WO2019151121A1 - Compound, composition containing same, and molded body and light-emitting device using same - Google Patents

Abstract

A compound represented by general formula (1). (In general formula (1), Ar1 and Ar2 may be the same or different, and are either a 5-membered aromatic ring, a 6-membered aromatic ring, or a fused aromatic ring in which two or more five-membered rings and/or 6-membered rings have been fused. The aromatic rings and fused aromatic ring may have a substituent group. Xa and Xb are either CR7 or a nitrogen atom, and R7 is an electron-withdrawing group. R1 and R2 may be the same or different, and are either a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R3-R6 may be the same or different, and are selected from the group consisting of: cyano groups; halogens; substituted or unsubstituted alkyl groups; substituted or unsubstituted alkoxy groups; substituted or unsubstituted alkynyl groups; substituted or unsubstituted aryl groups; and substituted or unsubstituted heteroaryl groups. In addition, at least one from R3-R6 is a cyano group.)

Description

COMPOUND, COMPOSITION CONTAINING THE SAME, MOLDED BODY USING SAME, AND LIGHT EMITTING DEVICE

The present invention relates to a compound that emits light in the near-infrared region, a composition containing the compound, a molded body using the composition, and a light emitting device including the molded body.

Compounds having luminescence in the near infrared region are used in various industrial products such as home appliance remote control, optical communication such as wireless digital communication, and various measuring devices such as sugar content sensors. Recently, it has been used for medical applications such as bioimaging probes because it has little impact on the living body. Furthermore, with the further development of the digital society, biometric authentication technologies such as vein authentication and face authentication are also being used. It is also used.

Of these, higher performance compounds are required for use in medical applications and biometric authentication technologies. For example, in the field of biometric authentication technology, with the development of mobile devices and digital home appliances, development to incorporate biometric authentication technology into these products is actively progressing, in terms of miniaturization, high reliability, shape flexibility, etc. There is a need for higher performance. However, in order to realize these, a near-infrared light emitting technology having high efficiency, high reliability, and flexibility is required.

As compounds having light emission in the near infrared region, inorganic compounds such as rare earth metals and semiconductor compounds are known. These have restrictions that a certain size and shape are required for the expression of characteristics, such as the necessity of using a uniform particle size and the need for a pn junction. On the other hand, since an organic compound has a light emitting function with a single molecule, it has high flexibility, and development aimed at application to medical use is being performed (for example, Patent Document 1). However, organic compounds generally have a low quantum yield and do not have high reliability that is assumed to be mounted on mobile devices and digital home appliances. In addition, an organic compound that efficiently absorbs light in the near-infrared region has been developed (for example, Patent Document 2), but high-efficiency and high-reliability light emission has not been confirmed.

International Publication No. 2015/056779 JP 2009-263614 A

The problem to be solved by the present invention is that a compound having light emission in the near infrared region (hereinafter, abbreviated as “near infrared light emission” as appropriate), for example, an organic compound having flexibility, is highly efficient near infrared. This is to achieve both light emission and highly reliable near-infrared light emission against oxidation by excitation light.

In order to solve the above-described problems and achieve the object, the compound according to the present invention is a compound represented by the general formula (1).

（一般式（１）において、Ａｒ^１およびＡｒ^２は、同じでも異なってもよく、５員環の芳香族環、６員環の芳香族環、または、２個以上の５員環および／または６員環が縮合した縮合芳香族環である。これらの芳香族環および縮合芳香族環は、置換基を有していてもよい。Ｘ^ａおよびＸ^ｂはＣＲ^７または窒素原子であり、Ｒ^７は電子求引性基である。Ｒ^１およびＲ^２は、同じでも異なってもよく、置換もしくは無置換のアリール基または置換もしくは無置換のヘテロアリール基である。Ｒ^３～Ｒ^６は、同じでも異なってもよく、シアノ基、ハロゲン、置換もしくは無置換のアルキル基、　置換もしくは無置換のアルコキシ基、置換もしくは無置換のアルキニル基、置換もしくは無置換のアリール基、および置換もしくは無置換のヘテロアリール基からなる群より選ばれる。且つ、Ｒ^３～Ｒ^６のうち少なくとも１つはシアノ基である。）

(In the general formula (1), Ar ¹ and Ar ² may be the same or different, and are a 5-membered aromatic ring, a 6-membered aromatic ring, or two or more 5-membered rings and / or A condensed aromatic ring in which a 6-membered ring is condensed, and these aromatic ring and condensed aromatic ring may have a substituent, and X ^a and X ^b are CR ⁷ or a nitrogen atom; ⁷ is an electron withdrawing group, and R ¹ and R ² may be the same or different and are a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ³ to R ⁶ are Cyano group, halogen, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, and substituted or unsubstituted Hetero Selected from the group consisting of aryl group. And at least one of R 3 ^~ R ⁶ is a cyano group.)

In addition, in the compound according to the present invention, the compound represented by the general formula (1) is a compound represented by the general formula (2), a compound represented by the general formula (3), A compound represented by formula (4), a compound represented by formula (5), a compound represented by formula (6), or a compound represented by formula (7), It is characterized by.

（一般式（２）～（７）において、Ｘ^ａおよびＸ^ｂはＣＲ^７または窒素原子であり、Ｒ^７は電子求引性基である。Ｘ^１およびＸ^２は、同じでも異なってもよく、硫黄原子、酸素原子、窒素原子またはリン原子である。Ｘ^３およびＸ^４は、同じでも異なってもよく、窒素原子またはリン原子である。Ｒ^１０１およびＲ^１０２は、同じでも異なってもよく、置換もしくは無置換のアリール基または置換もしくは無置換のヘテロアリール基である。Ｒ^１０３～Ｒ^１０６は、同じでも異なってもよく、シアノ基、ハロゲン、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアルキニル基、置換もしくは無置換のアリール基および置換もしくは無置換のヘテロアリール基からなる群より選ばれる。且つ、Ｒ^１０３～Ｒ^１０６のうち少なくとも１つはシアノ基である。Ｒ^１０７～Ｒ^１１８は、同じでも異なっていてもよく、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換の複素環基、置換もしくは無置換のアルケニル基、置換もしくは無置換のシクロアルケニル基、置換もしくは無置換のアルキニル基、水酸基、チオール基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアルキルチオ基、置換もしくは無置換のアリールエーテル基、置換もしくは無置換のアリールチオエーテル基、置換もしくは無置換のアリール基、置換もしくは無置換のヘテロアリール基、ハロゲン、シアノ基、アルデヒド基、置換もしくは無置換のカルボニル基、カルボキシル基、置換もしくは無置換のオキシカルボニル基、置換もしくは無置換のカルバモイル基、置換もしくは無置換のエステル基、置換もしくは無置換のスルホニル基、置換もしくは無置換のアミド基、置換もしくは無置換のアミノ基、ニトロ基、置換もしくは無置換のシリル基、置換もしくは無置換のシロキサニル基、置換もしくは無置換のボリル基、置換もしくは無置換のホスフィンオキシド基および隣接置換基との間に形成される環構造からなる群より選ばれる。）

(In the general formulas (2) to (7), X ^a and X ^b are CR ⁷ or a nitrogen atom, and R ⁷ is an electron withdrawing group. X ¹ and X ² may be the same or different. A sulfur atom, an oxygen atom, a nitrogen atom or a phosphorus atom, X ³ and X ⁴ may be the same or different, and a nitrogen atom or a phosphorus atom, and R ¹⁰¹ and R ¹⁰² may be the same or different. A substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ¹⁰³ to R ¹⁰⁶ may be the same or different, and may be a cyano group, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group; It is selected from the group consisting of a substituted alkoxy group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group. At least one of R ¹⁰³ to R ¹⁰⁶ is a cyano group, and R ¹⁰⁷ to R ¹¹⁸ may be the same or different, and may be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclohexane. An alkyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted alkynyl group, a hydroxyl group, a thiol group, a substituted or unsubstituted alkoxy group, Substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl ether group, substituted or unsubstituted aryl thioether group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, halogen, cyano group, aldehyde group , Substituted or unsubstituted carbonyl group, carboxyl group, substituted Or an unsubstituted oxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted sulfonyl group, a substituted or unsubstituted amide group, a substituted or unsubstituted amino group, a nitro A ring structure formed between a group, a substituted or unsubstituted silyl group, a substituted or unsubstituted siloxanyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted phosphine oxide group and an adjacent substituent Selected.)

Further, in the compound according to the present invention, in the above invention, the compound represented by the general formula (1) is a compound represented by the general formula (8), a compound represented by the general formula (9), It is either a compound represented by Formula (10) or a compound represented by General Formula (11).

