JP7018632B2 - Ultraviolet light emitting materials and their uses - Google Patents

Description

The present invention is capable of emitting ultraviolet light, and is a light emitting material (ultraviolet light emitting material or ultraviolet light emitting fluorene compound) formed of a specific fluorene compound, and its use, for example, ultraviolet light emitting property such as a coating agent. The present invention relates to a composition, a light emitting element (or a photoelectric conversion element), etc., and a novel fluorene compound and a method for producing the same.

Ultraviolet light (ultraviolet or UV) with a wavelength of 400 nm or less, which has high energy, is used in various applications such as fluorescent tubes, mercury lamps, and backlights, typically for sterilization, scientific analysis, resin curing, and white light emission. It is widely used as a light source for a diode (LED), and mercury is usually used as the light source. However, from the viewpoint of harmfulness to the human body and the global environment, the use of mercury has been regulated in recent years, and the development of new ultraviolet light emitting materials to replace mercury is being promoted. An example that has already been put into practical use is a near-ultraviolet LED having a wavelength of 365 nm using gallium nitride (GaN). However, since the device uses an inorganic light emitting material, the manufacturing process tends to be complicated. Therefore, there is a demand for an organic light emitting material that can be easily or efficiently produced by a method such as a coating method. As such an ultraviolet light emitting organic material, a compound having a fluorene skeleton and the like are known.

For example, in Non-Patent Documents 1 and 2, 9,9-bis (4-methylbenzyl) fluorene (BMBF) has an emission peak with a wavelength of 322 nm in a solid state at room temperature, and its half width is narrow. It is disclosed that (or highly monochromatic) ultraviolet light is emitted.

Further, Non-Patent Documents 3 and 4 disclose that the emission quantum efficiency of BMBF is 7.6% in the solid state and 18.8% in the dichloromethane solution state. Further, in the hybrid thin film formed by mixing polyphenylsilsesquioxane (PPSQ) prepared from phenyltrimethoxysilane and BMBF, the concentration quenching is suppressed, and the emission quantum efficiency is about 3 in the solid state. It is disclosed that the improvement is doubled to 18.2%.

Japanese Patent Application Laid-Open No. 2009-96782 (Patent Document 1) discloses a fluorene compound represented by the following formula (1), and examples of the alkyl group represented by R ¹ include a t-butyl group and the like. ing.

(In the formula, X represents an alkylidene group or an alkylene group, Y represents a hydroxyl group or the like, ring Z represents an aromatic hydrocarbon ring, R ¹ represents a halogen atom, a cyano group or an alkyl group, and R ² represents a halogen atom, a cyano group or an alkyl group. A hydrocarbon group or the like, k is an integer of 0 to 4, m and n are 0 or an integer of 1 or more, and when k, m or n is 2 or more, R ¹ , R ² or Y is They may be the same or different groups, respectively).

Japanese Unexamined Patent Publication No. 2009-96782

Proceedings of the 97th Annual Meeting of the Chemical Society of Japan (2017), 3PA-017 "Crystal Structure and Emission Characteristics of Fluorene Derivatives", Chemical Society of Japan The 97th Annual Meeting of the Chemical Society of Japan (2017) Poster, 3PA-017 "Crystal Structure and Emission Characteristics of Fluorene Derivatives" Proceedings of the Society of Polymer Science, Vol. 66, No. 1, 66th Annual Meeting of the Society of Polymer Science, 1Pc071 "Preparation and emission characteristics of polysilsesquioxane thin film hybridized with fluorene", Society of Polymer Science, Japan The 66th (2017) Annual Meeting of the Society of Polymer Science, Japan Poster, 1Pc071 "Preparation and emission characteristics of polysilsesquioxane thin film hybridized with fluorene"

However, although the fluorene compounds described in Non-Patent Documents 1 to 4 can emit ultraviolet light having a short wavelength and high monochromaticity even in a room temperature environment, the emission quantum efficiency is still insufficient. In particular, in order to put it into practical use as a photoelectric conversion element such as an ultraviolet light emitting organic EL element, high emission quantum efficiency in a solid state of an ultraviolet light emitting material is required, and therefore further improvement in emission quantum efficiency is expected.

Patent Document 1 describes that it is particularly preferable that the substitution number k of ^R1 is 0, and even in the examples, no fluorene compound having a substitution number k of 1 or more has been prepared. Further, as the use of the fluorene compound, although additives for resists, raw materials such as pharmaceuticals and pesticides, intermediates and the like are described, not only the luminescent material is not described at all, but also the fluorene compound is described in the examples. The emission characteristics of Fluorene have not been evaluated at all.

Therefore, an object of the present invention is to provide an ultraviolet light emitting material capable of emitting ultraviolet light with high emission quantum efficiency (quantum efficiency or quantum yield) and its use.

Another object of the present invention is to provide an ultraviolet light emitting material showing high emission quantum efficiency even in a solid state and its use.

Still another object of the present invention is to provide an ultraviolet light emitting material capable of emitting ultraviolet light having a short wavelength and high monochromaticity (or having a narrow peak width in an emission spectrum) in a room temperature environment, and an application thereof. To do.

Another object of the present invention is to provide an ultraviolet light emitting material having high heat resistance and its use.

Yet another object of the present invention is to provide a novel fluorene compound capable of emitting ultraviolet light and having high heat resistance and a method for producing the same.

As a result of diligent studies to achieve the above-mentioned problems, the present inventors not only can emit highly monochromatic ultraviolet light at a short wavelength, but also surprisingly, higher emission than before. We have found that it exhibits quantum efficiency and completed the present invention.

That is, the ultraviolet light emitting material of the present invention is represented by the following formula (1).

(In the formula, A is an independently linear or branched alkylene group, Z is an independent allene ring, and R ¹ is an independently linear or branched alkyl group or trialkylsilyl group. , R ² are independently substituents other than R ¹ , R ³ are independent substituents, k1 and k2 are independently integers of 1 to 4, and m1 and m2 are independently 0 to 0 to each. The integer of 3 and n each independently indicate an integer of 0 or more, and k1 + m1 and k2 + m2 are independently integers of 1 to 4).

In the formula (1), A is a linear or branched C _1-6 alkylene group, Z is a C _6-14 arene ring, R ¹ is a branched alkyl group or a tri C _1-6 alkyl silyl group. k1 and k2 may be an integer of about 1 to 2, and m1 and m2 may be an integer of about 0 to 2.

In the above formula (1), A is a linear or branched C _1-4 alkylene group, Z is a benzene ring, a naphthalene ring or a biphenyl ring, and R ¹ is a branched C _3-10 alkyl group or tri C ₁ . _-4 Alkylsilyl groups, k1 and k2 may be 1.

The ultraviolet light emitting material may be a fluorene compound represented by the following formula (1a).

(In the formula, A, Z, R ¹ , R ² , R ³ , m1, m2, and n are the same as those in the above formula (1), respectively).

The ultraviolet light emitting material contains at least one emission peak having a maximum wavelength λ _{em, max} of 300 to 400 nm and a half width of 50 nm or less in the emission spectrum in a solid state, and has an emission quantum efficiency of 12% or more. You may. The present invention also includes a method of exciting a fluorene compound represented by the above formula (1) to emit ultraviolet light.

The present invention also includes an ultraviolet light emitting composition containing the ultraviolet light emitting material. The ultraviolet light emitting composition may further contain a binder component. The ultraviolet light emitting composition may be a coating agent.

The present invention also includes a method of irradiating a coating film formed of the ultraviolet light emitting composition with light and detecting the ultraviolet light emitted by the coating film by a detector equipped with a spectroscope and a detector. do.

Furthermore, the present invention also includes a light emitting device (or photoelectric conversion element) containing the ultraviolet light emitting material.

The present invention also includes a fluorene compound represented by the following formula (1).

(In the formula, A is an independently linear or branched alkylene group, Z is an independent allene ring, R ¹ is an independent trialkylsilyl group, and R ² is an independent R. Substituents other than ¹ , R3 ^are independent substituents, k1 and k2 are independently integers of 1 to 4, m1 and m2 are independently integers of 0 to 3, and n are independent. It indicates an integer of 0 or more, and k1 + m1 and k2 + m2 are independently integers of 1 to 4).

The present invention also includes a method for producing the fluorene compound, which comprises a step of reacting the fluorene represented by the following formula (2) with the compound represented by the following formula (3).

(In the formula, R ⁴ indicates a trialkylsilyl group or a group capable of producing a trialkylsilyl group, and ^R2 , k1, k2, m1 and m2 are the same as those in the above formula (1)).

(In the formula, X ² represents a halogen atom, and A, Z, R ³ and n are the same as in the above formula (1)).

In the present specification and claims, the number of carbon atoms may be indicated by C ₁ , C ₆ , C ₁₀ , or the like. For example, an alkyl group having 1 carbon atom is represented by "C ₁ alkyl", and an aryl group having 6 to 10 carbon atoms is represented by "C _6-10 aryl".

In the present specification and claims, the "solid state" means a state in which fluidity is lost and solidified without being dispersed in a dispersion medium such as a resin or a matrix.

Since the ultraviolet light emitting material of the present invention has a specific chemical structure, it can emit ultraviolet light with high emission quantum efficiency. Further, the ultraviolet light emitting material of the present invention exhibits high emission quantum efficiency even in a solid state where it is expected that it is difficult to improve the emission quantum efficiency. Further, in a room temperature environment, it is possible to emit ultraviolet light having a short wavelength and showing high monochromaticity (or having a narrow peak width in the emission spectrum). Further, the ultraviolet light emitting material of the present invention has high heat resistance.

Furthermore, the present invention can provide a novel fluorene compound capable of emitting ultraviolet light and having high heat resistance.

FIG. 1 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 1. FIG. 2 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 2. FIG. 3 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Reference Example 2. FIG. 4 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 3. FIG. 5 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Reference Example 4. FIG. 6 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 4. FIG. 7 is a measurement result of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 5. FIG. 8 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Reference Example 5. FIG. 9 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 6. FIG. 10 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Reference Example 6. FIG. 11 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 7. FIG. 12 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 8. FIG. 13 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Reference Example 7. FIG. 14 is a measurement result of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 9. FIG. 15 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 10. FIG. 16 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 11. FIG. 17 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 12. FIG. 18 is a measurement result of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 13. FIG. 19 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 14. FIG. 20 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 15. FIG. 21 is a measurement result of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 16. FIG. 22 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 17. FIG. 23 shows the measurement results of the excitation spectrum (solid line) and the emission spectrum (dashed line) of Example 18.

[Ultraviolet light emitting material]
The light emitting material of the present invention (ultraviolet light emitting material or ultraviolet light emitting fluorene compound) is represented by the following formula (1). In the following formula (1), the fluorene compound in which R ¹ is a trialkylsilyl group is a novel compound.

(In the formula, A is an independently linear or branched alkylene group, Z is an independent allene ring, and R ¹ is an independently linear or branched alkyl group or trialkylsilyl group. , R ² are independently substituents other than R ¹ , R ³ are independent substituents, k1 and k2 are independently integers of 1 to 4, and m1 and m2 are independently 0 to 0 to each. The integer of 3 and n each independently indicate an integer of 0 or more, and k1 + m1 and k2 + m2 are independently integers of 1 to 4).

In the above formula (1), examples of the linear or branched alkyl group represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and an s-butyl. Linear group such as group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, hexyl group, isohexyl group, octyl group, isooctyl group, 2-ethylhexyl group, decyl group, isodecyl group, dodecyl group, isododecyl group. Examples thereof include a linear or branched C _1-20 alkyl group, preferably a linear or branched C _1-16 alkyl group, and more preferably a linear or branched C _1-12 alkyl group. .. Among these alkyl groups, a branched chain alkyl group seems to be preferable to a linear alkyl group in terms of bulkiness. The linear or branched alkyl groups may be used alone or in combination of two or more.

Among the alkyl groups, a branched chain alkyl group is preferable. Branched chain alkyl groups include isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, isohexyl group, isooctyl group, 2-ethylhexyl group and other branched C _3-20 alkyl. Examples of the preferred branched alkyl group include a branched C _3-16 alkyl group, a branched C _3-12 alkyl group, a branched C _3-10 alkyl group, and the like. It is a branched C _3-8 alkyl group, a branched C _3-6 alkyl group, and more preferably a branched C _3-5 alkyl group such as an isopropyl group, a t-butyl group, and a neopentyl group. However, it is a branched _C4 alkyl group, especially a t-butyl group.

