Polymeric fluorescent substance and polymer light-emitting device using the same

专利摘要:
PURPOSE: Provided are a polymeric fluorescent substance containing a specific phenylene structure and showing strong fluorescence and/or excellent charge transporting property, and a polymer light emitting device(LED) of high performance which is driven at low voltage with high efficiency using the polymeric fluorescent substance. CONSTITUTION: The polymeric fluorescent substance showing fluorescence in the solid state and having a polystyrene reduced number-average molecular weight of 103 to 108, which comprises one or more repeating units of formula 1; and one or more repeating units of formula 2: -Ar1-. In the formula 1 and 2, R1, R2, R3 and R4 each independently represents a hydrogen atom or a substituent, and at least one of R1, R2, R3 and R4 is a group selected from alkoxy groups, aryl groups substituted with an alkoxy group, aryloxy groups and arylalkoxy groups, Ar1 represents a different group from that of formula 1 and is a group selected from substituted phenylene groups(having one or more substituents other than alkoxy groups, aryl groups substituted with an alkoxy group, aryloxy groups and arylalkoxy groups), substituted stilbene groups (having on a benzene ring one or more groups selected from alkoxy groups, aryl groups substituted with an alkoxy group, aryloxy groups and arylalkoxy groups), distilbene group, condensed polycyclic aromatic compound groups, condensed polycyclic heterocyclic compound groups, aromatic amine compound groups, and groups of formula 3: -Ar2-Ar3-Ar4-(wherein Ar2, Ar3 and Ar4 are groups different from those of formula 1 and each independently represents an arylene group or a divalent heterocyclic compound group, wherein the total amount of repeating units of formula 1 is 10 mol% or more and 90 mol% or less based on the total amount of repeating units of formula 1 and 2).
公开号:KR20020083494A
申请号:KR1020020023048
申请日:2002-04-26
公开日:2002-11-02
发明作者:도이슈지；노구치다카노부；우에오카다카히로
申请人:스미또모 가가꾸 고교 가부시끼가이샤；
IPC主号:

专利说明:

Polymeric fluorescent substance and polymer light-emitting device using the same
[1] The present invention relates to a polymer phosphor and a polymer light emitting device (hereinafter referred to as a polymer LED) containing the same in a light emitting layer.
[2] High molecular weight luminescent materials (polymeric phosphors) have been variously studied because they are soluble in a solvent and can form a light emitting layer in a light emitting device by a different application method from that of a low molecular weight. As polymer materials that can be used in polymer LEDs as light emitting materials or charge transport materials, there are commonly known polyphenylenevinylene derivatives, polyfluorene derivatives and polyphenylene derivatives. For example, Japanese Laid-Open Patent Publication No. 11-502248 describes a copolymer of oligophenylene. One example thereof is oligophenylenevinylene. Japanese Laid-Open Patent Publication No. 11-246660 describes a copolymer of an aromatic amine compound group and an unsaturated double bond group. Specifically, examples thereof include copolymers of dimers of triphenylamine and unsubstituted terphenylene. In addition, as polymer materials containing 2,5-dialkoxyphenylene, copolymers such as phenylene, thiophene, pyridine, biphenylene and bithiophene are known (see Synthetic Metals, vol. 102, p). 1060 (1999).
[3] SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer phosphor containing a specific phenylene structure and exhibiting strong fluorescence and / or excellent charge transport properties, and a high performance polymer LED that can be driven with high efficiency at low voltage using such a polymer phosphor. will be.
[4] The inventors have studied intensively, and as a result, polymers exhibiting fluorescence in the solid state, having a polystyrene reduced number average molecular weight of 10 ³ to 10 ⁸ , and containing at least one repeating unit of formula 1 and at least one repeating unit of formula 2 The present invention has been completed by finding that a high-performance polymer LED exhibiting strong fluorescence and / or good charge transport properties, and which can be driven at high efficiency at low voltage, is obtained using such a polymeric phosphor.
[5] That is, the present invention relates to the following [1] to [18].
[6] [1] exhibits fluorescence in the solid state, has a polystyrene reduced number average molecular weight of 10 ³ to 10 ⁸ , and contains at least one repeating unit of formula (1) and at least one repeating unit of formula (2); The polymeric fluorescent substance of the amount of 10 mol% to 90 mol% based on the total amount of the repeating units of the formula (1) and (2).
[7]
[8] -Ar _1-
[9] In Chemical Formulas 1 and 2,
[10] R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a substituent, at least one of R ₁ , R ₂ , R ₃ and R ₄ is an alkoxy group, an aryl group substituted by an alkoxy group, aryl Selected from the group consisting of an oxy group and an arylalkoxy group,
[11] Ar ₁ represents a group different from that of Formula 1, a substituted phenylene group (having one or more substituents other than an alkoxy group, an aryl group substituted by an alkoxy group, an aryloxy group and an arylalkoxy group), substituted stilbene Groups (having at least one group selected from an alkoxy group, an aryl group substituted by an alkoxy group, an aryloxy group and an arylalkoxy group in the benzene ring), a distilbene group, a condensed polycyclic aromatic compound group, a condensed poly A cyclic heterocyclic compound group, an aromatic amine compound group and a group selected from the group consisting of
[12] -Ar ₂ -Ar ₃ -Ar _4-
[13] (In Formula 3, Ar ₂ , Ar ₃ and Ar ₄ are different groups from those of Formula 1, and each independently represent an arylene group or a divalent heterocyclic compound group).
[14] [2] The polymeric fluorescent substance according to [1], wherein the repeating unit of formula (1) is selected from repeating units of formulas (4) and (5).
[15]
[16]
[17] In Chemical Formulas 4 and 5,
[18] R ₅ represents a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms and a monovalent heterocyclic compound group having 4 to 60 carbon atoms,
[19] n represents an integer of 1 to 4, when n is 2 or more, a plurality of OR ₅ may be the same or different,
[20] R ₆ and R ₇ are each independently a group consisting of an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms and a monovalent heterocyclic compound group having 4 to 60 carbon atoms. Represents a group selected from
[21] l represents an integer of 1 to 5,
[22] m represents an integer of 1 to 3, and when l is 2 or more, the number of OR ₆ may be the same or different, and when m is 2 or more, the number of OR ₇ may be the same or different.
[23] [3] The polymeric fluorescent substance according to [1] or [2], wherein the repeating unit of formula (2) is selected from the repeating unit of formula (6).
