Block copolymer and polymeric luminescent element Number:7,125,930 from the United States Patent and Trademark Office (PTO) owispatent A block copolymer comprising two or more blocks and having fluorescence in the solid state, wherein blocks thereof may be the same or different, and in each of the blocks, one or more kinds of repeating units are bonded through conjugated bonds, and bonding between the blocks is made by junction unit having conjugated bond, and the polystyrene reduced number average molecular weight of at least one block is 1.times.10.sup.3 to 1.times.10.sup.8.<H luminescent, polymeric, Block, copolymer, 7125930.html, Patent, pto, 7125930

Title: Block copolymer and polymeric luminescent element

Abstract: A block copolymer comprising two or more blocks and having fluorescence in the solid state, wherein blocks thereof may be the same or different, and in each of the blocks, one or more kinds of repeating units are bonded through conjugated bonds, and bonding between the blocks is made by junction unit having conjugated bond, and the polystyrene reduced number average molecular weight of at least one block is 1.times.10.sup.3 to 1.times.10.sup.8.

Patent Number: 7,125,930 Issued on 10/24/2006 to Noguchi, et al.

Inventors: Noguchi; Takanobu (Tsukuba, JP), Tsubata; Yoshiaki (Tsukuba, JP), Doi; Shuji (Tsukuba, JP)
Assignee: Sumitomo Chemical Company, Limited (Osaka, JP)

Appl. No.: 10/476,132

Filed: April 24, 2002

PCT Filed: April 24, 2002

PCT No.: PCT/JP02/04060

371(c)(1),(2),(4) Date: October 27, 2003

PCT Pub. No.: WO02/088223

PCT Pub. Date: November 07, 2002

Foreign Application Priority Data


Apr 27, 2001 [JP]			2001-132002
Apr 27, 2001 [JP]			2001-132011

Current U.S. Class: 525/89 ; 525/133; 525/137; 525/241; 526/103; 526/346

Current International Class: C08L 25/08 (20060101); C08F 112/02 (20060101)

Field of Search: 525/89,241,101,104 526/346,103

References Cited [Referenced By]

U.S. Patent Documents


5589320	December 1996	Ohnishi et al.
5856434	January 1999	Stern

Foreign Patent Documents


0 637 621	Feb., 1995	EP
0 672 741	Sep., 1995	EP
5-202355	Aug., 1993	JP
2000-104057	Apr., 2000	JP
2000-154334	Jun., 2000	JP
2000-169839	Jun., 2000	JP
2000-252065	Sep., 2000	JP
92/03490	Mar., 1992	WO

Primary Examiner: Seidleck; James J.
Assistant Examiner: Asinovsky; Olga
Attorney, Agent or Firm: Sughrue Mion, PLLC

Claims

The invention claimed is:

1. A block copolymer comprising two or more blocks and having fluorescence in the solid state, in each of the blocks, one or more kinds of repeating unit are bonded through conjugated bonds, and the polystyrene reduced number average molecular weight of at least one block is 1.times.10.sup.3 to 1.times.10.sup.8, wherein the block copolymer is represented by general formula (1a) or (1b) -A-block-(B)-block-C- (1a) (wherein, A and C represent blocks which may be the same or different; B represents a junction unit having a conjugated bond; the fluorescence peak wavelength shown by a thin film of the polymer represented by general formula (1a) is longer by 5 nm or more than the fluorescence peak wavelengths shown by either a thin film of the polymer solely composed of block A, or a thin film of the polymer solely composed of block C), -A-block-C- (1b) (wherein, A and C represent blocks which are mutually different, the fluorescence peak wavelength shown by a thin film of the polymer represented by general formula (1b) is longer by 5 nm or more than the fluorescence peak wavelength shown by a thin film of the polymer solely composed of block A), wherein at least one of A and C which represent blocks in the above formula (1a) or (1b) has one or more kinds of the repeating unit represented by the below formula (3), ##STR00051## (wherein, Ar.sub.2 is a divalent aromatic amine group represented by the following general formula (4), R.sub.3 and R.sub.4 each independently represent a group selected from a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic compound group and a cyano group, and m is 0 or 1) ##STR00052## (wherein, Ar.sub.3 and Ar.sub.5 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 represented by the following general formula (6), and Ar.sub.4 represents an aryl group, a monovalent heterocyclic compound group, or a group having an aromatic amine skeleton represented by the following general formula (7), or a group having an aromatic ethenylene skeleton represented by the following general formula (8); a ring may be formed between Ar.sub.3 and Ar.sub.4, between Ar.sub.4 and Ar.sub.5, or between Ar.sub.3 and Ar.sub.5) ##STR00053## (wherein, Ar.sub.6 and Ar.sub.7 each independently represent an arylene group, R.sub.5 and R.sub.6 are the same group with those of R.sub.3 and R.sub.4 and 1 is 0 or 1) ##STR00054## (wherein, Ar.sub.8 and Ar.sub.9 each independently represent an arylene group, and Ar.sub.10 represent an aryl group, a ring may be formed between Ar.sub.8 and Ar.sub.10, between Ar.sub.8 and Ar.sub.9, or between Ar.sub.9 and Ar.sub.10) ##STR00055## (wherein, Ar.sub.11 represents an arylene group, R.sub.7 and R.sub.8 each independently represent the same group with those of R.sub.3 and R.sub.4, and a ring may be formed between Ar.sub.11 and R.sub.7, between Ar.sub.11 and R.sub.8, or between R.sub.7 and R.sub.8) ##STR00056## (wherein, Ar.sub.12 and Ar.sub.13 each independently represent an arylene group, R.sub.9 and R.sub.10 each independently represent the same group with those of R.sub.3 and R.sub.4, and p is 0 or 1).

2. A block copolymer according to claim 1, wherein Ar.sub.2 in the above formula (3) is a block copolymer represented by the below formula (9), --(Ar.sub.14--N(Ar.sub.15))t-Ar.sub.16-- (9) (wherein, Ar.sub.14 and Ar.sub.16 represent the same group with those of Ar.sub.3 and Ar.sub.5, and Ar.sub.15 represents the same group with those of Ar.sub.4 and t is 1 or 2).

3. A block copolymer according to claim 1, wherein the junction unit B in the above formula (1a) is represented by the following general formula (10), when m is 0 in the above formula (3), ##STR00057## (wherein, Ar.sub.17 and Ar.sub.18 are an arylene group or a divalent heterocyclic compound group, and R.sub.11 and R.sub.12 represent the same group with those of R.sub.1 and R.sub.2).