In the trialkylsilyl group represented by ^R1 , the alkyl group substituted with the silyl group (or silicon atom) includes, for example, the group exemplified as the linear or branched alkyl group represented by ^R1 . Similar groups can be mentioned. The types of the three alkyl groups substituted with the silyl group (or silicon atom) may be the same or different from each other, and are usually the same.

Typical trialkylsilyl groups include trilinear or branched C1- such as trimethylsilyl group, ethyldimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group and trit _- butylsilyl group. ₆ Alkylsilyl group and the like can be mentioned. These trialkylsilyl groups may be used alone or in combination of two or more. Preferred trialkylsilyl groups include tri-linear or branched C _1-4 alkylsilyl groups, more preferably tri-linear or branched C _1-3 alkylsilyl groups, and even more preferably tri-C _1- . It is a ₂ -alkylsilyl group, and a trimethylsilyl group is particularly preferable.

These ^R1s may be used alone or in combination of two or more. In the ultraviolet light emitting material of the present invention, by substituting a specific substituent, particularly a bulky (or bulky) substituent, in the fluorene skeleton, not only the emission quantum efficiency can be greatly improved, but also the heat resistance is greatly improved. It seems that it can be done. Among these ^R1 , the trialkylsilyl group is preferable from the viewpoint of easily improving the emission quantum efficiency in the solution state or the form of the coating film supported on the binder component. Further, among the emission quantum efficiencies, a linear or branched alkyl group is preferable from the viewpoint that the emission quantum efficiency in a solid state can be easily improved and the heat resistance can be further improved. In particular, a linear or branched alkyl group that can greatly improve the emission quantum efficiency in a solid state is most preferable because it can be more effectively used as a photoelectric conversion element such as an ultraviolet light emitting organic EL element.

The substitution numbers k1 and k2 of ^R1 are, for example, integers of about 1 to 3, preferably 1 or 2, and more preferably 1. Although k1 and k2 may be different from each other, they are usually often the same. When k1 and k2 are 2 or more, the types of ^a plurality of R1s substituted with the same benzene ring among the two benzene rings forming the fluorene skeleton may be the same or different. Further, of the two benzene rings forming the fluorene skeleton, the types of ^R1 substituted with different benzene rings may be the same or different, and are usually the same.

Further, when k1 and k2 are ¹ , the substitution position of R1 may be substituted at any of the 1st to 4th positions and the 5th to 8th positions of the fluorene skeleton, but the preferred substitution position is 1 , 8th, 2nd, 7th, 3rd, 6th, 4th, and 5th positions are the substitution positions having a symmetrical relationship on the paper in the above formula (1), and the 2nd and 7th positions are particularly preferable. Further, when k1 and k2 are 2 or more, the replacement position of ^R1 is not particularly limited.

R ² may be a substituent other than R ¹ , and typical examples thereof include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, and a cyano group.

The substitution numbers m1 and ^m2 of R2 are, for example, integers of about 0 to 2, preferably 0 or 1, and more preferably 0. Although m1 and m2 may be different from each other, they are usually often the same. When m1 and m2 are ² or more, the types of a plurality of R2s substituted with the same benzene ring among the two benzene rings forming the fluorene skeleton may be the same or different. Further, of the two benzene rings forming the fluorene skeleton, the types of R ² substituted with different benzene rings may be the same or different, and are usually the same. Further, the replacement position of R ² is not particularly limited.

k1 + m1 and k2 + m2 are, for example, integers of about 1 to 3, preferably 1 or 2, and more preferably 1. k1 + m1 and k2 + m2 may be different from each other, but usually they are often the same.

Examples of the linear or branched alkylene group represented by A include a methylene group, an ethylene group, a methylmethylene group (ethylidene group), a propylene group, a 1,3-propane-diyl group and a 2,2-propane group. Examples thereof include a linear or branched C _1-6 alkylene group such as a diyl group and a 1,4-butane-diyl group. The types of the two alkylene groups A may be different, but they are usually the same. Preferred alkylene group A includes a linear or branched C _1-4 alkylene group, more preferably a linear or branched C _1-3 alkylene group, and particularly C _1-2 alkylene. Groups, particularly methylene and ethylene groups, are preferred. When R ¹ is a trialkylsilyl group and A is an ethylene group, the emission quantum efficiency and heat resistance may be significantly improved as compared with the methylene group.

Examples of the arene ring (aromatic hydrocarbon ring) represented by Z include a monocyclic arene ring such as a benzene ring and a polycyclic arene ring. Examples of the polycyclic arene ring include a fused polycyclic arene ring (condensed polycyclic aromatic hydrocarbon ring) and a ring-assembled arene ring (ring-aggregated polycyclic aromatic hydrocarbon ring).

Examples of the fused polycyclic arene ring include fused bicyclic arene rings, fused tricyclic arene rings and the like, and the like. Examples of the fused bicyclic arene ring include a fused bicyclic _C10-16 arene ring such as a naphthalene ring and an indene ring. Examples of the fused tricyclic arene ring include fused tricyclic C _14-20 arene rings such as an anthracene ring and phenanthrene ring.

Examples of the ring-assembled arene ring include a beerene ring such as a biphenyl ring, a phenylnaphthalene ring, and a binaphthyl ring; and a terarene ring such as a terphenyl ring.

Preferred ring Z includes C _6-14 arene ring, more preferably C _6-12 arene ring such as benzene ring, naphthalene ring and biphenyl ring, and further preferably C _6-10 such as benzene ring and naphthalene ring. It is an arene ring, especially a benzene ring. The types of the two rings Z may differ from each other, but are usually often the same. The bonding position between the ring Z and the alkylene group A is not particularly limited.

Examples of the substituent represented by R ³ include a hydrocarbon group, a halogen atom, a hydroxyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, a hydroxy (poly) alkoxy group and a thiol group (mercapto). Group), alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, acyl group, carboxyl group, alkoxycarbonyl group, amino group, substituted amino group, cyano group, nitro group and the like. In the present specification and claims, "(poly) alkoxy group" is used to mean that both an alkoxy group and a polyalkoxy group are included.

Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and a group in which two or more of these hydrocarbon groups are combined (or bonded).

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group, n-octyl group and 2-ethylhexyl. Examples thereof include a linear or branched C _1-20 alkyl group such as a group, an n-decyl group and an n-dodecyl group. It is preferably a linear or branched C _1-12 alkyl group, and more preferably a linear or branched C _1-6 alkyl group.

Examples of the cycloalkyl group include a C _5-10 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. It is preferably a C _5-8 cycloalkyl group.

Examples of the aryl group include a naphthyl group such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group, and a _C6-14 aryl group such as a biphenylyl group, an anthryl group and a phenanthryl group. It is preferably a C _6-10 aryl group.

Examples of the group in which two or more kinds of hydrocarbon groups are combined (bonded) include an alkylaryl group and an aralkyl group. Examples of the alkylaryl group include mono or diC _1-6 alkyl C _6-10 aryl groups such as a methylphenyl group (tolyl group) and a dimethylphenyl group (kisilyl group). Examples of the aralkyl group include a C _6-10 aryl C _1-6 alkyl group such as a phenylmethyl group (benzyl group) and a 2-phenylethyl group (phenethyl group).

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

Examples of the alkoxy group include a linear or branched C _1-10 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group and a t-butoxy group. Can be mentioned.

Examples of the cycloalkyloxy group include C _5-10 cycloalkyloxy groups such as cyclohexyloxy groups.

Examples of the aryloxy group include a _C6-10 aryloxy group such as a phenoxy group.

Examples of the aralkyloxy group include a C _6-10 aryl-C _1-4 alkyloxy group such as a benzyloxy group.

Examples of the hydroxy (poly) alkoxy group include hydroxy (poly) C _2-6 alkoxy groups such as 2-hydroxyethoxy group, 2-hydroxypropoxy group and 2- (2-hydroxyethoxy) ethoxy group.

Examples of the alkylthio group include a C _1-10 alkylthio group such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group and a t-butylthio group.

Examples of the cycloalkylthio group include a C _5-10 cycloalkylthio group such as a cyclohexylthio group.

Examples of the arylthio group include a _C6-10 arylthio group such as a thiophenoxy group.

Examples of the aralkylthio group include a C _6-10 aryl-C _1-4 alkylthio group such as a benzylthio group.

Examples of the acyl group include a C _1-6 acyl group such as an acetyl group.

Examples of the alkoxycarbonyl group include C _1-6 alkoxy-carbonyl such as a methoxycarbonyl group.

Examples of the substituted amino group include a dialkylamino group and a diacylamino group. Examples of the dialkylamino group include a diC _1-4 alkylamino group such as a dimethylamino group. Examples of the diacylamino group include a di (C _1-6 acyl) amino group such as a diacetylamino group.

These groups R3 may be used alone or in combination of ^two or more. When the group R ³ is a cyclic hydrocarbon group such as an aryl group, an aggregate ring such as a ring-aggregated arene ring may be formed together with the ring Z. When the number of substitutions n is 1 or more ^, preferred groups R3 include an alkyl group, an aryl group, a hydroxyl group, a hydroxy (poly) alkoxy group, a carboxyl group and the like. The alkyl group is more preferably a linear or branched C _1-6 alkyl group such as a methyl group, and the aryl group is more preferably a C _6-10 aryl group such as a phenyl group. The hydroxy (poly) alkoxy group is more preferably a hydroxy (mono to deca) C _2-4 alkoxy group such as a 2-hydroxyethoxy group. Among these groups R ³ , C _1-4 alkyl groups such as methyl groups, hydroxyl groups and carboxyl groups are preferable.

The substitution number n of the group R ³ may be selected depending on the type of the ring Z, and can be selected from, for example, an integer of about 0 to 7, and the preferred range is an integer of 0 to 6 in a stepwise manner. It is an integer of 0 to 5, an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, and particularly 0. The two substitution numbers n may be different from each other, but usually they are often the same. When the number of substitutions n is 2 or more, the types of the ^two or more groups R3 substituted with the same ring Z may be the same or different from each other. Further ^, the types of the groups R3 to be substituted with different rings Z may be different, but usually they are often the same.

The substitution position of the group R3 is not particularly limited and may be selected depending ^on the type of the ring Z. When Z is a benzene ring, the substitution position of the group R3 is relative to the 9-position of the fluorene ring or the phenyl group bonded to the group A. For example, it is 3rd, 4th, 3rd, 4th, 3rd, 5th, 3rd, 4th, 5th, preferably 4th, 3rd, 4th, and more preferably 4th. For example, when Z is a naphthalene ring ^, the substitution position of the group R3 is, for example, at the 9-position of the fluorene ring or with respect to the 1-naphthyl group or 2-naphthyl group bonded to the group A, for example, the 1,5-position, 2, In many cases, it is replaced by the positional relationship of the 6th position, preferably the 2nd and 6th positions.

Typical examples of the fluorene compound represented by the formula (1) include a compound represented by the following formula (1a).

(In the formula, A, Z, R ¹ , R ² , R ³ , m1, m2, and n are the same as the above formula (1) including preferable embodiments, respectively).

The fluorene compound represented by the formula (1) includes a fluorene compound (1A) in which the group R1 in the formula ( ¹ ) is a linear or branched alkyl group, and a group R in the formula (1). ¹ is roughly classified into a fluorene compound (1B) which is a trialkylsilyl group. The fluorene compound (1B) is a novel fluorene compound.

Specifically, the fluorene compound (1A) is 9,9-bisbenzyl-2,7-di (t-butyl) fluorene, 9,9-bisbenzyl-2,7-diisopropylfluorene, 9,9-bis (2). 9,9-bis (C _6-14 aryl C ₁ ) such as -phenylethyl) -2,7-di (t-butyl) fluorene, 9,9-bis (2-phenylethyl) -2,7-diisopropylfluorene -6alkyl) _-2,7 -di (linear or branched C _1-6 alkyl) fluorene and the like can be mentioned.