[24]
[25] In Chemical Formula 6,
[26] R ₈ , R ₉ and R ₁₀ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, or 1 to 20 carbon atoms. 40 alkylamino groups, aryl groups of 6 to 60 carbon atoms, aryloxy groups of 6 to 60 carbon atoms, arylsilyl groups of 6 to 60 carbon atoms, arylamino groups of 6 to 60 carbon atoms, arylalkyl groups of 7 to 60 carbon atoms, Arylalkoxy group having 7 to 60 carbon atoms, arylalkylsilyl group having 7 to 60 carbon atoms, arylalkylamino group having 7 to 60 carbon atoms, arylalkenyl group having 8 to 60 carbon atoms, arylalkynyl group having 8 to 60 carbon atoms A group selected from the group consisting of a monovalent heterocyclic compound group of 4 to 60 and a cyano group,
[27] i and j each independently represent an integer of 0 to 4,
[28] k represents an integer of 0 to 5,
[29] h represents an integer of 1 or 2, and when i is 2 or more, a plurality of R ₈ may be the same or different; when j is 2 or more, a plurality of R ₉ may be the same or different, and k is 2 or more; If multiple R ₁₀ may be the same or different,
[30] R ₈ to R ₁₀ may be bonded to form a ring, and when R ₈ to R ₁₀ are a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a hetero atom. It may be substituted by a group containing.
[31] [4] The polymeric fluorescent substance according to [1] or [2], wherein the repeating unit of formula (2) is selected from the repeating unit of formula (7).
[32]
[33] In Chemical Formula 7,
[34] R ₁₁ and R ₁₂ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, and an alkyl having 1 to 40 carbon atoms. Amino group, aryl group of 6 to 60 carbon atoms, aryloxy group of 6 to 60 carbon atoms, arylsilyl group of 6 to 60 carbon atoms, arylamino group of 6 to 60 carbon atoms, arylalkyl group of 7 to 60 carbon atoms, 7 to 6 carbon atoms Arylalkoxy group of 60, arylalkylsilyl group of 7 to 60 carbon atoms, arylalkylamino group of 7 to 60 carbon atoms, arylalkenyl group of 8 to 60 carbon atoms, arylalkynyl group of 8 to 60 carbon atoms, 4 to 60 carbon atoms Represents a group selected from the group consisting of a monovalent heterocyclic compound group and a cyano group,
[35] a and b each independently represent an integer of 0 to 3, and when a is 2 or more, a plurality of R ₁₁ may be the same or different, and when b is 2 or more, a plurality of R ₁₂ may be identical or different. There is,
[36] R ₁₁ and R ₁₂ may be bonded to form a ring, and when R ₁₁ and R ₁₂ are a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a hetero atom. It may be substituted by a group containing.
[37] [5] The polymeric fluorescent substance according to [1] or [2], wherein the repeating unit of formula (2) is selected from the repeating unit of formula (8).
[38]
[39] In Chemical Formula 8,
[40] R ₁₃ and R ₁₆ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, and an alkyl having 1 to 40 carbon atoms. Amino group, aryl group of 6 to 60 carbon atoms, aryloxy group of 6 to 60 carbon atoms, arylsilyl group of 6 to 60 carbon atoms, arylamino group of 6 to 60 carbon atoms, arylalkyl group of 7 to 60 carbon atoms, 7 to 6 carbon atoms Arylalkoxy group of 60, arylalkylsilyl group of 7 to 60 carbon atoms, arylalkylamino group of 7 to 60 carbon atoms, arylalkenyl group of 8 to 60 carbon atoms, arylalkynyl group of 8 to 60 carbon atoms, 4 to 60 carbon atoms Represents a group selected from the group consisting of a monovalent heterocyclic compound group and a cyano group,
[41] c and d each independently represent an integer of 0 to 4, and when c is 2 or more, a plurality of R ₁₃ may be the same or different, and when d is 2 or more, a plurality of R ₁₆ may be the same or different. There is,
[42] One or two substituents of the benzene ring is a group selected from the group consisting of an alkoxy group, an aryl group substituted by an alkoxy group, an aryloxy group and an arylalkoxy group,
[43] R ₁₄ and R ₁₅ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, or a monovalent heterocyclic compound group having 4 to 60 carbon atoms. And a group selected from the group consisting of cyano group,
[44] R ₁₃ to R ₁₆ may be bonded to form a ring, and when R ₁₃ to R ₁₆ are a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a hetero atom. It may be substituted by a group containing.
[45] [6] The polymeric fluorescent substance according to [1] or [2], wherein the repeating unit of formula (2) is selected from the repeating unit of formula (9).
[46]
[47] In Chemical Formula 9,
[48] R ₁₇ and R ₂₀ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, and an alkyl having 1 to 40 carbon atoms. Amino group, aryl group of 6 to 60 carbon atoms, aryloxy group of 6 to 60 carbon atoms, arylsilyl group of 6 to 60 carbon atoms, arylamino group of 6 to 60 carbon atoms, arylalkyl group of 7 to 60 carbon atoms, 7 to 6 carbon atoms Arylalkoxy group of 60, arylalkylsilyl group of 7 to 60 carbon atoms, arylalkylamino group of 7 to 60 carbon atoms, arylalkenyl group of 8 to 60 carbon atoms, arylalkynyl group of 8 to 60 carbon atoms, 4 to 60 carbon atoms Represents a group selected from the group consisting of a monovalent heterocyclic compound group and a cyano group,
[49] e represents an integer of 0 to 5,
[50] f represents an integer of 0 to 3, when e is 2 or more, a plurality of R ₁₇ may be the same or different, and if f is 2 or more, a plurality of R ₂₀ may be the same or different,
[51] R ₁₈ and R ₁₉ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, or a monovalent heterocyclic compound group having 4 to 60 carbon atoms. And a cyano group, a group selected from the group consisting of
[52] R ₁₇ to R ₂₀ may be bonded to form a ring, and when R ₁₇ to R ₂₀ are a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a hetero atom. It may be substituted by a group containing.
[53] [7] The polymeric fluorescent substance according to [1] or [2], wherein the repeating unit of formula (2) is selected from the repeating unit of formula (10).
[54]
[55] In Chemical Formula 10,
[56] R ₂₁ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, or 6 to 60 carbon atoms. Aryl group, aryloxy group having 6 to 60 carbon atoms, arylsilyl group having 6 to 60 carbon atoms, arylamino group having 6 to 60 carbon atoms, arylalkyl group having 7 to 60 carbon atoms, arylalkoxy group having 7 to 60 carbon atoms, carbon atom Arylalkylsilyl group having 7 to 60, arylalkylamino group having 7 to 60 carbon atoms, arylalkenyl group having 8 to 60 carbon atoms, arylalkynyl group having 8 to 60 carbon atoms, monovalent heterocyclic compound having 4 to 60 carbon atoms A group selected from the group consisting of a group and a cyano group,
[57] g represents an integer of 0 to 2, and if g is 2, a plurality of R ₂₁ may be the same or different,
[58] A plurality of R ₂₁ may be bonded to form a ring, and when R ₂₁ is a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a group containing a hetero atom. May be substituted by
[59] X ₁ is selected from O and S.
