JP2005154404A - Blue color light-emitting compound, blue color light-emitting polymer, method for producing blue color light-emitting compound and light-emitting element utilizing blue color light-emitting polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light-emitting compound and light-emitting polymer, capable of emitting blue color light for a long period and excellent in durability. <P>SOLUTION: This blue color light-emitting compound having a structure expressed by general formula (1). The method for producing the blue color light-emitting compound having the structure expressed by formula (1) is provided by performing the reaction of a halogen compound expressed by a specific formula with a hydrazide compound to obtain an intermediate compound and then subjecting the intermediate to dehydration and dehydrohalogenation. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a blue light-emitting compound, a blue light-emitting polymer, a method for producing a blue light-emitting compound, and a light-emitting element using the blue light-emitting polymer, and more specifically, high luminance and long light emission time when electrically applied energy is applied. The present invention relates to a blue light emitting compound and a blue light emitting polymer capable of emitting blue light, and further relates to a method for producing a blue light emitting compound and a light emitting device using the blue light emitting polymer.

  Conventionally, various light-emitting compounds and light-emitting polymers have been proposed as organic light-emitting elements (also referred to as organic EL elements). However, the present situation is that a light-emitting compound and a light-emitting polymer that can emit blue light and can have a longer light emission time and have excellent durability have not yet been developed.

  An object of the present invention is to provide a blue light-emitting compound and a blue light-emitting polymer that can ensure high light emission luminance, can emit light over a long period of time, and have excellent durability, and a method for producing a blue light-emitting compound and An object of the present invention is to provide a light emitting element using a blue light emitting polymer.

  A first means of the present invention for solving the above problems is a blue light emitting compound having a structure represented by the following general formula (1).

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a substituent represented by the following general formula (2), and the two R ^{1 s} are the same or different from each other. In addition, n represents an integer of 1 to 4.)

(However, in the formula, R ² represents an aryl group represented by the following general formulas (2-1) to (2-8).)

(In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and q represents an integer of 1 to 5)

(Wherein, R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxyl group having an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ are the same as each other. And p represents an integer of 1 to 4, and r represents an integer of 1 to 3.)

(However, in the formula, R ⁴ , R ⁵ , p and r have the same meaning as described above, and R ⁴ and R ⁵ may be the same as or different from each other.)

(In the formula, R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁶ , R ⁷ and R ⁸ may be the same or different from each other. Moreover, p and r have the same meaning as described above, and s represents an integer of 1 or 2.)

(However, in the formula, R ⁶ , R ⁷ , R ⁸ , p, r, and s have the same meaning as described above, and R ⁶ , R ^7, and R ⁸ are the same as or different from each other. May be.)

(In the formula, R ⁶ , R ⁷ , R ⁸ and p have the same meaning as described above, and R ⁶ , R ⁷ and R ⁸ may be the same or different from each other. .)

(In the formula, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

(In the formula, R ¹² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and two R ^{12 s} may be the same or different from each other. It has the same meaning as above.)

  A second means is a blue light-emitting compound characterized by having a structure represented by the following general formula (1 ′).

(In the formula, R ¹ ′ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a substituent represented by the following general formula (2 ′), and the two R ¹ ′ are identical to each other. And n is an integer of 1 to 4.)

(Wherein, R ² represents an aryl group represented by the general formulas (2-1) to (2-8) or a substituent represented by the following general formula (2′-1), and m represents Represents an integer of 0 to 3.)

(In the formula, Ar ¹ represents a phenylene group, a naphthylene group or an anthrylene group, and R ^{2 ′} represents an aryl group represented by the general formulas (2-1) to (2-8)).

  The third means is to dehydrate and dehydrohalogenate an intermediate represented by the following general formula (5) obtained by reacting a halogen compound represented by the following general formula (4) with a hydrazide compound. This is a method for producing a blue light-emitting compound having the structure represented by the general formula (1).

(In the formula, X ¹ and two X ² represent a halogen atom, and X ¹ and two X ² may be the same or different from each other. It is as shown in the means.)

(However, in the formula, R ² , X ¹ and p have the same meaning as described above. Note that two R ² may be the same or different from each other.)

  The fourth means is the dehydrohalogenation reaction of the organic halogen compound represented by the following general formula (5 ′) produced by the Friedel-Crafts reaction of the halogen compound represented by the following general formula (4 ′). A method for producing a blue light-emitting compound having a structure represented by the general formula (1 ′).

(However, in the formula, X ¹ is as described in the third means.)

(In the formula, R ² , X ¹ and m have the same meanings as the second means and the third means.)

  The fifth means is a blue light-emitting polymer comprising a repeating unit represented by the following general formula (1 ″).

(However, in the formula, R ¹ and n are as described in the first means.)
The sixth means is a blue light-emitting polymer comprising a repeating unit represented by the following general formula (1 ′ ″).

(In the formula, R ¹ ′ and n are as described in the second means.)

  The seventh means is characterized in that a light emitting layer containing a blue light emitting polymer composed of a repeating unit represented by the general formula (1 ″) or (1 ′ ″) is provided between a pair of electrodes. It is a light emitting element.

  According to the present invention, it is possible to provide a blue light emitting compound and a blue light emitting polymer that can ensure high light emission luminance and can emit light over a long period of time, and further, a method for producing a blue light emitting compound and a blue light emitting polymer are used. A light-emitting element can be provided.

  The blue light-emitting compound according to the present invention has a structure represented by the following general formula (1).

The blue light-emitting compound has N-vinylcarbazole as a basic skeleton (hereinafter referred to as a carbazole skeleton), and R ¹ is bonded to each of two benzene rings in the carbazole skeleton. The blue light-emitting compound has a structure in which a vinyl group is bonded to nitrogen of the carbazole.

N in the general formula (1) represents an integer of 1 to 4, and one benzene ring in the carbazole skeleton can be bonded to ¹ to 4 R ¹ .

Moreover, two R ¹ in the said General formula (1) may mutually be same or different.

R ¹ in the general formula (1) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. Group, sec-pentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc., among which methyl group, ethyl group, propyl group, isopropyl group, n- Alkyl groups having 1 to 5 carbons such as butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, tert-pentyl group and the like are preferable.

R ¹ in the general formula (1) represents a substituent represented by the following general formula (2). In the formula, the numbers 1 to 5 indicate position numbers.

The substituent represented by the general formula (2) has 1,3,4-oxadiazole as a basic skeleton, and the carbon at the 5-position is bonded to R ² .

R ² in the general formula (2) represents an aryl group represented by the following general formulas (2-1) to (2-8).

The aryl group represented by the general formula (2-1) has a phenyl group as a basic skeleton, and is bonded to at most five R ³ groups.

R ³ in the general formula (2-1) represents a hydrogen atom or an alkyl group having 1 to 10 carbons, and q represents an integer of 1 to 5.

  Examples of the alkyl group having 1 to 10 carbons include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec -Pentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group etc. can be mentioned, among them, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, Alkyl groups having 1 to 5 carbon atoms such as isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group and tert-pentyl group are preferred.

R ² in the general formula (2) can be represented by an aryl group represented by the following general formula (2-2). In the formula, numerals 1 to 8 indicate position numbers.

The aryl group represented by the general formula (2-2) has a naphthyl group as a basic skeleton, and is bonded to R ⁴ at the 2-position, 3-position, or 4-position to form the 5-position, 6-position, 7-position, or 8 In the position, it binds to R ⁵ .

R ⁴ and R ⁵ in the general formula (2-2) represent a hydrogen atom or an alkyl group having 1 to 10 carbons.

  Examples of the alkyl group having 1 to 10 carbons include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec -Pentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group etc. can be mentioned, among them, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, Alkyl groups having 1 to 5 carbon atoms such as isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group and tert-pentyl group are preferred.

P in the general formula (2-2) represents an integer of 1 to 4, and the naphthyl group in the general formula (2-2) is bonded to at most four R ⁵ .

Further, r is showed integer of 1 to 3, a naphthyl group in the general formula (2-2) binds to three ^{R 4} most.

The R ⁴ and R ⁵ may be the same or different from each other.

R ² in the general formula (2) can be represented by an aryl group represented by the following general formula (2-3). In the formula, numerals 1 to 8 indicate position numbers.

The aryl group represented by the general formula (2-3) has a naphthyl group as a basic skeleton, and is bonded to R ⁴ at the 1-position, 3-position and / or 4-position, and the 5-position, 6-position, 7-position And / or at position 8 it binds R ⁵ .

R ⁴ , R ⁵ , p and r in the general formula (2-3) have the same meaning as described above, and the naphthyl group in the general formula (2-3) is bonded to at most three R ^4. And at most four R ⁵ bonds.

The R ⁴ and R ⁵ may be the same or different from each other.

Furthermore, R ² in the general formula (2) can represent an aryl group represented by the following general formula (2-4). In the formula, the numbers 1 to 10 indicate position numbers.

The aryl group represented by the general formula (2-4) has a 2-anthryl group as a basic skeleton, and is bonded to R ⁶ at the 1-position, 3-position and / or 4-position, and 5-position, 6 It binds to R ^{8 at} the position, 7 and / or 8 position, and further binds to R ^{7 at} the 9 and / or 10 position.

R ⁶ , R ⁷ and R ⁸ in the general formula (2-4) represent a hydrogen atom or an alkyl group having 1 to 5 carbons.

  Examples of the alkyl group having 1 to 5 carbons include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec -Pentyl group, tert-pentyl group and the like can be mentioned.

P in the general formula (2-4) represents an integer of 1 to 4, and the 2-anthryl group in the general formula (2-4) is bonded to at most four R ⁸ .

R in the general formula (2-4) represents an integer of 1 to 3, and the 2-anthryl group in the general formula (2-4) is bonded to at most three R ⁶ .

Furthermore, s in the general formula (2-4) represents an integer of 1 to 2, and the 2-anthryl group in the general formula (2-4) is bonded to at most two R ⁷ .

In the general formula (2-4), R ⁶ , R ⁷ and R ⁸ may be the same or different from each other.

R ² in the general formula (2) can be represented by an aryl group represented by the following general formula (2-5). In the formula, numbers 1 to 10 indicate position numbers.

The aryl group represented by the general formula (2-5) has a 1-anthryl group as a basic skeleton, and is bonded to R ⁶ at the 2nd, 3rd, or 4th position, and the 5th, 6th position, It binds to R ^{8 at the} 7-position and / or 8-position, and further binds to R ^{7 at} the 9-position and / or 10-position.

R ⁶ , R ⁷ , R ⁸ , p, r and s in the general formula (2-5) have the same meaning as described above, and the 1-anthryl group in the general formula (2-5) is at most bonded to three R ^6, also bound to four R ^8, further binds to two R ⁷ most.

In the general formula (2-5), R ⁶ , R ⁷ and R ⁸ may be the same as or different from each other.

Furthermore, R ² in the general formula (2) can be represented by an aryl group represented by the following general formula (2-6). In the formula, numbers 1 to 10 indicate position numbers.

