JP5317313B2 - Fluorene polymer and polymer light emitting device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorene polymer exhibiting excellent properties as a light-emitting material of a light-emitting layer of a polymeric LED. <P>SOLUTION: The fluorene polymer has a terminal group represented by formula (2) (wherein B<SB>1</SB>is -O- or the like; Ar<SP>02</SP>is a hydrogen atom or the like; R<SP>06</SP>is a direct bond or the like; R<SB>1</SB>is an alkylene group or the like; R<SB>20</SB>is a hydrogen atom or the like; R<SP>03</SP>and R<SP>04</SP>are each independently a substituent group; c is an integer of 0-4; d is an integer of 0-3; and a plurality of R<SP>03</SP>and R<SP>04</SP>may be the same or different) at the end of the molecular chain thereof. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a fluorene polymer and a polymer light emitting device using the polymer (hereinafter sometimes referred to as polymer LED).

  High molecular weight light-emitting materials are variously studied because they are soluble in a solvent unlike low molecular weight materials and can form a light-emitting layer in a light-emitting element by a coating method. Examples thereof include phenoxazine-diyl groups and phenothiazine- A fluorene polymer compound having a repeating unit containing a diyl group but having a terminal group not sealed with these groups is known (see Patent Document 1 and Patent Document 2).

  However, the above polymer compound is not yet sufficient for practical use in terms of characteristics such as fluorescence intensity as a light emitting material of a light emitting layer of a polymer LED, and as a light emitting material of a light emitting layer of a polymer LED, There has been a demand for a polymer compound exhibiting superior characteristics.

U.S. Patent No. 2004-72989 JP 2004-137456 A

  The objective of this invention is providing the fluorene polymer which shows the outstanding characteristic as a light emitting material of the light emitting layer of polymer LED.

  As a result of intensive studies to solve the above problems, the present inventors have found that a fluorene polymer having a monovalent end group represented by the following formula (2) at at least one of the molecular chain ends of polyfluorene has strong fluorescence intensity. As a light-emitting material for a light-emitting layer of a polymer LED, the present inventors have found that it exhibits excellent characteristics, leading to the present invention.

  The fluorene polymer of the present invention exhibits excellent characteristics as a light emitting material. A polymer light emitting device using the fluorene polymer has high performance, and can be used as a planar light source as a backlight, a device such as a flat panel display. It is also useful for thin films, organic transistors, solar cells and the like.

（ここで、Ｒ^０１及びＲ^０２は、それぞれ独立に、置換基を示す。Ｒ^０５及びＲ^０７は、それぞれ独立に、水素原子又は置換基を示す。ａ及びｂは、それぞれ独立に０から３の整数であり、複数のＲ^０１及びＲ^０２は同一であってもよいし、異なっていてもよい。）

（式中、Ｂ_１は、−Ｏ−、−Ｓ−又は−Ｃ（Ｏ）−を表し、Ａｒ^０２は、水素原子、アリール基、１価の複素環基又は１価の芳香族アミン基を表し、Ｒ^０６は、直接結合、―Ｒ_１−、−Ｏ―Ｒ_１−＊、−Ｒ_１−Ｏ−＊、−Ｒ_１−Ｃ（Ｏ）Ｏ−＊、−Ｒ_１−ＯＣ（Ｏ）−＊、−Ｒ_１−Ｎ（Ｒ_２０）−＊、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）Ｏ−＊、又は−Ｃ（Ｏ）−を表し（ただし、＊印は、＊印側でＡｒ^０２と結合することを意味する。）、Ｒ_１は、アルキレン基又はアルケニレン基を表し、Ｒ_２０は、水素原子、アルキル基、アリール基、１価の複素環基又はシアノ基を表し、Ｒ^０３及びＲ^０４は、それぞれ独立に、置換基を示す。ｃは０から４の整数であり、ｄは０から３の整数である。複数のＲ^０３及びＲ^０４は同一であってもよいし、異なっていてもよい。） The fluorene polymer of the present invention contains one or more repeating units represented by the following formula (1).
That is, the present invention is a fluorene polymer having one or more types of repeating units selected from the group consisting of repeating units represented by the following formula (1), wherein at least one of the molecular chain ends of the polymer has the following formula: The fluorene polymer has a terminal group selected from the group consisting of monovalent groups represented by (2).

(Here, R ⁰¹ and R ⁰² each independently represent a substituent. R ⁰⁵ and R ⁰⁷ each independently represent a hydrogen atom or a substituent. A and b each independently represent 0 to 3) And a plurality of R ⁰¹ and R ⁰² may be the same or different.)

(In the formula, B ₁ represents —O—, —S— or —C (O) —, and Ar ⁰² represents a hydrogen atom, an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine group. R ⁰⁶ represents a direct bond, —R ₁ —, —O—R ₁ — *, —R ₁ —O— *, —R ₁ —C (O) O— *, —R ₁ —OC (O). -*, -R ₁ -N (R ₂₀ )-*, -O-, -S-, -C (O) O- *, or -C (O)-(where * is the meant binding with Ar ⁰² in the side.), R ₁ represents an alkylene group or alkenylene group, R ₂₀ represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or cyano group , ^{R 03} and ^{R 04} are each independently, .c indicating a substituent is an integer from 0 4, d is an integer from 0 to 3. more ^{R 03} and ^{R 04} are a same May be, it may be different.)

In the formula (1), R ⁰¹ and R ⁰² are each independently a substituent. Examples of the substituent include alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group, 1 A valent heterocyclic group or a cyano group. R ⁰⁵ and R ⁰⁷ are each independently a hydrogen atom or a substituent. Examples of the substituent include alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group, 1 A valent heterocyclic group or a cyano group.
Here, the alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl. Group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group and the like, and pentyl group Hexyl group, octyl group, 2-ethylhexyl group, decyl group and 3,7-dimethyloctyl group are preferred.

  The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group T-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group A pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, and a 3,7-dimethyloctyloxy group are preferable.

  The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, specifically, methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group. , T-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, etc. A pentylthio group, a hexylthio group, an octylthio group, a 2-ethylhexylthio group, a decylthio group, and a 3,7-dimethyloctylthio group are preferred.

  The alkylsilyl group may be linear, branched or cyclic, and usually has about 1 to 60 carbon atoms. Specifically, methylsilyl group, ethylsilyl group, propylsilyl group, isopropylsilyl group, butylsilyl group, isobutyl Silyl group, t-butylsilyl group, pentylsilyl group, hexylsilyl group, cyclohexylsilyl group, heptylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, nonylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl group, lauryl Silyl group, trimethylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, isopropyldimethylsilyl group, butyldimethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, Examples include octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, pentylsilyl group, hexylsilyl group Octylsilyl group, 2-ethylhexylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, decyldimethylsilyl group 3,7-dimethyloctyl-dimethylsilyl group is preferred.

  The alkylamino group may be linear, branched or cyclic, and may be a monoalkylamino group or a dialkylamino group, and usually has about 1 to 40 carbon atoms. Specifically, a methylamino group or a dimethylamino group , Ethylamino group, diethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group and the like can be mentioned, including pentylamino group, hexylamino group, octylamino group, 2-ethylhexylamino group, decylamino group, 3,7-dimethyloctylamino It is preferred.

The aryl group usually has about 6 to 60 carbon atoms, specifically, a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ represents ₁ to ₁₂ carbon atoms). The same shall apply hereinafter.), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl group, 2-naphthyl group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl group are preferred. .

Aryloxy group, the carbon number of usually about 6 to 60, specifically, phenoxy _group, C 1 _{-C 12} alkoxy phenoxy _group, C 1 _{-C 12} alkylphenoxy group, 1-naphthyloxy group, 2- naphthyloxy group and the _like, C 1 _{-C 12} alkoxy phenoxy _group, a C 1 _{-C 12} alkylphenoxy group are preferable.

Arylalkyl group has a carbon number of usually about 7 to 60, specifically, phenyl _-C 1 _{-C 12} alkyl _group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkyl _{group, C} 1 ~ C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl group, 1-naphthyl-C ₁ -C ₁₂ alkyl group, 2-naphthyl-C ₁ -C ₁₂ alkyl group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl _group, C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkyl group are preferable.

Arylalkoxy group has a carbon number of usually about 7 to 60, specifically, phenyl _-C 1 _{-C 12} alkoxy _group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkoxy _{group, C} 1 ~ C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkoxy group, 1-naphthyl-C ₁ -C ₁₂ alkoxy group, 2-naphthyl-C ₁ -C ₁₂ alkoxy group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C _{A 1 to} C ₁₂ alkoxy group and a C _{1 to} C ₁₂ alkylphenyl-C _{1 to} C ₁₂ alkoxy group are preferred.

The arylalkenyl group has a carbon number of usually about 8 to 60, specifically, a phenyl _-C 2 _{-C 12} alkenyl _group, C 1 _{-C 12} alkoxyphenyl _-C 2 _{-C 12} alkenyl group, _{C 1} -C ₁₂ alkylphenyl _-C 2 _{-C 12} alkenyl group, 1-naphthyl _-C 2 _{-C 12} alkenyl group, 2-naphthyl _-C 2 _{-C 12} alkenyl groups and the _like, C 1 _{-C 12} alkoxyphenyl - C ₂ -C ₁₂ alkenyl _group, C 1 _{-C 12} alkylphenyl _-C 2 _{-C 12} alkenyl groups are preferred.

