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WO2021145052A1 - Élément électroluminescent, composé électroluminescent et élément de conversion photoélectrique - Google Patents

Élément électroluminescent, composé électroluminescent et élément de conversion photoélectrique Download PDF

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Publication number
WO2021145052A1
WO2021145052A1 PCT/JP2020/041019 JP2020041019W WO2021145052A1 WO 2021145052 A1 WO2021145052 A1 WO 2021145052A1 JP 2020041019 W JP2020041019 W JP 2020041019W WO 2021145052 A1 WO2021145052 A1 WO 2021145052A1
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group
general formula
compound
structure represented
substituent
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Japanese (ja)
Inventor
植田　則子
中林　亮
康生 宮田
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Konica Minolta Inc
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Konica Minolta Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a light emitting member, a luminescent compound, and a photoelectric conversion member. More specifically, the present invention emits light in a long wavelength region (hereinafter, also referred to as “near infrared long wavelength region”) in near infrared light and a high concentration to the member.
  • the present invention relates to a light emitting member or the like, which contains a luminescent compound that can be blended in the above, and which can achieve a high emission quantum yield in the near infrared long wavelength region.
  • the near-infrared light emitting member can ignore the influence of the self-fluorescence background of living cells under near-infrared excitation, and since near-infrared light scatters less in the living body than visible light, imaging in the deeper part of the living body , Bioauthentication by vein imaging, biometric measurement such as pulse oximeter, etc. are attracting attention. Therefore, compounds having light emission in the near infrared region are being studied.
  • the squarylium compound is known as a near-infrared absorber (see, for example, Patent Document 1). It is also known that the squarylium compound is used in combination with a delayed fluorescent substance or a phosphorescent compound in an organic EL device (see, for example, Patent Document 2). However, there has been no case in which the molecular structure of a squarylium compound has been studied from the viewpoint that a high emission quantum yield can be obtained even when it is contained at a high concentration for the purpose of applying it to a light emitting member.
  • the present invention has been made in view of the above problems and situations, and the problem to be solved is to contain a luminescent compound capable of emitting light in a near-infrared long wavelength region and blending into a member at a high concentration. It is an object of the present invention to provide a light emitting member capable of achieving a high emission quantum yield in the near infrared long wavelength region. Another object of the present invention is to provide a luminescent compound capable of emitting light in a near-infrared long wavelength region and blending with a member at a high concentration.
  • the present inventor has made a compound having a squarylium ring at the center of the molecular structure having a molecular structure having an emission peak in the near-infrared long wavelength region in the process of examining the cause of the above problem.
  • a soluble group on the outer group of the squarylium ring so as to extend in the direction toward the squarylium ring, the compound emits light in the near-infrared long wavelength region while relaxing concentration extinction and at a high concentration on the matrix.
  • a to L independently represent an aromatic hydrocarbon ring or a heteroaromatic ring.
  • n1 to n6 independently represent an integer of 0 to 2.
  • Ya and Yb are independently OH group, NHCORa (Ra represents a hydrocarbon group) group, NHSO 2 Rb (Rb represents a hydrocarbon group) group, or NHPO (ORf) (ORg) ( Rf and Rg each represent a hydrocarbon group.) Represents a group.
  • Yc to Yl independently represent a hydrogen atom or a substituent.
  • At least one of Ya to Yl contains a linear or branched alkyl group (a) having 4 to 12 carbon atoms or a group (P) having a structure represented by the following general formula (P). It is a group containing.
  • P represents a substitution site.
  • Q represents a single bond or a divalent linking group.
  • N represents an integer of 1 to 9.
  • R 51 represents a hydrogen atom or a methyl group.
  • a to L represent aromatic hydrocarbon rings
  • n1 to n6 are independently 0 or 1
  • at least one of Ya and Yb is a direct chain having 4 to 12 carbon atoms.
  • a to L represent aromatic hydrocarbon rings
  • n1 to n6 are independently 0 or 1
  • at least one of Ye to Yl is a direct chain having 4 to 12 carbon atoms.
  • L 1 represents a group having a structure represented by the following formula (L1), formula (L2) or formula (L3).
  • L 2 represents a group having a structure represented by the following formula (L4), formula (L5) or formula (L6).
  • * 1 and * 4 represent sites that bind to N in the general formula (1), respectively.
  • * 2 and * 3 represent the carbon-bonding sites of the squarylium ring of the general formula (1), respectively.
  • R 1 , R 5 , R 21 and R 27 are independently OH group, NHCORa (Ra represents a hydrocarbon group) group, NHSO 2 Rb (Rb represents a hydrocarbon group) group, or R 27.
  • R 2 ⁇ R 4, R 6 ⁇ R 8, R 11 ⁇ R 18, R 22 ⁇ R 26 and R 28 ⁇ R 32 each independently represent a hydrogen atom or a substituent.
  • Ar 1 to Ar 4 independently represent groups having a structure represented by the following formula (A), formula (B) or formula (C). (In formulas (A) to (C), * indicates a connection site with an N atom.
  • any one of L 1 , L 2 and Ar 1 to Ar 4 is a linear or branched alkyl having 4 to 12 carbon atoms at at least one of the following predetermined positions. It has a group (a) or a group (P) having a structure represented by the general formula (P).
  • the predetermined positions in L 1 or L 2 are Ra (excluding the group (P)), R 1 , R 5 , R 21 and when R 1 , R 5 , R 21 and R 27 are NHCORa groups.
  • the predetermined positions in Ar 1 to Ar 4 are X 1 , X 5 , X 11 , X 21 and X 27 , and X 31 and X 35 of the following formula (D).
  • Ar 1 to Ar 4 , X 2 , X 3 , X 4 , X 12 , X 13 , X 14 , X 15 , X 22 , X 23 , X 24 and X 25 are carbon. It does not have a linear or branched alkyl group or (poly) oxyalkylene group of number 4 or more.
  • X 3 , X 13 and X 24 may be groups having a structure represented by the following formula (D).
  • * indicates a connection site.
  • X 31 to X 35 each independently represent a hydrogen atom or a substituent. However, at least one of X 31 and X 35 has 4 carbon atoms. It is a group having a linear or branched alkyl group (a) of to 12 or a group (P) having a structure represented by the general formula (P), and X 32 to X 34 have 4 carbon atoms. It does not have the above linear or branched alkyl group or (poly) oxyalkylene group.)]
  • L 1 is a group having a structure represented by the formula (L1)
  • L 2 is a group having a structure represented by the formula (L4). The light emitting member described.
  • each Rc independently represents a hydrogen atom or a substituent, and at least one of the four Rc may have —O— as a linking group.
  • each Ra independently represents a hydrocarbon group.
  • Each Rc independently represents a hydrogen atom or a substituent. Either of the two Ras has the number of carbon atoms. Directly having 4 to 12 carbon atoms representing 4 to 12 linear or branched alkyl groups (a) or at least one of the four Rcs may have —O— as a linking group. Represents a chain or branched alkyl group (a) or a group (P) having a structure represented by the general formula (P).
  • each Rd independently represents a hydrogen atom or a substituent, and at least one of the four Rds may have —O— as a linking group. It represents a linear or branched alkyl group (a) of 4 to 12, or a group (P) having a structure represented by the general formula (P). Each Xa independently has 1 carbon atom. Represents an alkyl or alkoxy group of ⁇ 3 or a substituted or unsubstituted phenyl group. M represents an integer of 0-4.
  • each Ra independently represents a hydrocarbon group.
  • Each Re independently represents a hydrogen atom or a substituent.
  • Each Xa independently represents a carbon.
  • Representing an alkyl group or an alkoxy group of Nos. 1 to 3 or a substituted or unsubstituted phenyl group, Xa when bonded to the 4-position may be a group having a structure represented by the above formula (D).
  • m represents an integer of 0 to 4.
  • the general formula (1d) does any of the two Ras represent a linear or branched alkyl group (a) having 4 to 12 carbon atoms?
  • At least one of the four Res may have —O— as a linking group, a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or the general formula (P).
  • a linking group a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or the general formula (P).
  • P represents a group (P) having a structure represented by, or a group having a structure represented by the formula (D) is bonded to the 4-position as Xa.
  • each Rc independently represents a hydrogen atom or a substituent, and at least one of the four Rc may have —O— as a linking group.
  • Q represents a single bond or a divalent linking group.
  • N represents an integer of 1 to 9.
  • R 51 represents a hydrogen atom or a methyl group.
  • each Ra independently represents a hydrocarbon group.
  • Each Rc independently represents a hydrogen atom or a substituent. Either of the two Ras has the number of carbon atoms. Directly having 4 to 12 carbon atoms representing 4 to 12 linear or branched alkyl groups (a) or at least one of the four Rcs may have —O— as a linking group. It represents a chain or branched alkyl group (a) or a group (P) having a structure represented by the following general formula (P).) (In the general formula (P), * represents a substitution site. Q represents a single bond or a divalent linking group. N represents an integer of 1 to 9.
  • R 51 represents a hydrogen atom or a methyl group.
  • each Rd independently represents a hydrogen atom or a substituent, and at least one of the four Rds may have —O— as a linking group. It represents a linear or branched alkyl group (a) of 4 to 12, or a group (P) having a structure represented by the following general formula (P). Each Xa independently has 1 carbon atom. Represents an alkyl or alkoxy group of ⁇ 3 or a substituted or unsubstituted phenyl group. M represents an integer of 0-4.) (In the general formula (P), * represents a substitution site. Q represents a single bond or a divalent linking group. N represents an integer of 1 to 9.
  • R 51 represents a hydrogen atom or a methyl group.
  • each Ra independently represents a hydrocarbon group.
  • Each Re independently represents a hydrogen atom or a substituent.
  • Each Xa independently represents a carbon.
  • Representing an alkyl group or an alkoxy group of Nos. 1 to 3 or a substituted or unsubstituted phenyl group, Xa when bonded to the 4-position may be a group having a structure represented by the following formula (D).
  • m represents an integer of 0 to 4.
  • any one of Ra represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or four.
  • At least one of Re is represented by a linear or branched alkyl group (a) having 4 to 12 carbon atoms which may have —O— as a linking group, or the following general formula (P).
  • a group having a structure (P), or a group having a structure represented by the following formula (D) as Xa is bonded to the 4-position.
  • * indicates a connection site.
  • X 31 to X 35 each independently represent a hydrogen atom or a substituent. However, at least one of X 31 and X 35 has 4 carbon atoms.
  • Ya and Yb each independently represent an OH group or an NHCORa (Ra represents a hydrocarbon group) group.
  • Each Re independently represents a hydrogen atom or a substitution.
  • Each Xa independently represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms, or a substituted or unsubstituted phenyl group.
  • M represents an integer of 0 to 3, where Ra represents.
  • P represents a substitution site.
  • Q represents a single bond or a divalent linking group.
  • N represents an integer of 1 to 9.
  • R 51 represents a hydrogen atom or a methyl group.
  • a to L independently represent an aromatic hydrocarbon ring or a heteroaromatic ring.
  • n1 to n6 independently represent an integer of 0 to 2.
  • Ya and Yb are independently OH group, NHCORa (Ra represents a hydrocarbon group) group, NHSO 2 Rb (Rb represents a hydrocarbon group) group, or NHPO (ORf) (ORg) ( Rf and Rg each represent a hydrocarbon group.) Represents a group.
  • Yc to Yl independently represent a hydrogen atom or a substituent.
  • At least one of Ya to Yl contains a linear or branched alkyl group (a) having 4 to 12 carbon atoms or a group (P) having a structure represented by the following general formula (P). It is a group containing.
  • P represents a substitution site.
  • Q represents a single bond or a divalent linking group.
  • N represents an integer of 1 to 9.
  • R 51 represents a hydrogen atom or a methyl group.
