Resin composition and molded body

Abstract

Provided are a resin composition which emits near-infrared fluorescence, has high luminous efficiency, and is easy to manufacture, and a molded body obtained from the resin composition. More specifically, provided is a resin composition comprising a near-infrared fluorescent material (A), a thermoplastic resin other than a polyamide resin (B), and a resin (C) different from the aforementioned thermoplastic resin (B), the aforementioned resin (C) forming a continuous phase, and a dispersed phase comprising the aforementioned near-infrared fluorescent material (A) and the aforementioned thermoplastic resin (B) being formed in the aforementioned continuous phase.

Description

Technical Field

[0001] The present invention relates to resin compositions and molded articles obtained from the resin compositions. Background Technology

[0002] Near-infrared fluorescent dyes are used in industrial products primarily for identification and anti-counterfeiting of various products, and in recent years have also been used in medical applications such as bioimaging probes and diagnostic drugs. Characteristics of the near-infrared wavelength region include: invisibility to the naked eye, minimal impact on organisms, and high permeability to biological tissues such as skin. These characteristics can be utilized by incorporating near-infrared fluorescent dyes into medical devices. For example, a system has been disclosed that uses near-infrared fluorescent dyes in medical devices such as shunt tubes to identify the location of medical devices implanted within a living organism by irradiating near-infrared light from outside the organism (see, for example, Patent Document 1).

[0003] To visualize medical implants inserted under the skin, excitation under near-infrared light, which has high skin transmittance, is required. Consequently, the fluorescence emitted by the implant must also be in the near-infrared region, which also has high skin transmittance. That is, typically, to ensure visual recognition, the near-infrared fluorescent pigment contained in the medical implant must strongly absorb light in the near-infrared region and emit strong fluorescence. Therefore, for the near-infrared fluorescent pigment contained in the resin composition used as a raw material for the medical implant, it is preferable that the wavelength of maximum absorption in the resin is located in the near-infrared region.

[0004] Near-infrared fluorescent dyes include inorganic and organic types. Generally, inorganic near-infrared fluorescent dyes have the advantage of easily adjusting the emission wavelength to the desired range by using various metals, but they require rare and expensive rare earth elements and nanoparticles with uniform particle size. On the other hand, while organic near-infrared fluorescent dyes are easier to synthesize and have easier wavelength adjustment, there is almost no known substance that can be stably incorporated into resins.

[0005] If near-infrared fluorescent pigments can be mixed and dispersed in a resin, then using that resin as a raw material, various molded articles emitting near-infrared fluorescence can be manufactured. For example, Patent Document 2 discloses a near-infrared fluorescent resin in which a reactive near-infrared fluorescent pigment, incorporating polyester reactive groups into phthalocyanine, naphthyl phthalocyanine, or squaraine pigment, is copolymerized in PET (polyethylene terephthalate).

[0006] On the other hand, as organic fluorescent pigments with high luminescence quantum yields, boron complexes of π-conjugated compounds are known. For example, BODIPY pigments with a boron dipyrrolemethane skeleton having a complex formed by disubstituted boron atoms and dipyrrolemethane (or its derivatives) are known (see, for example, Non-Patent Document 1). Furthermore, as a type of BODIPY pigment emitting near-infrared fluorescence, Patent Document 3 discloses a BODIPY pigment having a heterocyclic ring in its BODIPY skeleton. Moreover, Non-Patent Document 2 discloses a near-infrared fluorescent pigment of a DPP-based boron complex having two boron coordination units within the molecule, obtained by boron complexation of a pyrrolopyrroledione (DPP) derivative. These BODIPY pigments and DPP-based boron complexes are mainly used as biomarkers for identifying biological molecules such as nucleic acids and proteins, as well as tumor tissues. Resins containing BODIPY pigments or DPP-based boron complexes have been largely not reported. Patent Document 4 discloses a resin composition containing BODIPY pigments, obtained by copolymerizing a siloxane-containing BODIPY pigment with an organosiloxane group introduced via an alkylene group in an organosilicon resin to obtain a resin that emits fluorescence in the visible light region. Patent Document 5 discloses a composition emitting fluorescence in the visible light region, in which a solvent is mixed together with the polymer, in order to improve the compatibility of the visible-light-emitting BODIPY pigment. Furthermore, Patent Document 6 discloses a filter containing a BODIPY pigment having at least one electron-withdrawing group and a resin, and exhibiting high absorption of light in the visible light region; Patent Document 7 discloses a color conversion material containing a BODIPY pigment and a resin, which converts short-wavelength light into long-wavelength light.

[0007] Furthermore, Patent Document 8 cites a DPP-based boron complex as a compound that has absorption in the infrared region but no absorption in the visible light region, and Patent Document 9 discloses an infrared absorption composition comprising the compound and a hydrophobic polymer.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2012-115535

[0011] Patent Document 2: Japanese Patent Application Publication No. 2003-176289

[0012] Patent Document 3: Japanese Patent No. 5177427

[0013] Patent Document 4: Japanese Patent Application Publication No. 2013-060399

[0014] Patent Document 5: U.S. Patent Application Publication No. 2013 / 0249137

[0015] Patent Document 6: U.S. Patent Application Publication No. 2013 / 0252000

[0016] Patent Document 7: Japanese Patent Application Publication No. 2011-241160

[0017] Patent Document 8: Japanese Patent No. 5380019

[0018] Patent Document 9: Japanese Patent Application Publication No. 2010-090313

[0019] Non-patent literature

[0020] Non-patent literature 1: Tomimori, 6 others, Tetrahedron, 2011, Vol. 67, pp. 3187-3193

[0021] Non-patent literature 2: Fischer, 3 others, Angewandte Chemie International Edition, 2007, Volume 46, pp. 3750-3753 Summary of the Invention

[0022] The problem the invention aims to solve

[0023] Although patent document 3 discloses BODIPY pigments that emit near-infrared fluorescence, it does not describe whether resins can contain them.

[0024] On the other hand, due to the low luminescence quantum yield of pigment skeletons such as phthalocyanine pigments, the near-infrared fluorescent materials containing reactive groups described in Patent Document 2 containing these pigments have the problem of not being able to obtain sufficient luminescence intensity.

[0025] Furthermore, while the siloxane-containing BODIPY pigment described in Patent Document 4 exhibits good compatibility with the silicone monomer solution before curing, resulting in a uniformly dispersed silicone resin after curing, it suffers from low compatibility with other resins and resin solutions. Additionally, the resin composition described in Patent Document 5 raises concerns about solvent residue remaining in the resin, thus raising safety concerns. Patent Documents 4, 5, 6, and 7 do not describe BODIPY pigments emitting near-infrared fluorescence, nor do they describe their application in medical applications. Similarly, Patent Documents 8 and 9 do not describe DPP-based boron complexes emitting near-infrared light, nor do they report their application in medical applications.

[0026] Furthermore, polymers directly covalently bonded to resins, such as the fluorescent dyes described in Patent Documents 2 and 4, are difficult to manufacture and have low versatility. Additionally, the introduction of reactive groups into the dye increases production costs due to the complex synthetic pathway, making it unsuitable for industrial mass production. Considering versatility, it is preferable to manufacture a resin that emits near-infrared fluorescence simply by mixing and dispersing the near-infrared fluorescent dye in the resin. Especially when dispersed in thermoplastic resins, a melt-blending method of resin and dye is considered. However, even when melt-blending is performed at temperatures below the dye's decomposition point, depending on the type of resin and dye and the blending conditions, fluorescence may not be produced due to poor dispersion or dye decomposition. For example, it is known that dyes can sometimes be deactivated when blended with amino-containing resins such as polyamide resins or thermosetting resins.

[0027] Therefore, it is difficult to predict whether the aforementioned pigments can be dispersed in thermoplastic resins based on their thermal properties.

[0028] Therefore, the object of the present invention is to provide a resin composition that emits near-infrared fluorescence, has high luminous efficiency, and is thus easier to manufacture, and a molded article obtained from the resin composition.

[0029] Solution for solving the problem

[0030] The resin composition and molded body of the present invention are as follows [1] to

[12] .

[0031] [1] A resin composition comprising a near-infrared fluorescent material (A), a thermoplastic resin other than a polyamide resin (B), and a resin (C) different from the aforementioned thermoplastic resin (B), wherein the aforementioned resin (C) forms a continuous phase, and a dispersed phase comprising the aforementioned near-infrared fluorescent material (A) and the aforementioned thermoplastic resin (B) is formed in the aforementioned continuous phase.

[0032] [2] According to the resin composition described above [1], wherein the near-infrared fluorescent material (A) is at least one compound selected from the group consisting of the compounds represented by the following general formula (II1), the following general formula (II2), the following general formula (II3), and the following general formula (II4).

[0033]

[0034] In formula (II1),

[0035] R a and R b With R a The bonded nitrogen atom and R bThe bonded carbon atoms together form an aromatic 5-membered ring, an aromatic 6-membered ring, or a fused aromatic ring formed by the condensation of 2 to 3 5-membered or 6-membered rings.

[0036] R c and R d With R c The bonded nitrogen atom and R d The bonded carbon atoms together form an aromatic 5-membered ring, an aromatic 6-membered ring, or a fused aromatic ring formed by the condensation of 2 to 3 5-membered or 6-membered rings.

[0037] R e and R f Each can independently represent a halogen atom or an oxygen atom;

[0038] R g It represents a hydrogen atom or an electron-withdrawing group.

[0039] Among them, R e and R f In the case of oxygen atoms, R e 、and R e Bonded boron atoms, R a and R a The bonded nitrogen atoms can be chosen to form a ring together, R f 、and R f Bonded boron atoms, R c and R c The bonded nitrogen atoms can optionally form a ring together. R e In the case where R is an oxygen atom and does not form a ring, e For oxygen atoms with substituents, R f In the case where R is an oxygen atom and does not form a ring, f [This refers to an oxygen atom with a substituent.]

[0040]

[0041] In formula (II2), R a ~R f Same as in equation (II1) above.

[0042]

[0043] In formula (II3),

[0044] R h and R i With R h The bonded nitrogen atom and R i The bonded carbon atoms together form an aromatic 5-membered ring, an aromatic 6-membered ring, or a fused aromatic ring formed by the condensation of 2 to 3 5-membered or 6-membered rings.

[0045] R j and R k With R j The bonded nitrogen atom and R k The bonded carbon atoms together form an aromatic 5-membered ring, an aromatic 6-membered ring, or a fused aromatic ring formed by the condensation of 2 to 3 5-membered or 6-membered rings.

[0046] R l R m R n and R o Each independently represents a halogen atom and a carbon atom. 1-20 Alkyl, C 1-20 Alkyl, aryl, or heteroaryl;

[0047] R p and R q Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl,

[0048] R r and R s Each can independently represent a hydrogen atom or an electron-withdrawing group.

[0049]

[0050] In formula (II4), R h ~R q Same as in equation (II3) above.

[0051] The maximum fluorescence wavelength of the resin composition is above 650 nm.

[0052] [3] According to the resin composition described above [2], wherein the aforementioned near-infrared fluorescent material (A) contains at least one compound selected from the group consisting of a compound represented by any one of the following general formulas (II3-1) to (II3-6) and a compound represented by any one of the following general formulas (II4-1) to (II4-6).

[0053]

[0054] In formula (II3-1),

[0055] R 23 R 24 R 25 and R 26 Each independently represents a halogen atom and a carbon atom. 1-20 Alkyl, C 1-20 Alkyl, aryl, or heteroaryl;

[0056] R 27 and R 28 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 Alkyl, aryl, or heteroaryl;

[0057] R 29 and R 30 Each can independently represent a hydrogen atom or an electron-withdrawing group;

[0058] Y 9 and Y 10 Each atom can be independently represented as a sulfur atom, oxygen atom, nitrogen atom, or phosphorus atom;

[0059] For R 31 and R 32 :

[0060] (p4) Each of the following can be represented independently: hydrogen atom, halogen atom, and carbon atom. 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl, or

[0061] (p5)R 31 and R 32 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents;

[0062] For R 33 and R 34 :

[0063] (q4) Each of the following can be represented independently: hydrogen atom, halogen atom, and C atom. 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl, or

[0064] (q5)R 33 and R 34 Together, they form an aromatic 5-membered ring or an aromatic 6-membered ring, optionally with substituents.

[0065]

[0066] In equations (II3-2) to (II3-6), R 23 ~R 30 Same as in the aforementioned formula (II3-1);

[0067] X 1 and X 2 Each can independently represent a nitrogen atom or a phosphorus atom;

[0068] For R 35 R 36 R37 and R 38 :

[0069] (p6) Each of the following can be represented independently: hydrogen atom, halogen atom, and carbon atom. 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl,

[0070] (p7)R 35 and R 36 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents, R 37 and R 38 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl,

[0071] (p8)R 36 and R 37 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents, R 35 and R 38 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl, or

[0072] (p9)R 37 and R 38 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents, R 35 and R 36 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 Alkyl, aryl, or heteroaryl;

[0073] For R 39 R 40 R 41 and R 42 :

[0074] (q6) Each of the following can be represented independently: hydrogen atom, halogen atom, and C atom. 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl,

[0075] (q7)R 39 and R 40 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents, R 41 and R 42 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C1-20 alkoxy, aryl, or heteroaryl,

[0076] (q8)R 40 and R 41 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents, R 39 and R 42 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl, or

[0077] (q9)R 41 and R 42 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents, R 39 and R 40 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 Alkyl, aryl, or heteroaryl.

[0078]

[0079] [In formula (II4-1)~(II4-6), R 23 ~R 28 Same as in equation (II3-1) above. In equation (II4-1), R 31 ~R 34 Y 9 and Y 10 Similar to equation (II3-1) above, in equations (II4-2) to (II4-6), R 35 ~R 42 Similar to equation (II3-2) above, in equations (II4-3) to (II4-6), X 1 and X 2 Same as in equation (II3-3) above.

[0080] [4] According to the resin composition described above [3], wherein the aforementioned near-infrared fluorescent material (A) contains at least one compound selected from the group consisting of compounds represented by any one of the following general formulas (II3-7) to (II3-9) and (II4-7) to (II4-9).

[0081]

[0082] [In the formula, Y] 23 and Y 24 Each can independently represent a carbon atom or a nitrogen atom;

[0083] Y13 and Y 14 Each can independently represent an oxygen atom or a sulfur atom;

[0084] Y 25 and Y 26 Each can independently represent a carbon atom or a nitrogen atom;

[0085] R 47 and R 48 Each can independently represent a hydrogen atom or an electron-withdrawing group;

[0086] R 43 R 44 R 45 and R 46 Each can independently represent a halogen atom or an aryl group with optional substituents;

[0087] P 15 and P 16 Each independently represents a halogen atom and a carbon atom. 1-20 Alkyl, C 1-20 Alkoxy, amino, monoalkylamino, dialkylamino;

[0088] n15 and n16 each independently represent integers from 0 to 3;

[0089] A 15 and A 16 Each independently represents a hydrogen atom, optionally having 1 to 3 halogen atoms, and C 1-20 Alkyl, C 1-20 The phenyl group consisting of substituents in the group consisting of alkoxy, amino, monoalkylamino, and dialkylamino groups.

[0090] [5] The resin composition according to any one of [1] to [4] above, wherein, relative to 100% by mass of the total of the near-infrared fluorescent material (A) and the thermoplastic resin (B) other than the polyamide resin, the content of the near-infrared fluorescent material (A) is 0.001% by mass or more and 0.5% by mass or less.

[0091] [6] The resin composition according to any one of [1] to [5] above, wherein the aforementioned thermoplastic resin (B) comprises at least one selected from the group consisting of thermoplastic polyurethane (TPU) resin, polycarbonate (PC) resin, vinyl chloride resin, acrylic resin, polyester resin, polystyrene resin, olefin resin and polyacetal (POM) resin.

[0092] [7] The resin composition according to any one of [1] to [6] above, wherein the resin (C) comprises at least one selected from the group consisting of polyamide resin, polyethylene resin, polypropylene resin, thermosetting resin and cross-linked polyethylene resin.

[0093] [8] The resin composition according to [7] above, wherein the resin (C) comprises a polyamide resin.

[0094] [9] The resin composition according to [7] above, wherein the resin (C) comprises a thermosetting resin.

[0095]

[10] The resin composition according to any one of [1] to [9] above, wherein, relative to 100% by mass of the total of the aforementioned near-infrared fluorescent material (A), the aforementioned thermoplastic resin (B) and the aforementioned resin (C), the total content of the aforementioned near-infrared fluorescent material (A) and the aforementioned thermoplastic resin (B) is 5% by mass or more and 60% by mass or less.

[0096]

[11] The resin composition according to any one of [1] to

[10] above is used in medical materials.

[0097]

[12] A molded article obtained from any of the resin compositions described in any one of [1] to

[11] .

[0098]

[13] The shaped body described above

[12] is a medical device used in the body of a patient in at least a portion thereof.

[0099] The effects of the invention

[0100] According to the present invention, a resin composition that emits near-infrared fluorescence, has high luminous efficiency, and is therefore relatively easy to manufacture, and a molded article obtained from the resin composition can be provided. Attached Figure Description

[0101] Figure 1 A schematic diagram of the apparatus used to measure luminous efficiency. Detailed Implementation

[0102] The present invention is a resin composition comprising a near-infrared fluorescent material (A), a thermoplastic resin (B) other than a polyamide resin (hereinafter also simply referred to as thermoplastic resin (B)), and a resin (C) different from the aforementioned thermoplastic resin (B), wherein the aforementioned resin (C) forms a continuous phase, and a dispersed phase comprising the aforementioned near-infrared fluorescent material (A) and the aforementioned thermoplastic resin (B) is formed in the aforementioned continuous phase.

[0103] The resin composition of the present invention, having this structure, can suppress the deactivation of near-infrared fluorescent material (A), and has excellent effects such as high near-infrared fluorescence efficiency and ease of manufacturing. Furthermore, the molded article obtained from this resin composition also has excellent effects such as high near-infrared fluorescence efficiency and ease of manufacturing.

[0104] It should be noted that in the resin composition of the present invention, it can be confirmed by digital microscopy or the like that the near-infrared fluorescent material (A) and the thermoplastic resin (B) form a dispersed phase (the so-called island part of the island structure), and the resin (C) forms a continuous phase (the so-called sea part of the island structure).