The arylalkynyl group has a carbon number of usually about 8 to 60, specifically, a phenyl _-C 2 _{-C 12} alkynyl _group, C 1 _{-C 12} alkoxyphenyl _-C 2 _{-C 12} alkynyl group, _{C 1} -C ₁₂ alkylphenyl _-C 2 _{-C 12} alkynyl group, 1-naphthyl _-C 2 _{-C 12} alkynyl group, 2-naphthyl _-C 2 _{-C 12} alkynyl groups and the _like, C 1 _{-C 12} alkoxyphenyl - C ₂ -C ₁₂ alkynyl _group, C 1 _{-C 12} alkylphenyl _-C 2 _{-C 12} alkynyl group are preferable.

Arylamino group has a carbon number of usually about 6 to 60, phenylamino group, diphenylamino _group, C 1 _{-C 12} alkoxyphenyl amino group, di _(C 1 _{-C 12} alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, a 2-naphthylamino group and the _like, C 1 _{-C 12} alkylphenyl group, di _(C 1 _{-C 12} alkylphenyl) amino group are preferable .

The monovalent heterocyclic group refers to a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms. Specifically, a thienyl group, C _{1 to} C Examples include ₁₂ alkyl thienyl groups, pyrrolyl groups, furyl groups, pyridyl groups, C ₁ -C ₁₂ alkyl pyridyl groups, and the like, and thienyl groups, C ₁ -C ₁₂ alkyl thienyl groups, pyridyl groups, C ₁ -C ₁₂ alkyl pyridyl groups. Is preferred.

  When the substituent is a group containing an alkyl chain, the alkyl chain may be interrupted by a hetero atom or a group containing a hetero atom. Here, examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the hetero atom or the group containing a hetero atom include the following groups.

  Here, examples of R ′ include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, and a monovalent heterocyclic group having 4 to 60 carbon atoms.

a and b are each independently an integer of 0 to 3, and a plurality of R ⁰¹ and R ⁰² may be the same or different.

In the formula (2), B ₁ represents —O—, —S—, or —C (O) —.
In the formula (2), Ar ⁰² represents a hydrogen atom, an aryl group, a monovalent heterocyclic group, or a monovalent aromatic amine group.

Here, the aryl group usually has about 6 to 60 carbon atoms, and specifically includes a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ have ₁ to ₁₂ carbon atoms). The same applies to the following.), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl group, 2-naphthyl group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl are exemplified. Groups are preferred.

The monovalent heterocyclic group means a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 2 to 60 carbon atoms.
Examples of the monovalent heterocyclic group include the following.
Monovalent heterocyclic group containing nitrogen as a hetero atom: pyridinyl group, diazaphenyl group, quinolinyl group, quinoxalinyl group, acridinyl group, bipyridinyl group, phenanthroline-yl group and the like.
A group having a fluorene structure containing silicon, nitrogen, sulfur, selenium, oxygen and the like as a hetero atom (a group having a ring represented by the following formulas 79 to 93).

A 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium, oxygen or the like as a hetero atom (a group having a ring represented by the following formulas 94 to 98).
A 5-membered condensed heterocyclic group containing silicon, nitrogen, sulfur, selenium, oxygen and the like as a hetero atom (a group having a ring represented by the following formulas 99 to 108).
A 5-membered ring heterocyclic group containing sulfur or the like as a heteroatom, which is bonded to the α-position of the heteroatom to form two-bodies or oligomers (a group having a ring represented by the following formulas 109 to 110).
A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, oxygen, etc. as a heteroatom, and a group bonded to the phenyl group at the α-position of the heteroatom (having a ring represented by the following formulas 111 to 117) Group).

  The monovalent aromatic amine group refers to the remaining atomic group obtained by removing one hydrogen atom from the aromatic amine, and usually has about 4 to 60 carbon atoms. The carbon number does not include the carbon number of the substituent. Examples of the monovalent aromatic amine group include groups represented by the following formulas 123 to 127.

ここにＲは、水素原子又はＲ^０１と同様の意味を表す。

Here, R represents a hydrogen atom or the same meaning as R ⁰¹ .

In the formula (2), R ⁰⁶ represents a direct bond, —R ₁ —, —O—R ₁ — *, —R ₁ —O— *, —R ₁ —C (O) O— *, —R _{1. -OC (O) - *, -} R 1 -N (R 20) - *, - O -, - S -, - C (O) O- *, or -C (O) - and represents (where * The mark means that it is bonded to Ar ⁰² on the * mark side. The same applies to the following.), R ₁ represents an alkylene group or an alkenylene group. R ₂₀ represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. From the viewpoint of ease of synthesis and stability, R ⁰⁶ is preferably a direct bond, —R ₁ — *, or —R ₁ —O— *.

R ⁰³ and R ⁰⁴ each independently represent the same meaning as R ⁰¹ .
c is an integer from 0 to 4, and d is an integer from 0 to 3. A plurality of R ⁰³ and R ⁰⁴ may be the same or different.

Specific examples of the group represented by the formula (2) include the following groups.

Here, R represents a hydrogen atom or the same meaning as R ^01, and R ₁ represents the same meaning as described above.

Among the fluorene polymers of the present invention, those containing a repeating unit represented by the following formula (3) are preferable from the viewpoint of increasing the fluorescence intensity and changing the fluorescence wavelength.
^{- Ar 1 - (Z ')} p- (3)

Ar ¹ in the above formula (3) is an arylene group, a divalent heterocyclic group, or a divalent aromatic amine group.

In the formula (3), Ar ¹ represents an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, or an arylalkynyl group. May have a substituent such as an arylamino group or a monovalent heterocyclic group. When Ar ₁ has a plurality of substituents, they may be the same or different.

In said Formula (3), an arylene group is the remaining atomic group remove | excluding two hydrogen atoms from aromatic hydrocarbon, and carbon number is about 6-60 normally. The carbon number does not include the carbon number of the substituent. Here, the aromatic hydrocarbon includes those having a condensed ring and those having two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene.
Examples of the arylene group include a phenylene group (for example, the following formulas 1 to 3), a naphthalenediyl group (the following formulas 4 to 13), an anthracenylene group (the following formulas 14 to 19), a biphenylene group (the following formulas 20 to 25), and a triphenylene group. (Following formulas 26 to 28), condensed ring compound groups (following formulas 29 to 38), stilbene-diyl (following formulas A to D), distilben-diyl (following formulas E and F), benzofluorene-diyl (following formula G) , H, I, and K).

  In the above formulas 1 to 38, A to I and K, R is a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group. , An arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group. In the above example, a plurality of Rs are included, but they may be the same or different.

In the formula (3), the divalent heterocyclic group refers to the remaining atomic group obtained by removing two hydrogen atoms from the heterocyclic compound, and usually has about 4 to 60 carbon atoms. The carbon number does not include the carbon number of the substituent.
Here, a heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, and boron in the ring. Good examples include the following:
As a hetero atom, a group containing nitrogen: pyridine-diyl group (following formulas 39 to 44), diazaphenylene group (following formulas 45 to 48), quinoline diyl group (following formulas 49 to 63), quinoxaline diyl group (following formula 64) -68), acridinediyl group (following formulas 69-72), bipyridyldiyl group (following formulas 73-75), phenanthroline diyl group (following formulas 76-78), and the like.
Groups having a fluorene structure containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom (the following formulas 79 to 93).
5-membered heterocyclic groups containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom (the following formulas 94 to 98).
A 5-membered condensed heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom (the following formulas 99 to 108).
A 5-membered ring heterocyclic group containing sulfur or the like as a heteroatom and bonded to the α-position of the heteroatom to form a dimer or oligomer (the following formulas 109 to 110).
A 5-membered heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium or the like as a heteroatom and bonded to a phenyl group at the α-position of the heteroatom (the following formulas 111 to 117).

  In the above formulas 39 to 117, R represents the same meaning as described above.

  In the formula (3), the divalent aromatic amine group refers to the remaining atomic group obtained by removing two hydrogen atoms from the aromatic amine, and usually has about 4 to 60 carbon atoms. The number of carbon atoms of the substituent is not included. Examples of the divalent aromatic amine group include a group represented by the following general formula (30).

—Ar ₆ —N (Ar ₅ ) —Ar ₇ — (30)

In the formula, Ar ₆ and Ar ₇ are each independently an arylene group which may have a substituent, a group represented by the following general formula (4), or a group represented by the following general formula (5). is there. Ar ₅ represents an aryl group which may have a substituent, a group represented by the following general formula (6), or a group represented by the following general formula (7). In addition, a ring may be formed between Ar ₆ and Ar ₅ , between Ar ₅ and Ar ₆ , or between Ar ₆ and Ar ₇ .

式中、Ａｒ_８及びＡｒ_９は、それぞれ独立に、置換基を有していてもよいアリーレン基を示す。Ｒ_７及びＲ_８は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基又はシアノ基を示す。ｌは０又は１である。

In the formula, Ar ₈ and Ar ₉ each independently represent an arylene group which may have a substituent. R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. l is 0 or 1.

