WO2023127507A1 - 粉末状色素組成物、粉末状色素組成物の製造方法、樹脂組成物及び成形体 - Google Patents

粉末状色素組成物、粉末状色素組成物の製造方法、樹脂組成物及び成形体 Download PDF

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WO2023127507A1
WO2023127507A1 PCT/JP2022/046123 JP2022046123W WO2023127507A1 WO 2023127507 A1 WO2023127507 A1 WO 2023127507A1 JP 2022046123 W JP2022046123 W JP 2022046123W WO 2023127507 A1 WO2023127507 A1 WO 2023127507A1
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group
atom
ring
aromatic
alkyl group
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PCT/JP2022/046123
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English (en)
French (fr)
Japanese (ja)
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豊 竹澤
直人 櫻井
拓矢 吉田
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to CN202280082514.9A priority Critical patent/CN118434822A/zh
Priority to US18/719,506 priority patent/US20250051638A1/en
Priority to JP2023570827A priority patent/JP7598065B2/ja
Publication of WO2023127507A1 publication Critical patent/WO2023127507A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds

Definitions

  • the present invention relates to a powdery dye composition comprising a near-infrared fluorescent dye, a method for producing the same, a resin composition that emits near-infrared fluorescence, and a molded article obtained by processing the resin composition.
  • Near-infrared fluorescent dyes are used in industrial products, mainly for the identification and prevention of counterfeiting of various products.In recent years, they have also been used for medical applications such as bioimaging probes and test drugs.
  • Known characteristics of the near-infrared wavelength region include that it is invisible to the naked eye of humans, that it has little effect on living organisms, and that it is highly permeable to living organisms such as the skin. Such characteristics can be utilized by including a near-infrared fluorescent dye in the medical device itself.
  • a system has been disclosed in which a near-infrared fluorescent dye is contained in a medical device such as a shunt tube, and the position of the medical device implanted in the body is confirmed by irradiating the device with near-infrared light from outside the body.
  • a medical device such as a shunt tube
  • the near-infrared fluorescent dye contained in the medical implant In order to visualize medical implants embedded under the skin, excitation with near-infrared light, which has high skin permeability, is necessary. Must be in the infrared region. In other words, usually, 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 in addition, emit strong fluorescence. There is a need. Therefore, it is preferable that the near-infrared fluorescent dye contained in the resin composition used as a raw material for medical implants has a maximum absorption wavelength in the near-infrared region.
  • a near-infrared fluorescent dye in a resin, it is possible to manufacture various moldings that emit near-infrared fluorescence using the resin as a raw material.
  • a resin in which a near-infrared fluorescent dye is dispersed for example, in Patent Document 2, a reactive group-containing near-infrared fluorescent dye obtained by introducing a polyester reactive group into a phthalocyanine dye, a naphthalocyanine dye, or a squaline dye is PET.
  • a near-infrared fluorescent resin copolymerized in (polyethylene terephthalate) is disclosed.
  • Patent Document 3 a BODIPY dye or a DPP-based boron complex that is excellent in heat resistance and emission quantum yield and emits near-infrared fluorescence is mixed and dispersed in a resin to obtain a near-infrared light with strong emission intensity. It is disclosed that a fluorescent resin composition and a molded article obtained by processing the composition are obtained.
  • the near-infrared fluorescent dye When producing a resin composition containing a near-infrared fluorescent dye, if the dispersibility of the near-infrared fluorescent dye in the resin is low, the near-infrared fluorescent dye is unevenly present in the resin composition. In some cases, aggregates of near-infrared fluorescent dyes are formed. A molded article molded from such a resin composition is likely to have appearance defects such as dots or streaks.
  • An object of the present invention is to provide a near-infrared fluorescent dye having good dispersibility in a resin, a resin composition containing the near-infrared fluorescent dye, and a molded article obtained by processing the resin composition. is.
  • a powdery dye composition comprising a near-infrared fluorescent dye,
  • the near-infrared fluorescent dye is The following general formula (I 1 )
  • R a and R b are aromatic 5-membered rings, aromatic 6-membered rings, or 2 to 3 5- or 6-membered rings together with the nitrogen atom to which R a is attached and the carbon atom to which R b is attached. condensed to form a condensed aromatic ring; R c and R d are, together with the nitrogen atom to which R c is attached and the carbon atom to which R d is attached, an aromatic 5-membered ring, an aromatic 6-membered ring, or 2 to 3 5- or 6-membered rings.
  • R e and R f represent a halogen atom or an oxygen atom
  • Rg represents a hydrogen atom or an electron-withdrawing group.
  • R e and R f are oxygen atoms
  • R e the boron atom bonded to R e , R a , and the nitrogen atom bonded to R a may together form a ring
  • R f The boron atom bonded to R f , R c , and the nitrogen atom bonded to R c may together form a ring.
  • R h and R i are, together with the nitrogen atom to which R h is attached and the carbon atom to which R i is attached, an aromatic 5-membered ring, an aromatic 6-membered ring, or 2 to 3 5- or 6-membered rings condensed to form a condensed aromatic ring;
  • R j and R k are, together with the nitrogen atom to which R j is attached and the carbon atom to which R k is attached, an aromatic 5-membered ring, an aromatic 6-membered ring, or 2 to 3 5- or 6-membered rings.
  • R l , R m , R n , and R o 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 p and R q 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 r and R s independently represent a hydrogen atom or an electron-withdrawing group.
  • the reflection spectrum of the powdery dye composition is There is no peak with a peak top within the range of 520 to 560 nm, or Although there is a peak with a peak top in the range of 520 to 560 nm, 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.
  • a powdery pigment composition is
  • R 1 , R 2 and R 3 are (p1) independently of each other, representing a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 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, R 3 is a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl or (p3) R 2 and R 3 together form an aromatic 5-membered ring or 6-membered aromatic ring, and R 1 is a hydrogen atom, a halogen atom, or a C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, or heteroaryl group.
  • R 4 , R 5 and R 6 are (q1) each independently represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group; (q2) R 4 and R 5 together form a 5-membered aromatic ring or 6-membered aromatic ring, R 6 is a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl or (q3) R 5 and R 6 together form a 5-membered or 6-membered aromatic ring, and R 4 is a hydrogen atom, a halogen atom, or a C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, or heteroaryl group.
  • R 7 and R 8 represent a halogen atom or an oxygen atom; R9 represents a hydrogen atom or an electron-withdrawing group.
  • R 7 and R 8 are oxygen atoms
  • R 7 , the boron atom bonded to R 7 , the nitrogen atom bonded to the boron atom, R 1 , and the carbon atom bonded to R 1 together form a ring.
  • R 8 , the boron atom bonded to R 8 , the nitrogen atom bonded to the boron atom, R 4 , and the carbon atom bonded to R 4 may together form a ring.
  • R 7 is an oxygen atom and does not form a ring
  • R 7 is an oxygen atom having a substituent
  • R 8 is an oxygen atom and does not form a ring
  • R8 is an oxygen atom having a substituent.
  • R 1 and R 2 form a ring
  • R 4 and R 5 form a ring
  • R 2 and R 3 form a ring
  • R 5 and R 6 form a ring
  • the rings are represented by the following general formulas (C-1) to (C-9) (formula (C-1) to In (C-9)
  • Y 1 to Y 8 each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom
  • R 11 to R 22 each independently represent a hydrogen atom, or the compound any group that does not inhibit the fluorescence of ), the powdery dye composition of [2] above.
  • R 23 , R 24 , R 25 and R 26 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 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 independently represent a hydrogen atom or an electron-withdrawing group
  • Y 9 and Y 10 independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom
  • R 31 and R 32 are (p4) each independently represent a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group, or (p5) R 31 and R 32 are both forming an optionally substituted
  • R 23 to R 30 are the same as in formula (I 3 -1);
  • X 1 and X 2 independently represent a nitrogen atom or a phosphorus atom;
  • R 35 , R 36 , R 37 and R 38 are (p6) independently of each other, representing a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group;
  • R 35 and R 36 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, and
  • R 37 and R 38 independently of each other, 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 36 and R 37 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-member
  • Y 11 and Y 12 independently represent an oxygen atom or a sulfur atom; Y 21 and Y 22 independently of each other represent a carbon atom or a nitrogen atom; Q 11 represents a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group; X independently represents a halogen atom, a C 1-20 alkoxy group, an aryloxy group, or an acyloxy group; P 11 to P 14 and P 17 independently represent a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group, a dialkylamino group; A 11 to A 14 are each independently 1 to 1 selected from the group consisting of a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group and a dialkylamino group; a phenyl group
  • Y 23 and Y 24 independently represent a carbon atom or a nitrogen atom
  • Y 13 and Y 14 independently represent an oxygen atom or a sulfur atom
  • Y 25 and Y 26 independently of each other represent a carbon atom or a nitrogen atom
  • R 47 and R 48 independently represent a hydrogen atom or an electron-withdrawing group
  • R 43 , R 44 , R 45 and R 46 represent a halogen atom or an optionally substituted aryl group
  • P 15 and P 16 independently represent a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group, a dialkylamino group
  • n15 and n16 independently represent an integer from 0 to 3
  • a 15 and A 16 are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, a
  • a method for producing a powdery dye composition comprising a near-infrared fluorescent dye, comprising: A crystallization step of heating and dissolving the near-infrared fluorescent dye in a low-polar solvent, followed by slow cooling to recrystallize; a powdering step of powdering the crystals obtained in the crystallization step to produce a powdery dye composition; has The reflection spectrum of the powdery dye composition is There is no peak with a peak top within the range of 520 to 560 nm, or Although there is a peak with a peak top in the range of 520 to 560 nm, 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. can be,
  • the near-infrared fluorescent dye is The following general formula (I
  • R a and R b are, together with the nitrogen atom to which R a is attached and the carbon atom to which R b is attached, an aromatic 5-membered ring, an aromatic 6-membered ring, or 2 to 3 5- or 6-membered rings condensed to form a condensed aromatic ring;
  • R c and R d are aromatic 5-membered rings, aromatic 6-membered rings, or 2 to 3 5- or 6-membered rings together with the nitrogen atom to which R c is attached and the carbon atom to which R d is attached.
  • R e and R f represent a halogen atom or an oxygen atom
  • Rg represents a hydrogen atom or an electron-withdrawing group.
  • R e and R f are oxygen atoms
  • R e the boron atom bonded to R e , R a , and the nitrogen atom bonded to R a may together form a ring
  • R f The boron atom bonded to R f , R c , and the nitrogen atom bonded to R c may together form a ring.
  • R h and R i are, together with the nitrogen atom to which R h is attached and the carbon atom to which R i is attached, an aromatic 5-membered ring, an aromatic 6-membered ring, or 2 to 3 5- or 6-membered rings condensed to form a condensed aromatic ring;
  • R j and R k are, together with the nitrogen atom to which R j is attached and the carbon atom to which R k is attached, an aromatic 5-membered ring, an aromatic 6-membered ring, or 2 to 3 5- or 6-membered rings.
  • R l , R m , R n , and R o 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 p and R q 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 r and R s independently represent a hydrogen atom or an electron-withdrawing group.
  • R h to R q are the same as in formula (I 3 ).
  • One or more compounds selected from the group consisting of compounds represented by formula (I 3 ), A method for producing a powdery dye composition.
  • 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] and a resin, and having a maximum fluorescence wavelength of 650 nm or more.
  • the resin composition according to any one of [12] to [15] 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].
  • [18] The molded article according to [17] above, at least a part of which is a medical device used inside a patient's body.
  • the powdery dye composition according to the present invention is composed of a near-infrared fluorescent dye that is excellent in heat resistance and emission quantum yield, and also has good dispersibility in resin.
  • the near-infrared fluorescent dye is uniformly dispersed in the composition, and when molded using the resin composition, the molded body has dots. and streak-like appearance defects are less likely to occur. Therefore, a resin composition containing the powdery dye composition is particularly suitable as a medical material for which uniform product quality is particularly required.
  • the powdery dye composition according to the present invention is a powdery dye composition comprising a near-infrared fluorescent dye.
  • the near-infrared fluorescent dye contained in the powdery dye composition according to the present invention is specifically represented by the following general formula (I 1 ), general formula (I 2 ), general formula (I 3 ), or general formula (I 4 ).
  • the compound may be hereinafter referred to as "the near-infrared fluorescent dye according to the present invention".
