Powdered dye composition, method for producing powdered dye composition, resin composition and molded product

Abstract

Provided are a near-infrared fluorescent pigment having good dispersibility in a resin, a resin composition containing said near-infrared fluorescent pigment, and a molded body obtained by processing said resin composition. More specifically, provided are: a powdered pigment composition comprising a near-infrared fluorescent pigment composed of one or more compounds selected from the group consisting of compounds represented by general formulae (I1) to (I4); and a molded body obtained by processing said resin composition.

Description

[Technical field]

[0001] The present invention relates to a powdered dye composition comprising a near-infrared fluorescent dye and a method for producing the same, a resin composition that emits near-infrared fluorescence, and a molded article obtained by processing the resin composition. [Background technology]

[0002] Near-infrared fluorescent dyes are used in industrial products, mainly for identifying various products and preventing counterfeiting, and in recent years, they are also used in medical applications such as bioimaging probes and diagnostic agents. Known characteristics of the near-infrared wavelength region include being invisible to the naked human eye, having little effect on the living body, and being highly permeable through the skin and other living bodies. By incorporating a near-infrared fluorescent dye into the medical device itself, such characteristics can be utilized. For example, a system has been disclosed in which a medical device such as a shunt tube is incorporated with a near-infrared fluorescent dye, and the position of the medical device embedded in the living body is confirmed by irradiating the medical device with near-infrared light from outside the living body (see, for example, Patent Document 1).

[0003] In order to visualize a medical implant embedded under the skin, etc., excitation with near-infrared light with high skin permeability is required, and the fluorescence emitted from the medical implant must also be in the near-infrared region with high skin permeability. That is, in order to ensure visibility, the near-infrared fluorescent dye contained in the medical implant itself must strongly absorb light in the near-infrared region, and must also emit strong fluorescence. For this reason, it is preferable that the near-infrared fluorescent dye contained in the resin composition used as the raw material for the medical implant has a maximum absorption wavelength in the near-infrared region in the resin.

[0004] If a near-infrared fluorescent dye can be mixed and dispersed in a resin, various molded articles that emit near-infrared fluorescence can be manufactured using the resin as a raw material. For example, Patent Document 2 discloses a near-infrared fluorescent resin in which a reactive group-containing near-infrared fluorescent dye, which is a phthalocyanine dye, a naphthalocyanine dye, or a squaraine dye with a polyester reactive group introduced therein, is copolymerized in PET (polyethylene terephthalate). Patent Document 3 discloses that a near-infrared fluorescent resin composition with high luminescence intensity and a molded article made by processing the composition can be obtained by mixing and dispersing a BODIPY dye or a DPP-based boron complex, which is excellent in heat resistance and luminescence quantum yield and emits near-infrared fluorescence, in a resin. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2012-115535 A [Patent Document 2] JP 2003-176289 A [Patent Document 3] International Publication No. 2015 / 056779 Summary of the Invention [Problem to be solved by the invention]

[0006] When a resin composition containing a near-infrared fluorescent dye is produced, if the near-infrared fluorescent dye has low dispersibility in the resin, the near-infrared fluorescent dye may be present non-uniformly in the resin composition, and aggregates of the near-infrared fluorescent dye may occur. Molded articles made from such resin compositions are prone to have dot-like or streak-like appearance defects.

[0007] An object of the present invention is to provide a near-infrared fluorescent dye having good dispersibility in resin, a resin composition containing the near-infrared fluorescent dye, and a molded article obtained by processing the resin composition. [Means for solving the problem]

[0008] The powdered dye composition and its production method, resin composition, and molded article according to the present invention are as follows [1] to

[18] . [1] A powdered dye composition comprising a near-infrared fluorescent dye, The near-infrared fluorescent dye is The following general formula (I1)

[0009] [ka]

[0010] (In formula (I1), R a and R b is R a The nitrogen atom to which R is bonded b forms, together with the carbon atom to which it is bonded, an aromatic 5-membered ring, an aromatic 6-membered ring, or a condensed aromatic ring formed by condensing 2 to 3 5-membered or 6-membered rings; R c and R d is R c The nitrogen atom to which R is bonded d forms, together with the carbon atom to which it is bonded, an aromatic 5-membered ring, an aromatic 6-membered ring, or a condensed aromatic ring formed by condensing 2 to 3 5-membered or 6-membered rings; R e and R f represents a halogen atom or an oxygen atom; R g represents a hydrogen atom or an electron-withdrawing group. However, R e and R f If is an oxygen atom, R e , R e A boron atom bonded to R a , and R a may form a ring together with the nitrogen atom to which R is bonded; f , R f A boron atom bonded to R c , and R c The nitrogen atoms to which R is bonded may together form a ring. e is an oxygen atom and does not form a ring, R eis an oxygen atom having a substituent, and R f is an oxygen atom and does not form a ring, R f is an oxygen atom having a substituent. The following general formula (I2)

[0011] [ka]

[0012] (In formula (I2), R a ~R f is the same as the above formula (I1). The following general formula (I3)

[0013] [ka]

[0014] (In formula (I3), R h and R i is R h The nitrogen atom to which R is bonded i forms, together with the carbon atom to which it is bonded, an aromatic 5-membered ring, an aromatic 6-membered ring, or a condensed aromatic ring formed by condensing 2 to 3 5-membered or 6-membered rings; R j and R k is R j The nitrogen atom to which R is bonded k forms, together with the carbon atom to which it is bonded, an aromatic 5-membered ring, an aromatic 6-membered ring, or a condensed aromatic ring formed by condensing 2 to 3 5-membered or 6-membered rings; R l , R m , R n , and R o are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; R p and R q are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20represents an alkoxy group, an aryl group, or a heteroaryl group; R r and R s each independently represents a hydrogen atom or an electron-withdrawing group; and the following general formula (I4)

[0015] [ka]

[0016] (In formula (I4), R h ~R q is the same as the above formula (I3). The reflectance spectrum of the powdered dye composition is There is no peak having a peak top within the range of 520 to 560 nm, or A powdered dye composition having a peak having a peak top within the range of 520 to 560 nm, in which the maximum value of the relative reflectance within said range minus the average value of the relative reflectance within the range of 300 to 400 nm is 5% or less.

[0017] [2] The following general formula (I1-0) (In formula (I1-0), R 1 , R 2 , and R 3 teeth, (p1) independently of each other a hydrogen atom, a halogen atom, 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 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 3 is a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; or (p3)R 2 and R 3together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 1 is a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an aryl group, or a heteroaryl group. R 4 , R 5 , and R 6 teeth, (q1) independently represent a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group, (q2)R 4 and R 5 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 6 is a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; or (q3)R 5 and R 6 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 4 is a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 It 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 represents a hydrogen atom or an electron-withdrawing group. However, R 7 and R 8 If is an oxygen atom, R 7 , R 7 The boron atom bonded to the nitrogen atom, the boron atom bonded to the nitrogen atom, R 1 , and R 1 and the carbon atom to which they are bonded may together form a ring, 8 , R 8 The boron atom bonded to the nitrogen atom, the boron atom bonded to the nitrogen atom, R 4 , and R 4 The carbon atoms to which R is bonded may together form a ring. 7is an oxygen atom and does not form a ring, R 7 is an oxygen atom having a substituent, and R 8 is an oxygen atom and does not form a ring, R 8 is an oxygen atom having a substituent.) and a compound represented by the following general formula (I2-0): (In formula (I2-0), R 1 ~R 8 is the same as the above formula (I1-0).

[0018] [ka]

[0019] [3] In the general formula (I1-0) or the general formula (I2-0), R 1 and R 2 forms a ring, and R 4 and R 5 forms a ring, or R 2 and R 3 forms a ring, and R 5 and R 6 form a ring, and the ring is represented by the following general formulas (C-1) to (C-9) (in formulas (C-1) to (C-9), Y 1 ~Y 8 each independently represents a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom; R 11 ~R 22 each independently represents a hydrogen atom or any group that does not inhibit the fluorescence of the compound.

[0020] [ka]

[0021] [4] The following general formulas (I3-1) to (I3-6)

[0022] [ka]

[0023] (In formula (I3-1), R 23 , R 24 , R 25 , and R 26 are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; R 27 and R 28 are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; R 29 and R 30 represent, independently of each other, a hydrogen atom or an electron-withdrawing group; Y 9 and Y 10 represent, independently of one another, a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom; R 31 and R 32 teeth, (p4) independently of each other a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; or (p5)R 31 and R 32 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring; R 33 and R 34 teeth, (q4) independently of each other a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; or (q5)R 33 and R 34 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring.

[0024] [ka]

[0025] (In formulas (I3-2) to (I3-6), R 23 ~R 30 is the same as the above formula (I3-1); X 1 and X 2 represent, independently of each other, a nitrogen atom or a phosphorus atom; R 35 , R 36 , R 37 , and R 38 teeth, (p6) Independently of each other, a hydrogen atom, a halogen atom, 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 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 37 and R 38 are each independently a hydrogen atom, a halogen atom, or 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 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 35 and R 38 are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; or (p9)R 37 and R 38 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 35 and R 36 are each independently a hydrogen atom, a halogen atom, or C1-20 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 a hydrogen atom, a halogen atom, 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 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 41 and R 42 are each independently a hydrogen atom, a halogen atom, or 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 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 39 and R 42 are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; or (q9)R 41 and R 42 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 39 and R 40 are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 and a compound represented by any one of the following general formulas (I4-1) to (I4-6):

[0026] [ka]

[0027] (In formulas (I4-1) to (I4-6), R 23 ~R 28 is the same as in formula (I3-1). In formula (I4-1), R 31 ~R 34 , Y 9 , and Y 10 is the same as the above formula (I3-1), and in formulas (I4-2) to (I4-6), R 35 ~R 42 is the same as the formula (I3-2), and in the formulas (I4-3) to (I4-6), X 1 , and X 2 is the same as the above formula (I3-3).

[0028] [5] The following general formulae (I1-1-1) to (I1-1-6), (I1-2-1) to (I1-2-12), (I2-1-1) to (I2-1-6), and (I2-2-1) to (I2-2-12):

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] [In the formula, Y 11 and Y 12 represent, independently of each other, an oxygen atom or a sulfur atom; Y 21 and Y 22 represent, independently of each other, a carbon atom or a nitrogen atom; Q 11 represents a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group; X is independently a halogen atom, C 1-20 represents an alkoxy group, an aryloxy group, or an acyloxy group; P 11 ~P 14 and P 17 are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group; A 11 ~A 14 are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 a phenyl group which may have 1 to 3 substituents selected from the group consisting of an alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group, or a halogen atom, C 1-20 Alkyl group, C 1-20 a heteroaryl group optionally having 1 to 3 substituents selected from the group consisting of an alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group; n11 to n14 and n17 each independently represent an integer of 0 to 3; m1 represents 0 or 1.] The powdery dye composition according to [1] above, which contains one or more compounds selected from the group consisting of compounds represented by any one of the following formulas: [6] The following general formulas (I3-7) to (I3-9) and (I4-7) to (I4-9)

[0036] [ka]

[0037] [In the formula, Y 23 and Y 24 represent, independently of each other, a carbon atom or a nitrogen atom; Y 13 and Y 14 represent, independently of each other, an oxygen atom or a sulfur atom; Y 25 and Y 26 represent, independently of each other, a carbon atom or a nitrogen atom; R 47 and R 48 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 optionally substituted aryl group; P 15 and P 16 are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group; n15 and n16 each independently represent an integer of 0 to 3; A 15 and A 16 are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 It represents a phenyl group which may have 1 to 3 substituents selected from the group consisting of an alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group.] The powdery dye composition according to [1] above, which contains one or more compounds selected from the group consisting of compounds represented by any one of the following formulas:

[0038] [7] The powdered dye composition according to any one of the above [1] to [6], wherein the reflectance spectrum is a spectrum obtained by diffuse reflectance measurement using an integrating sphere. [8] A method for producing a powdered dye composition comprising a near-infrared fluorescent dye, comprising the steps of: a crystallization step of dissolving the near-infrared fluorescent dye in a low-polarity solvent by heating, and then slowly cooling the solution to recrystallize the dye; a powdering step of powdering the crystals obtained in the crystallization step to produce a powdered dye composition; having The reflectance spectrum of the powdered dye composition is There is no peak having a peak top within the range of 520 to 560 nm, or Although there is a peak having a peak top within the range of 520 to 560 nm, the value obtained by subtracting the average value of the relative reflectance within the range of 300 to 400 nm from the maximum value of the relative reflectance within the range is 5% or less, The near-infrared fluorescent dye is The following general formula (I1)

[0039] [ka]

[0040] (In formula (I1), R a and R b is R a The nitrogen atom to which R is bonded b forms, together with the carbon atom to which it is bonded, an aromatic 5-membered ring, an aromatic 6-membered ring, or a condensed aromatic ring formed by condensing 2 to 3 5-membered or 6-membered rings; R c and R d is R c The nitrogen atom to which R is bonded d forms, together with the carbon atom to which it is bonded, an aromatic 5-membered ring, an aromatic 6-membered ring, or a condensed aromatic ring formed by condensing 2 to 3 5-membered or 6-membered rings; R e and R f represents a halogen atom or an oxygen atom; R g represents a hydrogen atom or an electron-withdrawing group. However, R e and R fIf is an oxygen atom, R e , R e A boron atom bonded to R a , and R a may form a ring together with the nitrogen atom to which R is bonded; f , R f A boron atom bonded to R c , and R c The nitrogen atoms to which R is bonded may together form a ring. e is an oxygen atom and does not form a ring, R e is an oxygen atom having a substituent, and R f is an oxygen atom and does not form a ring, R f is an oxygen atom having a substituent. The following general formula (I2)

[0041] [ka]

[0042] (In formula (I2), R a ~R f is the same as the above formula (I1), a compound represented by the following general formula (I3):

[0043] [ka]

[0044] (In formula (I3), R h and R i is R h The nitrogen atom to which R is bonded i forms, together with the carbon atom to which it is bonded, an aromatic 5-membered ring, an aromatic 6-membered ring, or a condensed aromatic ring formed by condensing 2 to 3 5-membered or 6-membered rings; R j and R k is R j The nitrogen atom to which R is bonded k forms, together with the carbon atom to which it is bonded, an aromatic 5-membered ring, an aromatic 6-membered ring, or a condensed aromatic ring formed by condensing 2 to 3 5-membered or 6-membered rings; R l , R m , R n , and R o are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; R p and R q are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; R r and R s each independently represents a hydrogen atom or an electron-withdrawing group; and the following general formula (I4)

[0045] [ka]

[0046] (In formula (I4), R h ~R q is the same as the above formula (I3). [9] The method for producing a powdered dye composition according to the above item [8], wherein the low polarity solvent is toluene.

[10] The method for producing a powdered dye composition according to [8] or [9] above, wherein the low-polarity solvent contains 30 wt % or less of a polar solvent.

[11] The method for producing a powdery dye composition according to

[10] above, wherein the polar solvent is an alcohol having 1 to 4 carbon atoms.

[12] A resin composition comprising the powdery dye composition according to any one of [1] to [7] above and a resin, the resin composition having a maximum fluorescence wavelength of 650 nm or longer.

[13] The resin composition according to

[12] , wherein the resin is a thermoplastic resin.

[14] The resin composition according to

[12] or

[13] , wherein the near-infrared fluorescent dye and the resin are melt-kneaded.

[15] The resin composition according to any one of the above

[12] to

[14] , which has a maximum fluorescence wavelength of 700 nm or more.

[16] The resin composition according to any one of

[12] to

[15] above, which is used as a medical material.

[17] A molded article obtained by processing the resin composition according to any one of

[12] to

[16] above.

[18] The molded article according to

[17] above, at least a part of which is a medical device to be used inside a patient's body. Effect of the Invention

[0047] The powdered dye composition according to the present invention is made of a near-infrared fluorescent dye that is excellent in heat resistance and luminescence quantum yield, and further has good dispersibility in resin. In a resin composition containing the powdered dye composition, the near-infrared fluorescent dye is uniformly dispersed in the composition, and when the resin composition is used for molding, the molded product is unlikely to have dot-like or streak-like appearance defects. For this reason, the resin composition containing the powdered dye composition is particularly suitable as a medical material, which particularly requires uniformity in product quality. [Brief description of the drawings]

[0048] [Figure 1] 1 shows the reflectance spectra of near-infrared fluorescent dye A2 and near-infrared fluorescent dye A3 from 300 to 600 nm. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0049] <Near-infrared fluorescent dye> The powdered dye composition according to the present invention is a powdered dye composition comprising a near-infrared fluorescent dye. The near-infrared fluorescent dye contained in the powdered dye composition according to the present invention is specifically a compound represented by the following general formula (I1), general formula (I2), general formula (I3), or general formula (I4). Hereinafter, this compound may be referred to as the "near-infrared fluorescent dye according to the present invention."

[0050] [ka]

[0051] [ka]

[0052] In the general formula (I1) or (I2), R a and R b is R a The nitrogen atom to which R is bonded b In the same manner, in the general formula (I1) or (I2), R c and R d is R c The nitrogen atom to which R is bonded d R 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 R c and R d Each ring of the aromatic ring formed by is a 5-membered ring or a 6-membered ring. a and R b The aromatic ring formed by and R c and R d The aromatic ring formed by the formula (I1) or (I2) has a ring structure condensed with a ring containing a boron atom bonded to two nitrogen atoms. That is, the compound represented by the formula (I1) or (I2) has a robust condensed ring structure consisting of a wide conjugated plane.

[0053] In general formula (I3) or general formula (I4), R h and R i is R h The nitrogen atom to which R is bonded i In the same manner, in the general formula (I3) or (I4), R j and R k is R j The nitrogen atom to which R is bonded k R 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 R j and R kEach ring of the aromatic ring formed by R is a 5-membered ring or a 6-membered ring. h and R i a ring formed by condensing an aromatic ring formed by the above formula, a ring containing a boron atom bonded to two nitrogen atoms, and a five-membered hetero ring containing one nitrogen atom; and R j and R k and a ring containing a boron atom bonded to two nitrogen atoms and a five-membered heterocycle containing one nitrogen atom are fused to form an aromatic ring, and three rings are fused to the five-membered heterocycles, that is, a ring structure in which at least six rings are fused. Thus, the compound represented by general formula (I3) or general formula (I4) has a robust fused ring structure consisting of a very wide conjugated plane.

[0054] R a and R b Aromatic ring formed by R c and R d Aromatic ring formed by R h and R i The aromatic ring formed by R j and R k The aromatic ring formed by is not particularly limited as long as it has aromaticity. Examples of the aromatic ring include a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, an isoindole ring, an indole ring, an indazole ring, a purine ring, a perimidine ring, a thienopyrrole ring, a furopyrrole ring, a pyrrolothiazole ring, and a pyrrolooxazole ring. Since the maximum fluorescence wavelength is extended to the near infrared region, the aromatic ring preferably has 2 or 3 condensed rings, and more preferably has 2 condensed rings from the viewpoint of the complexity of synthesis, in particular, in the case of general formula (I1) or general formula (I3). However, even if the aromatic ring has 1 condensed ring, it is possible to extend the wavelength by modifying the substituent on the ring or the substituent on the boron. In particular, in the case of formula (I2) or (I4), the wavelength can be increased to the near infrared region simply by bonding a substituted aryl group or heteroaryl group.

[0055] R a and Rb Aromatic ring formed by R c and R d Aromatic ring formed by R h and R i The aromatic ring formed by R j and R k The aromatic ring formed by may have no substituent, or may have one or more substituents. The substituent on the aromatic ring may be any group that does not inhibit the fluorescence of the compound.

[0056] When the resin composition according to the present invention is used as a medical material (raw material for medical devices), the near-infrared fluorescent dye according to the present invention is preferably one that is free from mutagenicity, cytotoxicity, sensitization, skin irritation, etc. in the necessary biological safety tests. In addition, from the viewpoint of safety, it is preferable that the near-infrared fluorescent dye according to the present invention is not eluted from the molded product obtained by processing the resin composition according to the present invention by body fluids such as blood and 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. However, even if the near-infrared fluorescent dye according to the present invention is water-soluble, if the resin component itself in the resin composition according to the present invention is hardly eluted in body fluids, etc., and the content of the near-infrared fluorescent dye itself is small, the molded product of the resin composition according to the present invention can be used in vivo while avoiding elution of the near-infrared fluorescent dye. In consideration of these, it is preferable to select the substituent that is unlikely to exhibit mutagenicity, etc., or that reduces water solubility.

