WO2023182121A1 - マスターバッチ、それを用いた樹脂組成物および成形体の製造方法 - Google Patents

マスターバッチ、それを用いた樹脂組成物および成形体の製造方法 Download PDF

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WO2023182121A1
WO2023182121A1 PCT/JP2023/010218 JP2023010218W WO2023182121A1 WO 2023182121 A1 WO2023182121 A1 WO 2023182121A1 JP 2023010218 W JP2023010218 W JP 2023010218W WO 2023182121 A1 WO2023182121 A1 WO 2023182121A1
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Prior art keywords
group
resin
atom
alkyl group
hydrogen atom
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PCT/JP2023/010218
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English (en)
French (fr)
Japanese (ja)
Inventor
豊 竹澤
直人 櫻井
恭一 豊村
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to EP23774717.5A priority Critical patent/EP4497774A4/en
Priority to CN202380026629.0A priority patent/CN118871508A/zh
Priority to JP2024510075A priority patent/JPWO2023182121A1/ja
Priority to US18/843,759 priority patent/US20250179256A1/en
Publication of WO2023182121A1 publication Critical patent/WO2023182121A1/ja
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    • C08J3/00—Processes of treating or compounding macromolecular substances
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
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    • C09K2211/10—Non-macromolecular compounds
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    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms

Definitions

  • the present invention relates to a masterbatch, a method for producing a resin composition using the masterbatch, and a method for producing a molded article obtained from the resin composition. More specifically, a resin composition that emits near-infrared fluorescence, has high luminous efficiency, and is relatively easy to manufacture, a method for manufacturing a molded article obtained from the resin composition, and a method for manufacturing a molded article from the resin composition.
  • the present invention relates to a masterbatch and a method for producing the same.
  • Near-infrared fluorescent dyes are used in industrial products, mainly to identify various products and prevent counterfeiting, and in recent years, they have also been used in medical applications such as biological imaging probes and test drugs. It is known that the characteristics of the near-infrared wavelength region include that it cannot be seen with the naked human eye, that it has little effect on living organisms, and that it is highly permeable to living organisms such as the skin. Such characteristics can be utilized by containing a near-infrared fluorescent dye in the medical device itself.
  • a system has been disclosed in which the position of a medical device implanted in a living body is confirmed by irradiating near-infrared light from outside the living body by incorporating a near-infrared fluorescent dye into a medical device such as a shunt tube.
  • a medical device such as a shunt tube.
  • the near-infrared fluorescent dye contained in medical implants must itself strongly absorb light in the near-infrared region, and in addition, emit strong fluorescence. There is a need. For this reason, it is preferable that the near-infrared fluorescent dye contained in the resin composition used as a raw material for medical implants has a maximum absorption wavelength in the near-infrared region in the resin.
  • Near-infrared fluorescent dyes include inorganic fluorescent dyes and organic fluorescent dyes.
  • inorganic near-infrared fluorescent dyes have the advantage that the emission wavelength can be easily adjusted within the desired range by using various metals, but it is difficult to adjust the emission wavelength within the desired range by using various metals. nanoparticles are needed.
  • organic near-infrared fluorescent dyes can be synthesized relatively easily and their wavelengths can be easily adjusted, very few are known that can be stably mixed into resins. .
  • a near-infrared fluorescent dye can be mixed and dispersed in a resin, various molded objects that emit near-infrared fluorescence can be manufactured using the resin as a raw material.
  • a resin in which a near-infrared fluorescent dye is dispersed for example, Patent Document 2 describes a reactive group-containing near-infrared fluorescent dye in which a polyester reactive group is introduced into a phthalocyanine dye, a naphthalocyanine dye, or a squarein dye.
  • a near-infrared fluorescent resin copolymerized in (polyethylene terephthalate) is disclosed.
  • boron complexes of ⁇ -conjugated compounds are known as organic fluorescent dyes with high emission quantum yields.
  • BODIPY pigments having the following properties are known (for example, see Non-Patent Document 1).
  • Patent Document 3 discloses a BODIPY dye having a heterocycle 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, which is obtained by complexing a diketopyrrolopyrrole (DPP) derivative with boron. .
  • DPP diketopyrrolopyrrole
  • Patent Document 4 discloses that a siloxane-containing BODIPY dye into which an organosiloxanyl group has been introduced via an alkylene group is copolymerized into a silicone resin to produce visible light. It is disclosed that a resin has been obtained that emits a fluorescent region.
  • Patent Document 5 discloses a composition that emits fluorescence in the visible light region and is mixed with a polymer together with a solvent in order to improve the compatibility of a BODIPY dye that emits visible light.
  • Patent Document 6 discloses an optical filter that contains BODIPY dyes having at least one electron-withdrawing group and a resin and has high absorption of light in the visible light region; discloses a color conversion material that contains BODIPY dyes and a resin and converts short wavelength light into long wavelength light.
  • Patent Document 8 lists 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
  • Patent Document 9 lists the compound and An infrared absorbing composition comprising a hydrophobic polymer is disclosed.
  • Patent Document 3 discloses BODIPY dyes that emit near-infrared fluorescence, there is no description as to whether these can be incorporated into a resin.
  • the siloxane-containing BODIPY dye described in Patent Document 4 has good compatibility with the silicone monomer solution before curing, and when cured, a silicone resin in which the dye is uniformly dispersed can be obtained. There is a problem in that the compatibility in solutions is low. Further, the resin composition described in Patent Document 5 has a safety problem because the solvent may remain in the resin. Furthermore, Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7 do not describe the BODIPY dye that emits near-infrared fluorescence, nor do they describe application to medical use. Similarly, Patent Document 8 and Patent Document 9 do not include any description of DPP-based boron complexes that emit near-infrared light, nor do they report on application to medical applications.
  • fluorescent dyes described in Patent Document 2 and Patent Document 4 that are directly covalently bonded to resin polymers are difficult to manufacture and have low versatility.
  • the introduction of a reactive group into a dye complicates the synthesis route, resulting in high production costs, and there is also the problem that it is not very suitable for industrial mass production.
  • a resin that emits near-infrared fluorescence can be produced simply by mixing and dispersing a near-infrared fluorescent dye in the resin.
  • thermoplastic resin etc.
  • a method of melting and kneading the resin and pigment may be considered, but even if melt-kneading is performed at a temperature below the decomposition point of the pigment, depending on the type of resin and pigment and the kneading conditions, may not emit fluorescence due to reasons such as poor dispersion or decomposition of the dye.
  • the dye may be deactivated when kneaded with a resin having an amino group such as a polyamide resin or a thermosetting resin.
  • thermoplastic resin As described above, it is difficult to predict whether the above-mentioned dye can be dispersed in a thermoplastic resin or not based on the thermophysical properties of the dye.
  • an object of the present invention is to provide a resin composition that emits near-infrared fluorescence, has high luminous efficiency, and is relatively easy to manufacture, and a method for manufacturing a molded article obtained from the resin composition.
  • An object of the present invention is to provide a masterbatch capable of producing a resin composition and a method for producing the same.
  • the masterbatch, the resin composition using the same, and the method for producing a molded article according to the present invention are as follows [1] to [12].
  • [1] Contains a near-infrared fluorescent material (A), a thermoplastic resin other than polyamide resin (B), and a resin (C) different from the thermoplastic resin (B), A masterbatch, wherein the resin (C) forms a continuous phase, and a dispersed phase containing the near-infrared fluorescent material (A) and the thermoplastic resin (B) is formed in the continuous phase.
  • the near-infrared fluorescent material (A) is The following general formula (II 1 )
  • R a and R b are an aromatic 5-membered ring, an aromatic 6-membered ring, or 2 to 3 5- or 6-membered rings, together with the nitrogen atom to which R a is bonded and the carbon atom to which R b is bonded. fused to form a fused aromatic ring;
  • R c and R d are an aromatic 5-membered ring, an aromatic 6-membered ring, or 2 to 3 5- or 6-membered rings, together with the nitrogen atom to which R c is bonded and the carbon atom to which R d is bonded.
  • R e and R f independently 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
  • R e the boron atom bonded to R e , R a , and the nitrogen atom bonded to R a may together form a ring
  • R f The boron atom bonded to R f , R c , and the nitrogen atom bonded to R c may together form a ring.
  • R h and R i are an aromatic 5-membered ring, an aromatic 6-membered ring , or 2 to 3 5- or 6-membered rings, together with the nitrogen atom to which R h is bonded and the carbon atom to which R i is bonded. fused to form a fused aromatic ring;
  • R j and R k are an aromatic 5-membered ring, an aromatic 6-membered ring, or 2 to 3 5- or 6-membered rings, together with the nitrogen atom to which R j is bonded and the carbon atom to which R k is bonded.
  • R l , R m , R n , and R o each independently represent a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group
  • R p and R q 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 in formula (II 3 ) above.
  • the near-infrared fluorescent material (A) is The following general formulas (II 3 -1) to (II 3 -6)
  • 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 independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group
  • R 29 and R 30 independently represent a hydrogen atom or an electron-withdrawing group
  • Y 9 and Y 10 independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom
  • R 31 and R 32 are (p4) Each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group, or (p5)
  • R 31 and R 32 both represent Forms an
  • R 23 to R 30 are the same as in the above formula (II 3 -1);
  • X 1 and X 2 independently represent a nitrogen atom or a phosphorus atom;
  • R 35 , R 36 , R 37 , and R 38 are (p6) each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group, (p7)
  • R 35 and R 36 together form an aromatic 5-membered ring which may have a substituent or a 6-membered aromatic ring which may have a substituent
  • R 37 and R 38 each independently representing 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 aromatic 5-membered ring which may have
  • R 35 and R 36 each independently represent a hydrogen atom, a halogen atom, a C represents a 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group;
  • R 39 , R 40 , R 41 , and R 42 are (q6) each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group;
  • 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,
  • R 23 to R 28 are the same as in formula (II 3 -1) above.
  • R 31 to R 34 , Y 9 and Y 10 are the same as in formula (II 3 -1) above, and in formula (II 4 -2) to (II 4 -6)
  • R 35 to R 42 are the same as those in the formula (II 3 -2), and in the formulas (II 4 -3) to (II 4 -6), X 1 and Same as 3-3 ).
  • the masterbatch according to [2] which contains at least one compound selected from the group consisting of compounds represented by any of the following.
  • the near-infrared fluorescent material (A) is The following general formulas (II 3 -7) to (II 3 -9) and (II 4 -7) to (II 4 -9)
  • Y 23 and Y 24 independently represent a carbon atom or a nitrogen atom
  • Y 13 and Y 14 independently represent an oxygen atom or a sulfur atom
  • Y 25 and Y 26 independently represent a carbon atom or a nitrogen atom
  • R 47 and R 48 independently represent a hydrogen atom or an electron-withdrawing group
  • R 43 , R 44 , R 45 , and R 46 each independently represent a halogen atom or an aryl group that may have a substituent
  • P 15 and P 16 independently represent a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group, a dialkylamino group
  • n15 and n16 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
  • the content of the near-infrared fluorescent material (A) is 0.001% by mass with respect to the total of 100% by mass of the near-infrared fluorescent material (A) and the thermoplastic resin (B) other than the polyamide resin.
  • thermoplastic resin (B) other than the polyamide resin includes thermoplastic polyurethane (TPU) resin, polycarbonate (PC) resin, vinyl chloride resin, acrylic resin, polyester resin, polystyrene resin, olefin resin, and polyacetal (POM).
  • TPU thermoplastic polyurethane
  • PC polycarbonate
  • vinyl chloride resin vinyl chloride resin
  • acrylic resin acrylic resin
  • polyester resin polystyrene resin
  • olefin resin polyacetal
  • the masterbatch according to any one of [1] to [5], containing at least one selected from the group consisting of resins.
  • the total content of the near-infrared fluorescent material (A) and the thermoplastic resin (B) is the same as that of the near-infrared fluorescent material (A), the thermoplastic resin (B), and the resin (C).
  • the resin (C) and the resin (D) include at least one selected from the group consisting of polyamide resin, polyethylene resin, polypropylene resin, thermosetting resin, and crosslinked polyethylene resin, [12] ] The method for producing a resin composition according to.