  • R a and R b form an aromatic ring consisting of 1 to 3 rings together with the nitrogen atom to which R a is attached and the carbon atom to which R b is attached. do.
  • R c and R d are an aromatic ring consisting of 1 to 3 rings together with the nitrogen atom to which R c is attached and the carbon atom to which R d is attached. form a ring.
  • Each ring of the aromatic ring formed by R a and R b and the aromatic ring formed by R c and R d is a 5- or 6-membered ring.
  • the aromatic ring formed by R a and R b and the aromatic ring formed by R c and R d are bonded to two nitrogen atoms. It has a ring structure condensed with a ring containing a boron atom. That is, the compound represented by general formula (I 1 ) or general formula (I 2 ) has a rigid condensed ring structure consisting of a wide conjugation plane.
  • R h and R i form an aromatic ring consisting of 1 to 3 rings together with the nitrogen atom to which R h is attached and the carbon atom to which R i is attached. do.
  • R j and R k are aromatic atoms consisting of 1 to 3 rings together with the nitrogen atom to which R j is attached and the carbon atom to which R k is attached. form a ring.
  • Each ring of the aromatic ring formed by R h and R i and the aromatic ring formed by R j and R k is a 5- or 6-membered ring.
  • the compound represented by general formula (I 3 ) or general formula (I 4 ) is an aromatic ring formed by R h and R i , a ring containing a boron atom bonded to two nitrogen atoms, and one nitrogen atom 3 rings condensed with a 5-membered hetero ring containing and a 5-membered ring containing a boron atom bonded to an aromatic ring formed by R j and R k and 2 nitrogen atoms and a 5-membered ring containing a nitrogen atom It has a ring structure in which three rings condensed with a hetero ring are condensed between five-membered hetero rings, that is, a ring structure in which at least six rings are condensed.
  • the compound represented by general formula (I 3 ) or general formula (I 4 ) has a rigid condensed ring structure consisting of a very wide conjugation plane.
  • the aromatic ring formed by R a and R b , the aromatic ring formed by R c and R d , the aromatic ring formed by R h and Ri , and the aromatic ring formed by R j and R k have aromaticity. It is not particularly limited as long as it has.
  • the aromatic ring include pyrrole ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyridine ring, pyrimidine ring, pyridazine ring, isoindole ring, indole ring, indazole ring, purine ring, perimidine ring, thienopyrrole ring, and furopyrrole.
  • the aromatic ring has a condensed ring number of 2 or 3. is preferable, and 2 is more preferable from the viewpoint of complicated synthesis.
  • the wavelength can be lengthened by devising a substituent on the ring or a substituent on boron.
  • the wavelength can be lengthened to the near-infrared region simply by bonding a substituted aryl group or heteroaryl group.
  • the aromatic ring formed by Ra and Rb , the aromatic ring formed by Rc and Rd , the aromatic ring formed by Rh and Ri , and the aromatic ring formed by Rj and Rk each have a substituent It may not have one or may have one or more substituents.
  • the substituent of the aromatic ring may be any group that does not inhibit the fluorescence of the compound.
  • the near-infrared fluorescent dye according to the present invention 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 has mutagenicity, cell Those without toxicity, sensitization, skin irritation, etc. are preferred. 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 article obtained by processing the resin composition according to the present invention with body fluids such as blood and interstitial fluid. Therefore, the near-infrared fluorescent dye according to the present invention preferably has low solubility in biological components such as blood.
  • the resin component itself in the resin composition according to the present invention is hardly eluted into body fluids, etc., and the near-infrared fluorescent dye itself
  • the molded article of the resin composition according to the present invention can be used without elution of the near-infrared fluorescent dye even in vivo.
  • substituents include halogen atoms, nitro groups, cyano groups, hydroxyl groups, carboxyl groups, aldehyde groups, sulfonic acid groups, alkylsulfonyl groups, halogenosulfonyl groups, thiol groups, alkylthio groups, isocyanate groups, and thioisocyanate groups.
  • an alkyl group an alkenyl group, an alkynyl group, an alkoxy group, an alkoxycarbonyl group, an alkylamidecarbonyl group, an alkylcarbonylamide group, an acyl group, an amino group, a monoalkylamino group, a dialkylamino group, a silyl group, a monoalkylsilyl group, Dialkylsilyl groups, trialkylsilyl groups, monoalkoxysilyl groups, dialkoxysilyl groups, trialkoxysilyl groups, aryl groups, heteroaryl groups, and the like.
  • these substituents may further have a substituent. However, even if it is a substituent other than these substituents, it is not limited to these substituents because the safety can be improved by further introducing a suitable substituent.
  • the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom, a chlorine atom and a bromine atom, more preferably a fluorine atom.
  • the alkyl group, alkenyl group, and alkynyl group may be linear, branched, or cyclic (aliphatic cyclic group). These groups preferably have 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms.
  • alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group (tert-butyl group), pentyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like.
  • alkenyl groups include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, and 2-hexenyl groups.
  • alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, isopropynyl, 1-butynyl and isobutynyl groups.
  • alkylsulfonyl group alkylthio group, alkoxy group, alkoxycarbonyl group, alkylamidocarbonyl group, alkylcarbonylamido group, monoalkylamino group, dialkylamino group, monoalkylsilyl group, dialkylsilyl group, trialkylsilyl group, monoalkoxysilyl
  • alkyl group moiety in the group, the dialkoxysilyl group, and the trialkoxysilyl group include the same alkyl groups as those described above.
  • alkoxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, t-butyloxy, pentyloxy, isoamyloxy, hexyloxy and heptyloxy groups. , octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.
  • monoalkylamino groups include methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, t-butylamino, pentylamino and hexylamino groups.
  • dialkylamino groups include dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, dipentylamino, dihexylamino, ethylmethylamino, methylpropyl Amino group, butylmethylamino group, ethylpropylamino group, butylethylamino group and the like can be mentioned.
  • aryl groups include phenyl, naphthyl, indenyl, and biphenyl groups.
  • a phenyl group is preferred.
  • heteroaryl groups include pyrrolyl, imidazolyl, pyrazolyl, thienyl, furanyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, thiadiazole, and other five-membered ring heteroaryl groups; pyridinyl, pyrazinyl 6-membered ring heteroaryl groups such as groups, pyrimidinyl groups, pyridazinyl groups; and fused heteroaryl groups such as benzoisoxazolyl, benzothiazolyl, and benzoisothiazolyl groups.
  • Alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and heteroaryl groups may be unsubstituted groups, or one or more hydrogen atoms may be substituted by a substituent.
  • substituents include halogen atoms, alkyl groups, alkoxy groups, nitro groups, cyano groups, hydroxy groups, amino groups, thiol groups, carboxyl groups, aldehyde groups, sulfonic acid groups, isocyanate groups, thioisocyanate groups, and aryl groups. , a heteroaryl group, and the like.
  • the absorption wavelength and fluorescence wavelength of the fluorescent dye depend on the surrounding environment. Therefore, the absorption wavelength of the fluorescent dye in the resin may be shorter or longer than that in the solution.
  • the absorption wavelength of the near-infrared fluorescent dye itself according to the present invention is lengthened, it is preferable because the maximum absorption wavelength is in the near-infrared region among various resins.
  • the maximum absorption wavelength of a fluorescent dye is determined by introducing an electron-donating group and an electron-withdrawing group at appropriate positions in the molecule, thereby changing the bandgap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). It can be narrowed and the wavelength can be made longer.
  • an electron-donating group is introduced into the aromatic ring formed by R a and R b and the aromatic ring formed by R c and R d , and an electron
  • an attracting group By introducing an attracting group, the maximum absorption wavelength and the maximum fluorescence wavelength of the compound can be made longer.
  • the maximum absorption wavelength and maximum fluorescence of the compound The wavelength can be made longer.
  • the compound represented by the general formula (I 2 ) having an aza-BODIPY skeleton has a relatively long wavelength even if the aromatic rings formed by R a and R b and the aromatic rings formed by R c and R d are unsubstituted. It is a skeleton that absorbs into Unlike the compound represented by the general formula (I 1 ), a substituent cannot be introduced on the nitrogen because the pyrrole bridge portion is a nitrogen atom in the skeleton, but the pyrrole portion (R a and R b By introducing an electron-donating group into the aromatic ring formed by and the aromatic ring formed by Rc and Rd ), the maximum absorption wavelength and maximum fluorescence wavelength of the compound can be made longer.
  • an electron-donating group is introduced into the pyrrole moiety (the aromatic ring formed by R h and R i and the aromatic ring formed by R j and R k )
  • R p and R q are aromatic rings
  • the maximum absorption wavelength and maximum fluorescence wavelength of the compound can be made longer by introducing an electron-donating group into the aromatic rings.
  • the aromatic ring formed by R a and R b , the aromatic ring formed by R c and R d , the aromatic ring formed by R h and Ri , and the aromatic ring formed by R j and R k have substitution As the group, among "any group that does not inhibit the fluorescence of the compound", a group that functions as an electron-donating group to the aromatic ring is preferable. By introducing an electron-donating group into the aromatic ring, the fluorescence of the compound represented by general formula (I 1 ), general formula (I 2 ), general formula (I 3 ), or general formula (I 4 ) is on the longer wavelength side.
  • groups that function as electron-donating groups include alkyl groups; alkoxy groups such as methoxy groups; aryl groups (aromatic ring group); heteroaryl groups (heteroaromatic ring groups) such as 2-thienyl group and 2-furanyl group;
  • the alkyl group, the alkyl group in the substituent of the phenyl group, and the alkyl group portion in the alkoxy group are preferably linear or branched alkyl groups having 1 to 10 carbon atoms.
  • the number of carbon atoms in the alkyl group portion and the presence or absence of branching may be appropriately selected in consideration of various physical properties of the dye.
  • the number of carbon atoms is preferably 6 or more, and where branching is preferred.
  • Substituents possessed by the aromatic ring formed by Ra and Rb , the aromatic ring formed by Rc and Rd , the aromatic ring formed by Rh and Ri , and the aromatic ring formed by Rj and Rk , C 1-6 alkyl group, C 1-6 alkoxy group, aryl group or heteroaryl group are preferred, methyl group, ethyl group, methoxy group, phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p -Dimethylaminophenyl group, dimethoxyphenyl group, thienyl group or furanyl group is more preferable, and methyl group, ethyl group, methoxy group, phenyl group or p-methoxyphenyl group is more preferable.
  • the BODIPY skeleton has a high degree of planarity, molecules tend to aggregate together due to ⁇ - ⁇ stacking.
  • an aryl group or heteroaryl group having a bulky substituent into the BODIPY skeleton, aggregation of molecules can be suppressed, and the emission quantum yield of the resin composition according to the present invention can be increased.
  • the aromatic ring formed by R a and R b and the aromatic ring formed by R c and R d may be different or the same.
  • the aromatic ring formed by R h and R i and the aromatic ring formed by R j and R k may be different or the same.
  • the emission quantum yield tends to be higher . or the aromatic ring formed by R h and R i and the aromatic ring formed by R j and R k are preferably the same.
  • R e and R f each independently represent a halogen atom or an oxygen atom.
  • R e and R f are halogen atoms, fluorine, chlorine, bromine, or iodine atoms are preferable, fluorine or chlorine atoms are more preferable, and fluorine atoms are particularly preferable since they have a strong bond with boron atoms. .
  • Compounds in which R e and R f are fluorine atoms have high heat resistance and are therefore advantageous when melt-kneaded with a resin at high temperatures.
  • R e and R f are not halogen atoms or oxygen atoms, but substituents containing atoms capable of bonding to boron atoms. Even if there is, it can be contained in the resin in the same manner as the near-infrared fluorescent dye according to the present invention. Any substituent that does not inhibit fluorescence is acceptable.
  • the ring formed by R e , the boron atom bonded to R e , R a , and the nitrogen atom bonded to R a is condensed with the aromatic ring formed by R a and R b
  • the ring formed by R f , the boron atom bonded to R f , the nitrogen atom bonded to R c , and R c is condensed with the aromatic ring formed by R c and R d .
  • the ring formed by R e and the like and the ring formed by R f and the like are preferably six-membered rings.
  • R e when R e is an oxygen atom and does not form a ring, R e is an oxygen atom having a substituent (an oxygen atom bonded to a substituent atom).
  • substituents include C 1-20 alkyl groups, aryl groups, heteroaryl groups, alkylcarbonyl groups, arylcarbonyl groups, heteroarylcarbonyl groups, and the like.