4. A block copolymer according to claim 1, wherein the junction unit B in the above formula (1a) is a block copolymer represented by the following general formula (11), when m is 1 in the above formula (3), -Ar.sub.19- (11) (wherein, Ar.sub.19 is an arylene group or a divalent heterocyclic compound group).

5. A polymeric fluorescent substance composition comprising the block copolymer according to claim 1.

6. A polymeric fluorescent substance composition according to claim 5, wherein the composition comprises the block copolymer in an amount of 10% by weight or more.

7. A process for producing a block copolymer, wherein an initial polymer having a group (Y.sub.1) on the molecular terminal, is obtained by reacting a monomer (I) having two reactive groups (X.sub.1, X.sub.2) in a molecule which can react mutually, with a monomer (II) having a reactive group (X.sub.3) which is reactive with the reactive groups (X.sub.1, X.sub.2) and a group (Y.sub.1) which is not reactive with the reactive groups (X.sub.1, X.sub.2) under a reaction condition at which said reactive groups (X.sub.1, X.sub.2) can react with X.sub.3 to form a linkage; and said initial polymer is reacted under a condition at which group (Y.sub.1) can mutually react to form linkage.

8. A process for producing a block copolymer, wherein an initial polymer having a group (Y.sub.1) on the molecular terminal, is obtained by reacting a monomer (I) having two reactive groups (X.sub.1, X.sub.2) in a molecule which can react mutually, with a monomer (II) having a reactive group (X.sub.3) which is reactive with the reactive groups (X.sub.1, X.sub.2) and a group (Y.sub.1) which is not reactive with the reactive groups (X.sub.1, X.sub.2) under a reaction condition at which said reactive groups (X.sub.1, X.sub.2) can react with X.sub.3 to form a linkage; and said initial polymer is reacted with a monomer (III) having two groups (Y.sub.2, Y.sub.3) in a molecule which is reactive with a group (Y.sub.1) to form a linkage under a reaction condition at which groups (Y.sub.2, Y.sub.3) can react with group (Y.sub.1) to form a linkage.

9. A process for producing a block copolymer according to claim 7 or 8, wherein two or more kinds of the initial polymer are used.

10. A process for producing a block copolymer according to claim 8, wherein the above groups (Y.sub.1, Y.sub.2, Y.sub.3) are those which can generate .pi.--.pi. bond.

11. A process for producing a block copolymer according to claim 10, wherein the .pi.--.pi. bond generated by the reaction of the above groups (Y.sub.1, Y.sub.2, Y.sub.3) is a double bond.

12. A process for producing a block copolymer according to claim 7, wherein the monomer (I) is one or more kinds of monomer represented by the below formula (12), and the monomer (II) is one or more kinds of monomer represented by the below formula (13), X.sub.1-Ar.sub.20-X.sub.2 (12) (wherein, X.sub.1 and X.sub.2 represent reactive groups which react mutually to form a linkage, and these may be the same or different; Ar.sub.20 represents the same group with those of the above Ar.sub.1) X.sub.3-Ar.sub.21-Y.sub.1 (13) (wherein, Ar.sub.21 represents the same group with those of Ar.sub.1. X.sub.3 represents a reactive group which reacts mutually with the above X.sub.1, X.sub.2, and X.sub.3 to form a linkage, and Y.sub.1 represents a group which does not react, under a reaction condition at which X.sub.1, X.sub.2 and X.sub.3 can react to form a linkage).

13. A process for producing a block copolymer according to claim 8, wherein monomer (III) is a monomer represented by the below formula (14), Y.sub.2-Ar.sub.25-Y.sub.3 (14) (wherein, Ar.sub.25 represents the same group with those of Ar.sub.1. Y.sub.2 and Y.sub.3 each independently represent the same group with those of Y.sub.1, and they may be the same or different).

14. A process for producing a block copolymer according to claim 12 or 13, wherein X.sub.1, X.sub.2 and X.sub.3 in the monomer shown by formulas (12) and (13) each independently represent a halogen atom, alkylsulfonyloxy group which may be substituted by a fluorine atom, arylsulfonyloxy group which may be substituted by an alkyl group, boric acid, or boric ester (wherein, at least one of them are a halogen atom, alkylsulfonyloxy group which may be substituted by a fluorine atom, or arylsulfonyloxy group which may be substituted by an alkyl group); and Y.sub.1, Y.sub.2 and Y.sub.3 in the monomer shown by formulas (13) and (14) each independently represent an aldehyde group, a carbonyl group, a phosphonate, or a phosphonium salt (wherein, at least one of them are an aldehyde group, or a carbonyl group).

15. A process for producing a block copolymer according to claim 12 or 13, wherein X.sub.1, X.sub.2 and X.sub.3 in the monomer shown by formulas (12) and (13) each independently represent an aldehyde group, a carbonyl group, phosphonate group, or a phosphonium salt (wherein, at least one of them are an aldehyde group or a carbonyl group); and Y.sub.1, Y.sub.2 and Y.sub.3 in the monomer shown by formulas (13) and (14) each independently represent a halogen atom, an alkylsulfonyloxy group which may be substituted by a fluorine atom, or an arylsulfonyloxy group which may be substituted by an alkyl group, a boric acid or a boric ester (wherein, at least one of them are a halogen atom, an arylsulfonyloxy group which may be substituted by an alkyl sulfonyloxy group or an alkyl group which may be substituted by a fluorine atom.

16. A process for producing a block copolymer according to claim 12 or 13, wherein at least one group selected from X.sub.1, X.sub.2 and X.sub.3 in the monomer shown by formulas (12) and (13) is a boric acid or a boric ester, at least one group is a halogen atom, an alkylsulfonyloxy group which may be substituted by a fluorine atom, or an arylsulfonyloxy group which may be substituted by an alkyl group; Y.sub.1 in the monomer shown by general formula (13), and Y.sub.2 and Y.sub.3 in the monomer shown by general formula (14) are reactive groups selected from an aldehyde group, a carbonyl group, a phosphonate group, or a phosphonium salt; and the initial polymer is obtained by a reaction under existence of Pd(0) catalyst.

17. A process for producing a block copolymer according to claim 12 or 13, wherein X.sub.1, X.sub.2 and X.sub.3 in the monomer shown by formulas (12) and (13) are a halogen atom, an alkylsulfonyloxy group which may be substituted by a fluorine atom, or an arylsulfonyloxy group which may be substituted by an alkyl group; Y.sub.1 in the monomer shown by general formula (13), and Y.sub.2 and Y.sub.3 in the monomer shown by general formula (14) are reactive groups selected from an aldehyde group, a carbonyl group, a phosphonate group, or a phosphonium salt; and the initial polymer is obtained by a reaction under existence of Ni(0).