  • the content of the resin (D) is based on the total of 100% by mass of the near-infrared fluorescent material (A), the thermoplastic resin (B), the resin (C), and the resin (D). , the method for producing a resin composition according to [12] or [13], wherein the content ranges from 20% by mass or more to 80% by mass or less.
  • a method for producing a molded article comprising a step of melt-molding a resin composition obtained by the production method according to any one of [12] to [16].
  • the present invention it is possible to provide a resin composition that emits near-infrared fluorescence, has high luminous efficiency, and is relatively easy to manufacture, and a method for manufacturing a molded article obtained from the resin composition. It is possible to provide a masterbatch that can produce products and a method for producing the same.
  • FIG. 2 is a schematic diagram of an apparatus used for measuring luminous efficiency.
  • the present invention provides a near-infrared fluorescent material (A), a thermoplastic resin (B) other than polyamide resin (hereinafter also simply referred to as thermoplastic resin (B)), and a resin different from the thermoplastic resin (B) ( C), the resin (C) forms a continuous phase, and a dispersed phase containing the near-infrared fluorescent material (A) and the thermoplastic resin (B) is formed in the continuous phase. It's a batch.
  • the masterbatch of the present invention having such a configuration, deactivation of the near-infrared fluorescent material (A) can be suppressed, the near-infrared fluorescent light emission efficiency is high, and manufacturing is relatively easy. It is possible to provide a resin composition having the following excellent effects. In addition, a molded article obtained from the resin composition produced via the masterbatch also has excellent near-infrared fluorescence luminous efficiency and is relatively easy to manufacture.
  • the near-infrared fluorescent material (A) and the thermoplastic resin (B) form a dispersed phase (so-called island part of a sea-island structure), and the resin (C) forms a continuous phase (so-called The formation of a sea-island structure (ocean part) can be confirmed using a digital microscope, etc.
  • X to Y indicating a range means "more than or equal to X and less than or equal to Y.”
  • operations and measurements of physical properties, etc. are performed under conditions of room temperature (20 to 25° C.)/relative humidity of 40 to 50% RH.
  • the near-infrared fluorescent material (A) used in the present invention is a compound whose maximum fluorescence wavelength is in the near-infrared region.
  • the resin composition produced via the masterbatch according to the present invention contains the above-mentioned near-infrared fluorescent material (A).
  • the resin composition and the molded article obtained therefrom can be excited and detected by invisible light in the near-infrared region, so the excitation light and fluorescence can be detected without changing the color tone of biological tissue.
  • Examples of the near-infrared fluorescent material (A) include polymethine dyes, anthraquinone dyes, dithiol metal salt dyes, cyanine dyes, phthalocyanine dyes, indophenol dyes, cyamine dyes, styryl dyes, Aluminum dyes, diimonium dyes, azo dyes, azo-boron dyes, boron dipyrromethene (BODIPY) dyes described in International Publication No. 2007/126052, diketopyrrolopyrrole (DPP) boron complexes, squalium Examples include compounds such as perylene-based dyes and perylene-based dyes. These near-infrared fluorescent materials (A) can be used alone or in combination of two or more.
  • examples of the near-infrared fluorescent material (A) used in the present invention include cyanine dyes, azo-boron dyes, borondipyrromethene (BODIPY) dyes, and diketopyrrolopyrrole (DPP) dyes.
  • a boron complex, a phthalocyanine dye, or a squalium dye is preferable from the viewpoint of luminous efficiency, and in particular, a BODIPY dye represented by the following general formula (II 1 ) or the following general formula (II 2 ) or the following general formula (II 3 ) or a DPP-based boron complex represented by the following general formula (II 4 ) is preferable from the viewpoint of heat resistance. This is because if the luminous efficiency is low, sufficient luminous intensity may not be obtained, and if the heat resistance is low, the material may decompose during kneading with the resin.
  • a compound represented by the following general formula (II 3 ) or general formula (II 4 ) is also preferable. These compounds may be hereinafter referred to as "DPP-based boron complexes used in 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. do.
  • R c and R d are an aromatic compound consisting 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 rings 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. It has a ring structure fused with a ring containing a boron atom. That is, the compound represented by the general formula (II 1 ) or the general formula (II 2 ) has a robust fused ring structure consisting of a wide conjugated plane.
  • R h and R i form an aromatic ring consisting of 1 to 3 rings together with the nitrogen atom to which R h is bonded and the carbon atom to which R i is bonded. do.
  • R j and R k are an aromatic compound consisting 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 rings 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 (II 3 ) or the general formula (II 4 ) has 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.
  • the compound represented by the general formula (II 3 ) or the general formula (II 4 ) has a robust fused ring structure consisting of a very wide conjugated 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 have aromatic properties. It is not particularly limited as long as it has.
  • the aromatic rings include a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, an isoindole ring, an indole ring, an indazole ring, a purine ring, a perimidine ring, a thienopyrrole ring, and a furopyrrole ring.
  • the number of condensed rings is 2 or 3 as the aromatic ring. is preferable, and 2 is more preferable from the viewpoint of complexity in synthesis.
  • the wavelength can be extended to the near infrared region simply 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 have substituents. It may have no substituent, or it may have one or more substituents.
  • the substituent that the aromatic ring has may be "any group that does not inhibit the fluorescence of the compound".
  • the near-infrared fluorescent material to be contained When the resin composition according to the present invention is used as a medical material (raw material for medical devices), the near-infrared fluorescent material to be contained must have mutagenicity, cytotoxicity, Those with negative sensitization, skin irritation, etc. properties are preferred. Moreover, from the viewpoint of safety, it is preferable that the near-infrared fluorescent material is not eluted by body fluids such as blood and tissue fluid from the molded article obtained by processing the resin composition according to the present invention. For this reason, the near-infrared fluorescent material used in the present invention preferably has low solubility in biological components such as blood.
  • the resin component itself in the resin composition according to the present invention hardly dissolves into body fluids, etc., and the near-infrared fluorescent material
  • the molded article of the resin composition according to the present invention can be used in vivo while avoiding elution of the near-infrared fluorescent material.
  • the substituents in the aromatic ring formed by R a and R b or the aromatic ring formed by R c and R d are unlikely to exhibit mutagenicity. It is preferable to select a substance that reduces water solubility.
  • the substituents of the aromatic ring formed by R h and R i or the aromatic ring formed by R j and R k are unlikely to exhibit mutagenicity. It is preferable to select a substance that reduces water solubility.
  • substituents examples include a halogen atom, a nitro group, a cyano group, a hydroxy group, a carboxyl group, an aldehyde group, a sulfonic acid group, an alkylsulfonyl group, a halogenosulfonyl group, a thiol group, an alkylthio group, an isocyanate group, and a 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 include dialkylsilyl groups, trialkylsilyl groups, monoalkoxysilyl groups, dialkoxysilyl groups, trialkoxysilyl groups, aryl groups, and heteroaryl groups.
  • the substituents of 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 , or the aromatic ring formed by R j and R k are: , 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 for living organisms. is preferable, and these substituents may further have a substituent. However, the present invention is not limited to these substituents, since safety can be improved by further introducing a suitable substituent other than these substituents.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom, a chlorine atom, and a bromine atom being preferred, and a fluorine atom being more preferred.
  • the alkyl group, alkenyl group, and alkynyl group may be linear, branched, or cyclic (aliphatic cyclic group).
  • the number of carbon atoms in these groups is preferably 1 to 20, more preferably 1 to 12, even more preferably 1 to 8, and particularly preferably 1 to 6.
  • 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, and dodecyl group.
  • alkenyl group examples include vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, and 2-hexenyl group.
  • alkynyl group examples include ethynyl group, 1-propynyl group, 2-propynyl group, isopropynyl group, 1-butynyl group, and isobutynyl group.
  • alkyl group moiety in the group, dialkoxysilyl group, and trialkoxysilyl group include the same alkyl groups as mentioned above.
  • alkoxy groups include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, t-butyloxy group, pentyloxy group, isoamyloxy group, hexyloxy group, heptyloxy group. , octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.
  • examples of monoalkylamino groups include methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, t-butylamino group, pentylamino group, hexylamino group, etc.
  • examples of the dialkylamino group include dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, dipentylamino group, dihexylamino group, ethylmethylamino group, and methylpropyl group.
  • examples include an amino group, a butylmethylamino group, an ethylpropylamino group, a butylethylamino group, and the like.
  • aryl group examples include phenyl group, naphthyl group, indenyl group, and biphenyl group. Preferably it is a phenyl group.
  • heteroaryl group examples include 5-membered heteroaryl groups such as pyrrolyl group, imidazolyl group, pyrazolyl group, thienyl group, furanyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, and thiadiazole group; pyridinyl group, pyrazinyl group; 6-membered heteroaryl groups such as pyrimidinyl group, pyridazinyl group; indolyl group, isoindolyl group, indazolyl group, quinolidinyl group, quinolinyl group, isoquinolinyl group, benzofuranyl group, isobenzofuranyl group, chromenyl group, benzoxazolyl group fused heteroaryl groups such as a benzisoxazolyl group, a benzothiazolyl group, and a benzisothiazolyl group.
  • the alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group may be unsubstituted groups, or one or more hydrogen atoms may be substituted with a substituent.
  • substituents include halogen atoms, alkyl groups, alkoxy groups, nitro groups, cyano groups, hydroxy groups, amino groups, thiol groups, carboxyl groups, aldehyde groups, sulfonic acid groups, isocyanate groups, thioisocyanate groups, and aryl groups. , heteroaryl group, and the like.
  • the absorption wavelength and fluorescence wavelength of fluorescent materials depend on the surrounding environment. Therefore, the absorption wavelength of the fluorescent material in the resin may be shorter or longer than that in the solution.
  • the absorption wavelength of the BODIPY dye or DPP-based boron complex used in the present invention is extended, it is preferable because the maximum absorption wavelength of various resins is in the near-infrared region.
  • the maximum absorption wavelength of a fluorescent material can be determined by adjusting the band gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) by introducing an electron-donating group and an electron-withdrawing group at appropriate positions within the molecule. can be narrowed and the wavelength can be made longer.
  • an electron-donating group is introduced into the aromatic ring formed by R a and R b and the aromatic ring formed by R c and R d , and R g is By introducing an electron-withdrawing group, the maximum absorption wavelength and maximum fluorescence wavelength of the compound can be made longer.
  • the compound represented by the general formula (II 3 ) introducing an electron donating group into the aromatic ring formed by R h and R i and the aromatic ring formed by R j and R k , When p and Rq have aromatic rings, the maximum absorption wavelength and The maximum fluorescence wavelength can be made longer. By combining these designs, it is possible to adjust to the desired wavelength.
  • the aromatic ring formed by R a and R b and the aromatic ring formed by R c and R d are relatively long even if they are unsubstituted. It is a skeleton that absorbs wavelengths.
  • the crosslinking moiety of pyrrole is a nitrogen atom, so no substituent can be introduced on the nitrogen, but the pyrrole moiety (R a and R b
  • the maximum absorption wavelength and maximum fluorescence wavelength of the compound can be made longer.
  • an electron-donating group is introduced into the pyrrole moiety (the aromatic ring formed by R h and R i and the aromatic ring formed by R j and R k ). or when R p and R q have an aromatic ring, the maximum absorption wavelength and maximum fluorescence wavelength of the compound can be made longer by introducing an electron-donating group into the aromatic ring. can.
  • 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 substitutions.
  • the group is preferably a group that functions as an electron-donating group for the aromatic ring.
  • Groups that function as electron-donating groups include, for example, alkyl groups; alkoxy groups such as methoxy groups; aryl groups (aromatic rings) such as phenyl groups, p-alkoxyphenyl groups, p-dialkylaminophenyl groups, and dialkoxyphenyl groups. (group); Examples include heteroaryl groups (heteroaromatic ring groups) such as 2-thienyl group and 2-furanyl group.
  • the alkyl group, the alkyl group in the substituent of the phenyl group, and the alkyl group in the alkoxy group are preferably linear or branched alkyl groups having 1 to 10 carbon atoms.