  • R f when R f is an oxygen atom and does not form a ring, R f is an oxygen atom having a substituent (substituent and bonded oxygen atoms).
  • substituents include C 1-20 alkyl groups, aryl groups, heteroaryl groups, alkylcarbonyl groups, arylcarbonyl groups, heteroarylcarbonyl groups, and the like.
  • R e and R f are oxygen atoms having a substituent
  • the substituent of R e and the substituent of R f may be the same or different.
  • R e and R f are oxygen atoms
  • R e , R f and the boron atom bonded to R e and R f together form a ring good too.
  • the ring structure include a structure in which R e and R f are linked to the same aryl ring or heteroaryl ring, and a structure in which R e and R f are linked by an alkylene group.
  • R 1 , R m , R n , and R 0 are each independently a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group , represents an aryl group or a heteroaryl group.
  • R l , R m , R n , or R o 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 has a strong bond with a boron atom. Therefore, a fluorine atom is particularly preferred.
  • Compounds in which R 1 , R m , R n , and R 0 are fluorine atoms have high heat resistance and are therefore advantageous when melt-kneaded with a resin at high temperatures.
  • C 1-20 alkyl group means an alkyl group having 1 to 20 carbon atoms
  • C 1-20 alkoxy group means an alkoxy group having 1 to 20 carbon atoms. do.
  • the alkyl group may be linear, branched, cyclic (aliphatic group).
  • the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, heptyl group, octyl group and nonyl group. , decyl group, undecyl group, dodecyl group and the like.
  • the alkyl group portion of the alkoxy group may be linear, branched or cyclic. (aliphatic ring group).
  • the alkoxy group include methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, t-butyloxy, pentyloxy, isoamyloxy, hexyloxy, heptyloxy, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.
  • R l , R m , R n or R o is an aryl group
  • the aryl group includes a phenyl group, a naphthyl group, an indenyl group, a biphenyl group and the like.
  • the heteroaryl group includes pyrrolyl group, imidazolyl group, pyrazolyl group, thienyl group, furanyl group, oxazolyl group, isoxazolyl group, thiazolyl group, 5-membered ring heteroaryl groups such as isothiazolyl group and thiadiazole group; 6-membered ring heteroaryl groups such as pyridinyl group, pyrazinyl group, pyrimidinyl group and pyridazinyl group; indolyl group, isoindolyl group, indazolyl group, quinolidinyl group, quinolinyl group, isoquinolinyl and fused heteroaryl groups such as benzofuranyl, isobenzofuranyl, chromenyl, benzoxazolyl, benzoisoxazolyl, benzothiazoly
  • the C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, and heteroaryl group represented by R l , R m , R n , or R o may be an unsubstituted group, and may be one or more A hydrogen atom may be substituted by a substituent.
  • substituents include halogen atoms, alkyl groups, alkoxy groups, nitro groups, cyano groups, hydroxy groups, amino groups, thiol groups, carboxyl groups, aldehyde groups, sulfonic acid groups, isocyanate groups, thioisocyanate groups, and aryl groups. , a heteroaryl group, and the like.
  • R l , R m , R n , and R o are halogen atoms, unsubstituted aryl groups, or substituted aryl groups is preferred, a fluorine atom, a chlorine atom, a bromine atom, an unsubstituted phenyl group, or a phenyl group substituted with a C 1-20 alkyl group or a C 1-20 alkoxy group is preferred, and a fluorine atom, a chlorine atom, an unsubstituted A phenyl group, or a phenyl group substituted with a C 1-10 alkyl group or a C 1-10 alkoxy group is more preferable, and a fluorine atom or an unsubstituted phenyl group is particularly preferable.
  • R p and R q are each independently a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or represents a heteroaryl group.
  • Halogen atoms, C 1-20 alkyl groups, C 1-20 alkoxy groups, aryl groups, and heteroaryl groups represented by R p and R q are R l , R m , and R n in general formula (I 3 ). , or similar to Ro .
  • R p and R q are preferably a hydrogen atom or an aryl group, an unsubstituted phenyl group, or a C 1-20 alkyl group. or a phenyl group substituted with a C 1-20 alkoxy group, more preferably an unsubstituted phenyl group or a phenyl group substituted with a C 1-20 alkoxy group, and unsubstituted phenyl or a phenyl group substituted with a C 1-10 alkoxy group.
  • R g represents a hydrogen atom or an electron-withdrawing group.
  • R r and R s each independently represent a hydrogen atom or an electron-withdrawing group.
  • the electron-withdrawing group include halogenated methyl groups such as trifluoromethyl group; nitro group; cyano group; aryl group; heteroaryl group; alkynyl group; An oxy group, an amide group, a substituent having a carbonyl group such as an aldehyde group; a sulfoxide group; a sulfonyl group; an alkoxymethyl group; Heteroaryl groups and the like can also be used.
  • a trifluoromethyl group, a nitro group, a cyano group, a phenyl group, a sulfonyl group, and the like, which can function as a strong electron-withdrawing group, are preferable from the viewpoint of lengthening the maximum fluorescence wavelength.
  • a compound represented by the following general formula (I 1 -0) or general formula (I 2 -0) is preferable as the near-infrared fluorescent dye according to the present invention.
  • a compound having a boron dipyrromethene skeleton is preferable because the maximum fluorescence wavelength becomes longer, and in particular the following (p2), (p3), (q2), or (q3) is satisfied, and the pyrrole ring is an aromatic ring or
  • a compound condensed with a heteroaromatic ring is preferable as a near-infrared fluorescent dye because the maximum wavelength is longer.
  • R 1 , R 2 and R 3 satisfy any one of the following (p1) to (p3).
  • (p1) independently of each other, representing a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 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
  • R 3 is a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl or (p3)
  • R 2 and R 3 together form an aromatic 5-membered ring or 6-membered aromatic ring
  • R 1 is a hydrogen atom, a halogen atom, or a C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, or heteroaryl group.
  • R 4 , R 5 and R 6 satisfy any one of the following (q1) to (q3).
  • (q1) each independently represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group;
  • (q2) R 4 and R 5 together form a 5-membered aromatic ring or 6-membered aromatic ring
  • R 6 is a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl or
  • R 5 and R 6 together form a 5-membered or 6-membered aromatic ring
  • R 4 is a hydrogen atom, a halogen atom, or a C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, or heteroaryl group.
  • halogen atom, C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, and heteroaryl group in (p1) to (p3) or (q1) to (q3) are respectively R a and R Those exemplified as "any group that does not inhibit the fluorescence of the compound" in b can be used.
  • the aromatic 5-membered ring or aromatic 6-membered ring formed together by R 1 and R 2 the aromatic ring formed together by R 4 and R 5 5-membered ring or 6-membered aromatic ring, 5-membered aromatic ring or 6-membered aromatic ring formed together by R 2 and R 3 , 5 -membered aromatic ring or 6- membered aromatic ring formed together by R 5 and R 6
  • the ring is preferably represented by any one of the following general formulas (C-1) to (C-9), and the following general formulas (C-1), (C-2), or (C-9) Those represented by any one of are more preferable.
  • Y 1 to Y 8 each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom.
  • the Y 1 to Y 8 are each independently preferably a sulfur atom, an oxygen atom or a nitrogen atom, and are more preferably each independently a sulfur atom or an oxygen atom.
  • R 11 to R 22 each independently represent a hydrogen atom or any group that does not inhibit the fluorescence of the compound.
  • the "arbitrary group that does not inhibit the fluorescence of the compound” those exemplified for the "arbitrary group that does not inhibit the fluorescence of the compound” for Ra and Rb can be used.
  • R 11 to R 22 are each independently preferably a hydrogen atom, an unsubstituted aryl group, an aryl group having a substituent, an unsubstituted heteroaryl group, or a heteroaryl group having a substituent,
  • a hydrogen atom, a (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 is more preferred, and a hydrogen atom, (unsubstituted ) phenyl group or p-methoxyphenyl group is more preferred.
  • the compound contains at least one of the unsubstituted aryl group, the aryl group having a substituent, and the unsubstituted heteroaryl group. , or a heteroaryl group having a substituent is particularly preferred.
  • R 1 and R 4 , R 2 and R 5 , and R 3 and R 6 may be different. , are preferably groups of the same type. That is, when R 1 , R 2 , and R 3 satisfy (p1) above, R 4 , R 5 , and R 6 preferably satisfy (q1) above, and R 1 , R 2 , and when R 3 satisfies the above (p2), R 4 , R 5 and R 6 preferably satisfy the above (q2), and R 1 , R 2 and R 3 preferably satisfy the above (p3) is satisfied, R 4 , R 5 and R 6 preferably satisfy (q3) above.
  • R 1 and R 2 form a ring and R 4 and R 5 form a ring, or R 2 and R 3 form a ring, and R 5 and R 6 preferably form a ring. That is, R 1 , R 2 and R 3 preferably satisfy (p2) or (p3) above, and R 4 , R 5 and R 6 preferably satisfy (q2) or (q3) above. This is because condensing an aromatic ring or a heteroaromatic ring to the boron dipyrromethene skeleton further shifts the maximum fluorescence wavelength to the longer wavelength side.
  • R 7 and R 8 represent a halogen atom or an oxygen atom.
  • R 7 and R 8 are oxygen atoms
  • R 7 , the boron atom bonded to R 7 , the nitrogen atom bonded to the boron atom, R 1 , and the carbon atom bonded to R 1 together form a ring
  • R 8 , the boron atom bonded to R 8 , the nitrogen atom bonded to the boron atom, R 4 , and the carbon atom bonded to R 4 may together form a ring.
  • the ring formed by R7 , a boron atom, R1 , etc., and the ring formed by R8 , a boron atom, R4, etc. are both condensed with the boron dipyrromethene skeleton.
  • the ring formed by R7 , a boron atom, R1 , etc. and the ring formed by R8 , a boron atom, R4, etc. are preferably six-membered rings.
  • R 7 when R 7 is an oxygen atom and does not form a ring, R 7 is an oxygen atom having a substituent (substituent and oxygen atoms). Examples of the substituent include a C 1-20 alkyl group, an aryl group, a heteroaryl group, and the like.
  • R 8 when R 8 is an oxygen atom and does not form a ring, R 8 is an oxygen atom having a substituent (an oxygen atom bonded to a substituent). Examples of the substituent include a C 1-20 alkyl group, an aryl group, a heteroaryl group, and the like.
  • the substituents of R 7 and R 8 may be the same or different.
  • R 9 represents a hydrogen atom or an electron-withdrawing group.
  • the electron-withdrawing group include the same groups as those mentioned above for Rg .
  • a fluoroalkyl group, a nitro group, a cyano group, an aryl group, and a sulfonyl group, which can function as a strong electron-withdrawing group are preferred from the viewpoint of lengthening the maximum fluorescence wavelength, and a trifluoromethyl group, a nitro group, and a cyano group, phenyl group, sulfonyl group and the like are more preferred, and trifluoromethyl group, cyano group, phenyl group and sulfonyl group are more preferred from the viewpoint of safety to the living body.
  • both R 1 and R 2 are represented by the general formula (C -1)
  • one of R 11 and R 12 is a hydrogen atom, and the remaining one has 1 to 3 hydrogen atoms of a halogen atom, a C 1-20 alkyl group, or a C 1-20 forming a ring which is a phenyl group, thienyl group or furanyl group optionally substituted by an alkoxy group
  • R 4 and R 5 together form the same kind of ring as the ring formed by R 1 and R 2 and R 3 and R 6 are hydrogen atoms
  • R 7 and R 8 are halogen atoms
  • one of 13 and R 14 is a hydrogen atom, and the remaining one may have 1 to 3 hydrogen atoms substituted with a halogen atom, a C 1-20 alkyl group, or a C 1-20 alkoxy group
  • one of 13 and R 14 is a hydrogen atom, and the remaining one may have 1 to 3 hydrogen atoms substituted with a halogen
  • R 5 and R 6 are both R 2 and A compound in which R 1 and R 4 are hydrogen atoms, and R 7 and R 8 are halogen atoms; -9), 1 to 3 hydrogen atoms in any one of R 19 to R 22 are replaced by a halogen atom, a C 1-20 alkyl group, or a C 1-20 alkoxy group optionally substituted phenyl group, thienyl group or furanyl group, the remaining 3 groups form a ring in which the remaining 3 are hydrogen atoms, and both R 5 and R 6 are the same as the ring formed by R 2 and R 3 forming a ring, wherein R 1 and R 4 are a hydrogen atom, a halogen atom, a C 1-20 alkyl group
  • Preferred compounds for the near-infrared fluorescent dye according to the present invention include the following general compounds (I 1 -1), (I 1 -2), (I 1 -3), (I 2 -1), (I 2 - 2) and (I 2 -3).