Of these fluorene compounds (1A), 9,9-bis (C _6-10aryl C _1-4 alkyl) -2,7-di (branched chain C _3-10 alkyl) fluorene is preferable, and 9,9. -Bis (phenyl C _1-3 alkyl) -2,7-di (branched chain C _3-8 alkyl) fluorene is more preferable, and 9,9-bisbenzyl-2,7-di (t-butyl) is more preferable. 9,9-bis (Phenyl C _1-2alkyl ) -2,7-di (branched chain) such as fluorene, 9,9-bis (2-phenylethyl) -2,7-di (t-butyl) fluorene C _3-6 alkyl) fluorene is preferred.

Specifically, the fluorene compound (1B) is 9,9-bisbenzyl-2,7-bis (trimethylsilyl) fluorene, 9,9-bisbenzyl-2,7-bis (triethylsilyl) fluorene, 9,9-bisbenzyl. -2,7-bis (triisopropylsilyl) fluorene, 9,9-bisbenzyl-2,7-bis (trit-butylsilyl) fluorene, 9,9-bis (2-phenylethyl) -2,7-bis ( Trimethylsilyl) fluorene, 9,9-bis (2-phenylethyl) -2,7-bis (triethylsilyl) fluorene, 9,9-bis (2-phenylethyl) -2,7-bis (triisopropylsilyl) fluorene , 9,9-bis (2-phenylethyl) -2,7-bis (trit-butylsilyl) fluorene and the like 9,9-bis (C _6-14aryl C _1-6 alkyl) -2,7-bis (Tri-linear or branched C _1-6 alkylsilyl) Fluorene and the like can be mentioned.

Of these fluorene compounds (1B), 9,9-bis (C _6-10aryl C _1-4 alkyl) -2,7-bis (tri-linear or branched C _1-4 alkylsilyl) fluorene , 9,9-bis (Phenyl C _1-3 alkyl) -2,7-bis (tri-linear or branched C _1-3 alkylsilyl) fluorene is more preferable, and 9,9- 9,9-Bis (Phenyl C _1-2 Alkyl) -2 such as bisbenzyl-2,7-bis (trimethylsilyl) fluorene, 9,9-bis (2-phenylethyl) -2,7-bis (trimethylsilyl) fluorene , 7-Bis (Tri-C _1-2 alkylsilyl) fluorene is preferable, and 9,9-bis (2-phenylethyl) -2,7-bis (trimethylsilyl) fluorene is particularly preferable.

(Method for producing fluorene compound)
The method for producing the fluorene compound represented by the formula (1) is not particularly limited, and a conventional method, for example, 9H-fluorenes in which the 9-position represented by the following formula (2) is unsubstituted and the following formula A method including a step of reacting with the compound represented by (3) may be used.

(In the formula, R ⁴ indicates a group capable of producing R ¹ or R ¹ , and R ¹ , R ² , k1, k2, m1 and m2 are the same as those in the above formula (1) including preferred embodiments).

(In the formula, X ² represents a halogen atom, and A, Z, R ³ and n are the same as the above formula (1) including a preferable embodiment).

In the formula (2), the group capable of producing R ¹ represented by R ⁴ (or the group convertible to R ¹ ) is non-reactive in the reaction step with the compound represented by the formula (3). It is not particularly limited as long as it is a substituent and can generate R ¹ by a conventional reaction such as a substitution reaction, and examples thereof include a halogen atom. Therefore, typical examples of the fluorenes represented by the above formula (2) include fluorenes represented by the following formula (2-1) or (2-2).

(In the formula, X ¹ represents a halogen atom, R ^2a represents a cyano group, and R ¹ , R ² , k1, k2, m1 and m2 are the same as the above formula (1) including preferred embodiments).

Examples of the compound represented by the formula (2-1) include compounds corresponding to specific examples of the fluorene compound represented by the formula (1), and typically 2,7-di (). 2,7-di (branched chain C _3-8 alkyl) fluorene such as t-butyl) fluorene, 2,7-bis (trilinear or branched C) such as 2,7-bis (trimethylsilyl) fluorene _1-4 Alkylsilyl) Fluorene and the like can be mentioned.

In the above formula (2-2), examples of the halogen atom represented by X ¹ include a chlorine atom, a bromine atom, and an iodine atom. Preferred halogen atoms X ¹ are chlorine atoms and bromine atoms, and bromine atoms are usually often used. When k1 and k2 are ² or more, the types of X1 substituted with the same benzene ring among the two benzene rings forming the fluorene skeleton may be the same or different from each other. Further, of the two benzene rings forming the fluorene skeleton, the types of X1 that are substituted with different benzene rings may be different from ^each other, but are usually the same. Further, the substitution position of R ^2a is the same as that of R ² in the above formula (1), including a preferable embodiment.

Examples of the compound represented by the formula (2-2) include 2,7-dihalofluorene such as 2,7-dibromofluorene and 2,7-dichlorofluorene.

In the above formula (3), examples of the halogen atom represented by X ² include a chlorine atom, a bromine atom, and an iodine atom. Preferred halogen atoms X ² are chlorine atoms and bromine atoms, and bromine is usually often used.

Examples of the compound represented by the formula (3) include compounds corresponding to specific examples of the fluorene compound represented by the formula (1), and typical examples thereof include benzyl bromide and benzyl chloride. Examples thereof include C _6-10 aryl C _1-3 alkyl halides such as 2-phenylethyl) bromide and (2-phenylethyl) chloride.

The ratio of the compound represented by the formula (3) can be selected from the range of, for example, about 2 to 10 mol, preferably 2.5 to 1 mol, with respect to 1 mol of the fluorene represented by the formula (2). It is 5 mol, more preferably 2.8 to 4 mol, and more preferably 3 to 3.5 mol.

The reaction may be carried out in the presence or absence of a catalyst, and a base catalyst is usually used. The base catalyst is not particularly limited as long as it can generate an anion (fluorene anion) of the compound represented by the above formula (2), and a conventional inorganic base or organic base can be used. Examples of the inorganic base include metal hydroxides such as alkali metal hydroxides and alkaline earth metal hydroxides. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. Examples of the alkaline earth metal hydroxide include calcium hydroxide and barium hydroxide.

Examples of the organic base include metal alkoxide and quaternary ammonium hydroxide. Examples of the metal alkoxide include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium butoxide, and potassium t-butoxide. Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetraalkylammonium hydroxide such as tetra-n-butylammonium hydroxide, and trimethylbenzylammonium hydroxide.

These base catalysts may be used alone or in combination of two or more. Among these catalysts, metal alkoxides such as potassium t-butoxide are often used.

The ratio of the catalyst can be selected from the range of, for example, about 1 to 10 mol, preferably 1.5 to 5 mol, and more preferably 2 to 4 mol, with respect to 1 mol of the fluorene represented by the above formula (2). The moles, especially 2.2-3.8 moles.

The reaction may be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it is non-reactive with the base catalyst and can dissolve the fluorenes represented by the formula (2) and the compound represented by the formula (3), and is wide-ranging. A range of solvents can be used. Typical solvents include ethers, aromatics, amides, sulfoxides and the like.

Examples of the ethers include dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane, and the like.

Examples of aromatics include aromatic hydrocarbons such as benzene, toluene and xylene, anisole and the like.

Examples of the amides include N, N-dimethylformamide (DMF), N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP) and the like.

Examples of sulfoxides include dimethyl sulfoxide (DMSO) and the like.

These solvents may be used alone or in combination of two or more. Of these solvents, sulfoxides such as DMSO are often used.

If a protonic solvent (water, alcohol, etc.) is present in the reaction system (in the solvent), the activity of the fluorene anion as an intermediate may be lost. Therefore, the solvent from which the protonic solvent has been removed by dehydration or the like in advance. May be used in the reaction.

The amount of the solvent used may be selected from the range of, for example, about 0.5 to 100 parts by mass with respect to 1 part by mass of the fluorenes, as long as at least the fluorenes represented by the formula (2) are dissolved. It is preferably 5 to 80 parts by mass, more preferably 10 to 50 parts by mass, and further preferably 20 to 30 parts by mass.

The reaction temperature is not particularly limited, but can be selected from the range of, for example, about -10 to 120 ° C., preferably 0 to 100 ° C., more preferably 20 to 70 ° C., and usually, from the viewpoint of stability of the fluorene anion. , 50-70 ° C. The reaction time may be appropriately adjusted according to the type of raw material, reaction conditions, etc., and can be selected from the range of, for example, about 30 minutes to 48 hours, preferably 1 to 36 hours, more preferably 2 to 24 hours. The time, more preferably 2.5-12 hours, especially 3-6 hours.

Further, the reaction may be carried out with stirring, may be carried out in the air, or in an atmosphere of an inert gas such as nitrogen gas or a rare gas, or may be carried out under normal pressure or pressure. The reaction is usually carried out by mixing each component, but the mixing may be carried out step by step.

The reaction product is separated and purified by a conventional method, for example, a separation means such as filtration, washing, concentration, drying, extraction, crystallization, recrystallization, reprecipitation, column chromatography, or a separation means combining these. can.

Further, when fluorene having a group capable of producing R ¹ such as fluorene represented by the above formula (2-2) is used in the reaction step, the reaction product obtained in the reaction step is substituted. The compound represented by the above formula (1) may be prepared by producing R ¹ by subjecting it to a conventional reaction such as a reaction. As such a method, for example, a reaction product obtained by using the fluorenes represented by the above formula (2-2), that is, a compound represented by the following formula (4) and a trialkylhalosilane. In the above formula (1), a method for preparing a fluorene compound in which ^R1 is a trialkylsilyl group by reacting with and in the presence of metallic magnesium can be mentioned.

(In the formula, A, Z, R ³ , k1, k2, m1, m2 and n are the same as the above formula (1) including the preferable embodiment, and X ¹ and R ^2a are the same as the above formula including the preferable mode. Same as (2-2)).

Examples of the compound represented by the formula (4) include compounds corresponding to the compounds exemplified in the early formulas (2-2) and (3), and examples thereof include 9,9-bisbenzyl-2.7-dibromo. Examples include 9,9-bis (C _6-10 aryl C _1-3 alkyl) -2,7-dihalofluorene such as fluorene and 9,9-bis (2-phenylethyl) -2.7-dibromofluorene. Be done.

Examples of the trialkylhalosilane include compounds corresponding to the trialkylsilyl group represented by ^R1 in the above formula (1), and examples thereof include trimethylfluorosilane, trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, and triethyl. Examples thereof include trilinear or branched C _1-6 alkylhalosilanes such as chlorosilane, triisopropylchlorosilane, and trit-butylchlorosilane.

The ratio of the trialkylhalosilane can be selected from, for example, about ¹ to 10 mol, preferably 1. It is 1 to 5 mol, more preferably 1.2 to 2 mol.

The ratio of metallic magnesium can be selected from the range of, for example, about 1 to 10 mol, preferably 2 to 5 mol, with respect to ¹ mol of the group represented by X1 in the compound represented by the above formula (4). , More preferably 3-4 mol.

The reaction may be carried out in the presence or absence of a solvent. Examples of the solvent include ethers such as tetrahydrofuran (THF), dipropyl ether and anisole. These solvents can also be used alone or in combination of two or more. Of these solvents, THF is usually commonly used. The solvent is preferably dehydrated in advance from the viewpoint of suppressing the decrease in reactivity.

The amount of the solvent used may be such that the reaction system can be made uniform, and can be selected from the range of, for example, about 0.01 to 100 parts by mass with respect to 1 part by mass of the compound represented by the above formula (4). It is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 10 parts by mass, and further preferably 1 to 3 parts by mass.

The reaction temperature is not particularly limited, but can be selected from, for example, in the range of about 5 to 150 ° C., preferably 10 to 100 ° C., more preferably 15 to 50 ° C., and particularly 20 to 40 ° C., particularly 25 to 35 ° C. ℃. Usually, the reaction is often carried out at about room temperature, for example, 20 to 30 ° C. The reaction time may be appropriately adjusted according to the type of raw material, reaction conditions, etc., and can be selected from the range of, for example, about 30 minutes to 24 hours, preferably 1 to 12 hours, and more preferably 2 to 6 hours. It's time.