（一般式（８）～（１１）において、Ｘ^ａおよびＸ^ｂはＣＲ^７または窒素原子であり、Ｒ^７は電子求引性基である。Ｘ^５およびＸ^６は、同じでも異なってもよく、硫黄原子、酸素原子、窒素原子またはリン原子である。Ｘ^７～Ｘ^１０は、同じでも異なってもよく、窒素原子またはリン原子である。Ｒ^２０１およびＲ^２０２は、同じでも異なってもよく、置換もしくは無置換のアリール基または置換もしくは無置換のヘテロアリール基である。Ｒ^２０３～Ｒ^２０６は、同じでも異なってもよく、シアノ基、ハロゲン、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアルキニル基、置換もしくは無置換のアリール基および置換もしくは無置換のヘテロアリール基からなる群より選ばれる。且つ、Ｒ^２０３～Ｒ^２０６のうち少なくとも１つはシアノ基である。Ｒ^２０７～Ｒ^２１６は、同じでも異なっていてもよく、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換の複素環基、置換もしくは無置換のアルケニル基、置換もしくは無置換のシクロアルケニル基、置換もしくは無置換のアルキニル基、水酸基、チオール基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアルキルチオ基、置換もしくは無置換のアリールエーテル基、置換もしくは無置換のアリールチオエーテル基、置換もしくは無置換のアリール基、置換もしくは無置換のヘテロアリール基、ハロゲン、シアノ基、アルデヒド基、置換もしくは無置換のカルボニル基、カルボキシル基、置換もしくは無置換のオキシカルボニル基、置換もしくは無置換のカルバモイル基、置換もしくは無置換のエステル基、置換もしくは無置換のスルホニル基、置換もしくは無置換のアミド基、置換もしくは無置換のアミノ基、ニトロ基、置換もしくは無置換のシリル基、置換もしくは無置換のシロキサニル基、置換もしくは無置換のボリル基、置換もしくは無置換のホスフィンオキシド基、および隣接置換基との間に形成される環構造からなる群より選ばれる。ｎ１およびｎ２は、同じでも異なってもよく、０～３の整数である。ｎ１およびｎ２が２以上である場合、各Ｒ^２０７および各Ｒ^２０８は、同じでも異なってもよい。）

(In the general formulas (8) to (11), X ^a and X ^b are CR ⁷ or a nitrogen atom, and R ⁷ is an electron withdrawing group. X ⁵ and X ⁶ may be the same or different. A sulfur atom, an oxygen atom, a nitrogen atom or a phosphorus atom, X ⁷ to X ¹⁰ may be the same or different, and a nitrogen atom or a phosphorus atom, and R ²⁰¹ and R ²⁰² may be the same or different. A substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ²⁰³ to R ^{206, which} may be the same or different, are a cyano group, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group; Selected from the group consisting of a substituted alkoxy group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group ^{And, .R} 207 ^{~ R 216} at least one of them is a cyano group of R 203 ^{~ R 206} may be the same or different, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl An alkyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted alkynyl group, a hydroxyl group, a thiol group, a substituted or unsubstituted alkoxy group, Substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl ether group, substituted or unsubstituted aryl thioether group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, halogen, cyano group, aldehyde group , Substituted or unsubstituted carbonyl group, carboxyl group, substituted Or unsubstituted oxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted ester group, substituted or unsubstituted sulfonyl group, substituted or unsubstituted amide group, substituted or unsubstituted amino group, nitro group , A substituted or unsubstituted silyl group, a substituted or unsubstituted siloxanyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted phosphine oxide group, and a ring structure formed between adjacent substituents N1 and n2 may be the same or different and each is an integer of 0 to 3. When n1 and n2 are 2 or more, each R ²⁰⁷ and each R ²⁰⁸ may be the same or different. )

In the compound according to the present invention, in the above-described invention, in the general formula (11), at least one of R ²⁰⁹ to R ²¹⁶ is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group. Or a ring structure formed between adjacent substituents.

Further, in the compound according to the present invention, in the above invention, the compound represented by the general formula (1) is a compound represented by the general formula (12), a compound represented by the general formula (13), A compound represented by formula (14), a compound represented by formula (15), a compound represented by formula (16), or a compound represented by formula (17), It is characterized by.

（一般式（１２）～（１７）において、Ｒ^３０１～Ｒ^３０４は、同じでも異なってもよく、シアノ基、ハロゲン、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアルキニル基、置換もしくは無置換のアリール基および置換もしくは無置換のヘテロアリール基からなる群より選ばれる。且つ、Ｒ^３０１～Ｒ^３０４のうち少なくとも１つはシアノ基である。Ｒ^３０５～Ｒ^３１６は、同じでも異なっていてもよく、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換の複素環基、置換もしくは無置換のアルケニル基、置換もしくは無置換のシクロアルケニル基、置換もしくは無置換のアルキニル基、水酸基、チオール基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアルキルチオ基、置換もしくは無置換のアリールエーテル基、置換もしくは無置換のアリールチオエーテル基、置換もしくは無置換のアリール基、置換もしくは無置換のヘテロアリール基、ハロゲン、シアノ基、アルデヒド基、置換もしくは無置換のカルボニル基、カルボキシル基、置換もしくは無置換のオキシカルボニル基、置換もしくは無置換のカルバモイル基、置換もしくは無置換のエステル基、置換もしくは無置換のスルホニル基、置換もしくは無置換のアミド基、置換もしくは無置換のアミノ基、ニトロ基、置換もしくは無置換のシリル基、置換もしくは無置換のシロキサニル基、置換もしくは無置換のボリル基、置換もしくは無置換のホスフィンオキシド基、および隣接置換基との間に形成される環構造からなる群より選ばれる。ｎ３～ｎ６は、同じでも異なってもよく、０～３の整数である。ｎ３～ｎ６が２以上である場合、各Ｒ^３０５、各Ｒ^３０６、各Ｒ^３０７および各Ｒ^３０８は、同じでも異なってもよい。）

(In the general formulas (12) to (17), R ³⁰¹ to R ³⁰⁴ may be the same or different, and are a cyano group, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. Selected from the group consisting of a substituted alkynyl group, a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group, and at least one of R ³⁰¹ to R ³⁰⁴ is a cyano group, R ³⁰⁵ to R ³¹⁶ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Unsubstituted cycloalkenyl group, substituted or unsubstituted alkynyl group, hydroxyl group, thiol group, substituted or Substituted alkoxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl ether group, substituted or unsubstituted aryl thioether group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, halogen, A cyano group, an aldehyde group, a substituted or unsubstituted carbonyl group, a carboxyl group, a substituted or unsubstituted oxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted sulfonyl group, Substituted or unsubstituted amide group, substituted or unsubstituted amino group, nitro group, substituted or unsubstituted silyl group, substituted or unsubstituted siloxanyl group, substituted or unsubstituted boryl group, substituted or unsubstituted phosphine oxide Groups, and adjacent substituents .N3 ~ selected from the group consisting of ring structure formed n6 may be the same or different, when an integer of 0 ~ 3 .n3 ~ n6 is 2 or more, each ^{R 305} and each ^{R 306} , Each R ³⁰⁷ and each R ³⁰⁸ may be the same or different.)

In the compound according to the present invention, in the above general formula (17), at least one of R ³⁰⁹ to R ³¹⁶ is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group. Or a ring structure formed between adjacent substituents.

The compound according to the present invention is characterized in that, in the above-mentioned invention, in the general formula (1), R ³ to R ⁶ are all cyano groups.

The compound according to the present invention is characterized in that, in the above invention, the compound represented by the general formula (1) has a maximum light emission in a wavelength range of 700 nm or more.

Further, a composition according to the present invention is characterized by including the compound according to any one of the above inventions and a bainter resin.

The molded body according to the present invention is a molded body molded using the composition described in the above invention.

Moreover, the light-emitting device according to the present invention is a light-emitting device including a light source and a near-infrared light conversion unit, wherein the near-infrared light conversion unit includes the molded body described in the above invention. To do.

According to the present invention, there is an effect that it is possible to provide a compound that emits light in the near infrared region while having high luminous efficiency and excellent reliability. Moreover, there exists an effect that the composition containing the said compound, the molded object using the same, and a light-emitting device can be provided.

FIG. 1 is a schematic cross-sectional view showing a configuration of a first example of a light emitting device according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing the configuration of the second example of the light emitting device according to the embodiment of the invention. FIG. 3 is a schematic cross-sectional view showing the configuration of the third example of the light emitting device according to the embodiment of the invention. FIG. 4 is a schematic cross-sectional view showing the configuration of the fourth example of the light emitting device according to the embodiment of the invention. FIG. 5 is a schematic cross-sectional view showing the configuration of the fifth example of the light-emitting device according to the embodiment of the present invention.

Hereinafter, a compound according to an embodiment of the present invention, a composition containing the compound, a molded body using the same, and a light emitting device will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with various modifications according to the purpose and application.

<Compound represented by the general formula (1)>
The compound according to the embodiment of the present invention is a compound represented by the following general formula (1).

In the general formula (1), Ar ¹ and Ar ² may be the same or different, and are a 5-membered aromatic ring, a 6-membered aromatic ring, or two or more 5-membered rings and / or 6 It is a condensed aromatic ring in which member rings are condensed. These aromatic rings and condensed aromatic rings may have a substituent. X ^a and X ^b are CR ⁷ or a nitrogen atom, and R ⁷ is an electron withdrawing group. R ¹ and R ² may be the same or different and each represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ³ to R ⁶ may be the same or different, and are a cyano group, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group And a group consisting of a substituted or unsubstituted heteroaryl group. At least one of R ³ to R ⁶ is a cyano group.

In all the above groups, hydrogen may be deuterium. The same applies to the compound described below or a partial structure thereof. In the following description, for example, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms includes 6 to 40 carbon atoms including the number of carbon atoms contained in the substituent group substituted on the aryl group. An aryl group. The same applies to other substituents that define the number of carbon atoms.

Moreover, in all the above groups, the substituents in the case of substitution include alkyl groups, cycloalkyl groups, heterocyclic groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, hydroxyl groups, thiol groups, alkoxy groups, alkylthio groups. , Aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl Group and a phosphine oxide group are preferable, and specific substituents that are preferable in the description of each substituent are preferable. Moreover, these substituents may be further substituted with the above-mentioned substituents.