[60] [8] The polymeric fluorescent substance according to [1] or [2], wherein the repeating unit of formula (2) is selected from the repeating unit of formula (11).
[61]
[62] In Chemical Formula 11,
[63] R ₂₂ and R ₂₃ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, and an alkyl having 1 to 40 carbon atoms. Amino group, aryl group of 6 to 60 carbon atoms, aryloxy group of 6 to 60 carbon atoms, arylsilyl group of 6 to 60 carbon atoms, arylamino group of 6 to 60 carbon atoms, arylalkyl group of 7 to 60 carbon atoms, 7 to 6 carbon atoms Arylalkoxy group of 60, arylalkylsilyl group of 7 to 60 carbon atoms, arylalkylamino group of 7 to 60 carbon atoms, arylalkenyl group of 8 to 60 carbon atoms, arylalkynyl group of 8 to 60 carbon atoms, 4 to 60 carbon atoms Represents a group selected from the group consisting of a monovalent heterocyclic compound group and a cyano group,
[64] o and p each independently represent an integer of 0 to 4, when o is 2, a plurality of R ₂₂ may be the same or different, and if p is 2, a plurality of R ₂₃ may be the same or different,
[65] R ₂₂ and R ₂₃ may be bonded to form a ring, and when R ₂₂ and R ₂₃ are a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a hetero atom. May be substituted by a group containing
[66] X ₂ represents a group selected from O, S, NR ₂₄ or SiR ₂₅ R ₂₆ ,
[67] X ₃ and X ₄ each independently represent a group selected from N or CR ₂₇ ,
[68] R ₂₄ to R ₂₇ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms and a monovalent heterocyclic compound group having 4 to 60 carbon atoms. It represents a group selected from the group consisting of.
[69] [9] The polymeric fluorescent substance according to [1] or [2], wherein the repeating unit of formula (2) is selected from the repeating unit of formula (12).
[70]
[71] In Chemical Formula 12,
[72] Ar ₅ represents an arylene group or a divalent heterocyclic compound group,
[73] R ₂₄ and R ₂₉ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, and an alkyl having 1 to 40 carbon atoms. Amino group, aryl group of 6 to 60 carbon atoms, aryloxy group of 6 to 60 carbon atoms, arylsilyl group of 6 to 60 carbon atoms, arylamino group of 6 to 60 carbon atoms, arylalkyl group of 7 to 60 carbon atoms, 7 to 6 carbon atoms Arylalkoxy group of 60, arylalkylsilyl group of 7 to 60 carbon atoms, arylalkylamino group of 7 to 60 carbon atoms, arylalkenyl group of 8 to 60 carbon atoms, arylalkynyl group of 8 to 60 carbon atoms, 4 to 60 carbon atoms Represents a group selected from the group consisting of a monovalent heterocyclic compound group and a cyano group,
[74] q and r each independently represent an integer of 0 to 4, and if q is 2 or more, a plurality of R ₂₄ may be the same or different, and if r is 2 or more, a plurality of R ₂₉ may be the same or different. There is,
[75] R ₂₅ to R ₂₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, or a monovalent heterocyclic compound group having 4 to 60 carbon atoms. And a cyano group, a group selected from the group consisting of
[76] R ₂₄ to R ₂₉ may be bonded to form a ring, and when R ₂₄ to R ₂₉ are a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a hetero atom. It may be substituted by a group containing.
[77] [10] A polymer light emitting device comprising at least one light emitting layer comprising a pair of electrodes composed of one or more transparent or semitransparent anodes and cathodes and the polymer phosphor according to any one of [1] to [9]. .
[78] [11] The polymer light emitting device according to [10], wherein the layer containing the conductive polymer is at least positioned between the one electrode and the light emitting layer so as to be adjacent to the electrode.
[79] [12] The polymer light emitting device according to [10], wherein the insulating layer having a thickness of 2 nm or less is at least located between one electrode and the light emitting layer so as to be adjacent to the electrode.
[80] [13] The polymer light emitting device according to any one of [10] to [12], wherein the layer containing the electron transport compound is positioned between the cathode and the light emitting layer so as to be adjacent to the light emitting layer.
[81] [14] The polymer light emitting device according to any one of [10] to [12], wherein a layer containing a hole transport compound is positioned between the anode and the light emitting layer so as to be adjacent to the light emitting layer.
[82] [15] The composition of [10] to [12], wherein the layer containing the electron transport compound is positioned between the cathode and the light emitting layer so as to be adjacent to the light emitting layer, and the layer containing the hole transport compound is positioned between the anode and the light emitting layer so as to be adjacent to the light emitting layer. Polymer light emitting device according to any one.
[83] [16] A planar light source comprising the polymer light emitting device according to any one of [10] to [15].
[84] [17] A segment display comprising the polymer light emitting device according to any one of [10] to [15].
[85] [18] A dot matrix display comprising the polymer light emitting device according to any one of [10] to [15].
[86] [19] A liquid crystal display comprising the polymer light emitting device according to any one of [10] to [15] as back light.
[87] The polymeric fluorescent substance of the present invention exhibits fluorescence in the solid state, and the polystyrene reduced number average molecular weight is 10 ³ to 10 ⁸ , and contains at least one repeating unit of Formula 1 described above and at least one repeating unit of Formula 2 described above. The total amount of the repeating units of Formula 1 is 10 mol% to 90 mol% based on the total amount of the repeating units of Formulas 1 and 2.
[88] The total amount of repeating units of formula (1) is more preferably at least 20 mol% and even more preferably at least 30 mol%, based on the total amount of repeating units of formulas (1) and (2).
[89] In terms of solubility and fluorescence properties, the total amount of repeating units of the formulas (1) and (2) is preferably at least 50 mol%, more preferably at least 60 mol%, even more preferably at least 70 mol%.
[90] Wherein at least one repeating unit of formula (1) has a group selected from alkoxy groups, aryl groups substituted by alkoxy groups, aryloxy groups and arylalkoxy groups as substituent groups.
[91] In the present invention, an aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. At this time, the aromatic hydrocarbon is a parent of an aromatic compound and a hydrocarbon containing a benzene ring, and examples thereof include those having a condensed ring and those in which the subordinate benzene ring or condensed ring is directly or through a group such as vinylene.