The aryl group represented by the general formula (2-6) has a 9-anthryl group as a basic skeleton, and is bonded to R ⁶ at the 1-position, 2-position, 3-position and / or 4-position, It binds to R ^{8 at} the position, 6-position, 7-position and / or 8-position, and further binds to R ^{7 at the} 10-position.

R ⁶ , R ⁷ , R ⁸ , p, r and s in the general formula (2-6) have the same meaning as described above, and the 9-anthryl group in the general formula (2-6) is at most It binds to four R ⁶ and R ⁸ and further binds to one R ⁷ .

In the general formula (2-6), R ⁶ , R ⁷ and R ⁸ may be the same or different from each other.

Furthermore, R ² in the general formula (2) can be represented by an aryl group represented by the following general formula (2-7). In the formula, numerals 1 to 9 indicate position numbers.

The substituent represented by the general formula (2-7) has fluorene as a basic skeleton, and is bonded to the carbon of the oxadiazol ring of the general formula (2) or (3) at the 7-position, The carbon in position is bonded to two R ¹³ .

R ¹³ in the general formula (2-7) represents a hydrogen atom or an alkyl group having 1 to 10 carbons, and examples of the alkyl group having 1 to 10 carbons include a methyl group, an ethyl group, and propyl Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group Decyl group, etc., among which methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group Group, a C1-C5 alkyl group, such as a tert-pentyl group, is preferable, and a C1-C3 alkyl group is especially preferable.

In addition, two R ¹³ in the general formula (2-7) may be the same as or different from each other.

Furthermore, R ² in the general formula (2) can be represented by an aryl group represented by the following general formula (2-8). In the formula, the numbers 1 to 4 and 1 ′ to 4 ′ indicate position numbers.

  The substituent represented by the general formula (2-8) has biphenyl as a basic skeleton. For example, as shown in the formula (2-8), the substituent represented by the general formula (2) or (3 ) In the oxadiazol ring.

R ¹² in the general formula (2-8) represents a hydrogen atom or an alkyl group having 1 to 10 carbons, and examples of the alkyl group having 1 to 10 carbons include a methyl group, an ethyl group, and propyl Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group Decyl group, etc., among which methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group And an alkyl group having 1 to 5 carbon atoms such as a tert-pentyl group.

Incidentally, the two R ¹² in the general formula (2-8) may be different even identical to each other.

P in the formula (2-8) has the same meaning as described above, q represents an integer of 1 to 5, and the biphenyl group in the general formula (2-8) has at most nine R ^12. Combine with.

  The blue light-emitting compound according to the present invention has a structure represented by the following general formula (1 ').

The blue light-emitting compound represented by the general formula (1 ′) has N-vinylcarbazole as a basic skeleton (hereinafter referred to as a carbazole skeleton), and R ¹ ′ is bonded to each of two benzene rings in the carbazole skeleton. The blue light-emitting compound has a structure in which a vinyl group is bonded to nitrogen of the carbazole skeleton.

N in the general formula (1 ′) represents an integer of 1 to 4, and one benzene ring in the carbazole skeleton can be bonded to ^{1 to} 4 R ¹ ′.

Moreover, two R ¹ ′ in the general formula (1) may be the same or different from each other.

R ¹ ′ in the general formula (1 ′) represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ ′ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- A pentyl group, a sec-pentyl group, a tert-pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like can be mentioned. Among them, a methyl group, an ethyl group, a propyl group, an isopropyl group, Alkyl groups having 1 to 5 carbon atoms such as -butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group and tert-pentyl group are preferred.

In the general formula (1 ′), R ¹ ′ represents a substituent represented by the following general formula (2 ′).

R ² in the general formula (2 ′) represents a substituent represented by the general formulas (2-1) to (2-8).

M in the general formula (2 ′) represents an integer of 0 to 3, and is interposed between the carbon of the benzene ring in the general formula (1 ′) and R ² in the general formula (2 ′). Represents the number of bonds of the methylene group.

Furthermore, R ² in the general formula (2 ′) represents a substituent represented by the following general formula (2′-1).

The substituent represented by the general formula (2′-1) is composed of Ar ¹ , 1,3,4-oxadiazol and R ^{2 ′} .

Ar ¹ represents an anthrylene group which is a group formed by losing two hydrogens from a phenylene group, a naphthylene group and an anthracene.

One carbon of the 1,3,4-oxadiazol is bonded to R ^{2 ′,} and the other carbon is bonded to Ar ¹ .

Further, Ar ¹ is an alkylene group in the general formula (2 ′) when m is 1 to 3, and a benzene in the general formula (1 ′) when m is 0. Bonds to ring carbon.

The carbon of the alkylene group or benzene ring in the general formula (2 ′) and the carbon of the 1,3,4-oxadiazol are bonded to the Ar ^{1 in the} following positional relationship, for example.

For example, when Ar ¹ is a phenylene group and the carbon of the alkylene group or benzene ring in the general formula (2 ′) is bonded to the carbon at the 1-position of the phenylene group, the 1,3,4- The carbon possessed by the oxadiazol can be bonded to the 3rd or 4th carbon of the phenylene group.

Further, when Ar ¹ is a naphthylene group and the carbon of the alkylene group or benzene ring in the general formula (2 ′) is bonded to the carbon at the 1-position of the naphthylene group, the 1,3,4- The carbon possessed by the oxadiazol can be bonded to the 3rd, 4th, 5th, 6th or 7th carbon of the naphthylene group.

Further, when Ar ¹ is a naphthylene group and, for example, the alkylene group or carbon of the benzene ring in the general formula (2 ′) is bonded to the carbon at the 2-position of the naphthylene group, the 1,3, The carbon possessed by 4-oxadiazol can be bonded to the 4th, 5th, 6th, 7th or 8th carbon of the naphthylene group.

When Ar ¹ is an anthrylene group, for example, when the carbon of the alkylene group or the benzene ring in the general formula (2 ′) is bonded to the carbon at the 1-position of the anthrylene group, the 1,3, The carbon of 4-oxadiazol can be bonded to the 3rd, 4th, 5th, 6th, 7th, 8th or 10th carbon of the anthrylene group.

Further, when Ar ¹ is an anthrylene group and, for example, the alkylene group or the carbon of the benzene ring in the general formula (2 ′) is bonded to the carbon at the 2-position of the anthrylene group, the 1,3, The carbon possessed by 4-oxadiazol can be bonded to the 4th, 5th, 6th, 7th, 8th, 9th or 10th carbon of the anthrylene group.

Furthermore, when Ar ¹ is an anthrylene group and, for example, the alkylene group or carbon of the benzene ring in the general formula (2 ′) is bonded to the 9-position carbon of the anthrylene group, the 1,3, The carbon possessed by 4-oxadiazol can be bonded to the 2nd, 3rd, 4th, 5th, 6th, 7th or 10th carbon of the anthrylene group.
R2 ′ in the formula (2′-1) represents a substituent represented by any one of the formulas (2-1) to (2-8).

  The blue light-emitting compound represented by the general formula (1) can be produced as follows.

  That is, by heating carbazole and 2-halogenated ethyl-p-toluenesulfonate as starting materials in a solvent, a hydrogen atom bonded to a nitrogen atom in the carbazole is substituted with an alkyl halide.

  Examples of the solvent include ethanol, methanol, acetic anhydride, acetic acid, ether, acetone and the like.

  The temperature in the reaction of substituting the hydrogen atom with an alkyl halide is 40 to 80 ° C, preferably 50 to 70 ° C.

  After completion of the reaction, N-2- (ethyl halide) carbazole is obtained by purification and separation according to conventional methods.

  Next, by heating the N-2- (ethyl halide) carbazole and phosphoryl chloride in a solvent to formylate the aldehyde compound obtained by further oxidation, a carboxylic acid compound obtained by oxidation and a halogenating agent To obtain a halogen compound represented by the following general formula (4).

X ¹ and X ² in the general formula (4) represent a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, p represents an integer of 1 to 4, and one molecule of the benzene ring represents At most four haloformyl groups (—COX ² ) can be bonded.

X ¹ and X ² in the general formula (4) may be the same or different from each other.

  Solvents used in the formylation include ethanol, methanol, formic acid, acetic anhydride, acetic acid, diethyl ether, epoxide, acid anhydrides having 5 or less carbon atoms, dichloroethane, dichloromethane, trichloroethane, chloroform, carbon tetrachloride, benzene, Examples include toluene, pyridine, dioxane, DMF, and THF.

  In the formylation, a catalyst can be appropriately used. Examples of the catalyst include aluminum chloride, zinc chloride, zinc cyanide, thionyl chloride, phosphoryl chloride and the like.

  The reaction temperature in the formylation is 60 to 100 ° C, preferably 75 to 95 ° C.

  Examples of the halogenating agent include general agents such as thionyl chloride, sulfenyl chloride, sulfuryl chloride, phosphoryl chloride, phosphorus trichloride, phosphorus pentachloride, hydrogen fluoride, chlorine trifluoride, phosphorus trifluoride, five Examples thereof include iodine fluoride, hydrogen bromide, hypobromite, thionyl bromide, etc. Among them, thionyl chloride, sulfenyl chloride, and sulfuryl chloride are preferable.

  After completion of the reaction, a halogen compound is obtained by purification and separation according to a conventional method.

  Next, the reaction proceeds easily by heating the halogen compound represented by the general formula (4) and the hydrazide compound represented by the formula (4a) to 50 to 80 ° C. in a solvent, and the following general formula ( The intermediate shown in 5) can be obtained.

なお、前記式（４ａ）におけるＲ^２は前記と同様の意味を示す。

In the formula (4a), R ² has the same meaning as described above.

X ¹ in the general formula (5) has the same meaning as described above, and p represents an integer of 1 to 4.

  Examples of the solvent include acetic anhydride, acetic acid, acid anhydrides having 5 or less carbon atoms, aromatic solvents such as benzene and toluene, and polycyclic compound solvents such as pyridine, dioxane, DMF, and THF. it can.

  The blue light-emitting compound according to the present invention can be obtained by subjecting the intermediate obtained as described above to dehydration and dehalogenation reactions.

  Examples of the dehydrating agent used in the dehydration reaction include phosphorus pentoxide, phosphorus pentachloride, phosphorus pentasulfide, phosphorus trichloride, thionyl chloride, sulfonyl chloride, phosphoryl chloride and other inorganic dehydrating agents, acetic anhydride, and carbon number of 5 or less. Among them, organic dehydrating agents such as acid anhydrides can be mentioned, among which inorganic dehydrating agents are preferable, and this reaction proceeds easily at 100 to 150 ° C.

  By the dehydration reaction, a dehydration reaction occurs between the hydrogen atom of the hydrazo group (—NHNH—) and the oxygen atom of the carbonyl group, and at the same time, an oxadiazol ring is formed.

  The dehalogenation reaction proceeds easily at a temperature of 50 to 150 ° C., preferably 70 to 120 ° C., by a known method.

  After completion of the reaction, the blue light-emitting monomer according to the present invention can be obtained by performing purification and separation according to a conventional method.