  • the number of carbon atoms in the alkyl group moiety and the presence or absence of branching may be appropriately selected in consideration of various physical properties of the fluorescent material. From the viewpoint of solubility and compatibility, it is preferable that the carbon number is 6 or more, and that it is branched.
  • the substituents of 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 as follows: , C 1-6 alkyl group, C 1-6 alkoxy group, aryl group, or heteroaryl group, and methyl group, ethyl group, methoxy group, phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p -dimethylaminophenyl group, dimethoxyphenyl group, thienyl group, or furanyl group is more preferred, and methyl group, ethyl group, methoxy group, phenyl group, or p-methoxyphenyl group is even more preferred.
  • the BODIPY skeleton and the DPP skeleton have high planarity, molecules tend to aggregate with each other due to ⁇ - ⁇ stacking.
  • an aryl group or a heteroaryl group having a bulky substituent into the BODIPY skeleton or DPP skeleton, molecular aggregation can be suppressed and the luminescence quantum yield of the resin composition and molded products thereof according to the present invention can be increased. can do.
  • the BODIPY dye or DPP-based boron complex used in the present invention is easy to synthesize and tends to have a higher luminescence quantum yield, so the aromatic ring formed by R a and R b and R c It is preferable that the aromatic ring formed by R d and the aromatic ring formed by R h and R i and the aromatic ring formed by R j and R k are of the same type.
  • 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.
  • Compounds in which R e and R f are fluorine atoms have high heat resistance and are therefore advantageous when melt-kneaded with a resin at high temperatures.
  • R e and R f are not halogen atoms or oxygen atoms, but are substituents containing an atom capable of bonding with a boron atom. Even if it exists, it can be included in the resin in the same way as the BODIPY dye used in the present invention. The substituent is permissible as long as it does not inhibit fluorescence.
  • the ring formed by R e , the boron atom bonded to R e , and the nitrogen atom bonded to R a is condensed with the aromatic ring formed by R a and R b
  • R The ring formed by f , the boron atom bonded to R f , 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.
  • Re when Re is an oxygen atom and Re does not form a ring, Re is an oxygen atom having a substituent (substituted (an oxygen atom bonded to a group).
  • substituent include a C 1-20 alkyl group, an aryl group, a heteroaryl group, an alkylcarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, and the like.
  • R f when R f is an oxygen atom and R f does not form a ring, R f is an oxygen atom having a substituent.
  • an atom an oxygen atom bonded to a substituent.
  • substituents include a C 1-20 alkyl group, an aryl group, a heteroaryl group, an alkylcarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, and the like.
  • R e and R f are both oxygen atoms having a substituent, the substituent that R e has and the substituent that R f has may be the same type or different types.
  • R e and R f are oxygen atoms
  • R e , R f when R e and R f are oxygen atoms, R e , R f , and the boron atom bonded to R e and R f together form a ring.
  • the ring structure include a structure in which R e and R f are connected to the same aryl ring or heteroaryl ring, a structure in which R e and R f are connected through an alkylene group, and the like.
  • R l , 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 l , R m , R n , or R o is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom or a chlorine atom, and has a strong bond with a boron atom.
  • fluorine atoms are particularly preferred.
  • Compounds in which R l , R m , R n , and R o are fluorine atoms have high heat resistance, and are therefore advantageous when melt-kneaded with a resin at high temperatures.
  • C 1-20 alkyl group means an alkyl group having 1 to 20 carbon atoms
  • C 1-20 alkoxy group means an alkoxy group having 1 to 20 carbon atoms. do.
  • the alkyl group may be linear, branched, or cyclic (aliphatic ring). (base) may be used.
  • the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, heptyl group, octyl group, and nonyl group. , decyl group, undecyl group, dodecyl group, etc.
  • R l , R m , R n , or R o is a C 1-20 alkoxy group
  • the alkyl group portion of the alkoxy group may be linear, branched, or cyclic. (aliphatic cyclic group).
  • 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, Examples include octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, and dodecyloxy group.
  • R l , R m , R n , or R o is an aryl group
  • examples of the aryl group include a phenyl group, a naphthyl group, an indenyl group, a biphenyl group, and the like.
  • the heteroaryl group includes a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a thienyl group, a furanyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, 5-membered heteroaryl groups such as isothiazolyl group and thiadiazole group; 6-membered heteroaryl groups such as pyridinyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group; indolyl group, isoindolyl group, indazolyl group, quinolidinyl group, quinolinyl group, isoquinolinyl group
  • fused heteroaryl groups such as a benzofuranyl group, an isobenzofuranyl group, a chromenyl group,
  • the C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, and heteroaryl group represented by R l , R m , R n , or R o may be an unsubstituted group, and one or more A hydrogen atom may be substituted with a substituent.
  • substituents include halogen atoms, alkyl groups, alkoxy groups, nitro groups, cyano groups, hydroxy groups, amino groups, thiol groups, carboxyl groups, aldehyde groups, sulfonic acid groups, isocyanate groups, thioisocyanate groups, and aryl groups. , heteroaryl group, and the like.
  • R l , R m , R n , and R o are a halogen atom, an unsubstituted aryl group, or an aryl group having a substituent.
  • 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;
  • a phenyl group, or a phenyl group substituted with a C 1-10 alkyl group or a C 1-10 alkoxy group is more preferred, and a fluorine atom or an unsubstituted phenyl group is particularly preferred.
  • R p and R q are each independently a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or represents a heteroaryl group.
  • the halogen atom, C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, and heteroaryl group represented by R p and R q include R l , R m , R n of the general formula (II 3 ) above; , or the same as R o .
  • the compound represented by the general formula (II 3 ) or the general formula (II 4 ) is preferably one in which R p and R q are a hydrogen atom or an aryl group, and a hydrogen atom, an unsubstituted phenyl group, or a C 1 A phenyl group substituted with a -20 alkyl group or a C 1-20 alkoxy group is preferred, and a phenyl group substituted with a hydrogen atom, an unsubstituted phenyl group, or a C 1-20 alkoxy group is more preferred. Particularly preferred is a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C 1-10 alkoxy group.
  • R g represents a hydrogen atom or an electron-withdrawing group.
  • R r and R s each independently represent a hydrogen atom or an electron-withdrawing group.
  • the electron-withdrawing group include 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.
  • Examples include substituents having carbonyl groups such as oxy, amide, and aldehyde groups; sulfoxide groups; sulfonyl groups; alkoxymethyl groups; and aminomethyl groups; Heteroaryl groups and the like can also be used.
  • substituents having carbonyl groups such as oxy, amide, and aldehyde groups; sulfoxide groups; sulfonyl groups; alkoxymethyl groups; and aminomethyl groups; Heteroaryl groups and the like can also be used.
  • these electron-withdrawing groups trifluoromethyl groups, nitro groups, cyano groups, sulfonyl groups, and the like, which can function as strong electron-withdrawing groups, are preferred from the viewpoint of increasing the maximum fluorescence wavelength.
  • a compound represented by the following general formula (II 1 -0) or general formula (II 2 -0) is preferable.
  • a compound having a boron dipyrromethene skeleton is preferable because the maximum fluorescence wavelength becomes a longer wavelength.
  • a compound having a pyrrole ring that satisfies the following (p2), (p3), (q2), or (q3) is an aromatic ring or
  • a compound condensed with a heteroaromatic ring is preferable as the near-infrared fluorescent material used in the present invention because the maximum wavelength becomes a longer wavelength.
  • R 101 , R 102 , and R 103 satisfy any of the following (p1) to (p3):
  • (p1) each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group;
  • R 101 and R 102 together form an aromatic 5-membered ring or an aromatic 6-membered ring
  • R 103 is a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl or
  • R 102 and R 103 together form an aromatic 5-membered ring or an aromatic 6-membered ring
  • R 101 is a hydrogen atom, a halogen atom, a C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, or heteroaryl group.
  • R 104 , R 105 , and R 106 satisfy any of the following (q1) to (q3):
  • (q1) each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group;
  • (q2) R 104 and R 105 together form an aromatic 5-membered ring or an aromatic 6-membered ring
  • R 106 is a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl or
  • R 105 and R 106 together form an aromatic 5-membered ring or an aromatic 6-membered ring
  • R 104 is a hydrogen atom, a halogen atom, a C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, or heteroaryl group.
  • halogen atom, C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, and heteroaryl group in (p1) to (p3) or (q1) to (q3) are R a and R, respectively.
  • Those exemplified as "any group that does not inhibit the fluorescence of the compound" in b can be used.
  • R 101 and R 102 together form an aromatic 5-membered ring or aromatic 6-membered ring
  • R 104 and R 105 together form an aromatic ring
  • R 102 and R 103 together form an aromatic 5-membered ring or aromatic 6-membered ring
  • R 105 and R 106 together form an aromatic 5-membered ring or aromatic 6-membered ring
  • the ring is preferably one represented by any of the following general formulas (C-1) to (C-9), and the following general formulas (C-1), (C-2), or (C-9) It is more preferable to use one of the following.
  • Y 1 to Y 8 each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom.
  • the Y 1 to Y 8 are preferably, independently of each other, a sulfur atom, an oxygen atom, or a nitrogen atom, and more preferably, independently of each other, a sulfur atom or an oxygen atom.
  • R 11 to R 22 independently represent a hydrogen atom or any group that does not inhibit the fluorescence of the compound.
  • any group that does not inhibit the fluorescence of the compound those exemplified as “any 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, (unsubstituted) phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-dimethylaminophenyl group, dimethoxyphenyl group, thienyl group, or furanyl group is more preferable; phenyl group or p-methoxyphenyl group is more preferred.
  • the above compound has at least one of the above-mentioned unsubstituted aryl group, aryl group having a substituent, or unsubstituted heteroaryl group. , or a heteroaryl group having a substituent.
  • R 101 and R 104 , R 102 and R 105 , and R 103 and R 106 may be different from each other. , are preferably the same groups. That is, when R 101 , R 102 , and R 103 satisfy the above (p1), it is preferable that R 104 , R 105 , and R 106 satisfy the above (q1), and R 101 , R 102 , and R 103 satisfies the above (p2), R 104 , R 105 , and R 106 preferably satisfy the above (q2), and R 101 , R 102 , and R 103 satisfy the above (p3). When satisfying the following, it is preferable that R 104 , R 105 , and R 106 satisfy the above (q3).
  • R 101 and R 102 form a ring
  • R 104 and R 105 form a ring
  • R 105 and R 106 form a ring. That is, it is preferable that R 101 , R 102 , and R 103 satisfy the above (p2) or (p3), and R 104 , R 105 , and R 106 satisfy the above (q2) or (q3). This is because when an aromatic ring or a heteroaromatic ring is further condensed to the boron dipyrromethene skeleton, the maximum fluorescence wavelength becomes longer wavelength side.
  • R 107 and R 108 represent a halogen atom or an oxygen atom.
  • R 107 and R 108 are oxygen atoms
  • R 107 , the boron atom to which R 107 is bonded, the nitrogen atom to which the boron atom is bonded, R 101 , and the carbon atom to which R 101 is bonded together form a ring.
  • R 108 , the boron atom to which R 108 is bonded, the nitrogen atom to which the boron atom is bonded, R 104 , and the carbon atom to which R 104 is bonded may form a ring together.
  • the ring formed by R 107 , a boron atom, R 101 , etc., and the ring formed by R 108 , a boron atom, R 104 , etc. are both condensed with the boron dipyrromethene skeleton.
  • the ring formed by R 107 , a boron atom, R 101, etc., and the ring formed by R 108 , a boron atom, R 104 , etc. are preferably 6-membered rings.
  • R 107 when R 107 is an oxygen atom and does not form a ring, R 107 is an oxygen atom having a substituent (substituent (oxygen atom bonded with). Examples of the substituent include a C 1-20 alkyl group, an aryl group, a heteroaryl group, and the like.
  • R 108 when R 108 is an oxygen atom and does not form a ring, R 108 is an oxygen atom having a substituent. (oxygen atom bonded to a substituent).
