of 50 to 200 mm independently for both length and width.

[0196] To suppress variations in near-infrared fluorescence intensity measurements depending on the type of measuring instrument, it is preferable that the standard plate has a uniform thickness. Specifically, it is preferable that the absolute difference between the maximum and minimum thicknesses across the entire standard plate is 20% or less of the average thickness, more preferably 10% or less, even more preferably 5% or less, and particularly preferably 1% or less. The average thickness is the numerical average of any 20 points on the plate.

[0197] While there are no specific requirements for the thickness of the standard plate, it is preferably 1 μm or more, more preferably 50 μm or more, and even more preferably 100 μm or more, as this suppresses the effects of fine scratches and other damage from use and allows for stable use over a long period. Therefore, it is particularly preferable that the thickness be 1 mm or more, and most preferably 2 mm or more. Furthermore, since it is suitable for measurement with various spectrofluorometers, the thickness of the standard plate is preferably 15 mm or less, more preferably 10 mm or less, and even more preferably 5 mm or less.

[0198] When using a plate in which a coating film containing a near-infrared fluorescent dye is formed on the surface of a glass substrate as a standard plate, there is no particular specification for the thickness of the glass substrate. However, when a film is formed on the glass substrate and used without peeling it off, from the viewpoint of ensuring transparency and mechanical strength, the thickness is preferably 1 μm or more, more preferably 50 μm or more, even more preferably 100 μm or more, particularly preferably 1 mm or more, and most preferably 2 mm or more. Furthermore, the thickness of the standard plate is preferably 15 mm or less, more preferably 10 mm or less, and even more preferably 5 mm or less.

[0199] The content of the near-infrared fluorescent dye in the standard plate is not particularly limited as long as the concentration causes the standard plate to emit near-infrared fluorescence. However, from the viewpoint of fluorescence intensity and detection sensitivity, a concentration of 0.0001% by mass or more is preferred, 0.0005% by mass or more is more preferred, and 0.001% by mass or more is even more preferred. A low dye concentration is desirable because it reduces the possibility of elution and the possibility of bleed-out from the standard plate. On the other hand, to avoid concentration quenching, the content of the near-infrared fluorescent dye in the standard plate is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0200] When using a plate with a coating containing a near-infrared fluorescent dye formed on the surface of a glass substrate as a standard plate, the near-infrared fluorescent dye content of the standard plate is calculated as the ratio of the near-infrared fluorescent dye content in the coated liquid resin composition to the total amount of the solid content of the liquid resin composition coated on the surface of the glass substrate used as the base material ([Amount of near-infrared fluorescent dye in the coated liquid resin composition (g)] / [Amount of solid content of the coated liquid resin composition (g)] × 100%).

[0201] The fluorescence intensity of a standard plate depends on the content of near-infrared fluorescent dye in the standard plate. Therefore, the concentration of near-infrared fluorescent dye in the standard plate can be appropriately adjusted according to the range of fluorescence intensity values ​​that the test sample can take. It is also preferable to prepare multiple standard plates with different concentrations within the range of 0.001% by mass to 10% by mass, and use the appropriate standard plate according to the fluorescence intensity of the test sample.

[0202] <Additives> The resin composition containing a near-infrared fluorescent dye and an amorphous resin, which are melt-kneaded for molding the standard plate, may contain other additives to the extent that they do not impair the function of the standard plate. Examples of such additives include colorants, ultraviolet absorbers, heat stabilizers, light stabilizers, antioxidants, flame retardants, flame retardant aids, plasticizers, antistatic agents, and mold release agents. For example, by incorporating colorants that do not affect fluorescence, such as titanium or pigments, an easily visible standard plate can be obtained.

[0203] <Blank Plate> By using a blank plate that does not contain near-infrared fluorescent dye, a blank value for fluorescence intensity measurement can be obtained. This blank plate is manufactured with the same composition and manufacturing method as the standard plate, except that it does not contain near-infrared fluorescent dye. Specifically, first, a raw material mixture is prepared that has the same composition as the raw material mixture prepared for melt-kneading when manufacturing the standard plate, except that it does not contain near-infrared fluorescent dye. In other words, the raw material mixture for manufacturing the blank plate is a mixture with the composition of the raw material mixture for manufacturing the standard plate, with the near-infrared fluorescent dye removed. This raw material mixture is melt-kneaded under the same conditions as when manufacturing the standard plate and molded into the same shape as the standard plate. Note that the presence or absence and content of components that do not affect fluorescence among the components of the raw material mixture prepared for melt-kneading when manufacturing the standard plate may differ in the raw material mixture prepared for melt-kneading when manufacturing the blank plate. For example, the raw material mixture prepared for melt-kneading when manufacturing the blank plate may contain a coloring agent that does not affect fluorescence and has a different color tone than the standard plate.

[0204] <Standard plate set for relative fluorescence intensity measurement> The standard plate and blank plate used in the relative fluorescence intensity measurement method according to the present invention may also be provided as a set. By using a standard plate set for relative fluorescence intensity measurement that includes these plates, the relative fluorescence intensity measurement method according to the present invention can be carried out more easily. The standard plate set for relative fluorescence intensity measurement may include multiple standard plates with different concentrations of near-infrared fluorescent dyes.

[0205] <Test sample> The test sample used in the relative fluorescence intensity measurement method according to the present invention is not particularly limited, as long as it is a molded body of a resin composition containing a near-infrared fluorescent dye and has a maximum fluorescence wavelength in the range of 650 nm to 1000 nm. The near-infrared fluorescent dye contained in the test sample may be the same type as or different from the near-infrared fluorescent dye in the standard plate used for measurement. Examples of such test samples include a molded body obtained by molding a resin composition that already contains a near-infrared fluorescent dye, or a molded body obtained by molding a resin composition that does not contain a near-infrared fluorescent dye and then adhering a near-infrared fluorescent dye to the surface of the resulting molded body.

[0206] If the test sample is a molded article obtained by molding a resin composition that already contains a near-infrared fluorescent dye, the test sample can be manufactured, for example, by preparing a raw material mixture containing a near-infrared fluorescent dye and a resin, and then molding it. The raw material mixture may further contain additives. The same additives as described above can be used. The raw material mixture only needs to be one in which the near-infrared fluorescent dye is uniformly mixed and dispersed in the resin component, and may be prepared by any known method.