[0105] The preferred embodiments of the present invention will be described below. It should be noted that in this specification, the range "X~Y" means "X or more and Y or less". Furthermore, unless otherwise specified, the operation and physical property measurements are performed at room temperature (20~25°C) and relative humidity 40~50%RH.

[0106] [Composition of the resin composition]

[0107] <Near-infrared fluorescent materials (A)>

[0108] The near-infrared fluorescent material (A) contained in the resin composition of the present invention is a compound whose fluorescence maximum wavelength is in the near-infrared region. When the resin composition of the present invention is used, for example, as a raw material for medical devices or safety devices used in living organisms, the resin composition containing the above-mentioned near-infrared fluorescent material (A) and the molded articles obtained therefrom can be excited and detected by light in the near-infrared region invisible to the eye, and therefore the excitation light and fluorescence can be detected without changing the color tone of biological tissues, etc.

[0109] Examples of near-infrared fluorescent materials (A) include compounds such as polymethimide pigments, anthraquinone pigments, dithiol metal salt pigments, anthocyanin pigments, phthalocyanine pigments, indophenol pigments, cyamine pigments, styryl pigments, aluminum pigments, diimonium pigments, azo pigments, azo-boron pigments, boron dipyrrolemethane pigments, pyrrolopyrroledione (DPP) boron complexes, squarylium pigments, and perylene pigments, as described in International Publication No. 2007 / 126052. These near-infrared fluorescent materials (A) can be used alone or in combination of two or more.

[0110] As the near-infrared fluorescent material (A) contained in the resin composition of the present invention, among the materials described above, anthocyanin pigments, azo-boron pigments, boron dipyrrolemethane (BODIPY) pigments, pyrrolopyrroledione (DPP) boron complexes, phthalocyanine pigments, or squaric acid cyanine pigments are preferred from the perspective of luminous efficiency. In particular, BODIPY pigments represented by general formula (II1) or general formula (II2) below, or DPP boron complexes represented by general formula (II3) or general formula (II4) below, are preferred from the perspective of heat resistance. This is because: if the luminous efficiency is low, there is a concern that sufficient luminous intensity cannot be obtained; in addition, if the heat resistance is low, there is a concern that the material will decompose when mixed with the resin.

[0111] <Compounds represented by general formula (II1), general formula (II2), general formula (II3), or general formula (II4)>

[0112] As the near-infrared fluorescent material (A) used in this invention, compounds of the following general formula (II1) or general formula (II2) are preferred. These compounds are sometimes referred to below as "BODIPY pigments used in this invention".

[0113]

[0114] As the near-infrared fluorescent material used in this invention, compounds represented by the following general formula (II3) or general formula (II4) are also preferred. These compounds are sometimes referred to below as "DPP-based boron complexes used in this invention".

[0115]

[0116] In general formula (II1) or general formula (II2), R a and R b With R a The bonded nitrogen atom and R b The bonded carbon atoms together form an aromatic ring containing 1 to 3 rings. Similarly, in general formula (II1) or general formula (II2), R... c and R d With R c The bonded nitrogen atom and R d The bonded carbon atoms together form an aromatic ring containing 1 to 3 rings. R a and R b The formed aromatic ring, and R c and R d The aromatic rings formed are either 5-membered or 6-membered rings. Compounds represented by general formula (II1) or general formula (II2) have the following ring structures: R a and R b The formed aromatic ring and R c and Rd The resulting aromatic ring utilizes a ring structure formed by the condensation of a ring containing boron atoms bonded to two nitrogen atoms. That is, the compounds represented by general formula (II1) or general formula (II2) have a robust fused ring structure formed by a wide conjugated plane.

[0117] In general formula (II3) or general formula (II4), R h and R i With R h The bonded nitrogen atom and R i The bonded carbon atoms together form an aromatic ring containing 1 to 3 rings. Similarly, in general formula (II3) or general formula (II4), R j and R k With R j The bonded nitrogen atom and R k The bonded carbon atoms together form an aromatic ring containing 1 to 3 rings. R h and R i The formed aromatic ring, and R j and R k The aromatic rings formed are either 5-membered or 6-membered rings. Compounds represented by general formula (II3) or general formula (II4) have the following ring structures: R h and R i The resulting aromatic ring, along with a ring containing boron atoms bonded to two nitrogen atoms and a five-membered heterocycle containing one nitrogen atom, condenses to form three rings, R. j and R k The resulting aromatic ring, along with a ring containing a boron atom bonded to two nitrogen atoms and a five-membered heterocycle containing one nitrogen atom, condenses to form a three-ring structure. The five-membered heterocycles of these two rings then condense with each other, resulting in a ring structure consisting of at least six rings condensed together. Thus, the compounds represented by general formula (II3) or (II4) possess a robust fused-ring structure formed by very broad conjugated planes.

[0118] As R a and R b The formed aromatic ring, R c and R d The formed aromatic ring, R h and R i The formed aromatic ring, and R j and R kThe aromatic ring formed is not particularly limited as long as it is aromatic. Examples of such aromatic rings include pyrrole rings, imidazole rings, pyrazole rings, oxazole rings, thiazole rings, pyridine rings, pyrimidine rings, pyridazine rings, isoindole rings, indole rings, indazole rings, purine rings, pyrimidine rings, thienopyrrole rings, furopyrrole rings, pyrrolothiazole rings, and pyrrolooxazole rings. From the perspective of extending the maximum fluorescence wavelength to the near-infrared region, especially in the case of general formula (II1) or general formula (II3), the number of fused rings of this aromatic ring is preferably 2 or 3, and more preferably 2 from the perspective of synthetic complexity. Among them, when the number of fused rings of this aromatic ring is 1, the wavelength extension can also be achieved by working on the substituents on the ring and the substituents on the boron. In addition, especially in the case of general formula (II2) or general formula (II4), the wavelength extension to the near-infrared region can be achieved simply by bonding substituted aryl or heteroaryl groups.

[0119] As R a and R b The formed aromatic ring, R c and R d The formed aromatic ring, R h and R i The formed aromatic ring, and R j and R k The formed aromatic ring may be without substituents or may have one or more substituents. Any substituent in the aromatic ring that does not impede the fluorescence of the compound is acceptable.

[0120] When the resin composition of the present invention is used as a medical material (raw material for medical devices), the near-infrared fluorescent material contained therein preferably shows negative results for mutagenicity, cytotoxicity, sensitization, and skin irritation in necessary biological safety tests. Furthermore, from a safety viewpoint, this near-infrared fluorescent material preferably does not dissolve from the molded body obtained by processing the resin composition of the present invention due to blood, tissue fluid, or other bodily fluids. Therefore, the near-infrared fluorescent material used in the present invention preferably has low solubility in biological components such as blood. Even if the near-infrared fluorescent material used in the present invention is water-soluble, and the resin component in the resin composition of the present invention is substantially non-dissolving in bodily fluids, and the content of the near-infrared fluorescent material itself is trace, the molded body of the resin composition of the present invention can be used in vivo without the dissolution of the near-infrared fluorescent material. Considering these factors, the BODIPY pigment used in the present invention, as R... a and R b The formed aromatic ring or R c and R dThe substituents in the formed aromatic ring are preferably selected from those that are less likely to exhibit mutagenicity and those that reduce water solubility. Similarly, in the DPP-based boron complex used in this invention, as R... h and R i The formed aromatic ring or R j and R k The substituents in the formed aromatic ring are preferably those that are less likely to exhibit mutagenicity and reduce water solubility.

[0121] Examples of substituents include halogen atoms, nitro groups, cyano groups, hydroxyl groups, carboxyl groups, aldehyde groups, sulfonic acid groups, alkyl sulfonyl groups, halosulfonyl groups, mercapto groups, alkylthio groups, isocyanate groups, thioisocyanate groups, alkyl groups, alkenyl groups, alkoxy groups, alkoxy carbonyl groups, alkylamide carbonyl groups, alkyl carbonyl amide groups, acyl groups, amino groups, monoalkylamino groups, dialkylamino groups, silyl groups, monoalkylsilyl groups, dialkylsilyl groups, trialkylsilyl groups, monoalkoxysilyl groups, dialkoxysilyl groups, trialkoxysilyl groups, aryl groups, and heteroaryl groups. As R a and R b The formed aromatic ring, R c and R d The substituents and R in the formed aromatic ring h and R i The formed aromatic ring, or R j and R k From the perspective of safety for organisms, the formed aromatic ring is preferably cyano, hydroxyl, carboxyl, alkylthio, alkyl, alkoxy, alkoxycarbonyl, amide, alkylsulfonyl, fluorine, chlorine, aryl, or heteroaryl. These substituents may also have other substituents. However, even if the substituent is not one of these, safety can be improved by introducing a suitable substituent, so it is not limited to these substituents.

[0122] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with fluorine, chlorine, and bromine being preferred, and fluorine being even more preferred.

[0123] The alkyl, alkenyl, and alkynyl groups can be linear, branched, or cyclic (aliphatic cyclic). The number of carbon atoms in these groups is preferably 1 to 20, more preferably 1 to 12, further preferably 1 to 8, and particularly preferably 1 to 6. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Examples of alkenyl groups include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, and 2-hexenyl. Examples of alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, isopropynyl, 1-butynyl, and isobutynyl.

[0124] Examples of the alkyl moiety in alkylsulfonyl, alkylthio, alkoxy, alkoxycarbonyl, alkylamide carbonyl, alkylcarbonylamide, monoalkylamino, dialkylamino, monoalkylsilyl, dialkylsilyl, trialkylsilyl, monoalkoxysilyl, dialkoxysilyl, and trialkoxysilyl can be similar to those of the aforementioned alkyl groups. For example, examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, and dodecoxy. In addition, examples of monoalkylamino groups include methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, tert-butylamino, pentylamino, and hexylamino, while examples of dialkylamino groups include dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, dipentylamino, dihexylamino, ethylmethylamino, methylpropylamino, butylmethylamino, ethylpropylamino, and butylethylamino.

[0125] Examples of aryl groups include phenyl, naphthyl, indene, and biphenyl. Phenyl is preferred.

[0126] Examples of heteroaryl groups include, for instance, 5-membered ring heteroaryl groups such as pyrrole, imidazolyl, pyrazolyl, thiophene, furanyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, and thiadiazolyl; 6-membered ring heteroaryl groups such as pyridinyl, pyrazinyl, pyrimidinyl, and pyridazinyl; and fused heteroaryl groups such as indolyl, isoindolyl, indolyl, quinolizinyl, quinolinyl, isoquinolinyl, benzofuranyl, isobenzofuranyl, chromenyl, benzooxazolyl, benzoisooxazolyl, benzothiazolyl, and benzoisothiazolyl.

[0127] Alkyl, alkenyl, alkynyl, aryl, and heteroaryl groups can be unsubstituted or have one or more hydrogen atoms substituted by substituents. Examples of substituents include halogen atoms, alkyl, alkoxy, nitro, cyano, hydroxyl, amino, mercapto, carboxyl, aldehyde, sulfonic acid, isocyanate, thioisocyanate, aryl, and heteroaryl groups.

[0128] The absorption and fluorescence wavelengths of fluorescent materials depend on the surrounding environment. Therefore, the absorption wavelengths of fluorescent materials in resins can be either shorter or longer compared to those in solution. In this invention, the absorption wavelengths of BODIPY pigments and DPP-based boron complexes are lengthened, resulting in maximum absorption wavelengths in the near-infrared region in various resins, which is preferred. For the maximum absorption wavelength of fluorescent materials, further lengthening can be achieved by introducing electron-donating and electron-withdrawing groups into appropriate positions within the molecule, thereby reducing the band gap between the highest occupied orbital (HOMO) and lowest vacant orbital (LUMO).

[0129] For example, in compounds represented by general formula (II1), by introducing R a and R b The formed aromatic ring, and R c and R d The formed aromatic ring introduces an electron-donating group and moves towards R g Introducing electron-withdrawing groups can further extend the wavelengths of the compound's maximum absorption and fluorescence. Similarly, in compounds represented by general formula (II3), by introducing electron-withdrawing groups into R... h and R i The formed aromatic ring, and R j and R k The formed aromatic ring introduces an electron-donating group, R p and R q In the case of an aromatic ring, an electron-donating group is introduced into the aromatic ring, or an electron-donating group is introduced into R. r and R s Introducing electron-withdrawing groups can further extend the maximum absorption and maximum fluorescence wavelengths of this compound. By combining these designs, the target wavelength can be achieved.

[0130] Compounds of general formula (II2) with an aza-BODIPY skeleton, even in R a and R b The formed aromatic ring, and R c and R dEven without substitution, the resulting aromatic ring forms a backbone that absorbs at longer wavelengths. Unlike compounds of general formula (II1), the crosslinking portion of pyrrole in this backbone is a nitrogen atom, thus making it impossible to introduce substituents onto the nitrogen atom. However, by adding substituents to the pyrrole moiety (R... a and R b The formed aromatic ring, and R c and R d By introducing an electron-donating group into the formed aromatic ring, the maximum absorption wavelength and maximum fluorescence wavelength of the compound can be further extended. Similarly, in the case of the compound represented by general formula (II4), by introducing an electron-donating group into the pyrrole moiety (R... h and R i The formed aromatic ring, and R j and R k The formed aromatic ring introduces an electron-donating group, or R p and R q In the case of an aromatic ring, introducing an electron-donating group into the aromatic ring can further extend the maximum absorption wavelength and maximum fluorescence wavelength of the compound.

[0131] Therefore, as R a and R b The formed aromatic ring, R c and R d The formed aromatic ring, R h and R i The formed aromatic ring, and R j and R k The substituents in the formed aromatic ring are preferably groups that function as electron-donating groups on the aromatic ring, which are "any groups that do not hinder the fluorescence of the compound". By introducing an electron-donating group into the aromatic ring, the fluorescence of the compounds represented by general formulas (II1), (II2), (II3), or (II4) changes to a longer wavelength side. Examples of groups that function as electron-donating groups include alkyl groups; alkoxy groups such as methoxy groups; aryl groups (aromatic cyclic groups) such as phenyl, p-alkoxyphenyl, p-dialkylaminophenyl, and diekoxyphenyl; and heteroaryl groups (heteroaromatic cyclic groups) such as 2-thienyl and 2-furanyl. The alkyl or alkyl moiety in the alkyl or alkoxy substituents of alkyl or phenyl groups is preferably a straight-chain or branched alkyl group with 1 to 10 carbon atoms. It should be noted that the number of carbon atoms in the alkyl moiety and the presence or absence of branches can be appropriately selected based on the various physical properties of the fluorescent material. From the viewpoint of solubility and compatibility, it is also preferable to have 6 or more carbon atoms or to have branches. a and R b The formed aromatic ring, R c and R d The formed aromatic ring, R h and R iThe formed aromatic ring, and R j and R k The substituents in the formed aromatic ring are preferably C. 1-6 Alkyl, C 1-6 Alkoxy, aryl, or heteroaryl groups are preferred, with methyl, ethyl, methoxy, phenyl, p-methoxyphenyl, p-ethoxyphenyl, p-dimethylaminophenyl, dimethoxyphenyl, thiophene, or furanyl groups being even more preferred. Due to their high planarity, the BODIPY and DPP skeletons are prone to molecular aggregation due to π-π stacking. By introducing aryl or heteroaryl groups with large substituents into the BODIPY or DPP skeletons, molecular aggregation can be suppressed, thereby improving the luminescence quantum yield of the resin composition of the present invention.

[0132] In general formula (II1) or general formula (II2), R a and R b The formed aromatic ring and R c and R d The aromatic rings formed can be different or the same. In general formula (II3) or general formula (II4), R h and R i The formed aromatic ring and R j and R k The aromatic rings formed can be different or the same. As for the BODIPY pigment or DPP-based boron complex used in this invention, R is preferred from the perspective of ease of synthesis and a tendency to have higher luminescence quantum yield. a and R b The formed aromatic ring and R c and R d The formed aromatic ring, or R h and R i The formed aromatic ring and R j and R k The aromatic rings formed are of the same type.

[0133] In general formula (II1) or general formula (II2), R e and R f Each can be used independently to represent a halogen atom or an oxygen atom. R e and R f When the atom is a halogen atom, fluorine, chlorine, bromine, or iodine atoms are preferred, with fluorine or chlorine atoms being more preferred. From the perspective of having a strong bond with boron atoms, fluorine atoms are particularly preferred. e and R f Compounds containing fluorine atoms are advantageous for melt mixing with resins at high temperatures due to their high heat resistance. It should be noted that, as compounds represented by general formula (II1) or general formula (II2), even if R...e and R f Substituents containing atoms that can bond with boron atoms, rather than halogen or oxygen atoms, can also be included in the resin, similar to the BODIPY pigment used in this invention. Such substituents are permissible as long as they do not impede fluorescence.

[0134] In general formula (II1) or general formula (II2), R e and R f In the case of oxygen atoms, R e 、and R e Bonded boron atoms, R a and R a The bonded nitrogen atoms can form a ring together, R f 、and R f Bonded boron atoms, R c and R c The bonded nitrogen atoms can form a ring together. That is, in the case of a ring structure, R e 、and R e Bonded boron atoms, and R a The ring formed by the bonded nitrogen atoms and R a and R b The formed aromatic ring undergoes condensation, R f 、and R f Bonded boron atoms, and R c The ring formed by the bonded nitrogen atoms and R c and R d The formed aromatic ring undergoes condensation. R e The rings formed and R f The rings formed are preferably 6-membered rings.

[0135] In general formula (II1) or general formula (II2), R e It is an oxygen atom, and R e In the absence of a loop, R e This refers to an oxygen atom with a substituent (an oxygen atom bonded to the substituent). Examples of such a substituent include C. 1-20 Alkyl, aryl, heteroaryl, alkylcarbonyl, arylcarbonyl, or heteroarylcarbonyl, etc. Similarly, in general formula (II1) or general formula (II2), R... f It is an oxygen atom, and R f In the absence of a loop, R f This refers to an oxygen atom with a substituent (an oxygen atom bonded to the substituent). Examples of such a substituent include C. 1-20 Alkyl, aryl, heteroaryl, alkylcarbonyl, arylcarbonyl, or heteroarylcarbonyl, etc. It should be noted that R... e and R f When all oxygen atoms are substituents, Re The substituents and R f The substituents can be of the same kind or different kinds.