  • substituents examples include a C 1-20 alkyl group, an aryl group, a heteroaryl group, and the like.
  • R 107 and R 108 are both oxygen atoms having a substituent
  • the substituent that R 107 has and the substituent that R 108 has may be the same type or different types.
  • R 109 represents a hydrogen atom or an electron-withdrawing group.
  • the electron-withdrawing group include the same groups as those listed for Rg above. Among these, from the viewpoint of increasing the maximum fluorescence wavelength, fluoroalkyl groups, nitro groups, cyano groups, aryl groups, and sulfonyl groups that can function as strong electron-withdrawing groups are preferred, and trifluoromethyl groups, nitro groups, and cyano groups are preferred.
  • a phenyl group, a sulfonyl group, and the like are more preferred, and a trifluoromethyl group, a cyano group, a phenyl group, and a sulfonyl group are even more preferred from the viewpoint of safety for living organisms. However, it is not limited to these substituents.
  • the BODIPY dye used in the present invention is a compound represented by the general formula (II 1 -0) or the general formula (II 2 -0), in which both R 101 and R 102 are the above general formula (C-1 ), one of R 11 and R 12 is a hydrogen atom, and in the remaining one, 1 to 3 hydrogen atoms are a halogen atom, a C 1-20 alkyl group, or a C 1-20 alkyl group.
  • R 20 forms a ring that is a phenyl group, thienyl group, or furanyl group optionally substituted with an alkoxy group
  • R 104 and R 105 together form the same ring as the ring formed by R 101 and R 102
  • R 101 and R 102 are both R 13 and One of R 14 is a hydrogen atom, and the remaining one is a phenyl group in which 1 to 3 hydrogen atoms may be substituted with a halogen atom, a C 1-20 alkyl group, or a C 1-20 alkoxy group , a thienyl group, or a furanyl group
  • R 104 and R 105 together form the same ring as the ring formed by R 101 and R 102
  • R 103 and R 106 are hydrogen atoms
  • R 105 and R 106 together form a ring of the same type as the ring formed by R 102 and R 103 , R 101 and R 104 are hydrogen atoms, and R 107 and R 108 are halogen atoms; R 102 and R 103 are both represented by the above general formula (C-2), one of R 13 and R 14 is a hydrogen atom, and in the remaining one, 1 to 3 hydrogen atoms are halogen atoms.
  • R 101 and R 102 A compound in which R 101 and R 104 are hydrogen atoms, and R 107 and R 108 are halogen atoms; R 102 and R 103 both represent the above general formula (C-9 ), any one of R 19 to R 22 has 1 to 3 hydrogen atoms substituted with a halogen atom, a C 1-20 alkyl group, or a C 1-20 alkoxy group.
  • R 105 and R 106 together form a ring of the same type as the ring formed by R 101 and R 102 .
  • R 101 and R 104 are phenyl, thienyl, or furanyl groups optionally substituted with a hydrogen atom, a halogen atom, a C 1-20 alkyl group, or a C 1-20 alkoxy group, and R 107 and a compound in which R 108 is a halogen atom are preferred.
  • R 109 is a trifluoromethyl group, a cyano group, a nitro group, or a phenyl group; Particularly preferred are groups.
  • R 23 , R 24 , R 25 and R 26 are each independently represents a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group.
  • the halogen atom, C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, and heteroaryl group represented by R 23 , R 24 , R 25 , or R 26 include R in the general formula (II 3 ) Examples include those similar to l , R m , R n , or R o .
  • R 23 , R 24 , R 25 , and R 26 are preferably halogen atoms, unsubstituted aryl groups, or aryl groups having a substituent, and specifically, fluorine atoms, 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 preferable, and a fluorine atom , a chlorine atom, an unsubstituted phenyl group, or a C 1-20 alkyl group is preferable.
  • 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 is particularly preferred since a compound having both high luminous efficiency and thermal stability can be obtained.
  • R 27 and R 28 are each independently a hydrogen atom or a halogen atom. , represents a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group.
  • the halogen atom, C 1-20 alkyl group, C 1-20 alkoxy group, aryl group, and heteroaryl group represented by R 27 or R 28 are the same as R p or R q in the general formula (II 3 ). Things can be mentioned.
  • the compounds represented by any of the general formulas (II 3 -1) to (II 3 -6) or the compounds represented by any of the general formulas (II 4 -1) to (II 4 -6) include: It is preferable that R 27 and R 28 are a hydrogen atom or an aryl group, and since a compound with high luminous efficiency can be obtained, a hydrogen atom, an unsubstituted phenyl group, a C 1-20 alkyl group or a C 1-20 alkoxy A phenyl group substituted with a group is preferable, and a phenyl group substituted with a hydrogen atom, an unsubstituted phenyl group, or a linear or branched C 1-20 alkoxy group is more preferable.
  • a phenyl group substituted with a hydrogen atom, an unsubstituted phenyl group, or a linear or branched C 1-10 alkoxy group can be used to obtain a compound with high luminous efficiency and excellent compatibility with resins. Particularly preferred are those.
  • 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 those similar to R r or R s in the general formula (II 3 ).
  • R 29 and R 30 are strong electron-withdrawing groups.
  • a fluoroalkyl group, a nitro group, a cyano group, or an aryl group that can function as A trifluoromethyl group or a cyano group is more preferable because a compound having high luminous efficiency and excellent compatibility with resin can be obtained.
  • Y 9 and Y 10 each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom.
  • Y 9 and Y 10 are independently sulfur atoms. , an oxygen atom, or a nitrogen atom, and independently of each other, a sulfur atom or an oxygen atom is more preferable. Since a compound having both high luminous efficiency and thermal stability is obtained, both sulfur atoms are preferable. More preferably, one or both of them are oxygen atoms.
  • X 1 and X 2 are each independently a nitrogen atom or a phosphorus atom. represents.
  • X 1 and X 2 have high luminous efficiency. Since a compound can be obtained, it is preferable that both atoms are nitrogen atoms or phosphorus atoms, and since a compound having both high luminous efficiency and thermal stability can be obtained, it is more preferable that both atoms are nitrogen atoms.
  • R 31 and R 32 satisfy the following (p4) or (p5): (p4) each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group; (p5) R 31 and R 32 together form a 5-membered aromatic ring which may have a substituent or a 6-membered aromatic ring which may have a substituent.
  • R 33 and R 34 satisfy the following (q4) or (q5).
  • R 33 and R 34 both represent, A 5-membered aromatic ring which may have a substituent or a 6-membered aromatic ring which may have a substituent is formed.
  • R 35 , R 36 , R 37 and R 38 are the following (p6 ) to (p9).
  • R 35 and R 36 together form an aromatic 5-membered ring which may have a substituent or a 6-membered aromatic ring which may have a substituent
  • R 37 and R 38 each independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group.
  • R 36 and R 37 together form an aromatic 5-membered ring which may have a substituent or a 6-membered aromatic ring which may have a substituent
  • R 35 and R 38 each independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group.
  • R 37 and R 38 together form an aromatic 5-membered ring which may have a substituent or a 6-membered aromatic ring which may have a substituent
  • R 35 and R 36 each independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group.
  • R 39 , R 40 , R 41 and R 42 are the following (q6 ) to (q9) are satisfied.
  • (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.
  • R 39 and R 40 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring
  • R 41 and R 42 are , each independently 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 40 and R 41 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring
  • R 39 and R 42 are , each independently 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 41 and R 42 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring
  • R 39 and R 40 are , each independently 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.
  • 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) can use those exemplified as "any group that does not inhibit the fluorescence of the compound" in R a and R b , respectively.
  • R 31 and R 32 together form an aromatic 5-membered ring or an aromatic 6-membered ring, R 33 and An aromatic 5-membered ring or 6-membered ring formed by R 34 together, an aromatic 5-membered ring or 6-membered ring formed by R 35 and R 36 , and an aromatic ring formed by R 36 and R 37 together.
  • the aromatic 5-membered ring or aromatic 6-membered ring formed by R 40 and R 41 together, and the aromatic 5-membered ring or aromatic 6-membered ring formed by R 41 and R 42 include the general formula ( Those represented by any of C-1) to (C-9) are preferred, and those represented by the general formula (C-9) are more preferred since a compound with high thermal stability can be obtained.
  • 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 is 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 each independently hydrogen atom or a C 1-20 alkyl group, or R 31 and R 32 together form a phenyl group which may have a substituent;
  • R 33 and R 34 independently of each other are a hydrogen atom or
  • R 27 and R 28 are both a hydrogen atom, 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 both a trifluoromethyl group, a nitro group, or a cyano 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 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group;
  • R 33 and R 34 independently of each other are hydrogen
  • a compound in which R 33 and R 34 are both an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group has high luminous efficiency and is highly effective against resins. It is more preferred because of its excellent compatibil
  • 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 is 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 trifluoromethyl group, nitro group, cyano group, or phenyl group;
  • 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 an alkyl group together form a phenyl group which may have a substituent, and
  • 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 form
  • 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
  • R 39 and R 40 are independently a hydrogen atom or a C 1-20 alkyl group is preferable
  • R 23 , R 24 , R 25 , and R 26 are all halogen atoms or unsubstituted phenyl groups
  • R 27 and R 28 are both hydrogen atoms, unsubstituted phenyl groups, or linear or branched
  • R 29 and R 30 are both a trifluoromethyl group, a nitro group, or a cyano group
  • R 35 , R 36 , R 37 , and R 38 is independently
  • R 40 and R 41 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group
  • R 39 and R 42 each independently represent a hydrogen atom or a C 1-20 alkyl group. is an alkyl group, or R 41 and R 42 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group
  • R 39 and R 40 are each independently a hydrogen atom or a C 1 Compounds having a -20 alkyl group are more preferable because they have high luminous efficiency and excellent compatibility with resins.
  • 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 is 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 trifluoromethyl group, nitro group, cyano group, or phenyl group;
  • X 1 and X 2 are both nitrogen atoms;
  • R 36 , R 37 , and R 38 are each independently is a hydrogen atom or a C 1-20 alkyl group, R 36 and R 37 together form a phenyl group which may have a substituent, and R 38 is a hydrogen atom or a C 1-20 alkyl group, or R
  • R 37 and R 38 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group
  • R 36 is a hydrogen atom or a C 1-20 alkyl group.
  • R 40 , R 41 , and R 42 are each independently a hydrogen atom or a C 1-20 alkyl group; R 40 and R 41 are both an unsubstituted phenyl group or a C 1-10 alkyl group; A phenyl group forming a substituted phenyl group, in which R 42 is a hydrogen atom or a C 1-20 alkyl group, or R 41 and R 42 are both substituted with an unsubstituted phenyl group or a C 1-10 alkyl group A compound in which R 40 is a hydrogen atom or a C 1-20 alkyl group is more preferable because it has high luminous efficiency and excellent compatibility with resins.
  • 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 is 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 trifluoromethyl group, nitro group, cyano group, or phenyl group;
  • X 1 and X 2 are both nitrogen atoms;
  • R 35 , R 36 , and R 37 are each independently is a hydrogen atom or a C 1-20 alkyl group, R 35 and R 36 together form a phenyl group which may have a substituent, and
  • R 37 is a hydrogen atom or a C 1-20 alkyl group, or R
  • R 36 and R 37 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group, and R 35 is a hydrogen atom or a C 1-20 alkyl group.
  • R 39 , R 40 , and R 41 are each independently a hydrogen atom or a C 1-20 alkyl group; R 39 and R 40 are both an unsubstituted phenyl group or a C 1-10 alkyl group; A phenyl group forming a substituted phenyl group, in which R 41 is a hydrogen atom or a C 1-20 alkyl group, or R 40 and R 41 are both substituted with an unsubstituted phenyl group or a C 1-10 alkyl group A compound in which R 39 is a hydrogen atom or a C 1-20 alkyl group is more preferable because it has high luminous efficiency and excellent compatibility with resins.
