WO2015056779A1 - 樹脂組成物及び成形体 - Google Patents
樹脂組成物及び成形体 Download PDFInfo
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- WO2015056779A1 WO2015056779A1 PCT/JP2014/077696 JP2014077696W WO2015056779A1 WO 2015056779 A1 WO2015056779 A1 WO 2015056779A1 JP 2014077696 W JP2014077696 W JP 2014077696W WO 2015056779 A1 WO2015056779 A1 WO 2015056779A1
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- Prior art keywords
- group
- atom
- aromatic
- hydrogen atom
- alkyl group
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- 125000003118 aryl group Chemical group 0.000 claims abstract description 287
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 223
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims abstract description 222
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- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 105
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- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 50
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 294
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- -1 R 1 Chemical group 0.000 claims description 104
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 61
- 125000000217 alkyl group Chemical group 0.000 claims description 58
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 58
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- 125000004093 cyano group Chemical group *C#N 0.000 claims description 31
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 27
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 27
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- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 26
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 26
- 125000003277 amino group Chemical group 0.000 claims description 25
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- 230000005284 excitation Effects 0.000 description 15
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- 0 CC1*=C(C)*(*)*(*)(*)*1* Chemical compound CC1*=C(C)*(*)*(*)(*)*1* 0.000 description 12
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- 238000003786 synthesis reaction Methods 0.000 description 10
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 9
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- 238000003756 stirring Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
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- 238000001816 cooling Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 8
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
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- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- YPLYFEUBZLLLIY-UHFFFAOYSA-N dipropan-2-yl butanedioate Chemical compound CC(C)OC(=O)CCC(=O)OC(C)C YPLYFEUBZLLLIY-UHFFFAOYSA-N 0.000 description 1
- 125000004914 dipropylamino group Chemical group C(CC)N(CCC)* 0.000 description 1
- OVTCUIZCVUGJHS-UHFFFAOYSA-N dipyrrin Chemical compound C=1C=CNC=1C=C1C=CC=N1 OVTCUIZCVUGJHS-UHFFFAOYSA-N 0.000 description 1
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UMXADXYSYVKRJV-UHFFFAOYSA-N ethyl 2-cyanoethanimidate;hydrochloride Chemical compound Cl.CCOC(=N)CC#N UMXADXYSYVKRJV-UHFFFAOYSA-N 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000001245 hexylamino group Chemical group [H]N([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000006316 iso-butyl amino group Chemical group [H]N(*)C([H])([H])C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000401 methanolic extract Substances 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical group 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000004894 pentylamino group Chemical group C(CCCC)N* 0.000 description 1
- 125000005327 perimidinyl group Chemical group N1C(=NC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 229940031439 squalene Drugs 0.000 description 1
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 125000006253 t-butylcarbonyl group Chemical group [H]C([H])([H])C(C(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BFNYNEMRWHFIMR-UHFFFAOYSA-N tert-butyl 2-cyanoacetate Chemical compound CC(C)(C)OC(=O)CC#N BFNYNEMRWHFIMR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
Classifications
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
- A61K49/0021—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules the fluorescent group being a small organic molecule
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
Definitions
- the present invention relates to a resin composition that emits near-infrared fluorescence, and a molded body obtained by processing the resin composition.
- Near-infrared fluorescent dyes are used in industrial products centered on identification of various products and prevention of counterfeiting, and in recent years, they are also used in medical applications such as bioimaging probes and test drugs.
- As features of the near-infrared wavelength region it is known that it cannot be seen with the human naked eye, has little influence on the living body, and has high permeability to living bodies such as skin.
- Such characteristics can be utilized by including a near-infrared fluorescent dye in the medical device itself.
- a system for confirming the position of a medical device embedded in a living body by irradiating near-infrared light from outside the living body by including a near-infrared fluorescent dye in a medical device such as a shunt tube is disclosed. (For example, refer to Patent Document 1).
- Near-infrared fluorescent dyes include inorganic fluorescent dyes and organic fluorescent dyes.
- inorganic near-infrared fluorescent dyes have an advantage that the emission wavelength can be easily adjusted within a desired range by using various metals, but rare earths such as rare and expensive rare earths and particle sizes are uniform. Nanoparticles are needed.
- organic near-infrared fluorescent dyes can be synthesized relatively easily and are easy to adjust the wavelength, but few are known that can be stably mixed into the resin. .
- Patent Document 2 discloses a reactive group-containing near-infrared fluorescent dye obtained by introducing a polyester reactive group into a phthalocyanine dye, a naphthalocyanine dye, or a squalene dye.
- a near-infrared fluorescent resin copolymerized in (polyethylene terephthalate) is disclosed.
- a boron complex of a ⁇ -conjugated compound is known as an organic fluorescent dye having a high emission quantum yield.
- a boron dipyrromethene skeleton in which a disubstituted boron atom and dipyrromethene (or a derivative thereof) form a complex are known (for example, see Non-Patent Document 1).
- Patent Document 3 discloses a BODIPY dye having a hetero ring in the BODIPY skeleton.
- Non-Patent Document 2 discloses a near-infrared fluorescent dye of a DPP-based boron complex having two boron complex units in the molecule, obtained by complexing a diketopyrrolopyrrole (DPP) derivative with a boron complex.
- DPP diketopyrrolopyrrole
- BODIPY dyes and DPP-based boron complexes are mainly used as biomarkers for labeling biomolecules such as nucleic acids and proteins and tumor tissues, and contain BODIPY dyes and DPP-based boron complexes. There is almost no report about the resin.
- Patent Document 5 discloses a composition that emits fluorescence in the visible light region mixed with a polymer together with a solvent in order to enhance the compatibility of the visible light emitting BODIPY dye.
- Patent Document 6 discloses an optical filter containing BODIPY dyes having at least one electron-withdrawing group and a resin, and having high light absorption in the visible light region.
- Patent Document 8 mentions a DPP-based boron complex as a compound that has absorption in the infrared region and does not have absorption in the visible light region.
- An infrared absorbing composition comprising a hydrophobic polymer is disclosed.
- Patent Document 3 discloses BODIPY dyes that emit near-infrared fluorescence, but does not describe whether these can be contained in a resin.
- the reactive group-containing near-infrared fluorescent dyes described in Patent Document 2 composed of these dyes have sufficient emission intensity. There is a problem that can not be.
- the siloxane-containing BODIPY dye described in Patent Document 4 has good compatibility with the silicone monomer solution before curing, and a silicone resin in which the dye is uniformly dispersed can be obtained by curing, but other resins and resins There is a problem that the compatibility with the solution is low.
- Patent Document 5 has a problem in safety because the solvent may remain in the resin.
- Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7 do not describe a BODIPY dye that emits near-infrared fluorescence in the first place, and do not describe application to medical use.
- Patent Document 8 and Patent Document 9 do not describe a DPP-based boron complex that emits near-infrared light, and do not report application to medical use.
- a near-infrared fluorescent resin can be produced simply by mixing and dispersing a near-infrared fluorescent dye in the resin.
- melt-kneading the resin and the dye when dispersed in a thermoplastic resin or the like, a method of melt-kneading the resin and the dye can be considered, but even when melt-kneading is performed at a temperature below the decomposition point of the dye, depending on the type of the resin and the dye and the kneading conditions Fluorescence may not occur due to causes such as poor dispersion or decomposition of the dye, and whether or not the dye described above can be dispersed in a thermoplastic resin is predicted from the thermophysical properties of the dye It is difficult to do.
- An object of the present invention is to provide a resin composition that emits near-infrared fluorescence, has a high emission quantum yield, and is relatively easy to manufacture, and a molded body obtained by processing the resin composition. .
- the resin composition and molded product according to the present invention are the following [1] to [12].
- a resin composition containing a near-infrared fluorescent dye and a resin, The near-infrared fluorescent dye is The following general formula (I 1 )
- R a and R b are an aromatic 5-membered ring, aromatic 6-membered ring, or 2 to 3 5-membered or 6-membered ring, together with a nitrogen atom to which R a is bonded and a carbon atom to which R b is bonded.
- R c and R d together with the nitrogen atom to which R c is bonded and the carbon atom to which R d is bonded, are an aromatic 5-membered ring, an aromatic 6-membered ring, or 2 to 3 5-membered rings or 6-membered rings.
- R e and R f represent a halogen atom or an oxygen atom
- R g represents a hydrogen atom or an electron withdrawing group.
- R e and R f are oxygen atoms
- a boron atom bonded to R e , R e , a nitrogen atom bonded to R a , and R a may form a ring together
- R f A boron atom bonded to R f , R c , and a nitrogen atom bonded to R c may form a ring together.
- R h and R i together with the nitrogen atom to which R h is bonded and the carbon atom to which R i is bonded, are an aromatic 5-membered ring, an aromatic 6-membered ring, or 2 to 3 5-membered rings or 6-membered rings.
- R j and R k together with the nitrogen atom to which R j is bonded and the carbon atom to which R k are bonded together are an aromatic 5-membered ring, an aromatic 6-membered ring, or 2 to 3 5-membered rings or 6-membered rings.
- R 1 , 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 each independently represent a hydrogen atom or an electron withdrawing group.
- R h to R q are the same as those in the formula (I 3 )), and are one or more compounds selected from the group consisting of compounds A resin composition having a maximum fluorescence wavelength of 650 nm or more.
- R 1 , R 2 , and R 3 are (P1) represents 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, (P2) R 1 and R 2 together form an aromatic 5-membered ring or an aromatic 6-membered ring, and R 3 is a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl Represents a group or a heteroaryl group, or (p3) R 2 and R 3 together form an aromatic 5-membered ring or an aromatic 6-membered ring, and R 1 represents a hydrogen atom, a halogen atom, a C 1-20 alkyl A group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl
- R 7 and R 8 are oxygen atoms
- a boron atom bonded to R 7 , R 7 , a nitrogen atom bonded to the boron atom, R 1 , and a carbon atom bonded to R 1 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 having a substituent.
- R 23 , R 24 , R 25 , and R 26 each independently represent a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group
- R 27 and R 28 each independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group
- R 29 and R 30 each independently represent a hydrogen atom or an electron withdrawing group
- Y 9 and Y 10 each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom
- R 31 and R 32 are (P4) represents 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, or (p5)
- R 31 and R 32 are both Forming
- R 23 to R 30 are the same as those in the formula (I 3 -1);
- X 1 and X 2 each independently represent a nitrogen atom or a phosphorus atom;
- R 35 , R 36 , R 37 , and R 38 are (P6) 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 35 and R 36 together form an optionally substituted aromatic 5-membered ring or optionally substituted aromatic 6-membered ring, and
- R 37 and R 38 are Each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group
- R 36 and R 37 together form an optionally substituted aromatic 5-membered ring or optionally substituted aromatic
- R 35 and R 36 are each independently a hydrogen atom, halogen atom, C 1- 20 represents an alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group;
- R 39 , R 40 , R 41 , and R 42 are (Q6) each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group, (Q7)
- R 39 and R 40 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, and
- R 41 and R 42 are Each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group, (Q8) R 40 and R 41
- Y 11 and Y 12 each independently represent an oxygen atom or a sulfur atom; Y 21 and Y 22 each independently 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 represents independently of each other a halogen atom, a C 1-20 alkoxy group, an aryloxy group, or an acyloxy group; P 11 to P 14 and P 17 each independently represent a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group; A 11 to A 14 are each independently 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.
- Y 23 and Y 24 each independently represent a carbon atom or a nitrogen atom
- Y 13 and Y 14 each independently represent an oxygen atom or a sulfur atom
- Y 25 and Y 26 each independently represent a carbon atom or a nitrogen atom
- R 47 and R 48 each 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 each independently represent a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group
- n15 and n16 each independently represent an integer of 0 to 3
- a 15 and A 16 are 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
- 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 used. Therefore, it is possible to obtain a near-infrared fluorescent resin composition having high emission intensity and a molded body obtained by processing the composition without copolymerizing the organic near-infrared fluorescent dye with the resin component.
- Example 9 a dye-containing film of the near-infrared fluorescent dye F (“Dye F-containing” in the figure) and a dye-free film (“Dye-free” in the figure) were taken with a near-infrared fluorescence detection camera. It is a photograph.
- a pigment-containing film of the near-infrared fluorescent pigment F (“Dye F-containing” in the drawing) and a pigment-free film (“Dye-free” in the drawing) were applied to a pork having a thickness of 2 mm. It is the photograph image
- Example 12 a film containing 0.03% by mass of near-infrared fluorescent dye A (“Dye A 0.03%” in the figure) and a film containing 0.005% by mass (“Dye A 0.005” in the figure) % ”) And a dye-free film (“ dye-free "in the figure) taken with a near infrared fluorescence detection camera.
- Example 12 a film containing 0.03% by mass of near-infrared fluorescent dye A (“Dye A 0.03%” in the figure) and a film containing 0.005% by mass (“Dye A 0.005” in the figure) % ”) And a pigment-free film (“ pigment-free "in the figure) were taken with a near-infrared fluorescence detection camera on pork meat having a thickness of 2 mm.
- Example 13 a film containing 0.03% by mass of near-infrared fluorescent dye B (“Dye B 0.03%” in the figure) and a film containing 0.005% by mass (“Dye B 0.005” in the figure) % ”) And a dye-free film (“ dye-free "in the figure) taken with a near infrared fluorescence detection camera.
- Example 13 a film containing 0.03% by mass of near-infrared fluorescent dye B (“Dye B 0.03%” in the figure) and a film containing 0.005% by mass (“Dye B 0.005” in the figure) % ”) And a pigment-free film (“ pigment-free "in the figure) were taken with a near-infrared fluorescence detection camera on pork meat having a thickness of 2 mm.
- the resin composition according to the present invention contains a near-infrared fluorescent dye and a resin, 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 emits near-infrared fluorescence and can be easily molded, it is suitably used as a medical material such as a raw material for medical devices used in vivo.
- the near-infrared fluorescent dye contained in the resin composition according to the present invention is represented by the following general formula (I 1 ), general formula (I 2 ), general formula (I 3 ), or general formula (I 4 ). It is a compound represented by these. Hereinafter, the compound is sometimes referred to as “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 bonded and the carbon atom to which R b is bonded.
- R c and R d are aromatics composed of 1 to 3 rings together with the nitrogen atom to which R c is bonded and the carbon atom to which R d is bonded. Form a ring.
- Each 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-membered ring or a 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. Having a ring structure condensed with a ring containing a boron atom. That is, the compound represented by the general formula (I 1 ) or the general formula (I 2 ) has a robust condensed ring structure composed of a wide conjugate plane.
- R h and R i together with the nitrogen atom to which R h is bonded and the carbon atom to which R i is bonded form an aromatic ring consisting of 1 to 3 rings.
- R j and R k are aromatics composed of 1 to 3 rings together with the nitrogen atom to which R j is bonded and the carbon atom to which R k is bonded. Form a ring.
- Each 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-membered ring or a 6-membered ring.
- the compound represented by the general formula (I 3 ) or the general formula (I 4 ) includes 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.
- a five-membered heterocycle containing a 5-ring heterocycle, an aromatic ring formed by R j and R k , a ring containing a boron atom bonded to two nitrogen atoms, and a five-membered ring containing one nitrogen atom It has a ring structure in which a 3-ring condensed with a heterocycle is condensed between 5-membered heterocycles, that is, a ring structure in which at least 6 rings are condensed.
- the compound represented by the general formula (I 3 ) or the general formula (I 4 ) has a robust condensed ring structure composed of a very wide conjugate 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 R i, and the aromatic ring formed by R j and R k are aromatic. If it has, it will not specifically limit.
- 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, fluropyrrole.
- a ring, a pyrrolothiazole ring, a pyrrolooxazole ring, and the like is 2 or 3 because the maximum fluorescence wavelength is increased to the near infrared region. It is preferably 2, and more preferably 2 from the viewpoint of complexity of synthesis.