[0207] For example, a molded body made from a resin composition obtained by melt-kneading a raw material mixture containing a near-infrared fluorescent dye, a resin, and additives as needed, can be used as a test sample. The molding method is not particularly limited and may be carried out by any known method such as casting, injection molding using a mold, compression molding, extrusion molding using a T-die, blow molding, etc.

[0208] Furthermore, a film formed by curing a raw material mixture obtained by dissolving or dispersing a near-infrared fluorescent dye, a resin, and additives as needed in a solvent, after coating it onto a substrate, can also be used as a test sample. The coating method is not particularly limited and includes spray coating, spin coating, slit coating, and roll coating. Various materials can be used as substrates, such as glass plates, metal plates, and resin plates. The solvent is not particularly limited as long as it can dissolve the resin and includes, for example, toluene, xylene, naphthalene, hexane, benzene, tetrachloromethane, methanol, ethanol, propanol, butanol, acetone, formic acid, methyl ethyl ketone, acetonitrile, dimethyl sulfoxide, and dimethylformamide, and may also be a mixture of two or more of these solvents.

[0209] The resin constituting the test sample is not particularly limited, and for example, thermoplastic resins and thermosetting resins can be used. Examples of thermoplastic resins include urethane-based resins such as polyurethane (PU) and thermoplastic polyurethane (TPU); polycarbonate (PC); vinyl chloride-based resins such as polyvinyl chloride (PVC) and vinyl chloride-vinyl acetate copolymer resins; acrylic-based resins such as polyacrylic acid, polymethacrylic acid, polymethyl polyacrylate, polymethyl methacrylate (PMMA), and polyethyl methacrylate; and polyester-based resins such as polyethylene terephthalate (PET), polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. Examples of resins include: polyamide resins such as nylon (registered trademark); polystyrene resins such as polystyrene (PS), imide-modified polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, imide-modified ABS resin, styrene-acrylonitrile copolymer (SAN) resin, and acrylonitrile-ethylene-propylene-diene-styrene (AES) resin; olefin resins such as polyethylene (PE) resin, polypropylene (PP) resin, and cycloolefin resin; cellulose resins such as nitrocellulose and cellulose acetate; silicone resins; and fluororesins. Examples of thermosetting resins include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, isocyanurate-based epoxy resin, and hydantoin-based epoxy resin; amino resins such as melamine-based resin and urea resin; phenolic resins; and unsaturated polyester resins.

[0210] If the test sample is a molded body obtained by molding a resin composition that does not contain a near-infrared fluorescent dye and then adhering a near-infrared fluorescent dye to the surface of the resulting molded body, methods for adhering the near-infrared fluorescent dye to the surface of the molded body include coating the surface of the molded body with a near-infrared fluorescent dye solution dissolved in a volatile solvent, or immersing the molded body itself in a near-infrared fluorescent dye solution and then removing the solvent. The solvent is not particularly limited as long as it is a solvent in which the near-infrared fluorescent dye can be dissolved, but a volatile solvent is preferred. Specifically, the solvents mentioned above can be used as appropriate. The method of applying the near-infrared fluorescent dye solution is not particularly limited and includes spray coating, spin coating, slit coating, roll coating, etc.

[0211] Furthermore, a molded body with a near-infrared fluorescent dye adhered to its surface can also be obtained by applying a liquid resin composition containing a near-infrared fluorescent dye to the surface of a molded body made of a resin composition that does not contain a near-infrared fluorescent dye, and then curing the resin composition to form a coating film. This molded body can be used as a test sample. The method for applying the liquid resin composition containing a near-infrared fluorescent dye to the surface of the molded body is not particularly limited and can be the same as described above, such as spray coating. The dry film thickness of the resin coating film containing the near-infrared fluorescent dye on the surface of the molded body is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 50 μm.

[0212] The shape of the test sample is not particularly limited. While the test sample is preferably a film (sheet) or plate-shaped molded body for ease of measurement, it may also be a tubular or other more complex shaped molded body. If the test sample is plate-shaped, its shape, such as the shape, size, and thickness of the top surface, can be the same as that of the standard plate.

[0213] The content of near-infrared fluorescent dye in the test sample is not particularly limited, but is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, and even more preferably 0.001% by mass or more. On the other hand, the content of near-infrared fluorescent dye in the test sample is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0214] The relative fluorescence intensity measurement method according to the present invention is particularly useful for evaluating the fluorescence intensity of industrial products. Specifically, industrial products are preferred as the test samples used in the present invention. From a quality control standpoint, it is desirable to minimize variations between manufacturing lots of industrial products. The standard plate used in the relative fluorescence intensity measurement method according to the present invention has excellent temporal stability of fluorescence intensity, and the same standard plate can be used in common for near-infrared fluorescence measurements of products from multiple manufacturing lots. Therefore, by using this standard plate, variations between manufacturing lots can be sufficiently suppressed, and highly reliable relative fluorescence intensity can be obtained for the test samples.

[0215] In the present invention, the test specimen is preferably a molded body used as a medical device. This is because medical devices require particularly high uniformity of product quality and demand higher quality control than other industrial products. As the characteristics of near-infrared fluorescence are utilized, it is particularly preferable that at least a portion of the medical device is used inside the patient's body. Examples of medical devices in which at least a portion is inserted or left inside the patient's body include stents, coil embolizers, catheter tubes, medical clips, injection needles, indwelling needles, ports, shunt tubes, drain tubes, implants, etc. Examples of catheter tubes include ureteral / urethral catheters, biliary catheters, vascular catheters, etc. Examples of medical clips include gastrointestinal clips, etc.

[0216] In the present invention, the test sample may preferably be a molded body of a resin composition that is a raw material for various industrial products that emit near-infrared fluorescence, including medical devices. For example, the near-infrared fluorescence intensity of a catheter tube manufactured by molding a resin composition containing a near-infrared fluorescent dye into a tube can also be measured as the near-infrared fluorescence intensity of a plate manufactured by molding the same resin composition under the same molding conditions.

[0217] <Test sample blank> In the relative fluorescence intensity measurement method according to the present invention, a molded body having the same composition as the test sample, except that it does not contain the near-infrared fluorescent dye contained in the test sample, is used as a test sample blank to measure the blank value of the fluorescence intensity. However, a molded body with a composition that excludes components contained in the test sample that do not affect the near-infrared fluorescence intensity of the test sample can also be used as a test sample blank.

