JP5003297B2 - Block copolymer and polymer light emitting device - Google Patents

Description

The present invention relates to a block copolymer having fluorescence in a solid state, a method for producing the same, and a polymer light emitting device using the block copolymer (hereinafter sometimes referred to as polymer LED).

High molecular weight light emitting materials (polymer phosphors) are variously studied because they are soluble in a solvent and can form a light emitting layer in a light emitting element by a coating method, unlike low molecular weight materials.

A block copolymer is known as one of polymers that can be used as a polymeric fluorescent substance. As such a block copolymer, for example, Tokuhei Hei 8-5
05167 discloses a block copolymer composed of a thiophenediyl repeating unit and a block bonded with a conjugated bond and a block composed of a repeating unit represented by -SiMe2- and not bonded with a conjugated bond. ing.
Further, a block copolymer in which the repeating units are not bonded by a conjugated bond and the main chain has a polyethylene structure is also known (Japanese Patent Application Laid-Open No. 11-60660, JP-A-2
000-159846). For example, JP-T-11-60660 discloses a block copolymer composed of a block formed by polymerizing vinyl carbazole and a block formed by polymerizing a vinyl compound having a group containing oxadiazole. .

However, characteristics such as luminous efficiency and lifetime of a polymer light emitting device using the above known block copolymer as a polymeric fluorescent substance are still insufficient.
An object of the present invention is a novel block copolymer, and when the block copolymer is used as a polymeric fluorescent substance in a polymer light emitting device, the block copolymer can exhibit excellent characteristics. Polymer and polymer light emitting device using the polymer (hereinafter referred to as polymer LED)
Is to provide).

That is, the present invention is a block copolymer containing two or more blocks and having fluorescence in a solid state, and these blocks may be the same or different, and one or more types in each block Are connected by a conjugated bond, and the blocks are connected by a bonding unit having a conjugated bond.
And at least one block has a polystyrene equivalent number average molecular weight of 1 × 10 ^3.
It relates to a block copolymer characterized by being ˜1 × 10 ⁸ .

The present invention also relates to a block copolymer containing two or more blocks and having fluorescence in a solid state, wherein at least two of the blocks are not identical to each other, and one or more types of repeating units are contained in each block. Are connected by a conjugated bond, and the blocks are connected by a direct bond without breaking the conjugated chain,
And at least one block has a polystyrene equivalent number average molecular weight of 1 × 10 ^3.
It relates to a block copolymer characterized by being ˜1 × 10 ⁸ .
In the block copolymer of the present invention, the polystyrene-equivalent number average molecular weight of at least one block is preferably 2 × 10 ³ to 1 × 10 ⁸ .
Furthermore, the block copolymer of the present invention is a block copolymer containing two or more blocks, two of which are not the same, and one or more repeating units are π-π conjugate within each block. It is preferable that they are bonded by a bond, have fluorescence in a solid state, and are connected by a π-π conjugate bond between the blocks.

When the block copolymer of the present invention is used as a polymeric fluorescent substance in a polymer light emitting device, the device can exhibit excellent characteristics. The polymeric fluorescent substance of the present invention is
It can also be used as a laser pigment, an organic solar cell material, an organic semiconductor for an organic transistor, or a conductive thin film material. Furthermore, the polymer LED using the polymer fluorescent substance is a high-performance polymer LED that can be driven with low voltage and high efficiency. 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, a dot matrix flat panel display.

The block copolymer of the present invention is represented, for example, by the following general formula (1a).
-A-block- (B) -block-C- (1a)
(In the formula, A and C represent blocks that may be the same or different, and B represents a bonding unit that is not part of the block and has a conjugated bond.)

In the case where A and C are composed of only one type of repeating unit, when A has the same repeating unit a as C, when the bonding unit is represented by B, the block copolymer is
-Aaaaaaaaa-block-B-block-aaaaaa-
Indicated by

When A and C are different, the block copolymer of the present invention may or may not have the bonding unit B. In this case, when the repeating unit constituting A is a and the repeating unit constituting C is c, the block copolymer is:
-Aaaaaaaaa-block-B-block-cccccccc-
Or
-Aaaaaaaaa-block-cccccccc-
Indicated by

When one of A and C is composed of two or more types of repeating units, the block copolymer of the present invention may or may not have the bonding unit B.
For example, when the repeating units constituting A are a and c and the repeating unit constituting C is c, the block copolymer is
-Accacaaaca-block-B-block-cccccccc-
Or
-Accacaaaca-block-cccccccc-
Indicated by In this case, c constituting A and C may be the same or different, and the repeating units a and c constituting A may be regularly arranged or randomly arranged.

In the case where both A and C are composed of two or more kinds of repeating units, A
When C and C are composed of the same repeating unit, the block copolymer of the present invention has a bonding unit B.
For example, when both A and C are repeating units constituting a and c, the block copolymer is
-Accacaaaca-block-B-block-accacacaaaa-
Indicated by
The repeating units a and c constituting A and C may be regularly arranged or randomly arranged.

When both A and C are composed of two or more types of repeating units, and at least one of the repeating units constituting A is not included in the repeating unit constituting C, or the repeating unit constituting C In the case where at least one of them is not included in the repeating unit constituting A, the block copolymer of the present invention may or may not have the bonding unit B in the general formula (1a). .
For example, when the repeating units constituting A are a, b and c, and the repeating units constituting C are a and c, the block copolymer is
-Acbacababa-block-B-block-accacaaca-
Or -acbacababa-block-accacaaaca-
Indicated by

Among the above examples, in the case of a block copolymer having the bonding unit B, the space between the bonding unit and the bonding unit is called a block.
The block copolymer of the present invention has fluorescence in a solid state, for example, the above general formula (1
It is a block copolymer represented by a). In the formula, A and C represent blocks that may be the same or different, and B represents a bonding unit having a conjugated bond that is not a part of the block. Further, the fluorescence peak wavelength indicated by the polymer thin film represented by the general formula (1a) is any of the fluorescence peak wavelength indicated by the polymer thin film consisting only of the block A and the fluorescence peak wavelength indicated by the polymer thin film consisting only of the block C. 5nm
A long wavelength is preferred.

Furthermore, the block copolymer of the present invention is a block copolymer having fluorescence in a solid state, for example, represented by the following general formula (1b).
-A-block-C- (1b)
Here, A and C represent different blocks, and the blocks are connected by a direct bond without breaking the conjugated chain. The fluorescence peak wavelength exhibited by the polymer thin film represented by the formula (1b) is preferably 5 nm or longer than the fluorescence peak wavelength exhibited by the polymer thin film consisting only of block A.

In the present invention, a block copolymer having two or more blocks, where at least one set of adjacent blocks D and E is the lowest unoccupied orbit of a polymer consisting only of each of these blocks ( LUMO) and highest occupied orbit (
Comparing the value of (HOMO)
HOMO (D)> HOMO (E)
LUMO (D) <LUMO (E)
Those satisfying this relationship are particularly preferable.

As a method of comparing the magnitude relationship of the HOMO values, when there is a sufficiently large difference, the values may be compared with values corresponding to the ionization potential and work function obtained by calculation or measurement. Further, as a method for comparing the magnitude relationship of LUMO values, when there is a sufficiently large difference, comparison may be made with a value corresponding to the electron affinity obtained by calculation or measurement. Hereinafter, in the present application, including these parameters, each is simply HO.
They are referred to as MO and LUMO.

As a method for obtaining HOMO and LUMO, a method of calculating by UPS (ultraviolet photoelectron spectroscopy) or a molecular orbital method is known. The calculation method by the molecular orbital method can be a preferable method if sufficient accuracy can be obtained in the future.
Since it is difficult to apply to complex polymers at present, it is preferably obtained by UPS or the method shown below. For example, for UPS, Polymer for Advanced Technologies (Polymer for Advanced)
Technologies), Vol. 9, 419 (1998) and the literature cited therein.

As a method for obtaining HOMO, in addition to UPS, Japanese Patent No. 12347
There are photoelectron spectroscopy described in No. 03, a method of electrochemically obtaining and converting an oxidation potential, and the like.

The photoelectron spectroscopy described in Japanese Patent No. 12347703 can be used by, for example, an apparatus (AC-2) manufactured by Riken Keiki Co., Ltd. As a method for electrochemically obtaining and converting the oxidation potential, specifically, a method for obtaining and converting the oxidation start potential of the material is exemplified.

As a specific method for obtaining the oxidation start potential, the following electrochemical method can be used. That is, the cyclic voltammetry of the target material is performed, and the potential at which the oxidation wave rises from the baseline (oxidation start potential) is obtained. Specifically, for example, a thin film is first formed on a platinum electrode by dipping from a solution of the material to be measured. Then, an organic solvent containing an appropriate supporting electrolyte, for example, 0.1 N tetrabutylammonium tetrafluoroborate in acetonitrile,
The platinum electrode coated with the material is the working electrode, the other uncoated platinum electrode is the counter electrode,
And cyclic voltammetry is performed using, for example, a silver / silver chloride electrode, a saturated calomel electrode, a standard hydrogen electrode, or the like as a reference electrode. When the material to be measured is easily dissolved in the solvent used as the electrolytic solution, the measurement may be performed by dissolving these materials in the electrolytic solution instead of coating the electrode. The concentration at this time may be selected so that the oxidation wave can be easily detected.

At this time, the conditions such as the potential sweep rate and sweep range are the same in the measurement of any material. For example, the sweep rate is 50 mV / second, and the sweep range is -2.
Examples include 00 to 1500 mV (potential with respect to a silver / silver chloride electrode). For the obtained cyclic voltammogram, the potential at the intersection of the base line and the straight line in contact with the rising portion of the oxidation wave is obtained.

A value obtained by converting the obtained oxidation initiation potential into a value relative to a standard hydrogen electrode is Eox (V
), HOMO can be obtained by the following equation.

HOMO = Eox + C ₁ (eV)
(C ₁ is a value relative to the vacuum level of the standard hydrogen electrode and can be regarded as a constant.
5 is used. )
When comparing the HOMO values (eV) of the two materials, the constant C in the above equation is subtracted, so it is not necessary to consider the exact value.

As a method for obtaining LUMO, in addition to the UPS described above, a method of converting from an electrochemical reduction potential, and a method of converting from the absorption edge wavelength of the absorption spectrum of the material and the HOMO value are exemplified.

As a method for conversion from the electrochemical reduction potential, the oxidation potential may be replaced with the reduction potential and converted in the same manner.

