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JP-7856949-B2 - Masterbatch, resin composition using the same, and method for manufacturing molded articles

JP7856949B2JP 7856949 B2JP7856949 B2JP 7856949B2JP-7856949-B2

Inventors

  • 竹澤 豊
  • 櫻井 直人
  • 豊村 恭一

Assignees

  • ＤＩＣ株式会社

Dates

Publication Date
20260512
Application Date
20230316
Priority Date
20220322

Claims (17)

  1. The material comprises 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). A masterbatch in which the resin (C) forms a continuous phase, and a dispersed phase containing the near-infrared fluorescent material (A) and the thermoplastic resin (B) is formed in the continuous phase, The near-infrared fluorescent material (A) is The following general formula (II 1 ) [In formula (II 1 ), Ra and Rb , together with the nitrogen atom to which Ra is bonded and the carbon atom to which Rb is bonded, form an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R c and R d , together with the nitrogen atom to which R c is bonded and the carbon atom to which R d is bonded, form an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; Re and R f independently represent a halogen atom or an oxygen atom; R g represents a hydrogen atom or an electron-withdrawing group. However, if Re and Rf are oxygen atoms, Re , the boron atom bonded to Re, Ra, and the nitrogen atom bonded to Ra may all form a ring, and Rf, the boron atom bonded to Rf , Rc , and the nitrogen atom bonded to Rc may all form a ring. If Re is an oxygen atom and does not form a ring, then Re is a substituted oxygen atom, and if Rf is an oxygen atom and does not form a ring, then Rf is a substituted oxygen atom. The following general formula (II 2 ) A compound represented by [Formula (II 2 ), where Ra a to R f are the same as in Formula (II 1 )], The following general formula (II 3 ) [In formula (II 3 ), Rh and Ri , together with the nitrogen atom to which Rh is bonded and the carbon atom to which Ri is bonded , form an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R j and R k , together with the nitrogen atom to which R j is bonded and the carbon atom to which R k is bonded, form an aromatic five-membered ring, an aromatic six-membered ring, or a condensed aromatic ring formed by the condensation of two or three five-membered or six-membered rings; R l , R m , R n , and R o independently represent a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group; R p and R q independently represent a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group; R r and R s independently represent a hydrogen atom or an electron-withdrawing group. [The compound represented by...] Furthermore, the following general formula (II 4 ) [In formula (II 4 ), Rh to Rq are the same as in formula (II 3 ).] At least one compound selected from the group consisting of compounds represented by: A masterbatch with a maximum fluorescence wavelength of 650 nm or higher .
  2. The near-infrared fluorescent material (A) is The following general formulas (II 3 - 1) to (II 3 - 6) [In formula (II 3 -1), R23 , R24 , R25 , and R26 independently represent a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group; R27 and R28 independently represent a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group; R 29 and R 30 independently represent a hydrogen atom or an electron-withdrawing group; Y9 and Y10 independently represent a sulfur atom, an oxygen atom, a nitrogen atom, or a phosphorus atom; R 31 and R 32 are, (p4) Independently, each represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group, or (p5) R31 and R32 together form an optionally substituted aromatic five-membered ring or an optionally substituted aromatic six-membered ring; R33 and R34 are, (q4) Independently, each represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group, or (q5) R 33 and R 34 together form an optionally substituted aromatic five-membered ring or an optionally substituted aromatic six-membered ring. [In equations (II 3-2 ) to (II 3-6 ), R 23 to R 30 are the same as in equation (II 3-1 ); X1 and X2 independently represent a nitrogen atom or a phosphorus atom; R35 , R36 , R37 , and R38 are, (p6) Each independently represents a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group. (p7) R 35 and R 36 both form optionally substituted aromatic five-membered rings or optionally substituted aromatic six-membered rings, and R 37 and R 38 independently represent a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group. (p8) R 36 and R 37 together form an optionally substituted aromatic five-membered ring or an optionally substituted aromatic six-membered ring, and R 35 and R 38 independently represent a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group, or (p9) R 37 and R 38 together form an optionally substituted aromatic five-membered ring or an optionally substituted aromatic six-membered ring, and R 35 and R 36 independently represent a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group; R39 , R40 , R41 , and R42 are, (q6) Independently representing a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group, (q7) R 39 and R 40 together form an optionally substituted aromatic five-membered ring or an optionally substituted aromatic six-membered ring, and R 41 and R 42 independently represent a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group. Compounds represented by either of the following general formulas (II 4-1) to (II 4-6): (q8) R 40 and R 41 together form an optionally substituted aromatic five-membered ring or an optionally substituted aromatic six-membered ring, and R 39 and R 42 independently represent a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group; or (q9) R 41 and R 42 together form an optionally substituted aromatic five-membered ring or an optionally substituted aromatic six-membered ring, and R 39 and R 40 independently represent a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an aryl group, or a heteroaryl group. A masterbatch according to claim 1, comprising at least one compound selected from the group consisting of compounds represented by any of the following formulas: [In formulas (II 4-1 ) to (II 4-6 ), R 23 to R 28 are the same as in formula (II 3-1 ). In formula (II 4-1 ), R 31 to R 34 , Y 9 , and Y 10 are the same as in formula (II 3-1 ). In formulas (II 4-2 ) to (II 4-6 ), R 35 to R 42 are the same as in formula (II 3-2 ). In formulas (II 4-3 ) to (II 4-6 ) , X 1 and X 2 are the same as in formula (II 3-3).]