- the wavelength can be increased by devising a substituent on the ring or a substituent on boron.
- the general formula (I 2 ) or the general formula (I 4 ) it is possible to increase the wavelength to the near infrared region only by bonding a substituted aryl group or a heteroaryl group.
- 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 R i, and the aromatic ring formed by R j and R k include a substituent. It may not have, and may have one or a plurality of 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 has a mutagenicity, cell, Those having no toxicity, sensitization and skin irritation are preferred. From the viewpoint of safety, it is preferable that the near-infrared fluorescent dye according to the present invention does not elute from a molded product obtained by processing the resin composition according to the present invention with a body fluid such as blood or tissue fluid. For this reason, it is preferable that the near-infrared fluorescent dye according to the present invention has low solubility in biological components such as blood.
- the resin component itself in the resin composition according to the present invention hardly elutes in body fluids and the near-infrared fluorescent dye itself
- the molded article of the resin composition according to the present invention can be used while avoiding elution of the near-infrared fluorescent dye even in vivo.
- substituents examples include a halogen atom, nitro group, cyano group, hydroxy group, carboxyl group, aldehyde group, sulfonic acid group, alkylsulfonyl group, halogenosulfonyl group, thiol group, alkylthio group, isocyanate group, and thioisocyanate group.
- Alkyl group alkenyl group, alkynyl group, alkoxy group, alkoxycarbonyl group, alkylamidocarbonyl group, alkylcarbonylamide group, acyl group, amino group, monoalkylamino group, dialkylamino group, silyl group, monoalkylsilyl group, Examples thereof include a dialkylsilyl group, a trialkylsilyl group, a monoalkoxysilyl group, a dialkoxysilyl group, a trialkoxysilyl group, an aryl group, and a heteroaryl group.
- Examples of the substituent that 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 R i, and the aromatic ring formed by R j and R k include A cyano group, hydroxy group, carboxyl group, alkylthio group, alkyl group, alkoxy group, alkoxycarbonyl group, amide group, alkylsulfonyl group, fluorine, chlorine, aryl group, or heteroaryl group from the viewpoint of safety to living bodies It is preferable that these substituents may further have a substituent. However, the substituents other than these substituents are not limited to these substituents because the safety can be improved by further introducing appropriate substituents.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom, a chlorine atom and a bromine atom, and 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 still more preferably 1 to 6 carbon atoms.
- alkyl group examples 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, Examples include octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like.
- alkenyl group examples include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, and a 2-hexenyl group.
- alkynyl group examples include ethynyl group, 1-propynyl group, 2-propynyl group, isopropynyl group, 1-butynyl group, isobutynyl group and the like.
- alkyl group moiety in the group, dialkoxysilyl group, and trialkoxysilyl group include the same alkyl groups as those described above.
- the alkoxy group includes methoxy group, ethoxy group, propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, t-butyloxy group, pentyloxy group, isoamyloxy group, hexyloxy group, heptyloxy group Octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.
- dialkylamino group examples include dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, dipentylamino group, dihexylamino group, ethylmethylamino group, and methylpropyl group.
- examples thereof include an amino group, a butylmethylamino group, an ethylpropylamino group, and a butylethylamino group.
- Examples of the aryl group include a phenyl group, a naphthyl group, an indenyl group, and a biphenyl group.
- a phenyl group is preferred.
- Examples of the heteroaryl group include a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a thienyl group, a furanyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, and a thiadiazole group; a pyridinyl group and a pyrazinyl group Groups, 6-membered heteroaryl groups such as pyrimidinyl group, pyridazinyl group; indolyl group, isoindolyl group, indazolyl group, quinolidinyl group, quinolinyl group, isoquinolinyl group, benzofuranyl group,
- the alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group may be an unsubstituted group, and one or more hydrogen atoms may be substituted with a substituent.
- substituents include a halogen atom, alkyl group, alkoxy group, nitro group, cyano group, hydroxy group, amino group, thiol group, carboxyl group, aldehyde group, sulfonic acid group, isocyanate group, thioisocyanate group, and aryl group.
- heteroaryl groups include a halogen atom, alkyl group, alkoxy group, nitro group, cyano group, hydroxy group, amino group, thiol group, carboxyl group, aldehyde group, sulfonic acid group, isocyanate group, thioisocyanate group, and aryl group.
- heteroaryl groups include a halogen atom, alkyl group, al
- the absorption wavelength and fluorescence wavelength of fluorescent dyes 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 increased, it is preferable because the maximum absorption wavelength is in the near-infrared region among various resins.
- the maximum absorption wavelength of the fluorescent dye is obtained by introducing the electron donating group and the electron withdrawing group at an appropriate position in the molecule, thereby reducing the band gap between the highest occupied orbital (HOMO) and the lowest unoccupied orbit (LUMO). Narrower and longer wavelength can be achieved.
- 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 is introduced into R g .
- an attractive group By introducing an attractive group, the maximum absorption wavelength and the maximum fluorescence wavelength of the compound can be made longer.
- an electron donating group is introduced into the aromatic ring formed by R h and R i and the aromatic ring formed by R j and R k , R p And when R q is an aromatic ring, by introducing an electron donating group into the aromatic ring, or by introducing an electron withdrawing group into R r and R s , the maximum absorption wavelength and maximum fluorescence of the compound are obtained.
- the wavelength can be made longer. By combining these designs, it is possible to adjust to the target wavelength.
- the compound represented by the general formula (I 2 ) having an aza-BODIPY skeleton has a relatively long wavelength even if the aromatic ring formed by R a and R b and the aromatic ring formed by R c and R d are unsubstituted. Is a skeleton having absorption.
- the pyrrole cross-linked moiety is a nitrogen atom, a substituent cannot be introduced onto the nitrogen, but the pyrrole moiety (R a and R b There by introducing an electron donating group on the aromatic ring) aromatic ring and where R c and R d form to form, it a longer wavelength the maximum absorption wavelength and maximum fluorescence wavelength of the compound.
- 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 the maximum fluorescence wavelength of the compound can be made longer by introducing an electron donating group into the aromatic ring.
- 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 R i, and the aromatic ring formed by R j and R k have As the group, among “any group that does not inhibit the fluorescence of the compound”, a group that functions as an electron-donating group for the aromatic ring is preferable. By introducing an electron donating group into the aromatic ring, fluorescence of the compound represented by the general formula (I 1 ), the general formula (I 2 ), the general formula (I 3 ), or the general formula (I 4 ) Becomes longer wavelength side.
- Examples of the group that functions as an electron donating group include alkyl groups; alkoxy groups such as methoxy groups; aryl groups such as phenyl groups, p-alkoxyphenyl groups, p-dialkylaminophenyl groups, dialkoxyphenyl groups (aromatic rings). Group); heteroaryl groups (heteroaromatic ring groups) such as 2-thienyl group and 2-furanyl group.
- alkyl group the alkyl group in the substituent of the phenyl group, and the alkyl group portion in the alkoxy group, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable.
- the carbon number of an alkyl group part is 6 or more or that it is branched.
- Examples of the substituent that 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 R i, and the aromatic ring formed by R j and R k include C 1-6 alkyl group, C 1-6 alkoxy group, aryl group or heteroaryl group is preferred, methyl group, ethyl group, methoxy group, phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p -A dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group is more preferable, and a methyl group, an ethyl group, a methoxy group, a phenyl group, or a p-methoxyphenyl group is more preferable.
- the BODIPY skeleton has high planarity, molecules are likely to aggregate by ⁇ - ⁇ stacking.
- an aryl group or heteroaryl group having a bulky substituent into the BODIPY skeleton, molecular aggregation 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 R c and R d It is preferable that the aromatic ring formed by R h and R i and the aromatic ring formed by R j and R k are 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, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is preferable, a fluorine atom or a chlorine atom is more preferable, and a fluorine atom is particularly preferable because it has a strong bond with a boron atom.
- a compound in which R e and R f are fluorine atoms has high heat resistance, and thus is advantageous when melt kneaded with a resin at a high temperature.
- the compound represented by the general formula (I 1) or the general formula (I 2) rather than the R e and R f is a halogen atom or an oxygen atom, by a substituent containing an atom capable of binding with the boron atom Even if it exists, it can be made to contain in resin similarly to the near-infrared fluorescent pigment
- the substituent is acceptable as long as it does not inhibit fluorescence.
- a ring formed by a boron atom bonded to R e , R e , R a , and a nitrogen atom bonded to R a is condensed with an aromatic ring formed by R a and R b.
- the ring formed by the boron atom bonded to R f , R f , R c , and the nitrogen atom bonded to 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 6-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 (oxygen bonded to the substituent). Atom).
- substituent include a C 1-20 alkyl group, an aryl group, a heteroaryl group, an alkylcarbonyl group, an arylcarbonyl group, and a heteroarylcarbonyl group.
- R f when R f is an oxygen atom and does not form a ring, R f is a substituted oxygen atom (with a substituent) Bonded oxygen atoms).
- substituents examples include a C 1-20 alkyl group, an aryl group, a heteroaryl group, an alkylcarbonyl group, an arylcarbonyl group, and a heteroarylcarbonyl group.
- R e and R f are oxygen atoms having a substituent
- the substituent that R e has and the substituent that R f has may be the same or different.
- R e and R f are oxygen atoms
- R e , R f , and a boron atom bonded to R e and R f together form a ring.
- the ring structure include a structure in which R e and R f are connected to the same aryl ring or heteroaryl ring, and a structure in which R e and R f are connected by an alkylene group.
- R 1 , R m , R n , and R o are each independently a halogen atom, a C 1-20 alkyl group, or a C 1-20 alkoxy group. Represents an aryl group or a heteroaryl group.
- R 1 , R m , R n , or Ro is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is preferable, a fluorine atom or a chlorine atom is more preferable, and a strong bond with a boron atom is provided. Therefore, a fluorine atom is particularly preferable.
- a compound in which R l , R m , R n , and R o are fluorine atoms has high heat resistance, and therefore is advantageous when melt kneaded with a resin at a high temperature.
- 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.
- the alkyl group may be linear, branched, or cyclic (aliphatic ring) Group).
- the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isoamyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Decyl group, undecyl group, dodecyl group and the like.
- R 1 , R m , R n , or Ro is a C 1-20 alkoxy group
- the alkyl group portion of the alkoxy group may be linear, branched, or cyclic (Aliphatic cyclic group) may be used.
- alkoxy group examples include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, t-butyloxy group, pentyloxy group, isoamyloxy group, hexyloxy group, heptyloxy group, Examples include octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.
- R 1 , R m , R n , or Ro is an aryl group
- examples of the aryl group include a phenyl group, a naphthyl group, an indenyl group, and a biphenyl group.
- R 1 , R m , R n , or Ro is a heteroaryl group
- examples of the heteroaryl group include 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 group And a condensed heteroaryl group such as a benzofuranyl group, an isobenzofuranyl group, a chromenyl group, a benzoxazoly
- the C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, and heteroaryl group represented by R 1 , R m , R n , or R o may be an unsubstituted group, and one or more
- the hydrogen atom may be substituted with a substituent.
- the substituent include a halogen atom, alkyl group, alkoxy group, nitro group, cyano group, hydroxy group, amino group, thiol group, carboxyl group, aldehyde group, sulfonic acid group, isocyanate group, thioisocyanate group, and aryl group. And heteroaryl groups.
- R 1 , R m , R n , and R o are a halogen atom, an unsubstituted aryl group, or an aryl group having a substituent.
- 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 represents a heteroaryl group.
- Examples of the halogen atom, the C 1-20 alkyl group, the C 1-20 alkoxy group, the aryl group, and the heteroaryl group represented by R p and R q include R 1 , R m , and R n in the general formula (I 3 ). Or the same as R o .
- R p and R q are a hydrogen atom or an aryl group are preferable, an unsubstituted phenyl group, or a C 1-20 alkyl 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 an unsubstituted phenyl A group or a phenyl group substituted with a C 1-10 alkoxy group is particularly preferred.
- 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 a halogenated methyl group such as a trifluoromethyl group, a nitro group, a cyano group, an aryl group, a heteroaryl group, an alkynyl group, an alkenyl group, a carboxyl group, an acyl group, and a carbonyl group.
- Substituents having a carbonyl group such as an oxy group, an amide group, and an aldehyde group; sulfoxide groups; sulfonyl groups; alkoxymethyl groups; aminomethyl groups and the like, and aryl groups having these electron-withdrawing groups as substituents;
- a heteroaryl group or the like can also be used.
- these electron-withdrawing groups a trifluoromethyl group, a nitro group, a cyano group, a phenyl group, a sulfonyl group and the like that can function as a strong electron-withdrawing group are preferable from the viewpoint of lengthening the maximum fluorescence wavelength. .
- the near-infrared fluorescent dye according to the present invention a compound represented by the following general formula (I 1 -0) or the general formula (I 2 -0) are preferred.
- a compound having a boron dipyrromethene skeleton is preferable because the maximum fluorescence wavelength becomes longer, and particularly, the pyrrole ring satisfying the following (p2), (p3), (q2), or (q3) is an aromatic ring or
- a compound condensed with a heteroaromatic ring is preferable as a near-infrared fluorescent dye because the maximum wavelength becomes a longer wavelength.
- R 1 , R 2 , and R 3 satisfy any of the following (p1) to (p3).
- P1 represents 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
- 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 Represents a group or a heteroaryl group, or
- R 2 and R 3 together form an aromatic 5-membered ring or an aromatic 6-membered ring
- R 1 represents a hydrogen atom, a halogen atom, a C 1-20 alkyl A group, a C 1-20 alkoxy group, an aryl group
- R 4 , R 5 , and R 6 satisfy any of the following (q1) to (q3).
- (Q1) 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;
- (Q2) R 4 and R 5 together form an aromatic 5-membered ring or an aromatic 6-membered ring
- R 6 is a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl Represents a group, or a heteroaryl group, or
- R 5 and R 6 together form an aromatic 5-membered ring or an aromatic 6-membered ring
- R 4 represents a hydrogen atom, a halogen atom, a C 1-20 alkyl A group, a C 1-20 alkoxy group, an
- halogen atom C 1-20 alkyl group, C 1-20 alkoxy group, aryl group and heteroaryl group in the above (p1) to (p3) or (q1) to (q3), R a and R What was illustrated as "any group which does not inhibit the fluorescence of a compound" in b can be used.
- the ring those represented by any of the following general formulas (C-1) to (C-9) are preferred, and the following general formulas (C-1), (C-2), or (C-9) Those represented by any of the above are more preferred.
- Y 1 to Y 8 each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom.
- Y 1 to Y 8 are preferably a sulfur atom, an oxygen atom or a nitrogen atom independently of each other, and more preferably a sulfur atom or an oxygen atom independently of each other.
- R 11 to R 22 each independently represent a hydrogen atom or an arbitrary group that does not inhibit the fluorescence of the compound.
- an arbitrary group that does not inhibit the fluorescence of the compound those exemplified in “an arbitrary group that does not inhibit the fluorescence of the compound” in R a and R b can be used.
- R 11 to R 22 are preferably each independently a hydrogen atom, an unsubstituted aryl group, an aryl group having a substituent, an unsubstituted heteroaryl group, or a heteroaryl group having a substituent,
- a hydrogen atom, an (unsubstituted) phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-dimethylaminophenyl group, a dimethoxyphenyl group, a thienyl group, or a furanyl group is more preferred, and a hydrogen atom, (unsubstituted) A phenyl group or a p-methoxyphenyl group is more preferable.
- the compound includes at least one of the above-described unsubstituted aryl group, aryl group having a substituent, and unsubstituted heteroaryl group. Or a heteroaryl group having a substituent is particularly preferred.