  When the blue light-emitting compound is heated in an organic solvent to undergo a polymerization reaction, the blue light-emitting polymer according to the present invention can be obtained.

  Examples of the solvent include benzene, toluene, ether, THF, DMF, and the like. These solvents can be used alone or in admixture of two or more.

  The temperature in the polymerization reaction is 60 to 120 ° C, preferably 80 to 100 ° C.

  The blue light-emitting compound represented by the general formula (1 ′) can be produced as follows.

  That is, by heating the starting materials carbazole and 2-halogenated ethyl-p-toluenesulfonate in a solvent, a hydrogen atom bonded to a nitrogen atom in the carbazole is substituted with an alkyl halide, and the following: N-2- (ethyl halide) carbazole represented by the general formula (4 ′) is obtained.

X ¹ in the general formula (4 ′) represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

  Examples of the solvent include ethanol, methanol, acetic anhydride, acetic acid, ether, acetone and the like.

  The temperature in the reaction of substituting the hydrogen atom with an alkyl halide is 40 to 80 ° C, preferably 50 to 70 ° C.

  After completion of the reaction, N-2- (ethyl halide) carbazole represented by the general formula (4 ') is obtained by purification and separation according to a conventional method.

Next, N-2- (halogenated ethyl) carbazole represented by the general formula (4 ′) and a halogen compound represented by the general formula: R ² —CH ₂ CH ₂ X ² are added in a solvent to which a catalyst is added. By heating to 140 to 160 ° C., the reaction easily proceeds and an organic halogen compound represented by the following general formula (5 ′) can be obtained.

X ¹ and R ² in the general formula (5 ′) have the same meaning as described above, and m represents an integer of 0 to 3.

Further, the ^{formula: X 2} in the R ^₂ -CH _{2 CH 2} ^X ₂ represents a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom.

  The organic halogen compound can be obtained by heating an aromatic hydrocarbon in a solvent while introducing a hydrogen halide gas.

  Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, biphenyl, and derivatives thereof. Among these, benzene, naphthalene, and derivatives thereof are preferable.

  Examples of the benzene derivative include toluene, o-xylene, m-xylene, p-xylene and the like.

  Examples of the naphthalene derivative include 1-methylnaphthalene, 2-methylnaphthalene monomethylnaphthalene, 1,2-dimethylnaphthalene, 1,3-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1,5-dimethylnaphthalene, Dimethylnaphthalene such as 1,6-dimethylnaphthalene and 1,7-dimethylnaphthalene or trimethylnaphthalene such as 1,3,4-trimethylnaphthalene 1,3,5-trimethylnaphthalene and the like.

  Examples of the solvent include acetic anhydride, acetic acid, acid anhydrides having 5 or less carbon atoms, aromatic solvents such as benzene and toluene, and polycyclic compound solvents such as pyridine, dioxane, DMF, and THF. it can.

  Examples of the hydrogen halide gas include hydrogen fluoride gas and hydrogen chloride gas.

  The concentration of the hydrogen halide gas may be 100%, but is preferably 1 to 95%. Further, it is preferable to use an inert gas such as nitrogen gas or argon gas as the gas for dilution.

  The reaction temperature is preferably 40 to 60 ° C, particularly 50 to 55 ° C.

  As a catalyst in the reaction for producing the organic halogen compound represented by the general formula (5 '), aluminum chloride, zinc, sulfuric acid and the like can be raised.

  Examples of the solvent in the reaction for producing the organic halogen compound represented by the general formula (5 ′) include acetic anhydride, acetic acid, acid anhydrides having 5 or less carbon atoms, aromatic solvents such as benzene and toluene, Examples thereof include polycyclic compound solvents such as pyridine, dioxane, DMF, and THF.

  The organic halogen compound obtained as described above is subjected to dehydrohalogenation reaction, and after completion of the reaction, purification and separation are performed according to a conventional method, whereby the blue color represented by the general formula (1 ′) is obtained. A luminescent compound can be obtained.

  Furthermore, when the blue light-emitting compound is heated in an organic solvent to undergo a polymerization reaction, a blue light-emitting polymer represented by the general formula (1 ′ ″) can be obtained.

  Examples of the solvent include benzene, toluene, ether, THF, DMF, and the like. These solvents can be used alone or in admixture of two or more.

  The temperature in the polymerization reaction is 70 to 130 ° C, preferably 90 to 110 ° C.

  The blue light-emitting compound according to the present invention, that is, the blue light-emitting compound represented by the general formulas (1) and (1 ′) can be easily produced from an inexpensive raw material using a simple reaction. Moreover, since the reaction proceeds at a relatively low temperature, it can be produced safely. Therefore, such a simple method for producing a blue light-emitting compound is an industrial production method. Therefore, it can be said that the method for producing the blue light-emitting polymer is also an industrial production method.

  The blue light-emitting polymer according to the present invention obtained as described above, that is, the blue light-emitting polymer represented by the general formulas (1 ″) and (1 ′ ″) has an average molecular weight of 10,000 to 10,000. It is preferably 500,000, particularly 20,000 to 300,000.

The blue light-emitting compound and the blue light-emitting polymer according to the present invention have a carbazole skeleton having a large π electron cloud, and the influence from the surroundings is blocked by the aryl group represented by R ¹ or R ¹ ′. Therefore, in the repeating unit, the density of the π electron cloud becomes higher and more stable, so it is presumed that blue light emission is facilitated by a small amount of energy. The blue light-emitting polymer according to the present invention is characterized by having a repeating unit having a structure in which a polycyclic compound R ¹ is bonded to carbon of a benzene ring in a carbazole skeleton having a large π electron cloud. Since this blue light emitting polymer has a stable repeating unit, it is chemically stable and exhibits the specificity that it does not deteriorate even under severe use conditions.

  The light emitting element using the blue light emitting polymer according to the present invention will be described below.

  FIG. 1 is an explanatory diagram showing a cross-sectional structure of a light-emitting element that is also a single-layer organic EL element. As shown in FIG. 1, the light emitting element A is formed by laminating a light emitting layer 3 containing a light emitting material and an electrode layer 4 in this order on a substrate 1 on which a transparent electrode 2 is formed.

  The light-emitting element shown in FIG. 1 energizes the transparent electrode 2 and the electrode layer 4 when the light-emitting layer 3 contains the blue light-emitting polymer, red light-emitting compound, and green light-emitting compound according to the present invention in a balanced manner. Then, it emits white light. The total content and each content ratio of the blue light emitting polymer, the red light emitting compound, and the green light emitting compound according to the present invention contained in the light emitting layer 3 in order to emit white light depend on the type of each light emitting compound. Specifically, it is determined appropriately according to the type of each light emitting compound. If the light emitting element is intended to emit blue light, the light emitting layer 3 should contain the blue light emitting polymer according to the present invention. Further, if it is intended to emit light of any color other than white and blue with this light emitting device, the total content and each content of the blue light emitting polymer, the red light emitting compound, and the green light emitting compound according to the present invention It is preferable to change the amount ratio appropriately. For example, in order to cause a light emitting device using the blue light emitting polymer according to the present invention to emit white light, the mixing ratio of the blue light emitting polymer, the red light emitting compound and the green light emitting compound in the light emitting layer is usually 5 to 5 by weight. It is 200: 10-100: 50-200000, Preferably it is 10-100: 50-500: 100-10000.

  As the red light emitting compound, a Nile red red light emitting compound represented by the following formula (6) is suitable.

  Examples of the green light emitting compound include a coumarin green light emitting compound, an indophenol green light emitting compound, and an indigo green light emitting compound, and among them, a coumarin green light emitting compound represented by the following formula (7) is preferable. It is.

  For light emission, when an electric field is applied between the transparent electrode 2 and the electrode layer 4, electrons are injected from the electrode layer 4 side, holes are injected from the transparent electrode 2, and electrons are further emitted from the light emitting layer 3. It is a phenomenon in which energy is released as light when recombining with holes and the energy level returns from the conduction band to the valence band.

  When the entire shape of the light emitting element A shown in FIG. 1 is a large area planar shape, the light emitting element A is attached to, for example, a wall surface or a ceiling, and is a surface such as a large area wall surface white light emitting element and a large area ceiling surface white light emitting element. It can be set as a light emitting lighting device. That is, this light emitting element can be used as a surface light source in place of a conventional linear light source such as a fluorescent lamp or a point light source such as a light bulb. In particular, a wall surface, a ceiling surface, or a floor surface of a living room, an office room, a vehicle room, or the like can be emitted or illuminated as a surface light source using the light emitting element according to the present invention. Furthermore, the light emitting element A can be used for backlights such as a display screen in a computer, a display screen in a mobile phone, and a numeric display screen in a cash register. In addition, the light-emitting element A can be used as various light sources such as direct illumination and indirect illumination, and can be lit at night and has good visibility, a traffic signal device, and a road sign device. It can also be used for light sources such as a light-emitting bulletin board. Moreover, since the light emitting element A has a blue light emitting polymer having a specific chemical structure in the light emitting layer, the light emitting life is long. Therefore, the light emitting element A can be a light source that emits light with a long lifetime.

  As understood from the above, when the light emitting layer in the light emitting element A contains the blue light emitting polymer according to the present invention and does not contain the red light emitting compound and the green light emitting compound, the light emitting element A is Emits a bright blue color.

  Further, the light-emitting element A is a tubular light-emitting body in which the substrate 1 formed in a cylindrical shape and the transparent electrode 2, the light-emitting layer 3, and the electrode layer 4 are laminated in this order on the inner surface side of the substrate 1. it can. Since this light emitting element A does not use mercury, it can be used as an environmentally friendly light source instead of a conventional fluorescent lamp using mercury.

  As the substrate 1, a known substrate can be adopted as long as the transparent electrode 2 can be formed on the surface thereof. Examples of the substrate 1 include a glass substrate, a plastic sheet, a ceramic, and a metal plate obtained by processing the surface into an insulating property such as forming an insulating coating layer on the surface.

  When the substrate 1 is opaque, the light emitting element containing the red light emitting compound, the green light emitting compound and the blue light emitting polymer according to the present invention in the light emitting layer can irradiate white light on the side opposite to the substrate 1. It is a single-sided lighting device. Moreover, when this board | substrate 1 is transparent, it is a double-sided illuminating device which can irradiate white light from the board | substrate 1 side of a light emitting element, and the surface on the opposite side.

As the transparent electrode 2, various materials can be employed as long as they have a large work function and are transparent and can act as an anode by applying a voltage to inject holes into the light emitting layer 3. Specifically, the transparent electrode 2 is made of an inorganic transparent conductive material such as ITO, In ₂ O ₃ , SnO ₂ , ZnO, or CdO, or a compound thereof, or a conductive polymer material such as polyaniline. Can do.

  The transparent electrode 2 is formed on the substrate 1 by chemical vapor deposition, spray pyrolysis, vacuum deposition, electron beam deposition, sputtering, ion beam sputtering, ion plating, ion assisted deposition, and others. It can be formed by the method.

  When the substrate is formed of an opaque member, the electrode formed on the substrate does not need to be a transparent electrode.