  • a light emitting member capable of achieving a high emission quantum yield in the near infrared long wavelength region which contains a light emitting compound capable of emitting light in the near infrared long wavelength region and blending into the member at a high concentration by the above means of the present invention.
  • a luminescent compound capable of emitting light in a near-infrared long wavelength region and blending with a member at a high concentration can be provided.
  • a photoelectric conversion member capable of obtaining high external quantum efficiency by using a luminescent compound capable of emitting light in a near-infrared long wavelength region and blending with a member at a high concentration.
  • a compound having a structure represented by the general formula (T) (hereinafter, also referred to as compound (T)) is a compound having a squarylium ring at the center of its molecular structure.
  • compound (T) a nitrogen atom is bonded to the left and right of the squarylium ring as the main skeleton via an aromatic hydrocarbon ring or a heteroaromatic ring, and two aromatic hydrocarbon rings or heteroaromatic rings are attached to the nitrogen atom. It has a combined structure.
  • these aromatic hydrocarbon rings or heteroaromatic rings also include a structure in which two or three are linked in a chain.
  • the compound (T) has the above aromatic hydrocarbon ring or heteroaromatic ring OH group in position, NHCORa group, NHSO 2 Rb group, or NHPO (ORf) (ORg) group bonded to the squarylium ring .
  • the compound (T) may be a linear or branched alkyl group (a) having 4 to 12 carbon atoms or a group (P) having a structure represented by the above general formula (P) as a soluble group. , A structure that binds to the aromatic hydrocarbon ring or heteroaromatic ring directly or via a linking group so that the group is located in the direction toward the central squarylium ring.
  • the present inventor By adopting the squarylium compound as the above-mentioned molecular structure of the compound (T), the present inventor has a molecular structure having an emission peak in a long wavelength region of near-infrared light, and relaxes concentration extinction to the matrix. It enables compounding at high concentrations.
  • a light emitting member capable of achieving a high emission quantum yield in the near infrared long wavelength region can be obtained.
  • a compound (T) having a structure represented by the general formula (1) (hereinafter, also referred to as compound (1)) is particularly preferable.
  • the compound having the above-mentioned specific molecular structure that is, the compound having the structure represented by the general formulas (1a), (1b), (1c), (1d) or (1e) has been used so far. It is a novel compound not described in the literature.
  • compound (T) when compound (T) is used as a photoelectric conversion element, a photoelectric conversion element having high external quantum efficiency can be obtained. This is because the compound (T), particularly the compound (1), has an emission peak in the near-infrared long wavelength region and exhibits a high emission quantum yield, so that the exciter when the molecule is excited does not emit radiation. It is presumed that such an effect was exhibited because it became difficult to pass through a quenching path such as deactivation.
  • the light emitting member of the present invention is characterized by containing a compound having a structure represented by the above general formula (T). This feature is a technical feature common to each of the following embodiments.
  • a to L represent aromatic hydrocarbon rings
  • n1 to n6 are independently 0 or 1, respectively.
  • Ya and Yb are groups containing a linear or branched alkyl group (a) having 4 to 12 carbon atoms or a group (P) having a structure represented by the above general formula (P). Is preferable.
  • a to L represent aromatic hydrocarbon rings, and n1 to n6 are independently 0 or 1, respectively.
  • Ye to Yl at least one of which contains a linear or branched alkyl group (a) having 4 to 12 carbon atoms or a group (P) having a structure represented by the above general formula (P). Is preferable.
  • the structure represented by the general formula (T) is a structure represented by the general formula (1).
  • a compound having a structure represented by the general formula (1) (hereinafter, also referred to as compound (1)) has a main skeleton bonded to the left and right of a squarylium ring via a benzene ring, a biphenyl ring or a naphthalene ring. However, it has a structure in which two benzene rings or naphthalene rings are bonded to the nitrogen atom. Further, the compound (1) has a linear or branched alkyl group (a) having 4 to 12 carbon atoms as a soluble group of the compound (T), or a structure represented by the above general formula (P).
  • Such a compound (1) is a compound having a particularly remarkable feature that the compound (T) can emit light in a near-infrared long wavelength region and can be blended in a member at a high concentration.
  • L 1 is represented by the above formula (L1) in the above general formula (1) from the viewpoint that light emission in the near infrared long wavelength region and high concentration can be blended into the member. It is preferable that the group has a structure represented by the above formula (L4) and L 2 has a structure represented by the above formula (L4).
  • the structure represented by the general formula (1) is described in the general formula (1a), from the viewpoint of being able to emit light in the near-infrared long wavelength region and to be blended into the member at a high concentration. It is preferable that the structure is represented by the general formula (1b), the general formula (1c) or the general formula (1d).
  • the light emitting member is a light emitting thin film or a light emitting particle from the viewpoint of exhibiting the effect of the present invention.
  • the luminescent compound having a structure represented by the above general formula (1a), general formula (1b), general formula (1c), general formula (1d) or general formula (1e) of the present invention is a novel compound. Is.
  • the photoelectric conversion member of the present invention is characterized by containing a compound having a structure represented by the above general formula (T). As a result, a photoelectric conversion element having high external quantum efficiency can be obtained.
  • the compound having the structure represented by the general formula (T) is also referred to as the compound (T) as described above.
  • the chemical structural formula may be indicated by adding an abbreviation of a compound having a structure represented by the chemical structural formula, such as compound (1a) -1.
  • a group having a structure represented by the general formula (P) is also referred to as a group (P)
  • a group having a structure represented by the formula (L1) is also referred to as a group (L1). The same applies to other compounds and groups.
  • the light emitting member of the present invention is characterized by containing the compound (T).
  • the compound (T) acts as a near infrared light emitting agent.
  • the light emitting member of the present invention is a member having a predetermined shape, and contains, in addition to the compound (T), a matrix material for uniformly dispersing the compound (T) in the light emitting member and molding the compound (T) into a predetermined shape. You may. Further, the light emitting member of the present invention may contain various additives in addition to the compound (T) as long as the effects of the present invention are not impaired.
  • the components of the light emitting member of the present invention will be described in detail.
  • the compound (T) is a compound having a structure represented by the general formula (T).
  • a to L independently represent an aromatic hydrocarbon ring or a heteroaromatic ring.
  • n1 to n6 independently represent an integer of 0 to 2.
  • Ya and Yb are independently OH group, NHCORa (Ra represents a hydrocarbon group) group, NHSO 2 Rb (Rb represents a hydrocarbon group) group, or NHPO (ORf) (ORg) ( Rf and Rg each represent a hydrocarbon group.) Represents a group.
  • Yc to Yl independently represent a hydrogen atom or a substituent.
  • At least one of Ya to Yl contains a linear or branched alkyl group (a) having 4 to 12 carbon atoms or a group (P) having a structure represented by the following general formula (P). It is a group containing.
  • P represents a substitution site.
  • Q represents a single bond or a divalent linking group.
  • N represents an integer of 1 to 9.
  • R 51 represents a hydrogen atom or a methyl group.
  • a to L independently represent an aromatic hydrocarbon ring or a heteroaromatic ring.
  • the number of carbon atoms in the aromatic hydrocarbon ring or heteroaromatic ring is preferably 4 to 10.
  • Examples of the hetero atom in the hetero aromatic ring include an oxygen atom, a nitrogen atom or a sulfur atom.
  • Specific examples of the aromatic hydrocarbon ring or heteroaromatic ring include a benzene ring, a naphthalene ring, a pyridine ring, a thiophene ring, a pyrrole ring or a furan ring, and a benzene ring and a naphthalene ring are preferable.
  • n1 to n6 independently represent an integer of 0 to 2, and 0 or 1 is preferable.
  • a benzene ring, a biphenyl ring or a naphthalene ring is preferable as the structure connecting the squarylium ring and the nitrogen atom. Specifically, it is as described in compound (1).
  • At least one of Ya to Yl is a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group having a structure represented by the above general formula (P). It is a group containing (P) (hereinafter, also referred to as a substituent (E)).
  • the position substituted with the substituent (E), that is, the positions Ya to Yl are the positions bonded in the direction toward the central squarylium ring.
  • Ya and Yb are independently OH group, NHCORa (Ra represents a hydrocarbon group) group, NHSO 2 Rb (Rb represents a hydrocarbon group) group, or NHPO (ORf) (ORg). ) (Rf and Rg each represent a hydrocarbon group.) Represents a group.
  • NHCORa Ra represents a hydrocarbon group
  • NHSO 2 Rb Rb represents a hydrocarbon group
  • NHPO ORf
  • Rg each represent a hydrocarbon group.
  • Ra, Rb, Rf or Rg is a substituent (E).
  • the substituent (E) in this case is limited to the substituent (E) containing the alkyl group (a).
  • the substituent (E) may be the alkyl group (a) or the group (P) itself, and is a group in which the alkyl group (a) or the group (P) is bonded to the main skeleton via a divalent linking group.
  • a divalent linking group There may be.
  • —O— and a phenylene group are preferable, and a 1,4-phenylene group is particularly preferable.
  • the substituent (E) is preferably an alkyl group (a) or a group (P) itself which may have —O— as a linking group.
  • Ra, Rb, Rf or Rg is a substituent (E), it is preferably an alkyl group (a).
  • the number of substituents (E) in the compound (T) may be 1 or more, preferably in the range of 1 to 8, more preferably in the range of 2 to 8, and even more preferably in the range of 2 to 4.
  • the preferable position of the substituent (E) in the compound (T) will be described in a more specific compound described later.
  • the linear alkyl group (a) having 4 to 12 carbon atoms includes an n-butyl group, an n-pentyl group, an n-hexyl group, and n-. Examples thereof include a heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group and an n-dodecyl group.
  • Examples of the branched alkyl group (a) having 4 to 12 carbon atoms include an isobutyl group, an s-butyl group, a t-butyl group, a 1-propylbutyl group, a 1-ethylpentyl group, and a 2,4,4-trimethylpentyl group. Examples thereof include a group, a 2-ethylbutyl group, a 2,2-dimethylpropyl group, a 2-ethylhexyl group, a 2-butyloctyl group and the like.
  • a branched alkyl group (a) having 4 to 12 carbon atoms is preferable from the viewpoint of solubility.
  • a group having a structure represented by any of the following formulas (a1) to (a7) is preferable.
  • the group (a1) is a 1-propylbutyl group
  • the group (a2) is a 1-ethylpentyl group
  • the group (a3) is a 2,4,4-trimethylpentyl group
  • the group (a4) is an isobutyl group and a group (a5).
  • the group (a6) is a 2-ethylhexyl group
  • the group (a7) is a 2-butyloctyl group.
  • the alkyl group (a) may be a group (a1), a group (a2), a group (a3) or a group (a4). preferable.
  • the branched alkyl group (a) is bonded to another position, the branched alkyl group (a) is a group (a4), a group (a5), a group (a6) or a group (a7). Is preferable.
  • the number of n indicating the number of repetitions of the oxyethylene group may be in the range of 1 to 9.
  • the number of n is more preferably 2, 3, 4, and 8 from the viewpoint of ease of manufacture.
  • Q is a single bond or divalent linking group.
  • Q a single bond, an alkylene group having 1 to 2 carbon atoms, or a carbonyl group is preferable.
  • a phenylene group is preferable, and a 1,4-phenylene group is particularly preferable.
  • Ra, Rb, Rf, Rg, and Yc to Yl are a hydrogen atom, an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and an aryl group, respectively.
  • Examples thereof include an atom or group selected from the above.
  • the aryl group include a phenyl group, a tolyl group, a xsilyl group and the like.
  • Ra, Rb, Rf and Rg are preferably methyl groups.
  • Yc to Yl are preferably a hydrogen atom or an alkyl group or a phenyl group having 1 to 3 carbon atoms.