- R 1 and R 4 , R 5 , and R 6 which may be different from each It is preferable that they are the same kind of group. That is, when R 1 , R 2 , and R 3 satisfy (p1), R 4 , R 5 , and R 6 preferably satisfy (q1), and R 1 , R 2 , When R 3 and R 3 satisfy (p2), R 4 , R 5 , and R 6 preferably satisfy (q2), and R 1 , R 2 , and R 3 satisfy (p3). R 4 , R 5 , and R 6 preferably satisfy (q3).
- R 1 and R 2 form a ring
- R 4 and R 5 form a ring
- R 2 And R 3 forms a ring
- R 5 and R 6 preferably form a ring. That is, it is preferable that R 1 , R 2 , and R 3 satisfy (p2) or (p3), and R 4 , R 5 , and R 6 satisfy (q2) or (q3). This is because when the aromatic ring or heteroaromatic ring is further condensed to the boron dipyrromethene skeleton, the maximum fluorescence wavelength becomes longer.
- R 7 and R 8 represent a halogen atom or an oxygen atom.
- R 7 and R 8 are oxygen atoms
- a boron atom bonded to R 7 , R 7 , a nitrogen atom bonded to the boron atom, R 1 , and a carbon atom bonded to R 1 together form a ring.
- a boron atom bonded to R 8 and R 8 , a nitrogen atom bonded to the boron atom, R 4 , and a carbon atom bonded to R 4 may form a ring together.
- the ring formed by R 7 , boron atom, R 1 and the like, and the ring formed by R 8 , boron atom, R 4 and the like are both condensed with the boron dipyrromethene skeleton.
- the ring formed by R 7 , boron atom, R 1 and the like, and the ring formed by R 8 , boron atom, R 4 and the like are preferably 6-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 Oxygen atoms bonded to each other).
- substituent include a C 1-20 alkyl group, an aryl group, and a heteroaryl group.
- R 8 when R 8 is an oxygen atom, and do not form a ring, R 8 is an oxygen atom having a substituent group (Oxygen atom bonded to a substituent).
- substituents examples include a C 1-20 alkyl group, an aryl group, and a heteroaryl group.
- R 7 and R 8 are oxygen atoms having a substituent
- the substituent that R 7 has and the substituent that R 8 has 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 described above for R g . Among these, from the viewpoint of lengthening the maximum fluorescence wavelength, a fluoroalkyl group, a nitro group, a cyano group, an aryl group, and a sulfonyl group that can function as a strong electron-attracting group are preferable.
- a trifluoromethyl group, a nitro group, and a cyano group Group, phenyl group, sulfonyl group and the like are more preferable, and trifluoromethyl group, cyano group, phenyl group and sulfonyl group are more preferable from the viewpoint of safety to living bodies.
- R 1 and R 2 are both represented by the general formula (C In the ring represented by -1), one of R 11 and R 12 is a hydrogen atom, and the remaining one is one to three hydrogen atoms are a halogen atom, a C 1-20 alkyl group, or C 1 Forms a ring that is a phenyl group, thienyl group, or furanyl group optionally substituted by a 1-20 alkoxy group, and R 4 and R 5 together form the same ring as the ring formed by R 1 and R 2 R 3 and R 6 are hydrogen atoms, and R 7 and R 8 are halogen atoms; R 1 and R 2 are both R 2 in the ring represented by the general formula (C-2).
- R 13 and one of R 14 is a hydrogen atom, while the remaining is one to three hydrogen atoms are halogen atom , C 1-20 alkyl, or C 1-20 alkoxy phenyl group which may be substituted by a group, to form a ring is thienyl or furanyl group
- R 4 and R 5 are both R 1 and R 2
- R 3 and R 6 are hydrogen atoms and R 7 and R 8 are halogen atoms
- R 2 and R 3 are both represented by the above general formula (C-1 )
- One of R 11 and R 12 is a hydrogen atom, and the remaining one is 1 to 3 hydrogen atoms are a halogen atom, a C 1-20 alkyl group, or a C 1-20 A ring that is a phenyl group, a thienyl group, or a furanyl group that may be substituted by an alkoxy group is formed, and R 5 and R 6 together form a ring of the same type as the ring
- R 9 is a trifluoromethyl group, a cyano group, more preferably those which are nitro group, or a phenyl group, a trifluoromethyl group or a phenyl Those which are groups are particularly preferred.
- Preferred compounds of the near-infrared fluorescent dye according to the present invention include the following general (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 represents a 5-membered or 6-membered aryl group, or a 5-membered or 6-membered heteroaryl group.
- the following general formula (I 1 -1 ) compounds represented by the following general formulas (I 1 -1-1) to (I 1 -1-6) are preferable, and as the following general formula (I 1 -2), Are preferably the compounds represented by the following general formulas (I 1 -2-1) to (I 1 -12-12).
- the following general formula (I 2 -1) is the general formula (I 2 -1) -1) to (I 2 -1-6) are preferable, and the following general formula (I 2 -2) includes the following general formulas (I 2 -2-1) to (I 2 -2-)
- the compound represented by 12) is preferred.
- Q 11 represents a hydrogen atom or an electron withdrawing property. Represents a group. Examples of the electron withdrawing group include the same groups as those described above for R g .
- a compound in which Q 11 is a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group which may have a substituent is preferable.
- a compound which is a trifluoromethyl group or a phenyl group which may have a substituent is more preferable.
- the alkyl group portion of the alkoxy group may be linear, branched, or cyclic (aliphatic ring group).
- the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, t-butyloxy group, pentyloxy group, isoamyloxy group, hexyloxy group, heptyloxy group, Examples include octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.
- aryloxy group examples include a phenyloxy group, a naphthyloxy group, an indenyloxy group, and a biphenyloxy group.
- 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-butylcarbonyl group.
- Examples of the arylcarbonyloxy group include a phenylcarbonyloxy group (benzoyloxy group), a naphthylcarbonyloxy group, an indenylcarbonyloxy group, and a biphenylcarbonyloxy group.
- X is preferably a halogen atom, and X is particularly preferably a fluorine atom.
- P 11 to P 14 and P 17 are each independently a halogen atom, C 1 A -20 alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group, a dialkylamino group; As the C 1-20 alkyl group, C 1-20 alkoxy group, monoalkylamino group, or dialkylamino group in P 11 to P 14 , R g and (p1) to (p3), (q1) The same as those described in (q3).
- 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.
- Group, dimethoxyphenyl group, thienyl group, or furanyl group and 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.
- the substituents other than these substituents are not limited to these substituents because the safety can be improved by further introducing appropriate substituents.
- n11 to n14 and n17 each independently represent an integer of 0 to 3.
- n11 to n14 and n17 each independently represent an integer of 0 to 3.
- 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 dialkylamino groups, or a halogen atom, C 1-20 alkyl group, C 1-20 alkoxy group, amino group, monoalkyl It represents a heteroaryl group optionally having 1 to 3 substituents selected from the group consisting of an amino group and a dialkylamino group.
- heteroaryl group wherein R l in formula (I 3), R m, R n, or the like can be mentioned and R o, thienyl group or preferably a furanyl group.
- R g As 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, R g or Examples are the same as those described in (p1) to (p3) and (q1) to (q3).
- an unsubstituted phenyl group, a phenyl group having 1 or 2 C 1-20 alkoxy groups as a substituent, or a heteroaryl group is preferable, an unsubstituted phenyl group, or 1 A phenyl group having a C 1-20 alkoxy group as a substituent is more preferable, an unsubstituted phenyl group, or a phenyl group having one C 1-10 alkoxy group as a substituent is more preferable, an unsubstituted phenyl group, Or the phenyl group which has one C1-6 alkoxy group as a substituent is still more preferable.
- 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), (5-1) to (5-2) are preferred, and the following general formulas (1-1) to (1-12) ), (1-25) to (1-31), (2-1) to (2-7), and (3-25) to (3-31) are more preferred.
- Formulas (1-1), (1-3), (1-4), (1-6), (1-25), (1-27), (2-1), (3-1), A compound represented by any one of (3-3), (3-4), (3-6), (3-25), (3-27), and (4-1) is more preferable.
- P 1 to P 4 and P 18 are independently of each other a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, or a monoalkyl.
- An amino group and a dialkylamino group are represented.
- the C 1-20 alkyl group, C 1-20 alkoxy group, monoalkylamino group, or dialkylamino group in P 1 to P 4 R g and (p1) to (p3), (q1) The same as those described in (q3).
- P 1 to P 4 and P 18 include 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 and 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.
- the substituents other than these substituents are not limited to these substituents because the safety can be improved by further introducing appropriate substituents.
- n1 to n4 and n18 each independently represent an integer of 0 to 3.
- all of the plurality of P 1 may be the same or different functional groups. Also good. The same applies to P 2 to P 4 and P 18 .
- Q is a trifluoromethyl group, a cyano group, a nitro group, or a substituted group.
- Examples of the substituent that the phenyl group may have include 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.
- X is the same as in general formula (I 1 -1-1).
- X is a halogen atom
- a fluorine atom is particularly preferable.
- m2 is 0 or 1. In the compound represented by the general formula (1-32), m2 is preferably 1.
- the compounds represented by the general formulas (3-1) to (3-37), (4-1) to (4-7), (5-2) include P 1 to P 4 and P 18 are independently of each other a C 1-20 alkyl group, C 1-20 alkoxy group, (unsubstituted) phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-dimethylaminophenyl group, dimethoxyphenyl.
- the compound represented by any one of the following general formulas (I 3 -1) to (I 3 -6), or A compound represented by any one of formulas (I 4 -1) to (I 4 -6) is also preferred.
- R 23 , R 24 , R 25 , and R 26 are independent of each other.
- Examples of the 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 include R in the general formula (I 3 ). l, R m, R n, or are the same as those of the R o.
- R 23 , R 24 , R 25 and R 26 are preferably a halogen atom, an unsubstituted aryl group, or an aryl group having a substituent, specifically, 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 phenyl group, or C 1 A phenyl group substituted with a -10 alkyl group or a C 1-10 alkoxy group is more preferred, and a fluorine atom or an unsubstituted phenyl group
- R 27 and R 28 each independently represent a hydrogen atom or a halogen atom.
- 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.
- R 27 and R 28 are preferably a hydrogen atom or an aryl group, and a compound having high luminous efficiency is obtained. Therefore, a hydrogen atom, an unsubstituted phenyl group, a C 1-20 alkyl group or a C 1-20 alkoxy group is obtained.
- a compound having a high luminous efficiency and excellent compatibility with a resin, so that it is an unsubstituted phenyl group or a phenyl group substituted with a linear or branched C 1-10 alkoxy group 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 groups as those described above for R r or R s in formula (I 3 ).
- R 29 and R 30 is preferably a fluoroalkyl group, a nitro group, a cyano group, or an aryl group that can function as a strong electron-attracting group, and may have a trifluoromethyl group, a nitro group, a cyano group, or a substituent. What is a good phenyl group is more preferable, and what is a trifluoromethyl group or a cyano group is more preferable from the viewpoint of obtaining a compound having high luminous efficiency and excellent compatibility with a resin.
- Y 9 and Y 10 each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom.
- a compound having high luminous efficiency can be obtained. Therefore, Y 9 and Y 10 are independently a sulfur atom, Those which are oxygen atoms or nitrogen atoms are preferable, those which are sulfur atoms or oxygen atoms independently of each other are more preferable, and since a compound having high luminous efficiency and thermal stability is obtained, both are sulfur atoms or More preferably, both are oxygen atoms.
- X 1 and X 2 are each independently a nitrogen atom or a phosphorus atom.
- X 1 and X 2 are Since both compounds are nitrogen atoms or phosphorus atoms, compounds that are both nitrogen atoms or phosphorus atoms are preferable, and since compounds that have both high luminous efficiency and thermal stability are obtained, those that are both nitrogen atoms are more preferable.
- R 31 and R 32 satisfy the following (p4) or (p5).
- P4 Independently of each other, 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 is represented.
- P5 R 31 and R 32 together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent.
- R 33 and R 34 satisfy the following (q4) or (q5).
- (Q4) 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, or (q5)
- R 33 and R 34 are both An aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent is formed.
- R 35 , R 36 , R 37 , and R 38 are represented by the following (p6 ) To (p9) are satisfied.
- P6 Independently of each other, 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 is represented.
- R 35 and R 36 together form an optionally substituted aromatic 5-membered ring or optionally substituted aromatic 6-membered ring
- R 37 and R 38 are Independently of each other, 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 is represented.
- R 36 and R 37 together form an optionally substituted aromatic 5-membered ring or optionally substituted aromatic 6-membered ring, and R 35 and R 38 are Independently of each other, 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 is represented.
- R 37 and R 38 together form an optionally substituted aromatic 5-membered ring or optionally substituted aromatic 6-membered ring, and R 35 and R 36 are Independently of each other, 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 is represented.
- R 39 , R 40 , R 41 , and R 42 are represented by the following (q6 ) To (q9) are satisfied.
- Q6 Independently of each other, 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 is represented.
- R 39 and R 40 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring
- R 41 and R 42 are Independently of each other, 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 is represented.
- R 40 and R 41 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring
- R 39 and R 42 are Independently of each other, 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 is represented.
- R 41 and R 42 together form an optionally substituted aromatic 5-membered ring or optionally substituted aromatic 6-membered ring
- R 39 and R 40 are Independently of each other, 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 is represented.
- C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, and heteroaryl group in the above (p4), (p6) to (p9) and (q4), (q6) to (q9) May be those exemplified as “any group that does not inhibit the fluorescence of the compound” in R a and R b , respectively.
- 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;
- R 27 and R 28 are both 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 independently hydrogen.
- R 33 and R 34 are independently of each other a hydrogen atom or C 1- 20 alkyl Is a group or preferably a compound R 33 and R 34 together form a phenyl group which may have a substituent, R 23, R 24, R 25, and R 26 is a halogen atom or an unsubstituted both 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 29 and R 30 are both tri A fluoromethyl group, a nitro group, or a cyano group; Y 9 and Y 10 are both sulfur atoms or oxygen atoms; and R 31 and R 32 are each independently a hydrogen atom or a C 1-20 alkyl group.
- R 31 and R 32 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group;
- R 33 and R 34 are independently of each other a hydrogen atom or a C 1-20 alkyl group.
- a compound which is a group or forms a phenyl group in which both R 33 and R 34 are substituted with an unsubstituted phenyl group or a C 1-10 alkyl group has high luminous efficiency and excellent compatibility with a resin. preferable.
- 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;
- R 27 and R 28 are both 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;
- 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 optionally substituted phenyl group, and
- R 37 and R 38 are each independently a hydrogen atom or a C 1-20 alkyl group, R 36 and R 37 is Substitute
- R 41 and R 42 are A compound in which an optionally substituted phenyl group is formed and R 39 and R 40 are each independently a hydrogen atom or a C 1-20 alkyl group is preferred, and R 23 , R 24 , R 25 , and R 26 is a halogen atom or an unsubstituted phenyl group; 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 29 and R 30 is a trifluoromethyl group, a nitro group, or a cyano 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
- R 37 and R 38 are independently of each other 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
- R 35 and R 38 are independently of each other a hydrogen atom or a C 1-20 alkyl group.