  The light emitting layer 3 contains a blue light emitting polymer according to the present invention when emitting blue light, and a layer containing a red light emitting compound, a green light emitting compound and a blue light emitting polymer according to the present invention when emitting white light, Further, the blue light emitting polymer according to the present invention, or the red light emitting compound, the green light emitting compound and the blue light emitting polymer according to the present invention can be formed on the transparent electrode 2.

  Examples of the method for forming the blue light emitting polymer on the transparent electrode 2 include a method in which the blue light emitting polymer is dissolved in an appropriate solvent and applied in the form of a transparent electrode. Examples of the coating method include a spinner method and a brush coating method.

  The content of the blue light emitting polymer according to the present invention in the light emitting layer 3, or the total content of the red light emitting compound, the green light emitting compound and the blue light emitting polymer according to the present invention is usually 0.01 to 2% by weight, preferably Is 0.05 to 0.5% by weight.

  The light emitting layer 3 has a thickness of usually 30 to 500 nm, preferably 100 to 300 nm. If the thickness of the light emitting layer 3 is too thin, the amount of emitted light may be insufficient, and if the thickness of the light emitting layer 3 is too large, the driving voltage may become too high, which may be undesirable. Flexibility may be lacking when using a curved or annular body.

  The electrode layer 4 employs a material having a small work function, and may be formed of a single metal or a metal alloy such as MgAg, an aluminum alloy, and metal calcium. A preferred electrode layer 4 is an alloy electrode of aluminum and a small amount of lithium. The electrode layer 4 can be easily formed on the surface including the light emitting layer 3 formed on the substrate 1, for example, by a vapor deposition technique.

  Even when the coating method is employed to form the light emitting layer, it is preferable to interpose a buffer layer between the electrode layer and the light emitting layer.

  Examples of a material that can form the buffer layer include alkali metal compounds such as lithium fluoride, alkaline earth metal compounds such as magnesium fluoride, oxides such as aluminum oxide, 4,4′-biscarbazole biphenyl ( Cz-TPD). Further, as a material for forming a buffer layer formed between an anode such as ITO and an organic layer, for example, m-MTDATA (4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenyl Amine), phthalocyanine, polyaniline, polythiophene derivatives, inorganic oxides such as molybdenum oxide, ruthenium oxide, vanadium oxide, and lithium fluoride. By appropriately selecting the material of these buffer layers, the driving voltage of the organic EL element, which is a light emitting element, can be reduced, the quantum efficiency of light emission can be improved, and the emission luminance can be improved can do.

  Next, the 2nd example of the light emitting element which concerns on this invention is shown in a figure. FIG. 2 is an explanatory view showing a cross section of a multilayer organic EL element which is a light emitting element.

  As shown in FIG. 2, the light-emitting element B is formed by laminating a transparent electrode 2, a hole transport layer 5, light-emitting layers 3a and 3b, an electron transport layer 6 and an electrode layer 4 in this order on the surface of a substrate 1.

  The substrate 1, the transparent electrode 2, and the electrode layer 4 are the same as those in the light emitting element A shown in FIG.

  The light emitting layer in the light emitting element B shown in FIG. 2 includes a light emitting layer 3a and a light emitting layer 3b. The light emitting layer 3b is a layer having a host function.

  Examples of the hole transport material contained in the hole transport layer 5 include triphenylamine compounds such as N, N′-diphenyl-N, N′-di (m-tolyl) -benzidine (TPD) and α-NPD. Examples thereof include hydrazone compounds, stilbene compounds, heterocyclic compounds, and π electron starburst hole transport materials.

  Examples of the electron transport material contained in the electron transport layer 6 include 2- (4-tert-butylphenyl) -5- (4-biphenyl) -1,3,4-oxadiazole and 2,5-bis. Examples thereof include oxadiazole derivatives such as (1-naphthyl) -1,3,4-oxadiazole, 2,5-bis (5′-tert-butyl-2′-benzoxazolyl) thiophene, and the like. As the electron transporting substance, for example, a metal complex material such as a quinolinol aluminum complex (Alq3) or a benzoquinolinol beryllium complex (Bebq2) can be preferably used.

  In the light emitting element B in FIG. 2, the electron transport layer 6 contains Alq3.

  The thickness of each layer is the same as that in a conventionally known multilayer organic EL element.

  The light emitting element B shown in FIG. 2 operates in the same manner as the light emitting element A shown in FIG. 1 and emits light. Therefore, the light-emitting element B shown in FIG. 2 has the same application as the light-emitting element A shown in FIG.

  FIG. 3 shows a third example of the light emitting device according to the present invention. FIG. 3 is an explanatory view showing a cross section of a light emitting device which is a multilayer organic EL device.

  The light-emitting element C shown in FIG. 3 is formed by laminating a transparent electrode 2, a hole transport layer 5, a light-emitting layer 3, an electron transport layer 8 and an electrode layer 4 in this order on the surface of a substrate 1.

  The light emitting element C shown in FIG. 3 is the same as the light emitting element B.

  FIG. 4 shows another example of the light emitting element. The light emitting element D shown in FIG. 4 is formed by laminating a substrate 1, a transparent electrode 2, a hole transport layer 5, a light emitting layer 3 and an electrode layer 4 in this order.

  In addition to the light emitting device shown in FIGS. 1 to 4, a hole transport layer containing a hole transport material between an anode that is a transparent electrode and a cathode that is an electrode layer formed on a substrate, and the present invention A two-layer organic low-molecular light-emitting device comprising a blue light-emitting polymer-containing electron-transporting light-emitting layer according to the present invention (for example, a hole transport layer between an anode and a cathode, and a blue color according to the present invention as a guest dye) A two-layer dye-doped light-emitting device formed by laminating a light-emitting polymer and a light-emitting layer containing a host dye), a hole transport layer containing a hole-transporting substance between the anode and the cathode; A two-layer organic light emitting device in which a blue light emitting polymer and an electron transporting light emitting layer formed by co-evaporation of an electron transporting material are laminated (for example, a hole transporting layer, a guest dye between an anode and a cathode) As a blue light emitting device according to the present invention A two-layer dye-doped organic light-emitting device comprising a laminate of an electron-transporting light-emitting layer containing a monomer and a host dye), a hole-transporting layer between the anode and the cathode, and the blue light-emitting polymer according to the present invention And a three-layer organic light-emitting device formed by laminating the light emitting layer and the electron transport layer.

  The light emitting layer preferably contains rubrene as a sensitizer, and particularly preferably contains rubrene and Alq3.

  The blue light emitting element using the blue light emitting polymer according to the present invention, or the red light emitting compound, the green light emitting compound, and the white light emitting element using the blue light emitting polymer according to the present invention are generally used as, for example, a direct current drive type organic EL element. It can also be used as a pulse-driven organic EL element and an AC-driven organic EL element.

Example 1 “Synthesis of Blue Light-Emitting Polymer Part 1”
<Synthesis of organic halogen compounds>
A 2 L three-necked flask was charged with 46.49 g of carbazole, 100 g of 2-chloroethyl-p-toluenesulfonate, 52.9 g of sodium hydroxide, 33 ml of water and 1200 ml of acetone. The solution in the three-necked flask was heated to 60 ° C. with a water bath and reacted for 19 hours. After completion of the reaction, 1500 ml of toluene was added to the solid obtained by concentrating and drying the filtrate obtained by filtering the hot reaction product solution. Thereafter, the filtrate obtained by filtering this solution was concentrated and dried to obtain 25 g of milky white solid.

  The NMR spectrum chart of the obtained solid is shown in FIG. From this, the obtained solid was identified as N- (2-chloroethyl) carbazole having a structure represented by the following formula (8).

<Formylation of organic halogen compounds>
A 500 ml three-necked flask was charged with 28.1 g of the organic halogen compound, 196 g of phosphoryl chloride, 93.6 g of DMF, and 200 ml of dichloroethane. The solution in the three-necked flask was heated to 85 ° C. with a water bath and reacted for 2.5 hours. After completion of the reaction, the solution was ice-cooled. After cooling with ice, the mixture was put into ice and then made alkaline by adding caustic soda, followed by extraction and separation with chloroform. The collected oil layer was dried, 200 ml of methanol was added, and the mixture was stirred well and then filtered. The solid content obtained by filtration was dried to obtain 25 g of a solid.

  The NMR spectrum chart of the obtained solid is shown in FIG. From this, the obtained solid was identified as an aldehyde compound having a structure represented by the following formula (9).

<Synthesis of carboxylic acid compound>
In a 1 L four-necked flask, 25 g of the aldehyde compound and 367 ml of water were placed, and the solution in the four-necked flask was heated to 80 ° C. in a water bath. Thereafter, an aqueous potassium permanganate solution consisting of 20.7 g of potassium permanganate and 437 ml of water was added to the solution in the four-necked flask, and heated with stirring for 30 minutes. Thereafter, 20 ml of 10% aqueous potassium hydroxide solution was added and filtered. The filtrate was acidified and the precipitated solid was filtered and dried to give 3.1 g of an ocher solid.

  An NMR spectrum chart of the obtained solid is shown in FIG. From this, the obtained solid was identified as a carboxylic acid compound having a structure represented by the following formula (10).

<Synthesis of acid chloride compound>
A 200 ml eggplant flask was charged with 3.0 g of the carboxylic acid compound and 50 ml of thionyl chloride. The solution in the eggplant flask was heated to 80 ° C. with a silicon oil bath and reacted for 2 hours. After completion of the reaction, the solid content obtained by removing the solvent was dissolved in 100 ml of THF. Thereafter, the solvent was removed again to obtain 3.0 g of a light blue powdery solid.

  An NMR spectrum chart of the obtained solid is shown in FIG. From this, the obtained solid was identified as an acid chloride compound having a structure represented by the following formula (11).

<Synthesis of Intermediate>
A 200 ml three-necked flask was charged with 1.5 g of the acid chloride compound, 0.92 g of 1-naphthyl hydrazide, 0.47 g of pyridine and 100 ml of THF. The solution in the three-necked flask was heated to 60 ° C. with a water bath and reacted for 2 hours. After completion of the reaction, the mixture was ice-cooled, water was added and the precipitated solid was filtered. The solid content obtained by filtration was dried to obtain 2.1 g of a solid.

  The NMR spectrum chart of the obtained solid is shown in FIG. From this, the obtained solid was identified as an intermediate having a structure represented by the following formula (12).

<Dehydration and cyclization reaction>
A 200 ml three-necked flask was charged with 2.1 g of the above intermediate and 100 ml of phosphoryl chloride. The solution in the three-necked flask was heated to 120 ° C. with a silicon oil bath and reacted for 5 hours. After completion of the reaction, the solvent was removed, the solution was poured into ice water, and the precipitated solid was dissolved in chloroform, washed with water, and concentrated to dryness to obtain 1.7 g of a yellow solid.

  FIG. 10 shows an NMR spectrum chart of the obtained solid, and FIG. 11 shows an IR spectrum chart. From these, the obtained solid was identified as an oxadiazole compound having a structure represented by the following formula (13).