[0057] Examples of the substituent include a halogen atom, a nitro group, a cyano group, a hydroxy group, a carboxyl group, an aldehyde group, a sulfonic acid group, an alkylsulfonyl group, a halogenosulfonyl group, a thiol group, an alkylthio group, an isocyanate group, a thioisocyanate group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkoxycarbonyl group, an alkylamidocarbonyl group, an alkylcarbonylamido group, an acyl group, an amino group, a monoalkylamino group, a dialkylamino group, a silyl group, a monoalkylsilyl group, a dialkylsilyl group, a trialkylsilyl group, a monoalkoxysilyl group, a dialkoxysilyl group, a trialkoxysilyl group, an aryl group, and a heteroaryl group. a and R b Aromatic ring formed by R c and R d Aromatic ring formed by R h and R i The aromatic ring formed by R j and R k From the viewpoint of safety to living organisms, the substituents on the aromatic ring formed by are preferably a cyano group, a hydroxy group, a carboxyl group, an alkylthio group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an amide group, an alkylsulfonyl group, fluorine, chlorine, an aryl group, or a heteroaryl group, and these substituents may further have a substituent. However, even if the substituent is other than these substituents, safety can be improved by introducing a further appropriate substituent, so that the substituents are not limited to these substituents.

[0058] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom, a chlorine atom and a bromine atom being preferred, and a fluorine atom being more preferred.

[0059] The alkyl group, alkenyl group, and alkynyl group may be linear, branched, or cyclic (aliphatic ring). 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 the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group (tert-butyl group), a pentyl group, an isoamyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, and a 2-hexenyl group. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, an isopropynyl group, a 1-butynyl group, and an isobutynyl group.

[0060] The alkyl group moiety in the alkylsulfonyl group, alkylthio group, alkoxy group, alkoxycarbonyl group, alkylamidocarbonyl group, alkylcarbonylamido group, monoalkylamino group, dialkylamino group, monoalkylsilyl group, dialkylsilyl group, trialkylsilyl group, monoalkoxysilyl group, dialkoxysilyl group, and trialkoxysilyl group can be the same as the alkyl group. For example, the alkoxy group can be a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group, a pentyloxy group, an isoamyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, etc. Furthermore, for example, examples of monoalkylamino groups include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, an isobutylamino group, a t-butylamino group, a pentylamino group, and a hexylamino group. Examples of dialkylamino groups include a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group, a dibutylamino group, a diisobutylamino group, a dipentylamino group, a dihexylamino group, an ethylmethylamino group, a methylpropylamino group, a butylmethylamino group, an ethylpropylamino group, and a butylethylamino group.

[0061] Examples of the aryl group include a phenyl group, a naphthyl group, an indenyl group, a biphenyl group, etc. Of these, a phenyl group is preferable. Examples of heteroaryl groups include 5-membered ring heteroaryl groups such as pyrrolyl, imidazolyl, pyrazolyl, thienyl, furanyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, and thiadiazole groups; 6-membered ring heteroaryl groups such as pyridinyl, pyrazinyl, pyrimidinyl, and pyridazinyl groups; and fused heteroaryl groups such as indolyl, isoindolyl, indazolyl, quinolidinyl, quinolinyl, isoquinolinyl, benzofuranyl, isobenzofuranyl, chromenyl, benzoxazolyl, benzoisoxazolyl, benzothiazolyl, and benzoisothiazolyl groups.

[0062] The alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group may be unsubstituted or one or more hydrogen atoms may be substituted with a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, a hydroxyl group, an amino group, a thiol group, a carboxyl group, an aldehyde group, a sulfonic acid group, an isocyanate group, a thioisocyanate group, an aryl group, and a heteroaryl group.

[0063] The absorption wavelength and fluorescence wavelength of a fluorescent dye depend on the surrounding environment. Therefore, the absorption wavelength of a fluorescent dye in a resin may be shorter or longer than that in a solution. When the absorption wavelength of the near-infrared fluorescent dye of the present invention itself is longer, the maximum absorption wavelength is preferably in the near-infrared region even in various resins. The maximum absorption wavelength of the fluorescent dye can be made longer by narrowing the band gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) by introducing an electron-donating group and an electron-withdrawing group into an appropriate position in the molecule.

[0064] For example, among the compounds represented by the general formula (I1), R a and R b The aromatic ring formed by and R c and R d An electron donating group is introduced into the aromatic ring formed by R gBy introducing an electron-withdrawing group into R, the maximum absorption wavelength and maximum fluorescence wavelength of the compound can be shifted to longer wavelengths. h and R i The aromatic ring formed by and R j and R k Introduction of an electron donating group into the aromatic ring formed by R p and R q When R is an aromatic ring, an electron donating group is introduced into the aromatic ring, or r and R s By introducing an electron-withdrawing group into the compound, the maximum absorption wavelength and maximum fluorescence wavelength of the compound can be made longer. By combining these designs, it is possible to adjust the wavelength to the desired wavelength.

[0065] The compound represented by general formula (I2) having an aza-BODIPY skeleton is R a and R b The aromatic ring formed by and R c and R d Even if the aromatic ring formed by is unsubstituted, this skeleton has absorption at relatively long wavelengths. Unlike the compound represented by general formula (I1), the pyrrole bridge part in this skeleton is a nitrogen atom, so it is not possible to introduce a substituent onto the nitrogen. a and R b The aromatic ring formed by and R c and R d By introducing an electron donating group into the aromatic ring formed by the pyrrole moiety (R h and R i The aromatic ring formed by and R j and R k or introducing an electron donating group into the aromatic ring formed by R p and R q When is an aromatic ring, the maximum absorption wavelength and maximum fluorescence wavelength of the compound can be shifted to longer wavelengths by introducing an electron-donating group into the aromatic ring.

[0066] For this reason, Ra and R b Aromatic ring formed by R c and R d Aromatic ring formed by R h and R i The aromatic ring formed by R j and R k As the substituent of the aromatic ring formed by the formula (I1), the group that functions as an electron donating group to the aromatic ring is preferable among "any group that does not inhibit the fluorescence of the compound". By introducing the electron donating group into the aromatic ring, the fluorescence of the compound represented by the formula (I1), the formula (I2), the formula (I3), or the formula (I4) becomes longer wavelength side. Examples of the group that functions as an electron donating group include an alkyl group; an alkoxy group such as a methoxy group; an aryl group (aromatic ring group) such as a phenyl group, a p-alkoxyphenyl group, a p-dialkylaminophenyl group, a dialkoxyphenyl group; and a heteroaryl group (heteroaromatic ring group) such as a 2-thienyl group, a 2-furanyl group, and the like. As the alkyl group, the alkyl group in the substituent of the phenyl group, and the alkyl group portion in the alkoxy group, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The number of carbon atoms of the alkyl group portion and the presence or absence of branching may be appropriately selected in consideration of various physical properties of the dye. From the viewpoint of solubility and compatibility, there are cases where a carbon number of 6 or more is preferable, and in other cases where a branched structure is preferable. a and R b Aromatic ring formed by R c and R d Aromatic ring formed by R h and R i The aromatic ring formed by R j and R k The substituents on the aromatic ring formed by the formula are: 1-6 Alkyl group, C 1-6An alkoxy group, an aryl group, or a heteroaryl group is preferred, a methyl group, an ethyl group, a methoxy group, a phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group is more preferred, and a methyl group, an ethyl group, a methoxy group, a phenyl group, or a p-methoxyphenyl group is even more preferred. Since the BODIPY skeleton has high planarity, the molecules tend to aggregate with each other due to π-π stacking. By introducing an aryl group or a heteroaryl group having a bulky substituent into the BODIPY skeleton, the aggregation of the molecules can be suppressed, and the luminescence quantum yield of the resin composition according to the present invention can be increased.

[0067] In the general formula (I1) or (I2), R a and R b and an aromatic ring formed by R c and R d In the general formula (I3) or (I4), the aromatic ring formed by R may be different from or may be the same as the aromatic ring formed by R h and R i and an aromatic ring formed by R j and R k The aromatic ring formed by R may be different from or may be the same as the aromatic ring formed by R. a and R b The aromatic ring formed by and R c and R d or R h and R i The aromatic ring formed by and R j and R k It is preferable that the aromatic rings formed by the formula (I) are the same.

[0068] In the general formula (I1) or (I2), R e and R f R each independently represents a halogen atom or an oxygen atom. e and R fWhen R is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom because it has a strong bond with a boron atom. e and R f Compounds in which R is a fluorine atom have high heat resistance, and are therefore advantageous when melt-kneaded with resins at high temperatures. e and R f Even if the substituent is not a halogen atom or an oxygen atom but contains an atom capable of bonding to a boron atom, it can be contained in the resin in the same manner as the near-infrared fluorescent dye according to the present invention. The substituent is acceptable as long as it does not inhibit fluorescence.

[0069] In the general formula (I1) or (I2), R e and R f If is an oxygen atom, R e , R e A boron atom bonded to R a , and R a may form a ring together with the nitrogen atom to which R is bonded; f , R f A boron atom bonded to R c , and R c The nitrogen atoms to which R are attached may together form a ring. e , R e A boron atom bonded to R a , and R a The ring formed by the nitrogen atom to which is bonded is R a and R b is condensed with the aromatic ring formed by R f , R f A boron atom bonded to R c , and R c The ring formed by the nitrogen atom to which is bonded is R c and R d R e etc. and R f The ring formed by these and the like is preferably a six-membered ring.

[0070] In the general formula (I1) or (I2), R e is an oxygen atom and does not form a ring, R e is an oxygen atom having a substituent (oxygen atom bonded to a substituent). The substituent is, for example, C 1-20 Examples of the alkyl group include an alkyl group, an aryl group, a heteroaryl group, an alkylcarbonyl group, an arylcarbonyl group, and a heteroarylcarbonyl group. Similarly, in the general formula (I1) or the general formula (I2), R f is an oxygen atom and does not form a ring, R f is an oxygen atom having a substituent (oxygen atom bonded to a substituent). The substituent is, for example, C 1-20 Examples of the alkyl group include an alkyl group, an aryl group, a heteroaryl group, an alkylcarbonyl group, an arylcarbonyl group, and a heteroarylcarbonyl group. e and R f When both are oxygen atoms having substituents, R e The substituents and R f The substituents possessed by may be the same or different.

[0071] In the general formula (I1) or (I2), R e and R f If is an oxygen atom, R e , R f , and R e and R f and the boron atom bonded to the ring may form a ring. Examples of such a ring structure include R e and R f and R are linked to the same aryl or heteroaryl ring; e and R f are linked via an alkylene group.

[0072] In general formula (I3) or general formula (I4), R l , R m , R n , and R o are each independently a halogen atom, C 1-20 Alkyl group, C 1-20R represents an alkoxy group, an aryl group, or a heteroaryl group. l , R m , R n , or R o When R is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom because it has a strong bond with a boron atom. l , R m , R n , and R o Compounds containing fluorine atoms have high heat resistance and are therefore advantageous when melt-kneaded with resins at high temperatures.

[0073] In the present invention and the present specification, "C 1-20 "Alkyl group" means an alkyl group having 1 to 20 carbon atoms, 1-20 The term "alkoxy group" means an alkoxy group having 1 to 20 carbon atoms.

[0074] R l , R m , R n , or R o C 1-20 In the case of an alkyl group, the alkyl group may be linear, branched, or cyclic (aliphatic cyclic group). Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isoamyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

[0075] 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 cyclic group). Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group, a pentyloxy group, an isoamyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group.

[0076] R l , R m , R n , or R o When is an aryl group, examples of the aryl group include a phenyl group, a naphthyl group, an indenyl group, and a biphenyl group. R l , R m , R n , or R o is a heteroaryl group, examples of the heteroaryl group include 5-membered ring heteroaryl groups such as a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a thienyl group, a furanyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, and a thiadiazole group; 6-membered ring heteroaryl groups such as a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, and a pyridazinyl group; and fused heteroaryl groups such as an indolyl group, an isoindolyl group, an indazolyl group, a quinolidinyl group, a quinolinyl group, an isoquinolinyl group, a benzofuranyl group, an isobenzofuranyl group, a chromenyl group, a benzoxazolyl group, a benzoisoxazolyl group, a benzothiazolyl group, and a benzoisothiazolyl group.

[0077] R l , R m , R n , or R o C represents 1-20 Alkyl group, C 1-20The alkoxy group, aryl group, and heteroaryl group may be unsubstituted or one or more hydrogen atoms may be substituted with a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, a hydroxyl group, an amino group, a thiol group, a carboxyl group, an aldehyde group, a sulfonic acid group, an isocyanate group, a thioisocyanate group, an aryl group, and a heteroaryl group.

[0078] The compound represented by the general formula (I3) or (I4) is R l , R m , R n , and R o is preferably a halogen atom, an unsubstituted aryl group, or an aryl group having a substituent, and is preferably a fluorine atom, a chlorine atom, a bromine atom, an unsubstituted phenyl group, or 1-20 Alkyl group or C 1-20 A phenyl group substituted with an alkoxy group is preferred, and a fluorine atom, a chlorine atom, an unsubstituted phenyl group, or a C 1-10 Alkyl group or C 1-10 A phenyl group substituted with an alkoxy group is more preferred, and a fluorine atom or an unsubstituted phenyl group is particularly preferred.

[0079] In general formula (I3) or general formula (I4), R p and R q are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 R represents an alkoxy group, an aryl group, or a heteroaryl group. p and R q Halogen atoms represented by C 1-20 Alkyl group, C 1-20 The alkoxy group, the aryl group, and the heteroaryl group are R l , R m , R n , or R o The same can be mentioned.

[0080] The compound represented by the general formula (I3) or (I4) is R p and Rq is preferably a hydrogen atom or an aryl group, and is preferably an unsubstituted phenyl group or 1-20 Alkyl group or C 1-20 A phenyl group substituted with an alkoxy group is preferred, and an unsubstituted phenyl group or 1-20 A phenyl group substituted with an alkoxy group is more preferred, and an unsubstituted phenyl group or 1-10 Phenyl groups substituted with alkoxy groups are particularly preferred.

[0081] In general formula (I1), R g represents a hydrogen atom or an electron-withdrawing group. r and R s Each of the represents independently a hydrogen atom or an electron-withdrawing group. Examples of the electron-withdrawing group include halogenated methyl groups such as trifluoromethyl groups; nitro groups; cyano groups; aryl groups; heteroaryl groups; alkynyl groups; alkenyl groups; carboxyl groups, acyl groups, carbonyloxy groups, amide groups, and carbonyl-containing substituents such as aldehyde groups; sulfoxide groups; sulfonyl groups; alkoxymethyl groups; and aminomethyl groups. Aryl groups and heteroaryl groups having these electron-withdrawing groups as substituents can also be used. Among these electron-withdrawing groups, trifluoromethyl groups, nitro groups, cyano groups, phenyl groups, sulfonyl groups, and the like that can function as strong electron-withdrawing groups are preferred from the viewpoint of increasing the maximum fluorescence wavelength.

[0082] As the near-infrared fluorescent dye according to the present invention, a compound represented by the following general formula (I1-0) or general formula (I2-0) is preferred. A compound having a boron dipyrromethene skeleton is preferred because it has a longer maximum fluorescence wavelength, and in particular, a compound in which a pyrrole ring is condensed with an aromatic ring or a heteroaromatic ring, which satisfies the following (p2), (p3), (q2), or (q3), is preferred as a near-infrared fluorescent dye because it has a longer maximum fluorescence wavelength.

[0083] [ka]

[0084] In the general formula (I1-0) or the general formula (I2-0), R 1 , R 2 , and R 3 satisfies any one of the following (p1) to (p3). (p1) independently of each other a hydrogen atom, a halogen atom, 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 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 3 is a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; or (p3)R 2 and R 3 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 1 is a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an aryl group, or a heteroaryl group.

[0085] In the general formula (I1-0) or the general formula (I2-0), R 4 , R 5 , and R 6 satisfies any one of the following (q1) to (q3). (q1) independently represent a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group, (q2)R 4 and R 5 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 6 is a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; or (q3)R 5 and R 6together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 4 is a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an aryl group, or a heteroaryl group.

[0086] The halogen atoms in (p1) to (p3) or (q1) to (q3), C 1-20 Alkyl group, C 1-20 The alkoxy group, the aryl group, and the heteroaryl group are each R a and R b Any of the groups exemplified in the above as "any group that does not inhibit the fluorescence of the compound" can be used.

[0087] In the above (p2) to (p3) or (q2) to (q3), R 1 and R 2 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 4 and R 5 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 2 and R 3 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 5 and R 6 The aromatic 5-membered ring or aromatic 6-membered ring formed by these together is preferably one represented by any one of the following general formulae (C-1) to (C-9), more preferably one represented by any one of the following general formulae (C-1), (C-2), or (C-9). In the following general formulae (C-1) to (C-9), the position marked with an asterisk is the part that bonds to the boron dipyrromethene skeleton in general formula (I1-0) or general formula (I2-0).

[0088] [ka]

[0089] In the general formulas (C-1) to (C-8), Y 1 ~Y 8 Each of Y independently represents a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom. 1 ~Y 8is preferably each independently a sulfur atom, an oxygen atom, or a nitrogen atom, and more preferably each independently a sulfur atom or an oxygen atom.

[0090] In the general formulas (C-1) to (C-9), R 11 ~R 22 Each of R independently represents a hydrogen atom or an arbitrary group that does not inhibit the fluorescence of the compound. a and R b Any of the groups exemplified in "any group that does not inhibit the fluorescence of the compound" in R 11 ~R 22 are preferably each independently a hydrogen atom, an unsubstituted aryl group, an aryl group having a substituent, an unsubstituted heteroaryl group, or a heteroaryl group having a substituent, 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 further preferably a hydrogen atom, an (unsubstituted) phenyl group, or a p-methoxyphenyl group. In order to increase the electron donating property and to suppress the aggregation of the BODIPY skeleton by the bulky substituent, it is particularly preferable that the compound is substituted with at least one of the unsubstituted aryl group, aryl group having a substituent, unsubstituted heteroaryl group, or heteroaryl group having a substituent.

[0091] The compound of general formula (I1-0) or general formula (I2-0) is R 1 and R 4 , R 2 and R 5 , and R 3 and R 6 may be different from each other, but are preferably the same group. 1 , R 2 , and R 3 If satisfies (p1) above, then R 4 , R 5 , and R 6 It is preferable that R satisfies (q1) above. 1 , R2 , and R 3 If satisfies (p2) above, then R 4 , R 5 , and R 6 It is preferable that R satisfies (q2) above. 1 , R 2 , and R 3 If satisfies (p3) above, then R 4 , R 5 , and R 6 It is preferable that the above (q3) is satisfied.

[0092] The compound of general formula (I1-0) or general formula (I2-0) is R 1 and R 2 forms a ring, and R 4 and R 5 forms a ring, or R 2 and R 3 forms a ring, and R 5 and R 6 It is preferable that R 1 , R 2 , and R 3 satisfies (p2) or (p3) above, and R 4 , R 5 , and R 6 It is preferable that the compound satisfies the above (q2) or (q3). This is because the maximum fluorescence wavelength shifts to the longer wavelength side by further condensing an aromatic ring or a heteroaromatic ring to the boron dipyrromethene skeleton.

[0093] In the general formula (I1-0) or the general formula (I2-0), R 7 and R 8 R represents a halogen atom or an oxygen atom. 7 and R 8 If is an oxygen atom, R 7 , R 7 The boron atom bonded to the nitrogen atom, the boron atom bonded to the nitrogen atom, R 1 , and R 1 and the carbon atom to which they are bonded may together form a ring, 8 , R 8 The boron atom bonded to the nitrogen atom, the boron atom bonded to the nitrogen atom, R 4, and R 4 The carbon atoms to which R is attached may together form a ring. 7 and boron atom and R 1 etc., and R 8 and boron atom and R 4 The rings formed by these are all condensed with the boron dipyrromethene skeleton. 7 and boron atom and R 1 etc., and R 8 and boron atom and R 4 The ring formed by these and the like is preferably a six-membered ring.

[0094] In the general formula (I1-0) or the general formula (I2-0), R 7 is an oxygen atom and does not form a ring, R 7 is an oxygen atom having a substituent (oxygen atom bonded to a substituent). The substituent is, for example, C 1-20 Examples of the alkyl group include an alkyl group, an aryl group, and a heteroaryl group. Similarly, in the general formula (I1-0) or the general formula (I2-0), R 8 is an oxygen atom and does not form a ring, R 8 is an oxygen atom having a substituent (oxygen atom bonded to a substituent). The substituent is, for example, C 1-20 Examples of the alkyl group include an alkyl group, an aryl group, and a heteroaryl group. 7 and R 8 When both are oxygen atoms having substituents, R 7 The substituents and R 8 The substituents possessed by may be the same or different.

[0095] In general formula (I1-0), R 9 represents a hydrogen atom or an electron-withdrawing group. The electron-withdrawing group may be any of the above-mentioned R gExamples of the substituents are the same as those listed in 1. Among them, from the viewpoint of increasing the maximum fluorescence wavelength, fluoroalkyl groups, nitro groups, cyano groups, aryl groups, and sulfonyl groups that can function as strong electron-attracting groups are preferred, and trifluoromethyl groups, nitro groups, cyano groups, phenyl groups, and sulfonyl groups are more preferred, and from the viewpoint of safety to living organisms, trifluoromethyl groups, cyano groups, phenyl groups, and sulfonyl groups are even more preferred. However, the substituents are not limited to these.