式中、Ａｒ_１０及びＡｒ_１１は、それぞれ独立に、置換基を有していてもよいアリーレン基を示す。Ａｒ_１２は、置換基を有していてもよいアリール基である。また、Ａｒ_１０とＡｒ_１２の間、Ａｒ_１０とＡｒ_１１の間、又はＡｒ_１１とＡｒ_１２の間に環を形成していてもよい。

In the formula, Ar ₁₀ and Ar ₁₁ each independently represent an arylene group which may have a substituent. Ar ₁₂ is an aryl group which may have a substituent. Further, a ring may be formed between Ar ₁₀ and Ar ₁₂ , between Ar ₁₀ and Ar ₁₁ , or between Ar ₁₁ and Ar ₁₂ .

式中、Ａｒ_１３は、置換基を有していてもよいアリーレン基を示す。Ａｒ_１６及びＡｒ_１７は、それぞれ独立に、置換基を有していてもよいアリール基である。また、Ａｒ_１３とＡｒ_１６の間、Ａｒ_１３とＡｒ_１７の間、又はＡｒ_１６とＡｒ_１７の間に環を形成していてもよい。

In the formula, Ar ₁₃ represents an arylene group which may have a substituent. Ar ₁₆ and Ar ₁₇ are each independently an aryl group which may have a substituent. In addition, a ring may be formed between Ar ₁₃ and Ar ₁₆ , between Ar ₁₃ and Ar ₁₇ , or between Ar ₁₆ and Ar ₁₇ .

式中、Ａｒ_１４は、置換基を有していてもよいアリーレン基を示す。Ａｒ_１５は、置換基を有していてもよいアリール基を示す。Ｒ_１１及びＲ_１２は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基又はシアノ基を示す。ｒは０又は１である。

In the formula, Ar ₁₄ represents an arylene group which may have a substituent. Ar ₁₅ represents an aryl group which may have a substituent. R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. r is 0 or 1;

Ar ₈ and Ar _{9 in} the above formula (4), Ar ₁₀ and Ar _{11 in} the formula (5), Ar _{13 in} the formula (6) and Ar _{14 in the} formula (7) are alkyl groups, alkoxy groups, alkylthio groups, alkyls Has substituents such as silyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group, cyano group, etc. It may be.
Ar _{5 in the} above formula (30), Ar _{12 in} the above formula (5), Ar ₁₆ and Ar _{17 in} the above formula (6), and Ar _{15 in the} above formula (7) are an alkyl group, an alkoxy group, an alkylthio group, Alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group, cyano group, etc. You may do it.

Specific examples of the divalent aromatic amine group include the following groups.

  In the above formulas 118 to 122, R represents the same meaning as described above.

  Among them, a phenylene group (for example, the above formulas 1 to 3), a naphthalenediyl group (the above formulas 4 to 13), an anthracenylene group (the above formulas 14 to 19), a biphenylene group (the above formulas 20 to 25), a triphenylene group (the above formula) 26-28), condensed ring compound groups (above formulas 29-38), dibenzofuran-diyl groups (above formulas 85-87), dibenzothiophene-diyl groups (above formulas 88-90), stilbene-diyl groups (above formula A). -D), a distilbene-diyl group (the above formulas E and F), a benzofluorene-diyl group (the above formulas G, H, I and K), a divalent aromatic amine group (the above formulas 118-119 and 122), Among them, phenylene group, biphenylene group, fluorene-diyl group (the above formulas 36 to 38), dibenzofuran-diyl group (the above formulas 85 to 87), diben Thiophene-diyl groups (formulas 88-90), stilbene-diyl groups (formulas AD), distilben-diyl groups (formulas E and F), benzofluorene-diyl groups (formulas G, H, I and K) A divalent aromatic amine group is particularly preferred.

In the formula (3), Z ′ represents —C (R ₄ ) ═C (R ₅ ) — or —C≡C—. R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. —C (R ₄ ) ═C (R ₅ ) — is preferable from the viewpoint of stability.
As the repeating unit in which Z ′ is —C (R ₄ ) ═C (R ₅ ) —, those represented by the following formulas 128 to 135 are preferable.

ここにＲは前記と同じ意味を表す。
ｐは、０又は１である。光酸化安定性の観点からは、ｐは０であることが好ましい。

Here, R represents the same meaning as described above.
p is 0 or 1. From the viewpoint of photooxidation stability, p is preferably 0.

  Among the fluorene polymers containing the repeating units represented by the formulas (1) and (3), the sum of the repeating units represented by the formulas (1) and (3) is 50 mol% or more of the total repeating units. Is more preferable from the viewpoint of luminous efficiency. In addition, the number of the repeating units represented by the formula (1) is 0.1 mol% or more and 90 mol% or less with respect to the total of the repeating units represented by the formulas (1) and (3). Is more preferable.

As substantially consisting of repeating units represented by the formulas (1) and (3), specifically, as the repeating unit represented by the formula (1), one or more kinds selected from the following:

  Examples of the repeating unit represented by the formula (3) include copolymers with one or more selected from the following.

（ただし、Ｒは、前記と同様の意味を表す。）

(However, R represents the same meaning as described above.)

  The fluorene polymer of this invention should just have the terminal group chosen from the monovalent group shown by the said Formula (2) in at least one of the molecular chain terminal. This end group may be one type or two or more types. The terminal group other than the terminal group of the formula (2) is preferably 50% or less, more preferably 40% or less of all terminals. The terminal group other than the terminal group of the above formula (2) is a leaving group of the monomer used in the polymerization, and is a leaving group present at the terminal of the fluorene polymer without being removed during the polymerization. The term “proton” refers to a proton or the like that is bonded to a terminal monomer but is not bonded to an aromatic terminal group although the polymer leaving group is removed. Of these molecular chain terminals, the leaving group of the monomer used for the polymerization, and the leaving group present at the terminal of the fluorene polymer without being eliminated during the polymerization, for example, a monomer having a halogen atom as a raw material In the case of producing the fluorene polymer of the present invention by using, for example, if the halogen remains at the end of the fluorene polymer, there is a tendency that the fluorescence characteristics and the like tend to deteriorate. It is preferable that substantially no residue remains.

The fluorene polymer of the present invention has a number average molecular weight of 10 ³ to 10 ⁸ in terms of polystyrene, preferably 3 × 10 ^{3 to} 5 × 10 ⁶ , more preferably 5 × 10 ³ from the viewpoint of film formability. It is ˜2 × 10 ⁶ , more preferably 1 × 10 ⁴ to 1 × 10 ⁶ .
The fluorene polymer of the present invention preferably has fluorescence in the solid state. More preferably, it has fluorescence in a solid state and has a number average molecular weight of 10 ³ to 10 ⁸ in terms of polystyrene.
Further, the fluorene polymer of the present invention may have phosphorescence.

  Examples of the good solvent for the fluorene polymer of the present invention include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, decalin, and n-butylbenzene. Although depending on the structure and molecular weight of the fluorene polymer, it can usually be dissolved in these solvents in an amount of 0.1% by weight or more.

  The fluorene polymer of the present invention is obtained by polymerizing a monomer corresponding to one or more kinds of repeating units to obtain a polymer having a leaving group at the terminal, and the polymer and a single unit corresponding to the above formula (2). It can be produced by a method of reacting a monomer, a method of polymerizing a monomer corresponding to one or more kinds of repeating units in the presence of a monomer corresponding to the above formula (2), and the like.

The fluorene polymer of the present invention includes, for example, one or more monomers represented by the general formula (101) and / or (102) and the monomer represented by the general formula (104) and / or (105). It can be produced by reacting.
Y ₁ -Ar ₁ -Y ₂ (101)
Y ₃ —Ar ₂ —Y ₄ (102)
Y ₇ -E ₁ (104)
Y ₈ -E ₂ (105)
(In the formula, Ar ₁ and Ar ₂ each independently represent a fluorene-diyl group or an arylene group, a divalent heterocyclic group, or a divalent aromatic amine group. Here, an arylene group, a divalent group, The heterocyclic group and the divalent aromatic amine group represent the same groups as described above, except that at least one of Ar ₁ and Ar ₂ is a fluorene-diyl group, and E ₁ and E ₂ are each independently the above. Represents a group of formula (2), Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₇ and Y ₈ each independently represent a leaving group.)

Examples of the leaving group include a halogen atom, an alkylsulfonyloxy group, an arylsulfonyloxy group, or a group represented by —B (OR ₁₁ ) ₂ (wherein R ₁₁ is a hydrogen atom or an alkyl group).

  Here, examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom, a chlorine atom and a bromine atom are preferable, and a bromine atom is most preferable. The alkylsulfonyloxy group may be substituted with a fluorine atom, and examples thereof include a trifluoromethanesulfonyloxy group. The arylsulfonyloxy group may be substituted with an alkyl group, and examples thereof include a phenylsulfonyloxy group and a trisulfonyloxy group.

In the group represented by —B (OR ₁₁ ) ₂ , R ₁₁ is a hydrogen atom or an alkyl group. As an alkyl group, carbon number is about 1-20 normally, and a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group etc. are mentioned. Further, the alkyl groups may be connected to form a ring.