<Dehydrohalogenation>
A 300 ml eggplant flask was charged with 1.7 g of the oxadiazole compound, 2.3 g of potassium hydroxide and 100 ml of ethanol. The solution in the eggplant flask was heated in a silicon oil bath at 80 ° C. for 30 minutes, 50 ml of dioxane was added, and the mixture was further heated at 110 ° C. for 2 hours. After completion of the reaction, the reaction mixture was poured into ice water and extracted with 400 ml of chloroform. After the extract was washed with water, the solid obtained by drying was loaded onto a column packed with silica gel and purified with chloroform as a developing solution to obtain 0.9 g of a milky white solid.

  An NMR spectrum chart of the obtained solid is shown in FIG. From this, the obtained solid was identified as a vinyl compound having a structure represented by the following formula (14).

<Polymerization 1>
Next, the vinyl compound was polymerized using a radical reaction initiator.

  Into the polymerization tube, 480 mg of the vinyl compound, 10 mg of AIBN, and 30 ml of toluene were placed. The solution in the polymerization tube was heated in a silicon oil bath at 80 ° C. for 3 hours, and then heated at 100 ° C. for 15 hours. After heating, the solid content obtained by allowing to cool and concentrating was purified by a reprecipitation method to obtain 0.19 g of a white solid. It was 260-295 degreeC when melting | fusing point of this solid was measured.

  FIG. 13 shows an NMR spectrum chart of the obtained solid, FIG. 14 shows an IR spectrum chart, and FIG. 15 shows a fluorescence spectrum chart. From these, the obtained solid was identified as a blue light emitting polymer having a repeating unit represented by the following formula (15).

<Polymerization 2>
The vinyl compound was polymerized using a transition metal catalyst.

  In a 200 ml eggplant flask, 0.5 g of the vinyl compound, 60 ml of chlorobenzene and 75 μl of a solution obtained by dissolving tungsten chloride (VI) in chlorobenzene so as to be 0.05 mol / L were put. The solution in the eggplant flask was heated with a silicone oil bath at 200 ° C. for 12 hours. After completion of the reaction, the mixture was concentrated, filtered and dried to obtain a yellow powder. Next, the powder was washed with methanol and then dissolved in chloroform, followed by filtration. The obtained filtrate was poured into methanol, and the precipitated crystals were taken out and dried to obtain 200 mg of a white solid. It was.

  The melting point of the obtained white solid was measured and found to be about 181 ° C.

  FIG. 16 shows an NMR spectrum chart of the obtained solid, FIG. 17 shows an IR spectrum chart, and FIG. 18 shows a fluorescence spectrum chart. From these, the obtained solid was identified as a blue light emitting polymer having a repeating unit represented by the following formula (15).

Example 2 “Synthesis of Blue Light-Emitting Polymer 2”
<Synthesis of Intermediate>
A 200 ml three-necked flask was charged with 1.5 g of the acid chloride compound represented by the above formula (11), 1.3 g of the hydrazide compound represented by the following formula (16), 1.1 g of pyridine and 60 ml of THF. The solution in the three-necked flask was heated to 60 ° C. with a water bath and reacted for 2 hours. After completion of the reaction, the mixture was ice-cooled, water was added and the precipitated solid was filtered. The solid content obtained by filtration was dried to obtain 3.3 g of a solid.

  An NMR spectrum chart of the obtained solid is shown in FIG. From this, the obtained solid was identified as an intermediate having a structure represented by the following formula (17).

<Dehydration and cyclization reaction>
In a 200 ml three-necked flask, 3.3 g of the above intermediate and 50 ml of phosphoryl chloride were placed. The solution in the three-necked flask was heated to 120 ° C. with a silicon oil bath and reacted for 5 hours. After completion of the reaction, the solvent was removed, the solution was poured into ice water, the precipitated solid was dissolved in chloroform, washed with water, and concentrated to dryness to obtain a liquid. This liquid was loaded into a column packed with silica gel and purified with an equal amount of toluene and chloroform as a developing solution to obtain 0.46 g of a yellow solid.

  The NMR spectrum chart of the obtained solid is shown in FIG. From this, the obtained solid was identified as an oxadiazole compound having a structure represented by the following formula (18).

<Dehydrohalogenation>
A 50 ml eggplant flask was charged with 0.46 g of the oxadiazole compound, 0.5 g of potassium hydroxide, 20 ml of ethanol and 10 ml of dioxane. The solution in the eggplant flask was heated in a silicon oil bath at 80 ° C. for 30 minutes, 50 ml of dioxane was added, and the mixture was further heated at 110 ° C. for 2 hours. After completion of the reaction, the reaction mixture was poured into ice water and extracted with 400 ml of chloroform. The extract was washed with water and dried to obtain a liquid. This liquid was dissolved in an equal volume of toluene and chloroform and then concentrated to dryness to obtain 0.33 g of a pale yellow solid.

  An NMR spectrum chart of the obtained solid is shown in FIG. 21, and an IR spectrum chart is shown in FIG. From these, the obtained solid was identified as a vinyl compound having a structure represented by the following formula (19).

<Polymerization>
Next, the vinyl compound was polymerized using a radical reaction initiator.

  In the polymerization tube, 0.2 g of the vinyl compound, 0.82 mg of AIBN and 15 g of chlorobenzene were placed. The solution in the polymerization tube was heated in a silicon oil bath at 85 ° C. for 20 hours. After heating, the mixture was allowed to cool, added with 30 ml of methanol, and filtered to obtain a pale yellow solid. Further, this solid was reprecipitated with 5 ml of toluene and 20 ml of methanol, and the solid substance obtained by filtration was dried to obtain 34 mg of a white solid.

  An NMR spectrum chart of the obtained solid is shown in FIG. 23, and an IR spectrum chart is shown in FIG. From these, the obtained solid was identified as a blue light-emitting polymer having a repeating unit represented by the following formula (20).

Example 3 “Synthesis of Blue Light-Emitting Polymer 3”
<Synthesis of Intermediate>
A 200 ml three-necked flask was charged with 1.5 g of the acid chloride compound represented by the above formula (11), 1.9 g of the hydrazide compound represented by the following formula (21), 1.1 g of pyridine and 100 ml of THF. The solution in the three-necked flask was heated to 60 ° C. with a water bath and reacted for 2 hours. After completion of the reaction, the mixture was ice-cooled, water was added and the precipitated solid was filtered. The solid content obtained by filtration was dried to obtain 3.7 g of a light brown solid.

  The NMR spectrum chart of the obtained solid is shown in FIG. From this, the obtained solid was identified as an intermediate having a structure represented by the following formula (22).

<Dehydration and cyclization reaction>
A 200 ml three-necked flask was charged with 3.7 g of the intermediate and 50 ml of phosphoryl chloride. The solution in the three-necked flask was heated to 120 ° C. with a silicone oil bath and allowed to react for 15 hours. After completion of the reaction, the solvent was removed, the solution was poured into ice water, and the precipitated solid was dissolved in chloroform, then washed with water and concentrated to dryness to obtain 1 g of a pale yellow solid.

  The NMR spectrum chart of the obtained solid is shown in FIG. From this, the obtained solid was identified as an oxadiazole compound having a structure represented by the following formula (23).

<Dehydrohalogenation>


A 200 ml eggplant flask was charged with 1.0 g of the oxadiazole compound, 1.0 g of potassium hydroxide, 40 ml of ethanol and 20 ml of dioxane. The solution in the eggplant flask was heated in a silicon oil bath at 80 ° C. for 30 minutes, 50 ml of dioxane was added, and the mixture was further heated at 110 ° C. for 2 hours. After completion of the reaction, the reaction mixture was poured into ice water and extracted with 400 ml of chloroform. After the extract was washed with water, the solid obtained by drying was loaded onto a column packed with silica gel and purified with chloroform as a developing solution to obtain 0.77 g of a pale yellow solid.

  An NMR spectrum chart of the obtained solid is shown in FIG. 27, and an IR spectrum chart is shown in FIG. From these, the obtained solid was identified as a vinyl compound having a structure represented by the following formula (24).

<Polymerization>
Next, the vinyl compound was polymerized using a radical reaction initiator.

  In the polymerization tube, 0.2 g of the vinyl compound, 1.35 mg of AIBN and 10 g of chlorobenzene were placed. The solution in the polymerization tube was heated in a silicon oil bath at 80 ° C. for 3 hours, and then heated at 100 ° C. for 15 hours. After heating, the solid content obtained by allowing to cool and concentrating was purified by a reprecipitation method to obtain 6 mg of a white solid.

  An NMR spectrum chart of the obtained solid is shown in FIG. 29, and an IR spectrum chart is shown in FIG. From these, the obtained solid was identified as a blue light emitting polymer having a repeating unit represented by the following formula (25).

Example 4 “Synthesis of Blue Light-Emitting Polymer, Part 4”
<Synthesis of Intermediate>
In a 200 ml three-necked flask, 2.25 g of the acid chloride compound represented by the above formula (11), 2.0 g of the hydrazide compound represented by the following formula (26), 0.73 g of pyridine and 165 ml of THF were placed. The solution in the three-necked flask was heated to 60 ° C. with a water bath and reacted for 2 hours. After completion of the reaction, the mixture was ice-cooled, water was added, and the precipitated solid was filtered. The solid content obtained by filtration was dried to obtain 3.4 g of a solid.

  An NMR spectrum chart of the obtained solid is shown in FIG. From this, the obtained solid was identified as an intermediate having a structure represented by the following formula (27).

<Dehydration and cyclization reaction>
In a 200 ml three-necked flask, 3.3 g of the intermediate and 80 ml of phosphoryl chloride were added. The solution in the three-necked flask was heated to 120 ° C. with a silicon oil bath and reacted for 5 hours. After completion of the reaction, the solvent was removed, the solution was poured into ice water, and the precipitated solid was placed in chloroform, then washed with water and concentrated to dryness to obtain 2.2 g of a yellow solid.

  The NMR spectrum chart of the obtained solid is shown in FIG. From this, the obtained solid was identified as an oxadiazole compound having a structure represented by the following formula (28).

<Dehydrohalogenation>
A 300 ml eggplant flask was charged with 2.2 g of the oxadiazole compound, 2.2 g of potassium hydroxide, 30 ml of ethanol and 35 ml of dioxane. The solution in the eggplant flask was heated in a silicon oil bath at 80 ° C. for 30 minutes, 50 ml of dioxane was added, and the mixture was further heated at 110 ° C. for 2 hours. After completion of the reaction, the reaction mixture was poured into ice water and extracted with 400 ml of chloroform. After the extract was washed with water, the solid obtained by drying was loaded onto a column packed with silica gel and purified with chloroform as a developing solution to obtain 1.1 g of an orange solid.

  FIG. 33 shows an NMR spectrum chart of the obtained solid, and FIG. 34 shows an IR spectrum chart. From these, the obtained solid was identified as a vinyl compound having a structure represented by the following formula (29).

<Polymerization>
Next, the vinyl compound was polymerized using a radical reaction initiator.