[0096] The near-infrared fluorescent dye according to the present invention is a compound represented by general formula (I1-0) or general formula (I2-0), 1 and R 2 Among the rings represented by the above general formula (C-1), R 11 and R 12 One of the two is a hydrogen atom, and the other is a halogen atom, C 1-20 Alkyl group or C 1-20 R forms a ring which is a phenyl group, a thienyl group, or a furanyl group which may be substituted by an alkoxy group; 4 and R 5 Both are R 1 and R 2 forms a ring similar to that formed by R 3 and R 6 is a hydrogen atom, and R 7 and R 8 Compounds in which R is a halogen atom; 1 and R 2 Among the rings represented by the above general formula (C-2), R 13 and R 14 One of the two is a hydrogen atom, and the other is a halogen atom, C 1-20 Alkyl group or C 1-20 R forms a ring which is a phenyl group, a thienyl group, or a furanyl group which may be substituted by an alkoxy group; 4 and R 5 Both are R 1 and R 2 forms a ring similar to that formed by R 3 and R 6 is a hydrogen atom, and R 7and R 8 Compounds in which R is a halogen atom; 2 and R 3 Among the rings represented by the above general formula (C-1), R 11 and R 12 One of the two is a hydrogen atom, and the other is a halogen atom or C. 1-20 Alkyl group or C 1-20 R forms a ring which is a phenyl group, a thienyl group, or a furanyl group which may be substituted by an alkoxy group; 5 and R 6 Both are R 2 and R 3 forms a ring similar to that formed by R 1 and R 4 is a hydrogen atom, and R 7 and R 8 Compounds in which R is a halogen atom; 2 and R 3 Among the rings represented by the following general formula (C-2), R 13 and R 14 One of the two is a hydrogen atom, and the other is a halogen atom or C. 1-20 Alkyl group or C 1-20 R forms a ring which is a phenyl group, a thienyl group, or a furanyl group which may be substituted by an alkoxy group; 5 and R 6 Both are R 2 and R 3 forms a ring similar to that formed by R 1 and R 4 is a hydrogen atom, and R 7 and R 8 Compounds in which R is a halogen atom; 2 and R 3 Among the rings represented by the following general formula (C-9), R 19 ~R 22 Any one of the following has 1 to 3 hydrogen atoms, or a halogen atom, C 1-20 Alkyl group or C 1-20 a phenyl group, a thienyl group, or a furanyl group optionally substituted by an alkoxy group, the remaining three of which form a ring consisting of hydrogen atoms; R 5 and R 6Both are R 2 and R 3 forms a ring similar to that formed by R 1 and R 4 is a hydrogen atom, halogen atom, C 1-20 Alkyl group or C 1-20 R is a phenyl group, a thienyl group, or a furanyl group, which may be substituted by an alkoxy group; 7 and R 8 is a halogen atom; when these compounds are compounds represented by the general formula (I1-0), R 9 is more preferably a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group, and particularly preferably a trifluoromethyl group or a phenyl group.

[0097] Preferred compounds of 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). In the following general compound (I1-1), R 1 , R 3 , R 4 , and R 6 ~R 8 is as defined above, ED represents an electron donating group, EW represents an electron withdrawing group, Z 1 ~Z 4 Each ring independently represents a 5- or 6-membered aryl group, or a 5- or 6-membered heteroaryl group.

[0098] [ka]

[0099] As the following general formula (I1-1), the compounds represented by the following general formulae (I1-1-1) to (I1-1-6) are preferred, as the following general formula (I1-2), the compounds represented by the following general formulae (I1-2-1) to (I1-2-12) are preferred, as the following general formula (I2-1), the compounds represented by the following general formulae (I2-1-1) to (I2-1-6) are preferred, and as the following general formula (I2-2), the compounds represented by the following general formulae (I2-2-1) to (I2-2-12) are preferred.

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] In the general formulae (I1-1-1) to (I1-1-6), (I1-2-1) to (I1-2-4), (I1-2-7) to (I1-2-10), (I2-1-1) to (I2-1-6), (I2-2-1) to (I2-2-4), and (I2-2-7) to (I2-2-10), Y 11 and Y 12 each independently represents an oxygen atom or a sulfur atom; Y 21 and Y22 Each of Y independently represents a carbon atom or a nitrogen atom. 11 and Y 12 are preferably the same type of atoms, and Y 21 and Y 22 are preferably the same type of atoms.

[0107] In general formulas (I1-1-1)~(I1-1-6), (I1-2-1)~(I1-2-12), Q 11 represents a hydrogen atom or an electron-withdrawing group. The electron-withdrawing group may be any of the above-mentioned R g The compounds represented by the general formula (I1-1-1) and the like include the following: 11 is preferably a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group which may have a substituent, and more preferably a trifluoromethyl group or a phenyl group which may have a substituent.

[0108] In the general formulae (I1-1-1) to (I1-1-2), (I1-2-1) to (I1-2-2), (I1-2-6), (I2-1-1) to (I2-1-2), and (I2-2-1) to (I2-2-2), and (I2-2-6), X is each independently a halogen atom, C 1-20 It represents an alkoxy group, an aryloxy group, or an acyloxy group.

[0109] 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 cyclic group). Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group, a pentyloxy group, an isoamyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group.

[0110] When X is an aryloxy group, examples of the aryloxy group include a phenyloxy group, a naphthyloxy group, an indenyloxy group, and a biphenyloxy group.

[0111] When X is an acyloxy group, the acyloxy group is preferably an alkylcarbonyloxy group or an arylcarbonyloxy group. Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group (acetoxy group), an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, a t-butylcarbonyloxy group, a pentylcarbonyloxy group, an isoamylcarbonyloxy group, a hexylcarbonyloxy group, a heptylcarbonyloxy group, an octylcarbonyloxy group, a nonylcarbonyloxy group, a decylcarbonyloxy group, an undecylcarbonyloxy group, and a dodecylcarbonyloxy group. Examples of the arylcarbonyloxy group include a phenylcarbonyloxy group (benzoyloxy group), a naphthylcarbonyloxy group, an indenylcarbonyloxy group, and a biphenylcarbonyloxy group.

[0112] As the compound represented by any one of general formulas (I1-1-1) to (I1-1-2), (I1-2-1) to (I1-2-2), (I1-2-6), (I2-1-1) to (I2-1-2), (I2-2-1) to (I2-2-2), and (I2-2-6), each X is preferably a halogen atom, and each X is particularly preferably a fluorine atom.

[0113] In the general formulae (I1-1-3) to (I1-1-4), (I1-2-7), (I1-2-9), (I1-2-11), (I2-1-3) to (I2-1-4), (I2-2-7), (I2-2-9), and (I2-2-11), m1 represents 0 or 1.

[0114] In the general formulae (I1-1-5) to (I1-1-6), (I1-2-3) to (I1-2-6), (I1-2-8), (I1-2-10) to (I1-2-12), (I2-1-5) to (I2-1-6), (I2-2-3) to (I1-2-6), (I2-2-8), and (I2-2-10) to (I2-2-12), P 11 ~P 14 and P 17 are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group. 11 ~P 14 C in 1-20 Alkyl group, C 1-20 The alkoxy group, monoalkylamino group, and dialkylamino group are each defined as R g The same things as those listed in (p1)-(p3) and (q1)-(q3) are included. 11 ~P 14 and P 17 As for C 1-20 Alkyl group, C 1-20 An alkoxy group, a (non-substituted) phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group is preferred. From the viewpoint of safety to living bodies, 1-20 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 further have a substituent. However, even if the substituent is a substituent other than these substituents, safety can be improved by introducing a further appropriate substituent, so the substituent is not limited to these substituents.

[0115] In the general formulae (I1-1-5) to (I1-1-6), (I1-2-3) to (I1-2-6), (I1-2-8), (I1-2-10) to (I1-2-12), (I2-1-5) to (I2-1-6), (I2-2-3) to (I1-2-6), (I2-2-8), and (I2-2-10) to (I2-2-12), n11 to n14 and n17 each independently represent an integer of 0 to 3. 11 If there are multiple P 11 may be the same type of functional group or different types of functional groups. 12 ~P 14 and P 17 The same applies to.

[0116] In the general formulae (I1-1-1) to (I1-1-6), (I1-2-1) to (I1-2-4), (I1-2-6) to (I1-2-12), (I2-1-1) to (I2-1-6), (I2-2-1) to (I2-2-4), and (I2-2-6) to (I2-2-12), A 11 ~A 14 are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 a phenyl group which may have 1 to 3 substituents selected from the group consisting of an alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group, or a halogen atom, C 1-20 Alkyl group, C 1-20 The heteroaryl group may have 1 to 3 substituents selected from the group consisting of an alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group. The heteroaryl group is R l , R m , R n , or R o The C in the substituent that the phenyl group or the heteroaryl group may have is preferably a thienyl group or a furanyl group. 1-20 Alkyl group, C 1-20 The alkoxy group, monoalkylamino group, and dialkylamino group are each defined as R gThe same things as those mentioned in (p1)-(p3) and (q1)-(q3) are included. 11 ~A 14 Examples of the alkyl group include an unsubstituted phenyl group, one or two C 1-20 A phenyl group or a heteroaryl group having an alkoxy group as a substituent is preferred, and an unsubstituted phenyl group or a group having one C 1-20 A phenyl group having an alkoxy group as a substituent is more preferable, and an unsubstituted phenyl group or one C 1-10 A phenyl group having an alkoxy group as a substituent is more preferred, and an unsubstituted phenyl group or a phenyl group having one C 1-6 A phenyl group having an alkoxy group as a substituent is more preferable. 11 ~A 14 are preferably the same type of functional group.

[0117] As the near-infrared fluorescent dye according to the present invention, in particular, a compound represented by any one of the following general formulae (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) is preferable, a compound represented by any one of the following general formulae (1-1) to (1-12), (1-25) to (1-31), (2-1) to (2-7), and (3-25) to (3-31) is more preferable, and a compound represented by any one of the following general formulae (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) is even more preferable.

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] 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 are each independently a halogen atom, C 1-20 Alkyl group, C 1-20It represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group. 1 ~P 4 C in 1-20 Alkyl group, C 1-20 The alkoxy group, monoalkylamino group, and dialkylamino group are each defined as R g The same things as those listed in (p1)-(p3) and (q1)-(q3) are included. 1 ~P 4 and P 18 As for C 1-20 Alkyl group, C 1-20 An alkoxy group, a (non-substituted) phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group is preferred. From the viewpoint of safety to living bodies, 1-20 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 further have a substituent. However, even if the substituent is a substituent other than these substituents, safety can be improved by introducing a further appropriate substituent, so the substituent is not limited to these substituents.

[0130] In the general formulae (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), n1 to n4 and n18 each independently represent an integer of 0 to 3. 1 If there are multiple P 1 may be the same type of functional group or different types of functional groups. 2 ~P 4 and P 18 The same applies to.

[0131] In the general formulae (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 a phenyl group which may have a substituent, preferably a trifluoromethyl group or a phenyl group which may have a substituent, and more preferably a trifluoromethyl group or an unsubstituted phenyl group. The substituent which the phenyl group may have is, for example, a halogen atom, 1-20 Alkyl group, C 1-20 Examples of the alkyl group include an alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group.

[0132] In the general formulas (1-1) to (1-31) and (3-1) to (3-31), X is the same as in the general formula (I1-1-1) etc. As the compound represented by the general formula (1-1) etc., X is preferably a halogen atom, and particularly preferably a fluorine atom.

[0133] In the general formulae (1-32) to (1-34) and (3-32) to (3-34), m2 is 0 or 1. In the compound represented by the general formula (1-32) etc., m2 is preferably 1.

[0134] The compounds represented by the general formulas (1-1) to (1-37), (2-1) to (2-7), and (5-1) include P 1 ~P 4 and P 18 are independent of each other, C 1-20 Alkyl group, C 1-20 Preferred are those in which n1 to n4 and n18 are each independently 0 to 2, and Q is a trifluoromethyl group or a phenyl group. Similarly, the compounds represented by the general formulae (3-1) to (3-37), (4-1) to (4-7), and (5-2) include P 1 ~P 4 and P 18 are independent of each other, C 1-20 Alkyl group, C 1-20It 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, and n1 to n4 and n18 are each independently 0 to 2.

[0135] As the near-infrared fluorescent dye according to the present invention, a compound represented by any one of the following general formulae (I3-1) to (I3-6) or a compound represented by any one of the general formulae (I4-1) to (I4-6) is also preferred since the maximum fluorescence wavelength is longer.

[0136] [ka]

[0137] [ka]

[0138] 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 are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 R represents an alkoxy group, an aryl group, or a heteroaryl group. 23 , R 24 , R 25 , or R 26 Halogen atoms represented by C 1-20 Alkyl group, C 1-20 The alkoxy group, the aryl group, and the heteroaryl group are R l , R m , R n , or R o The compounds represented by any one of the general formulae (I3-1) to (I3-6) or the compounds represented by any one of the general formulae (I4-1) to (I4-6) are preferably those represented by the general formulae (I4-1) to (I4-6) in the form of R 23 , R 24 , R25 , and R 26 is preferably a halogen atom, an unsubstituted aryl group, or an aryl group having a substituent, and specifically, is preferably a fluorine atom, a chlorine atom, a bromine atom, an unsubstituted phenyl group, or 1-20 Alkyl group or C 1-20 A phenyl group substituted with an alkoxy group is preferred, and a fluorine atom, a chlorine atom, an unsubstituted phenyl group, or a C 1-10 Alkyl group or C 1-10 A phenyl group substituted with an alkoxy group is more preferable, and a fluorine atom or an unsubstituted phenyl group is particularly preferable, since a compound having both high luminous efficiency and thermal stability can be obtained.

[0139] In general formulas (I3-1) to (I3-6) and general formulas (I4-1) to (I4-6), R 27 and R 28 are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 R represents an alkoxy group, an aryl group, or a heteroaryl group. 27 or R 28 Halogen atoms represented by C 1-20 Alkyl group, C 1-20 The alkoxy group, the aryl group, and the heteroaryl group are R p or R q The compounds represented by any one of the general formulae (I3-1) to (I3-6) or the compounds represented by any one of the general formulae (I4-1) to (I4-6) include those represented by R 27 and R 28 is preferably a hydrogen atom or an aryl group, and a compound having high luminous efficiency can be obtained. 1-20 Alkyl group or C 1-20 A phenyl group substituted with an alkoxy group is preferred, and a hydrogen atom, an unsubstituted phenyl group, or a linear or branched C 1-20 A phenyl group substituted with an alkoxy group is more preferable, and a compound having high luminous efficiency and excellent compatibility with resins can be obtained. Therefore, an unsubstituted phenyl group or a linear or branched C1-10 Phenyl groups substituted with alkoxy groups are particularly preferred.

[0140] In general formulas (I3-1) to (I3-6), R 29 and R 30 R each independently represents a hydrogen atom or an electron-withdrawing group. 29 or R 30 The electron-withdrawing group represented by R r or R s The compounds represented by any one of the general formulas (I3-1) to (I3-6) are preferably those represented by the general formula (I3-1) and (I3-2), because they have a longer fluorescent wavelength and a higher luminous efficiency. 29 and R 30 However, those which are fluoroalkyl groups, nitro groups, cyano groups, or aryl groups capable of functioning as strong electron-withdrawing groups are preferred, and those which are trifluoromethyl groups, nitro groups, cyano groups, or phenyl groups which may have a substituent are more preferred, with trifluoromethyl groups or cyano groups being more preferred since they provide compounds which have high luminous efficiency and excellent compatibility with resins.

[0141] In general formula (I3-1) and general formula (I4-1), Y 9 and Y 10 each independently represents a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom. As the compound represented by general formula (I3-1) or general formula (I4-1), a compound having high luminous efficiency can be obtained, and therefore, Y 9 and Y 10 However, it is preferable that they are each independently a sulfur atom, an oxygen atom, or a nitrogen atom, it is more preferable that they are each independently a sulfur atom or an oxygen atom, and it is even more preferable that they are both sulfur atoms or both oxygen atoms, since this will give a compound that has both high luminous efficiency and thermal stability.

[0142] In general formulas (I3-3) to (I3-6) and general formulas (I4-3) to (I4-6), X 1 and X 2each independently represents a nitrogen atom or a phosphorus atom. As the compounds represented by the general formulae (I3-3) to (I3-6) or (I4-3) to (I4-6), X 1 and X 2 However, it is preferable that both are nitrogen atoms or phosphorus atoms, since this will result in a compound with high luminous efficiency, and it is more preferable that both are nitrogen atoms, since this will result in a compound that has both high luminous efficiency and thermal stability.

[0143] In general formula (I3-1) and general formula (I4-1), R 31 and R 32 satisfies (p4) or (p5) below. (p4) independently of each other a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an aryl group, or a heteroaryl group. (p5)R 31 and R 32 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring.

[0144] In general formula (I3-1) and general formula (I4-1), R 33 and R 34 satisfies (q4) or (q5) below. (q4) independently of each other a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an aryl group, or a heteroaryl group; or (q5)R 33 and R 34 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring.

[0145] 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 satisfies any of the following (p6) to (p9). (p6) Independently of each other, a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an aryl group, or a heteroaryl group. (p7)R 35 and R 36 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 37 and R 38 are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an aryl group, or a heteroaryl group. (p8)R 36 and R 37 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 35 and R 38 are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an aryl group, or a heteroaryl group. (p9)R 37 and R 38 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 35 and R 36 are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an aryl group, or a heteroaryl group.

[0146] 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 satisfies any of the following (q6) to (q9). (q6) independently of each other a hydrogen atom, a halogen atom, C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an aryl group, or a heteroaryl group. (q7)R 39 and R40 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 41 and R 42 are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an aryl group, or a heteroaryl group. (q8)R 40 and R 41 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 39 and R 42 are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an aryl group, or a heteroaryl group. (q9)R 41 and R 42 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 39 and R 40 are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an aryl group, or a heteroaryl group.

[0147] The halogen atoms in (p4), (p6) to (p9), (q4), (q6) to (q9), C 1-20 Alkyl group, C 1-20 The alkoxy group, the aryl group, and the heteroaryl group are each R a and R b Any of the groups exemplified in the above as "any group that does not inhibit the fluorescence of the compound" can be used.

[0148] In the above (p5), (p7) to (p9), (q5), (q7) to (q9), R 31 and R 32 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 33 and R 34 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 35 and R36 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 36 and R 37 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 37 and R 38 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 39 and R 40 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 40 and R 41 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 41 and R 42 The aromatic 5-membered ring or aromatic 6-membered ring formed by these together is preferably one represented by any of the general formulas (C-1) to (C-9), and more preferably one represented by the general formula (C-9) since it gives a compound with high thermal stability.

[0149] The compound represented by (I3-1) is R 23 , R 24 , R 25 , and R 26 are both halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl group or C 1-10 R is a phenyl group substituted with an alkoxy group; 27 and R 28 are both hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl group or C 1-20 R is a phenyl group substituted with an alkoxy group; 29 and R 30 are both trifluoromethyl, nitro, cyano, or phenyl; Y 9 and Y 10 are both sulfur atoms or oxygen atoms; R 31 and R 32 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 31 and R 32 together form an optionally substituted phenyl group; R 33 and R 34 are independently a hydrogen atom or C 1-20 is an alkyl group, or R33 and R 34 and R 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups; R 27 and R 28 are both unsubstituted phenyl groups or linear or branched C 1-20 R is a phenyl group substituted with an alkoxy group; 29 and R 30 are both trifluoromethyl, nitro, or cyano groups; Y 9 and Y 10 are both sulfur atoms or oxygen atoms; R 31 and R 32 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 31 and R 32 are both unsubstituted phenyl groups or C 1-10 R forms a phenyl group substituted with an alkyl group; 33 and R 34 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 33 and R 34 are both unsubstituted phenyl groups or C 1-10 Compounds that form a phenyl group substituted with an alkyl group are more preferred because they have high luminous efficiency and excellent compatibility with resins.

[0150] The compound represented by (I3-2) is R 23 , R 24 , R 25 , and R 26 are both halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl group or C 1-10 R is a phenyl group substituted with an alkoxy group; 27 and R 28 are both hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl group or C 1-20 R is a phenyl group substituted with an alkoxy group;29 and R 30 are both trifluoromethyl, nitro, cyano, or phenyl; R 35 , R 36 , R 37 , and R 38 are independently a hydrogen atom or C 1-20 R is an alkyl group. 35 and R 36 together form an optionally substituted phenyl group, R 37 and R 38 are independently a hydrogen atom or C 1-20 R is an alkyl group. 36 and R 37 together form an optionally substituted phenyl group, R 35 and R 38 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 37 and R 38 together form an optionally substituted phenyl group, R 35 and R 36 are independently a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 40 , R 41 , and R 42 are independently a hydrogen atom or C 1-20 R is an alkyl group. 39 and R 40 together form an optionally substituted phenyl group, R 41 and R 42 are independently a hydrogen atom or C 1-20 R is an alkyl group. 40 and R 41 together form an optionally substituted phenyl group, R 39 and R 42 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 41 and R 42 together form an optionally substituted phenyl group, R 39 and R 40 are independently a hydrogen atom or C 1-20Preferred are compounds in which R is an alkyl group. 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups; R 27 and R 28 are both unsubstituted phenyl groups or linear or branched C 1-20 R is a phenyl group substituted with an alkoxy group; 29 and R 30 are both trifluoromethyl, nitro, or cyano groups; R 35 , R 36 , R 37 , and R 38 are independently a hydrogen atom or C 1-20 R is an alkyl group. 35 and R 36 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 37 and R 38 are independently a hydrogen atom or C 1-20 R is an alkyl group. 36 and R 37 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 35 and R 38 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 37 and R 38 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 35 and R 36 are independently a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 40 , R 41 , and R 42 are independently a hydrogen atom or C 1-20 R is an alkyl group. 39 and R 40 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 41and R 42 are independently a hydrogen atom or C 1-20 R is an alkyl group. 40 and R 41 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 39 and R 42 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 41 and R 42 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 39 and R 40 are independently a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferred because they have high luminous efficiency and excellent compatibility with resins.