  • 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 is 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 trifluoromethyl group, nitro group, cyano group, or phenyl group;
  • X 1 and X 2 are both nitrogen atoms;
  • R 35 , R 36 , and R 38 are each independently is a hydrogen atom or a C 1-20 alkyl group, or R 35 and R 36 together form a phenyl group which may have a substituent, and R 38 is a hydrogen atom or a C 1-20 alkyl group;
  • R 38 is
  • 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 is 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 trifluoromethyl group, nitro group, cyano group, or phenyl group;
  • X 1 and X 2 are both nitrogen atoms;
  • R 35 , R 37 , and R 38 are each independently is a hydrogen atom or a C 1-20 alkyl group, or R 37 and R 38 together form a phenyl group which may have a substituent, and
  • R 35 is a hydrogen atom or a C 1-20 alkyl group;
  • R 35
  • 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 sulfur atoms or oxygen atoms;
  • R 31 and R 32 are independently hydrogen atoms or C 1-20 alkyl groups, 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 both optionally have a substituent;
  • a compound forming a group is preferable, in which R 23 , R 24 , R 25 , and R 26 are
  • R 33 and R 34 are each independently Compounds that are a hydrogen atom or a C 1-20 alkyl group, or in which both R 33 and R 34 form a phenyl group substituted with an unsubstituted phenyl group or a C 1-10 alkyl group have high luminous efficiency and are suitable for resins. It is more preferable because it has excellent compatibility with.
  • 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 is 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, R 35 and R 36 together form a phenyl group which 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 a phenyl group which may have a substituent, and
  • R 35 and R 38 are each independently a hydrogen atom or a hydrogen a C 1-20 al
  • R 39 and R 42 are each independently a hydrogen atom or a C 1-20 alkyl group, and R 23 , R 24 , R 25 , and R 26 are all a halogen atom or an unsubstituted phenyl group.
  • R 27 and R 28 are both a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a linear or branched C 1-20 alkoxy group;
  • R 35 , R 36 , R 37 and R 38 are each independently a hydrogen atom or a C 1-20 alkyl group, and R 35 and R 36 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group.
  • R 41 and R 42 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group, and R 39 and R 42 independently of each other are hydrogen atoms.
  • a compound having a C 1-20 alkyl group is more preferable because it has high luminous efficiency and excellent compatibility with resin.
  • 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 is 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 both form a phenyl group which may have a substituent, and
  • R 36 is a hydrogen atom or a C 1-20 alkyl group;
  • R 40
  • R 37 and R 38 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group
  • R 36 is a hydrogen atom or a C 1-20 alkyl group
  • R 40 ; R 41 and R 42 are each independently a hydrogen atom or a C 1-20 alkyl group, and R 40 and R 41 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group.
  • R 42 is a hydrogen atom or a C 1-20 alkyl group, or R 41 and R 42 together form an unsubstituted phenyl group or a phenyl group substituted with a C 1-10 alkyl group, and R 40 is A compound having a hydrogen atom or a C 1-20 alkyl group is more preferable because it has high luminous efficiency and excellent compatibility with resin.
  • 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 is 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 both form a phenyl group which may have a substituent, and
  • R 35 is a hydrogen atom or a C 1-20 alkyl group;
  • R 39 R
  • R 23 , R 24 , R 25 , and R 26 are all halogen atoms, unsubstituted phenyl groups, C 1-10 alkyl groups, or C 1-10 is 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 each independently a hydrogen atom or a C 1-20 alkyl group;
  • R 39 and R 40 together form a phenyl group which
  • 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 is 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 each independently a hydrogen atom or a C 1-20 alkyl group;
  • Examples of the compounds represented by any of the above (II 3 -1) to (II 3 -6) include compounds represented by any of the following general formulas (II 3 -7) to (II 3 -9).
  • the compound represented by any one of (II 4 -1) to (II 4 -6) is represented by any one of the following general formulas (II 4 -7) to (II 4 -9).
  • Compounds are preferred.
  • Y 23 and Y 24 independently represent a carbon atom or a nitrogen atom. In general formula (II 3-7 ), etc., Y 23 and Y 24 are preferably the same type of atoms.
  • Y 13 and Y 14 independently represent an oxygen atom or a sulfur atom.
  • Y 23 and Y 24 are preferably the same type of atoms.
  • Y 25 and Y 26 each independently represent a carbon atom or a nitrogen atom. In general formula (II 3 -9), etc., Y 25 and Y 26 are preferably the same type of atoms.
  • R 47 and R 48 independently represent a hydrogen atom or an electron-withdrawing group, and trifluoromethyl A cyano group, a nitro group, a sulfonyl group, or a phenyl group is preferable, and a trifluoromethyl group or a cyano group is particularly preferable.
  • R 47 and R 48 are preferably the same functional group.
  • R 43 , R 44 , R 45 and R 46 are halogen atoms or substituted Represents an aryl group that may have a group.
  • 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, or a heteroaryl group.
  • R 43 to R 46 may be different groups, but they are all of the same type. It is preferable that it is a group of In the compounds represented by any of the general formulas (II 3 -7) to (II 3 -9) and (II 4 -7) to (II 4 -9), R 43 to R 46 are all of the same type. Those that are halogen atoms or phenyl groups that may have the same type of substituents are preferable, those that are all fluorine atoms or unsubstituted phenyl groups are more preferable, and those that are all fluorine atoms are particularly preferable. .
  • P 15 to P 16 are each independently a halogen atom
  • C 1-20 represents an alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group.
  • the C 1-20 alkyl group, C 1-20 alkoxy group, monoalkylamino group, or dialkylamino group in P 15 to P 16 include the above R g , (p1) to (p3), and (q1), respectively. The same things listed in ⁇ (q3) can be mentioned.
  • 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 A phenyl group, a thienyl group, or a furanyl group is preferable, and from the viewpoint of safety for living organisms, a C 1-20 alkyl group, a C 1-20 alkoxy group, a phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group , dimethoxyphenyl group, thienyl group, or furanyl group, and these substituents may further have a substituent. However, even if it is a substituent other than these substituents, the safety can be improved by further introducing a suitable substituent, so the present invention is not limited to these substituents.
  • n15 to n16 each independently represent an integer of 0 to 3.
  • the plurality of P 15s may all be the same type of functional group, or may be different types of functional groups. Good too. The same applies to P16 .
  • a 15 to A 16 each independently represent a hydrogen atom, a halogen atom, a C Represents a phenyl group that may have 1 to 3 substituents selected from the group consisting of a 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group. .
  • Examples of the C 1-20 alkyl group, C 1-20 alkoxy group, monoalkylamino group, or dialkylamino group in the substituent that the phenyl group may have include the above-mentioned R g and (p1) to ( p3), (q1) to (q3).
  • a 15 to A 16 are preferably unsubstituted phenyl groups or phenyl groups having one or two C 1-20 alkoxy groups as substituents; A phenyl group having an alkoxy group as a substituent is more preferred, and an unsubstituted phenyl group or a phenyl group having one C 1-10 alkoxy group as a substituent is even more preferred.
  • the compound represented by the general formula (II 3 -7) etc. it is preferable that A 15 to A 16 are all the same type of functional group.
  • Compounds represented by any of the above (II 3 -1) to (II 3 -6) include the following general formulas (6-1) to (6-12), (7-1) to (7-12). ).
  • Ph means an unsubstituted phenyl group.
  • the DPP-based boron complexes used in the present invention include general formulas (6-4), (6-5), (6-7), (6-8), (7-4), (7-5 ), (7-7), (7-8) are preferred, and compounds represented by general formulas (6-4), (6-5), (6-7), (6-8) are preferred. Compounds are more preferred.
  • P 5 to P 8 are each independently a halogen atom, a C 1-20 alkyl group, a C 1-20 represents an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group.
  • the C 1-20 alkyl group, C 1-20 alkoxy group, monoalkylamino group, or dialkylamino group in P 5 to P 8 include the above R g , (p1) to (p3), and (q1), respectively. The same things listed in ⁇ (q3) can be mentioned.
  • P 5 to P 8 are C 1-20 alkyl group, C 1-20 alkoxy group, (unsubstituted) phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-dimethylaminophenyl group, dimethoxy A phenyl group, a thienyl group, or a furanyl group is preferable, and from the viewpoint of safety for living organisms, a C 1-20 alkyl group, a C 1-20 alkoxy group, a phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group , dimethoxyphenyl group, thienyl group, or furanyl group, and even more preferably a C 1-20 alkyl group or a C 1-20 alkoxy group, and a C 1-10 alkyl group or a C 1-10 alkoxy group.
  • a group is even more preferable, and these substituents may further
  • n5 to n8 each independently represent an integer of 0 to 3.
  • the plurality of P5s may all be the same type of functional group or different types of functional groups. Good too. The same applies to P 6 to P 8 .
  • P 5 to P 8 are each independently a C 1-20 alkyl group or Preferably, it is a C 1-20 alkoxy group, and n5 to n8 are independently 0 to 2, P 5 and P 6 are independently a C 1-20 alkyl group, and n5 and n6 are each independently 0 to 2.
  • P 7 and P 8 are each independently a C 1-20 alkoxy group, and n7 and n8 are independently 0 to 1; 6 is independently a C 1-20 alkyl group, n5 and n6 are independently 1-2, P 7 and P 8 are independently a C 1-20 alkoxy group, and n7 and More preferably, n8 is 1.
  • the compounds represented by the general formulas (6-1) to (6-12) include the compounds represented by the following formulas (6-1-1) to (6-12-1). Can be mentioned.
  • ⁇ is the peak wavelength of the absorption spectrum of each compound in solution
  • Em is the peak wavelength of the fluorescence spectrum.
  • the near-infrared fluorescent material (A) according to the present invention may be a commercially available product or a synthetic product.
  • Examples of the synthesis method include, for example, the synthesis method described in Chemistry A European Journal, 2009, Volume 15, pages 4857-4864.
  • the content of the near-infrared fluorescent material (A) is not particularly limited as long as the near-infrared fluorescent material (A) has a concentration that can be mixed with the thermoplastic resin (B).
  • the content of the near-infrared fluorescent material (A) is preferably based on the total of 100% by mass of the near-infrared fluorescent material (A) and the thermoplastic resin (B).
  • the near-infrared fluorescent material used in the present invention has a high molar extinction coefficient and high quantum yield even in the resin, so even if the concentration of the near-infrared fluorescent material in the resin is relatively low, The light emission can be clearly seen with a camera, etc.
  • a low concentration of near-infrared fluorescent material means that it is less likely to be eluted, less likely to bleed out from a molded article processed from a resin composition, and to be used in molded articles that require transparency. It is preferable because it can be processed.
  • thermoplastic resin other than polyamide resin (B) forms a dispersed phase in the masterbatch, resin composition, or molded article together with the near-infrared fluorescent material.
  • the thermoplastic resin (B) used in the present invention is not particularly limited as long as it is a thermoplastic resin other than polyamide resin, and the type of near-infrared fluorescent substance to be blended and the type required when forming the molded article are not particularly limited. In consideration of product quality and the like, it is possible to appropriately select and use known resins.
  • the thermoplastic resin (B) used in the present invention may be used alone or in a mixture of two or more. When mixing two or more types, it is preferable to use a combination of highly compatible resins.
  • the thermoplastic resin (B) may be a commercially available product or a synthetic product.
  • thermoplastic resin (B) used in the present invention examples include thermoplastic polyurethane (TPU); polycarbonate (PC) resin; polyvinyl chloride (PVC), vinyl chloride-vinyl acetate copolymer resin, etc. Vinyl resin; Acrylic resin such as polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate (PMMA), polyethyl methacrylate; polyethylene terephthalate (PET), polybutylene terephthalate, polytrimethylene terephthalate, polyethylene terephthalate, etc.
  • TPU thermoplastic polyurethane
  • PC polycarbonate
  • PVC polyvinyl chloride
  • Vinyl resin vinyl resin
  • Acrylic resin such as polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate (PMMA), polyethyl methacrylate
  • PET polyethylene terephthalate
  • PET polybutylene terephthalate
  • polytrimethylene terephthalate poly
  • Polyester resins such as phthalate and polybutylene naphthalate; polystyrene (PS), imide-modified polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, imide-modified ABS resin, styrene-acrylonitrile copolymer (SAN) resin, acrylonitrile-ethylene-propylene -
  • Polystyrene resins such as diene styrene (AES) resins, olefin resins such as polyethylene (PE) resins, polypropylene (PP) resins, and cycloolefin resins; polyacetal (POM) resins; cellulose resins such as nitrocellulose and cellulose acetate; silicones Resin; Examples include fluororesin.