[92] The alkoxy group may be one of linear, branched or cyclic, and usually has 1 to 20 carbon atoms, and specific examples thereof include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy Group, isobutoxy group, tert-butoxy group, pentyloxy group, isoamyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy Group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy and the like, pentyloxy group, isoamyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, Preference is given to decyloxy groups and 3,7-dimethyloctyloxy groups.
[93] In the aryl group substituted by an alkoxy group, the number of carbon atoms of the aryl group is usually 6 to 60, and specific examples thereof include phenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group and the like. have. The aryl group substituted by an alkoxy group is usually the above-mentioned aryl group having the above-mentioned alkoxy group as a substituent, and specifically, a C ₁ to C ₁₂ alkoxyphenyl group (C ₁ to C ₁₂ has 1 to 12 carbon atoms). Game, this expression also applies to the following description), di-C ₁ to C ₁₂ alkoxyphenyl group, tri-C ₁ to C ₁₂ alkoxyphenyl group, C ₁ to C ₁₂ alkoxynaphthyl group, di- And C ₁ to C ₁₂ alkoxynaphthyl groups, C ₁ to C ₁₂ alkoxyanthryl groups and the like.
[94] Aryloxy groups usually have about 6 to 60 carbon atoms, specifically phenoxy group, C ₁ to C ₁₂ alkoxyphenoxy group, C ₁ to C ₁₂ alkylphenoxy group, 1-naphthyloxy group and 2-naphthyl there may be mentioned oxy and the like, the phenoxy group, C ₁ to C ₁₂ alkoxy phenoxy group, and C ₁ to C ₁₂ alkyl phenoxy groups are preferred.
[95] The arylalkoxy group usually has about 7 to 60 carbon atoms, specifically, phenyl-C ₁ to C ₁₂ alkoxy group, C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkoxy group, C ₁ to C ₁₂ alkylphenyl- C ₁ to C ₁₂ alkoxy groups, 1-naphthyl-C ₁ to C ₁₂ alkoxy groups, 2-naphthyl-C ₁ to C ₁₂ alkoxy groups, and the like, and the like, and C ₁ to C ₁₂ alkoxyphenyl-C ₁ To C ₁₂ alkoxy groups and C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkoxy groups are preferred.
[96] By including these substituents containing oxygen atoms, the polymeric fluorescent substance of the present invention has appropriate solubility and strong fluorescence.
[97] The repeating unit of formula 1 may have substituents other than alkoxy groups, aryl groups substituted by alkoxy groups, aryloxy groups and arylalkoxy groups. Examples of these substituents include alkyl groups, alkylthio groups, alkylsilyl groups, alkylamino groups, aryl groups (not substituted by alkoxy groups), arylalkyl groups, arylalkenyl groups, arylalkynyl groups, arylamino groups And monovalent heterocyclic compound groups and cyano groups. When the repeating unit of formula (1) has a plurality of substituents, they may be the same or different. In order to enhance the solubility in the solvent, it is preferable to contain one or more substituents, and the form of the repeating unit including the substituents is preferably almost symmetrical.
[98] Alkyl groups can be straight, branched or cyclic, usually having from about 1 to 20 carbon atoms, specific examples of which are methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group Tertiary butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group and lauryl group Pentyl groups, isoamyl groups, hexyl groups, octyl groups, 2-ethylhexyl groups, decyl groups and 3,7-dimethyloctyl groups are preferred.
[99] Alkylthio groups can be either straight, branched or cyclic, usually having from about 1 to 20 carbon atoms, specific examples of which include methylthio group, ethylthio group, propylthio group, isopropylthio group, butyl Thio group, isobutylthio group, tertiary butylthio group, pentylthio group, isoamylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group , Decylthio group, 3,7-dimethyloctylthio group and laurylthio group, and the like, pentylthio group, isoamylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group And 3,7-dimethyloctylthio group.
[100] Alkylsilyl groups can be either straight, branched or cyclic, usually having from about 1 to 60 carbon atoms, specific examples of which are methylsilyl groups, ethylsilyl groups, propylsilyl groups, isopropylsilyl groups, butyl Silyl group, isobutylsilyl group, tertiary butylsilyl group, pentylsilyl group, isoamylsilyl group, hexylsilyl group, cyclohexylsilyl group, heptylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, nonylsilyl group , Decylsilyl group, 3,7-dimethyloctylsilyl group, laurylsilyl group, trimethylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, isopropyldimethylsilyl group, butyldimethylsilyl group, tertiary butyldimethylsilyl group , Pentyldimethylsilyl group, isoamyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyldimethylsilyl group, Nyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyldimethylsilyl group and lauryldimethylsilyl group, and the like, and include pentylsilyl group, isoamylsilyl group, hexylsilyl group, octylsilyl group, 2-ethyl Hexylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl group, pentyldimethylsilyl group, isoamyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyldimethylsilyl group, decyldimethylsilyl group And 3,7-dimethyloctyldimethylsilyl group.
[101] The alkylamino group can be either straight, branched or cyclic, and can be a monoalkyl group or a dialkylamino group, usually having about 1 to 40 carbon atoms, specific examples of which include methylamino group, dimethylamino Group, ethylamino group, diethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, tertiary butylamino group, pentylamino group, isoamylamino group, hexylamino group, cyclohexyl Amino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group and the like, and the like, pentylamino group, isoamyl Amino group, hexylamino group, octylamino group, 2-ethylhexylamino group, decylamino group and 3,7-dimethyloctylami The group is preferable.
[102] Aryl groups usually have about 6 to 60 carbon atoms, specific examples of which include phenyl groups, C ₁ to C ₁₂ alkoxyphenyl groups (C ₁ to C ₁₂ represent 1 to 12 carbon atoms, and the same applies to the following), C ₁ to C ₁₂ alkylphenyl groups, 1-naphthyl groups, 2-naphthyl groups and the like, and C ₁ to C ₁₂ alkoxyphenyl groups and C ₁ to C ₁₂ alkylphenyl groups are preferred. Aryl groups are atomic groups obtained by removing one hydrogen atom from an aromatic hydrocarbon.
[103] Arylalkyl groups usually have about 7 to 60 carbon atoms, specific examples of which include phenyl-C ₁ to C ₁₂ alkyl groups, C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkyl groups, C ₁ to C ₁₂ alkylphenyl -C ₁ to C ₁₂ alkyl groups, 1-naphthyl-C ₁ to C ₁₂ alkyl groups, 2-naphthyl-C ₁ to C ₁₂ alkyl groups, and the like, and C ₁ to C ₁₂ alkoxyphenyl-C ₁ to Preferred are C ₁₂ alkyl groups and C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkyl groups.