Further, the reaction may be carried out with stirring, or may be carried out under normal pressure or pressure. In addition, the reaction is usually carried out in an atmosphere of an inert gas such as nitrogen gas or noble gas. The reaction is usually carried out by mixing each component, but the mixing may be carried out step by step.

The reaction product is separated and purified by a conventional method, for example, a separation means such as filtration, washing, concentration, drying, extraction, crystallization, recrystallization, reprecipitation, column chromatography, or a separation means combining these. can.

(Characteristics of fluorene compound)
The ultraviolet light emitting material (or fluorene compound) of the present invention can emit highly monochromatic ultraviolet light at a short wavelength by being excited by energy (or external energy) such as light energy or electric energy. Therefore, the present invention also includes a method of exciting a fluorene compound represented by the early equation (1) to emit ultraviolet light. In the ultraviolet light emitting material (or fluorene compound) of the present invention, by substituting a specific substituent, particularly a bulky (or bulky) substituent, in the fluorene skeleton, mutual overlap (or stacking) between molecules is performed. Probably because the action can be suppressed, not only the emission of ultraviolet light having a short wavelength and high monochromaticity can be obtained, but also the emission quantum efficiency can be greatly improved. In particular, the emission quantum efficiency in the solid state, which was conventionally low, can be greatly improved.

Therefore, the fluorene compound represented by the above formula (1) has a maximum wavelength λ _em in the range of, for example, about 300 to 400 nm in the emission (fluorescence or phosphorescence) spectrum at room temperature, for example, at 25 ° C. in a solid state. _{, Max} may contain at least one emission peak, preferably in stages of 300 to 380 nm, 305 to 360 nm, 310 to 350 nm, 315 to 345 nm, more preferably 320 to 340 nm, particularly 325 to. It contains at least one emission peak having a maximum wavelength of λ _{em and max} in the range of 335 nm.

In the emission spectrum in the solid state, the emission peak (or absorption band) having the maximum wavelengths λ _{em and max} has a narrow half-value width, so that light having high monochromaticity can be emitted. The half width can be selected from, for example, 50 nm or less and 0.1 to 50 nm, and the preferred range is 1 to 45 nm, 3 to 40 nm, 5 to 35 nm, 7 to 33 nm, and 10 to the following stepwise. It is 30 nm, more preferably 12 to 28 nm, particularly 15 to 25 nm, and particularly 17 to 23 nm.

Further, the fluorene compound represented by the above formula (1) has a maximum wavelength λ _ex. It may contain at least one emission or absorption peak having _max , and the preferred range is as follows, in stages of 250 to 370 nm, 270 to 350 nm, 280 to 345 nm, 290 to 340 nm, 300 to 335 nm, 305 to 330 nm, It contains at least one emission or absorption peak having a maximum wavelength of λ _{ex, max} in the range of 310 to 325 nm.

Examples of the solid state include single crystals, polycrystals, and amorphous (amorphous), and are usually polycrystals.

The fluorene compound represented by the formula (1) exhibits high emission quantum efficiency, and is, for example, 10% or more in a solid state at room temperature, for example, 25 ° C., and preferably 12% or more in a stepwise manner. It is 15% or more, 20% or more, 25% or more, and more preferably 30% or more. Further, the emission quantum efficiency can be selected from a range of, for example, about 10 to 100% at room temperature, for example, 25 ° C., in a solid state, and the preferable range is 12 to 80% and 15 to 60 in the following steps. %, 20-50%, 25-45%, more preferably 30-40%.

Further, the fluorene compound represented by the above formula (1) has a maximum wavelength λ in the range of, for example, about 280 to 400 nm in the emission (fluorescence or phosphorescence) spectrum at room temperature, for example, at 25 ° C. in a dichloromethane solution state. It may contain at least one emission peak having _{em, max} , preferably 290 to 380 nm, 295 to 360 nm, 300 to 350 nm, 305 to 340 nm, more preferably 310 to 335 nm, particularly 315, in a stepwise manner. It contains at least one emission peak having a maximum wavelength of λ _{em and max} in the range of about 330 nm.

In the emission spectrum in the state of a dichloromethane solution, the half width of the emission peak (or absorption band) having the maximum wavelength λ _{em, max} can be selected from, for example, 50 nm or less and 0.1 to 50 nm, which is a preferable range. It is 1 to 45 nm, 5 to 43 nm, 10 to 40 nm, 12 to 38 nm, 15 to 35 nm, more preferably 18 to 33 nm, and particularly 20 to 30 nm, particularly 22 to 28 nm.

Further, the fluorene compound represented by the above formula (1) has a maximum wavelength λ _ex in the range of, for example, about 200 to 380 nm in the excitation spectrum (or absorption spectrum) at room temperature, for example, at 25 ° C. in a dichloromethane solution state. _{, Max} may contain at least one emission or absorption peak, preferably in stages of 250-350 nm, 270-340 nm, 280-335 nm, 290-330 nm, 300-325 nm, 305-320 nm. , 310-315 nm contains at least one emission or absorption peak having a maximum wavelength of λ _{ex, max} .

The fluorene compound represented by the formula (1) exhibits high emission quantum efficiency, and at room temperature, for example, at 25 ° C. and in a dichloromethane solution state, for example, 10% or more, preferably 15% or more in a stepwise manner. , 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, and more preferably 45% or more. Further, the emission quantum efficiency can be selected from a range of, for example, about 10 to 100% at room temperature, for example, at 25 ° C. and in a dichloromethane solution state, and the preferable range is 15 to 90% and 20 to 20 in the following steps. It is 80%, 25 to 75%, 30 to 70%, 35 to 65%, 40 to 60%, and more preferably 45 to 55%.

In the present specification and claims, the emission spectrum, the excitation spectrum, and the emission quantum efficiency can be measured by the methods described in Examples described later.

(Ultraviolet light emitting composition)
The ultraviolet light emitting composition of the present invention contains at least an ultraviolet light emitting material (or a fluorene compound) represented by the above formula (1). The ultraviolet light emitting material represented by the formula (1) may be used alone or in combination of two or more. Such an ultraviolet light emitting composition can be used in various forms or uses, and examples thereof include coating agents such as paints and ink compositions.

The ultraviolet light emitting composition of the present invention may or may not contain a binder component, if necessary, in addition to the fluorene compound represented by the above formula (1). As the binder component, for example, a conventional resin (or a polymer compound) can be used, and it can be roughly classified into a thermoplastic resin and a curable resin (thermosetting resin or photocurable resin).

Examples of the thermoplastic resin include olefin-based resin; (meth) acrylic-based resin; styrene-based resin; vinyl-based resin, for example, vinyl chloride resin, vinyl alcohol-based resin, etc .; fluororesin; polycarbonate-based resin; thermoplastic polyester-based resin. Resins such as polyethylene terephthalate, polybutylene terephthalate, polyalkylene allylate such as polyethylene naphthalate, polyarylate, liquid crystal polyester and the like; polyamide-based resins such as polyamide 6 and aliphatic polyamides such as polyamide 66, polyamide 6T and polyamide MXD. Semi-aromatic polyamide, etc .; Polyacetal-based resin; Polyphenylene ether-based resin; Polyphenylene sulfide-based resin; Polysulfone-based resin, for example, polysulfone, polyethersulfone, etc .; Polyetherketone-based resin, for example, polyetherketone, polyetheretherketone , Polyether ketone, ether ketone ketone, etc .; thermoplastic polyimide-based resin, for example, polyetherimide-based resin, polyamideimide-based resin, etc .; thermoplastic elastomer; cellulose-based resin, for example, cellulose ester-based resin such as triacetylcellulose, ethylcellulose. Such as cellulose ether-based resin;

Examples of the curable resin (thermosetting resin or photocurable resin) include epoxy resin; urethane resin; thermosetting polyester resin, for example, alkyd resin, unsaturated polyester resin, diallyl phthalate resin, and vinyl ester. Resins and the like; phenolic resins; amino resins such as melamine resins, urea resins, guanamine resins and the like; furan resins; thermosetting polyimide resins such as bismaleimide-based resins and bismaleimide triazine resins; silicon-based resins and the like. Be done.

These binder components may be used alone or in combination of two or more. Among these binder components, (meth) acrylic resin and styrene resin from the viewpoint that the fluorene compound represented by the above formula (1) is difficult to absorb the ultraviolet light emitted and the fluorene compound is easily dispersed uniformly. , Polycarbonate-based resin and silicon-based resin are preferable.

Examples of the (meth) acrylic resin include (meth) acrylic acid, (meth) acrylic acid C _1-18 alkyl ester, (meth) hydroxy acid C _2-18 alkyl, (meth) glycidyl acrylate, and (meth) acrylic acid. ) Alone or a copolymer of a (meth) acrylic monomer such as acrylonitrile; a copolymer of a (meth) acrylic monomer and another copolymerizable monomer can be mentioned.

Examples of the (meth) acrylic monomer alone or a copolymer include poly (meth) acrylic acid esters such as methyl poly (meth) acrylic acid, methyl methacrylate- (meth) acrylic acid copolymer, and methacrylic. Examples thereof include acid methyl-acrylic acid ester- (meth) acrylic acid copolymer and methyl methacrylate- (meth) acrylic acid ester copolymer.

In a copolymer of a (meth) acrylic monomer and another copolymerizable monomer, the copolymerizable monomer may be, for example, a styrene-based monomer such as styrene or α-methylstyrene. Examples include maleic anhydride.

Among these (meth) acrylic resins, poly (meth) acrylic acid C _1-8 alkyl esters such as polymethyl methacrylate are preferable.

Examples of the styrene-based resin include a single or copolymer of a styrene-based monomer such as styrene, α-methylstyrene, and vinyltoluene; a copolymer of a styrene-based monomer and a copolymerizable monomer; resistance to resistance. Impact-resistant styrene-based resins [that is, graft copolymers and / or blends (mixtures) with rubber components] and the like can be mentioned.

Examples of the styrene-based monomer alone or a copolymer include polystyrenes such as atactic polystyrene, isotactic polystyrene (IPS), syndiotactic polystyrene (SPS), styrene-vinyltoluene copolymer, and styrene-α. -Methylstyrene copolymer and the like can be mentioned.

Examples of the copolymer of the styrene-based monomer and the copolymerizable monomer include a styrene-acrylonitrile copolymer (AS resin), a styrene- (meth) acrylic acid copolymer, and a styrene- (meth) acrylic. Examples thereof include acid ester copolymers (MS resin and the like), styrene-maleic anhydride copolymers, styrene-phenylmaleimide copolymers, styrene-butadiene block copolymers, styrene-butadiene-styrene block copolymers and the like.

Examples of the impact-resistant styrene resin include impact-resistant polystyrene (HIPS); acrylonitrile-butadiene-styrene copolymer (ABS resin); instead of the ABS resin butadiene rubber B, acrylic rubber A and chlorinated polyethylene. AXS resin using a rubber component such as C, ethylene propylene rubber (or ethylene propylene diene rubber) E, specifically, AAS resin, ACS resin, AES resin, etc .; (meth) acrylic acid ester-butadiene-styrene co-weight. Combinations include, for example, methyl methacrylate-butadiene-styrene copolymer (MBS resin);

Among these styrene-based resins, a styrene-based monomer alone or a copolymer, particularly a homopolymer is preferable.

Examples of the polycarbonate-based resin include aromatic polycarbonate resins, specifically, bisphenol-type polycarbonate resins containing bisphenols as polymerization components such as bisphenol A-type polycarbonate resin and bisphenol F-type polycarbonate resin.

Examples of the bisphenols include bis (hydroxyaryl) alkanes, bis (hydroxyaryl) -arylalkans, bis (hydroxyaryl) cycloalkans, bis (hydroxyaryl) ethers, and bis (hydroxyaryl) ketones. , Bis (hydroxyaryl) sulfides, bis (hydroxyaryl) sulfoxides, bis (hydroxyaryl) sulfones, biphenols and the like.

Examples of bis (hydroxyaryl) alkanes include bis (4-hydroxyphenyl) methane (bisphenol F), 1,1-bis (4-hydroxyphenyl) ethane (bisphenol AD), and 2,2-bis (4-). Hydroxyphenyl) Propane (bisphenol A), 1,1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane (bisphenol B), 2,2-bis (4-hydroxyphenyl) -3-Methylbutane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4) -Hydroxy-3-isopropylphenyl) propane (bisphenol G) and the like can be mentioned.