  • thermoplastic resins (B) because the near-infrared fluorescent material has high dispersibility, thermoplastic resins (B) include thermoplastic polyurethane (TPU) resin, polycarbonate (PC) resin, vinyl chloride resin, It is preferable to include at least one selected from the group consisting of acrylic resin, polyester resin, polystyrene resin, olefin resin, and polyacetal (POM) resin.
  • TPU thermoplastic polyurethane
  • PC polycarbonate
  • POM polyacetal
  • thermoplastic resin As B
  • TPU, PC, PVC, PMMA, PET, PS, PE, and PP are more preferable
  • TPU, PC, PMMA, PS, and PE are even more preferable.
  • the content of the thermoplastic resin (B) is not particularly limited as long as the concentration allows the near-infrared fluorescent material (A) to be mixed with the thermoplastic resin (B).
  • the content of the thermoplastic resin (B) is preferably 100% by mass in total of the near-infrared fluorescent material (A) and the thermoplastic resin (B).
  • the range may be 99% by mass or more, more preferably 99.2% by mass or more, even more preferably 99.5% by mass or more, and preferably 99.9995% by mass or less, more preferably 99.999% by mass.
  • the range may be as follows.
  • the resin (C) used in the present invention is a resin different from the thermoplastic resin (B), and forms a continuous phase in a masterbatch, resin composition, or molded article.
  • the resin (C) is not particularly limited as long as it is different from the thermoplastic resin (B), and may be a thermoplastic resin or a thermosetting resin.
  • Polyamide resins and thermosetting resins that can deactivate the above-mentioned near-infrared fluorescent materials can also be used as the resin (C) that forms the continuous phase, and resin compositions with high near-infrared fluorescent light emission efficiency and their A molded body can be obtained.
  • resin (C) Only one type of resin (C) may be used, or a mixture of two or more types may be used. Further, as the resin (C), a commercially available product or a synthetic product may be used.
  • the resin (C) used in the present invention include urethane resins such as polyurethane (PU) resins and thermoplastic polyurethane (TPU) resins; polycarbonate (PC) resins; polyvinyl chloride (PVC), vinyl chloride- Vinyl chloride resins such as vinyl acetate copolymer resin; 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, and polybutylene naphthalate; polyamide resins such as nylon (registered trademark); polystyrene (PS), imide-modified polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, imide-modified resin ABS resin, styrene
  • Olefin resins cellulose resins such as nitrocellulose and cellulose acetate; silicone resins; thermoplastic resins such as fluororesins, epoxies such as bisphenol A epoxy resins, bisphenol F epoxy resins, isocyanurate epoxy resins, and hydantoin epoxy resins.
  • Resin Amino resin such as melamine resin or urea resin; Phenol resin; Thermosetting resin such as unsaturated polyester resin.
  • the resin (C) is selected from the group consisting of polyamide resin, polyethylene resin, polypropylene resin, and thermosetting resin from the viewpoint of deactivating the near-infrared fluorescent material (A) or improving fluorescence intensity. It is preferable to include at least one kind of. Furthermore, from the viewpoint of heat resistance and chemical resistance, it is more preferable that the resin (C) contains a polyamide resin. Further, from the viewpoint of insulation properties and voltage resistance, it is more preferable that the resin (C) contains a thermosetting resin.
  • the content of the resin (C) in the masterbatch according to the present invention is the concentration at which the particles (powder) containing the near-infrared fluorescent material (A) and the thermoplastic resin (B) can be mixed with the resin (C). If so, there are no particular restrictions. However, the resin (C) efficiently forms a continuous phase, and the resin composition and its molded product produced through the masterbatch can obtain excellent luminous efficiency.
  • the content is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total of 100% by mass of the near-infrared fluorescent material (A), thermoplastic resin (B), and resin (C). and preferably in a range of 80% by mass or less, more preferably 70% by mass or less.
  • the total content of the near-infrared fluorescent material (A) and the thermoplastic resin (B) in the masterbatch according to the present invention is the sum of the near-infrared fluorescent material (A), the thermoplastic resin (B), and the resin (
  • the range may be preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, based on the total 100% by mass of C). It can be a range.
  • the method for producing a masterbatch according to the present invention includes a step of melt-kneading a near-infrared fluorescent material (A) and a thermoplastic resin other than a polyamide resin (B) to obtain a kneaded product; , a step of powdering to obtain particles containing powdered near-infrared fluorescent material (A) and thermoplastic resin (B), and a step of mixing or kneading the particles obtained in the above step with resin (C).
  • At least the near-infrared fluorescent material (A) and the thermoplastic resin (B) are blended as essential ingredients so as to have the above-mentioned content, and are uniformly mixed in a tumbler or Henschel mixer (registered trademark), and then It is put into a melt-kneading extruder such as a twin-screw kneading extruder, and melt-kneaded in a temperature range from the melting temperature of the thermoplastic resin (B) to the temperature plus 100°C, for example, from 180°C to 300°C.
  • a kneaded product of the near-infrared fluorescent material and the thermoplastic resin (B) which will become a dispersed phase, is obtained.
  • the melting temperature of a thermoplastic resin refers to the melting point for crystalline resins and the softening point (glass transition point) for amorphous resins (the same applies hereinafter).
  • the kneaded material is powdered. For example, after extruding the kneaded material into strands, it is left at room temperature or cooled by immersing it in water in a temperature range of 5°C to 60°C, and then cut into particles such as pellets and chips. can do. Thereafter, if necessary, the obtained particles are freeze-pulverized to obtain particles (powder) containing powdered near-infrared fluorescent material (A) and thermoplastic resin (B) having a desired size. I can do it.
  • the average particle diameter of the particles (powder) after pulverization is not particularly limited, but is preferably in the range of 5 ⁇ m or more, more preferably in the range of 10 ⁇ m or more, still more preferably in the range of 15 ⁇ m or more, and , preferably in the range of 500 ⁇ m or less, more preferably in the range of 200 ⁇ m or less, still more preferably in the range of 100 ⁇ m or less.
  • the particles (powder) containing at least the near-infrared fluorescent material (A) and thermoplastic resin (B) obtained in this way are blended with the resin (C) to the above content, and Alternatively, a resin mixture can be obtained by uniformly mixing with a Henschel mixer (registered trademark) or the like.
  • the resin (C) is a thermoplastic resin
  • the obtained resin mixture is put into a melt-kneading extruder such as a twin-screw kneading extruder, and the thermoplastic resin (B )
  • the masterbatch of the present invention can be obtained by melt-kneading at a temperature below the melting temperature of (1). Furthermore, after extruding the masterbatch into strands, it is left at room temperature or cooled by immersing it in water at a temperature range of 5°C to 60°C, and then cut into particles such as pellets and chips. It can be done.
  • the resin (C) When a thermosetting resin is used as the resin (C), the resin (C) is still in the intermediate state of a prepolymer or an initial polycondensate, so a curing agent may be added to the resin mixture as necessary. By adding and further molding (shaping) and performing a heating step, the resin (C) forms a three-dimensional structure, and the resin composition of the present invention can be obtained as a molded article.
  • the temperature in the heating step is preferably from room temperature to less than the melting temperature of the thermoplastic resin (B).
  • the resin composition of the present invention has a step of adding resin (D) as a diluting resin to the masterbatch and mixing or kneading the mixture.
  • the resin (D) is used as a diluent resin in the masterbatch, and the diluted resin (D) is a resin different from the thermoplastic resin (B), and together with the resin (C), the resin composition is Or form a continuous phase in a molded body.
  • the diluent resin (D) the same resins as the resin (C) can be mentioned.
  • different types of resins can be used as the resin (C) and the diluent resin (D), it is preferable to use the same type of resin.
  • an epoxy resin when used as the resin (D), it may be in the form of an epoxy resin composition containing a curing agent.
  • the resin (D) may be a resin having a crosslinked structure.
  • a crosslinking agent for creating a crosslinked structure may be added to an olefin resin such as polyethylene resin or polybutylene resin, and the resulting product may be molded into a molded body.
  • resins having a crosslinked structure include crosslinked olefin resins such as crosslinked polyethylene resin and crosslinked polybutylene resin, and silane-modified products thereof.
  • thermoplastic resin (B), resin (C), and resin (D) include the following forms; -
  • the thermoplastic resin (B) is a polycarbonate resin, and the resin (D), more preferably the resin (C) and the resin (D) are polyamide resins -
  • the thermoplastic resin (B) is a polycarbonate resin,
  • the resin (D) is more preferably a resin (C) and the resin (D) is a crosslinked polyethylene resin.
  • the thermoplastic resin (B) is a polycarbonate resin, and the resin (D) is more preferably a resin (C).
  • thermoplastic resin (B) is a polycarbonate resin
  • the resin (D), more preferably the resin (C) and the resin (D) are thermoplastic polyurethane A form in which the thermoplastic resin (B) is a polymethyl methacrylate resin, and a form in which the resin (D), more preferably resin (C) and resin (D) are crosslinked polyethylene resins - A form in which the thermoplastic resin (B) is a crosslinked polyethylene resin ) is a polypropylene resin, and the resin (D) is, more preferably, the resin (C) and the resin (D) are polyethylene resins.
  • the content of the resin (D) in the resin composition according to the present invention is not particularly limited as long as the masterbatch has a concentration that can be mixed with the resin (D).
  • the content of the resin (D) is Preferably 20% by mass or more, more preferably 30% by mass or more, based on the total of 100% by mass of near-infrared fluorescent material (A), thermoplastic resin (B), resin (C), and resin (D). and preferably in a range of 80% by mass or less, more preferably 70% by mass or less.
  • the total content of the near-infrared fluorescent material (A), the thermoplastic resin (B), and the resin (C) in the resin composition according to the present invention is as follows:
  • the amount may be preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 80% by mass, based on the total of 100% by mass of (B), resin (C), and resin (D).
  • the content may be more preferably 70% by mass or less.
  • the resin (D) is a thermoplastic resin
  • the resin (D) is blended with the above masterbatch, mixed uniformly with a tumbler or Henschel mixer (registered trademark), and then mixed with the resin.
  • a mixture can be obtained.
  • the obtained resin mixture is put into a melt-kneading extruder such as a twin-screw kneading extruder, and the melting temperature is higher than the melting temperature of the resin (C) and the resin (D) and lower than the melting temperature of the thermoplastic resin (B).
  • the resin composition of the present invention can be obtained by melt-kneading the resin composition within the range.
  • the resin composition of the present invention can be extruded into strands, left at room temperature, or cooled by immersing in water at a temperature range of 5°C or more and 60°C or less, and then cut into pellets or chips. It can be made into a particulate form such as.
  • a resin composition capable of forming a crosslinked structure such as a crosslinked polyolefin resin
  • a chemical crosslinking method using a crosslinking agent organic peroxide
  • irradiation with electron beams or X-rays is used.
  • a resin composition is obtained as a molded article according to a conventional method by employing a conventionally known crosslinking method such as an active energy ray crosslinking method or a water crosslinking method that utilizes a dehydration condensation reaction of an alkoxysilane after silane modification of a polyolefin resin, etc. be able to.
  • the obtained resin mixture is heated under conditions such that the temperature ranges from the melting temperature of resin (C) and resin (D) to the melting temperature of resin (B), and if a crosslinking agent is added, the crosslinking agent
  • a known kneading device such as a two-roll, kneader, Banbury mixer, or extruder, with the addition of conditions that result in a temperature range below the thermal decomposition temperature of crosslinking process (for example, in the chemical crosslinking method, heating above the thermal decomposition temperature of the crosslinking agent, in the active energy ray crosslinking method, irradiation with active energy rays, and in the water crosslinking
  • resin (D) is a thermosetting resin (in a preferred form
  • resin (C) and resin (D) are thermosetting resins
  • resin (D) is added to the obtained masterbatch.