In the case of “substituted or unsubstituted”, “unsubstituted” means that a hydrogen atom or a deuterium atom is substituted. In the compound described below or a partial structure thereof, the case of “substituted or unsubstituted” is the same as described above.

Among all the above groups, the alkyl group is, for example, a saturated aliphatic hydrocarbon such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, etc. Represents a group, which may or may not have a substituent. There are no particular limitations on the additional substituent when it is substituted, and examples thereof include an alkyl group, a halogen, an aryl group, a heteroaryl group, and the like, and this point is common to the following description. Further, the number of carbon atoms of the alkyl group is not particularly limited, but is preferably in the range of 1 to 20 and more preferably 1 to 8 from the viewpoint of availability and cost.

The cycloalkyl group refers to, for example, a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, which may or may not have a substituent. . Although carbon number of an alkyl group part is not specifically limited, Preferably it is the range of 3-20.

The heterocyclic group refers to, for example, an aliphatic ring having an atom other than carbon, such as a pyran ring, piperidine ring, or cyclic amide, in the ring, which may or may not have a substituent. Good. Although carbon number of a heterocyclic group is not specifically limited, Preferably it is the range of 2-20.

An alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, which may or may not have a substituent. . Although carbon number of an alkenyl group is not specifically limited, Preferably it is the range of 2-20.

The cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, a cyclohexenyl group, and the like, which may have a substituent. It may not have.

The alkynyl group refers to, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, which may or may not have a substituent. Although carbon number of an alkynyl group is not specifically limited, Preferably it is the range of 2-20.

An alkoxy group refers to a functional group to which an aliphatic hydrocarbon group is bonded through an ether bond such as a methoxy group, an ethoxy group, or a propoxy group, and the aliphatic hydrocarbon group has a substituent. May not be included. Although carbon number of an alkoxy group is not specifically limited, Preferably it is the range of 1-20.

The alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom. The hydrocarbon group of the alkylthio group may or may not have a substituent. Although carbon number of an alkylthio group is not specifically limited, Preferably it is the range of 1-20.

An aryl ether group refers to a functional group to which an aromatic hydrocarbon group is bonded via an ether bond, such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. Also good. Although carbon number of an aryl ether group is not specifically limited, Preferably, it is the range of 6-40.

The aryl thioether group is a group in which an oxygen atom of an ether bond of an aryl ether group is substituted with a sulfur atom. The aromatic hydrocarbon group in the aryl thioether group may or may not have a substituent. The number of carbon atoms of the arylthioether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.

The aryl group is, for example, phenyl group, biphenyl group, terphenyl group, naphthyl group, fluorenyl group, benzofluorenyl group, dibenzofluorenyl group, phenanthryl group, anthracenyl group, benzophenanthryl group, benzoanthracene group. An aromatic hydrocarbon group such as a nyl group, a chrycenyl group, a pyrenyl group, a fluoranthenyl group, a triphenylenyl group, a benzofluoranthenyl group, a dibenzoanthracenyl group, a perylenyl group, or a helicenyl group. Among these, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, a fluoranthenyl group, and a triphenylenyl group are preferable. The aryl group may or may not have a substituent. Although carbon number of an aryl group is not specifically limited, Preferably it is 6-40, More preferably, it is the range of 6-30.

When each substituent is further substituted with an aryl group, the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, or an anthracenyl group. A phenyl group and a naphthyl group are more preferable. Particularly preferred is a phenyl group.

Heteroaryl group is, for example, pyridyl group, furanyl group, thienyl group, quinolinyl group, isoquinolinyl group, pyrazinyl group, pyrimidyl group, pyridazinyl group, triazinyl group, naphthyridinyl group, cinnolinyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, Benzofuranyl group, benzothienyl group, indolyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, benzocarbazolyl group, carbolinyl group, indolocarbazolyl group, benzofurocarbazolyl group, benzothienocarbazolyl Group, dihydroindenocarbazolyl group, benzoquinolinyl group, acridinyl group, dibenzoacridinyl group, benzimidazolyl group, imidazopyridyl group, benzoxazolyl group, benzothiazolyl group, phenanthrolinyl group, etc. Shows a cyclic aromatic group having atoms other than carbon in one or in multiple rings. However, the naphthyridinyl group is any of 1,5-naphthyridinyl group, 1,6-naphthyridinyl group, 1,7-naphthyridinyl group, 1,8-naphthyridinyl group, 2,6-naphthyridinyl group, and 2,7-naphthyridinyl group. Indicate. The heteroaryl group may or may not have a substituent. Although carbon number of a heteroaryl group is not specifically limited, Preferably it is 2-40, More preferably, it is the range of 2-30.

When each substituent is further substituted with a heteroaryl group, the heteroaryl group includes pyridyl, furanyl, thienyl, quinolinyl, pyrimidyl, triazinyl, benzofuranyl, benzothienyl, indolyl, dibenzo A furanyl group, a dibenzothienyl group, a carbazolyl group, a benzimidazolyl group, an imidazopyridyl group, a benzoxazolyl group, a benzothiazolyl group, and a phenanthrolinyl group are preferable, and a pyridyl group, a furanyl group, a thienyl group, and a quinolinyl group are more preferable. Particularly preferred is a pyridyl group.

Halogen refers to an atom selected from fluorine, chlorine, bromine and iodine. The carbonyl group, carboxyl group, oxycarbonyl group, and carbamoyl group may or may not have a substituent. Here, examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group, and these substituents may be further substituted.

The ester group refers to a functional group having a substituent bonded thereto through an ester bond such as an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group, and this substituent may be further substituted. Although carbon number of an ester group is not specifically limited, Preferably it is the range of 1-20. More specifically, examples of the ester group include a methyl ester group, an ethyl ester group, a propyl ester group, a butyl ester group, an isopropyl ester group, a hexyl ester group, and a phenyl ester group.

The amide group refers to a functional group in which a substituent such as an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group is bonded via an amide bond, and this substituent may be further substituted. Although carbon number of an amide group is not specifically limited, Preferably it is the range of 1-20. More specifically, examples of the amide group include a methylamide group, an ethylamide group, a propylamide group, a butylamide group, an isopropylamide group, a hexylamide group, and a phenylamide group.

An amino group is a substituted or unsubstituted amino group. The amino group may or may not have a substituent. Examples of the substituent in the case of substitution include an aryl group, a heteroaryl group, a linear alkyl group, and a branched alkyl group. As the aryl group and heteroaryl group, a phenyl group, a naphthyl group, a pyridyl group, and a quinolinyl group are preferable. These substituents may be further substituted. Although carbon number of an amino group is not specifically limited, Preferably it is 2-50, More preferably, it is 6-40, Most preferably, it is the range of 6-30.

Examples of silyl groups include trimethylsilyl groups, triethylsilyl groups, tert-butyldimethylsilyl groups, propyldimethylsilyl groups, vinyldimethylsilyl groups, and other alkylsilyl groups, phenyldimethylsilyl groups, tert-butyldiphenylsilyl groups, An arylsilyl group such as a phenylsilyl group or a trinaphthylsilyl group is shown. Substituents on silicon may be further substituted. Although carbon number of a silyl group is not specifically limited, Preferably it is the range of 1-30.

The siloxanyl group refers to a silicon compound group via an ether bond such as a trimethylsiloxanyl group. Substituents on silicon may be further substituted. The boryl group is a substituted or unsubstituted boryl group. The boryl group may or may not have a substituent. Examples of the substituent in the case of substitution include an aryl group, a heteroaryl group, a linear alkyl group, a branched alkyl group, and an aryl ether group. , An alkoxy group, and a hydroxyl group. Of these, an aryl group and an aryl ether group are preferable. The phosphine oxide group is a group represented by —P (═O) R ⁸ R ⁹ . R ⁸ and R ⁹ are selected from the above substituents in the same manner as R ¹ to R ^{6 in} the general formula (1).

Acyl group refers to a functional group in which substituents such as an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group are bonded via a carbonyl bond, and this substituent may be further substituted. Although carbon number of an acyl group is not specifically limited, Preferably it is the range of 1-20. More specifically, examples of the acyl group include an acetyl group, a propionyl group, a benzoyl group, and an acrylyl group.

The sulfonyl group refers to a functional group in which a substituent such as an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group is bonded via a —S (═O) ₂ — bond. May be substituted.

The arylene group refers to a divalent or higher valent group derived from an aromatic hydrocarbon group such as benzene, naphthalene, biphenyl, fluorene, phenanthrene, etc., which may or may not have a substituent. . A divalent or trivalent arylene group is preferable. Specifically as an arylene group, a phenylene group, a biphenylene group, a naphthylene group etc. are mentioned as an arylene group.

The heteroarylene group is a divalent or higher valent group derived from an aromatic group having one or more atoms other than carbon in the ring, such as pyridine, quinoline, pyrimidine, pyrazine, triazine, quinoxaline, quinazoline, dibenzofuran, dibenzothiophene. This may or may not have a substituent. A divalent or trivalent heteroarylene group is preferable. The number of carbon atoms in the heteroarylene group is not particularly limited, but is preferably in the range of 2-30. Specific examples of the heteroarylene group include 2,6-pyridylene group, 2,5-pyridylene group, 2,4-pyridylene group, 3,5-pyridylene group, 3,6-pyridylene group, 2,4, 6-pyridylene group, 2,4-pyrimidinylene group, 2,5-pyrimidinylene group, 4,6-pyrimidinylene group, 2,4,6-pyrimidinylene group, 2,4,6-triazinylene group, 4,6-dibenzofurani Examples include a len group, a 2,6-dibenzofuranylene group, a 2,8-dibenzofuranylene group, and a 3,7-dibenzofuranylene group.