  • the hydrogen atom bonded to the aromatic hydrocarbon ring or the heteroaromatic ring at a position other than Ya to Yl may be substituted.
  • the substituent (E) may be further provided at a position other than Ya to Yl as long as the effect of the present invention is not impaired.
  • the position is, for example, a position other than Ya to Yl, but is a position where the ring is coupled in the direction toward the central squarylium ring.
  • a substituent other than the substituent (E) may be bonded to the position, and as the substituent in that case, a substituent similar to the substituent when Ya to Yl is other than the substituent (E) is used. Can be mentioned.
  • the substituents A to L of the compound (T) have a substituent at a position other than the above, the substituent does not have a linear or branched alkyl group having 4 or more carbon atoms or a (poly) oxyalkylene group. It is preferably a group. Specific examples of such a substituent include an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and an aryl group (however, a linear or branched alkyl group having 4 or more carbon atoms and a (poly) oxyalkylene group. It does not have any of the groups.) Etc. can be mentioned.
  • the compound (T) is preferably a compound (1) having a structure represented by the following general formula (1).
  • L 1 represents a group having a structure represented by the following formula (L1), formula (L2) or formula (L3).
  • L 2 represents a group having a structure represented by the following formula (L4), formula (L5) or formula (L6).
  • * 1 and * 4 represent sites that bind to N in the general formula (1), respectively.
  • * 2 and * 3 represent the carbon-bonding sites of the squarylium ring of the general formula (1), respectively.
  • R 1 , R 5 , R 21 and R 27 are independently OH group, NHCORa (Ra represents a hydrocarbon group) group, NHSO 2 Rb (Rb represents a hydrocarbon group) group, or R 27.
  • NHPO ORf
  • ORg Rf and Rg each represent a hydrocarbon group
  • R 2 ⁇ R 4, R 6 ⁇ R 8, R 11 ⁇ R 18, R 22 ⁇ R 26 and R 28 ⁇ R 32 each independently represent a hydrogen atom or a substituent.
  • Ar 1 to Ar 4 independently represent groups having a structure represented by the following formula (A), formula (B) or formula (C).
  • X 1 to X 27 each independently represent a hydrogen atom or a substituent.
  • any one of L 1 , L 2 and Ar 1 to Ar 4 is a linear or branched alkyl having 4 to 12 carbon atoms at at least one of the following predetermined positions. It has a group (a) or a group (P) having a structure represented by the general formula (P).
  • the predetermined positions in L 1 or L 2 are Ra (excluding the group (P)), R 1 , R 5 , R 21 and when R 1 , R 5 , R 21 and R 27 are NHCORa groups.
  • a R 2, R 11, R 12 , R 6, R 15, R 16, R 26 and R 32 are X 1 , X 5 , X 11 , X 21 and X 27 , and X 31 and X 35 of the following formula (D).
  • Ar 1 to Ar 4 , X 2 , X 3 , X 4 , X 12 , X 13 , X 14 , X 15 , X 22 , X 23 , X 24 and X 25 are carbon. It does not have a linear or branched alkyl group or (poly) oxyalkylene group of number 4 or more.
  • X 3 , X 13 and X 24 may be groups having a structure represented by the following formula (D).
  • X 31 to X 35 each independently represent a hydrogen atom or a substituent. However, at least one of X 31 and X 35 is a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group (P) having a structure represented by the general formula (P). X 32 to X 34 do not have a linear or branched alkyl group having 4 or more carbon atoms or a (poly) oxyalkylene group.
  • any of L 1 , L 2 , Ar 1 to Ar 4 has an alkyl group (a) or a group (P) at at least one of the predetermined positions
  • the compound (1) In 1) it means that at least one of the predetermined positions is substituted with a substituent (substituent (E)) containing an alkyl group (a) or a group (P).
  • the predetermined position substituted with the substituent (E) is the position where the compound (1) is bonded in the direction toward the central squarylium ring.
  • the predetermined positions in L 1 or L 2 are Ra (excluding the group (P)), R 1 , R 5 when R 1 , R 5 , R 21 and R 27 are NHCORa groups. , Rb when R 21 and R 27 are NHSO 2 Rb groups (excluding the group (P)), Rf when R 1 , R 5 , R 21 and R 27 are NHPO (ORf) (ORg) groups. or Rg (where group (P) is excluded), a R 2, R 11, R 12 , R 6, R 15, R 16, R 26 and R 32.
  • the predetermined positions in Ar 1 to Ar 4 are groups in which X 1 , X 5 , X 11 , X 21 and X 27 , and X 3 , X 13 and X 24 have a structure represented by the above formula (D). X 31 and X 35 in the case of (group (D)).
  • Ra, Rb, Rf and Rg are limited to the substituent (E) containing the alkyl group (a).
  • the substituent (E) is the same as that of the substituent (E) in the case of the compound (T), including a preferred embodiment.
  • R 2 , R 11 , R 12 , R 6 , R 15 , R 16 , R 26 or R 32 are substituents (E)
  • the substituent (E) has —O— as a linking group. It is also preferable that it is an alkyl group (a) or a group (P) itself.
  • Ra, Rb, Rf or Rg is a substituent (E)
  • it is preferably an alkyl group (a).
  • L 1 or L 2 has a substituent (E)
  • R 1 , R 5 , R 21 or R 27 is NHCORa and Ra is an alkyl group (a).
  • a substituent ( E) may be the alkyl group (a) or the group (P) itself, or the alkyl group (a) or the group (P) having a linking group.
  • the compound (1) optionally has a substituent (E) on R 22 and R 28 in L 1 or L 2, and X 16 , X 17 and X 26 in Ar 1 to Ar 4. ) May have.
  • the number of substituents (E) in compound (1) is the same as that in the case of compound (T).
  • the preferable position of the substituent (E) in the compound (1) will be described in a more specific compound described later.
  • the Ra, Rb, Rf and Rg are an alkyl group having 1 to 3 carbon atoms, a linear or branched alkyl group having 4 or more carbon atoms, or a polyoxy. Examples thereof include an aryl group having no alkylene group.
  • R 2 , R 11 , R 12 , R 6 , R 15 , R 16 , R 22 , R 26 , R 28 , R 32 , X 1 , X 5 , X 11 , X 16 , X 17 , X 21 , X 26 , X 27 , X 31 and X 35 include hydrogen atoms, alkyl or alkoxy groups having 1 to 3 carbon atoms, and aryls having no linear or branched alkyl group or polyoxyalkylene group having 4 or more carbon atoms. The basis etc. can be mentioned. Examples of the aryl group include a phenyl group, a tolyl group, a xsilyl group and the like.
  • Ra, Rb, Rf and Rg are preferably methyl groups.
  • R 2 , R 11 , R 12 , R 6 , R 15 , R 16 , R 22 , R 26 , R 28 and R 32 are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms. It is preferably present, and more preferably a hydrogen atom.
  • X 1 , X 5 , X 11 , X 16 , X 17 , X 21 , X 26 , X 27 , X 31 and X 35 are hydrogen atoms and alkyl groups having 1 to 3 carbon atoms. , Or a phenyl group, more preferably a hydrogen atom, a methyl group or a phenyl group.
  • X 32 to X 34 in the case of (D) include a hydrogen atom, an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and an aryl group (however, a linear or branched group having 4 or more carbon atoms). It does not have an alkyl group or a polyoxyalkylene group).
  • R 3 , R 4 , R 13 , R 14 , R 23 , R 24 , R 25 , R 7 , R 8 , R 17 , R 18 , R 29 , R 30 and R 31 are hydrogen atoms.
  • X 2 , X 3 , X 4 , X 12 , X 13 , X 14 , X 15 , X 22 , X 23 , X 24 , X 25 and X 32 to X 34 are hydrogen atoms, methyl. It is preferably a group or a phenyl group.
  • Compound (1) is preferably a compound having a symmetrical skeleton centered on the central squarylium ring.
  • Specific examples of such compounds include compounds (3) to (11) having structures represented by the following general formulas (3) to (11).
  • the reference numerals in the general formulas (3) to (11) represent the same categories as those in the general formula (1), including preferred embodiments.
  • Compounds (3) to (5) are compounds in which L 1 is a group (L1) and L 2 is a group (L4) in the compound (1).
  • Compounds (6) to (8) are compounds in which L 1 is a group (L 2 ) and L 2 is a group (L 5) in the compound (1).
  • Compounds (9) to (11) are compounds in which L 1 is a group (L 3) and L 2 is a group (L 6) in the compound (1).
  • the compounds (3) to (5) are preferable, and the compound (3) is more preferable, from the viewpoint of being able to emit light in the near-infrared long wavelength region and being blended into the member at a high concentration.
  • preferable compounds include compounds (1a) to (1d) having structures represented by the following general formulas (1a) to (1d).
  • the compound (1c) and the compound (1d) the more preferable structure of the compound (1e) is shown in the following general formula (1e).
  • Compounds (1a) to (1e) are novel compounds that have not been described in the literature so far.
  • the compounds (3) to (11) and the compounds (1a) to (1e) not only have a symmetrical skeleton centered on the central squarylium ring, but also include a substituent. Is preferable from the viewpoint of ease of manufacture.
  • the compound (3) having the structure represented by the general formula (3) has L 1 as a group (L1), L 2 as a group (L 4), and Ar 1 to Ar 4 as a group. Both are compounds which are the group (A).
  • R 1 and R 5 are OH groups (the compound is also referred to as compound (31)), R 2 , R 6 and X 1 and X in each of the four groups (A). At least one of 5 is a substituent (E). Instead of or in addition to these, X 3 may be the group (D). In compound (31), it is preferable that at least one of each X 1 and X 5 in the four groups (A) is a substituent (E). Further, it is preferable that one substituent (E) is present in each of the four groups (A).
  • the groups (A) corresponding to Ar 1 , Ar 2 , Ar 3 , and Ar 4 of the general formula (1) are grouped (A1), group (A2), and group (A3), respectively.
  • the group (A4) the compound (31), substituent (E) is, X 1 or X 5 groups (A1), X 1 or X 5 groups (A2), X 1 group (A3) or X 5, and is preferably present one each in X 1 or X 5 groups (A4).
  • R 2 , R 6 , R 3 , R 4 , R 7 and R 8 are preferably hydrogen atoms.
  • Group (A1), group (A2), X 1 or X 5 is not a substituent (E) of X 1 and X 5 in the group (A3) and group (A4), X 2, X 3 and X 4, It is preferably a hydrogen atom, a methyl group or a phenyl group.
  • substituent (E) in the compound (31) each group described above can be applied without particular limitation.
  • each X 1 and X 5 in the four groups (A) is a substituent (E)
  • a structure represented by the following general formula (1a) is used.
  • Examples thereof include the compound (1a) having a structure and the compound (1c) having a structure represented by the following general formula (1c).
  • each Rc independently represents a hydrogen atom or a substituent, and at least one of the four Rc is an alkyl group which may have —O— as a linking group (1a). a) or group (P).
  • the substituent (E) contained in the compound (1a) is a group having a structure in which an alkyl group (a) or a group (P) is bonded to a 1,4-phenylene group which is a linking group.
  • the substituent (E) may be a group having a 1,4-phenylene group and —O— as a linking group in that order, and an alkyl group (a) bonded to the —O—.
  • Table I shows an example of the compound in which all four Rc of the compound (1a) are the same alkyl group (a) and the alkyl group (a) or group (P) having —O— as a linking group.
  • Table I lists the compound names and the types of Rc contained in the compounds. In Table I, only abbreviations are shown for compound names. Similarly, in the table illustrating other compounds shown below, only abbreviations are shown for compound names.
  • n-butyl is an n-butyl group
  • n-pentyl is an n-pentyl group
  • n-hexyl is an n-hexyl group
  • n-heptyl is an n-heptyl group.