が挙げられ、

が好ましい。 As the group represented by —B (OR ₁₁ ) ₂ , specifically,

Are mentioned,

Is preferred.

  The total charge of the monomers of the general formulas (104) and (105) is generally 0.1 to 20 with respect to the total charge of the monomers of the general formulas (101) and (102). It is mol% and 0.2-10 mol% is preferable.

As a method for producing the fluorene polymer of the present invention, for example, a method in which the above-mentioned corresponding monomer is polymerized by a Suzuki reaction (Chem. Rev., 95, 2457 (1995)), Grignard Polymerization by reaction (Kyoritsu Shuppan, Polymer Functional Materials Series Vol. 2, Polymer Synthesis and Reaction (2), pages 432-3), Polymerization by Yamamoto Polymerization (Progressive Polymer Science (Prog. Polym. Sci.), Vol. 17, 1153-1205, 1992), a method of polymerizing with an oxidizing agent such as FeCl _3, a method of electrochemical oxidative polymerization (Maruzen, Experimental Chemistry Course 4th Edition, Vol. 28, 339). -340 pages).

The case where the Suzuki reaction is used will be described. In this case, for example, Y ₁ and Y ₂ are each independently a group represented by —B (OR ₁₁ ) ₂ (where R ₁₁ is a hydrogen atom or an alkyl group), and Y ₃ and Y ₄ are each Independently, it is a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group, and Y ₇ is a group represented by —B (OR ₁₁ ) ₂ (wherein R ₁₁ is a hydrogen atom or an alkyl group), Y ₈ is a monomer having a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group, and can be produced by reacting these monomers in the presence of a Pd (0) catalyst.

In this case, at least one of the two or more monomers having two leaving groups to be used for the reaction is —B (OR ₁₁ ) ₂ (where R ₁₁ is a hydrogen atom or an alkyl group). In a reaction that requires a monomer having two halogen atoms, an alkylsulfonyloxy group, or an arylsulfonyloxy group, the compound represented by formula (101) ) To (102) are allowed to react for about 1 to 100 hours, and then the monomer (105) is added to the system and allowed to react for about 0.5 to 50 hours. The monomer (104) is added to the system and reacted for about 0.5 to 50 hours.

  As the Pd (0) catalyst, for example, palladium [tetrakis (triphenylphosphine)], palladium acetates (for example, a catalyst system obtained by reducing palladium acetate with a triphenylphosphine derivative) and the like are used, and potassium carbonate, sodium carbonate, hydroxide The reaction is carried out by adding an inorganic base such as barium, an organic base such as triethylamine, or an inorganic salt such as cesium fluoride in an amount of not less than an equivalent amount, preferably 1 to 10 equivalents relative to the monomer. The reaction may be carried out in a two-phase system using an inorganic salt as an aqueous solution. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. Although depending on the solvent, a temperature of about 50 to 160 ° C. is preferably used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours. The polymerization reaction is usually carried out in a reaction system in which the Pd (0) catalyst is not deactivated under an inert gas atmosphere such as argon or nitrogen.

The case where the Yamamoto polymerization method is used will be described. In this case, for example, monomers in which Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₇ and Y ₈ are each independently a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group are used. The target polymer can be produced by reacting the monomer in the presence of a Ni (0) complex. The reaction is usually carried out by mixing all of the monomers (101), (102), (104) and (105).

The polymerization is carried out in the presence of a Ni (0) complex (zerovalent nickel complex). As the nickel complex, there are a method in which zero-valent nickel is used as it is, and a method in which a nickel salt is reacted in the presence of a reducing agent to generate zero-valent nickel in the system and react. Examples of the zero-valent nickel complex include bis (1,5-cyclooctadiene) nickel (0), (ethylene) bis (triphenylphosphine) nickel (0), tetrakis (triphenylphosphine) nickel, Bis (1,5-cyclooctadiene) nickel (0) is preferred from the viewpoint of versatility and low cost. Moreover, it is preferable from a viewpoint of a yield improvement to add a neutral ligand. Here, the neutral ligand is a ligand having no anion or cation, and 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N′-tetramethylethylenediamine. Nitrogen-containing ligands such as triphenylphosphine, tolylphosphine, tributylphosphine, triphenoxyphosphine, and the like, and nitrogen-containing ligands are preferred in terms of versatility and low cost. 2,2′-bipyridyl is particularly preferable in terms of high reactivity and high yield. In particular, from the viewpoint of improving the yield of the polymer, a system in which 2,2′-bipyridyl is added as a neutral ligand to a system containing bis (1,5-cyclooctadiene) nickel (0) is preferable. In the method of reacting zero-valent nickel in the system, nickel salts such as nickel chloride and nickel acetate can be used. Examples of the reducing agent include zinc, sodium hydride, hydrazine and derivatives thereof, lithium aluminum hydride, and the like, and ammonium iodide, lithium iodide, potassium iodide, and the like are used as additives. The polymerization solvent is not particularly limited as long as it does not inhibit the polymerization, but preferably contains one or more aromatic hydrocarbon solvents and / or ether solvents. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, butylbenzene, naphthalene, and tetralin, and toluene, xylene, tetralin, and tetramethylbenzene are preferable.
Examples of the ether solvent include diisopropyl ether, tetrahydrofuran, 1,4-dioxane, diphenyl ether, ethylene glycol dimethyl ether, tert-butyl methyl ether, and the like. Tetrahydrofuran, which is a good solvent for the fluorene polymer, 1, 4-dioxane and the like are preferable. Of the solvents, tetrahydrofuran is most preferred. In addition, from the viewpoint of improving the polymerizability and solubility, the solvent may be an aromatic hydrocarbon solvent and / or an ether solvent, an aromatic hydrocarbon solvent and an ether solvent as long as it does not inhibit the polymerization reaction. A mixed solvent with a solvent other than the above may be used.

  Reaction operation etc. can be performed according to the method as described in Unexamined-Japanese-Patent No. 2000-44544, for example. In the Yamamoto polymerization method, for example, the polymerization reaction is usually performed in an inert gas atmosphere such as argon or nitrogen, in a tetrahydrofuran solvent at a temperature of 60 ° C., in the presence of a zero-valent nickel complex or a neutral ligand. . The polymerization time is usually about 0.5 to 100 hours, but is preferably within 10 hours from the viewpoint of production cost. The polymerization temperature is usually about 0 to 200 ° C, but 20 to 100 ° C is preferable from the viewpoint of high yield and low heating cost.

  Moreover, when using a neutral ligand, as the usage-amount, about 0.5-10 mol is preferable with respect to 1 mol of zerovalent nickel complexes from the point of reaction yield and cost, 0 .8 to 1.5 mol is more preferable, and 0.9 to 1.1 mol is more preferable.

  The amount of the zero-valent nickel complex is not particularly limited as long as it does not inhibit the polymerization reaction. However, if the amount used is too small, the molecular weight tends to be low, and if it is too large, the post-treatment is complicated. Tend to be. Therefore, 0.1-10 mol is preferable with respect to 1 mol of monomers, 1-5 mol is more preferable, and 1.7-3.5 mol is further more preferable.

  When the fluorene polymer of the present invention is used as a light emitting material of a polymer LED, the purity affects the light emission characteristics, and therefore, the monomer before polymerization is polymerized after being purified by methods such as distillation, sublimation purification, and recrystallization. It is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography after the synthesis.

The polymer composition of the present invention is a polymer compound having fluorescence in a solid state and having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ (the polymer compound includes the fluorene polymer of the present invention). And the fluorene polymer of the present invention. The polymer compound is not particularly limited as long as it improves the properties of the device such as solubility in a solvent, fluorescence intensity, lifetime, and luminance, and specifically, Japanese Patent Application Laid-Open No. 2001-247861. , JP-A-2001-507511, JP-A-2001-504533, JP-A-2001-278958, JP-A-2001-261969, JP-A-2001-226469, JP-A-3161058, and the like. However, it is not limited to these. Types of polymer compounds include polyfluorene compounds, polyfluorene polymer compounds, polyarylene compounds, polyarylene polymer compounds, polyarylene vinylene compounds, polyarylene vinylene polymer compounds, polystilbene compounds, Examples include polystilbene polymer compounds, polystilbenvinylene compounds, polystilbenvinylene polymer compounds, polypyridinediyl compounds, polypyridinediyl polymer compounds, alkoxypolythiophene compounds, and alkoxypolythiophene polymer compounds. However, it is not limited to these. Among these, polyfluorene polymer compounds, polyarylene polymer compounds, polyarylene vinylene polymer compounds, polystilbene polymer compounds, and polystilbene vinylene polymer compounds are preferable.

  The mixing ratio may be anything as long as it improves the solubility in a solvent, the fluorescence intensity, the characteristics of the device such as lifetime and luminance, and the like, but the ratio of the fluorene polymer of the present invention is a polymer composition. It is usually in the range of 5 to 95% by weight with respect to the whole product.

  Moreover, what contains 2 or more types of fluorene polymers which have a terminal group of this invention as a polymer composition of this invention is mentioned. The polymer composition of the present invention can be obtained by appropriately combining two or more of these fluorene polymers. Further, the blending ratio is not particularly limited, but it is also preferable that the ratio of the fluorene polymer contained most in the composition is in the range of 5 to 90% by weight with respect to the entire polymer composition.