- R 37 and R 38 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group
- R 35 and R 36 are each independently a hydrogen atom or C 1- 20 is an alkyl group
- R 39, R 40, R 41, and R 42 are each independently of the other hydrogen or C 1-20 alkyl group
- R 39 and R 40 are both unsubstituted phenyl group or C 1 A phenyl group substituted with a -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 are both unsubstituted phenyl groups or C 1 A phenyl group substituted with a -10 alkyl group
- R 39 and R 42 are each independently a hydrogen atom or a C 1-20 alkyl group
- R 41 and R 42 are both an unsubstituted phenyl group or A compound in which a pheny
- 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;
- R 27 and R 28 are both 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;
- X 1 and X 2 are both nitrogen atoms;
- R 36 , R 37 , and R 38 are independently of each other 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
- 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;
- R 27 and R 28 are both 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;
- X 1 and X 2 are both nitrogen atoms;
- R 35 , R 36 , and R 37 are independently from each other 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 3
- 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;
- R 27 and R 28 are both 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;
- X 1 and X 2 are both nitrogen atoms;
- R 35 , R 36 , and R 38 are independently of each other 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 23 , R 24, R 25, and R 26 are both halogen atoms, an unsubstituted phenyl group, or a C 1-10 alkyl group or C 1-10 A phenyl group substituted with an alkoxy group;
- R 27 and R 28 are both 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;
- X 1 and X 2 are both nitrogen atoms;
- R 35 , R 37 , and R 38 are independently of each other 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 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;
- R 27 and R 28 are both 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;
- Y 9 and Y 10 are both 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 R 31 and R 32 both 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 may both have a substituent.
- Compound forming group Preferably, R 23, R 24, R 25, and R 26 are are both a halogen atom or an unsubstituted phenyl group; R 27 and R 28 are both unsubstituted phenyl group, or a linear or branched A phenyl group substituted with a C 1-20 alkoxy group; Y 9 and Y 10 are both 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; R 31 and R 32 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group; R 33 and R 34 are independently of each other a hydrogen atom or a C 1-20 alkyl group.
- a compound that is a group or forms a phenyl group in which both R 33 and R 34 are both substituted with an unsubstituted phenyl group or a C 1-10 alkyl group has high luminous efficiency and excellent compatibility with a resin. Therefore, it is more preferable.
- Examples of the compound represented by (I 4 -2) include that 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; R 27 and R 28 are both 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 R 35 and R 36 together form a phenyl group that may have a substituent.
- 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 independent of each other Or a C 1-20 alkyl group, or R 37 and R 38 together form a phenyl group which may have a substituent, a hydrogen atom or a C 1-20 independently R 35 and R 36 are mutually An alkyl group; R 39 , R 40 , R 41 , and R 42 are each independently a hydrogen atom or a C 1-20 alkyl group, and R 39 and R 40 may both have a substituent.
- 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 a phenyl group which may have a substituent, R 39 and R 42 are each independently a hydrogen atom or a C 1-20 alkyl group, or R 41 and R 42 together form a phenyl group which may have a substituent, and R 39 and R 42 Are independent of each other Or a compound having a C 1-20 alkyl group, and R 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups; and R 27 and R 28 are both unsubstituted phenyl.
- R 35 , R 36 , R 37 , and R 38 are each independently a hydrogen atom or C 1-20 R 35 and R 36 which are alkyl groups together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group
- R 37 and R 38 are each independently a hydrogen atom or C 1- R 36 and R 37 , which are 20 alkyl groups, together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group
- R 35 and R 38 are each independently a hydrogen atom or C 1 -20
- a kill group, or R 37 and R 38 form a phenyl group substituted both with unsubstituted phenyl group or a C 1-10 alkyl group
- a hydrogen atom or a C 1 independently R 35 and R 36 are mutually -20 is an alky
- 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;
- R 27 and R 28 are both 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 36 and R 37 both have a substituent.
- R 38 is 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 36 There hydrogen atom or C 1-20 Al There Le group;
- R 40, R 41, and R 42 are each independently of the other hydrogen or C 1-20 alkyl group, a phenyl group which may R 40 and R 41 are have together substituent
- R 42 is a hydrogen atom or a C 1-20 alkyl group, or R 41 and R 42 together form a phenyl group which may have a substituent
- R 40 is a hydrogen atom or a C 1-
- R 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups
- both R 27 and R 28 are unsubstituted phenyl groups, or linear be Jo or branched C 1-20 phenyl group substituted with an alk
- a compound in which R 41 and R 42 both form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group and R 40 is a hydrogen atom or a C 1-20 alkyl group has a luminous efficiency. high, Since compatibility with resin is excellent, it is more preferable.
- Examples of the compound represented by (I 4 -4) include that 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; R 27 and R 28 are both 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, R 35 and R 36 both have a substituent.
- R 37 is a hydrogen atom or a C 1-20 alkyl group, or R 36 and R 37 together form an optionally substituted phenyl group, and R 35 There hydrogen atom or C 1-20 Al There Le group;
- R 39, R 40, and R 41 is a hydrogen atom or a C 1-20 alkyl group independently of one another, a phenyl group optionally R 39 and R 40 are not both substituted R 41 is a hydrogen atom or a C 1-20 alkyl group, or R 40 and R 41 together form a phenyl group which may have a substituent, and
- R 39 is a hydrogen atom or a C 1- Compounds having 20 alkyl groups are preferred, and R 23 , R 24 , R 25 , and R 26 are both halogen atoms or unsubstituted phenyl groups; both R 27 and R 28 are unsubstituted phenyl groups, or linear A phenyl group substituted with a linear or
- R 23 , R 24, R 25, and R 26 are both halogen atoms, an unsubstituted phenyl group, or a C 1-10 alkyl group or C 1-10 A phenyl group substituted with an alkoxy group;
- R 27 and R 28 are both 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 a hydrogen atom or a C 1-20 alkyl group, or R 35 and R 36 both have a substituent.
- R 38 is a hydrogen atom or a C 1-20 alkyl group
- R 39 , R 40 , and R 42 are independently of each other a hydrogen atom or a C 1-20 alkyl group
- the compound R 42 is a hydrogen atom or a C 1-20 alkyl group is preferable
- R 23, R 24, R 25, and R 26 are both A halogen atom or an unsubstituted phenyl group
- both R 27 and R 28 are an unsubstituted phenyl group, or a phenyl group substituted with a linear or branched C 1-20 alkoxy group
- X 1 And X 2 are both nitrogen atoms
- 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 are both unsubstituted phenyl groups or Forming
- 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;
- R 27 and R 28 are both 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 a hydrogen atom or a C 1-20 alkyl group, or R 37 and R 38 both have a substituent.
- R 35 is a hydrogen atom or a C 1-20 alkyl group
- R 39 , R 41 , and R 42 are independently of each other a hydrogen atom or a C 1-20 alkyl group; some, or R 41 and R 2 also forms a phenyl group optionally both have a substituent
- the compound R 39 is a hydrogen atom or a C 1-20 alkyl group is preferable
- R 23, R 24, R 25, and R 26 are both A halogen atom or an unsubstituted phenyl group
- both R 27 and R 28 are an unsubstituted phenyl group, or a phenyl group substituted with a linear or branched C 1-20 alkoxy group
- X 1 And X 2 are both nitrogen atoms
- 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 are both unsubstituted phenyl groups or Forming a
- Examples of the compound represented by any one of (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. In general formula (I 3 -7) and the like, Y 23 and Y 24 are preferably the same kind of atoms.
- Y 13 and Y 14 each independently represent an oxygen atom or a sulfur atom.
- Y 13 and Y 14 are preferably the same kind of atoms.
- Y 25 and Y 26 each independently represent a carbon atom or a nitrogen atom.
- Y 25 and Y 26 are preferably the same kind of atoms.
- R 47 and R 48 each independently represent a hydrogen atom or an electron withdrawing group, and the fluorescence intensity becomes high. It is preferably a group, a cyano group, a nitro group, a sulfonyl group, or a phenyl group, and particularly preferably a trifluoromethyl group or a cyano group. In general formula (I 3 -7) and the like, 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
- An aryl group which may have a group is represented.
- the aryl group those exemplified as “any group that does not inhibit the fluorescence of the compound” in R a and R b 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 a C 1-6 alkyl group, a C 1-6 alkoxy group, an aryl Group, heteroaryl group, and the like.
- R 43 to R 46 may be different from each other, but they are all the same.
- the group is preferably.
- R 43 to R 46 are all of the same type. Those that are halogen atoms or are all phenyl groups that may have the same type of substituent are preferred, those that are all fluorine atoms or unsubstituted phenyl groups are more preferred, and those that are all fluorine atoms are particularly preferred. .
- P 15 to P 16 are each independently a halogen atom, C 1-20 An alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group is represented.
- Examples of the C 1-20 alkyl group, C 1-20 alkoxy group, monoalkylamino group, or dialkylamino group in P 15 to P 16 include R g and (p1) to (p3) and (q1), respectively. The same as those described in (q3).
- P 15 to P 16 include C 1-20 alkyl group, C 1-20 alkoxy group, (unsubstituted) phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-dimethylaminophenyl group, dimethoxy. It is preferably a phenyl group, a thienyl group, or a furanyl group.
- a C 1-20 alkyl group, a C 1-20 alkoxy group, a phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group , A dimethoxyphenyl group, a thienyl group, or a furanyl group, and these substituents may further have a substituent.
- the substituents other than these substituents are not limited to these substituents because the safety can be improved by further introducing appropriate substituents.
- n15 to n16 each independently represent an integer of 0 to 3.
- all of the plurality of P 15 may be the same or different functional groups. Also good. The same is true for P 16.
- a 15 to A 16 are independently of each other a hydrogen atom, a halogen atom, C 1-20 represents a phenyl group optionally having 1 to 3 substituents selected from the group consisting of an 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 substituent that the phenyl group may have, R g and (p1) to (p p3) and the same as those mentioned in (q1) to (q3).
- a 15 to A 16 are preferably an unsubstituted phenyl group, a phenyl group having 1 or 2 C 1-20 alkoxy groups as a substituent, an unsubstituted phenyl group, or one 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 more preferable.
- 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 the same functional group.
- the compounds represented by any one of (I 3 -1) to (I 3 -6) and (I 4 -1) to (I 4 -6) are represented by the following general formulas (6-1) to (6 -12), and compounds represented by any one of (7-1) to (7-12).
- Ph represents an unsubstituted phenyl group.
- the compounds represented by any of the above (I 3 -1) to (I 3 -6) and (I 4 -1) to (I 4 -6) the compounds represented by general formulas (6-4), ( 6-5), (6-7), (6-8), (7-4), (7-5), (7-7), and compounds represented by (7-8) are preferred.
- the compounds represented by (6-4), (6-5), (6-7) and (6-8) are more preferred.
- Formula (6-1) to (6-12), (7-1) in - (7-12), P 5 - P 8 are, independently of one another, a halogen atom, C 1-20 alkyl groups, C 1-20 represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group.
- C 1-20 alkyl group, C 1-20 alkoxy group, monoalkylamino group, or dialkylamino group in P 5 to P 8 R g and (p1) to (p3), (q1) The same as those described in (q3).
- 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. It is preferably a phenyl group, a thienyl group, or a furanyl group.
- n5 to n8 each independently represents an integer of 0 to 3.
- all of the plurality of P 5 may be the same or different functional groups. Also good. The same applies to P 6 to P 8 .
- P 5 to P 8 are each independently a C 1-20 alkyl group or A C 1-20 alkoxy group in which n5 to n8 are independently 0 to 2, P 5 and P 6 are independently C 1-20 alkyl groups, and n5 and n6 are More preferably, it is independently 0 to 2, P 7 and P 8 are each independently a C 1-20 alkoxy group, and n7 and n8 are each independently 0 to 1, and P 5 and P 8 6 is independently a C 1-20 alkyl group, n5 and n6 are independently 1-2, P 7 and P 8 are independently C 1-20 alkoxy groups, n7 and More preferably, n8 is 1.
- Specific examples of the compounds represented by the general formulas (6-1) to (6-12) include compounds represented by the following formulas (6-1-1) to (6-12-1). Can be mentioned. “ ⁇ ” is the peak wavelength of the absorption spectrum of each compound, and “Em” is the peak wavelength of the fluorescence spectrum.
- the resin component contained in the resin composition according to the present invention is not particularly limited, considering the type of near-infrared fluorescent pigment to be blended, the product quality required when forming a molded body, It can be appropriately selected from known resin compositions and improvements thereof.
- the resin component may be a thermoplastic resin or a thermosetting resin. When used in a molded article, the thermosetting resin may be cured during melt-kneading, so the resin component contained in the resin composition according to the present invention is preferably a thermoplastic resin.
- a resin component used in this invention only 1 type may be used and 2 or more types may be mixed and used. When two or more types are mixed, it is preferable to use a combination of highly compatible resins.
- urethane resins such as polyurethane (PU) and thermoplastic polyurethane (TPU); polycarbonate (PC); polyvinyl chloride (PVC), vinyl chloride-vinyl acetate copolymer resin, and the like.
- 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 ⁇ Butadiene styrene (A S) resin, imide-modified ABS resin, styrene / acrylonitrile copolymer (SAN) resin, polystyrene resin such as acrylonitrile / ethylene-propylene-diene / styrene (AES) resin, polyethylene (PE) resin, polypropylene (PP) resin, Olefin resins such as
- the resin component contained in the resin composition according to the present invention since the dispersibility of the near-infrared fluorescent dye according to the present invention is high, the resin component includes a fluorine resin, a silicone resin, a urethane resin, and an olefin.
- Resin, vinyl chloride resin, polyester resin, polystyrene resin, polycarbonate resin, polyamide resin or acrylic resin are preferred, urethane resin, olefin resin, polystyrene resin, polyester resin, and vinyl chloride resin Is more preferable.
- PTFE Teflon
- silicone PU, TPU, PP, PE, PC, PET, PS, polyamide, and PVC are preferable, and TPU, PU, PP, PE, PET, and PS are more preferable.
- the resin component when the resin composition according to the present invention is a thermoplastic resin composition, the resin component may be a thermoplastic resin as a whole resin component, and may contain a small amount of a 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 a whole resin component and contains a small amount of a non-thermosetting resin. Also good.
- the resin composition according to the present invention can be produced by mixing and dispersing the near-infrared fluorescent dye according to the present invention in a resin component.
- the near-infrared fluorescent dye according to the present invention contained in the resin composition according to the present invention may be only one type or may contain two or more types.
- 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 are not limited. Is preferably 0.0001% by mass or more, from the viewpoint of detection sensitivity due to concentration quenching or fluorescence reabsorption, preferably 1% by mass or less, more preferably in the range of 0.001 to 0.5% by mass. A range of 0.001 to 0.05% by mass is more preferable.
- the near-infrared fluorescent dye according to the present invention has a high molar extinction 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 by a camera. Etc. are sufficiently visible.
- Low pigment concentration means low possibility of elution, low possibility of bleeding out from a molded product processed from a resin composition, and processing of a molded product requiring transparency. Desirable from.
- 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 an additive 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 a resin composition and melt-kneading the resin composition.
- 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 actual production is preferable.
- the type and kneading of the resin and the fluorescent material are performed even when melt-kneading is performed at a temperature lower than the decomposition point of the fluorescent material.
- fluorescence may not be emitted due to causes such as poor dispersion or decomposition of the fluorescent material. Therefore, it is difficult to predict whether or not the fluorescent material can be dispersed in the thermoplastic resin or the like from the thermophysical properties of the fluorescent material.
- 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 high quantum yield even in the resin.
- the reason is not clear, but can be inferred as follows.
- the pigment is dispersed by a method such as melt-kneading, if the aggregation or the like occurs, it is considered that the quantum yield of fluorescence decreases due to concentration quenching. Therefore, in order for the dye to emit fluorescence efficiently, it is desirable that the dye is highly compatible with the resin and can be uniformly dispersed.
- One index of whether the compatibility is high is the SP value.
- the compatibility with the resin can be explained from calculated values such as solubility, distribution coefficient, relative dielectric constant, polarizability, and the like of dyes or measured values.
- 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 molecule preferably has a hydrophobic group.