[0136] In general formula (II1) or general formula (II2), R e and R f In the case of oxygen atoms, R e R f and R e and R f Bonded boron atoms can form a ring together. For example, R0 can be considered as such a ring structure. e and R f Structures connected to the same aryl ring or heteroaryl ring, R e and R f Structures using alkylene linkages, etc.

[0137] In general formula (II3) or general formula (II4), R l R m R n and R o Each independently represents a halogen atom and a carbon atom. 1-20 Alkyl, C 1-20 Alkyl, aryl, or heteroaryl. R l R m R n 、or R o When the atom is a halogen atom, fluorine, chlorine, bromine, or iodine atoms are preferred, with fluorine or chlorine atoms being more preferred. From the perspective of having a strong bond with boron atoms, fluorine atoms are particularly preferred. l R m R n and R o Compounds containing fluorine atoms are advantageous when melt-blended with resins at high temperatures due to their high heat resistance.

[0138] It should be noted that in this application and in the specification of this application, "C" refers to the invention. 1-20 "Alkyl" refers to an alkyl group having 1 to 20 carbon atoms, and "C" is a carbon atom. 1-20 "Alkoxy group" refers to alkoxy groups with 1 to 20 carbon atoms.

[0139] R l R m R n 、or R o C 1-20In the case of an alkyl group, the alkyl group can be linear, branched, or cyclic (aliphatic cyclic). Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.

[0140] R l R m R n 、or R o C 1-20 In the case of an alkoxy group, the alkyl moiety of the alkoxy group can be linear, branched, or cyclic (aliphatic cyclic). Examples of such alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecyloxy, and dodecyloxy.

[0141] R l R m R n 、or R o In the case of an aryl group, examples of such aryl groups include phenyl, naphthyl, indene, and biphenyl.

[0142] R l R m R n 、or R o In the case of a heteroaryl group, examples of such heteroaryl groups include 5-membered ring heteroaryl groups such as pyrroleyl, imidazolyl, pyrazolyl, thiophene, furanyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, isothiazolyl, and thiadiazolyl; 6-membered ring heteroaryl groups such as pyridyl, pyrazinyl, pyrimidinyl, and pyridazinyl; and fused heteroaryl groups such as indolyl, isindolyl, inzolyl, quinazinyl, quinolinyl, isoquinolinyl, benzofuranyl, isobenzofuranyl, benzopyranyl, benzooxazolyl, benzoisooxazolyl, benzothiazolyl, and benzoisothiazolyl.

[0143] R l R m R n 、or R o C represents 1-20 Alkyl, C 1-20 Alkoxy, aryl, and heteroaryl groups can be unsubstituted or have one or more hydrogen atoms substituted by substituents. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, nitro groups, cyano groups, hydroxyl groups, amino groups, mercapto groups, carboxyl groups, aldehyde groups, sulfonic acid groups, isocyanate groups, thioisocyanate groups, aryl groups, and heteroaryl groups.

[0144] As a compound represented by general formula (II3) or general formula (II4), Rl R m R n and R o Preferably, halogen atoms, unsubstituted aryl groups, or aryl groups with substituents are preferred; fluorine atoms, chlorine atoms, bromine atoms, unsubstituted phenyl groups, or C-terminated aryl groups are preferred. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl groups, more preferably fluorine atoms, chlorine atoms, unsubstituted phenyl groups, or phenyl groups with C atoms. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl groups, with particular preference for fluorine-atom-substituted or unsubstituted phenyl groups.

[0145] In general formula (II3) or general formula (II4), R p and R q Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 Alkyl, aryl, or heteroaryl. As R p and R q The halogen atom represented, C 1-20 Alkyl, C 1-20 Alkoxy, aryl, and heteroaryl groups, such as R of the aforementioned general formula (II3), can be cited as examples. l R m R n 、or R o The same example.

[0146] As a compound represented by general formula (II3) or general formula (II4), R p and R q Preferably, it is a hydrogen atom or an aryl group, more preferably a hydrogen atom, an unsubstituted phenyl group, or a C-shaped group. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl groups, more preferably hydrogen atoms, unsubstituted phenyl groups, or C-substituted phenyl groups. 1-20 Alkoxy-substituted phenyl groups, particularly preferably hydrogen-atom-, unsubstituted phenyl groups, or C-substituted phenyl groups. 1-10 Alkoxy-substituted phenyl groups.

[0147] In general formula (II1), R g This represents a hydrogen atom or an electron-withdrawing group. Additionally, in general formula (II3), R... r and R sEach group can independently represent a hydrogen atom or an electron-withdrawing group. Examples of such electron-withdrawing groups include halogenated methyl groups such as trifluoromethyl; nitro; cyano; aryl; heteroaryl; alkynyl; alkenyl; carboxyl, acyl, carbonyloxy, amide, aldehyde, and other substituents containing a carbonyl group; sulfoxide; sulfonyl; alkoxymethyl; aminomethyl, etc. Aryl and heteroaryl groups with these electron-withdrawing groups as substituents can also be used. Among these electron-withdrawing groups, from the perspective of extending the maximum fluorescence wavelength, trifluoromethyl, nitro, cyano, sulfonyl, etc., which can function as strong electron-withdrawing groups, are preferred.

[0148] As the BODIPY pigment used in this invention, compounds of the following general formula (II1-0) or general formula (II2-0) are preferred. Compounds having a boron dipyrrolemethane skeleton are preferred because their maximum fluorescence wavelength becomes a longer wavelength, and in particular, compounds that satisfy (p2), (p3), (q2), or (q3) and are formed by the condensation of a pyrrole ring with an aromatic ring or a heteroaromatic ring are preferred as near-infrared fluorescent materials used in this invention because their maximum wavelength becomes a longer wavelength.

[0149]

[0150] In general formula (II1-0) or general formula (II2-0), R 101 R 102 and R 103 Satisfying any of the following (p1) to (p3):

[0151] (p1) Each of the following can be represented independently: hydrogen atom, halogen atom, and carbon atom. 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl,

[0152] (p2)R 101 and R 102 Together they form an aromatic 5-membered ring or an aromatic 6-membered ring, R 103 Represents hydrogen atom, halogen atom, C 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl, or

[0153] (p3)R 102 and R 103 Together they form an aromatic 5-membered ring or an aromatic 6-membered ring, R 101 Represents hydrogen atom, halogen atom, C 1-20 Alkyl, C 1-20 Alkoxy, aryl, or heteroaryl.

[0154] In general formula (II1-0) or general formula (II2-0), R 104 R 105and R 106 Satisfying any of the following (q1) to (q3):

[0155] (q1) Each of the following can be represented independently: hydrogen atom, halogen atom, and C atom. 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl,

[0156] (q2)R 104 and R 105 Together they form an aromatic 5-membered ring or an aromatic 6-membered ring, R 106 Represents hydrogen atom, halogen atom, C 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl, or

[0157] (q3)R 105 and R 106 Together they form an aromatic 5-membered ring or an aromatic 6-membered ring, R 104 Represents hydrogen atom, halogen atom, C 1-20 Alkyl, C 1-20 Alkoxy, aryl, or heteroaryl.

[0158] As the halogen atom in (p1)~(p3) or (q1~(q3) mentioned above, C 1-20 Alkyl, C 1-20 Alkoxy, aryl, and heteroaryl groups can each be represented by R. a and R b Examples are given in the text as "any group that does not impede the fluorescence of the compound".

[0159] In the aforementioned (p2)~(p3) or (q2)~(q3), as R 101 and R 102 The aromatic 5-membered ring or aromatic 6-membered ring formed together, R 104 and R 105 The aromatic 5-membered ring or aromatic 6-membered ring formed together, R 102 and R 103 The aromatic 5-membered ring or aromatic 6-membered ring formed together, R 105 and R 106 The aromatic 5-membered ring or aromatic 6-membered ring formed together is preferably an example shown in any one of the following general formulas (C-1) to (C-9), and more preferably an example shown in any one of the following general formulas (C-1), (C-2), or (C-9). In the following general formulas (C-1) to (C-9), the part marked with an asterisk is the part that is bonded to the boron dipyrrolemethane skeleton in general formula (II1-0) or general formula (II2-0).

[0160]

[0161] In the aforementioned general formulas (C-1) to (C-8), Y 1 ~Y 8 Each atom can be independently represented as a sulfur atom, oxygen atom, nitrogen atom, or phosphorus atom. As for the Y... 1 ~Y 8 Each atom is preferably a sulfur atom, an oxygen atom, or a nitrogen atom, and each atom is more preferably a sulfur atom or an oxygen atom.

[0162] In the aforementioned general formulas (C-1) to (C-9), R 11 ~R 22 Each can independently represent a hydrogen atom, or any of the aforementioned groups that do not impede the fluorescence of the compound. As "any group that does not impede the fluorescence of the compound," R can be used. a and R b Examples are given in the section on "any group that does not impede the fluorescence of the compound". As R 11 ~R 22 Each of the aforementioned compounds is preferably a hydrogen atom, an unsubstituted aryl group, a substituted aryl group, an unsubstituted heteroaryl group, or a substituted heteroaryl group, more preferably a hydrogen atom, an (unsubstituted) phenyl group, p-methoxyphenyl group, p-ethoxyphenyl group, p-dimethylaminophenyl group, dimethoxyphenyl group, thiophene group, or furanyl group, and even more preferably a hydrogen atom, an (unsubstituted) phenyl group, or p-methoxyphenyl group. From the perspective of improving electron-donating ability and being able to suppress the aggregation of the BODIPY skeleton using bulky substituents, the aforementioned compounds are particularly preferably substituted with at least one of the aforementioned unsubstituted aryl group, substituted aryl group, unsubstituted heteroaryl group, or substituted heteroaryl group.

[0163] As a compound of general formula (II1-0) or general formula (II2-0), R 101 With R 104 R 102 With R 105 and R 103 With R 106 They can be different, but are preferably made of the same group. That is, R 101 R 102 and R 103 Under the aforementioned condition (p1), R 104 R 105 and R 106 Preferably, R satisfies the aforementioned condition (q1). 101 R 102 and R 103 Under the aforementioned condition (p2), R 104 R 105 and R 106 Preferably, R satisfies the aforementioned condition (q2). 101 R 102and R 103 Under the aforementioned condition (p3), R 104 R 105 and R 106 Preferably, the aforementioned (q3) is satisfied.

[0164] As a compound of general formula (II1-0) or general formula (II2-0), R is preferred. 101 and R 102 Forming a ring, R 104 and R 105 Forming a ring, or R 102 and R 103 Forming a ring, R 105 and R 106 Forming a ring. That is, R is preferred. 101 R 102 and R 103 Satisfying the aforementioned (p2) or (p3), and R 104 R 105 and R 106 Satisfying the aforementioned (q2) or (q3). This is because, through further condensation with the boron dipyrrolemethane skeleton via the aromatic or heteroaromatic rings, the maximum fluorescence wavelength becomes the longer wavelength side.

[0165] In general formula (II1-0) or general formula (II2-0), R 107 and R 108 Represents a halogen atom or an oxygen atom. R 107 and R 108 In the case of oxygen atoms, R 107 、and R 107 Bonded boron atoms, nitrogen atoms bonded to boron atoms, R 101 and R 101 Bonded carbon atoms can form a ring together, R 108 、and R 108 Bonded boron atoms, nitrogen atoms bonded to boron atoms, R 104 and R 104 Bonded carbon atoms can form a ring together. That is, R 107 With boron atoms and R 101 The rings formed by these elements, and R 108 With boron atoms and R 104 The rings formed by these reactions all condense with the boron dipyrrolemethane skeleton. R 107 With boron atoms and R 101 The rings formed, and R 108 With boron atoms and R 104 The rings formed are preferably 6-membered rings.

[0166] In general formula (II1-0) or general formula (II2-0), R 107In the case where R is an oxygen atom and does not form a ring, 107 This refers to an oxygen atom with a substituent (an oxygen atom bonded to the substituent). Examples of such a substituent include C. 1-20 Alkyl, aryl, or heteroaryl, etc. Similarly, in general formula (II1-0) or general formula (II2-0), R... 108 In the case where R is an oxygen atom and does not form a ring, 108 This refers to an oxygen atom with a substituent (an oxygen atom bonded to the substituent). Examples of such a substituent include C. 1-20 Alkyl, aryl, or heteroaryl groups, etc. It should be noted that R... 107 and R 108 When all oxygen atoms are substituents, R 107 The substituents and R 108 The substituents can be of the same kind or different kinds.

[0167] In general formula (II1-0), R 109 This indicates a hydrogen atom or an electron-withdrawing group. Examples of electron-withdrawing groups include those related to the aforementioned R. g The same substituents listed herein are preferred. From the perspective of extending the maximum fluorescence wavelength, fluoroalkyl, nitro, cyano, aryl, and sulfonyl groups that function as strong electron-withdrawing groups are preferred; trifluoromethyl, nitro, cyano, phenyl, and sulfonyl groups are more preferred; and from the perspective of biosafety, trifluoromethyl, cyano, phenyl, and sulfonyl groups are even more preferred. However, these substituents are not limited to.

[0168] As the BODIPY pigment used in this invention, among the compounds represented by general formula (II1-0) or general formula (II2-0), the following compounds are preferred: R 101 and R 102 Together they form the ring R shown in the above general formula (C-1) 11 and R 12 One of them is a hydrogen atom and the other is 1 to 3 hydrogen atoms, which can be halogen atoms, C 1-20 Alkyl, or C 1-20 The ring of alkoxy-substituted phenyl, thiophene, or furanyl groups, R 104 and R 105 Together with R 101 and R 102 The rings formed are of the same kind, R 103 and R 106 For hydrogen atoms, R 107 and R 108 Compounds containing halogen atoms; R 101 and R 102 Together they form the ring R shown in the above general formula (C-2) 13 and R14 One of them is a hydrogen atom and the other is 1 to 3 hydrogen atoms, which can be halogen atoms, C 1-20 Alkyl, or C 1-20 The ring of alkoxy-substituted phenyl, thiophene, or furanyl groups, R 104 and R 105 Together with R 101 and R 102 The rings formed are of the same kind, R 103 and R 106 For hydrogen atoms, R 107 and R 108 Compounds containing halogen atoms; R 102 and R 103 Together they form the ring R shown in the above general formula (C-1) 11 and R 12 One of them is a hydrogen atom and the other is 1 to 3 hydrogen atoms, which can be halogen atoms, C 1-20 Alkyl, or C 1-20 The ring of alkoxy-substituted phenyl, thiophene, or furanyl groups, R 105 and R 106 Together with R 102 and R 103 The rings formed are of the same kind, R 101 and R 104 For hydrogen atoms, R 107 and R 108 Compounds containing halogen atoms; R 102 and R 103 Together they form the ring shown in the following general formula (C-2) with R 13 and R 14 One of them is a hydrogen atom and the other is 1 to 3 hydrogen atoms, which can be halogen atoms, C 1-20 Alkyl, or C 1-20 The ring of alkoxy-substituted phenyl, thiophene, or furanyl groups, R 105 and R 106 Together with R 101 and R 102 The rings formed are of the same kind, R 101 and R 104 For hydrogen atoms, R 107 and R 108 Compounds containing halogen atoms; R 102 and R 103 Together they form the ring R shown in the following general formula (C-9) 19 ~R 22 Any one of the atoms in the middle, consisting of 1 to 3 hydrogen atoms, can be replaced by halogen atoms, carbon atoms, etc. 1-20 Alkyl, or C 1-20A ring consisting of an alkoxy-substituted phenyl, thiophene, or furanyl group, with the remaining three atoms being hydrogen atoms, R 105 and R 106 Together with R 101 and R 102 The rings formed are of the same kind, R 101 and R 104 It is a hydrogen atom, can be halogenated, C 1-20 Alkyl, or C 1-20 Alkoxy-substituted phenyl, thiophene, or furanyl groups, R 107 and R 108 Compounds containing halogen atoms. In the case of compounds represented by the general formula (II1-0), R... 109 Further preferred are trifluoromethyl, cyano, nitro, or phenyl, with trifluoromethyl or phenyl being particularly preferred.

[0169] As the near-infrared fluorescent material of the present invention, the compound shown in any one of the following general formulas (II3-1) to (II3-6), or the compound shown in any one of the following general formulas (II4-1) to (II4-6), is preferred because its maximum fluorescence wavelength is a longer wavelength.

[0170]

[0171] In general formulas (II3-1) to (II3-6) and (II4-1) to (II4-6), R 23 R 24 R 25 and R 26 Each independently represents a halogen atom and a carbon atom. 1-20 Alkyl, C 1-20 Alkyl, aryl, or heteroaryl. As R 23 R 24 R 25 、or R 26 The halogen atom represented, C 1-20 Alkyl, C 1-20 Alkoxy, aryl, and heteroaryl groups, such as R of the aforementioned general formula (II3), can be cited as examples. l R m R n 、or R o A similar example. As compounds represented by any one of general formulas (II3-1) to (II3-6) or any one of general formulas (II4-1) to (II4-6), from the perspective of high thermal stability, R 23 R 24 R 25 and R 26Preferably, the halogen atom, the unsubstituted aryl group, or the aryl group with a substituent is preferred; specifically, the fluorine atom, chlorine atom, bromine atom, unsubstituted phenyl group, or C-terminated aryl group is preferred. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl groups, more preferably fluorine atoms, chlorine atoms, unsubstituted phenyl groups, or phenyl groups with C atoms. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl groups are preferred from the perspective of obtaining compounds with both high luminescence efficiency and thermal stability. Phenyl groups with fluorine atoms or no substitution are particularly preferred.

[0172] In general formulas (II3-1) to (II3-6) and (II4-1) to (II4-6), R 27 and R 28 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 Alkyl, aryl, or heteroaryl. As R 27 or R 28 The halogen atom represented, C 1-20 Alkyl, C 1-20 Alkoxy, aryl, and heteroaryl groups, such as R of the aforementioned general formula (II3), can be cited as examples. p or R q Similarly, as a compound represented by any one of general formulas (II3-1) to (II3-6) or any one of general formulas (II4-1) to (II4-6), R 27 and R 28 Preferably, it is a hydrogen atom or an aryl group. From the perspective of obtaining a compound with high luminescence efficiency, it is preferably a hydrogen atom, an unsubstituted phenyl group, or a C-shaped phenyl group. 1-20 Alkyl or C 1-20 The alkoxy-substituted phenyl group, more preferably a hydrogen atom, an unsubstituted phenyl group, or a C-type phenyl group with a straight or branched chain, is preferred. 1-20 Alkoxy-substituted phenyl groups are particularly preferred from the perspective of obtaining compounds with high luminous efficiency and excellent compatibility with resins. These compounds may contain hydrogen atoms, be unsubstituted phenyl groups, or have C atoms that are linear or branched. 1-10 Alkoxy-substituted phenyl groups.