18. A process for producing a block copolymer according to claim 12 or 13, wherein at least one group of X.sub.1, X.sub.2 and X.sub.3 in the monomer shown by formulas (12) and (13) is an aldehyde group or a carbonyl group, at least one group is a phosphonate or a phosphonium salt; Y.sub.1 in the monomer shown by general formula (13), and Y.sub.2 and Y.sub.3 in the monomer shown by general formula (14) are reactive groups selected from a halogen atom, an alkylsulfonyloxy group which may be substituted by a fluorine atom, or an arylsulfonyloxy group which may be substituted by an alkyl group; and the initial polymer is obtained by a reaction under existence of a base.

19. A polymer light-emitting device comprising a pair of electrodes composed of an anode and a cathode at least one of which is transparent or semitransparent and at least containing a light emitting layer between the electrodes, wherein the light emitting layer comprises a block copolymer according to claim 1.

20. A polymer light-emitting device comprising a pair of electrodes composed of an anode and a cathode at least one of which is transparent or semitransparent and at least containing a light emitting layer between the electrodes, wherein the light emitting layer comprises a polymeric fluorescent substance composition according to claim 5 or 6.

21. A polymer light-emitting device according to claim 19, wherein a layer comprising an electron-transporting compound is disposed between the cathode and the light emitting layer such that the layer comprising an electron-transporting compound is adjacent to said light-emitting layer.

22. A polymer light-emitting device according to claim 19, wherein a layer comprising a hole-transporting compound is disposed between the anode and the light emitting layer such that the layer comprising a hole-transporting compound is adjacent to said light-emitting layer.

23. A polymer light-emitting device according to claim 19, wherein a layer comprising an electron-transporting compound is disposed between the cathode and the light emitting layer such that the layer comprising an electron-transporting compound is adjacent to said light-emitting layer, and a layer comprising a hole-transporting compound is disposed between the anode and the light emitting layer such that the layer comprising a hole-transporting compound is adjacent to said light-emitting layer.

24. A flat light source comprising a polymer light-emitting device according to claim 19.

25. A segment display comprising a polymer light-emitting device according to claim 19.

26. A dot matrix display comprising a polymer light-emitting device according to claim 19.

27. A liquid crystal display comprising a polymer light-emitting device according to claim 19 as a back light.

28. A electronic device comprising a display according to any one of claims 25 to 27 as a display part.

Description

TECHNICAL FIELD

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

BACKGROUND TECHNOLOGY

Unlike a low molecular weight light-emitting material, a polymer light-emitting material (polymeric fluorescent substance) is soluble in a solvent, and a light emitting layer in a light-emitting device can be formed by a coating method, and it has been variously studied.

For example, polyarylene type polymeric fluorescent substances are disclosed, such as, a polyfluorene (Jpn. J. Appl. Phys. volume 30, page L1941 (1991)), and a poly para-phenylene derivative (Adv. Mater. volume 4, page 36 (1992)).

As a block copolymer having fluorescence in the solid state used as a polymeric fluorescent substance, for example, JP-W-8-505167 discloses a block copolymer comprising blocks in which polythiophene are bonded not through .pi.--.pi. conjugated bonds, and JP-W-11-60660 discloses a block copolymer comprising blocks in which polyethylene main chains have substituents of carbazole group and blocks which have substituents containing oxadiazole groups.

JP-A-2000-159846 discloses a block copolymer which is obtained by copolymerizing a block in which monomers having hole transportation property and electron transporting property are alternatively copolymerized, with a block in which monomers having hole transportation property are polymerized. Furthermore, JP-W-8-510483 discloses a copolymer of phenylene vinylene (PPV).

However, a block copolymer in which blocks are bonded through conjugated bond has not been known.

As the above conventional manufacture method of block copolymer, there have been known are: a process which is complicated such that functional groups are introduced after polymerizing block parts, and then the functional groups are reacted with other block parts (JP-W-8-505167); and a process which seems difficult to reliably construct block portions (JP-W-11-60660, JP-W-8-510483, JP-A-2000-159846). Anyway, there has been a problem that they are complicated.

An object of the present invention is to provide a new block copolymer having fluorescence in the solid state, and the blocks are bonded through conjugated bonds, and a polymer light-emitting device (hereinafter, sometimes referred to as "polymer LED").

DISCLOSURE OF THE INVENTION

The present invention relates to a block copolymer comprising two or more blocks and having fluorescence in the solid state, wherein blocks thereof may be the same or different, and in each of the blocks, one or more kinds of repeating units are bonded through conjugated bonds, and bonding between the blocks is made by junction unit having conjugated bond, and the polystyrene reduced number average molecular weight of at least one block is 1.times.10.sup.3 to 1.times.10.sup.8.

Furthermore, the present invention relates to a block copolymer comprising two or more blocks and having fluorescence in the solid state, wherein at least two blocks thereof are not the same each other, and in each of the blocks, one or more kinds of repeating units are bonded through conjugated bonds, and bonding between the blocks is made by a direct bond without interrupting the conjugated sequence, and the polystyrene reduced number average molecular weight of at least one block is 1.times.10.sup.3 to 1.times.10.sup.8. Moreover, in said block copolymer, the polystyrene reduced number average molecular weight of at least one block is suitably 2.times.10.sup.3 to 1.times.10.sup.8.

Furthermore, the block copolymer of the present invention is a block copolymer comprising two or more blocks, two of them are not the same, and in each of the blocks, one or more repeating units are bonded through .pi.--.pi. conjugated bonds, having fluorescence in the solid state, and preferably, bonding between the blocks is made by .pi.--.pi. conjugated bond.

The block copolymer of the present invention is, for example, represented by the following general formula (1a), -A-block-(B)-block-C- (1a) (in the formula, A and C show blocks which may be the same or different, and B shows a junction unit of not being a part of block, and having a conjugated bond.)

When A and C composed of only one kind of repeating unit, and A has a repeating unit a, which is the same repeating unit of C, the block copolymer is represented by -aaaaaaa-block-B-block-aaaaaaa- wherein, B is a junction unit.

When A differs from C, junction unit B may be contained or not contained. In this case, when the repeating unit constituting A is shown by a, and the repeating unit constituting C is shown by c, said block copolymer is represented by -aaaaaaa-block-B-block-cccccccc- or -aaaaaaa-block-cccccccc-.

When either one of A and C is constituted by two or more kinds of repeating units, junction unit B may be contained or not contained.

