JP6255529B2 - Resin composition, method for producing the same, and molded article - Google Patents

Description

  The present invention relates to a resin composition that emits near-infrared fluorescence, and a molded body obtained by processing the resin composition.

  Near-infrared fluorescent dyes are used in industrial products centering on identification of various products and prevention of counterfeiting, and in recent years, they are also used in medical applications such as bioimaging probes and test drugs. As features of the near-infrared wavelength region, it is known that it cannot be seen with the human naked eye, has little influence on the living body, and has high permeability to living bodies such as skin. Such characteristics can be utilized by including a near-infrared fluorescent dye in the medical device itself. For example, a system for confirming the position of a medical device embedded in a living body by irradiating near-infrared light from outside the living body by including a near-infrared fluorescent dye in a medical device such as a shunt tube is disclosed. (For example, refer to Patent Document 1).

  In order to visualize medical implants implanted under the skin, etc., excitation with near-infrared light having high skin permeability is required, and fluorescence emitted from the medical implants also has high skin permeability. Must be in the infrared region. That is, normally, in order to ensure visibility, the near-infrared fluorescent dye itself contained in the medical implant must absorb light strongly in the near-infrared region, and additionally emits strong fluorescence. There is a need. For this reason, as a near-infrared fluorescent pigment | dye contained in the resin composition used as the raw material of a medical implant, it is preferable that the maximum absorption wavelength exists in a near-infrared area | region in resin.

  Near-infrared fluorescent dyes include inorganic fluorescent dyes and organic fluorescent dyes. In general, inorganic near-infrared fluorescent dyes have an advantage that the emission wavelength can be easily adjusted within a desired range by using various metals, but rare earths such as rare and expensive rare earths and particle sizes are uniform. Nanoparticles are needed. On the other hand, organic near-infrared fluorescent dyes can be synthesized relatively easily and are easy to adjust the wavelength, but few are known that can be stably mixed into the resin. .

  If the near-infrared fluorescent dye can be mixed and dispersed in the resin, various molded products that emit near-infrared fluorescence can be produced using the resin as a raw material. As a resin in which a near-infrared fluorescent dye is dispersed, for example, Patent Document 2 discloses a reactive group-containing near-infrared fluorescent dye obtained by introducing a polyester reactive group into a phthalocyanine dye, a naphthalocyanine dye, or a squalene dye. A near-infrared fluorescent resin copolymerized in (polyethylene terephthalate) is disclosed.

On the other hand, a boron complex of a π-conjugated compound is known as an organic fluorescent dye having a high emission quantum yield. For example, a boron dipyrromethene skeleton in which a disubstituted boron atom and dipyrromethene (or a derivative thereof) form a complex. BODIPY dyes having the above are known (for example, see Non-Patent Document 1). As BODIPY dyes that emit near-infrared fluorescence, Patent Document 3 discloses a BODIPY dye having a hetero ring in the BODIPY skeleton.
Furthermore, Non-Patent Document 2 discloses a near-infrared fluorescent dye of a DPP-based boron complex having two boron complex units in the molecule, obtained by complexing a diketopyrrolopyrrole (DPP) derivative with a boron complex. . These BODIPY dyes and DPP-based boron complexes are mainly used as biomarkers for labeling biomolecules such as nucleic acids and proteins and tumor tissues, and contain BODIPY dyes and DPP-based boron complexes. There is almost no report about the resin. As a resin composition containing BODIPY dyes, visible light can be obtained by copolymerizing a siloxane-containing BODIPY dye having an organosiloxanyl group introduced through an alkylene group in Patent Document 4 into a silicone resin. It is disclosed that a resin emitting region fluorescence is obtained. Patent Document 5 discloses a composition that emits fluorescence in the visible light region mixed with a polymer together with a solvent in order to enhance the compatibility of the visible light emitting BODIPY dye. In addition, Patent Document 6 discloses an optical filter containing BODIPY dyes having at least one electron-withdrawing group and a resin, and having high light absorption in the visible light region. Discloses a color conversion material that contains BODIPY pigments and a resin and converts short-wavelength light into long-wavelength light.
In addition, Patent Document 8 mentions a DPP-based boron complex as a compound that has absorption in the infrared region and does not have absorption in the visible light region. An infrared absorbing composition comprising a hydrophobic polymer is disclosed.

JP 2012-115535 A JP 2003-176289 A Japanese Patent No. 5177427 JP 2013-060399 A US Patent Application Publication No. 2013/0249137 US Patent Application Publication No. 2013/0252000 JP 2011-241160 A Japanese Patent No. 5380019 JP 2010-090313 A

Tomomimori, 6 others, Tetrahedron, 2011, Vol. 67, pages 3187-3193. Fischer, 3 others, Angewante Chemie International Edition, 2007, 46, 3750-3753.

Patent Document 3 discloses BODIPY dyes that emit near-infrared fluorescence, but does not describe whether these can be contained in a resin.
On the other hand, since phthalocyanine dyes and the like have low emission quantum yields of the dye skeletons themselves, the reactive group-containing near-infrared fluorescent dyes described in Patent Document 2 composed of these dyes have sufficient emission intensity. There is a problem that can not be.
In addition, the siloxane-containing BODIPY dye described in Patent Document 4 has good compatibility with the silicone monomer solution before curing, and a silicone resin in which the dye is uniformly dispersed can be obtained by curing, but other resins and resins There is a problem that the compatibility with the solution is low. Further, the resin composition described in Patent Document 5 has a problem in safety because the solvent may remain in the resin. In addition, Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7 do not describe a BODIPY dye that emits near-infrared fluorescence in the first place, and do not describe application to medical use. Similarly, Patent Document 8 and Patent Document 9 do not describe a DPP-based boron complex that emits near-infrared light, and do not report application to medical use.

  Furthermore, those that are directly covalently bonded to the polymer of the resin, such as the fluorescent dyes described in Patent Documents 2 and 4, are difficult to manufacture and have low versatility. In addition, introduction of a reactive group into a dye has a problem that the synthesis route is complicated, resulting in high production costs and not so suitable for industrial mass production. In view of versatility, it is preferable that a near-infrared fluorescent resin can be produced simply by mixing and dispersing a near-infrared fluorescent dye in the resin. In particular, when dispersed in a thermoplastic resin or the like, a method of melt-kneading the resin and the dye can be considered, but even when melt-kneading is performed at a temperature lower than the decomposition point of the dye, Fluorescence may not occur due to causes such as poor dispersion or decomposition of the dye. Therefore, when the dye described above is dispersed in a thermoplastic resin or the like by melt kneading, it can be kneaded without being decomposed, and whether the resin composition and the molded body can efficiently emit near infrared light. It is difficult to predict from the physical properties of the pigment.

  An object of the present invention is to provide a resin composition that emits near-infrared fluorescence, has a high emission quantum yield, and is suitable for production by melt kneading, and a molded body obtained by processing the resin composition. is there.

The resin composition, the molded body , and the method for producing the resin composition according to the present invention are the following [1] to [ 8 ].
[1] Near-infrared fluorescent dye and resin (however, the resin contains one or more selected from the group consisting of urethane resin, olefin resin, polystyrene resin, and polyester resin) excluded.) containing a resin composition that does not contain a radiopaque material,
The near-infrared fluorescent dye is
Following general formula _{(I 1 -7) ~ (I} 1 -9) and _{(I 2 -7) ~ (I} 2 -9)

(In the formula _{(I 1 -7) ~ (I} 1 -9) and _{(I 2 -7) ~ (I} 2 -9),
Y ²³ and Y ²⁴ each independently represent —CH— or a nitrogen atom;
Y ¹³ and Y ¹⁴ each independently represent an oxygen atom or a sulfur atom;
Y ²⁵ and Y ²⁶ each independently represent —CH— or a nitrogen atom;
R ⁴⁷ and R ⁴⁸ each independently represent a hydrogen atom or an electron withdrawing group;
R ⁴³ , R ⁴⁴ , R ⁴⁵ , and R ⁴⁶ represent a halogen atom or an optionally substituted aryl group;
P ¹⁵ and ^{P 16} are independently of each other, represent a halogen _{atom, C 1-20 alkyl, C 1-20} alkoxy group, an amino group, a monoalkylamino group, a dialkylamino group, ^{and, P 15} and ^{P 16} At least one of n is a n-butyl group, an isobutyl group, or a t-butyl group;
n15 and n16 each independently represent an integer of 1 to 3;
A ¹⁵ and A ¹⁶ are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group. Represents a phenyl group optionally having 1 to 3 substituents. )

In a one or more compounds selected from the group consisting of compounds represented by, and the maximum fluorescence wavelength of 650nm or more, the content of the near-infrared fluorescent dye of the resin composition is 0 0.0001 to 0.5% by mass of a resin composition.
[2] As the near-infrared fluorescent dye, the following general formulas (1-1) to (1-12) and general formulas (2-1) to (2-12)

(In the above formulas (1-1) to (1-12) and (2-1) to (2-12),
P ^{5 to} P ⁸ each independently represent a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an amino group, a monoalkylamino group or a dialkylamino group, and P ⁵ and P ⁶ At least one of n is a n-butyl group, an isobutyl group, or a t-butyl group;
n5 and n6 each independently represent an integer of 1 to 3,
n7 and n8 represent the integer of 0-3 independently of each other. The resin composition according to [1] above, containing one or more compounds selected from the group consisting of compounds represented by:

[ 3 ] The resin composition according to any one of [1] or [ 2 ], wherein the resin is a thermoplastic resin.
[ 4 ] The resin composition according to any one of [1] to [ 3 ], wherein the maximum fluorescence wavelength is 700 nm or more.
[ 5 ] The resin composition according to any one of [1] to [ 4 ], which is used as a medical material.
[ 6 ] A molded article obtained by processing the resin composition of any one of [1] to [ 5 ].
[ 7 ] The molded article according to [ 6 ], wherein at least a part is a medical device used in a patient's body.
[ 8 ] A method for producing the resin composition according to any one of [1] to [5],
Wherein comprising the step of melt-kneading with the resin and a near-infrared fluorescent dye, the production method of the resin composition.

  In the present invention, a DPP boron complex that is excellent in heat resistance and emission quantum yield and emits near-infrared fluorescence is used. For this reason, it is possible to obtain a near-infrared fluorescent resin composition having high emission intensity by melt kneading without causing a copolymerization reaction of the organic near-infrared fluorescent dye with the resin component, and further processing the composition. Can be obtained.

In Example 1, it is the graph which showed the absorption spectrum according to the kneading | mixing conditions of the pigment | dye containing film of the near-infrared fluorescent pigment | dye A. In Example 2, it is the graph which showed the absorption spectrum according to kneading | mixing conditions of the pigment | dye containing film of the near-infrared fluorescent pigment | dye B. In Example 2, a dye-containing film of the near-infrared fluorescent dye B (“Dye B-containing” in the figure) and a dye-free film (“Dye-free” in the figure) were taken with a near-infrared fluorescence detection camera. It is a photograph. In Example 2, a pigment-containing film of the near-infrared fluorescent pigment B (“Dye B” in the figure) and a pigment-free film (“Dye-free” in the figure) were applied to pork having a thickness of 2 mm. It is the photograph image | photographed with the near-infrared fluorescence detection camera. In Comparative Example 1, it is a graph showing an absorption spectrum for each kneading condition of a dye-containing film of an azo-boron complex compound. In Example 9, a film containing 0.03% by mass of near-infrared fluorescent dye A (“Dye B 0.03%” in the figure) and a film containing 0.005% by mass (“Dye A 0.005” in the figure) % ") And a dye-free film (" dye-free "in the figure) taken with a near infrared fluorescence detection camera. In Example 9, a film containing 0.03% by mass of near-infrared fluorescent dye A (“Dye A 0.03%” in the figure) and a film containing 0.005% by mass (“Dye A 0.005” in the figure) % ") And a pigment-free film (" pigment-free "in the figure) were taken with a near-infrared fluorescence detection camera on pork meat having a thickness of 2 mm.

  The resin composition according to the present invention contains a near-infrared fluorescent dye and a resin, and has a maximum fluorescence wavelength of 650 nm or more. Since the resin composition according to the present invention is a resin composition that emits near-infrared fluorescence and can be easily molded, it is suitably used as a medical material such as a raw material for medical devices used in vivo.

<Near-infrared fluorescent dye>
Specifically, the near-infrared fluorescent dye contained in the resin composition according to the present invention is a compound represented by the following general formula (I ₁ ) and general formula (I ₂ ). Hereinafter, the compound is sometimes referred to as “near-infrared fluorescent dye according to the present invention”.

In general formula (I ₁ ) or general formula (I ₂ ), R ^h and R ⁱ form an aromatic ring composed 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. To do. Similarly, in general formula (I ₁ ) or general formula (I ₂ ), R ^j and R ^k are aromatics composed of 1 to 3 rings together with the nitrogen atom to which R ^j is bonded and the carbon atom to which R ^k is bonded. Form a ring. Each of the aromatic ring formed by R ^h and R ⁱ and the aromatic ring formed by R ^j and R ^k is a 5-membered ring or a 6-membered ring. The compound represented by the general formula (I ₁ ) or the general formula (I ₂ ) includes an aromatic ring formed by R ^h and R ⁱ , a ring containing a boron atom bonded to two nitrogen atoms, and one nitrogen atom. A five-membered heterocycle containing a 5-ring heterocycle, an aromatic ring formed by R ^j and R ^k , a ring containing a boron atom bonded to two nitrogen atoms, and a five-membered ring containing one nitrogen atom It has a ring structure in which a 3-ring condensed with a heterocycle is condensed between 5-membered heterocycles, that is, a ring structure in which at least 6 rings are condensed. Thus, the compound represented by the general formula (I ₁ ) or the general formula (I ₂ ) has a robust condensed ring structure composed of a very wide conjugated plane.

The aromatic ring formed by R ^h and R ⁱ and the aromatic ring formed by R ^j and R ^k are not particularly limited as long as they have aromaticity. Examples of the aromatic ring include pyrrole ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyridine ring, pyrimidine ring, pyridazine ring, isoindole ring, indole ring, indazole ring, purine ring, perimidine ring, thienopyrrole ring, and fluropyrrole. A ring, a pyrrolothiazole ring, a pyrrolooxazole ring, and the like. In particular, since the maximum fluorescence wavelength is extended to the near infrared region, the general formula (I ₁ ) preferably has 2 or 3 condensed rings as the aromatic ring. It is more preferable that it is 2 from such points. However, even when the number of condensed rings of the aromatic ring is 1, the wavelength can be increased by devising a substituent on the ring or a substituent on boron. In particular, in the case of the general formula (I ₂ ), it is possible to increase the wavelength to the near infrared region simply by bonding a substituted aryl group or a heteroaryl group.

The aromatic ring formed by R ^h and R ⁱ and the aromatic ring formed by R ^j and R ^k may have no substituent or may have one or more substituents. It may be. The substituent of the aromatic ring may be “any group that does not inhibit the fluorescence of the compound”.