[104] The arylamino group usually has about 6 to 60 carbon atoms, and specific examples thereof include phenylamino group, diphenylamino group, C ₁ to C ₁₂ alkoxyphenylamino group, di (C ₁ to C ₁₂ alkoxyphenyl) amino group, di (C ₁ to C ₁₂ alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group and the like, and C ₁ to C ₁₂ alkylphenylamino group and di (C ₁ to C ₁₂ alkylphenyl) Amino groups are preferred.
[105] Monovalent heterocyclic compound group means a residual atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and the number of carbon atoms is usually about 4 to 60, preferably 4 to 20. The number of carbon atoms in the heterocyclic compound group does not include the number of carbon atoms in the substituent. In this case, the term heterocyclic compound refers to an organic compound having a cyclic structure in which not only the elements constituting the ring are composed of carbon atoms, but also hetero atoms (for example, oxygen, sulfur, nitrogen, phosphorus and boron) are included in the ring. Include. In particular, thienyl group, C ₁ to C ₁₂ alkylthienyl group, pyrrolyl group, furyl group, pyridyl group and C ₁ to C ₁₂ alkylpyridyl group and the like can be exemplified, for example, thienyl group, C ₁ to a C ₁₂ alkyl thienyl group, pyridyl group and C ₁ to C ₁₂ alkyl pyridyl group are preferable.
[106] In the example of a substituent, the substituent containing an alkyl chain may be linear, branched or cyclic, or a combination thereof, and if it is not linear, isoamyl group, 2-ethylhexyl group, 3,7-dimethyl and the like octyl group, cyclohexyl group and 4-C ₁ to C ₁₂ alkyl group, for example cyclohexyl. In order to enhance the solubility of the polymeric fluorescent substance in the solvent, at least one substituent in the repeating unit of formula (1) preferably contains a cyclic or branched alkyl chain. The positions of the two alkyl chains can be joined to form a ring. In addition, a part of the carbon atoms in the alkyl chain may be substituted by a group containing a hetero atom, and examples of the hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom.
[107] In addition, as examples of substituents, when the aryl group and the heterocyclic compound group are partially included, they may further have one or more substituents.
[108] Of the repeating units of formula (1), the above-mentioned groups of formula (4) or (5) are more preferred examples.
[109] R ₅ of Formula 4 and R ₆ and R ₇ of Formula 5 each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms and 1 to 4 carbon atoms. Represents a group selected from the group of heterocyclic compounds. Specific examples of these substituents are as described above.
[110] In formula (4), n represents an integer of 1 to 4. If n is 2 or more, the number of OR ₅ may be the same or different.
[111] In formula (5), l represents an integer of 1 to 5, m represents an integer of 1 to 3. If l is 2 or more, the number of OR ₆ may be the same or different. In addition, when m is two or more, many OR <_7> may be the same or different.
[112] The repeating unit of formula 4 or 5 may have substituents other than those mentioned above. Examples of such substituents include alkyl groups, alkylthio groups, alkylsilyl groups, alkylamino groups, aryl groups, arylalkyl groups, arylalkenyl groups, arylalkynyl groups, arylamino groups, monovalent heterocyclic compound groups, and Cyano group etc. are mentioned, for example. Specific examples of these substituents are as described above.
[113] The repeating unit represented by Ar ₁ in Formula 2 is a group different from the group of Formula 1, and substituted phenylene group (alkoxy group, aryl group substituted by alkoxy group, aryloxy group and at least one substituent other than arylalkoxy group) Substituted stilbene group (having one or more substituents on the benzene ring selected from the group consisting of alkoxy groups, aryl groups substituted by alkoxy groups, aryloxy groups and arylalkoxy groups), ditylbene groups, Condensed polycyclic aromatic compound group, condensed polycyclic heterocyclic compound group, aromatic amine compound group and group selected from the group of formula (3).
[114] At this time, the substituted phenylene group has one or more other substituents other than an alkoxy group, an aryl group substituted by an alkoxy group, an aryloxy group and an arylalkoxy group. As such a substituent, an alkyl group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, an aryl group having 6 to 60 carbon atoms (alkoxy group) Unsubstituted), arylsilyl group having 6 to 60 carbon atoms, arylamino group having 6 to 60 carbon atoms, arylalkyl group having 7 to 60 carbon atoms, arylalkylsilyl group having 7 to 60 carbon atoms, arylalkyl having 7 to 60 carbon atoms And an amino group, an arylalkenyl group having 8 to 60 carbon atoms, an arylalkynyl group having 8 to 60 carbon atoms, a monovalent heterocyclic compound group having 4 to 60 carbon atoms, and a cyano group. Specific examples of these substituents are as described above.
[115] Substituted stilbene groups have one or two groups selected from an alkoxy group, an aryl group substituted by an alkoxy group, an aryloxy group and an arylalkoxy group in the benzene ring. Specific examples of these substituents are as described above.
[116] The distilbene group is a group having an arylene group or a divalent heterocyclic compound group in the center and a vinylene group between two phenylene groups. The arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon compound. Divalent heterocyclic compound groups are atomic groups obtained by removing two hydrogen atoms from a heterocyclic compound. Condensed polycyclic aromatic compound groups are atomic groups obtained by removing two hydrogen atoms from a condensed polycyclic aromatic compound. In this case, the condensed polycyclic aromatic compound is preferably an aromatic compound obtained by condensing 2 to 5 benzene rings having usually 6 to 60 carbon atoms contained in the ring. In particular, naphthalene, anthracene, phenanthrene, pyrene, perylene, naphthacene, pentacene, chrysene and coronene and the like are mentioned, with naphthalene and anthracene being preferred. In terms of solubility, it is preferred that at least one substituent is contained.
[117] Condensed polycyclic aromatic compound groups are atomic groups obtained by removing two hydrogen atoms from a condensed polycyclic aromatic compound. In this case, in the condensed polycyclic aromatic compound represented by Ar ₁ , not only the element constituting the ring is composed of carbon atoms, but also two or more hetero atoms (eg, oxygen, sulfur, nitrogen, phosphorus, boron, etc.) are included in the ring. Organic compounds having a cyclic structure obtained by condensing a ring are included. The number of carbon atoms contained in the ring is preferably about 6 to 60, more preferably 6 to 30. In particular, quinoline, quinoxaline, acridine, phenanthroline, benzoxazole, benzotriazole, benzoxadiazole, benzothiadiazole, dibenzofuran, dibenzothiophene and carbazole and the like are given, and quinoline, Preference is given to benzoxazoles, benzothiadiazoles and carbazoles. In terms of solubility, it is preferred that at least one substituent is contained.