For example, when the repeating unit which constitutes A is shown by a, and the repeating unit which constitutes C is shown by c, the block copolymer is represented by -accacaaaca-block-B-block-cccccccc- or preferably by, -accacaaaca-block-cccccccc-. Here, the "c"s which constitutes A and C may be the same of different, and the repeating units a and c which constitute A may be arranged either randomly or regularly.

In A and C, when the both composed of two or more kinds of repeating units, and A and C composed of the same repeating unit, junction unit B is contained.

For example, in both A and C, the repeating unit constituting thereof are a and c, the block copolymer is represented by -accacaaaca-block-B-block-accacacaaa-.

The repeating units a and c which constitute A and C may be arranged either randomly or regularly.

In case of both of A and C composed of two or more kinds of repeating units, when at least one repeating units which constitute A is not the same with the repeating unit which constitute C, or when at least one repeating units which constitute C is not the same with the repeating unit which constitute A, junction unit B may be contained or not contained.

For example, when the repeating units which constitute A are a, b and c, and the repeating units which constitute C is a and c, the block copolymer is represented by -acbacabacab-block-B-block-accacaaca- or -acbacabacab-block-accacaaaca-.

In the above exemplification, when the block copolymer has junction unit B, the portion between junction unit and junction unit is referred to as "block".

The block copolymer of the present invention is a block copolymer which has fluorescence in the solid state, and for example, is represented by the above general formula (1a). In the formula, A and C represent blocks which may be the same or different, and B represents a junction unit having conjugated bond which is not a part of the block. It is preferable that the fluorescence peak wavelength shown by a thin film of the polymer represented by general formula (1a) is longer by 5 nm or more than the fluorescence peak wavelengths shown by either a thin film of the polymer solely composed of block A, or a thin film of the polymer solely composed of block C.

Furthermore, the block copolymer of the present invention is a block copolymer which has fluorescence in the solid state, and for example, is represented by the following general formula (1b). -A-block-C- (1b) Here, A and C represent different blocks, and bonding between the blocks is made by a direct bond without interrupting the conjugated sequence. It is preferable that the fluorescence peak wavelength shown by a thin film of the polymer represented by general formula (1b) is longer by 5 nm or more than the fluorescence peak wavelengths shown by a thin film of the polymer solely composed of block A.

In the present invention, the block copolymer particularly preferred, when values of the Lowest Unoccupied Molecular Orbital (LUMO) and the Highest Occupied Molecular Orbital (HOMO) of polymers consisting only of respective blocks are compared, is a block copolymer comprising two or more blocks having a relationships: HOMO(D)>HOMO(E) LUMO(D)<LUMO(E) wherein D and E are at least a pair of neighboring blocks.

In a method for comparing numerical values of HOMO, when there is a sufficient difference between them, values corresponding to the ionization potential or work function obtained by calculation or by experiment may be compared. In a method for comparing numerical values of LUMO, when there is a sufficient difference between them, values corresponding to the electron affinity obtained by calculation or by experiment may be compared. Hereinafter, simple terms HOMO and LUMO extend to these parameters.

For calculating HOMO and LUMO, methods have been known in which they are calculated according to UPS (ultraviolet photoelectron spectroscopy) or molecular orbital method. The method in which values are calculated according to the molecular orbital method may become a preferred method when sufficient accuracy can be obtained in the future, but in the present state, it is difficult to apply this method to complicated polymers. Therefore, it is preferred to apply UPS or methods described below. Examples of method according to UPS include methods described in Polymer for Advanced Technologies, Vol. 9, Page 419 (1998) and literatures cited therein.

Methods for calculating HOMO include, in addition to UPS, a method according to photoelectron spectroscopy described in Japanese Patent 1234703, a method in which the electrochemically obtained oxidation potential is converted to such value.

The method described in Japanese Patent 1234703 can be carried out, for example, with an apparatus (AC-2) manufactured by Riken Keiki Co., Ltd. Specific examples of the method in which the electrochemically obtained oxidation potential is converted to such value include a method with the conversion of oxidation initiating potential of a material.

Specific methods for the oxidation initiating potential include the following electrochemical method. That is, the targeted material is subjected to the cyclic voltammetry and a potential at which an oxidation wave rises from the baseline (i.e. the oxidation initiating potential) is observed. Specifically, for example, a thin film is formed from a solution of a material to be analyzed on a platinum electrode by dipping. Then, the cyclic voltammetry is conducted in an organic solution containing a support electrolyte at an appropriate concentration, for example 0.1 N solution of tetrabutylammonium tetrafluoroborate in acetonitrile, using a platinum electrode coated with the material as a working electrode, another platinum electrode without coating as a counter electrode and a silver/silver chloride electrode, saturated calomel electrode, standard hydrogen electrode or the like, for example, as the reference electrode. When the material to be analyzed easily dissolves in a solution used as the electrolytic solution, the analysis may be carried out with an electrolytic solution containing the material dissolved therein in place of coating the electrode. The concentration in this case is selected such that the oxidation wave is easily detected.

Various conditions containing the sweep rate, sweep area and so on are identical for every analysis of materials and may be a sweep rate of 50 mV/second, a sweep area of -200 to 1500 mV (the potential for silver/silver chloride electrode) and the like. The potential at the intersection of the tangents which touches the baseline and the rising part of the oxidation wave, respectively, is measured in the obtained cyclic voltammogram.

When a value obtained by converting the obtained oxidation initiating potential to that for the standard hydrogen electrode is represented by Eox(V), HOMO can be calculated by the following equation: HOMO=Eox+C.sub.1 (eV) wherein C.sub.1 is a value for the vacuum potential of the standard hydrogen electrode and can be considered to be a constant. Usually, it is assumed to be 4.5.

Since, in the comparison of HOMO values (eV) for two materials, the constant Cs in the above equation are balanced, precise values need not be considered.

Examples of methods for calculating LUMO include, in addition to UPS described above, a method in which the electrochemically determined reduction potential is converted to such value, and a method in which the value is calculated from the absorption edge wavelength in the absorption spectrum of the material and the value of HOMO described above.

The method in which the electrochemically determined reduction potential is converted to such value can be carried out by calculating in a manner similar to the above method replacing the oxidation potential by the reduction potential.

In the method in which the value is calculated from the absorption edge wavelength in the absorption spectrum of the material and the value of HOMO described above, the absorption edge wavelength in the absorption spectrum can be obtained by measuring the absorption spectrum and observing the wavelength at which an absorption rises from the baseline. Specifically, for example, first a thin film having a thickness of about 50 to 300 nm is formed from a solution of a material to be analyzed on a quartz plate by a spin coating method, and an absorption spectrum is measured. In the spectrum, the wavelength at the intersection of the tangents which touches the baseline and the rising part of the absorption, respectively, is taken as the absorption edge wavelength.