  • the resin mixture is then stirred and mixed to produce a resin mixture.
  • the resin mixture since the resin (D) (in a preferred form, the resin (C) and the resin (D)) is still in the intermediate state of a prepolymer or an initial polycondensate, the resin mixture may be added as necessary.
  • the resin (D) in a preferred form, the resin (C) and the resin (D) formed a three-dimensional structure.
  • resin (D) and a curing agent are added to the obtained masterbatch, stirred and mixed, and further molded (shaped), followed by a heating process to convert resin (D) (in a preferred form, resin ( C) and resin (D)) can be obtained as a molded article in which a three-dimensional structure is formed.
  • the temperature in the heating step is preferably from room temperature to less than the melting temperature of the thermoplastic resin (B).
  • the content of the near-infrared fluorescent material (A) in the resin composition according to the present invention is not particularly limited, the content of the near-infrared fluorescent material (A), the thermoplastic resin (B), the resin (C), and the resin ( The amount may be preferably 0.000025% by mass or more, more preferably 0.00005% by mass or more, even more preferably 0.0001% by mass or more, and preferably The content may be in the range of 0.6% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.48% by mass or less.
  • the diameter (dispersion diameter) of the dispersed phase formed by the near-infrared fluorescent material (A) and the thermoplastic resin (B) may preferably be in the range of 1 nm or more, and preferably It may be in the range of 300 ⁇ m or less, more preferably 200 ⁇ m or less. By setting it as such a range, the luminous efficiency of the resin composition and molded object manufactured via the masterbatch based on this invention will improve more.
  • the diameter of the dispersed phase depends on the resin (D), such as the freeze-pulverization conditions of the particles containing the near-infrared fluorescent material (A) and the thermoplastic resin (B), the melt-kneading conditions when mixing the resin (C), etc. It can be controlled by the mixing or kneading conditions when mixing. Further, the diameter of the dispersed phase can be measured by the method described in Examples.
  • the resin such as the freeze-pulverization conditions of the particles containing the near-infrared fluorescent material (A) and the thermoplastic resin (B), the melt-kneading conditions when mixing the resin (C), etc. It can be controlled by the mixing or kneading conditions when mixing. Further, the diameter of the dispersed phase can be measured by the method described in Examples.
  • the resin composition according to the present invention When a molded body is irradiated with excitation light and its luminescence is detected, when using a general luminescence detector equipped with a filter to cut noise caused by the excitation light, the resin composition according to the present invention may be used. If the Stokes shift is small, the emitted light will be cut by the filter, making it difficult to detect with high sensitivity. Therefore, the resin composition according to the present invention preferably has a Stokes shift (difference between maximum absorption wavelength and maximum emission wavelength) of 10 nm or more, and more preferably has a Stokes shift of 20 nm or more. The larger the Stokes shift, the more sensitive it is to detect the light emitted from the molded object, even when using a general detector equipped with a filter to cut noise caused by excitation light. be.
  • a Stokes shift difference between maximum absorption wavelength and maximum emission wavelength
  • near-infrared fluorescence from the resin composition according to the present invention can be detected with high sensitivity under the following conditions. For example, if it is possible to excite with light with a wavelength shorter than the maximum absorption wavelength, it is possible to detect fluorescence even if noise is cut. Further, when the fluorescence spectrum is broad, it is possible to sufficiently detect fluorescence even if noise is cut. On the other hand, some fluorescent materials have multiple fluorescence peaks. In that case, even if the Stokes shift is small, if there is a fluorescence peak (second peak) on the longer wavelength side, it can be detected with high sensitivity even if a detector equipped with a noise-cutting filter is used. is possible.
  • the fluorescence peak wavelength on the longer wavelength side should have a difference from the maximum absorption wavelength of 30 nm or more, preferably 50 nm or more. Note that the conditions are not limited to those described above as long as the excitation light source, cut filter, etc. are appropriately selected.
  • the resin composition according to the present invention containing the near-infrared fluorescent material (A) does not change color under visual observation even when excited with excitation light in the near-infrared region, and has invisible fluorescence in the near-infrared region. emits and can be detected by a detector. Therefore, for excitation light in the near-infrared region, it is sufficient that the maximum absorption wavelength is 600 nm or more, but from the viewpoint of absorption efficiency, it is preferable that the maximum absorption wavelength is close to the wavelength of the excitation light, and 650 nm or more is more preferable.
  • the wavelength is preferably 665 nm or more, more preferably 680 nm or more, and particularly preferably 680 nm or more. Furthermore, when used as a medical device such as an implant, the wavelength is preferably 700 nm or more.
  • the masterbatch, resin composition, and molded article obtained from the composition according to the present invention containing the near-infrared fluorescent material (A) do not change the color of the irradiated object, and when considering the detection sensitivity, Although there is no practical problem if the fluorescence wavelength is 650 nm or more, it is preferably 700 nm or more, and more preferably 720 nm or more. 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 longer wavelength side is preferably 5% or more, more preferably 10% or more, of the intensity of the maximum fluorescence wavelength.
  • the resin composition according to the present invention and the molded article obtained from the composition preferably have strong absorption in the range of 650 nm or more and 1500 nm or less, and emit strong fluorescence in this range.
  • Light of 650 nm or more is less affected by hemoglobin, and light of 1500 nm or less is less affected by water.
  • light in the range of 650 nm or more and 1500 nm or less has high skin permeability and is less affected by contaminants in the body, so it is the light that is used to visualize medical implants implanted under the skin. This is suitable as a wavelength range.
  • the resin composition according to the present invention and the molded article obtained from the composition are suitable for detection with light in the range of 650 nm or more and 1500 nm or less. Therefore, it is suitable as a medical device used in vivo.
  • the masterbatch or resin composition according to the present invention may contain other components other than the resin component and the near-infrared fluorescent material (A) as long as the effects of the present invention are not impaired.
  • Other components include ultraviolet absorbers, heat stabilizers, light stabilizers, antioxidants, flame retardants, flame retardant aids, crystallization promoters, plasticizers, antistatic agents, colorants, mold release agents, etc. can be mentioned.
  • a molded body capable of detecting luminescence can be obtained. That is, according to another embodiment of the present invention, a molded article obtained from the resin composition according to the present invention is provided.
  • the molding method is not particularly limited, and examples thereof include casting (pouring method), injection molding using a mold, compression molding, extrusion molding using a T-die, etc., blow molding, and the like.
  • a molded article it may be formed only from the resin composition according to the present invention, or the resin composition according to the present invention and other resin compositions may be used as raw materials.
  • the entire molded body may be molded using the resin composition according to the present invention, or only a portion of the molded body may be molded using 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 a molded article.
  • the distal end portion of the catheter is molded using the resin composition according to the present invention, and the remaining portion is molded using a resin composition that does not contain a near-infrared fluorescent material.
  • a catheter whose only part emits near-infrared fluorescence. Further, by alternately laminating and molding the resin composition according to the present invention and a resin composition not containing a near-infrared fluorescent material, a molded article that emits near-infrared fluorescence in a striped form can be manufactured. In addition, a surface coating may be applied to improve the visibility of the molded product.
  • Luminescence detection can be carried out by a conventional method using a commercially available fluorescence or phosphorescence detection device.
  • any light source can be used, and in addition to a near-infrared lamp with a long wavelength width, a laser, an LED, etc. with a narrow wavelength width can be used.
  • the molded article obtained from the resin composition according to the present invention containing the near-infrared fluorescent material (A) does not change color even when irradiated with light in the near-infrared region, and can be detected with higher sensitivity than before. Emit near-infrared fluorescence. Therefore, the molded article is particularly suitable for a medical device, at least a portion of which is inserted or left in a patient's body.
  • the near-infrared fluorescent material (A) When performing fluorescence detection on a molded article obtained from the resin composition of the present invention containing the near-infrared fluorescent material (A), it is preferable to irradiate the object with excitation light in the near-infrared region. If it is acceptable for the color to be slightly reddish, it is not necessarily necessary to use excitation light in the near-infrared region. For example, when trying to detect the fluorescence of medical devices inside the body by irradiating excitation light, it is necessary to use the excitation light in a wavelength range that is highly transparent to living organisms such as the skin. Excitation light of 650 nm or more with high transparency may be used.
  • Examples of such medical devices include stents, coil embolizers, catheter tubes, injection needles, indwelling needles, ports, shunt tubes, drain tubes, implants, and the like.
  • the detection method of the present invention includes a step of irradiating near-infrared light toward the molded object, and a step of detecting near-infrared light emitted by the molded object using a device that detects near-infrared light emission.
  • the detection device of the present invention includes means for irradiating near-infrared light toward the molded body, and means for detecting near-infrared light emitted by the molded body.
  • any light source can be used as long as it is capable of emitting excitation light used for luminescence detection.
  • a near-infrared lamp with a long wavelength width Narrow lasers, LEDs, etc. can be used.
  • the wavelength of the irradiating light source may be any wavelength that can excite the near-infrared fluorescent dye contained in the molded article, and there is no particular problem with the wavelength generally being called near-infrared light, but for example, 650 nm. or more is preferable, 700 nm or more is more preferable, 2500 nm or less is preferable, and 1100 nm or less is more preferable.
  • Irradiation of near-infrared light onto the molded product is not particularly limited as long as it is a conventional method, but for example, one or more light sources may be applied from above or below the molded product in the vertical direction, or irradiation may be performed from an oblique direction. Alternatively, the molded article may be irradiated from different directions.
  • a light source and a near-infrared emission detection device described below are arranged at substantially the same position with respect to the molded body, it is preferable to use a ring illumination or a line illumination as the light source.
  • the means for detecting near-infrared emission may be any commonly available near-infrared emission detection device, and is not particularly limited.
  • CCD Charge Coupled Device
  • CMOS Complementary MOS
  • imaging devices such as digital cameras, and detection devices such as spectrometers, photomultiplier tubes, PbS detectors, and photodiodes can be used.
  • the imaging device may be an area camera or a line camera.
  • a detector other than an imaging device such as a photodiode is used as a means for detecting near-infrared emission, the electric signal from the detector is transferred to a circuit board equipped with a signal amplification unit such as a head amplifier. The presence or absence of light emission can be detected based on the output value of the amplified electrical signal.
  • the analysis means may be generally commercially available and is not particularly limited, but may include, for example, a personal computer with image analysis software installed, or hardware capable of implementing an image processing algorithm (e.g. A microcomputer, a PLC (programmable controller), an FPGA (field-programmable gate array), etc.) can be used.
  • a personal computer with image analysis software installed, or hardware capable of implementing an image processing algorithm (e.g. A microcomputer, a PLC (programmable controller), an FPGA (field-programmable gate array), etc.) can be used.
  • the position confirmation system of the present invention includes, in addition to the detection device of the present invention, a monitor that displays a captured image. If the molded article of the present invention is a medical device, it can be used as a medical device position confirmation system, and the position of a medical device inserted or left in the body during surgery or the like can be visually confirmed.
  • tert-butyloxypotassium 25.18 g, 224.4 mmol
  • tert-amyl alcohol 160 mL
  • the compound (1- A solution of 1) (14.8 g, 64 mmol) mixed with tert-amyl alcohol (7 mL) was added, and the mixture was heated to reflux.
  • a solution of succinic acid diisopropyl ester (6.5 g, 32 mmol) in tert-amyl alcohol (10 mL) was added dropwise over about 3 hours, and after the dropwise addition was completed, 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.
  • Bromine (4.5 mL, 87 mmol) was added dropwise over about 20 minutes while keeping the inside of the system at 15°C or lower, and then stirred at 15°C or lower for 3.5 hours.
  • the reaction solution was poured into 28% aqueous ammonia (150 mL), stirred for a while, and the precipitated solid was filtered off, the solid was extracted with diethyl ether, and the organic layer was washed with water.
  • acetic acid (872 mg, 14.5 mmol) and acetonitrile (30 mL) were placed in a 100 mL three-necked flask, and the system was placed under an argon atmosphere. Under an argon atmosphere, malononitrile (2.4 g, 36.3 mmol) and compound (1-4) (2.39 g, 13.2 mmol) were added, and the mixture was heated under 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.