[0151] The compound represented by (I3-3) is R 23 , R 24 , R 25 , and R 26 are both halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl group or C 1-10 R is a phenyl group substituted with an alkoxy group; 27 and R 28 are both hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl group or C 1-20 R is a phenyl group substituted with an alkoxy group; 29 and R 30 are both trifluoromethyl, nitro, cyano, or phenyl groups; X 1 and X 2 are both nitrogen atoms; R 36 , R 37 , and R 38 are independently a hydrogen atom or C 1-20 R is an alkyl group. 36 and R 37 together form an optionally substituted phenyl group, R 38 is a hydrogen atom or C 1-20 is an alkyl group, or R37 and R 38 together form an optionally substituted phenyl group, R 36 is a hydrogen atom or C 1-20 R is an alkyl group; 40 , R 41 , and R 42 are independently a hydrogen atom or C 1-20 R is an alkyl group. 40 and R 41 together form an optionally substituted phenyl group, R 42 is a hydrogen atom or C 1-20 is an alkyl group, or R 41 and R 42 together form an optionally substituted phenyl group, R 40 is a hydrogen atom or C 1-20 Preferred are compounds in which R is an alkyl group. 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups; R 27 and R 28 are both unsubstituted phenyl groups or linear or branched C 1-20 R is a phenyl group substituted with an alkoxy group; 29 and R 30 are both trifluoromethyl, nitro, or cyano groups; X 1 and X 2 are both nitrogen atoms; R 36 , R 37 , and R 38 are independently a hydrogen atom or C 1-20 R is an alkyl group. 36 and R 37 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 38 is a hydrogen atom or C 1-20 is an alkyl group, or R 37 and R 38 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 36 is a hydrogen atom or C1-20 R is an alkyl group; 40 , R 41 , and R 42 are independently a hydrogen atom or C 1-20 R is an alkyl group. 40 and R 41 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 42 is a hydrogen atom or C 1-20 is an alkyl group, or R 41 and R 42 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 40 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferred because they have high luminous efficiency and excellent compatibility with resins.

[0152] The compound represented by (I3-4) is R 23 , R 24 , R 25 , and R 26 are both halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl group or C 1-10 R is a phenyl group substituted with an alkoxy group; 27 and R 28 are both hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl group or C 1-20 R is a phenyl group substituted with an alkoxy group; 29 and R 30 are both trifluoromethyl, nitro, cyano, or phenyl groups; X 1 and X 2 are both nitrogen atoms; R 35 , R 36 , and R 37 are independently a hydrogen atom or C 1-20 R is an alkyl group. 35 and R 36 together form an optionally substituted phenyl group, R 37 is a hydrogen atom or C 1-20 is an alkyl group, or R36 and R 37 together form an optionally substituted phenyl group, R 35 is a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 40 , and R 41 are independently a hydrogen atom or C 1-20 R is an alkyl group. 39 and R 40 together form an optionally substituted phenyl group, R 41 is a hydrogen atom or C 1-20 is an alkyl group, or R 40 and R 41 together form an optionally substituted phenyl group, R 39 is a hydrogen atom or C 1-20 Preferred are compounds in which R is an alkyl group. 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups; R 27 and R 28 are both unsubstituted phenyl groups or linear or branched C 1-20 R is a phenyl group substituted with an alkoxy group; 29 and R 30 are both trifluoromethyl, nitro, or cyano groups; X 1 and X 2 are both nitrogen atoms; R 35 , R 36 , and R 37 are independently a hydrogen atom or C 1-20 R is an alkyl group. 35 and R 36 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 37 is a hydrogen atom or C 1-20 is an alkyl group, or R 36 and R 37 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 35 is a hydrogen atom or C1-20 R is an alkyl group; 39 , R 40 , and R 41 are independently a hydrogen atom or C 1-20 R is an alkyl group. 39 and R 40 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 41 is a hydrogen atom or C 1-20 is an alkyl group, or R 40 and R 41 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 39 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferred because they have high luminous efficiency and excellent compatibility with resins.

[0153] The compound represented by (I3-5) is R 23 , R 24 , R 25 , and R 26 are both halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl group or C 1-10 R is a phenyl group substituted with an alkoxy group; 27 and R 28 are both hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl group or C 1-20 R is a phenyl group substituted with an alkoxy group; 29 and R 30 are both trifluoromethyl, nitro, cyano, or phenyl groups; X 1 and X 2 are both nitrogen atoms; R 35 , R 36 , and R 38 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 35 and R 36 together form an optionally substituted phenyl group, R 38 is a hydrogen atom or C 1-20 R is an alkyl group;39 , R 40 , and R 42 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 39 and R 40 together form an optionally substituted phenyl group, R 42 is a hydrogen atom or C 1-20 Preferred are compounds in which R is an alkyl group. 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups; R 27 and R 28 are both unsubstituted phenyl groups or linear or branched C 1-20 R is a phenyl group substituted with an alkoxy group; 29 and R 30 are both trifluoromethyl, nitro, or cyano groups; X 1 and X 2 are both nitrogen atoms; R 35 , R 36 , and R 38 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 35 and R 36 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 38 is a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 40 , and R 42 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 39 and R 40 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 42 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferred because they have high luminous efficiency and excellent compatibility with resins.

[0154] The compound represented by (I3-6) is R23 , R 24 , R 25 , and R 26 are both halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl group or C 1-10 R is a phenyl group substituted with an alkoxy group; 27 and R 28 are both hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl group or C 1-20 R is a phenyl group substituted with an alkoxy group; 29 and R 30 are both trifluoromethyl, nitro, cyano, or phenyl groups; X 1 and X 2 are both nitrogen atoms; R 35 , R 37 , and R 38 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 37 and R 38 together form an optionally substituted phenyl group, R 35 is a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 41 , and R 42 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 41 and R 42 together form an optionally substituted phenyl group, R 39 is a hydrogen atom or C 1-20 Preferred are compounds in which R is an alkyl group. 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups; R 27 and R 28 are both unsubstituted phenyl groups or linear or branched C 1-20 R is a phenyl group substituted with an alkoxy group; 29 and R 30 are both trifluoromethyl, nitro, or cyano groups; X 1 and X 2are both nitrogen atoms; R 35 , R 37 , and R 38 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 37 and R 38 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 35 is a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 41 , and R 42 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 41 and R 42 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 39 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferred because they have high luminous efficiency and excellent compatibility with resins.

[0155] The compound represented by (I4-1) is R 23 , R 24 , R 25 , and R 26 are both halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl group or C 1-10 R is a phenyl group substituted with an alkoxy group; 27 and R 28 are both hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl group or C 1-20 Y is a phenyl group substituted with an alkoxy group; 9 and Y 10 are both sulfur atoms or oxygen atoms; R 31 and R 32 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 31 and R 32 together form an optionally substituted phenyl group; R 33 and R 34are independently a hydrogen atom or C 1-20 is an alkyl group, or R 33 and R 34 and R 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups; R 27 and R 28 are both unsubstituted phenyl groups or linear or branched C 1-20 Y is a phenyl group substituted with an alkoxy group; 9 and Y 10 are both sulfur atoms or oxygen atoms; R 31 and R 32 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 31 and R 32 are both unsubstituted phenyl groups or C 1-10 R forms a phenyl group substituted with an alkyl group; 33 and R 34 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 33 and R 34 are both unsubstituted phenyl groups or C 1-10 Compounds that form a phenyl group substituted with an alkyl group are more preferred because they have high luminous efficiency and excellent compatibility with resins.

[0156] The compound represented by (I4-2) is R 23 , R 24 , R 25 , and R 26 are both halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl group or C 1-10 R is a phenyl group substituted with an alkoxy group; 27 and R 28 are both hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl group or C 1-20 R is a phenyl group substituted with an alkoxy group; 35 , R36 , R 37 , and R 38 are independently a hydrogen atom or C 1-20 R is an alkyl group. 35 and R 36 together form an optionally substituted phenyl group, R 37 and R 38 are independently a hydrogen atom or C 1-20 R is an alkyl group. 36 and R 37 together form an optionally substituted phenyl group, R 35 and R 38 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 37 and R 38 together form an optionally substituted phenyl group, R 35 and R 36 are independently a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 40 , R 41 , and R 42 are independently a hydrogen atom or C 1-20 R is an alkyl group. 39 and R 40 together form an optionally substituted phenyl group, R 41 and R 42 are independently a hydrogen atom or C 1-20 R is an alkyl group. 40 and R 41 together form an optionally substituted phenyl group, R 39 and R 42 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 41 and R 42 together form an optionally substituted phenyl group, R 39 and R 42 are independently a hydrogen atom or C 1-20 Preferred are compounds in which R is an alkyl group. 23 , R 24 , R 25 , and R 26are both halogen atoms or unsubstituted phenyl groups; R 27 and R 28 are both unsubstituted phenyl groups or linear or branched C 1-20 R is a phenyl group substituted with an alkoxy group; 35 , R 36 , R 37 , and R 38 are independently a hydrogen atom or C 1-20 R is an alkyl group. 35 and R 36 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 37 and R 38 are independently a hydrogen atom or C 1-20 R is an alkyl group. 36 and R 37 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 35 and R 38 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 37 and R 38 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 35 and R 36 are independently a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 40 , R 41 , and R 42 are independently a hydrogen atom or C 1-20 R is an alkyl group. 39 and R 40 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 41 and R 42 are independently a hydrogen atom or C 1-20 R is an alkyl group. 40 and R 41 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R39 and R 42 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 41 and R 42 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 39 and R 42 are independently a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferred because they have high luminous efficiency and excellent compatibility with resins.

[0157] The compound represented by (I4-3) is R 23 , R 24 , R 25 , and R 26 are both halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl group or C 1-10 R is a phenyl group substituted with an alkoxy group; 27 and R 28 are both hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl group or C 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 are both nitrogen atoms; R 36 , R 37 , and R 38 are independently a hydrogen atom or C 1-20 R is an alkyl group. 36 and R 37 together form an optionally substituted phenyl group, R 38 is a hydrogen atom or C 1-20 is an alkyl group, or R 37 and R 38 together form an optionally substituted phenyl group, R 36 is a hydrogen atom or C 1-20 R is an alkyl group; 40 , R 41 , and R 42 are independently a hydrogen atom or C 1-20 R is an alkyl group. 40 and R41 together form an optionally substituted phenyl group, R 42 is a hydrogen atom or C 1-20 is an alkyl group, or R 41 and R 42 together form an optionally substituted phenyl group, R 40 is a hydrogen atom or C 1-20 Preferred are compounds in which R is an alkyl group. 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups; R 27 and R 28 are both unsubstituted phenyl groups or linear or branched C 1-20 R is a phenyl group substituted with an alkoxy group; 36 , R 37 , and R 38 are independently a hydrogen atom or C 1-20 R is an alkyl group. 36 and R 37 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 38 is a hydrogen atom or C 1-20 is an alkyl group, or R 37 and R 38 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 36 is a hydrogen atom or C 1-20 R is an alkyl group; 40 , R 41 , and R 42 are independently a hydrogen atom or C 1-20 R is an alkyl group. 40 and R 41 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 42 is a hydrogen atom or C 1-20 is an alkyl group, or R 41 and R 42 are both unsubstituted phenyl groups or C 1-10Forming a phenyl group substituted with an alkyl group, R 40 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferred because they have high luminous efficiency and excellent compatibility with resins.

[0158] The compound represented by (I4-4) is R 23 , R 24 , R 25 , and R 26 are both halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl group or C 1-10 R is a phenyl group substituted with an alkoxy group; 27 and R 28 are both hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl group or C 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 are both nitrogen atoms; R 35 , R 36 , and R 37 are independently a hydrogen atom or C 1-20 R is an alkyl group. 35 and R 36 together form an optionally substituted phenyl group, R 37 is a hydrogen atom or C 1-20 is an alkyl group, or R 36 and R 37 together form an optionally substituted phenyl group, R 35 is a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 40 , and R 41 are independently a hydrogen atom or C 1-20 R is an alkyl group. 39 and R 40 together form an optionally substituted phenyl group, R 41 is a hydrogen atom or C 1-20 is an alkyl group, or R 40 and R 41 together form an optionally substituted phenyl group, R 39is a hydrogen atom or C 1-20 Preferred are compounds in which R is an alkyl group. 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups; R 27 and R 28 are both unsubstituted phenyl groups or linear or branched C 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 are both nitrogen atoms; R 35 , R 36 , and R 37 are independently a hydrogen atom or C 1-20 R is an alkyl group. 35 and R 36 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 37 is a hydrogen atom or C 1-20 is an alkyl group, or R 36 and R 37 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 35 is a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 40 , and R 41 are independently a hydrogen atom or C 1-20 R is an alkyl group. 39 and R 40 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 41 is a hydrogen atom or C 1-20 is an alkyl group, or R 40 and R 41 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 39 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferred because they have high luminous efficiency and excellent compatibility with resins.

[0159] The compound represented by (I4-5) is R 23 , R 24 , R 25 , and R 26 are both halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl group or C 1-10 R is a phenyl group substituted with an alkoxy group; 27 and R 28 are both hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl group or C 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 are both nitrogen atoms; R 35 , R 36 , and R 38 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 35 and R 36 together form an optionally substituted phenyl group, R 38 is a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 40 , and R 42 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 39 and R 40 together form an optionally substituted phenyl group, R 42 is a hydrogen atom or C 1-20 Preferred are compounds in which R is an alkyl group. 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups; R 27 and R 28 are both unsubstituted phenyl groups or linear or branched C 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 are both nitrogen atoms; R 35 , R 36 , and R 38 are independently a hydrogen atom or C 1-20is an alkyl group, or R 35 and R 36 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 38 is a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 40 , and R 42 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 39 and R 40 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 42 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferred because they have high luminous efficiency and excellent compatibility with resins.

[0160] The compound represented by (I4-6) is R 23 , R 24 , R 25 , and R 26 are both halogen atoms, unsubstituted phenyl groups, or C 1-10 Alkyl group or C 1-10 R is a phenyl group substituted with an alkoxy group; 27 and R 28 are both hydrogen atoms, unsubstituted phenyl groups, or C 1-20 Alkyl group or C 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 are both nitrogen atoms; R 35 , R 37 , and R 38 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 37 and R 38 together form an optionally substituted phenyl group, R 35 is a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 41 , and R 42 are independently a hydrogen atom or C 1-20is an alkyl group, or R 41 and R 42 together form an optionally substituted phenyl group, R 39 is a hydrogen atom or C 1-20 Preferred are compounds in which R is an alkyl group. 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups; R 27 and R 28 are both unsubstituted phenyl groups or linear or branched C 1-20 A phenyl group substituted with an alkoxy group; X 1 and X 2 are both nitrogen atoms; R 35 , R 37 , and R 38 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 37 and R 38 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 35 is a hydrogen atom or C 1-20 R is an alkyl group; 39 , R 41 , and R 42 are independently a hydrogen atom or C 1-20 is an alkyl group, or R 41 and R 42 are both unsubstituted phenyl groups or C 1-10 Forming a phenyl group substituted with an alkyl group, R 39 is a hydrogen atom or C 1-20 Compounds that are alkyl groups are more preferred because they have high luminous efficiency and excellent compatibility with resins.

[0161] As the compound represented by any one of (I3-1) to (I3-6), a compound represented by any one of the following general formulas (I3-7) to (I3-9) is preferable, and as the compound represented by any one of (I4-1) to (I4-6), a compound represented by any one of the following general formulas (I4-7) to (I4-9) is preferable.

[0162] [ka]

[0163] In general formulas (I3-7) and (I4-7), Y 23 and Y 24 Each of Y independently represents a carbon atom or a nitrogen atom. 23 and Y 24 are preferably the same type of atoms.

[0164] In general formulas (I3-8) and (I4-8), Y 13 and Y 14 Each of Y independently represents an oxygen atom or a sulfur atom. 13 and Y 14 are preferably the same type of atoms.

[0165] In general formulas (I3-9) and (I4-9), Y 25 and Y 26 Each of Y independently represents a carbon atom or a nitrogen atom. 25 and Y 26 are preferably the same type of atoms.

[0166] In general formulas (I3-7) to (I3-9), R 47 and R 48 Each of R independently represents a hydrogen atom or an electron-withdrawing group, and is preferably a trifluoromethyl group, a cyano group, a nitro group, a sulfonyl group, or a phenyl group, since the fluorescence intensity is high, and is particularly preferably a trifluoromethyl group or a cyano group. 47 and R 48 are preferably the same type of functional group.

[0167] In general formulas (I3-7) to (I3-9) and (I4-7) to (I4-9), R 43 , R 44 , R 45 , and R 46represents a halogen atom or an aryl group which may have a substituent. The aryl group is, for example, R a and R b In the above, any of the groups exemplified as "any group that does not inhibit the fluorescence of the compound" can be used. In addition, the substituent that the aryl group may have may be any group that does not inhibit the fluorescence of the compound, and for example, 1-6 Alkyl group, C 1-6 In the general formulae (I3-7) to (I3-9) and (I4-7) to (I4-9), R 43 ~R 46 may be different groups, but are preferably all the same type of group. 43 ~R 46 are preferably all the same type of halogen atoms or all the same type of phenyl groups which may have a substituent, more preferably all fluorine atoms or unsubstituted phenyl groups, and particularly preferably all fluorine atoms.

[0168] In general formulas (I3-7) to (I3-9) and (I4-7) to (I4-9), P 15 ~P 16 are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group. 15 ~P 16 C in 1-20 Alkyl group, C 1-20 The alkoxy group, monoalkylamino group, and dialkylamino group are each defined as R g The same things as those listed in (p1)-(p3) and (q1)-(q3) are included. 15 ~P 16 As for C 1-20 Alkyl group, C 1-20An alkoxy group, a (non-substituted) phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group is preferred. From the viewpoint of safety to living bodies, 1-20 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 further have a substituent. However, even if the substituent is a substituent other than these substituents, safety can be improved by introducing a further appropriate substituent, so the substituent is not limited to these substituents.

[0169] In the general formulae (I3-7) to (I3-9) and (I4-7) to (I4-9), n15 and n16 each independently represent an integer of 0 to 3. 15 If there are multiple P 15 may be the same type of functional group or different types of functional groups. 16 The same applies to.

[0170] In the general formulae (I3-7) to (I3-9) and (I4-7) to (I4-9), A 15 ~A 16 are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 It represents a phenyl group which may have 1 to 3 substituents selected from the group consisting of an alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group. 1-20 Alkyl group, C 1-20 The alkoxy group, monoalkylamino group, and dialkylamino group are each defined as R g The same things as those mentioned in (p1)-(p3) and (q1)-(q3) are included. 15 ~A 16 Examples of the alkyl group include an unsubstituted phenyl group, a alkyl group having one or two C 1-20A phenyl group having an alkoxy group as a substituent is preferred, and an unsubstituted phenyl group or a phenyl group having one C 1-20 A phenyl group having an alkoxy group as a substituent is more preferable, and an unsubstituted phenyl group or one C 1-10 A phenyl group having an alkoxy group as a substituent is more preferable. 15 ~A 16 are preferably the same type of functional group.

[0171] The compounds represented by any of the above (I3-1) to (I3-6) and (I4-1) to (I4-6) include compounds represented by any of the following general formulae (6-1) to (6-12) and (7-1) to (7-12). In the general formulae (6-7) to (6-12) and (7-7) to (7-12), Ph means an unsubstituted phenyl group. As the compounds represented by any of the above (I3-1) to (I3-6) and (I4-1) to (I4-6), the compounds represented by the general formulae (6-4), (6-5), (6-7), (6-8), (7-4), (7-5), (7-7), and (7-8) are particularly preferred, and the compounds represented by the general formulae (6-4), (6-5), (6-7), and (6-8) are more preferred.

