JP5469359B2 - Luminescent resin composition and white light emitting material - Google Patents

Description

  The present invention relates to a novel light-emitting resin composition that can be suitably used as a white light-emitting material and a film formed from the resin composition.

  White light emission used in devices such as display elements and lighting is a method of simultaneously emitting light having three emission colors of red, green, and blue, and two-color materials that are complementary colors. (A combination of a blue light-emitting material and an orange light-emitting material or a combination of a blue-green light-emitting material and a red light-emitting material) can be obtained by a method of simultaneously emitting light. For example, Japanese Patent Application Laid-Open No. 2002-237386 (Patent Document 1) combines a specific pyrene derivative (blue light emitting material) as a host material and a specific chalcone type compound (orange light emitting material) as a guest material. Is disclosed to form a white light-emitting layer.

  Japanese Patent Laying-Open No. 2004-200162 (Patent Document 2) discloses a white light-emitting layer containing a specific pyromethene compound or a metal complex thereof. This document describes that a white light-emitting layer can be formed by using such a pyromethene compound or a metal complex thereof as a dopant material and selecting a specific pyrrolopyrrole derivative as a host material to be combined with the dopant material. . In addition, in this document, the light emitting layer includes (i) a method of mixing and laminating the above materials, (ii) polyvinyl chloride, polycarbonate, polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, and the like. It is described that it can be formed by a method in which it is used after being dispersed in a polymer binder such as a solvent-soluble resin or a curable resin such as a phenol resin.

  However, in the white light emitting layer described in these documents, it is necessary to dope the guest material to the host material, and the light emitting layer cannot be formed easily and efficiently. Moreover, in the white light emitting layer described in these documents, it is difficult to control white color purity. Furthermore, even when dispersed in a polymer binder, the dispersibility with respect to the binder is low, and the light emission efficiency tends to decrease.

JP 2002-237386 A (claims, paragraph numbers [0024] and [0025]) JP 2004-200162 A (claims, paragraph number [0075])

  Accordingly, an object of the present invention is to provide a light-emitting resin composition suitable as a white light-emitting material, and a film (coating film or film) formed from the light-emitting resin composition.

  Another object of the present invention is to provide a light-emitting resin composition excellent in durability as a white light-emitting material, and a film formed from the light-emitting resin composition.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a compound having a diketopyrrolopyrrole skeleton and a condensed polycyclic aromatic skeleton (for example, a condensed polycyclic aromatic such as a pyrene skeleton or a fluorene skeleton). When combined with a compound having a hydrocarbon skeleton), the white color purity can be easily controlled, the whiteness can be easily increased, and further, by dispersing these compounds in a binder resin, white light emission is possible. In addition, the present inventors have found that a resin composition capable of forming a film having excellent durability can be obtained, thereby completing the present invention.

  That is, the resin composition (light emitting resin composition) of the present invention is a resin composition containing a diketopyrrolopyrrole compound, a condensed polycyclic aromatic compound, and a binder resin. In such a resin composition, the diketopyrrolopyrrole compound may be, for example, a compound represented by the following formula (1).

(In the formula, ring Z ¹ represents an aromatic hydrocarbon ring, R ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and R ² represents a halogen atom, an alkyl group or a cycloalkyl group. An aryl group, an aralkyl group, or an alkoxy group, and m represents an integer of 0 or more.)
In the above formula (1), in particular, the ring Z ¹ may be a benzene ring, m may be 0 to 3, and R ¹ is an alkyl group having 4 or more carbon atoms (for example, C _4-12 alkyl). Group).

  In the resin composition, the condensed polycyclic aromatic compound may be a condensed polycyclic aromatic hydrocarbon compound. In particular, the condensed polycyclic aromatic compound may contain at least one selected from a fluorene compound and a pyrene compound (particularly, at least a fluorene compound).

  The fluorene compound may be, for example, a compound represented by the following formula (2A).

(In the formula, R ³ represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxy group; R ⁴ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; n1 represents an integer of 0 to 4.)
Further, the pyrene compound may be, for example, a compound represented by the following formula (2B).

(In the formula, n2 represents an integer of 0 to 3, n3 represents an integer of 0 to 2, and R ³ is the same as described above.)
In the resin composition, the ratio of the condensed polycyclic aromatic compound may be, for example, about 20 to 5000 mol with respect to 1 mol of the diketopyrrolopyrrole compound.

  The resin composition of the present invention may be a resin composition that exhibits an emission color of x = 0.2 to 0.4 and y = 0.2 to 0.4 in the CIE chromaticity diagram.

  The present invention also includes a film formed of the resin composition. Such a film may be a film (thin film) having a thickness of 100 μm or less. In particular, such a film may be a light emitting film of a light emitting element. The present invention also includes a light emitting element using the resin composition as a light emitting material. Specifically, such a light emitting element may be a light emitting element in which a light emitting layer is formed of the resin composition.