  When the resin composition according to the present invention is used as a medical material (a raw material for a medical device), the near-infrared fluorescent dye according to the present invention has a mutagenicity, cell, Those having no toxicity, sensitization and skin irritation are preferred. From the viewpoint of safety, it is preferable that the near-infrared fluorescent dye according to the present invention does not elute from a molded product obtained by processing the resin composition according to the present invention with a body fluid such as blood or tissue fluid. For this reason, it is preferable that the near-infrared fluorescent dye according to the present invention has low solubility in biological components such as blood. However, even if the near-infrared fluorescent dye itself according to the present invention is water-soluble, the resin component itself in the resin composition according to the present invention hardly elutes in body fluids and the near-infrared fluorescent dye itself When the content of is small, the molded article of the resin composition according to the present invention can be used while avoiding elution of the near-infrared fluorescent dye even in vivo. In consideration of these, it is preferable to select a substituent that does not easily exhibit mutagenicity or the like or that reduces water solubility.

Examples of the substituent include a halogen atom, nitro group, cyano group, hydroxy group, carboxyl group, aldehyde group, sulfonic acid group, alkylsulfonyl group, halogenosulfonyl group, thiol group, alkylthio group, isocyanate group, and thioisocyanate group. Alkyl group, alkenyl group, alkynyl group, alkoxy group, alkoxycarbonyl group, alkylamidocarbonyl group, alkylcarbonylamide group, acyl group, amino group, monoalkylamino group, dialkylamino group, silyl group, monoalkylsilyl group, Examples thereof include a dialkylsilyl group, a trialkylsilyl group, a monoalkoxysilyl group, a dialkoxysilyl group, a trialkoxysilyl group, an aryl group, and a heteroaryl group. The aromatic ring formed by R ^h and R ⁱ and the aromatic ring formed by R ^j and R ^k include a cyano group, a hydroxy group, a carboxyl group, an alkylthio group, and an alkyl group from the viewpoint of safety to the living body. , An alkoxy group, an alkoxycarbonyl group, an amide group, an alkylsulfonyl group, fluorine, chlorine, an aryl group, or a heteroaryl group, and these substituents may further have a substituent. However, the substituents other than these substituents are not limited to these substituents because the safety can be improved by further introducing appropriate substituents.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned, a fluorine atom, a chlorine atom, and a bromine atom are preferable, and a fluorine atom is more preferable.

  The alkyl group, alkenyl group, and alkynyl group may be linear, branched, or cyclic (aliphatic ring group). 1-20 are preferable, as for carbon number of these groups, 1-12 are more preferable, and 1-6 are more preferable. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group (tert-butyl group), pentyl group, isoamyl group, hexyl group, heptyl group, Examples include octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, and a 2-hexenyl group. Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, isopropynyl group, 1-butynyl group, isobutynyl group and the like.

  Alkylsulfonyl group, alkylthio group, alkoxy group, alkoxycarbonyl group, alkylamidocarbonyl group, alkylcarbonylamide group, monoalkylamino group, dialkylamino group, monoalkylsilyl group, dialkylsilyl group, trialkylsilyl group, monoalkoxysilyl Examples of the alkyl group moiety in the group, dialkoxysilyl group, and trialkoxysilyl group include the same alkyl groups as those described above. For example, as alkoxy group, 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. Also, for example, as monoalkylamino group, 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 thereof include an amino group, a butylmethylamino group, an ethylpropylamino group, and a butylethylamino group.

Examples of the aryl group include a phenyl group, a naphthyl group, an indenyl group, and a biphenyl group. A phenyl group is preferred.
Examples of the heteroaryl group include a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a thienyl group, a furanyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, and a thiadiazole group; a pyridinyl group and a pyrazinyl group Groups, 6-membered heteroaryl groups such as pyrimidinyl group, pyridazinyl group; indolyl group, isoindolyl group, indazolyl group, quinolidinyl group, quinolinyl group, isoquinolinyl group, benzofuranyl group, isobenzofuranyl group, chromenyl group, benzoxazolyl And a condensed heteroaryl group such as a benzoisoxazolyl group, a benzothiazolyl group, and a benzoisothiazolyl group.

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

  The absorption wavelength and fluorescence wavelength of the fluorescent dye depend on the surrounding environment. Therefore, the absorption wavelength of the fluorescent dye in the resin may be shorter or longer than that in the solution. When the absorption wavelength of the near-infrared fluorescent dye itself according to the present invention is increased, it is preferable because the maximum absorption wavelength is in the near-infrared region among various resins. The maximum absorption wavelength of the fluorescent dye is obtained by introducing the electron donating group and the electron withdrawing group at an appropriate position in the molecule, thereby reducing the band gap between the highest occupied orbital (HOMO) and the lowest unoccupied orbit (LUMO). Narrower and longer wavelength can be achieved.

For example, among the compounds represented by the general formula (I ₁ ), 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 , R ^p and In the case where R ^q is an aromatic ring, by introducing an electron donating group into the aromatic ring, or by introducing an electron withdrawing group into R ^r and R ^s , the maximum absorption wavelength and the maximum fluorescence wavelength of the compound Can be made longer. By combining these designs, it is possible to adjust to the target wavelength.

Therefore, the aromatic ring formed by R ^h and R ⁱ and the substituent possessed by the aromatic ring formed by R ^j and R ^k include, among the “any group that does not inhibit the fluorescence of the compound”, the aromatic ring. On the other hand, a group that functions as an electron-donating group is preferred. By introducing an electron donating group into the aromatic ring, the fluorescence of the compound represented by the general formula (I ₁ ) or the general formula (I ₂ ) becomes longer. Examples of the group that functions as an electron donating group include alkyl groups; alkoxy groups such as methoxy groups; aryl groups such as phenyl groups, p-alkoxyphenyl groups, p-dialkylaminophenyl groups, dialkoxyphenyl groups (aromatic rings). Group); heteroaryl groups (heteroaromatic ring groups) such as 2-thienyl group and 2-furanyl group. As the alkyl group, the alkyl group in the substituent of the phenyl group, and the alkyl group part in the alkoxy group, a linear or branched alkyl group having 1 to 20 carbon atoms is preferable. In addition, what is necessary is just to select suitably the carbon number of an alkyl group part, and the presence or absence of a branch in view of the various physical properties of a pigment | dye. The alkyl group may be linear, branched, or cyclic (aliphatic ring group). Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, heptyl group, octyl group, and nonyl group. Decyl group, undecyl group, dodecyl group and the like. Among these, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group are preferable, an n-butyl group, an isobutyl group, and a t-butyl group are more preferable, and a t-butyl group is preferable. Particularly preferred.
The alkyl group portion of the alkoxy group may be linear, branched, or cyclic (aliphatic ring group). Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, t-butyloxy group, pentyloxy group, isoamyloxy group, hexyloxy group, heptyloxy group, Examples include octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.

In general formula (I ₁ ) or general formula (I ₂ ), the aromatic ring formed by R ^h and R ⁱ and the aromatic ring formed by R ^j and R ^k may be different or the same. May be. Since the near-infrared fluorescent dye according to the present invention tends to have a higher emission quantum yield in addition to being easy to synthesize, the aromatic ring formed by R ^h and R ⁱ and R ^j and R ^k The aromatic rings formed by are preferably the same.

In the general formula (I ₁ ) or the general formula (I ₂ ), R ¹ , R ^m , R ⁿ , and R ^o are each independently a halogen atom, a C _1-20 alkyl group, or a C _1-20 alkoxy group. Represents an aryl group or a heteroaryl group. When R ¹ , R ^m , R ⁿ , or R ^o is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is preferable, a fluorine atom or a chlorine atom is more preferable, and a solid bond is formed with a boron atom. Therefore, a fluorine atom is particularly preferable. A compound in which R ^l , R ^m , R ⁿ , and R ^o are fluorine atoms has high heat resistance, and therefore is advantageous when melt kneaded with a resin at a high temperature.

In the present invention and the present specification, “C _1-20 alkyl group” means an alkyl group having 1 to 20 carbon atoms, and “C _1-20 alkoxy group” means an alkoxy group having 1 to 20 carbon atoms. To do.

When R ¹ , R ^m , R ⁿ , or ^Ro is a C _1-20 alkyl group, the alkyl group may be linear, branched, or cyclic (aliphatic ring) Group). Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, heptyl group, octyl group, and nonyl group. Decyl group, undecyl group, dodecyl group and the like.

When R ¹ , R ^m , R ⁿ , or ^Ro is a C _1-20 alkoxy group, the alkyl group portion of the alkoxy group may be linear, branched, or cyclic (Aliphatic cyclic group) may be used. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, t-butyloxy group, pentyloxy group, isoamyloxy group, hexyloxy group, heptyloxy group, Examples include octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.

When R ¹ , R ^m , R ⁿ , or ^Ro is an aryl group, examples of the aryl group include a phenyl group, a naphthyl group, an indenyl group, and a biphenyl group.
When R ¹ , R ^m , R ⁿ , or ^Ro is a heteroaryl group, examples of the heteroaryl group include pyrrolyl group, imidazolyl group, pyrazolyl group, thienyl group, furanyl group, oxazolyl group, isoxazolyl group, thiazolyl group, 5-membered ring heteroaryl groups such as isothiazolyl group and thiadiazole group; 6-membered ring heteroaryl groups such as pyridinyl group, pyrazinyl group, pyrimidinyl group and pyridazinyl group; indolyl group, isoindolyl group, indazolyl group, quinolidinyl group, quinolinyl group, isoquinolinyl group And a condensed heteroaryl group such as a benzofuranyl group, an isobenzofuranyl group, a chromenyl group, a benzoxazolyl group, a benzoisoxazolyl group, a benzothiazolyl group, and a benzoisothiazolyl group.

The C _1-20 alkyl group, C _1-20 alkoxy group, aryl group, and heteroaryl group represented by R ¹ , R ^m , R ⁿ , or R ^o may be an unsubstituted group or one or more The hydrogen atom may be substituted with a substituent. Examples of the substituent include a halogen atom, alkyl group, alkoxy group, nitro group, cyano group, hydroxy group, amino group, thiol group, carboxyl group, aldehyde group, sulfonic acid group, isocyanate group, thioisocyanate group, and aryl group. And heteroaryl groups.

As the compound represented by the general formula (I ₁ ) or the general formula (I ₂ ), R ¹ , R ^m , R ⁿ , and R ^o are a halogen atom, an unsubstituted aryl group, or an aryl group having a substituent. Preferred is 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, and a fluorine atom, a chlorine atom, an unsubstituted A phenyl group or a phenyl group substituted with a C _1-10 alkyl group or a C _1-10 alkoxy group is more preferred, and a fluorine atom or an unsubstituted phenyl group is particularly preferred.

In general formula (I ₁ ) or general formula (I ₂ ), R ^p and R ^q each independently represent a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an aryl group, Or represents a heteroaryl group. Examples of the halogen atom, C _1-20 alkyl group, C _1-20 alkoxy group, aryl group, and heteroaryl group represented by R ^p and R ^q include R ¹ , R ^m , and R ^{n in the} general formula (I ₁ ). Or the same as R ^o .

As the compound represented by the general formula (I ₁ ) or the general formula (I ₂ ), those in which R ^p and R ^q are a hydrogen atom or an aryl group are preferable, an unsubstituted phenyl group, or a C _1-20 alkyl. Group or a phenyl group substituted with a C _1-20 alkoxy group is preferable, and a phenyl group substituted with a linear or branched C _1-20 alkoxy group is more preferable, and high luminous efficiency From the viewpoint of obtaining a compound having excellent compatibility with the resin, a phenyl group substituted with a linear or branched C _1-10 alkoxy group is more preferred, and the linear or branched chain is more preferable. are particularly preferable is a phenyl group substituted with Jo of C _4-10 alkoxy groups, those which are phenyl group substituted by a straight chain or branched octyloxy group It is also preferred.

In the general formula (I ₁ ), R ^r and R ^s each independently represent a hydrogen atom or an electron withdrawing group. Examples of the electron withdrawing group include a halogenated methyl group such as a trifluoromethyl group, a nitro group, a cyano group, an aryl group, a heteroaryl group, an alkynyl group, an alkenyl group, a carboxyl group, an acyl group, and a carbonyl group. Substituents having a carbonyl group such as an oxy group, an amide group, and an aldehyde group; sulfoxide groups; sulfonyl groups; alkoxymethyl groups; aminomethyl groups and the like, and aryl groups having these electron-withdrawing groups as substituents; A heteroaryl group or the like can also be used. Among these electron-withdrawing groups, a trifluoromethyl group, a nitro group, a cyano group, a phenyl group, a sulfonyl group and the like that can function as a strong electron-withdrawing group are preferable from the viewpoint of lengthening the maximum fluorescence wavelength. .

As the near-infrared fluorescent dye according to the present invention, since the maximum fluorescence wavelength is longer, the compound represented by any one of the following general formulas (I ₁ -1) to (I ₁ -6), or A compound represented by any one of formulas (I ₂ -1) to (I ₂ -6) is also preferable.

Formula _{(I 1 -1) ~ (I} 1 -6) and the general formula _{(I 2 -1) ~ (I} 2 -6), R 23, R 24, R 25 and ^{R 26,} are, independently of one another A halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an aryl group, or a heteroaryl group. Examples of the halogen atom, C _1-20 alkyl group, C _1-20 alkoxy group, aryl group, and heteroaryl group represented by R ²³ , R ²⁴ , R ²⁵ , or R ²⁶ include R in the general formula (I ₁ ). ^{l, R} m, ^{R n,} or are the same as those of the ^{R o.} As the compound represented by any one of the general formulas (I ₁ -1) to (I ₁ -6) or the compound represented by any one of the general formulas (I ₂ -1) to (I ₂ -6), In view of the high thermal stability of the compound, R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are preferably a halogen atom, an unsubstituted aryl group, or an aryl group having a substituent, specifically, a fluorine atom, A chlorine atom, a bromine atom, an unsubstituted phenyl group, or a phenyl group substituted with a C _1-20 alkyl group or a C _1-20 alkoxy group is preferred, and a fluorine atom, a chlorine atom, an unsubstituted phenyl group, or C ₁ A phenyl group substituted with a _-10 alkyl group or a C _1-10 alkoxy group is more preferred, and a compound having both high luminous efficiency and thermal stability is obtained. Is preferred.