[0172] In general formulas (6-1) to (6-12), (7-1) to (7-12), P 5 ~P 8 are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 It represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group. 5 ~P 8 C in 1-20 Alkyl group, C 1-20 The alkoxy group, monoalkylamino group, and dialkylamino group are each defined as R g The same things as those listed in (p1)-(p3) and (q1)-(q3) are included. 5 ~P 8 As for C 1-20 Alkyl group, C 1-20An alkoxy group, a (non-substituted) phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group is preferred. From the viewpoint of safety to living bodies, 1-20 Alkyl group, C 1-20 More preferably, it 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, 1-20 Alkyl group or C 1-20 More preferably, it is an alkoxy group, and C 1-10 Alkyl group or C 1-10 An alkoxy group is even more preferable, and these substituents may further have a substituent. However, even if the substituent is a substituent other than these substituents, safety can be improved by introducing a further appropriate substituent, so the substituents are not limited to these substituents.

[0173] In the general formulae (6-1) to (6-12) and (7-1) to (7-12), n5 to n8 each independently represent an integer of 0 to 3. 5 If there are multiple P 5 may be the same type of functional group or different types of functional groups. 6 ~P 8 The same applies to.

[0174] [ka]

[0175] [ka]

[0176] [ka]

[0177] [ka]

[0178] The compounds represented by the general formulas (6-1) to (6-12) and (7-1) to (7-12) include P 5 ~P 8 are independent of each other, C 1-20 Alkyl group or C 1-20 It is preferable that n5 to n8 are each independently 0 to 2. P 5 and P 6 are independent of each other, C 1-20 is an alkyl group, n5 and n6 are each independently 0 to 2, P 7 and P 8 are independent of each other, C 1-20 More preferably, n7 and n8 are each independently 0 to 1. 5 and P 6 are independent of each other, C 1-20 is an alkyl group, n5 and n6 are each independently 1 to 2, P 7 and P 8 are independent of each other, C 1-20 An alkoxy group in which n7 and n8 are 1 is more preferred.

[0179] Specific examples of the compounds represented by the general formulas (6-1) to (6-12) include the compounds represented by the following formulas (6-1-1) to (6-12-1), where "λ" is the peak wavelength of the absorption spectrum of each compound, and "Em" is the peak wavelength of the fluorescence spectrum.

[0180] [ka]

[0181] [ka]

[0182] <Powdered pigment composition> The powdered dye composition according to the present invention is a powdered dye composition comprising the near-infrared fluorescent dye according to the present invention, and has the characteristic that it hardly reflects light having a wavelength in the range of 520 to 560 nm. Specifically, the reflection spectrum of the powdered dye composition according to the present invention is such that (a) there is no peak having a peak top in the range of 520 to 560 nm, or (b) there is a peak having a peak top in the range of 520 to 560 nm, but the value obtained by subtracting the average value of the relative reflectance in the range of 300 to 400 nm from the maximum value of the relative reflectance in the range is 5% or less. Since the powdered dye composition according to the present invention has the above-mentioned characteristic (a) or (b) in its reflection spectrum, it has good dispersibility in resin, and by mixing and dispersing it in resin, it is uniformly dispersed in the resin composition, and aggregates of the near-infrared fluorescent dye are unlikely to occur.

[0183] The reflectance spectrum of the powdered dye composition according to the present invention may be measured by any measuring method as long as it can detect reflected light in the range of 520 to 560 nm of a powder sample. The reflectance spectrum of the powdered dye composition according to the present invention is preferably a spectrum obtained by diffuse reflectance measurement using an integrating sphere with white light (200 to 870 nm) as the measurement light. The diffuse reflectance measurement using an integrating sphere can accurately measure the reflectance (%) of a powdered composition with high scattering properties. The diffuse reflectance measurement using an integrating sphere can be performed by a conventional method using an apparatus equipped with an integrating sphere unit in various ultraviolet-visible spectrophotometers or ultraviolet-visible near-infrared spectrophotometers capable of detecting diffuse reflected light.

[0184] The reflectance obtained by measuring the diffuse reflectance using an integrating sphere is a relative reflectance based on a standard white plate. Examples of commonly used standard white plates include white plates made of materials with high reflectance such as barium sulfate, aluminum oxide, and magnesium oxide. In measuring the powdered dye composition according to the present invention, a suitable standard white plate can be selected from those commonly used.

[0185] The powdered dye composition comprising the near-infrared fluorescent dye according to the present invention hardly reflects light in the range of 300 to 400 nm. Therefore, in the reflection spectrum, the relative reflectance in the range of 300 to 400 nm is almost the lowest value, and no peak is detected in the range. On the other hand, the shape of the reflection spectrum of the near-infrared fluorescent dye according to the present invention changes in the range of 500 to 700 nm depending on the shape of the particles. Among the powdered dye compositions comprising the near-infrared fluorescent dye according to the present invention, if the powder composition has the reflection spectrum having the above-mentioned characteristic (a) or (b), the dispersibility in resin is good. The inventors of the present invention have found for the first time that the shape of the reflection spectrum in the range of 520 to 560 nm is an index of dispersibility in resin.

[0186] In the above characteristic (a), the absence of a peak having a peak top within the range of 520 to 560 nm means that the light within the range of 520 to 560 nm is hardly reflected, and specifically, in the reflection spectrum, the relative reflectance within the range of 520 to 560 nm is almost the lowest value, similar to the relative reflectance within the range of 300 to 400 nm, and no peak is detected within the range. Therefore, the value obtained by subtracting the average value of the relative reflectance within the range of 300 to 400 nm (Rbase) from the maximum value of the relative reflectance within the range of 520 to 560 nm (Rmax (%)) is preferably 1% or less, more preferably 0% or less. In addition, [Rmax (%)] - [Rbase (%)] is preferably -3% or more, more preferably -2% or more, and even more preferably -1% or more.

[0187] In the above characteristic (b), when the maximum value of relative reflectance (Rmax) in the range of 520 to 560 nm minus the average value of relative reflectance (Rbase) in the range of 300 to 400 nm ([Rmax(%)]-[Rbase(%)]) is 5% or less, this means that although reflection is observed in the range of 520 to 560 nm, the reflection is extremely small and can be almost ignored. When the powdered dye composition according to the present invention has characteristic (b), [Rmax(%)]-[Rbase(%)] is preferably 2.5% or less.

[0188] The sizes of the primary particles and the secondary particles (aggregates of the primary particles) of the near-infrared fluorescent dye particles constituting the powdered dye composition according to the present invention are not particularly limited. In the powdered dye composition according to the present invention, it is preferable that the major axis of the near-infrared fluorescent dye particles of 95% or more of the entire composition is 3 μm or less. When the size of the near-infrared fluorescent dye particles in the composition is sufficiently small, the dispersibility in the resin is further improved.

[0189] The major axis of the near-infrared fluorescent dye particles can be determined by measuring the major axis of the particles captured in a transmission electron microscope (TEM) image using image analysis. In the image, a set of parallel lines that has the shortest distance between two parallel lines tangent to the particle's contour is specified, the distance between the parallel lines of the set of parallel lines is the minor axis of the particle, and the straight line connecting the points where the two parallel lines of the set of parallel lines and the contour of the particle intersect is the minor axis of the particle. A set of parallel lines that has the longest distance between two parallel lines that are perpendicular to the minor axis and tangent to the contour of the particle is specified, the distance between the parallel lines of the set of parallel lines is the major axis of the particle, and the straight line connecting the points where the two parallel lines of the set of parallel lines and the contour of the particle intersect is the major axis of the particle. The particle size distribution of the major axis of the near-infrared fluorescent dye particles of each powdery dye composition is preferably determined by measuring 1000 or more particles.

[0190] The near-infrared fluorescent dye according to the present invention can be uniformly dispersed and mixed in the resin component due to its good dispersibility, and aggregates of the near-infrared fluorescent dye that cause appearance defects in molded articles are unlikely to occur. Therefore, the resin composition in which the near-infrared fluorescent dye according to the present invention is dispersed and the molded article processed from the resin composition can stably emit near-infrared fluorescence with a high emission quantum yield, and the occurrence of dot-like or streak-like appearance defects can be suppressed.

[0191] <Method of producing powdered dye composition> A powdered composition having a reflection spectrum with the above-mentioned characteristic (a) or (b) can be produced, for example, by a method including a crystallization step of dissolving the near-infrared fluorescent dye of the present invention in a low-polarity solvent by heating and then slowly cooling to recrystallize the dye, and a powdering step of powdering the crystals obtained in the crystallization step to produce a powdered dye composition.

[0192] In the crystallization step, the solvent used when dissolving the near-infrared fluorescent dye of the present invention by heating is not particularly limited as long as it is a low-polarity solvent. Examples of low-polarity solvents include toluene, xylene, naphthalene, hexane, benzene, tetrachloromethane, etc. In the present invention, toluene and xylene are particularly preferred because they have a relatively high boiling point and are easy to dissolve the near-infrared fluorescent dye of the present invention by heating.

[0193] The low polarity solvent may be a mixed solvent containing a small amount of a polar solvent. The content ratio of the polar solvent to the total amount of the solvent is, for example, preferably 30 v / v% or less, more preferably 20 v / v% or less, and even more preferably 10 v / v% or less. Examples of the polar solvent include methanol, ethanol, propanol, butanol, acetone, formic acid, methyl ethyl ketone, acetonitrile, dimethyl sulfoxide, and dimethylformamide. When the low polarity solvent used in the present invention is a mixed solvent with a polar solvent, a toluene / alcohol mixed solvent containing 30 v / v% or less of an alcohol having 1 to 4 carbon atoms is preferred, and a toluene / alcohol mixed solvent containing 30 v / v% or less of one or more selected from the group consisting of methanol, propanol, and isopropyl alcohol is more preferred.

[0194] In the crystallization step, the temperature at which the near-infrared fluorescent dye is heated and dissolved is not particularly limited as long as it is equal to or lower than the boiling point of the solvent to be dissolved, but is preferably within the range from a temperature 20°C lower than the boiling point of the solvent to be dissolved ([boiling point (°C)]-20°C) to the boiling point, and more preferably within the range from a temperature 10°C lower than the boiling point ([boiling point (°C)]-10°C) to the boiling point. Specifically, the temperature is preferably 50°C or higher, more preferably 60°C or higher, even more preferably 80°C or higher, and even more preferably 90°C or higher.

[0195] The solution in which the near-infrared fluorescent dye is heated and dissolved in a low-polarity solvent is slowly cooled to recrystallize. The recrystallization can be carried out, for example, by leaving the heated solution of the near-infrared fluorescent dye at room temperature and cooling it to about room temperature. The recrystallization can also be carried out by cooling the heated solution of the near-infrared fluorescent dye at a cooling rate of preferably 20° C. / min or less, more preferably 10° C. / min or less, even more preferably 5° C. / min or less, and even more preferably 1° C. / min or less.

[0196] The crystals obtained in the crystallization step are dried and powdered to produce the powdered dye composition of the present invention. The powdering can be carried out by collecting the crystals from the solution in which they are precipitated by filtration, and then drying them. The drying method is not particularly limited, and can be appropriately selected from various drying methods such as natural drying, heat drying, spray drying, and freeze drying.

[0197] <Resin composition> The resin composition according to the present invention contains the near-infrared fluorescent dye and resin according to the present invention, and has a maximum fluorescence wavelength of 650 nm or more. The resin composition according to the present invention is capable of stably emitting near-infrared fluorescence with a high luminescence quantum yield, and is a resin composition in which the generation of aggregates of the near-infrared fluorescent dye is suppressed, and therefore is suitably used as a medical material such as a raw material for medical devices that are used in vivo and for which stability of product quality is highly required.

[0198] The resin composition according to the present invention can be produced by mixing and dispersing the near-infrared fluorescent dye according to the present invention in a resin component. The resin composition according to the present invention may contain only one type of near-infrared fluorescent dye according to the present invention, or may contain two or more types of near-infrared fluorescent dyes.

[0199] The resin component contained in the resin composition according to the present invention is not particularly limited, and can be appropriately selected from known resin compositions or their improvements, taking into consideration the type of near-infrared fluorescent dye to be blended and the product quality required when a molded body is formed. For example, the resin component may be a thermoplastic resin or a thermosetting resin. When used in a molded body, since a thermosetting resin may harden during melt kneading, it is preferable that the resin component contained in the resin composition according to the present invention is a thermoplastic resin. The resin component used in the present invention may be one type only, or two or more types may be mixed and used. When two or more types are mixed, it is preferable to use a combination of resins with high compatibility.

[0200] Examples of the resin component used in the present invention 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 resin; acrylic resins such as polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate (PMMA), and polyethyl methacrylate; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate; polyamide resins such as nylon (registered trademark); polystyrene (PS), imide-modified polystyrene, acrylonitrile-butadiene Examples of suitable resins include polystyrene-based resins such as acrylonitrile-styrene (ABS) resin, imide-modified ABS resin, styrene-acrylonitrile copolymer (SAN) resin, and acrylonitrile-ethylene-propylene-diene-styrene (AES) resin, olefin-based resins such as polyethylene (PE) resin, polypropylene (PP) resin, and cycloolefin resin; cellulose-based resins such as nitrocellulose and cellulose acetate; silicone-based resins; thermoplastic resins such as fluorine-based resins; epoxy-based resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, isocyanurate-based epoxy resin, and hydantoin-based epoxy resin; amino-based resins such as melamine resin and urea resin; phenol-based resins; and thermosetting resins such as unsaturated polyester resin.

[0201] As the resin component contained in the resin composition according to the present invention, since the dispersibility of the near-infrared fluorescent dye according to the present invention is high, the resin component is preferably a fluorine-based resin, a silicone-based resin, a urethane-based resin, an olefin-based resin, a vinyl chloride-based resin, a polyester-based resin, a polystyrene-based resin, a polycarbonate resin, a polyamide-based resin or an acrylic-based resin, and more preferably a urethane-based resin, an olefin-based resin, a polystyrene-based resin, a polyester-based resin and a vinyl chloride-based resin. In particular, when the resin composition according to the present invention is used as a medical material, in consideration of low solubility in body fluids such as blood, difficulty in elution under the use environment and biocompatibility, PTFE, Teflon (registered trademark), silicone, PU, ​​TPU, PP, PE, PC, PET, PS, polyamide, PVC are preferred, and TPU, PU, ​​PP, PE, PET, PS are more preferred.

[0202] In addition, when the resin composition according to the present invention is a thermoplastic resin composition, the resin component may be a thermoplastic resin as a whole, and may contain a small amount of a non-thermoplastic resin. Similarly, when the resin composition according to the present invention is a thermosetting resin composition, the resin component may be a thermosetting resin as a whole, and may contain a small amount of a non-thermosetting resin.

[0203] The content of the near-infrared fluorescent dye according to the present invention in the resin composition is not particularly limited as long as the near-infrared fluorescent dye can be mixed into the resin, but from the viewpoint of the fluorescence intensity and its detection sensitivity, it 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. Since the near-infrared fluorescent dye according to the present invention has a high molar absorption coefficient and a high quantum yield even in the resin, its emission can be sufficiently visually recognized by a camera or the like even if the dye concentration in the resin is relatively low. A low dye concentration is desirable in terms of reducing the possibility of elution, reducing the possibility of bleeding out from a molded product processed from the resin composition, and being able to process a molded product that requires transparency.

[0204] From the viewpoint of detection sensitivity, the content of the near-infrared fluorescent dye according to the present invention in the resin composition is preferably somewhat high. The near-infrared fluorescent dye will undergo concentration quenching in the state of aggregates, but the near-infrared fluorescent dye according to the present invention has good dispersibility in the resin, so that concentration quenching can be avoided even when a relatively large amount of the near-infrared fluorescent dye is contained. The content of the near-infrared fluorescent dye according to the present invention in the resin composition is, for example, preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0205] The method of mixing and dispersing the near-infrared fluorescent dye according to the present invention in the resin component is not particularly limited, and any known method may be used, and additives may be used in combination. For example, the near-infrared fluorescent dye according to the present invention may be added to a resin composition and melt-kneaded to obtain the resin composition according to the present invention. In this way, a resin composition in which the near-infrared fluorescent dye according to the present invention is uniformly dispersed in the resin is obtained. Among these known mixing and dispersing methods, melt-kneading suitable for practical production is preferred.

[0206] The near-infrared fluorescent dye according to the present invention can be mixed and dispersed uniformly in various resin components, and can emit fluorescence with a high quantum yield even in the resin. The reason is not clear, but can be inferred as follows. When dispersing the dye by a method such as melt kneading, it is desirable that the resin and the dye have high compatibility in order to suppress aggregation. The SP value can be cited as one index of whether compatibility is high or not. If the difference between the SP value of the dye and the SP value of the resin is small, compatibility is high and the dye can be dispersed uniformly. On the other hand, even if the SP values ​​are different, it can also be explained by other physical property parameters. For example, the compatibility with the resin can be explained from the calculated values ​​or actual values ​​of the solubility, partition coefficient, relative dielectric constant, polarizability, etc. of the dye. In addition, the compatibility of the resin and the fluorescent dye may differ depending on the crystallinity of the resin.

[0207] In addition, the compatibility between the resin and the fluorescent dye can be controlled by the functional group of the fluorescent dye molecule itself. For example, when dispersing in a fat-soluble (hydrophobic) polyolefin resin such as polypropylene or polyethylene, it is preferable that the fluorescent dye molecule has a hydrophobic group. For example, by introducing a hydrophobic group such as an alicyclic alkyl group, a long-chain alkyl group, a halogenated alkyl group, or an aromatic ring into the dye molecule, the compatibility with the resin can be improved. However, it is not limited to these functional groups. Furthermore, when dispersing in a highly polar resin such as polyurethane or polyamide, it is preferable that the fluorescent dye molecule has a hydrophilic group such as a carboxyl group, a hydroxyl group, an amino group, an alkoxy group, an aryloxy group, an alkylamino group, an ester, or an amide. However, it is not limited to these.

[0208] In order to improve compatibility with resins, it is necessary to suppress the aggregation of dye molecules. In the case of fluorescent dyes, aromatic rings and heterocyclic rings are introduced into the molecules to ensure the extension of the conjugated system and flatness. However, the introduction of these rings makes the molecules highly flat and prone to stacking, which makes them prone to aggregation. The near-infrared fluorescent dye of the present invention has a dye skeleton consisting of a wide conjugated plane centered on a boron atom, so it is prone to aggregation, but the aggregation of the dye is suppressed by polarizing it by introducing an electron-donating group or an electron-withdrawing substituent, or by introducing a bulky functional group, and it is presumed that compatibility with various resins has been achieved.

[0209] The partition coefficient and SP value, which are indicators of compatibility, can be estimated as the water / octanol partition coefficient and Hildebrand SP value from the "Hansen solubility parameter" calculated using commercially available software. For example, the partition coefficients and SP values ​​of the compounds represented by the following compounds (8-1) to (8-8) among the near-infrared fluorescent dyes according to the present invention are as follows:

[0210] [ka]

[0211] The resin composition according to the present invention does not change color when visually observed even when excited by excitation light in the near-infrared region, and emits invisible fluorescence in the near-infrared region, which can be detected by a detector. Therefore, the resin composition according to the present invention may have a maximum absorption wavelength of 600 nm or more for excitation light in the near-infrared region, but from the viewpoint of absorption efficiency, it is preferable that the maximum absorption wavelength is close to the wavelength of the excitation light, more preferably 650 nm or more, and particularly preferably 680 nm or more. Furthermore, when used as a medical device such as an implant, it is preferably 700 nm or more.

[0212] When using a general luminescence detector equipped with a filter for cutting noise due to excitation light, if the difference between the maximum absorption wavelength and the maximum fluorescence wavelength of the resin composition according to the present invention (Stokes shift) is small, the fluorescence is cut by the filter, making it difficult to detect with high sensitivity. Therefore, the resin composition according to the present invention preferably has a difference between the maximum absorption wavelength and the maximum fluorescence wavelength of 10 nm or more, more preferably 20 nm or more. The larger the Stokes shift, the more sensitive the fluorescence emitted from the molded product can be detected, even when using a general detector equipped with a filter for cutting noise due to excitation light.

[0213] However, even if the Stokes shift is small, the near-infrared fluorescence from the resin composition according to the present invention can be detected with high sensitivity under the following conditions. For example, if the fluorescence can be excited with light having a wavelength shorter than the maximum absorption wavelength, it is possible to detect the fluorescence even with noise cut. In addition, if the fluorescence spectrum is broad, it is possible to detect the fluorescence sufficiently even with noise cut. On the other hand, some fluorescent dyes have multiple fluorescence peaks. In that case, even if the Stokes shift is small, if there is a fluorescence peak (second peak) on the longer wavelength side, it is possible to detect it with high sensitivity even when a detector equipped with a noise cut filter is used. When the resin composition according to the present invention has multiple fluorescence, the difference between the fluorescence peak wavelength on the longer wavelength side and the maximum absorption wavelength may be 30 nm or more, and preferably 50 nm or more. In addition, if the excitation light source, cut filter, etc. are appropriately selected, the above conditions are not limited.