In the compound represented by the general formula (1), Ar ¹ is a X ^a and boron atoms, is bonded to the pyrrolo-pyrrole skeleton. Ar ² is bonded to the pyrrolopyrrole skeleton through ^Xb and a boron atom. Therefore, since the compound represented by the general formula (1) is a strong and highly planar skeleton, it exhibits a high fluorescence quantum yield. In addition, since the intramolecular conjugation of the compound represented by the general formula (1) can be expanded using such a skeleton, the compound represented by the general formula (1) has a maximum emission wavelength. It becomes 700 nm or more and shows near-infrared emission characteristics.

In addition, in the compound represented by the general formula (1), the maximum emission wavelength can be further increased. Therefore, Ar ¹ and Ar ² are condensed by condensing two or more 5-membered rings and / or 6-membered rings. An aromatic ring is preferred. Specifically, as such a condensed aromatic ring, a condensed aromatic ring in which two or more five-membered rings are condensed, a condensed aromatic ring in which two or more six-membered rings are condensed, and one or more five-membered rings Examples thereof include a condensed aromatic ring in which a ring and one or more 6-membered rings are condensed. From the viewpoint of ease of synthesis and availability of raw materials, the condensed aromatic ring is more preferably a structure in which 2 to 3 5-membered or 6-membered rings are condensed. As such a condensed aromatic ring having a suitable structure, specifically, a condensed aromatic ring in which two 5-membered rings are condensed, a condensed aromatic ring in which two six-membered rings are condensed, one 5 A condensed aromatic ring in which a member ring and one 6-membered ring are condensed, a condensed aromatic ring in which three 5-membered rings are condensed, a condensed aromatic ring in which three 6-membered rings are condensed, one 5 Examples thereof include a condensed aromatic ring in which a member ring and two 6-membered rings are condensed, and a condensed aromatic ring in which two 5-membered rings and one 6-membered ring are condensed. Further, from the viewpoint of ease of synthesis and availability of raw materials, a structure in which two 5-membered rings or 6-membered rings are condensed is more preferable. As such a condensed aromatic ring having a more preferable structure, specifically, a condensed aromatic ring in which two 5-membered rings are condensed, a condensed aromatic ring in which two six-membered rings are condensed, A condensed aromatic ring obtained by condensing a 5-membered ring and one 6-membered ring is exemplified. Among them, the condensed aromatic ring includes a condensed aromatic ring in which two 6-membered rings are condensed, a condensed aromatic ring in which one 5-membered ring and one 6-membered ring are condensed, and one 5 A condensed aromatic ring in which a member ring and two 6-membered rings are condensed, or a condensed aromatic ring in which two 5-membered rings and one 6-membered ring are condensed is particularly preferable.

Specific examples of the aromatic ring structure include ring structures such as a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, and a triazine ring. However, the aromatic ring structure is not particularly limited as long as it is a skeleton having aromaticity. In addition, the above aromatic ring may or may not have a substituent.

Specific condensed aromatic ring structures include isoindole ring, indole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, indazole ring, purine ring, thienopyrrole ring, pyrrolothiazole ring, pyrrolooxazole ring, quinoline. Examples of the ring structure include a ring, an isoquinoline ring, a quinoxaline ring, an imidazopyridine ring, a perimidine ring, and a phenanthridine ring. However, the condensed aromatic ring structure is not particularly limited as long as it is a skeleton having aromaticity. In addition, the above condensed aromatic ring may or may not have a substituent.

An electron-withdrawing group is also called an electron-accepting group, and is an atomic group that attracts electrons from a substituted atomic group by an induced effect or a resonance effect in organic electron theory. Examples of the electron withdrawing group include those having a positive value as the Hammett's rule substituent constant (σp (para)). The Hammett's rule substituent constant (σp (para)) can be cited from the Chemical Handbook, Basic Revision 5 (II-380). In addition, although a phenyl group also has the example which takes the said positive value, a phenyl group is not contained in the electron withdrawing group in this invention.

Examples of electron withdrawing groups include, for example, -F (σp: +0.06), -Cl (σp: +0.23), -Br (σp: +0.23), -I (σp: +0.18) , -CO ₂ R ¹⁰ (σp: when R ¹⁰ is an ethyl group +0.45), -CONH ₂ (σp: +0.38), -COR ¹⁰ (σp: when R ¹⁰ is a methyl group +0.49), —CF ₃ (σp: +0.50), —CN (σp: +0.66), —SO ₂ R ¹⁰ (σp: +0.69 when R ¹⁰ is a methyl group), —NO ₂ (σp: +0.81) ) And the like. R ¹⁰ represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, a substituted or unsubstituted carbon number, It represents an alkyl group having 1 to 30 or a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms. Specific examples of these groups include the same examples as described above.

Preferred electron withdrawing groups include fluorine, fluorine-containing aryl groups, fluorine-containing heteroaryl groups, fluorine-containing alkyl groups, substituted or unsubstituted acyl groups, substituted or unsubstituted ester groups, substituted or unsubstituted amide groups. A substituted or unsubstituted sulfonyl group or a cyano group. This is because these groups are difficult to decompose chemically. In the present invention, the fluorine-containing aryl group is an aryl group containing a fluorine atom. The fluorine-containing heteroaryl group is a heteroaryl group containing fluorine. The fluorine-containing alkyl group is an alkyl group containing fluorine.

More preferable electron withdrawing groups include a fluorine-containing alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group, or a cyano group. This is because these groups prevent concentration quenching and lead to the effect of improving the emission quantum yield. Among these, a cyano group is particularly preferable as the electron withdrawing group.

Preferred examples of R ¹⁰ contained in the electron withdrawing group include a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms and a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. And a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms. More preferred substituents (R ¹⁰ ) include substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms from the viewpoint of solubility. Specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. From the viewpoint of ease of synthesis and availability of raw materials, an ethyl group is preferably used as the alkyl group.

In the compound represented by the general formula (1), when X ^a and X ^b are nitrogen atoms, the nitrogen atom forms a multiple bond with an adjacent atom, and the nitrogen atom is a high electron. Since it has a negative degree, the multiple bond has an electron withdrawing property. In this case, ^Xa and ^Xb have electron withdrawing properties.

In the compound represented by the general formula (1), since X ^a and X ^b have electron withdrawing properties, the electron density in the molecule can be lowered. Thereby, the stability with respect to oxygen of the compound represented by the general formula (1) is improved, and as a result, the reliability of the compound represented by the general formula (1) can be improved.

The compound represented by the general formula (1) can prevent concentration quenching due to aggregation because R ¹ and R ² are a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. As a result, the compound represented by the general formula (1) can obtain a high fluorescence quantum yield. From the viewpoint of obtaining a higher fluorescence quantum yield, R ¹ and R ² are preferably a substituted or unsubstituted aryl group. Among the aryl groups, a phenyl group and a naphthyl group are particularly preferable examples.

From the viewpoints of controlling the fluorescence wavelength and absorption wavelength, increasing dispersibility, and improving luminous efficiency, R ¹ and R ² are substituted aryl groups or substituted heteroaryl groups, and the substitution thereof The group is preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group. Among them, the substituent is more preferably an alkyl group having 1 to 20 carbon atoms or an alkoxy group. From the viewpoint of compatibility with the solvent, the substituent is particularly preferably a branched alkyl group or alkoxy group.

In the compound represented by the general formula (1), since at least one of R ³ to R ⁶ is a cyano group, the electron density in the molecule can be lowered, so that the reliability can be improved. From the viewpoint of further improving the reliability of the compound represented by the general formula (1), it is preferable that all of R ³ to R ⁶ are cyano groups.

In addition, the compound represented by the general formula (1) includes a compound represented by the following general formula (2), a compound represented by the general formula (3), a compound represented by the general formula (4), It is preferably any one of a compound represented by the formula (5), a compound represented by the general formula (6), or a compound represented by the general formula (7).

In the general formulas (2) to (7), X ^a and X ^b are CR ⁷ or a nitrogen atom, and R ⁷ is an electron withdrawing group. X ¹ and X ² may be the same or different and are a sulfur atom, an oxygen atom, a nitrogen atom or a phosphorus atom. X ³ and X ⁴ may be the same or different and are a nitrogen atom or a phosphorus atom. R ¹⁰¹ and R ¹⁰² may be the same or different and are a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ¹⁰³ to R ¹⁰⁶ may be the same or different, and are a cyano group, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group And selected from the group consisting of substituted or unsubstituted heteroaryl groups. At least one of R ¹⁰³ to R ¹⁰⁶ is a cyano group. R ¹⁰⁷ to R ¹¹⁸ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl Group, substituted or unsubstituted cycloalkenyl group, substituted or unsubstituted alkynyl group, hydroxyl group, thiol group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl ether group, substituted Or an unsubstituted arylthioether group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a halogen, a cyano group, an aldehyde group, a substituted or unsubstituted carbonyl group, a carboxyl group, a substituted or unsubstituted oxy Carbonyl group, substituted or unsubstituted carbamo Group, substituted or unsubstituted ester group, substituted or unsubstituted sulfonyl group, substituted or unsubstituted amide group, substituted or unsubstituted amino group, nitro group, substituted or unsubstituted silyl group, substituted or unsubstituted Selected from the group consisting of a ring structure formed between a siloxanyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted phosphine oxide group and an adjacent substituent.