  In a polymerization tube, 0.2 g of the vinyl compound, 1.4 mg of AIBN and 15 g of chlorobenzene were placed. The solution in the polymerization tube was heated in a silicon oil bath at 80 ° C. for 3 hours, and then heated at 100 ° C. for 15 hours. After heating, the solid content obtained by allowing to cool and concentrating was purified by a reprecipitation method to obtain 0.1 g of a white solid.

  FIG. 35 shows an NMR spectrum chart of the obtained solid, and FIG. 36 shows an IR spectrum chart. From these, the obtained solid was identified as a blue light-emitting polymer having a repeating unit represented by the following formula (30).

  Example 5 “Synthesis of Blue Light-Emitting Polymer, Part 5”

<Alkylation reaction>
A 300 ml three-necked flask was charged with 6 g of 1-chloromethyl-2,4-dimethylnaphthalene, 5.6 g of N- (2-chloroethyl) carbazole represented by the above formula (8), 1.9 g of zinc and 100 ml of orthodichlorobenzene. . The solution in the three-necked flask was heated to 155 ° C. in a silicon oil bath and reacted for 2 hours. After completion of the reaction, this solution was poured into ice water and then extracted by adding chloroform. After extraction, chloroform was distilled off and dried to obtain 6.6 g of a reddish brown paste.

  From the NMR spectrum chart and IR spectrum chart of the obtained paste-like material, the obtained paste-like material was identified as an organic halogen compound having a structure represented by the following formula (46).

<Dehydrohalogenation>
In a 300 ml eggplant flask, 5.9 g of the organic halogen compound represented by the formula (46), 3.0 g of potassium hydroxide, 80 ml of ethanol and 120 ml of 1,4-dioxane were added. The solution in the eggplant flask was heated to 110 ° C. for 14 hours in a silicone oil bath to be reacted. After completion of the reaction, the mixture was concentrated to 1/3 volume, poured into ice water, and extracted with chloroform. The extract obtained by extraction was washed with water and dried to obtain a solid. This solid was loaded onto a column packed with silica gel and purified using chloroform as a developing solution to obtain a paste.

  From the NMR spectrum chart and IR spectrum chart of the obtained paste-like product, the obtained paste-like product was identified as a vinyl compound having a structure represented by the following formula (47).

<Polymerization>
The polymerization tube was charged with 15 g of the vinyl compound, 13.6 mg of AIBN, and 10 ml of chlorobenzene. The solution in the polymerization tube was heated to 85 ° C. with a silicon oil bath and reacted for 20 hours. After completion of the reaction, the mixture was allowed to cool, concentrated, and filtered to obtain a precipitate. Further, this precipitate was redissolved in chloroform, and then activated carbon was added and heated, followed by filtration to obtain a filtrate. Next, this filtrate was added dropwise to 200 ml of methanol, and then the precipitate obtained by filtration was dried to obtain a solid.

  From the NMR spectrum chart, IR spectrum chart, and fluorescence spectrum chart of the obtained solid, the obtained solid was identified as a blue light-emitting polymer compound having a structure represented by the following formula (48).

  Example 6 “Synthesis of Blue Light-Emitting Polymer Part 6”

<Alkylation reaction>
A 300 ml three-necked flask was charged with 8 g of N- (2-chloroethyl) carbazole represented by the above formula (8), 2.7 g of zinc and 50 ml of orthodichlorobenzene. The solution in the three-necked flask was heated to 150 ° C. in a silicon oil bath, and a solution prepared by dissolving 6.2 g of 1-chloromethylnaphthalene in 30 ml of orthodichlorobenzene was dropped into the solution in the three-necked flask. The reaction was performed for 2 hours. After completion of the reaction, this solution was ice-cooled, poured into ice water, made alkaline with sodium hydroxide, and extracted with 200 ml of chloroform. After extraction, 80 g of sodium sulfate was added to remove water, and then chloroform was distilled off to obtain 12.7 g of a pale yellowish green paste. The obtained paste was loaded onto a column filled with silica gel, and toluene was developed and purified to obtain 10.3 g of a pale yellowish green paste.

  The NMR spectrum chart of the obtained paste is shown in FIG. 37, and the IR spectrum chart is shown in FIG. From this, the obtained paste was identified as an organic halogen compound having a structure represented by the following formula (50).

<Dehydrohalogenation>
In a 300 ml eggplant flask, 5.8 g of the organic halogen compound represented by the formula (50), 4 g of potassium hydroxide, 60 ml of ethanol and 100 ml of 1,4-dioxane were placed. The solution in the eggplant flask was heated to 100 ° C. with a silicon oil bath and allowed to react for 2 hours. After completion of the reaction, the solution was concentrated, the concentrated solution was poured into ice water, and extracted with 200 ml of chloroform. The extract obtained by extraction was washed with water and dried to obtain a paste. This pasty substance was loaded into a column packed with silica gel and purified with toluene as a developing solution to obtain 4.5 g of a pale yellowish green paste.

  The NMR spectrum chart of the pale yellowish green paste obtained is shown in FIG. 39, and the IR spectrum chart is shown in FIG. From this, the obtained paste was identified as a vinyl compound having a structure represented by the following formula (51).

<Polymerization>
In a polymerization tube, 2 g of the vinyl compound, 10 mg of AIBN and 10 mg of chlorobenzene were placed. The solution in the polymerization tube was heated to 85 ° C. with a silicon oil bath and reacted for 20 hours. After the completion of the reaction, the mixture was allowed to cool and concentrated, and then the concentrated solution was added dropwise to 200 ml of methanol and further filtered to obtain a precipitate. Further, the precipitate was redissolved in chloroform and then filtered to obtain a filtrate. Then, the filtrate was added dropwise to 200 ml of methanol, and the precipitate obtained by filtration was dried to obtain 0.45 g of a white solid.

  An NMR spectrum chart of the obtained solid is shown in FIG. 41, and an IR spectrum chart is shown in FIG. From this, the obtained solid was identified as a blue light emitting polymer having a structure represented by the following formula (52).

  Example 7 “Synthesis of Blue Light-Emitting Polymer, Part 7”

<Alkylation reaction>
In a 300 ml three-necked flask, 18.6 g of N- (2-chloroethyl) carbazole represented by the above formula (8), 6.3 g of zinc and 100 ml of orthodichlorobenzene were placed. The solution in the three-necked flask was heated to 150 ° C. in a silicon oil bath, and a solution prepared by dissolving 12.5 g of 2,4-dimethylbenzyl chloride in 40 ml of orthodichlorobenzene was added dropwise to the solution in the three-necked flask. Reacted for hours. After completion of the reaction, this solution was poured into ice water, made alkaline with sodium hydroxide, and extracted with 300 ml of chloroform. After extraction, 100 g of sodium sulfate was added to remove water, and then chloroform was distilled off to obtain 28.2 g of a paste. The obtained paste was loaded onto a column packed with silica gel, and toluene was developed to purify and purify to obtain 22 g of a greenish brown paste.

  The NMR spectrum chart of the obtained paste is shown in FIG. 43, and the IR spectrum chart is shown in FIG. From this, the obtained paste was identified as an organic halogen compound having a structure represented by the following formula (54).

<Dehydrohalogenation>
A 300 ml eggplant flask was charged with 22 g of the organic halogen compound represented by the formula (54), 11 g of potassium hydroxide, 80 ml of ethanol and 120 ml of 1,4-dioxane. The solution in the eggplant flask was heated to 100 ° C. with a silicon oil bath and allowed to react for 2.5 hours. After completion of the reaction, the reaction mixture was concentrated, and the concentrated solution obtained by concentration was added dropwise to ice water, followed by extraction with 300 ml of chloroform. The extract obtained by extraction was washed with water and dried to obtain a paste. This paste was loaded on a column packed with silica gel and purified with toluene as a developing solution to obtain 11 g of a greenish brown paste.

  The NMR spectrum chart of the obtained paste is shown in FIG. 45, and the IR spectrum chart is shown in FIG. From this, the obtained paste-like substance was identified as a vinyl compound having a structure represented by the following formula (55).

<Polymerization>
Into the polymerization tube, 5 g of the vinyl compound represented by the formula (55), 13 mg of AIBN, and 50 ml of chlorobenzene were placed. The solution in the polymerization tube was heated to 80 ° C. with a silicon oil bath and reacted for 20 hours. After completion of the reaction, the mixture was allowed to cool and concentrated, and then dropped into 200 ml of methanol, followed by filtration to obtain a precipitate. Further, this precipitate was redissolved in chloroform, and then activated carbon was added and heated, followed by filtration to obtain a filtrate. Next, the filtrate was added dropwise to 200 ml of methanol, and then the precipitate obtained by filtration was dried to obtain 0.2 g of a white solid.

  An NMR spectrum chart of the obtained solid is shown in FIG. 47, and an IR spectrum chart is shown in FIG. From this, the obtained solid was identified as a blue light emitting polymer having a structure represented by the following formula (56).

Example 8 {Production of Light-Emitting Element}
<Luminescent characteristics>
In a 5 ml volumetric flask, 0.5 mg of the compound represented by the following formula (57) and 100 mg of the powder represented by formula (15) obtained in the above (Example 1) were weighed, dichloroethane was added and 5 ml was added. A blue light emitting polymer-containing solution was prepared.

This blue light emitting polymer-containing solution was made sufficiently uniform by irradiating ultrasonic waves with an ultrasonic cleaner (US-2, manufactured by SND Corporation) for 20 minutes. An ITO substrate (50 × 50 mm, ITO transparent electrode thickness 150 μm, Sanyo Vacuum Industry Co., Ltd.) was ultrasonically cleaned with acetone for 10 minutes, then ultrasonically cleaned with 2-propanol for 10 minutes, blown with nitrogen and dried. I let you. Thereafter, UV was irradiated for 5 minutes with a photo face processor / photo surface processor (manufactured by Sen Special Light Source Co., Ltd., wavelength 254 nm) for cleaning. The prepared blue light-emitting polymer-containing solution is dropped onto an ITO substrate that has been washed and dried using a spin coater (Mikasa Co., Ltd., 1H-D7) at a rotation speed of 1,500 rpm and a rotation time of 3 seconds. And spin-coated to form a film having a dry thickness of 100 μm. The substrate thus formed was dried in a constant temperature bath at 50 ° C. for 30 minutes, and then an aluminum alloy (Al: Li = 99: with a vacuum deposition apparatus (VDS-M2-46 type, manufactured by Daia Vacuum Engineering Co., Ltd.)) 1 weight ratio, manufactured by Kojundo Chemical Laboratory Co., Ltd.) electrode was deposited at 4 × 10 ⁻⁶ Torr to a thickness of about 150 nm to produce a blue light emitting device having the structure shown in FIG.