[0214] The resin composition according to the present invention and the molded article obtained from the composition have a maximum fluorescent wavelength of 650 nm or more. In consideration of the color of the irradiated object not changing and the detection sensitivity, there is no practical problem if the maximum fluorescent wavelength is 650 nm or more, but it is preferably 700 nm or more, and more preferably 720 nm or more. When there are multiple fluorescent peaks, even if the wavelength of the maximum fluorescent peak is 720 nm or less, it is sufficient as long as there is a fluorescent peak with sufficient detection sensitivity at 740 nm or more. In that case, the intensity of the fluorescent peak on the long wavelength side (second peak) is preferably 5% or more, more preferably 10% or more, of the intensity of the maximum fluorescent wavelength.

[0215] The resin composition according to the present invention and the molded article obtained from the composition preferably have strong absorption in the range of 650nm to 1500nm and emit strong fluorescence in this range. Light of 650nm or more is less affected by hemoglobin, and light of 1500nm or less is less affected by water. In other words, light in the range of 650nm to 1500nm has high skin permeability and is less affected by impurities in the living body, so it is suitable as a wavelength region of light used to visualize medical implants embedded subcutaneously, etc. When the maximum absorption wavelength and maximum fluorescence wavelength are in the range of 650nm to 1500nm, the resin composition according to the present invention and the molded article obtained from the composition are suitable for detection by light in the range of 650nm to 1500nm, and are suitable as medical devices, etc. used in the living body.

[0216] The resin composition according to the present invention may contain other components in addition to the resin component and the near-infrared fluorescent dye, so long as the effects of the present invention are not impaired. Examples of the other components include ultraviolet absorbers, heat stabilizers, light stabilizers, antioxidants, flame retardants, flame retardant assistants, crystallization accelerators, plasticizers, antistatic agents, colorants, and mold release agents.

[0217] <Molded body> By processing the resin composition according to the present invention, a molded article that can be detected by near-infrared fluorescence can be obtained. The molding method is not particularly limited, but examples thereof include casting (casting method), injection molding using a mold, compression molding, extrusion molding using a T-die or the like, and blow molding.

[0218] In the manufacture of a molded body, the molded body may be formed only from the resin composition according to the present invention, or the resin composition according to the present invention and other resin compositions may be used as raw materials. For example, the entire molded body may be molded from the resin composition according to the present invention, or only a part of the molded body may be molded from the resin composition according to the present invention. The resin composition according to the present invention is preferably used as a raw material constituting the surface part of the molded body. For example, when molding a catheter, only the tip part of the catheter is molded from the resin composition according to the present invention, and the remaining part is molded from a resin composition not containing a near-infrared fluorescent dye, thereby producing a catheter in which only the tip part emits near-infrared fluorescence. In addition, a molded body that emits near-infrared fluorescence in a stripe shape can be produced by alternately laminating and molding the resin composition according to the present invention and a resin composition not containing a near-infrared fluorescent dye. In addition, a surface coating may be performed to improve the visibility of the molded body.

[0219] Fluorescence detection can be performed in a conventional manner using a commercially available fluorescence detection device, etc. As the excitation light used for fluorescence detection, any light source can be used, and in addition to a near-infrared lamp with a long wavelength range, a laser with a narrow wavelength range, an LED, etc. can be used.

[0220] A molded article obtained from a resin composition containing the near-infrared fluorescent dye of the present invention does not change color when irradiated with light in the near-infrared region and emits near-infrared fluorescence that can be detected with higher sensitivity than conventional molded articles, making the molded article particularly suitable for medical devices, at least a part of which will be inserted or left in the patient's body.

[0221] Examples of the medical device include stents, coil obturators, catheter tubes, medical clips, injection needles, indwelling needles, ports, shunt tubes, drain tubes, implants, etc. Examples of the catheter tube include ureteral / urethral catheters, bile duct catheters, vascular catheters, etc. Examples of the medical clips include digestive tract clips, etc.

[0222] When detecting the fluorescence of a molded article obtained from a resin composition containing the near-infrared fluorescent dye according to the present invention, it is preferable to irradiate it with excitation light in the near-infrared region, but if it does not matter if the color of the irradiated object is somewhat reddish, it is not necessary to use excitation light in the near-infrared region. For example, when attempting to detect the fluorescence of a medical device inside the body by irradiating it with excitation light, it is necessary to use excitation light in a wavelength region that is highly permeable to living organisms such as the skin, and in this case, excitation light of 650 nm or more that is highly permeable to living organisms may be used. EXAMPLES

[0223] 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.

[0224] [Synthesis Example 1] Synthesis of near-infrared fluorescent dye A1 Under an argon atmosphere, 4-methoxyphenylboronic acid (2.99 g, 19.7 mmol) was placed in a 500 mL three-neck flask and dissolved in toluene (120 mL). Then, [1,1'-bis(diphenylphosphino)-ferrocene]palladium(II) dichloride-dichloromethane complex (1:1) (100 mg), 30 mL of ethanol, 5-bromo-2-furaldehyde (3.46 g, 19.8 mmol) and 2 mol / L aqueous sodium carbonate solution (20 mL) were added and stirred at 80° C. for 14 hours. After the reaction was completed, the organic phase was washed with water and saturated saline, dried over anhydrous sodium sulfate, and the desiccant was filtered off and the solvent was concentrated under reduced pressure. The obtained crude product was separated and purified by flash silica gel chromatography (eluent: hexane / ethyl acetate = 19 / 1 → 4 / 1) to obtain 5-(4-methoxyphenyl)-furan-2-carbaldehyde (a-1) as a pale yellow liquid (yield: 3.39 g, 84.8%).

[0225] Next, in a 1L three-neck flask, compound (a-1) (3.39 g, 16.8 mmol) and ethyl azide acetate (8.65 g, 67.0 mmol) were dissolved in ethanol (300 mL) under an argon atmosphere, and then 20 mass% sodium ethoxide ethanol solution (22.8 g, 67.0 mmol) was slowly dropped into the resulting solution in a 0°C ice bath and stirred for 2 hours. After the reaction was completed, a saturated aqueous ammonium chloride solution was added to adjust the pH to a weak acidic state, and water was added and suction filtration was performed. The resulting filtrate was dried to obtain a yellow solid of 2-azido-3-[5-(4-methoxyphenyl)-furan-2-yl]-acrylic acid ethyl ester (a-2) (yield: 3.31 g, yield: 63.1%).

[0226] Further, compound (a-2) (3.31 g, 10.6 mmol) was placed in a 200 mL eggplant flask, dissolved in toluene (60 mL), and stirred under reflux for 1.5 hours. The solution after reflux was concentrated under reduced pressure, and the resulting crude product was recrystallized (solution: hexane, ethyl acetate), suction filtered, and the residue was dried to obtain brown crystals of 2-(4-methoxyphenyl)-4H-furo[3.2-b]pyrrole-5-carboxylic acid ethyl ester (a-3) (yield: 2.32 g, yield: 76.8%).

[0227] Next, compound (a-3) (1.90 g, 6.66 mmol) was placed in a 300 mL flask, and an aqueous solution of ethanol (60 mL) and sodium hydroxide (3.90 g, 97.5 mmol) dissolved in 30 mL of water was added, followed by reflux stirring for 1 hour. After reflux stirring, the solution was allowed to cool, and then 6 mol / L aqueous hydrochloric acid was added to adjust the solution to acidity, after which water was added and suction filtration was performed. The resulting filtrate was dried in vacuum to obtain a gray solid of 2-(4-methoxyphenyl)-4H-furo[3.2-b]pyrrole-5-carboxylic acid (a-4) (yield: 1.56 g, yield: 91%).

[0228] Next, compound (a-4) (327 mg, 5.52 mmol) and trifluoroacetic acid (16.5 mL) were placed in a 200 mL three-neck flask and stirred at 45° C. After compound (a-4) was dissolved, the mixture was stirred for 15 minutes until the foaming subsided. Trifluoroacetic anhydride (3.3 mL) was added to the stirred solution and reacted at 80° C. for 1 hour. After the reaction was completed, a saturated aqueous solution of sodium bicarbonate and ice were added to neutralize the solution, followed by suction filtration and drying the residue in vacuum to obtain a black solid of compound (a-5) (yield: 320 mg). Compound (a-5) was used in the next reaction as it was without purification.

[0229] Compound (a-5) (320 mg) was placed in a 200 mL three-neck flask under an argon atmosphere, and toluene (70 mL), triethylamine (1.0 mL), and boron trifluoride diethyl ether complex (1.5 mL) were added dropwise, followed by heating to reflux for 30 minutes. After the reaction was completed, a saturated aqueous solution of sodium bicarbonate was added, and the organic phase was recovered. The organic phase was washed with water and saturated saline, then dried over anhydrous magnesium sulfate, and the desiccant was filtered off and the solvent was concentrated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: toluene / ethyl acetate = 20 / 1 (volume ratio)), and a powder composition consisting of green crystals of near-infrared fluorescent dye A1 was obtained (yield: 20 mg, yield: 6%).

[0230] [ka]

[0231] [Synthesis Example 2] Synthesis of near-infrared fluorescent dye B1 The near-infrared fluorescent dye B1 was prepared as follows, with reference to Organic Letters, 2012, vol. 4, pp. 2670-2673 and Chemistry A European Journal, 2009, vol. 15, pp. 4857-4864.

[0232] 4-Hydroxybenzonitrile (25.3 g, 212 mmol), acetone 800 mL, potassium carbonate (100 g, 724 mmol), and 1-bromooctane (48 g, 249 mmol) were placed in a 2 L four-neck flask and heated to reflux overnight. After filtering the inorganic salts, acetone was removed under reduced pressure, ethyl acetate was added to the resulting residue, the organic layer was washed with water and saturated saline, and treated with anhydrous magnesium sulfate. Magnesium sulfate was filtered off, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain a colorless, transparent liquid of 4-octoxybenzonitrile (b-1) (yield: 45.2 g, yield: 92%).

[0233] Next, under an argon atmosphere, tert-butyloxypotassium (25.18 g, 224.4 mmol) and 160 mL of tert-amyl alcohol were placed in a 500 mL four-neck flask. A solution of the previously synthesized compound (b-1) (14.8 g, 64 mmol) mixed with 7 mL of tert-amyl alcohol was added thereto. A solution of succinic acid diisopropyl ester (6.5 g, 32 mmol) mixed with 10 mL of tert-amyl alcohol was added dropwise over about 3 hours under heating and refluxing, and after the dropwise addition was completed, the mixture was heated and refluxed for 6 hours. After returning to room temperature, the highly viscous reaction solution was placed in a solution of acetic acid:methanol:water = 1:1:1, and heated and refluxed for several minutes, causing a red solid to precipitate. The solid was filtered off and washed with heated methanol and water to give a red solid of 3,6-(4-octyloxyphenyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (b-2) (yield: 5.6 g, 32%).

[0234] In addition, 4-tert-butylaniline (10 g, 67 mmol), acetic acid 70 mL, and sodium thiocyanate (13 g, 160 mmol) were placed in a 200 mL three-neck flask. While keeping the temperature in the system at 15°C or less, bromine (4.5 mL, 87 mmol) was added dropwise over about 20 minutes, and then the mixture was stirred at 15°C or less for 3.5 hours. The reaction solution was added to 150 mL of 28% ammonia water, stirred for a while, and the precipitated solid was filtered off. The solid was extracted with diethyl ether, and the organic layer was washed with water. After concentrating the diethyl ether under reduced pressure, the residue was purified by silica gel column chromatography (eluent: dichloromethane / ethyl acetate) to obtain 2-amino-6-tert-butylbenzothiazole (b-3) as a pale yellow solid (yield: 10.32 g, yield: 69%).

[0235] Next, potassium hydroxide (75.4 g, 1340 mmol) and ethylene glycol (175 mL) were placed in a 1 L four-neck flask under water cooling. The system was placed under an argon atmosphere, and compound (b-3) (7.8 g, 37.8 mmol) was placed in the system. In order to remove oxygen from the system, argon was bubbled into the system, and the system was reacted at 110°C for 18 hours. The reaction solution was cooled to below 40°C with water, and 2 mol / L hydrochloric acid that had been bubbled with argon in advance was dropped into the system to neutralize the system (pH about 7). The precipitated white solid was filtered, washed with water, and then dried under reduced pressure. The white solid was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain a white solid of 4-tert-butyl-2-mercaptoaniline (b-4) (yield: 2.39 g, yield: 35%).

[0236] Furthermore, acetic acid (872 mg, 14.5 mmol) and 30 mL of acetonitrile were placed in a 100 mL three-neck flask, and the system was placed under an argon atmosphere. Under an argon atmosphere, malononitrile (2.4 g, 36.3 mmol) and compound (b-4) (2.39 g, 13.2 mmol) were added, and the mixture was heated under reflux for 2 hours. The acetonitrile was removed under reduced pressure, the residue was dissolved in ethyl acetate, the organic layer was washed with water and saturated saline, and treated with anhydrous magnesium sulfate. The magnesium sulfate was filtered off, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain a pale yellow solid of 2-(6-tert-butylbenzothiazol-2-yl)acetonitrile (b-5) (yield: 1.98 g, yield: 65%).

[0237] Subsequently, compound (b-2) (1.91 g, 3.5 mmol), compound (b-5) (1.77 g, 7.68 mmol), and 68 mL of toluene were added to a 200 mL three-neck flask under an argon atmosphere, and the mixture was heated to reflux. Under heating to reflux, phosphorus oxychloride (2.56 mL, 27.4 mmol) was added dropwise with a syringe, and the mixture was heated to reflux for another 2 hours. After the reaction was completed, 40 mL of dichloromethane and 40 mL of saturated aqueous sodium bicarbonate solution were added while cooling with ice, and the mixture was extracted with dichloromethane. The organic layer was treated with anhydrous magnesium sulfate, the magnesium sulfate was filtered off, 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: hexane / dichloromethane) to obtain a green solid of precursor (b-6) (yield: 1.56 g, yield: 46%).

[0238] Finally, in an argon atmosphere, precursor (b-6) (1.52 g, 1.57 mmol), toluene 45 mL, triethylamine (4.35 mL, 31.4 mmol), and boron trifluoride diethyl ether complex (7.88 mL, 62.7 mmol) were added to a 200 mL three-neck flask, and the mixture was heated under reflux for 1 hour. The reaction solution was ice-cooled, and the precipitated solid was filtered off, washed with water, a saturated aqueous solution of sodium bicarbonate, a 50% aqueous solution of methanol, and methanol, and dried under reduced pressure. The resulting residue was dissolved in toluene, and methanol was added to precipitate the mixture, yielding a powder composition consisting of a dark green solid of near-infrared fluorescent dye B1 (yield: 1.25 g, yield: 75%).

[0239] 1 H-NMR (300MHz, CDCl3): δ7.90ppm(d, 2H), 7.72-7.69(m, 6H), 7.51(dd, 2H), 7.08( d, 2H), 4.07(t, 4H), 1.84(m, 4H), 1.52(s, 18H), 1.35-1.32(m, 24H), 0.92(t, 6H).

[0240] [ka]

[0241] [Synthesis Example 3] Synthesis of near-infrared fluorescent dye C1 Near-infrared fluorescent dye C1 was synthesized according to the method described in Journal of Organic Chemistry, 2011, Vol. 76, pp. 4489-4505.

[0242] In a 500mL four-neck flask, 2-ethylthiophene (11.2g, 100mmol) and dehydrated THF (80mL) were added under argon gas flow, and the mixture was stirred at -78℃. n-Butyllithium (68.8mL, 1.6mol / L hexane solution) was added dropwise to this solution, and the mixture was stirred at the same temperature for 1 hour, after which a dehydrated THF solution (50mL) of ethyl chloroformate (10.9mL, 120mmol) was added dropwise and stirred for another 1 hour. After the reaction solution was returned to room temperature, a saturated aqueous ammonium chloride solution (110mL) was added, and the mixture was extracted with dichloromethane. The organic phase was washed with water and saturated saline in that order, dried over anhydrous magnesium sulfate, and then concentrated. The residue was separated and purified by silica gel chromatography (eluent: dichloromethane / cyclohexane = 6 / 4 (volume ratio)), and a colorless liquid of 5-ethylthiophene-2-carboxylate (c-1) was obtained (yield: 15.4g, yield: 83.7%).

[0243] Next, compound (c-1) (15.0 g, 81.5 mmol) and ethanol (40 mL) were added to a 200 mL four-neck flask, and hydrazine monohydrate (12.2 g, 244 mmol) was added dropwise to this solution, followed by reflux stirring for 12 hours. After cooling the reaction solution, the solvent was distilled off under reduced pressure, and the residue was dissolved in dichloromethane, washed with water and saturated saline in that order, dried over anhydrous magnesium sulfate, and then concentrated. The residue was recrystallized with cyclohexane, collected by filtration, and dried to obtain a white solid of 5-ethylthiophene-2-carbohydrazine (c-2) (yield: 8.6 g, yield: 62.1%).

[0244] Furthermore, compound (c-2) (8.5 g, 50 mmol) and 2-hydroxy-4-methoxyacetophenone (7.5 g, 50 mmol) were added to a 50 mL three-neck flask and stirred at 75° C. for 1 hour. The residue was recrystallized from dichloromethane / methanol, collected by filtration, and dried to obtain a white solid of (E)-5-ethyl-N'-(1-(2-hydroxy-4-methoxyphenyl)ethylidene)-thiophene-2-carbohydrazine (c-3) (yield: 12.4 g, 78%).

[0245] Next, compound (c-3) (9.5 g, 29.8 mmol) and THF (300 mL) were added to a 500 mL four-neck flask and dissolved, and then lead acetate (15.9 g, 35.9 mmol) was added to this solution and stirred at room temperature for 1 hour. After filtering the reaction solution, the filtrate was concentrated under reduced pressure, and the resulting residue was extracted with water / dichloromethane. The organic phase was washed with water and saturated saline in that order, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residue was separated and purified by alumina chromatography (eluent: dichloromethane / cyclohexane = 4 / 6 (volume ratio)), and a white solid of (5-ethyl-2-thienyl)(2-acetyl-5-methoxy-1-phenyl)ketone (c-4) was obtained (yield: 7.6 g, 88.6%).

[0246] Further, in a 500mL four-neck flask, compound (c-4) (6.6g, 22.8mmol), acetic acid (48mL), and ethanol (240mL) were added under argon gas flow and stirred at 65°C. Ammonium chloride (1.22g, 22.8mmol) and ammonium acetate (10.7g, 139mmol) were added to this solution, and the mixture was refluxed and stirred for 30 minutes. After filtering the reaction solution, the filtrate was concentrated under reduced pressure, and the resulting residue was extracted with water / dichloromethane. The organic phase was washed with water and saturated saline in that order, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residue was separated and purified by silica gel chromatography (eluent: dichloromethane) to obtain a dark blue solid of compound (c-5) (yield: 2.1g, yield: 35.2%).

[0247] Finally, under an argon atmosphere, compound (c-5) (2.0 g, 3.8 mmol) and dichloromethane (250 mL) were added to a 2 L flask and stirred at room temperature for 5 minutes. N,N-diisopropylethylamine (1.48 g, 11.5 mmol) and boron trifluoride diethyl ether complex (3.27 g, 23 mmol) were added dropwise and stirred at room temperature for 1 hour. The reaction solution was concentrated, and the residue was separated and purified by silica gel column chromatography (eluent: dichloromethane) to obtain a powder composition consisting of a dark green solid of near-infrared fluorescent dye C1 (yield: 1.66 g, yield: 76%).

[0248] 1H-NMR (300MHz, CDCl3 / CCl4=1 / 1): δ7.85(s,2H), δ7.64(d,2H), δ7.39(s,1H) ,δ7.29(s,2H),δ6.98(m,4H),δ3.86(s,6H),δ2.98(q,4H),δ1.43(t,6H)ppm.

[0249] [ka]

[0250] [Synthesis Example 4] Synthesis of near-infrared fluorescent dye D1 Near-infrared fluorescent dye D1 was synthesized according to the method described in Chemistry An Asian Journal, 2013, Vol. 8, pp. 3123-3132.

[0251] In a 2L four-neck flask, 5-bromo-2-thiophene carboxaldehyde (19.1g, 0.1mol) and ethyl azidoacetate (51.6g, 0.4mol) were dissolved in ethanol (800mL) under an argon stream, and then 20% by mass sodium ethoxide ethanol solution (136g, 0.4mol) was slowly added dropwise to the resulting solution in a 0°C ice bath and stirred for 2 hours. After the reaction was completed, a saturated aqueous ammonium chloride solution was added to adjust the pH to weak acidity. Furthermore, water was added, and the precipitate was collected by filtration and dried to obtain a yellow solid of 2-azido-3-(5-bromo-thiophen-2-yl)-acrylic acid ethyl ester (yield: 18.4g, yield: 61.3%).

[0252] Next, 2-azido-3-(5-bromo-thiophen-2-yl)-acrylic acid ethyl ester (18.1 g, 60 mmol) was placed in a 500 mL eggplant flask, dissolved in o-xylene (200 mL), and stirred under reflux for 1.5 hours. The solution after reflux stirring was concentrated under reduced pressure, and the resulting crude product was recrystallized (solution: hexane, ethyl acetate), then suction filtered, and the resulting filter cake was dried to obtain 2-bromo-4H-thieno[3.2-b]pyrrole-5-carboxylic acid ethyl ester (d-1) (yield: 12.1 g, yield: 73.8%).