In the method of converting from the absorption edge wavelength of the absorption spectrum of the material and the HOMO value, the absorption edge wavelength of the absorption spectrum can be obtained by measuring the absorption spectrum and obtaining the wavelength at which the absorption rises from the baseline. Specifically, first, for example, a thickness of 50 to 300 n is formed by spin coating from a solution of a material to be measured on a quartz plate.
A thin film of about m is formed and an absorption spectrum is obtained. For this spectrum, the wavelength at the intersection of the base line and the straight line in contact with the rising portion of the absorption is defined as the absorption edge wavelength.

When the obtained absorption edge wavelength is λedge (nm), the LUMO
Can be requested.

LUMO = HOMO over C ₂ / λedge (eV)
(C ₂ is a constant for converting the unit. Usually, 1239 is used.)
Here, as the value of HOMO, a value obtained by any of the various methods described above can be used.

In the block copolymer of the present invention, at least one of the blocks A and C represented by the above formula (1a) or (1b) formed by bonding repeating units with a conjugated bond is represented by the following formula (2): It is more preferable to have one or more repeating units selected from the repeating units of formula (3).

（ここで、Ａｒ₁は、アリーレン基または２価の複素環基であり、該アリーレン
基、２価の複素環基は置換基を有していてもよい。Ｒ₁およびＲ₂は、それぞれ独
立に水素原子、アルキル基、アリール基、1価の複素環基またはシアノ基を示し
、該アリール基、1価の複素環基は置換基を有していてもよい。ｎは０または１
である）
−Ａｒ₂−（ＣＲ₃＝ＣＲ₄）_m− （３）
（ここで、Ａｒ₂は下記一般式（４）で示される２価の芳香族アミン基である。
Ｒ₃およびＲ₄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
複素環基またはシアノ基を表し、ｍは０または１である）
−Ａｒ₃−Ｎ（Ａｒ₄）−Ａｒ₅− （４）
（ここで、Ａｒ₃およびＡｒ₅はそれぞれ独立にアリーレン基、下記一般式（５
）で表される芳香族化合物基、または下記一般式（６）の芳香族アミン骨格を有
する基であり、Ａｒ₄は、アリール基、1価の複素環基、下記一般式（７）で表
される芳香族アミン骨格を有する基、または、下記一般式（８）で表される芳香
族エテニレン骨格を有する基を示す。また、Ａｒ₃とＡｒ₄の間、Ａｒ₄とＡｒ
₅の間、またはＡｒ₃とＡｒ₅の間に環を形成していてもよい）

（ここで、Ａｒ₆およびＡｒ₇は、それぞれ独立に、アリーレン基を示し、該ア
リーレン基は置換基を有していてもよい。Ｒ₅およびＲ₆は、それぞれ独立に水
素原子、アルキル基、アリール基、1価の複素環基またはシアノ基、ｌは０また
は１である）

（ここで、Ａｒ₈およびＡｒ₉は、それぞれ独立に、アリーレン基を示し、該ア
リーレン基は置換基を有していてもよい。Ａｒ₁₀は、置換基を有してもよいア
リール基である。また、Ａｒ₈とＡｒ₁₀の間、Ａｒ₈とＡｒ₉の間、またはＡ
ｒ₉とＡｒ₁₀の間に環を形成していてもよい）

（ここで、Ａｒ₁₁は、アリーレン基を示し、該アリーレン基は置換基を有して
いてもよい。Ｒ₇およびＲ₈は、それぞれ独立にそれぞれ独立に水素原子、アル
キル基、アリール基、1価の複素環基またはシアノ基を表し、また、Ａｒ₁₁と
Ｒ₇の間、Ａｒ₁₁とＲ₈の間、またはＲ₇とＲ₈の間に環を形成していてもよ
い）

（ここで、Ａｒ₁₂およびＡｒ₁₃は、それぞれ独立に、アリーレン基を示し、
該アリーレン基は置換基を有していてもよい。Ｒ₉およびＲ₁₀は、それぞれ独
立にそれぞれ独立に水素原子、アルキル基、アリール基、1価の複素環基または
シアノ基を表し、ｐは０または１である）。

(Here, Ar ₁ is an arylene group or a divalent heterocyclic group, and the arylene group and divalent heterocyclic group may have a substituent. R ₁ and R ₂ are each independently selected. Represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group, and the aryl group and the monovalent heterocyclic group may have a substituent, and n is 0 or 1
Is)
-Ar _2- (CR ₃ = CR ₄ ) _m- (3)
(Here, Ar ₂ is a divalent aromatic amine group represented by the following general formula (4).
R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group, and m is 0 or 1)
—Ar ₃ —N (Ar ₄ ) —Ar ₅ — (4)
(Wherein Ar ₃ and Ar ₅ are each independently an arylene group, the following general formula (5
) Or a group having an aromatic amine skeleton of the following general formula (6), Ar ₄ is an aryl group, a monovalent heterocyclic group, and a general formula (7) below. A group having an aromatic amine skeleton or a group having an aromatic ethenylene skeleton represented by the following general formula (8). Also, between Ar ₃ and Ar ₄ , Ar ₄ and Ar
₅ or a ring may be formed between Ar ₃ and Ar ₅ )

(Here, Ar ₆ and Ar ₇ each independently represent an arylene group, and the arylene group may have a substituent. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, Aryl group, monovalent heterocyclic group or cyano group, l is 0 or 1)

(Here, Ar ₈ and Ar ₉ each independently represent an arylene group, and the arylene group may have a substituent. Ar ₁₀ is an aryl group that may have a substituent. Also, between Ar ₈ and Ar ₁₀ , between Ar ₈ and Ar ₉ , or A
a ring may be formed between r ₉ and Ar ₁₀ )

(Here, Ar ₁₁ represents an arylene group, and the arylene group may have a substituent. R ₇ and R ₈ are each independently a hydrogen atom, an alkyl group, an aryl group, 1 A valent heterocyclic group or a cyano group, and a ring may be formed between Ar ₁₁ and R ₇ , Ar ₁₁ and R ₈ , or R ₇ and R ₈ )

(Wherein Ar ₁₂ and Ar ₁₃ each independently represent an arylene group,
The arylene group may have a substituent. R ₉ and R ₁₀ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group, and p is 0 or 1.

Ar ₂ represented by the above formula (3) is preferably represented by the following formula (9).
_{- (Ar 14 -N (Ar 15} )) t -Ar 16 - (9)
(Here, Ar ₁₄ and Ar ₁₆ each independently represent an arylene group, an aromatic compound group represented by the above general formula (5), or a group having an aromatic amine skeleton of the above general formula (6); Ar ₁₅ is an aryl group, a monovalent heterocyclic group, the above general formula (7)
Or a group having an aromatic ethenylene skeleton represented by the general formula (8). t is 1 or 2).

In the present invention, the bonding unit B having a conjugated bond is not particularly limited as long as it is a conjugated system that is not a part of a block, but is an arylene group, a divalent heterocyclic group, or an arylene vinylene group represented by the above formula (2). And a divalent aromatic amino group represented by the above formulas (3) and (9) are preferred.

（ここで、Ａｒ₁₇およびＡｒ₁₈はそれぞれ独立にアリーレン基または２価の
複素環基であり、Ｒ₁₁およびＲ₁₂はそれぞれ独立に水素原子、アルキル基、
アリール基、1価の複素環基またはシアノ基を表す）。

また、上記式（２）においてｎが１である場合、および上記式（３）においてｍ
が１である場合、接合単位Ｂは下記一般式（１１）で表される構造であることが
好ましい。
―Ａｒ₁₉― （１１）
（式中Ａｒ₁₉はアリーレン基、または２価の複素環基である。） Further, the bonding unit B preferably has a structure represented by the following general formula (10) when n is 0 in the above formula (2) and when m is 0 in the above formula (3). ,

(Wherein Ar ₁₇ and Ar ₁₈ are each independently an arylene group or a divalent heterocyclic group, and R ₁₁ and R ₁₂ are each independently a hydrogen atom, an alkyl group,
An aryl group, a monovalent heterocyclic group or a cyano group).

Further, in the above formula (2), when n is 1, and in the above formula (3), m
Is 1, the bonding unit B preferably has a structure represented by the following general formula (11).
―Ar ₁₉ ― (11)
(In the formula, Ar ₁₉ is an arylene group or a divalent heterocyclic group.)

Although the manufacturing method of the block copolymer in this invention will not be specifically limited if the structure mentioned above is given, Manufacturing by the following method is preferable when performing structure control.
Further, according to the following method, a block copolymer that is difficult to produce by other methods such as the block copolymer of the present invention can be produced with a relatively small number of steps.

[1] monomer having two reactive groups capable of reacting with each other in the molecule (X _1, X ₂₎ and (I), by reacting with the reactive group (X _1, X ₂₎ in the molecule A reactive group (X ₃ ) capable of forming a bond and a group (Y ₁ ) which does not react under the reaction conditions where the reactive group (X ₁ , X ₂ ) and (X ₃ ) react to form a bond. Reacting an initial polymer having a group (Y ₁ ) at the molecular end obtained by reacting with the monomer (II) having a reaction under conditions where the groups (Y ₁ ) react with each other to form a bond. A process for producing a block copolymer. And [2] to react a monomer having a molecular two reactive groups capable of reacting with each other in the (X _1, X ₂₎ and (I), with the reactive groups in the molecule (X _1, X ₂₎ A reactive group (X ₃ ) that can form a bond and a group (Y ₁ ) that does not react under the reaction conditions where the reactive group (X ₁ , X ₂ ) and (X ₃ ) can react to form a bond. An initial polymer having a group (Y ₁ ) at the molecular end obtained by reacting with the monomer (II) having a group (Y ₁ ) is reacted with the group (Y ₁ ) to form a bond (Y ₂ and Y ₃ ) in the molecule (III
And a group Y ₁ , Y ₂ and Y ₃ are reacted under the conditions that can form a bond.

In the production method of the present invention, although not particularly limited, groups (Y ₁ , Y ₂ , Y ₃ )
It is preferable that a π-π bond can be generated by reacting each other, and further π
The -π bond is preferably a double bond or an aryl-aryl bond.

In the production method of the present invention, the structure of the monomer used is not particularly limited, but those having the following structures are preferred. That is, at least one monomer (I) selected from the following general formula (12) and at least one monomer selected from the following general formula (13) (
After obtaining an initial polymer by reacting II), it is preferable to react with one or more initial polymers or with one or more monomers (III) represented by the general formula (14) .