When the obtained absorption edge wavelength is represented by .lamda.edge (nm), LUMO can be calculated by the following equation: LUMO=HOMO-C.sub.2/.lamda.edge (eV) wherein C.sub.2 is a value for changing the units and usually assumed to be 1239.

As HOMO, any values obtained by various methods described above can be used.

In the block copolymer of the present invention, it is more preferable that at least one of blocks A and C represented by the above formula (1a) or (1b) whose repeating units are connected by conjugated bond, has one or more kinds of the repeating units selected from the repeating unit represented by the below formula (2) or formula (3).

##STR00001## (wherein, Ar.sub.1 is an arylene group or a divalent heterocyclic compound group, and the arylene group and the divalent heterocyclic compound group may have a substituent. R.sub.1 and R.sub.2 each independently represent a group selected from a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic compound group, and cyano group, and the aryl group and the monovalent heterocyclic compound group may have a substituent. n is 0 or 1.) --Ar.sub.2--(CR.sub.3.dbd.CR.sub.4)m- (3) (wherein, Ar.sub.2 is a divalent aromatic amine group shown by the following general formula (4). R.sub.3 and R.sub.4 each independently represent the same group with those of R.sub.1 and R.sub.2, and m is 0 or 1.) --Ar.sub.3--N(Ar.sub.4)--Ar.sub.5-- (4) (wherein, Ar.sub.3 and Ar.sub.5 are each independently an arylene group, an aromatic compound group represented by the following general formula (5), or a group having an aromatic amine skelton of the following general formula (6), and Ar.sub.4 represents an aryl group, a group having an aromatic amine skelton represented by the following general formula (7), or a group having an aromatic ethenylene skelton represented by the following general formula (8). A ring may be formed between Ar.sub.3 and Ar.sub.4, between Ar.sub.4 and Ar.sub.5, or between Ar.sub.3 and Ar.sub.5.

##STR00002## (In the formula, Ar.sub.6 and Ar.sub.7 each independently show an arylene group, and the arylene group may have a substituent. R.sub.5 and R.sub.6 each independently represent the same group with those of R.sub.1 and R.sub.2, and l is 0 or 1.)

##STR00003## (wherein, Ar.sub.8 and Ar.sub.9 each independently show an arylene group and the arylene group may have a substituent. Ar.sub.10 is an aryl group which may have a substituent. A ring may be formed between Ar.sub.8 and Ar.sub.10, between Ar.sub.8 and Ar.sub.9, or between Ar.sub.9 and Ar.sub.10.)

##STR00004## (wherein, Ar.sub.11 show an arylene group and the arylene group may have a substituent. R.sub.7 and R.sub.8 each independently represent a group of R.sub.1 and R.sub.2, and they may form a ring between Ar.sub.11 and R.sub.7, between Ar.sub.11 and R.sub.8, or between R.sub.7 and R.sub.8.)

##STR00005## (In the formula, Ar.sub.12 and Ar.sub.13 each independently show an arylene group, and the arylene group may have a substituent. R.sub.9 and R.sub.10 each independently represent a group of R.sub.1 and R.sub.2, and p is 0 or 1.)

Ar.sub.2 shown by the above formula (3) is preferably a group represented by the below formula (9). --(Ar.sub.14--N(Ar.sub.15)).sub.t--Ar.sub.16-- (9) (wherein, Ar.sub.14 and Ar.sub.16 represent the same group with those of Ar.sub.3, and Ar.sub.5 and Ar.sub.15 represent the same group with those of Ar.sub.4. t is 1 or 2.)

In the present invention, junction unit B having a conjugated bond is not restricted so long that it is a conjugated system which is not a part of block. It is preferably an arylene group shown by the above formula (2), a divalent heterocyclic compound group, an arylenevinylene group, and a divalent aromatic amino group shown by the above formula (3) or (9).

Furthermore, as junction unit B, when n is 0 in the above formula (2), and when m is 0 in the above formula (3), the structure represented by the following general formula (10) is preferable.

##STR00006## (In the formula, Ar.sub.17 and Ar.sub.18 represent an arylene group or a divalent heterocyclic compound group, and R.sub.11 and R.sub.12 represent the same group with those of R.sub.1 and R.sub.2.)

Moreover, when n is 1 in the above formula (2), and m is 1 in the above formula (3), it is preferable that the junction unit B has a structure represented by the following formula (11). --Ar.sub.19-- (11) (In the formula, Ar.sub.19 is an arylene group or a divalent heterocyclic compound group.)

Although the process for producing the block copolymer in the present invention is not especially limited as long as the structure mentioned above is produced, the following processess are preferable for structure controlling. [1] A process for producing a block copolymer, wherein an initial polymer having a group (Y.sub.1) on the molecular terminal, is obtained by reacting a monomer (I) having two reactive groups (X.sub.1, X.sub.2) in a molecule which can react mutually, with a monomer (II) having a reactive group (X.sub.3) which is reactive with the reactive groups (X.sub.1, X.sub.2) and a group (Y.sub.1) which is not reactive with the reactive groups (X.sub.1, X.sub.2) under a reaction condition at which said reactive groups (X.sub.1, X.sub.2) can react with X.sub.3 to form a linkage; and said initial polymer is reacted under a condition at which group (Y.sub.1) can mutually react to form linkage. [2] A process for producing a block copolymer, wherein an initial polymer having a group (Y.sub.1) on the molecular terminal, is obtained by reacting a monomer (I) having two reactive groups (X.sub.1, X.sub.2) in a molecule which can react mutually, with a monomer (II) having a reactive group (X.sub.3) which is reactive with the reactive groups (X.sub.1, X.sub.2) and a group (Y.sub.1) which is not reactive with the reactive groups (X.sub.1, X.sub.2) under a reaction condition at which said reactive groups (X.sub.1, X.sub.2) can react with X.sub.3 to form a linkage; and said initial polymer is reacted with a monomer (III) having two groups (Y.sub.2, Y.sub.3) in a molecule which is reactive with a group (Y.sub.1) to form a linkage under a reaction condition at which groups (Y.sub.2, Y.sub.3) can react with group (Y.sub.1) to form a linkage

In the process of the present invention, although it is not limited, it is suitable that groups (Y.sub.1, Y.sub.2, Y.sub.3) react among themselves to form .pi.--.pi. bonds, and it is more preferable that the .pi.--.pi. bond is a double bond or aryl-aryl bond.

In the process of the present invention, although the structure of the monomer to be used is not limited, those having following structures are preferable.