In the general formulas (I ₁ -1) to (I ₁ -6) and the general formulas (I ₂ -1) to (I ₂ -6), 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 (I ₁ ). Things. As the compound represented by any one of the general formulas (I ₁ -1) to (I ₁ -6) or the compound represented by any one of the general formulas (I ₂ -1) to (I ₂ -6), R ²⁷ and R ²⁸ are preferably a hydrogen atom or an aryl group, and a compound having high luminous efficiency can be obtained. Therefore, a hydrogen atom, an unsubstituted phenyl group, a C _1-20 alkyl group or a C _1-20 alkoxy is obtained. Preferred is a phenyl group substituted with a group, more preferred is a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a linear or branched C _1-20 alkoxy group, Since a compound having high luminous efficiency and excellent compatibility with a resin can be obtained, a compound having high luminous efficiency and excellent compatibility with a resin can be obtained. Therefore, linear or branched C _{1 -10} A More preferably those which are substituted phenyl groups in Kokishi group, especially preferable is a phenyl group substituted with linear or branched C _4-10 alkoxy group, a linear or branched Most preferred is a phenyl group substituted with an octyloxy group.

In general formulas (I ₁ -1) to (I ₁ -6), 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} formula (I ₁ ). As the compound represented by any one of the general formulas (I ₁ -1) to (I ₁ -6), since the fluorescence wavelength is increased and a compound having high luminous efficiency is obtained, R ²⁹ and R ³⁰ is preferably a fluoroalkyl group, a nitro group, a cyano group, or an aryl group that can function as a strong electron-attracting group, and may have a trifluoromethyl group, a nitro group, a cyano group, or a substituent. What is a good phenyl group is more preferable, and what is a trifluoromethyl group or a cyano group is more preferable from the viewpoint of obtaining a compound having high luminous efficiency and excellent compatibility with a resin.

In General Formula (I ₁ -1) and General Formula (I ₂ -1), Y ⁹ and Y ¹⁰ each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom. As a compound represented by the general formula (I ₁ -1) or the general formula (I ₂ -1), a compound having high luminous efficiency can be obtained. Therefore, Y ⁹ and Y ¹⁰ are each independently a sulfur atom, Those which are oxygen atoms or nitrogen atoms are preferable, those which are sulfur atoms or oxygen atoms independently of each other are more preferable, and since a compound having high luminous efficiency and thermal stability is obtained, both are sulfur atoms or More preferably, both are oxygen atoms.

In the general formulas (I ₁ -3) to (I ₁ -6) and the general formulas (I ₂ -3) to (I ₂ -6), X ¹ and X ² are each independently a nitrogen atom or a phosphorus atom. Represent. Formula Examples _{(I 1 -3) ~ (I} 1 -6) or a compound represented by the general formula _{(I 2 -3) ~ (I} 2 -6), X 1 and ^{X 2} are, the higher luminous efficiency Since both compounds are nitrogen atoms or phosphorus atoms, compounds that are both nitrogen atoms or phosphorus atoms are preferable, and since compounds that have both high luminous efficiency and thermal stability are obtained, those that are both nitrogen atoms are more preferable.

In the general formula (I ₁ -1) and the general formula (I ₂ -1), R ³¹ and R ³² satisfy the following (p1) or (p2).
(P1) Independently of each other, a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an aryl group, or a heteroaryl group is represented.
(P2) R ³¹ and R ³² together form an aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent.

In general formula (I ₁ -1) and general formula (I ₂ -1), R ³³ and R ³⁴ satisfy the following (q1) or (q2).
(Q1) represents each independently a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an aryl group, or a heteroaryl group, or (q2) R ³³ and R ³⁴ are both An aromatic 5-membered ring which may have a substituent or an aromatic 6-membered ring which may have a substituent is formed.

Formula _(I 1 -2) in _{~ (I} 1 -6) and the general formula _{(I 2 -2) ~ (I} 2 -6), R 35, R 36, R 37, and ^{R 38,} the following (p3 ) To (p6) are satisfied.
(P3) Independently of each other, a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an aryl group, or a heteroaryl group is represented.
(P4) R ³⁵ and R ³⁶ together form an optionally substituted aromatic 5-membered ring or optionally substituted aromatic 6-membered ring, and R ³⁷ and R ³⁸ are Independently of each other, a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an aryl group, or a heteroaryl group is represented.
(P5) R ³⁶ and R ³⁷ together form an optionally substituted aromatic 5-membered ring or optionally substituted aromatic 6-membered ring, and R ³⁵ and R ³⁸ are Independently of each other, a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an aryl group, or a heteroaryl group is represented.
(P6) R ³⁷ and R ³⁸ together form an optionally substituted aromatic 5-membered ring or optionally substituted aromatic 6-membered ring, and R ³⁵ and R ³⁶ are Independently of each other, a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an aryl group, or a heteroaryl group is represented.

Formula _(I 1 -2) in _{~ (I} 1 -6) and the general formula _{(I 2 -2) ~ (I} 2 -6), R 39, R 40, R 41, and ^{R 42,} the following (q3 ) To (q6) are satisfied.
(Q3) 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.
(Q4) R ³⁹ and R ⁴⁰ together form an optionally substituted aromatic 5-membered ring or optionally substituted aromatic 6-membered ring, and R ⁴¹ and R ⁴² are Independently of each other, a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an aryl group, or a heteroaryl group is represented.
(Q5) R ⁴⁰ and R ⁴¹ together form an optionally substituted aromatic 5-membered ring or optionally substituted aromatic 6-membered ring, and R ³⁹ and R ⁴² are Independently of each other, a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an aryl group, or a heteroaryl group is represented.
(Q6) R ⁴¹ and R ⁴² together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, and R ³⁹ and R ⁴⁰ are Independently of each other, a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an aryl group, or a heteroaryl group is represented.

As the halogen atom, C _1-20 alkyl group, C _1-20 alkoxy group, aryl group, and heteroaryl group in the above (p1), (p3) to (p6) and (q1), (q3) to (q6) May be those exemplified as “any group that does not inhibit the fluorescence of the compound” in R ^h and R ⁱ , R ^j and R ^k , respectively.

In (p2), (p4) to (p6), (q2), (q4) to (q6), R ³¹ and R ³² together form an aromatic 5-membered ring or aromatic 6-membered ring, R ³³ and An aromatic 5-membered ring or an aromatic 6-membered ring formed by R ^34, an aromatic 5-membered ring or an aromatic 6-membered ring formed by R ³⁵ and R ^36, and an aromatic formed by R ³⁶ and R ³⁷ together 5- or 6-membered aromatic ring, R ³⁷ and R ³⁸ are both aromatic 5- or 6-membered aromatic ring to form an aromatic 5-membered R ³⁹ and R ⁴⁰ form together a ring or a 6-membered aromatic 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 together are represented by the following general formula ( Those represented by any one of (C-1) to (C-9) are preferred and represented by the following general formula (C-9). Those are more preferable. In the following general formulas (C-1) to (C-9), the locations marked with an asterisk are general formulas (I ₁ -1) to (I ₁ -6) and general formulas (I ₂ -2) to it is a moiety that binds the boron dipyrromethene skeleton of (I 2 _-6) in.

In the general formulas (C-1) to (C-8), Y ^{1 to} Y ⁸ each independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom. Y ^{1 to} Y ⁸ are preferably a sulfur atom, an oxygen atom, or a nitrogen atom independently of each other, and more preferably a sulfur atom or an oxygen atom independently of each other.

In the general formulas (C-1) to (C-9), R ^{11 to} R ²² each independently represent a hydrogen atom or any group that does not inhibit the fluorescence of the compound. As “an arbitrary group that does not inhibit the fluorescence of the compound”, those exemplified in “an arbitrary group that does not inhibit the fluorescence of the compound” in R ^h and R ⁱ and R ^j and R ^k can be used. For example, alkyl group; alkoxy group such as methoxy group; aryl group (aromatic ring group) such as phenyl group, p-alkoxyphenyl group, p-dialkylaminophenyl group, dialkoxyphenyl group; 2-thienyl group, 2-furanyl And heteroaryl groups (heteroaromatic ring groups) such as groups. As the alkyl group, the alkyl group in the substituent of the phenyl group, and the alkyl group part in the alkoxy group, a linear or branched alkyl group having 1 to 20 carbon atoms is preferable. In addition, what is necessary is just to select suitably the carbon number of an alkyl group part, and the presence or absence of a branch in view of the various physical properties of a pigment | dye. The alkyl group may be linear, branched, or cyclic (aliphatic ring group). Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, heptyl group, octyl group, and nonyl group. Decyl group, undecyl group, dodecyl group and the like. Among these, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group are preferable, an n-butyl group, an isobutyl group, and a t-butyl group are more preferable, and a t-butyl group is preferable. Particularly preferred.
The alkyl group portion of the alkoxy group may be linear, branched, or cyclic (aliphatic ring group). Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, t-butyloxy group, pentyloxy group, isoamyloxy group, hexyloxy group, heptyloxy group, Examples include octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.

As the compound represented by the above (I ₁ -1), R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are all halogen atoms, unsubstituted phenyl groups, C _1-10 alkyl groups, or C _1-10. A phenyl group substituted with an alkoxy group; R ²⁷ and R ²⁸ are both a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C _1-20 alkyl group or a C _1-20 alkoxy group; R ²⁹ and R ³⁰ are both a trifluoromethyl group, a nitro group, a cyano group, or a phenyl group; Y ⁹ and Y ¹⁰ are both a sulfur atom or an oxygen atom; R ³¹ and R ³² are independently hydrogen. is an atom or a _{C 1-20} alkyl group, or ^{R 31} and ^{R 32} together form a phenyl group which may have a ^{substituent; R 33} and ^{R 34} are independently of each other A atom or _{C 1-20} alkyl group, or a ^{compound R 33} and ^{R 34} together form a phenyl group which may have a substituent is ^{preferable, R 23, R 24, R} 25, and ^{R 26} Are both a halogen atom or an unsubstituted phenyl group; R ²⁷ and R ²⁸ are both an unsubstituted phenyl group or a phenyl group substituted with a linear or branched C _1-20 alkoxy group; R ²⁹ and R ³⁰ are 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 independently a hydrogen atom or C an _1-20 alkyl group, or ^{R 31} and ^{R 32} form a substituted phenyl group together with an unsubstituted phenyl group or a _{C 1-10} alkyl ^{group; R 33} and R ⁴ is a independently of one another represent hydrogen or _{C 1-20} alkyl group, or a ^{compound R 33} and ^{R 34} form a phenyl group substituted both with unsubstituted phenyl group or a _{C 1-10} alkyl group, It is more preferable because of high luminous efficiency and excellent compatibility with the resin.

As the compound represented by the above (I ₁ -2), R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are all halogen atoms, unsubstituted phenyl groups, C _1-10 alkyl groups or C _1-10. A phenyl group substituted with an alkoxy group; R ²⁷ and R ²⁸ are both a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C _1-20 alkyl group or a C _1-20 alkoxy group; R ²⁹ and R ³⁰ are both a trifluoromethyl group, a nitro group, a cyano group, or a phenyl group; R ³⁵ , R ³⁶ , R ³⁷ , and R ³⁸ are each independently a hydrogen atom or a C _1-20 alkyl group in ^it, form a phenyl group which may have a ^{R 35} and ^{R 36} are both ^{substituents,} a hydrogen atom or a _{C 1-20} alkyl ^{R 37} and ^{R 38} are independently of each other Is a ^group, have ^{R 36} and ^{R 37} are both substituents form a well phenyl ^group, a hydrogen atom or a _{C 1-20} alkyl group independently ^{R 35} and ^{R 38} are each other, or R ³⁷ and R ³⁸ together form an optionally substituted phenyl group, and R ³⁵ and R ³⁶ are each independently a hydrogen atom or a C _1-20 alkyl group; R ³⁹ , R ⁴⁰ , R ⁴¹ and R ⁴² are each independently a hydrogen atom or a C _1-20 alkyl group, R ³⁹ and R ⁴⁰ together form an optionally substituted phenyl group, and R ⁴¹ and R ⁴² are R ⁴⁰ and R ⁴¹ are each independently a hydrogen atom or a C _1-20 alkyl group, and both R ⁴⁰ and R ^{41 form an} optionally substituted phenyl group, and R ³⁹ and R ⁴² are independently hydrogen atoms. Young Is a C _1-20 alkyl group, or ^{R 41} and ^{R 42} together form a phenyl group which may have a ^substituent, a hydrogen atom or a _{C 1-20} alkyl independently ^{R 39} and ^{R 40} are mutually R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are both halogen atoms or unsubstituted phenyl groups; R ²⁷ and R ²⁸ are both unsubstituted phenyl groups, or linear or A phenyl group substituted with a branched C _1-20 alkoxy group; R ²⁹ and R ³⁰ are both a trifluoromethyl group, a nitro group, or a cyano group; R ³⁵ , R ³⁶ , R ³⁷ , and is a hydrogen atom or a _{C 1-20} alkyl group R ³⁸ independently of one ^{another, R 35} and ^{R 36} are both substituted with an unsubstituted phenyl group or a _{C 1-10} alkyl group Fe Form a ^group, a hydrogen atom or a _{C 1-20} alkyl group independently ^{R 37} and ^{R 38} are each ^{other, R 36} and ^{R 37} are both substituted with an unsubstituted phenyl group or a _{C 1-10} alkyl group R ³⁵ and R ³⁸ are each independently a hydrogen atom or a C _1-20 alkyl group, or both R ³⁷ and R ³⁸ are an unsubstituted phenyl group or a C _1-10 alkyl group. Forming a substituted phenyl group, R ³⁵ and R ³⁶ are independently a hydrogen atom or a C _1-20 alkyl group; R ³⁹ , R ⁴⁰ , R ⁴¹ , and R ⁴² are independently a hydrogen atom; or a _{C 1-20} alkyl ^group, form a phenyl group substituted with ^{R 39} and ^{R 40} are both unsubstituted phenyl group or a _{C 1-10} alkyl ^{group, R 41} Fine ^{R 42} are mutually independently a hydrogen atom or a _{C 1-20} alkyl ^group, form a phenyl group substituted with ^{R 40} and ^{R 41} are both unsubstituted phenyl group or a _{C 1-10} alkyl radical, R ³⁹ and R ⁴² are each independently a hydrogen atom or a C _1-20 alkyl group, or R ⁴¹ and R ⁴² together form a phenyl group substituted with an unsubstituted phenyl group or a C _1-10 alkyl group. , R ³⁹ and R ⁴⁰ are each independently a hydrogen atom or a C _1-20 alkyl group, which is more preferable because of high luminous efficiency and excellent compatibility with resins.