Here, a preferable monomer (I) is represented by the following general formula (12).
_{X 1 -Ar 20 -X 2 (12} )
(Here, X ₁ and X ₂ represent reactive groups capable of reacting with each other to form a bond, and these may be the same or different. Ar ₂₀ represents the same group as Ar ₁ described above. )

A preferable monomer (II) is represented by the following general formula (13).
X ₃ —Ar ₂₁ —Y ₁ (13)
(Here, Ar ₂₁ represents the same group as Ar _1. X ₃ represents a reactive group capable of reacting with X ₁ and X ₂ to form a bond, and Y ₁ represents X ₁ and X ₂ . This represents a group that does not react under the reaction conditions in which X ₃ reacts to form a bond.)

（ここで、ｓは１以上の整数を示す。ａ，ｂは、１である。） The initial polymer obtained by the above production method is represented by the following general formula.

(Here, s represents an integer of 1 or more. A and b are 1.)

Moreover, what is preferable in monomer (III) is shown by following formula (14).
Y ₂ —Ar ₂₅ —Y ₃ (14)
(Here, Ar ₂₅ represents the same group as Ar _1. Y ₂ and Y ₃ each independently represent the same group as Y _1, and these may be the same or different.)

In the present invention, an arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and usually has about 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms. 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, formulas 1 to 3 in the following figure), a naphthalene-diyl group (formulas 4 to 13 in the following figure), and an anthracenylene group (formulas 14 to 14 in the following figure).
19), a biphenylene group (formulas 20 to 25 in the following figure), a fluorene-diyl group (formulas 36 to 38 in the figure below), a triphenylene group (formulas 26 to 28 in the figure below), stilbene-diyl (formulas AD in the figure below), Examples include distilbene-diyl (formulas E and F in the figure below), condensed ring compound groups (formulas 29 to 38 in the figure below), and the like. Among them, phenylene group,
A biphenylene group, a fluorene-diyl group, and a stilbene-diyl group are preferred.

In the present invention, the divalent heterocyclic group means a remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound, and usually has about 3 to 60 carbon atoms.
Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. Say things.

Examples of the divalent heterocyclic group include the following.
Divalent heterocyclic group containing nitrogen as a hetero atom; pyridine-diyl group (formulas 39 to 44 in the following figure), diazaphenylene group (formulas 45 to 48 in the following figure), quinoline-diyl group (formulas 49 to 48 in the following figure) 63), a quinoxaline-diyl group (formulas 64-68 in the figure below)
An acridine-diyl group (formulas 69-72 in the lower figure), a bipyridyl-diyl group (formulas 73-75 in the lower figure), a phenanthroline-diyl group (formulas 76-78 in the lower figure), and the like. Groups having a fluorene structure containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom (formulas 79 to 93 in the following figure).

5-membered heterocyclic groups containing silicon, nitrogen, sulfur, selenium, etc. as heteroatoms:
(Equations 94 to 98 in the following figure).

5-membered ring condensed heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom: (formulas 99 to 108 in the following figure).

A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, and bonded to the α-position of the heteroatom to form a dimer or oligomer: (Formulas 109 to 113 in the figure below) Can be mentioned.

A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium or the like as a heteroatom, which is bonded to the phenyl group at the α-position of the heteroatom: (formulas 113 to 119 in the following figure)
).

Examples include groups in which a phenyl group, a furyl group, or a thienyl group is substituted on a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, and the like as a hetero atom (formulas 120 to 125 in the following figure).

In the examples shown in the above formulas 1 to 125, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group. , Arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imino group, amide group, imide group, monovalent heterocyclic group, carboxyl group Represents a substituted carboxyl group or a cyano group. Moreover, the carbon atom which the group of Formula 1-132 has may be substituted with the nitrogen atom, the oxygen atom, or the sulfur atom, and the hydrogen atom may be substituted with the fluorine atom.

In the present invention, a divalent aromatic amine group refers to the remaining atomic group obtained by removing two hydrogen atoms from an aromatic amine, and usually has about 4 to 60 carbon atoms. Examples are groups.

In the above formula, R is the same as that in formulas 1-125. In the above example, one structural formula has a plurality of Rs, but they may be the same or different groups. In order to increase the solubility in a solvent, it is preferable to have at least one other than a hydrogen atom, and it is preferable that the symmetry of the shape of the repeating unit including a substituent is small.

The alkyl group in the present invention may be linear, branched or cyclic. The number of carbon atoms is usually about 1 to 20, specifically, methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl 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, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, Examples include perfluorooctyl group, and pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, and 3,7-dimethyloctyl group are preferable.

The alkoxy group may be linear, branched or cyclic. Carbon number is usually 1
About 20, specifically, methoxy group, ethoxy group, propyloxy group, i
-Propyloxy group, butoxy group, i-butoxy 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, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorohexyl group Fluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group, etc. are mentioned, and pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, 3,7-dimethyloctyloxy group preferable.

The alkylthio group may be linear, branched or cyclic. Usually 1 carbon
Specifically, methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i-butylthio 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, trifluoromethylthio group and the like can be mentioned, and pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group and 3,7-dimethyloctylthio group are preferable.

The aryl group usually has about 6 to 60 carbon atoms, specifically, a phenyl group,
A C ₁ -C ₁₂ alkoxyphenyl group (C ₁ -C ₁₂ indicate that it has 1 to 12 carbon atoms; the same shall apply hereinafter), a C ₁ -C ₁₂ alkylphenyl group, a 1-naphthyl group,
Examples include a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a pentafluorophenyl group, and the like, and a C _{1 to} C ₁₂ alkoxyphenyl group and a C _{1 to} C ₁₂ alkylphenyl group are preferable. Here, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. 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.
Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkylphenyl group as specifically methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, i- propylphenyl group, butylphenyl group, i- butyl Examples include phenyl group, t-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like.

As an aryloxy group, carbon number is about 6-60 normally, Specifically,
Phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group are exemplified, C ₁ -C ₁₂ alkoxyphenoxy The group C ₁ -C ₁₂ alkylphenoxy is preferred.
Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkylphenoxy such as methyl phenoxy groups as group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, i- propyl phenoxy group,
Examples include butylphenoxy, i-butylphenoxy, t-butylphenoxy, pentylphenoxy, isoamylphenoxy, hexylphenoxy, heptylphenoxy, octylphenoxy, nonylphenoxy, decylphenoxy, dodecylphenoxy Is done.

The arylthio group, the carbon number of usually about 3 to 60, specifically, phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2 - naphthylthio group, pentafluorophenylthio group and the like, C ₁ -C ₁₂ alkoxyphenyl-thio group, a C ₁ -C ₁₂ alkyl phenylthio 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 groups and the like, C ₁ ~
C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl-
C ₁ -C ₁₂ alkyl group are preferable.

The arylalkoxy group usually has about 7 to 60 carbon atoms, and specifically includes a phenylmethoxy group, a phenylethoxy group, a phenylbutoxy group, a phenylpentyloxy group, a phenylhexyloxy group, a phenylheptyloxy group, a phenyl group. 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 groups such as octyloxy, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group are preferable.

The arylalkylthio group usually has about 7 to 60 carbon atoms, specifically,
Phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C _1
2 alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1
- naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group,
C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group are preferable.

Arylalkenyl group has a carbon number of usually about 7 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 group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, C ₂ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl groups are preferred.

Arylalkynyl group has a carbon number of usually about 7 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 group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.

The substituted amino group refers to an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and the alkyl group, aryl group, arylalkyl group or The monovalent heterocyclic group may have a substituent. The carbon number is usually about 1 to 60 without including the carbon number of the substituent.

Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino group, butylamino group, i-butylamino 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, Cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group,
Dicyclohexyl amino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, 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, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, triazyl amino group phenyl -C _{1 to} C _1
2 alkylamino groups, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂
Alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl) amino group, 1-naphthyl-C ₁ -C ₁₂ alkylamino group, 2-naphthyl- such as C ₁ -C ₁₂ alkylamino groups.

The substituted silyl group means a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and usually has about 1 to 60 carbon atoms. is there. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.

Specifically, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethyl Silyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, a phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ ~
C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl -C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, t- butyl diphenyl silyl group,
Examples thereof include a dimethylphenylsilyl group.

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

The acyl group usually has about 2 to 20 carbon atoms, specifically, an acetyl group,
Propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group,
Examples include a trifluoroacetyl group and a pentafluorobenzoyl group.

The acyloxy group usually has about 2 to 20 carbon atoms. Specifically, the acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetyloxy group, pentane Examples include a fluorobenzoyloxy group.

The imino group has about 2 to 20 carbon atoms, and specific examples thereof include groups represented by the following structural formulas.

The amide group usually has about 1 to 20 carbon atoms, specifically, a formamide group (1 carbon number), an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, Examples include diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoroacetamide group, dipentafluorobenzamide group, and the like.

The imide group usually has about 2 to 60 carbon atoms, and specific examples thereof include the following groups.

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, preferably 4 to 20 carbon atoms. The carbon number of the heterocyclic group does not include the carbon number of the substituent. Here, the heterocyclic compound is
Among organic compounds having a cyclic structure, an element that constitutes a ring contains not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, etc. in the ring. Specifically, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, a thienyl group , C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.
The substituted carboxyl group usually has about 2 to 60 carbon atoms, and refers to a carboxyl group substituted with an alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group, such as a methoxycarbonyl group, an ethoxycarbonyl group, or a propoxycarbonyl group. Group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2 -Ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoro Butoxycarbonyl group, perfluoro-butoxycarbonyl group, perfluorohexyloxy carbonyl group, perfluorooctyloxy carbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group, and the like. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent.

Among the examples of the above substituents, in a substituent containing an alkyl chain, they are linear,
It may be either branched or cyclic or a combination thereof, and when it is not linear, for example, isoamyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, cyclohexyl group, 4-C ₁ -C ₁₂ alkyl Examples include a cyclohexyl group. Moreover, the tips of two alkyl chains may be connected to form a ring. Furthermore, some methyl groups or methylene groups of the alkyl chain may be replaced with groups containing hetero atoms or methyl groups or methylene groups substituted with one or more fluorine atoms. An atom, a sulfur atom, a nitrogen atom, etc. are illustrated.

Furthermore, among the examples of substituents, when an aryl group or a heterocyclic group is included as a part thereof,
They may further have one or more substituents.