Examples of bis (hydroxyaryl) -arylalkanes include 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP) and bis (4-hydroxyphenyl) -diphenylmethane (bisphenol BP). Can be mentioned.

Examples of bis (hydroxyaryl) cycloalkanes include 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), and 1,1-bis (bisphenol Z). 4-Hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC) and the like can be mentioned.

Examples of bis (hydroxyaryl) ethers include bis (4-hydroxyphenyl) ethers.

Examples of the bis (hydroxyaryl) ketone include bis (4-hydroxyphenyl) ketone.

Examples of the bis (hydroxyaryl) sulfides include bis (4-hydroxyphenyl) sulfides.

Examples of bis (hydroxyaryl) sulfoxides include bis (4-hydroxyphenyl) sulfoxide.

Examples of the bis (hydroxyaryl) sulfone include bis (4-hydroxyphenyl) sulfone (bisphenol S).

Examples of biphenols include o, o'-biphenol, m, m'-biphenol, p, p'-biphenol and the like.

These bisphenols can also be used alone or in combination of two or more.

Among these polycarbonate-based resins, a bisphenol-type polycarbonate resin containing bis (hydroxyaryl) alkanes such as bisphenol A as a polymerization component is preferable.

In a silicon-based resin, the polyorganosiloxane (silicone) skeleton has a monofunctional M unit (generally represented by R ₃ SiO _1/2 ) and a bifunctional D unit (generally R ₂ SiO). A unit represented by _2/2 ), a trifunctional T unit (generally represented by RSiO _3/2 ), and a tetrafunctional Q unit (generally represented by SiO _4/2 ). It may contain at least one unit selected from the group consisting of units).

The group R in the formulas representing the M unit, the D unit and the T unit is a substituent. Examples of the substituent include an alkyl group, an aryl group, a cycloalkyl group, a vinyl group and the like.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-hexyl group and an n-octyl group, 2 Examples thereof include C _1-12 alkyl groups such as an ethylhexyl group and an n-decyl group.

Examples of the aryl group include a _C6-14 aryl group such as a phenyl group, a methylphenyl group (tolyl group), a dimethylphenyl group (chysilyl group), a biphenylyl group, and a naphthyl group.

Examples of the cycloalkyl group include a C _5-10 cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a methylcyclohexyl group.

These substituents can be used alone or in combination of two or more. Among these substituents, a C _1-4 alkyl group such as a methyl group and a C _6-12 aryl group such as a phenyl group are preferable, and they are difficult to absorb ultraviolet light and easily disperse the fluorene compound uniformly. A C _6-10 aryl group such as a phenyl group is particularly preferred.

Examples of the terminal group (group bonded to the terminal silicon (Si) atom) include a hydroxyl group, an alkoxy group, a halogen atom such as a chlorine atom, and the like. Examples of the alkoxy group include a C _1-4 alkoxy group such as a methoxy group and an ethoxy group, and a C _1-2 alkoxy group is preferable.

These terminal groups can also be used alone or in combination of two or more. Of these terminal groups, there are usually many cases such as a hydroxyl group and a C _1-2 alkoxy group.

The silicon-based resin preferably contains at least one unit selected from the above T units and Q units from the viewpoint of easily forming a coating film, and particularly preferably contains T units. The ratio of T units in the entire silicon-based resin is, for example, 50 mol% or more, preferably 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, and further in stages. It is preferably silsesquioxane (or polysilsesquioxane) in an amount of 95 mol% or more, particularly 100 mol%. The ratio of T units in the entire silicon-based resin can be selected from, for example, in the range of about 60 to 100 mol%, and is preferably 80 to 99.9 mol%.

The silsesquioxane (or polysilsesquioxane) may be ladder-shaped (or ladder-shaped) or cage-shaped (or cage-shaped), but it has a three-dimensional network shape because it is easy to form a coating film. It is preferably in the form of (network or random structure). Examples of such silsesquioxane include polyalkylsilsesquioxane formed of T units (alkylsilsesquioxane units) in which the substituent R is an alkyl group, for example, polymethylsilsesquioxane. PolyC _1-4 alkylsilsesquioxane, etc .; polyarylsylsesquioxane formed in T units (arylsylsesquioxane units) in which R is an aryl group, for example, polyphenylsilsesquioxane, etc. Poly C _6-12 aryl sesquioxane and the like; polysil sesquioxane formed by a T unit in which R is an alkyl group and a T unit in which R is an aryl group can be mentioned.

These silsesquioxane can also be used alone or in combination of two or more. Of these silsesquioxane, polyarylsilsesquioxane formed in units of T in which R is an aryl group is preferable, and among them, poly-C _6-10 aryl silsesquioxane such as polyphenyl silsesquioxane is preferable. Sun is preferred.

Among these binder components, silicon-based resins, especially silsesquioxane, are excellent in thermal stability and heat dissipation because they are not easily deteriorated (or decomposed) even when exposed to ultraviolet light due to excitation light or light emission. preferable. A silicon-based resin, particularly silsesquioxane, has a total light transmittance of, for example, 85% or more, preferably 90% or more, probably because it interacts with the fluorene compound represented by the above formula (1). It is high and has a low haze value of, for example, 3% or less, preferably 1% or less, and it seems that it is easy to form a coating film in which the fluorene compound represented by the formula (1) is uniformly dispersed. Moreover, when a styrene resin is contained as a binder component, the emission quantum efficiency seems to be relatively high.

The ratio of the binder component can be selected from, for example, about 1 to 99.99% by mass, usually about 10 to 99.9% by mass with respect to the total solid content, and the preferable range is 20 in the following steps. It is about 90% by mass, 30 to 70% by mass, 35 to 65% by mass, 40 to 60% by mass, and 45 to 55% by mass. Further, from the viewpoint of further improving the emission quantum efficiency, the more preferable range of the ratio of the binder component to the total solid content is 50 to 99% by mass, 60 to 97% by mass, and 70 to 95% by mass in the following steps. , 80-94% by mass, 85-93% by mass, and particularly 90-92% by mass.

Further, the ultraviolet light emitting composition (or coating agent) may further contain a solvent in order to adjust the viscosity and improve the coatability (or handleability), and is dried and removed from the coating film after coating. You may. Examples of the solvent include hydrocarbons, halogenated hydrocarbons, alcohols, glycols, ethers, glycol ethers, glycol ether acetates, ketones, carboxylic acids, esters, carbonates, nitriles, and amides. , Sulfoxides, water, and mixed solvents thereof.

Examples of the hydrocarbons include aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene and xylene.

Examples of the halogenated hydrocarbons include dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and the like.

Examples of alcohols include C _1-6 alkanols such as methanol, ethanol, 1-propanol, 2-propanol, n-butanol, isobutanol, s-butanol and t-butanol.

Examples of glycols include (poly) C _2-4 alkylene glycols such as ethylene glycol, propylene glycol and diethylene glycol.

Examples of the ethers include chain ethers such as diethyl ether and cyclic ethers such as tetrahydrofuran and 1,4-dioxane.

Examples of glycol ethers include (poly) C _2-4 alkylene glycol mono C _1-4 alkyl ethers such as cellosolves, carbitols, triethylene glycol monomethyl ethers, propylene glycol monomethyl ethers and dipropylene glycol monomethyl ethers; Examples thereof include (poly) C _2-4 alkylene glycol di C _1-4 alkyl ethers such as ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether.

Examples of the cellosolves include C _1-4 alkyl cellosolves such as methyl cellosolve and ethyl cellosolve. Examples of the carbitols include C _1-4 alkyl carbitols such as methyl carbitol and ethyl carbitol.

Examples of glycol ether acetates include (poly) C _2-4 alkylene glycol mono C _1-4 alkyl ether acetates such as cellosolve acetates, carbitol acetates, propylene glycol monomethyl ether acetates and dipropylene glycol monobutyl ether acetates. Can be mentioned.

Examples of the cellosolve acetate include C _1-4 alkyl cellosolve acetate such as methyl cellosolve acetate. Examples of the carbitol acetates include C _1-4 alkyl carbitol acetate such as methyl carbitol acetate.

Examples of the ketone include chain ketones such as acetone and methyl ethyl ketone, and cyclic ketones such as cyclohexanone.

Examples of carboxylic acids include acetic acid and propionic acid.

Examples of the esters include acetic acid esters such as methyl acetate, ethyl acetate and butyl acetate, and lactic acid esters such as methyl lactate.

Examples of the carbonates include chain carbonates such as dimethyl carbonate and cyclic carbonates such as propylene carbonate.

Examples of nitriles include acetonitrile, propionitrile, benzonitrile and the like.

Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.

Examples of sulfoxides include dimethyl sulfoxide and the like.

These solvents may be used alone or in combination of two or more. Of these solvents, halogenated hydrocarbons such as chloroform are often used.

The ratio of the solvent can be appropriately selected depending on the viscosity of the ultraviolet light emitting composition and the like, and is not particularly limited. The solid content concentration of the ultraviolet light emitting composition is, for example, 0.01 to 50% by mass, preferably 0.1 to 10% by mass, and more preferably 0.5 to 2% by mass.

The ultraviolet light emitting composition may contain a conventional additive. Conventional additives include, for example, dyes, pigments, pigment dispersants, wetting agents, thickeners, coupling agents, defoaming agents, antisettling agents, antiskinning agents, polymerization inhibitors, polymerization initiators, and curing agents. , Leveling agents, thixotropic agents, color separation inhibitors, matting agents, flame retardants, stabilizers, plasticizers, softeners, lubricants, mold release agents, antistatic agents and the like. Examples of the stabilizer include antioxidants, ultraviolet absorbers, light stabilizers, ozone deterioration inhibitors and the like.

Since the additive may absorb the excitation light for exciting the ultraviolet light emitting material and the light emitted by the excited ultraviolet light emitting material, the coating agent may be substantially free of the additive. Therefore, the ultraviolet light emitting composition contains at least the fluorene compound represented by the above formula (1), and if necessary, contains only the binder component and / or the solvent, that is, substantially an additive. A configuration that does not include it is preferable.

The emission characteristics of the ultraviolet light emitting composition containing a binder component or the coating film (or coating film) containing a binder component formed by using this composition are appropriately determined according to the type and concentration of the fluorene compound, the binder component, and the like. You may adjust. The ultraviolet light emitting composition (or coating film) has an emission peak having a maximum wavelength of λ _{em, max} in the range of, for example, about 300 to 400 nm in the emission (fluorescence or phosphorescence) spectrum at room temperature, for example, 25 ° C. It may contain at least one of, preferably 300 to 380 nm, 305 to 360 nm, 305 to 350 nm, more preferably 310 to 345 nm, particularly 315 to 340 nm, and particularly 315 to 335 nm. The range contains at least one emission peak having a maximum wavelength of λ _{em, max} .

In the emission spectrum of the ultraviolet light emitting composition (or coating film) containing the binder component, the half width of the emission peak (or absorption band) having the maximum wavelength λ _{em, max} is, for example, 50 nm or less, 0.1. It can be selected from a range of about 50 nm, and the preferred range is 1 to 45 nm, 10 to 40 nm, 12 to 38 nm, 15 to 35 nm, and 17 to 33 nm in a stepwise manner, more preferably 20 to 30 nm, and particularly 22. It is ~ 28 nm.

Further, the ultraviolet light emitting composition (or coating film) containing a binder component has a maximum wavelength λ _ex, in the range of, for example, about 200 to 380 nm in an excitation spectrum (or absorption spectrum) at room temperature, for example, 25 ° C. It may contain at least one emission or absorption peak having _max , and is preferably a maximum wavelength in the range of 250 to 350 nm, 280 to 330 nm, 300 to 325 nm, 305 to 320 nm, and 310 to 315 nm in a stepwise manner. It contains at least one emission or absorption peak with λ _{ex, max} .