As the compound represented by the above (I ₁ -3), R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are all halogen atoms, unsubstituted phenyl groups, C _1-10 alkyl groups, or C _1-10. A phenyl group substituted with an alkoxy group; R ²⁷ and R ²⁸ are both a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C _1-20 alkyl group or a C _1-20 alkoxy group; R ²⁹ and R ³⁰ are both a trifluoromethyl group, a nitro group, a cyano group, or a phenyl group; X ¹ and X ² are both nitrogen atoms; R ³⁶ , R ³⁷ , and R ³⁸ are independently of each other is a hydrogen atom or a _{C 1-20} alkyl ^group, and ^{R 36} and ^{R 37} are have both substituents form a well phenyl ^{group, R 38} is a hydrogen atom or a _{C 1-20} aralkyl Is a group, or ^{R 37} and ^{R 38} together form a phenyl group which may have a ^{substituent, R 36} is hydrogen atom or a _{C 1-20} alkyl ^group; R ^{40, R 41} and, R ⁴² is independently a hydrogen atom or a C _1-20 alkyl group, R ⁴⁰ and R ⁴¹ together form an optionally substituted phenyl group, and R ⁴² is a hydrogen atom or C _1-1 Preferred is a compound that is a ₂₀ alkyl group, or R ⁴¹ and R ⁴² together form an optionally substituted phenyl group, and R ⁴⁰ is a hydrogen atom or a C _1-20 alkyl group, R ²³ , R ^{24, R 25,} and ^{R 26} are are both a halogen atom or an unsubstituted phenyl ^{group; R 27} and ^{R 28} are both unsubstituted phenyl group, or a linear or branched _{C 1-20} alkoxy It is substituted ^{phenyl; R 29} and ^{R 30} are both trifluoromethyl group, a nitro group, or a cyano group; ^{X 1} and ^{X 2} are both nitrogen ^atoms; R ^{36, R 37} and, R ³⁸ independently of one another represent a hydrogen atom or a _{C 1-20} alkyl ^group, to form a phenyl group substituted by ^{R 36} and ^{R 37} are both unsubstituted phenyl group or a _{C 1-10} alkyl ^{group, R 38} _{Are a} hydrogen atom or a C _1-20 alkyl group, or R ³⁷ and R ³⁸ together form an unsubstituted phenyl group or a phenyl group substituted with a C _1-10 alkyl group, and R ³⁶ is a hydrogen atom or C 1 be _1-20 alkyl ^group; R ^{40, R 41,} and ^{R 42} are each independently of the other hydrogen or _{C 1-20} alkyl ^{group, R 40} and ^{R 41} are both Mu置Phenyl group or _{C 1-10} form a phenyl group substituted with an alkyl ^{group, R 42} is a hydrogen atom or a _{C 1-20} alkyl group, or ^{R 41} and ^{R 42} are both unsubstituted phenyl group or a C A compound in which a phenyl group substituted with a _1-10 alkyl group and R ⁴⁰ is a hydrogen atom or a C _1-20 alkyl group is more preferable because of high luminous efficiency and excellent compatibility with a resin.

As the compound represented by the above (I ₁ -4), R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are all halogen atoms, unsubstituted phenyl groups, C _1-10 alkyl groups, or C _1-10. A phenyl group substituted with an alkoxy group; R ²⁷ and R ²⁸ are both a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C _1-20 alkyl group or a C _1-20 alkoxy group; R ²⁹ and R ³⁰ are both a trifluoromethyl group, a nitro group, a cyano group, or a phenyl group; X ¹ and X ² are both nitrogen atoms; R ³⁵ , R ³⁶ , and R ³⁷ are independently from each other is a hydrogen atom or a _{C 1-20} alkyl ^group, and ^{R 35} and ^{R 36} are have both substituents form a well phenyl ^{group, R 37} is a hydrogen atom or a _{C 1-20} aralkyl Is a group, or ^{R 36} and ^{R 37} together form a phenyl group which may have a ^{substituent, R 35} is hydrogen atom or a _{C 1-20} alkyl ^group; R ^{39, R 40} and, R ⁴¹ is a hydrogen atom or a _{C 1-20} alkyl group independently of one ^another, are ^{R 39} and ^{R 40} are have both substituents form a well phenyl ^{group, R 41} is a hydrogen atom or a _{C 1- A} compound that is a ₂₀ alkyl group, or R ⁴⁰ and R ⁴¹ together form an optionally substituted phenyl group, and R ³⁹ is a hydrogen atom or a C _1-20 alkyl group, is preferably R ²³ , R ^{24, R 25,} and ^{R 26} are are both a halogen atom or an unsubstituted phenyl ^{group; R 27} and ^{R 28} are both unsubstituted phenyl group, or a linear or branched _{C 1-20} alkoxy It is substituted ^{phenyl; R 29} and ^{R 30} are both trifluoromethyl group, a nitro group, or a cyano group; ^{X 1} and ^{X 2} are both nitrogen ^atoms; R ^{35, R 36} and, R ³⁷ is independently a hydrogen atom or a C _1-20 alkyl group, R ³⁵ and R ³⁶ together form a phenyl group substituted with an unsubstituted phenyl group or a C _1-10 alkyl group, and R ³⁷ _{Are a} hydrogen atom or a C _1-20 alkyl group, or R ³⁶ and R ³⁷ together form an unsubstituted phenyl group or a phenyl group substituted with a C _1-10 alkyl group, and R ³⁵ is a hydrogen atom or a C _1-20 alkyl group. be _1-20 alkyl ^group; R ^{39, R 40,} and ^{R 41} independently of one another represent a hydrogen atom or a _{C 1-20} alkyl ^{group, R 39} and ^{R 40} are both Mu置The form a phenyl group or a _{C 1-10} phenyl group substituted by an alkyl ^{group, R 41} is a hydrogen atom or a _{C 1-20} alkyl group, or ^{R 40} and ^{R 41} are both unsubstituted phenyl group or a C A compound in which a phenyl group substituted with a _1-10 alkyl group is formed, and R ³⁹ is a hydrogen atom or a C _1-20 alkyl group is more preferable because of high luminous efficiency and excellent compatibility with a resin.

Examples of the compounds represented by _{^{(I 1 -5), R 23}} , R 24, R 25, and ^{R 26} are both halogen atoms, an unsubstituted phenyl group, or a _{C 1-10} alkyl group or _{C 1-10} A phenyl group substituted with an alkoxy group; R ²⁷ and R ²⁸ are both a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C _1-20 alkyl group or a C _1-20 alkoxy group; R ²⁹ and R ³⁰ are both a trifluoromethyl group, a nitro group, a cyano group, or a phenyl group; X ¹ and X ² are both nitrogen atoms; R ³⁵ , R ³⁶ , and R ³⁸ are independently of each other 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, R 38} is a hydrogen atom or a _{C 1-20} It is alkyl ^group; R ^{39, R 40,} and ^{R 42} are each independently of the other hydrogen or _{C 1-20} alkyl group, or a phenyl group which may have a ^{R 39} and ^{R 40} are both substituents And R ⁴² is a hydrogen atom or a C _1-20 alkyl group, and R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are both halogen atoms or unsubstituted phenyl groups; R ²⁷ and R ²⁸ is an unsubstituted phenyl group, or a phenyl group substituted with a linear or branched C _1-20 alkoxy group; R ²⁹ and R ³⁰ are both a trifluoromethyl group, a nitro group, or cyano group; ^{X 1} and ^{X 2} are both nitrogen ^atoms; an R ^{35, R 36,} and ^{R 38} are each independently of the other hydrogen or _{C 1-20} alkyl group, or R ⁵ and ^{R 36} to form a phenyl group substituted both with unsubstituted phenyl group or a _{C 1-10} alkyl ^{group, R 38} is hydrogen atom or a _{C 1-20} alkyl ^group; R ^{39, R 40} and, R ⁴² is independently a hydrogen atom or a C _1-20 alkyl group, or R ³⁹ and R ⁴⁰ together form a phenyl group substituted with an unsubstituted phenyl group or a C _1-10 alkyl group, ^A compound in which ⁴² is a hydrogen atom or a C _1-20 alkyl group is more preferable because of high luminous efficiency and excellent compatibility with a resin.

Examples of the compounds represented by _{^{(I 1 -6), R 23}} , R 24, R 25, and ^{R 26} are both halogen atoms, an unsubstituted phenyl group, or a _{C 1-10} alkyl group or _{C 1-10} A phenyl group substituted with an alkoxy group; R ²⁷ and R ²⁸ are both a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C _1-20 alkyl group or a C _1-20 alkoxy group; R ²⁹ and R ³⁰ are both a trifluoromethyl group, a nitro group, a cyano group, or a phenyl group; X ¹ and X ² are both nitrogen atoms; R ³⁵ , R ³⁷ , and R ³⁸ are independently of each other 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, R 35} is a hydrogen atom or a _{C 1-20} It is alkyl ^group; R ^{39, R 41,} and ^{R 42} are each independently of the other hydrogen or _{C 1-20} alkyl group, or ^{R 41} and ^{R 42} is a phenyl group optionally both have a substituent Wherein R ³⁹ is a hydrogen atom or a C _1-20 alkyl group, and R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are both halogen atoms or unsubstituted phenyl groups; and R ²⁷ and R ²⁸ is an unsubstituted phenyl group, or a phenyl group substituted with a linear or branched C _1-20 alkoxy group; R ²⁹ and R ³⁰ are both a trifluoromethyl group, a nitro group, or cyano group; ^{X 1} and ^{X 2} are both nitrogen ^atoms; an R ^{35, R 37,} and ^{R 38} are each independently of the other hydrogen or _{C 1-20} alkyl group, or R ⁷ and ^{R 38} form a phenyl group substituted both with unsubstituted phenyl group or a _{C 1-10} alkyl ^{group, R 35} is hydrogen atom or a _{C 1-20} alkyl ^group; R ^{39, R 41} and, R ⁴² is independently a hydrogen atom or a C _1-20 alkyl group, or R ⁴¹ and R ⁴² together form a phenyl group substituted with an unsubstituted phenyl group or a C _1-10 alkyl group, ^A compound in which 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 a resin.

As the compound represented by the above (I ₂ -1), R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are all halogen atoms, unsubstituted phenyl groups, C _1-10 alkyl groups, or C _1-10. A phenyl group substituted with an alkoxy group; R ²⁷ and R ²⁸ are both a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C _1-20 alkyl group or a C _1-20 alkoxy group; Y ⁹ and Y ¹⁰ are both a sulfur atom or an oxygen atom; R ³¹ and R ³² are independently a hydrogen atom or a C _1-20 alkyl group, or R ³¹ and R ³² both have a substituent. also form a phenyl group ^{optionally; R 33} and ^{R 34} independently of one another represent a hydrogen atom or a _{C 1-20} alkyl group, or ^{R 33} and ^{R 34} are not both substituted Preferably compounds that form even phenyl ^{group, R 23, R 24, R} 25, and ^{R 26} are are both a halogen atom or an unsubstituted phenyl ^{group; R 27} and ^{R 28} are both unsubstituted phenyl group, or A phenyl group substituted with a linear or branched C _1-20 alkoxy group; Y ⁹ and Y ¹⁰ are both a sulfur atom or an oxygen atom; R ³¹ and R ³² are 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 are independently of each other is a hydrogen atom or a _{C 1-20} alkyl group, or a phenyl ^{group R 33} and ^{R 34} are both substituted with an unsubstituted phenyl group or a _{C 1-10} alkyl group Compounds formed, the light emitting efficiency is high, since the compatibility with the resin is excellent, more preferred.

Examples of the compounds represented by _{^{(I 2 -2), R 23}} , R 24, R 25, and ^{R 26} are both halogen atoms, an unsubstituted phenyl group, or a _{C 1-10} alkyl group or _{C 1-10} A phenyl group substituted with an alkoxy group; R ²⁷ and R ²⁸ are both a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C _1-20 alkyl group or a C _1-20 alkoxy group; R 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 And R ³⁸ are each independently a hydrogen atom or a C _1-20 alkyl group, or R ³⁷ and R ³⁸ together form an optionally substituted phenyl group, and R ³⁵ and R ³⁶ are Independently a hydrogen atom or a C _1-20 alkyl group; R ³⁹ , R ⁴⁰ , R ⁴¹ , and R ⁴² are independently a hydrogen atom or a C _1-20 alkyl group, and R ³⁹ and R ⁴⁰ are Both form an optionally substituted phenyl group, R ⁴¹ and R ⁴² are each independently a hydrogen atom or a C _1-20 alkyl group, R ⁴⁰ and R ⁴¹ both have a substituent also form a phenyl group ^optionally, a hydrogen atom or a _{C 1-20} alkyl group independently ^{R 39} and ^{R 42} each other, or ^{R 41} and ^{R 42} is optionally both substituted phenylene Form a ^group, preferably represent hydrogen atom or a _{C 1-20} alkyl group independently ^{R 39} and ^{R 42} are each ^{other, R 23, R 24, R} 25, and ^{R 26} is a halogen atom or an unsubstituted both R ²⁷ and R ²⁸ are both an unsubstituted phenyl group or a phenyl group substituted with a linear or branched C _1-20 alkoxy group; R ³⁵ , R ³⁶ , R ³⁷ And R ³⁸ is independently a hydrogen atom or a C _1-20 alkyl group, R ³⁵ and R ³⁶ together form a phenyl group substituted with an unsubstituted phenyl group or a C _1-10 alkyl group, R ³⁷ and ^{R 38} is a hydrogen atom or a _{C 1-20} alkyl group independently from each ^other, the ^{R 36} and ^{R 37} are both unsubstituted phenyl group or a _{C 1-10} alkyl In forming a substituted phenyl ^{group, R 35} and ^{R 38} are each independently of the other hydrogen or _{C 1-20} alkyl group, or ^{R 37} and ^{R 38} in both unsubstituted phenyl group or a _{C 1-10} Forming a phenyl group substituted with an alkyl group, wherein R ³⁵ and R ³⁶ are each independently a hydrogen atom or a C _1-20 alkyl group; R ³⁹ , R ⁴⁰ , R ⁴¹ , and R ⁴² are independently A hydrogen atom or a C _1-20 alkyl group, R ³⁹ and R ⁴⁰ together form an unsubstituted phenyl group or a phenyl group substituted with a C _1-10 alkyl group, and R ⁴¹ and R ⁴² are independent of each other to a hydrogen atom or a _{C 1-20} alkyl ^group, a phenyl group ^{which R 40} and ^{R 41} are both substituted with an unsubstituted phenyl group or a _{C 1-10} alkyl group ^Formed, a hydrogen atom or a _{C 1-20} alkyl group independently ^{R 39} and ^{R 42} each other, or ^{R 41} and ^{R 42} are both substituted with an unsubstituted phenyl group or a _{C 1-10} alkyl group phenyl A compound in which a group is formed and R ³⁹ and R ⁴² are each independently a hydrogen atom or a C _1-20 alkyl group is more preferable because of high luminous efficiency and excellent compatibility with a resin.