X ₁ , X ₂ and X ₃ of the monomers represented by the formulas (12) and (13) used for the production of the block copolymer of the present invention are preferably each independently a halogen atom,
Alkylsulfonyloxy group, arylsulfonyloxy group, boric acid group (-B (
OH) ₂ ), or a boric acid ester group (provided that at least one or more is a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group), and in this case, a monomer represented by the formula (13) Y _1, and wherein Y ₂ of the monomer represented by (14), Y ₃ of each independently represent an aldehyde group, an acyl group, a phosphonic acid ester group or a phosphonium salt (however, 1 or more, is It is preferably an aldehyde group or an acyl group.

Here, as a halogen atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, A chlorine atom and a bromine atom are preferable and a bromine atom is especially preferable.

The alkylsulfonyloxy group may be substituted with a fluorine atom. Specific examples include a trifluoromethanesulfonyloxy group. The arylsulfonyloxy group may be substituted with an alkyl group. Specific examples include a phenylsulfonyloxy group and a tolylsulfonyloxy group.

式中、Ｍｅはメチル基を、Ｅｔはエチル基を示す。 Examples of the borate group include groups represented by the following formula.

In the formula, Me represents a methyl group, and Et represents an ethyl group.

Examples of the phosphonic acid ester group include groups represented by the following formula.
—CH ₂ PO (OR ′) ₂ (R ′ represents an alkyl group, an aryl group, or an arylalkyl group.)

Examples of the phosphonium base include groups represented by the following formula.
_{^{-CH 2 P + Ph 3 X -}} (X represents a halogen atom.)

Further, X ₁ , X ₂ and X ₃ of the monomers represented by the formulas (12) and (13) used for the production of the block copolymer of the present invention are preferably each independently an aldehyde group, An acyl group, a phosphonic acid ester group or a phosphonium base (
However, one or more is an aldehyde group or an acyl group), in this case, the formula (13
Y _{1 of the} monomer represented by formula ( ₁ ) and Y ₂ and Y ₃ of the monomer represented by formula (14) are each independently a halogen atom, an alkylsulfonyloxy group, an arylsulfonyloxy group, or boric acid. Or a borate group (provided that one or more are a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group).

In addition, as a method for producing the block copolymer of the present invention, at least one of groups selected from X ₁ , X ₂ and X _{3 of the} monomers represented by the general formulas (12) and (13) may be used. A boric acid group or a boric acid ester group, at least one of which is a halogen atom, an alkylsulfonyloxy group, or an arylsulfonyloxy group,
Y _{1 of the} monomer represented by is a reactive group selected from an aldehyde group, a carbonyl group, a phosphonic acid ester group, or a phosphonium base, and is reacted in the presence of a Pd (0) catalyst to terminate the aldehyde group, Preference is given to obtaining an initial polymer having an acyl group, a phosphonic acid ester group or a phosphonium base.

Moreover, as a manufacturing method of the block copolymer of this invention, general formula (12) and (
13) X ₁ , X ₂ , X _{3 of the} monomer represented by 13) are a halogen atom, an alkylsulfonyloxy group, or an arylsulfonyloxy group, and Y _{1 of the} monomer represented by the general formula (13) is an aldehyde group , A reactive group selected from an acyl group, a phosphonic acid ester group or a phosphonium base, and having an aldehyde group, an acyl group, a phosphonic acid ester group or a phosphonium base at the terminal by reacting in the presence of Ni (0) It is preferable to carry out by obtaining a polymer.

The obtained initial polymer has a double bond by reacting reductively in the presence of low-valent titanium or the like in the case of a combination of those having an aldehyde group and / or an acyl group at the terminal. A block copolymer can be obtained.
Similarly, Y ₂ and Y ₃ of the monomer represented by the general formula (14) are an aldehyde group and
In the case of / or an acyl group, a block copolymer having a double bond can be obtained by reacting with the initial polymer.
In the case of a combination of an aldehyde group and / or an acyl group and a phosphonate ester group and / or a phosphonium base at the terminal, a block copolymer having a double bond can be obtained in the presence of a base.
Similarly, when Y ₂ and Y ₃ of the monomer represented by the general formula (14) are an aldehyde group and / or an acyl group, a phosphonic acid ester group and / or a phosphonium base, the monomer is reacted with the initial polymer. Thus, a block copolymer having a double bond can be obtained.

In addition, as a method for producing the block copolymer of the present invention, at _{least one} of X ₁ , X ₂ and X ₃ of the monomer represented by the general formulas (12) and (13) is an aldehyde group or an acyl group. And at least one is a phosphonic acid ester group or a phosphonium base, and Y _{1 of the} monomer represented by the general formula (13) is a reactive group selected from a halogen atom, an alkylsulfonyloxy group, and an arylsulfonyloxy group. More preferably, the reaction is carried out in the presence of a base to obtain an initial polymer having a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group at the terminal.
The obtained initial polymer having a halogen atom, an alkylsulfonyloxy group, and an arylsulfonyloxy group can be reacted in the presence of Ni (0) to obtain a block copolymer having an aryl-aryl bond. I can do it.

Similarly, when Y ₂ and Y ₃ of the monomer represented by the general formula (14) are a halogen atom, an alkylsulfonyloxy group, or an arylsulfonyloxy group, by reacting with the initial polymer, aryl-aryl Can be obtained.
In the above production method, a mixture containing a block copolymer is obtained depending on the combination. For example, initial polymers having different repeating structures (the following formulas (16), (1
7))
Y ₁ -F-Y ₁ (16)
Y ₁ -G-Y ₂ (17)
When the polymer obtained by reacting these has a bonding unit,
-F-block- (B) -block-G-
-F-block- (B) -block-F-
-G-block- (B) -block-G-
Is obtained. If you do not have a unit
-F-block-G-
-F-block-F-
-G-block-G-
A mixture of
This also applies to the method using the initial polymer and the monomer represented by the general formula (14).

Moreover, as a halogen atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, A chlorine atom and a bromine atom are preferable and a bromine atom is especially preferable.

The alkylsulfonyloxy group may be substituted with a fluorine atom. Specific examples include a trifluoromethanesulfonyloxy group. The arylsulfonyloxy group may be substituted with an alkyl group. Specific examples include a phenylsulfonyloxy group and a tolylsulfonyloxy group.

In the above production method, the method for synthesizing the initial polymer is not particularly limited as long as it is a reaction that does not decompose the group (Y ₁ ) at the time of synthesis, and similar methods described in known documents can be used.
Further, in the above production method, the initial polymers or their reactive groups (Y ₂
, Y ₃ ), a monomer having two reactive groups in the molecule that can generate a bond (
The method of reacting III) is not particularly limited, but the methods described in the following publicly known documents and the like can be used.
Preferably, Wittig reaction, Horner reaction, McMurry reaction, Su
Zuki reaction, aryl-aryl coupling reaction using Ni (0), and the like.

Further, if necessary, the reactive group (Y ₁ ) can be protected with an appropriate protective group, and after obtaining an initial polymer, it can be deprotected and used for production.

Examples of known literature include, for example, “Organic Reactions (Orga
nic Reactions ", Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965.
“Organic Reactions”
27, 345-390, John Wiley and Sons (John)
Wiley & Sons, Inc. ), 1982, “Organic Synthesis”, Collective Volume 6 (Coll).
(Ective Volume VI), 407-411, John Wiley & Sons, Inc., 1988, Chem. Rev., 95, 2457 (1995), Journal of Organometallic Chemistry. (J. Organo
met. Chem. 576, 147 (1999), Journal of Practical Chemistry (J. Prakt. Chem.), 336.
Vol. 247 (1994), Macromolecular Chemistry Macromolecular Symposium (Macromol. Chem., Macromol.
Symp. ), Vol. 12, p. 229 (1987).

The organic solvent varies depending on the compound and reaction to be used, but it is generally preferable that the solvent to be used is sufficiently deoxygenated and the reaction proceeds in an inert atmosphere in order to suppress side reactions. Similarly, it is preferable to perform a dehydration treatment.
(However, this is not the case in the case of a two-phase reaction with water such as the Suzuki coupling reaction.)
More specifically, the reaction conditions are described as follows: Wittig reaction, Horne
In the case of r reaction or the like, the reaction is carried out using an equivalent or more, preferably 1 to 3 equivalents of alkali with respect to the functional group of the monomer. Examples of the alkali include, but are not limited to, metal alcoholates such as potassium tert-butoxide, sodium tert-butoxide, sodium ethylate and lithium methylate, hydride reagents such as sodium hydride, and amides such as sodium amide. Etc. can be used. As the solvent, N, N-dimethylformamide, tetrahydrofuran, dioxane, toluene and the like are used. The reaction can be allowed to proceed at a reaction temperature of usually from room temperature to about 150 ° C. The reaction time is, for example, 5 minutes to 40 hours, but may be any time that allows sufficient polymerization to proceed, and it is not necessary to leave the reaction for a long time after the reaction is completed. is there. The concentration at the time of the reaction is poor if the reaction is too dilute, and if it is too thick, it becomes difficult to control the reaction.
It is in the range of 0.1 wt% to 20 wt%.

In the case of the Suzuki coupling reaction, for example, palladium [
Tetrakis (triphenylphosphine)], palladium acetates, etc., an inorganic base such as potassium carbonate, sodium carbonate, barium hydroxide, an organic base such as triethylamine, and an inorganic salt such as cesium fluoride in an equivalent amount or more with respect to the monomer,
Preferably, 1 to 10 equivalents are added and reacted. An inorganic salt may be used as an aqueous solution and reacted in a two-phase system. As the solvent, N, N-dimethylformamide, toluene,
Examples include dimethoxyethane and tetrahydrofuran. 50 depending on the solvent
A temperature of about ~ 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 case where a zerovalent nickel complex is used will be described. 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, Screw (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, tritolylphosphine, 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 chloride such as nickel chloride nickel acetate can be used as the nickel salt. 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 as necessary.

The polymerization solvent is not particularly limited as long as it does not inhibit the polymerization.
Those containing at least one kind of aromatic hydrocarbon solvent and / or ether solvent are preferred.

Here, the aromatic hydrocarbon solvent is a solvent composed of an aromatic hydrocarbon compound, and examples thereof include benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, butylbenzene, naphthalene, tetralin, and the like. Xylene, tetralin and tetramethylbenzene are preferred.