  • R 1 , R 3 , R 4 , and R 6 to R 8 are as defined above
  • ED represents an electron-donating group
  • EW represents an electron-withdrawing group.
  • Z 1 to Z 4 rings each independently represent a 5- or 6-membered aryl group or a 5- or 6-membered heteroaryl group.
  • general formula (I 1 -1) compounds represented by general formulas (I 1 -1-1) to (I 1 -1-6) below are preferred, and general formula (I 1 -2) below is is preferably a compound represented by the following general formulas (I 1 -2-1) to (I 1 -2-12 ). -1) to (I 2 -1-6) are preferred, and the following general formulas (I 2 -2-1) to (I 2 -2- Compounds represented by 12) are preferred.
  • Q 11 is a hydrogen atom or an electron-withdrawing represents a group.
  • the electron-withdrawing group include the same groups as those mentioned above for Rg .
  • Compounds represented by general formula (I 1 -1-1) and the like are preferably compounds in which Q 11 is a trifluoromethyl group, a cyano group, a nitro group, or an optionally substituted phenyl group, A compound that is a trifluoromethyl group or an optionally substituted phenyl group is more preferred.
  • X is independently represents a halogen atom, a C1-20 alkoxy group, an aryloxy group, or an acyloxy group.
  • the alkyl group portion of the alkoxy group may be linear, branched, or cyclic (aliphatic ring group).
  • the alkoxy group include methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, t-butyloxy, pentyloxy, isoamyloxy, hexyloxy, heptyloxy, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.
  • the aryloxy group includes a phenyloxy group, a naphthyloxy group, an indenyloxy group, a biphenyloxy group, and the like.
  • the acyloxy group is preferably an alkylcarbonyloxy group or an arylcarbonyloxy group.
  • alkylcarbonyloxy group include a methylcarbonyloxy group (acetoxy group), an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, and a t-butylcarbonyloxy group.
  • arylcarbonyloxy group examples include phenylcarbonyloxy group (benzoyloxy group), naphthylcarbonyloxy group, indenylcarbonyloxy group, biphenylcarbonyloxy group and the like.
  • all Xs are halogen atoms, and particularly preferably all Xs are fluorine atoms.
  • P 11 to P 14 and P 17 are each independently a halogen atom
  • C 1 represents a -20 alkyl group, a C1-20 alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group
  • the C 1-20 alkyl group, C 1-20 alkoxy group, monoalkylamino group, or dialkylamino group for P 11 to P 14 are represented by R g , (p1) to (p3), and (q1), respectively.
  • P 11 to P 14 and P 17 are C 1-20 alkyl group, C 1-20 alkoxy group, (unsubstituted) phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-dimethylaminophenyl is preferably C 1-20 alkyl group, C 1-20 alkoxy group, phenyl group, p-methoxyphenyl group, p- More preferably, it is an ethoxyphenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group, and these substituents may further have a substituent. However, even if it is a substituent other than these substituents, it is not limited to these substituents because the safety can be improved by further introducing a suitable substituent.
  • n11 to n14 and n17 each independently represent an integer of 0 to 3.
  • the plurality of P 11 may all be the same type of functional group, or different types of functional groups. good too. The same is true for P 12 to P 14 and P 17 .
  • a 11 to A 14 are each independently a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group, and a phenyl group optionally having 1 to 3 substituents selected from the group consisting of a dialkylamino group, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, and a monoalkyl; represents a heteroaryl group optionally having 1 to 3 substituents selected from the group consisting of an amino group and a dialkylamino group; Examples
  • the C 1-20 alkyl group, C 1-20 alkoxy group, monoalkylamino group, or dialkylamino group in the substituent that the phenyl group or the heteroaryl group may have may be R g or The same as those mentioned in (p1) to (p3) and (q1) to (q3) can be mentioned.
  • a 11 to A 14 are preferably an unsubstituted phenyl group, a phenyl group having one or two C 1-20 alkoxy groups as substituents, or a heteroaryl group, an unsubstituted phenyl group, or one more preferably a phenyl group having a C 1-20 alkoxy group as a substituent, more preferably an unsubstituted phenyl group or a phenyl group having one C 1-10 alkoxy group as a substituent, an unsubstituted phenyl group, Or a phenyl group having one C 1-6 alkoxy group as a substituent is more preferred.
  • all of A 11 to A 14 are preferably the same functional group.
  • the following general formulas (1-1) to (1-37), (2-1) to (2-7), (3-1) to (3- 37), (4-1) to (4-7), and compounds represented by any of (5-1) to (5-2) are preferable, and the following general formulas (1-1) to (1-12) ), (1-25) ⁇ (1-31), (2-1) ⁇ (2-7), compounds represented by any of (3-25) ⁇ (3-31) are more preferable, and the following general formulas (1-1), (1-3), (1-4), (1-6), (1-25), (1-27), (2-1), (3-1), Compounds represented by any one of (3-3), (3-4), (3-6), (3-25), (3-27) and (4-1) are more preferred.
  • P 1 to P 4 and P 18 are each independently a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkyl Represents an amino group and a dialkylamino group.
  • the C 1-20 alkyl group, C 1-20 alkoxy group, monoalkylamino group, or dialkylamino group for P 1 to P 4 are represented by R g , (p1) to (p3), and (q1), respectively. The same as those mentioned in (q3) can be mentioned.
  • P 1 to P 4 and P 18 are C 1-20 alkyl group, C 1-20 alkoxy group, (unsubstituted) phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-dimethylaminophenyl group, dimethoxyphenyl group, thienyl group , or furanyl group. More preferably, it is an ethoxyphenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group, and these substituents may further have a substituent. However, even if it is a substituent other than these substituents, it is not limited to these substituents because the safety can be improved by further introducing a suitable substituent.
  • n1 to n4 and n18 each independently represent an integer of 0 to 3.
  • the plurality of P 1 may all be the same type of functional group, or different types of functional groups. good too. The same is true for P 2 to P 4 and P 18 .
  • Q is a trifluoromethyl group, a cyano group, a nitro group, or substituted It represents a phenyl group which may have a group, preferably a trifluoromethyl group or a phenyl group which may have a substituent, more preferably a trifluoromethyl group or an unsubstituted phenyl group.
  • substituents that the phenyl group may have include halogen atoms, C 1-20 alkyl groups, C 1-20 alkoxy groups, amino groups, monoalkylamino groups, dialkylamino groups and the like.
  • X is the same as in general formula (I 1 -1-1) and the like.
  • X is preferably a halogen atom, particularly preferably a fluorine atom.
  • n2 is 0 or 1 in general formulas (1-32) to (1-34) and (3-32) to (3-34). In the compound represented by general formula (1-32) or the like, m2 is preferably 1.
  • P 1 to P 4 and P 18 are independent of each other C 1-20 alkyl group, C 1-20 alkoxy group, (unsubstituted) phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-dimethylaminophenyl group, dimethoxyphenyl group, thienyl group , or a furanyl group, n1 to n4 and n18 independently of each other are 0 to 2, and Q is a trifluoromethyl group or a phenyl group.
  • compounds represented by general formulas (3-1) to (3-37), (4-1) to (4-7), and (5-2) include P 1 to P 4 and P 18 are each independently a C 1-20 alkyl group, a C 1-20 alkoxy group, a (unsubstituted) phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-dimethylaminophenyl group, dimethoxyphenyl; thienyl group or furanyl group, wherein n1-n4 and n18 are each independently 0-2.
  • the near-infrared fluorescent dye according to the present invention since the maximum fluorescence wavelength is longer, a compound represented by any one of the following general formulas (I 3 -1) to (I 3 -6), or general Compounds represented by any one of formulas (I 4 -1) to (I 4 -6) are also preferred.
  • R 23 , R 24 , R 25 and R 26 are independently represents a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group.
  • halogen atom C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, and heteroaryl group represented by R 23 , R 24 , R 25 or R 26 , R The same as l , R m , R n , or R o can be mentioned.
  • R 23 , R 24 , R 25 and R 26 are preferably halogen atoms, unsubstituted aryl groups, or substituted aryl groups, specifically fluorine atoms, A chlorine atom, a bromine atom, an unsubstituted phenyl group, or a phenyl group substituted with a C1-20 alkyl group or a C1-20 alkoxy group is preferred, and a fluorine atom, a chlorine atom, an unsubstituted phenyl group, or a C1 A phenyl group substituted with a -10 alkyl group or a C 1-10 alkoxy group is more preferable, and a fluorine atom or an unsubstituted phenyl group is
  • R 27 and R 28 are each independently 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.
  • the halogen atom, C 1-20 alkyl group, C 1-20 alkoxy group, aryl group and heteroaryl group represented by R 27 or R 28 are the same as R p or R q in the general formula (I 3 ). things are mentioned.
  • R 27 and R 28 are a hydrogen atom or an aryl group, and a hydrogen atom, an unsubstituted phenyl group, a C 1-20 alkyl group, or a C 1-20 alkoxy group, since a compound with high luminous efficiency can be obtained.
  • a phenyl group substituted with a group is preferably a phenyl group substituted with a group, more preferably a phenyl group substituted with a hydrogen atom, an unsubstituted phenyl group, or a linear or branched C 1-20 alkoxy group, An unsubstituted phenyl group or a phenyl group substituted with a linear or branched C 1-10 alkoxy group, since a compound with high luminous efficiency and excellent compatibility with resins can be obtained. is particularly preferred.
  • R 29 and R 30 each independently represent a hydrogen atom or an electron-withdrawing group.
  • Examples of the electron-withdrawing group represented by R 29 or R 30 include the same as R r or R s in the general formula (I 3 ).
  • R 29 and R 30 is preferably a fluoroalkyl group, nitro group, cyano group, or aryl group that can function as a strong electron-withdrawing group, and may have a trifluoromethyl group, a nitro group, a cyano group, or a substituent.
  • a phenyl group is more preferable, and a trifluoromethyl group or a cyano group is more preferable because a compound having high luminous efficiency and excellent compatibility with a resin can be obtained.
  • Y 9 and Y 10 each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom.
  • Y 9 and Y 10 are each independently a sulfur atom, An oxygen atom or a nitrogen atom is preferred, and a sulfur atom or an oxygen atom independently of each other is more preferred, and a compound having both high luminous efficiency and thermal stability is obtained. More preferably, both are oxygen atoms.
  • X 1 and X 2 each independently represent a nitrogen atom or a phosphorus atom. show.
  • X 1 and X 2 have high luminous efficiency.
  • a nitrogen atom or a phosphorus atom is preferable because a compound can be obtained, and a nitrogen atom is more preferable because a compound having both high luminous efficiency and thermal stability can be obtained.
  • R 31 and R 32 satisfy (p4) or (p5) below.
  • (p4) each independently represent a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group;
  • 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 satisfy (q4) or (q5) below.
  • (q4) each independently represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group, or (q5) R 33 and R 34 are both It forms an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring.
  • R 35 , R 36 , R 37 and R 38 are the following (p6 ) to (p9) are satisfied.
  • (p6) each independently represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group;
  • R 35 and R 36 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, and
  • R 37 and R 38 Each independently represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group.
  • 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 represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group.
  • 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 Each independently represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group.
  • R 39 , R 40 , R 41 and R 42 are the following (q6 ) to (q9) are satisfied.
  • (q6) each independently represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group;
  • R 39 and R 40 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, and
  • R 41 and R 42 Each independently represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group.
  • 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 Each independently represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group.
  • 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 Each independently represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group.
  • halogen atoms C 1-20 alkyl groups, C 1-20 alkoxy groups, aryl groups and heteroaryl groups in (p4), (p6) to (p9) and (q4) and (q6) to (q9) can use those exemplified as “any group that does not inhibit the fluorescence of the compound” for R a and R b , respectively.