  In the present invention, a resin composition suitable as a white light-emitting material can be provided by combining a compound having a diketopyrrolopyrrole skeleton and a compound having a condensed polycyclic aromatic skeleton. In particular, such a resin composition is composed of a diketopyrrolopyrrole compound known as a pigment, and is dispersed into a binder resin with high dispersibility to form a pseudo polymer. Therefore, it is excellent in durability as a white light emitting material. Moreover, in the present invention, the color purity of white can be easily controlled by combining the diketopyrrolopyrrole compound and the condensed polycyclic aromatic compound, and therefore the whiteness can be easily increased.

FIG. 1 is a fluorescence spectrum of the thin film produced in Example 1.

[Resin composition]
The resin composition of the present invention comprises a diketopyrrolopyrrole compound (a compound having a diketopyrrolopyrrole skeleton), a condensed polycyclic aromatic compound (a compound having a condensed polycyclic aromatic skeleton), and a binder resin. Including.

(Diketopyrrolopyrrole compound)
The diketopyrrolopyrrole compound may be a compound having a diketopyrrolopyrrole skeleton {specifically, a pyrrolo [3,4-c] pyrrole-1,4-dione skeleton (or structure))}. It may be a compound having a skeleton in which aromatic hydrocarbon groups are substituted at the 3 and 6 positions of [3,4-c] pyrrole-1,4-dione. Such a diketopyrrolopyrrole compound may have a substituent as long as it has the skeleton as described above. A typical diketopyrrolopyrrole compound has an aromatic hydrocarbon group at the 3- and 6-positions of a compound {or pyrrolo [3,4-c] pyrrole-1,4-dione represented by the following formula (1): A compound having a substituted skeleton}.

(In the formula, ring Z ¹ represents an aromatic hydrocarbon ring, R ¹ represents a hydrogen atom or a hydrocarbon group, R ² represents a substituent, and m represents an integer of 0 or more.)
In the above formula (1), examples of the aromatic hydrocarbon ring Z ¹ include a benzene ring and a condensed polycyclic hydrocarbon ring (a condensed 2- to 6-ring hydrocarbon ring such as a naphthalene ring and an anthracene ring). It is done. A preferred ring Z ¹ may be a benzene ring. In the formula (1), the two rings Z ¹ bonded to the 3- and 6-positions of pyrrolo [3,4-c] pyrrole-1,4-dione may be the same or different aromatic hydrocarbon rings, Usually, they may be the same.

In R ¹ of the formula (1), examples of the hydrocarbon group include a saturated aliphatic hydrocarbon group [for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, an s-butyl group). , N-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-decyl group and other C _1-16 alkyl groups), cycloalkyl groups (for example, cyclopentyl group, cyclohexyl) A C _5-10 cycloalkyl group such as a group)], an unsaturated aliphatic hydrocarbon group [for example, an alkenyl group (for example, a C _2-20 alkenyl group such as an allyl group), an alkynyl group (C ₂₋ such as an ethynyl group). ₁₀ alkynyl group), a cycloalkenyl group (e.g., _{C 5-10} cycloalkenyl groups such as cyclohexenyl group), etc.], an aromatic hydrocarbon group [for example, ants Le group (e.g., phenyl group, C _6-10 aryl groups such as naphthyl group), a ring assembly aromatic hydrocarbon group (e.g., biphenyl two drill group), etc.], aromatic aliphatic hydrocarbon group [for example, an aralkyl group (For example, C _6-10 aryl C _1-4 alkyl groups such as benzyl group and phenethyl group)] and the like. These hydrocarbon groups are further substituted with a substituent [halogen atom, alkoxy group (for example, C _1-4 alkoxy group such as methoxy group), cyano group, substituted amino group (for example, dialkylamino group), heterocyclic group. (For example, a nitrogen-containing heterocyclic group such as a carbazolyl group) and the like] may or may not be present.

Typical R ¹ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. In particular, R ¹ is a long chain alkyl group [for example, an alkyl group having 4 or more carbon atoms (for example, a C _4-16 alkyl group such as a hexyl group, an octyl group, etc., preferably from the viewpoint of solvent solubility and film-forming property, A C _4-14 alkyl group, more preferably a C _4-12 alkyl group, particularly a C _6-12 alkyl group)] or the like (hydrophobic group). In the formula (1), the two groups R ¹ bonded to the nitrogen atom of pyrrolo [3,4-c] pyrrole-1,4-dione may be the same or different groups and are usually the same. There may be.