- 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 molecule When dispersed in a highly polar resin such as polyurethane or polyamide, the fluorescent dye molecule has a hydrophilic group such as a carboxyl group, a hydroxyl group, an amino group, an alkoxy group, an aryloxy group, an alkylamino group, an ester or an amide. It is preferable. However, it is not limited to these.
- the near-infrared fluorescent dye according to the present invention has a dye skeleton composed of a wide conjugate plane centered on a boron atom, it tends to aggregate, but an electron donating group or an electron withdrawing substituent is introduced. Thus, it is presumed that the aggregation of the dye is suppressed by polarizing and introducing a bulky functional group, and compatibility with various resins can be realized.
- the partition coefficient and SP value which are indicators of compatibility, can be estimated as the water / octanol partition coefficient and the Hildebrand SP value from the “Hansen solubility parameter” obtained by calculation from commercially available software.
- the distribution coefficients and SP values of the compounds represented by the following compounds (8-1) to (8-8) are as follows.
- the near-infrared fluorescent dye according to the present invention can be melt-kneaded and uniformly dispersed and mixed with a resin component such as PP, and the kneaded resin composition or a molded body processed from the resin composition Can emit near-infrared fluorescence stably with high emission quantum yield.
- a resin component such as PP
- the near-infrared fluorescent dye according to the present invention is different from many other organic near-infrared fluorescent dyes, the reason why it exhibits high emission characteristics even when melt-kneaded with a resin composition is not clear. Infrared fluorescent dyes are presumed to have high heat resistance and excellent compatibility with resins because they have a robust dye skeleton consisting of a wide conjugate plane.
- the resin composition according to the present invention preferably has a difference between the maximum absorption wavelength and the maximum fluorescence wavelength of 10 nm or more, and more preferably 20 nm or more. The larger the Stokes shift, the more sensitive it is to detect fluorescence emitted from the molded body even when using a general detector equipped with a filter for noise reduction by excitation light. is there.
- 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 excitation can be performed with light having a wavelength shorter than the maximum absorption wavelength, fluorescence can be detected even if noise is cut. In addition, when the fluorescence spectrum is broad, it is possible to sufficiently detect fluorescence even if noise is cut. On the other hand, some fluorescent dyes have a plurality of fluorescent peaks. In that case, even if the Stokes shift is small, if there is a fluorescence peak (second peak) on the longer wavelength side, detection should be performed with high sensitivity even when a detector equipped with a filter by noise cut is used. Is possible.
- the fluorescence peak wavelength on the long wavelength side may have a difference from the maximum absorption wavelength of 30 nm or more, and preferably 50 nm or more.
- an excitation light source, a cut filter, etc. are selected appropriately, it will not be limited to the conditions mentioned above.
- the resin composition according to the present invention does not change its color in the visible state even when excited with excitation light in the near infrared region, and emits invisible near infrared region fluorescence, which can be detected by a detector. Therefore, it is sufficient that the maximum absorption wavelength is 600 nm or more for the excitation light in the near infrared region. However, from the viewpoint of absorption efficiency, the maximum absorption wavelength is preferably close to the wavelength of the excitation light, and more than 650 nm is more preferable. It is preferably 680 nm or more. Furthermore, when used as a medical device such as an implant, 700 nm or more is preferable.
- the resin composition according to the present invention and the molded product obtained from the composition have a maximum fluorescence wavelength of 650 nm or more. If the color of the object to be irradiated 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 having sufficient detection sensitivity at 740 nm or more. In that case, the intensity of the fluorescence peak (second peak) on the long wavelength side is preferably 5% or more and more preferably 10% or more with respect to the intensity of the maximum fluorescence wavelength.
- the resin composition according to the present invention and the molded product obtained from the composition have strong absorption in the range of 650 nm to 1500 nm, and preferably emit strong fluorescence in this range.
- Light of 650 nm or more is not easily affected by hemoglobin, and light of 1500 nm or less is hardly affected by water.
- light within the range of 650 nm to 1500 nm has high skin permeability and is not easily affected by contaminants in the living body. Therefore, the wavelength of light used for visualizing medical implants implanted under the skin or the like. It is suitable as a region.
- the resin composition according to the present invention and the molded product obtained from the composition are suitable for detection by light in the range of 650 nm to 1500 nm, It is suitable as a medical device 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 effects of the present invention are not impaired.
- the other components include an ultraviolet absorber, a heat stabilizer, a light stabilizer, an antioxidant, a flame retardant, a flame retardant aid, a crystallization accelerator, a plasticizer, an antistatic agent, a colorant, and a release agent. Is mentioned.
- a molded body that can be detected by near-infrared fluorescence can be obtained.
- the molding method is not particularly limited, and examples thereof include casting (casting method), injection molding using a mold, compression molding, extrusion molding using a T die, blow molding, and the like.
- the molded body may be formed only from the resin composition according to the present invention, or the resin composition according to the present invention and other resin compositions may be used as raw materials.
- the entire molded body may be molded with the resin composition according to the present invention, or only a part of the molded body may be molded with the resin composition according to the present invention.
- the resin composition according to the present invention is preferably used as a raw material constituting the surface portion of the molded body.
- the distal end portion of the catheter is molded with the resin composition according to the present invention, and the remaining portion is molded with a resin composition containing no near-infrared fluorescent dye.
- the molded object which emits near-infrared fluorescence in stripe form can be manufactured by alternately laminating
- surface coating for improving the visibility of the molded body may be performed.
- Fluorescence detection can be performed by a conventional method using a commercially available fluorescence detection device or the like.
- excitation light used for fluorescence detection an arbitrary light source can be used, and in addition to a near-infrared lamp having a long wavelength width, a laser, LED, or the like having a narrow wavelength width can be used.
- the molded product obtained from the resin composition containing the near-infrared fluorescent dye according to the present invention does not change color even when irradiated with light in the near-infrared region, and can be detected with higher sensitivity than before.
- the molded body is particularly suitable for a medical device that is inserted into or placed in the body of a patient.
- the color of the irradiated object is When it may be somewhat reddish, it is not always necessary to use excitation light in the near infrared region.
- excitation light when an excitation light is irradiated to detect fluorescence in a medical device in the body, it is necessary to use the excitation light in a wavelength region with high permeability to a living body such as skin. Excitation light having a high transmittance of 650 nm or more may be used.
- Examples of the medical device include a stent, a coil embolus, a catheter tube, an injection needle, an indwelling needle, a port, a shunt tube, a drain tube, and an implant.
- compound (a-3) (1.90 g, 6.66 mmol) was placed in a 300 mL flask, and an aqueous solution in which ethanol (60 mL) and sodium hydroxide (3.90 g, 97.5 mmol) were dissolved in 30 mL of water was added. Stir at reflux for 1 hour.
- 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 firing stopped. To the stirred solution, trifluoroacetic anhydride (3.3 mL) was added and reacted at 80 ° C. for 1 hour. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution and ice were added to neutralize the solution, followed by suction filtration, and the filtrate was vacuum dried to obtain a black solid of compound (a-5) (yield: 320 mg). Compound (a-5) was directly used in the next reaction without purification.
- compound (a-5) (320 mg) was placed in a 200 mL three-necked flask, and 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 hydrogen carbonate solution was added, and the organic phase was recovered. The organic phase was washed with water and saturated brine, dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was concentrated under reduced pressure.
- Example 1 TPU pellets (product name: Tecoflex EG85A, manufactured by Lubrizol) (100 g) and near-infrared fluorescent dye A (5 mg) synthesized in Production Example 1 were mixed, and the dye was adhered to the pellet surface. Next, the pellets were put into a lab plast mill and melt kneaded at a preset temperature of 190 ° C. for 10 minutes. Thereafter, the kneaded dye-containing resin was taken out and formed into a film. Film formation was performed as follows. First, the melt-kneaded dye-containing resin was heated for 5 minutes while being sandwiched between iron plates heated to 200 ° C., and pressed at 5 to 10 mPa while cooling the iron plates.
- the absorption spectrum of the obtained film was measured with an ultraviolet-visible near-infrared spectrophotometer “UV3600” manufactured by SHIMADZU, and the emission spectrum was measured with an absolute PL quantum yield measuring device “Quantaurus-QY C11347” manufactured by Hamamatsu Photonics.
- UV3600 ultraviolet-visible near-infrared spectrophotometer
- absolute PL quantum yield measuring device Quantantaurus-QY C11347 manufactured by Hamamatsu Photonics.
- the maximum absorption wavelength was 730 nm
- the maximum fluorescence wavelength was 755 nm
- a fluorescence peak was observed at 823 nm.
- the fluorescence quantum yield was 26%.
- the visibility with the near-infrared fluorescence detection camera of the said film was high.
- Example 2 In Example 1, PP pellets (product name: PC630A, manufactured by Sun Allomer Co., Ltd.) were used instead of TPU pellets, and PP pellets (100 g) and near-infrared fluorescent dye A (10 mg) synthesized in Production Example 1 were mixed. Then, a dye-containing resin was obtained in the same manner as in Example 1 except that the dye was attached to the pellet surface, and the obtained dye-containing resin was formed into a film. When the fluorescence spectrum of the obtained film was measured in the same manner as in Example 1, the maximum fluorescence wavelength was 810 nm, and the fluorescence quantum yield was 24%. Moreover, the visibility with the near-infrared fluorescence detection camera of the said film was high.
- Example 3 The elution property of the near-infrared fluorescent dye A from the resin film containing the near-infrared fluorescent dye A was examined.
- Example 1 except that 100 mg of near-infrared fluorescent dye A was used, the same operation as in Example 1 was performed, and the dye concentration of near-infrared fluorescent dye A was 0.1 mass% and the film thickness was about 300 ⁇ m.
- a containing TPU film was produced.
- the resulting dye-containing TPU film was subjected to a dissolution test.
- the elution operation of the film was performed as follows according to ISO10993-10 Annex E.
- a dye-containing TPU film was cut into a size of 2 ⁇ 2 cm or less, added to a 300 mL Erlenmeyer flask with 100 mL of methanol, and shaken at room temperature of 25 ° C. for 8 hours.
- the methanol was then filtered once and extracted twice more with the same amount of methanol using the same film strip.
- the methanol extract obtained by a total of three operations was concentrated with an evaporator, and the residue was dissolved in 5 mL of dichloromethane to obtain a test solution.
- the medical implant molded using the resin composition according to the present invention can be highly safe.
- tert-butyloxypotassium (25.18 g, 224.4 mmol) and tert-amyl alcohol 160 mL were placed in a 500 mL four-necked flask under an argon stream. Thereto was added a solution prepared by mixing the compound (b-1) synthesized earlier (14.8 g, 64 mmol) with 7 mL of tert-amyl alcohol. A solution prepared by mixing succinic acid diisopropyl ester (6.5 g, 32 mmol) in 10 mL of tert-amyl alcohol was added dropwise over about 3 hours while heating under reflux, and after completion of the addition, the mixture was heated under reflux for 6 hours.
- 4-tert-butylaniline (10 g, 67 mmol), acetic acid 70 mL, and sodium thiocyanate (13 g, 160 mmol) were placed in a 200 mL three-necked flask. While maintaining the system at 15 ° C. or lower, bromine (4.5 mL, 87 mmol) was added dropwise over about 20 minutes, and then stirred at 15 ° C. or lower for 3.5 hours. The reaction solution was poured into 150 mL of 28% aqueous ammonia, stirred for a while, the precipitated solid was filtered off, this solid was extracted with diethyl ether, and the organic layer was washed with water.
- 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 inside of the system was placed in an argon atmosphere. Under an argon atmosphere, malononitrile (2.4 g, 36.3 mmol) and compound (b-4) (2.39 g, 13.2 mmol) were added, and the mixture was heated to reflux for 2 hours. Acetonitrile was removed under reduced pressure, the residue was dissolved in ethyl acetate, and the organic layer was washed with water and saturated brine, and treated with anhydrous magnesium sulfate.
- 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 the mixture was stirred at the same temperature for 1 hour, and then ethyl chloroformate (10.9 mL, 120 mmol) in dehydrated THF (50 mL). was added dropwise and the mixture was further stirred for 1 hour.
- reaction solution was concentrated, and the residue was separated and purified by silica gel column chromatography (eluent: dichloromethane) to obtain a dark green solid of near-infrared fluorescent dye C (yield: 1.66 g, yield: 76%).
- compound (d-1) (6.0 g, 22 mmol) was placed in a 500 mL flask, an aqueous solution in which ethanol (200 mL) and sodium hydroxide (12.4 g, 310 mmol) were dissolved in 100 mL of water was added, and refluxed for 1 hour. Stir.
- the 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 stopped. To the stirred solution, trifluoroacetic anhydride (36 mL) was added and reacted at 80 ° C. for 4 hours. After completion of the reaction, the reaction solution was added to a saturated aqueous sodium hydrogen carbonate solution containing ice, and the solution was neutralized, and then suction filtered and vacuum dried to obtain a crude product of compound (d-3).
- Example 4 Characteristic Evaluation of Near-Infrared Fluorescent Dye B
- Example 1 is the same as Example 1 except that near-infrared fluorescent dye B synthesized in Production Example 2 was used in place of near-infrared fluorescent dye A. The same operation was performed to obtain a dye-containing resin, and the obtained dye-containing resin was formed into a film.
- the peak wavelength of the absorption spectrum was 739 nm
- the peak wavelengths of the fluorescence spectrum were 758 nm and 833 nm. Yes, the fluorescence quantum yield was 37%.
- the visibility with the near-infrared fluorescence detection camera of the said film was evaluated, the visibility was very good.
- the near-infrared fluorescence detection camera used was a general CMOS camera provided with an LED ring illuminator having a center wavelength of 740 nm as an excitation light source and having an optical filter that transmits light having a wavelength longer than 800 nm.
- Example 5 Characteristic Evaluation of Near-Infrared Fluorescent Dye C
- Example 1 is the same as Example 1 except that the near-infrared fluorescent dye C synthesized in Production Example 3 was used in place of the near-infrared fluorescent dye A. The same operation was performed to obtain a dye-containing resin, and the obtained dye-containing resin was formed into a film.
- the absorption spectrum, fluorescence spectrum, and fluorescence quantum yield of the obtained dye-containing film were measured in the same manner as in Example 1, the peak wavelength of the absorption spectrum was 741 nm, and the peak wavelength of the fluorescence spectrum was 782 nm.
- the fluorescence quantum yield was 14%.
- the visibility of the film with a near-infrared fluorescence detection camera was evaluated, the visibility was good.
- Example 6 Characteristic evaluation of near-infrared fluorescent dye D
- Example 1 is the same as Example 1 except that near-infrared fluorescent dye D synthesized in Production Example 4 was used instead of near-infrared fluorescent dye A. The same operation was performed to obtain a dye-containing resin, and the obtained dye-containing resin was formed into a film.
- the absorption spectrum, fluorescence spectrum, and fluorescence quantum yield of the obtained dye-containing film were measured in the same manner as in Example 1, the peak wavelength of the absorption spectrum was 737 nm, and the peak wavelength of the fluorescence spectrum was 765 nm.
- the fluorescence quantum yield was 17%. Furthermore, when the visibility of the film with a near-infrared fluorescence detection camera was evaluated, the visibility was good.
- Example 7 Characteristic evaluation of near-infrared fluorescent dye E
- the near-infrared fluorescent dye E synthesized in Production Example 5 was used in place of the near-infrared fluorescent dye A. The same operation was performed to obtain a dye-containing resin, and the obtained dye-containing resin was formed into a film.
- the absorption spectrum, fluorescence spectrum, and fluorescence quantum yield of the obtained dye-containing film were measured in the same manner as in Example 1, the peak wavelength of the absorption spectrum was 741 nm, and the peak wavelength of the fluorescence spectrum was 772 nm.