The emission quantum efficiency of the ultraviolet light emitting composition (or coating film) containing the binder component can be selected from the range of, for example, about 10 to 100% at room temperature, for example, 25 ° C., and the preferable range is as follows. In addition, it is 12 to 80%, 14 to 50%, and 15 to 25%. Further, since the emission quantum efficiency can be improved by adjusting the concentration of the fluorene compound and the like, the more preferable range of the emission quantum efficiency including the binder component is as follows, in stages, 20 to 90%, 25 to 70%, and so on. It is 30 to 65%, 35 to 60%, 38 to 58%, 40 to 55%, 45 to 54%, 47 to 53%.

Such an ultraviolet light emitting composition or coating agent is effective as, for example, invisible ink such as security ink (or security marker) for the purpose of identifying counterfeit products and preventing forgery of documents such as banknotes, cash vouchers, and warranty cards. Can be used for. As the invisible ink, a fluorescent substance or the like that emits visible light by irradiation with ultraviolet light is often used, and it is usually colorless and invisible, but it can be visualized by irradiating it with ultraviolet light such as black light. However, in recent years, black light is commercially available as a toy and is easily available, and can be easily visualized by a third party. Therefore, there is a concern that the security (confidentiality) of the information given by the invisible ink may be reduced. However, the coating agent of the present invention can effectively improve security.

Specifically, the wavelength of the ultraviolet light emitted by a commercially available black light is about 365 nm, and the fluorene compound represented by the above formula (1) cannot be excited and does not emit light unless the ultraviolet light has a shorter wavelength. Furthermore, even if the fluorene compound can be emitted by ultraviolet light having a short wavelength, it cannot be visually recognized without using a detection device because the emitted light is not visible light. Therefore, it becomes difficult for a third party to even determine whether or not the invisible ink is applied, and the security can be effectively improved.

Therefore, in the present invention, the ultraviolet light emitting composition (or a coating film formed by applying the ultraviolet light emitting composition and removing a solvent as necessary) is irradiated with light to obtain a coating film. It also includes a method of detecting the light emitted by a spectroscope and a detection device equipped with a detector.

The coating film may be formed by applying an ultraviolet light emitting composition (or a coating agent), and a conventional coating method, for example, a spin coating method, a gravure printing method, a screen printing method, an inkjet printing method, or the like is used. May be formed.

The light source used for detection is ultraviolet light having a shorter wavelength than the ultraviolet light emitted by a commercially available black light, for example, ultraviolet light having a wavelength of 10 nm or more, preferably 20 nm or more shorter than the detection wavelength, specifically. Specifically, a light source capable of irradiating ultraviolet light having a wavelength of 250 to 350 nm, preferably about 270 to 330 nm is used. Typical examples of such a light source include a xenon lamp, a deuterium lamp, an ultraviolet fluorescent lamp (UV fluorescent lamp), and an ultraviolet light emitting diode (UVLED).

The detection device may be provided with at least a specific spectroscope and a detector, and may also be provided with the light source. Examples of the spectroscope include a spectroscope that can separate the light of a light source from the light emitted by a coating agent or a coating film, such as a diffraction grating, a prism, and an optical cut filter. Examples of the detector include a detector capable of detecting the emission of an ultraviolet light emitting composition or a coating film, for example, a photomultiplier tube, a photodiode, a CCD (Charge Coupled Device) sensor and the like. As such a detection device, a commercially available spectrofluorometer or the like may be used.

The invisible ink may be printed or applied to printed matter in various forms such as characters (or sentences) and figures (or patterns), and may be in the form of a barcode, QR (Quick Response) code (registered trademark), or the like. A lot of information may be given by applying to. Further, more information may be given by combining the plurality of the ultraviolet light emitting materials. Specifically, since the ultraviolet light emitting material has a small half-value width of the maximum emission peak in the emission spectrum, even if a plurality of ultraviolet light emitting materials are included, the emission peaks are less likely to overlap and can be easily detected as separate peaks. .. Therefore, not only the presence or absence of emission peaks by a single ultraviolet light emitting material, but also the intensity ratio of a plurality of emission peaks obtained by adjusting the ratio of a plurality of ultraviolet light emitting materials is used as a signal to further increase the number. Information may be given.

(Light emitting element or photoelectric conversion element)
The light emitting device (or photoelectric conversion element) of the present invention includes at least an ultraviolet light emitting material represented by the above formula (1). Typical examples of the light emitting element include a current injection type light emitting element such as an inorganic light emitting diode (LED) and an organic EL element (or an organic light emitting diode (OLED)), and may be usually an organic EL element. many. The current injection type light emission of an organic EL element or the like is formed by an anode (transparent electrode) and a cathode (metal electrode), and an organic layer (organic thin film) or an organic-inorganic hybrid layer interposed between the electrodes. As a typical configuration, each layer is often formed in the order of transparent substrate / anode (anode) / hole (hole) transport layer / light emitting layer / electron transport layer / cathode (cathode). When the light emitting layer has a function as a hole transport layer or an electron transport layer, the hole transport layer or the electron transport layer is not always necessary.

Examples of the transparent substrate include a substrate made of an inorganic material such as glass; and a substrate made of an organic material such as a (meth) acrylic resin, a styrene resin, a polycarbonate resin, and a polyester resin.

Examples of the (meth) acrylic resin include the (meth) acrylic resin exemplified in the section of the ultraviolet light emitting composition. Examples of the styrene-based resin include the styrene-based resin exemplified in the section of the ultraviolet light emitting composition. Examples of the polycarbonate-based resin include the polycarbonate-based resin exemplified in the section of the ultraviolet light emitting composition. Examples of the polyester-based resin include polyalkylene allylate-based resins such as polyethylene terephthalate.

Further, the substrate may be in the form of a plate, but may be in the form of a sheet or a film.

As the anode, a transparent electrode is usually used, and it is often formed of a conductive metal oxide such as ITO (Indium Tin Oxide), FTO (Fluorine-doped Tin Oxide), and ZnO (Zinc Oxide). In the present specification and claims, the "transparent electrode" means an electrode capable of transmitting at least a part of ultraviolet light emitted by the ultraviolet light emitting material represented by the formula (1). Such an anode may be manufactured, for example, by forming it thin or by making a slit.

Examples of the hole transport material forming the hole transport layer include 4,4'-bis (trilphenylamino) biphenyl (TPD) and 4,4'-bis (α-naphthyl-phenylamino) biphenyl (α-naphthyl-phenylamino) biphenyl (). α-NPD), 1,1-bis [4- (trilphenylamino) phenyl] cyclohexane (TAPC), tris [4- (trilphenylamino) phenyl] amine (m-TDATA), tris [4- (9-) Aromatic amines such as carbazolyl) phenyl] amine (TCTA); phthalocyanines such as copper phthalocyanine; conductive polymers such as poly (3,4-ethylenedioxythiophene): polystyrene sulfonic acid complex (PEDOT: Polythiophenes such as PSS); and the like. These hole transport materials can also be used alone or in combination of two or more. Of these, conductive polymers such as PEDOT: PSS are often used.

The light emitting layer contains at least an ultraviolet light emitting material represented by the above formula (1) as a light emitting material. These luminescent materials may be used alone or in combination of two or more. The light emitting layer may be composed of only a light emitting material, and the light emitting material may be used as a guest material (or a dopant) and may further contain a host material. Examples of the host material include biphenyls such as 4,4'-bis (2,2-diphenylvinyl) biphenyl (DPvBi) and 4,4'-bis (9-carbazolyl) biphenyl (CBP); (meth) acrylic. Examples thereof include the binder component exemplified in the section of the ultraviolet light emitting composition such as a based resin, a polycarbonate based resin, and a silicon based resin.

Examples of the electron transporting material forming the electron transporting layer include light metal organic complexes such as aluminum complex and beryllium complex, bisstyrylarene derivative, oxadiazole derivative, triazole derivative, phenanthroline derivative, and silol derivative.

Examples of the aluminum complex include tris (8-quinolinolato) aluminum (III) (Alq ₃ ), bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum (III) (BAlq ₂ ), and tris (BAlq 2). Examples thereof include 4-methyl-8-quinolinolato) aluminum (III) (Almq ₃ ) and tris (5-hydroxy-benzo [f] quinolinato) aluminum (III) (Alph ₃ ).

Examples of the beryllium complex include bis [10-hydroxy-benzo [h] quinolinato] beryllium (II) (Bebq ₂ ).

Examples of the bisstyrylarene derivative include 4,4'-bis (2,2-di-p-tolyl-vinyl) biphenyl (DTVbi) and 9,10-bis [4- (diphenylamino) styryl] anthracene (BSA). -2), 4,4'-bis [2- (9-ethyl-3-carbazolyl) vinyl] biphenyl (BCzVBi), 1,4-bis [4- (di-p-tolylamino) styryl] benzene, etc. Be done.

Examples of the oxadiazole derivative include 2- (4-t-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole (t-Bu-PBD) and 1,3-bis. [5- (4-t-Butylphenyl) -1,3,4-oxadiazole-2-yl] benzene (OXD-7) and the like can be mentioned.

Examples of the triazole derivative include 3- (biphenyl-4-yl) -5- (4-t-butylphenyl) -4-phenyl-4H-1,2,4-triazole (TAZ).

Examples of the phenanthroline derivative include 4,7-diphenyl-1,10-phenanthroline (BPhen), 4,7-diphenyl-2,9-dimethyl-1,10-phenanthroline (BCP) and the like.

Examples of the siror derivative include 1,1-dimethyl-3,4-diphenyl-2.5-di (2,2'-bipyridirou-3-yl) siror.

These electron transport materials can also be used alone or in combination of two or more.

The cathode (metal electrode) is often formed of, for example, a simple substance of a metal such as aluminum (Al), magnesium (Mg), or silver (Ag), or an alloy thereof.

An anode buffer layer (hole injection layer) such as a copper phthalocyanine thin film may be formed between the anode and the hole transport layer, and a cathode may be formed between the cathode and the electron transport layer. Even if a buffer layer (electron injection layer), for example, an inorganic thin film such as a lithium fluoride (LiF) thin film or a lithium oxide (Li _2O ) thin film, or a metal-doped organic thin film such as lithium (Li) is formed. good.

The thickness of each layer (organic phase) interposed between the anode and the cathode is, for example, 0.1 to 500 nm, preferably 1 to 200 nm, and the thickness of the entire organic phase may be about 1 μm or less.

Such an organic EL element may be used as a light source for ultraviolet light (UV lamp) for various purposes such as sterilization, analysis, and light source of high color rendering white LED.

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

[Evaluation methods]
(NMR)
It was measured using "ULTRASHIELD 300" manufactured by BRUKER.

(HPLC)
The measurement was performed using "LC-20A" manufactured by Shimadzu Corporation.

(Light emission characteristics)
Excitation spectrum and emission (fluorescence or emission) of a sample using a spectral fluorescence photometer (“F-4500” manufactured by Hitachi High-Technologies Co., Ltd., light source: xenon lamp, detector: photoelectron multiplying tube, spectroscope: diffraction grid) Phosphorus) The spectrum is measured at room temperature (25 ° C.), and the half-value width of the peak (or absorption band) including the maximum wavelengths λ _{ex, max} of the excitation spectrum and the maximum wavelengths λ _{em, max} and λ _{em, max} of the emission spectrum. Asked.

(Quantum Efficiency)
Fluorescence spectrophotometer ("FP-6500" manufactured by Nippon Spectroscopy Co., Ltd., light source: xenon lamp, detector: photoelectron increase) equipped with a fluorescence integrating sphere unit ("ILF-533" manufactured by Nippon Spectroscopy Co., Ltd., diameter 100 mmφ) The double tube, spectroscope: diffraction grid) is spectrally corrected by the device function obtained using the attached standard light source for calibration, and the spectral area and the number of photons are made proportional to each other, and then the emission quantum efficiency is determined by the absolute method. Calculated. The excitation light is measured without the sample installed to determine the spectral area of the excitation light to be irradiated, and then the excitation light is measured with the sample installed to determine the spectral area of the irradiation excitation light not absorbed by the sample. By obtaining these differences, the number of photons absorbed in the sample was calculated. At the same time, the emission spectrum of the sample was also observed, and the number of photons emitted was calculated from the spectrum area. The emission quantum efficiency was calculated from the number of emitted photons with respect to the number of last absorbed photons.