The blue light-emitting element was measured for luminance and chromaticity while gradually increasing the voltage with BM-7 Fast manufactured by Topcon Corporation. As a result, a voltage of 30 V, current of 12.55 mA, luminance of 185.50 Cd / m ² , chromaticity X of 0.4290, and chromaticity Y of 0.5710 were obtained.
Example 9 “Synthesis of Blue Light-Emitting Polymer 8”

<Alkylation reaction>
In a 300 ml three-necked flask, 10.0 g of 9- (2-chloro-1-ethyl) carbazole synthesized in the same manner as described in <Synthesis of organohalogen compound> in Example 1 and 4.27 g of zinc. And 250 ml of carbon disulfide. Further, in this three-necked flask, a solution prepared by dissolving 20.2 g of 2,4-dimethylbenzyl chloride in 50 ml of carbon disulfide was dropped and reacted for 39 hours while heating to 45 ° C. After completion of the reaction, this solution was poured into ice water and extracted with 300 ml of chloroform. After extraction, sodium sulfate was added to remove water, and then chloroform was distilled off to obtain a paste. The obtained paste was reprecipitated with methanol and dried to obtain 7.4 g of a paste.

  The obtained pasty substance was a compound (3,6-di (3,4-dimethylbenzyl) -9- (2-chloroethyl) carbazole) having a structure represented by the formula (58).

<Dehydrohalogenation>
A 300 ml eggplant flask was charged with 4 g of the compound represented by the formula (58), 2.4 g of potassium hydroxide, 60 ml of ethanol and 142.8 ml of 1,4-dioxane. The solution in the eggplant flask was heated to 110 ° C. with a silicone oil bath and allowed to react for 19 hours. After completion of the reaction, the reaction solution is poured into ice water, the formed precipitate is filtered, dried, dissolved in toluene, and the filtrate obtained by filtration is recrystallized with 2-propanol to obtain crystals having a melting point of 55 ° C. 1.27 g was obtained.

  The NMR spectrum chart of the obtained crystal is shown in FIG. 49, and the IR spectrum chart is shown in FIG. From this, the obtained crystal was identified as a vinyl compound having a structure represented by the following formula (59).

<Polymerization>
The polymerization tube was charged with 0.988 g of the vinyl compound represented by the formula (59) and 30 mg of chlorobenzene, and the polymerization tube was filled with nitrogen gas. To this solution in the polymerization tube, 1 ml of a catalyst solution prepared by dissolving 0.0264 g of tungsten hexachloride in 10 ml of chlorobenzene was added. After the addition, the polymerization tube was shaken for 64 hours. Thereafter, the polymerization tube was opened and the solid was obtained by evaporating the solvent from the reaction product liquid in the polymerization tube, and the solid was reprecipitated using chloroform and methanol to obtain a crystal. .

  The melting point of this crystal is 85 to 160 ° C., and its NMR spectrum chart is shown in FIG. From these, the obtained solid was identified as a polymer having a structure represented by the following formula (60).

Example 10 {Light Emitting Element}
A polymer solution is prepared by weighing the dinaphthyl oxadiazole and the polymer represented by the formula (60) so as to have a mass ratio of 3: 7 and dissolving them in dichloromethane to a concentration of 15% by mass. did. The polymer solution was slightly removed to give a concentrated solution. On the other hand, an ITO substrate (50 × 50 mm, manufactured by Sanyo Vacuum Industry Co., Ltd.) was ultrasonically cleaned with acetone for 10 minutes, then ultrasonically cleaned with 2-propanol for 10 minutes, and blown with nitrogen to dry. Then, it was cleaned by UV irradiation for 30 seconds with a UV irradiation apparatus (manufactured by M.D. Excimer, wavelength 172 nm). On the surface of the cleaned ITO substrate, an electron injection layer having a thickness of 500 mm was formed by P dots (trade name, manufactured by Bayer) using a spin coater (manufactured by Mikasa Co., Ltd., 1H-D7). Further, the prepared polymer solution was dropped on the surface of the electron injection layer, and spin coating was performed at a rotation speed of 1,500 rpm and a rotation time of 3 seconds to form a polymer layer as a hole transport layer. The substrate thus formed was dried in a constant temperature bath at 50 ° C. for 30 minutes, and then an aluminum alloy (Al: Li = 99: with a vacuum vapor deposition apparatus (VDS-M2-46 type, manufactured by Daia Vacuum Engineering Co., Ltd.)). 1 weight ratio, manufactured by Kojundo Chemical Laboratory Co., Ltd.) electrode was deposited at 4 × 10 ⁻⁶ Torr to a thickness of about 150 nm to produce an EL device (hereinafter also referred to as a blue light emitting device). did.
The EL device was measured for luminance and chromaticity while gradually increasing the voltage with BM-7 Fast manufactured by Topcon Corporation. As a result, a luminance of 200 Cd / m ² , a chromaticity X of 0.1877, and a chromaticity Y of 0.1520 over a voltage of 15 to 30 V were obtained. From this XY chromaticity coordinate, it was confirmed that the light emitting element using this polymer emitted blue light.
Example 11 {Light Emitting Element}
Instead of the polymer represented by the formula (60), the blue light emitting polymer compound represented by the formula (56) obtained in the example 7 was used except that the blue light emitting polymer compound was used. It implemented and produced the blue light emitting element.
The luminance and formula emitted from the blue light emitting element were measured in the same manner as in Example 10. As a result, the luminance was 200 Cd / m ² , the chromaticity X was 0.2896, and the chromaticity Y was 0.3333. It was confirmed that blue light was emitted.
Example 12 “Synthesis of Blue Light-Emitting Polymer, Part 9”
<Alkylation reaction>
In a 1-liter three-necked flask, 20.26 g of 9- (2-chloro-1-ethyl) carbazole synthesized by the same method as described in <Synthesis of organic halogen compound> in Example 1, 5.77 g of zinc and 100 ml of carbon disulfide were added. The solution in the three-necked flask was heated to 45 ° C. in a silicon oil bath, and a solution prepared by dissolving 20 g of 9-chloromethylanthracene in 400 ml of carbon disulfide was dropped into the solution in the three-necked flask. Reacted for hours. After completion of the reaction, this solution was ice-cooled, poured into ice water, made alkaline with sodium hydroxide, and extracted with 200 ml of chloroform. After extraction, sodium sulfate is added to remove water, and then chloroform is distilled off, followed by washing with hot ethanol, so that an ethanol solution containing a first ethanol-insoluble component and a second component that is soluble in ethanol And the crystals precipitated by recrystallizing the first ethanol-insoluble component with benzene / cyclohexane (hereinafter referred to as “first crystals”) were filtered off. The melting point of the first crystal was 248 ° C.
Crystals precipitated by recrystallizing the solid matter produced by concentrating the ethanol solution containing the second component with benzene / cyclohexane (hereinafter referred to as “second crystals”) are filtered off. did. The melting point of the second crystal was 169 ° C.

  From the NMR spectrum chart and IR spectrum chart of the first crystal, the first crystal is the first organic halogen compound having the structure represented by the formula (61), and the NMR spectrum of the second crystal. From the chart and the IR spectrum chart, the second crystal was identified as the second organic halogen compound having the structure represented by the formula (62).

<Dehydrohalogenation>
A 1 liter eggplant flask was charged with 5.44 g of the first organic halogen compound represented by the formula (61), 4.35 g of potassium hydroxide, 120 ml of ethanol and 240 ml of 1,4-dioxane. The solution in the eggplant flask was heated while boiling in a silicone oil bath and allowed to react all day and night. After completion of the reaction, the solution was concentrated, the concentrated solution was poured into ice water, and extracted with 200 ml of chloroform. The extract obtained by extraction was washed with water and dried to obtain a paste. This pasty substance was loaded into a column packed with silica gel, purified with toluene as a developing solution, and recrystallized with benzene / cyclohexane to obtain 2.30 g of crystals having a melting point of 241 ° C.

  The NMR spectrum chart of the obtained crystal is shown in FIG. 53, and the IR spectrum chart is shown in FIG. From this, the obtained paste was identified as a vinyl compound having a structure represented by the following formula (63) (hereinafter referred to as “first vinyl compound”).

前記式（６１）で示される第一の有機ハロゲン化合物５．４４ｇ、水酸化カリウム４．３５ｇ、エタノール１２０ｍｌおよび１，４−ジオキサン２４０ｍｌを用いる代わりに、前記式（６２）で示される第二の有機ハロゲン化合物１．４７ｇ、水酸化カリウム１．１８ｇ、エタノール５０ｍｌおよび１，４−ジオキサン５０ｍｌを用いた外は、前記＜脱ハロゲン化水素反応＞欄におけるのと同様の操作を行った。
その結果、融点が１６７〜１６９℃である式（６４）に示されるビニル化合物（以下において、「第二のビニル化合物」と称する）を得た。このビニル化合物のＮＭＲスペクトルチャートを図５５に、ＩＲスペクトルチャートを図５６に示す。

Instead of using 5.44 g of the first organic halogen compound represented by the formula (61), 4.35 g of potassium hydroxide, 120 ml of ethanol and 240 ml of 1,4-dioxane, the second formula represented by the formula (62) The same operation as in the above <Dehydrohalogenation> column was performed except that 1.47 g of organic halogen compound, 1.18 g of potassium hydroxide, 50 ml of ethanol and 50 ml of 1,4-dioxane were used.
As a result, a vinyl compound represented by the formula (64) having a melting point of 167 to 169 ° C. (hereinafter referred to as “second vinyl compound”) was obtained. The NMR spectrum chart of this vinyl compound is shown in FIG. 55, and the IR spectrum chart is shown in FIG.

<Polymerization>
The polymerization tube was charged with 1.50 g of the first vinyl compound represented by the formula (63) and 100 mg of chlorobenzene, and the polymerization tube was filled with nitrogen gas. 1 ml of a catalyst solution prepared by dissolving 0.0029 g of tungsten hexachloride in 10 ml of chlorobenzene was added to the solution in the polymerization tube. After the addition, the polymerization tube was shaken for 64 hours.
Subsequent operations were performed in the same manner as in <Polymerization> in Example 9 to obtain a solid. The solid NMR spectrum chart is shown in FIG. 57, and the IR spectrum chart is shown in FIG. From these, the obtained solid was identified as the first polymer having a structure represented by the following formula (65).

重合管に、前記式（６４）で示される第二のビニル化合物１．３０ｇ、クロロベンゼン６０ｍｇを入れ、重合管内を窒素ガスで満たした。この重合管内の溶液に、クロロベンゼン１０ｍｌに六塩化タングステン０．００４０ｇを溶解してなる触媒溶液１ｍｌを、添加した。添加後、その重合管を６４時間揺すぶった。
以後の操作を前記実施例９における＜重合＞と同様に行って固体を得た。この固体のＮＭＲスペクトルチャートを図５９に、ＩＲスペクトルチャートを図６０に示す。これらより、得られた固体は、以下の式（６６）で示される構造を有する第二のポリマーであると同定した。

The polymerization tube was charged with 1.30 g of the second vinyl compound represented by the formula (64) and 60 mg of chlorobenzene, and the polymerization tube was filled with nitrogen gas. 1 ml of a catalyst solution prepared by dissolving 0.0040 g of tungsten hexachloride in 10 ml of chlorobenzene was added to the solution in the polymerization tube. After the addition, the polymerization tube was shaken for 64 hours.
Subsequent operations were performed in the same manner as in <Polymerization> in Example 9 to obtain a solid. The NMR spectrum chart of this solid is shown in FIG. 59, and the IR spectrum chart is shown in FIG. From these, the obtained solid was identified as the second polymer having a structure represented by the following formula (66).