<Composition (Liquid composition)>
The composition of this invention contains the said fluorene polymer and the high molecular compound whose number average molecular weights of polystyrene other than this fluorene polymer are 10 < ³ > -10 < ⁸ >. Examples of the polymer compound having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ other than the fluorene polymer include poly (phenylene) and its derivatives, poly (benzofluorene) and its derivatives, poly (dibenzofuran) and its Derivatives, poly (dibenzothiophene) and derivatives thereof, poly (carbazole) and derivatives thereof, poly (thiophene) and derivatives thereof, poly (phenylene vinylene) and derivatives thereof, poly (fluorene vinylene) and derivatives thereof, poly (benzofluorene vinylene) ) And derivatives thereof, poly (dibenzofuranvinylene) and derivatives thereof, and the like. However, these derivatives are other than the repeating unit represented by the formula (1).

  The liquid composition of the present invention is useful for production of light-emitting elements such as polymer light-emitting elements and organic transistors. The liquid composition comprises the fluorene polymer and a solvent. In the present specification, the “liquid composition” means a liquid that is liquid at the time of device fabrication, and typically means a liquid at normal pressure (ie, 1 atm) and 25 ° C. The liquid composition is generally called an ink, an ink composition, a solution or the like.

  In addition to the fluorene polymer, the liquid composition of the present invention includes a low molecular light emitting material, a hole transport material, an electron transport material, a stabilizer, an additive for adjusting viscosity and / or surface tension, an antioxidant, and the like. May be included. Each of these optional components may be used alone or in combination of two or more.

  Examples of the low-molecular fluorescent material that may be contained in the liquid composition of the present invention include naphthalene derivatives, anthracene, anthracene derivatives, perylene, perylene derivatives, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes, Metal complexes having a metal complex of 8-hydroxyquinoline as a ligand, metal complexes having an 8-hydroxyquinoline derivative as a ligand, other fluorescent metal complexes, aromatic amines, tetraphenylcyclopentadiene, tetraphenylcyclopentadiene Derivative, tetraphenylcyclobutadiene, tetraphenylcyclobutadiene derivative, stilbene, silicon-containing aromatic, oxazole, furoxan, thiazole, tetraarylmethane, thiadiazole, pyrazole, metacyclophane, Fluorescent material of low molecular weight compounds of acetylene-based, and the like. Specific examples include those described in JP-A-57-51781, JP-A-59-194393, and the like.

  Examples of the hole transport material that the liquid composition of the present invention may contain include, for example, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, Arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof Derivatives and the like.

  Examples of the electron transport material that may be contained in the liquid composition of the present invention include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyano Anthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, etc. Can be mentioned.

  Examples of the stabilizer that may be contained in the liquid composition of the present invention include phenolic antioxidants and phosphorus antioxidants.

  As an additive for adjusting the viscosity and / or surface tension which the liquid composition of the present invention may contain, for example, a high molecular weight compound (thickener) for increasing the viscosity, a poor solvent, a viscosity A low molecular weight compound for lowering, a surfactant for lowering surface tension, and the like may be used in appropriate combination.

  The high molecular weight compound is not particularly limited as long as it does not inhibit light emission or charge transport, and is usually soluble in the solvent of the liquid composition. As the high molecular weight compound, for example, high molecular weight polystyrene, high molecular weight polymethyl methacrylate, or the like can be used. The high molecular weight compound has a polystyrene-equivalent weight average molecular weight of preferably 500,000 or more, more preferably 1,000,000 or more. A poor solvent can also be used as a thickener.

  The antioxidant that may be contained in the liquid composition of the present invention is not limited as long as it does not inhibit light emission or charge transport. When the composition contains a solvent, it is usually soluble in the solvent. is there. Examples of the antioxidant include phenolic antioxidants and phosphorus antioxidants. By using an antioxidant, the storage stability of the polymer compound and the solvent can be improved.

  When the liquid composition of the present invention contains a hole transport material, the ratio of the hole transport material in the liquid composition is usually 1 wt% to 80 wt%, preferably 5 wt% to 60% by weight. When the liquid composition of the present invention contains an electron transport material, the ratio of the electron transport material in the liquid composition is usually 1% by weight to 80% by weight, preferably 5% by weight to 60% by weight. %.

When forming a film using this liquid composition in the preparation of a polymer light emitting device, it is only necessary to remove the solvent by drying after applying the liquid composition, and also to mix the charge transport material and the light emitting material. In this case, the same technique can be applied, which is very advantageous in manufacturing. In addition, in the case of drying, you may dry in the state heated at about 50-150 degreeC, and may be dried under reduced pressure to about 10 ^<-3 > Pa.

  The film formation method using the liquid composition includes spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  The proportion of the solvent in the liquid composition is usually 1% by weight to 99.9% by weight, preferably 60% by weight to 99.9% by weight, based on the total weight of the liquid composition. Preferably it is 90 weight%-99.8 weight%. Although the viscosity of the liquid composition varies depending on the printing method, it is preferably in the range of 0.5 to 500 mPa · s at 25 ° C. When the liquid composition passes through a discharge device, such as an ink jet printing method, an eye at the time of discharge is used. The viscosity is preferably in the range of 0.5 to 20 mPa · s at 25 ° C. in order to prevent jamming and flight bending.

  As the solvent contained in the liquid composition, those capable of dissolving or dispersing components other than the solvent in the liquid composition are preferable. Examples of the solvent include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorinated solvents such as chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, toluene, xylene, and trimethyl. Aromatic hydrocarbon solvents such as benzene and mesitylene, aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, methyl benzoate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether Polyethylene alcohol and its derivatives such as ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerol, 1,2-hexanediol, methanol, ethanol, propanol, isopropanol, cyclohexanol, etc. Examples thereof include alcohol-based solvents, sulfoxide-based solvents such as dimethyl sulfoxide, and amide-based solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These solvents may be used alone or in combination. Among the solvents, it is preferable to include one or more organic solvents having a structure containing at least one benzene ring and having a melting point of 0 ° C. or lower and a boiling point of 100 ° C. or higher in view of viscosity, film formability, and the like. To preferred.

  Solvents include aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents from the viewpoints of solubility in organic solvents other than the solvent in the liquid composition, uniformity during film formation, viscosity characteristics, etc. Ester solvents and ketone solvents are preferred, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, mesitylene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, s-butylbenzene, anisole, ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexylbenzene, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, methylbenzoate, 2-propylcyclohexanone, 2-heptanone, - heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone, dicyclohexyl ketone are preferred, xylene, anisole, mesitylene, cyclohexylbenzene, and it is more preferable to contain at least one of bicyclohexyl methyl benzoate.

  The type of solvent contained in the liquid composition is preferably two or more, more preferably two to three, and more preferably two from the viewpoints of film forming properties and device characteristics. Further preferred.

  When two kinds of solvents are contained in the liquid composition, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, it is preferable that one type of solvent has a boiling point of 180 ° C. or higher, and the other one type of solvent preferably has a boiling point of less than 180 ° C. One type of solvent has a boiling point of 200 ° C. More preferably, the solvent has a boiling point of less than 180 ° C. From the viewpoint of viscosity, at 60 ° C., it is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition is dissolved in the solvent, and one of the two solvents includes At 25 ° C., it is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition is dissolved.

  When three types of solvents are contained in the liquid composition, one or two of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, at least one of the three solvents is preferably a solvent having a boiling point of 180 ° C. or higher, and at least one solvent is preferably a solvent having a boiling point of 180 ° C. or lower. At least one of the types of solvents is a solvent having a boiling point of 200 ° C. or more and 300 ° C. or less, and at least one of the solvents is more preferably a solvent having a boiling point of 180 ° C. or less. In addition, from the viewpoint of viscosity, it is preferable that two of the three solvents have a solubility of 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition at 60 ° C., In one of the three solvents, 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition is preferably dissolved in the solvent at 25 ° C.

  When two or more kinds of solvents are contained in the liquid composition, the solvent having the highest boiling point may be 40 to 90% by weight of the total solvent contained in the liquid composition from the viewpoints of viscosity and film formability. Preferably, it is 50 to 90% by weight, more preferably 65 to 85% by weight.

-Thin film-
The thin film of the present invention will be described. This thin film is formed using the fluorene polymer. Examples of the thin film include a light-emitting thin film, a conductive thin film, and an organic semiconductor thin film.

  The light-emitting thin film preferably has a quantum yield of light emission of 50% or more, more preferably 60% or more, and still more preferably 70% or more, from the viewpoint of device brightness, light emission voltage, and the like. .

  The conductive thin film preferably has a surface resistance of 1 KΩ / □ or less. The electrical conductivity can be increased by doping the thin film with a Lewis acid, an ionic compound or the like. The surface resistance is more preferably 100Ω / □ or less, and further preferably 10Ω / □ or less.

In the organic semiconductor thin film, the higher one of the electron mobility and the hole mobility is preferably 10 ⁻⁵ cm ² / V / second or more, more preferably 10 ⁻³ cm ² / V / second or more. More preferably, it is 10 ⁻¹ cm ² / V / second or more. In addition, an organic transistor can be manufactured using an organic semiconductor thin film. Specifically, an organic transistor can be formed by forming an organic semiconductor thin film on a Si substrate on which an insulating film such as SiO ₂ and a gate electrode are formed, and forming a source electrode and a drain electrode with Au or the like. .