As the compound represented by the above (I ₂ -3), R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are all halogen atoms, unsubstituted phenyl groups, C _1-10 alkyl groups or C _1-10. A phenyl group substituted with an alkoxy group; R ²⁷ and R ²⁸ are both a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C _1-20 alkyl group or a C _1-20 alkoxy group; 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. also form a phenyl group optionally, R ³⁸ 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 radical, R ⁶ is hydrogen atom or a _{C 1-20} alkyl ^group; R ^{40, R 41,} and ^{R 42} are each independently of the other hydrogen or _{C 1-20} alkyl ^group, the ^{R 40} and ^{R 41} are both substituents An _optionally substituted phenyl group, R ⁴² is a hydrogen atom or a C _1-20 alkyl group, or R ⁴¹ and R ⁴² together form an optionally substituted phenyl group, A compound in which R ⁴⁰ is a hydrogen atom or a C _1-20 alkyl group is preferred, and R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are both halogen atoms or unsubstituted phenyl groups; and R ²⁷ and R ²⁸ are both unsubstituted phenyl group, or a linear or branched _{C 1-20} phenyl group substituted by alkoxy group; be ^{X 1} and ^{X 2} are both nitrogen ^atoms; R ^{36, R 37,} Fine ^{R 38} are mutually independently a hydrogen atom or a _{C 1-20} alkyl ^group, form a phenyl group substituted with ^{R 36} and ^{R 37} are both unsubstituted phenyl group or a _{C 1-10} alkyl radical, R ³⁸ is a hydrogen atom or a C _1-20 alkyl group, or R ³⁷ and R ³⁸ together form an unsubstituted phenyl group or a phenyl group substituted with a C _1-10 alkyl group, and R ³⁶ is a hydrogen atom or A C _1-20 alkyl group; R ⁴⁰ , R ⁴¹ , and R ⁴² are each independently a hydrogen atom or a C _1-20 alkyl group, R ⁴⁰ and R ⁴¹ are both unsubstituted phenyl groups or C ₁ a phenyl group substituted at _-10 alkyl group to ^{form, R 42} is a hydrogen atom or a _{C 1-20} alkyl group, or ^{R 41} and ^{R 42} are both unsubstituted Form a phenyl group substituted with Eniru group or C _1-10 alkyl group, the compound R ⁴⁰ is a hydrogen atom or a C _1-20 alkyl group, the emission efficiency is high, since the compatibility with the resin is excellent, and more preferable.

As the compound represented by the above (I ₂ -4), R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are all halogen atoms, unsubstituted phenyl groups, C _1-10 alkyl groups, or C _1-10. A phenyl group substituted with an alkoxy group; R ²⁷ and R ²⁸ are both a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C _1-20 alkyl group or a C _1-20 alkoxy group; X ¹ and X ² are both nitrogen atoms; R ³⁵ , R ³⁶ , and R ³⁷ are each independently a hydrogen atom or a C _1-20 alkyl group, R ³⁵ and R ³⁶ both have a substituent. also form a phenyl group optionally, R ³⁷ is a hydrogen atom or a C _1-20 alkyl group, or R ³⁶ and R ³⁷ together form a phenyl group which may have a substituent radical, R ⁵ is hydrogen atom or a _{C 1-20} alkyl ^group; R ^{39, R 40,} and ^{R 41} are each independently of the other hydrogen or _{C 1-20} alkyl ^group, the ^{R 39} and ^{R 40} are both substituents An _optionally substituted phenyl group, and R ⁴¹ is a hydrogen atom or a C _1-20 alkyl group, or R ⁴⁰ and R ⁴¹ together form an optionally substituted phenyl group, A compound in which R ³⁹ is a hydrogen atom or a C _1-20 alkyl group is preferred, and R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are both halogen atoms or unsubstituted phenyl groups; and R ²⁷ and R ²⁸ are both unsubstituted phenyl group, or a linear or branched _{C 1-20} phenyl group substituted by alkoxy group; be ^{X 1} and ^{X 2} are both nitrogen ^atoms; R ^{35, R 36,} Fine ^{R 37} independently of one another represent a hydrogen atom or a _{C 1-20} alkyl ^group, to form a phenyl group substituted by ^{R 35} and ^{R 36} are both unsubstituted phenyl group or a _{C 1-10} alkyl radical, R ³⁷ is a hydrogen atom or a C _1-20 alkyl group, or R ³⁶ and R ³⁷ together form an unsubstituted phenyl group or a phenyl group substituted with a C _1-10 alkyl group, and R ³⁵ is a hydrogen atom or A C _1-20 alkyl group; R ³⁹ , R ⁴⁰ , and R ⁴¹ are each independently a hydrogen atom or a C _1-20 alkyl group, and R ³⁹ and R ⁴⁰ are both an unsubstituted phenyl group or C _{1 -10} to form a phenyl group substituted with an alkyl ^{group, R 41} is a hydrogen atom or a _{C 1-20} alkyl group, or ^{R 40} and ^{R 41} are both unsubstituted Form a phenyl group substituted with Eniru group or C _1-10 alkyl group, the compound R ³⁹ is a hydrogen atom or a C _1-20 alkyl group, the emission efficiency is high, since the compatibility with the resin is excellent, and more preferable.

Examples of the compounds represented by _{^{(I 2 -5), R 23}} , R 24, R 25, and ^{R 26} are both halogen atoms, an unsubstituted phenyl group, or a _{C 1-10} alkyl group or _{C 1-10} A phenyl group substituted with an alkoxy group; R ²⁷ and R ²⁸ are both a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C _1-20 alkyl group or a C _1-20 alkoxy group; X ¹ and X ² are both nitrogen atoms; R ³⁵ , R ³⁶ , and R ³⁸ are each independently a hydrogen atom or a C _1-20 alkyl group, or R ³⁵ and R ³⁶ both have a substituent. also to form a phenyl group ^{optionally, R 38} is hydrogen atom or a _{C 1-20} alkyl ^{group; R 39,} R ^40, and ^{R 42} are each independently of the other hydrogen or _{C 1-2} An alkyl group, or ^{R 39} and ^{R 40} together form a phenyl group which may have a ^substituent, the compound ^{R 42} is a hydrogen atom or a _{C 1-20} alkyl group is ^{preferable, R} 23, R ²⁴ , R ²⁵ , and R ²⁶ are both halogen atoms or unsubstituted phenyl groups; R ²⁷ and R ²⁸ are both unsubstituted phenyl groups, or linear or branched C _1-20 alkoxy groups. A substituted phenyl 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 together forms an unsubstituted phenyl group or a phenyl group substituted with a C _1-10 alkyl group, and R ³⁸ is a hydrogen atom or a C _1-20 alkyl group; R ³⁹ , R ⁴⁰ and R ⁴² are each independently a hydrogen atom or a C _1-20 alkyl group, or R ³⁹ and R ⁴⁰ together form a phenyl group substituted with an unsubstituted phenyl group or a C _1-10 alkyl group. A compound in which R ⁴² is a hydrogen atom or a C _1-20 alkyl group is more preferable because of high luminous efficiency and excellent compatibility with a resin.

Examples of the compounds represented by _{^{(I 2 -6), R 23}} , R 24, R 25, and ^{R 26} are both halogen atoms, an unsubstituted phenyl group, or a _{C 1-10} alkyl group or _{C 1-10} A phenyl group substituted with an alkoxy group; R ²⁷ and R ²⁸ are both a hydrogen atom, an unsubstituted phenyl group, or a phenyl group substituted with a C _1-20 alkyl group or a C _1-20 alkoxy group; X ¹ and X ² are both nitrogen atoms; R ³⁵ , R 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. also to form a phenyl group ^{optionally, R 35} is hydrogen atom or a _{C 1-20} alkyl ^{group; R 39,} R ^41, and ^{R 42} are each independently of the other hydrogen or _{C 1-2} An alkyl group, or ^{R 41} and ^{R 42} together form a phenyl group which may have a ^substituent, the compound ^{R 39} is a hydrogen atom or a _{C 1-20} alkyl group is ^{preferable, R} 23, R ²⁴ , R ²⁵ , and R ²⁶ are both halogen atoms or unsubstituted phenyl groups; R ²⁷ and R ²⁸ are both unsubstituted phenyl groups, or linear or branched C _1-20 alkoxy groups. A substituted phenyl 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 together forms 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 ⁴¹ and R ⁴² are each independently a hydrogen atom or a C _1-20 alkyl group, or R ⁴¹ and R ⁴² together form a phenyl group 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 of high luminous efficiency and excellent compatibility with a resin.

Examples of the compound represented by any one of (I ₁ -1) to (I ₁ -6) include compounds represented by any one of the following general formulas (I ₁ -7) to (I ₁ -9). Preferably, the compound represented by any one of (I ₂ -1) to (I ₂ -6) is represented by any one of the following general formulas (I ₂ -7) to (I ₂ -9). Compounds are preferred.

Formula _(I 1 -7) and in _(I 2 ^{-7), Y 23} and ^{Y 24} independently of one another, represent a carbon atom or a nitrogen atom. In the general formula _(I 1 -7) and _(I 2 ^{-7), Y 23} and ^{Y 24} is preferably an atom of the same kind.

In the general formula _(I 1 -8) and _(I 2 ^{-8), Y 13} and ^{Y 14} independently of one another represent an oxygen atom or a sulfur atom. In the general formula _(I 1 -8) and _(I 2 ^-8), it is preferable ^{Y 13} and ^{Y 14} are atoms like.

Formula _(I 1 -9) and _(I 2 -9) ^{in, Y 25} and ^{Y 26} independently of one another, represent a carbon atom or a nitrogen atom. In formula _(I 1 -9) and _(I 2 ^-9), it is preferable ^{Y 25} and ^{Y 26} are atoms like.

In the general formula _{(I 1 -7) ~ (I} 1 -9), R 47 and ^{R 48} independently of one another, represent a hydrogen atom or an electron-withdrawing group, trifluoromethyl since the fluorescence intensity is high It is preferably a group, a cyano group, a nitro group, a sulfonyl group, or a phenyl group, and particularly preferably a trifluoromethyl group or a cyano group. In the general formula _{(I 1 -7) ~ (I} 1 -9), it is preferred that ^{R 47} and ^{R 48} is a functional group of the same type.

Formula _(I 1 -7) in _{~ (I} 1 -9) and _{(I 2 -7) ~ (I} 2 -9), R 43, R 44, R 45, and ^{R 46} is a halogen atom, or a substituted An aryl group which may have a group is represented. As the aryl group, those exemplified as “any group that does not inhibit the fluorescence of the compound” in R ^h and R ⁱ and R ^j and R ^k can be used. In addition, the substituent that the aryl group may have is any “any group that does not inhibit the fluorescence of the compound”, and examples thereof include a C _1-6 alkyl group, a C _1-6 alkoxy group, and an aryl group. Group, heteroaryl group, and the like. Formula _(I 1 -7) in _{~ (I} 1 -9) and _{(I 2 -7) ~ (I} 2 -9), R 43 ~R 46 is may be a different group respectively, all the same type The group is preferably. The general formula _{(I 1 -7) ~ (I} 1 -9) and _(I 2 -7) _~ compound represented by any one of ^{_{(I 2 -9), R 43}} ~R 46 is, all the same type Those that are halogen atoms or are all phenyl groups that may have the same type of substituent are preferred, those that are all fluorine atoms or unsubstituted phenyl groups are more preferred, and those that are all fluorine atoms are particularly preferred. .

In the general formula _{(I 1 -7) ~ (I} 1 -9) and _{(I 2 -7) ~ (I} 2 -9), P 15 ~P 16 , independently of one another, a halogen _{atom, C 1-20} An alkyl group, a C _1-20 alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group is represented. As the C _1-20 alkyl group, C _1-20 alkoxy group, monoalkylamino group, or dialkylamino group in P ^{15 to} P ^16, an aromatic ring formed by R ^h and R ⁱ , and R ^j , respectively, and it may be the same as those listed with a substituent an aromatic ring having the R ^k are formed. The P ¹⁵ ~P _{^16, C 1-20 alkyl, C 1-20} alkoxy group, (unsubstituted) phenyl group, p- methoxyphenyl group, p- ethoxyphenyl group, p- dimethylaminophenyl group, dimethoxy It is preferably a phenyl group, a thienyl group, or a furanyl group. From the viewpoint of safety to living bodies, a C _1-20 alkyl group, a C _1-20 alkoxy group, a phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group , A dimethoxyphenyl group, a thienyl group, or a furanyl group, and these substituents may further have a substituent. However, the substituents other than these substituents are not limited to these substituents because the safety can be improved by further introducing appropriate substituents.

In the general formula _{(I 1 -7) ~ (I} 1 -9) and _{(I 2 -7) ~ (I} 2 -9), n15~n16 independently of one another, an integer of 0 to 3. When a plurality of P ¹⁵ are present in one molecule (that is, when n15 is 2 or 3), all of the plurality of P ¹⁵ may be the same or different functional groups. Also good. The same is true for P ^16.

Formula _{(I 1 -7) ~ (I} 1 -9) and _{(I 2 -7) ~ (I} 2 -9) ^in, A 15 ^{to A 16} are independently of one another, a hydrogen atom, a halogen atom, C _1-20 alkyl group, _C1-20 alkoxy group, an amino group, a monoalkylamino group, and the phenyl group which may have 1-3 substituents selected from the group which consists of a dialkylamino group are represented. . As 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, R ^h and R ⁱ form, respectively. The same thing as what was mentioned by the aromatic ring and the substituent which the aromatic ring which ^Rj and ^Rk form has is mentioned. A ^{15 to} A ¹⁶ are preferably an unsubstituted phenyl group, a phenyl group having 1 or 2 C _1-20 alkoxy groups as a substituent, an unsubstituted phenyl group, or one C _1-20 alkoxy. A phenyl group having a group as a substituent is more preferable, and an unsubstituted phenyl group or a phenyl group having one C _1-10 alkoxy group as a substituent is more preferable. As the general formula _(I 1 -7) a compound represented by ^like, it is preferable either A 15 ^{to A 16} is a functional group of the same type.

Wherein _{(I 1} -1) - _{(I 1} -6), as the (I 2 -1) _- compound represented by any one of _(I 2 -6), the following general formula (1-1) to (1 -12) and a compound represented by any one of (2-1) to (2-12). In the general formulas (1-7) to (1-12) and (2-7) to (2-12), Ph means an unsubstituted phenyl group. Wherein _{(I 1 -1) ~ (I} 1 -6), as the (I 2 -1) _~ compound represented by any one of _(I 2 -6), in particular, the general formula (1-4), ( 1-5), (1-7), (1-8), (2-4), (2-5), (2-7), and the compounds represented by (2-8) are preferred. The compounds represented by (1-4), (1-5), (1-7) and (1-8) are more preferred.

In general formulas (1-1) to (1-12) and (2-1) to (2-12), P ^{5 to} P ⁸ are each independently a halogen atom, a C _1-20 alkyl group, C _{1-20 represents an} alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group. As the C _1-20 alkyl group, C _1-20 alkoxy group, monoalkylamino group, or dialkylamino group in P ^{5 to} P ^8, an aromatic ring formed by R ^h and R ⁱ , and R ^j , respectively, and it may be the same as those listed with a substituent an aromatic ring having the R ^k are formed. P ^{5 to} P ⁸ include C _1-20 alkyl group, C _1-20 alkoxy group, (unsubstituted) phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-dimethylaminophenyl group, dimethoxy. It is preferably a phenyl group, a thienyl group, or a furanyl group. From the viewpoint of safety to living bodies, a C _1-20 alkyl group, a C _1-20 alkoxy group, a phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group , A dimethoxyphenyl group, a thienyl group, or a furanyl group, 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. More preferably, it is a group, and these substituents may further have a substituent. However, the substituents other than these substituents are not limited to these substituents because the safety can be improved by further introducing appropriate substituents.