  • R 23 , R 24 , R 25 and R 26 are all halogen atoms, unsubstituted phenyl groups, or C 1-10 alkyl groups or C 1-10 a phenyl group substituted with an alkoxy group; both R 27 and R 28 are a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C 1-20 alkyl group or a C 1-20 alkoxy group; R 29 and R 30 are both a trifluoromethyl group, a nitro group, a cyano group, or a phenyl group; Y 9 and Y 10 are both a sulfur atom or an oxygen atom; R 31 and R 32 are each independently hydrogen an atom or a C 1-20 alkyl group, or R 31 and R 32 together form a phenyl group which may have a substituent ; 20 alkyl group, or a compound in which R 33 and R 34 together form form a phenyl group which may have
  • 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 a phenyl group substituted with an alkoxy group;
  • both R 29 and R 30 are a trifluoromethyl group, a nitro group, or a cyano group;
  • R 35 , R 36 , R 37 and R 38 are independent is a hydrogen atom or a C 1-20 alkyl group, R 35 and R 36 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group, and
  • R 37 and R 38 are independent of each other are a hydrogen atom or a C 1-20 alkyl group,
  • R 36 and R 37 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10
  • R 40 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group
  • R 41 and R 42 are each independently a hydrogen atom or a C 1-20 alkyl group
  • R 40 and R 41 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group
  • R 39 and R 42 are each independently a hydrogen atom or a C 1-20 alkyl group, or R a compound in which 41 and R 42 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group
  • R 39 and R 40 are each independently a hydrogen atom or a C 1-20 alkyl group is more preferable because it has high luminous efficiency and excellent compatibility with the resin.
  • R 23 , R 24 , R 25 and R 26 are all halogen atoms, unsubstituted phenyl groups, or C 1-10 alkyl groups or C 1-10 a phenyl group substituted with an alkoxy group; both R 27 and R 28 are a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C 1-20 alkyl group or a C 1-20 alkoxy group; R 29 and R 30 are both trifluoromethyl group, nitro group, cyano group, or phenyl group; X 1 and X 2 are both nitrogen atoms; R 36 , R 37 and R 38 are each independently a hydrogen atom or a C 1-20 alkyl group, R 36 and R 37 together form an optionally substituted phenyl group, and R 38 is a hydrogen atom or a C 1-20 alkyl group, or R 37 and R 38 together form an optionally substituted phen
  • R 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 each independently which is a hydrogen atom or a C 1-20 alkyl group, R 36 and R 37 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group, and R 38 is a hydrogen atom or a C 1- 20 alkyl group, or R 37 and R 38 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group, and R 36 is a hydrogen atom or a C 1-20 alkyl group;
  • R 40 , R 41 , and R 42 are each independently a hydrogen atom or a C 1-20 alkyl group, and both R 40 and R 41 are substituted with an unsubstituted phenyl group or a C 1-10 alky
  • R 23 , R 24 , R 25 and R 26 are all halogen atoms, unsubstituted phenyl groups, or C 1-10 alkyl groups or C 1-10 a phenyl group substituted with an alkoxy group; both R 27 and R 28 are a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C 1-20 alkyl group or a C 1-20 alkoxy group; R 29 and R 30 are both trifluoromethyl group, nitro group, cyano group, or phenyl group; X 1 and X 2 are both nitrogen atoms; R 35 , R 36 and R 37 are each independently a hydrogen atom or a C 1-20 alkyl group, R 35 and R 36 together form an optionally substituted phenyl group, and R 37 is a hydrogen atom or a C 1-20 alkyl group, or R 36 and R 37 together form an optionally substituted phen
  • R 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 each independently which is a hydrogen atom or a C 1-20 alkyl group, R 35 and R 36 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group, and R 37 is a hydrogen atom or a C 1- 20 alkyl group, or R 36 and R 37 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group, and R 35 is a hydrogen atom or a C 1-20 alkyl group;
  • R 39 , R 40 and R 41 are each independently a hydrogen atom or a C 1-20 alkyl group, and both R 39 and R 40 are substituted with an unsubstituted phenyl group or a C 1-10 alkyl group
  • R 23 , R 24 , R 25 and R 26 are all halogen atoms, unsubstituted phenyl groups, or C 1-10 alkyl groups or C 1-10 a phenyl group substituted with an alkoxy group; both R 27 and R 28 are a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C 1-20 alkyl group or a C 1-20 alkoxy group; R 29 and R 30 are both a trifluoromethyl group, a nitro group, a cyano group, or a phenyl group; both X 1 and X 2 are a nitrogen atom; R 35 , R 36 and R 38 are each independently a hydrogen atom or a C 1-20 alkyl group, or R 35 and R 36 together form an optionally substituted phenyl group, and R 38 is a hydrogen atom or a C 1-20 alkyl group; R 39 , R
  • R 23 , R 24 , R 25 and R 26 are all halogen atoms, unsubstituted phenyl groups, or C 1-10 alkyl groups or C 1-10 a phenyl group substituted with an alkoxy group; both R 27 and R 28 are a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C 1-20 alkyl group or a C 1-20 alkoxy group; both R 29 and R 30 are a trifluoromethyl group, a nitro group, a cyano group, or a phenyl group; both X 1 and X 2 are a nitrogen atom; R 35 , R 37 and R 38 are each independently a hydrogen atom or a C 1-20 alkyl group, or R 37 and R 38 together form an optionally substituted phenyl group, and R 35 is a hydrogen atom or a C 1-20 alkyl group; R 39 , R
  • R 23 , R 24 , R 25 and R 26 are all halogen atoms, unsubstituted phenyl groups, or C 1-10 alkyl groups or C 1-10 a phenyl group substituted with an alkoxy group; both R 27 and R 28 are a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C 1-20 alkyl group or a C 1-20 alkoxy group; both Y 9 and Y 10 are a sulfur atom or an oxygen atom; R 31 and R 32 are each independently a hydrogen atom or a C 1-20 alkyl group, or both R 31 and R 32 have a substituent; R 33 and R 34 are each independently a hydrogen atom or a C 1-20 alkyl group, or R 33 and R 34 are both optionally substituted phenyl R 23 , R 24 , R 25 and R 26 are both halogen atoms or unsubstituted
  • R 23 , R 24 , R 25 and R 26 are all halogen atoms, unsubstituted phenyl groups, C 1-10 alkyl groups or C 1-10 a phenyl group substituted with an alkoxy group; both R 27 and R 28 are a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C 1-20 alkyl group or a C 1-20 alkoxy group; R 35 , R 36 , R 37 and R 38 are each independently a hydrogen atom or a C 1-20 alkyl group, and both R 35 and R 36 form an optionally substituted phenyl group; , R 37 and R 38 are each independently a hydrogen atom or a C 1-20 alkyl group, R 36 and R 37 together form an optionally substituted phenyl group, and R 35 and R 38 are each independently a hydrogen atom or a C 1-20 alkyl group, or R 37 and R 38
  • R 27 and R 28 are both an unsubstituted phenyl group or a phenyl group substituted with a linear or branched C 1-20 alkoxy group;
  • R 35 , R 36 , R 37 and R 38 are each independently a hydrogen atom or a C 1-20 alkyl group, R 35 and R 36 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group, and
  • R 37 and R 38 is independently a hydrogen atom or a C 1-20 alkyl group, R 36 and R 37 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group, and
  • R 35 and R 38 are each independently a hydrogen atom or a C 1-20 alkyl group, or R 37 and R 38 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group, R
  • R 23 , R 24 , R 25 and R 26 are all halogen atoms, unsubstituted phenyl groups, or C 1-10 alkyl groups or C 1-10 a phenyl group substituted with an alkoxy group; both R 27 and R 28 are a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C 1-20 alkyl group or a C 1-20 alkoxy group; X 1 and X 2 are both nitrogen atoms; R 36 , R 37 and R 38 are each independently a hydrogen atom or a C 1-20 alkyl group; R 38 is a hydrogen atom or a C 1-20 alkyl group, or both R 37 and R 38 form a phenyl group which may be substituted, and R 36 is a hydrogen atom or a C 1-20 alkyl group ; R 42 is a hydrogen atom or a C 1-20 alkyl group, or both R
  • R 23 , R 24 , R 25 and R 26 are all halogen atoms, unsubstituted phenyl groups, or C 1-10 alkyl groups or C 1-10 a phenyl group substituted with an alkoxy group; both R 27 and R 28 are a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C 1-20 alkyl group or a C 1-20 alkoxy group; X 1 and X 2 are both nitrogen atoms; R 35 , R 36 and R 37 are each independently a hydrogen atom or a C 1-20 alkyl group, and both R 35 and R 36 have a substituent; R 37 is a hydrogen atom or a C 1-20 alkyl group, or both R 36 and R 37 form a phenyl group which may be substituted, and R 35 is a hydrogen atom or a C 1-20 alkyl group; R 39 , R 40 and R 41 are
  • R 23 , R 24 , R 25 and R 26 are all halogen atoms, unsubstituted phenyl groups, or C 1-10 alkyl groups or C 1-10 a phenyl group substituted with an alkoxy group; both R 27 and R 28 are a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C 1-20 alkyl group or a C 1-20 alkoxy group; X 1 and X 2 are both nitrogen atoms; R 35 , R 36 and R 38 are each independently hydrogen atoms or C 1-20 alkyl groups, or R 35 and R 36 both have substituents; R 38 is a hydrogen atom or a C 1-20 alkyl group; R 39 , R 40 and R 42 are each independently a hydrogen atom or a C 1-20 alkyl group; or R 39 and R 40 together form an optionally substituted phenyl group, and R 42 is a hydrogen
  • R 23 , R 24 , R 25 and R 26 are all halogen atoms, unsubstituted phenyl groups, or C 1-10 alkyl groups or C 1-10 a phenyl group substituted with an alkoxy group; both R 27 and R 28 are a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C 1-20 alkyl group or a C 1-20 alkoxy group; X 1 and X 2 are both nitrogen atoms; R 35 , R 37 and R 38 are each independently hydrogen atoms or C 1-20 alkyl groups, or R 37 and R 38 both have substituents; R 35 is a hydrogen atom or a C 1-20 alkyl group; R 39 , R 41 and R 42 are each independently a hydrogen atom or a C 1-20 alkyl group; or R 41 and R 42 together form an optionally substituted phenyl group, and R 39 is a hydrogen atoms, and R 39 is a hydrogen
  • Examples of the compound represented by any one of the above formulas (I 3 -1) to (I 3 -6) include compounds represented by any one of the following general formulas (I 3 -7) to (I 3 -9).
  • the compound represented by any one of (I 4 -1) to (I 4 -6) is represented by any one of the following general formulas (I 4 -7) to (I 4 -9) Compounds are preferred.
  • Y 23 and Y 24 each independently represent a carbon atom or a nitrogen atom.
  • Y 23 and Y 24 are preferably atoms of the same type.
  • Y 13 and Y 14 each independently represent an oxygen atom or a sulfur atom.
  • Y 13 and Y 14 are preferably atoms of the same type.
  • Y 25 and Y 26 each independently represent a carbon atom or a nitrogen atom.
  • Y 25 and Y 26 are preferably atoms of the same type.
  • R 47 and R 48 each independently represent a hydrogen atom or an electron-withdrawing group, and since the fluorescence intensity increases, trifluoromethyl is preferably a group, a cyano group, a nitro group, a sulfonyl group or a phenyl group, particularly preferably a trifluoromethyl group or a cyano group.
  • R 47 and R 48 are preferably the same functional group.
  • R 43 , R 44 , R 45 and R 46 are halogen atoms or substituted represents an aryl group which may have a group.
  • the aryl group those exemplified as "any group that does not inhibit the fluorescence of the compound" for Ra and Rb can be used.
  • the substituent that the aryl group may have may be "any group that does not inhibit the fluorescence of the compound", such as C 1-6 alkyl group, C 1-6 alkoxy group, groups, heteroaryl groups, and the like.
  • R 43 to R 46 may each be different groups, but they are all the same is preferably a group of As the compounds represented by any of general formulas (I 3 -7) to (I 3 -9) and (I 4 -7) to (I 4 -9), R 43 to R 46 are all the same All of them are preferably halogen atoms or phenyl groups which may have the same type of substituents, more preferably all fluorine atoms or unsubstituted phenyl groups, and particularly preferably all fluorine atoms. .
  • P 15 to P 16 are each independently a halogen atom
  • C 1-20 represents an alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group or a dialkylamino group
  • the C 1-20 alkyl group, C 1-20 alkoxy group, monoalkylamino group, or dialkylamino group for P 15 to P 16 are represented by R g , (p1) to (p3), and (q1), respectively. The same ones as mentioned in (q3) can be mentioned.