-Organic transistors (polymer field effect transistors)-
Next, a polymer field effect transistor which is an embodiment of the organic transistor will be described.

  The fluorene polymer of the present invention can be suitably used as a material for a polymer field effect transistor, particularly as an active layer. As a structure of a polymer field effect transistor, a source electrode and a drain electrode are usually provided in contact with an active layer made of a polymer, and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween. Just do it.

  The polymer field effect transistor is usually formed on a supporting substrate. The material of the support substrate is not particularly limited as long as the characteristics as a field effect transistor are not hindered, but a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

  The polymer field effect transistor can be produced by a known method, for example, a method described in JP-A-5-110069.

  In forming the active layer, it is very advantageous and preferable to use an organic solvent-soluble fluorene polymer. As a film-forming method from a solution obtained by dissolving an organic solvent-soluble polymer compound in a solvent, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating Application methods such as a method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method can be used.

  A sealed polymer field effect transistor obtained by sealing after producing a polymer field effect transistor is preferred. Thereby, the polymer field effect transistor is shielded from the atmosphere, and deterioration of the characteristics of the polymer field effect transistor can be suppressed.

  Examples of the sealing method include a method of covering with an ultraviolet (UV) curable resin, a thermosetting resin, an inorganic SiONx film, or the like, and a method of bonding a glass plate or film with a UV curable resin, a thermosetting resin, or the like. In order to effectively cut off from the atmosphere, it is preferable to carry out the steps from the preparation of the polymer field effect transistor to the sealing without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

-Organic solar cells-
Next, an organic solar cell will be described. A solid photoelectric conversion element utilizing the photovoltaic effect as an organic photoelectric conversion element which is one embodiment of an organic solar battery will be described.

  The fluorene polymer of the present invention is used as a material for an organic photoelectric conversion element, particularly as an organic semiconductor layer of a Schottky barrier type element utilizing an interface between an organic semiconductor and a metal, and between an organic semiconductor and an inorganic semiconductor, or between organic semiconductors. It can be suitably used as an organic semiconductor layer of a pn heterojunction element utilizing the interface.

  Furthermore, as an electron-donating polymer and an electron-accepting polymer in a bulk heterojunction device with an increased donor-acceptor contact area, an organic photoelectric conversion device using a polymer / low-molecular composite system, for example, electron accepting It can be suitably used as an electron donating conjugated polymer (dispersion support) of a bulk heterojunction organic photoelectric conversion element in which a fullerene derivative is dispersed as a body.

  As the structure of the organic photoelectric conversion element, for example, in a pn heterojunction type element, a p-type semiconductor layer is formed on an ohmic electrode, for example, ITO, and an n-type semiconductor layer is further stacked thereon. It is sufficient that an ohmic electrode is provided.

  The organic photoelectric conversion element is usually formed on a support substrate. The material of the support substrate is not particularly limited as long as the characteristics as the organic photoelectric conversion element are not impaired, but a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

  The organic photoelectric conversion element can be formed by a known method, for example, Synth. Met. , 102, 982 (1999) and the method described in Science, 270, 1789 (1995).

  The polymer LED of the present invention has a light emitting layer between electrodes composed of an anode and a cathode, and the light emitting layer contains the fluorene polymer or polymer composition of the present invention. The polymer LED of the present invention includes a polymer light-emitting device in which a layer containing a conductive polymer is provided adjacent to the electrode between at least one electrode and the light-emitting layer, and at least one electrode and the light-emitting layer. Also included is a polymer light emitting device in which an insulating layer having an average film thickness of 2 nm or less is provided adjacent to the electrode.

  In addition, as the polymer LED of the present invention, a polymer LED having an electron transport layer provided between the cathode and the light emitting layer, a polymer LED having a hole transport layer provided between the anode and the light emitting layer, Examples include a polymer LED in which an electron transport layer is provided between the cathode and the light emitting layer, and a hole transport layer is provided between the anode and the light emitting layer.

Specific examples of the structure of the polymer LED of the present invention include the following structures a) to d).
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)

  Here, the light emitting layer is a layer having a function of emitting light, the hole transporting layer is a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. It is. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently.

  Further, among the charge transport layers provided adjacent to the electrodes, those having a function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers). , An electron injection layer).

  Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be improved. In order to prevent mixing, a thin insulating layer may be inserted at the interface between the charge transport layer and the light emitting layer. The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

In the present invention, a polymer LED provided with a charge injection layer (electron injection layer, hole injection layer) includes a polymer LED provided with a charge injection layer adjacent to the cathode, and a charge injection layer adjacent to the anode. The provided polymer LED is mentioned. For example, the following structures e) to p) are specifically mentioned.
e) Anode / charge injection layer / light emitting layer / cathode f) Anode / light emitting layer / charge injection layer / cathode g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode h) Anode / charge injection layer / hole Transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / charge injection layer / cathode j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode k) anode / charge Injection layer / light emitting layer / electron transport layer / cathode l) anode / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode n) anode / Charge injection layer / hole transport layer / light emitting layer / electron transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) anode / charge injection layer / hole transport Layer / light emitting layer / electron transport layer / charge injection layer / cathode

  Specific examples of the charge injection layer include a layer containing a conductive polymer, an anode and a hole transport layer provided between the anode material and the hole transport material included in the hole transport layer. A layer containing a material having an ionization potential of a value, a layer provided between a cathode and an electron transport layer, and a layer containing a material having an electron affinity of an intermediate value between the cathode material and the electron transport material contained in the electron transport layer, etc. Is exemplified.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ or less, and the leakage current between the light emitting pixels is reduced. to ^is more preferably ¹⁰ -5 S / cm to 10 ² or ^less, further preferably ¹⁰ -5 S / cm to 10 ¹ or less.

In the case where the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less. in order to reduce the ^current, more preferably less ¹⁰ -5 S / cm or more and ¹⁰ 2 S / ^cm, more preferably less ¹⁰ -5 S / cm or more and ¹⁰ 1 S / cm. Usually, in order to make the electric conductivity of the conductive polymer 10 ⁻⁵ S / cm or more and 10 ³ or less, the conductive polymer is doped with an appropriate amount of ions.

  The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions, and the like. The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

  The material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer. Polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene And derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanines (such as copper phthalocyanine), and carbon .

  An insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. As the polymer LED provided with the insulating layer having a thickness of 2 nm or less, the polymer LED provided with the insulating layer having a thickness of 2 nm or less adjacent to the cathode, or the insulating layer having a thickness of 2 nm or less provided adjacent to the anode. Polymer LED is mentioned.

Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode u) Anode / hole transporting layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode w) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode x) anode / Light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode y) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode z) anode / film Insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode aa) anode / hole transport layer / light emitting layer / electron transport Layer / thickness 2nm or less of the insulating layer / cathode ab) anode / thickness 2nm or less of the insulating layer / hole transport layer / light emitting layer / electron transporting layer / thickness 2nm or less of the insulating layer / cathode

  The light emitting layer contains the fluorene polymer or polymer composition of the present invention, but a light emitting material other than the fluorene polymer may be mixed and used in the light emitting layer. In the polymer LED of the present invention, a light emitting layer containing a light emitting material other than the fluorene polymer may be laminated with a light emitting layer containing the fluorene polymer. As the light emitting material, known materials can be used. Examples of low molecular weight compounds include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or its metal complexes, aromatic amines, and the like. , Tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used. Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

Furthermore, as the light emitting material, a triplet light emitting complex or a derivative thereof as described below can be used.

また、例えば、ＷＯ０３／００１６１６に記載されている、三重項発光錯体基を含む高分子化合物などを用いることができる。

For example, a high molecular compound containing a triplet light emitting complex group described in WO03 / 001616 can be used.

  Although there is no restriction | limiting in the film-forming method of a light emitting layer, For example, the method by the film-forming from a solution is illustrated.

  As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, Application methods such as a flexographic printing method, an offset printing method, and an ink jet printing method can be used.

  Examples of the solvent used for film formation from a solution include toluene, xylene, chloroform, and tetrahydrofuran.

  As the film thickness of the light emitting layer, the optimum value varies depending on the material to be used, and it may be selected so that the drive voltage and the light emission efficiency are appropriate values. For example, the thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. More preferably, it is 5 nm-200 nm.

  When the polymer LED of the present invention has a hole transport layer, the hole transport material used includes polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in a side chain or a main chain. , Pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thieni Lembinylene) or a derivative thereof is exemplified.

  Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

  Among these, as a hole transport material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Polymeric hole transport materials such as polythiophene or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thienylene vinylene) or derivatives thereof are preferred, more preferably polyvinyl carbazole or derivatives thereof, Polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

  Polyvinylcarbazole or a derivative thereof is obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

  Examples of polysilane or derivatives thereof include compounds described in Chem. Rev., 89, 1359 (1989), and GB 2300196 published specification. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

Since polysiloxane or a derivative thereof has almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular hole transporting material in the side chain or main chain are preferably used.
Particularly, those having a hole transporting aromatic amine in the side chain or main chain are exemplified.