(Pyrolysis temperature (or mass reduction temperature))
Using a thermal weight measuring device (“TGA4000” manufactured by Perkin Elmer Japan Co., Ltd.), the temperature was raised at a rate of 10 ° C./min in the range of 50 to 400 ° C. under a nitrogen atmosphere, and the mass decreased by 5% and 10%. The temperature at the hour (5% by mass reduction temperature and 10% by mass reduction temperature) was measured.

<Preparation of fluorene compound>
[Reference Example 1]

In a 500 mL four-necked eggplant flask, 2,7-dibromofluorene (9.66 g, 30.0 mmol), potassium t-butoxide (t-BuOK, 8.08 g, 72 mmol, 2.4 eq.) And dimethyl sulfoxide (DMSO, 210 mL). ) Was added and heated to 50 ° C. to dissolve, and then benzyl bromide (15.39 g, 90 mmol, 3 eq.) Was added dropwise. After completion of the dropping, the mixture was heated and stirred at 60 ° C. for 3.5 hours. After returning to room temperature, the precipitated white solid is collected by filtration, washed with distilled water, and dried to make 9,9-bis (benzyl) -2,7-dibromofluorene (BMPF-Br) white. Obtained as a solid (10.3 g, yield 68%). ¹ The structure was confirmed by 1 H NMR. From HPLC, the purity was 99%.

^{1 1} H NMR (300 MHz, CDCl ₃ ): δ (ppm) 3.32 (s, 4H), 6.65 (d, 4H), 6.93-7.01 (m, 6H), 7.19-7 .51 (m, 6H).

[Example 1]

BMPF-Br (1.51 g, 3 mmol) was placed in a 100 mL eggplant flask, dried under reduced pressure, dehydrated under a nitrogen atmosphere (THF, 2.5 mL) and trimethylchlorosilane (Me ₃ SiCl, 0.98 g, 9 mmol, 3 eq). ) Was added and dissolved. Magnesium (0.51 g, 21 mmol, 7 eq.) Was placed in another 100 mL eggplant flask, dried under reduced pressure with stirring, and then dehydrated THF (0.5 mL) was added under a nitrogen atmosphere. A solution containing the BMPF-Br was added dropwise to this flask. After completion of the dropping, the mixture was stirred at room temperature for 3 hours. Magnesium was dissolved by adding 10% by weight hydrochloric acid (20 mL) and THF (30 mL) was added to extract the reaction product. The solvent of the organic layer (or the extract) was removed to obtain a pale yellow solid (0.6 g). By purifying the obtained solid by silica gel chromatography (silica gel: 15 g, elution solvent: hexane), 9,9-bis (benzyl) -2,7-bis (trimethylsilyl) fluorene (BMPF-Si) is white crystallized. (0.50 g, yield 34%). ¹ The structure was confirmed by 1 H NMR. From HPLC, the purity was 99%.

^{1 1} H NMR (300 MHz, CDCl ₃ ): δ (ppm) 0.30 (s, 18H) 3.32 (s, 4H), 6.65 (d, 4H), 6.91-7.03 (m) , 6H), 7.35-7.38 (q, 6H).

For the BMPF-Si prepared in Example 1, the excitation spectrum and emission spectrum in the solid state, and the emission quantum efficiency were measured. In the excitation spectrum, the emission intensity at a wavelength of 370 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 1 and FIG.

[Example 2]

2,7-di (t-butyl) -9H-fluorene (8.35 g, 30 mmol), t-BuOK (12.12 g, 108 mmol, 3.6 eq.), And DMSO (200 mL) in a 500 mL four-necked eggplant flask. Was added and heated to 60 ° C. to dissolve it, and then benzyl bromide (18.0 g, 105 mmol, 3.5 eq.) Was added dropwise. After completion of the dropping, the mixture was heated and stirred at 60 ° C. for 5 hours. After returning to room temperature, distilled water (400 mL) was added to obtain an orange powder. This powder is reprecipitated and purified with toluene (40 mL) / methanol (300 mL), and then further purified by silica gel chromatography (silica gel: 50 g, elution solvent: hexane / dichloromethane (volume ratio) = 10/1). 9-Bis (benzyl) -2,7-di (t-butyl) fluorene (BMPF-tBu) was obtained as white crystals (0.85 g, yield 6.2%). ¹ The structure was confirmed by 1 H NMR. From HPLC, the purity was 99%.

^{1 1} H NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.36 (s, 18H), 3.30 (s, 4H), 6.68-6.71 (q, 4H), 6.91-7 .99 (m, 6H), 7.19-7.31 (m, 6H).

For the BMPF-tBu prepared in Example 2, the excitation spectrum and emission spectrum in the solid state, and the emission quantum efficiency were measured. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 1 and FIG.

[Reference Example 2]

Put 9H-fluorene (1.66 g, 10.0 mmol), t-BuOK (3.36 g, 30 mmol, 3.0 eq.) And DMSO (90 mL) in a 500 mL four-necked eggplant flask and heat to 60 ° C to dissolve. After that, benzyl bromide (4.10 g, 24 mmol, 2.4 eq.) Was added dropwise. After completion of the dropping, the mixture was heated and stirred at 60 ° C. for 3.5 hours. After returning to room temperature, distilled water (20 mL) was added to extract the reaction product. The solvent of the organic layer (or the extract) was removed to obtain a pale yellow solid (3.0 g). Recrystallization from a mixed solvent of ethyl acetate (100 mL) / hexane (100 mL), filtration and drying gave 9,9-bis (benzyl) -fluorene (BMPF) as a white solid (2.4 g, yield). Rate 69%). ¹ The structure was confirmed by 1 H NMR. From HPLC, the purity was 99%.

^{1 1} H NMR (300 MHz, CDCl ₃ ): δ (ppm) 3.40 (s, 4H), 6.69 (d, 4H), 6.91-7.01 (m, 6H), 7.17-7 .44 (m, 8H).

For the BMPF prepared in Reference Example 2, the excitation spectrum and emission spectrum in the solid state, and the emission quantum efficiency were measured. In the excitation spectrum, the emission intensity at a wavelength of 360 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 1 and FIG.

[Reference Example 3]

Put 2,7-dibromofluorene (14.9 g, 46 mmol), t-BuOK (12.39 g, 110.4 mmol, 2.4 eq.), And DMSO (300 mL) in a 500 mL four-necked eggplant flask and heat to 50 ° C. After heating to dissolve, (2-bromoethyl) benzene (25.54 g, 138 mmol, 3 eq.) Was added dropwise. After completion of the dropping, the mixture was heated and stirred at 60 ° C. for 5 hours. After returning to room temperature, toluene (490 mL) and distilled water (580 mL) were added, and the reaction product was extracted into an organic layer. Further, the organic layer was washed with distilled water (580 mL × 3 times), and then the solvent of the organic layer was removed to obtain a pale yellow solid. Reprecipitation with toluene (25 mL) / methanol (240 mL) was repeated 3 times at about 70 ° C., and the obtained solid was dried to obtain 9,9-bis (2-phenylethyl) -2,7-dibromofluorene (2,7-dibromofluorene). PEPF-Br) was obtained as a white solid (3.4 g, yield 14%). ¹ The structure was confirmed by 1 H NMR. From HPLC, the purity was 99%.

^{1 1} H NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.86-1.94 (m, 4H), 2.28-2-33 (quin, 4H), 6.93 (q, 4H), 7 .08-7.20 (m, 6H), 7.50-7.61 (m, 6H).

[Example 3]

BEPF-Br (2.13 g, 4 mmol) was placed in a 100 mL eggplant flask, dried under reduced pressure, and dehydrated THF (3 mL) and Me ₃ SiCl (1.3 g, 12 mmol, 3eq.) Were added and dissolved under a nitrogen atmosphere. .. Magnesium (0.68 g, 28 mmol, 7 eq.) Was placed in another 100 mL eggplant flask, dried under reduced pressure with stirring, and then dehydrated THF (0.9 mL) was added under a nitrogen atmosphere. The solution containing BEPF-Br was added dropwise to this flask. After completion of the dropping, the mixture was stirred at room temperature for 3 hours. After returning to room temperature, 10% by mass hydrochloric acid (20 mL) was added to dissolve magnesium, and THF (30 mL) was added to extract the reaction product. The solvent of the organic layer (or the extract) was removed to obtain an orange oily substance (about 1 g). By purifying the obtained oily substance by silica gel chromatography (silica gel: 20 g, elution solvent: hexane), 9,9-bis (2-phenylethyl) -2,7-bis (trimethylsilyl) fluorene (BEPF-) Si) was obtained as white crystals (0.6 g, yield 29%). ¹ The structure was confirmed by 1 H NMR. From HPLC, the purity was 99%.

^{1 1} H NMR (300 MHz, CDCl ₃ ): δ (ppm) 0.34 (s, 18H), 1.92-1.97 (m, 4H), 2.32-2.37 (m, 4H), 6 .89-6.92 (m, 4H), 7.06-7.19 (m, 6H), 7.52-7.77 (m, 6H).

For BEPF-Si prepared in Example 3, the excitation spectrum and emission spectrum in the solid state, and the emission quantum efficiency were measured. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 1 and FIG.

[Reference example 4]

Put 9H-fluorene (1.66 g, 10.0 mmol), t-BuOK (3.36 g, 30 mmol, 3.0 eq.) And DMSO (90 mL) in a 500 mL four-necked eggplant flask and heat to 60 ° C to dissolve. After that, (2-bromoethyl) benzene (4.44 g, 24 mmol, 2.4 eq.) Was added dropwise. After completion of the dropping, the mixture was heated and stirred at 60 ° C. for 5 hours. After returning to room temperature, distilled water (20 mL) was added to extract the reaction product. The solvent of the organic layer (or the extract) was removed to obtain a pale yellow solid (3.2 g). By recrystallization with methanol, filtration and drying, 9,9-bis (2-phenylethyl) fluorene (BEPF) was obtained as a white solid (1.2 g, yield 32%). ¹ The structure was confirmed by 1 H NMR. From HPLC, the purity was 99%.

^{1 1} H NMR (300 MHz, CDCl ₃ ): δ (ppm) 1.86-1.94 (m, 4H), 2.31-2.36 (m, 4H), 6.94 (t, 4H), 7 .06-7.11 (d, 6H), 7.14-7.19 (m, 8H).

For the BEPF prepared in Reference Example 4, the excitation spectrum and emission spectrum in the solid state, and the emission quantum efficiency were measured. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 1 and FIG.

<Light emission characteristics of fluorene compounds>
The excitation spectrum and emission spectrum of the fluorene compound prepared in Examples and Reference Examples in the solid state, and the emission quantum efficiency were measured. Unless otherwise specified in each Example and Reference Example, the emission spectrum was measured by monitoring the emission intensity at a wavelength of 350 nm, and the emission spectrum was measured by excitation light having a wavelength of 280 nm. The results are shown in Table 1 and FIGS. 1-5.

As is clear from Table 1 and FIGS. 1 to 5, the fluorene compounds obtained in the examples have a maximum wavelength λ _{em, max} of 329 to 336 nm and a half width of 20 to 30 nm in a solid state, and have high monochromaticity. It was found that it emits ultraviolet light.

Also, usually, the emission quantum efficiency in the solid state cannot be easily predicted from the molecular structure. In the solid state, the orbital of the molecule, the type (mode) of the molecular motion, and its degree (mode) based on various factors such as the distance and orientation with neighboring molecules, the distortion of the molecular structure, and the unexpected interaction between molecules. This is because the strength) changes. Since it is not possible to design the environment around the molecule, it is extremely difficult to estimate the emission quantum efficiency from the structure of the molecule and to predict the improvement of the emission quantum efficiency by molecular design.

In spite of these circumstances, the fluorene compound obtained in the examples could greatly improve the emission quantum efficiency as compared with the reference example having no substituent on the fluorene ring.

[Example 4]
The BMPF-Si prepared in Example 1 was dissolved in dichloromethane (concentration 6.4 × 10 ^-6 mol / L), and the excitation spectrum and emission spectrum in the solution state, as well as the emission quantum efficiency were measured. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 2 and FIG.

[Example 5]
The BMPF-tBu prepared in Example 2 was dissolved in dichloromethane (concentration 6.4 × 10 ^-6 mol / L), and the excitation spectrum and emission spectrum in the solution state, as well as the emission quantum efficiency were measured. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 2 and FIG.