[0253] Further, compound (d-1) (6.0 g, 22 mmol) was placed in a 500 mL flask, and an aqueous solution of ethanol (200 mL) and sodium hydroxide (12.4 g, 310 mmol) dissolved in 100 mL of water was added, followed by refluxing and stirring for 1 hour. After refluxing and stirring, the solution was allowed to cool, and then 6 mol / L hydrochloric acid was added to adjust it to an acidic state. Water was then added, and the mixture was subjected to suction filtration. The residue was dried in vacuum to obtain a gray solid of 2-bromo-4H-thieno[3.2-b]pyrrole-5-carboxylic acid (d-2) (yield: 4.1 g, yield: 75.8%).

[0254] Next, compound (d-2) (4.0 g, 16.3 mmol) and trifluoroacetic acid (100 mL) were placed in a 300 mL three-neck flask and stirred at 40° C. After compound (d-2) was dissolved, the mixture was stirred for 15 minutes until the foaming subsided. Trifluoroacetic anhydride (36 mL) was added to the stirred solution and reacted at 80° C. for 4 hours. After the reaction was completed, the reaction solution was added to a saturated aqueous sodium bicarbonate solution containing ice to neutralize the solution, followed by suction filtration and vacuum drying to obtain a crude product of compound (d-3).

[0255] Further, under an argon atmosphere, compound (d-3) and dichloromethane (1L) were added to a 2L flask and stirred at room temperature for 5 minutes. Triethylamine (12mL) and boron trifluoride diethyl ether complex (16mL) were added dropwise and stirred at room temperature for 1 hour. The reaction solution was concentrated, and the residue was separated and purified by silica gel column chromatography (eluent: dichloromethane) to obtain a dark blue-green solid of 2,8-dibromo-11-trifluoromethyl-dithieno[2,3-b][3,2-g]-5,5-difluoro-5-bora-3a,4a-dithio-s-indacene (d-4) (yield: 580mg, yield: 13.4%).

[0256] Finally, under an argon stream, compound (d-4) (200 mg, 0.378 mmol), 4-methoxyphenylboronic acid (240 mg, 1.6 mmol), sodium carbonate (120 mg, 1.2 mmol), and toluene / THF / water = 1:1:1 (60 mL) were added to a 200 mL three-neck flask, and argon gas was bubbled for 30 minutes, after which tetrakis(triphenylphosphine)palladium(0) (22 mg) was added and the coupling reaction was carried out at 80 ° C for 4 hours. After cooling, 10 mL of water was added to the reaction solution, and it was extracted three times with diethyl ether. The obtained organic phase was washed with water and saturated saline, then dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography (eluent: toluene / ethyl acetate = 20 / 1 (volume ratio)), and a powder composition consisting of dark green crystals of near-infrared fluorescent dye D1 was obtained (yield: 110 mg, yield: 49.8%).

[0257] 1 H-NMR (300MHz, CD2Cl2): δ7.76(d,4H), δ7.34(s,2H), δ7.32(s,2H), δ7.03(d,4H), δ3.91(s,6H)ppm.

[0258] [ka]

[0259] [Synthesis Example 5] Synthesis of near-infrared fluorescent dye E1 The same procedure as in Synthesis Example 4 was carried out except that thiophene-2-boric acid (205 mg, 1.6 mmol) was used instead of 4-methoxyphenylboric acid in the coupling reaction of Synthesis Example 4, thereby obtaining a powder composition consisting of deep green crystals of the near-infrared fluorescent dye E1 (yield: 94 mg, yield: 46.4%).

[0260] 1 H-NMR (300MHz, CD2Cl2): δ7.57(m,4H), δ7.54(d,2H), δ7.53(s,2H), δ7.34(s,2H), δ7.24(m,2H)ppm.

[0261] [ka]

[0262] [Synthesis Example 6] Synthesis of near-infrared fluorescent dye F1 The near-infrared fluorescent dye F1 was prepared as follows, with reference to Organic Letters, 2012, vol. 4, pp. 2670-2673 and Chemistry A European Journal, 2009, vol. 15, pp. 4857-4864.

[0263] 4-tert-butylaniline (29.8 g, 0.2 mol) and 6 mol / L hydrochloric acid (100 mL) were added to a 300 mL three-neck flask, and crotonaldehyde (15.4 g, 0.22 mol) was added dropwise while refluxing, and the mixture was refluxed for another 2 hours. The reflux was stopped, and zinc chloride (27.2 g, 0.2 mol) was added to the reaction solution in the 300 mL three-neck flask while it was still hot, and the mixture was stirred at room temperature overnight. The supernatant was removed, and isopropyl alcohol was added to the yellow syrup-like residue, and the mixture was refluxed for 2 hours. The resulting mixture was cooled to 70°C, petroleum ether (200 mL) was added, and the precipitated crystals were collected by filtration, washed with diethyl ether, and then dried to obtain a zinc complex. This zinc complex was added to a mixture of water / ammonia (120 mL / 60 mL) and extracted three times with diethyl ether (80 mL). The obtained organic layer was dried over anhydrous magnesium sulfate and then concentrated to obtain 6-tert-butyl-2-methyl-quinoline (f-1) as a yellow liquid (yield: 16.2 g, 41%).

[0264] Next, compound (f-1) (16.0 g, 80 mmol) and chloroform (50 mL) were added to a 200 mL two-neck flask and stirred, and trichloroisocyanuric acid (6.52 g, 28 mmol) was added in portions. The resulting mixture was refluxed for 1 hour, and the precipitated solid was filtered and washed with chloroform. The resulting organic layer was extracted three times with 1 mol / L sulfuric acid. The collected aqueous layers were combined, adjusted to pH 3 with an aqueous sodium carbonate solution, and extracted three times with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate and concentrated to obtain pale yellow crystals of 2-chloromethyl-6-tert-butyl-quinoline (f-2) (yield 4.8 g, 25.7%).

[0265] Furthermore, compound (f-2) (4.7 g, 20 mmol), sodium cyanide (1.47 g, 30 mmol), a small amount of sodium iodide, and DMF (50 mL) were placed in a 100 mL three-neck flask and reacted at 60° C. for 2 hours. After cooling the reaction solution, it was extracted with water (200 mL) / ethyl acetate (300 mL), and the obtained ethyl acetate layer was further washed with water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized from petroleum ether to obtain yellow crystals of 2-(6-tert-butylquinolin-2-yl)acetonitrile (f-3) (yield 1.9 g, 42.4%).

[0266] Subsequently, under an argon atmosphere, the compound (b-2) (2.18 g, 4.0 mmol) obtained in Synthesis Example 2, the compound (f-3) (1.9 g, 8.5 mmol), and dehydrated toluene (68 mL) were added to a 200 mL three-neck flask and heated to reflux. Under heating to reflux, phosphorus oxychloride (2.62 mL, 28 mmol) was added dropwise with a syringe, and the mixture was heated to reflux for another 2 hours. After the reaction was completed, dichloromethane (40 mL) and a saturated aqueous solution of sodium bicarbonate (40 mL) were added while cooling with ice, and the mixture was extracted with dichloromethane. The organic layer was treated with anhydrous magnesium sulfate, and the magnesium sulfate was filtered off, and 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: hexane / dichloromethane) to obtain a green solid of precursor (f-4) (yield: 1.84 g, 48%).

[0267] Finally, in an argon stream, precursor (f-4) (1.72 g, 1.8 mmol), toluene (45 mL), triethylamine (4.35 mL, 31.4 mmol), and boron trifluoride diethyl ether complex (7.88 mL, 62.7 mmol) were added to a 200 mL three-neck flask, and the mixture was heated to reflux for 1 hour. The reaction solution was ice-cooled, and the precipitated solid was filtered off. The solid was washed with water, a saturated aqueous solution of sodium bicarbonate, a 50% aqueous solution of methanol, and methanol, and then dried under reduced pressure. The resulting residue was dissolved in toluene, and methanol was added to cause precipitation, yielding a powder composition consisting of a green solid of near-infrared fluorescent dye F1 (yield: 1.10 g, yield: 58%).

[0268] 1 H-NMR (300MHz, CDCl3): δ=8.42(m, 2H), 8.14(d, 2H), 7.74(dd, 2H), 7.72(d, 4H), 7.66(m, 4H), 7.06 (m, 4H), 4.08(t, 4H), 1.85(m, 4H), 1.53(m, 4H), 1.45-1.2(m, 16H), 1.36(s, 18H), 0.91(t, 6H)ppm.

[0269] [ka]

[0270] [Synthesis Example 7] Synthesis of near-infrared fluorescent dye G1 The near-infrared fluorescent dye G1 was prepared as follows, with reference to Organic Letters, 2012, vol. 4, pp. 2670-2673 and Chemistry A European Journal, 2009, vol. 15, pp. 4857-4864.

[0271] Under an argon atmosphere, sodium hydride (60% dispersion, liquid paraffin) (4.0 g, 100 mmol) and dehydrated DMF (40 mL) were added to a 200 mL three-neck flask and cooled to 0°C. Cyanoacetic acid tert-butyl ester (11.9 g, 85 mmol) was slowly added while stirring at the same temperature, and the mixture was stirred at room temperature for 1 hour. Then, 2-chloro-4,6-dimethylpyrimidine (10 g, 70 mmol) was added, and the mixture was reacted at 90°C for 36 hours. The reaction solution was poured into an Erlenmeyer flask containing a 5% aqueous sodium chloride solution (200 ml) and neutralized with acetic acid. The precipitated yellow precipitate was collected by filtration, washed with water, and then dried to obtain cyano-(4,6-dimethyl-pyrimidin-2-yl)acetic acid tert-butyl ester (g-1) (yield 9.8 g, 56.9%).

[0272] Next, compound (g-1) (9.8 g, 40 mmol), dichloromethane (60 mL), and trifluoroacetic acid (30 mL) were added to a 300 mL three-neck flask and reacted overnight at room temperature. The reaction solution was neutralized with a saturated aqueous sodium carbonate solution, and the dichloromethane layer was separated and washed with water. The organic layer was dried over anhydrous magnesium sulfate and concentrated to obtain a residue, which was purified by column chromatography (petroleum ether / ethyl acetate=1 / 5) to obtain white crystals of (4,6-dimethyl-pyrimidin-2-yl)acetonitrile (g-2) (yield 0.85 g, 14.5%).

[0273] Subsequently, under an argon atmosphere, the compound (b-2) (1.36 g, 2.5 mmol) obtained in Synthesis Example 2, the compound (g-2) (0.81 g, 5.5 mmol), and dehydrated toluene (50 mL) were added to a 200 mL three-neck flask and heated under reflux. Under heating under reflux, phosphoryl chloride (2.34 mL, 25 mmol) was added dropwise with a syringe, and the mixture was heated under reflux for another 2 hours. After the reaction was completed, dichloromethane (40 mL) and a saturated aqueous solution of sodium bicarbonate (40 mL) were added while cooling with ice, and the mixture was extracted with dichloromethane. The organic layer was treated with anhydrous magnesium sulfate, and the magnesium sulfate was filtered off, and 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 / ethyl acetate = 50 / 1) to obtain a green solid of precursor (g-3) (yield: 0.54 g, 27%).

[0274] Finally, in an argon atmosphere, precursor (g-3) (522 mg, 0.65 mmol), N,N-diisopropylethylamine (258 mg, 2.0 mmol), and dichloromethane (20 mL) were placed in a 100 mL two-neck flask, and chlorodiphenylborane (600 mg, 3.0 mmol) was added under reflux, and the reaction was carried out overnight. After washing the reaction solution 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 / ethyl acetate = 100 / 1) to obtain a powder composition consisting of a green solid of near-infrared fluorescent dye G1 (yield: 0.24 g, yield: 32.6%).

[0275] 1 H-NMR (300MHz, CDCl3): δ=7.11(m, 20H), 6.43(m, 4H), 6.25(s, 2H), 6.02(m, 4H) ), 3.92(t, 4H), 2.27(s, 6H), 1.78(m, 10H), 1.5-1.2(m, 20H), 0.85(t, 6H)ppm.

[0276] [ka]

[0277] [Synthesis Example 8] Synthesis of near-infrared fluorescent dye H1 The near-infrared fluorescent dye H1 was prepared as follows, with reference to Organic Letters, 2012, vol. 4, pp. 2670-2673 and Chemistry A European Journal, 2009, vol. 15, pp. 4857-4864.

[0278] The same procedure as in Synthesis Example 2 was carried out except that 1-bromo-2-ethylhexane (48 g, 249 mmol) was used instead of 1-bromooctane (48 g, 249 mmol), to obtain a red solid of 3,6-(4-(2-ethylhexyl)oxyphenyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (h-2) (yield: 4.6 g).

[0279] Next, 2-amino-4-tert-butylphenol (5.24 g, 31.7 mmol), 2-cyano-acetimidic acid ethyl ester hydrochloride (4.45 g, 33.3 mmol), and dichloromethane (30 mL) were added to a 100 mL two-neck flask and refluxed overnight. The reaction solution was diluted with dichloromethane (100 mL) and washed twice with 1 mol / L aqueous sodium hydroxide solution. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a yellow liquid of (5-tert-butyl-benzoxazol-2-yl)-acetonitrile (h-3) (yield 6.3 g, 88%).

[0280] Subsequently, under an argon atmosphere, compound (h-2) (1.64 g, 3.0 mmol), compound (h-3) (1.41 g, 6.6 mmol), and dehydrated toluene (50 mL) were added to a 200 mL three-neck flask and heated to reflux. Under heating to reflux, phosphoryl chloride (2.34 mL, 25 mmol) was added dropwise with a syringe, and the mixture was heated to reflux for another 2 hours. After the reaction was completed, dichloromethane (40 mL) and a saturated aqueous solution of sodium bicarbonate (40 mL) were added while cooling with ice, and the mixture was extracted with dichloromethane. The organic layer was treated with anhydrous magnesium sulfate, and the magnesium sulfate was filtered off, and 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 of precursor (h-4) (yield: 0.98 g, 35%).

[0281] Finally, in an argon stream, 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-neck flask, and chlorodiphenylborane (900 mg, 4.5 mmol) was added under reflux, and the reaction was carried out overnight. After washing the reaction solution 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 H1 (yield: 0.42 g, yield: 35%).

[0282] 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.

[0283] [ka]

[0284] [Comparative Example 1] The near-infrared fluorescent dye A1 obtained in Synthesis Example 1 was purified by recrystallization as follows. To the near-infrared fluorescent dye A1 powder (1.2 g), toluene was added in an amount of about 8 to 10 times the amount of the powder, and dissolved under heating under reflux. The toluene solution dissolved by heating was added to pre-cooled isopropyl alcohol (toluene solution:isopropyl alcohol=2:1 (volume ratio)) to cause precipitation. The precipitate was collected by filtration to obtain a powder composition consisting of a green solid of the near-infrared fluorescent dye A2 (yield: 0.74 g, yield: 62%).

[0285] [Example 1] The near-infrared fluorescent dye A1 obtained in Synthesis Example 1 was purified by recrystallization as follows. To the near-infrared fluorescent dye A1 powder (1.2 g), toluene was added in an amount of about 15 to 20 times the amount of the powder, and dissolved under heating and reflux. The toluene solution that had been heated and dissolved was left as it was, slowly removed heat, and cooled to about room temperature to precipitate crystals. The precipitated crystals were collected by filtration, and a powder composition consisting of a reddish-black solid of the near-infrared fluorescent dye A3 was obtained (yield: 0.5 g, yield: 45%).

[0286] [Comparative Example 2] The near-infrared fluorescent dye B1 obtained in Synthesis Example 2 was purified by recrystallization as follows. To the near-infrared fluorescent dye B1 powder (1.0 g), toluene was added in an amount of about 8 to 10 times the amount of the powder, and dissolved under heating under reflux. The toluene solution dissolved by heating was added to pre-cooled isopropyl alcohol (toluene solution:isopropyl alcohol=2:1 (volume ratio)) to cause precipitation. The precipitate was collected by filtration to obtain a powder composition consisting of a green solid of the near-infrared fluorescent dye B2 (yield: 0.8 g, yield: 80%).

[0287] [Example 2] The near-infrared fluorescent dye B1 obtained in Synthesis Example 2 was purified by recrystallization as follows. To the near-infrared fluorescent dye B1 powder (1.0 g), toluene was added in an amount of about 15 to 20 times the amount of the powder, and dissolved under heating and reflux. The toluene solution that had been heated and dissolved was left as it was, slowly removed heat, and cooled to about room temperature to precipitate crystals. The precipitated crystals were collected by filtration, and a powder composition consisting of a reddish-black solid of the near-infrared fluorescent dye B3 was obtained (yield: 0.75 g, yield: 63%).

[0288] [Comparative Example 3] The near-infrared fluorescent dye C1 obtained in Synthesis Example 3 was purified by recrystallization as follows. To the near-infrared fluorescent dye C1 powder (1.0 g), toluene was added in an amount of about 8 to 10 times the amount of the powder, and dissolved under heating and reflux. The toluene solution dissolved by heating was added to pre-cooled isopropyl alcohol (toluene solution:isopropyl alcohol=2:1 (volume ratio)) to cause precipitation. The precipitate was collected by filtration to obtain a powder composition consisting of a green solid of the near-infrared fluorescent dye C2 (yield: 0.5 g, yield: 50%).

[0289] [Example 3] The near-infrared fluorescent dye C1 obtained in Synthesis Example 3 was purified by recrystallization as follows. To the near-infrared fluorescent dye C1 powder (1.0 g), toluene was added in an amount of about 15 to 20 times the amount of the powder, and dissolved under heating and reflux. The toluene solution that had been heated and dissolved was left to stand as it was, slowly removed heat, and cooled to about room temperature to precipitate crystals. The precipitated crystals were collected by filtration, and a powder composition consisting of a reddish-black solid of the near-infrared fluorescent dye C3 was obtained (yield: 0.4 g, yield: 33%).

[0290] [Comparative Example 4] The near-infrared fluorescent dye D1 obtained in Synthesis Example 4 was purified by recrystallization as follows. To the near-infrared fluorescent dye D1 powder (1.0 g), toluene was added in an amount of about 8 to 10 times the amount of the powder, and dissolved under heating and reflux. The toluene solution dissolved by heating was added to pre-cooled isopropyl alcohol (toluene solution:isopropyl alcohol=2:1 (volume ratio)) to cause precipitation. The precipitate was collected by filtration to obtain a powder composition consisting of a green solid of the near-infrared fluorescent dye D2 (yield: 0.8 g, yield: 80%).

[0291] [Example 4] The near-infrared fluorescent dye D1 obtained in Synthesis Example 4 was purified by recrystallization as follows. To the near-infrared fluorescent dye D1 powder (1.0 g), toluene was added in an amount of about 15 to 20 times the amount of the powder, and dissolved under heating and reflux. The toluene solution that had been heated and dissolved was left as it was, slowly removed heat, and cooled to about room temperature to precipitate crystals. The precipitated crystals were collected by filtration to obtain a powder composition consisting of a reddish-black solid of the near-infrared fluorescent dye D3 (yield: 0.5 g, yield: 50%).

[0292] [Comparative Example 5] The near-infrared fluorescent dye E1 obtained in Synthesis Example 5 was purified by recrystallization as follows. To the near-infrared fluorescent dye E1 powder (1.0 g), toluene was added in an amount of about 8 to 10 times the amount of the powder, and dissolved under heating and reflux. The toluene solution dissolved by heating was added to pre-cooled isopropyl alcohol (toluene solution:isopropyl alcohol=2:1 (volume ratio)) to cause precipitation. The precipitate was collected by filtration to obtain a powder composition consisting of a green solid of the near-infrared fluorescent dye E2 (yield: 0.7 g, yield: 70%).

[0293] [Example 5] The near-infrared fluorescent dye E1 obtained in Synthesis Example 5 was purified by recrystallization as follows. To the near-infrared fluorescent dye E1 powder (1.0 g), toluene was added in an amount of about 15 to 20 times the amount of the powder, and dissolved under heating and reflux. The toluene solution that had been heated and dissolved was left to stand as it was, slowly removed heat, and cooled to about room temperature to precipitate crystals. The precipitated crystals were collected by filtration, and a powder composition consisting of a reddish-black solid of the near-infrared fluorescent dye E3 was obtained (yield: 0.5 g, yield: 50%).

[0294] [Comparative Example 6] The near-infrared fluorescent dye F1 obtained in Synthesis Example 6 was purified by recrystallization as follows. To the near-infrared fluorescent dye F1 powder (1.0 g), toluene was added in an amount of about 8 to 10 times the amount of the powder, and dissolved under heating under reflux. The toluene solution dissolved by heating was added to pre-cooled isopropyl alcohol (toluene solution:isopropyl alcohol=2:1 (volume ratio)) to cause precipitation. The precipitate was collected by filtration to obtain a powder composition consisting of a green solid of the near-infrared fluorescent dye F2 (yield: 0.7 g, yield: 70%).