  • P 15 to P 16 are C 1-20 alkyl group, C 1-20 alkoxy group, (unsubstituted) phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-dimethylaminophenyl group, dimethoxy A phenyl group, a thienyl group, or a furanyl group is preferable, and from the viewpoint of safety to living organisms, a C 1-20 alkyl group, a C 1-20 alkoxy group, a phenyl group, a p-methoxyphenyl group, and a p-ethoxyphenyl group.
  • substituents may further have a substituent.
  • it is not limited to these substituents because the safety can be improved by further introducing a suitable substituent.
  • n15 to n16 each independently represent an integer of 0 to 3.
  • the plurality of P 15 may all be the same type of functional group, or different types of functional groups. good too. The same is true for P16 .
  • a 15 to A 16 each independently represent a hydrogen atom, a halogen atom, C represents a phenyl group optionally having 1 to 3 substituents selected from the group consisting of a 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group and a dialkylamino group; .
  • C 1-20 alkyl group C 1-20 alkoxy group, monoalkylamino group, or dialkylamino group in the substituents that the phenyl group may have, R g and (p1) to ( p3), and the same as those listed in (q1) to (q3).
  • a 15 to A 16 are preferably an unsubstituted phenyl group or a phenyl group having 1 or 2 C 1-20 alkoxy groups as substituents, and are preferably an unsubstituted phenyl group or 1 C 1-20 alkoxy A phenyl group having a group as a substituent is more preferable, and an unsubstituted phenyl group or a phenyl group having one C 1-10 alkoxy group as a substituent is even more preferable. Further, as for the compound represented by the general formula (I 3 -7) or the like, it is preferable that all of A 15 to A 16 are functional groups of the same type.
  • Compounds represented by any one of (I 3 -1) to (I 3 -6) and (I 4 -1) to (I 4 -6) include the following general formulas (6-1) to (6 -12), and compounds represented by any one of (7-1) to (7-12).
  • Ph means an unsubstituted phenyl group.
  • Compounds represented by any one of (I 3 -1) to (I 3 -6) and (I 4 -1) to (I 4 -6) include general formulas (6-4), ( 6-5), (6-7), (6-8), (7-4), (7-5), (7-7), and (7-8) are preferred compounds represented by the general formula Compounds represented by (6-4), (6-5), (6-7) and (6-8) are more preferred.
  • P 5 to P 8 are each independently a halogen atom, a C 1-20 alkyl group, a C Represents a 1-20 alkoxy group, amino group, monoalkylamino group, and dialkylamino group.
  • the C 1-20 alkyl group, C 1-20 alkoxy group, monoalkylamino group, or dialkylamino group for P 5 to P 8 are represented by R g , (p1) to (p3), and (q1), respectively. The same ones as mentioned in (q3) can be mentioned.
  • P 5 to P 8 are C 1-20 alkyl group, C 1-20 alkoxy group, (unsubstituted) phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-dimethylaminophenyl group, dimethoxy A phenyl group, a thienyl group, or a furanyl group is preferable, and from the viewpoint of safety to living organisms, a C 1-20 alkyl group, a C 1-20 alkoxy group, a phenyl group, a p-methoxyphenyl group, and a p-ethoxyphenyl group.
  • a dimethoxyphenyl group, a thienyl group or a furanyl group more preferably a C 1-20 alkyl group or a C 1-20 alkoxy group
  • a C 1-10 alkyl group or a C 1-10 alkoxy is more preferably a group
  • these substituents may further have a substituent.
  • it is a substituent other than these substituents, it is not limited to these substituents because the safety can be improved by further introducing a suitable substituent.
  • n5 to n8 each independently represents an integer of 0 to 3.
  • the plurality of P5 may all be the same type of functional group, or different types of functional groups. good too. The same applies to P 6 to P 8 .
  • P 5 to P 8 are each independently a C 1-20 alkyl group or It is preferably a C 1-20 alkoxy group
  • n5 to n8 are each independently 0 to 2
  • P 5 and P 6 are each independently a C 1-20 alkyl group
  • n5 and n6 are each independently 0 to 2
  • P 7 and P 8 are each independently a C 1-20 alkoxy group
  • n7 and n8 are each independently 0 to 1
  • P 5 and P 6 is independently a C 1-20 alkyl group
  • n5 and n6 are independently 1 to 2
  • P 7 and P 8 are independently a C 1-20 alkoxy group
  • n7 and More preferably, n8 is 1.
  • Specific examples of compounds represented by general formulas (6-1) to (6-12) include compounds represented by the following formulas (6-1-1) to (6-12-1). mentioned. “ ⁇ ” is the peak wavelength of the absorption spectrum of each compound, and “Em” is the peak wavelength of the fluorescence spectrum.
  • the powdery dye composition according to the present invention is a powdery dye composition comprising the near-infrared fluorescent dye according to the present invention, and is characterized in that it hardly reflects light with a wavelength within the range of 520 to 560 nm.
  • the reflection spectrum of the powdery dye composition according to the present invention has (a) no peak having a peak top within the range of 520 to 560 nm, or (b) a peak within the range of 520 to 560 nm. Although there is a peak with a top, the value obtained by subtracting the average value of relative reflectance in the range of 300 to 400 nm from the maximum value of relative reflectance in that range is 5% or less.
  • the powdery dye composition according to the present invention has good dispersibility in a resin by having the characteristic (a) or (b) in its reflection spectrum. It disperses uniformly in the resin composition, and aggregates of the near-infrared fluorescent dye are less likely to occur.
  • the reflection spectrum of the powdery dye composition according to the present invention may be measured by any measuring method as long as it can detect the reflected light within the range of 520 to 560 nm of the powder sample.
  • the reflection spectrum of the powdery dye composition according to the present invention is preferably a spectrum obtained by diffuse reflection measurement using white light (200 to 870 nm) as measurement light and an integrating sphere. Diffuse reflectance measurement using an integrating sphere makes it possible to accurately measure the reflectance (%) of a highly scattering powdery composition.
  • Diffuse reflectance measurement using an integrating sphere is performed by a standard method using various UV-visible spectrophotometers and UV-visible/near-infrared spectrophotometers capable of detecting diffusely reflected light and a device equipped with an integrating sphere unit. can.
  • the reflectance obtained by diffuse reflectance measurement using an integrating sphere is the relative reflectance based on the standard white plate.
  • standard white plates include white plates made of highly reflective materials such as barium sulfate, aluminum oxide, and magnesium oxide. In the measurement of the powdery dye composition according to the present invention, it is possible to appropriately select and use standard white plates that are generally used.
  • a powdery dye composition comprising a near-infrared fluorescent dye according to the present invention hardly reflects light within the range of 300 to 400 nm. Therefore, in the reflectance spectrum, the relative reflectance within the range of 300 to 400 nm has almost the lowest value, and no peak is detected within this range.
  • the near-infrared fluorescent dye according to the present invention changes the shape of the reflection spectrum within the range of 500 to 700 nm depending on the shape of the particles.
  • a powdery composition having the characteristic (a) or (b) in the reflection spectrum has good dispersibility in a resin. The present inventors have found for the first time that the shape of the reflection spectrum within the range of 520 to 560 nm serves as an indicator of the dispersibility in the resin.
  • the absence of a peak having a peak top within the range of 520 to 560 nm means that light within the range of 520 to 560 nm is hardly reflected.
  • the relative reflectance in the range 520-560 nm also has a near minimum, meaning that no peaks are detected in this range. Therefore, the value ([Rmax (%)] - [Rbase (%)]) is preferably 1% or less, more preferably 0% or less.
  • [Rmax (%)] - [Rbase (%)] is preferably -3% or more, more preferably -2% or more, and still more preferably -1% or more.
  • the value ([Rmax (% )]-[Rbase(%)]) is 5% or less, although reflection is observed in the range of 520 to 560 nm, the reflection is extremely small and can be almost ignored.
  • [Rmax (%)] - [Rbase (%)] is preferably 2.5% or less.
  • the sizes of the primary particles and secondary particles (aggregates of primary particles) of the near-infrared fluorescent pigment particles constituting the powdery pigment composition according to the present invention are not particularly limited.
  • the powdery dye composition according to the present invention it is preferable that 95% or more of the near-infrared fluorescent dye particles in the entire composition have a long diameter of 3 ⁇ m or less.
  • the size of the near-infrared fluorescent dye particles in the composition is sufficiently small, the dispersibility in the resin is further improved.
  • the long diameter of the near-infrared fluorescent pigment particles can be obtained by measuring the long diameter of the particles taken with a transmission electron microscope (TEM) image using image analysis.
  • TEM transmission electron microscope
  • a parallel line set with the shortest distance between two parallel lines touching the outline of the particle is specified, the distance between the parallel lines of the parallel line set is the minor axis of the particle, and the parallel line set A straight line connecting points where the two parallel lines intersect the outline of the particle is defined as the minor axis of the particle.
  • the particle size distribution of the long diameter of the near-infrared fluorescent dye particles of each powdery dye composition is preferably determined by measuring 1000 or more particles.
  • 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 defects in the appearance of the molded product are eliminated. Hard to come by. 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. In addition, it is possible to suppress the occurrence of dot-like and streak-like appearance defects.
  • a powdery composition having a reflection spectrum having the characteristic (a) or (b) is obtained by, for example, dissolving the near-infrared fluorescent dye according to the present invention by heating in a low-polar solvent, and then slowly cooling and recrystallizing the composition. and a powdering step of pulverizing the crystals obtained in the crystallization step to produce a powdery dye composition.
  • the solvent used for heating and dissolving the near-infrared fluorescent dye according to the present invention is not particularly limited as long as it is a low-polarity solvent.
  • low-polar solvents include toluene, xylene, naphthalene, hexane, benzene, tetrachloromethane, and the like.
  • toluene and xylene are particularly preferred because they have a relatively high boiling point and can easily dissolve the near-infrared fluorescent dye according to the present invention by heating.
  • the low-polarity solvent may be a mixed solvent containing a small amount of polar solvent.
  • the content of the polar solvent relative to the total amount of the solvent is, for example, preferably 30 v/v% or less, more preferably 20 v/v% or less, even more preferably 10 v/v% or less.
  • the polar solvent include methanol, ethanol, propanol, butanol, acetone, formic acid, methyl ethyl ketone, acetonitrile, dimethylsulfoxide, dimethylformamide and the like.
  • the low polar 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 alcohol having 1 to 4 carbon atoms is preferable, and 30 v/v% or less methanol
  • a toluene/alcohol mixed solvent containing one or more selected from the group consisting of propanol and isopropyl alcohol is more preferred.
  • the temperature is 10°C lower than the boiling point ([boiling point (°C)] -10°C) to the boiling point. is more preferable.
  • 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.
  • a solution in which a near-infrared fluorescent dye is heated and dissolved in a low-polarity solvent is slowly cooled and recrystallized.
  • the recrystallization can be performed, for example, by allowing the heated solution of the near-infrared fluorescent dye to stand at room temperature and allowing it to cool to around room temperature.
  • the heated solution of the near-infrared fluorescent dye is preferably cooled at 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.
  • Such recrystallization can also be achieved by cooling at a rate.
  • the powdery dye composition according to the present invention can be produced.
  • Powdering can be carried out by collecting the crystals by filtration from the solution in which the crystals were precipitated, and then drying the crystals.
  • the drying method is not particularly limited, and can be appropriately selected from among various drying methods such as air drying, heat drying, spray drying, and freeze drying.
  • 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. Since the resin composition according to the present invention is a resin composition that can stably emit near-infrared fluorescence with a high emission quantum yield and in which the generation of aggregates of the near-infrared fluorescent dye is suppressed. , and is suitably used as a medical material such as a raw material for medical equipment that is used in vivo and for which stability of product quality is strongly required.
  • 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 the resin component.
  • the near-infrared fluorescent dye according to the present invention contained in the resin composition according to the present invention may be of one type or may contain two or more types.
  • the resin component contained in the resin composition according to the present invention is not particularly limited. It can be used by appropriately selecting from known resin compositions and improved products thereof.
  • the resin component may be a thermoplastic resin or a thermosetting resin. Thermosetting resins may be cured during melt-kneading when used in molded articles, and thus the resin component contained in the resin composition according to the present invention is preferably a thermoplastic resin.