  Although there is no restriction | limiting in the film-forming method of a positive hole transport layer, In the low molecular hole transport material, the method by the film-forming from a mixed solution with a polymer binder is illustrated. In the case of a polymer hole transport material, a method of film formation from a solution is exemplified.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  The film thickness of the hole transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If it is too thick, the driving voltage of the element becomes high, which is not preferable. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the polymer LED of the present invention has an electron transport layer, known electron transport materials can be used, such as oxadiazole derivatives, anthraquinodimethane or its derivatives, benzoquinone or its derivatives, naphthoquinone or its Derivatives, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or Examples thereof include polyfluorene or a derivative thereof.

  Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, The thing etc. which are described in the same 3-152184 gazette are illustrated.

  Of these, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  Although there is no particular limitation on the method for forming the electron transport layer, in the case of a low molecular electron transport material, a vacuum deposition method from powder or a method by film formation from a solution or a molten state is used. Each method is exemplified by film formation from a molten state. When forming a film from a solution or a molten state, a polymer binder may be used in combination.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve an electron transport material and / or a polymer binder. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of film formation methods from a solution or a molten state include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those not strongly absorbing visible light are suitably used. As the polymer binder, poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, poly (2,5-thienylenevinylene) or a derivative thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, or polysiloxane.

  The film thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are moderate values, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the drive voltage of the element becomes high, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  The substrate on which the polymer LED of the present invention is formed may be any substrate that does not change when the electrode is formed and the organic layer is formed, and examples thereof include glass, plastic, polymer film, and silicon substrate. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

  Usually, it is preferable that at least one of the electrode composed of the anode and the cathode is transparent or translucent, and the anode side is transparent or translucent. As the material of the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Further, as the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used. The film thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there. In order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

  As a material of the cathode used in the polymer LED of the present invention, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and their Two or more of these alloys, or one or more of them and an alloy of one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, or graphite or graphite intercalation compound Etc. are used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The cathode may have a laminated structure of two or more layers. The thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used. In addition, a layer made of a conductive polymer or a layer having an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided between the cathode and the organic material layer. A protective layer for protecting the polymer LED may be attached. In order to stably use the polymer LED for a long period of time, it is preferable to attach a protective layer and / or protective cover in order to protect the element from the outside.

  As the protective layer, a polymer compound, metal oxide, metal fluoride, metal boride and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing the cover by bonding it to the element substrate with a heat effect resin or a photo-curing resin is preferable. Used for. If the space is maintained by using the spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It is easy to suppress damage to the element. Among these, it is preferable to take any one or more measures.

  The polymer light emitting device of the present invention can be used as a planar light source, a segment display device, a dot matrix display device, a backlight of a liquid crystal display device, and the like.

  In order to obtain planar light emission using the polymer LED of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic material layer of a non-light-emitting portion is formed extremely thick and substantially non- There are a method of emitting light and a method of forming either one of the anode or the cathode or both electrodes in a pattern. A segment type display element capable of displaying numbers, letters, simple symbols, etc. can be obtained by forming a pattern by any of these methods and arranging several electrodes so that they can be turned ON / OFF independently. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of polymer phosphors having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively or may be driven actively in combination with TFTs. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

  Furthermore, the planar light emitting element is a self-luminous thin type, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

  Moreover, the fluorene polymer of this invention can be used as a pigment | dye for lasers, a material for organic solar cells, an organic semiconductor for organic transistors, and a material for conductive thin films.

Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
Here, regarding the number average molecular weight and the weight average molecular weight, the number average molecular weight and the weight average molecular weight in terms of polystyrene were determined by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation: LC-10Avp) using tetrahydrofuran as a solvent.

３．１５ｇをＮ，Ｎ−ジメチルホルムアミド１００ｇに溶解した。この溶液を氷冷した後、この溶液に、あらかじめ、Ｎ−ブロモスクシンイミド１．６２ｇをＮ，Ｎ−ジメチルホルムアミド５０ｇに溶解した溶液を、約８０分間で、滴下した。
滴下後、引き続き、０〜５℃で４時間反応した。次に、この反応溶液を、室温まで昇温し、引き続いて、室温で、一夜反応した。なお、反応は窒素ガス雰囲気下で行った。
反応後、この反応溶液に、イオン交換水を加え、洗浄した後、この溶液から、減圧下、溶媒を留去した。次に、得られた沈殿に、トルエンを加え、溶解した後、このトルエン溶液をろ過し、不溶物を除去した。次に、このトルエン溶液をアルミナを充填したカラムを通して、精製した。この溶液から、減圧下、溶媒を留去した後、減圧乾燥して、下記単量体（５）２．０ｇを得た。
［Ｈ−ＮＭＲ：溶媒ＣＤＣｌ３；０．９〜１．０ｐｐｍ（３Ｈ）、１．３〜１．７ｐｐｍ（４Ｈ）、２．６〜２．７ｐｐｍ（２Ｈ）、５．７〜６．０ｐｐｍ（２Ｈ）、６．５〜６．８（５Ｈ、７．１〜７．４（４Ｈ））

＜フルオレン重合体１の合成＞
前記単量体（５）０．０５９ｇと２，７−ジブロム−９，９−ジオクチルフルオレン０．５９ｇと２，７−ジブロム−９，９−ジイソペンチルフルオレン０．１３ｇと２、２’−ビピリジル０．５６ｇとを反応容器に仕込んだ後、反応系内を窒素ガスで置換した。これに、あらかじめアルゴンガスでバブリングして、脱気したテトラヒドロフラン（脱水溶媒）６０ｇを加えた。次に、この混合溶液に、ビス（１，５−シクロオクタジエン）ニッケル（０）を１．０ｇ加え、６０℃で４時間反応させた。なお、反応は、窒素ガス雰囲気下で行った。
反応後、この溶液を冷却した後、メタノール４０ｍｌ／イオン交換水４０ｍｌ混合溶液をそそぎ込み、約１時間攪拌した。次に、生成した沈殿を、ろ過することにより回収した。次に、この沈殿を減圧乾燥した後、トルエンに溶解した。このトルエン溶液を濾過し、不溶物を除去した後、このトルエン溶液を、アルミナを充填したカラムに通すことで精製した。次に、このトルエン溶液を、１規定塩酸水溶液で洗浄し、静置、分液した後、トルエン溶液を回収した。次に、このトルエン溶液を、約５％アンモニア水で洗浄し、静置、分液した後、トルエン溶液を回収した。次に、このトルエン溶液をイオン交換水で洗浄し、静置、分液した後、トルエン溶液を回収した。次に、このトルエン溶液を、メタノール中にそそぎ込み、再沈殿物を生成させた。
次に、生成した沈殿を回収し、この沈殿を減圧乾燥して、重合体０．２０ｇを得た。この重合体をフルオレン重合体１と呼ぶ。得られたフルオレン重合体１のポリスチレン換算重量平均分子量は、３．２ｘ１０^４であり、数平均分子量は、１．６ｘ１０^４であった。 Example 1
<Synthesis of monomer (5)>
Synthesis example (1)
The following compound (D):

3.15 g was dissolved in 100 g of N, N-dimethylformamide. After this solution was ice-cooled, a solution prepared by dissolving 1.62 g of N-bromosuccinimide in 50 g of N, N-dimethylformamide in advance was added dropwise to this solution in about 80 minutes.
After the dropping, the reaction was continued at 0 to 5 ° C. for 4 hours. Next, this reaction solution was warmed to room temperature, and subsequently reacted overnight at room temperature. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, ion-exchanged water was added to the reaction solution for washing, and then the solvent was distilled off from the solution under reduced pressure. Next, toluene was added to and dissolved in the obtained precipitate, and then this toluene solution was filtered to remove insoluble matters. Next, this toluene solution was purified through a column packed with alumina. From this solution, the solvent was distilled off under reduced pressure, followed by drying under reduced pressure to obtain 2.0 g of the following monomer (5).
[H-NMR: solvent CDCl3; 0.9 to 1.0 ppm (3H), 1.3 to 1.7 ppm (4H), 2.6 to 2.7 ppm (2H), 5.7 to 6.0 ppm (2H ), 6.5-6.8 (5H, 7.1-7.4 (4H))

<Synthesis of fluorene polymer 1>
0.059 g of the monomer (5), 0.59 g of 2,7-dibromo-9,9-dioctylfluorene, 0.13 g of 2,7-dibromo-9,9-diisopentylfluorene, 2,2,2′- After charging 0.56 g of bipyridyl into the reaction vessel, the inside of the reaction system was replaced with nitrogen gas. To this was added 60 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.0 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution and reacted at 60 ° C. for 4 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled and then poured into a mixed solution of methanol 40 ml / ion exchanged water 40 ml and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration. Next, this precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was washed with a 1N aqueous hydrochloric acid solution, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was washed with about 5% aqueous ammonia, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was washed with ion-exchanged water, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was poured into methanol to generate a reprecipitate.
Next, the produced precipitate was recovered, and this precipitate was dried under reduced pressure to obtain 0.20 g of a polymer. This polymer is referred to as fluorene polymer 1. The resulting fluorene polymer 1 had a polystyrene equivalent weight average molecular weight of 3.2 × 10 ⁴ and a number average molecular weight of 1.6 × 10 ⁴ .