In the formula (1), R ² is, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) or a group having an active hydrogen atom (eg, hydroxyl group, mercapto group, amino group). Etc.), acid groups (for example, carboxyl groups, sulfo groups, etc.), cyano groups, substituted amino groups [for example, dialkylamino groups (for example, diC _1-4 alkylamino groups such as dimethylamino groups)], acyl groups [ For example, an alkylcarbonyl group (for example, a C _1-4 alkylcarbonyl group such as an acetyl group), a hydrocarbon group (such as the hydrocarbon group illustrated above), a heterocyclic group (such as the heterocyclic group illustrated above), alkoxy Group (for example, C _1-10 alkoxy group such as methoxy group and ethoxy group) and the like. These groups (for example, an acyl group, a hydrocarbon group, etc.) are further substituted with a substituent (a halogen atom, a group having an active hydrogen atom, an acid group, a cyano group, a substituted amino group, an acyl group, a heterocyclic group, etc.). You may have.

Among these, typical R ² includes a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxy group. The substitution number m of R ² depends on the type of ring Z ¹ , but may be, for example, 0 to 10, preferably 0 to 6, and more preferably 0 to 4 (for example, 0 to 2). In particular, when Z ¹ is a benzene ring, m may be 0-4, preferably 0-3, more preferably 0-2, especially 0-1. Incidentally, different R ² is substituted in the ring Z ¹ may be the same or different groups, R ² is replaced by the same ring Z ¹ also, the number of m may be a plurality of case identical or different radicals . Further, the number m of substitutions of R ² in different rings Z ¹ may be the same or different.

Specific diketopyrrolopyrrole compounds (or compounds represented by the formula (1)) include, for example, 2,5-dihydro-2,5-dialkyl-3,6-diaryl-pyrrolo [3,4 c] pyrrole-1,4-dione {for example, 2,5-dihydro-2,5-di-n-hexyl-3,6-diphenyl-pyrrolo [3,4-c] pyrrole-1,4-dione, etc. Of 2,5-dihydro-2,5-diC _4-16 alkyl-3,6-diC _6-10 aryl-pyrrolo [3,4-c] pyrrole-1,4-dione, preferably 2,5 -Dihydro-2,5-diC _4-14 alkyl-3,6-diphenyl-pyrrolo [3,4-c] pyrrole-1,4-dione, more preferably 2,5-dihydro-2,5-di C _6-12 alkyl-3,6-diphenyl-pyrrolo [3,4-c] pi Roll-1,4-dione and the like}, 2,5-dihydro-2,5-dialkyl-3,6-di (haloaryl) -pyrrolo [3,4-c] pyrrole-1,4-dione {eg, 2 2,5-dihydro- such as 1,5-dihydro-2,5-di-n-hexyl-3,6-di (4-bromophenyl) -pyrrolo [3,4-c] pyrrole-1,4-dione 2,5-diC _4-16 alkyl-3,6-di (haloC _6-10 aryl) -pyrrolo [3,4-c] pyrrole-1,4-dione, preferably 2,5-dihydro-2 , 5-diC _4-14 alkyl-3,6-di (halophenyl) -pyrrolo [3,4-c] pyrrole-1,4-dione, more preferably 2,5-dihydro-2,5-diC _6-12 alkyl-3,6-di (halophenyl) -pyrrolo [3,4-c] pyrrole- 1,4-dione, etc.}.

  The diketopyrrolopyrrole compounds may be used alone or in combination of two or more.

(Condensed polycyclic aromatic compounds)
The condensed polycyclic aromatic compound may be a compound having a condensed polycyclic aromatic skeleton. Such a condensed polycyclic aromatic skeleton may be a condensed polycyclic aromatic heterocyclic skeleton. Alternatively, it may be a condensed polycyclic aromatic heterocycle [a condensed polycyclic aromatic skeleton in which at least one ring is a heterocycle (aromatic heterocycle)]. In particular, the condensed polycyclic aromatic skeleton may be a condensed polycyclic aromatic hydrocarbon skeleton. In addition, the condensed polycyclic aromatic compound may have a substituent (such as the substituent exemplified in the above R ² ) as long as it has the condensed polycyclic aromatic skeleton as described above. Good.

  Specifically, the condensed polycyclic aromatic compound may be a compound represented by the following formula (2).