  • the resin component used in the present invention only one kind may be used, or two or more kinds may be mixed and used. When two or more types are mixed, it is preferable to use resins having high compatibility in combination.
  • urethane-based resins such as polyurethane (PU) and thermoplastic polyurethane (TPU); polycarbonate (PC); polyvinyl chloride (PVC); vinyl chloride-vinyl acetate copolymer resin; vinyl chloride resins; acrylic resins such as polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate (PMMA), polyethyl methacrylate; polyethylene terephthalate (PET), polybutylene terephthalate polyester resins such as polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate; polyamide resins such as nylon (registered trademark); polystyrene (PS), imide-modified polystyrene, acrylonitrile ⁇ Polystyrene resins such as butadiene-styrene (ABS) resin, imide-modified ABS resin, styrene-
  • ABS butadiene-st
  • the resin component contained in the resin composition according to the present invention since the near-infrared fluorescent dye according to the present invention has high dispersibility, the resin component may be fluorine-based resin, silicone-based resin, urethane-based resin, olefin -based resin, vinyl chloride-based resin, polyester-based resin, polystyrene-based resin, polycarbonate resin, polyamide-based resin or acrylic-based resin is preferred, urethane-based resin, olefin-based resin, polystyrene-based resin, polyester-based resin, and vinyl chloride-based resin is more preferred.
  • PTFE Teflon (registered trademark)
  • silicone PU, TPU, PP, PE, PC, PET, PS, polyamide and PVC
  • TPU, PU, PP, PE, PET and PS are more preferred.
  • the resin component as a whole may be a thermoplastic resin, and may contain a small amount of non-thermoplastic resin.
  • the resin component when the resin composition according to the present invention is a thermosetting resin composition, the resin component may be a thermosetting resin as the entire resin component, and may contain a small amount of non-thermosetting resin. good too.
  • 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 with the resin, but the fluorescence intensity and its detection sensitivity 0.0001% by mass or more is preferable, 0.0005% by mass or more is more preferable, and 0.001% by mass or more is even more preferable.
  • 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, so even if the dye concentration in the resin is relatively low, the light emission can be detected with a camera or the like. Sufficiently visible.
  • a low pigment concentration reduces the possibility of elution, reduces the possibility of bleeding out from molded articles processed from the resin composition, and allows processing of molded articles that require transparency. desirable from
  • the content of the near-infrared fluorescent dye according to the present invention in the resin composition is somewhat large.
  • the near-infrared fluorescent dye causes concentration quenching in the state of aggregates, but the near-infrared fluorescent dye according to the present invention has good dispersibility in resin, so a relatively large amount of the near-infrared fluorescent dye can be used. Even when included, concentration quenching can be avoided.
  • 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.
  • 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.
  • the resin composition according to the present invention can be obtained by adding the near-infrared fluorescent dye according to the present invention to the resin composition and melt-kneading the mixture. 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.
  • melt-kneading suitable for practical production is preferred.
  • the near-infrared fluorescent dye according to the present invention can be uniformly mixed and dispersed in various resin components, and can emit fluorescence with a high quantum yield even in the resin. Although the reason is not clear, it can be inferred as follows.
  • the pigment is dispersed by a method such as melt-kneading, it is desirable that the compatibility between the resin and the pigment is high in order to suppress aggregation.
  • SP value is mentioned as one index of whether the compatibility is high. If the difference between the SP value of the dye and the SP value of the resin is small, the compatibility is high and can be uniformly dispersed. On the other hand, even when the SP value or the like is different, it can be explained by other physical parameters.
  • the compatibility with the resin can be explained from calculated values, such as the solubility, partition coefficient, dielectric constant, and polarizability of the dye, or measured values. Also, the compatibility between the resin and the fluorescent dye may vary depending on the crystallinity of the resin.
  • the compatibility between the resin and the fluorescent dye can be controlled by the functional group of the fluorescent dye molecule itself.
  • the fluorescent dye molecules when dispersed in a fat-soluble (hydrophobic) polyolefin resin such as polypropylene or polyethylene, the fluorescent dye molecules preferably have a hydrophobic group.
  • the compatibility with the resin can be improved 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.
  • 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 fluorescent dye molecules When dispersing in highly polar resins such as polyurethane and polyamide, the fluorescent dye molecules have hydrophilic groups such as carboxyl groups, hydroxyl groups, amino groups, alkoxy groups, aryloxy groups, alkylamino groups, esters, and amides. preferably. However, it is not limited to these.
  • the near-infrared fluorescent dye according to the present invention has a dye skeleton consisting of a wide conjugation plane centered on a boron atom, so it easily aggregates. It is presumed that the aggregation of the pigment is suppressed by polarizing the pigment with a large amount and by introducing a bulky functional group, and compatibility with various resins can be realized.
  • the partition coefficient and SP value which are indices of compatibility, can be estimated as the water/octanol partition coefficient and Hildebrand SP value from the "Hansen solubility parameter" calculated from commercially available software.
  • the partition coefficients and SP values of compounds represented by the following compounds (8-1) to (8-8) are as follows.
  • the resin composition according to the present invention does not visually change color even when excited by excitation light in the near-infrared region, emits fluorescence in the invisible near-infrared region, and 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. Closer is preferable, 650 nm or more is more preferable, and 680 nm or more is particularly preferable. Furthermore, it is preferably 700 nm or more when used as a medical device such as an implant.
  • the resin composition according to the present invention preferably has a difference of 10 nm or more between the maximum absorption wavelength and the maximum fluorescence wavelength, 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 to cut noise caused by excitation light. be.
  • 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 it is possible to excite with light having a wavelength shorter than the maximum absorption wavelength, it is possible to detect fluorescence even if noise is cut. Moreover, when the fluorescence spectrum is broad, it is possible to sufficiently detect the fluorescence even if the noise is 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 can be detected with high sensitivity even when using a detector equipped with a noise-cut filter. is possible.
  • the difference between the fluorescence peak wavelength on the long wavelength side and the maximum absorption wavelength is 30 nm or more, preferably 50 nm or more. It should be noted that the conditions are not limited to those described above as long as the excitation light source, cut filter, and the like are appropriately selected.
  • the resin composition according to the present invention and the molded article obtained from the composition have a maximum fluorescence wavelength of 650 nm or more. Considering the color of the irradiated object does not change and the detection sensitivity is taken into consideration, there is no practical problem if the maximum fluorescence wavelength is 650 nm or more, but it is preferably 700 nm or more, more preferably 720 nm or more. preferable. In the case of having a plurality of fluorescence peaks, even if the wavelength of the maximum fluorescence peak is 720 nm or less, it is sufficient if there is a fluorescence peak at 740 nm or more with sufficient detection sensitivity. In this case, the intensity of the fluorescence peak (second peak) on the longer wavelength side is preferably 5% or more, more preferably 10% or more, of the intensity of the maximum fluorescence wavelength.
  • the resin composition according to the present invention and the molded article obtained from the composition preferably have strong absorption in the range of 650 nm to 1500 nm and emit strong fluorescence in this range.
  • Light above 650 nm is less affected by hemoglobin, and light below 1500 nm is less affected by water.
  • light in the range of 650 nm to 1500 nm has high skin permeability and is not easily affected by contaminants in the body, so the wavelength of light used for visualizing medical implants embedded under the skin It is suitable as a region.
  • the resin composition according to the present invention and the molded article obtained from the composition are suitable for detection with light in the range of 650 nm to 1500 nm, It is suitable as a medical device or the like used in vivo.
  • the resin composition according to the present invention may contain components other than the resin component and the near-infrared fluorescent dye as long as the effect of the present invention is not impaired.
  • Such other components include UV absorbers, heat stabilizers, light stabilizers, antioxidants, flame retardants, flame retardant aids, crystallization accelerators, plasticizers, antistatic agents, colorants, release agents, etc. is mentioned.
  • a molded article that can be detected by near-infrared fluorescence can be obtained.
  • the molding method is not particularly limited, but includes casting (casting method), injection molding using a mold, compression molding, extrusion molding using a T-die or the like, and blow molding.
  • a molded body In the production of a molded body, it 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.
  • the entire molded article may be molded from the resin composition of the present invention, or only a portion of the molded article may be molded from the resin composition of the present invention.
  • the resin composition according to the present invention is preferably used as a raw material for forming the surface portion of a molded article.
  • the tip portion of the catheter is molded from the resin composition according to the present invention, and the remaining portion is molded from a resin composition that does not contain a near-infrared fluorescent dye.
  • Catheters can be made that only emit near-infrared fluorescence.
  • a molded body that emits near-infrared fluorescence in stripes can be produced.
  • a surface coating may be applied to enhance the visibility of the molded product.
  • Fluorescence detection can be performed by a conventional method using a commercially available fluorescence detection device. Any light source can be used as the excitation light for fluorescence detection, and in addition to a near-infrared lamp with a long wavelength width, a laser with a narrow wavelength width, an LED, or the like can be used.
  • the molded article obtained from the resin composition containing the near-infrared fluorescent dye according to the present invention does not change in color even when irradiated with light in the near-infrared region, and can be detected with higher sensitivity than before. Since the molded article emits external fluorescence, it is particularly suitable for a medical device at least a part of which is to be inserted or left in the body of a patient.
  • Examples of such medical devices include stents, coil embolizers, catheter tubes, medical clips, injection needles, indwelling needles, ports, shunt tubes, drain tubes, implants, and the like.
  • Catheter tubes include ureter/urethral catheters, bile duct catheters, blood vessel catheters, and the like.
  • Medical clips include gastrointestinal clips and the like.
  • the color of the irradiated object may vary. If a little redness is acceptable, it is not always necessary to use excitation light in the near-infrared region.
  • excitation light when trying 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 range that is highly permeable to the living body such as the skin. Exciting light of 650 nm or more, which has high transmittance, may be used.
  • compound (a-1) (3.39 g, 16.8 mmol) and ethyl azidoacetate (8.65 g, 67.0 mmol) were dissolved in ethanol (300 mL) in a 1 L three-necked flask under an argon stream.
  • a 20% by mass sodium ethoxide ethanol solution (22.8 g, 67.0 mmol) was slowly added dropwise to the obtained solution in a 0° C. ice bath, and the mixture was stirred for 2 hours.
  • compound (a-2) (3.31 g, 10.6 mmol) was added to a 200 mL eggplant flask, dissolved in toluene (60 mL), and then stirred under reflux for 1.5 hours. After stirring the solution under reflux, the solution was concentrated under reduced pressure, and the obtained crude product was recrystallized (solution: hexane, ethyl acetate) and then suction-filtered. A brown crystal of methoxyphenyl)-4H-furo[3.2-b]pyrrole-5-carboxylic acid ethyl ester (a-3) was obtained (yield: 2.32 g, yield: 76.8%).
  • compound (a-4) (327 mg, 5.52 mmol) and trifluoroacetic acid (16.5 mL) were placed in a 200 mL three-necked flask and stirred at 45°C. After the 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 completion of the reaction, a saturated aqueous sodium hydrogencarbonate solution and ice were added to neutralize the solution, followed by suction filtration and vacuum drying of the filter cake to obtain a black solid compound (a-5) (yield: 320 mg). Compound (a-5) was used in the next reaction without purification.
  • compound (a-5) (320 mg) was placed in a 200 mL three-necked flask, toluene (70 mL), triethylamine (1.0 mL), and boron trifluoride diethyl ether complex (1.5 mL) were added dropwise, Heated to reflux for 30 minutes. After completion of the reaction, a saturated aqueous sodium hydrogencarbonate solution was added, and then the organic phase was recovered. The organic phase was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered to remove the desiccant, and concentrated under reduced pressure to remove the solvent.
  • tert-butyloxypotassium 25.18 g, 224.4 mmol
  • 160 mL of tert-amyl alcohol 160 mL
  • a solution of diisopropyl succinate 6.5 g, 32 mmol
  • 10 mL of tert-amyl alcohol was added dropwise over about 3 hours, and after completion of the dropwise addition, the mixture was heated under reflux for 6 hours.
  • the white solid was purified by silica gel column chromatography (eluent: hexane/ethyl acetate) to give 4-tert-butyl-2-mercaptoaniline (b-4) as a white solid (yield: 2.39 g, yield : 35%).
  • acetic acid (872 mg, 14.5 mmol) and 30 mL of acetonitrile were placed in a 100 mL three-necked 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 heated under reflux for 2 hours. Acetonitrile was removed under reduced pressure, the residue was dissolved in ethyl acetate, the organic layer was washed with water and saturated brine, and treated with anhydrous magnesium sulfate.