[0218] For example, if the test sample is a molded body of a resin composition obtained by melt-kneading a raw material mixture containing a near-infrared fluorescent dye, a molded body of a resin composition obtained by melt-kneading a raw material mixture having the same composition as the raw material mixture of the test sample, except that it does not contain the near-infrared fluorescent dye, can be used as the test sample blank. If the test sample is a molded body with a near-infrared fluorescent dye adhered to its surface, the molded body before the near-infrared fluorescent dye was adhered to its surface can be used as the test sample blank. Furthermore, if the test sample is a molded body in which a liquid resin composition containing a near-infrared fluorescent dye is applied to the surface of a molded body that does not contain a near-infrared fluorescent dye to form a coating film, a molded body in which a liquid resin composition having the same composition as the liquid resin composition except that it does not contain a near-infrared fluorescent dye is applied to the surface of a molded body that does not contain a near-infrared fluorescent dye to form a coating film can be used as the test sample blank.

[0219] The shape of the test sample blank may be the same as or different from the shape of the test sample. In this invention, by making the test sample blank a molded body with the same shape as the test sample, the accuracy of measuring the fluorescence intensity of the test sample can be improved. When the test sample is a molded body with a complex shape, it is preferable that the test sample blank be a molded body with the same shape as the test sample, but it is also preferable that it be a film-like or plate-like molded body.

[0220] <Measurement of fluorescence intensity> In the relative fluorescence intensity measurement method according to the present invention, the fluorescence intensity of the near-infrared fluorescence wavelength is measured for the test sample, the test sample blank, the standard plate, and the blank plate. Specifically, the fluorescence spectra in the wavelength range of 650 nm or higher are measured for the test sample, the test sample blank, the standard plate, and the blank plate, and the fluorescence intensity of fluorescence wavelengths present in the range of 650 to 1000 nm is determined from the obtained fluorescence spectra.

[0221] Fluorescence spectra can be measured using commercially available fluorescence detection devices and other conventional methods. In this invention, it is preferable to use a spectrofluorometer for measurement, and various commercially available devices can be used as the spectrofluorometer. Any light source can be used as the excitation light for fluorescence detection, including near-infrared lamps with a long wavelength range, as well as lasers, LEDs, and other devices with a narrow wavelength range.

[0222] Fluorescence intensity also depends on the thickness of the sample. Therefore, if the thickness of the test sample and the standard plate is very large, the fluorescence intensity value can be corrected by adjusting the thickness.

[0223] Fluorescence intensity F1 at fluorescence wavelength λ1 of the test sample, fluorescence wavelength λ of the test sample blank 1B Fluorescence intensity F 1B , fluorescence wavelength λ of the standard plate S The fluorescence intensity Fs of the blank plate, and the fluorescence wavelength λ of the blank plate. SB Fluorescence intensity F SB Based on these values, the relative fluorescence intensity (F1-F) of the test sample can be calculated. 1B) / (Fs-F SB The standard plate used in this invention has excellent temporal stability of fluorescence and allows for the mass production of homogeneous plates. Therefore, the relative fluorescence intensity measurement method according to the present invention using this standard plate makes it possible to compare relative fluorescence intensity values ​​measured at different facilities and at different time points. In other words, by using this standard plate, it becomes possible to confirm data correlation with a third party.

[0224] If the test sample or test sample blank is not in film or plate form, it can be prepared into a film or plate form before being subjected to fluorescence intensity measurement. For example, if the test sample is a tubular molded body, the fluorescence intensity of the film or plate formed by opening the tube can be measured. Furthermore, if the test sample is a molded body with a more complex shape, the molded body can be sliced, and the fluorescence intensity of the resulting film or plate-like sections can be measured. [Examples]

[0225] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0226] [Synthesis Example 1] Synthesis of near-infrared fluorescent dye H The near-infrared fluorescent dye H was analyzed as follows, referring to Organic Letters, 2012, Vol. 4, pp. 2670-2673 and Chemistry A European Journal, 2009, Vol. 15, pp. 4857-4864.

[0227] The procedure was the same as in Synthesis Example 2, except that 1-bromo-2-ethylhexane (48 g, 249 mmol) was used instead of 1-bromooctane (48 g, 249 mmol), and a red solid of 3,6-(4-(2-ethylhexyl)oxyphenyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione(h-2) was obtained (yield: 4.6 g).

[0228] Next, 2-amino-4-tert-butylphenol (5.24 g, 31.7 mmol), 2-cyano-acetylmidic acid ethyl hydrochloride (4.45 g, 33.3 mmol), and dichloromethane (30 mL) were added to a 100 mL two-necked flask, and the mixture was refluxed overnight. The reaction mixture was diluted with dichloromethane (100 mL) and washed twice with 1 mol / L sodium hydroxide aqueous solution. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed by distillation to obtain a yellow liquid (5-tert-butyl-benzoxazole-2-yl)acetonitrile (H-3) (yield 6.3 g, yield 88%).

[0229] Next, under an argon stream, compound (H-2) (1.64 g, 3.0 mmol), compound (H-3) (1.41 g, 6.6 mmol), and anhydrous toluene (50 mL) were added to a 200 mL three-necked flask and heated under reflux. Under reflux, phosphoryl chloride (2.34 mL, 25 mmol) was added dropwise using a syringe, and the mixture was heated under reflux for a further 2 hours. After the reaction was complete, while cooling with ice, dichloromethane (40 mL) and saturated sodium bicarbonate aqueous solution (40 mL) were added, and the mixture was extracted with dichloromethane. The organic layer was treated with anhydrous magnesium sulfate, and after filtering off the magnesium sulfate, the solvent was removed under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: hexane / ethyl acetate) to roughly remove impurities. The residue obtained by distilling off the solvent was purified again by silica gel column chromatography (eluent: dichloromethane) to obtain a blue-green solid precursor (H-4) (yield: 0.98 g, yield: 35%).

[0230] Finally, under an argon stream, the precursor (h-4) (973 mg, 1.0 mmol), N,N-diisopropylethylamine (387 mg, 3.0 mmol), and dichloromethane (30 mL) were placed in a 100 mL two-necked flask, and chlorodiphenylborane (900 mg, 4.5 mmol) was added under reflux, and the reaction was carried out overnight. After washing the reaction mixture with water, the organic layer was dried over anhydrous magnesium sulfate and concentrated. After washing the residue with methanol, it was purified by column chromatography (eluent: dichloromethane) to obtain a powder composition consisting of a green solid of near-infrared fluorescent dye H (yield: 0.42 g, yield: 35%).