- the fluorescence quantum yield was 11%. Furthermore, when the visibility with the near-infrared fluorescence detection camera of the said film was evaluated, it was visually recognizable.
- Example 8 Characteristic evaluation of mixture of near-infrared fluorescent dye A and near-infrared fluorescent dye B
- near-infrared fluorescent dye A 5 mg
- near-infrared fluorescent dye B 2 0.5 mg
- a near-infrared fluorescent dye B 2.5 mg
- the peak wavelength of the absorption spectrum was 735 nm
- the peak wavelengths of the fluorescence spectrum were 755 nm and 831 nm.
- the fluorescence quantum yield was 32%.
- the visibility with the near-infrared fluorescence detection camera of the said film was evaluated, the visibility was very good.
- Example 1 The same procedure as in Example 3 was performed except that a near-infrared fluorescent dye IR-140 (manufactured by Sigma-Aldrich Japan Co., Ltd.) represented by the following formula was used instead of the near-infrared fluorescent dye A.
- a containing resin was obtained, the resulting dye-containing resin was filmed, and the elution of the dye from the resulting dye-containing film was tested.
- the obtained test solution showed an absorption spectrum having a peak wavelength of 812 nm derived from IR-140 and a fluorescence spectrum having an emission peak wavelength of 846 nm. From the above results, it is clear that IR-140 is eluted from the film, and the dye is difficult to apply to medical implants from the viewpoint of safety.
- the obtained 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.
- This zinc complex was added to a mixed solution of water / ammonia (120 mL / 60 mL) and extracted three times with diethyl ether diethyl ether (80 mL).
- the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated to obtain a yellow liquid of 6-tert-butyl-2-methyl-quinoline (f-1) (yield 16.2 g, yield 41%).
- 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 the mixture was stirred at 60 ° C. for 2 hours. Reacted for hours. The reaction mixture was cooled and extracted with water (200 mL) / ethyl acetate (300 mL), and the resulting ethyl acetate layer was further washed with water.
- reaction solution was poured into an Erlenmeyer flask containing a 5% aqueous sodium chloride solution (200 ml) and neutralized with acetic acid.
- the precipitated yellow precipitate was collected by filtration, washed with water and dried to obtain cyano- (4,6-dimethyl-pyrimidin-2-yl) acetic acid tert-butyl ester (g-1) (yield) 9.8 g, yield 56.9%).
- dichloromethane 40 mL
- saturated aqueous sodium hydrogen carbonate 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 roughly removed by silica gel column chromatography (eluent: hexane / ethyl acetate).
- a precursor (g-3) (522 mg, 0.65 mmol), N, N-diisopropylethylamine (258 mg, 2.0 mmol), dichloromethane (20 mL) was placed in a 100 mL two-necked flask under an argon stream. Chlorodiphenylborane (600 mg, 3.0 mmol) was added under reflux, and the reaction was continued overnight. The reaction solution was washed with water, and the organic layer was dried over anhydrous magnesium sulfate and concentrated.
- a precursor (h-4) (973 mg, 1.0 mmol), N, N-diisopropylethylamine (387 mg, 3.0 mmol) and dichloromethane (30 mL) were placed in a 100 mL two-necked flask under an argon stream.
- Chlorodiphenylborane (900 mg, 4.5 mmol) was added while refluxing, and the reaction was continued overnight.
- the reaction solution was washed with water, and the organic layer was dried over anhydrous magnesium sulfate and concentrated.
- the residue was washed with methanol and purified by column chromatography (eluent: dichloromethane) to obtain a green solid of near-infrared fluorescent dye H (yield: 0.42 g, yield: 35%).
- Example 9 Results of property evaluation of near-infrared fluorescent dye F Example 1 except that the near-infrared fluorescent dye F synthesized in Production Example 6 was used instead of the near-infrared fluorescent dye A in Example 1. The same operation was performed to obtain a dye-containing resin, and the obtained dye-containing resin was formed into a film.
- the peak wavelength of the absorption spectrum was 764 nm
- the peak wavelengths of the fluorescence spectrum were 776 nm and 865 nm. Yes, the fluorescence quantum yield was 38%.
- FIG. Fig. 2 shows a photograph taken with a camera with pork.
- the film made of the resin composition according to the present invention has excellent visibility with a near-infrared fluorescent camera (FIG. 1), and can be clearly observed even with 2 mm thick pork. (FIG. 2).
- Example 3 the same operation as in Example 3 was performed except that the near-infrared fluorescent dye F synthesized in Production Example 6 was used in place of the near-infrared fluorescent dye A, and the dye was eluted from the obtained dye-containing film. Sex was tested. As a result, absorption and fluorescence derived from the near-infrared fluorescent dye F were not observed from the test solution, and it became clear that the near-infrared fluorescent dye F was not eluted from the TPU film. Also from this result, it is clear that the medical implant molded using the resin composition according to the present invention can be highly safe.
- Example 10 Characteristic evaluation result of near-infrared fluorescent dye G Example 1 except that the near-infrared fluorescent dye G synthesized in Production Example 7 was used instead of the near-infrared fluorescent dye A in Example 1. The same operation was performed to obtain a dye-containing resin, and the obtained dye-containing resin was formed into a film.
- the absorption spectrum, fluorescence spectrum, and fluorescence quantum yield of the obtained dye-containing film were measured in the same manner as in Example 1, the peak wavelength of the absorption spectrum was 756 nm, and the peak wavelengths of the fluorescence spectrum were 778 and 870 nm. Yes, the fluorescence quantum yield was 35%. Furthermore, when the visibility with the near-infrared fluorescence detection camera of the said film was evaluated, it was visually recognizable.
- Example 3 the same operation as in Example 3 was performed except that the near-infrared fluorescent dye G synthesized in Production Example 7 was used, and the dye was eluted from the obtained dye-containing film. Sex was tested. As a result, absorption and fluorescence derived from the near-infrared fluorescent dye G were not observed from the test solution, and it became clear that the near-infrared fluorescent dye G was not eluted from the TPU film. Also from this result, it is clear that the medical implant molded using the resin composition according to the present invention can be highly safe.
- Example 11 Results of property evaluation of near-infrared fluorescent dye H Example 1 except that the near-infrared fluorescent dye H synthesized in Production Example 8 was used instead of the near-infrared fluorescent dye A in Example 1. The same operation was performed to obtain a dye-containing resin, and the obtained dye-containing resin was formed into a film.
- the peak wavelength of the absorption spectrum was 744 nm
- the peak wavelengths of the fluorescence spectrum were 787 and 865 nm. Yes, the fluorescence quantum yield was 36%.
- the visibility with the near-infrared fluorescence detection camera of the said film was evaluated, it was visually recognizable.
- Example 3 the same operation as in Example 3 was performed except that the near-infrared fluorescent dye H synthesized in Production Example 8 was used, and the dye was eluted from the obtained dye-containing film. Sex was tested.
- absorption and fluorescence derived from the near-infrared fluorescent dye H were not recognized from the test solution, and it became clear that the near-infrared fluorescent dye H was not eluted from the TPU film. Also from this result, it is clear that the medical implant molded using the resin composition according to the present invention can be highly safe.
- Example 12 Camera visibility results of near-infrared fluorescent dye A
- Example 1 the same operation as in Example 1 was performed except that 30 mg of near-infrared fluorescent dye A was used, and the concentration was 0.03% by mass.
- a film containing a near-infrared fluorescent dye A was obtained (Dye A 0.03% film).
- photographs taken with the near-infrared fluorescence detection camera described in Example 4 are shown in FIG. 3, and photographs taken with the camera with 2 mm thick pork placed on these films.
- the film made of the resin composition according to the present invention has excellent visibility with a near-infrared fluorescent camera (FIG. 3), and can be clearly observed even with 2 mm thick pork. (FIG. 4).
- Example 13 Camera visibility results of near-infrared fluorescent dye B
- the near-infrared fluorescent dye B (30 mg) synthesized in Production Example 2 was used instead of the near-infrared fluorescent dye A (5 mg).
- the same operation as Example 1 was performed except having used, and the film containing the near-infrared fluorescent pigment
- Example 14 Evaluation of polystyrene film containing near-infrared fluorescent dye B
- polystyrene Dow Styrene (trademark) LP-6000, manufactured by DIC Corporation
- TPU pellets TPU pellets
- a polystyrene film having a pigment concentration of 0.005% by mass was prepared in the same manner as in Example 4 except that the temperature was changed to 230 ° C., and the same evaluation as in Example 4 was performed.
- Example 15 Evaluation of PET film containing near-infrared fluorescent dye B
- PET Byron (trademark) SI-173C, manufactured by Toyobo Co., Ltd.
- TPU glass transition temperature
- a PET film having a pigment concentration of 0.005% by mass was prepared in the same manner as in Example 4 except that the temperature was 210 ° C., and the same evaluation as in Example 4 was performed. The results are shown in Tables 1 and 2.
- Example 16 Evaluation of polyethylene film containing near-infrared fluorescent dye B
- polyethylene UBE polyethylene (trademark) F522N, manufactured by Ube Industries) was used instead of TPU pellets, and the kneading temperature was further changed.
- a polyethylene film having a pigment concentration of 0.005% by mass was prepared in the same manner as in Example 4 except that the temperature was 130 ° C., and the same evaluation as in Example 4 was performed. The results are shown in Tables 1 and 2.
- Example 17 Evaluation of PP Film Containing Near-Infrared Fluorescent Dye B
- Example 4 is the same as Example 4 except that PP pellets (product name: PC630A, manufactured by Sun Allomer Co.) were used instead of TPU pellets.
- a PP film having a pigment concentration of 0.005% by mass was prepared and evaluated in the same manner as in Example 4. The results are shown in Tables 1 and 2.
- Example 18 Evaluation of PP film containing near-infrared fluorescent dye F