  • N-octyl is an n-octyl group
  • n-nonyl is an n-nonyl group
  • n-decyl is an n-decyl group
  • n-undecyl is an n-undecyl group.
  • N-dodecyl indicates each n-dodecyl group.
  • n-butyl group having —O— as a linking group is designated as “—On-butyl”.
  • the group (a1) is indicated by (a1).
  • each Rd independently represents a hydrogen atom or a substituent, and at least one of the four Rds is an alkyl group (a) and an alkyl having —O— as a linking group.
  • Each Xa independently represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms or a substituted or unsubstituted phenyl group, and Xa when bonded to the 4-position may be a group (D). .. In other cases, Xa does not have a linear or branched alkyl group having 4 or more carbon atoms or a (poly) oxyalkylene group as a substituent.
  • m represents an integer of 0 to 4.
  • the substituent (E) contained in the compound (1c) is an alkyl group (a) or a group (P) itself, or an alkyl group (a) having —O— as a linking group.
  • the hydrogen atom at a position other than the one to which Rd is bonded may be substituted with the substituent Xa.
  • the substituent Xa is bonded to a carbon atom other than the carbon atom next to the carbon atom bonded to the nitrogen atom.
  • the compound (1c) does not have a substituent Xa, or if it has, the number thereof is preferably 1 or 2, and more preferably 1.
  • Table II shows an example of a compound in which all four groups (A) are the same in the compound (1c).
  • the Rds in the four groups (A) are all the same alkyl group (a) or group (P).
  • the compound name, the type of Rd possessed by the compound, the group or atom bonded to a carbon atom other than the carbon atom to which Rd is bonded in the group (A), and the nitrogen atom of the carbon atom to which Rd is bonded are listed. It is shown by X11, X12, X13, and X14 in order from the group bonded to the adjacent carbon atom on the opposite side.
  • R 1 and R 5 are NHCORa groups (the compound is also referred to as compound (32)), Ra, R 2 , R 6 and each X 1 in the four groups (A). and at least one of X 5 is a substituent (E). Instead of or in addition to these, X 3 may be the group (D). However, Ra is limited to the substituent (E) containing the alkyl group (a). In compound (32), it is preferable that at least one of each X 1 and X 5 in Ra and four groups (A) is a substituent (E). Further, it is preferable that one substituent (E) is present in each of the four groups (A).
  • substituent (E) is one as X 1 or X 5 based on (A1), as X 1 or X 5 based on (A2) 1
  • group (A3) has one as X 1 or X 5
  • the group (A4) has one as X 1 or X 5.
  • Ra is preferably an alkyl group (a) or a methyl group.
  • R 2 , R 6 , R 7 and R 8 are preferably hydrogen atoms.
  • Group (A1), group (A2), X 1 or X 5 is not a substituent (E) of X 1 and X 5 in the group (A3) and group (A4), X 2, X 3 and X 4, It is preferably a hydrogen atom, a methyl group or a phenyl group.
  • substituent (E) in the compound (32) each group described above can be applied without particular limitation.
  • each X 1 and X 5 in the four groups (A) is a substituent (E)
  • a structure represented by the following general formula (1b) is used as a compound in which at least one of each X 1 and X 5 in the four groups (A) is a substituent (E).
  • Examples thereof include the compound (1b) having a structure and the compound (1d) having a structure represented by the following general formula (1d).
  • each Ra independently represents a hydrocarbon group.
  • Each Rc independently represents a hydrogen atom or a substituent.
  • Either one of the two Ras represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or at least one of the four Rcs has —O— as a linking group. It represents a linear or branched alkyl group (a) having 4 to 12 carbon atoms, or a group (P) having a structure represented by the general formula (P).
  • the group corresponding to Ar 1 , Ar 2 , Ar 3 , and Ar 4 of the general formula (1) is the group (A), and the substituent (E) contained in the group (A) is It is a group having a structure in which an alkyl group (a) or a group (P) is bonded to a 1,4-phenylene group which is a linking group.
  • the substituent (E) contained in the group (A) may have a 1,4-phenylene group and —O— as linking groups in that order, and the alkyl group (a) may be bonded to the —O— in that order. good.
  • Ra an alkyl group (a) or an alkyl group having 1 to 3 carbon atoms is preferable.
  • each Ra independently represents a hydrocarbon group.
  • Each Re independently represents a hydrogen atom or a substituent.
  • Each Xa independently represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms or a substituted or unsubstituted phenyl group, and Xa when bonded to the 4-position may be a group (D). .. In other cases, Xa does not have a linear or branched alkyl group having 4 or more carbon atoms or a (poly) oxyalkylene group as a substituent.
  • m represents an integer of 0 to 4.
  • Ra represents an alkyl group (a)
  • at least one of the four Res has an alkyl group (a) and an —O— as a linking group. It is a group (a) or a group (P), or the group (D) is bonded as Xa to the above-mentioned 4-position.
  • the hydrogen atom at a position other than the position where Re is bonded may be substituted with the substituent Xa.
  • the substituent Xa is bonded to a carbon atom other than the carbon atom next to the carbon atom bonded to the nitrogen atom.
  • the compound (1d) does not have a substituent Xa, or if it has, the number thereof is preferably 1 or 2, and more preferably 1.
  • the group (D) is preferable as the Xa.
  • Ra or Re corresponds to the substituent (E).
  • Xa is bonded to the 4-position of the benzene ring having Re, and the Xa is the group (D).
  • only Ra may be a substituent (E)
  • only Re may be a substituent (E).
  • the structure may be such that Ra and Re are not the substituent (E), but Xa is bonded to the 4-position of the benzene ring having Re, and the Xa is the group (D).
  • These 2 or 3 may be a substituent (E) or have a substituent (E).
  • the substituent (E) is an alkyl group (a).
  • Ra is not the substituent (E)
  • Ra is preferably an alkyl group having 1 to 3 carbon atoms.
  • the substituent (E) is an alkyl group (a), an alkyl group (a) having —O— as a linking group, or the group (P) itself.
  • the substituent (E) having the group (D) at X 31 or X 35 is preferably the alkyl group (a), the alkyl group (a) having —O— as the linking group, or the group (P) itself.
  • Re is preferably the substituent (E).
  • Table IV shows an example of the compound (1d) in which the two Ra and the four groups (A) are all the same.
  • the two Ras are a methyl group, an ethyl group (indicated by "Et” in the table) or an alkyl group (a).
  • Re in the four groups (A) are all the same alkyl group (a), group (P), methyl group or phenyl group.
  • Table IV shows the name of the compound, the types of Ra and Re possessed by the compound, and the nitrogen atom of the carbon atom to which Re is bonded to the group or atom bonded to the carbon atom other than the carbon atom to which Re is bonded in the group (A).
  • compound (1c) and compound (1d) it is preferable that the 4-position of the four groups (A) bonded to the nitrogen atom in the benzene ring does not have a substituent.
  • a compound (1e) having a structure represented by the following general formula (1e) can be exemplified.
  • Ya and Yb independently represent an OH group or an NHCORa (Ra represents a hydrocarbon group) group.
  • Each Re independently represents a hydrogen atom or a substituent.
  • Each Xa independently represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms, or a substituted or unsubstituted phenyl group. However, Xa does not have a linear or branched alkyl group having 4 or more carbon atoms or a (poly) oxyalkylene group as a substituent.
  • m represents an integer of 0 to 3.
  • Ra represents an alkyl group (a)
  • at least one of the four Res is an alkyl group (a), an alkyl group (a) having —O— as a linking group, or a group.
  • Specific examples of the compounds classified into the compound (1e) include compounds (1c) -1 to (1c) -38 and compounds (1c) -40 among the compounds shown in Table II above. Further, among the compounds shown in Table IV above, compounds (1d) -1 to (1d) -31, compound (1d) -33, compound (1d) -35, compound (1d) -37, compound (1d)- 39 and compound (1d) -41.
  • the compound (4) having the structure represented by the general formula (4) has L 1 as a group (L1), L 2 as a group (L 4), and Ar 1 to Ar 4 as a group. Both are compounds which are the group (B).
  • each X 11 in the four groups (B) is a substituent (E). Further, it is preferable that one substituent (E) is present in each of the four groups (B).
  • the groups (B) corresponding to Ar 1 , Ar 2 , Ar 3 , and Ar 4 of the general formula (1) are grouped (B1), group (B2), and group (B3), respectively.
  • the group (B4), in the compound (41), the substituent (E) is the group (B1) X 11 , the group (B2) X 11 , the group (B3) X 11 , and the group (B4). It is preferable that they are present in each of X 11 of the above.
  • R 2, R 6, R 7 and R 8 is preferably a hydrogen atom.
  • X 12 , X 13 , X 14 , X 15 , X 16 and X 17 in the group (B1), group (B2), group (B3) and group (B4) shall be hydrogen atoms, methyl groups or phenyl groups. Is preferable.
  • substituent (E) in the compound (41) each group described above can be applied without particular limitation.
  • R 1 and R 5 in the general formula (4) are NHCORa group, NHSO 2 Rb group, or NHPO (ORf) (ORg) group
  • the compound is also referred to as compound (42).
  • X 13 may be the group (D).
  • Each of X 16 and X 17 can be optionally used as a substituent (E).
  • Ra, Rb, Rf and Rg are limited to the substituent (E) containing the alkyl group (a).
  • each X 11 in the four groups (B) of Ra, Rb, Rf and Rg is a substituent (E).
  • the four groups (B) have a substituent (E)
  • one substituent (E) is present in each of the four groups (B).
  • Ra, Rb, Rf and Rg when not the substituent (E) include an alkyl group having 1 to 3 carbon atoms, an aryl group such as a phenyl group, a tolyl group and a xsilyl group.
  • R 2 and R 6 and R 3 , R 4 , R 7 and R 8 are preferably hydrogen atoms.
  • X 12 , X 13 , X 14 , X 15 , X 16 and X 17 in the group (B1), group (B2), group (B3) and group (B4) shall be hydrogen atoms, methyl groups or phenyl groups. Is preferable.
  • substituent (E) in the compound (42) each group described above can be applied without particular limitation.
  • Table V exemplifies compound (4).
  • “tolyl” indicates a tolyl group.
  • the compound (5) having the structure represented by the general formula (5) has L 1 as a group (L1), L 2 as a group (L 4), and Ar 1 to Ar 4 as a group. Both are compounds which are the group (C).
  • compound (5) when R 1 and R 5 in the general formula (5) are OH groups, the compound is also referred to as compound (51).
  • Each X 26 can be optionally used as a substituent (E).
  • the groups (C) corresponding to Ar 1 , Ar 2 , Ar 3 , and Ar 4 of the general formula (1) are grouped (C1), group (C2), and group (C3), respectively.
  • the group (C4) the compound (51), X 21 substituents (E) is, X 21 or X 27 groups (C1), X 21 or X 27 groups (C2), based on (C3) or X 27, and are preferably present one each in X 21 or X 27 group (C4).
  • R 2 and R 6 and R 3 , R 4 , R 7 and R 8 are preferably hydrogen atoms.
  • Group (C1), group (C2), X 21 and X 27 is not a substituent (E) of the X 21 and X 27 in the group (C3) and group (C4), and X 22, X 23, X 24 , X 25 and X 26 are preferably hydrogen atoms, methyl groups or phenyl groups.
  • substituent (E) in the compound (51) each group described above can be applied without particular limitation.
  • R 1 and R 5 in the general formula (5) are NHCORa group, NHSO 2 Rb group, or NHPO (ORf) (ORg) group
  • the compound is also referred to as compound (52).