  3. The near-infrared fluorescent material (A) is The following general formulas (II 3-7 ) to (II 3-9 ) and (II 4-7 ) to (II 4-9 ) [In the formula, Y23 and Y24 independently represent a carbon atom or a nitrogen atom; Y13 and Y14 independently represent either an oxygen atom or a sulfur atom; Y25 and Y26 independently represent a carbon atom or a nitrogen atom; R 47 and R 48 independently represent a hydrogen atom or an electron-withdrawing group; R 43 , R 44 , R 45 , and R 46 independently represent a halogen atom or an aryl group which may have a substituent; P15 and P16 independently represent a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group; n15 and n16 represent integers between 0 and 3, independently of each other; A15 and A16 independently represent a phenyl group which may have 1 to 3 substituents selected from the group consisting of a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, an amino group, a monoalkylamino group, and a dialkylamino group. The masterbatch according to claim 2 , comprising at least one compound selected from the group consisting of compounds represented by any of the following.
  4. The masterbatch according to claim 1 or 2, wherein the content of the near-infrared fluorescent material (A) 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 is 0.001% by mass or more and 0.5% by mass or less.
  5. The material comprises 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). A masterbatch in which the resin (C) forms a continuous phase, and a dispersed phase containing the near-infrared fluorescent material (A) and the thermoplastic resin (B) is formed in the continuous phase, A masterbatch in which the content of the near-infrared fluorescent material (A) is 0.001% by mass or more and 0.5% by mass or less, 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.
  6. The masterbatch according to claim 1 or 5, wherein the thermoplastic resin (B) other than the polyamide resin 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.
  7. The masterbatch according to claim 1 or 5 , wherein the resin (C) comprises at least one selected from the group consisting of polyamide resin, polyethylene resin, polypropylene resin, and thermosetting resin.
  8. The masterbatch according to claim 1 or 5 , wherein the resin (C) comprises a polyamide resin.
  9. The masterbatch according to claim 1 or 5 , wherein the resin (C) comprises a thermosetting resin.
  10. The masterbatch according to claim 1 or 5, wherein the total content of the near-infrared fluorescent material (A) and the thermoplastic resin (B) is in the range of 20% by mass or more and 80% by mass or less, based on 100% by mass of the total of the near-infrared fluorescent material (A), the thermoplastic resin (B) , and the resin (C) .
  11. The process comprises the steps of: melting and kneading a near-infrared fluorescent material (A) and a thermoplastic resin other than a polyamide resin (B) to obtain a kneaded product; pulverizing the kneaded product obtained in the first step to obtain particles containing powdered near-infrared fluorescent material (A) and thermoplastic resin (B); and mixing or kneading the particles obtained in the first step with a resin (C). A method for manufacturing a masterbatch in which the resin (C) forms a continuous phase, and a dispersed phase containing the near-infrared fluorescent material (A) and the thermoplastic resin (B) is formed in the continuous phase.
  12. The process comprises adding a diluent resin (D) to the masterbatch according to claim 1 or 5 , and then mixing or kneading it. The material comprises a near-infrared fluorescent material (A), a thermoplastic resin other than polyamide resin (B), a resin different from the thermoplastic resin (B) (C), and a resin different from the thermoplastic resin (B) (D). A method for producing a resin composition, wherein the resins (C) and (D) form a continuous phase, and a dispersed phase containing the near-infrared fluorescent material (A) and the thermoplastic resin (B) is formed in the continuous phase.
  13. The method for producing the resin composition according to claim 12, wherein the resin (D) comprises at least one selected from the group consisting of polyamide resin, polyethylene resin, polypropylene resin, thermosetting resin, and crosslinked polyethylene resin.
  14. A method for producing a resin composition according to claim 12, wherein the content of the resin (D) is in the range of 20% by mass or more and 80% by mass or less, based on 100% by mass of the total of the near-infrared fluorescent material (A), the thermoplastic resin (B), the resin (C), and the resin (D ) .
  15. A method for producing the resin composition according to claim 1 or 2 , wherein the resin composition is used as a medical material.
  16. A method for producing the resin composition according to claim 1 or 2 , wherein at least a portion of the resin composition is used as a material for a medical device used in the body of a patient.
  17. A method for producing a molded article, comprising the step of melt-molding a resin composition obtained by the manufacturing method of claim 1 or 2 .