The ring structure formed between adjacent substituents means R ¹⁰⁷ and R ¹⁰⁸ , R ¹⁰⁹ and R ¹¹⁰ in the above general formula (2), or R ¹¹¹ to R ^{114 in the} general formulas (3) to (7). And any two substituents selected from R ¹¹⁵ to R ¹¹⁸ (for example, R ¹¹¹ and R ¹¹² ) are bonded to each other to form a conjugated or non-conjugated condensed ring. These condensed rings may contain at least one nitrogen atom, oxygen atom or sulfur atom in the ring structure, or may be further condensed with another ring.

As the compound represented by the general formula (1), among the compounds of the above general formulas (2) to (7), a compound represented by the general formula (2) or a compound represented by the general formula (3) Is more preferable, and the compound represented by the general formula (3) is particularly preferable.

The compound represented by the general formula (1) is a compound represented by the following general formula (8), a compound represented by the general formula (9), a compound represented by the general formula (10), or More preferably, it is one of the compounds represented by the general formula (11).

In the general formulas (8) to (11), X ^a and X ^b are CR ⁷ or a nitrogen atom, and R ⁷ is an electron withdrawing group. X ⁵ and X ⁶ may be the same or different and are a sulfur atom, an oxygen atom, a nitrogen atom or a phosphorus atom. X ⁷ to X ¹⁰ may be the same or different and are a nitrogen atom or a phosphorus atom. R ²⁰¹ and R ²⁰² may be the same or different and each represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ²⁰³ to R ²⁰⁶ may be the same or different and are each a cyano group, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group And selected from the group consisting of substituted or unsubstituted heteroaryl groups. At least one of R ²⁰³ to R ²⁰⁶ is a cyano group. R ²⁰⁷ to R ²¹⁶ may be the same or different and are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl Group, substituted or unsubstituted cycloalkenyl group, substituted or unsubstituted alkynyl group, hydroxyl group, thiol group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl ether group, substituted Or an unsubstituted arylthioether group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a halogen, a cyano group, an aldehyde group, a substituted or unsubstituted carbonyl group, a carboxyl group, a substituted or unsubstituted oxy Carbonyl group, substituted or unsubstituted carbamo Group, substituted or unsubstituted ester group, substituted or unsubstituted sulfonyl group, substituted or unsubstituted amide group, substituted or unsubstituted amino group, nitro group, substituted or unsubstituted silyl group, substituted or unsubstituted Selected from the group consisting of a siloxanyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted phosphine oxide group, and a ring structure formed between adjacent substituents. n1 and n2 may be the same or different and are integers of 0 to 3. When n1 and n2 are 2 or more, each R ²⁰⁷ and each R ²⁰⁸ may be the same or different.

In the general formula (11), R ²⁰⁹ to R ²¹⁶ may be the same or different, and are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocyclic group. Substituted or unsubstituted alkenyl group, substituted or unsubstituted cycloalkenyl group, substituted or unsubstituted alkynyl group, hydroxyl group, thiol group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted Substituted aryl ether group, substituted or unsubstituted aryl thioether group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, halogen, cyano group, aldehyde group, substituted or unsubstituted carbonyl group, carboxyl group Substituted or unsubstituted oxycarbonyl group, substituted Or an unsubstituted carbamoyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted sulfonyl group, a substituted or unsubstituted amide group, a substituted or unsubstituted amino group, a nitro group, a substituted or unsubstituted silyl group And a substituted or unsubstituted siloxanyl group, a substituted or unsubstituted boryl group, and a substituted or unsubstituted phosphine oxide group. Further, at least one of R ²⁰⁹ to R ²¹⁶ is more preferably a ring structure formed between a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an adjacent substituent. . Further, at least one of R ²⁰⁹ to R ²¹² and at least one of R ²¹³ to R ²¹⁶ are formed between a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an adjacent substituent. More preferably, the ring structure is

In addition, the compound represented by the general formula (1) includes a compound represented by the following general formula (12), a compound represented by the general formula (13), a compound represented by the general formula (14), The compound represented by the formula (15), the compound represented by the general formula (16), or the compound represented by the general formula (17) is particularly preferable.

In general formulas (12) to (17), R ³⁰¹ to R ³⁰⁴ may be the same or different, and are a cyano group, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. Selected from the group consisting of a alkynyl group, a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group. At least one of R ³⁰¹ to R ³⁰⁴ is a cyano group. R ³⁰⁵ to R ³¹⁶ may be the same or different and are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl Group, substituted or unsubstituted cycloalkenyl group, substituted or unsubstituted alkynyl group, hydroxyl group, thiol group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl ether group, substituted Or an unsubstituted arylthioether group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a halogen, a cyano group, an aldehyde group, a substituted or unsubstituted carbonyl group, a carboxyl group, a substituted or unsubstituted oxy Carbonyl group, substituted or unsubstituted carbamo Group, substituted or unsubstituted ester group, substituted or unsubstituted sulfonyl group, substituted or unsubstituted amide group, substituted or unsubstituted amino group, nitro group, substituted or unsubstituted silyl group, substituted or unsubstituted Selected from the group consisting of a siloxanyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted phosphine oxide group, and a ring structure formed between adjacent substituents. n3 to n6 may be the same or different and are integers of 0 to 3. When n3 to n6 are 2 or more, each R ³⁰⁵ , each R ³⁰⁶ , each R ³⁰⁷ and each R ³⁰⁸ may be the same or different.

In the general formula (17), R ³⁰⁹ to R ³¹⁶ may be the same or different, and represent a hydrogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and an adjacent substituent. It is preferably selected from ring structures formed therebetween. In particular, at least one of R ³⁰⁹ to R ³¹⁶ is more preferably a ring structure formed between a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an adjacent substituent. .

As the compound represented by the general formula (1), among the compounds represented by the general formulas (12) to (17), a compound represented by the general formula (12), represented by the general formula (13) More preferably, the compound represented by the general formula (14), the compound represented by the general formula (16), and the compound represented by the general formula (17) are represented by the general formula (14). The compound, the compound represented by the general formula (16), and the compound represented by the general formula (17) are particularly preferable.

An example of the compound represented by the general formula (1) is shown below. The compound represented by General formula (1) is not limited to the compound shown below.

The compound represented by the general formula (1) can be synthesized, for example, by the following method. That is, after condensing an active methylene compound to the corresponding intermediate having a diketopyrrolopyrrole skeleton, the target compound is obtained by reacting the metal salt in the presence of a base.

For the synthesis of an intermediate having a diketopyrrolopyrrole skeleton, see JP-A-9-323993, Adv. Optical Mater. Vol. 3, pp. 280-320 (2015) and the like. For the boron complexation of an intermediate having a diketopyrrolopyrrole skeleton, see J. Pat. Org. Chem. , Vol. 64, no. 21, pp. 7813-7819 (1999), Angew. Chem. , Int. Ed. Engl. , Vol. 46, pp. 3750-3753 (2007) and the like. Furthermore, introduction of a cyano group into a boron complex is described in Bioorganic & Medicinal Chemistry Letters, vol. 18, pp. The method described in 3112-3116 (2008) can be referred to.

Furthermore, when introducing an aryl group or a heteroaryl group, a method of generating a carbon-carbon bond by using a coupling reaction between a halogenated derivative and a boronic acid or a boronic acid esterified derivative can be mentioned. However, the present invention is not limited to this. Similarly, when introducing an amino group or a carbazolyl group, for example, there is a method of generating a carbon-nitrogen bond by using a coupling reaction between a halogenated derivative and an amine or a carbazole derivative under a metal catalyst such as palladium. However, the present invention is not limited to this.

The compound represented by the general formula (1) preferably has a maximum light emission in a wavelength range of 700 nm or more. The compound represented by the general formula (1) can emit near infrared light by having maximum light emission in a wavelength range of 700 nm or more. As a result, the compound represented by the general formula (1) can be used as a sensing function material in biometric authentication.

<Composition>
The composition according to the embodiment of the present invention preferably includes a compound represented by the general formula (1) and a binder resin. In the present invention, the content of the compound represented by the general formula (1) in this composition is the molar extinction coefficient of the compound, the fluorescence quantum yield and the absorption intensity at the excitation wavelength, and the thickness of the molded product such as a film to be produced. Although it depends on the transmittance, it is usually 1.0 × 10 ⁻⁴ to 30 parts by weight, and 1.0 × 10 ⁻³ to 10 parts by weight with respect to 100 parts by weight of the binder resin. More preferably, it is 1.0 × 10 ⁻² to 5 parts by weight.

(Binder resin)
The binder resin forms a continuous phase and may be any material that is excellent in molding processability, transparency, heat resistance, and the like. Examples of binder resins include photocurable resist materials having reactive vinyl groups such as acrylic acid, methacrylic acid, polyvinyl cinnamate, and ring rubber, epoxy resins, silicone resins (silicone rubber, silicone gel, etc. Organopolysiloxane cured products (including crosslinked products), urea resins, fluororesins, polycarbonate resins, acrylic resins, urethane resins, melamine resins, polyvinyl resins, polyamide resins, phenol resins, polyvinyl alcohol resins, cellulose resins, aliphatics Well-known things, such as ester resin, aromatic ester resin, aliphatic polyolefin resin, aromatic polyolefin resin, are mentioned. Further, as the binder resin, these copolymer resins may be used. By appropriately designing these resins, resins useful for the composition according to the embodiment of the present invention (for example, a color conversion composition) can be obtained.