[Reference Example 5]
The BMPF prepared in Reference Example 2 was dissolved in dichloromethane (concentration 6.4 × 10 ^-6 mol / L), and the excitation spectrum and emission spectrum in the solution state, and the emission quantum efficiency were measured. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 2 and FIG.

[Example 6]
BEPF-Si prepared in Example 3 was dissolved in dichloromethane (concentration 6.4 × 10 ^-6 mol / L), and the excitation spectrum and emission spectrum in a solution state, and emission quantum efficiency were measured. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 2 and FIG.

[Reference Example 6]
The BEPF prepared in Reference Example 4 was dissolved in dichloromethane (concentration 6.4 × 10 ^-6 mol / L), and the excitation spectrum and emission spectrum in the solution state, as well as the emission quantum efficiency were measured. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 2 and FIG.

As is clear from Table 2 and FIGS. 6 to 10, the fluorene compounds obtained in the examples have a maximum wavelength λ _{em, max} of 318 to 329 nm and a half width of 25 to 30 nm in a solution state, and have high monochromaticity. It was found to emit ultraviolet light. In addition, the fluorene compound obtained in Example was able to greatly improve the emission quantum efficiency as compared with the reference example having no substituent on the fluorene ring, and the tendency was particularly remarkable in Example 4.

[Example 7]
0.01 g of BMPF-Si prepared in Example 1 and 0.01 g of polystyrene (PS, PS Japan Corporation) are mixed with chloroform so that the solid content concentration is 1% by mass, and a mixed solution ( Coating agent) was prepared. This coating agent is applied on a quartz substrate (“Labo-USQ” manufactured by Daiko Seisakusho Co., Ltd.) with a spin coater (“1H-D7” manufactured by Mikasa Co., Ltd., 1000 rpm), and is applied on a hot plate at 90 ° C. and 30 ° C. It was dried for a minute to form a coating film. The excitation spectrum, emission spectrum, and emission quantum efficiency were measured using the formed coating film. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 3 and FIG.

[Example 8]
A coating film was formed in the same manner as in Example 7 except that BMPF-tBu prepared in Example 2 was used instead of BMPF-Si. The excitation spectrum, emission spectrum, and emission quantum efficiency were measured using the formed coating film. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 3 and FIG.

[Reference Example 7]
A coating film was formed in the same manner as in Example 7 except that BMPF-Br prepared in Reference Example 1 was used instead of BMPF-Si. The excitation spectrum and the emission spectrum were measured using the formed coating film. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 3 and FIG.

[Example 9]
A coating film was formed in the same manner as in Example 7 except that BEPF-Si prepared in Example 3 was used instead of BMPF-Si. The excitation spectrum, emission spectrum, and emission quantum efficiency were measured using the formed coating film. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 3 and FIG.

[Example 10]
Apply in the same manner as in Example 7 except that BEPF-Si prepared in Example 3 is used instead of BMPF-Si and polycarbonate (PC, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) is used instead of PS. A film was formed. The excitation spectrum, emission spectrum, and emission quantum efficiency were measured using the formed coating film. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 3 and FIG.

[Example 11]
Apply in the same manner as in Example 7 except that BEPF-Si prepared in Example 3 is used instead of BMPF-Si and polymethylmethacrylate (PMMA, manufactured by Mitsubishi Rayon Co., Ltd.) is used instead of PS. A film was formed. The excitation spectrum, emission spectrum, and emission quantum efficiency were measured using the formed coating film. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 3 and FIG.

[Example 12]
Except for using BEPF-Si prepared in Example 3 in place of BMPF-Si and polyphenylsilsesquioxane (PPSQ) prepared in Synthesis Example 1 described later in place of PS, the same as in Example 7. A coating film was formed in the same manner. The excitation spectrum, emission spectrum, and emission quantum efficiency were measured using the formed coating film. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 3 and FIG.

[Synthesis Example 1]
1 mmol of trimethoxyphenylsilane, 1.5 mL of tetrahydrofuran as a solvent, formic acid (60 μL) as an acid catalyst, and water (60 μL) are mixed and heated and stirred at 90 ° C. for 3 hours for hydrolysis reaction and condensation reaction. Was performed and dried. After allowing to cool, wash away the residual acid with pure water, then add 1.5 mL of tetrahydrofuran to make a solution again, heat and stir at 110 ° C. for 2 hours, and dry to dry to polyphenylsilsesquioxane (PPSQ). , A compound represented by the following formula) was synthesized.

In Reference Example 7, the luminescence was low and the emission quantum efficiency could not be measured.

As is clear from Table 3 and FIGS. 11 to 17, it was found that in the examples, near-ultraviolet light having a wavelength of 318 to 336 nm and a half width of 25 to 40 nm was emitted. Further, in the examples, it can be seen that even if a coating film is formed, it emits near-ultraviolet light having a narrow half-value width as in the solid state or the solution state, so that it can be effectively used as a coating agent such as security ink. ..

[Example 13]
0.01 g of BMPF-Si prepared in Example 1 and 0.1 g of polystyrene (PS) described in Example 7 are mixed with chloroform so that the solid content concentration is 5% by mass, and a mixed solution (coating agent) is used. ) Was prepared, and a coating film was formed in the same manner as in Example 7. The excitation spectrum, emission spectrum, and emission quantum efficiency were measured using the formed coating film. In the excitation spectrum, the emission intensity at a wavelength of 370 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 4 and FIG.

[Example 14]
A coating film was formed in the same manner as in Example 13 except that 0.01 g of BMPF-tBu prepared in Example 2 was used instead of BMPF-Si. The excitation spectrum, emission spectrum, and emission quantum efficiency were measured using the formed coating film. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 4 and FIG.

[Example 15]
A coating film was formed in the same manner as in Example 13 except that 0.01 g of BEPF-Si prepared in Example 3 was used instead of BMPF-Si. The excitation spectrum, emission spectrum, and emission quantum efficiency were measured using the formed coating film. In the excitation spectrum, the emission intensity at a wavelength of 350 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 280 nm was used for measurement. The results are shown in Table 4 and FIG.

[Example 16]
Same as Example 13 except that 0.01 g of BEPF-Si prepared in Example 3 is used instead of BMPF-Si, and 0.1 g of the polycarbonate (PC) described in Example 10 is used instead of PS. To form a coating film. The excitation spectrum, emission spectrum, and emission quantum efficiency were measured using the formed coating film. In the excitation spectrum, the emission intensity at a wavelength of 370 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 270 nm was used for measurement. The results are shown in Table 4 and FIG.

[Example 17]
Example 13 except that 0.01 g of BEPF-Si prepared in Example 3 was used instead of BMPF-Si, and 0.1 g of polymethylmethacrylate (PMMA) described in Example 11 was used instead of PS. A coating film was formed in the same manner. The excitation spectrum, emission spectrum, and emission quantum efficiency were measured using the formed coating film. In the excitation spectrum, the emission intensity at a wavelength of 370 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 270 nm was used for measurement. The results are shown in Table 4 and FIG.

[Example 18]
This was carried out except that 0.01 g of BEPF-Si prepared in Example 3 was used instead of BMPF-Si, and 0.1 g of the polyphenylsilsesquioxane (PPSQ) described in Example 12 was used instead of PS. A coating film was formed in the same manner as in Example 13. The excitation spectrum, emission spectrum, and emission quantum efficiency were measured using the formed coating film. In the excitation spectrum, the emission intensity at a wavelength of 370 nm was monitored and measured, and in the emission spectrum, the emission light at a wavelength of 270 nm was used for measurement. The results are shown in Table 4 and FIG.

As is clear from Table 4 and FIGS. 18 to 23, in Examples 13 to 18 in which the mass ratio of the fluorene compound and the binder component was the former / the latter = 1/10, the mass ratio was the former / the latter = 1 /. Compared with Examples 7 to 12, which is No. 1, the emission quantum efficiency could be greatly improved. In Examples 13 to 18, it is presumed that the influence of concentration quenching was reduced.

<Heat resistance of fluorene compounds>
The 5% by mass reduction temperature and the 10% by mass reduction temperature of the fluorene compound prepared in Examples and Reference Examples were measured. The results are shown in Table 5.

As is clear from Table 5, the fluorene compound prepared in the examples had higher heat resistance than the fluorene compound prepared in the reference example.

The light emitting material (or ultraviolet light emitting fluorene compound) of the present invention is soluble in an organic solvent unlike an inorganic light emitting substance formed of an inorganic material, and is easily uniformly dispersed in a matrix material such as various resins. , A coating layer or a coating film can be easily or efficiently formed on a substrate having a complicated shape. Therefore, the light emitting material of the present invention can be effectively used, for example, as a coating agent for invisible ink, a photoelectric conversion element, and the like.

Examples of the photoelectric conversion element include a current injection type light emitting element such as an organic EL element. A typical example is an ultraviolet light source (UV lamp), and specifically, it can be effectively used for various applications such as sterilization, analysis, and high color rendering white LED light source. ..

Further, since the novel fluorene compound of the present invention is also excellent in heat resistance, it can be effectively used as an additive such as a heat resistance improver and a resin modifier.

Claims (12)

The following formula (1)

(In the formula, A is an independently linear or branched alkylene group, Z is an independent allene ring, and R ¹ is an independently linear or branched alkyl group or trialkylsilyl group. , R ² are independent substituents other than R ¹ , R ³ are independent substituents, k1 and k2 are independently integers of 1 to 4, and m1 and m2 are independently 0 to 0 to each. The integer of 3 and n each independently indicate an integer of 0 or more, and k1 + m1 and k2 + m2 are independently integers of 1 to 4).
Luminescent material represented by. In formula (1), A is a linear or branched C _1-6 alkylene group, Z is a C _6-14 arene ring, R ¹ is a branched alkyl group or a tri C _1-6 alkylsilyl group, k1. The light emitting material according to claim 1, wherein k2 is an integer of 1 to 2, and m1 and m2 are integers of 0 to 2. In formula (1), A is a linear or branched C _1-4 alkylene group, Z is a benzene ring, a naphthalene ring or a biphenyl ring, and R ¹ is a branched C _3-10 alkyl group or tri C _1- . ₄ The light emitting material according to claim 1 or 2, wherein the alkylsilyl group, k1 and k2 are 1. The following formula (1a)

(In the formula, A, Z, R ¹ , R ² , R ³ , m1, m2, and n are the same as those in the above formula (1), respectively.)
The light emitting material according to any one of claims 1 to 3. Any of claims 1 to 4 in which the emission spectrum in the solid state includes at least one emission peak having a maximum wavelength λ _{em, max} of 300 to 400 nm and a half width of 50 nm or less, and an emission quantum efficiency of 12% or more. Luminous material described in Crab. An ultraviolet light emitting composition comprising the light emitting material according to any one of claims 1 to 5. The ultraviolet light emitting composition according to claim 6, further comprising a binder component. The ultraviolet light emitting composition according to claim 6 or 7, which is a coating agent. The coating film formed of the ultraviolet light emitting composition according to any one of claims 6 to 8 is irradiated with light, and the ultraviolet light emitted by the coating film is detected by a detection device including a spectroscope and a detector. how to. A light emitting device containing the light emitting material according to any one of claims 1 to 5. The following formula (1)

(In the formula, A is an independently linear or branched alkylene group, Z is an independent allene ring, R ¹ is an independent trialkylsilyl group, and R ² is an independent R. Substituents other than ¹ , R3 ^are independent substituents, k1 and k2 are independently integers of 1 to 4, m1 and m2 are independently integers of 0 to 3, and n are independent. It indicates an integer of 0 or more, and k1 + m1 and k2 + m2 are independently integers of 1 to 4).
Fluorene compound represented by. The following formula (2)

(In the formula, R ⁴ indicates a group capable of producing R ¹ or R ¹ , and R ¹ , R ² , k1, k2, m1 and m2 are the same as in claim 11.)
Fluorene represented by and the following formula (3)

(In the formula, X ² represents a halogen atom, and A, Z, R ³ and n are the same as in claim 11.)
The method for producing a fluorene compound according to claim 11, which comprises a step of reacting with the compound represented by.

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