- near-infrared fluorescent dye F was used instead of near-infrared fluorescent dye B
- PP pellet product name was used instead of TPU pellet.
- PC630A manufactured by Sun Allomer Co., Ltd.
- Tables 1 and 2 show the results. It was shown to.
- Table 1 shows the results of Examples 1, 2, 4 to 11, and 14 to 18.
- ⁇ indicates very good visibility
- ⁇ indicates good visibility
- ⁇ indicates visual recognition
- ⁇ indicates poor visibility. means. From Table 1, it is clear that all the films obtained from the resin composition of the present invention emit light at 700 nm or more, have a high quantum yield, and excellent visibility with a near-infrared camera.
- Table 2 shows the results of dissolution tests of Examples 3 to 11, 14 to 18, and Comparative Example 1. From Table 2, since the film obtained from the resin composition of the present invention was unable to observe luminescence caused by the near-infrared fluorescent dye from the eluate, there was no elution of the near-infrared fluorescent dye, and medical use It is clear that it is safe to use. On the other hand, in the film obtained from the resin composition of Comparative Example 1, light emission due to the near-infrared fluorescent dye was observed from the eluate, and it was revealed that the dye was eluted.
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Abstract
Description
さらに、非特許文献2には、ジケトピロロピロール(DPP)誘導体をホウ素錯体化して得られる、分子内に2つのホウ素錯体ユニットを持つDPP系ホウ素錯体の近赤外蛍光色素が開示されている。これらのBODIPY色素類やDPP系ホウ素錯体類は、主に、核酸やタンパク質等の生体分子や腫瘍組織等を標識するバイオマーカーとして使用されており、BODIPY色素類やDPP系ホウ素錯体類を含有させた樹脂については、ほとんど報告がない。BODIPY色素類を含有させた樹脂組成物としては、特許文献4に、アルキレン基を介してオルガノシロキサニル基が導入されたシロキサン含有BODIPY色素を、シリコーン樹脂中に共重合させることにより、可視光領域の蛍光を発する樹脂が得られたことが開示されている。また、特許文献5には、可視光発光のBODIPY色素の相溶性を高めるために、溶媒と伴にポリマーに混合した可視光領域の蛍光を発する組成物が開示されている。その他、特許文献6には、少なくとも1つの電子求引性基を持つBODIPY色素類と樹脂とを含有し、可視光領域の光の吸収性が高い光学フィルターが開示されており、特許文献7には、BODIPY色素類と樹脂とを含有し、短波長光を長波長光に変換する色変換材料が開示されている。
その他、特許文献8には、赤外線領域に吸収を有しており、かつ可視光領域に吸収を有さない化合物として、DPP系ホウ素錯体が挙げられており、特許文献9には、当該化合物と疎水性ポリマーとを含む赤外線吸収用組成物が開示されている。
一方で、フタロシアニン色素等は、色素骨格自体の発光量子収率が低いため、これらの色素からなる特許文献2に記載されている反応性基含有近赤外蛍光色素は、充分な発光強度を得ることができない、という問題がある。
また、特許文献4に記載のシロキサン含有BODIPY色素は、硬化前のシリコーンモノマー溶液との相溶性は良好で、硬化することにより均一に色素が分散したシリコーン樹脂が得られるものの、その他の樹脂や樹脂溶液への相溶性は低い、という問題がある。また、特許文献5に記載の樹脂組成物は、溶媒が樹脂中に残留する可能性があるため、安全性に問題がある。そのうえ、特許文献4、特許文献5、特許文献6、及び特許文献7には、そもそも近赤外蛍光を発するBODIPY色素についての記載はなく、医療用途への適用についても記載されていない。同様に、特許文献8及び特許文献9にも、近赤外発光するDPP系ホウ素錯体に関する記述はなく、医療用途への適用についても報告されていない。
[1] 近赤外蛍光色素及び樹脂を含有する樹脂組成物であり、
前記近赤外蛍光色素が、
下記一般式(I1)
Ra及びRbは、Raが結合する窒素原子及びRbが結合する炭素原子と共に、芳香族5員環、芳香族6員環、又は2~3個の5員環若しくは6員環が縮合してなる縮合芳香環を形成し;
Rc及びRdは、Rcが結合する窒素原子及びRdが結合する炭素原子と共に、芳香族5員環、芳香族6員環、又は2~3個の5員環若しくは6員環が縮合してなる縮合芳香環を形成し;
Re及びRfは、ハロゲン原子又は酸素原子を表し;
Rgは、水素原子、又は電子求引性基を表す。
ただし、Re及びRfが酸素原子の場合には、Re、Reと結合するホウ素原子、Ra、及びRaが結合する窒素原子が共に環を形成してもよく、Rf、Rfと結合するホウ素原子、Rc、及びRcが結合する窒素原子が共に環を形成してもよい。Reが酸素原子であり、かつ環を形成していない場合には、Reは置換基を有する酸素原子であり、Rfが酸素原子であり、かつ環を形成していない場合には、Rfは置換基を有する酸素原子である。)、
下記一般式(I2)
下記一般式(I3)
Rh及びRiは、Rhが結合する窒素原子及びRiが結合する炭素原子と共に、芳香族5員環、芳香族6員環、又は2~3個の5員環若しくは6員環が縮合してなる縮合芳香環を形成し;
Rj及びRkは、Rjが結合する窒素原子及びRkが結合する炭素原子と共に、芳香族5員環、芳香族6員環、又は2~3個の5員環若しくは6員環が縮合してなる縮合芳香環を形成し;
Rl、Rm、Rn、及びRoは、互いに独立して、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表し;
Rp及びRqは、互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表し、
Rr及びRsは、互いに独立して、水素原子、又は電子求引性基を表す。)で表される化合物、
及び下記一般式(I4)
(式(I1-0)中、
R1、R2、及びR3は、
(p1)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(p2)R1及びR2は共に、芳香族5員環又は芳香族6員環を形成し、R3は水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(p3)R2及びR3は共に、芳香族5員環又は芳香族6員環を形成し、R1は水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
R4、R5、及びR6は、
(q1)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(q2)R4及びR5は共に、芳香族5員環又は芳香族6員環を形成し、R6は水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(q3)R5及びR6は共に、芳香族5員環又は芳香族6員環を形成し、R4は水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
R7及びR8は、ハロゲン原子又は酸素原子を表し;
R9は、水素原子、又は電子求引性基を表す。
ただし、R7及びR8が酸素原子の場合には、R7、R7と結合するホウ素原子、ホウ素原子が結合する窒素原子、R1、及びR1と結合する炭素原子が共に環を形成してもよく、R8、R8と結合するホウ素原子、ホウ素原子が結合する窒素原子、R4、及びR4と結合する炭素原子が共に環を形成してもよい。R7が酸素原子であり、かつ環を形成していない場合には、R7は置換基を有する酸素原子であり、R8が酸素原子であり、かつ環を形成していない場合には、R8は置換基を有する酸素原子である。)で表される化合物、及び下記一般式(I2-0)
(式(I2-0)中、R1~R8は、前記式(I1-0)と同じである。)で表される化合物からなる群より選択される1種又は2種以上の化合物を含有する、前記[1]の樹脂組成物。
R23、R24、R25、及びR26は、互いに独立して、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表し;
R27及びR28は、互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表し;
R29及びR30は、互いに独立して、水素原子、又は電子求引性基を表し;
Y9及びY10は、互いに独立して硫黄原子、酸素原子、窒素原子、又はリン原子を表し;
R31及びR32は、
(p4)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(p5)R31及びR32は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成する;
R33及びR34は、
(q4)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(q5)R33及びR34は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成する。)
X1及びX2は、互いに独立して窒素原子又はリン原子を表し;
R35、R36、R37、及びR38は、
(p6)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(p7)R35及びR36は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R37及びR38は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(p8)R36及びR37は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R35及びR38は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(p9)R37及びR38は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R35及びR36は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表し;
R39、R40、R41、及びR42は、
(q6)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(q7)R39及びR40は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R41及びR42は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(q8)R40及びR41は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R39及びR42は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(q9)R41及びR42は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R39及びR40は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。)のいずれかで表される化合物、及び下記一般式(I4-1)~(I4-6)
Y21及びY22は、互いに独立して、炭素原子又は窒素原子を表し;
Q11は、トリフルオロメチル基、シアノ基、ニトロ基、又はフェニル基を表し;
Xは、互いに独立して、ハロゲン原子、C1-20アルコキシ基、アリールオキシ基、又はアシルオキシ基を表し;
P11~P14及びP17は、互いに独立して、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基を表し;
A11~A14は、互いに独立して、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アミノ基、モノアルキルアミノ基、及びジアルキルアミノ基からなる群より選択される1~3個の置換基を有していてもよいフェニル基、又はハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アミノ基、モノアルキルアミノ基、及びジアルキルアミノ基からなる群より選択される1~3個の置換基を有していてもよいヘテロアリール基を表し;
n11~n14及びn17は、互いに独立して、0~3の整数を表し;
m1は0又は1を表す。]
のいずれかで表される化合物からなる群より選択される1種又は2種以上の化合物を含有する、前記[1]の樹脂組成物。
[6] 下記一般式(I3-7)~(I3-9)及び(I4-7)~(I4-9)
Y13及びY14は、互いに独立して、酸素原子又は硫黄原子を表し;
Y25及びY26は、互いに独立して、炭素原子又は窒素原子を表し;
R47及びR48は、互いに独立して、水素原子又は電子求引性基を表し;
R43、R44、R45、及びR46は、ハロゲン原子又は置換基を有していてもよいアリール基を表し;
P15及びP16は、互いに独立して、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基を表し;
n15及びn16は、互いに独立して、0~3の整数を表し;
A15及びA16は、互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アミノ基、モノアルキルアミノ基、及びジアルキルアミノ基からなる群より選択される1~3個の置換基を有していてもよいフェニル基を表す。]
のいずれかで表される化合物からなる群より選択される1種又は2種以上の化合物を含有する、前記[1]の樹脂組成物。
[8] 前記近赤外蛍光色素と前記樹脂とが溶融混練されたものである、前記[1]~[7]のいずれかの樹脂組成物。
[9] 極大蛍光波長が700nm以上である、前記[1]~[8]のいずれかの樹脂組成物。
[10] 医療用材料として用いられる、前記[1]~[9]のいずれかの樹脂組成物。
[11] 前記[1]~[10]のいずれかの樹脂組成物を加工して得られる成形体。
[12] 少なくとも一部が、患者の体内で使用される医療用具である、前記[11]の成形体。
本発明に係る樹脂組成物が含有する近赤外蛍光色素は、具体的には、下記一般式(I1)一般式(I2)、一般式(I3)、又は一般式(I4)で表される化合物である。当該化合物を、以下、「本発明に係る近赤外蛍光色素」ということがある。
ヘテロアリール基としては、例えば、ピロリル基、イミダゾリル基、ピラゾリル基、チエニル基、フラニル基、オキサゾリル基、イソオキサゾリル基、チアゾリル基、イソチアゾリル基、チアジアゾール基等の5員環ヘテロアリール基;ピリジニル基、ピラジニル基、ピリミジニル基、ピリダジニル基等の6員環ヘテロアリール基;インドリル基、イソインドリル基、インダゾリル基、キノリジニル基、キノリニル基、イソキノリニル基、ベンゾフラニル基、イソベンゾフラニル基、クロメニル基、ベンゾオキサゾリル基、ベンゾイソオキサゾリル基、ベンゾチアゾリル基、ベンゾイソチアゾリル基などの縮合ヘテロアリール基を挙げることができる。
Rl、Rm、Rn、又はRoがヘテロアリール基の場合、当該ヘテロアリール基としては、ピロリル基、イミダゾリル基、ピラゾリル基、チエニル基、フラニル基、オキサゾリル基、イソオキサゾリル基、チアゾリル基、イソチアゾリル基、チアジアゾール基等の5員環ヘテロアリール基;ピリジニル基、ピラジニル基、ピリミジニル基、ピリダジニル基等の6員環ヘテロアリール基;インドリル基、イソインドリル基、インダゾリル基、キノリジニル基、キノリニル基、イソキノリニル基、ベンゾフラニル基、イソベンゾフラニル基、クロメニル基、ベンゾオキサゾリル基、ベンゾイソオキサゾリル基、ベンゾチアゾリル基、ベンゾイソチアゾリル基などの縮合ヘテロアリール基を挙げることができる。
(p1)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(p2)R1及びR2は共に、芳香族5員環又は芳香族6員環を形成し、R3は水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(p3)R2及びR3は共に、芳香族5員環又は芳香族6員環を形成し、R1は水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
(q1)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(q2)R4及びR5は共に、芳香族5員環又は芳香族6員環を形成し、R6は水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(q3)R5及びR6は共に、芳香族5員環又は芳香族6員環を形成し、R4は水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
(p4)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
(p5)R31及びR32は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成する。
(q4)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(q5)R33及びR34は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成する。
(p6)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
(p7)R35及びR36は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R37及びR38は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
(p8)R36及びR37は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R35及びR38は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
(p9)R37及びR38は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R35及びR36は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
(q6)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
(q7)R39及びR40は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R41及びR42は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
(q8)R40及びR41は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R39及びR42は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
(q9)R41及びR42は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R39及びR40は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
本発明に係る樹脂組成物が含有する樹脂成分は、特に限定されるものではなく、配合させる近赤外蛍光色素の種類、成形体を形成した際に要求される製品品質等を考慮して、公知の樹脂組成物やその改良物から適宜選択して用いることができる。例えば、当該樹脂成分は、熱可塑性樹脂であってもよく、熱硬化性樹脂であってもよい。成形体に使用する場合には、熱硬化樹脂は溶融混練時に硬化する可能性があることから、本発明に係る樹脂組成物が含有する樹脂成分としては、熱可塑性樹脂であることが好ましい。本発明において用いられる樹脂成分としては、1種のみを用いてもよく、2種類以上を混合して用いてもよい。2種類以上を混合する場合には、相溶性の高い樹脂同士を組み合わせて用いることが好ましい。
本発明に係る樹脂組成物は、樹脂成分に本発明に係る近赤外蛍光色素を混合・分散させることにより製造できる。本発明に係る樹脂組成物が含有する本発明に係る近赤外蛍光色素は、1種類のみであってもよく、2種類以上を含有していてもよい。
本発明に係る樹脂組成物を加工することにより、近赤外蛍光による検出が可能な成形体が得られる。成形方法は、特に限定されないが、キャスティング(注型法)、金型を用いた射出成形、圧縮成形及びTダイ等による押し出し成形、ブロー成形などが挙げられる。
アルゴン気流下、500mL容三口フラスコに4-メトキシフェニルボロン酸(2.99g、19.7mmol)を入れ、トルエン(120mL)に溶解し、[1,1’-ビス(ジフェニルホスフィノ)-フェロセン]パラジウム(II)ジクロリド-ジクロロメタン複合体(1:1)(100mg)、エタノール30mL、5-ブロモ-2-フラルデヒド(3.46g、19.8mmol)及び2mol/L炭酸ナトリウム水溶液(20mL)を加え、80℃で14時間撹拌した。反応終了後、有機相を水及び飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥後、乾燥剤をろ別して溶媒を減圧濃縮した。得られた粗生成物を、フラッシュシリカゲルクロマトグラフィー(溶離液:ヘキサン/酢酸エチル=19/1→4/1)で分離精製することにより、5-(4-メトキシフェニル)-フラン-2-カルボアルデヒド(a-1)を薄黄色液体として得た(収量:3.39g、収率:84.8%)。
TPUペレット(製品名:Tecoflex EG85A、Lubrizol社製)(100g)と、製造例1で合成した近赤外蛍光色素A(5mg)を混合し、ペレット表面に色素を付着させた。次いで、当該ペレットをラボプラストミルに投入し、設定温度190℃で10分間溶融混練(kneading)した。その後、混練された色素含有樹脂を取り出し、フィルム化した。
フィルム化は、以下のようにして行った。まず、溶融混練された色素含有樹脂を200℃に熱した鉄板で挟みながら5分間加熱し、当該鉄板を冷却しながら、5~10mPaでプレスした。
実施例1において、TPUペレットに代えて、PPペレット(製品名:PC630A、サンアロマー社製)を使用し、PPペレット(100g)と製造例1で合成した近赤外蛍光色素A(10mg)を混合し、ペレット表面に色素を付着させた以外は実施例1と同様にして、色素含有樹脂を得、得られた色素含有樹脂をフィルム化した。得られたフィルムの蛍光スペクトルを実施例1と同様にして測定したところ、極大蛍光波長が810nmであり、蛍光量子収率は24%であった。また、当該フィルムの近赤外蛍光検出カメラでの視認性は高かった。
近赤外蛍光色素Aを含有する樹脂フィルムからの近赤外蛍光色素Aの溶出性について調べた。
実施例1において、近赤外蛍光色素Aを100mg使用した以外は実施例1と同様の操作を行い、近赤外蛍光色素Aの色素濃度が0.1質量%である膜厚約300μmの色素含有TPUフィルムを製造した。