[0231] 1 H-NMR (300MHz, CDCl3): δ=7.11(m, 24H), 6.62(m, 4H), 6.32(m, 6H), 3.8-3.9(m, 4H ), 2.27(s, 6H), 1.8(m, 2H), 1.6-1.3(m, 16H), 1.38(s, 18H), 0.9-1.0(m, 12H)ppm.

[0232] [ka]

[0233] [Example 1] A resin composition was prepared by melt-kneading using the near-infrared fluorescent dye H obtained in Synthesis Example 1 and resin pellets, and a plate was molded from the obtained resin composition. As the resin pellets, "SD Polycarbonate (trademark) 301-4" (manufactured by Sumika Polycarbonate Co., Ltd.), an amorphous resin, was used as PC pellets.

[0234] First, near-infrared fluorescent dye H and resin pellets were mixed so that the concentration of near-infrared fluorescent dye H was 0.005% by mass (50 ppm). Next, the resulting mixture was melt-kneaded, and a near-infrared fluorescent dye-containing plate (90 mm × 50 mm × 3 mm) was injection-molded. The melt-kneading and injection molding of the plate were performed using an injection molding machine under the following conditions. The cylinder temperature and mold temperature of the injection molding machine were set according to the type of resin pellet.

[0235] Conditions for melt mixing and injection molding Equipment: Injection molding machine (product name: EC50SXII-1.5A, manufactured by Toshiba Corporation) Hopper bottom temperature setting: 60℃ Injection pressure: 99 MPa Back pressure: 20 MPa Screw rotation: 140 / min Injection speed: 70mm / s Ejection time: 10 seconds Cooling time: 20 seconds Nozzle operation: Retracts for 2 seconds after metering is complete. Cylinder temperature setting: 280℃ Mold temperature: 80℃

[0236] A plate was formed in the same manner as the near-infrared fluorescent dye-containing plate described above, except that it did not contain the near-infrared fluorescent dye H, and this was used as a blank plate.

[0237] Six sets (sets 1-6) were manufactured, one set containing a near-infrared fluorescent dye and one blank plate, with one set produced each week. The fluorescence intensity profile of each plate was measured on the day of manufacture. The fluorescence intensity profile was measured using a fluorescence spectrophotometer under the following measurement conditions.

[0238] <Measurement conditions for the fluorescence spectrum of the plate> Fluorescence spectrophotometer: "FP-8600" (manufactured by JASCO Corporation) Excitation bandwidth: 10 nm Fluorescence bandwidth: 10 nm Response time: 0.2 seconds PMT voltage: 740V Measurement range: 680~1000nm Data acquisition interval: 1nm Excitation wavelength: 700.0 nm Scanning speed: 500 nm / min Light source: Xenon lamp

[0239] For both the near-infrared fluorescent dye-containing plate and the blank plate of each plate, the fluorescence intensity at the maximum fluorescence wavelength was measured from the fluorescence spectra at wavelengths of 600 to 1000 nm. The fluorescence intensity value obtained by subtracting the fluorescence intensity value at the maximum fluorescence wavelength of the blank plate from the fluorescence intensity value at the maximum fluorescence wavelength of the near-infrared fluorescent dye-containing plate was defined as the fluorescence intensity value at the maximum fluorescence wavelength of each resin plate.

[0240] [Table 1]

[0241] Table 1 shows the measurement results of the fluorescence intensity values ​​at the maximum fluorescence wavelength for each resin plate. As shown in Table 1, the fluorescence intensity values ​​at the maximum fluorescence wavelength for the PC plates were all similar for six near-infrared fluorescent dye-containing plates prepared on different dates, indicating very little variation. Plates made by melt-kneading near-infrared fluorescent dyes into the amorphous resin PC exhibited very stable fluorescence intensity values ​​at the maximum fluorescence wavelength, confirming their suitability as standard plates for measuring the fluorescence intensity of molded bodies containing near-infrared fluorescent dyes.

[0242] [Comparative Example 1] Rhodamine B standard solutions were prepared once approximately every two weeks for a total of six times, and their fluorescence intensity profiles were measured to investigate the variability between measurements. Because rhodamine B undergoes significant degradation of fluorescence over time, the rhodamine B standard solution (concentration: 0.005% by mass (50 ppm), solvent: ethylene glycol) was prepared by opening a new bottle of rhodamine B and dissolving it in the solvent immediately before measuring the fluorescence intensity. This was used as a blank solution. The fluorescence intensity profiles of the rhodamine B standard solution and the blank solution were measured using a fluorescence spectrophotometer under the following measurement conditions.

[0243] <Measurement conditions for the fluorescence spectrum of rhodamine B standard solution> Fluorescence spectrophotometer: "FP-8600" (manufactured by JASCO Corporation) Excitation bandwidth: 10 nm Fluorescence bandwidth: 10 nm Response time: 0.2 seconds PMT voltage: 780V Measurement range: 4300~800nm Data acquisition interval: 1nm Excitation wavelength: 450.0 nm Scanning speed: 500 nm / min Light source: Xenon lamp

[0244] For both the rhodamine B standard solution and the blank solution, the fluorescence intensity at the maximum fluorescence wavelength was measured from the measured fluorescence spectrum. The fluorescence intensity value at the maximum fluorescence wavelength of each rhodamine B standard solution was obtained by subtracting the fluorescence intensity value at the maximum fluorescence wavelength of the blank solution from the fluorescence intensity value at the maximum fluorescence wavelength of the rhodamine B standard solution. The measurement results are shown in Table 2. As shown in Table 2, despite being prepared on demand, the fluorescence intensity values ​​of the rhodamine B standard solutions showed large measurement variability, making them unsuitable as standard solutions.

[0245] [Table 2]

[0246] [Example 2] Using the near-infrared fluorescent dye H and PC pellets obtained in Synthesis Example 1, five types of near-infrared fluorescent dye-containing plates with different near-infrared fluorescent dye concentrations were prepared, and the relationship between the relative fluorescence intensity value at the maximum fluorescence wavelength and the near-infrared fluorescent dye concentration was investigated. The same PC pellets as those used in Example 1 were used, and PC plates containing near-infrared fluorescent dye H and corresponding blank plates were prepared in the same manner as in Example 1, except that the near-infrared fluorescent dye H concentration was set to 0.001, 0.002, 0.003, 0.004, or 0.005 mass% (10, 20, 30, 40, or 50 ppm).