  • the organic layer was treated with anhydrous magnesium sulfate, the magnesium sulfate was filtered off, the solvent was removed under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: hexane/ethyl acetate) to roughly remove impurities.
  • the residue obtained by evaporating the solvent was purified again by silica gel column chromatography (eluent: hexane/dichloromethane) to obtain a green solid of precursor (1-6) (yield: 1.56 g, yield :46%).
  • Dye 2 was performed as follows with reference to Organic Letters, 2012, Volume 4, pages 2670-2673 and Chemestry A European Journal, 2009, Volume 15, pages 4857-4864.
  • compound (2-2) (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 heated at 60°C. It reacted for 2 hours. After cooling the reaction solution, it was extracted with water (200 mL)/ethyl acetate (300 mL), and the obtained ethyl acetate layer was further washed with water.
  • dichloromethane 40 mL
  • saturated aqueous sodium hydrogen carbonate solution 40 mL
  • the organic layer was treated with anhydrous magnesium sulfate, and after filtering off the magnesium sulfate, the solvent was removed under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: hexane/ethyl acetate) to roughly remove impurities.
  • thermoplastic resins (B) were used.
  • the values in Table 1 are based on parts by mass: ⁇ B1: Polycarbonate resin (manufactured by Sumika Polycarbonate Co., Ltd., "SD Polycarbonate (trademark) 301-4")
  • B4 Polypropylene resin (Prime Polypro (registered trademark) J106G, manufactured by Prime Polymer Co., Ltd.)
  • the pellets (1) to (8) obtained above were ground using a frozen grinder JFC-2000 manufactured by Japan Analysis Industry Co., Ltd. That is, the pellets and tungsten steel balls were placed in a stainless steel container, the container was covered with a lid, and the container was freeze-pulverized under the following conditions: pre-cooling with liquid nitrogen for 10 minutes, crushing time for 15 minutes, and reciprocating at 1200 times/min to obtain powder. Ta. Next, the powder was dispersed in ethanol, and the resulting dispersion was filtered under pressure using a filter with a fixed capture particle size (300 ⁇ m) to obtain powders (1) to (1) having the average particle size listed in Table 1. 8) was obtained.
  • a frozen grinder JFC-2000 manufactured by Japan Analysis Industry Co., Ltd. That is, the pellets and tungsten steel balls were placed in a stainless steel container, the container was covered with a lid, and the container was freeze-pulverized under the following conditions: pre-cooling with liquid nitrogen for 10 minutes, crushing time for 15 minutes, and reciprocating at 1
  • pellets (1) were freeze-pulverized using a similar cryo-pulverizer under the conditions of 5 minutes of preliminary cooling with liquid nitrogen, 8 minutes of crushing time, and 1200 reciprocations/min to obtain a powder.
  • the powder was dispersed in ethanol, and the resulting dispersion was filtered under pressure using a filter with a fixed capture particle size (500 ⁇ m) to obtain powder (9) having the average particle size listed in Table 1. Obtained.
  • the maximum particle size of powder (9) measured by the method described below (Measurement of average particle size of pulverized product) was 324 ⁇ m.
  • Luminescence evaluation of the obtained powders (1) to (9) was performed by the following method.
  • composition and evaluation results of powders (1) to (9) are shown in Table 1 below. Note that a blank column in Table 1 indicates that the material was not used.
  • Example 1 Island of Production Example 1 (dye-containing PC) and polyamide sea MB and sheet)
  • a 30 mm ⁇ biaxial vent was used.
  • the mixture was melt-kneaded in a type extruder (temperature set at 220°C), and then pelletized to produce a masterbatch (1).
  • Example 2 Island of Production Example 1 (dye-containing PC) and MB and sheet of cross-linked polyethylene sea) 60 parts by mass of the powder (1) obtained in Production Example 1 and 40 parts by mass of polyethylene resin (Novatec (trademark) LL UJ580, linear low-density polyethylene, manufactured by Japan Polyethylene Co., Ltd.) were stirred in a tumbler. After mixing, the mixture was melt-kneaded in a 30 mm ⁇ twin-screw vent extruder (temperature set at 140° C.) and pelletized to produce a masterbatch (2).
  • polyethylene resin Novatec (trademark) LL UJ580, linear low-density polyethylene, manufactured by Japan Polyethylene Co., Ltd.
  • Masterbatch (2) 33.4 parts by mass, polyethylene resin (Novatec (trademark) LL UJ580, manufactured by Japan Polyethylene Co., Ltd., linear low density polyethylene) 64.6 parts by mass, crosslinking agent (manufactured by NOF Corporation, Perhexa (registered trademark) 25B-40, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane) in a tumbler, then roll the blend into two rolls at 125°C. The mixture was kneaded and heated at 200° C. for 2 minutes at 10 MPa to produce a sheet sample (2) with a length of 127 mm, a width of 12.7 mm, and a thickness of 1 mm.
  • polyethylene resin Novatec (trademark) LL UJ580, manufactured by Japan Polyethylene Co., Ltd., linear low density polyethylene
  • crosslinking agent manufactured by NOF Corporation, Perhexa (registered trademark) 25B-40, 2,5-dimethyl-2,5-d
  • Example 3 (Islands of Production Example 2 (dye-containing PMMA) and a sea of crosslinked polyethylene) 60 parts by mass of the powder (2) obtained in Production Example 2 and 40 parts by mass of polyethylene resin (Novatec (trademark) LL UJ580, linear low-density polyethylene, manufactured by Japan Polyethylene Co., Ltd.) were stirred in a tumbler. After mixing, the mixture was melt-kneaded in a 30 mm ⁇ twin-screw vent extruder (temperature set at 140° C.) and pelletized to produce a masterbatch (3).
  • polyethylene resin Novatec (trademark) LL UJ580, linear low-density polyethylene, manufactured by Japan Polyethylene Co., Ltd.
  • Example 4 Island of Production Example 3 (dye-containing PS) and MB and sheet of cross-linked polyethylene sea) 60 parts by mass of the powder (3) obtained in Production Example 3 and 40 parts by mass of polyethylene resin (Novatec (trademark) LL UJ580, linear low density polyethylene, manufactured by Japan Polyethylene Co., Ltd.) were stirred in a tumbler. After mixing, the mixture was melt-kneaded in a 30 mm ⁇ twin-screw vent extruder (temperature set at 140° C.) and pelletized to produce a masterbatch (4).
  • polyethylene resin Novatec (trademark) LL UJ580, linear low density polyethylene, manufactured by Japan Polyethylene Co., Ltd.
  • Example 5 Island of Production Example 1 (dye-containing PC) and sea of epoxy resin
  • an epoxy resin composition manufactured by DIC Corporation, Epicron (registered trademark) 850
  • decompression was carried out under reduced pressure.
  • a masterbatch (5) was obtained by foaming.
  • Example 6 Island of Production Example 4 (dye-containing PP) and MB and sheet of polyethylene resin sea) 60 parts by mass of the powder (4) obtained in Production Example 4, 40 parts by mass of polyethylene resin (manufactured by Japan Polyethylene Co., Ltd., Novatec (trademark) LL UJ580, linear low density polyethylene) as the resin (C), The mixture was stirred and mixed in a tumbler, then melted and kneaded in a 30 mm ⁇ twin-screw vent extruder (temperature set at 140°C), and then pelletized to produce a masterbatch (6).
  • polyethylene resin manufactured by Japan Polyethylene Co., Ltd., Novatec (trademark) LL UJ580, linear low density polyethylene
  • Example 7 Island of Production Example 1 (dye-containing PC) and MB and sheet of TPU resin sea) After stirring and mixing 60 parts by mass of the powder (1) obtained in Production Example 1 and 40 parts by mass of a thermoplastic polyurethane resin (manufactured by Lubrizol, Tecoflex EG65D) as the resin (C) in a tumbler, The mixture was melt-kneaded in a vented shaft extruder (temperature set at 190°C), and then pelletized to produce a masterbatch (7).
  • a thermoplastic polyurethane resin manufactured by Lubrizol, Tecoflex EG65D
  • thermoplastic polyurethane resin (Tecoflex EG65D, manufactured by Lubrizol) in a tumbler
  • the blend was transferred to an extruder equipped with a T-die (temperature set at 200°C).
  • a sheet sample (7) having a length of 127 mm, a width of 12.7 mm and a thickness of 1 mm was prepared by melt molding.
  • Example 8 Island of Production Example 5 (dye-containing PC) and polyamide sea MB and sheet)
  • a 30 mm ⁇ biaxial vent was used.
  • the mixture was melt-kneaded in a type extruder (temperature set at 200°C) and then pelletized to produce a masterbatch (8).
  • Example 9 Island of Production Example 6 (dye-containing PC) and polyamide sea MB and sheet)
  • a 30 mm ⁇ biaxial vent was used.
  • the mixture was melt-kneaded in a type extruder (temperature set at 200°C), and then pelletized to produce a masterbatch (9).
  • Example 10 Island of Production Example 7 (dye-containing PC) and polyamide sea MB and sheet) After stirring and mixing 60 parts by mass of the powder (7) obtained in Production Example 7 and 40 parts by mass of polyamide resin (manufactured by Arkema, PEBAX (registered trademark) 4033SA01) in a tumbler, The mixture was melt-kneaded in a vented extruder (temperature set at 200°C) and then pelletized to produce a masterbatch (10).
  • polyamide resin manufactured by Arkema, PEBAX (registered trademark) 4033SA01
  • Example 11 Island of Production Example 8 (dye-containing PC) and polyamide sea MB and sheet)
  • polyamide resin manufactured by Arkema, PEBAX (registered trademark) 4033SA01
  • Example 12 Island of Production Example 9 (Dye-containing PC coarse material), MB and sheet of polyamide sea) After stirring and mixing 60 parts by mass of the powder (9) obtained in Production Example 9 and 40 parts by mass of polyamide resin (manufactured by Arkema, PEBAX (registered trademark) 4033SA01) in a tumbler, a 30 mm ⁇ twin-screw vent was used. The mixture was melt-kneaded in a type extruder (temperature set at 200°C) and then pelletized to produce a masterbatch (12).
  • polyamide resin manufactured by Arkema, PEBAX (registered trademark) 4033SA01
  • sheet samples (1) to (12) were cut vertically from the surface, the exposed cut surfaces were polished to make them smooth, and then observed with a digital microscope (manufactured by Keyence Corporation: VHX-7000). The image was taken. Next, at a magnification (200 times), 50 non-overlapping arbitrary dispersed phases (island portions of a sea-island structure) were selected and measured as circular equivalent diameters to determine their particle size distribution. The average diameter was calculated as the number average.
  • the luminous efficiency of the obtained sheet samples (1) to (12) was evaluated by the following method: Camera: Sentech Co., Ltd., STC-MBCM200U3V-NIR Light source unit: Manufactured by Revox Co., Ltd., a 720-850 nm lamp is installed on an SPL-CC board in a dark room. The distance between the light source and the sheet sample is 20 cm, and the sheet sample is placed horizontally at a distance of 30 cm from the vertical camera. The sample was set up and imaged with a camera (see Figure 1). The obtained image was processed into 256 steps from 0 to 255 steps using image processing software "Image" and evaluated. The case where no light was emitted was defined as 0 stage, and the highest number of stages in the image was defined as the luminous efficiency of the sheet. The higher the number of stages, the higher the luminous efficiency.

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PCT/JP2023/010218 2022-03-22 2023-03-16 マスターバッチ、それを用いた樹脂組成物および成形体の製造方法 Ceased WO2023182121A1 (ja)

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JP2006028227A (ja) * 2004-07-12 2006-02-02 Dainichiseika Color & Chem Mfg Co Ltd 着色剤組成物の製造方法
JP2006516999A (ja) * 2003-01-21 2006-07-13 バイオアレイ ソリューションズ リミテッド ポリマ微粒子の溶質充填量の制御方法
WO2007126052A1 (ja) 2006-04-28 2007-11-08 Keio University 蛍光性化合物及びそれから成る標識剤
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