[0173] In general formulas (II3-1) to (II3-6), R 29 and R 30 Each can independently represent a hydrogen atom or an electron-withdrawing group. As R 29 or R 30 Examples of electron-withdrawing groups represented by R in the aforementioned general formula (II3) can be found. r or R sA similar example. As compounds represented by any one of the general formulas (II3-1) to (II3-6), from the perspective of obtaining compounds with high luminescence efficiency, R... 29 and R 30 Preferably, the fluoroalkyl, nitro, cyano, or aryl groups can function as strong electron-withdrawing groups; more preferably, trifluoromethyl, nitro, cyano, or phenyl groups that can have substituents. From the viewpoint of obtaining compounds with high luminous efficiency and excellent compatibility with resins, trifluoromethyl or cyano groups are even more preferred.

[0174] In general formulas (II3-1) and (II4-1), Y 9 and Y 10 Each atom independently represents a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom. As compounds represented by general formula (II3-1) or general formula (II4-1), from the perspective of obtaining compounds with high luminescence efficiency, Y... 9 and Y 10 Each atom is preferably a sulfur atom, an oxygen atom, or a nitrogen atom, and each atom is more preferably a sulfur atom or an oxygen atom. From the perspective of obtaining a compound that has both high luminous efficiency and thermal stability, it is even more preferable that each atom is a sulfur atom or that each atom is an oxygen atom.

[0175] In general formulas (II3-3) to (II3-6) and (II4-3) to (II4-6), X 1 and X 2 Each represents either a nitrogen atom or a phosphorus atom independently. As compounds represented by general formulas (II3-3) to (II3-6) or (II4-3) to (II4-6), X 1 and X 2 From the perspective of obtaining compounds with high luminous efficiency, it is preferable that the compounds are composed entirely of nitrogen atoms or phosphorus atoms; from the perspective of obtaining compounds that have both high luminous efficiency and thermal stability, it is more preferable that the compounds are composed entirely of nitrogen atoms.

[0176] In general formulas (II3-1) and (II4-1), R 31 and R 32 Satisfy the following conditions (p4) or (p5):

[0177] (p4) Each of the following can be represented independently: hydrogen atom, halogen atom, and carbon atom. 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl,

[0178] (p5)R 31 and R 32 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents.

[0179] In general formulas (II3-1) and (II4-1), R 33 and R 34 Satisfy either (q4) or (q5) below.

[0180] (q4) Each of the following can be represented independently: hydrogen atom, halogen atom, and C atom. 1-20 Alkyl, C 1-20 alkoxy, aryl, or heteroaryl, or

[0181] (q5)R 33 and R 34 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents.

[0182] In general formulas (II3-2) to (II3-6) and (II4-2) to (II4-6), R 35 R 36 R 37 and R 38 It satisfies any of the following (p6) to (p9).

[0183] (p6) Each of the following can be represented independently: hydrogen atom, halogen atom, and carbon atom. 1-20 Alkyl, C 1-20 Alkoxy, aryl, or heteroaryl.

[0184] (p7)R 35 and R 36 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents, R 37 and R 38 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 Alkoxy, aryl, or heteroaryl.

[0185] (p8)R 36 and R 37 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents, R 35 and R 38 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 Alkoxy, aryl, or heteroaryl.

[0186] (p9)R 37 and R 38 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents, R 35 and R 36 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C1-20 Alkoxy, aryl, or heteroaryl.

[0187] In general formulas (II3-2) to (II3-6) and (II4-2) to (II4-6), R 39 R 40 R 41 and R 42 It satisfies any of the following conditions (q6) to (q9).

[0188] (q6) Each of the following can be represented independently: hydrogen atom, halogen atom, and C atom. 1-20 Alkyl, C 1-20 Alkoxy, aryl, or heteroaryl.

[0189] (q7)R 39 and R 40 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents, R 41 and R 42 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 Alkoxy, aryl, or heteroaryl.

[0190] (q8)R 40 and R 41 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents, R 39 and R 42 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 Alkoxy, aryl, or heteroaryl.

[0191] (q9)R 41 and R 42 Together they form an aromatic 5-membered ring with optional substituents or an aromatic 6-membered ring with optional substituents, R 39 and R 40 Each independently represents a hydrogen atom, a halogen atom, and a carbon atom. 1-20 Alkyl, C 1-20 Alkoxy, aryl, or heteroaryl.

[0192] As mentioned above, the halogen atoms (p4), (p6) to (p9) and (q4), (q6) to (q9), C 1-20 Alkyl, C 1-20 Alkoxy, aryl, and heteroaryl groups can each be represented by R. a and R b Examples are given in the text as "any group that does not impede the fluorescence of the compound".

[0193] In the aforementioned (p5), (p7)~(p9), (q5), (q7)~(q9), as R 31 and R 32 The aromatic 5-membered ring or aromatic 6-membered ring formed together, R 33 and R 34 The aromatic 5-membered ring or aromatic 6-membered ring formed together, R 35 and R 36 The aromatic 5-membered ring or aromatic 6-membered ring formed together, R 36 and R 37 The aromatic 5-membered ring or aromatic 6-membered ring formed together, R 37 and R 38 The aromatic 5-membered ring or aromatic 6-membered ring formed together, R 39 and R 40 The aromatic 5-membered ring or aromatic 6-membered ring formed together, R 40 and R 41 The aromatic 5-membered ring or aromatic 6-membered ring formed together, R 41 and R 42 The aromatic 5-membered ring or aromatic 6-membered ring formed together is preferably the structure shown in any one of the aforementioned general formulas (C-1) to (C-9), and from the viewpoint of obtaining a compound with high thermal stability, the structure shown in the aforementioned general formula (C-9) is more preferred.

[0194] As the compound shown in (II3-1) above, the following compound is preferred: wherein R 23 R 24 R 25 and R 26 All are halogen atoms, unsubstituted phenyl groups, or C-terminated. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C-terminated. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl; R 29 and R 30 All are trifluoromethyl, nitro, cyano, or phenyl; Y 9 and Y 10 All are sulfur atoms or oxygen atoms; R 31 and R 32 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 31 and R 32 Together they form a phenyl group with optional substituents; R 33 and R 34 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 33 and R34 Together, they form a phenyl group optionally with substituents. The following compounds exhibit high luminescence efficiency and excellent compatibility with resins; therefore, it is preferred that R in this compound... 23 R 24 R 25 and R 26 All are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C atoms in straight or branched form. 1-20 Alkoxy-substituted phenyl; R 29 and R 30 All are trifluoromethyl, nitro, or cyano; Y 9 and Y 10 All are sulfur atoms or oxygen atoms; R 31 and R 32 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 31 and R 32 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl; R 33 and R 34 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 33 and R 34 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl groups.

[0195] As the compound shown in (II3-2) above, the following compound is preferred: wherein R 23 R 24 R 25 and R 26 All are halogen atoms, unsubstituted phenyl groups, or C-terminated. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C-terminated. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl; R 29 and R 30 All are trifluoromethyl, nitro, cyano, or phenyl; R 35 R 36 R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 35 and R 36 Together they form phenyl groups with optional substituents and R 37 and R 38Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 36 and R 37 Together they form phenyl groups with optional substituents and R 35 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 37 and R 38 Together they form phenyl groups with optional substituents and R 35 and R 36 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 40 R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 39 and R 40 Together they form phenyl groups with optional substituents and R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 40 and R 41 Together they form phenyl groups with optional substituents and R 39 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 41 and R 42 Together they form phenyl groups with optional substituents and R 39 and R 40 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl groups. The following compounds exhibit high luminescence efficiency and excellent compatibility with resins, therefore they are more preferred, especially those containing R. 23 R 24 R 25 and R 26 All are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C atoms in straight or branched form. 1-20 Alkoxy-substituted phenyl; R 29 and R 30 All are trifluoromethyl, nitro, or cyano; R 35 R 36 R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 35 and R 36 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 36 and R 37 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 35 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 37 and R 38 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 35 and R 36 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 40 R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 39 and R 40 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 40 and R 41 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 39 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 41 and R 42 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 39 and R 40 Each is independently a hydrogen atom or a carbon atom. 1-20 alkyl.

[0196] As the compound shown in (II3-3) above, the following compound is preferred: wherein R 23 R 24 R 25 and R 26 All are halogen atoms, unsubstituted phenyl groups, or C-terminated. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C-terminated. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl; R29 and R 30 All are trifluoromethyl, nitro, cyano, or phenyl; X 1 and X 2 All are nitrogen atoms; R 36 R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 36 and R 37 Together they form phenyl groups with optional substituents and R 38 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 37 and R 38 Together they form phenyl groups with optional substituents and R 36 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 40 R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 40 and R 41 Together they form phenyl groups with optional substituents and R 42 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 41 and R 42 Together they form phenyl groups with optional substituents and R 40 It is a hydrogen atom or a carbon atom. 1-20 Alkyl groups. The following compounds exhibit high luminescence efficiency and excellent compatibility with resins, therefore they are more preferred, especially those containing R. 23 R 24 R 25 and R 26 All are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C atoms in straight or branched form. 1-20 Alkoxy-substituted phenyl; R 29 and R 30 All are trifluoromethyl, nitro, or cyano; X 1 and X 2 All are nitrogen atoms; R 36 R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 36 and R 37 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 38 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 37 and R38 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 36 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 40 R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 40 and R 41 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 42 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 41 and R 42 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 40 It is a hydrogen atom or a carbon atom. 1-20 alkyl.

[0197] As the compounds shown in (II3-4) above, the following compounds are preferred: wherein R 23 R 24 R 25 and R 26 All are halogen atoms, unsubstituted phenyl groups, or C-terminated. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C-terminated. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl; R 29 and R 30 All are trifluoromethyl, nitro, cyano, or phenyl; X 1 and X 2 All are nitrogen atoms; R 35 R 36 and R 37 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 35 and R 36 Together they form phenyl groups with optional substituents and R 37 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 36 and R 37 Together they form phenyl groups with optional substituents and R 35 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 40 and R 41 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R39 and R 40 Together they form phenyl groups with optional substituents and R 41 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 40 and R 41 Together they form phenyl groups with optional substituents and R 39 It is a hydrogen atom or a carbon atom. 1-20 Alkyl groups. The following compounds exhibit high luminescence efficiency and excellent compatibility with resins, therefore they are more preferred, especially those containing R. 23 R 24 R 25 and R 26 All are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C atoms in straight or branched form. 1-20 Alkoxy-substituted phenyl; R 29 and R 30 All are trifluoromethyl, nitro, or cyano; X 1 and X 2 All are nitrogen atoms; R 35 R 36 and R 37 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 35 and R 36 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 37 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 36 and R 37 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 35 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 40 and R 41 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 39 and R 40 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 41 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 40 and R 41 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 39 It is a hydrogen atom or a carbon atom. 1-20 alkyl.

[0198] As the compounds shown above (II3-5), the following compounds are preferred: wherein R 23 R 24 R 25 and R 26 All are halogen atoms, unsubstituted phenyl groups, or C-terminated. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C-terminated. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl; R 29 and R 30 All are trifluoromethyl, nitro, cyano, or phenyl; X 1 and X 2 All are nitrogen atoms; R 35 R 36 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 35 and R 36 Together they form phenyl groups with optional substituents and R 38 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 40 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 39 and R 40 Together they form phenyl groups with optional substituents and R 42 It is a hydrogen atom or a carbon atom. 1-20 Alkyl groups. The following compounds are preferred because they exhibit high luminescence efficiency and excellent compatibility with resins. 23 R 24 R 25 and R 26 All are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C atoms in straight or branched form. 1-20 Alkoxy-substituted phenyl; R 29 and R 30 All are trifluoromethyl, nitro, or cyano; X 1 and X 2 All are nitrogen atoms; R 35 R 36 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 35 and R 36 Together they form an unsubstituted phenyl group or are C1-10 Alkyl-substituted phenyl and R 38 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 40 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 39 and R 40 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 42 It is a hydrogen atom or a carbon atom. 1-20 alkyl.

[0199] As the compounds shown above (II3-6), the following compounds are preferred: wherein R 23 R 24 R 25 and R 26 All are halogen atoms, unsubstituted phenyl groups, or C-terminated. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C-terminated. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl; R 29 and R 30 All are trifluoromethyl, nitro, cyano, or phenyl; X 1 and X 2 All are nitrogen atoms; R 35 R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 37 and R 38 Together they form phenyl groups with optional substituents and R 35 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 41 and R 42 Together they form phenyl groups with optional substituents and R 39 It is a hydrogen atom or a carbon atom. 1-20 Alkyl groups. The following compounds exhibit high luminescence efficiency and excellent compatibility with resins, therefore they are more preferred, especially those containing R. 23 R 24 R 25 and R 26 All are halogen atoms or unsubstituted phenyl groups; R 27 and R28 All are hydrogen atoms, unsubstituted phenyl groups, or C atoms in straight or branched form. 1-20 Alkoxy-substituted phenyl; R 29 and R 30 All are trifluoromethyl, nitro, or cyano; X 1 and X 2 All are nitrogen atoms; R 35 R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 37 and R 38 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 35 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 41 and R 42 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 39 It is a hydrogen atom or a carbon atom. 1-20 alkyl.

[0200] As the compound shown in (II4-1) above, the following compound is preferred: wherein R 23 R 24 R 25 and R 26 All are halogen atoms, unsubstituted phenyl groups, or C-terminated. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C-terminated. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl; Y 9 and Y 10 All are sulfur atoms or oxygen atoms; R 31 and R 32 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 31 and R 32 Together they form a phenyl group with optional substituents; R 33 and R 34 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 33 and R 34Together, they form a phenyl group optionally with substituents. The following compounds exhibit high luminescence efficiency and excellent compatibility with resins; therefore, it is preferred that R in this compound... 23 R 24 R 25 and R 26 All are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C atoms in straight or branched form. 1-20 Alkoxy-substituted phenyl; Y 9 and Y 10 All are sulfur atoms or oxygen atoms; R 31 and R 32 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 31 and R 32 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl; R 33 and R 34 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 33 and R 34 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl groups.

[0201] As the compound shown in (II4-2) above, the following compound is preferred: wherein R 23 R 24 R 25 and R 26 All are halogen atoms, unsubstituted phenyl groups, or C-terminated. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C-terminated. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl; R 35 R 36 R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 35 and R 36 Together they form phenyl groups with optional substituents and R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 36 and R 37 Together they form phenyl groups with optional substituents and R 35 and R 38Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 37 and R 38 Together they form phenyl groups with optional substituents and R 35 and R 36 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 40 R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 39 and R 40 Together they form phenyl groups with optional substituents and R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 40 and R 41 Together they form phenyl groups with optional substituents and R 39 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 41 and R 42 Together they form phenyl groups with optional substituents and R 39 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl groups. The following compounds exhibit high luminescence efficiency and excellent compatibility with resins, therefore they are more preferred, especially those containing R. 23 R 24 R 25 and R 26 All are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C atoms in straight or branched form. 1-20 Alkoxy-substituted phenyl; R 35 R 36 R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 35 and R 36 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 36 and R 37 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 35 and R 38Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 37 and R 38 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 35 and R 36 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 40 R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 39 and R 40 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 40 and R 41 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 39 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 41 and R 42 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 39 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 alkyl.

[0202] As the compound shown in (II4-3) above, the following compound is preferred: wherein R 23 R 24 R 25 and R 26 All are halogen atoms, unsubstituted phenyl groups, or C-terminated. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C-terminated. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl; X 1 and X 2 All are nitrogen atoms; R 36 R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 36 and R 37 Together they form phenyl groups with optional substituents and R38 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 37 and R 38 Together they form phenyl groups with optional substituents and R 36 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 40 R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 40 and R 41 Together they form phenyl groups with optional substituents and R 42 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 41 and R 42 Together they form phenyl groups with optional substituents and R 40 It is a hydrogen atom or a carbon atom. 1-20 Alkyl groups. The following compounds exhibit high luminescence efficiency and excellent compatibility with resins, therefore they are more preferred, especially those containing R. 23 R 24 R 25 and R 26 All are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C atoms in straight or branched form. 1-20 Alkoxy-substituted phenyl; R 36 R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 36 and R 37 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 38 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 37 and R 38 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 36 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 40 R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 40 and R 41 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 42 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 41 and R42 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 40 It is a hydrogen atom or a carbon atom. 1-20 alkyl.

[0203] As the compounds shown above (II4-4), the following compounds are preferred: wherein R 23 R 24 R 25 and R 26 All are halogen atoms, unsubstituted phenyl groups, or C-terminated. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C-terminated. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl; X 1 and X 2 All are nitrogen atoms; R 35 R 36 and R 37 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 35 and R 36 Together they form phenyl groups with optional substituents and R 37 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 36 and R 37 Together they form phenyl groups with optional substituents and R 35 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 40 and R 41 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 39 and R 40 Together they form phenyl groups with optional substituents and R 41 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 40 and R 41 Together they form phenyl groups with optional substituents and R 39 It is a hydrogen atom or a carbon atom. 1-20 Alkyl groups. The following compounds exhibit high luminescence efficiency and excellent compatibility with resins, therefore they are more preferred, especially those containing R. 23 R 24 R 25 and R 26 All are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C atoms in straight or branched form.1-20 Alkoxy-substituted phenyl; X 1 and X 2 All are nitrogen atoms; R 35 R 36 and R 37 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 35 and R 36 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 37 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 36 and R 37 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 35 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 40 and R 41 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, R 39 and R 40 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 41 It is a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 40 and R 41 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 39 It is a hydrogen atom or a carbon atom. 1-20 alkyl.