得られた色素含有TPUフィルムについて、溶出試験を行った。フィルムの溶出操作は、ISO10993-10AnnexEに従って、以下の通り行った。まず、色素含有TPUフィルム5gを2×2cm以下の大きさに裁断し、100mLのメタノールと共に300mL容の三角フラスコに添加し、25℃の室温で8時間振とうした。次いで、一旦メタノールをろ過し、同じフィルム細片を使用して更に2回、同量のメタノールで抽出した。合計3回の操作で得たメタノール抽出液をエバポレーターで濃縮し、残渣をジクロロメタン5mLに溶解して試験液とした。
得られた試験液の吸収スペクトルと発光スペクトルを測定したところ、近赤外蛍光色素Aに由来する吸収及び蛍光は認められず、TPUフィルムから近赤外蛍光色素Aがほとんど溶出しないことが明らかとなった。近赤外蛍光色素Aがほとんど溶出しなかったことから、本発明に係る樹脂組成物を用いて成形した医療用インプラントは、安全性の高いものになり得る。
近赤外蛍光色素Bは、Organic Letters、2012年、第4巻、2670~2673ページ及びChmestry A European Journal、2009年、第15巻、4857~4864ページを参照にして、以下のように行なった。
近赤外蛍光色素CはJournal of Organic Chemistry、2011年、第76巻、4489~4505ページ記載の方法に従って合成した。
近赤外蛍光色素DはChemistry An Asian Journal、2013年、第8巻、3123~3132ページ記載の方法に従って合成した。
製造例4のカップリング反応において、4-メトキシフェニルホウ酸の代わりにチオフェン-2-ホウ酸(205mg、1.6mmol)を使用した以外は、製造例4と同様の操作を行い、近赤外色素Eの濃緑色結晶を得た(収量:94mg、収率:46.4%)。
実施例1において、近赤外蛍光色素Aに代えて、製造例2で合成した近赤外蛍光色素Bを使用した以外は実施例1と同様の操作を行い、色素含有樹脂を得、得られた色素含有樹脂をフィルム化した。得られた色素含有フィルムの吸収スペクトル、蛍光スペクトル、及び蛍光量子収率を実施例1と同様にして測定したところ、吸収スペクトルのピーク波長が739nmであり、蛍光スペクトルのピーク波長が758nm、833nmであり、蛍光量子収率は37%であった。さらに、当該フィルムの近赤外蛍光検出カメラでの視認性を評価したところ、視認性は非常に良かった。
実施例1において、近赤外蛍光色素Aに代えて、製造例3で合成した近赤外蛍光色素Cを使用した以外は実施例1と同様の操作を行い、色素含有樹脂を得、得られた色素含有樹脂をフィルム化した。得られた色素含有フィルムの吸収スペクトル、蛍光スペクトル、及び蛍光量子収率を実施例1と同様にして測定したところ、吸収スペクトルのピーク波長が741nmであり、蛍光スペクトルのピーク波長が782nmであり、蛍光量子収率は14%であった。さらに、当該フィルムの近赤外蛍光検出カメラでの視認性を評価したところ、視認性は良かった。
実施例1において、近赤外蛍光色素Aに代えて、製造例4で合成した近赤外蛍光色素Dを使用した以外は実施例1と同様の操作を行い、色素含有樹脂を得、得られた色素含有樹脂をフィルム化した。得られた色素含有フィルムの吸収スペクトル、蛍光スペクトル、及び蛍光量子収率を実施例1と同様にして測定したところ、吸収スペクトルのピーク波長が737nmであり、蛍光スペクトルのピーク波長が765nmであり、蛍光量子収率は17%であった。さらに、当該フィルムの近赤外蛍光検出カメラでの視認性を評価したところ、視認性は良かった。
実施例1において、近赤外蛍光色素Aに代えて、製造例5で合成した近赤外蛍光色素Eを使用した以外は実施例1と同様の操作を行い、色素含有樹脂を得、得られた色素含有樹脂をフィルム化した。得られた色素含有フィルムの吸収スペクトル、蛍光スペクトル、及び蛍光量子収率を実施例1と同様にして測定したところ、吸収スペクトルのピーク波長が741nmであり、蛍光スペクトルのピーク波長が772nmであり、蛍光量子収率は11%であった。さらに、当該フィルムの近赤外蛍光検出カメラでの視認性を評価したところ、視認できた。
実施例1において、近赤外蛍光色素A(5mg)に代えて、近赤外蛍光色素A(2.5mg)と製造例2で合成した近赤外蛍光色素B(2.5mg)の混合物を使用した以外は実施例1と同様の操作を行い、色素含有樹脂を得、得られた色素含有樹脂をフィルム化した。得られた色素含有フィルムの吸収スペクトル、蛍光スペクトル、及び蛍光量子収率を実施例1と同様にして測定したところ、吸収スペクトルのピーク波長が735nmであり、蛍光スペクトルのピーク波長が755nm、831nmであり、蛍光量子収率は32%であった。さらに、当該フィルムの近赤外蛍光検出カメラでの視認性を評価したところ、視認性は非常に良かった。
近赤外蛍光色素Aに代えて、下記式で表される近赤外蛍光色素IR-140(シグマアルドリッチジャパン(株)社製)を使用した以外は実施例3と同様の操作を行い、色素含有樹脂を得、得られた色素含有樹脂をフィルム化し、得られた色素含有フィルムからの色素の溶出性を試験した。この結果、得られた試験液は、IR-140に由来するピーク波長が812nmの吸収スペクトルと、発光ピーク波長が846nmの蛍光スペクトルを示した。以上の結果から、IR-140がフィルム中から溶出していることは明らかであり、当該色素は安全性の観点から医療用インプラントには応用困難であった。
近赤外蛍光色素Fは、Organic Letters、2012年、第4巻、2670~2673ページ及びChmestry A European Journal、2009年、第15巻、4857~4864ページを参照にして、以下のように行った。
近赤外蛍光色素Gは、Organic Letters、2012年、第4巻、2670~2673ページ及びChmestry A European Journal、2009年、第15巻、4857~4864ページを参照し、以下のように行った。
近赤外蛍光色素Hは、Organic Letters、2012年、第4巻、2670~2673ページ及びChmestry A European Journal、2009年、第15巻、4857~4864ページを参照し、以下のように行った。
実施例1において、近赤外蛍光色素Aに代えて、製造例6で合成した近赤外蛍光色素Fを使用した以外は実施例1と同様の操作を行い、色素含有樹脂を得、得られた色素含有樹脂をフィルム化した。得られた色素含有フィルムの吸収スペクトル、蛍光スペクトル、及び蛍光量子収率を実施例1と同様にして測定したところ、吸収スペクトルのピーク波長が764nmであり、蛍光スペクトルのピーク波長が776nm、865nmであり、蛍光量子収率は38%であった。
実施例1において、近赤外蛍光色素Aに代えて、製造例7で合成した近赤外蛍光色素Gを使用した以外は実施例1と同様の操作を行い、色素含有樹脂を得、得られた色素含有樹脂をフィルム化した。得られた色素含有フィルムの吸収スペクトル、蛍光スペクトル、及び蛍光量子収率を実施例1と同様にして測定したところ、吸収スペクトルのピーク波長が756nmであり、蛍光スペクトルのピーク波長が778、870nmであり、蛍光量子収率は35%であった。さらに、当該フィルムの近赤外蛍光検出カメラでの視認性を評価したところ、視認できた。
実施例1において、近赤外蛍光色素Aに代えて、製造例8で合成した近赤外蛍光色素Hを使用した以外は実施例1と同様の操作を行い、色素含有樹脂を得、得られた色素含有樹脂をフィルム化した。得られた色素含有フィルムの吸収スペクトル、蛍光スペクトル、及び蛍光量子収率を実施例1と同様にして測定したところ、吸収スペクトルのピーク波長が744nmであり、蛍光スペクトルのピーク波長が787、865nmであり、蛍光量子収率は36%であった。さらに、当該フィルムの近赤外蛍光検出カメラでの視認性を評価したところ、視認できた。
実施例1において、近赤外蛍光色素Aを30mg使用した以外は実施例1と同様の操作を行い、濃度が0.03質量%の近赤外蛍光色素Aを含有するフィルムを得た(色素A0.03%フィルム)。この色素A0.03%フィルムと、実施例1で得た濃度が0.005質量%の近赤外蛍光色素Aを含有するフィルム(色素A0.005%フィルム)、更に色素不含有のフィルム(色素不含フィルム)を並べ、実施例4に記載の近赤外蛍光検出カメラで撮影した写真を図3に、また、これらのフィルム上に厚さ2mmの豚肉を置いてカメラで撮影した写真を図4に示した。結果より明らかなように、本発明に係る樹脂組成物からなるフィルムは、近赤外蛍光カメラでの視認性が優れ(図3)、厚さ2mmの豚肉ごしでもはっきりと観察することができた(図4)。
実施例1において、近赤外蛍光色素A(5mg)に代えて、製造例2で合成した近赤外蛍光色素B(30mg)を使用した以外は実施例1と同様の操作を行い、濃度が0.03質量%の近赤外蛍光色素Bを含有するフィルムを得た(色素B0.03%フィルム)。この色素B0.03%フィルムと、実施例4で得た濃度が0.005質量%の近赤外蛍光色素Bを含有するフィルム(色素B0.005%フィルム)、更に色素不含有のフィルム(色素不含フィルム)を並べ、実施例4に記載の近赤外蛍光検出カメラで撮影した写真を図5に、また、これらのフィルム上に厚さ2mmの豚肉を置いてカメラで撮影した写真を図6に示した。結果より明らかなように、本発明に係る樹脂組成物からなるフィルムは、近赤外蛍光カメラでの視認性が優れ(図5)、厚さ2mmの豚肉ごしでもはっきりと観察することができた(図6)。
実施例4において、TPUペレットに代えてポリスチレン(ディックスチレン(商標)LP-6000、DIC社製)を使用し、さらに混練温度を230℃にした以外は実施例4と同様にして色素濃度0.005質量%のポリスチレンフィルムを作成し、実施例4と同様の評価を行い、結果を表1ならびに表2に示した。
実施例4において、TPUペレットに代えてPET(バイロン(商標)SI-173C、東洋紡社製)を使用し、さらに混練温度を210℃にした以外は実施例4と同様にして色素濃度0.005質量%のPETフィルムを作成し、実施例4と同様の評価を行い、結果を表1ならびに表2に示した。
実施例4において、TPUペレットに代えてポリエチレン(UBEポリエチレン(商標)F522N、宇部興産社製)を使用し、さらに混練温度を130℃にした以外は実施例4と同様にして色素濃度0.005質量%のポリエチレンフィルムを作成し、実施例4と同様の評価を行い、結果を表1ならびに表2に示した。
実施例4において、TPUペレットに代えてPPペレット(製品名:PC630A、サンアロマー社製)を使用した以外は実施例4と同様にして色素濃度0.005質量%のPPフィルムを作成し、実施例4と同様の評価を行い、結果を表1ならびに表2に示した。
実施例4において、近赤外蛍光色素Bに代えて近赤外蛍光色素Fを、TPUペレットに代えてPPペレット(製品名:PC630A、サンアロマー社製)を使用した以外は実施例4と同様にして色素濃度0.005質量%のPPフィルムを作成し、実施例4と同様の評価を行い、結果を表1ならびに表2に示した。
Claims (12)
- 近赤外蛍光色素及び樹脂を含有する樹脂組成物であり、
前記近赤外蛍光色素が、
下記一般式(I1)
Ra及びRbは、Raが結合する窒素原子及びRbが結合する炭素原子と共に、芳香族5員環、芳香族6員環、又は2~3個の5員環若しくは6員環が縮合してなる縮合芳香環を形成し;
Rc及びRdは、Rcが結合する窒素原子及びRdが結合する炭素原子と共に、芳香族5員環、芳香族6員環、又は2~3個の5員環若しくは6員環が縮合してなる縮合芳香環を形成し;
Re及びRfは、ハロゲン原子又は酸素原子を表し;
Rgは、水素原子、又は電子求引性基を表す。
ただし、Re及びRfが酸素原子の場合には、Re、Reと結合するホウ素原子、Ra、及びRaが結合する窒素原子が共に環を形成してもよく、Rf、Rfと結合するホウ素原子、Rc、及びRcが結合する窒素原子が共に環を形成してもよい。Reが酸素原子であり、かつ環を形成していない場合には、Reは置換基を有する酸素原子であり、Rfが酸素原子であり、かつ環を形成していない場合には、Rfは置換基を有する酸素原子である。)、
下記一般式(I2)
下記一般式(I3)
Rh及びRiは、Rhが結合する窒素原子及びRiが結合する炭素原子と共に、芳香族5員環、芳香族6員環、又は2~3個の5員環若しくは6員環が縮合してなる縮合芳香環を形成し;
Rj及びRkは、Rjが結合する窒素原子及びRkが結合する炭素原子と共に、芳香族5員環、芳香族6員環、又は2~3個の5員環若しくは6員環が縮合してなる縮合芳香環を形成し;
Rl、Rm、Rn、及びRoは、互いに独立して、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表し;
Rp及びRqは、互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表し、
Rr及びRsは、互いに独立して、水素原子、又は電子求引性基を表す。)で表される化合物、
及び下記一般式(I4)
極大蛍光波長が650nm以上であることを特徴とする樹脂組成物。 - 下記一般式(I1-0)
R1、R2、及びR3は、
(p1)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(p2)R1及びR2は共に、芳香族5員環又は芳香族6員環を形成し、R3は水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(p3)R2及びR3は共に、芳香族5員環又は芳香族6員環を形成し、R1は水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
R4、R5、及びR6は、
(q1)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(q2)R4及びR5は共に、芳香族5員環又は芳香族6員環を形成し、R6は水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(q3)R5及びR6は共に、芳香族5員環又は芳香族6員環を形成し、R4は水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。
R7及びR8は、ハロゲン原子又は酸素原子を表し;
R9は、水素原子、又は電子求引性基を表す。
ただし、R7及びR8が酸素原子の場合には、R7、R7と結合するホウ素原子、ホウ素原子が結合する窒素原子、R1、及びR1と結合する炭素原子が共に環を形成してもよく、R8、R8と結合するホウ素原子、ホウ素原子が結合する窒素原子、R4、及びR4と結合する炭素原子が共に環を形成してもよい。R7が酸素原子であり、かつ環を形成していない場合には、R7は置換基を有する酸素原子であり、R8が酸素原子であり、かつ環を形成していない場合には、R8は置換基を有する酸素原子である。)で表される化合物、及び下記一般式(I2-0)
- 下記一般式(I3-1)~(I3-6)
R23、R24、R25、及びR26は、互いに独立して、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表し;
R27及びR28は、互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表し;
R29及びR30は、互いに独立して、水素原子、又は電子求引性基を表し;
Y9及びY10は、互いに独立して硫黄原子、酸素原子、窒素原子、又はリン原子を表し;
R31及びR32は、
(p4)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(p5)R31及びR32は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成する;
R33及びR34は、
(q4)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(q5)R33及びR34は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成する。)
X1及びX2は、互いに独立して窒素原子又はリン原子を表し;
R35、R36、R37、及びR38は、
(p6)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(p7)R35及びR36は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R37及びR38は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(p8)R36及びR37は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R35及びR38は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(p9)R37及びR38は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R35及びR36は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表し;
R39、R40、R41、及びR42は、
(q6)互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(q7)R39及びR40は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R41及びR42は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、
(q8)R40及びR41は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R39及びR42は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す、又は
(q9)R41及びR42は共に、置換基を有していてもよい芳香族5員環又は置換基を有していてもよい芳香族6員環を形成し、R39及びR40は互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アリール基、又はヘテロアリール基を表す。)のいずれかで表される化合物、及び下記一般式(I4-1)~(I4-6)
- 下記一般式(I1-1-1)~(I1-1-6)、(I1-2-1)~(I1-2-12)、(I2-1-1)~(I2-1-6)、及び(I2-2-1)~(I2-2-12)
Y21及びY22は、互いに独立して、炭素原子又は窒素原子を表し;
Q11は、トリフルオロメチル基、シアノ基、ニトロ基、又はフェニル基を表し;
Xは、互いに独立して、ハロゲン原子、C1-20アルコキシ基、アリールオキシ基、又はアシルオキシ基を表し;
P11~P14及びP17は、互いに独立して、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基を表し;
A11~A14は、互いに独立して、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アミノ基、モノアルキルアミノ基、及びジアルキルアミノ基からなる群より選択される1~3個の置換基を有していてもよいフェニル基、又はハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アミノ基、モノアルキルアミノ基、及びジアルキルアミノ基からなる群より選択される1~3個の置換基を有していてもよいヘテロアリール基を表し;
n11~n14及びn17は、互いに独立して、0~3の整数を表し;
m1は0又は1を表す。]
のいずれかで表される化合物からなる群より選択される1種又は2種以上の化合物を含有する、請求項1に記載の樹脂組成物。 - 下記一般式(I3-7)~(I3-9)及び(I4-7)~(I4-9)
Y13及びY14は、互いに独立して、酸素原子又は硫黄原子を表し;
Y25及びY26は、互いに独立して、炭素原子又は窒素原子を表し;
R47及びR48は、互いに独立して、水素原子又は電子求引性基を表し;
R43、R44、R45、及びR46は、ハロゲン原子又は置換基を有していてもよいアリール基を表し;
P15及びP16は、互いに独立して、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基を表し;
n15及びn16は、互いに独立して、0~3の整数を表し;
A15及びA16は、互いに独立して、水素原子、ハロゲン原子、C1-20アルキル基、C1-20アルコキシ基、アミノ基、モノアルキルアミノ基、及びジアルキルアミノ基からなる群より選択される1~3個の置換基を有していてもよいフェニル基を表す。]
のいずれかで表される化合物からなる群より選択される1種又は2種以上の化合物を含有する、請求項1に記載の樹脂組成物。 - 前記樹脂が熱可塑性樹脂である、請求項1~6のいずれか一項に記載の樹脂組成物。
- 前記近赤外蛍光色素と前記樹脂とが溶融混練されたものである、請求項1~7のいずれか一項に記載の樹脂組成物。
- 極大蛍光波長が700nm以上である、請求項1~8のいずれか一項に記載の樹脂組成物。
- 医療用材料として用いられる、請求項1~9のいずれか一項に記載の樹脂組成物。
- 請求項1~10のいずれか一項に記載の樹脂組成物を加工して得られる成形体。
- 少なくとも一部が、患者の体内で使用される医療用具である、請求項11に記載の成形体。
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WO2016132596A1 (ja) * | 2015-02-18 | 2016-08-25 | Dic株式会社 | 樹脂組成物及び成形体 |
WO2016132597A1 (ja) * | 2015-02-18 | 2016-08-25 | Dic株式会社 | 樹脂組成物及び成形体 |
WO2016190283A1 (ja) * | 2015-05-26 | 2016-12-01 | 東レ株式会社 | ピロメテンホウ素錯体、色変換組成物、色変換フィルムならびにそれを含む光源ユニット、ディスプレイおよび照明 |
WO2018117074A1 (ja) * | 2016-12-19 | 2018-06-28 | 富士フイルム株式会社 | 波長変換用発光性樹脂組成物及びその製造方法、並びに波長変換部材及び発光素子 |
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WO2019151121A1 (ja) * | 2018-01-31 | 2019-08-08 | 東レ株式会社 | 化合物、それを含む組成物、それを用いた成形体および発光装置 |
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WO2023127507A1 (ja) * | 2021-12-27 | 2023-07-06 | Dic株式会社 | 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 |
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US20160200970A1 (en) * | 2013-08-13 | 2016-07-14 | Dic Corporation | Resin composition and molded article |
WO2021039205A1 (ja) * | 2019-08-29 | 2021-03-04 | 富士フイルム株式会社 | 組成物、膜、近赤外線カットフィルタ、パターン形成方法、積層体、固体撮像素子、赤外線センサ、画像表示装置、カメラモジュール、及び、化合物 |
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US20210030895A1 (en) | 2021-02-04 |
EP3059288A1 (en) | 2016-08-24 |
EP3059288A4 (en) | 2017-06-21 |
EP3059288B1 (en) | 2021-12-22 |
US20160271273A1 (en) | 2016-09-22 |
CA2927521A1 (en) | 2015-04-23 |
JP5943530B2 (ja) | 2016-07-05 |
CA2927521C (en) | 2023-02-07 |
JPWO2015056779A1 (ja) | 2017-03-09 |
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