  • Ra, Rb, Rf, Rg, R 2 , R 6 and at least one of each X 21 and X 27 in the four groups (C) are substituents (E). Or, in place of these, or it may be X 24 In addition to these groups (D).
  • Each X 26 can be optionally used as a substituent (E).
  • Ra, Rb, Rf and Rg are limited to the substituent (E) containing the alkyl group (a).
  • each of X 21 and X 27 in the four groups (C) of Ra, Rb, Rf and Rg is a substituent (E).
  • the four groups (C) have a substituent (E)
  • one substituent (E) is present in each of the four groups (C).
  • Ra, Rb, Rf and Rg when not the substituent (E) include an alkyl group having 1 to 3 carbon atoms, an aryl group such as a phenyl group, a tolyl group and a xsilyl group.
  • R 2 and R 6 and R 3 , R 4 , R 7 and R 8 are preferably hydrogen atoms.
  • Group (C1), group (C2), X 21 and X 27 is not a substituent (E) of the X 21 and X 27 in the group (C3) and group (C4), and X 22, X 23, X 24 , X 25 and X 26 are preferably hydrogen atoms, methyl groups or phenyl groups.
  • each group described above can be applied without particular limitation.
  • L 1 is a group (L2), with L 2 is a group (L5) It is a compound.
  • Compound (6) is a compound in which Ar 1 to Ar 4 are all groups (A), and compound (7) is a compound in which Ar 1 to Ar 4 are all groups (B). 8) is a compound in which Ar 1 to Ar 4 are all groups (C).
  • R 2 , R 6 , R 11 , R 12 , R 15 , R 16 , and at least one of each X 1 and X 5 in the four groups (A) are substituents (E).
  • the compound (71) is R 2, R 6, R 11 , R 12, R 15, at least one substituent of each X 11 in R 16, and four groups (B) (E) .
  • compound (81) at least one of each of X 21 and X 27 in the four groups (C) of R 2 , R 6 , R 11 , R 12 , R 15 , R 16 , and 4 groups (C) is a substituent (E).
  • X 3 in compound (61), X 13 in compound (71), and X 24 in compound (81) are groups (D), respectively. You may.
  • each of X 16 and X 17 can be optionally used as a substituent (E).
  • each X 26 can be optionally used as a substituent (E).
  • compound (61), compound (71) and compound (81) it is preferable that one substituent (E) is present in each of the four groups (A), group (B) or group (C).
  • R 2 , R 6 , R 11 , R 12 , R 15 and R 16 and R 3 , R 4 , R when not the substituent (E). 7 , R 8 , R 13 , R 14 , R 17 and R 18 are preferably hydrogen atoms or methyl groups.
  • X 1 ⁇ X 5 is not a substituent (E) or a group (D) of the X 1 ⁇ X 5 having four groups (A) is a hydrogen atom, is a methyl group or a phenyl group Is preferable.
  • X 11 ⁇ X 17 is not a substituent (E) or a group (D) of the X 11 ⁇ X 17 having four groups (B) is a hydrogen atom, is a methyl group or a phenyl group Is preferable.
  • X 21 ⁇ X 27 is not a substituent (E) or a group (D) of the X 21 ⁇ X 27 having four groups (C) is a hydrogen atom, is a methyl group or a phenyl group Is preferable.
  • Ra, Rb, Rf, Rg, of R 2, R 6, R 11 , R 12, R 15, R 16, each X 21 in four groups (C) and X 27 At least one is a substituent (E).
  • X 3 in compound (62), X 13 in compound (72), and X 24 in compound (82) are groups (D), respectively. You may.
  • each of X 16 and X 17 can be optionally used as a substituent (E).
  • each X 26 can be optionally used as a substituent (E).
  • Ra, Rb, Rf and Rg are limited to the substituent (E) containing the alkyl group (a).
  • R 2 , R 6 , R 11 , R 12 , R 15 and R 16 and R 3 , R 4 , R when not the substituent (E). 7 , R 8 , R 13 , R 14 , R 17 and R 18 are preferably hydrogen atoms.
  • X 1 ⁇ X 5 is not a substituent (E) or a group (D) of the X 1 ⁇ X 5 having four groups (A) is a hydrogen atom, is a methyl group or a phenyl group Is preferable.
  • X 11 ⁇ X 17 is not a substituent (E) or a group (D) of the X 11 ⁇ X 17 having four groups (B) is a hydrogen atom, is a methyl group or a phenyl group Is preferable.
  • X 21 ⁇ X 27 is not a substituent (E) or a group (D) of the X 21 ⁇ X 27 having four groups (C) is a hydrogen atom, is a methyl group or a phenyl group Is preferable.
  • Compound (9) is a compound in which Ar 1 to Ar 4 are all groups (A), and compound (10) is a compound in which Ar 1 to Ar 4 are all groups (B).
  • 11) is a compound in which Ar 1 to Ar 4 are all groups (C).
  • At least one of R 26 , R 32 , and each of X 1 and X 5 in the four groups (A) is the substituent (E).
  • at least one of R 26 , R 32 , and each X 11 of the four groups (B) is the substituent (E).
  • at least one of R 26 , R 32 , and each of X 21 and X 27 in the four groups (C) is the substituent (E).
  • X 3 in compound (91), X 13 in compound (101), and X 24 in compound (111) are groups (D), respectively. You may.
  • R 22 and R 28 can be optionally used as the substituent (E).
  • each X 16 and X 17 can be optionally used as the substituent (E).
  • R 22 , R 28 and each X 26 can be optionally used as a substituent (E).
  • compound (91), compound (101) and compound (111) it is preferable that one substituent (E) is present in each of the four groups (A), group (B) or group (C).
  • R 22 to R 26 and R 28 to R 32 which are not substituents (E), are preferably hydrogen atoms or methyl groups.
  • X 1 ⁇ X 5 is not a substituent (E) or a group (D) of the X 1 ⁇ X 5 having four groups (A) is a hydrogen atom, is a methyl group or a phenyl group Is preferable.
  • X 11 ⁇ X 17 is not a substituent (E) or a group (D) of the X 11 ⁇ X 17 having four groups (B) is a hydrogen atom, is a methyl group or a phenyl group Is preferable.
  • X 21 ⁇ X 27 is not a substituent (E) or a group (D) of the X 21 ⁇ X 27 having four groups (C) is a hydrogen atom, is a methyl group or a phenyl group Is preferable.
  • Ra, Rb, Rf, Rg, R 22 , R 26 , R 28 , R 32 , and at least one of each X 1 and X 5 in the four groups (A) is a substituent ( E).
  • Ra, Rb, Rf, Rg, R 22 , R 26 , R 28 , R 32 , and at least one of each X 11 of the four groups (B) are substituents (E).
  • Ra, Rb, Rf, Rg, R 22 , R 26 , R 28 , R 32 , and at least one of each X 21 and X 27 in the four groups (C) is a substituent ( E).
  • X 3 in compound (92), X 13 in compound (102), and X 24 in compound (112) are groups (D), respectively. You may.
  • R 22 and R 28 can be optionally used as the substituent (E).
  • each X 16 and X 17 can be optionally used as the substituent (E).
  • R 22 , R 28 and each X 26 can be optionally used as a substituent (E).
  • Ra, Rb, Rf and Rg are limited to the substituent (E) containing the alkyl group (a).
  • R 22 to R 26 and R 28 to R 32 which are not substituents (E), are preferably hydrogen atoms.
  • X 1 ⁇ X 5 is not a substituent (E) or a group (D) of the X 1 ⁇ X 5 having four groups (A) is a hydrogen atom, is a methyl group or a phenyl group Is preferable.
  • X 11 ⁇ X 17 is not a substituent (E) or a group (D) of the X 11 ⁇ X 17 having four groups (B) is a hydrogen atom, is a methyl group or a phenyl group Is preferable.
  • X 21 ⁇ X 27 is not a substituent (E) or a group (D) of the X 21 ⁇ X 27 having four groups (C) is a hydrogen atom, is a methyl group or a phenyl group Is preferable.
  • the compound (1) has been illustrated above.
  • the compounds (1a) to (1d) are preferable as described above.
  • compound (1a) -1, compound (1a) -12 and compound (1a) -20 are preferable from the viewpoint that the effects of the present invention can be more exhibited.
  • compound (1b) -14 and compound (1b) -18 are preferable.
  • compound (1c) -9, compound (1c) -12, compound (1c) -31, and compound (1c) -42 are preferable.
  • compound (1d) -1, compound (1d) -14, compound (1d) -36, compound (1d) -39, and compound (1d) -40 are preferable.
  • compound (4) compound (4) -5, compound (4) -6, compound (4) -9 and compound (4) -10 are preferable.
  • compound (5) compound (5) -3, compound (5) -4 and compound (5) -9 are preferable.
  • compound (6) compound (6) -3, compound (6) -4 and compound (6) -8 are preferable.
  • compound (7) compound (7) -4, compound (7) -5, compound (7) -6 and compound (7) -8 are preferable.
  • compound (8) compound (8) -3, compound (8) -4 and compound (8) -10 are preferable.
  • compound (9) As the compound (9), compound (9) -4, compound (9) -6, compound (9) -7 and compound (9) -10 are preferable.
  • compound (10) As the compound (10), compound (10) -2, compound (10) -4, compound (10) -5 and compound (10) -8 are preferable.
  • compound (11) As the compound (11), compound (11) -2, compound (11) -3 and compound (11) -7 are preferable.
  • the compound (1) according to the present invention is, for example, the method described in Chemistry of Materials, Vol. 23, p. 4789 (2011), The Journal of Physical Chemistry, Vol. 91, p. 5184 (1987), or It can be synthesized by referring to the methods described in the references described in these documents.
  • a synthetic example of the exemplified compounds (1a) -1, (1b) -1, (1c) -1 and (1d) -1 is shown below.
  • Compound (1a) -1 can be synthesized, for example, by the following scheme (A).
  • the amount of the compound used, the treatment temperature, the time, etc. are examples and can be appropriately adjusted. The same applies to the synthesis of other compounds.
  • Step 1 m-anisidine (reagent 1-1, 1.5 equal amounts of 1-bromo-2-iodobenzene (reagent 1-2), 5% tris (dibenzylideneacetone) dipalladium (0), 10% tris-tert- Butylphosphonium tetrafluoroborate, 3 equal volumes of tert-butoxysodium is refluxed in 30 mL of xylene. This is extracted, concentrated and purified by silica gel column chromatography to give intermediate 1-1.
  • Step 2 Intermediate 1-1, 1.1 equivalents of 4-butylphenylboronic acid (reagent 1-3), 5% bis (dibenzylideneacetone) palladium (0), 10% 2-dicyclohexylphosphino-2', 6 ⁇ -Dimethoxybiphenyl, 6 eq potassium phosphate, is heated in a 10: 1 mixed solvent of 1,2-dimethoxyethane and water. This is extracted, concentrated, and then purified by silica gel chromatography to obtain Intermediate 1-2.
  • Step 3 Next, Intermediate 1-2 is cooled to 0 ° C. in methylene chloride, a 1 M methylene chloride solution of boron tribromide is added dropwise with a dropping funnel, and the mixture is stirred at 0 ° C. for 1 hour. Then, the temperature is returned to room temperature, the mixture is stirred for 1 hour, water is added, the mixture is extracted and concentrated, and the mixture is produced by silica gel chromatography to obtain Intermediate 1-3.
  • Step 4 The finally obtained intermediates 1-3 and 3,4-dihydroxy-3-cyclobutene-1,2-dione are heated in a 1: 1 mixed solvent of toluene and butanol for 6 hours. After cooling, the fallen green crystals are collected by filtration to obtain compound (1a) -1.
  • the structure of the compound can be confirmed by mass spectrometry (MS) and 1 H-NMR.
  • FIG. 1 shows a 1 H-NMR spectrum (400 MHz, measuring solvent CDCl3) of compound (1a) -1.