[118] An aromatic amine compound group is an atomic group obtained by removing two hydrogen atoms from an amine compound containing substituents by two or more aryl groups. At this time, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, etc. are mentioned as an aryl group. These aryl groups may have one or more substituents. Specific examples of these substituents are as described above.
[119] The group of formula (3) is a group obtained by combining three groups all different from the group of formula (1). Ar ₂ , Ar ₃ and Ar ₄ in Formula 3 each independently represent an arylene group or a divalent heterocyclic compound group. One or two of Ar ₂ , Ar _3, and Ar ₄ is an arylene group, and the remaining groups are a divalent heterocyclic compound in which Ar ₂ , Ar _3, and Ar ₄ are not all arylene groups or divalent heterocyclic compound groups. It is more preferable that it is a group. In this case, the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. Heterocyclic compound groups are atomic groups obtained by removing two hydrogen atoms from a heterocyclic compound. In particular, phenylene group, naphthalenediyl group, anthracenediyl group, thienylene group, furandiyl group, pyridinediyl group, quinolindiyl group and quinolinsaldiyl group, and the like can be exemplified, phenylene group, naphthalenediyl group, anthracene Diyl groups and thienylene groups are preferred.
[120] The repeating unit of formula (2) preferably has a structure of formulas (6) to (12). From the viewpoint of the durability of the material, structures represented by the formulas (6) to (8), (10) and (12) are more preferable. Moreover, the structures of the formulas (6) and (10) are particularly preferred because materials with excellent charge transport properties can be easily obtained.
[121] When the repeating unit of Formula 2 is a structure of Formula 6, R ₈ , R ₉ and R ₁₀ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkylthio having 1 to 20 carbon atoms. Group, C1-C60 alkylsilyl group, C1-C40 alkylamino group, C6-C60 aryl group, C6-C60 aryloxy group, C6-C60 arylsilyl group, C6-C60 Arylamino group, C7-60 arylalkyl group, C7-60 arylalkoxy group, C7-60 arylalkylsilyl group, C7-60 arylalkylamino group, C8-60 arylal And a group selected from the group consisting of a kenyl group, an arylalkynyl group having 8 to 60 carbon atoms, a monovalent heterocyclic compound group having 4 to 60 carbon atoms, and a cyano group. Specific examples of these substituents are as described above. i and j each independently represent the integer of 0-4. It is more preferred that i or j is not zero, or both of them are not zero. k represents the integer of 0-5. h represents the integer of 1-2. When h is 1, the structure of the triphenylamine derivative is formed, and when h is 2, the structure of the N, N'-tetraphenyl-phenalendiamine derivative is formed. When h is 1 and the two structures of formula 6 are adjacent, the structure of the N, N'-tetraphenyl-benzidine derivative is formed. When i is 2 or more, a plurality of R ₈ may be the same or different. When j is 2 or more, a plurality of R ₉ may be the same or different. When k is 2 or more, a plurality of R ₁₀ may be the same or different. R ₈ to R ₁₀ may be bonded to form a ring. In addition, two benzene rings adjacent to one N may be bonded by a carbon-carbon single bond to form a carbazole ring. In addition, when R ₈ to R ₁₀ are a group containing an alkyl chain, one or more methyl groups, methylene groups and methine groups constituting the alkyl chain may be substituted by a group containing a hetero atom.
[122] When the repeating unit of Formula 2 is a structure of Formula 7, R ₁₁ and R ₁₂ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and carbon atoms C1-C60 alkylsilyl group, C1-C40 alkylamino group, C6-C60 aryl group, C6-C60 aryloxy group, C6-C60 arylsilyl group, C6-C60 arylamino A group, an arylalkyl group having 7 to 60 carbon atoms, an arylalkoxy group having 7 to 60 carbon atoms, an arylalkylsilyl group having 7 to 60 carbon atoms, an arylalkylamino group having 7 to 60 carbon atoms, an arylalkenyl group having 8 to 60 carbon atoms, And a group selected from the group consisting of an arylalkynyl group having 8 to 60 carbon atoms, a monovalent heterocyclic compound group having 4 to 60 carbon atoms, and a cyano group. Specific examples of these substituents are as described above. a and b respectively independently represent the integer of 0-3. In terms of solubility, it is preferred that a or b is not zero. When a is 2 or more, a plurality of R ₁₁ may be the same or different. When b is 2 or more, a plurality of R ₁₂ may be the same or different. R ₁₁ and R ₁₂ may be combined to form a ring. In addition, when R ₁₁ and R ₁₂ are groups containing an alkyl chain, one or more methyl groups, methylene groups and methine groups constituting the alkyl chain may be substituted by a group containing a hetero atom.
[123] When the repeating unit of Formula 2 is a structure of Formula 8, R ₁₃ and R ₁₆ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and carbon atoms C1-C60 alkylsilyl group, C1-C40 alkylamino group, C6-C60 aryl group, C6-C60 aryloxy group, C6-C60 arylsilyl group, C6-C60 arylamino A group, an arylalkyl group having 7 to 60 carbon atoms, an arylalkoxy group having 7 to 60 carbon atoms, an arylalkylsilyl group having 7 to 60 carbon atoms, an arylalkylamino group having 7 to 60 carbon atoms, an arylalkenyl group having 8 to 60 carbon atoms, And a group selected from the group consisting of an arylalkynyl group having 8 to 60 carbon atoms, a monovalent heterocyclic compound group having 4 to 60 carbon atoms, and a cyano group. Specific examples of these substituents are as described above. c and d each independently represent an integer of 0 to 4; When c is 2 or more, a plurality of R ₁₃ may be the same or different. When d is 2 or more, a plurality of R ₁₆ may be the same or different. R ₁₄ and R ₁₅ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, or a monovalent heterocyclic compound group having 4 to 60 carbon atoms. And a cyano group. Specific examples of these substituents are as described above. R ₁₃ to R ₁₆ may be bonded to form a ring. In addition, when R ₁₃ to R ₁₆ are a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be substituted by a group containing a hetero atom.