[0247] For both the manufactured near-infrared fluorescent dye-containing plates and the blank plates, the fluorescence intensity at the maximum fluorescence wavelength was measured in the same manner as in Example 1. The fluorescence intensity value obtained by subtracting the fluorescence intensity value at the maximum fluorescence wavelength of the blank plate from the fluorescence intensity value at the maximum fluorescence wavelength of the near-infrared fluorescent dye-containing plate was taken as the fluorescence intensity value at the maximum fluorescence wavelength of each near-infrared fluorescent dye-containing plate.

[0248] [Table 3]

[0249] Table 3 shows the measurement results of the fluorescence intensity values ​​at the maximum fluorescence wavelength for plates containing near-infrared fluorescent dyes of various concentrations. As shown in Table 3, the fluorescence intensity values ​​at the maximum fluorescence wavelength for plates in which near-infrared fluorescent dyes and PCs were melt-kneaded together depended on the near-infrared fluorescent dye concentration.

[0250] [Example 3] Near-infrared fluorescent dye-containing plates were prepared using the near-infrared fluorescent dye H obtained in Synthesis Example 1 and PC pellets, and the effect of the storage environment on the relative fluorescence intensity value of the maximum fluorescence wavelength of the plates was investigated. The same PC pellets as those used in Example 1 were used, and near-infrared fluorescent dye-containing plates and corresponding blank plates were prepared in the same manner as in Example 1, with the near-infrared fluorescent dye H concentration set to 0.005% by mass (50 ppm).

[0251] The manufactured near-infrared fluorescent dye-containing plates and the corresponding blank plates were stored at 4°C, 23°C, 40°C, or 55°C for 19, 39, 68, 111, or 172 days, respectively. The fluorescence intensity values ​​at the maximum fluorescence wavelength of each near-infrared fluorescent dye-containing plate after storage were measured in the same manner as in Example 1. The measurement results are shown in Table 4.

[0252] [Table 4]

[0253] The fluorescence spectra of each plate showed that there was almost no change in the fluorescence spectrum at any storage temperature between 4 and 55°C, indicating that there was almost no decrease in fluorescence intensity due to storage temperature. As shown in Table 4, regardless of the number of days of storage, the relative fluorescence intensity values ​​of the near-infrared fluorescent dye-containing plates stored at 23, 40, or 55°C were approximately the same as those at 4°C. Furthermore, the relative fluorescence intensity values ​​at 111 and 172 days of storage were approximately the same as those at 68 days. These results confirm that storage in the 4-55°C temperature range has almost no effect on the fluorescence intensity of near-infrared fluorescent dye-containing plates, even for a very long period of 172 days, and that the relative fluorescence intensity values ​​at the maximum fluorescence wavelength of plates made by melt-kneading near-infrared fluorescent dyes and amorphous resin exhibit very high stability over time.

[0254] [Example 4] A near-infrared fluorescent dye-containing plate was prepared using the near-infrared fluorescent dye H obtained in Synthesis Example 1 and PC pellets, and the effect of measurement locations on the plate on the relative fluorescence intensity value of the plate's maximum fluorescence wavelength was investigated. The same PC pellets as those used in Example 1 were used, and a near-infrared fluorescent dye-containing plate and a corresponding blank plate were prepared in the same manner as in Example 1, with the near-infrared fluorescent dye H concentration set to 0.005% by mass (50 ppm).

[0255] For both the manufactured near-infrared fluorescent dye-containing plates and the blank plates, the fluorescence intensity at the maximum fluorescence wavelength was measured in the same manner as in Example 1. The fluorescence intensity value obtained by subtracting the fluorescence intensity value at the maximum fluorescence wavelength of the blank plate from the fluorescence intensity value at the maximum fluorescence wavelength of the near-infrared fluorescent dye-containing plate was taken as the fluorescence intensity value at the maximum fluorescence wavelength of each near-infrared fluorescent dye-containing plate. At this time, fluorescence spectra were measured at the center of the plate, the back of the center, a location 5 mm to the left of the center of the plate, a location 10 mm to the left of the center of the plate, or a damaged area in the plate. The measurement results of the fluorescence intensity values ​​at the maximum fluorescence wavelength at each measurement point are shown in Table 5.

[0256] [Table 5]

[0257] As shown in Table 5, the fluorescence intensity value at the maximum fluorescence wavelength of the near-infrared fluorescent dye-containing plate was almost unaffected by factors such as the position on the plate or the presence or absence of scratches, and was approximately the same at any position. These results indicate that the near-infrared fluorescent dye H is uniformly dispersed in the plate, allowing for stable measurement of fluorescence intensity regardless of the measurement location, and that minor scratches on the plate have almost no effect on the fluorescence intensity. In other words, a plate made from a molten mixture of a resin composition containing a near-infrared fluorescent dye and an amorphous resin is not only stable over time but also unaffected by scratches, etc., making it very suitable as a standard plate for near-infrared fluorescence measurement.

[0258] [Example 5] Using the near-infrared fluorescent dye H and PC pellets obtained in Synthesis Example 1, five types of near-infrared fluorescent dye-containing plates with different near-infrared fluorescent dye concentrations were prepared, and the relationship between the relative fluorescence intensity value at the fluorescence wavelength and the near-infrared fluorescent dye concentration was investigated.

[0259] Near-infrared fluorescent dye H and resin pellet "SD Polycarbonate (trademark) 301-4" were mixed to achieve a concentration of 0.2% by mass (2000 ppm) of near-infrared fluorescent dye H. Next, the resulting mixture was melt-kneaded (screw rotation: 140 rpm, cylinder setting temperature: 280°C, mold temperature: 80°C), extruded into strands, and then cut to form dye-containing resin pellets. Subsequently, the dye-containing resin pellets and resin pellet "SD Polycarbonate (trademark) 301-4" were dissolved in a solvent (dichloromethane) to achieve near-infrared fluorescent dye H concentrations of 500, 1000, 1500, or 2000 ppm after solvent removal, and the mixture was dropped onto a glass substrate (5 cm × 5 cm). After dropping, a 5-second wait was observed, then the rotation speed was increased to 1500 rpm over 10 seconds, followed by spin coating at that rotation speed for 180 seconds. The resulting film-like plate (7 μm thick) was subjected to spectral measurements without being peeled off the glass substrate.