  • Step 1 3-Nitroaniline (Reagent 2-1), 1-bromo-2-iodobenzene (Reagent 2-2), Tris (dibenzylideneacetone) dipalladium (0), Tris-tert-butylphosphonium tetrafluoroborate, tert- Reflux in 30 mL of sodium butoxylen and xylene. This is extracted, concentrated, and then purified by silica gel column chromatography to obtain Intermediate 2-1.
  • Step 2 Intermediates 2-1 and 4-butylphenylboronic acid (reagent 2-3), bis (dibenzylideneacetone) palladium (0), 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, potassium phosphate, Heat in a 4: 1 mixed solvent of 1,2-dimethoxyethane and water. This is extracted, concentrated, and then purified by silica gel chromatography to obtain Intermediate 2-2.
  • Step 3 a Pd-C (10%) catalyst is added to the ethanol-tetrahydrofuran 1: 1 mixed solvent of Intermediate 2-2, and catalytic reduction with hydrogen is performed. After 6 hours, it was confirmed that the reaction was completed, and Pd-C was removed by filtration through Celite and concentrated to obtain Intermediate 2-3.
  • Step 4 this intermediate 2-3 is reacted with Valeryl chloride (reagent 2-4) to obtain Intermediate 2-4.
  • Step 5 The finally obtained intermediates 2-4 and 3,4-dihydroxy-3-cyclobutene-1,2-dione (reagent 2-5) are heated in a toluene-butanol 1: 1 mixed solvent for 6 hours. After cooling, extraction, concentration, and purification by silica gel column chromatography give compound (1b) -1. The structure of the compound can be confirmed by MS and 1 1 H-NMR.
  • Step 1 2-butylaniline (reagent 3-1), 3-bromoanisole (reagent 3-2) 2.1 equal amount, tris (dibenzylideneacetone) dipalladium (0) 0.05 equal amount, tris-tert-butylphosphonium Stir at 100 ° C. for 6 hours in 0.15 equal amount of tetrafluoroborate, 1.5 equal amount of tert-butoxysodium, 20 mL of toluene. This is extracted and concentrated, and then produced by silica gel column chromatography to obtain Intermediate 3-1.
  • Step 1a Separately, p-toluenesulfonic acid is dissolved in 50 mL of acetonitrile in 3 equal volumes with respect to reagent 3-1 and cooled to 0 ° C., and 2 equal volumes of sodium nitrite and 2.5 equal volumes of potassium iodide are added to 20 mL of water. The dissolved solution is added dropwise over 30 minutes, and after the addition, the mixture is stirred at room temperature for 1 hour. This is extracted and purified by silica gel column chromatography to obtain Intermediate 3-2.
  • Step 2 1.3 equal amount of intermediate 3-2, 0.03 equal amount of tris (dibenzylideneacetone) dipalladium (0), 0.1 equal amount of tris-tert-butylphosphonium tetrafluoroborate relative to intermediate 3-1 React in equal volume, 1.5 equal volume of tert-butoxysodium, 30 mL of xylene at 135 ° C. for 16 hours. This is extracted and concentrated, and then produced by silica gel column chromatography to obtain Intermediate 3-3.
  • Step 3 An equal amount of a methylene chloride solution (1M) of boron tribromide is added dropwise to a solution prepared by dissolving the intermediate 3-3 in 30 mL of dehydrated methylene chloride and cooled to 0 ° C., and the mixture is stirred at room temperature for 8 hours after the addition. This is extracted, concentrated, and then purified by silica gel column chromatography to obtain Intermediate 3-4.
  • a methylene chloride solution (1M) of boron tribromide is added dropwise to a solution prepared by dissolving the intermediate 3-3 in 30 mL of dehydrated methylene chloride and cooled to 0 ° C., and the mixture is stirred at room temperature for 8 hours after the addition. This is extracted, concentrated, and then purified by silica gel column chromatography to obtain Intermediate 3-4.
  • Step 4 Finally, the obtained intermediate 3-4 and 0.4 equivalent of 3,4-dihydroxy-3-cyclobutene-1,2-dione (reagent 3-3) were mixed in a toluene-butanol 1: 2 mixed solvent at 115 ° C. Heat for 16 hours. After cooling, extraction, concentration, and purification by silica gel column chromatography give compound (1c) -1. The structure of the compound can be confirmed by MS and 1 1 H-NMR. FIG. 2 shows a 1 H-NMR spectrum (400 MHz, measuring solvent CDCl3) of compound (1c) -1.
  • Step 1 Addition of 1 equal amount of 2-bromotoluene (reagent 4-2) to o-toluidine (reagent 4-1), [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride / methylene chloride React at 100 ° C. for 6 hours in 0.03 equal volume of the product, 2 equal doses of tert-butoxysodium, and 200 mL of toluene. This is extracted and concentrated, and then produced by silica gel column chromatography to obtain Intermediate 4-1.
  • Step 2 To intermediate 4-1 1.2 equal amount of 3-bromonitrobenzene (reagent 4-3), 0.03 equal amount of tris (dibenzylideneacetone) dipalladium (0), tris-tert-butylphosphonium tetrafluoro A 0.05 equal amount of borate and 2 equal amounts of tert-butoxysodium are reacted in 150 mL of xylene at 130 ° C. for 16 hours. This is extracted and concentrated, and then produced by silica gel column chromatography to obtain Intermediate 4-2.
  • Step 3 this intermediate 4-2 is dissolved in 250 mL of ethyl acetate, and a catalytic reduction reaction with hydrogen is carried out at room temperature for 16 hours in the presence of 5 g of a Pd-C (10%) catalyst. Pd-C removed by Celite filtration is concentrated to give Intermediate 4-3.
  • Step 4 Next, this intermediate 4-3 was dissolved in 150 mL of methylene chloride, 1.5 equal amounts of triethylamine was added thereto, the mixture was cooled to 0 ° C., and 1.2 equal amounts of Valeryl chloride (reagent 4-4) were added. Stir at room temperature for 16 hours. This is extracted and concentrated, and then purified by silica gel column chromatography to obtain Intermediate 4-4.
  • Step 5 The finally obtained intermediates 4-4 and 3,4-dihydroxy-3-cyclobutene-1,2-dione (reagent 4-5) are heated in a toluene-butanol 1: 1 mixed solvent for 6 hours. After cooling, extraction, concentration, and purification by silica gel column chromatography give compound (1d) -1. The structure of the compound can be confirmed by MS and 1 1 H-NMR.
  • FIG. 3 shows a 1 H-NMR spectrum (400 MHz, measuring solvent CDCl3) of compound (1d) -1.
  • Compound (T) is a compound that absorbs red light and fluoresces near-infrared light.
  • the compound (1) is preferable from the viewpoint of the optical properties.
  • the emission spectrum of compound (T) can be confirmed by the following method.
  • Compound (T) is adjusted to 10-6 M in toluene solution and the emission spectrum of this sample is measured at room temperature (300 K).
  • a spectrofluorometer (F7000, manufactured by Hitachi High-Technos Co., Ltd.) is used for measuring the emission spectrum.
  • the compound (T) is a near-infrared light emitting compound exhibiting fluorescence emission having a maximum emission wavelength (wavelength having the maximum emission intensity; also referred to as "emission peak wavelength") exceeding 700 nm in the obtained emission spectrum.
  • the emission peak wavelength of the compound (T) is preferably 700 nm or more, more preferably 710 nm or more.
  • the absorption peak wavelength is adjusted to 10-6 M in a toluene solution of compound (T), and the absorption spectrum of this sample is measured at room temperature (300 K).
  • a spectrophotometer manufactured by Hitachi High-Technos Co., Ltd., F7000) is used for the measurement of the absorption spectrum.
  • the luminescence quantum yield of a solution in which compound (T) is dissolved in toluene or the like and the luminescence quantum yield of a thin film dispersed in a matrix material can be measured and used for evaluation by, for example, the following methods.
  • the emission quantum yield ⁇ (%) is expressed as the ratio of the number of absorbed photons to the number of emitted photons. If all the excited molecules return to the ground state by fluorescence, the emission quantum yield ⁇ (%) will be 100%, but if non-radiative deactivation occurs, it will not be 100%.
  • Non-radiative deactivation is a transition that returns to the ground state without emitting fluorescence.
  • the energy of the electronic state is converted to vibration energy and finally becomes thermal energy. There are internal conversions and energy transfers that transfer energy to other molecules.
  • the emission quantum yield ⁇ (%) (Kf / (Kf + Knr)) ⁇ 100
  • the light emitting member of the present invention has an emission peak in a long wavelength region of near infrared light and can achieve a high emission quantum yield.
  • the compound (1) is preferable from the viewpoint that the characteristics can be obtained at a higher level.
  • the light emitting member of the present invention include a light emitting thin film and light emitting particles. Further, the luminescent thin film can be used as a wavelength conversion film.
  • the light emitting member of the present invention can be used for bioimaging, for example, as a new type of dye for a fluorescent probe and as a marker in biology and medicine.
  • the compound (T) which emits fluorescence as extra energy when the excited electrons return to the ground state, has a wavelength conversion ability due to the difference in energy between absorption and emission, and is used as a dye as a color conversion filter.
  • Pigments, optical filters, agricultural films and the like are examples of the compound (T), which emits fluorescence as extra energy when the excited electrons return to the ground state.
  • the luminescent thin film according to the embodiment of the light emitting member of the present invention is characterized by containing a compound (T).
  • the luminescent thin film can be produced by forming a composition in which a matrix material is added to the compound (T) for film formation stability and the like, or a composition in which a solvent is further added, in the form of a thin film. ..
  • (meth) acrylate resin polyester resin, polyamide resin, polyimide resin, polystyrene resin, polyepoxy resin, polyester resin, amino resin, fluorine resin, phenol resin, polyurethane
  • examples thereof include based resins, polyethylene resins, polypropylene resins, polyvinyl chloride resins, polyvinyl alcohol resins, polyether resins, polyether ketone resins, polyphenylene sulfide resins, polycarbonate resins, aramid resins and the like, but are preferable.
  • a polystyrene-based resin a polyethylene-based resin, a polypropylene-based resin, a polyvinyl chloride-based resin, or the like.
  • these copolymers are also preferable.
  • the (meth) acrylate-based resin is synthesized by homopolymerizing or copolymerizing various methacrylate-based monomers or acrylate-based monomers, and by changing the monomer species and the monomer composition ratio in various ways, the desired (meth) acrylate is used.
  • a based resin can be obtained. Further, in the present invention, it can be used by copolymerizing with a (meth) acrylate-based monomer together with a copolymerizable monomer having an unsaturated double bond other than the (meth) acrylate-based monomer, and further in the present invention. Can also be used by mixing a plurality of other resins together with the poly (meth) acrylate-based resin.
  • Examples of the monomer component forming the (meth) acrylate-based resin used in the present invention include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate.
  • Polystyrene-based resins include homopolymers of styrene monomers, random copolymers copolymerized with other monomers copolymerizable with styrene monomers, block copolymers, and graft copolymers. Can be mentioned. Further included are blends and polymer alloys in which such polymers are blended with other polymers.
  • styrene monomer examples include nuclear alkyl substitutions such as styrene, ⁇ -methylstyrene, ⁇ -ethylstyrene, ⁇ -methylstyrene-p-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, etc.
  • nuclear halide styrenes such as styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, dichlorostyrene, dibromostyrene, trichlorostyrene, and tribromostyrene.
  • Styrene and ⁇ -methylstyrene are preferable.
  • Examples of the resin used in the present invention by homopolymerizing or copolymerizing these include a copolymer resin such as benzyl methacrylate / ethyl acrylate or butyl acrylate, and a copolymer resin such as methyl methacrylate / 2-ethylhexyl methacrylate.