[124] When the repeating unit of Formula 2 is a structure of Formula 9, R ₁₇ and R ₂₀ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and carbon atoms C1-C60 alkylsilyl group, C1-C40 alkylamino group, C6-C60 aryl group, C6-C60 aryloxy group, C6-C60 arylsilyl group, C6-C60 arylamino A group, an arylalkyl group having 7 to 60 carbon atoms, an arylalkoxy group having 7 to 60 carbon atoms, an arylalkylsilyl group having 7 to 60 carbon atoms, an arylalkylamino group having 7 to 60 carbon atoms, an arylalkenyl group having 8 to 60 carbon atoms, And a group selected from the group consisting of an arylalkynyl group having 8 to 60 carbon atoms, a monovalent heterocyclic compound group having 4 to 60 carbon atoms, and a cyano group. Specific examples of these substituents are as described above. e represents the integer of 0-5. f represents the integer of 0-3. When e is 2 or more, a plurality of R ₁₇ may be the same or different. When f is 2 or more, a plurality of R ₂₀ may be the same or different. R ₁₈ and R ₁₉ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, and a monovalent heterocyclic compound group having 4 to 60 carbon atoms. And a cyano group. Specific examples of these substituents are as described above. R ₁₇ to R ₂₀ may be bonded to form a ring. When R ₁₇ to R ₂₀ are groups containing an alkyl chain, one or more methyl groups, methylene groups and methine groups constituting the alkyl chain may be substituted by groups containing hetero atoms.
[125] When the repeating unit of Formula 2 is a structure of Formula 10, R ₂₁ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 60 carbon atoms , Alkylamino group having 1 to 40 carbon atoms, aryl group having 6 to 60 carbon atoms, aryloxy group having 6 to 60 carbon atoms, arylsilyl group having 6 to 60 carbon atoms, arylamino group having 6 to 60 carbon atoms, 7 to 60 carbon atoms Arylalkyl group, arylalkoxy group having 7 to 60 carbon atoms, arylalkylsilyl group having 7 to 60 carbon atoms, arylalkylamino group having 7 to 60 carbon atoms, arylalkenyl group having 8 to 60 carbon atoms, arylalkyi having 8 to 60 carbon atoms And a group selected from the group consisting of a silyl group, a monovalent heterocyclic compound group having 4 to 60 carbon atoms, and a cyano group. Specific examples of these substituents are as described above. g represents the integer of 0-2. When g is 2 or more, a plurality of R ₂₁ may be the same or different. Multiple R ₂₁ can be joined to form a ring. In addition, when R ₂₁ is a group containing an alkyl chain, one or more methyl groups, methylene groups and methine groups constituting the alkyl chain may be substituted by a group containing a hetero atom. X ₁ is selected from O and S.
[126] The repeating unit bonded to both sides of the structure of Formula 10 may not be that of Formula 1, for example, a thienylene group, a naphthalenediyl group, a phenyl group other than that of Formula 1, and the like may be used. These repeating units on both sides may have various substituents described above. As a structure including adjacent repeating units, the following structural formula can be more specifically illustrated.
[127]
[128] When the repeating unit of Formula 2 is a structure of Formula 11, R ₂₂ and R ₂₃ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and carbon atoms C1-C60 alkylsilyl group, C1-C40 alkylamino group, C6-C60 aryl group, C6-C60 aryloxy group, C6-C60 arylsilyl group, C6-C60 arylamino A group, an arylalkyl group having 7 to 60 carbon atoms, an arylalkoxy group having 7 to 60 carbon atoms, an arylalkylsilyl group having 7 to 60 carbon atoms, an arylalkylamino group having 7 to 60 carbon atoms, an arylalkenyl group having 8 to 60 carbon atoms, And a group selected from the group consisting of an arylalkynyl group having 8 to 60 carbon atoms, a monovalent heterocyclic compound group having 4 to 60 carbon atoms, and a cyano group. Specific examples of these substituents are as described above. o and p each independently represent an integer of 0 to 4; When o is 2 or more, a plurality of R ₂₂ may be the same or different. When p is 2 or more, a plurality of R ₂₃ may be the same or different. R ₂₂ and R ₂₃ may be joined to form a ring. In addition, when R ₂₂ or R ₂₃ is a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be substituted by a group containing a hetero atom. X ₂ represents a group selected from O, S, NR ₂₄ or SiR ₂₅ R ₂₆ . X ₃ and X ₄ each independently represent a group selected from N or CR ₂₇ . R ₂₄ to R ₂₇ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms and a monovalent heterocyclic compound group having 4 to 60 carbon atoms. Indicates.
[129] As examples of 5-membered rings in the center of the repeating unit of formula 11, oxadiazole, triazole, thiophene, furan, silol and the like are shown.
[130] When the repeating unit of formula (2) is the structure of formula (12), Ar ₅ represents an arylene group or a divalent heterocyclic compound group. Specific examples of these groups are the same as the examples of Ar ₂ to Ar ₄ mentioned above. R ₂₄ and R ₂₉ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, and an alkyl having 1 to 40 carbon atoms. Amino group, aryl group of 6 to 60 carbon atoms, aryloxy group of 6 to 60 carbon atoms, arylsilyl group of 6 to 60 carbon atoms, arylamino group of 6 to 60 carbon atoms, arylalkyl group of 7 to 60 carbon atoms, 7 to 6 carbon atoms Arylalkoxy group of 60, arylalkylsilyl group of 7 to 60 carbon atoms, arylalkylamino group of 7 to 60 carbon atoms, arylalkenyl group of 8 to 60 carbon atoms, arylalkynyl group of 8 to 60 carbon atoms, 4 to 60 carbon atoms Represents a group selected from the monovalent heterocyclic compound group and the cyano group. Specific examples of these substituents are as described above. q and r each independently represent an integer of 0 to 4; When q is 2 or more, a plurality of R ₂₄ may be the same or different. When r is 2 or more, a plurality of R ₂₉ may be the same or different. R ₂₅ to R ₂₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, or a monovalent heterocyclic compound group having 4 to 60 carbon atoms. And a cyano group. Specific examples of these substituents are as described above. R ₂₄ to R ₂₉ may be bonded to form a ring. In addition, when R ₂₄ to R ₂₉ are a group containing an alkyl chain, one or more methyl groups, methylene groups and methine groups constituting the alkyl chain may be substituted by a group containing a hetero atom.
[131] Such a polymeric fluorescent substance may contain repeating units different from the repeating units of the formulas (1) to (11) in a range in which the luminescence properties and the charge transport properties are not degraded. Units different from the repeating units of Formulas 1 to 11 or the repeating units of Formulas 1 to 11 may be joined via nonconjugated units, or such nonconjugated portions may also be included in the repeating units. Examples of the bonding structure include a bonding structure represented by the following formula, a combination of the bonding structure of the following formula and a vinylene group, and a combination of two or more bonding structures of the following formula.
[132] R is selected from the same substituents as described above, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms.
[133]
[134] Such polymeric phosphors may also be random, block or graft copolymers, or polymers having an intermediate structure thereof, for example random copolymers having blocking properties.