The structure of the repeating unit and terminal contained in the fluorene polymer 1 estimated from the charging is as follows, and the molar ratio estimated from the charging is repeating unit A / repeating unit B / terminal group C = 72/18. / 10.

で表される単量体（１）０．０７１ｇと２，７−ジブロム−９，９−ジオクチルフルオレン０．５９ｇと２，７−ジブロム−９，９−ジイソペンチルフルオレン０．１３ｇと２、２’−ビピリジル０．５６ｇとを反応容器に仕込んだ後、反応系内を窒素ガスで置換した。これに、あらかじめアルゴンガスでバブリングして、脱気したテトラヒドロフラン（脱水溶媒）６０ｇを加えた。次に、この混合溶液に、ビス（１，５−シクロオクタジエン）ニッケル（０）を１．０ｇ加え、６０℃で４時間反応させた。なお、反応は、窒素ガス雰囲気下で行った。
反応後、この溶液を冷却した後、メタノール４０ｍｌ／イオン交換水４０ｍｌ混合溶液をそそぎ込み、約１時間攪拌した。次に、生成した沈殿を、ろ過することにより回収した。次に、この沈殿を減圧乾燥した後、トルエンに溶解した。このトルエン溶液を濾過し、不溶物を除去した後、このトルエン溶液を、アルミナを充填したカラムに通すことで精製した。次に、このトルエン溶液を、１規定塩酸水溶液で洗浄し、静置、分液した後、トルエン溶液を回収した。次に、このトルエン溶液を、約５％アンモニア水で洗浄し、静置、分液した後、トルエン溶液を回収した。次に、このトルエン溶液をイオン交換水で洗浄し、静置、分液した後、トルエン溶液を回収した。次に、このトルエン溶液を、メタノール中にそそぎ込み、再沈殿物を生成させた。
次に、生成した沈殿を回収し、この沈殿を減圧乾燥して、重合体０．２９ｇを得た。この重合体をフルオレン重合体２と呼ぶ。得られたフルオレン重合体２のポリスチレン換算重量平均分子量は、４．２ｘ１０^５であり、数平均分子量は、８．９ｘ１０^４であった。 Comparative Example 1
<Synthesis of fluorene polymer 2>
The following structural formula:

Monomer (1) represented by the following formula: 0.071 g, 2,7-dibromo-9,9-dioctylfluorene 0.59 g, 2,7-dibromo-9,9-diisopentylfluorene 0.13 g and 2, After charging 0.56 g of 2′-bipyridyl into the reaction vessel, the inside of the reaction system was replaced with nitrogen gas. To this was added 60 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.0 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution and reacted at 60 ° C. for 4 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled and then poured into a mixed solution of methanol 40 ml / ion exchanged water 40 ml and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration. Next, this precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was washed with a 1N aqueous hydrochloric acid solution, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was washed with about 5% aqueous ammonia, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was washed with ion-exchanged water, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was poured into methanol to generate a reprecipitate.
Next, the produced precipitate was recovered, and this precipitate was dried under reduced pressure to obtain 0.29 g of a polymer. This polymer is referred to as fluorene polymer 2. The resulting fluorene polymer 2 had a polystyrene equivalent weight average molecular weight of 4.2 × 10 ⁵ and a number average molecular weight of 8.9 × 10 ⁴ .

The structure of the repeating unit contained in the fluorene polymer 2 estimated from the charging is as follows, and the molar ratio estimated from the charging is repeating unit D / repeating unit E / repeating unit F = 72/18/10. It is.

Example 2
<Fluorescence property evaluation of fluorene polymer>
A fluorene polymer thin film was prepared by spin-coating a 0.8 wt% toluene solution of a fluorene polymer on a quartz plate. The fluorescence spectrum of the thin film was measured using a fluorescence spectrophotometer (Fluorolog (trade name) manufactured by JOBINYVON-SPEX) at an excitation wavelength of 350 nm. In order to obtain the relative fluorescence intensity in the thin film, the value obtained by integrating the fluorescence spectrum plotted with the wavenumber with the intensity of the Raman line of water in the spectrum measurement range was used as a spectrophotometer (Cary5E (trade name) manufactured by Varian). ) Was used to determine the value divided by the absorbance at the excitation wavelength.
Table 1 shows the measurement results of the fluorescence peak wavelength and the fluorescence intensity. The fluorescence intensity of the fluorene polymer 1 containing a terminal group of the present invention was stronger than that of the fluorene polymer 2 containing a phenoxazine ring in the polymer chain.

Example 3
<Element characteristic evaluation>
A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is spin-coated with a poly (ethylenedioxythiophene) / polystyrene sulfonic acid solution (Bayer, BaytronP (trade name)) to a thickness of 50 nm. Film and dry on a hot plate at 200 ° C. for 10 minutes. Next, a film is formed at a rotational speed of 1500 rpm by spin coating using a toluene solution prepared such that a 3: 7 (weight ratio) mixture of fluorene polymer 1 and fluorene polymer 2 is 1.5 wt%. Furthermore, after drying this at 80 degreeC under pressure reduction for 1 hour, about 4 nm of lithium fluoride is vapor-deposited, about 20 nm of calcium is vapor-deposited as a cathode next, and about 50 nm of aluminum is vapor-deposited, and an EL element is produced. After the degree of vacuum reaches 1 × 10 ⁻⁴ Pa or less, metal deposition is started. By applying voltage to the obtained element, EL light emission can be obtained.

  When the fluorene polymer of the present invention is used as a light emitting material in a light emitting layer of a polymer LED, the polymer LED is excellent in characteristics. Therefore, the polymer LED can be preferably used in a device such as a curved or flat light source for a backlight or illumination of a liquid crystal display, a segment type display element, and a dot matrix flat panel display. Moreover, the fluorene polymer of this invention can be used as a pigment | dye for lasers, a material for organic solar cells, an organic semiconductor for organic transistors, and a material for conductive thin films.

Claims (22)

A fluorene polymer having one or more repeating units selected from the group consisting of repeating units represented by the following formula (I), which is represented by the following formula (II) on at least one of the molecular chain ends of the polymer. The fluorene polymer having a terminal group selected from the group consisting of monovalent groups.

(Where R is hydrogen, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino A monovalent heterocyclic group or a cyano group, in the above example, a plurality of Rs may be present, but they may be the same or different.)

(Where R is hydrogen, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino A monovalent heterocyclic group or a cyano group, and the plurality of R may be the same or different .) Furthermore, the fluorene polymer of Claim 1 containing the repeating unit shown by following formula (3).
^{- Ar 1 - (Z ')} p- (3)
(Here, Ar ¹ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group.
Z ′ represents —CR ₄ ═CR ₅ — or —C≡C—. R ₄ and R ₅ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. p represents 0 or 1. ) The fluorene polymer according to claim 1 or 2, which has a polystyrene-reduced number average molecular weight of 10 ³ to 10 ⁸ .   The fluorene polymer according to claim 1 or 2 having fluorescence in a solid state. The fluorene polymer according to claim 1, which has fluorescence in a solid state and has a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ . A polymer composition comprising a polymer compound having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ and having fluorescence in a solid state, and the fluorene polymer according to claim 1. Polymeric composition characterized in that it comprises two or more fluorene polymer according to claim 1 or 2. Between electrodes consisting of an anode and a cathode, a light-emitting layer, the light emitting layer, polymer light-emitting device which comprises a fluorene polymer according to claim 1 or 2, wherein. A polymer light emitting device comprising a light emitting layer between electrodes composed of an anode and a cathode, wherein the light emitting layer contains the polymer composition according to claim 6 or 7 .   The polymer light emitting device according to claim 8 or 9, wherein a layer containing a conductive polymer is provided between at least one electrode and the light emitting layer adjacent to the electrode.   The polymer light emitting device according to any one of claims 8 to 10, wherein an insulating layer having an average film thickness of 2 nm or less is provided between at least one electrode and the light emitting layer adjacent to the electrode.   The polymer light emitting device according to any one of claims 8 to 11, wherein an electron transport layer is provided adjacent to the light emitting layer between the cathode and the light emitting layer.   The polymer light emitting device according to any one of claims 8 to 12, wherein a hole transport layer is provided adjacent to the light emitting layer between the anode and the light emitting layer.   14. The electron transport layer provided adjacent to the light emitting layer between the cathode and the light emitting layer, and the hole transport layer provided adjacent to the light emitting layer between the anode and the light emitting layer. The polymer light-emitting device according to any one of the above.   A planar light source comprising the polymer light emitting device according to any one of claims 8 to 14.   A segment display device comprising the polymer light-emitting device according to claim 8.   A dot matrix display comprising the polymer light-emitting device according to claim 8.   The liquid crystal display device containing the polymer light emitting element as described in any one of Claims 8-14. The liquid composition containing the fluorene polymer as described in any one of Claims 1-5, and a solvent. The thin film containing the fluorene polymer as described in any one of Claims 1-5. The organic transistor containing the fluorene polymer as described in any one of Claims 1-5. The solar cell containing the fluorene polymer as described in any one of Claims 1-5.