(In the formula, ring Z ² represents a condensed polycyclic aromatic hydrocarbon ring or a condensed polycyclic aromatic heterocycle, R ³ represents a substituent, and n represents an integer of 0 or more.)
In the above formula (2), examples of the condensed polycyclic aromatic hydrocarbon ring Z ² include, for example, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, pyrene ring, fluoranthene ring, triphenylene ring, naphthacene ring, and perylene. Examples thereof include condensed 2 to 6 cyclic hydrocarbons such as a ring and a pentacene ring. The condensed polycyclic aromatic heterocycle Z ² includes, for example, a nitrogen-containing condensed polycyclic aromatic ring (eg, quinoline ring, carbazole ring, phenatridine ring, acridine ring, phenanthroline ring), oxygen-containing condensed poly ring. Cyclic aromatic rings (eg, xanthene rings), sulfur-containing fused polycyclic aromatic rings (eg, thianthrene rings), condensed polycyclic aromatic rings containing multiple heteroatoms (eg, phenothiazine rings, phenoxy rings) Sajin ring).

In the formula (2), examples of R ³ include the same substituents as those exemplified in the section of R ² . Typical R ³ includes a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxy group. In particular, from the viewpoint of solvent solubility and film-forming properties, long-chain alkyl groups [for example, C _4-16 such as alkyl groups having 4 or more carbon atoms (for example, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, etc.) R which is a group having a relatively large number of carbon atoms (particularly a hydrophobic group) such as an alkyl group, preferably a C _4-14 alkyl group, more preferably a C _4-12 alkyl group, particularly a C _6-12 alkyl group). ³ may be replaced with at least the ring Z ^2. R ³ may have a substituent (a halogen atom, a group having an active hydrogen atom, an acid group, a cyano group, a substituted amino group, an acyl group, a heterocyclic group, etc.) as in the case of R 2. The substitution number n of R ³ depends on the type of ring Z ² , but may be, for example, 0 to 10, preferably 1 to 8, more preferably 1 to 6, particularly about 2 to 4. In particular, when R ³ is a fluorene ring or a pyrene ring, n may be 1 to 6, preferably 1 to 4, and more preferably 2 to 4 (for example, 2). In the ring Z ² , R ³ may be the same or different when the number of n is plural.

  The condensed polycyclic aromatic compounds may be used alone or in combination of two or more.

Preferred condensed polycyclic aromatic compounds include a fluorene compound (or a compound having a fluorene skeleton, such as a compound in which the ring Z ² is a fluorene ring in the formula (2)), a pyrene compound (or a compound having a pyrene skeleton), For example, a compound in which ring Z ² is a condensed polycyclic aromatic hydrocarbon ring, such as a compound in which ring Z ² in formula (2) is a pyrene ring, is included.

  The fluorene compound may be, for example, a compound represented by the following formula (2A).

(Wherein R ⁴ represents a hydrogen atom or a hydrocarbon group, n1 represents an integer of 0 to 4, and R ³ is the same as above)
In the above formula (2A), the hydrocarbon group R ⁴ includes the same groups as described above, and typically includes an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. In particular, R ⁴ represents a long-chain alkyl group [for example, a C _4-16 alkyl group such as a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, etc.] , Preferably a C _4-14 alkyl group, more preferably a C _4-12 alkyl group, especially a C _6-12 alkyl group)], an aryl group (for example, a C _6-12 aryl group such as a phenyl group, a naphthyl group, etc.) Preferred is a C _6-10 aryl group). Two R ⁴ may be the same or different groups. In addition, R ⁴ has a substituent (a halogen atom, a group having an active hydrogen atom, an acid group, a cyano group, a substituted amino group, an acyl group, a heterocyclic group, etc.) as in the case of R ² or R ^3. You may do it.

In the formula (2A), R ³ is the same as described above, but typically, a halogen atom (eg, chlorine atom, bromine atom, etc.), a cyano group, an alkyl group (eg, methyl group, ethyl group). _Or a C _1-10 alkyl group, preferably a C _1-6 alkyl group). In the formula (2A), the substitution number n1 of R ³ is preferably 0 to 2, and particularly preferably 0 to 1. Moreover, in said Formula (2A), two n1 may be the same or different.

Specific examples of the fluorene compound (or the compound represented by the formula (2A)) include, for example, fluorene, alkylfluorene [for example, 9,9-dialkylfluorene (for example, 9,9-di-n-octylfluorene, 9,9-diC _4-16 alkyl fluorene such as 2,7-dimethyl-9,9-di n-octyl fluorene, 2,7-dibromo-9,9-di-n-octyl fluorene, preferably 9, 9-diC _4-14 alkylfluorene, more preferably 9,9-diC _6-12 alkylfluorene), mono- or dialkylfluorene (eg 2-methylfluorene, 2,3-dimethylfluorene, 2,7-dimethyl) fluorene, mono- or _{di-C 1-10} alkyl fluorene such as 2,7-diethyl-fluorene, preferably mono- or di _{C 1-} Alkyl fluorene, more preferably mono- or _{di-C 1-4} alkyl fluorene), etc.], aryl fluorene, halo fluorene [e.g., mono- or di-halo fluorene (e.g., 2-chloro-fluorene, 3-bromo fluorene, 2,3-dichloro Fluorene, 2,7-dibromofluorene, etc.)] and the like.