[0204] As the compounds shown in (II4-5) above, the following compounds are preferred: wherein R 23 R 24 R 25 and R 26 All are halogen atoms, unsubstituted phenyl groups, or C-terminated. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C-terminated. 1-20 Alkyl or C 1-20 Alkoxy-substituted phenyl; X 1 and X 2 All are nitrogen atoms; R 35 R 36 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 35 and R 36Together they form phenyl groups with optional substituents and R 38 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 40 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 39 and R 40 Together they form phenyl groups with optional substituents and R 42 It is a hydrogen atom or a carbon atom. 1-20 Alkyl groups. The following compounds exhibit high luminescence efficiency and excellent compatibility with resins, therefore they are more preferred, especially those containing R. 23 R 24 R 25 and R 26 All are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C atoms in straight or branched form. 1-20 Alkoxy-substituted phenyl; X 1 and X 2 All are nitrogen atoms; R 35 R 36 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 35 and R 36 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 38 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 40 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 39 and R 40 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 42 It is a hydrogen atom or a carbon atom. 1-20 alkyl.

[0205] As the compounds shown above (II4-6), the following compounds are preferred: wherein R 23 R 24 R 25 and R 26 All are halogen atoms, unsubstituted phenyl groups, or C-terminated. 1-10 Alkyl or C 1-10 Alkoxy-substituted phenyl; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C-terminated. 1-20Alkyl or C 1-20 Alkoxy-substituted phenyl; X 1 and X 2 All are nitrogen atoms; R 35 R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 37 and R 38 Together they form phenyl groups with optional substituents and R 35 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 41 and R 42 Together they form phenyl groups with optional substituents and R 39 It is a hydrogen atom or a carbon atom. 1-20 Alkyl groups. The following compounds exhibit high luminescence efficiency and excellent compatibility with resins, therefore they are more preferred, especially those containing R. 23 R 24 R 25 and R 26 All are halogen atoms or unsubstituted phenyl groups; R 27 and R 28 All are hydrogen atoms, unsubstituted phenyl groups, or C atoms in straight or branched form. 1-20 Alkoxy-substituted phenyl; X 1 and X 2 All are nitrogen atoms; R 35 R 37 and R 38 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 37 and R 38 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 35 It is a hydrogen atom or a carbon atom. 1-20 Alkyl; R 39 R 41 and R 42 Each is independently a hydrogen atom or a carbon atom. 1-20 Alkyl, or R 41 and R 42 Together they form an unsubstituted phenyl group or are C 1-10 Alkyl-substituted phenyl and R 39 It is a hydrogen atom or a carbon atom. 1-20 alkyl.

[0206] As the compound represented by any one of (II3-1) to (II3-6) above, the compound represented by any one of the following general formulas (II3-7) to (II3-9) is preferred. As the compound represented by any one of (II4-1) to (II4-6) above, the compound represented by any one of the following general formulas (II4-7) to (II4-9) is preferred.

[0207]

[0208] In general formulas (II3-7) and (II4-7), Y 23 and Y 24 Each can independently represent a carbon atom or a nitrogen atom. In general formulas (II3-7), Y... 23 and Y 24 Preferably, the atoms are of the same type.

[0209] In general formulas (II3-8) and (II4-8), Y 13 and Y 14 Each can independently represent an oxygen atom or a sulfur atom. In general formulas (II3-8), Y... 23 and Y 24 Preferably, the atoms are of the same type.

[0210] In general formulas (II3-9) and (II4-9), Y 25 and Y 26 Each can independently represent a carbon atom or a nitrogen atom. In general formulas (II3-9), Y... 25 and Y 26 Preferably, the atoms are of the same type.

[0211] In general formulas (II3-7) to (II3-9), R 47 and R 48 Each group independently represents a hydrogen atom or an electron-withdrawing group. From the perspective of high fluorescence intensity, trifluoromethyl, cyano, nitro, sulfonyl, or phenyl groups are preferred, with trifluoromethyl or cyano groups being particularly preferred. In general formulas (II3-7), R... 47 and R 48 Preferably, the functional groups are of the same type.

[0212] In general formulas (II3-7) to (II3-9) and (II4-7) to (II4-9), R 43 R 44 R 45 and R 46 Represents a halogen atom, or optionally an aryl group with substituents. R can be used as the aryl group. a and R bThe example shown is "any group that does not impede the fluorescence of the compound". Furthermore, any substituent that the aryl group can have is "any group that does not impede the fluorescence of the compound," for example, C... 1-6 Alkyl, C 1-6 Alkyl, aryl, or heteroaryl, etc. In general formulas (II3-7) to (II3-9) and (II4-7) to (II4-9), R 43 ~R 46 Each group may be a different group, but preferably all groups are of the same kind. As a compound represented by any one of general formulas (II3-7) to (II3-9) and (II4-7) to (II4-9), R 43 ~R 46 Preferably, all of them are halogen atoms, or all of them are phenyl groups with the same substituents, more preferably all of them are fluorine atoms or unsubstituted phenyl groups, and particularly preferably all of them are fluorine atoms.

[0213] In general formulas (II3-7) to (II3-9) and (II4-7) to (II4-9), P 15 ~P 16 Each independently represents a halogen atom and a carbon atom. 1-20 Alkyl, C 1-20 Alkyloxy, amino, monoalkylamino, dialkylamino. As this P 15 ~P 16 C in 1-20 Alkyl, C 1-20 Alkoxy, monoalkylamino, or dialkylamino, each of which can be named in relation to the aforementioned R g Examples that are the same as those given in (p1)~(p3) and (q1)~(q3). As P 15 ~P 16 C is preferred. 1-20 Alkyl, C 1-20 Alkoxy, (unsubstituted) phenyl, p-methoxyphenyl, p-ethoxyphenyl, p-dimethylaminophenyl, dimethoxyphenyl, thiophene, or furanyl, preferably C from the perspective of biosafety. 1-20 Alkyl, C 1-20 Alkoxy, phenyl, p-methoxyphenyl, p-ethoxyphenyl, dimethoxyphenyl, thiophene, or furanyl, and these substituents may also have other substituents. Even with substituents other than these, safety can be improved by further introducing suitable substituents, therefore the group is not limited to these substituents.

[0214] In general formulas (II3-7) to (II3-9) and (II4-7) to (II4-9), n15 to n16 each independently represent integers from 0 to 3. A molecule contains multiple P... 15In the case where n15 is 2 or 3, multiple P 15 They can all be the same type of functional group, or they can be different types of functional groups. Regarding P... 16 The same applies.

[0215] In general formulas (II3-7) to (II3-9) and (II4-7) to (II4-9), A 15 ~A 16 Each independently represents a hydrogen atom, and can be optionally selected from halogen atoms, C 1-20 Alkyl, C 1-20 A phenyl group consisting of 1 to 3 substituents from the group consisting of alkoxy, amino, monoalkylamino, and dialkylamino groups. The C-group is one of the substituents that this phenyl group may have. 1-20 Alkyl, C 1-20 Alkoxy, monoalkylamino, or dialkylamino, each of which can be named in relation to the aforementioned R g Examples that are the same as those given in (p1)~(p3) and (q1)~(q3). As A 15 ~A 16 Preferably, it is an unsubstituted phenyl group having one or two carbon atoms. 1-20 Phenyl groups with alkoxy groups as substituents, more preferably unsubstituted phenyl groups, or phenyl groups having one carbon atom. 1-20 Phenyl groups with alkoxy groups as substituents are preferred, with unsubstituted phenyl groups or those having one carbon atom being even more preferred. 1-10 The phenyl group has an alkoxy group as a substituent. Additionally, for compounds represented by general formulas (II3-7), A is preferred. 15 ~A 16 They are all the same type of functional group.

[0216] Examples of compounds represented by any one of (II3-1) to (II3-6) above include compounds represented by any one of the following general formulas (6-1) to (6-12) and (7-1) to (7-12). In general formulas (6-7) to (6-12) and (7-7) to (7-12), Ph refers to an unsubstituted phenyl group. As DPP-based boron complexes used in this invention, compounds represented by general formulas (6-4), (6-5), (6-7), (6-8), (7-4), (7-5), (7-7), and (7-8) are particularly preferred, and compounds represented by general formulas (6-4), (6-5), (6-7), and (6-8) are more preferred.

[0217] In general formulas (6-1) to (6-12) and (7-1) to (7-12), P 5 ~P 8 Each independently represents a halogen atom and a carbon atom. 1-20 Alkyl, C 1-20 Alkyloxy, amino, monoalkylamino, dialkylamino. As this P5 ~P 8 C in 1-20 Alkyl, C 1-20 Alkoxy, monoalkylamino, or dialkylamino, each of which can be named in relation to the aforementioned R g Examples that are the same as those given in (p1)~(p3) and (q1)~(q3). As P 5 ~P 8 C is preferred. 1-20 Alkyl, C 1-20 Alkoxy, (unsubstituted) phenyl, p-methoxyphenyl, p-ethoxyphenyl, p-dimethylaminophenyl, dimethoxyphenyl, thiophene, or furanyl, preferably C from the perspective of biosafety. 1-20 Alkyl, C 1-20 Alkoxy, phenyl, p-methoxyphenyl, p-ethoxyphenyl, dimethoxyphenyl, thiophene, or furanyl, more preferably C 1-20 Alkyl or C 1-20 Alkoxy, more preferably C 1-10 Alkyl or C 1-10 Alkoxy groups, and these substituents may also have other substituents. Even with substituents other than these, safety can be improved by further introducing appropriate substituents, therefore the group is not limited to these substituents.

[0218] In general formulas (6-1) to (6-12) and (7-1) to (7-12), n5 to n8 each independently represent integers from 0 to 3. A numerator contains multiple P... 5 In the case where n5 is 2 or 3, multiple P 5 They can all be the same type of functional group, or they can be different types of functional groups. Regarding P... 6 ~P 8 The same applies.

[0219]

[0220]

[0221]

[0222]

[0223] As compounds represented by general formulas (6-1) to (6-12) and (7-1) to (7-12), P is preferred. 5 ~P 8 C is independent of each other. 1-20 Alkyl or C 1-20 The alkoxy group and n5 to n8 are independently 0 to 2, more preferably P. 5 and P6 C is independent of each other. 1-20 Alkyl groups, n5, and n6 are independently 0–2, P 7 and P 8 C is independent of each other. 1-20 Alkoxy, n7, and n8 are each independently 0 to 1, with P being further preferred. 5 and P 6 C is independent of each other. 1-20 Alkyl groups, n5, and n6 are independently 1 to 2, P 7 and P 8 C is independent of each other. 1-20 The alkoxy group, n7, and n8 are all 1.

[0224] Specifically, examples of compounds represented by general formulas (6-1) to (6-12) include compounds represented by formulas (6-1-1) to (6-12-1). “λ” represents the peak wavelength of the absorption spectrum in solution of each compound, and “Em” represents the peak wavelength of the fluorescence spectrum.

[0225]

[0226]

[0227] The near-infrared fluorescent material (A) of the present invention can be a commercially available product or a synthetic product. As an example of a synthesis method, the synthesis method described in Chemistry A European Journal, 2009, Vol. 15, pp. 4857–4864 can be cited.

[0228] There are no particular limitations on the content of the near-infrared fluorescent material (A), as long as it is a concentration in which the near-infrared fluorescent material (A) can be mixed with the thermoplastic resin (B). However, from the viewpoint of fluorescence intensity and its detection sensitivity, the content of the near-infrared fluorescent material (A) relative to 100% by mass of the total near-infrared fluorescent material (A) and thermoplastic resin (B) can preferably be in the range of 0.0005% by mass or more, more preferably 0.001% by mass or more. From the viewpoint of detection sensitivity based on concentration quenching and fluorescence reabsorption, it can preferably be in the range of 1% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less.

[0229] The near-infrared fluorescent material used in this invention also has a high molar absorptivity and high quantum yield in the resin. Therefore, even if the concentration of the near-infrared fluorescent material in the resin is relatively low, its emission can be fully visually identified using a camera or the like. From the perspectives of reducing the possibility of dissolution, reducing the possibility of leakage from the molded body processed from the resin composition, and being able to process molded bodies requiring transparency, a low concentration of the near-infrared fluorescent material is preferred.

[0230] <Thermoplastic resins other than polyamide resins (B)>

[0231] The resin composition of the present invention contains a thermoplastic resin (B) other than a polyamide resin, which together with a near-infrared fluorescent material forms a dispersed phase.

[0232] The thermoplastic resin (B) used in this invention is not particularly limited as long as it is a thermoplastic resin other than polyamide resin. It can be appropriately selected from known resins, taking into account factors such as the type of near-infrared fluorescent material to be blended and the required product quality during molding. The thermoplastic resin (B) used in this invention can be a single type or a mixture of two or more types. When mixing two or more types, it is preferable to use resins with high compatibility with each other. Furthermore, the thermoplastic resin (B) can be a commercially available product or a synthetic product.

[0233] Specific examples of the thermoplastic resin (B) used in this invention include, for example, thermoplastic polyurethane (TPU); polycarbonate (PC) resin; polyvinyl chloride resins such as polyvinyl chloride (PVC) and vinyl chloride-vinyl acetate copolymer resin; acrylic resins such as polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate (PMMA), and polyethyl methacrylate; polyethylene terephthalate (PET), polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, and polynaphthalene. Polyester resins such as butylene diformate; polystyrene resins such as polystyrene (PS), imide-modified polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, imide-modified ABS resin, styrene-acrylonitrile copolymer (SAN) resin, acrylonitrile-ethylene-propylene-diene-styrene (AES) resin, polyethylene (PE) resin, polypropylene (PP) resin, cyclic olefin resins, etc.; polyacetal (POM) resin; cellulose resins such as nitrocellulose and cellulose acetate; silicone resins; fluoropolymers, etc.

[0234] Among these thermoplastic resins (B), from the perspective of high dispersibility of near-infrared fluorescent materials, the thermoplastic resin (B) preferably includes at least one selected from the group consisting of thermoplastic polyurethane (TPU) resin, polycarbonate (PC) resin, vinyl chloride resin, acrylic resin, polyester resin, polystyrene resin, olefin resin, and polyacetal (POM) resin. In particular, when the resin composition of the present invention is used as a medical material, considering its low solubility in bodily fluids such as blood, its difficulty in dissolving under the use environment, and its biocompatibility, TPU, PC, PVC, PMMA, PET, PS, PE, and PP are more preferred as the thermoplastic resin (B), and TPU, PC, PMMA, PS, and PE are even more preferred.

[0235] There are no particular limitations on the content of thermoplastic resin (B), as long as it is a concentration in which the near-infrared fluorescent material (A) can be mixed with the thermoplastic resin (B). However, from the viewpoint of fluorescence intensity and its detection sensitivity, the content of thermoplastic resin (B) relative to 100% by mass of the near-infrared fluorescent material (A) and thermoplastic resin (B) can preferably be 99% by mass or more, more preferably 99.2% by mass or more, and even more preferably 99.5% by mass or more. Moreover, it can preferably be 99.9995% by mass or less, and more preferably 99.999% by mass or less.

[0236] <Resin(C)>

[0237] The resin composition of the present invention contains a resin (C) that is different from the thermoplastic resin (B) and forms a continuous phase.

[0238] There are no particular restrictions on the resin (C) as long as it differs from the thermoplastic resin (B). It can be either a thermoplastic resin or a thermosetting resin. Polyamide resins and thermosetting resins that can deactivate the above-mentioned near-infrared fluorescent materials can also be used as resin (C) to form the continuous phase, thereby obtaining a resin composition with high near-infrared fluorescence luminescence efficiency.

[0239] Resin (C) can be used alone or in combination with two or more types. Furthermore, resin (C) can be commercially available or synthetic.

[0240] Specific examples of the resin (C) used in this invention include, for example, urethane resins such as polyurethane (PU) resin and thermoplastic polyurethane (TPU) resin; polycarbonate (PC) resin; vinyl chloride resins such as polyvinyl chloride (PVC) and vinyl chloride-vinyl acetate copolymer resin; acrylic resins such as polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate (PMMA), and polyethyl methacrylate; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate; polyamide resins such as nylon (registered trademark); polystyrene (PS), and amide resins. The epoxy resins include amine-modified polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, imide-modified ABS resin, styrene-acrylonitrile copolymer (SAN) resin, acrylonitrile-ethylene-propylene-diene-styrene (AES) resin, and other polystyrene resins; polyethylene (PE) resin, polypropylene (PP) resin, polybutene resin, cycloolefin resin, and other olefin resins; nitrocellulose, cellulose acetate, and other cellulose resins; silicone resins; thermoplastic resins such as fluoropolymers; bisphenol A type epoxy resin, bisphenol F type epoxy resin, isocyanurate-based epoxy resin, hydantoin-based epoxy resin, and other epoxy resins; melamine resin, urea resin, and other amino resins; phenolic resins; and unsaturated polyester resins and other thermosetting resins. The above-mentioned epoxy resins can be in the form of epoxy resin compositions containing curing agents.

[0241] Resin (C) can be a resin with a cross-linked structure. Examples of resins with a cross-linked structure include cross-linked polyethylene resin, cross-linked polybutene resin, and other cross-linked olefin resins, as well as their silane-modified derivatives.

[0242] From the viewpoint of deactivating the near-infrared fluorescent material (A) or increasing its fluorescence intensity, the resin (C) preferably comprises at least one selected from the group consisting of polyamide resin, polyethylene resin, polypropylene resin, thermosetting resin, and cross-linked polyethylene resin. Furthermore, from the viewpoint of heat resistance and chemical resistance, the resin (C) more preferably comprises a polyamide resin. In addition, from the viewpoint of insulation and voltage resistance, the resin (C) more preferably comprises a thermosetting resin.

[0243] The content of resin (C) in the resin composition of the present invention is not particularly limited as long as it is a concentration in which particles (powders) containing the near-infrared fluorescent material (A) and thermoplastic resin (B) can be mixed in resin (C). However, from the viewpoint that resin (C) can form a continuous phase with good efficiency and obtain excellent luminescence efficiency, the content of resin (C) can preferably be 40% by mass or more, more preferably 50% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, relative to 100% by mass of the total near-infrared fluorescent material (A), thermoplastic resin (B) and resin (C).

[0244] Therefore, relative to the total mass of near-infrared fluorescent material (A), thermoplastic resin (B), and resin (C), the total content of near-infrared fluorescent material (A) and thermoplastic resin (B) in the resin composition of the present invention can preferably be 5% by mass or more, more preferably 10% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less.