Among these resins, a thermoplastic resin is preferable because the molding process is easy. Furthermore, from the viewpoint of transparency and heat resistance, an aromatic ester resin, an epoxy resin, a silicone resin, an acrylic resin, or a mixture thereof can be suitably used.

(Other ingredients)
In addition to the compound represented by the general formula (1) and the binder resin, the composition according to the embodiment of the present invention includes, as an additive, a dispersant or a leveling agent for stabilizing a coating film, You may contain adhesion assistants, such as a silane coupling agent for modification, etc. Further, this composition may contain inorganic particles such as silica particles and silicone fine particles as a component for suppressing precipitation of the compound represented by the general formula (1). Furthermore, the composition may contain light-resistant stabilizers such as light stabilizers, antioxidants, processing and heat stabilizers, UV absorbers and the like.

Examples of the light stabilizer include tertiary amines, catechol derivatives, and nickel compounds, but are not particularly limited. These light stabilizers may be used alone or in combination.

Examples of the antioxidant include phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-ethylphenol. It is not particularly limited. These antioxidants may be used alone or in combination.

Examples of the processing and heat stabilizer include phosphorus stabilizers such as tributyl phosphite, tricyclohexyl phosphite, triethylphosphine, and diphenylbutylphosphine, but are not particularly limited. Moreover, these stabilizers may be used alone or in combination.

Examples of the light resistance stabilizer include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H- Although benzotriazoles, such as benzotriazole, can be mentioned, it is not specifically limited. Moreover, these light resistance stabilizers may be used alone or in combination.

In addition, the composition according to the embodiment of the present invention includes fine particles such as fumed silica, glass powder, and quartz powder, titanium oxide, zirconia oxide, and titanic acid as necessary, as long as the effects of the present invention are not impaired. You may contain inorganic fillers, such as barium and a zinc oxide, a pigment, a flame retardant, a heat-resistant agent.

In the composition according to the embodiment of the present invention, the content of these additives includes the molar extinction coefficient of the compound, the fluorescence quantum yield and the absorption intensity at the excitation wavelength, and the thickness and transmission of a molded article such as a film to be produced. Although it depends on the ratio, it is usually preferably 1.0 × 10 ⁻³ parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the compound represented by the general formula (1). The content of these additives is more preferably 1.0 × 10 ⁻² parts by weight to 15 parts by weight with respect to 100 parts by weight of the compound represented by the general formula (1). It is particularly preferably 1.0 × 10 ⁻¹ part by weight or more and 10 parts by weight or less.

(solvent)
The composition according to the embodiment of the present invention may contain a solvent. The solvent is not particularly limited as long as it can adjust the viscosity of the composition in a fluid state and does not excessively affect the light emission and reliability of the luminescent material. Examples of such solvents include toluene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, acetone, isopropanol, terpineol, texanol, methyl cellosolve, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. , Dimethoxyethane, tetrahydrofuran, dioxane, ethyl acetate and the like. These solvents can be used alone, but it is preferable to use a mixture of two or more.

Among these solvents, particularly toluene is preferably used because it does not affect the deterioration of the compound represented by the general formula (1) and there is little residual solvent after drying. When two or more kinds of solvents are used, the boiling point of each solvent is preferably 150 ° C. or less, and the difference between the highest and lowest of the boiling points is preferably 50 ° C. or less. The difference in boiling points is more preferably in the range from 20 ° C to 50 ° C. *

<Method for producing composition>
Below, an example of the manufacturing method of the composition which concerns on embodiment of this invention is demonstrated. In this production method, a predetermined amount of the compound represented by the general formula (1), a binder resin, a solvent, and the like is mixed. After mixing the above components so as to have a predetermined composition, the mixture is homogeneously mixed and dispersed with a homogenizer, a self-revolving stirrer, a three-roller, a ball mill, a planetary ball mill, a bead mill or the like. A composition is obtained. Defoaming is preferably carried out under vacuum or reduced pressure conditions after mixing or dispersing. Further, a specific component may be mixed in advance or a process such as aging may be performed. It is also possible to remove the solvent with an evaporator to obtain a desired solid content concentration.

<Molded body>
The molded body according to the embodiment of the present invention is a molded body molded using the composition according to the present invention. Examples of the molded body include a thin film, a film, a sheet, an injection molded product, an extrusion molded product, a vacuum / pressure air molded product, a blow molded product, and a composite with another material. This molded body is preferably a thin film, a sheet, or a film from the viewpoint of easily absorbing excitation light.

The molded body according to the embodiment of the present invention may be formed by desolvation of the composition used in the composition, or the composition used in the composition may be cured by heating, light irradiation, or the like. It may be molded.

<Light emitting device>
A light emitting device according to an embodiment of the present invention includes a light source and a near infrared light conversion unit. In this light-emitting device, the near-infrared light conversion unit includes the molded body according to the present invention. Such a light-emitting device can be configured by combining a near-infrared light conversion unit including the molded body and a light source.

As the light source applied to the light emitting device of the present invention, any light source can be used as long as it emits light in a wavelength region that can be absorbed by the compound represented by the general formula (1). Examples of such a light source include a fluorescent light source such as a hot cathode tube, a cold cathode tube, and an inorganic EL, an organic electroluminescence element light source, an LED, and an incandescent light source. Any of these light sources can be used in principle for the light emitting device of the present invention. In particular, from the viewpoints of high efficiency, high reliability, and flexibility, organic electroluminescence element light sources and LEDs can be cited as suitable light sources. The light source may have one type of emission peak or may have two or more types of emission peaks. In the light emitting device of the present invention, a plurality of excitation light sources having different types of emission peaks can be used in any combination.

The near-infrared light conversion unit including the molded body according to the embodiment of the present invention may be subjected to pattern processing as necessary. Examples of the pattern processing method include various printing methods such as photolithography, screen printing, and inkjet.

The light-emitting device according to the embodiment of the present invention is not limited in its configuration as long as the near-infrared light conversion unit includes the molded body of the present invention. FIG. 1 is a schematic cross-sectional view showing a configuration of a first example of a light emitting device according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing the configuration of the second example of the light emitting device according to the embodiment of the invention. FIG. 3 is a schematic cross-sectional view showing the configuration of the third example of the light emitting device according to the embodiment of the invention. FIG. 4 is a schematic cross-sectional view showing the configuration of the fourth example of the light emitting device according to the embodiment of the invention. FIG. 5 is a schematic cross-sectional view showing the configuration of the fifth example of the light-emitting device according to the embodiment of the present invention. In the drawings, the same components are denoted by the same reference numerals. Further, the light emitting device according to the embodiment of the present invention is not limited to the one having the structure illustrated in FIGS.

As shown in FIG. 1, the light emitting device 15A of the first example includes a light source 10 and a near-infrared light conversion unit 11 including the molded body of the present invention. As a typical structural example of the light emitting device 15A, as shown in FIG. 1, there is a structure of a laminated body in which a near infrared light conversion unit 11 is laminated on the light source 10.

As shown in FIG. 2, the light emitting device 15 </ b> B of the second example includes the light source 10, the near infrared light conversion unit 11, and the base material 12 described above. As a typical structural example of the light emitting device 15B, as shown in FIG. 2, there is a structure of a laminated body in which a base material 12 and a near infrared light conversion unit 11 are laminated in this order on a light source 10.

As shown in FIG. 3, the light emitting device 15 </ b> C of the third example includes the light source 10, the near infrared light conversion unit 11, and the base material 12 described above. As a typical structural example of the light emitting device 15C, as shown in FIG. 3, there is a structure of a laminated body in which a near-infrared light conversion unit 11 and a base material 12 are laminated in this order on a light source 10.

As shown in FIG. 4, the light emitting device 15 </ b> D of the fourth example includes the light source 10 and the near infrared light conversion unit 11 described above, and a plurality of base materials 12. As a typical structural example of the light emitting device 15D, as shown in FIG. 4, there is a structure of a laminated body in which a near infrared light conversion unit 11 sandwiched between a plurality of base materials 12 is laminated on a light source 10. It is done.

As shown in FIG. 5, the light emitting device 15E of the fifth example includes the light source 10, the near-infrared light conversion unit 11, the plurality of base materials 12, and the plurality of barrier films 13. The barrier film 13 is for preventing deterioration of the compound (specifically, the compound represented by the general formula (1)) contained in the near-infrared light conversion unit 11 due to oxygen, moisture, or heat. . As a typical structural example of the light emitting device 15E, as shown in FIG. 5, a near infrared light conversion unit 11 sandwiched between a plurality of barrier films 13 and a plurality of base materials 12 on a light source 10. The structure of a laminated body in which is laminated.

(Base material)
As the substrate (for example, the substrate 12 shown in FIGS. 2 to 5) applied to the light emitting device of the present invention, a known metal, film, glass, ceramic, paper, or the like can be used without particular limitation. Specifically, as a base material, metal (including aluminum alloy), zinc, copper, iron, and other metal plates and foils, cellulose acetate, polyethylene terephthalate (PET), polyethylene, polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene , Polypropylene, polycarbonate, polyvinyl acetal, aramid, silicone, polyolefin, thermoplastic fluororesin, plastic film such as tetrafluoroethylene and ethylene copolymer (ETFE), α-polyolefin resin, polycaprolactone resin, acrylic resin, silicone Plastic film made of a resin and a copolymer resin of these with ethylene, paper laminated with the plastic, or coated with the plastic Paper was, said metal laminated or vapor-deposited paper, the metals and plastic film laminated or deposited. Moreover, when the base material is a metal plate, the surface thereof may be subjected to a plating treatment or ceramic treatment such as chromium or nickel.