  • the 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 were added to a 200 mL three-necked flask. (7.88 mL, 62.7 mmol) was added and heated to reflux for 1 hour. The reaction solution was ice-cooled, and the precipitated solid was separated by filtration, washed with water, saturated aqueous sodium hydrogencarbonate solution, 50% aqueous methanol solution and methanol, and dried under reduced pressure.
  • the obtained residue was dissolved in toluene, and methanol was added for precipitation to obtain a powder composition composed of a dark green solid of the near-infrared fluorescent dye B1 (yield: 1.25 g, yield: 75%). .
  • 2-Ethylthiophene (11.2 g, 100 mmol) and dehydrated THF (80 mL) were added to a 500 mL four-necked flask under an argon stream, and the mixture was stirred at -78°C.
  • n-Butyllithium (68.8 mL, 1.6 mol/L hexane solution) was added dropwise to this solution, and after stirring at the same temperature for 1 hour, a dehydrated THF solution (50 mL) of ethyl chloroformate (10.9 mL, 120 mmol) was added. was added dropwise and stirred for an additional hour.
  • compound (c-1) (15.0 g, 81.5 mmol) and ethanol (40 mL) were added to a 200 mL four-necked flask, and hydrazine monohydrate (12.2 g, 244 mmol) was added dropwise to this solution. , and stirred at reflux for 12 hours. After cooling the reaction mixture, the solvent was distilled off under reduced pressure, the residue was dissolved in dichloromethane, washed with water and saturated brine in that order, dried over anhydrous magnesium sulfate, and concentrated.
  • compound (c-3) (9.5 g, 29.8 mmol) and THF (300 mL) were added and dissolved in a 500 mL four-necked flask, and lead acetate (15.9 g, 35.9 mmol) was added to the solution. was added and stirred at room temperature for 1 hour. After filtering the reaction mixture, 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 brine in that order, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • compound (c-5) 2.0 g, 3.8 mmol
  • dichloromethane 250 mL
  • N,N-diisopropylethylamine (1.48 g, 11.5 mmol
  • boron trifluoride diethyl etherate (3.27 g, 23 mmol) were added dropwise and stirred at room temperature for 1 hour.
  • 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 the near-infrared fluorescent dye C1 (yield: 1.66 g, yield : 76%).
  • 5-bromo-2-thiophenecarboxaldehyde (19.1 g, 0.1 mol) and ethyl azidoacetate (51.6 g, 0.4 mol) were dissolved in ethanol (800 mL) in a 2 L four-necked flask under an argon stream. Then, a 20% by mass sodium ethoxide ethanol solution (136 g, 0.4 mol) was slowly added dropwise to the resulting solution in a 0° C. ice bath and stirred for 2 hours. After completion of the reaction, a saturated ammonium chloride aqueous solution was added to adjust the pH to be weakly acidic.
  • compound (d-1) (6.0 g, 22 mmol) was placed in a 500 mL volumetric flask, ethanol (200 mL) and an aqueous solution of sodium hydroxide (12.4 g, 310 mmol) dissolved in 100 mL of water were added, and the mixture was refluxed for 1 hour. Stirred. After stirring under reflux, the solution was allowed to cool and then adjusted to be acidic by adding 6 mol/L hydrochloric acid, followed by adding water and performing suction filtration. A gray solid of thieno[3.2-b]pyrrole-5-carboxylic acid (d-2) was obtained (yield: 4.1 g, yield: 75.8%).
  • compound (d-2) (4.0 g, 16.3 mmol) and trifluoroacetic acid (100 mL) were placed in a 300 mL three-necked flask and stirred at 40°C. After the compound (d-2) was dissolved, the mixture was stirred for 15 minutes until foaming subsided. Trifluoroacetic anhydride (36 mL) was added to the stirred solution and reacted at 80° C. for 4 hours. After completion of the reaction, the reaction solution was added to a saturated aqueous sodium hydrogencarbonate solution containing ice to neutralize the solution, followed by suction filtration and vacuum drying to obtain a crude product of compound (d-3).
  • 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 dried to obtain a zinc complex.
  • the zinc complex was added to a mixture of water/ammonia (120 mL/60 mL) and extracted three times with diethyl ether diethyl ether (80 mL). The resulting organic layer was dried over anhydrous magnesium sulfate and then concentrated to give 6-tert-butyl-2-methyl-quinoline (f-1) as a yellow liquid (16.2 g, 41% yield).
  • 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-necked flask and time reacted. 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.
  • dichloromethane 40 mL
  • saturated aqueous sodium hydrogencarbonate solution 40 mL
  • 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 precursor (f-4) (1.72 g, 1.8 mmol), toluene (45 mL), triethylamine (4.35 mL, 31.4 mmol) and boron trifluoride were added to a 200 mL three-necked flask. Diethyl ether complex (7.88 mL, 62.7 mmol) was added and heated to reflux for 1 hour. The reaction solution was ice-cooled, and the precipitated solid was separated by filtration, washed with water, saturated aqueous sodium hydrogencarbonate solution, 50% aqueous methanol solution and methanol, and dried under reduced pressure. The obtained residue was dissolved in toluene, and methanol was added for precipitation to obtain a powder composition composed of a green solid of the near-infrared fluorescent dye F1 (yield: 1.10 g, yield: 58%). .
  • dichloromethane 40 mL
  • saturated aqueous sodium hydrogencarbonate solution 40 mL
  • 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.
  • 2-amino-4-tert-butylphenol (5.24 g, 31.7 mmol)
  • 2-cyano-acetimidic acid ethyl ester hydrochloride (4.45 g, 33.3 mmol) were added to a 100 mL two-necked flask.
  • dichloromethane (30 mL) was added and refluxed overnight.
  • the reaction solution was diluted with dichloromethane (100 mL) and washed twice with a 1 mol/L sodium hydroxide aqueous solution.
  • 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 evaporating the solvent was purified again by silica gel column chromatography (eluent: dichloromethane) to obtain a blue-green solid precursor (h-4) (yield: 0.98 g, yield: 35%).
  • Example 1 The near-infrared fluorescent dye A1 obtained in Synthesis Example 1 was purified by recrystallization as follows. Toluene in an amount of about 15 to 20 times the amount of the powder was added to the powder (1.2 g) of the near-infrared fluorescent dye A1, and dissolved under heating under reflux. The toluene solution dissolved by heating was allowed to stand as it was, the heat was slowly removed, and the solution was cooled to around 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 A3 (yield: 0.5 g, yield: 45%).
  • Example 2 The near-infrared fluorescent dye B1 obtained in Synthesis Example 2 was purified by recrystallization as follows. Toluene in an amount of about 15 to 20 times the powder amount was added to the powder (1.0 g) of the near-infrared fluorescent dye B1, and dissolved under heating under reflux. The toluene solution dissolved by heating was allowed to stand as it was, the heat was slowly removed, and the solution was cooled to around 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 B3 (yield: 0.75 g, yield: 63%).
  • Example 3 The near-infrared fluorescent dye C1 obtained in Synthesis Example 3 was purified by recrystallization as follows. Toluene in an amount of about 15 to 20 times the amount of the powder was added to the powder (1.0 g) of the near-infrared fluorescent dye C1, and dissolved under heating under reflux. The toluene solution dissolved by heating was allowed to stand as it was, the heat was slowly removed, and the solution was cooled to around room temperature to deposit 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 C3 (yield: 0.4 g, yield: 33%).
  • Example 4 The near-infrared fluorescent dye D1 obtained in Synthesis Example 4 was purified by recrystallization as follows. Toluene in an amount of about 15 to 20 times the powder amount was added to the near-infrared fluorescent dye D1 powder (1.0 g), and dissolved under heating under reflux. The toluene solution dissolved by heating was allowed to stand as it was, the heat was slowly removed, and the solution was cooled to around room temperature to deposit 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%).
  • Example 5 The near-infrared fluorescent dye E1 obtained in Synthesis Example 5 was purified by recrystallization as follows. Toluene in an amount of about 15 to 20 times the amount of the powder was added to the powder (1.0 g) of the near-infrared fluorescent dye E1, and dissolved under heating under reflux. The toluene solution dissolved by heating was allowed to stand as it was, the heat was slowly removed, and the solution was cooled to around 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 E3 (yield: 0.5 g, yield: 50%).
  • the near-infrared fluorescent dye F1 obtained in Synthesis Example 6 was purified by recrystallization as follows. Toluene was added to the powder (1.0 g) of the near-infrared fluorescent dye F1 in an amount about 15 to 20 times the amount of the powder, and dissolved under heating under reflux. The toluene solution dissolved by heating was allowed to stand as it was, the heat was slowly removed, and the solution was cooled to around room temperature to deposit 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 F3 (yield: 0.6 g, yield: 60%).
  • Example 7 The near-infrared fluorescent dye G1 obtained in Synthesis Example 7 was purified by recrystallization as follows. Toluene in an amount of about 15 to 20 times the powder amount was added to the powder (1.0 g) of the near-infrared fluorescent dye G1, and dissolved under heating under reflux. The toluene solution dissolved by heating was allowed to stand as it was, the heat was slowly removed, and the solution was cooled to around 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 G3 (yield: 0.4 g, yield: 33%).
  • Example 8 The near-infrared fluorescent dye H1 obtained in Synthesis Example 8 was purified by recrystallization as follows. Toluene in an amount of about 15 to 20 times the amount of the powder was added to the powder (1.0 g) of the near-infrared fluorescent dye H1, and dissolved under heating under reflux. The toluene solution dissolved by heating was allowed to stand as it was, the heat was slowly removed, and the solution was cooled to around 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 H3 (yield: 0.3 g, yield: 25%).
  • 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: Dick Styrene CR-2500, manufactured by DIC)
  • PP polypropylene resin pellets (product name: PC630A, manufactured by SunAllomer)
  • PE polyethylene resin pellets (product name: Novatec LD (trademark) LC600A, manufactured by Japan Polyethylene)
  • PC polycarbonate resin pellets (product name: Iupilon S3000, manufactured by Mitsubishi Engineering-Plastics)
  • PS Polystyrene resin pellets (product name: Dick Styrene (trademark) CR-2500, manufactured by DIC)
  • PET polyethylene terephthalate resin pellets (product name: Viropet (trademark) EMC-500, manufactured by Toyobo Co., Ltd
  • the powder composition of the near-infrared fluorescent dye and the resin pellet were mixed in the composition shown in Tables 3 to 6, and the powder composition of the near-infrared fluorescent dye was adhered to the surface of the resin pellet.
  • the resulting mixture was then melt kneaded and injection molded into a plate (90 mm x 50 mm x 3 mm). Melt kneading and plate injection molding were performed using an injection molding machine under the following conditions. The set cylinder temperature and mold temperature of the injection molding machine were set according to the type of resin pellets.
  • Evaluation A 10 plates were visually observed, and neither pigment aggregates nor streaks (streak-like appearance defects) were observed.
  • Evaluation B + Of the 10 plates, pigment aggregates or streaks were visually observed on 2 or less plates, and the length of the pigment aggregates measured with a microscope was less than 100 ⁇ m.
  • Evaluation B Of the 10 plates, dye aggregates or streaks were visually observed on 2 or less, and among the dye aggregates measured with a microscope, one had a major axis of 100 ⁇ m or more. That's all.
  • Evaluation B- Of the 10 plates, pigment aggregates or streaks were visually observed on 3 or less plates.

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PCT/JP2022/046123 2021-12-27 2022-12-15 粉末状色素組成物、粉末状色素組成物の製造方法、樹脂組成物及び成形体 Ceased WO2023127507A1 (ja)

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US5433896A (en) * 1994-05-20 1995-07-18 Molecular Probes, Inc. Dibenzopyrrometheneboron difluoride dyes
US6005113A (en) * 1996-05-15 1999-12-21 Molecular Probes, Inc. Long wavelength dyes for infrared tracing
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US5433896A (en) * 1994-05-20 1995-07-18 Molecular Probes, Inc. Dibenzopyrrometheneboron difluoride dyes
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WO2007126052A1 (ja) * 2006-04-28 2007-11-08 Keio University 蛍光性化合物及びそれから成る標識剤
WO2015056779A1 (ja) * 2013-10-17 2015-04-23 Dic株式会社 樹脂組成物及び成形体

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