The ether solvent is a solvent composed of a compound in which a hydrocarbon group is bonded with an oxygen atom, and examples thereof include diisopropyl ether, tetrahydrofuran, and 1,4.
-Dioxane, diphenyl ether, ethylene glycol dimethyl ether, t
Examples include ert-butyl methyl ether, and preferred are tetrahydrofuran and 1,4-dioxane, which are good solvents for polymeric fluorescent substances.

Further, 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 present invention, for example, the polymerization reaction is usually carried out in an atmosphere of an inert gas 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 from the viewpoint of production cost,
The polymerization temperature is preferably within 10 hours. Usually, the polymerization temperature is about 0 to 200 ° C. From the viewpoint of high yield and low heating cost,
20-100 degreeC is preferable.

After completion of the reaction, it may be used in the next reaction as it is.
If necessary, it may be subjected to conventional separation operations such as acid washing, alkali washing, neutralization, water washing, organic solvent washing, reprecipitation, centrifugation, extraction, column chromatography, purification operation, drying and other operations. . From the viewpoint of improving the yield of the next reaction, it is preferable to perform a separation operation, a purification operation, and drying.

Further, when used as a light emitting material for polymer LED, since light emitted from a thin film is used, a polymer fluorescent substance having fluorescence in a solid state is preferably used.

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

The polymeric fluorescent substance composition of the present invention includes the block copolymer of the present invention. The amount of the block copolymer is usually 10% by weight or more based on the whole polymeric fluorescent substance composition.

Next, the polymer LED of the present invention will be described. The polymer LED of the present invention has a light emitting layer between a pair of anodes and cathodes, at least one of which is transparent or translucent, and the block copolymer or polymer phosphor of the present invention. A composition is contained in the light emitting layer.

The polymer LED of the present invention includes a polymer LED provided with an electron transport layer between the cathode and the light emitting layer, and a polymer LED provided with a hole transport layer between the anode and the light emitting layer.
And 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.

For example, the following structures a) to d) are specifically exemplified.
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 buffer 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, polymer L provided with a charge injection layer (electron injection layer, hole injection layer)
Examples of the ED include a polymer LED provided with a charge injection layer adjacent to the cathode, and a polymer LED provided with a charge injection layer adjacent to the anode.

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. A layer containing a material having an ionization potential of an intermediate value between the anode material and the hole transport material included in the hole transport layer, provided between the cathode and the electron transport layer. Examples include a layer containing a material having an electron affinity with an intermediate value between the cathode material and the electron transport material contained in the electron transport layer.

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 S / cm or less. In order to reduce the current, 10 ⁻⁵ S / cm or more and 10 ² S / cm
The following is more preferable, and 10 ⁻⁵ S / cm or more and 10 ¹ S / cm or less is further preferable.

Usually, in order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ S / cm or more and 10 ³ S / cm 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 2 nm to 5 nm.
0 nm is preferable.

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 its derivatives, polythiophene and its derivatives,
Conductive polymers such as polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polymers containing aromatic amine structures in the main chain or side chain And metal phthalocyanine (copper phthalocyanine and the like), carbon and the like.

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 / insulating layer with a thickness of 2 nm or less / cathode ab) anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode In addition, by using these organic solvent-soluble polymeric fluorescent substances obtained by the production method of the present invention, when a film is formed from a solution, it is only necessary to remove the solvent by drying after coating the solution. A similar technique can be applied even when a charge transport material or a light emitting material is mixed, which is very advantageous in production. 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.

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, 5 nm to 200 n
m.

In the polymer LED of the present invention, a light emitting material other than the polymer fluorescent substance obtained by the production method of the present invention 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 polymer phosphor may be laminated with a light emitting layer containing the polymer phosphor.

As the light emitting material, known materials can be used. In the low molecular compound, for example, naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine series, xanthene series, coumarin series, cyanine series pigments,
A metal complex of 8-hydroxyquinoline or a derivative thereof, an aromatic amine, 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.

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, 6
3-175860, JP-A-2-135359, 2-135361.
Publication No. 2-209998 Publication No. 3-37992 Publication No. 3-1521
The thing etc. which are described in 84 gazette are illustrated.

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, Preferred is a polymer hole transport material such as polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or poly (2,5-thienylene vinylene) or a derivative thereof, more preferably polyvinyl carbazole or a derivative thereof, Polysilane or a derivative thereof, or 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.

Polysilane or its derivatives include chemical reviews (Chem.
Rev. 89, 1359 (1989), British Patent GB 2300196
The compounds described in the published specification are exemplified. 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, The method by the film-forming from a mixed solution with a polymer binder is illustrated with a low molecular hole transport material. 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. Accordingly, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm.
Preferably 2 nm to 500 nm, more preferably 5 nm to 20 nm.
0 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 derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof. 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, and JP-A-2-2099.
No. 88, No. 3-37992, No. 3-152184, etc. are exemplified.

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.

There is no particular limitation on the method of forming the electron transport layer, but in the low molecular electron transport material,
A method of vacuum deposition from powder, or film formation from solution or molten state,
Examples of the polymer electron transport material include a method of film formation from a solution or a molten state. In film formation 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 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 the thickness is too thick, the driving voltage of the element increases, which is not preferable. Accordingly, the thickness of the electron transport layer is, for example, 1 nm to 1 μm.
Preferably 2 nm to 500 nm, more preferably 5 nm to 20 nm.
0 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.

In general, it is preferable that at least one of the electrodes composed of the anode and the cathode is transparent or translucent, and the anode side is transparent or translucent.
As the material for 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, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.

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.

Further, 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 an alloy of one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. Is 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 film 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,
More preferably, it is 50 nm-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. Further, a layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material or the like having an average film thickness of 2 nm or less 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 use the polymer LED stably 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 a space is maintained using a 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 backlight for a planar light source, a segment display device, a dot matrix display device, and a liquid crystal display device. In addition, a conventional display device can be used for a display portion of an electronic device.

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,
Either a method of installing a mask provided with a patterned window on the surface of the planar light emitting element, a method of forming an organic material layer of a non-light emitting portion extremely thick and making it substantially non-light emitting, either an anode or a cathode Alternatively, there is a method of forming both electrodes in a pattern. A pattern is formed by any of these methods, and some electrodes are turned on / off independently.
By disposing as much as possible, a segment type display element capable of displaying numbers, letters, simple symbols, and the like can be obtained. 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 polymeric fluorescent substances 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.
The block copolymer of the present invention can also be used as materials for conductive thin films such as laser dyes, organic solar cell materials, organic semiconductors for organic transistors, conductive thin films, and organic semiconductor 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, with respect to the weight average molecular weight and the number average molecular weight, an average molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC) using chloroform as a solvent.

Example 1
<Synthesis of initial polymer (1)>
2.7 g of 9,9-dioctyl-2,7-dibromofluorene and 4-bromo-2
, 5- (3,7-dimethyloctyloxy) benzaldehyde 2.3 g and 2,2
After charging '-bipyridyl 2.7 into the reaction vessel, the inside of the reaction system was replaced with argon gas. To this, 150 ml of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, bis (1
, 5-Cyclooctadiene) nickel (0) was added, and the mixture was stirred at room temperature for 10 minutes and then reacted at 60 ° C. for 7 hours. The reaction was performed in an argon gas atmosphere. After the reaction, this solution was cooled, poured into a mixed solution of 25% aqueous ammonia 50 ml / methanol 200 ml / ion exchanged water 150 ml, and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried and then dissolved in chloroform. The solution was filtered to remove insoluble matters, and then the solution was poured into methanol and reprecipitated to recover the generated precipitate. This precipitate was dried under reduced pressure to obtain 1.4 g of an initial polymer (1).
The obtained initial polymer (1) has a weight average molecular weight in terms of polystyrene of 6.1 × 10 6.
⁴ and the number average molecular weight was 2.4 × 10 ⁴ .

The structure of the initial polymer (1) expected from the charged monomer is as follows.

<Synthesis of polymeric fluorescent substance 1>
Phosphonic acid ester 0.016 obtained by reacting 2-methoxy-5- (2-ethylhexyloxy) -p-xylylene dichloride with triethyl phosphite
g and 0.5 g of the above initial polymer (1) were charged into a reaction vessel, and the inside of the reaction system was replaced with argon gas. Bubbling with argon gas in advance,
50 ml of degassed tetrahydrofuran (dehydrated solvent) was added. Next, potassium tert. -A solution prepared by dissolving 0.07 g of butoxide in 5 ml of tetrahydrofuran (dehydrated solvent) deaerated by bubbling with argon gas was added dropwise over about 10 minutes at room temperature. The reaction was then continued for 2.5 hours at room temperature.
After the reaction, the reaction mixture was neutralized by adding acetic acid, and the solution was poured into methanol and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure to obtain 0.46 g of a polymer. The obtained polymer is referred to as polymeric fluorescent substance 1.
The polymeric fluorescent substance 1 has a polystyrene-equivalent weight average molecular weight of 9.6 × 10 ⁴ ,
The number average molecular weight was 3.7 × 10 ⁴ .
The structure of polymeric fluorescent substance 1 expected from the charged monomers is as follows. As a result of measuring the fluorescence spectrum of the thin film of the obtained polymeric fluorescent substance 1 by the method described in Example 9, the peak wavelength of fluorescence was 504 nm.

Comparative Example 1
<Synthesis of polyfluorene>
9,9-Dioctyl-2,7-dibromofluorene and 4-bromo-2,5- (
Poly (9,9) was synthesized in the same manner as in the synthesis of the polymer (1) except that only 9,9-dioctyl-2,7-dibromofluorene was used instead of 3,7-dimethyloctyloxy) benzaldehyde. -Dioctylfluorene-2,7-diyl) was obtained. The resulting polyfluorene had a polystyrene equivalent weight average molecular weight of 4.4x.
Is 10 ^5, the number-average molecular weight was 1.2x10 ^5. As a result of measuring the fluorescence spectrum of the obtained polyfluorene thin film by the method described in Example 9, the peak wavelength of fluorescence was 428 nm.
As described above, the fluorescence peak wavelength of the polymeric fluorescent substance 1 was 76 nm longer than that of polyfluorene constituting the block.
Example 2
<Synthesis of initial polymer (2)>
2.7 g of 9,9-dioctyl-2,7-dibromofluorene and 3-bromo-p-
After charging 1.1 g of anisaldehyde and 2,2′-bipyridyl 2.7 into the reaction vessel, the inside of the reaction system was replaced with argon gas. To this, 150 ml of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, this mixed solution is mixed with bis (1,5-cyclooctadiene) nickel (0).
Was added, and the mixture was stirred at room temperature for 10 minutes and reacted at 60 ° C. for 7 hours. The reaction was performed in an argon gas atmosphere. After the reaction, the solution was cooled and then 2
The solution was poured into a mixed solution of 5% aqueous ammonia 50 ml / methanol 200 ml / ion exchanged water 150 ml and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried and then dissolved in chloroform. The solution was filtered to remove insoluble matters, and then the solution was poured into methanol and reprecipitated to recover the generated precipitate. This precipitate was dried under reduced pressure to obtain 1.2 g of an initial polymer (2).
The resulting initial polymer (2) had a polystyrene equivalent weight average molecular weight of 2.9 × 10
⁴ and the number average molecular weight was 1.1 × 10 ⁴ .