  • the weight average molecular weight of the resin is preferably in the range of 1000 to 10000, more preferably 5000 to 800,000, and further preferably 10000 to 600,000.
  • one type of compound (T) may be used alone, or two or more types may be used in combination.
  • the preferable lower limit is 0.001 part by mass and the preferable upper limit is 50 parts by mass with respect to 100 parts by mass of the matrix material.
  • the luminescent thin film emits light in a long wavelength region of near-infrared light, and a high emission quantum yield can be achieved.
  • the more preferable lower limit of the content of the compound (T) is 0.01 parts by mass, the more preferable upper limit is 10 parts by mass, the further preferable lower limit is 0.05 parts by mass, the further preferable upper limit is 8 parts by mass, and the particularly preferable lower limit is 0. 1 part by mass, particularly preferably the upper limit is 5 parts by mass.
  • the luminescent thin film can be appropriately used within a thickness range of 0.1 nm to 1 mm.
  • the luminescent particles according to the embodiment of the light emitting member of the present invention are characterized by containing the compound (T).
  • the luminescent particles may be luminescent particles in which the compound (T) is adsorbed on the surface of the particles, or luminescent particles containing the compound (T).
  • luminescent particles can be produced by aggregating compound (T) in a polymer particle dispersion. Further, when the polymer particles are immersed in a solvent, the swellable polymer whose volume expands by absorbing the solvent may be used, and the luminescent particles may contain the compound (T).
  • the polymer particles commercially available products may be used, or those synthesized by a conventionally known method may be used.
  • the conventionally known method is not particularly limited, and examples thereof include a dispersion polymerization method, a suspension polymerization method, and an emulsion polymerization method, and an emulsion polymerization method is preferable.
  • a thermoplastic resin such as a melamine resin or a polystyrene resin is preferable.
  • the monomer used as the raw material of the polymer various monomers listed as the monomer of the matrix material in the above-mentioned luminescent thin film can be used.
  • the solvent for aggregating the compound (T) in the polymer particle dispersion is not particularly limited.
  • a known solvent can be used.
  • the volume average particle diameter of the polymer particles is preferably in the range of 0.01 to 50 ⁇ m, more preferably 0.02 to 1 ⁇ m, and even more preferably 0.04 to 0.5 ⁇ m.
  • the obtained luminescent particles can be applied to various uses.
  • the volume average particle size can be measured by a laser diffraction scattered light particle size distribution measuring device, LS13320 type.
  • the weight average molecular weight of the polymer particles is preferably in the range of 1000 to 10000, more preferably 5000 to 800,000, and even more preferably 10000 to 600,000.
  • the polymer particles contained in the luminescent particles may be one kind or two or more kinds, but usually one kind.
  • the raw material of the resin (monomer or oligomer or prepolymer, for example, methylol melamine which is a condensate of melamine and formaldehyde) and a compound (T).
  • a reaction mixture containing a surfactant and a polymerization reaction accelerator (acid or the like) and the polymerization reaction is allowed to proceed by an emulsion polymerization method to obtain luminescent particles containing the compound (T). Can be made.
  • thermoplastic resin such as a styrene-based copolymer
  • the raw material of the resin, the compound (T), and (the compound (T) as the raw material monomer of the resin are covalently bonded in advance.
  • a bonded monomer may be used)
  • a reaction mixture containing a polymerization initiator (benzoyl peroxide, azobisisobutyronitrile, etc.) is heated, and the polymerization reaction proceeds by a radical polymerization method or an ionic polymerization method. By doing so, luminescent particles containing the compound (T) can be produced.
  • silica can be used as a base, and compound (T) can be encapsulated therein to produce luminescent particles.
  • a solution in which the inorganic semiconductor nanoparticles, compound (T) and a silica precursor such as tetraethoxysilane are dissolved is added dropwise to a solution in which ethanol and ammonia are dissolved to add water to the silica precursor. It can be produced by disassembling.
  • one type of compound (T) may be used alone, or two or more types may be used in combination.
  • the preferable lower limit is 0.001 parts by mass and the preferable upper limit is 50 parts by mass with respect to 100 parts by mass of the polymer particles.
  • the luminescent thin film emits light in a long wavelength region of near-infrared light, and a high emission quantum yield can be achieved.
  • a more preferable lower limit of the content of the compound (T) is 0.01 parts by mass, a more preferable upper limit is 10 parts by mass, and a further preferable lower limit is 0.1 parts by mass.
  • An infrared light emitting surface light source can be produced by using the above-mentioned luminescent thin film as a light emitting member as a wavelength conversion film. Since the wavelength conversion film emits infrared light (near infrared light) by having a light emitting thin film containing the compound (T), it can be applied to an infrared light emitting surface light source.
  • the wavelength conversion film may be composed of only the above-mentioned luminescent thin film, or may be a laminated film laminated with another layer.
  • the infrared light emitting surface light source includes a surface light source that emits visible light and a wavelength conversion film that converts visible light emitted from the surface light source, particularly red light, into near infrared light, and has an infrared wavelength range of more than 700 nm. It is preferable to have a maximum emission wavelength.
  • FIG. 4 shows a basic configuration example of an infrared light emitting surface light source having a wavelength conversion film including a light emitting thin film containing the compound (T).
  • the infrared light emitting surface light source 1 shown in FIG. 4 is a surface light source 2 that emits visible light, for example, on an organic EL element that emits red light (R), the visible light of the surface light source 2 that emits red light (R) is near infrared.
  • This is a configuration in which a wavelength conversion film 3 that converts light (IR) is arranged.
  • a surface light source that emits visible light (red) is a light source that has at least a characteristic of emitting red light, and is preferably a surface light source that has a luminance uniformity of 70% or more when uniformly emitted, and is a specific surface.
  • the light source is preferably an organic EL element.
  • the form of the infrared light emitting surface light source 1 is also a form in which a wavelength conversion film 3 manufactured separately from the surface light source 2 that emits visible light (red) is superposed on the surface light source 2 that emits visible light (red). good.
  • the wavelength conversion film 3 may be laminated on a surface light source 2 that emits visible light (red).
  • the wavelength conversion film 3 may be composed of a single layer of a luminescent thin film containing the compound (T), and may be, for example, a laminated structure including a luminescent thin film as shown in FIG.
  • the wavelength conversion film 3 shown in FIG. 5 has a luminescent thin film 5 containing a compound (T), and a gas barrier film 4B is bonded to one surface of the luminescent thin film 5 via an adhesive layer 6.
  • the gas barrier film 4A is bonded to the other surface.
  • the thickness of the infrared light emitting surface light source 1 is appropriately determined depending on the application, but is preferably 0.1 to 1000 ⁇ m from the viewpoint of flexibility and miniaturization, and more preferably within the range of 1 to 500 ⁇ m. Is.
  • Such an infrared light emitting surface light source is suitably used for a biometric device and a biometric authentication device.
  • the photoelectric conversion member of the present invention contains compound (T).
  • the photoelectric conversion member can be used as a member of a near-infrared photoelectric conversion element.
  • the near-infrared photoelectric conversion element to which the photoelectric conversion member of the present invention is applied is an element having a photoelectric conversion unit between a pair of opposing electrodes, and light is incident on the photoelectric conversion unit from above the electrodes.
  • the photoelectric conversion unit is an element that generates electrons and holes in response to the incident light, reads out a signal corresponding to the electric charge by a semiconductor, and indicates the amount of incident light according to the absorption wavelength of the photoelectric conversion unit.
  • a transistor for reading may be connected to the electrode on the side where light is not incident.
  • the photoelectric conversion member containing the compound (T) can be applied as a member constituting the photoelectric conversion unit, specifically, a photoelectric conversion layer described below.
  • the photoelectric conversion unit is composed of a photoelectric conversion layer and an organic thin film layer other than one or a plurality of types of photoelectric conversion layers selected from the group consisting of an electron transport layer, a hole transport layer, an electron block layer, a hole block layer, and the like. Often consists of.
  • the photoelectric conversion layer may be composed of only the compound (T), but may contain a known infrared absorbing substance in addition to the compound (T).
  • the photoelectric conversion layer included in the photoelectric conversion unit described later has a hole transporting property, or the organic thin film layer other than the photoelectric conversion layer has a hole transporting property.
  • a hole transport layer it plays a role of extracting holes from the photoelectric conversion layer and other organic thin film layers and collecting them.
  • the photoelectric conversion layer included in the photoelectric conversion unit has electron transporting property, or when the organic thin film layer is an electron transporting layer having electron transporting property, electrons are transferred from the photoelectric conversion layer or other organic thin film layer. It plays a role of taking out and discharging this.
  • the material that can be used as the electrode film is not particularly limited as long as it has a certain degree of conductivity, but the adhesion to the adjacent photoelectric conversion layer and other organic thin film layers, electron affinity, ionization potential, stability, etc. It is preferable to select in consideration of.
  • Electrode film Materials that can be used as the electrode film include conductive metal oxides such as tin oxide (NESA), indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); gold, silver, platinum, chromium and aluminum.
  • conductive metal oxides such as tin oxide (NESA), indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); gold, silver, platinum, chromium and aluminum.
  • Metals such as iron, cobalt, nickel and tungsten: Inorganic conductive substances such as copper iodide and copper sulfide: Conductive polymers such as polythiophene, polypyrrole and polyaniline: Carbon and the like.
  • the conductivity of the material used for the electrode film is not particularly limited as long as it does not interfere with the light reception of the photoelectric conversion element more than necessary, but it is preferably as high as possible from the viewpoint of the signal strength of the photoelectric conversion element and the power consumption.
  • an ITO film having a conductivity of 300 ⁇ / ⁇ or less functions sufficiently as an electrode film, but a commercially available substrate having an ITO film having a conductivity of several ⁇ / ⁇ is also available. Therefore, it is desirable to use a substrate having such high conductivity.
  • the thickness of the ITO film can be arbitrarily selected in consideration of conductivity, but is usually about 5 to 500 nm, preferably about 10 to 300 nm.
  • Examples of the method for forming a film such as ITO include a conventionally known vapor deposition method, electron beam method, sputtering method, chemical reaction method, coating method and the like.
  • the ITO film provided on the substrate may be subjected to UV-ozone treatment, plasma treatment, or the like, if necessary.
  • ITO Indium-doped tin oxide
  • IZO Zinc-doped tin oxide
  • SnO 2 As the material of the transparent electrode film used for at least one of the electrode films on the side where light is incident, ITO, IZO, SnO 2 , ATO (antimony-doped tin oxide), ZnO, AZO (Al-doped zinc oxide) , GZO (gallium-doped zinc oxide), TiO 2 , FTO (fluorinated tin oxide) and the like.
  • the photoelectric conversion unit included in the photoelectric conversion element includes at least a photoelectric conversion layer and an organic thin film layer other than the photoelectric conversion layer.
  • An organic semiconductor film is generally used for the photoelectric conversion layer constituting the photoelectric conversion unit, and the compound (T) of the present invention is contained in the organic semiconductor thin film.
  • the organic semiconductor film may be one layer or a plurality of layers, and in the case of one layer, a P-type organic semiconductor film, an N-type organic semiconductor film, or a mixed film thereof (bulk heterostructure) is used.
  • a buffer layer may be inserted in.
  • the organic thin film layer other than the photoelectric conversion layer constituting the photoelectric conversion unit is a layer other than the photoelectric conversion layer, for example, an electron transport layer, a hole transport layer, an electron block layer, and a hole block. It is also used as a layer, a crystallization prevention layer, an interlayer contact improvement layer, and the like.
  • an element that efficiently converts even weak light energy into an electric signal can be obtained. Therefore, it is preferable.