In general formulas (1-1) to (1-12) and (2-1) to (2-12), n5 to n8 each independently represent an integer of 0 to 3. When a plurality of P ⁵ are present in one molecule (that is, when n5 is 2 or 3), all of the plurality of P ⁵ may be the same or different functional groups. Also good. The same applies to P ^{6 to} P ⁸ .

As the compounds represented by the general formulas (1-1) to (1-12) and (2-1) to (2-12), P ^{5 to} P ⁸ are each independently a C _1-20 alkyl group or A C _1-20 alkoxy group in which n5 to n8 are independently 0 to 2 is preferred, P ⁵ and P ⁶ are independently C _1-20 alkyl groups, and n5 and n6 are independently 0-2, a _{C 1-20} alkoxy group independently ^{P 7} and ^{P 8} each other, more preferably those n7 and n8 is 0-1 independently of one another, ^{P 5} and P ⁶ is independently a C _1-20 alkyl group, n 5 and n 6 are independently 1 to 2, P ⁷ and P ⁸ are independently C _1-20 alkoxy groups, n ⁷ and More preferably, n8 is 1. The alkyl group may be linear, branched, or cyclic (aliphatic ring group). Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, heptyl group, octyl group, and nonyl group. Decyl group, undecyl group, dodecyl group and the like. Among these, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group are preferable, an n-butyl group, an isobutyl group, and a t-butyl group are more preferable, and a t-butyl group is preferable. Particularly preferred.
The alkoxy group is preferably a linear or branched C _1-10 alkoxy group, more preferably a linear or branched C _4-10 alkoxy group, more preferably a linear Or a branched octyloxy group is particularly preferred.

  Specific examples of the compounds represented by the general formulas (1-1) to (1-12) include compounds represented by the following formulas (1-1-1) to (1-12-1). Can be mentioned. “Λ” is the peak wavelength of the absorption spectrum of each compound, and “Em” is the peak wavelength of the fluorescence spectrum.

<Resin component>
The resin component contained in the resin composition according to the present invention is not particularly limited. It can be appropriately selected from known resin compositions and improvements thereof. For example, the resin component may be a thermoplastic resin or a thermosetting resin. When used in a molded article, the thermosetting resin may be cured during melt-kneading, so the resin component contained in the resin composition according to the present invention is preferably a thermoplastic resin. As a resin component used in this invention, only 1 type may be used and 2 or more types may be mixed and used. When two or more types are mixed, it is preferable to use a combination of highly compatible resins.

  Examples of the resin component used in the present invention include urethane resins such as polyurethane (PU) and thermoplastic polyurethane (TPU); polycarbonate (PC); polyvinyl chloride (PVC), vinyl chloride-vinyl acetate copolymer resin, and the like. Polyvinyl chloride resins; acrylic resins such as polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate (PMMA), polyethyl methacrylate; polyethylene terephthalate (PET), polybutylene terephthalate -Polyester resins such as polytrimethylene terephthalate, polyethylene naphthalate and polybutylene naphthalate; Polyamide resins such as nylon (registered trademark); Polystyrene (PS), imide-modified polystyrene, acrylonitrile・ Butadiene styrene (AB ) Resin, imide-modified ABS resin, styrene / acrylonitrile copolymer (SAN) resin, polystyrene resin such as acrylonitrile / ethylene-propylene-diene / styrene (AES) resin, polyethylene (PE) resin, polypropylene (PP) resin, cyclo Olefin resins such as olefin resins; Cellulosic resins such as nitrocellulose and cellulose acetate; Silicone resins; Thermoplastic resins such as fluorine resins; Bisphenol A type epoxy resins, Bisphenol F type epoxy resins, Isocyanurate type epoxy resins, Examples thereof include epoxy resins such as hydantoin epoxy resins; amino resins such as melamine resins and urea resins; phenol resins; thermosetting resins such as unsaturated polyester resins.

  As the resin component contained in the resin composition according to the present invention, the dispersibility of the near-infrared fluorescent dye according to the present invention is high, so that the fluororesin, silicone resin, urethane resin, olefin resin, and vinyl chloride are used. Resin, polyester resin, polystyrene resin, polycarbonate resin, polyamide resin or acrylic resin are preferable, and urethane resin, olefin resin, polystyrene resin, polyester resin, and vinyl chloride resin are more preferable. In particular, when the resin composition according to the present invention is used as a medical material, PTFE, Teflon (which is low in solubility in bodily fluids such as blood and difficult to elute under the use environment and biocompatibility are considered. (Registered trademark), silicone, PU, TPU, PP, PE, PC, PET, PS, polyamide, PVC are preferable, TPU, PU, PP, PE, PET, PS are more preferable, PE, PP are more preferable, and PP are Particularly preferred.

  In the case where the resin composition according to the present invention is a thermoplastic resin composition, the resin component may be a thermoplastic resin as a whole resin component, and may contain a small amount of a non-thermoplastic resin. Similarly, when the resin composition according to the present invention is a thermosetting resin composition, the resin component may be a thermosetting resin as a whole resin component and contains a small amount of a non-thermosetting resin. Also good.

<Resin composition>
The resin composition according to the present invention can be produced by mixing and dispersing the near-infrared fluorescent dye according to the present invention in a resin component. The near-infrared fluorescent dye according to the present invention contained in the resin composition according to the present invention may be only one type or may contain two or more types.

  The content of the near-infrared fluorescent dye according to the present invention in the resin composition is not particularly limited as long as the near-infrared fluorescent dye can be mixed with the resin, but the fluorescence intensity and its detection sensitivity are not limited. Is preferably 0.0001% by mass or more, from the viewpoint of detection sensitivity due to concentration quenching or fluorescence reabsorption, preferably 1% by mass or less, more preferably in the range of 0.0005 to 1% by mass, and 0.001. The range of -0.5 mass% is further more preferable, the range of 0.005-0.5 mass% is especially preferable, and 0.01-0.5 mass% is the most preferable. In addition, the near-infrared fluorescent dye according to the present invention has a high molar extinction coefficient and a high quantum yield even in the resin, so even if the dye concentration in the resin is relatively low, the light emission can be detected by a camera. Etc. are sufficiently visible. Low pigment concentration means low possibility of elution, low possibility of bleeding out from a molded product processed from a resin composition, and processing of a molded product requiring transparency. Desirable from.

  The method of mixing and dispersing the near-infrared fluorescent dye according to the present invention is not particularly limited, and any known method may be used, and an additive may be used in combination. The resin composition according to the present invention can be obtained by adding the near-infrared fluorescent dye according to the present invention to the resin composition and melt-kneading the resin composition. Thus, a resin composition in which the near-infrared fluorescent dye according to the present invention is uniformly dispersed in the resin is obtained.

  When the fluorescent material is dispersed in a thermoplastic resin or the like by melt-kneading the resin and the fluorescent material, even if melt-kneading is performed at a temperature lower than the decomposition point of the fluorescent material, May not emit fluorescence due to causes such as poor dispersion or decomposition of the fluorescent material. Therefore, it is difficult to predict whether or not the fluorescent material can be dispersed in the thermoplastic resin or the like from the thermophysical properties of the fluorescent material.

  In contrast, the near-infrared fluorescent dye according to the present invention is hardly decomposed even when melt-kneaded. For this reason, it is possible to mix and disperse | distribute uniformly to various resin components, and can emit fluorescence with high quantum yield also in resin.

The reason why light can be emitted with high quantum yield in the resin is not clear, but can be presumed as follows. When the pigment is dispersed by a method such as melt-kneading, if the aggregation or the like occurs, it is considered that the quantum yield of fluorescence decreases due to concentration quenching. Therefore, in order for the dye to emit fluorescence efficiently, it is desirable that the dye is highly compatible with the resin and can be uniformly dispersed. One index of whether the compatibility is high is the SP value. If the difference between the SP value of the dye and the SP value of the resin is small, the compatibility is high and the resin can be dispersed uniformly. On the other hand, even when the SP value is different, it can be explained by other physical property parameters. For example, the compatibility with the resin can be explained from calculated values such as solubility, distribution coefficient, relative dielectric constant, polarizability, and the like of dyes or measured values.
In addition, the compatibility between the resin and the fluorescent dye may vary depending on the crystallinity of the resin.

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

  In order to increase the compatibility with the resin, it is necessary to suppress aggregation of the dye molecules. In the case of a fluorescent dye, an aromatic ring or a heterocyclic ring is introduced into the molecule in order to ensure the extension of the conjugated system and the flatness. However, by introducing these rings, the flatness is high, stacking tends to occur, and aggregation tends to occur. Since the near-infrared fluorescent dye according to the present invention has a dye skeleton composed of a wide conjugate plane centered on a boron atom, it tends to aggregate, but an electron donating group or an electron withdrawing substituent is introduced. Thus, it is presumed that the aggregation of the dye is suppressed by polarizing and introducing a bulky functional group, and compatibility with various resins can be realized.

  The partition coefficient and SP value, which are indicators of compatibility, can be estimated as the water / octanol partition coefficient and the Hildebrand SP value from the “Hansen solubility parameter” obtained by calculation from commercially available software.

  The near-infrared fluorescent dye according to the present invention can be melt-kneaded and uniformly dispersed and mixed with a resin component such as PP, and the kneaded resin composition or a molded body processed from the resin composition Can emit near-infrared fluorescence stably with high emission quantum yield. Although the near-infrared fluorescent dye according to the present invention is different from many other organic near-infrared fluorescent dyes, it does not decompose even when melt-kneaded with the resin composition, and the reason for exhibiting high emission characteristics is not clear. Since the near-infrared fluorescent dye according to the invention has a robust dye skeleton consisting of a wide conjugate plane, it is considered that π electrons are highly delocalized and the entire molecule is stabilized. It is also considered that the pyrrolopyrrole moiety, which is considered as an electron acceptor moiety in the molecule, is highly aromatized and stabilized via two boron atoms. Furthermore, when a substituent such as an aromatic ring is introduced into the pyrrolopyrrole moiety, it is presumed that the boron-nitrogen bond moiety is sterically protected by the steric hindrance. On the other hand, if an appropriate substituent is introduced at an appropriate position in the molecule, it is excellent in compatibility with various resins and can be uniformly dispersed. From this point, it is presumed that the near-infrared fluorescent dye according to the present invention can exhibit high light emission characteristics even when melt-kneaded with a resin. In addition, it is the knowledge which the present inventors discovered for the first time that a DPP type | system | group boron complex does not impair a fluorescence characteristic by processing with high load like melt-kneading.

  When using a general luminescence detector equipped with a filter for noise reduction by excitation light, if the difference (Stokes shift) between the maximum absorption wavelength and the maximum fluorescence wavelength of the resin composition according to the present invention is small, fluorescence Is cut by a filter, so it is difficult to detect with high sensitivity. Therefore, in the resin composition according to the present invention, the difference between the maximum absorption wavelength and the maximum fluorescence wavelength is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 10 nm or more. The larger the Stokes shift, the more sensitive it is to detect fluorescence emitted from the molded body even when using a general detector equipped with a filter for noise reduction by excitation light. is there.

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

  The resin composition according to the present invention does not change in color when viewed with excitation light in the near-infrared region, emits invisible near-infrared fluorescence, and can be detected by a detector. Therefore, it is sufficient that the maximum absorption wavelength is 600 nm or more for the excitation light in the near infrared region. However, from the viewpoint of absorption efficiency, the maximum absorption wavelength is preferably close to the wavelength of the excitation light, and more than 650 nm is more preferable. It is preferably 680 nm or more. Furthermore, when used as a medical device such as an implant, 700 nm or more is preferable.

  The resin composition according to the present invention and the molded product obtained from the composition have a maximum fluorescence wavelength of 650 nm or more. If the color of the object to be irradiated does not change and the detection sensitivity is taken into consideration, there is no practical problem if the maximum fluorescence wavelength is 650 nm or more, but it is preferably 700 nm or more, more preferably 720 nm or more. preferable. In the case of having a plurality of fluorescence peaks, even if the wavelength of the maximum fluorescence peak is 720 nm or less, it is sufficient if there is a fluorescence peak having sufficient detection sensitivity at 740 nm or more. In that case, the intensity of the fluorescence peak (second peak) on the long wavelength side is preferably 5% or more and more preferably 10% or more with respect to the intensity of the maximum fluorescence wavelength.

  The resin composition according to the present invention and the molded product obtained from the composition have strong absorption in the range of 650 nm to 1500 nm, and preferably emit strong fluorescence in this range. Light of 650 nm or more is not easily affected by hemoglobin, and light of 1500 nm or less is hardly affected by water. In other words, light in the range of 650 nm to 1500 nm has high skin permeability and is not easily affected by contaminants in the living body. Therefore, the wavelength of light used for visualizing medical implants implanted under the skin or the like. It is suitable as a region. When the maximum absorption wavelength and the maximum fluorescence wavelength are in the range of 650 nm to 1500 nm, the resin composition according to the present invention and the molded product obtained from the composition are suitable for detection by light in the range of 650 nm to 1500 nm, It is suitable as a medical device used in vivo.

  The resin composition according to the present invention may contain components other than the resin component and the near-infrared fluorescent dye as long as the effects of the present invention are not impaired. Examples of the other components include an ultraviolet absorber, a heat stabilizer, a light stabilizer, an antioxidant, a flame retardant, a flame retardant aid, a crystallization accelerator, a plasticizer, an antistatic agent, a colorant, and a release agent. Is mentioned.

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

  In the production of the molded body, the molded body may be formed only from the resin composition according to the present invention, or the resin composition according to the present invention and other resin compositions may be used as raw materials. For example, the entire molded body may be molded with the resin composition according to the present invention, or only a part of the molded body may be molded with the resin composition according to the present invention. The resin composition according to the present invention is preferably used as a raw material constituting the surface portion of the molded body. For example, when molding a catheter, only the distal end portion of the catheter is molded with the resin composition according to the present invention, and the remaining portion is molded with a resin composition containing no near-infrared fluorescent dye. Only a catheter that emits near-infrared fluorescence can be produced. Moreover, the molded object which emits near-infrared fluorescence in stripe form can be manufactured by alternately laminating | stacking and shape | molding the resin composition which concerns on this invention, and the resin composition which does not contain a near-infrared fluorescent pigment | dye. In addition, surface coating for improving the visibility of the molded body may be performed.

  The fluorescence detection can be carried out by a conventional method using a commercially available fluorescence detection device or the like. As excitation light used for fluorescence detection, an arbitrary light source can be used, and in addition to a near-infrared lamp having a long wavelength width, a laser, LED, or the like having a narrow wavelength width can be used.