[0245] Furthermore, relative to the total mass of near-infrared fluorescent material (A), thermoplastic resin (B), and resin (C) of 100%, the content of near-infrared fluorescent material (A) in the resin composition of the present invention can preferably be 0.000025% by mass or more, more preferably 0.00005% by mass or more, and even more preferably 0.0001%, and can preferably be 0.6% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.48% by mass or less.

[0246] Furthermore, from the viewpoints of formability and luminous efficiency, the following are examples of preferred combinations of thermoplastic resin (B) and resin (C);

[0247] • Thermoplastic resin (B) is polycarbonate resin, and resin (C) is polyamide resin.

[0248] • Thermoplastic resin (B) is polycarbonate resin, and resin (C) is cross-linked polyethylene resin.

[0249] • Thermoplastic resin (B) is polycarbonate resin, and resin (C) is epoxy resin.

[0250] • Thermoplastic resin (B) is polycarbonate resin, and resin (C) is thermoplastic polyurethane resin.

[0251] • Thermoplastic resin (B) is polymethyl methacrylate resin, and resin (C) is cross-linked polyethylene resin.

[0252] • The thermoplastic resin (B) is polystyrene resin and the resin (C) is cross-linked polyethylene resin.

[0253] • The thermoplastic resin (B) is polypropylene resin and the resin (C) is polyethylene resin.

[0254] <Method for manufacturing resin composition>

[0255] The method for manufacturing the resin composition of the present invention is not particularly limited and can be carried out by any known method, for example, the following methods can be cited.

[0256] First, at least near-infrared fluorescent material (A) and thermoplastic resin (B) are blended as essential components to achieve the aforementioned content ratio. The mixture is then uniformly mixed using a tumbler or Henschel mixer (registered trademark). Next, it is fed into a melt-blending extruder such as a twin-screw extruder, and melt-blended within a temperature range above the melt temperature of thermoplastic resin (B) to +100°C, for example, between 180°C and 300°C. This yields a compound of near-infrared fluorescent material and thermoplastic resin (B) as the dispersed phase. It should be noted that, regarding the melt temperature of thermoplastic resin, crystalline resin refers to its melting point, and amorphous resin refers to its softening point (glass transition point) (the same applies hereinafter). After extruding the compound into filaments, it is cooled at room temperature or by immersion in water at a temperature range of 5°C to 60°C, and then cut to produce granules, flakes, or other particulate forms. Subsequently, by cryogenically pulverizing the obtained particles as needed, it is possible to obtain powdered particles (powder) containing near-infrared fluorescent material (A) and thermoplastic resin (B) with a desired size.

[0257] At least the particles (powder) containing near-infrared fluorescent material (A) and thermoplastic resin (B) and resin (C) obtained in this way are mixed to achieve the above-mentioned content, and after being uniformly mixed with a drum or Henschel mixer (registered trademark), a resin mixture can be obtained.

[0258] Subsequently, if resin (C) is a thermoplastic resin, the obtained resin mixture is fed into a melt-mixing extruder such as a twin-screw compounding extruder, and melt-mixed within a range above the melt temperature of resin (C) and below the melt temperature of thermoplastic resin (B), thereby obtaining the resin composition of the present invention. Furthermore, after the resin composition is extruded into a filament, it is cooled by placing it at room temperature or immersing it in water at a temperature range of 5°C to 60°C, and then cut to produce granules, flakes, or other particulate forms. Next, the obtained resin composition is melt-molded to obtain a molded article.

[0259] When a thermosetting resin is used as resin (C), the resulting resin mixture contains resin (C) as an intermediate prepolymer or even an early condensation polymer. Therefore, a curing agent is added to the resin mixture as needed, followed by molding (shaping) and a heating process. This causes the resin (C) to form a three-dimensional structure, allowing the resin composition of the present invention to be molded into a shaped body. During this polymerization, the heating process is preferably performed in a temperature range from room temperature to below the melting temperature of the thermoplastic resin (B).

[0260] When manufacturing a resin composition containing a resin (C) having a cross-linked structure, such as a cross-linked polyolefin resin, the resin composition can be molded into a molded body by conventional methods, for example, using a chemical cross-linking method using a cross-linking agent (organic peroxide), an active energy line cross-linking method using electron beam or X-ray irradiation, or a water cross-linking method using a dehydration condensation reaction of an alkoxysilane after silane modification of a thermoplastic resin (B) such as a polyolefin resin. Therefore, by uniformly mixing the resin (C) before crosslinking (which is also the crosslinking agent in the chemical crosslinking method) with the near-infrared fluorescent material (A) and the thermoplastic resin (B) (which is the silane-modified thermoplastic resin (B) in the aqueous crosslinking method), and then further mixing the crosslinking agent into the resulting resin mixture at a temperature range above the melting temperature of resin (C) and below the melting temperature of resin (B), and by adding a temperature range below the thermal decomposition temperature of the crosslinking agent, the resin composition of the present invention, which includes the resin (C) having a crosslinked structure, can be molded into a shaped body through the following steps: a step of mixing using a known mixing apparatus such as a two-roll mill, a kneader, a Banbury mixer, or an extruder, and a step of molding; and a crosslinking step suitable for each crosslinking method (for example, heating to above the thermal decomposition temperature of the crosslinking agent in the chemical crosslinking method, irradiating with active energy lines in the active energy line crosslinking method, and exposing to an aqueous environment in the aqueous crosslinking method).

[0261] In the resin composition of the present invention, the diameter (dispersion diameter) of the dispersed phase formed by the near-infrared fluorescent material (A) and the thermoplastic resin (B) can preferably be in the range of 1 nm or more, and more preferably 300 μm or less, and more preferably 200 μm or less. By setting it to such a range, the luminous efficiency of the resin composition and the molded article of the present invention is further improved.

[0262] The diameter of the dispersed phase can be controlled by the conditions of cryogenic pulverization of particles containing near-infrared fluorescent material (A) and thermoplastic resin (B), and the conditions of melt mixing when mixing resin (C). Alternatively, the diameter of the dispersed phase can be determined by the method described in the examples.

[0263] It should be noted that when near-infrared fluorescent material (A) is dispersed in thermoplastic resin (B) by melt mixing of thermoplastic resin (B) and near-infrared fluorescent material (A), even when melt mixing is performed at a temperature below the decomposition point of near-infrared fluorescent material (A), fluorescence may not be produced due to poor dispersion or decomposition of near-infrared fluorescent material (A), depending on the types of thermoplastic resin (B), near-infrared fluorescent material (A), and mixing conditions. Furthermore, it is difficult to predict whether near-infrared fluorescent material (A) can be dispersed in thermoplastic resin (B) based on its thermophysical properties.

[0264] In contrast, the compounds represented by the above general formulas (II1), (II2), (II3), or (II4) can be uniformly mixed and dispersed in thermoplastic resins (B) other than polyamide resins, and can also emit fluorescence with a high quantum yield in the resin. The reason for this is not yet clear, but it can be speculated as follows. It is believed that when the near-infrared fluorescent material (A) is dispersed by methods such as melt mixing, if the near-infrared fluorescent material (A) aggregates, the quantum yield of fluorescence will decrease due to concentration quenching. Therefore, in order for the fluorescent material to emit fluorescence efficiently, it is ideal to have high compatibility with thermoplastic resin (B) and be able to disperse uniformly. As an indicator of high compatibility, the SP value can be cited. If the difference between the SP value of the near-infrared fluorescent material (A) and the SP value of the thermoplastic resin (B) is small, then the compatibility is high and it can be dispersed uniformly. On the other hand, even if the SP value and other parameters are different, it can be explained by other physical property parameters. For example, the compatibility with thermoplastic resin (B) can be explained based on calculated or measured values ​​such as the solubility, partition coefficient, relative permittivity, and polarizability of the fluorescent material. Furthermore, the compatibility between near-infrared fluorescent material (A) and thermoplastic resin (B) sometimes varies depending on the crystallinity of the thermoplastic resin (B).

[0265] Furthermore, the compatibility between the thermoplastic resin (B) and the near-infrared fluorescent material (A) can be controlled by the functional groups inherent in the molecules of the near-infrared fluorescent material (A). For example, when dispersed in lipophilic (hydrophobic) polyolefin resins such as polypropylene and polyethylene, the fluorescent material molecules preferably have hydrophobic groups. For example, by introducing hydrophobic groups such as alicyclic alkyl groups, long-chain alkyl groups, halogenated alkyl groups, or aromatic rings into the fluorescent material molecules, the compatibility with the resin can be improved. However, these functional groups are not limited to. Additionally, when dispersed in highly polar resins such as polyurethane, the near-infrared fluorescent material (A) molecules preferably have hydrophilic groups such as carboxyl groups, hydroxyl groups, amino groups, alkoxy groups, aryloxy groups, alkylamino groups, ester groups, or amide groups. However, these are not limited to.

[0266] To improve the compatibility between thermoplastic resin (B) and near-infrared fluorescent material (A), it is necessary to suppress the aggregation of near-infrared fluorescent material (A). In the case of near-infrared fluorescent material (A), aromatic rings and heterocycles are introduced into the molecule to extend the conjugated system and ensure planarity. However, due to the introduction of these rings, the intermolecular interactions become stronger, and there is a tendency for stacking and aggregation to occur easily. For the compounds shown in the above general formulas (II1), (II2), (II3), or (II4), it is speculated that they are prone to aggregation due to the framework formed by a broad conjugated plane centered on the boron atom. However, by introducing electron-donating groups, electron-withdrawing substituents for polarization, and by introducing large functional groups, the aggregation of pigments can be suppressed, and compatibility with thermoplastic resin (B) can be achieved.

[0267] The near-infrared fluorescent material (A) used in this invention can be melt-blended with a thermoplastic resin (B) to achieve uniform dispersion and mixing, thereby forming a resin composition comprising resin (C). The molded article obtained from this resin composition can stably emit near-infrared fluorescence with a high luminescence quantum yield. In particular, the near-infrared fluorescent material (A) represented by the above-mentioned general formulas (II1) to (II4) used in this invention differs from many other organic near-infrared fluorescent materials in that it exhibits high luminescence characteristics even when melt-blended with a thermoplastic resin (B). The reason for this is not yet clear, but it is speculated that it is because the near-infrared fluorescent material (A) used in this invention has a robust framework formed by a wide conjugated plane, high heat resistance, and excellent compatibility with the thermoplastic resin (B). In addition, by forming a dispersed phase by encapsulating the near-infrared fluorescent material (A) in a thermoplastic resin (B) other than a polyamide resin, the deactivation of the near-infrared fluorescent material (A) is suppressed, and various resins can be used as the resin (C) for forming the continuous phase. When the resin composition of the present invention has this form, even resins that can deactivate near-infrared fluorescent materials (A), such as polyamide resins and thermosetting resins, can be used as resins (C).

[0268] When the resin composition of the present invention contains luminescent material with a high quantum yield (number of emitted photons / number of absorbed photons) of 20% or more, it is not particularly problematic. However, when it contains luminescent material with a low quantum yield, understanding the Stokes shift (difference between the maximum absorption wavelength and the maximum emission wavelength) of the resin composition of the present invention is also important.

[0269] When using a conventional light-emitting detector equipped with a filter to reduce noise caused by excitation light, if the Stokes shift of the resin composition of the present invention is small, the light emission is reduced by the filter, making it difficult to detect with high sensitivity. Therefore, the resin composition of the present invention preferably has a Stokes shift (the difference between the maximum absorption wavelength and the maximum emission wavelength) of 10 nm or more, and more preferably a Stokes shift of 20 nm or more. The larger the Stokes shift, the higher the sensitivity at which the light emitted by the molded body can be detected, even when using a conventional detector equipped with a filter to reduce noise caused by excitation light.

[0270] However, even with a small Stokes shift, near-infrared fluorescence from the resin composition of the present invention can be detected with high sensitivity using the following conditions. For example, if excitation is performed with light of a wavelength shorter than the maximum absorption wavelength, fluorescence can be detected even with noise reduction. Furthermore, with a broad fluorescence spectrum, fluorescence can be sufficiently detected even with noise reduction. On the other hand, sometimes fluorescent materials have multiple fluorescence peaks. In this case, even with a small Stokes shift, as long as there is a fluorescence peak (second peak) on the longer wavelength side, high sensitivity can be achieved even when using a detector equipped with a noise-reduction-based filter. In the case where the resin composition of the present invention has multiple fluorescence peaks, the wavelength of the longer wavelength side fluorescence peak only needs to be at least 30 nm different from the maximum absorption wavelength, preferably at least 50 nm. It should be noted that the above conditions are not limited as long as the excitation light source, cutoff filter, etc., are appropriately selected.

[0271] The resin composition of the present invention, containing near-infrared fluorescent material (A), does not change color under visual conditions when excited by excitation light in the near-infrared region, and emits invisible near-infrared fluorescence that can be detected by a detector. Therefore, a maximum absorption wavelength of 600 nm or more is acceptable relative to the excitation light in the near-infrared region. From the viewpoint of absorption efficiency, the maximum absorption wavelength is preferably close to the wavelength of the excitation light, more preferably 650 nm or more, further preferably 665 nm or more, and particularly preferably 680 nm or more. Furthermore, when used as a medical device such as an implant, 700 nm or more is preferred.

[0272] For the resin composition of the present invention containing near-infrared fluorescent material (A) and the molded article obtained from the composition, the color of the irradiated object does not change, and considering the detection sensitivity, a maximum fluorescence wavelength of 650 nm or more is sufficient for practical use, preferably 700 nm or more, and more preferably 720 nm or more. In the case of multiple fluorescence peaks, even if the wavelength of the maximum fluorescence peak is below 720 nm, it is sufficient as long as there is a fluorescence peak with sufficient detection sensitivity above 740 nm. In this case, the intensity of the fluorescence peak on the longer wavelength side (the second peak) relative to the intensity of the maximum fluorescence wavelength is preferably 5% or more, and more preferably 10% or more.

[0273] The resin composition and the molded article obtained from the present invention preferably exhibit strong absorption in the range of 650 nm to 1500 nm and emit strong fluorescence in this range. Light above 650 nm is less affected by hemoglobin, and light below 1500 nm is less affected by water. That is, light in the range of 650 nm to 1500 nm is suitable as a wavelength region for visualizing medical implants implanted subcutaneously due to its high skin permeability and susceptibility to impurities in the body. When the wavelengths of maximum absorption and maximum fluorescence are in the range of 650 nm to 1500 nm, the resin composition and the molded article obtained from the present invention are suitable for detection using light in the range of 650 nm to 1500 nm, and are suitable for use as medical devices in the body.

[0274] The resin composition of the present invention may contain other components besides the above-described resin components and the near-infrared fluorescent material (A), provided that the effects of the present invention are not impaired. Examples of such other components include ultraviolet absorbers, heat stabilizers, light stabilizers, antioxidants, flame retardants, flame retardant additives, crystallization accelerators, plasticizers, antistatic agents, colorants, and mold release agents.

[0275] <molded body>

[0276] By molding the resin composition of the present invention, a molded article capable of luminescence detection can be obtained. That is, according to another aspect of the present invention, a molded article obtained from the resin composition of the present invention is provided.

[0277] There are no particular limitations on the forming method. Examples include casting, injection molding using molds, compression molding, extrusion molding based on T-dies, and blow molding.

[0278] In the manufacture of the molded article, it can be formed solely from the resin composition of the present invention, or it can use the resin composition of the present invention and other resin compositions as raw materials. For example, the entire molded article can be formed from the resin composition of the present invention, or only a portion of the molded article can be formed from the resin composition of the present invention. The resin composition of the present invention is preferably used as a raw material constituting the surface portion of the molded article. For example, in the case of forming a conduit, only the tip of the conduit can be formed from the resin composition of the present invention, while the remaining portion can be formed from a resin composition that does not contain near-infrared fluorescent material, thereby enabling the manufacture of a conduit that emits near-infrared fluorescence only at the tip. In addition, by alternately layering and forming the resin composition of the present invention and a resin composition that does not contain near-infrared fluorescent material, it is possible to manufacture a molded article that emits near-infrared fluorescence in a striped pattern. Furthermore, a surface coating can be applied to improve the visual recognizability of the molded article.

[0279] Luminescence detection can be performed using commercially available fluorescence or phosphorescence detection devices and conventional methods. As the excitation light used in fluorescence or phosphorescence detection, any light source can be used, including near-infrared lamps with a wide wavelength range, as well as lasers, LEDs, etc., with a narrow wavelength range.

[0280] The molded articles obtained from the resin composition of the present invention containing near-infrared fluorescent material (A) do not change color even when irradiated with light in the near-infrared region, emitting near-infrared fluorescence that can be detected with higher sensitivity than before. Therefore, this molded article is particularly suitable for medical devices that are inserted or left in the patient's body in at least a portion.

[0281] When performing fluorescence detection on molded articles obtained from the resin composition of the present invention containing near-infrared fluorescent material (A), it is preferable to irradiate with excitation light in the near-infrared region. However, if the color of the irradiated object is only slightly reddish, it is not necessary to use excitation light in the near-infrared region. For example, when performing fluorescence detection on medical devices inside the body by irradiating with excitation light, it is necessary to use excitation light in a wavelength region with high transmittance to biological bodies such as skin. However, in this case, excitation light with high transmittance to biological bodies at 650 nm or higher can be used.

[0282] Examples of such medical devices include, for example, stents, coil embolus, catheter tubes, injection needles, indwelling needles, ports, shunts, drainage tubes, and implants.

[0283] <Detection methods, detection devices, verification systems>

[0284] The detection method of the present invention includes a step of irradiating the molded body with near-infrared light, and a step of detecting the near-infrared emission emitted by the molded body using a device for detecting such emission.

[0285] In addition, the detection device of the present invention includes means for irradiating near-infrared light toward the aforementioned molded body, and means for detecting the near-infrared emission emitted by the aforementioned molded body.

[0286] As a means of irradiating the aforementioned molded body with near-infrared light, any light source can be used as long as it is a light source capable of irradiating the excitation light used for emission detection. In addition to near-infrared lamps with a wide wavelength range, lasers, LEDs, etc. with a narrow wavelength range can also be used. As for the wavelength of the irradiating light source, it is sufficient as long as it is a wavelength capable of exciting the near-infrared fluorescent pigment contained in the molded body. Generally, there is no particular problem as long as it is a wavelength referred to as near-infrared light. For example, 650 nm or more is preferred, 700 nm or more is more preferred, and 2500 nm or less is more preferred, and 1100 nm or less is more preferred.