Aryl fluorene includes, for example, 9,9-bisaryl fluorene (for example, 9,9-bis C _6-10 aryl fluorene such as 9,9-bisphenyl fluorene), 9,9-bis (hydroxyaryl) fluorene { For example, 9,9-bis (hydroxyphenyl) fluorene [eg, 9,9-bis (4-hydroxyphenylfluorene (bisphenolfluorene), etc.], 9,9-bis (alkyl-hydroxyphenyl) fluorene [eg, 9, 9,9-bis (mono- or di-C _1-4 alkyl-hydroxyphenyl such as 9-bis (4-hydroxy-3-methylphenylfluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenylfluorene) ) Fluorene], 9,9-bis (aryl-hydroxyphenyl) fluore [For example, 9,9-bis (4-hydroxy-3-phenyl-phenyl fluorene 9,9-bis _{(C 6-10} aryl - hydroxyphenyl) fluorene] 9,9-bis (hydroxyphenyl) fluorene such as 9,9-bis (hydroxynaphthyl) fluorenes such as 9,9-bis (hydroxynaphthyl) fluorene [eg, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, etc.]; (Polyhydroxyaryl) fluorenes [eg, 9,9-bis (di or trihydroxyphenyl) fluorene such as 9,9-bis (3,4-dihydroxyphenyl) fluorene]], 9,9-bis [ Hydroxy (poly) alkoxyaryl] fluorene {eg, 9,9-bis (hydroxy (poly) alkoxy ) Phenylfluorene [e.g., 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene, 9,9-bis {4- 9,9-bis [(hydroxy (poly) C _2-4 alkoxy) phenyl] fluorene, etc.] such as [2- (2-hydroxyethoxy) ethoxy] phenyl} fluorene, 9,9-bis (alkyl-hydroxy (poly ) Alkoxy) phenylfluorene [e.g. 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethyl) Phenyl] fluorene, 9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] -3-methylphenyl} fluor Emissions such as 9,9-bis (mono- or _{di-C 1-4} alkyl - hydroxy _{(poly) C 2-4} alkoxy) phenyl] fluorene, etc.], 9,9-bis (aryl - hydroxy (poly) alkoxy) phenyl fluorene [For example, 9,9-bis (C _6-10 aryl-hydroxy (poly) C _2-4 alkoxy) phenyl such as 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene] 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes such as fluorene etc .; 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorene [eg 9,9-bis [6- (2-hydroxy] 9,9-bis (hydroxy (poly) alkoxynaphthyl) fur, such as ethoxy) -2-naphthyl] fluorene and the like] 9,9-bis (polyhydroxy (poly) alkoxyaryl) fluorenes [e.g., 9,9-bis [3,4-di (2-hydroxyethoxy) phenyl] fluorene, etc. (Di- or trihydroxy (poly) _{C2-4alkoxyphenyl} ) fluorene and the like], 9,9- such as fluorene compounds in which the hydroxy group is substituted with a mercapto group, a carboxy group, an amino group or the like corresponding to these compounds Bisarylfluorenes and the like are included.

Preferred fluorene compounds include alkyl fluorene, aryl fluorene and the like, and in particular, 9,9-dialkyl fluorenes (eg, 9,9-diC _4-16 alkyl fluorene, etc.), 9,9-bisaryl fluorenes. [For example, 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (mono or di C _1-4 alkyl-hydroxyphenyl) fluorene, 9,9-bis (C _6-10 aryl-hydroxyphenyl) fluorene 9,9-bis (C _6-10 aryl) fluorenes such as 9,9-bis (hydroxy (poly) C _2-4 alkoxyphenyl) fluorene].

  Fluorene compounds may be used alone or in combination of two or more.

  Further, the pyrene compound may be, for example, a compound represented by the following formula (2B).

(In the formula, n2 represents an integer of 0 to 3, n3 represents an integer of 0 to 2, and R ³ is the same as described above.)
In the above formula (2B), R ³ is the same as described above, but typically, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl) A C _1-16 alkyl group such as a group, a butyl group, a pentyl group, or a hexyl group, preferably a C _1-12 alkyl group, more preferably a C _2-10 alkyl group, particularly a C _3-6 alkyl group). Also good. In the formula (2B), the substitution number n2 of R ³ is preferably 0 to 2, and may be 1, in particular. Further, the substitution number n3 is preferably 0 to 1, and may be 0 in particular. In the formula (2B), two n2 and two n3 may be the same or different from each other.