[0295] [Example 6] The near-infrared fluorescent dye F1 obtained in Synthesis Example 6 was purified by recrystallization as follows. To the near-infrared fluorescent dye F1 powder (1.0 g), toluene was added in an amount of about 15 to 20 times the amount of the powder, and dissolved under heating and reflux. The toluene solution that had been heated and dissolved was left to stand as it was, slowly removed heat, and cooled to about room temperature to precipitate crystals. The precipitated crystals were collected by filtration, and a powder composition consisting of a reddish-black solid of the near-infrared fluorescent dye F3 was obtained (yield: 0.6 g, yield: 60%).

[0296] [Comparative Example 7] The near-infrared fluorescent dye G1 obtained in Synthesis Example 7 was purified by recrystallization as follows. To the near-infrared fluorescent dye G1 powder (1.0 g), toluene was added in an amount of about 8 to 10 times the amount of the powder, and dissolved under heating under reflux. The toluene solution dissolved by heating was added to pre-cooled isopropyl alcohol (toluene solution:isopropyl alcohol=2:1 (volume ratio)) to cause precipitation. The precipitate was collected by filtration to obtain a powder composition consisting of a green solid of the near-infrared fluorescent dye G2 (yield: 0.7 g, yield: 70%).

[0297] [Example 7] The near-infrared fluorescent dye G1 obtained in Synthesis Example 7 was purified by recrystallization as follows. To the near-infrared fluorescent dye G1 powder (1.0 g), toluene was added in an amount of about 15 to 20 times the amount of the powder, and dissolved under heating and reflux. The toluene solution that had been heated and dissolved was left as it was, slowly removed heat, and cooled to about room temperature to precipitate crystals. The precipitated crystals were collected by filtration, and a powder composition consisting of a reddish-black solid of the near-infrared fluorescent dye G3 was obtained (yield: 0.4 g, yield: 33%).

[0298] [Comparative Example 8] The near-infrared fluorescent dye H1 obtained in Synthesis Example 8 was purified by recrystallization as follows. To the near-infrared fluorescent dye H1 powder (1.0 g), toluene was added in an amount of about 8 to 10 times the amount of the powder, and dissolved under heating and reflux. The toluene solution dissolved by heating was added to pre-cooled isopropyl alcohol (toluene solution:isopropyl alcohol=2:1 (volume ratio)) to cause precipitation. The precipitate was collected by filtration to obtain a powder composition consisting of a green solid of the near-infrared fluorescent dye H2 (yield: 0.5 g, yield: 42%).

[0299] [Example 8] The near-infrared fluorescent dye H1 obtained in Synthesis Example 8 was purified by recrystallization as follows. To the near-infrared fluorescent dye H1 powder (1.0 g), toluene was added in an amount of about 15 to 20 times the amount of the powder, and dissolved under heating and reflux. The toluene solution that had been heated and dissolved was left as it was, slowly removed heat, and cooled to about room temperature to precipitate crystals. The precipitated crystals were collected by filtration, and a powder composition consisting of a reddish-black solid of the near-infrared fluorescent dye H3 was obtained (yield: 0.3 g, yield: 25%).

[0300] [Test Example 1] The reflectance spectra of the powder compositions obtained in Synthesis Examples 1 to 8, Comparative Examples 1 to 8, and Examples 1 to 8 were measured. For the diffuse reflectance spectrum measurement, a spectrophotometer (model number: V-770, manufactured by JASCO Corporation), an integrating sphere unit (model number: ISN-923, manufactured by JASCO Corporation), and a powder cell (model number: PSH-002, manufactured by JASCO Corporation) were used. The relative reflectance was determined using a standard white plate for baseline correction, Spectralon (registered trademark), manufactured by Labsphere, as the standard white plate. Before the sample measurement, baseline correction was performed using the standard white plate, Spectralon. For the powder sample measurement, the thickness of the powder sample was set to 3 mm or more so that the entire window of the powder cell was completely covered.

[0301] [Table 1]

[0302] The measurement results are shown in Table 1. In the column "Whether or not there is a peak with a peak top at 520-560 nm", the number in parentheses after "Yes" indicates the wavelength of the peak top. In this column, "No" also includes cases where there is a peak at 520-560 nm, but the value obtained by subtracting the average reflectance at 300-400 nm from the maximum reflectance within the range of 520-560 nm is 5% or less, and the peak is negligible. The reflectance spectra of near-infrared fluorescent dye A2 and near-infrared fluorescent dye A3 from 300 to 600 nm are shown in Figure 1.

[0303] As shown in Table 1, the near-infrared fluorescent dyes that were dissolved in toluene by heating and then crystallized by adding isopropyl alcohol showed a peak having a top in the range of 520 to 560 nm. In contrast, the near-infrared fluorescent dyes that were dissolved in toluene by heating and then crystallized by slow cooling did not show a peak having a top in the range of 520 to 560 nm.

[0304] [Comparative Examples 9 to 24, Examples 9 to 16] Using the powder compositions and resin pellets obtained in Synthesis Examples 1 to 8, Comparative Examples 1 to 8, and Examples 1 to 8, resin compositions were produced by a melt kneading method, and plates were molded from the resulting resin compositions.

[0305] The following resin pellets were used: TPU: Thermoplastic polyurethane resin pellets (product name: Tecoflex EG80A, manufactured by Lubrizol) ABS: ABS resin pellets (product name: TECHNO ABS 330, manufactured by Techno Polymer) GPPS: Polystyrene resin pellets (product name: DIC Styrene CR-2500, manufactured by DIC Corporation) PP: Polypropylene resin pellets (product name: PC630A, manufactured by SunAllomer Co., Ltd.) PE: Polyethylene resin pellets (product name: Novatec LD (trademark) LC600A, made by Nippon Polyethylene) PC: Polycarbonate resin pellets (product name: Iupilon S3000, manufactured by Mitsubishi Engineering Plastics Corporation) PS: Polystyrene resin pellets (product name: DIC Styrene (trademark) CR-2500, manufactured by DIC Corporation) PET: Polyethylene terephthalate resin pellets (product name: Vylopet (trademark) EMC-500, manufactured by Toyobo Co., Ltd.)

[0306] First, the near-infrared fluorescent dye powder composition and resin pellets were mixed in the compositions shown in Tables 3 to 6, and the near-infrared fluorescent dye powder composition was attached to the surface of the resin pellets. The resulting mixture was then melt-kneaded and a plate (90 mm x 50 mm x 3 mm) was injection molded. The melt-kneading and plate injection molding were performed using an injection molding machine under the following conditions. The cylinder set temperature and mold temperature of the injection molding machine were set according to the type of resin pellets.

[0307] Melt mixing and injection molding conditions Equipment: Injection molding machine (product name: EC50SXII-1.5A, manufactured by Toshiba Corporation) Hopper bottom temperature setting: 60℃ Injection pressure: 99MPa Back pressure: 20MPa Screw rotation: 140 / min Injection speed: 70mm / s Ejection time: 10 seconds Cooling time: 20 seconds Nozzle operation: Retracts for 2 seconds after measurement is complete

[0308] [Table 2]

[0309] (Evaluation of the dispersibility of near-infrared fluorescent dyes) The surfaces of the produced plates, 10 of each type, were observed to evaluate the dispersibility of the near-infrared fluorescent dye. The evaluation criteria were as follows. Observation was performed visually and using a microscope (model number: VHX-7000, manufactured by Keyence Corporation). The evaluation results are shown in Tables 3 to 6.

[0310] Dispersibility evaluation in resin (molded product evaluation) Evaluation A: Ten plates were visually observed, and pigment aggregates and streaks (streak-like appearance defects) were not observed on any of the plates. Rating B + : Of 10 plates, pigment aggregates or streaks were visually observed on 2 or less plates, and the major axis of the pigment aggregates measured under a microscope was all less than 100 μm. Evaluation B: Of 10 plates, pigment aggregates or streaks were visually observed on 2 or less plates, and among the pigment aggregates measured under a microscope, at least one had a major axis of 100 μm or more. Rating B - : Of 10 plates, pigment aggregates or streaks were visually observed on 3 or fewer plates.

[0311] (Evaluation of optical properties of film) Furthermore, each of the produced plates was heated for 5 minutes while sandwiched between iron plates heated to 200°C, and pressed at 5 to 10 mPa while cooling the iron plates. The absorption spectrum of the obtained film was measured using an ultraviolet-visible-near infrared spectrophotometer (model number: UV3600, manufactured by SHIMADZU CORPORATION), and the emission spectrum was measured using an absolute PL quantum yield measurement device (product name: Quantaurus-QY C11347, manufactured by Hamamatsu Photonics KK). The measurement results are shown in Tables 3 to 6.

[0312] [Table 3]

[0313] [Table 4]

[0314] [Table 5]

[0315] [Table 6]

[0316] [Table 7]

[0317] As shown in Tables 3 to 7, in the molded bodies made of the resin compositions containing the near-infrared fluorescent dyes A3 to H3, which did not have a peak having a peak top in the range of 520 to 560 nm, almost no dye aggregates or appearance defects were observed, confirming that these near-infrared fluorescent dyes have very good dispersibility in the resin.

Claims

1. A powdered dye composition comprising a near-infrared fluorescent dye, The near-infrared fluorescent dye is The following general formula (I 1 -0): 【Chemistry 5】 (In formula (I 1 -0), R 1 , R 2 and R 3 are (p1) each independently 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; (p2) R 1 and R 2 together form an aromatic 5-membered ring or an aromatic 6-membered ring, and R 3 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; or (p3) R 2 and R 3 together form an aromatic 5-membered or 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 are (q1) each independently 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; (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, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group; or (q3) R 5 and R 6 together form an aromatic 5-membered or 6-membered ring, and R 4 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 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 , the boron atom bonded to R 7 , the nitrogen atom to which the boron atom is bonded, R 1 , and the carbon atom bonded to R 1 may together form a ring, and R 8 , the boron atom bonded to R 8 , the nitrogen atom to which the boron atom is bonded, R 4 , and the carbon atom bonded to R 4 may together form a ring. When R 7 is an oxygen atom and does not form a ring, R 7 is an oxygen atom having a substituent, and when R 8 is an oxygen atom and does not form a ring, R 8 is an oxygen atom having a substituent. and The compound represented by the following general formula (I 2 -0): 【Chemistry 6】 (In the formula (I 2 -0), R 1 to R 8 are the same as those in the formula (I 1 -0) above.) The composition contains one or more compounds selected from the group consisting of In the general formula (I 1 -0) or (I 2 -0), R 1 and R 2 form a ring, R 4 and R 5 form a ring, or R 2 and R 3 form a ring, R 5 and R 6 form a ring; The ring is represented by the following general formulas (C-1) to (C-9): 【Chemistry 7】 (In formulas (C-1) to (C-9), Y 1 to Y 8 each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom, and R 11 to R 22 each independently represent a hydrogen atom or any group that does not inhibit the fluorescence of the compound.) The reflectance spectrum of the powdered dye composition is There is no peak having a peak top in the range of 520 to 560 nm, or Although there is a peak having a peak top within the range of 520 to 560 nm, the value obtained by subtracting the average value of the relative reflectance within the range of 300 to 400 nm from the maximum value of the relative reflectance within the range is 5% or less. Powdered pigment composition.

2. The reflectance spectrum of the powdered dye composition is There is no peak having a peak top in the range of 520 to 560 nm, or Although there is a peak having a peak top within the range of 520 to 560 nm, the value obtained by subtracting the average value of the relative reflectance within the range of 300 to 400 nm from the maximum value of the relative reflectance within the range is 2.5% or less.

2. The powdered dye composition according to claim 1.

3. A powdered dye composition comprising a near-infrared fluorescent dye, The near-infrared fluorescent dye is The following general formulas (I 3 -1) to (I 3 -6): 【Chemistry 8】 (In formula (I 3 -1), R 23 , R 24 , R 25 , and R 26 each independently represent a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group; R 27 and R 28 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; R 29 and R 30 each independently represent a hydrogen atom or an electron-withdrawing group; Y 9 and Y 10 each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom; R 31 and R 32 are (p4) each independently 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; or (p5) R 31 and R 32 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring; R 33 and R 34 are (q4) each independently 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; or (q5) R 33 and R 34 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent. 【Chemistry 9】 In formulas (I 3 -2) to (I 3 -6), R 23 to R 30 are the same as those in formula (I 3 -1); X 1 and X 2 each independently represent a nitrogen atom or a phosphorus atom; R 35 , R 36 , R 37 and R 38 are (p6) each independently 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; (p7) R 35 and R 36 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent, R 37 and R 38 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; (p8) R 36 and R 37 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent, and R 35 and R 38 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; or (p9) R 37 and R 38 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent, R 35 and R 36 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; R 39 , R 40 , R 41 and R 42 are (q6) each independently 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; (q7) R 39 and R 40 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent, 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 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent, 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; or (q9) R 41 and R 42 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent, 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, and 【Chemistry 10】 (In formulas (I 4 -1) to (I 4 -6), R 23 to R 28 are the same as those in formula (I 3 -1) above; In formula (I 4 -1), R 31 to R 34 , Y 9 , and Y 10 are the same as those in formula (I 3 -1) above; In formulas (I 4 -2) to (I 4 -6), R 35 to R 42 are the same as those in formula (I 3 -2) above; and In formulas (I 4 -3) to (I 4 -6), X 1 and X 2 are the same as those in formula (I 3 -3) above.) The reflectance spectrum of the powdered dye composition is There is no peak having a peak top in the range of 520 to 560 nm, or Although there is a peak having a peak top within the range of 520 to 560 nm, the value obtained by subtracting the average value of the relative reflectance within the range of 300 to 400 nm from the maximum value of the relative reflectance within the range is 5% or less. Powdered pigment composition.

4. The reflectance spectrum of the powdered dye composition is There is no peak having a peak top in the range of 520 to 560 nm, or Although there is a peak having a peak top within the range of 520 to 560 nm, the value obtained by subtracting the average value of the relative reflectance within the range of 300 to 400 nm from the maximum value of the relative reflectance within the range is 2.5% or less.

4. The powdered dye composition according to claim 3.

5. 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 represent, independently of each other, an oxygen atom or a sulfur atom; Y ２１ and Y ２２ represent, independently of each other, a carbon atom or a nitrogen atom; Q １１ represents a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group; X is independently a halogen atom, C 1-20 represents an alkoxy group, an aryloxy group, or an acyloxy group; P １１ ~P １４ and P １７ are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group; A １１ ~A １４ are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 a phenyl group which may have 1 to 3 substituents selected from the group consisting of an alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group, or a halogen atom, 1-20 Alkyl group, C 1-20 a heteroaryl group which may have 1 to 3 substituents selected from the group consisting of an alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group; n11 to n14 and n17 each independently represent an integer of 0 to 3; m1 represents 0 or 1.

2. The powdered dye composition according to claim 1, comprising one or more compounds selected from the group consisting of compounds represented by any one of the following formulas:

6. The following general formula (I ３ -7) to (I ３ -9) and (I ４ -7) to (I ４ -9) 【Chemistry 17】 [In the formula, Y ２３ and Y ２４ represent, independently of each other, a carbon atom or a nitrogen atom; Y １３ and Y １４ represent, independently of each other, an oxygen atom or a sulfur atom; Y ２５ and Y ２６ represent, independently of each other, a carbon atom or a nitrogen atom; R ４７ and R ４８ 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 are each independently a halogen atom, C 1-20 Alkyl group, C 1-20 represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group; n15 and n16 each independently represent an integer of 0 to 3; A １５ and A １６ are each independently a hydrogen atom, a halogen atom, or C 1-20 Alkyl group, C 1-20 It represents a phenyl group which may have 1 to 3 substituents selected from the group consisting of an alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group.] 4. The powdered dye composition according to claim 3, which contains one or more compounds selected from the group consisting of compounds represented by any one of the following formulas:

7. 7. The powdered dye composition according to claim 1, wherein the reflectance spectrum is a spectrum obtained by diffuse reflectance measurement using an integrating sphere.

8. A method for producing a powdered dye composition comprising a near-infrared fluorescent dye, comprising the steps of: a crystallization step of dissolving the near-infrared fluorescent dye in a low-polarity solvent by heating, and then slowly cooling the solution to recrystallize the dye; a powdering step of powdering the crystals obtained in the crystallization step to produce a powdered dye composition; having The reflectance spectrum of the powdered dye composition is There is no peak having a peak top in the range of 520 to 560 nm, or Although there is a peak having a peak top within the range of 520 to 560 nm, the value obtained by subtracting the average value of the relative reflectance within the range of 300 to 400 nm from the maximum value of the relative reflectance within the range is 5% or less, The near-infrared fluorescent dye is The following general formula (I 1 -0): 【Chemistry 5】 (In formula (I 1 -0), R 1 , R 2 and R 3 are (p1) each independently 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; (p2) R 1 and R 2 together form an aromatic 5-membered ring or an aromatic 6-membered ring, and R 3 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; or (p3) R 2 and R 3 together form an aromatic 5-membered or 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 are (q1) each independently 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; (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, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group; or (q3) R 5 and R 6 together form an aromatic 5-membered or 6-membered ring, and R 4 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 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 , the boron atom bonded to R 7 , the nitrogen atom to which the boron atom is bonded, R 1 , and the carbon atom bonded to R 1 may together form a ring, and R 8 , the boron atom bonded to R 8 , the nitrogen atom to which the boron atom is bonded, R 4 , and the carbon atom bonded to R 4 may together form a ring. When R 7 is an oxygen atom and does not form a ring, R 7 is an oxygen atom having a substituent, and when R 8 is an oxygen atom and does not form a ring, R 8 is an oxygen atom having a substituent. The compound represented by the following general formula (I 2 -0): 【Chemistry 6】 (In formula (I 2 -0), R 1 to R 8 are the same as those in formula (I 1 -0) above), In the general formula (I 1 -0) or (I 2 -0), R 1 and R 2 form a ring, R 4 and R 5 form a ring, or R 2 and R 3 form a ring, R 5 and R 6 form a ring; The ring is represented by the following general formulas (C-1) to (C-9): 【Chemistry 7】 (In formulas (C-1) to (C-9), Y 1 to Y 8 each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom, and R 11 to R 22 each independently represent a hydrogen atom or any group that does not inhibit the fluorescence of the compound.) The following general formulas (I 3 -1) to (I 3 -6): 【Chemistry 8】 (In formula (I 3 -1), R 23 , R 24 , R 25 , and R 26 each independently represent a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group; R 27 and R 28 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; R 29 and R 30 each independently represent a hydrogen atom or an electron-withdrawing group; Y 9 and Y 10 each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom; R 31 and R 32 are (p4) each independently 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; or (p5) R 31 and R 32 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring; R 33 and R 34 are (q4) each independently 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; or (q5) R 33 and R 34 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent. 【Chemistry 9】 In formulas (I 3 -2) to (I 3 -6), R 23 to R 30 are the same as those in formula (I 3 -1); X 1 and X 2 each independently represent a nitrogen atom or a phosphorus atom; R 35 , R 36 , R 37 and R 38 are (p6) each independently 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; (p7) R 35 and R 36 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent, R 37 and R 38 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; (p8) R 36 and R 37 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent, and R 35 and R 38 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; or (p9) R 37 and R 38 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent, R 35 and R 36 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; R 39 , R 40 , R 41 and R 42 are (q6) each independently 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; (q7) R 39 and R 40 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent, 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 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent, 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; or (q9) A compound represented by any one of the following: wherein R 41 and R 42 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent, 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; and The following general formulas (I 4 -1) to (I 4 -6): 【Chemistry 10】 (In formulae (I 4 -1) to (I 4 -6), R 23 to R 28 are the same as those in formula (I 3 -1) above. In formula (I 4 -1), R 31 to R 34 , Y 9 , and Y 10 are the same as those in formula (I 3 -1) above. In formulae (I 4 -2) to (I 4 -6), R 35 to R 42 are the same as those in formula (I 3 -2) above. In formulae (I 4 -3) to (I 4 -6), X 1 and X 2 are the same as those in formula (I 3 -3) above.) One or more compounds selected from the group consisting of A method for producing a powdered dye composition.

9. 9. The method for producing a powdered dye composition according to claim 8, wherein the low polarity solvent is toluene.

10. 10. The method for producing a powdered dye composition according to claim 8, wherein the low polarity solvent contains 30 wt % or less of a polar solvent.

11. 11. The method for producing a powdered dye composition according to claim 10, wherein the polar solvent is an alcohol having 1 to 4 carbon atoms.

12. A powdered dye composition according to claim 1 or 3 and a resin are contained therein, A resin composition having a maximum fluorescence wavelength of 650 nm or more.

13. The resin composition according to claim 12, wherein the resin is a thermoplastic resin.

14. The resin composition according to claim 12 , wherein the near-infrared fluorescent dye and the resin are melt-kneaded.

15. The resin composition according to claim 12, having a maximum fluorescence wavelength of 700 nm or more.

16. The resin composition according to claim 12, which is used as a medical material.

17. A molded article obtained by processing the resin composition according to claim 12.

18. 18. The molded article according to claim 17, at least a portion of which is a medical device for use inside a patient's body.

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