[0287] There are no particular restrictions on the irradiation of the molded body by near-infrared light as long as it is done by conventional methods. For example, one or more light sources can irradiate from above or below the plumb line of the molded body, from an oblique angle, or from various different directions relative to the molded body. When the light source and the near-infrared emission detection device (described later) are positioned approximately in the same location relative to the molded body, ring illumination or line illumination is preferred as the light source.

[0288] As a means of detecting near-infrared emission, commercially available near-infrared emission detection devices can be used, without particular limitation. For example, imaging devices such as digital cameras using CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide-Semiconductor) imaging elements, as well as detection devices such as beam splitters, photomultiplier tubes, PbS detectors, and photodiodes can be used. The imaging device can be an area camera or a line camera. As a means of detecting near-infrared emission, for example, when using a detector other than an imaging device such as a photodiode, the electrical signal from the detector is amplified in a circuit board equipped with a signal amplification section such as a magnetic head amplifier. The presence or absence of emission can be detected based on the output value of the amplified electrical signal.

[0289] Furthermore, by having a means for analyzing the presence or absence of near-infrared emission detection, the presence or absence of the molded article of the present invention can be determined based on the emission information. This analysis means can be commercially available and is not particularly limited; for example, a personal computer with image analysis software installed, or hardware capable of implementing image processing algorithms (e.g., a microcomputer, a PLC (programmable logic controller), an FPGA (field-programmable gate array), etc.) can be used.

[0290] The location confirmation system of the present invention, in addition to the detection device of the present invention, also includes a monitor that displays the captured images. When the molded body of the present invention is a medical device, it can be used as a medical device location confirmation system, capable of visually identifying the location of medical devices inserted or left in the body through surgery or other procedures.

[0291] Example

[0292] The present invention will be described in more detail using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. In the following examples, the terms "%" and "parts" are used, which, unless otherwise specified, represent "mass %" or "parts by mass".

[0293] (Preparation of near-infrared fluorescent material (A))

[0294] Near-infrared fluorescent materials 1-3 (pigments 1-3 in the following formulas) were synthesized with reference to Chemistry A European Journal, 2009, Vol. 15, pp. 4857-4864.

[0295] Pigment 1 (a compound with the above chemical formula 6-4-1)

[0296]

[0297] Example of pigment 1 synthesis

[0298]

[0299] <Synthesis of Pigment 1>

[0300] For pigment 1, refer to Organic Letters, 2012, Vol. 4, pp. 2670–2673, and Chmestry A European Journal, 2009, Vol. 15, pp. 4857–4864, as follows.

[0301] In a 2L four-necked flask, 25.3 g (212 mmol) of 4-hydroxybenzonitrile, 800 mL of acetone, 100 g (724 mmol) of potassium carbonate, and 48 g (249 mmol) of 1-bromooctane were added and the mixture was heated under reflux overnight. After filtering out the inorganic salts, the acetone was removed under reduced pressure. Ethyl acetate was added to the residue, and the organic layer was washed with water and saturated brine. The residue was then treated with anhydrous magnesium sulfate. After filtering out the magnesium sulfate and removing the solvent under reduced pressure, the residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to give a colorless, transparent liquid of 4-octyloxybenzonitrile (1-1) (yield: 45.2 g, 92%).

[0302] Next, under an argon atmosphere, potassium tert-butoxide (25.18 g, 224.4 mmol) and tert-amyl alcohol (160 mL) were added to a 500 mL four-necked flask. Then, a solution of the previously synthesized compound (1-1) (14.8 g, 64 mmol) mixed with tert-amyl alcohol (7 mL) was added, and the mixture was heated to reflux. Under reflux, a solution of tert-amyl alcohol (10 mL) mixed with diisopropyl succinate (6.5 g, 32 mmol) was added dropwise over approximately 3 hours. After the addition was complete, the mixture was heated to reflux for 6 hours. After returning to room temperature, the resulting highly viscous reaction solution was placed in a solution of acetic acid:methanol:water = 1:1:1 (volume ratio) and heated to reflux for a few minutes, resulting in the precipitation of a red solid. The solid was filtered off and washed with heated methanol and water to give a red solid of 3,6-(4-octoxyphenyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (1-2) (yield: 5.6 g, 32%).

[0303] 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 below 15 °C, bromine (4.5 mL, 87 mmol) was added dropwise over approximately 20 minutes, followed by stirring at below 15 °C for 3.5 hours. The reaction mixture was then placed in 150 mL of 28% ammonia solution and stirred for a period of time. The precipitated solid was filtered off and extracted with diethyl ether. The organic layer was washed with water. After removing the diethyl ether under reduced pressure, the residue was purified by silica gel column chromatography (eluent: dichloromethane / ethyl acetate) to give 2-amino-6-tert-butylbenzothiazole (1-3) as a pale yellow solid (yield: 10.32 g, 69%).

[0304] Next, potassium hydroxide (75.4 g, 1340 mmol) and ethylene glycol (175 mL) were added to a 1 L four-necked flask under water cooling. Compounds (1-3) (7.8 g, 37.8 mmol) were added under an argon atmosphere. To remove oxygen from the system, the mixture was bubbled with argon, and the reaction was carried out at 110 °C for 18 hours. The reaction solution was cooled to below 40 °C, and 2 mol / L hydrochloric acid, which had been pre-bubbled with argon, was added dropwise to neutralize the system (to approximately pH 7). The precipitated white solid was filtered off, washed with water, and dried under reduced pressure. The white solid was then purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to give a white solid of 4-tert-butyl-2-mercaptoaniline (1-4) (yield: 2.39 g, 35%).

[0305] Next, acetic acid (872 mg, 14.5 mmol) and acetonitrile (30 mL) were placed in a 100 mL three-necked flask under an argon atmosphere. Under argon atmosphere, malononitrile (2.4 g, 36.3 mmol) and compounds (1-4) (2.39 g, 13.2 mmol) were added, and the mixture was heated to reflux for 2 hours. Acetonitrile was removed under reduced pressure, and the residue was dissolved in ethyl acetate. The organic layer was washed with water and saturated brine, and then treated with anhydrous magnesium sulfate. Magnesium sulfate was filtered off, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to give a pale yellow solid of 2-(6-tert-butylbenzothiazo-2-yl)acetonitrile (1-5) (yield: 1.98 g, 65%).

[0306] Next, under an argon atmosphere, compounds (b-2) (1.91 g, 3.5 mmol), (1-5) (1.77 g, 7.68 mmol), and dehydrated toluene (68 mL) were added to a 200 mL three-necked flask, and the mixture was heated to reflux. Phosphoryl chloride (2.56 mL, 27.4 mmol) was added dropwise using a syringe under reflux, and the mixture was heated to reflux for 2 hours. After the reaction was complete, dichloromethane (40 mL) and a saturated sodium bicarbonate aqueous solution (40 mL) were added while the mixture was ice-cold, and the mixture was extracted with dichloromethane. The organic layer was treated with anhydrous magnesium sulfate, the magnesium sulfate was filtered off, the solvent was removed under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: hexane / ethyl acetate) to largely remove impurities. The residue obtained after distilling off the solvent was purified again by silica gel column chromatography (elution: hexane / dichloromethane) to give the green solid of precursor (1-6) (yield: 1.56 g, yield: 46%).

[0307] Finally, under an argon atmosphere, precursors (1-6) (1.52 g, 1.57 mmol), toluene (45 mL), triethylamine (4.35 mL, 31.4 mmol), and boron trifluoride diethyl ether complex (7.88 mL, 62.7 mmol) were added to a 200 mL three-necked flask, and the mixture was heated under reflux for 1 hour. The reaction solution was cooled, and the precipitated solid was filtered off. The solid was washed with water, saturated sodium bicarbonate aqueous solution, 50% methanol aqueous solution, and methanol, and then dried under reduced pressure. The residue was dissolved in toluene, and methanol was added to precipitate it, thus giving pigment 1 as a dark green solid (yield: 1.25 g, 75%).

[0308] Pigment 2 (a compound with the above chemical formula 6-5-1)

[0309]

[0310] Example of pigment 2 synthesis

[0311]

[0312] <Synthesis of Pigment 2>

[0313] For pigment 2, refer to Organic Letters, 2012, Vol. 4, pp. 2670–2673, and Chmestry A European Journal, 2009, Vol. 15, pp. 4857–4864, as follows.

[0314] In a 300 mL three-necked flask, 29.8 g (0.2 mol) of 4-tert-butylaniline and 100 mL of 6 mol / L hydrochloric acid were added. Crotonaldehyde (15.4 g, 0.22 mol) was added dropwise while refluxing, and the mixture was refluxed for 2 hours. Reflux was stopped, and zinc chloride (27.2 g, 0.2 mol) was added while hot. The mixture was stirred at room temperature overnight. The supernatant was removed, and isopropanol was added to the yellow, slurry-like residue. The mixture was refluxed for 2 hours. The mixture was cooled to 70 °C, and 200 mL of petroleum ether was added. The precipitated crystals were filtered out and collected. After washing with diethyl ether, the crystals were dried to obtain the zinc complex. The zinc complex was added to a water / ammonia (120 mL / 60 mL) mixture and extracted three times with diethyl ether (80 mL). The obtained organic layer was dried with anhydrous magnesium sulfate and then concentrated to obtain a yellow liquid of 6-tert-butyl-2-methyl-quinoline (2-1) (yield 16.2 g, 41%).

[0315] Next, compound (2-1) (16.0 g, 80 mmol) and chloroform (50 mL) were placed in a 200 mL two-necked flask and stirred. Trichloroisocyanuric acid (6.52 g, 28 mmol) was added in portions. After refluxing the mixture for 1 hour, the precipitated solid was filtered off, washed with chloroform, and the resulting organic layer was extracted three times with 1 mol / L sulfuric acid. The aqueous layers were combined, adjusted to pH 3 with sodium carbonate solution, and extracted three times with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate and concentrated to give pale yellow crystals of 2-chloromethyl-6-tert-butyl-quinoline (2-2) (yield 4.8 g, 25.7%).

[0316] Next, compound (c-2) (4.7 g, 20 mmol), sodium cyanide (1.47 g, 30 mmol), a small amount of sodium iodide, and DMF (50 mL) were placed in a 100 mL three-necked flask, and the reaction was carried out at 60 °C for 2 hours. After cooling the reaction solution, it was extracted with water (200 mL) / ethyl acetate (300 mL), and the resulting ethyl acetate layer was washed with water. The organic layer was dried with anhydrous magnesium sulfate, concentrated, and recrystallized in petroleum ether to give white crystals of 2-(6-tert-butylquinoline-2-yl)acetonitrile (2-3) (yield 1.9 g, 42.4%).

[0317] Next, under an argon atmosphere, compounds (1-2) (2.18 g, 4.0 mmol), compounds (2-3) (1.9 g, 8.5 mmol), and dehydrated toluene (68 mL) used in the synthesis of pigment 1 were added to a 200 mL three-necked flask, and the mixture was heated to reflux. Phosphorus oxychloride (2.62 mL, 28 mmol) was added dropwise using a syringe under reflux, and the mixture was heated to reflux for 2 hours. After the reaction was complete, dichloromethane (40 mL) and a saturated sodium bicarbonate aqueous solution (40 mL) were added while the mixture was ice-cold, and the mixture was extracted with dichloromethane. The organic layer was treated with anhydrous magnesium sulfate, and after filtering out the magnesium sulfate, the solvent was removed under reduced pressure. The residue was subjected to silica gel column chromatography (elution: hexane / ethyl acetate) to largely remove impurities. The residue obtained after distilling off the solvent was purified again by silica gel column chromatography (elution: hexane / dichloromethane) to give the green solid of precursor (1-4) (yield: 1.84 g, yield: 48%).

[0318] Finally, under an argon atmosphere, precursor (2-4) (1.72 g, 1.8 mmol), toluene (45 mL), triethylamine (4.35 mL, 31.4 mmol), and boron trifluoride diethyl ether complex (7.88 mL, 62.7 mmol) were added to a 200 mL three-necked flask, and the mixture was heated under reflux for 1 hour. The reaction solution was cooled, and the precipitated solid was filtered off. The solid was then washed with water, saturated sodium bicarbonate aqueous solution, 50% methanol aqueous solution, and methanol, and dried under reduced pressure. The resulting residue was dissolved in toluene, and methanol was added to precipitate it, thus yielding a dark green solid of pigment 2 (yield: 1.10 g, 58%).

[0319] Pigment 3 (a compound with the above chemical formula 6-11-1)

[0320]

[0321] <Synthesis of Pigment 3>

[0322] Pigment 3 uses precursor 2-4, which was used in the synthesis of pigment 2. Under an argon atmosphere, precursor (2-4) (630 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. While refluxing, dichlorophenylborane (600 mg, 3.0 mmol) was added, and the reaction was carried out overnight. The reaction mixture 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 / 10) to obtain a brown solid of pigment 3 (yield: 186 mg, 22%).

[0323] (Manufacturing Examples 1-9)

[0324] Preparation of resin compositions for dispersed phase

[0325] According to the mixing amounts listed in Table 1 below, near-infrared fluorescent material (A) and thermoplastic resin (B) were premixed in a rotary drum and then melt-mixed in a 30 mm φ twin-screw vented extruder at the set temperature listed in Table 1. After cooling the resulting mixture, it was granulated using a granulator to manufacture the granules of Manufacturing Examples 1 to 8 (granules (1) to (8)).

[0326] It should be noted that the following substances are used as thermoplastic resin (B). Furthermore, the values ​​in Table 1 are based on parts by mass:

[0327] • B1: Polycarbonate resin (manufactured by Sumika Polycarbonate Limited, SD POLYCA (trademark) 301-4”)

[0328] •B2: Polymethyl methacrylate (PMMA) resin (manufactured by Mitsubishi Chemical Corporation, ACRYPET (trademark) VH001)

[0329] • B3: Polystyrene resin (manufactured by DIC Corporation, DICSTYRENE CR-4500)

[0330] •B4: Polypropylene resin (manufactured by Prime Polymer Co., Ltd., Prime Polypro (registered trademark) J106G).

[0331] • Pulverization of the resin composition for the dispersed phase

[0332] Next, the granules (1) to (8) obtained above were pulverized using a JFC-2000 cryogenic pulverizer manufactured by Japan Analysis Industries Co., Ltd. Specifically, the granules and tungsten carbide balls were placed in a stainless steel container, the container was covered, and the mixture was pre-cooled in liquid nitrogen for 10 minutes, pulverized for 15 minutes, and subjected to cryogenic pulverization at a reciprocating motion of 1200 times / minute to obtain powder. The powder was then dispersed in ethanol, and the resulting dispersion was pressure filtered using a filter with a defined capture particle size (300 μm) to obtain powders (1) to (8) having the average particle size described in Table 1.

[0333] In addition, the granules (1) were cryogenically pulverized using the same cryogenic pulverizer, pre-cooled in liquid nitrogen for 5 minutes, pulverized for 8 minutes, and reciprocated pulverization for 1200 times / minute to obtain powder. The powder was then dispersed in ethanol, and the resulting dispersion was pressure filtered using a filter with a defined capture particle size (500 μm) to obtain powder (9) having the average particle size described in Table 2. It should be noted that the maximum particle size of the powder (9) determined by the method described below (determination of the average particle size of the pulverized material) is 324 μm.

[0334] (Determination of the average particle size of the pulverized material)

[0335] The volume average particle size of the obtained powder was determined using a Solmix (registered trademark) A-7 (manufactured by Japan Alcohol Corporation) image resolution particle size analyzer (manufactured by JASCO INTERNATIONAL CO.,LTD.: IF-3200). The maximum particle size (cumulative 100%) of powder (9) was also determined.

[0336] (Luminescence Evaluation)

[0337] The luminescence evaluation of the obtained powders (1) to (9) was carried out by the following method.

[0338] Camera: STC-MBCM200U3V-NIR manufactured by OMRON SENTECH CO.,LTD.

[0339] Light source unit: manufactured by Revox, with a wavelength of 720-850nm mounted on an SPL-CC substrate.

[0340] The distance between the light source and the sample (0.5g of powder placed flat on a 52×76mm glass plate) was set to 20cm. The sample was placed horizontally and positioned 30cm vertically from the camera. The camera's imaging status was visually evaluated based on the following criteria:

[0341] A...very clear

[0342] B···Clear

[0343] C··· Confirm luminescence

[0344] ×··· No light emission detected (no light emission).

[0345] The composition and evaluation results of powders (1) to (9) are shown in Table 1 below. It should be noted that the blank columns in Table 1 indicate that the material was not used.