Among these, glass and resin films are preferably used because of the transmittance and the ease of molding of the near infrared light conversion part (for example, the near infrared light conversion part 11 shown in FIGS. 1 to 5). Moreover, a film with high strength is preferable so that there is no fear of breakage when handling a film-like substrate. Resin films are preferred in terms of their required characteristics and economy, and among these, plastic films selected from the group consisting of PET, polyphenylene sulfide, polycarbonate, and polypropylene are preferred in terms of economy and handleability. Moreover, when drying a molded object or press-molding at a high temperature of 200 degreeC or more with an extruder, a polyimide film is preferable at a heat resistant surface. In view of ease of peeling of the molded body, the surface of the base material may be subjected to a release treatment in advance.

The thickness of the substrate is not particularly limited, but the lower limit is preferably 25 μm or more, and more preferably 38 μm or more. Moreover, as an upper limit, 5000 micrometers or less are preferable and 3000 micrometers or less are more preferable.

(Barrier film)
The barrier film (for example, the barrier film 13 shown in FIG. 5) applied to the light emitting device of the present invention is appropriately used in the case of improving the gas barrier property with respect to the near infrared light conversion part. Examples of the barrier film include inorganic oxides such as silicon oxide, aluminum oxide, titanium oxide, tantalum oxide, zinc oxide, tin oxide, indium oxide, yttrium oxide, and magnesium oxide, silicon nitride, aluminum nitride, titanium nitride, Inorganic nitrides such as silicon carbonitride, or mixtures thereof, or metal oxide thin films and metal nitride thin films obtained by adding other elements to these, or polyvinylidene chloride, acrylic resins, silicon resins, melamine resins, Mention may be made of films made of various resins such as urethane resins, fluorine resins, polyvinyl alcohol resins such as saponified vinyl acetate. Examples of the film having a barrier function against moisture include polyethylene, polypropylene, nylon, polyvinylidene chloride, a copolymer of vinylidene chloride and vinyl chloride, a copolymer of vinylidene chloride and acrylonitrile, and a fluorine resin. And membranes made of various resins such as polyvinyl alcohol resins such as saponified vinyl acetate.

In the light emitting device of the present invention, the barrier film may be provided on both surfaces of the near-infrared light conversion unit 11 as in the barrier film 13 shown in FIG. 5, for example, or only on one surface of the near-infrared light conversion unit 11. It may be provided.

In addition, depending on the required functions of the near infrared light conversion unit, antireflection function, antiglare function, antireflection antiglare function, hard coat function (friction resistance function), antistatic function, antifouling function, electromagnetic wave shield An auxiliary layer having a function, a visible light cut function, an ultraviolet ray cut function, a polarization function, and a toning function may be further provided.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1)
Below, the synthesis | combining method of compound 1A of the synthesis example 1 in this invention is demonstrated. In the synthesis method of Compound 1A, under a nitrogen stream, 3-cyanophenol (25.0 g), 3,7-dimethyl-1-octanol (41.5 g), triphenylphosphine (68.8 g), tetrahydrofuran ( (500 mL) was stirred at 0 ° C. A mixture of diisopropyl azodicarboxylate (53 g) and tetrahydrofuran (30 mL) was added dropwise to the mixture, and the mixture was stirred overnight. After completion of the reaction, the reaction solution was concentrated and dried, and then the concentrate was extracted with toluene and washed with pure water. The organic layer was separated from the obtained solution, dried over magnesium sulfate, filtered, and the solvent was removed. Hexane (200 mL) was added to the resulting concentrate, stirred for 1 hour, dried, and purified by silica gel chromatography to give 4- (3,7-dimethyloctyloxy) benzonitrile (45 g). .

Subsequently, the above 4- (3,7-dimethyloctyloxy) benzonitrile (20.0 g), potassium tert-butoxide (11.3 g), tert-amyl alcohol (160 mL) were placed in a flask under a nitrogen stream. Was mixed and refluxed. A mixture of isopropyl succinate (6.8 g) and tert-amyl alcohol (10 mL) was added dropwise to the mixture over 3 hours, and the mixture was refluxed for 1 hour. After returning to room temperature, methanol (100 mL) and pure water (100 mL) were added and refluxed for 1 hour, and then the precipitate was filtered and washed with superheated methanol. The obtained solid was vacuum-dried, and red powder 3,6-bis (3- (3,7-dimethyloctyloxy) pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione ( 7.8 g) was obtained.

Next, a liquid mixture of the above red powder (7.0 g), pyridine acetonitrile (3.5 g) and dehydrated toluene was placed in a flask under a nitrogen stream and refluxed for 30 minutes, and then phosphoryl chloride (14. 3 g) was added and refluxed for 4 hours. After returning to room temperature, the mixture was concentrated and dried, and the concentrate was extracted with dichloromethane and washed with an aqueous sodium hydrogen carbonate solution. The obtained reaction solution was dried over magnesium sulfate and then purified by silica gel chromatography to obtain a green solid (8.35 g).

Then, the liquid mixture of said green solid (8.0g), diisopropyl ethylamine (10.8g), and dichloromethane (100mL) was stirred at 0 degreeC with the flask under nitrogen stream. Boron trifluoride diethyl ether complex (11.3 g) was added dropwise to the mixture, and the mixture was stirred overnight at room temperature. Next, pure water (100 mL) was added to the reaction solution, stirred for 30 minutes, and then the solution was extracted with dichloromethane. The resulting solution was dried over magnesium sulfate and then concentrated to dryness. The obtained concentrate was purified by silica gel chromatography to obtain compound 1a (6.1 g).

Subsequently, boron trifluoride diethyl etherate (0) was added to a mixture of the above compound 1a (1.0 g), trimethylsilyl cyanide (1.8 g), and dehydrated dichloromethane (60 mL) in a flask under a nitrogen stream. .3 g) was added and stirred at room temperature for 1 hour. Next, pure water (60 mL) was added to the reaction solution, stirred for 30 minutes, and then the solution was extracted with dichloromethane. The resulting solution was dried over magnesium sulfate and then concentrated to dryness. The obtained concentrate was purified by silica gel chromatography to obtain compound 1A (0.8 g). The results of ¹ H-NMR analysis of this compound 1A are as follows.
¹ H-NMR (CDCl ₃ (d = ppm)): 0.85-0.95 (m, 18H), 1.16-1.35 (m, 12H), 1.46-1.67 (m, 6H), 1.84-1.92 (m, 2H), 4.12-4.16 (t, 4H), 7.22-7.38 (m, 6H), 7.38-7.42 ( t, 2H), 7.49-7.54 (t, 2H), 7.74-7.77 (d, 2H), 7.99-8.04 (t, 2H), 8.44-8. 47 (d, 2H)

(Synthesis Example 2)
Below, the synthesis | combining method of compound 2A of the synthesis example 2 in this invention is demonstrated. In the synthesis method of Compound 2A, the same method as in Synthesis Example 1 except that 2- (quinolin-2-yl) acetonitrile (2.5 g) was used instead of 4- (3,7-dimethyloctyloxy) benzonitrile. To give 3.5 g of compound 2a. Subsequently, the compound 2A was synthesized in the same manner as in Synthesis Example 1 except that the obtained compound 2a was used instead of the compound 1a to obtain 2.1 g of compound 2A. The results of ¹ H-NMR analysis of this compound 2A are as follows.
¹ H-NMR (CDCl ₃ (d = ppm)): 0.85-0.88 (m, 10H), 1.12-1.37 (m, 12H), 1.50-1.54 (m, 4H), 1.64-1.69 (m, 4H), 1.90-1.92 (m, 2H), 4.15-4.20 (m, 4H), 7.23-7.27 ( m, 2H), 7.45-7.49 (m, 4H), 7.55-7.59 (t, 2H), 7.67-7.71 (t, 2H), 7.83-7. 95 (m, 6H), 8.31-8.33 (d, 2H), 8.53-8.55 (d, 2H)

(Synthesis Examples 3 to 8)
In Synthesis Examples 3 to 8 in the present invention, Compounds 3A to 9A were synthesized by the same method as Synthesis Example 1.

(Example 1)
Evaluation of the optical characteristics of Example 1 in the present invention will be described. In Example 1, 500 parts by weight of chlorobenzene and 0.5 part by weight of compound 1A as a light emitting material were mixed with 100 parts by weight of a polyester resin as a binder resin, and then stirred at 300 rpm for 3 hours. The thing was manufactured.

The composition was applied on a polyethylene terephthalic acid film (XG7PL2 manufactured by Toray Advanced Materials Co., Ltd.) using a bar coating method, and then dried at 150 ° C. for 5 minutes. As a result, a film (molded body of Example 1) on which a coating layer having an average film thickness of 10 μm was formed was obtained. In Example 1, which is an example of a molded body applied to the near-infrared light conversion part of the light-emitting device according to the present invention, the optical characteristics were evaluated using such a film.