Specific pyrene compounds (or the compounds represented by the formula (2B)) include pyrene and alkylpyrene [eg, di to tetraalkylpyrene (eg, 2,7-dibutylpyrene (2,7-di n- Butylpyrene, 2,7-di-t-butylpyrene, etc.), 1,3,6,8-tetramethylpyrene, 1,3,6,8-tetrapropylpyrene, 4,9-dibromo-2,7-dibutylpyrene, etc. Di to tetra C _1-16 alkylpyrene, preferably di to tetra C _1-12 alkyl pyrene, more preferably di to tetra C _2-10 alkyl pyrene, particularly di to tetra C _3-6 alkyl pyrene), etc.], Halopyrene [eg, di to tetrahalopyrene (eg, 1,6-dibromopyrene, 1,3,6,8-tetrabromopyrene, etc.)] and the like are included.

Preferred pyrene compounds include alkylpyrene, particularly di to tetraalkylpyrene (eg, di to tetra C _1-12 alkyl pyrene, preferably di to tetra C _1-10 alkyl pyrene, more preferably di to tetra C _2-8 alkylpyrene, especially di to tetra C _3-6 alkylpyrene) and the like are preferable.

  A pyrene compound may be individual or may combine 2 or more types.

  The condensed polycyclic aromatic compound is at least one selected from a fluorene compound (for example, a compound represented by the formula (2A)) and a pyrene compound (for example, a compound represented by the formula (2B)). It is preferable that a compound is contained, and particularly, at least a fluorene compound is preferably contained. A resin composition containing such a compound (such as a fluorene compound) has a high carrier transport ability. Moreover, it is suitable in light emitting materials for organic EL, etc. in terms of energy levels contributing to light emission. The ratio of such a compound (fluorene compound and / or pyrene compound) to the whole condensed polycyclic aromatic compound is, for example, 30 mol% or more, preferably 40 mol% or more, more preferably 50 mol% or more, particularly 60 It may be mol% or more.

  In particular, when a fluorene compound and another condensed polycyclic aromatic compound (for example, a pyrene compound) are combined, the ratio of the former / the latter (molar ratio) = 95/5 to 5/95, preferably 90 / It may be about 10 to 10/90 (for example, 90/10 to 20/80), more preferably about 85/15 to 40/60 (for example, 80/20 to 50/50).

  Further, the ratio of the condensed polycyclic aromatic compound (or the condensed polycyclic aromatic skeleton) depends on the kind thereof, but for example, with respect to 1 mol of the diketopyrrolopyrrole compound (or diketopyrrolopyrrole skeleton), for example 1 to 10,000 mol, preferably 20 to 5000 mol, more preferably about 30 to 3000 mol, and usually 50 to 2000 mol (for example, 60 to 1500 mol, preferably 70 to 1000 mol, more preferably). May be about 80 to 700 mol).

(Binder resin)
The binder resin is not particularly limited as long as the diketopyrrolopyrrole compound and the condensed polycyclic aromatic compound can be dispersed, and can be appropriately selected depending on the application. Examples of the binder resin include olefin resins (polyethylene, polypropylene, polymethylpentene, amorphous polyolefin, etc.), (meth) acrylic resins [for example, methacrylate homopolymers or copolymers (for example, polymethyl methacrylate). , C _1-6 alkyl methacrylate homo- or copolymer such as poly n-butyl methacrylate), methacrylate (C _1-6 alkyl methacrylate such as methyl methacrylate) and other copolymerizable monomers (eg, acrylic acid) (Meth) acrylic monomers other than methacrylates such as esters and (meth) acrylic acids; copolymers with styrene monomers; (anhydrous) unsaturated polycarboxylic acids such as (anhydrous) maleic acid) For example, methyl methacrylate-alkyl (meth) acrylate- (meth ) Acrylic acid copolymer, etc.], vinyl chloride resin (polyvinyl chloride, etc.), styrene resin (eg, polystyrene, MS resin, methyl methacrylate-styrene- (meth) acrylic acid copolymer, etc.), Polycarbonate resins (aromatic polycarbonate resins such as bisphenol A polycarbonate), polyester resins (copolymerized polyester, etc.), polyamide resins (aliphatic polyamides such as polyamide 66, polyamide MXD, etc.), polyphenylene ether resins, polyphenylene Thermoplastic resins such as sulfide resins, polysulfone resins, polyether ketone resins, and resins having a heterocyclic ring (for example, nitrogen-containing heterocyclic resins such as polyvinyl carbazole); phenol resins, furan resins, urea resins, melamine resins, Bad Examples thereof include heat or photo-curing resins such as saturated polyesters, epoxy resins, urethane resins, silicone resins, diallyl phthalate resins, and vinyl ester resins. These resins can be used alone or in combination of two or more.