The structure of the initial polymer (2) expected from the charged monomer is as follows.

<Synthesis of polymeric fluorescent substance 2>
0.032 g of phosphonic acid ester obtained by reacting 2-methoxy-5- (2-ethylhexyloxy) -p-xylylene dichloride with triethyl phosphite
And 0.66 g of the above initial polymer (2) were charged into a reaction vessel, and the inside of the reaction system was replaced with argon gas. Bubbling with argon gas in advance,
30 ml of degassed tetrahydrofuran (dehydrated solvent) was added. Next, potassium tert. -A solution prepared by dissolving 0.07 g of butoxide in 5 ml of tetrahydrofuran (dehydrated solvent) deaerated by bubbling with argon gas was added dropwise over about 10 minutes at room temperature. Subsequently, the reaction was allowed to proceed for 2 hours at room temperature.
After the reaction, the reaction mixture was neutralized by adding acetic acid, and the solution was poured into methanol and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure to obtain 0.6 g of a polymer. The obtained polymer is referred to as polymeric fluorescent substance 2.
The polymeric fluorescent substance 2 has a polystyrene-equivalent weight average molecular weight of 1.1 × 10 ⁵ ,
The number average molecular weight was 2.7 × 10 ⁴ .
The structure of polymeric fluorescent substance 2 expected from the charged monomers is as follows. As a result of measuring the fluorescence spectrum of the thin film of the obtained polymeric fluorescent substance 2 by the method described in Example 9, the peak wavelength of fluorescence was 456 nm.

As described above, the fluorescent peak wavelength of the polymeric fluorescent substance 2 was 26 nm longer than that of polyfluorene constituting the block.
Example 3
<Synthesis of initial polymer (3)>
3.4 g of N, N′-diphenyl-N, N′-di (3-methyl-4-bromophenyl) benzidine and 4-bromo-2,5- (3,7-dimethyloctyloxy)
After charging 2.3 g of benzaldehyde and 2,2′-bipyridyl 2.7 into the reaction vessel, the inside of the reaction system was replaced with argon gas. To this, 150 ml of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, this mixed solution is mixed with bis (1,5-cyclooctadiene) nickel (0).
Was added, and the mixture was stirred at room temperature for 10 minutes and reacted at 60 ° C. for 7 hours. The reaction was performed in an argon gas atmosphere. After the reaction, the solution was cooled and then 2
The solution was poured into a mixed solution of 5% aqueous ammonia 50 ml / methanol 200 ml / ion exchanged water 150 ml and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried and then dissolved in chloroform. The solution was filtered to remove insoluble matters, and then the solution was poured into methanol and reprecipitated to recover the generated precipitate. This precipitate was dried under reduced pressure to obtain 1.5 g of an initial polymer (3).
The weight average molecular weight in terms of polystyrene of the obtained initial polymer (3) is 1.1 × 10.
⁴ and the number average molecular weight was 5.8 × 10 ³ .
The structure of the initial polymer (3) expected from the charged monomer is as follows.

<Synthesis of initial polymer (4)>
2.8 g of 9,9-dioctyl-2,7-dibromofluorene and 4-bromo-2
, 5- (3,7-Dimethyloctyloxy) benzylphosphonic acid diethyl ester 2.3 g and 2,2′-bipyridyl 2.7 were charged into a reaction vessel, and the inside of the reaction system was replaced with argon gas. To this, 150 ml of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 5.0 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes, and then reacted at 60 ° C. for 7 hours. The reaction was performed in an argon gas atmosphere. After the reaction, this solution was cooled and then methanol 250
The mixture was poured into a mixed solution of ml / ion exchange water 150 ml and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried and then dissolved in chloroform. The solution was filtered to remove insoluble matters, and then the solution was poured into methanol and reprecipitated to recover the generated precipitate. This precipitate was dried under reduced pressure to obtain 1.1 g of an initial polymer (4).
The weight average molecular weight in terms of polystyrene of the obtained initial polymer (4) is 5.0 × 10
³ and the number average molecular weight was 4.0 × 10 ³ .

The structure of the initial polymer (4) expected from the charged monomer is as follows.

<Synthesis of polymeric fluorescent substance 3>
After charging 0.4 g of the above initial polymer (3) and 0.3 g of the above initial polymer (4) into a reaction vessel, the inside of the reaction system was replaced with argon gas. To this, 50 m of tetrahydrofuran (dehydrated solvent) deaerated by bubbling with argon gas in advance.
l was added. Next, potassium tert. -0.11 g of butoxide was bubbled with argon gas and degassed tetrahydrofuran (
A solution dissolved in 5 ml of dehydrated solvent was added dropwise at room temperature over approximately 10 minutes.
The reaction was then continued for 2.5 hours at room temperature.
After the reaction, the reaction mixture was neutralized by adding acetic acid, and the solution was poured into methanol and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure to obtain 0.5 g of a polymer. The obtained polymer is referred to as polymeric fluorescent substance 3.
The polymeric fluorescent substance 3 has a polystyrene equivalent weight average molecular weight of 2.5 × 10 ⁴ ,
The number average molecular weight was 1.0 × 10 ⁴ .
The structure of the polymeric fluorescent substance 3 expected from the charged monomers is as follows. As a result of measuring the fluorescence spectrum of the thin film of the obtained polymeric fluorescent substance 3 by the method described in Example 11, the peak wavelength of fluorescence was 470 nm.

Comparative Example 2
<Synthesis of Comparative Polymer 1>
As raw materials, N, N′-diphenyl-N, N′-di (3-methyl-4-bromophenyl) benzidine 2.0 g, 2,2′-bipyridyl 1.1 g, bis (1,
0.75 g of Comparative Polymer 1 was obtained in the same manner as in the synthesis of Example 1 <Polymer 1> except that 2.0 g of 5-cyclooctadiene) nickel (0) was used. The obtained polymer had a polystyrene-reduced weight average molecular weight of 2.8 × 10 ⁴ and a number average molecular weight of 1.8 × 10 ⁴ .

As a result of measuring the fluorescence spectrum of the thin film of the obtained comparative polymer 1 by the method described in Example 9, the peak wavelength of fluorescence was 422 nm.

As described above, the fluorescent peak wavelength of the polymeric fluorescent substance 3 is 42 nm longer than that of the polyfluorene constituting the block.
nm long wavelength.

Example 4
<Synthesis of initial polymer (5)>
2. Phosphonic acid ester obtained by reacting 2,5-bis (chloromethyl) -4 ′-(3,7-dimethyloctyloxy) biphenyl with triethyl phosphite
0 g, 0.6 g terephthalaldehyde and 0.28 g 4-bromobenzaldehyde
Were charged into a reaction vessel, and the inside of the reaction system was replaced with argon gas. To this, 40 ml of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, potassium tert. -A solution prepared by dissolving 2.2 g of butoxide in 10 ml of tetrahydrofuran (dehydrated solvent) deaerated by bubbling with argon gas was added dropwise at room temperature over approximately 20 minutes. The reaction was then continued for 3 hours at room temperature.
After the reaction, the reaction mixture was neutralized by adding acetic acid, and the solution was poured into methanol and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was washed with ethanol and then dried under reduced pressure to obtain 2.8 g of a polymer. The obtained polymer will be referred to as an initial polymer (5).
The polystyrene equivalent weight average molecular weight of the initial polymer (5) was 5.1 × 10 ³ , and the number average molecular weight was 1.8 × 10 ³ .
The units contained in the structure of the initial polymer (5) expected from the charged monomers are as follows.

<Synthesis of polymeric fluorescent substance 4>
9,9-dioctyl-2,7-dibromofluorene (2.1 g) and an initial polymer (5
) 0.25 g and 2,2′-bipyridyl 1.37 g were charged in a reaction vessel, and the inside of the reaction system was replaced with argon gas. To this, 100 ml of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. next,
To this mixed solution was added bis (1,5-cyclooctadiene) nickel (0) to 2.5.
After adding g and stirring at room temperature for 10 minutes, it reacted at 60 degreeC for 7 hours. The reaction was performed in an argon gas atmosphere. After the reaction, this solution was cooled, then poured into a mixed solution of 25% aqueous ammonia 25 ml / methanol 150 ml / ion exchanged water 100 ml, and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried and then dissolved in toluene. The solution was filtered to remove insoluble matters, and then the solution was poured into methanol and reprecipitated to recover the generated precipitate. This precipitate was dried under reduced pressure to obtain 1.1 g of a polymer. This polymer is called polymeric fluorescent substance 4.
The obtained polymeric fluorescent substance 4 has a polystyrene equivalent weight average molecular weight of 2.7 × 10 ^5.
The number average molecular weight was 5.8 × 10 ⁴ .
The units contained in the structure of the polymeric fluorescent substance 4 expected from the charged monomers are represented by the following two structures.
As a result of measuring the fluorescence spectrum of the thin film of the obtained polymeric fluorescent substance 4 by the method described in Example 9, the peak wavelength of fluorescence is 510 nm, which is 82 nm more than that of polyfluorene, which is a constituent block of the polymeric fluorescent substance 4. It was a long wavelength

Example 5
<Synthesis of initial polymer (6)>
4.8 g of a phosphonium salt obtained by reacting 2,5-dioctyloxy-p-xylylene dichloride with triphenylphosphine and 0.
After charging 6 g and 4-bromobenzaldehyde 0.28 g into the reaction vessel, the inside of the reaction system was replaced with argon gas. To this, 40 ml of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, potassium tert. -A solution prepared by dissolving 2.2 g of butoxide in 10 ml of tetrahydrofuran (dehydrated solvent) deaerated by bubbling with argon gas was added dropwise at room temperature over approximately 20 minutes. The reaction was then continued for 3 hours at room temperature.
After the reaction, the reaction mixture was neutralized by adding acetic acid, and the solution was poured into methanol and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. The precipitate was washed with ethanol and then dried under reduced pressure to obtain 1.5 g of a polymer. The obtained polymer will be referred to as an initial polymer (6).
The polystyrene equivalent weight average molecular weight of the initial polymer (6) was 4.7 × 10 ³ , and the number average molecular weight was 3.3 × 10 ³ .