That is, it is preferable that one or more kinds of monomer (I) selected from the below formula (12), and one or more kinds of monomer (II) selected from the below formula (13) are reacted to form an initial polymer, and then one or more kinds of the initial polymer are reacted among themselves, or reacted with one or more kinds of monomer (III).

As for the polymer having reactive group, a homopolymer or a copolymer is produced according to the kind of repeating unit Ar.sub.20 which constitutes the polymer.

When the repeating unit Ar.sub.20 consists of a single compound, a homopolymer is formed, and when the repeating unit Ar.sub.20 consists of two or more kinds of compounds, an alternating copolymer or a random copolymer is usually formed.

Preferable monomer (I) is shown by the following general formula (12). X.sub.1--Ar.sub.20--X.sub.2 (12) (wherein, X.sub.1 and X.sub.2 show reactive groups which react mutually and can form a linkage, these may be the same or different. Ar.sub.20 represents the same group with those of the above Ar.sub.1.)

Moreover, preferable monomer (II) is shown by the following general formula (13). X.sub.3--Ar.sub.21--Y.sub.1 (13) (wherein, Ar.sub.21 represents the same group with those of Ar.sub.1. X.sub.3 represents a reactive group which reacts with the above X.sub.1 and X.sub.2 to form a linkage, and Y.sub.1 represents a group which does not react under a reaction condition at which X.sub.1, X.sub.2, and X.sub.3 react to form a linkage.)

The initial polymer obtained by the above process is represented by the following general formula.

##STR00007## (wherein, s shows a integer of 1 or more. a, and b is 1.)

Preferable monomer (III) is shown by the below formula (14). Y.sub.2--Ar.sub.25--Y.sub.3 (14) (wherein, Ar.sub.25 represents the same group with those of Ar.sub.1. Y.sub.2 and Y.sub.3 each independently represents the same group with those of Y.sub.1, and these may be the same or different.)

As the arylene group, exemplified are phenylene group (for example, formulas 1 3), naphthalene-diyl group (following formulas 4 13), anthracenylene group (following formulas 14 19), biphenylene group (following formulas 20 25), fluorene-diyl group (following formulas 36 38), triphenylene group (following formulas 26 28), stilbene-diyl (following formulas A D), distilbene-diyl (following formulas E and F), condensed-ring compound group (following formulas 29 38) etc. Among them, phenylene group, biphenylene group, fluorene-diyl group, and stilbene-diyl group are preferable.

##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014##

In the present invention, the divalent heterocyclic group means an atomic group in which two hydrogen atoms are removed from a heterocyclic compound, and the number of carbon atoms is usually about 3 to 60.

The heterocyclic compound means an organic compound having a cyclic structure in which at least one heteroatom such as oxygen, sulfur, nitrogen, phosphorus, boron, arsenic, etc. is contained in the cyclic structure as the element other than carbon atoms.

As the divalent heterocyclic compound group, followings are exemplified.

Divalent heterocyclic groups containing a nitrogen as a hetero atom; pyridine-diyl group (following formulas 39 44), diazaphenylene group (following formulas 45 48), quinoline-diyl group (following formulas 49 63), quinoxaline-diyl group (following formulas 64 68), acridine-diyl group (following formulas 69 72), bipyridyl-diyl group (following formulas 73 75), phenanthroline-diyl group (following formulas 76 78), etc.; groups containing a hetero atom, such as silicon, nitrogen, sulfur, selenium, etc. and having a fluorene structure (following formulas 79 93).

5 membered-ring heterocyclic compound groups containing a hetero atom such as silicon, nitrogen, sulfur, selenium, etc. (following formulas 94 98).

5 membered-ring condensed heterocyclic compound groups containing a hetero atom such as silicon, nitrogen, sulfur, selenium, etc. (following formulas 99 108).

Groups in which 5 membered ring heterocyclic compound group containing silicon, nitrogen, sulfur, selenium, etc. as a hetero atom is connected with a phenyl group at the a position of the hetero atom to form a dimer or oligomer (following formulas 109 113).

Groups in which 5 membered ring heterocyclic compound group containing silicon, nitrogen, sulfur, selenium, etc. as a hetero atom is connected with a phenyl group at the a position of the hetero atom (following formulas 113 119).

Groups in which 5 membered ring heterocyclic compound group containing oxygen, nitrogen, sulfur, etc. as a hetero atom is connected with a phenyl group, a furyl group, or thienyl group (following formulas 120 125).

##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025##

In the example shown by the above formulas 1 125, R each independently shows a hydrogen atom, an 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, substituted carboxyl group, or cyano group. The carbon atom in the groups of formulas 1 132 may be replaced with a nitrogen atom, oxygen atom, or sulfur atom, and the hydrogen-atom may be replaced with a fluorine atom.

In the present invention, the divalent aromatic amine group means an atomic group in which two hydrogen atoms are removed from an aromatic amine, and the number of carbon atoms is usually about 4 to 60, and more specifically, following groups are exemplified.

##STR00026## ##STR00027##

In the above formula, R is the same as those of the above formulas 1 125. In the above example, although a plurality of Rs are contained in one structural formula, they may be the same or different. In order to improve the solubility in a solvent, it is preferable to have one or more groups other than a hydrogen atom, and it is preferable that the symmetry of the repeating unit including the substituent is little.

The alkyl group in the present invention may be any of linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specific examples thereof include 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-ethyl hexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl, perfluorohexyl group, perfluorooctyl group, etc. Pentyl group, hexyl group, octyl group, 2-ethyl hexyl group, decyl group, and 3,7-dimethyloctyl group are preferable.

The alkoxy group may be any of linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specific examples thereof include 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, perfluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group, etc. Pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, and 3,7-dimethyl octyloxy group are preferable.

The alkylthio group may be any of linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specific examples thereof include 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, etc. 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. Specific examples thereof include phenyl group, C.sub.1 C.sub.12 alkoxyphenyl group (C.sub.1 C.sub.12 shows carbon number of 1 12. Hereinafter, the same ), C.sub.1 C.sub.12 alkylphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, pentafluorophenyl group, etc. C.sub.1 C.sub.12 alkoxyphenyl group, and C.sub.1 C.sub.12 alkylphenyl group are prererable. The aryl group is an atomic group in which a hydrogen atom is removed from an aromatic hydrocarbon. The aromatic hydrocarbon includes those containing a condensed ring, and those containing two or more of independent benzene rings or condensed rings bonded through a group such as a direct bond, a vinylene group or the like.

Examples of C.sub.1 C.sub.12 alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyl oxy, heptyloxy, octyloxy, 2-ethyl hexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, etc.