Description

This invention relates to a masterbatch, a method for producing a resin composition using the masterbatch, and a method for producing a molded article obtained from the resin composition. More specifically, it relates to a resin composition that emits near-infrared fluorescence, has high luminescence efficiency, and is relatively easy to manufacture, a method for producing a molded article obtained from the resin composition, and a masterbatch capable of producing the resin composition and a method for producing the same. Near-infrared fluorescent dyes are used in industrial products, primarily for product identification and anti-counterfeiting. In recent years, they have also been used in medical applications such as bioimaging probes and diagnostic reagents. The near-infrared wavelength range is known to be invisible to the naked human eye, has minimal impact on living organisms, and exhibits high penetration into skin and other biological tissues. These characteristics can be utilized by incorporating near-infrared fluorescent dyes into medical devices themselves. For example, a system has been disclosed in which the position of a medical device implanted in the body can be confirmed by irradiating it with near-infrared light from outside the body, using a medical device such as a shunt tube containing a near-infrared fluorescent dye (see, for example, Patent Document 1). To visualize medical implants embedded subcutaneously, excitation with near-infrared light, which has high skin penetration, is necessary. Furthermore, the fluorescence emitted from the medical implant must also be in the near-infrared region, which also has high skin penetration. In other words, to ensure visibility, the near-infrared fluorescent dye contained in the medical implant must strongly absorb light in the near-infrared region and emit strong fluorescence. For this reason, it is preferable that the near-infrared fluorescent dye contained in the resin composition used as a raw material for medical implants has its maximum absorption wavelength in the near-infrared region within the resin. Near-infrared fluorescent dyes include inorganic and organic fluorescent dyes. Generally, inorganic near-infrared fluorescent dyes have the advantage of being easy to adjust the emission wavelength within a desired range by using various metals, but they require rare earth elements such as rare earths and nanoparticles of uniform size, which are rare and expensive. On the other hand, organic near-infrared fluorescent dyes can be synthesized relatively easily and have features such as easy wavelength adjustment, but very few are known that can be stably mixed into resins. If near-infrared fluorescent dyes can be mixed and dispersed in a resin, various molded articles that emit near-infrared fluorescence can be manufactured using the resin as a raw material. As an example of a resin in which near-infrared fluorescent dyes are dispersed, Patent Document 2 discloses a near-infrared fluorescent resin obtained by copolymerizing a reactive group-containing near-infrared fluorescent dye, which is a phthalocyanine dye, a naphthalocyanine dye, or a squalein dye into which a polyester reactive group has been introduced, in PET (polyethylene terephthalate). On the other hand, boron complexes of π-conjugated compounds are known as organic fluorescent dyes with high emission quantum yields. For example, BODIPY dyes having a boron-dipyrrometene skeleton formed by a complex of a disubstituted boron atom and dipyrrometene (or its derivatives) are known (see, for example, Non-Patent Document 1). Furthermore, as BODIPY dyes that emit near-infrared fluorescence, Patent Document 3 discloses a BODIPY dye having a heterocycle in the BODIPY skeleton. In addition, Non-Patent Document 2 discloses a near-infrared fluorescent dye of a DPP-based boron complex having two boron complex units in the molecule, obtained by boron-complexing a diketopyrrolopyrrole (DPP) derivative. These BODIPY dyes and DPP-based boron complexes are mainly used as biomarkers to label biomolecules such as nucleic acids and proteins, and tumor tissue, and there are almost no reports on resins containing BODIPY dyes or DPP-based boron complexes. Regarding resin compositions containing BODIPY dyes, Patent Document 4 discloses that a resin emitting fluorescence in the visible light region was obtained by copolymerizing a siloxane-containing BODIPY dye, in which an organosiloxanil group is introduced via an alkylene group, into a silicone resin. Patent Document 5 also discloses a composition emitting fluorescence in the visible light region, in which the BODIPY dye is mixed with a solvent and polymer to improve its compatibility with visible light emission. Furthermore, Patent Document 6 discloses an optical filter containing a resin and a BODIPY dye having at least one electron-withdrawing group, which has high absorption of light in the visible light region, and Patent Document 7 discloses a color