The units contained in the structure of the initial polymer (6) expected from the charged monomers are as follows.

<Synthesis of polymeric fluorescent substance 5>
9,9-dioctyl-2,7-dibromofluorene (2.1 g) and an initial polymer (
6) After charging 0.25g and 2,2'-bipyridyl 1.37g into the reaction vessel,
The reaction system was replaced with argon gas. To this, 100 ml of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, bis (1,5-cyclooctadiene) nickel (0) is added to the mixed solution.
5 g was added and stirred at room temperature for 10 minutes, and then reacted at 60 ° C. for 7 hours. The reaction was performed in an argon gas atmosphere. After the reaction, this solution was cooled, then poured into a mixed solution of 25% aqueous ammonia 25 ml / methanol 150 ml / ion exchanged water 100 ml, and stirred for about 1 hour. Next, the produced precipitate was filtered and collected.
This precipitate was dried and then dissolved in toluene. The solution was filtered to remove insoluble matters, and then the solution was poured into methanol and reprecipitated to recover the generated precipitate. This precipitate was dried under reduced pressure to obtain 1.0 g of a polymer. This polymer will be called polymeric fluorescent substance 5.
The obtained polymeric fluorescent substance 5 has a polystyrene equivalent weight average molecular weight of 2.4 × 10 ^5.
The number average molecular weight was 6.3 × 10 ⁴ .
The units included in the structure of the polymeric fluorescent substance 5 expected from the charged monomers are as follows.
As a result of measuring the fluorescence spectrum of the thin film of the obtained polymeric fluorescent substance 5 by the method described in Example 9, the peak wavelength of fluorescence is 524 nm, which is 96 nm than polyfluorene, which is a constituent block of the polymeric fluorescent substance 5. Long wavelength.

Example 6
<Synthesis of initial polymer (7)>
As raw materials, 1.64 g of 9,9-dioctyl-2,7-dibromofluorene, bis (4-bromophenyl)-(4- (4′-tertbutyl) styryl) amine 0
. 42 g, 0.09 g of 4-bromobenzaldehyde, 2,2′-bipyridyl
The initial polymer (7) was prepared in the same manner as in Example 1 <Polymer 1> except that 38 g and 2.5 g of bis (1,5-cyclooctadiene) nickel (0) were used.
0 g was obtained. The weight average molecular weight in terms of polystyrene of the obtained initial polymer (7) is 9
. 2x10 ^4, and a number average molecular weight was 4.2 x 10 ^4.
The units contained in the structure of the initial polymer (7) expected from the charged monomers are as follows.

<Synthesis of initial polymer (8)>
As raw materials, 3.6 g of 9,9-dioctyl-2,7-dibromofluorene and 4-
Example 3 <Polymer (except for the use of 0.61 g of bromobenzylphosphonic acid diethyl ester and 5.5 g of 2,2′-bipyridyl, 2.7 bis (1,5-cyclooctadiene) nickel (0)) 4)> In the same manner as in the synthesis of>
g was obtained. The polystyrene equivalent weight average molecular weight of the obtained polymer was 2.5 × 10 ^4.
The number average molecular weight was 1.1 × 10 ⁴ .
The units contained in the structure of the initial polymer (8) expected from the charged monomer are as follows.

<Synthesis of polymeric fluorescent substance 6>
As a raw material, 0.3 g of the above initial polymer (7) and 0.08 of the above initial polymer (8)
Example 3 <Polymer phosphor 3 except that 0.1 g of t-butoxypotassium was used.
As in the synthesis of>, 0.18 g of polymeric fluorescent substance 6 was obtained. The obtained polymer fluorescent substance 6 had a polystyrene-reduced weight average molecular weight of 9.2 × 10 ⁴ and a number average molecular weight of 4.2 × 10 ⁴ .
The units included in the structure of the polymeric fluorescent substance 6 expected from the charged monomers are as follows.

As a result of measuring the fluorescence spectrum of the thin film of the obtained polymeric fluorescent substance 6 by the method described in Example 9, the peak wavelength of fluorescence is 456 nm, which is 28 nm than polyfluorene, which is a constituent block of the polymeric fluorescent substance 6. Long wavelength.

Example 7
<Synthesis of initial polymer (9)>
As a raw material, 1.64 g of 9,9-dioctyl-2,7-dibromofluorene, N
, N′-bis (4-bromophenyl) -N, N′-diphenylphenylenediamine 1.0 g, 4-bromobenzaldehyde 0.09 g, 2,2′-bipyridyl 1
. 0.9 g of polymer 9 was obtained in the same manner as the synthesis of Example 1 <Polymer 1> except that 65 g and 3.0 g of bis (1,5-cyclooctadiene) nickel (0) were used. . The obtained polymer had a weight average molecular weight in terms of polystyrene of 3.9 × 10 ⁴ and a number average molecular weight of 1.4 × 10 ⁴ .
The units contained in the structure of the initial polymer (9) expected from the charged monomers are as follows.

<Synthesis of polymeric fluorescent substance 7>
As a raw material, 0.2 g of the above initial polymer (9) and the above initial polymer (9) polymer (8
) 0.24 g of polymeric fluorescent substance 7 was obtained in the same manner as in the synthesis of Example 3 <Polymeric fluorescent substance 3> except that 0.2 g and 0.1 g of t-butoxypotassium were used. The obtained polymeric fluorescent substance 7 has a polystyrene equivalent weight average molecular weight of 6.3 × 10 ⁴ ,
The number average molecular weight was 2.1 × 10 ⁴ .
The units contained in the structure of the polymeric fluorescent substance 7 expected from the charged monomers are as follows.

As a result of measuring the fluorescence spectrum of the thin film of the obtained polymeric fluorescent substance 7 by the method described in Example 9, the peak wavelength of fluorescence is 474 nm, which is 46 nm than polyfluorene, which is a constituent block of the polymeric fluorescent substance 7. Long wavelength.

Example 8
<Synthesis of initial polymer (10)>

As raw materials, 1,4-dibromo-2,5-bis (3,7-dimethyloctyloxy) benzene 1.54 g, N, N-bis (4-bromophenyl) -N ′, N′—
1.6 g diphenylphenylenediamine, 0.09 4-bromobenzaldehyde
g, similar to the synthesis of Example 1 <Initial polymer (1)>, except that 2.2 g of 2,2′-bipyridyl and 4.0 g of bis (1,5-cyclooctadiene) nickel (0) were used. 0.9 g of an initial polymer (10) was obtained by a simple method. The obtained polymer had a polystyrene equivalent weight average molecular weight of 2.0 × 10 ⁴ and a number average molecular weight of 1.1 × 1.
0 was ^4. The units contained in the structure of the initial polymer (10) expected from the charged monomers are as follows.

<Synthesis of initial polymer (11)>
As raw materials, 1.46 g of 4,4′-dibromo-3,3′-bis (3,7-dimethyloctyloxy) stilbene, 0.21 g of 4-bromobenzylphosphonic acid diethyl ester and 2,2′-bipyridyl Example 3 <Initial polymer (except for using 83 g, 2.7 bis (1,5-cyclooctadiene) nickel (0) 1.5 g)
4)> In the same manner as in the synthesis of>, 0.4 g of the initial polymer (11) was obtained. The obtained polymer had a weight average molecular weight in terms of polystyrene of 8.8 × 10 ³ and a number average molecular weight of 7.8 × 10 ³ .

<Synthesis of polymeric fluorescent substance 8>
0.1 g of the above initial polymer (10) and the above initial polymer (11) as raw materials
Except for using 14 g and 0.1 g of t-butoxypotassium, 0.12 g of polymeric fluorescent substance 7 was obtained in the same manner as in the synthesis of Example 3 <Polymeric fluorescent substance 3>. The obtained polymer had a polystyrene-reduced weight average molecular weight of 6.8 × 10 ⁴ and a number average molecular weight of 1.8 × 10 ⁴ .
The units contained in the structure of the polymeric fluorescent substance 8 predicted from the charged monomers are as follows.

原料として、４，４’−ジブロモ−３，３’−ビス（３，７−ジメチルオクチル
オキシ）スチルベン０．７１ｇ、２，２’−ビピリジル０．５ｇ、ビス（１，５
−シクロオクタジエン）ニッケル（０）を１．０ｇを用いた以外は実施例１＜重
合体１＞の合成と同様な方法にて比較重合体２を０．２８ｇ得た。得られた重合
体のポリスチレン換算重量平均分子量は、２．１ｘ１０⁵であり、数平均分子量
は、５．３ｘ１０⁴であった。
得られた高分子蛍光体８の薄膜の蛍光スペクトルを実施例９記載の方法で測定し
た結果、蛍光のピーク波長は４６５ｎｍであり、また高分子蛍光体８の構成ブロ
ックである、比較重合体２の蛍光ピーク波長は４３８ｎｍに比べ、よりも２７ｎ
ｍ長波長であった。 Comparative Example 3
<Synthesis of Comparative Polymer 2>

As raw materials, 0.74 g of 4,4′-dibromo-3,3′-bis (3,7-dimethyloctyloxy) stilbene, 0.5 g of 2,2′-bipyridyl, bis (1,5
0.28 g of Comparative Polymer 2 was obtained in the same manner as in the synthesis of Example 1 <Polymer 1> except that 1.0 g of cyclooctadiene) nickel (0) was used. The obtained polymer had a weight average molecular weight in terms of polystyrene of 2.1 × 10 ⁵ and a number average molecular weight of 5.3 × 10 ⁴ .
As a result of measuring the fluorescence spectrum of the thin film of the obtained polymeric fluorescent substance 8 by the method described in Example 9, the peak wavelength of fluorescent light was 465 nm, and the comparative polymer 2 was a building block of the polymeric fluorescent substance 8 Compared with 438 nm, the fluorescence peak wavelength is 27n
m long wavelength.

Example 9
<Fluorescence characteristics>
A 0.2 wt% chloroform solution of the polymeric fluorescent substances (1) to (8) was spin-coated on quartz to form thin polymeric fluorescent substance films. The fluorescence spectra of these thin films were measured using a fluorescence spectrophotometer (Hitachi, Ltd. 850). All had strong fluorescence.