Examples of C.sub.1 C.sub.12 alkylphenyl group include methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, i-propylphenyl group, butylphenyl group, i-butylphenyl group, t-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group, etc.

The aryloxy group usually has about 6 to 60 carbon atoms. Specific examples thereof include phenoxy group, C.sub.1 C.sub.12 alkoxyphenoxy group, C.sub.1 C.sub.12 alkylphenoxy group, 1-naphtyloxy group, 2-naphtyloxy group, pentafluorophenyloxy group, etc. C.sub.1 C.sub.12 alkoxyphenoxy group, and C.sub.1 C.sub.12 alkylphenoxy group are preferable.

Examples of C.sub.1 C.sub.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, etc.

Examples of C.sub.1 C.sub.12 alkyl phenoxy group include methyl phenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-trimethylphenoxy group, methylethylphenoxy group, i-propylphenoxy group, butylphenoxy group, i-butylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group, dodecylphenoxy group, etc.

The arylthio group usually has about 3 to 60 carbon atoms, and examples thereof include phenylthio group, C.sub.1 C.sub.12 alkoxyphenylthio group, C.sub.1 C.sub.12 alkylphenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group, etc. C.sub.1 C.sub.12 alkoxyphenylthio group, and C.sub.1 C.sub.12 alkylphenylthio group of carbon number are preferable.

The arylalkyl group usually has about 7 to 60 carbon atoms. Examples thereof include phenyl-C.sub.1 C.sub.12 alkyl group, C.sub.1 C.sub.12 alkoxyphenyl-C.sub.1 C.sub.12 alkyl group, C.sub.1 C.sub.12 alkylphenyl-C.sub.1 C.sub.12 alkyl group, 1-naphtyl-C.sub.1 C.sub.12 alkyl group, 2-naphtyl-C.sub.1 C.sub.12 alkyl group, etc. C.sub.1 C.sub.12 alkoxyphenyl-C.sub.1 C.sub.12 alkyl group, and C.sub.1 C.sub.12 alkylphenyl-C.sub.1 C.sub.12 alkyl group are preferable.

The arylalkoxy group usually has about 7 to 60 carbon atoms. Examples thereof include phenyl-C.sub.1 C.sub.12 alkoxy group, such as phenylmethoxy group, phenylethoxy group, phenylbutoxy group, phenylpentyloxy group, phenylhexyloxy group, phenylheptyloxy group, and phenyl octyloxy group; C.sub.1 C.sub.12 alkoxyphenyl-C.sub.1 C.sub.12 alkoxy group, C.sub.1 C.sub.12 alkylphenyl-C.sub.1 C.sub.12 alkoxy group, 1-naphtyl-C.sub.1 C.sub.12 alkoxy group, 2-naphtyl-C.sub.1 C.sub.12 alkoxy group, etc. C.sub.1 C.sub.12 alkoxyphenyl-C.sub.1 C.sub.12 alkoxy group, and C.sub.1 C.sub.12 alkylphenyl-C.sub.1 C.sub.12 alkoxy group are preferable.

The arylalkylthio group usually has about 7 to 60 carbon atoms. Examples thereof include phenyl-C.sub.1 C.sub.12 alkylthio group, C.sub.1 C.sub.12 alkoxyphenyl-C.sub.1 C.sub.12 alkylthio group, C.sub.1 C.sub.12 alkylphenyl-C.sub.1 C.sub.12 alkylthio group, 1-naphtyl-C.sub.1 C.sub.12 alkylthio group, 2-naphtyl-C.sub.1 C.sub.12 alkylthio group, etc. C.sub.1 C.sub.12 alkoxyphenyl-C.sub.1 C.sub.12 alkylthio group, and C.sub.1 C.sub.12 alkylphenyl-C.sub.1 C.sub.12 alkylthio group are preferable.

The arylalkenyl group usually has about 7 to 60 carbon atoms. Examples thereof include phenyl-C.sub.2 C.sub.12 alkenyl group, C.sub.1 C.sub.12 alkoxyphenyl-C.sub.2 C.sub.12 alkenyl group, C.sub.1 C.sub.12 alkylphenyl-C.sub.2 C.sub.12 alkenyl group, 1-naphtyl-C.sub.2 C.sub.12 alkenyl group, 2-naphtyl-C.sub.2 C.sub.12 alkenyl group, etc. C.sub.1 C.sub.12 alkoxyphenyl-C.sub.2 C.sub.12 alkenyl group, and C.sub.2 C.sub.12 alkylphenyl C.sub.1 C.sub.12 alkenyl group are preferable.

The arylalkynyl group usually has about 7 to 60 carbon atoms. Examples thereof include phenyl-C.sub.2 C.sub.12 alkynyl group, C.sub.1 C.sub.12 alkoxyphenyl-C.sub.2 C.sub.12 alkynyl group, C.sub.1 C.sub.12 alkylphenyl-C.sub.2 C.sub.12 alkynyl group, 1-naphtyl-C.sub.2 C.sub.12 alkynyl group, 2-naphtyl-C.sub.2 C.sub.12 alkynyl group, etc. C.sub.1 C.sub.12 alkoxyphenyl-C.sub.2 C.sub.12 alkynyl group, and C.sub.1 C.sub.12 alkylphenyl-C.sub.2 C.sub.12 alkynyl group are preferable.

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

Examples thereof include 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, cyclohexyl amino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C.sub.1 C.sub.12 alkoxyphenylamino group, di(C.sub.1 C.sub.12 alkoxyphenyl) amino group, di(C.sub.1 C.sub.12 alkyl henyl) amino group, 1-naphtylamino group, 2-naphtylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, pyrazylamino group, triazylamino group phenyl-C.sub.1 C.sub.12 alkylamino group, C.sub.1 C.sub.12 alkoxyphenyl-C.sub.1 C.sub.12 alkylamino group, C.sub.1 C.sub.12 alkylphenyl-C.sub.1 C.sub.12 alkylamino group, di(C.sub.1 C.sub.12 alkoxyphenyl-C.sub.1 C.sub.12 alkyl)amino group, di(C.sub.1 C.sub.12 alkylphenyl-C.sub.1 C.sub.12 alkyl)amino group, 1-naphtyl-C.sub.1 C.sub.12 alkylamino group, 2-naphtyl-C.sub.1 C.sub.12 alkylamino group, etc.

The substituted silyl group is a silyl group which has 1 to 3 substituents selected from an alkyl group, aryl group, arylalkyl group, or monovalent heterocyclic group. The number of carbon atoms is usually about 1 to 60. The alkyl group, aryl group, arylalkyl group, or monovalent heterocyclic group may have a substituent.