  In the resin composition of the present invention, the ratio of the total amount of the diketopyrrolopyrrole compound and the condensed polycyclic aromatic compound is, for example, 1 to 300 parts by weight, preferably 3 to 200 parts by weight with respect to 100 parts by weight of the binder resin. Part, more preferably about 5 to 100 parts by weight.

  In addition, the composition (coating composition) containing a solvent may be sufficient as the resin composition of this invention. Examples of the solvent include hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene), alcohols, and the like. [For example, alkanols such as methanol, ethanol and propanol; (poly) alkylene glycols such as ethylene glycol, propylene glycol and diethylene glycol; polyols such as glycerin), ethers (eg, chain ethers such as dimethyl ether and diethyl ether; dioxane, Cyclic ethers such as tetrahydrofuran), ketones (eg, dialkyl ketones such as acetone and methyl ethyl ketone; cyclic ketones such as cyclohexanone), esters (eg, methyl acetate, ethyl acetate, etc.) , Acetate esters such as butyl acetate), glycol ethers (eg cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, etc.), glycol ethers Examples include esters (cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, etc.). These solvents may be used alone or in combination of two or more. The resin composition containing such a solvent is useful as a coating composition for forming a coating film as described later.

  The resin composition may contain additives such as a dispersant, a stabilizer, a plasticizer, a softener, a lubricant, a mold release agent, and an antistatic agent as necessary.

  The resin composition of the present invention can be prepared by mixing a diketopyrrolopyrrole compound, a condensed polycyclic compound, and a binder resin (if necessary, other components such as a solvent). it can. Mixing may be melt mixing.

[Characteristics and uses of resin composition]
Since the diketopyrrolopyrrole compound and the condensed polycyclic aromatic compound can each emit light, the resin composition of the present invention can be suitably used as a light emitting material. In particular, the combination of these compounds can cause light emission complementary to each other, and the resin composition often exhibits white light emission. Therefore, the resin composition of the present invention is suitable as a white light emitting material. Although depending on the type of substituent, the diketopyrrolopyrrole skeleton often contributes to yellow (or orange) light emission, and the condensed polycyclic aromatic skeleton often contributes to blue light emission. A white light emission is exhibited by the combination.

  The resin composition of the present invention as such a white material has x = 0.2 to 0.45 (for example, 0.25 to 0) in the CIE (International Commission on Illumination) chromaticity diagram (xy chromaticity diagram). .42, preferably 0.3-0.4, usually 0.2-0.4) and y = 0.2-0.45 (eg, 0.25-0.42, preferably 0.3-0). .4, usually 0.2 to 0.4). In the CIE chromaticity diagram, a material exhibiting such an x value and y value exhibits white light emission. In addition, light emission can be obtained as fluorescence emitted by exciting (eg, exciting by electric or light energy) the diketopyrrolopyrrole compound and the condensed polycyclic aromatic compound.

  Such a resin composition of the present invention can be used in various applications as a light emitting material (particularly a white light emitting material). In particular, the resin composition of the present invention can form a film (light-emitting film) as it is. Therefore, the present invention includes a film (coating film or coating film) formed from the resin composition. The thickness of such a film (thin film) can be appropriately selected depending on the application, but may be, for example, 1 to 200 μm, preferably 3 to 150 μm, more preferably about 5 to 100 μm, and usually 100 μm or less (for example, 1-80 μm, preferably 3-60 μm, more preferably about 5-50 μm). In the present invention, even with such a thin thickness, a light emitting film having excellent durability and sufficient light emission characteristics can be obtained. As described above, such a film (light-emitting film) may usually be a white light-emitting film.

  In addition, such a film can be obtained by, for example, using the resin composition (or the coating composition, usually the resin composition containing a solvent) by a conventional method (spin coating method, spray coating method, cast method, bar coating method, It can be formed by applying to a substrate by a roll coating method, a gravure coating method, a coating method such as a dipping method, an ink jet method or the like. The coating film may be finely processed using a lithography technique or the like.