[0260] A film-like material was prepared in the same manner as the near-infrared fluorescent dye-containing plate described above, except that it did not contain the near-infrared fluorescent dye H, and this was used as a blank plate.

[0261] The fluorescence intensity was measured for both the manufactured near-infrared fluorescent dye-containing plates and the blank plates. The fluorescence intensity at a fluorescence wavelength of 835.0 nm was measured in the same manner as in Example 1, except that the excitation wavelength was changed from 700.0 nm to 760.0 nm. The fluorescence intensity value obtained by subtracting the fluorescence intensity value of the blank plate at the same fluorescence wavelength from the fluorescence intensity value of the near-infrared fluorescent dye-containing plate at that wavelength was taken as the fluorescence intensity value for that wavelength for each near-infrared fluorescent dye-containing plate.

[0262] [Table 6]

[0263] Table 6 shows the measurement results of the fluorescence intensity values ​​at the maximum fluorescence wavelength for near-infrared fluorescent dye-containing plates of various concentrations. As shown in Table 6, the fluorescence intensity values ​​in the near-infrared region of film-like near-infrared fluorescent dye-containing plates obtained via a solution containing near-infrared fluorescent dye and PC depended on the near-infrared fluorescent dye concentration. Furthermore, in Table 6, when the relative fluorescence intensity was calculated with the fluorescence intensity of 500 ppm set to 1, a high linearity was observed with respect to the near-infrared fluorescent dye concentration.

Claims

1. A method for measuring the relative fluorescence intensity of a test sample, The maximum fluorescence wavelength of the test sample is within the range of 650 nm to 1000 nm. A plate-shaped or film-shaped molded body of a resin composition obtained by melt-kneading a raw material mixture containing a near-infrared fluorescent dye and an amorphous resin is used as a standard plate. A plate-shaped or film-shaped molded body of a resin composition obtained by melt-kneading a raw material mixture having the same composition as the raw material mixture except that it does not contain the aforementioned near-infrared fluorescent dye is used as a blank plate. The test sample is a molded body of a resin composition containing the same or different near-infrared fluorescent dye as the near-infrared fluorescent dye in the standard plate. A molded body having the same composition as the test sample except that it does not contain the near-infrared fluorescent dye contained in the test sample is used as the test sample blank. The wavelength λ of the test sample １ of fluorescence intensity F １ The wavelength λ of the test sample blank １Ｂ of fluorescence intensity F １Ｂ The wavelength λ of the standard plate Ｓ of fluorescence intensity F Ｓ The wavelength λ of the blank plate ＳＢ of fluorescence intensity F ＳＢ are measured, and the wavelength λ １ is within the range of 650 to 1000 nm, and the difference between the wavelength λ １ and the wavelength λ １Ｂ is within 10 nm, and the wavelength λ Ｓ is within the range of 650 to 1000 nm, and the difference between the wavelength λ Ｓ and the wavelength λ ＳＢ is within 10 nm, (F １ -F １B ) / (Fs-F ＳＢ A method for measuring relative fluorescence intensity, wherein the value of the test sample is defined as the relative fluorescence intensity of the test sample.

2. The method for measuring relative fluorescence intensity according to claim 1, wherein the fluorescence intensity of the test sample, the test sample blank, the standard plate, and the blank plate is measured using a spectrofluorometer.

3. The method for measuring relative fluorescence intensity according to claim 1, wherein the amorphous resin is a transparent resin.

4. The method for measuring relative fluorescence intensity according to claim 1, wherein the amorphous resin is one or more selected from the group consisting of polycarbonate resins, polystyrene resins, acrylic resins, polyoxymethylene resins, polyester resins, and vinyl chloride resins.

5. The method for measuring relative fluorescence intensity according to claim 1, wherein the standard plate is a plate with a thickness of 1 μm to 15 mm.

6. The method for measuring relative fluorescence intensity according to claim 1, wherein the maximum fluorescence wavelength of the test sample is 700 nm or more.

7. The method for measuring relative fluorescence intensity according to claim 1, wherein the test sample is a molded article obtained by melt-molding a resin composition obtained by melt-kneading a mixture containing a near-infrared fluorescent dye as a raw material.

8. The aforementioned test sample is a molded body used as a medical device, The method for measuring relative fluorescence intensity according to claim 7, wherein the quality control of the test sample is performed by measuring the relative fluorescence intensity of the test sample in vitro.

9. The method for measuring relative fluorescence intensity according to claim 8, wherein at least a portion of the test sample is a medical device used in a patient's body.

10. The aforementioned near-infrared fluorescent dye, The following general formula (I １ ) 【Chemistry 1】 [Formula (I １ )middle, R ａ and R ｂ R ａ The nitrogen atom and R to which it is bonded ｂ Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R ｃ and R ｄ R ｃ The nitrogen atom and R to which it is bonded ｄ Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R ｅ and R ｆ represents a halogen atom or an oxygen atom; R ｇ This represents a hydrogen atom or an electron-withdrawing group. However, R ｅ and R ｆ If it is an oxygen atom, R ｅ , R ｅ The boron atom that bonds with R ａ , and R ａ The nitrogen atoms to which it is bonded may together form a ring, R ｆ , R ｆ The boron atom that bonds with R ｃ , and R ｃ The nitrogen atoms to which it is bonded may together form a ring. ｅ If it is an oxygen atom and does not form a ring, then R ｅ R is an oxygen atom having a substituent, ｆ If it is an oxygen atom and does not form a ring, then R ｆ is an oxygen atom having a substituent. Compounds represented by ] The following general formula (I ２ ) 【Chemistry 2】 [Form (I ２ ) Medium, R ａ ~R ｆ is the above formula (I １ It is the same as ). Compounds represented by the following general formula (I ３ ) 【Transformation 3】 [Formula (I ３ )middle, R ｈ and R ｉ R ｈ The nitrogen atom and R to which it is bonded ｉ Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R ｊ and R ｋ R ｊ The nitrogen atom and R to which it is bonded ｋ Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R ｌ , R ｍ , R ｎ , and R ｏ These are, independently of each other, halogen atoms, C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group; R ｐ and R ｑ These are, independently of each other, hydrogen atoms, halogen atoms, and C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. R ｒ and R ｓ These represent, independently of each other, a hydrogen atom or an electron-withdrawing group. [The compound represented by...] and the following general formula (I ４ ) 【Chemistry 4】 [Form (I ４ ) Medium, R ｈ ~R ｑ is the above formula (I ３ It is the same as ). It is one or more compounds selected from the group consisting of compounds represented by ]. The method for measuring relative fluorescence intensity according to claim 1.