  • the electron transport layer plays a role of transporting electrons generated in the photoelectric conversion layer to the electrode and a role of blocking holes from moving from the electrode of the electron transport destination to the photoelectric conversion layer.
  • the hole transport layer plays a role of transporting generated holes from the photoelectric conversion layer to the electrode and a role of blocking the movement of electrons from the electrode of the hole transport destination to the photoelectric conversion layer.
  • the electron block layer plays a role of hindering the movement of electrons from the electrode to the photoelectric conversion layer, preventing recombination in the photoelectric conversion layer, and reducing dark current.
  • the hole block layer has a function of hindering the movement of holes from the electrode to the photoelectric conversion layer, preventing recombination in the photoelectric conversion layer, and reducing dark current.
  • FIG. 6 illustrates a typical element structure of a photoelectric conversion element.
  • 11 is an insulating part
  • 12 is one electrode film
  • 13 is an electron block layer
  • 14 is a photoelectric conversion layer
  • 15 is a hole block layer
  • 16 is the other electrode
  • 17 is an insulating base material.
  • it represents another organic photoelectric conversion element.
  • the reading transistor is not shown in the figure, it suffices if it is connected to the electrodes 12 or 16, and if the photoelectric conversion layer 14 is transparent, it is on the side opposite to the side on which the light is incident.
  • a film may be formed on the outside of the electrode.
  • the incident of light on the organic photoelectric conversion element can be performed from either the upper part or the lower part unless the components other than the photoelectric conversion layer 14 extremely prevent the light of the main absorption wavelength of the photoelectric conversion layer from being incident. It may be from.
  • each compound having a structure shown below is classified into compound (3), specifically, compounds (1a) to (1d)), and compounds (4) to (11), respectively. Manufactured.
  • compound (4) -5, compound (4) -6, compound (4) -9 and compound (4) -10 were produced by a method according to the above schemes (A) to (D). , MS and 1 H-NMR confirmed the structure.
  • compound (5) -3, compound (5) -4 and compound (5) -9 were produced by a method according to the above schemes (A) to (D), and MS and 1 1 H-NMR were produced. The structure was confirmed by.
  • compound (7) -4, compound (7) -5, compound (7) -6 and compound (7) -8 were produced by a method according to the above schemes (A) to (D). , MS and 1 H-NMR confirmed the structure.
  • compound (8) -3, compound (8) -4 and compound (8) -10 were produced by a method according to the above schemes (A) to (D), and MS and 1 H-NMR were produced. The structure was confirmed by.
  • compound (9) -4, compound (9) -6, compound (9) -7 and compound (9) -10 were produced by a method according to the above schemes (A) to (D). , MS and 1 H-NMR confirmed the structure.
  • compound (10) -2, compound (10) -4, compound (10) -5 and compound (10) -8 were produced by a method according to the above schemes (A) to (D). , MS and 1 H-NMR confirmed the structure.
  • compound (11) -2, compound (11) -3 and compound (11) -7 were produced by a method according to the above schemes (A) to (D), and MS and 1 1 H-NMR were produced. The structure was confirmed by.
  • the obtained compound was adjusted to 10-6 M in a toluene solution, and the fluorescence spectrum of this sample was measured at room temperature (300 K).
  • a spectrofluorometer (F7000, manufactured by Hitachi High-Technos Co., Ltd.) was used for the measurement of the emission spectrum.
  • the absorption spectrum was measured using the sample prepared in the same manner.
  • a spectrophotometer (F7000, manufactured by Hitachi High-Technos Co., Ltd.) was used for the measurement of the absorption spectrum.
  • emission peaks were observed in the range of 700 to 900 nm.
  • Example 2 Among the compounds obtained in Example 1 above, the compounds shown in Table XIII below, the comparative compound R-1 having the structure shown below (the compound described in International Publication No. 2018/008721), and the comparative compound R-2. (Compounds described in Chem. Mater, 23, 4789, 2011) were evaluated for emission quantum yields in solution and in a thin film state by the following methods, respectively.
  • Compound R-1 for comparison with, the 10 -2 M in toluene were placed in a polystyrene flask and heated and stirred at 80 ° C. to sufficiently dissolve them.
  • a thin film was formed on a PET (polyethylene terephthalate) film using an applicator, dried at room temperature for 10 minutes, further dried by heating at 80 ° C. for 10 minutes, and peeled off from the PET film.
  • a luminescent thin film (comparative example) containing compound R-1 was prepared. Further, the compound R-1 was changed to the comparative compound R-2 to prepare a luminescent thin film (comparative example) containing the compound R-2. Further, the luminescent thin film of the present invention was prepared in the same manner except that the compound R-1 was changed to each compound according to the present invention shown in Table XIII.
  • the absolute PL (emission) quantum yield (hereinafter referred to as "PLQY film”) of these samples was measured at room temperature (300 K).
  • the absolute PL (emission) quantum yield was measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd .: C11347).
  • the absolute PL (emission) quantum yield of the corresponding luminescent thin film when the absolute PL (emission) quantum yield in the toluene solution of the luminescent thin film is 1.00 is the relative value of the luminescence quantum yield, that is, The PLQY film / PLQY solution is shown in Table XIII below.
  • the luminescent thin film using the comparative compound R-1 and the luminescent thin film using the compound R-2 maintained their emission quantum yields at 0.19 and 0.13, respectively, from the solution state.
  • the luminescent thin films using each compound according to the present invention achieved the emission quantum yield of 0.50 or more in the solution state, and the concentration quenching was remarkably suppressed.
  • the luminescent thin film using each compound according to the present invention had a luminescence quantum yield at a level that could be actually used.
  • Example 3 Among the compounds obtained in Example 1 above, the luminescence quantum yields of the compounds shown in Table XIV below and the comparative compounds R-1 and R-2 in the solution and in the luminescent particles were measured. ..
  • the particles were precipitated by a centrifugal purification method, the supernatant was removed, and then pure water was added to redisperse the particles. This operation (centrifugal purification and redispersion) was repeated 4 times to obtain luminescent particle dispersions 1 to 15 containing each compound.
  • the absolute PL (emission) quantum yields of the luminescent particle dispersions 1 to 15 obtained above were measured using an absolute PL quantum yield measuring device (C11347-01 manufactured by Hamamatsu Photonics).
  • the absolute PL (emission) quantum yield of the corresponding luminescent particle dispersion when the absolute PL (emission) quantum yield of the luminescent thin film in the toluene solution is 1.00 is the relative value of the emission quantum yield. That is, the PLQY particles / PLQY liquids are shown in Table XIV below.
  • the luminescent particles using the comparative compound R-1 and the luminescent particles using the compound R-2 were maintained at 0.30 and 0.20, respectively, from the solution state.
  • the luminescent particles using each compound according to the present invention achieved the emission quantum yield of 0.50 or more in the solution state, and the concentration extinction was remarkably suppressed.
  • the luminescent particles using each compound according to the present invention had a luminescence quantum yield at a level that could be actually used.
  • Example 4 A wavelength conversion film including a luminescent thin film containing compound (1a) -1 as the compound of the present invention was prepared according to the following method, and an infrared light emitting surface light source was further prepared using the wavelength conversion film.
  • the produced wavelength conversion film is the wavelength conversion film 3 having the structure shown in FIG. 5, and the infrared light emitting surface light source is the infrared light emitting surface light source 1 having the structure shown in FIG.
  • an inorganic gas barrier layer 4A made of SiO x was used on the entire surface of one side of the polyethylene naphthalate film (manufactured by Teijin DuPont) using the atmospheric pressure plasma discharge treatment apparatus having the configuration described in JP-A-2004-68143.
  • the obtained mixed solution was applied to the gas barrier film 4A formed so as to have a thickness of 500 nm using an applicator. After drying at room temperature for 10 minutes, it was further dried by heating at 80 ° C. for 10 minutes to form a luminescent thin film 5.
  • the wavelength conversion film 3 includes a polyethylene naphthalate film used as a base material.
  • the infrared light emitting surface light source 1 By bringing the light emitting surface of the organic EL element, which is the surface light source 2 that emits red light (R), into close contact with the wavelength conversion film 3, the infrared light emitting surface light source 1 having the configuration shown in FIG. 4 was produced. It was confirmed that the red light of the surface light source that emits red light (R) is converted into near-infrared light by emitting the surface light source that emits red light (R).
  • Example 5 a photoelectric conversion element having a photoelectric conversion layer containing the compound (1d) -39 obtained above as the compound of the present invention was prepared as follows, and its performance was evaluated.
  • a transparent electrode was formed by depositing a transparent conductive film of indium tin oxide (ITO) at 150 nm on a glass substrate and patterning it to a width of 2 mm using ordinary photolithography technology and hydrochloric acid etching.
  • the patterned transparent electrode was cleaned in the order of ultrasonic cleaning with a surfactant and ultrapure water, and ultrasonic cleaning with ultrapure water, dried with a nitrogen blow, and finally subjected to ultraviolet ozone cleaning.
  • a 1 mg / mL chloroform solution of compound (1d) -39 was spin-coated on this transparent substrate to a film thickness of 60 nm, and then heated and dried in the air at 140 ° C. for 10 minutes. After that, the substrate was brought into the glove box and worked in a nitrogen atmosphere. First, the substrate was heat-treated at 140 ° C. for 10 minutes in a nitrogen atmosphere. Next, the substrate on which the organic layer was formed was installed in the vacuum vapor deposition apparatus.
  • the element was set so that the shadow mask having a width of 2 mm was orthogonal to the transparent electrode, and the pressure inside the vacuum vapor deposition machine was reduced to 10-3 Pa or less, and then fullerene C60 was vapor-deposited at 40 nm, vasocuproin at 10 nm, and Al at 100 nm. Finally, heating was performed at 120 ° C. for 30 minutes to obtain a photoelectric conversion element 1 according to the present invention.
  • the vapor deposition rate was 2 nm / sec, and the size was 2 mm square.
  • the obtained photoelectric conversion element 1 was sealed with an aluminum cap and a UV curable resin (UV RESIN XNR5570-B1 manufactured by Nagase ChemteX Corporation) in a nitrogen atmosphere.
  • a UV curable resin UV RESIN XNR5570-B1 manufactured by Nagase ChemteX Corporation
  • compound (1d) -39 is compounded with compound (4) -6, compound (5) -4, compound (6) -8, compound (7) -6, compound (8) -4, compound (9).
  • a photoelectric conversion element was similarly prepared and evaluated by changing to -10, compound (10) -4, and compound (11) -2, an electric signal could be confirmed for each of these, and it was possible to sufficiently function as a photoelectric conversion element. It could be confirmed.
  • a light emitting member capable of achieving a high emission quantum yield in the near infrared long wavelength region, which contains a light emitting compound capable of emitting light in the near infrared long wavelength region and blending into the member at a high concentration.
  • a luminescent compound capable of emitting light in a near-infrared long wavelength region and blending with a member at a high concentration.
  • a photoelectric conversion member capable of obtaining high external quantum efficiency by using a luminescent compound capable of emitting light in a near-infrared long wavelength region and blending with a member at a high concentration.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un élément optique contenant un composé spécifique qui a un cycle de squarylium au centre de sa structure moléculaire et qui a une structure moléculaire ayant un pic d'émission dans une plage de longueur d'onde longue proche infrarouge, et dans lequel un groupe soluble (un groupe alkyle linéaire ou ramifié (a) ayant de 4 à 12 atomes de carbone, ou un groupe (P) ayant une structure polyoxyéthylène) est disposé sur un groupe extérieur du cycle de squarylium de façon à s'étendre dans la direction vers le cycle de squarylium.
PCT/JP2020/041019 2020-01-16 2020-11-02 Élément électroluminescent, composé électroluminescent et élément de conversion photoélectrique Ceased WO2021145052A1 (fr)

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