  The molded product obtained from the resin composition containing the near-infrared fluorescent dye according to the present invention does not change color even when irradiated with light in the near-infrared region, and can be detected with higher sensitivity than before. In order to emit external fluorescence, the molded body is particularly suitable for a medical device that is inserted into or placed in the body of a patient.

  In the case of fluorescence detection of a molded product obtained from the resin composition containing the near-infrared fluorescent dye according to the present invention, it is preferable to irradiate excitation light in the near-infrared region, but the color of the irradiated object is When it may be somewhat reddish, it is not always necessary to use excitation light in the near infrared region. For example, when an excitation light is irradiated to detect fluorescence in a medical device in the body, it is necessary to use the excitation light in a wavelength region with high permeability to a living body such as skin. Excitation light having a high transmittance of 650 nm or more may be used.

  Examples of the medical device include a stent, a coil embolus, a catheter tube, an injection needle, an indwelling needle, a port, a shunt tube, a drain tube, and an implant.

  EXAMPLES Hereinafter, although an Example and a comparative example etc. are given and this invention is further explained in full detail, this invention is not limited to these Examples.

[Production Example 1] Synthesis of Near-Infrared Fluorescent Dye A Near-Infrared Fluorescent Dye A is Organic Letters, 2012, Vol. 4, pages 2670-2673 and Chestry A European Journal, 2009, Vol. 15, 4857- With reference to page 4864, the procedure was as follows.

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

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

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

  Next, potassium hydroxide (75.4 g, 1340 mmol) and ethylene glycol (175 mL) were placed in a 1 L four-necked flask under water cooling. The system was placed in an argon atmosphere, compound (a-3) (7.8 g, 37.8 mmol) was added, and after bubbling with argon to remove oxygen in the system, the reaction was performed at 110 ° C. for 18 hours. I let you. The reaction solution was water-cooled to 40 ° C. or less, and 2 mol / L hydrochloric acid previously bubbled with argon was dropped into the system for neutralization (around pH 7). The precipitated white solid was filtered off, washed with water, and dried under reduced pressure. The white solid was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain a white solid of 4-tert-butyl-2-mercaptoaniline (a-4) (yield: 2.39 g, yield). : 35%).

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

  Subsequently, compound (a-2) (1.91 g, 3.5 mmol), compound (a-5) (1.77 g, 7.68 mmol), and 68 mL of toluene were added to a 200 mL three-necked flask under an argon stream, and heated to reflux. did. Under heating to reflux, phosphorus oxychloride (2.56 mL, 27.4 mmol) was added dropwise with a syringe, and the mixture was further heated to reflux for 2 hours. After completion of the reaction, 40 mL of dichloromethane and 40 mL of saturated aqueous sodium hydrogen carbonate solution were added while cooling with ice, and extracted with dichloromethane. The organic layer was treated with anhydrous magnesium sulfate, the magnesium sulfate was filtered off, the solvent was removed under reduced pressure, and the residue was roughly removed by silica gel column chromatography (eluent: hexane / ethyl acetate). The residue obtained by distilling off the solvent was purified again by silica gel column chromatography (eluent: hexane / dichloromethane) to obtain a green solid of the precursor (a-6) (yield: 1.56 g, yield). : 46%).

Finally, the precursor (a-6) (1.52 g, 1.57 mmol), toluene 45 mL, triethylamine (4.35 mL, 31.4 mmol), boron trifluoride diethyl ether complex in a 200 mL three-neck flask under an argon stream (7.88 mL, 62.7 mmol) was added and heated to reflux for 1 hour. The reaction solution was ice-cooled, and the precipitated solid was collected by filtration, washed with water, saturated aqueous sodium hydrogen carbonate solution, 50% aqueous methanol solution and methanol, and dried under reduced pressure.
The obtained residue was dissolved in toluene, methanol was added and precipitated to obtain a dark green solid of near-infrared fluorescent dye A (yield: 1.25 g, yield: 75%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ 7.90 ppm (d, 2H), 7.72-7.69 (m, 6H), 7.51 (dd, 2H), 7.08 (d, 2H) 4.07 (t, 4H), 1.84 (m, 4H), 1.52 (s, 18H), 1.35-1.32 (m, 24H), 0.92 (t, 6H).

[Production Example 2] Synthesis of Near-Infrared Fluorescent Dye B Near-Infrared Fluorescent Dye B is Organic Letters, 2012, Vol. 4, pages 2670-2673 and Chestry A European Journal, 2009, Vol. 15, 4857- With reference to page 4864, the procedure was as follows.

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

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

  Furthermore, compound (b-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, Reacted for hours. The reaction mixture was cooled and extracted with water (200 mL) / ethyl acetate (300 mL), and the resulting ethyl acetate layer was further washed with water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized with petroleum ether to obtain yellow crystals of 2- (6-tert-butylquinolin-2-yl) acetonitrile (b-3) (yield 1. 9 g, yield 42.4%).

  Subsequently, the compound (a-2) (2.18 g, 4.0 mmol) obtained in Production Example 1 and the compound (b-3) (1.9 g, 8.5 mmol) were placed in a 200 mL three-necked flask under an argon stream. ), Dehydrated toluene (68 mL) was added, and the mixture was heated to reflux. Under heating under reflux, phosphorus oxychloride (2.62 mL, 28 mmol) was added dropwise with a syringe, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, dichloromethane (40 mL) and saturated aqueous sodium hydrogen carbonate solution (40 mL) were added with ice cooling, and the mixture was extracted with dichloromethane. The organic layer was treated with anhydrous magnesium sulfate, the magnesium sulfate was filtered off, the solvent was removed under reduced pressure, and the residue was roughly removed by silica gel column chromatography (eluent: hexane / ethyl acetate). The residue obtained by distilling off the solvent was purified again by silica gel column chromatography (eluent: hexane / dichloromethane) to obtain a green solid of the precursor (b-4) (yield: 1.84 g, yield). : 48%).

  Finally, in a 200 mL three-necked flask under an argon stream, precursor (b-4) (1.72 g, 1.8 mmol), toluene (45 mL), triethylamine (4.35 mL, 31.4 mmol), boron trifluoride Diethyl ether complex (7.88 mL, 62.7 mmol) was added and heated to reflux for 1 hour. The reaction solution was ice-cooled, and the precipitated solid was filtered off. The solid was washed with water, a saturated aqueous sodium hydrogen carbonate solution, a 50% aqueous methanol solution and methanol, and dried under reduced pressure. The obtained residue was dissolved in toluene, and methanol was added for precipitation to obtain a green solid of near-infrared fluorescent dye B (yield: 1.10 g, yield: 58%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ = 8.42 (m, 2H), 8.14 (d, 2H), 7.74 (dd, 2H), 7.72 (d, 4H), 7 .66 (m, 4H), 7.06 (m, 4H), 4.08 (t, 4H), 1.85 (m, 4H), 1.53 (m, 4H), 1.45-1. 2 (m, 16H), 1.36 (s, 18H), 0.91 (t, 6H) ppm.

[Production Example 3] Synthesis of Near Infrared Fluorescent Dye C Near Infrared Fluorescent Dye C is Organic Letters, 2012, Vol. 4, pages 2670-2673, and Chestry A European Journal, 2009, Vol. 15, 4857-. With reference to page 4864, the procedure was as follows.

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

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

  Subsequently, the compound (a-2) (1.36 g, 2.5 mmol) obtained in Production Example 1 and the compound (c-2) (0.81 g, 5.5 mmol) were placed in a 200 mL three-necked flask under an argon stream. ), Dehydrated toluene (50 mL) was added, and the mixture was heated to reflux. Under heating and reflux, phosphoryl chloride (2.34 mL, 25 mmol) was added dropwise with a syringe, and the mixture was further heated to reflux for 2 hours. After completion of the reaction, dichloromethane (40 mL) and saturated aqueous sodium hydrogen carbonate solution (40 mL) were added with ice cooling, and the mixture was extracted with dichloromethane. The organic layer was treated with anhydrous magnesium sulfate, the magnesium sulfate was filtered off, the solvent was removed under reduced pressure, and the residue was roughly removed by silica gel column chromatography (eluent: hexane / ethyl acetate). The residue obtained by distilling off the solvent was purified again by silica gel column chromatography (eluent: dichloromethane / ethyl acetate = 50/1) to obtain a green solid of the precursor (c-3) (yield: 0). .54 g, yield: 27%).

  Finally, a precursor (c-3) (522 mg, 0.65 mmol), N, N-diisopropylethylamine (258 mg, 2.0 mmol) and dichloromethane (20 mL) were placed in a 100 mL two-necked flask under an argon stream. Chlorodiphenylborane (600 mg, 3.0 mmol) was added under reflux, and the reaction was continued overnight. The reaction solution was washed with water, and the organic layer was dried over anhydrous magnesium sulfate and concentrated. The residue was washed with methanol and purified by column chromatography (eluent: dichloromethane / ethyl acetate = 100/1) to obtain a near-infrared fluorescent dye C green solid (yield: 0.24 g, yield: 32). .6%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ = 7.11 (m, 20H), 6.43 (m, 4H), 6.25 (s, 2H), 6.02 (m, 4H), 3 .92 (t, 4H), 2.27 (s, 6H), 1.78 (m, 10H), 1.5-1.2 (m, 20H), 0.85 (t, 6H) ppm.

[Production Example 4] Synthesis of near-infrared fluorescent dye D Near-infrared fluorescent dye D is Organic Letters, 2012, volume 4, pages 2670-2673 and Chestry A European Journal, 2009, volume 15, 4857-. With reference to page 4864, the procedure was as follows.

  The same operation as in Production Example 1 was carried out except that 1-bromo-2-ethylhexane (48 g, 249 mmol) was used instead of 1-bromooctane (48 g, 249 mmol), and 3,6- (4- (2 A red solid of -ethylhexyl) oxyphenyl) pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione (d-2) was obtained (yield: 4.6 g).

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

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

  Finally, under a stream of argon, a 100 mL two-necked flask was charged with the precursor (d-4) (973 mg, 1.0 mmol), N, N-diisopropylethylamine (387 mg, 3.0 mmol), dichloromethane (30 mL), Chlorodiphenylborane (900 mg, 4.5 mmol) was added while refluxing, and the reaction was continued overnight. The reaction solution was washed with water, and the organic layer was dried over anhydrous magnesium sulfate and concentrated. The residue was washed with methanol and purified by column chromatography (eluent: dichloromethane) to obtain a green solid of near-infrared fluorescent dye D (yield: 0.42 g, yield: 35%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ = 7.11 (m, 24H), 6.62 (m, 4H), 6.32 (m, 6H), 3.8-3.9 (m, 4H), 2.27 (s, 6H), 1.8 (m, 2H), 1.6-1.3 (m, 16H), 1.38 (s, 18H), 0.9-1.0 (M, 12H) ppm.

[Comparative Production Example] Synthesis of azo-boron complex compound (1) Production of hydrazone compound In an eggplant flask for a synthesis apparatus, an orthoquinone derivative (200 mg, 5.33 x 10-4 mol) and 2-hydrazinobenzoic acid hydrochloride (402 mg, 2.13 × 10 −3 mol) was added, and then a mixed solvent (55 mL) of methanol: water: dimethylsulfoxide = 3: 4: 4 was added, and the mixture was heated and stirred at 50 ° C. When the reaction was started, crystals precipitated in the reaction solution. After 13 hours from the start of the reaction, the reaction solution was no longer heated and allowed to cool at room temperature with stirring. The precipitated crystals were separated by filtration and washed with a mixed solvent of methanol: water = 4: 1 to obtain reddish brown powdery crystals (yield: 96 mg, yield: 35.3%). Since this compound has low solubility, it was not purified any more and boron complexation was performed.

(2) Production of azo-boron complex compound The reddish brown powdery crystals (200 mg, 3.92 × 10 ⁻⁴ mol) obtained in (1) above were placed in a 300 mL eggplant flask and dichloromethane (70 mL) was added. Further, triethylamine (137 mg, 1.37 × 10 ⁻³ mol) was added to completely dissolve the hydrazone compound, and then boron trifluoride etherate (334 mg, 2.35 × 10 ⁻³ mol) was added dropwise at room temperature. The reaction was carried out with stirring. Three days after the start of the reaction, since the progress of the reaction could not be confirmed by TLC, water was added to stop the reaction. The dichloromethane layer was separated, washed with water, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: dichloromethane / ethyl acetate = 10/1) to obtain the target compound as green powder crystals (yield: 62.2 mg, yield: 29.4%). ).

¹ H-NMR (CDCl ₃ ) δ = 1.03 (6H, t, J = 7.46), 1.40-1.49 (ivH, m), 1.66-1.74 (ivH, m) 3.47 (ivH, t), 6.78 (1H, d, J = 2.20), 6.90 (1H, dd, J = 2.20, J = 9.16), 7.48 ( 1H, t, J = 7.44), 7.66-7.78 (iiiH, m), 8.13 (1H, d, J = 9.16), 8.30-8.33 (2H, m ), 8.39 (1H, d, J = 7.70), 8.75 (1H, d, J = 7.70)

[Example 1] Characterization of near-infrared fluorescent dye A TPU pellet (product name: Tecoflex EG-60D-B40, manufactured by Lubrizol) (100 g) and near-infrared fluorescent dye A (5 mg) synthesized in Production Example 1 ) Were mixed, and the dye was adhered to the pellet surface. Next, the pellets were put into a lab plast mill and dissolved and kneaded (kneading) under the following four conditions (i) to (iv).
(I) 190 ° C. · 10 minutes (ii) 220 ° C. · 3 minutes (iii) 220 ° C. · 6 minutes (iv) 220 ° C. · 10 minutes Then, the kneaded dye-containing resin was taken out and formed into a film. Film formation was performed as follows. First, the melt-kneaded dye-containing resin was heated for 5 minutes while being sandwiched between iron plates heated to 200 ° C., and pressed at 5 to 10 mPa while cooling the iron plates.

  The absorption spectrum of the obtained film was measured with an ultraviolet-visible near-infrared spectrophotometer “UV3600” manufactured by SHIMADZU, and the emission spectrum was measured with a spectrofluorophotometer “FP-8600” manufactured by JASCO Corporation. (Excitation wavelength: 740 nm), and the fluorescence quantum yield was measured with an absolute PL quantum yield measuring device “Quantaurus-QY C11347” manufactured by Hamamatsu Photonics.

(I) to (iv) Under any kneading condition, the peak wavelength of the absorption spectrum was not substantially changed (see FIG. 1). Moreover, the peak wavelength of the absorption spectrum was 739 nm, the peak wavelengths of the fluorescence spectrum were 758 nm and 833 nm, and the fluorescence quantum yield was 37%. Furthermore, when the visibility with the near-infrared fluorescence detection camera of the said film was evaluated, the visibility was very good.
As the near-infrared fluorescence detection camera, a general CMOS camera provided with an LED ring illuminator having a center wavelength of 740 nm as an excitation light source and having an optical filter that transmits light having a wavelength longer than 800 nm was used.