11. The aforementioned near-infrared fluorescent dye is defined by the following general formula (I １ -0) 【Transformation 5】 [Formula (I １ -0) in the middle, R １ , R ２ , and R ３ teeth, (p1) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. (p2) R １ and R ２ Both form an aromatic five-membered ring or an aromatic six-membered ring, R ３ is a hydrogen atom, halogen atom, C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (p3)R ２ and R ３ both form an aromatic 5-membered ring or an aromatic 6-membered ring, and R １ represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group. R ４ , R ５ , and R ６ teeth, (q1) Independently of each other, a hydrogen atom, a halogen atom, C 1-20 alkyl group, C 1-20 an alkoxy group, an aryl group, or a heteroaryl group, (q2)R ４ and R ５ Both form an aromatic five-membered ring or an aromatic six-membered ring, R ６ is a hydrogen atom, halogen atom, C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (q3)R ５ and R ６ Both form an aromatic five-membered ring or an aromatic six-membered ring, R ４ is a hydrogen atom, halogen atom, C 1-20 alkyl group, C 1-20 This represents an alkoxy group, an aryl group, or a heteroaryl group. R ７ and R ８ represents a halogen atom or an oxygen atom; R ９ This represents a hydrogen atom or an electron-withdrawing group. However, R ７ and R ８ If it is an oxygen atom, R ７ , R ７ A boron atom bonded to it, a nitrogen atom bonded to the boron atom, R １ , and R １ The carbon atoms bonded to it may together form a ring, R ８ , R ８ A boron atom bonded to it, a nitrogen atom bonded to the boron atom, R ４ , and R ４ The carbon atoms bonded to it may together form a ring. ７ If it is an oxygen atom and does not form a ring, then R ７ R is an oxygen atom having a substituent, ８ If it is an oxygen atom and does not form a ring, then R ８ is an oxygen atom having a substituent. Compounds represented by ] and the following general formula (I ２ -0) 【Transformation 6】 [Form (I ２ -0) Medium, R １ ~R ８ is the above formula (I １ The method for measuring relative fluorescence intensity according to claim 10, wherein the compound is one or more compounds selected from the group consisting of compounds represented by ], which is the same as -0).

12. The general formula (I １ -0) or the general formula (I ２ -0) In R １ and R ２ They form a ring, R ４ and R ５ The ring is formed, or R ２ and R ３ They form a ring, R ５ and R ６ They form a ring. The aforementioned ring is given by the following general formulas (C-1) to (C-9) 【Transformation 7】 [In formulas (C-1) to (C-9), Y １ ~Y ８ Each of these independently represents a sulfur atom, oxygen atom, nitrogen atom, or phosphorus atom, and R １１ ~R ２２ The method for measuring relative fluorescence intensity according to claim 11, wherein each of the following represents a hydrogen atom or any group that does not inhibit the fluorescence of the compound, independently of the other.

13. The aforementioned near-infrared fluorescent dye is defined by the following general formula (I ３ -1) ~ (I ３ -6) 【Transformation 8】 [Formula (I ３ -1) Middle R ２３ , R ２４ , R ２５ , and R ２６ These are, independently of each other, halogen atoms, C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group; R ２７ and R ２８ These are, independently of each other, hydrogen atoms, halogen atoms, and C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group; R ２９ and R ３０ These independently represent a hydrogen atom or an electron-withdrawing group; Y ９ and Y １０ Each represents a sulfur atom, oxygen atom, nitrogen atom, or phosphorus atom independently of the other; R ３１ and R ３２ teeth, (p4) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (p5) R ３１ and R ３２ Both form an aromatic five-membered ring or an aromatic six-membered ring, which may have substituents; R ３３ and R ３４ teeth, (q4) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (q5)R ３３ and R ３４ Both form an aromatic five-membered ring or an aromatic six-membered ring, which may have substituents. 【Chemistry 9】 [Form (I ３ -2) ~ (I ３ -6) Medium, R ２３ ~R ３０ is the above formula (I ３ -1) is the same as; X １ and X ２ Each represents a nitrogen atom or a phosphorus atom independently of the other; R ３５ , R ３６ , R ３７ , and R ３８ teeth, (p6) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. (p7) R ３５ and R ３６ Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R ３７ and R ３８ These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. (p8) R ３６ and R ３７ Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R ３５ and R ３８ These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (p9) R ３７ and R ３８ Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R ３５ and R ３６ These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group; R ３９ , R ４０ , R ４１ , and R ４２ teeth, (q6) Independently of each other, hydrogen atoms, halogen atoms, C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. (q7)R ３９ and R ４０ Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R ４１ and R ４２ These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. (q8)R ４０ and R ４１ Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R ３９ and R ４２ These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group, (x9)R ４１ and R ４２ Both form an aromatic five-membered ring or an aromatic six-membered ring which may have substituents, R ３９ and R ４０ These are independent of each other: hydrogen atoms, halogen atoms, and C 1-20 alkyl group, C 1-20 Compounds represented by any of the following general formulas (I ４ -1) ~ (I ４ -6) 【Chemistry 10】 [Form (I ４ -1) ~ (I ４ -6) Medium, R ２３ ~R ２８ is the above formula (I ３ -1) is the same. Equation (I ４ -1) Medium, R ３１ ~R ３４ , Y ９ , and Y １０ is the above formula (I ３ -1) is the same as equation (I ４ -2) ~ (I ４ -6) Medium, R ３５ ~R ４２ is the above formula (I ３ -2) is the same as equation (I ４ -3) ~ (I ４ -6) Medium, X １ , and X ２ is the above formula (I ３ The method for measuring relative fluorescence intensity according to claim 10, wherein the compound is one or more compounds selected from the group consisting of compounds represented by any of the following: -3).