[0346] [Table 1]

[0347]

[0348] (Example 1: Manufacturing islands and polyamide seas of Example 1 (encapsulated PC with pigment))

[0349] 20 parts by weight of the powder (1) obtained in Manufacturing Example 1 and 80 parts by weight of the polyamide resin (manufactured by Arkema, PEBAX (registered trademark) 4033SA01) as resin (C) were stirred and mixed in a rotary drum, and then melt-kneaded in a 30 mm φ twin-screw vented extruder (set temperature 200 °C). Subsequently, the mixture was granulated to produce a resin composition (1). The obtained resin composition (1) was shaped using an extruder equipped with a T-die (set temperature 220 °C) to produce a sheet sample (1) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0350] (Example 2: Manufacturing islands and seas of cross-linked polyethylene from Example 1 (encapsulated PC with pigment))

[0351] 20 parts by weight of the powder (1) obtained in Manufacturing Example 1, 78 parts by weight of polyethylene resin (manufactured by Japan Polyethylene Corporation, NOVATEC (trademark) LL UJ580, linear low-density polyethylene) as resin (C), and 2 parts by weight of crosslinking agent (manufactured by Nippon Oil Co., Ltd., PERHEXA (registered trademark) 25B-40, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane) as resin (C) were stirred and mixed in a rotary drum, and then kneaded in a two-roll mill at 125°C to obtain a resin composition (2). Subsequently, the sample (2) was heated and pressed at 200°C for 2 minutes and 10 MPa to produce a sheet sample (2) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0352] (Example 3: (Islands of manufacturing Example 2 (encapsulated PMMA with pigment) and seas of cross-linked polyethylene)

[0353] 20 parts by weight of the powder (2) obtained in Manufacturing Example 2, 78 parts by weight of polyethylene resin (manufactured by Japan Polyethylene Corporation, NOVATEC (trademark) LL UJ580, linear low-density polyethylene) as resin (C), and 2 parts by weight of crosslinking agent (manufactured by Nippon Oil Co., Ltd., PERHEXA (registered trademark) 25B-40, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane) as resin (C) were stirred and mixed in a rotary drum, and then kneaded in a two-roll mill at 125°C to obtain a resin composition (3). Subsequently, the sample (3) was heated and pressed at 200°C for 2 minutes and 10 MPa to produce a sheet sample (3) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0354] (Example 4: Manufacturing islands and cross-linked polyethylene seas of Example 3 (encapsulated pigmented PS))

[0355] 20 parts by weight of the powder (3) obtained in Manufacturing Example 3, 78 parts by weight of polyethylene resin (manufactured by Japan Polyethylene Corporation, NOVATEC (trademark) LL UJ580, linear low-density polyethylene) as resin (C), and 2 parts by weight of crosslinking agent (manufactured by Nippon Oil Co., Ltd., PERHEXA (registered trademark) 25B-40, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane) as resin (C) were stirred and mixed in a rotary drum, and then kneaded in a two-roll mill at 125°C to obtain a resin composition (4). Subsequently, the sample (4) was heated and pressed at 200°C for 2 minutes and 10 MPa to produce a sheet sample (4) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0356] (Example 5: Manufacturing the island and the sea of ​​epoxy resin of Example 1 (encapsulated PC with pigment))

[0357] 20 parts by weight of the powder (1) obtained in Manufacturing Example 1 and 80 parts by weight of the epoxy resin composition (made relative to 100 parts by weight of DIC Corporation and 90 parts by weight of EPICLON (registered trademark) 850 mixed curing agent (manufactured by DIC Corporation and EPICLON (registered trademark) B-5001)) were stirred and mixed in a mixer, and then degassed under reduced pressure to obtain a resin composition (5). Next, the obtained resin composition (5) was injected into a molding die and then cured at 120°C for 1 hour to produce a sheet sample (5) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0358] (Example 6: Manufacturing the island and the sea of ​​polyethylene resin of Example 4 (encapsulated pigmented PP))

[0359] 20 parts by weight of the powder (4) obtained in Manufacturing Example 4 and 80 parts by weight of polyethylene resin (manufactured by Japan Polyethylene Corporation, NOVATEC (trademark) LL UJ580, linear low-density polyethylene) as resin (C) were stirred and mixed in a rotary drum, and then melt-kneaded in a 30 mm φ twin-screw vented extruder (set temperature 140°C), and then granulated to produce a resin composition (6). The obtained resin composition (6) was shaped in an extruder equipped with a T die (set temperature 140°C) to produce a sheet sample (6) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0360] (Example 7: Manufacturing islands and seas of TPU resin from Example 1 (encapsulated PC with pigment))

[0361] 20 parts by weight of powder (1) obtained in Manufacturing Example 1 and 80 parts by weight of thermoplastic polyurethane resin (Lubrizol Corporation, Tecoflex EG65D) as resin (C) were stirred and mixed in a rotary drum, and then melt-kneaded in a 30 mm φ twin-screw vented extruder (set temperature 190 °C), and then granulated to produce resin composition (7). The obtained resin composition (7) was shaped in an extruder equipped with a T die (set temperature 200 °C) to produce sheet sample (7) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0362] (Example 8: Manufacturing islands and polyamide seas of Example 5 (encapsulated PC with pigment))

[0363] 20 parts by weight of the powder (5) obtained in Manufacturing Example 5 and 80 parts by weight of the polyamide resin (manufactured by Arkema, PEBAX (registered trademark) 4033SA01) as resin (C) were stirred and mixed in a rotary drum, and then melt-kneaded in a 30 mm φ twin-screw vented extruder (set temperature 200 °C). Subsequently, the mixture was granulated to produce a resin composition (8). The obtained resin composition (8) was shaped in an extruder equipped with a T-die (set temperature 220 °C) to produce a sheet sample (8) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0364] (Example 9: Manufacturing islands and polyamide seas of Example 6 (encapsulated PC with pigment))

[0365] 20 parts by weight of the powder (6) obtained in Manufacturing Example 6 and 80 parts by weight of the polyamide resin (manufactured by Arkema, PEBAX (registered trademark) 4033SA01) as resin (C) were stirred and mixed in a rotary drum. The mixture was then melt-kneaded in a 30 mm φ twin-screw vented extruder (set temperature 200 °C), and then granulated to produce a resin composition (9). The obtained resin composition (9) was formed in an extruder equipped with a T-die (set temperature 220 °C) to produce a sheet sample (9) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0366] (Example 10: Manufacturing islands and polyamide seas of Example 7 (encapsulated PC with pigment))

[0367] 20 parts by weight of the powder (7) obtained in Manufacturing Example 7 and 80 parts by weight of the polyamide resin (manufactured by Arkema, PEBAX (registered trademark) 4033SA01”) as resin (C) were stirred and mixed in a rotary drum, and then melt-kneaded in a 30 mm φ twin-screw vented extruder (set temperature 200°C), and then granulated to produce a resin composition (10). The obtained resin composition (10) was shaped in an extruder equipped with a T die (set temperature 220°C) to produce a sheet sample (10) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0368] (Example 11: Manufacturing islands and polyamide seas of Example 8 (encapsulated PC with pigment))

[0369] 20 parts by weight of the powder (8) obtained in Manufacturing Example 8 and 80 parts by weight of the polyamide resin (manufactured by Arkema, PEBAX (registered trademark) 4033SA01”) as resin (C) were stirred and mixed in a rotary drum, and then melt-kneaded in a 30 mm φ twin-screw vented extruder (set temperature 200°C), and then granulated to produce a resin composition (11). The obtained resin composition (11) was shaped in an extruder equipped with a T die (set temperature 220°C) to produce a sheet sample (11) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0370] (Example 12: Manufacturing islands and polyamide seas of Example 9 (encapsulated PC crude material with pigment))

[0371] 20 parts by weight of the powder (9) obtained in Manufacturing Example 9 and 80 parts by weight of the polyamide resin (manufactured by Arkema, PEBAX (registered trademark) 4033SA01) as resin (C) were stirred and mixed in a rotary drum, and then melt-kneaded in a 30 mm φ twin-screw vented extruder (set temperature 200°C), and then granulated to produce a resin composition (12). The obtained resin composition (12) was shaped in an extruder equipped with a T-die (set temperature 220°C) to produce a sheet sample (12) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0372] (Comparative Example 1: Islands of pigments and seas of polyamides)

[0373] 0.001 parts by weight of the near-infrared fluorescent material (pigment 1) obtained in Synthesis Example 1 and 99.995 parts by weight of polyamide resin (manufactured by Arkema, PEBAX (registered trademark) 4033SA01) were stirred and mixed in a rotary drum, and then melt-kneaded in a 30 mm φ twin-screw vented extruder (set temperature 200 °C). Subsequently, the mixture was granulated to produce a resin composition (c2). The obtained resin composition (c2) was shaped in an extruder equipped with a T-die (set temperature 220 °C) to produce a sheet sample (c1) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0374] (Comparative Example 2: Islands of pigment and seas of cross-linked polyethylene)

[0375] 0.001 parts by weight of the near-infrared fluorescent material (pigment 1) obtained in Synthesis Example 1, 97.495 parts by weight of polyethylene resin (manufactured by Japan Polyethylene Corporation, NOVATEC (trademark) LL UJ580), and 2.500 parts by weight of crosslinking agent (manufactured by Nippon Oil Co., Ltd., PERHEXA (registered trademark) 25B-40 (2,5-dimethyl-2,5-di(tert-butylperoxide)hexane)) were stirred and mixed in a rotary drum, and then kneaded in a two-roll mill at 125°C to obtain a resin composition (c2). The obtained resin composition (c2) was heated and pressed at 200°C for 2 minutes at 10 MPa to produce a sheet sample (c2) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0376] (Comparative Example 3: Islands of pigment and seas of epoxy resin)

[0377] 0.001 parts by weight of the near-infrared fluorescent material (pigment 1) obtained in Synthesis Example 1 and 99.995 parts by weight of the epoxy resin composition (DIC Corporation, EPICLON (registered trademark) 850, manufactured in 100 parts by weight) and the curing agent (DIC Corporation, EPICLON (registered trademark) B-5001, manufactured in 100 parts by weight) were stirred and mixed in a mixer, and then degassed under reduced pressure to obtain a resin composition (c3). Next, the obtained resin composition (c3) was injected into a molding die and cured at 120°C for 1 hour to produce a sheet sample (c3) with a length of 127 mm × width of 12.7 mm × thickness of 1 mm.

[0378] [evaluate]

[0379] (Diameter of the dispersed phase)

[0380] The average diameter of the dispersed phase in the obtained sheet samples (1) to (12) and the comparative sheet samples (c1) to (c3) was evaluated using the following method.

[0381] That is, the sample sheets (1) to (12) and the comparative sample sheets (c1) to (c3) were cut along a direction perpendicular to the surface. The exposed cut sections were smoothed by grinding and then observed and imaged using a digital microscope (KEYENCE CORPORATION: VHX-7000). Next, at a magnification of 200x, 50 non-repeating dispersed phases (island portions of the island structure) were selected and their particle size distribution was determined in the form of circular equivalent diameter. The average diameter was calculated as a number average.

[0382] (Luminous efficiency)

[0383] The luminous efficiency of the obtained sample sheets (1) to (12) and the comparative sample sheets (c1) to (c3) was evaluated using the following method:

[0384] Camera: SENTEC Corp., Ltd., STC-MBCM200U3V-NIR

[0385] Light source unit: manufactured by Revox, with 720-850nm lamps mounted on an SPL-CC substrate in a darkroom.

[0386] The distance between the light source and the sample was set to 20cm. The sample was placed horizontally and positioned 30cm perpendicularly to the camera. The camera was used to take a picture (see reference). Figure 1 The obtained image was processed using the image processing software "Image" to be divided into 256 orders from 0 to 255 and then evaluated. No emission was recorded as order 0, and the highest order in the image was taken as the luminous efficiency of the film. A higher order indicates higher luminous efficiency.

[0387] The evaluation results are shown in Table 2 below. It should be noted that in the "Average Diameter of Dispersed Phase" item in Table 2 below, "Cannot be identified" means that the dispersed phase could not be identified.

[0388] [Table 2]

[0389]

[0390] As can be clearly seen from Table 2 above, the resin compositions of Examples 1 to 12 exhibit superior luminous efficiency compared to the resin compositions of Comparative Examples 1 to 3.

[0391] Explanation of reference numerals in the attached figures

[0392] 1. Camera

[0393] 2. Analysis device

[0394] 3 light source units

[0395] 4. Samples (pieces).

Claims

1. A resin composition comprising: a near-infrared fluorescent material (A), a thermoplastic resin other than a polyamide resin (B), and a resin (C) different from the thermoplastic resin (B), the resin (C) forms a continuous phase, and a dispersed phase of the near-infrared fluorescent material (A) and the thermoplastic resin (B) is formed in the continuous phase, a diameter of the dispersed phase formed by the near-infrared fluorescent material (A) and the thermoplastic resin (B) is 27 μm or more and 150 μm or less, the near-infrared fluorescent material (A) is a compound having an extremely large fluorescent wavelength in a near-infrared region, the near-infrared fluorescent material (A) is at least one compound selected from the group consisting of a compound represented by the following general formula (II1), a compound represented by the following general formula (II2), a compound represented by the following general formula (II3), and a compound represented by the following general formula (II4), an extremely large fluorescent wavelength of the resin composition is 650 nm or more, in the formula (II1), R a and R b and R a and the carbon atom to which R b is bound form an aromatic 5-membered ring, an aromatic 6-membered ring, or a fused aromatic ring condensed from 2 to 3 5-membered or 6-membered rings; R c and R d and R c and the carbon atom to which R d is bound form an aromatic 5-membered ring, an aromatic 6-membered ring, or a fused aromatic ring condensed from 2 to 3 5-membered or 6-membered rings; R e and R f each independently represents a halogen atom or an oxygen atom; R g represents a hydrogen atom or an electron-withdrawing group, wherein R e and R f are oxygen atoms, the boron atom to which R e and R e are bonded, the nitrogen atom to which R a and R a are bonded optionally form a ring together; R f and R f are bonded, the boron atom to which R c and R c are bonded, the nitrogen atom to which R e and R e are bonded optionally form a ring together; R f is an oxygen atom, and is not formed into a ring, R f is an oxygen atom having a substituent, In formula (II2), R a ~R f is the same as in formula (II1) in the formula (II3), R h and R i With R h The bonded nitrogen atom and R i The bonded carbon atoms together form an aromatic 5-membered ring, an aromatic 6-membered ring, or a fused aromatic ring formed by the condensation of 2 to 3 5-membered or 6-membered rings. R j and R k With R j The bonded nitrogen atom and R k The bonded carbon atoms together form an aromatic 5-membered ring, an aromatic 6-membered ring, or a fused aromatic ring formed by the condensation of 2 to 3 5-membered or 6-membered rings. R l , R m , R n , and R o each independently represent a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group; R p and R q each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group; R r and R s each independently represents a hydrogen atom or an electron- withdrawing group, In formula (II4), R h ~R q is the same as in formula (II3).

2. The resin composition according to claim 1, wherein, the near-infrared fluorescent material (A) contains at least one compound selected from the group consisting of a compound represented by any one of the following general formulae (II3-1) to (II3-6) and a compound represented by any one of the following general formulae (II4-1) to (II4-6), in the formula (II3-1), R 23 , R 24 , R 25 , and R 26 each independently represent a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group; R 27 and R 28 each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group; R 29 and R 30 each independently represents a hydrogen atom or an electron- withdrawing group; Y 9 and Y 10 each independently represents a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom; For R 31 and R 32 : (p4) each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group, or (p5) R 31 and R 32 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring; For R 33 and R 34 : (q4) each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group, or (q5) R 33 and R 34 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring; In the formulae (II3-2) to (II3-6), R 23 ~R 30 are the same as in the formula (II3-1); X 1 and X 2 each independently represents a nitrogen atom or a phosphorus atom; For R 35 , R 36 , R 37 , and R 38 : (p6) each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, C 1-20 alkoxy group, an aryl group, or a heteroaryl group, (p7) R 35 and R 36 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 37 and R 38 each independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group, (p8)R 36 and R 37 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 35 and R 38 each independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group, or (p9) R 37 and R 38 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 35 and R 36 each independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group; For R 39 , R 40 , R 41 , and R 42 : (q6) each independently represents a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group, (q7) R 39 and R 40 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 41 and R 42 each independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group, (q8) R 40 and R 41 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 39 and R 42 each independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group, or (q9) R 41 and R 42 together form an optionally substituted aromatic 5-membered ring or an optionally substituted aromatic 6-membered ring, R 39 and R 40 each independently represent a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an aryl group, or a heteroaryl group, In formulae (II4-1) to (II4-6), R 23 ~R 28 In formula (II4-1), R 31 ~R 34 , Y 9 , and Y 10 are the same as in formula (II3-1). In formulae (II4-2) to (II4-6), R 35 ~R 42 are the same as in formula (II3-2). In formulae (II4-3) to (II4-6), X 1 , and X 2 are the same as in formula (II3-3).

3. The resin composition according to claim 2, wherein, the near-infrared fluorescent material (A) contains at least one compound selected from the group consisting of a compound represented by any one of the following general formulae (II3-7) to (II3-9) and (II4-7) to (II4-9), wherein Y 23 and Y 24 each independently represents a carbon atom or a nitrogen atom; Y 13 and Y 14 each independently represents an oxygen atom or a sulfur atom; Y 25 and Y 26 each independently represents a carbon atom or a nitrogen atom; R 47 and R 48 each independently represents a hydrogen atom or an electron- withdrawing group; R 43 , R 44 , R 45 , and R 46 each independently represent a halogen atom or an aryl group optionally having a substituent; P 15 and P 16 each independently represents a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group, a dialkylamino group; n15 and n16 each independently represent an integer of 0 to 3; A 15 and A 16 each independently represents a hydrogen atom, a phenyl group optionally having 1 to 3 substituents selected from the group consisting of a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group.

4. The resin composition according to any one of claims 1 to 3, wherein, a content ratio of the near-infrared fluorescent material (A) is 0.001 mass% or more and 0.5 mass% or less with respect to 100 mass% of a total of the near-infrared fluorescent material (A) and the thermoplastic resin other than a polyamide resin (B).

5. The resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin other than a polyamide resin (B) contains at least one selected from the group consisting of a thermoplastic polyurethane (TPU) resin, a polycarbonate (PC) resin, a vinyl chloride resin, an acrylic resin, a polyester resin, a polystyrene resin, an olefin resin, and a polyacetal (POM) resin.

6. The resin composition according to any one of claims 1 to 3, wherein the resin (C) contains at least one selected from the group consisting of a polyamide resin, a polyethylene resin, a polypropylene resin, a thermosetting resin, and a crosslinked polyethylene resin.

7. The resin composition according to claim 6, wherein, the resin (C) contains a polyamide resin.

8. The resin composition according to claim 6, wherein, the resin (C) contains a thermosetting resin.

9. The resin composition according to any one of claims 1 to 3, wherein a total content ratio of the near-infrared fluorescent material (A) and the thermoplastic resin (B) is 5 mass% or more and 60 mass% or less with respect to 100 mass% of a total of the near-infrared fluorescent material (A), the thermoplastic resin (B), and the resin (C).

10. The resin composition according to claim 4, wherein, a total content ratio of the near-infrared fluorescent material (A) and the thermoplastic resin (B) is 5 mass% or more and 60 mass% or less with respect to 100 mass% of a total of the near-infrared fluorescent material (A), the thermoplastic resin (B), and the resin (C).

11. The resin composition according to any one of claims 1 to 3, which is used as a medical material.

12. A shaped body obtained from the resin composition according to any one of claims 1 to 11.

13. The shaped body according to claim 12, which is a medical tool at least a part of which is used in a patient's body.

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