Examples thereof include trimethylsilyl group, triethyl silyl group,.tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propyl silyl group, diethyl-i-propyl silyl group, t-butylsilyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyl dimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyl dimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyl octyl-dimethylsilyl group, lauryldimethylsilyl group, phenyl-C.sub.1 C.sub.12 alkylsilyl group, C.sub.1 C.sub.12 alkoxyphenyl-C.sub.1 C.sub.12 alkylsilyl group, C.sub.1 C.sub.12 alkylphenyl-C.sub.1 C.sub.12 alkylsilyl group, 1-naphtyl-C.sub.1 C.sub.12 alkylsilyl group, 2-naphtyl-C.sub.1 C.sub.12 alkylsilyl group, phenyl-C.sub.1 C.sub.12 alkyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzyl silyl group, diphenylmethylsilyl group, t-butyldiphenyl silyl group, dimethylphenyl silyl group, etc.

As the halogen atom, a fluorine atom, chlorine atom, bromine atom, and iodine atom are exemplified.

The acyl group usually about 2 to 20 carbon atoms, and, specifically exemplified are an acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group, pentafluoro benzoyl, etc.

The acyloxy group usually has about 2 to 20 carbon atoms and, specifically exemplifeid are acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetyloxy group, pentafluorobenzoyl oxy group, etc.

The imino group has about 2 to 20 carbon atoms, and, specifically exemplified are a group shown by the following structural formula, etc.

##STR00028##

The amide group usually has about 1 to 20 carbon atoms, and, specifically exemplified are formamide group (carbon atom is 1), acetamide group, propioamide group, butyroamide group, benzamide group, trifluoro acetamide group, pentafluoro benzamide group, diformamide group, diacetoamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoroacetamide group, dipentafluorobenzamide group, etc.

The imide group usually has about 2 to 60 carbon atoms, and exemplified are groups specifically shown below.

##STR00029##

The monovalent heterocyclic group means an atomic group in which a hydrogen atom is removed from a heterocyclic compound, and usually has about 4 to 60 carbon atoms, preferably 4 to 20. The carbon atoms of the substituent are not counted as the number of carbon atoms of the heterocyclic group. The heterocyclic compound means an organic compound having a cyclic structure in which at least one heteroatom such as oxygen, sulfur, nitrogen, phosphorus, boron, etc. is contained in the cyclic structure as the element other than carbon atoms. Specific examples thereof include a thienyl group, C.sub.1 C.sub.12 alkylthienyl group, pyroryl group, furyl group, pyridyl group, C.sub.1 C.sub.12 alkylpyridyl group, piperidyl group, quinolyl group, isoquinolyl group, etc. A thienyl group, C.sub.1 C.sub.12 alkylthienyl group, pyridyl group, and C.sub.1 C.sub.12 alkyl pyridyl group are preferable.

The substituted carboxyl group usually has about 2 to 60 carbon atoms, and includes carboxyl groups having substituents of alkyl group, aryl group, arylalkyl group, or a monovalent heterocyclic group. Examples thereof include a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl 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-dimethyl octyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphtoxycarbonyl group, pyridyloxycarbonyl group, etc. The alkyl group, aryl group, arylalkyl group, or monovalent heterocyclic group may have a substituent. The carbon atoms of the substituent are not counted as the carbon number of the substituted carboxyl group.

In the above examples of substituents, the substituent containing an alkyl chain may be linear, branched or cyclic one, or the combination thereof. As the alkyl chain which is not linear, exemplified are isoamyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, cyclohexyl group, 4-C.sub.1 C.sub.12 alkylcyclohexyl group, etc. Moreover, two alkyl chain ends may be connected to form a ring. Furthermore, methyl or ethyl as a part of said alkyl chain may be replaced by a group containing a hetero atom, or a methyl or ethyl group which is substituted with one or more fluorine atoms. Here, as the hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are exemplified.

Furthermore, in the examples of substituents containing an aryl group or a heterocyclic group, they may have one or more substituents.

X.sub.1, X.sub.2 and X.sub.3 in the monomer shown by formulas (12) and (13) which are used for the block copolymer of the present invention are each independently an alkylsulfonyloxy group which may be substituted by a halogen atom or fluorine atom; an aryl sulfonyloxy group which may be substituted by an alkyl group; boric acid, or boric ester (at least one is an alkylsulfonyloxy group which may be substituted by a halogen atom or fluorine atom; or an aryl sulfonyloxy group which may be substituted by an alkyl group). Here, it is preferable that Y.sub.1 in a monomer represented by formula (13), and Y.sub.2 and Y.sub.3 in a monomer represented by formula (14) are each independently an aldehyde group, a carbonyl group, phosphonate, or a phosphonium salt (wherein, at least one is an aldehyde group or a carbonyl group).

Moreover, X.sub.1, X.sub.2 and X.sub.3 in the monomer shown by formulas (12) and (13) which are used for the block copolymer of the present invention are each independently an aldehyde group, a carbonyl group, phosphonate, or a phosphonium salt (wherein, at least one is an aldehyde group or a carbonyl group). Here, it is preferable that Y.sub.1 in a monomer represented by formula (13), and Y.sub.2 and Y.sub.3 in a monomer represented by formula (14) are each independently an alkylsulfonyloxy group which may be substituted by a halogen atom or fluorine atom; an aryl sulfonyloxy group which may be substituted by an alkyl group; boric acid, or boric ester (at least one is an alkylsulfonyloxy group which may be substituted by a halogen atom or fluorine atom; or an aryl sulfonyloxy group which may be substituted by an alkyl group).

Moreover, as the process for producing the block copolymer of the present invention, it is preferable that, among the groups selected from X.sub.1, X.sub.2, and X.sub.3 in a monomer represented by general formulas (12) and (13), one or more of the groups are boric acid or boric ester, one or more of the groups are a halogen atom, an alkylsulfonyloxy group which may be substituted by a fluorine atom, or an aryl sulfonyloxy group which may be substituted by an alkyl group; Y.sub.1 in a monomer represented by general formula (13) is a reactive group selected from an aldehyde group, carbonyl group, phosphonate group or phosphonium salt; and by reaction under the existence of Pd(0) catalyst, an initial polymer having an aldehyde group, carbonyl group, phosphonate group, or phosphonium salt at the terminal is obtained.

Moreover, as the process for producing the block copolymer of the present invention, it is preferable that, X.sub.1, X.sub.2, and X.sub.3 in a monomer represented by general formulas (12) and (13), are a halogen atom, an alkylsulfonyloxy group which may be substituted by a fluorine atom, or an aryl sulfonyloxy group which may be substituted by an alkyl group; Y.sub.1 in a mono