[Example 2] Results of property evaluation of near-infrared fluorescent dye B Example 1 except that the near-infrared fluorescent dye B synthesized in Production Example 2 was used instead of the near-infrared fluorescent dye A in Example 1. The same operation was performed to obtain a dye-containing resin, and the obtained dye-containing resin was formed into a film. The absorption spectrum, fluorescence spectrum, and fluorescence quantum yield of the obtained dye-containing film were measured in the same manner as in Example 1.

(I) to (iv) Under any kneading conditions, the peak wavelength of the absorption spectrum was not substantially changed (see FIG. 2). Moreover, the peak wavelength of the absorption spectrum was 764 nm, the peak wavelengths of the fluorescence spectrum were 776 nm and 865 nm, and the fluorescence quantum yield was 38%.
Further, a film containing a near-infrared fluorescent dye B and a film containing no dye are arranged, and a photograph taken with the near-infrared fluorescent detection camera described in Example 1 is shown in FIG. Fig. 4 shows a picture taken with a camera of the pork. As is clear from the results, the film made of the resin composition according to the present invention has excellent visibility with a near-infrared fluorescent camera (FIG. 3), and can be clearly observed even with 2 mm thick pork. (FIG. 4).

[Comparative Example 1] Characteristic evaluation results of azo-boron complex compound PP pellet (product name: B221WA, manufactured by Prime Polymer) (50 g) and the azo-boron complex compound (16.5 mg) synthesized in Comparative Production Example 1 Mixing was done to attach the dye to the pellet surface. Next, the pellets were put into a lab plast mill, and kneaded under the following four conditions (v) to (viii). Thereafter, the kneaded dye-containing resin was taken out and formed into a film in the same process as in Example 1.
(V) 180 ° C. · 10 minutes (vi) 230 ° C. · 3 minutes (vii) 230 ° C. · 6 minutes (viii) 230 ° C. · 10 minutes The absorption spectrum of the obtained dye-containing film was measured in the same manner as in Example 1. did.

  When the solution is kneaded at 230 ° C., the absorbance around 650 nm decreases with time, so it is considered that the product has decomposed (see FIG. 5).

  From the results of Examples 1 and 2 and Comparative Example 1, it was revealed that the dye having the structure according to the present invention has excellent thermal stability and is suitable for dissolution and kneading.

[Example 3] Characteristic evaluation results of near-infrared fluorescent dye C (reference example)
In Example 1, in place of the near-infrared fluorescent dye A, the near-infrared fluorescent dye C synthesized in Production Example 3 was used, and the conditions of dissolution and kneading were further performed at 190 ° C. for 10 minutes. The same operation was performed to obtain a dye-containing resin, and the obtained dye-containing resin was formed into a film. When the absorption spectrum, fluorescence spectrum, and fluorescence quantum yield of the obtained dye-containing film were measured in the same manner as in Example 1, the peak wavelength of the absorption spectrum was 756 nm, and the peak wavelengths of the fluorescence spectrum were 778 and 870 nm. Yes, the fluorescence quantum yield was 35%. Furthermore, when the visibility with the near-infrared fluorescence detection camera of the said film was evaluated, it was visually recognizable.

[Example 4] Characteristic evaluation result of near-infrared fluorescent dye D In Example 1, instead of the near-infrared fluorescent dye A, the near-infrared fluorescent dye D synthesized in Production Example 4 was used, and further dissolved and kneaded. Except that the conditions were set at 190 ° C. for 10 minutes, the same operation as in Example 1 was performed to obtain a dye-containing resin, and the obtained dye-containing resin was formed into a film. When the absorption spectrum, fluorescence spectrum, and fluorescence quantum yield of the obtained dye-containing film were measured in the same manner as in Example 1, the peak wavelength of the absorption spectrum was 744 nm, and the peak wavelengths of the fluorescence spectrum were 787 and 865 nm. Yes, the fluorescence quantum yield was 36%. Furthermore, when the visibility with the near-infrared fluorescence detection camera of the said film was evaluated, it was visually recognizable.

[Example 5]
The elution property of the near-infrared fluorescent dye A from the resin film containing the near-infrared fluorescent dye A was examined.
The same operation as in Example 1 was carried out except that 100 mg of the near infrared fluorescent dye A was used and the conditions of dissolution and kneading were carried out at 190 ° C. for 10 minutes. The dye concentration of the near infrared fluorescent dye A was 0.1 mass. %. A pigment-containing TPU film having a thickness of about 300 μm was produced.
The resulting dye-containing TPU film was subjected to a dissolution test. The elution operation of the film was performed as follows according to ISO10993-10 AnnexE. First, 5 g of a dye-containing TPU film was cut into a size of 2 × 2 cm or less, added to a 300 mL Erlenmeyer flask with 100 mL of methanol, and shaken at room temperature of 25 ° C. for 8 hours. The methanol was then filtered once and extracted twice more with the same amount of methanol using the same film strip. The methanol extract obtained by a total of three operations was concentrated with an evaporator, and the residue was dissolved in 5 mL of dichloromethane to obtain a test solution.
When the absorption spectrum and emission spectrum of the obtained test solution were measured, absorption and fluorescence derived from the near-infrared fluorescent dye A were not observed from the test solution, and the near-infrared fluorescent dye A was not eluted from the TPU film. It became clear. Also from this result, it is clear that the medical implant molded using the resin composition according to the present invention can be highly safe.

[Example 6]
Instead of the near-infrared fluorescent dye A, the same operation as in Example 5 was performed except that the near-infrared fluorescent dye B synthesized in Production Example 2 was used, and the elution of the dye from the obtained dye-containing film was performed. Tested.
As a result, absorption and fluorescence derived from the near-infrared fluorescent dye B were not observed from the test solution, and it was revealed that the near-infrared fluorescent dye B was not eluted from the TPU film. Also from this result, it is clear that the medical implant molded using the resin composition according to the present invention can be highly safe.

[Example 7] (Reference Example)
Instead of the near-infrared fluorescent dye A, the same operation as in Example 5 was carried out except that the near-infrared fluorescent dye C synthesized in Production Example 3 was used, and the elution of the dye from the obtained dye-containing film was performed. Tested.
As a result, absorption and fluorescence derived from the near-infrared fluorescent dye C were not observed from the test solution, and it became clear that the near-infrared fluorescent dye C was not eluted from the TPU film. Also from this result, it is clear that the medical implant molded using the resin composition according to the present invention can be highly safe.

[Example 8]
Instead of the near-infrared fluorescent dye A, the same operation as in Example 5 was carried out except that the near-infrared fluorescent dye D synthesized in Production Example 4 was used, and the dissolution property of the dye from the resulting dye-containing film was determined. Tested.
As a result, absorption and fluorescence derived from the near-infrared fluorescent dye D were not recognized from the test solution, and it became clear that the near-infrared fluorescent dye D did not elute from the TPU film. Also from this result, it is clear that the medical implant molded using the resin composition according to the present invention can be highly safe.

[Example 9] Camera visibility result of near-infrared fluorescent dye A Similar to Example 1 except that near-infrared fluorescent dye A (30 mg) was used and the conditions of dissolution and kneading were performed at 190 ° C for 10 minutes. Operation was performed to obtain a film containing near-infrared fluorescent dye A having a concentration of 0.03% by mass (Dye A 0.03% film). A film containing 0.03% by weight of this dye A, a near-infrared fluorescent dye A having a concentration of 0.005% by mass obtained in Example 1 (dye A 0.005% film), and a film containing no dye (dye) 6), photographs taken with the near-infrared fluorescence detection camera described in Example 1 are shown in FIG. 6, and photographs taken with the camera with 2 mm thick pork placed on these films. 7 shows. As is clear from the results, the film made of the resin composition according to the present invention has excellent visibility with a near-infrared fluorescent camera (FIG. 6), and can be clearly observed even with 2 mm thick pork. (FIG. 7).

Example 10 Evaluation of Polystyrene Film Containing Near-Infrared Fluorescent Dye A Polystyrene (Dick Styrene (trademark) LP-6000, manufactured by DIC Corporation) was used in place of TPU pellets, and the conditions for dissolution and kneading were 230 ° C. A polystyrene film having a pigment concentration of 0.005% by mass was prepared in the same manner as in Example 1 except that the test was performed for 10 minutes, and the same evaluation as in Example 1 was performed.

Example 11 Evaluation of PET Film Containing Near-Infrared Fluorescent Dye A PET (Byron (trademark) SI-173C, manufactured by Toyobo Co., Ltd.) was used in place of TPU pellets, and the conditions for dissolution and kneading were 210 ° C. 10 A PET film having a pigment concentration of 0.005% by mass was prepared in the same manner as in Example 1 except that the measurement was performed for a minute, and the same evaluation as in Example 1 was performed. The results are shown in Tables 1 and 2.

[Example 12] Evaluation of polyethylene film containing near-infrared fluorescent dye A Polyethylene (UBE polyethylene (trademark) F522N, manufactured by Ube Industries) was used in place of TPU pellets, and the conditions of dissolution and kneading were 130 ° C for 10 minutes. A polyethylene film having a pigment concentration of 0.005% by mass was prepared in the same manner as in Example 1 except that the above was performed, and the same evaluation as in Example 1 was performed.

[Example 13] Evaluation of PP film containing near-infrared fluorescent dye A PP pellets (product name: PC630A, manufactured by Sun Allomer Co., Ltd.) were used instead of TPU pellets, and the conditions of dissolution and kneading were performed at 190 ° C for 10 minutes. Except for the above, a PP film having a pigment concentration of 0.005% by mass was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[Example 14] Evaluation of PP film containing near-infrared fluorescent dye B Near-infrared fluorescent dye B was replaced with near-infrared fluorescent dye A, and PP pellets (product name: PC630A, Sun Allomer Co., Ltd.) were replaced with TPU pellets. A PP film having a pigment concentration of 0.005% by mass was prepared in the same manner as in Example 1 except that the melt kneading was performed at 190 ° C. for 10 minutes. The results are shown in Table 1 and Table 2.

[Comparative Example 2]
Instead of the near-infrared fluorescent dye A, a near-infrared fluorescent dye IR-140 (manufactured by Sigma-Aldrich Japan Co., Ltd.) represented by the following formula was used, and the conditions for dissolution and kneading were performed at 190 ° C. for 10 minutes. Except for the above, the same operation as in Example 1 was performed to obtain a dye-containing resin, the obtained dye-containing resin was formed into a film, and the elution of the dye from the obtained dye-containing film was tested. As a result, the obtained test solution showed an absorption spectrum having a peak wavelength derived from IR-140 of 812 nm and a fluorescence spectrum having an emission peak wavelength of 846 nm. From the above results, it is clear that IR-140 is eluted from the film, and the dye is difficult to apply to medical implants from the viewpoint of safety.

  The results of Examples 1-4 and 10-14 are shown in Table 1. In the column of “Camera Visibility” in Table 1, “◎” indicates very good visibility, “○” indicates good visibility, “△” indicates visual recognition, and “×” indicates poor visibility. means. From Table 1, it is clear that all the films obtained from the resin composition of the present invention emit light at 700 nm or more, have a high quantum yield, and excellent visibility with a near-infrared camera.

  Table 2 shows the results of dissolution tests of Examples 5 to 8, 10 to 14, and Comparative Example 2. From Table 2, since the film obtained from the resin composition of the present invention was unable to observe luminescence caused by the near-infrared fluorescent dye from the eluate, there was no elution of the near-infrared fluorescent dye, and medical use It is clear that it is safe to use. On the other hand, in the film obtained from the resin composition of Comparative Example 2, light emission due to the near-infrared fluorescent dye was observed from the eluate, and it was revealed that the dye was eluted.

Claims (8)

Near-infrared fluorescent dyes and resins (except that the resin contains one or more selected from the group consisting of urethane resins, olefin resins, polystyrene resins, and polyester resins). Is a resin composition that does not contain a radiopaque substance ,
The near-infrared fluorescent dye is
Following general formula _{(I 1 -7) ~ (I} 1 -9) and _{(I 2 -7) ~ (I} 2 -9)
(In the formula _{(I 1 -7) ~ (I} 1 -9) and _{(I 2 -7) ~ (I} 2 -9),
Y ²³ and Y ²⁴ each independently represent —CH— or a nitrogen atom;
Y ¹³ and Y ¹⁴ each independently represent an oxygen atom or a sulfur atom;
Y ²⁵ and Y ²⁶ each independently represent —CH— or a nitrogen atom;
R ⁴⁷ and R ⁴⁸ each independently represent a hydrogen atom or an electron withdrawing group;
R ⁴³ , R ⁴⁴ , R ⁴⁵ , and R ⁴⁶ represent a halogen atom or an optionally substituted aryl group;
P ¹⁵ and ^{P 16} are independently of each other, represent a halogen _{atom, C 1-20 alkyl, C 1-20} alkoxy group, an amino group, a monoalkylamino group, a dialkylamino group, ^{and, P 15} and ^{P 16} At least one of n is a n-butyl group, an isobutyl group, or a t-butyl group;
n15 and n16 each independently represent an integer of 1 to 3;
A ¹⁵ and A ¹⁶ are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group. Represents a phenyl group optionally having 1 to 3 substituents. ) Or one or more compounds selected from the group consisting of compounds represented by:
The maximum fluorescence wavelength is 650 nm or more,
Content of the said near-infrared fluorescent dye in the said resin composition is 0.0001-0.5 mass%, The resin composition characterized by the above-mentioned. As said near-infrared fluorescent pigment | dye, the following general formula (1-1)-(1-12) and general formula (2-1)-(2-12)
(In the above formulas (1-1) to (1-12) and (2-1) to (2-12),
P ^{5 to} P ⁸ each independently represent a halogen atom, a C _1-20 alkyl group, a C _1-20 alkoxy group, an amino group, a monoalkylamino group or a dialkylamino group, and P ⁵ and P ⁶ At least one of n is a n-butyl group, an isobutyl group, or a t-butyl group;
n5 and n6 each independently represent an integer of 1 to 3,
n7 and n8 represent the integer of 0-3 independently of each other. The resin composition of Claim 1 containing the 1 type, or 2 or more types of compound selected from the group which consists of a compound represented by this. The resin composition according to claim 1 or 2 , wherein the resin is a thermoplastic resin. The resin composition according to any one of claims 1 to 3 , wherein the maximum fluorescence wavelength is 700 nm or more. The resin composition according to any one of claims 1 to 4 , which is used as a medical material. The molded object obtained by processing the resin composition as described in any one of Claims 1-5 . The molded body according to claim 6 , wherein at least a part is a medical device used in a patient's body. It is a manufacturing method of the resin composition as described in any one of Claims 1-5,
A method for producing a resin composition, comprising a step of melt-kneading the near-infrared fluorescent dye and the resin.