FIG. 1 is an explanatory view showing a light emitting element as an example according to the present invention. FIG. 2 is an explanatory view showing a light emitting device as another example according to the present invention. FIG. 3 is an explanatory view showing a light emitting device as another example according to the present invention. FIG. 4 is an explanatory view showing a light emitting device as still another example according to the present invention. FIG. 5 is an NMR spectrum chart of N-2- (chloroethyl) carbazole obtained in Example 1 of the present invention. FIG. 6 is an NMR spectrum chart of the aldehyde compound obtained in Example 1 of the present invention. FIG. 7 is an NMR spectrum chart of the carboxylic acid compound obtained in Example 1 of the present invention. FIG. 8 is an NMR spectrum chart of the acid chloride compound obtained in Example 1 of the present invention. FIG. 9 is an NMR spectrum chart of the intermediate obtained in Example 1 of the present invention. FIG. 10 is an NMR spectrum chart of the oxadiazole compound obtained in Example 1 of the present invention. FIG. 11 is an IR spectrum chart of the oxadiazole compound obtained in Example 1 of the present invention. FIG. 12 is an NMR spectrum chart of the vinyl compound obtained in Example 1 of the present invention. FIG. 13 is an NMR spectrum chart of the blue light-emitting polymer obtained in Example 1 of the present invention by a reaction using a radical reaction initiator. FIG. 14 is an IR spectrum chart of the blue light-emitting polymer obtained by the reaction using the radical reaction initiator in Example 1 of the present invention. FIG. 15 is a fluorescence spectrum chart of a blue light-emitting polymer obtained in Example 1 of the present invention by a reaction using a radical reaction initiator. FIG. 16 is an NMR spectrum chart of the blue light-emitting polymer obtained by the reaction using the transition metal catalyst in Example 1 of the present invention. FIG. 17 is an IR spectrum chart of the blue light-emitting polymer obtained by the reaction using the transition metal catalyst in Example 1 of the present invention. FIG. 18 is a fluorescence spectrum chart of a blue light-emitting polymer obtained by a reaction using a transition metal catalyst in Example 1 of the present invention. FIG. 19 is an NMR spectrum chart of the intermediate obtained in Example 2 of the present invention. FIG. 20 is an NMR spectrum chart of the oxadiazole compound obtained in Example 2 of the present invention. FIG. 21 is an NMR spectrum chart of the vinyl compound obtained in Example 2 of the present invention. FIG. 22 is an IR spectrum chart of the vinyl compound obtained in Example 2 of the present invention. FIG. 23 is an NMR spectrum chart of the blue light-emitting polymer obtained in Example 2 of the present invention. FIG. 24 is an IR spectrum chart of the blue light-emitting polymer obtained in Example 2 of the present invention. FIG. 25 is an NMR spectrum chart of the intermediate obtained in Example 3 of the present invention. FIG. 26 is an NMR spectrum chart of the oxadiazole compound obtained in Example 3 of the present invention. FIG. 27 is an NMR spectrum chart of the vinyl compound obtained in Example 3 of the present invention. FIG. 28 is an IR spectrum chart of the vinyl compound obtained in Example 3 of the present invention. FIG. 29 is an NMR spectrum chart of the blue light-emitting polymer obtained in Example 3 of the present invention. FIG. 30 is an IR spectrum chart of the blue light-emitting polymer obtained in Example 3 of the present invention. FIG. 31 is an NMR spectrum chart of the intermediate obtained in Example 4 of the present invention. FIG. 32 is an NMR spectrum chart of the oxadiazole compound obtained in Example 4 of the present invention. FIG. 33 is an NMR spectrum chart of the vinyl compound obtained in Example 4 of the present invention. FIG. 34 is an IR spectrum chart of the vinyl compound obtained in Example 4 of the present invention. FIG. 35 is an NMR spectrum chart of the blue light-emitting polymer obtained in Example 4 of the present invention. FIG. 36 is an IR spectrum chart of the blue light-emitting polymer obtained in Example 4 of the present invention. FIG. 37 is an NMR spectrum chart of the organic halogen compound represented by the formula (50) obtained in Example 6 of the present invention. FIG. 38 is an IR spectrum chart of the organic halogen compound represented by the formula (50) obtained in Example 6 of the present invention. FIG. 39 is an NMR spectrum chart of the vinyl compound obtained in Example 6 of the present invention. FIG. 40 is an IR spectrum chart of the vinyl compound obtained in Example 6 of the present invention. FIG. 41 is an NMR spectrum chart of the blue light-emitting polymer obtained in Example 6 of the present invention. FIG. 42 is an IR spectrum chart of the blue light-emitting polymer obtained in Example 6 of the present invention. FIG. 43 is an NMR spectrum chart of the organic halogen compound represented by the formula (54) obtained in Example 7 of the present invention. FIG. 44 is an IR spectrum chart of the organic halogen compound represented by the formula (54) obtained in Example 7 of the present invention. FIG. 45 is an NMR spectrum chart of the vinyl compound obtained in Example 7 of the present invention. FIG. 46 is an IR spectrum chart of the vinyl compound obtained in Example 7 of the present invention. FIG. 47 is an NMR spectrum chart of the blue light-emitting polymer obtained in Example 7 of the present invention. FIG. 48 is an IR spectrum chart of the blue light-emitting polymer obtained in Example 7 of the present invention. FIG. 49 is an NMR spectrum chart of the organic halogen compound (Formula 58) obtained in Example 9 of the present invention. FIG. 50 is an IR spectrum chart of the organic halogen compound (Formula 58) obtained in Example 9 of the present invention. FIG. 51 is an NMR spectrum chart of the blue light-emitting polymer (Formula 59) obtained in Example 9 of the present invention. FIG. 51 is an IR spectrum chart of the blue light-emitting polymer (Formula 59) obtained in Example 9 of the present invention. FIG. 53 is an NMR spectrum chart of the first vinyl compound (Formula 63) obtained in Example 12 of the present invention. FIG. 54 is an IR spectrum chart of the first vinyl compound (Formula 63) obtained in Example 12 of the present invention. FIG. 55 is an NMR spectrum chart of the second vinyl compound (Formula 64) obtained in Example 12 of the present invention. FIG. 56 is an IR spectrum chart of the second vinyl compound (Formula 64) obtained in Example 12 of the present invention. FIG. 57 is an NMR spectrum chart of the first blue light-emitting polymer (Formula 65) obtained in Example 12 of the present invention. FIG. 58 is an IR spectrum chart of the first blue light-emitting polymer (Formula 65) obtained in Example 12 of the present invention. FIG. 59 is an NMR spectrum chart of the second blue light-emitting polymer (Formula 66) obtained in Example 12 of the present invention. FIG. 60 is an IR spectrum chart of the second blue light-emitting polymer (Formula 66) obtained in Example 12 of the present invention.

Explanation of symbols

A, B, C ... Blue light emitting element,
1 ... substrate
2 ... Transparent electrode,
3 ... light emitting layer,
3a, 3b ... light emitting layer,
4 ... electrode layer,
5 ... Hole transport layer,
6 ... electron transport layer,
8: Electron transport layer.

Claims (7)

A blue light-emitting compound having a structure represented by the following formula (1):

[In the formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituent represented by the following formula (2), and the two R ¹ are the same as each other. May be different. Moreover, n shows the integer of 1-4. ]

[In the formula (2), R ² represents an aryl group represented by the following formulas (2-1) to (2-8). ]

[In the formula (2-1), R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and q represents an integer of 1 to 5. ]

[In the formula (2-2), R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxyl group having an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ May be the same as or different from each other. Moreover, p shows the integer of 1-4 and r shows the integer of 1-3. ]

[However, in formula (2-3), R ⁴ , R ⁵ , p and r represent the same meaning as described above, and R ⁴ and R ⁵ may be the same or different from each other. ]

[In the formula (2-4), R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁶ , R ⁷ and R ⁸ are the same as each other. It may or may not be. P and r have the same meaning as described above, and s represents an integer of 1 or 2. ]

[However, in the formula (2-5), R ⁶ , R ⁷ , R ⁸ , p, r and s have the same meaning as described above, and R ⁶ , R ⁷ and R ⁸ are the same as each other] It may or may not be. ]

[However, in the formula (2-6), R ⁶ , R ⁷ , R ⁸ and p have the same meaning as described above, and R ⁶ , R ⁷ and R ⁸ may be the same as or different from each other. You may do it. ]

[In the formula (2-7), R ¹³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]

[In the formula (2-8), R ¹² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the two R ¹² may be the same or different from each other. P represents the same meaning as described above, and q represents an integer of 1 to 5. ] A blue light-emitting compound having a structure represented by the following formula (1 ′):

[In the formula (1 ′), R ¹ ′ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituent represented by the following formula (2 ′), and two R ¹ ′ They may be the same or different. Moreover, n shows the integer of 1-4. ]

[In the formula (2 ′), R ² represents an aryl group represented by the above formulas (2-1) to (2-8) or a substituent represented by the following formula (2′-1), m shows the integer of 0-3. ]

[In the formula (2′-1), Ar ¹ represents a phenylene group, a naphthylene group or an anthrylene group, and R ^{2 ′} represents an aryl group represented by the above formulas (2-1) to (2-8). Indicates. ] An intermediate represented by the following formula (5) obtained by reacting a halogen compound represented by the following formula (4) with a hydrazide compound is subjected to dehydration and dehydrohalogenation reaction. The manufacturing method of the blue light emitting compound which has a structure shown by this.

[In the formula (4), X ¹ and two X ² represents a halogen atom, X ¹ and two X ² may be different from be the same as each other. Further, p is as described in the first aspect. ]

[In the formula (5), R ² , X ¹ and p have the same meaning as described above. The two R ² may be the same or different from each other. A compound represented by the following formula (5 ′) produced by a Friedel-Crafts reaction of a halogen compound represented by the following formula (4 ′) is subjected to a dehydrohalogenation reaction. A method for producing a blue light-emitting compound having a structure represented by ').

[In the formula (4 ′), X ¹ is as defined in the third aspect. ]

[In the formula (5 ′), R ² , X ¹ and m have the same meaning as described above. ] A blue light-emitting polymer comprising a repeating unit represented by the following formula (1 ″).

[In the formula (1 ″), R ¹ and n are as defined in claim 1 above. ] A blue light-emitting polymer comprising a repeating unit represented by the following formula (1 ′ ″).

[In the formula (1 ′ ″), R ¹ ′ and n are as defined in the second aspect. ] A light emitting element comprising a light emitting layer containing a blue light emitting polymer composed of a repeating unit represented by the formula (1 ″) or (1 ′ ″) between a pair of electrodes.

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