  Such a coating film may form a light-emitting film, for example, a light-emitting film (or a light-emitting layer, particularly a white light-emitting layer) of a light-emitting element (display or the like). Note that the light-emitting element can usually be composed of a substrate (glass, plastic, etc.), a light-emitting film, electrodes (anode and cathode), an electron transport layer, a hole transport layer, an electron injection layer, a hole transport layer, and the like. Such a light-emitting element (light-emitting film) is suitable not only for display, for illumination, but also for backlight. In the light emitting element, the order of stacking is not particularly limited, but may be, for example, the order of substrate / anode / light emitting film / electron transport layer / cathode, or substrate / anode / hole transport layer / light emitting film / cathode. It may be the order. Such a sandwich-type structure (heterostructure) can efficiently cause a reaction. The thickness of each of these layers may be about 1 to 50 nm, preferably about 3 to 300 nm. Further, although depending on the application, the thickness of the entire light emitting element (such as a light emitting element for organic EL) may be, for example, about 300 nm to 5 μm, preferably about 500 nm to 3 μm. In addition, the quantum efficiency of light emission of the light emitting film (light emitting element) of the present invention is, for example, about 0.1 to 1, preferably about 0.2 to 0.95, and more preferably about 0.3 to 0.9. Also good.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
2,5-dihydro-2,5-di-n-hexyl-3,6-bis (4-bromophenyl) -pyrrolo [3,4-c] pyrrole-1,4-dione (represented by the following formula (a) Tetrahydrofuran solution (concentration 1.5 × 10 ⁻⁵ mol · dm ⁻³ ) and 2,7-di-t-butylpyrene (compound represented by the following formula (b)) containing 1.3 × 10 ⁻³ mol · dm ⁻³ ) were prepared, and polymer solutions were prepared by adding polymethyl methacrylate to each solution so that the polymethyl methacrylate concentration was 5% by weight. Then, the obtained two polymer solutions were mixed to obtain a pseudo polymer solution. The prepared pseudo polymer solution was spin-coated on a 25 mm square quartz substrate at 1000 rpm / 20 seconds. After coating, the sample was dried at 80 ° C. for 10 minutes to obtain a colorless pseudopolymer thin film sample (1.5 μm).

  The fluorescence spectrum when the obtained polymer thin film was excited at 339 nm was measured with a spectrofluorometer (manufactured by Shimadzu Corp.). The emission derived from the pyrene ring at 350 to 450 nm and the diketopyrrolopyrrole ring at 500 to 600 nm. White fluorescence with luminescence from origin was shown. The CIE chromaticity of this fluorescence was x = 0.32 and y = 0.30. FIG. 1 shows the fluorescence spectrum.

(Example 2)
2,5-dihydro-2,5-di-n-hexyl-3,6-bis (4-bromophenyl) -pyrrolo [3,4-c] pyrrole-1,4-dione (represented by the formula (a)) Compound concentration 1.5 × 10 ⁻⁵ mol · dm ⁻³ ) and 9,9-bis (4-hydroxyphenyl) fluorene (compound represented by the following formula (c) concentration 1.3 × 10 ⁻³ mol) -The tetrahydrofuran solution containing dm < ^-3 >) was prepared, and also the polymethylmethacrylate was added to each solution so that the polymethylmethacrylate density | concentration might be 5 weight%, and the polymer solution was prepared. Then, the obtained two polymer solutions were mixed to obtain a polymer solution. Then, the obtained two polymer solutions were mixed to obtain a pseudo polymer solution. The prepared pseudo polymer solution was spin-coated on a 25 mm square quartz substrate at 1000 rpm / 20 seconds. After coating, the sample was dried at 80 ° C. for 10 minutes to obtain a colorless pseudopolymer thin film sample (1.5 μm).

  Then, in the same manner as in Example 1, when the obtained polymer thin film was excited at 300 nm, white light having light emission derived from a fluorene ring from 340 nm to 450 nm and light emission derived from a pyrrolopyrrole ring from 500 nm to 600 nmn was obtained. Fluorescence was shown. The CIE chromaticity of this fluorescence was x = 0.35 and y = 0.31.

  The resin composition of the present invention can be suitably used as a light-emitting material (particularly a white light-emitting material) used in various applications, in particular, displays, lighting, light-emitting paints (for example, indicators, sensors, etc.). Such a resin composition of the present invention (or a film formed of this resin composition) specifically forms a light-emitting film (or a light-emitting layer, particularly a white light-emitting layer) of a light-emitting element (display, etc.). May be.

Claims (6)

The resin composition containing the diketopyrrolopyrrole compound represented by following formula (1), the condensed polycyclic aromatic compound containing at least 1 sort (s) selected from the fluorene compound and the pyrene compound, and binder resin.

(In the formula, ring Z ¹ represents a benzene ring, R ¹ represents a C _4-12 alkyl group, and R ² represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxy group. M represents an integer of 0 to 3.) Condensed polycyclic aromatic compound, according to claim 1 Symbol placement of the resin composition comprising at least fluorene compound. The resin composition according to claim 1 or 2 , wherein the ratio of the condensed polycyclic aromatic compound is 20 to 5000 mol with respect to 1 mol of the diketopyrrolopyrrole compound. The resin composition according to any one of claims 1 to 3 , wherein the CIE chromaticity diagram shows an emission color of x = 0.2 to 0.4 and y = 0.2 to 0.4. The film which is formed with the resin composition in any one of Claims 1-4, and whose thickness is 100 micrometers or less. The coating film according to claim 5, which is a light emitting film of a light emitting device.

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