Example 10
<Creation and evaluation of device>
A glass substrate having an ITO film with a thickness of 150 nm formed by sputtering is applied to a poly (
Ethylenedioxythiophene) / polystyrene sulfonic acid solution (Bayer,
A film having a thickness of 50 nm was formed by spin coating using Baytron and dried at 120 ° C. for 10 minutes on a hot plate. Next, 1.5 of the polymeric fluorescent substance (1)
A film having a thickness of about 100 nm was formed by spin coating using a wt% toluene solution. Furthermore, after drying this at 80 ° C. under reduced pressure for 1 hour, as a cathode buffer layer,
A polymer LED was produced by depositing lithium fluoride at 0.4 nm, cathode as calcium, 25 nm, and then aluminum at 40 nm. The degree of vacuum at the time of vapor deposition was 1 to 8 × 10 ⁻⁶ Torr. By applying voltage to the resulting device, EL light emission from the polymeric fluorescent substance (1) was obtained. The intensity of EL emission was almost proportional to the current density.
The element has a luminance of more than 1 cd / m ² at about 5.3 V and a luminous efficiency of up to 3.2 cd.
/ A, the maximum luminance reached 13000 cd / m ² or more.

Example 11
<Creation and evaluation of device>
A polymer LED was produced in the same manner as in Example 10 except that the polymer phosphor (4) was used instead of the polymer phosphor (1). The degree of vacuum during deposition is 1
It was ˜8 × 10 ⁻⁶ Torr. By applying voltage to the resulting device, EL light emission from the polymeric fluorescent substance (4) was obtained. The intensity of EL emission was almost proportional to the current density.
The element has a luminance exceeding 1 cd / m ² at about 6.1 V and a luminous efficiency of up to 1.8 cd.
/ A, the maximum luminance was 10440 cd / m ² .

Example 12
<Creation and evaluation of device>
A polymer LED was produced in the same manner as in Example 10 except that the polymer phosphor (5) was used instead of the polymer phosphor (1). The degree of vacuum during deposition is 1
It was ˜8 × 10 ⁻⁶ Torr. By applying voltage to the resulting device, EL light emission from the polymeric fluorescent substance (5) was obtained. The intensity of EL emission was almost proportional to the current density.
The device has a luminance exceeding 1 cd / m ² at about 6.3 V and a luminous efficiency of up to 2.2 cd.
/ A, the maximum luminance was 10542 cd / m ² .

Claims (17)

A block copolymer containing two or more blocks and having fluorescence in a solid state, and these blocks may be the same or different, and in each block, repeating units are bonded by a conjugated bond. A block copolymer in which the blocks are connected by a bonding unit having a conjugated bond, and the polystyrene-equivalent number average molecular weight of at least one block is 1 × 10 ³ to 1 × 10 ^8. The block copolymer is represented by the following general formula (1a):
-A-block- (B) -block-C- (1a)
(Here, A and C represent blocks that may be the same or different, B represents a bonding unit having a conjugated bond, and the fluorescence exhibited by the polymer thin film represented by the general formula (1a)) (The peak wavelength is 5 nm or longer than the fluorescence peak wavelength exhibited by the polymer thin film consisting only of block A and the fluorescence peak wavelength exhibited by the polymer thin film consisting only of block C)
In the above formula (1a), A representing a block is composed of at least one repeating unit selected from the group consisting of a phenylene group, a biphenylene group, a fluorenediyl group, and a stilbenediyl group, and C representing the block is A block copolymer having a repeating unit represented by the formula (2).

(Wherein Ar ₁ represents an arylene group or a divalent heterocyclic group, and R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. , N is 0 or 1)
(However,
In the above formula (1a), a block copolymer in which C representing a block has a repeating unit represented by the following formula (3) is excluded.
-Ar _2- (CR ₃ = CR ₄ ) _m- (3)
(Wherein Ar ₂ is a divalent aromatic amine group represented by the following general formula (9). R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group, an aryl group, or a monovalent heteroaromatic group. A cyclic group or a cyano group, m is 0 or 1)
_{- (Ar 14 -N (Ar 15} )) t-Ar 16 - (9)
(Wherein Ar ₁₄ and Ar ₁₆ are each independently an arylene group, an aromatic compound group represented by the following general formula (5), or a group having an aromatic amine skeleton of the following general formula (6); ₁₅ has an aryl group, a monovalent heteroaromatic ring group, a group having an aromatic amine skeleton represented by the following general formula (7), or an aromatic ethenylene skeleton represented by the following general formula (8) A t represents 1 or 2)

(Here, Ar ₆ and Ar ₇ each independently represent an arylene group, and the arylene group may have a substituent. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, Aryl group, monovalent heterocyclic group or cyano group, l is 0 or 1)

(Here, Ar ₈ and Ar ₉ each independently represent an arylene group, and Ar ₁₀ is an aryl group. Also, between Ar ₈ and Ar ₁₀ , between Ar ₈ and Ar ₉ , or Ar ₉ And Ar ₁₀ may form a ring)

(Wherein Ar ₁₁ represents an arylene group, R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heteroaromatic group or a cyano group, (A ring may be formed between Ar ₁₁ and R ₇ , Ar ₁₁ and R ₈ , or R ₇ and R ₈ )

(Wherein Ar ₁₂ and Ar ₁₃ each independently represent an arylene group, and R ₉ and R ₁₀ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heteroaromatic ring group or Represents a cyano group, and p is 0 or 1. ) A block copolymer containing two or more blocks and having fluorescence in a solid state, wherein at least two of the blocks are not identical to each other, and repeating units are bonded by a conjugated bond in each block; A block copolymer in which a conjugated chain is directly connected between the blocks without breaking, and the polystyrene-equivalent number average molecular weight of at least one block is 1 × 10 ³ to 1 × 10 ⁸ And the block copolymer is represented by the following general formula (1b):
-A-block-C- (1b)
(Here, A and C each represent a different block, and the fluorescence peak wavelength exhibited by the polymer thin film represented by the formula (1b) is 5 nm or more than the fluorescence peak wavelength exhibited by the polymer thin film comprising only block A. Long wavelength)
In the formula (1b), A representing a block is composed of at least one repeating unit selected from the group consisting of a phenylene group, a biphenylene group, a fluorenediyl group, and a stilbenediyl group, and C representing the block is A block copolymer having a repeating unit represented by the formula (2).

(Wherein Ar ₁ represents an arylene group or a divalent heterocyclic group, and R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. , N is 0 or 1)
(However,
In the above formula (1b), a block copolymer in which C representing a block has a repeating unit represented by the following formula (3) is excluded.
-Ar _2- (CR ₃ = CR ₄ ) _m- (3)
(Here, Ar ₂ is a divalent aromatic amine group represented by the following general formula (9).
R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heteroaromatic ring group or a cyano group, and m is 0 or 1)
_{- (Ar 14 -N (Ar 15} )) t-Ar 16 - (9)
(Wherein Ar ₁₄ and Ar ₁₆ are each independently an arylene group, an aromatic compound group represented by the following general formula (5), or a group having an aromatic amine skeleton of the following general formula (6); ₁₅ has an aryl group, a monovalent heteroaromatic ring group, a group having an aromatic amine skeleton represented by the following general formula (7), or an aromatic ethenylene skeleton represented by the following general formula (8) A t represents 1 or 2)

(Wherein Ar ₆ and Ar ₇ each independently represent an arylene group, R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heteroaromatic ring group or a cyano group, l is 0 or 1)

(Here, Ar ₈ and Ar ₉ each independently represent an arylene group, and Ar ₁₀ is an aryl group. Also, between Ar ₈ and Ar ₁₀ , between Ar ₈ and Ar ₉ , or Ar ₉ And Ar ₁₀ may form a ring)

(Wherein Ar ₁₁ represents an arylene group, R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heteroaromatic group or a cyano group, (A ring may be formed between Ar ₁₁ and R ₇ , Ar ₁₁ and R ₈ , or R ₇ and R ₈ )

(Wherein Ar ₁₂ and Ar ₁₃ each independently represent an arylene group, and R ₉ and R ₁₀ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heteroaromatic ring group or Represents a cyano group, and p is 0 or 1. The block copolymer according to claim 1 or 2, wherein A in the formulas (1a) and (1b) is a fluorenediyl group. In said Formula (2), when n is 0, the junction unit B of the said Formula (1a) is represented by following General formula (10), The block copolymer of Claim 1 or 3 .

(Wherein Ar ₁₇ and Ar ₁₈ are each independently an arylene group or a divalent heterocyclic group, and R ₁₁ and R ₁₂ are each independently a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or Represents a cyano group) In said Formula (2), when n is 1, the block unit of Claim 1 or 3 in which the junction unit B of the said Formula (1a) is represented by following General formula (11).
―Ar ₁₉ ― (11)
(Wherein Ar ₁₉ is an arylene group or a divalent heterocyclic group)   A polymeric phosphor composition comprising the block copolymer according to claim 1. 7. The polymeric fluorescent substance composition according to claim 6, comprising 10% by weight or more of a block copolymer.   A polymer light emitting device having at least a light emitting layer between electrodes composed of an anode and a cathode, wherein the light emitting layer comprises the block copolymer according to any one of claims 1 to 5. Light emitting element.   A polymer light-emitting device having at least a light-emitting layer between electrodes composed of an anode and a cathode, wherein the light-emitting layer contains the polymeric phosphor composition according to claim 6 or 7. . Between a cathode and a light emitting layer, polymer light-emitting device according to claim 8 or 9, wherein adjacent to the light emitting layer, characterized in that a layer formed of an electron transporting compound. Between an anode and a light emitting layer, polymer light-emitting device according to claim 8 or 9, wherein in that a layer consisting of adjacent to the light emitting layer a hole transporting compound. A layer made of an electron transporting compound adjacent to the light emitting layer between the cathode and the light emitting layer, and a layer made of a hole transporting compound adjacent to the light emitting layer between the anode and the light emitting layer. the polymer light emitting element according to claim 8 or 9, wherein the provided. A planar light source using the polymer light emitting device according to any one of claims 8 to 12 . Segment display device characterized by using the polymer light emitting device according to any one of claims 8-12. Dot matrix display device characterized by using the polymer light emitting device according to any one of claims 8-12. The liquid crystal display device, characterized in that the backlight polymer light-emitting device according to any one of claims 8-12. An electronic apparatus comprising the display device according to any one of claims 14 to 16 as a display unit.