Specifically, when the light emission characteristics of this film were evaluated using Quantaurus-QY manufactured by Hamamatsu Photonics, light emission in the near infrared region having a peak wavelength of 827 nm was obtained. The full width at half maximum of the emission spectrum at this peak wavelength was 110 nm. The emission intensity of Example 1 was 1.05, expressed by a relative value when the emission intensity in Conventional Comparative Example 2 described later was 1.00. In addition, when UV light having a wavelength of 365 nm was continuously irradiated at room temperature, the time until the light absorption characteristics of the film decreased by 5% (this is an index of “photoreliability”) was 600 hours. It was. The evaluation results of Example 1 are summarized in Table 1 described later.

(Examples 2 to 9 and Comparative Examples 1 to 3)
Evaluation of optical characteristics of Examples 2 to 9 in the present invention and Comparative Examples 1 to 3 with respect to the present invention will be described. In Examples 2 to 9 and Comparative Examples 1 to 3, films were prepared and optical characteristics were evaluated in the same manner as in Example 1 except that the compounds described in Table 1 were used as the light emitting materials. Compound R1 as the light emitting material of Comparative Example 1 is a compound shown below. The evaluation results of Examples 2 to 9 and Comparative Examples 1 to 3 are shown in Table 1.

 

 

As is clear with reference to Table 1, each film of Examples 1 to 9 had higher optical reliability than Comparative Examples 1 to 3. Moreover, as a film (molded article) applied to the near-infrared light conversion part of the light-emitting device, the peak wavelength of light emission is in the near-infrared light emission wavelength region (for example, a region of 700 nm or more) and the light emission intensity is relatively Higher ones, that is, higher ones that emit near-infrared light are preferred. From the viewpoint of improving the luminous efficiency of near-infrared light emission, the peak wavelength of near-infrared light emission is preferably a longer wavelength. Therefore, each of the films of Examples 1 to 9 has a higher near-infrared emission efficiency than Comparative Examples 1 to 3. From the above, it was confirmed that the films of Examples 1 to 9 had both high emission efficiency of near-infrared light emission and high light reliability.

Further, when Examples 1 to 9 are compared with each other, the film of Example 2 is the best from the viewpoint that the peak wavelength of near-infrared emission can be made longer, and Example 6 is followed by Example 6. It is good. Hereinafter, Example 7, Example 8, Example 1, Example 5, Example 3, Example 9, and Example 4 are favorable in this order. On the other hand, Examples 2, 7, and 8 are relatively good from the viewpoint of easily synthesizing a compound as a light emitting material. Following these, Example 6, Example 1, Example 5, Example 3, Example 9, and Example 4 are favorable in this order. From the above, Example 2 is the best from both the viewpoints of increasing the peak wavelength of near-infrared light emission and ease of synthesis of the light-emitting material. Compound 2A used for the synthesis of the film of Example 2 is an example of a compound represented by General Formula (14).

As described above, the compound according to the present invention, the composition containing the compound, the molded body using the compound, and the light-emitting device are suitable for achieving both high emission efficiency of near-infrared light emission and high reliability.

DESCRIPTION OF SYMBOLS 10 Light source 11 Near infrared light conversion part 12 Base material 13 Barrier film 15A, 15B, 15C, 15D, 15E Light-emitting device

Claims (11)

It is a compound represented by the general formula (1),
The compound characterized by the above-mentioned.

(In the general formula (1), Ar ¹ and Ar ² may be the same or different, and are a 5-membered aromatic ring, a 6-membered aromatic ring, or two or more 5-membered rings and / or A condensed aromatic ring in which a 6-membered ring is condensed, and these aromatic ring and condensed aromatic ring may have a substituent, and X ^a and X ^b are CR ⁷ or a nitrogen atom; ⁷ is an electron withdrawing group, and R ¹ and R ² may be the same or different and are a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ³ to R ⁶ are Cyano group, halogen, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, and substituted or unsubstituted Hetero Selected from the group consisting of aryl group. And at least one of R 3 ^~ R ⁶ is a cyano group.) The compound represented by the general formula (1) is a compound represented by the general formula (2), a compound represented by the general formula (3), a compound represented by the general formula (4), and the general formula (5). ), A compound represented by the general formula (6), or a compound represented by the general formula (7).
The compound according to claim 1.

(In the general formulas (2) to (7), X ^a and X ^b are CR ⁷ or a nitrogen atom, and R ⁷ is an electron withdrawing group. X ¹ and X ² may be the same or different. A sulfur atom, an oxygen atom, a nitrogen atom or a phosphorus atom, X ³ and X ⁴ may be the same or different, and a nitrogen atom or a phosphorus atom, and R ¹⁰¹ and R ¹⁰² may be the same or different. A substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ¹⁰³ to R ¹⁰⁶ may be the same or different, and may be a cyano group, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group; It is selected from the group consisting of a substituted alkoxy group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group. At least one of R ¹⁰³ to R ¹⁰⁶ is a cyano group, and R ¹⁰⁷ to R ¹¹⁸ may be the same or different, and may be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclohexane. An alkyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted alkynyl group, a hydroxyl group, a thiol group, a substituted or unsubstituted alkoxy group, Substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl ether group, substituted or unsubstituted aryl thioether group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, halogen, cyano group, aldehyde group , Substituted or unsubstituted carbonyl group, carboxyl group, substituted Or an unsubstituted oxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted sulfonyl group, a substituted or unsubstituted amide group, a substituted or unsubstituted amino group, a nitro A ring structure formed between a group, a substituted or unsubstituted silyl group, a substituted or unsubstituted siloxanyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted phosphine oxide group and an adjacent substituent Selected.) The compound represented by the general formula (1) is a compound represented by the general formula (8), a compound represented by the general formula (9), a compound represented by the general formula (10), or the general formula ( 11) any one of the compounds represented by
The compound according to claim 1 or 2, wherein

(In the general formulas (8) to (11), X ^a and X ^b are CR ⁷ or a nitrogen atom, and R ⁷ is an electron withdrawing group. X ⁵ and X ⁶ may be the same or different. A sulfur atom, an oxygen atom, a nitrogen atom or a phosphorus atom, X ⁷ to X ¹⁰ may be the same or different, and a nitrogen atom or a phosphorus atom, and R ²⁰¹ and R ²⁰² may be the same or different. A substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ²⁰³ to R ^{206, which} may be the same or different, are a cyano group, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group; Selected from the group consisting of a substituted alkoxy group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group ^{And, .R} 207 ^{~ R 216} at least one of them is a cyano group of R 203 ^{~ R 206} may be the same or different, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl An alkyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted alkynyl group, a hydroxyl group, a thiol group, a substituted or unsubstituted alkoxy group, Substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl ether group, substituted or unsubstituted aryl thioether group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, halogen, cyano group, aldehyde group , Substituted or unsubstituted carbonyl group, carboxyl group, substituted Or unsubstituted oxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted ester group, substituted or unsubstituted sulfonyl group, substituted or unsubstituted amide group, substituted or unsubstituted amino group, nitro group , A substituted or unsubstituted silyl group, a substituted or unsubstituted siloxanyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted phosphine oxide group, and a ring structure formed between adjacent substituents N1 and n2 may be the same or different and each is an integer of 0 to 3. When n1 and n2 are 2 or more, each R ²⁰⁷ and each R ²⁰⁸ may be the same or different. ) In the general formula (11), at least one of R ²⁰⁹ to R ²¹⁶ is a ring structure formed between a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an adjacent substituent. Is,
The compound according to claim 3. The compound represented by the general formula (1) is a compound represented by the general formula (12), a compound represented by the general formula (13), a compound represented by the general formula (14), or the general formula (15). ), A compound represented by the general formula (16), or a compound represented by the general formula (17).
The compound according to any one of claims 1 to 3, wherein:

(In the general formulas (12) to (17), R ³⁰¹ to R ³⁰⁴ may be the same or different, and are a cyano group, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. Selected from the group consisting of a substituted alkynyl group, a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group, and at least one of R ³⁰¹ to R ³⁰⁴ is a cyano group, R ³⁰⁵ to R ³¹⁶ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Unsubstituted cycloalkenyl group, substituted or unsubstituted alkynyl group, hydroxyl group, thiol group, substituted or Substituted alkoxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl ether group, substituted or unsubstituted aryl thioether group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, halogen, A cyano group, an aldehyde group, a substituted or unsubstituted carbonyl group, a carboxyl group, a substituted or unsubstituted oxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted sulfonyl group, Substituted or unsubstituted amide group, substituted or unsubstituted amino group, nitro group, substituted or unsubstituted silyl group, substituted or unsubstituted siloxanyl group, substituted or unsubstituted boryl group, substituted or unsubstituted phosphine oxide Groups, and adjacent substituents .N3 ~ selected from the group consisting of ring structure formed n6 may be the same or different, when an integer of 0 ~ 3 .n3 ~ n6 is 2 or more, each ^{R 305} and each ^{R 306} , Each R ³⁰⁷ and each R ³⁰⁸ may be the same or different.) In the general formula (17), at least one of R ³⁰⁹ to R ³¹⁶ is a ring structure formed between a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an adjacent substituent. Is,
6. The compound according to claim 5. In the general formula (1), R ³ to R ⁶ are all cyano groups.
The compound according to claim 1. The compound represented by the general formula (1) has a maximum light emission in a wavelength range of 700 nm or more,
The compound according to any one of claims 1 to 7, which is characterized in that A compound according to any one of claims 1 to 8;
A winter resin,
The composition characterized by including. A molded body molded using the composition according to claim 9,
A molded product characterized by that. A light-emitting device including a light source and a near-infrared light conversion unit,
The near-infrared light conversion part includes the molded body according to claim 10.
A light emitting device characterized by that.

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