14. The aforementioned near-infrared fluorescent dye is defined by the following general formula (I １ -1-1) ~ (I １ -1-6), (I １ -2-1) ~ (I １ -2-12), (I ２ -1-1) ~ (I ２ -1-6), and (I ２ -2-1) ~ (I ２ -2-12) 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 [In the formula, Y １１ and Y １２ Each represents an oxygen atom or a sulfur atom independently of the other; Y ２１ and Y ２２ Each represents a carbon atom or a nitrogen atom independently of the other; Q １１ represents a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group; X consists of halogen atoms and C, which are independent of each other. 1-20 Represents an alkoxy group, aryloxy group, or acyloxy group; P １１ ~P １４ and P １７ These are, independently of each other, halogen atoms, C 1-20 alkyl group, C 1-20 This represents alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups; A １１ ~A １４ These are, independently of each other, halogen atoms, C 1-20 alkyl group, C 1-20 A phenyl group having 1 to 3 substituents selected from the group consisting of alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups, or a halogen atom, C 1-20 alkyl group, C 1-20 Represents a heteroaryl group which may have one to three substituents selected from the group consisting of alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups; n11 to n14 and n17 represent integers from 0 to 3, independently of each other; m1 represents 0 or 1. The method for measuring relative fluorescence intensity according to claim 10, wherein the compound is one or more compounds selected from the group consisting of compounds represented by any of the following.

15. The aforementioned near-infrared fluorescent dye is defined by the following general formula (I ３ -7) ~ (I ３ -9) and (I ４ -7) ~ (I ４ -9) 【Chemistry 17】 [In the formula, Y ２３ and Y ２４ Each represents a carbon atom or a nitrogen atom independently of the other; Y １３ and Y １４ Each represents an oxygen atom or a sulfur atom independently of the other; Y ２５ and Y ２６ Each represents a carbon atom or a nitrogen atom independently of the other; R ４７ and R ４８ These independently represent a hydrogen atom or an electron-withdrawing group; R ４３ , R ４４ , R ４５ , and R ４６ represents a halogen atom or an aryl group which may have a substituent; P １５ and P １６ These are, independently of each other, halogen atoms, C 1-20 alkyl group, C 1-20 This represents alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups; n15 and n16 represent integers between 0 and 3, independently of each other; A １５ and A １６ These are, independently of each other, hydrogen atoms, halogen atoms, and C 1-20 alkyl group, C 1-20 This represents a phenyl group which may have one to three substituents selected from the group consisting of alkoxy groups, amino groups, monoalkylamino groups, and dialkylamino groups. The method for measuring relative fluorescence intensity according to claim 10, wherein the compound is one or more compounds selected from the group consisting of compounds represented by any of the following.

16. A standard plate set for measuring relative fluorescence intensity for measuring the relative fluorescence intensity of a test sample whose maximum fluorescence wavelength is in the range of 650 nm to 1000 nm, A standard plate comprising a plate-shaped or film-shaped molded body of a resin composition obtained by melt-kneading a raw material mixture containing a near-infrared fluorescent dye and an amorphous resin, The system comprises a blank plate made of a plate-shaped or film-shaped molded body of a resin composition obtained by melt-kneading a raw material mixture having the same composition as the raw material mixture except that it does not contain the aforementioned near-infrared fluorescent dye, In a test sample consisting of a molded body of a resin composition containing the same or different near-infrared fluorescent dyes as the near-infrared fluorescent dye in the standard plate, the fluorescence intensity F1 at wavelength λ1 is given by F1B at wavelength λ1B, the fluorescence intensity F1B at wavelength λ1B is given by a test sample blank consisting of a molded body having the same composition as the test sample except that it does not contain the near-infrared fluorescent dyes contained in the test sample, the fluorescence intensity FS at wavelength λS of the standard plate, and the fluorescence intensity FSB at wavelength λSB of the blank plate, where the wavelength λ1 is in the range of 650 to 1000 nm, the difference between wavelength λ1 and wavelength λ1B is within 10 nm, the wavelength λS is in the range of 650 to 1000 nm, and the difference between wavelength λS and wavelength λSB is within 10 nm, the relative fluorescence intensity of the test sample is given by (F1 - F1B) / (FS - FSB) A standard plate set for measuring relative fluorescence intensity, which is measured as follows.

17. The aforementioned near-infrared fluorescent dye, The following general formula (I １ ) [Chemistry 18] [Formula (I １ )middle, R ａ and R ｂ R ａ The nitrogen atom and R to which it is bonded ｂ Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R ｃ and R ｄ R ｃ The nitrogen atom and R to which it is bonded ｄ Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R ｅ and R ｆ represents a halogen atom or an oxygen atom; R ｇ This represents a hydrogen atom or an electron-withdrawing group. However, R ｅ and R ｆ If it is an oxygen atom, R ｅ , R ｅ The boron atom that bonds with R ａ , and R ａ The nitrogen atoms to which it is bonded may together form a ring, R ｆ , R ｆ The boron atom that bonds with R ｃ , and R ｃ The nitrogen atoms to which it is bonded may together form a ring. ｅ If it is an oxygen atom and does not form a ring, then R ｅ R is an oxygen atom having a substituent, ｆ If it is an oxygen atom and does not form a ring, then R ｆ is an oxygen atom having a substituent. Compounds represented by ] The following general formula (I ２ ) 【Chemistry 19】 [Form (I ２ ) Medium, R ａ ~R ｆ is the above formula (I １ It is the same as ). Compounds represented by the following general formula (I ３ ) 【Chemistry 20】 [Formula (I ３ )middle, R ｈ and R ｉ R ｈ The nitrogen atom and R to which it is bonded ｉ Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R ｊ and R ｋ R ｊ The nitrogen atom and R to which it is bonded ｋ Together with the carbon atom to which it is bonded, it forms an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R ｌ , R ｍ , R ｎ , and R ｏ These are, independently of each other, halogen atoms, C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group; R ｐ and R ｑ These are, independently of each other, hydrogen atoms, halogen atoms, and C 1-20 alkyl group, C 1-20 Represents an alkoxy group, an aryl group, or a heteroaryl group. R ｒ and R ｓ These represent, independently of each other, a hydrogen atom or an electron-withdrawing group. [The compound represented by...] and the following general formula (I ４ ) 【Chemistry 21】 [Form (I ４ ) Medium, R ｈ ~R ｑ is the above formula (I ３ The standard plate set for measuring relative fluorescence intensity according to claim 16, which is the same as ). The standard plate set for measuring relative fluorescence intensity according to claim 16, which is one or more compounds selected from the group consisting of compounds represented by ].

18. The standard plate set for measuring relative fluorescence intensity according to claim 16, wherein the standard plate is a plate with a thickness of 1 μm to 15 mm.

19. The standard plate set for measuring relative fluorescence intensity according to claim 16, wherein the amorphous resin is one or more selected from the group consisting of polycarbonate resins, polystyrene resins, acrylic resins, polyoxymethylene resins, polyester resins, and vinyl chloride resins.

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