[135] From the viewpoint of obtaining a polymeric fluorescent substance with high fluorescent quantum yield, the repeat regularity is preferably lower, for example, a random copolymer is preferred to an alternating copolymer. In order to obtain alternating copolymers, it is necessary to use monomers each having two kinds of active groups for polymerization. On the other hand, random copolymers can be obtained by adding a plurality of monomers having one type of active group in a desired ratio, and preparation is easily performed. Also preferred are block copolymers consisting of random copolymers with blocking properties and blocks of non-uniform size, or graft copolymers, than full random copolymers. Also included are side chain backbones and polymers having three or more ends. Also included are structures containing regularly grown dendrimers and random side chains.
[136] Also, as the polymeric fluorescent substance, it is suitable to use fluorescent substance which emits fluorescence in the solid state, since the material uses light emission from the thin film.
[137] Preferred solvents for the polymeric fluorescent substance include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin and n-butylbenzene. The polymeric fluorescent substance can vary in amount depending on the structure and molecular weight of the polymeric fluorescent substance, but can usually be dissolved in these solvents in an amount of at least 0.1% by weight.
[138] The polymeric fluorescent substance has a number average molecular weight of 10 ³ to 10 ^{8 on} a polystyrene basis, and the degree of polymerization thereof also varies depending on the repeating structure and the ratio thereof. In terms of film forming properties, generally the total amount of repeating structure is preferably 20 to 10000, more preferably 30 to 10000, particularly preferably 50 to 5000.
[139] When these polymeric phosphors are used as light emitting materials for polymer LEDs, their purity affects the luminescent properties, and therefore, the equivalents before polymerization are purified before polymerization by distillation, sublimation purification and recrystallization. It is preferable to carry out purification treatment, such as reprecipitation purification and chromatographic separation, after synthesis.
[140] The polymeric fluorescent substance of the present invention can be used not only as a light emitting material but also as an organic semiconductor material, an optical material or a conductive material by doping.
[141] The method for producing the polymeric fluorescent substance of the present invention will be described below.
[142] As a method for producing the polymeric fluorescent substance of the present invention, for example, the method described in JP-A No. 5-202355 is mentioned when the main chain has a vinylene group. That is, polymerization of a compound having an aldehyde group and a compound having a phosphonium salt group or a polymerization of a compound having an aldehyde group with a phosphonium salt group according to the Wittig reaction; Polymerization of a compound having a vinyl group and a compound having a halogen group, or a polymerization of a compound having a vinyl group and a halogen group, according to a Heck reaction; Polymerization of a compound having an aldehyde group and a compound having an alkylphosphonate group, or a compound having an aldehyde group and an alkylphosphonate group, according to the Horner-Wadsworth-Emmons reaction; Polycondensation reaction of a compound having two or more halogenated methyl groups according to the dehalogenation hydrogenation method; Polycondensation of compounds having two or more sulfonium salt groups, according to the sulfonium salt decomposition method; Both following polymerization of the aldehyde group and the compound having an acetonitrile group or the polymerization and the McMurry reaction of the compound having an aldehyde group and an acetonitrile group according to the knoevenagel reaction. Examples are methods such as polymerization of a compound having an aldehyde group on the phase.
[143] When the vinylene group is not included in the main chain, for example, polymerization by the Suzuki coupling reaction from the corresponding monomer, polymerization by the Grignard reaction, Ni (0) Examples include polymerization using a catalyst, polymerization using an oxidizing agent (such as FeCl ₃ ), electrochemically performing oxidative polymerization, and decomposition of an intermediate polymer having a suitable release group.
[144] Among them, the polymerization method according to the Beatig reaction, the polymerization method according to the heck reaction, the polymerization method according to the Horner-Wordsworth-Emons method, the polymerization method according to the Kneubenagel reaction, the polymerization method according to the Suzuki coupling reaction, Grignard Polymerization by reaction and polymerization using Ni (0) catalyst are preferred, since the structural control is easy in these methods.
[145] In particular, compounds used as monomers, having a large number of reactive substituents, may optionally be dissolved in organic solvents and reacted at the melting or boiling points of the organic solvents using alkalis or suitable catalysts. See, eg, "Organic Reactions", vol. 14, pp. 270 to 490, John Wiley & Sons, Inc., 1965, "Organic Reactions", vol. 27, pp. 345 to 390, John Wiley & Sons, Inc., 1982, "Organic Synthesis", Collective Volume VI, pp. 407 to 411, John Wiley & Sons, Inc., 1988, Chemical Review, vol. 95, p. 2457 (1995), Journal of Organometallic Chemistry, vol. 576, p. 147 (1999), Journal of Praktical Chemistry, vol. 336, p. 247 (1994), Makromolecular Chemistry Macromolecular Symposium, vol. 12, p. 229 (1987), etc.) Can be used.
[146] The organic solvent used is sufficiently deoxygenated and the reaction depends on the compound and the reaction in which the treatment is used, but in general it is preferably carried out under an inert atmosphere in order to suppress side reactions. Furthermore, it is likewise preferred to carry out the dehydration treatment (but this does not apply in the case of reactions of two-phase systems using water, such as the Suzuki coupling reaction).
[147] For the reaction, alkali or suitable catalyst is added appropriately. These may be selected depending on the reaction used. It is preferred that the alkali or catalyst is sufficiently soluble in the solvent used for the reaction. As a method of mixing an alkali or a catalyst, the method of gradually adding a solution of an alkali or a catalyst while stirring under inert atmosphere, such as argon and nitrogen, or the reverse method is a method of gradually adding a reaction solution to a solution of an alkali or a catalyst.
[148] More specifically, in the reaction conditions, in the case of the Beatig reaction, the Horner reaction, the kneubenagel reaction, and the like, the alkali is added in an amount of not less than equivalent, preferably 1 to 3 equivalents, based on the amount of functional groups of the monomer. To react. Alkali is not particularly limited and includes, for example, metal alcoholates (such as potassium tertiary butoxide, sodium tertiary butoxide, sodium ethylate and lithium methylate), hydride reagents (such as sodium hydride), and the like. Amides such as sodium amide and the like can be used. As the solvent, N, N-dimethylformamide, tetrahydrofuran, dioxane, toluene and the like are used. The reaction can usually proceed at a reaction temperature of room temperature to about 150 ° C. The reaction time is, for example, 5 minutes to 40 hours, a time for sufficient progress of the polymerization may be allowed, and since the reaction time does not need to be left for a long time after the completion of the reaction, the reaction time is preferably 10 minutes to 24 hours. It's time. The reaction concentration can be usefully selected from a range of about 0.01% by weight to the maximum solution concentration, because if the concentration is too low, the reaction efficiency is poor, if it is too high, the reaction control is difficult, and the usual concentration range is 0.1 to 20% by weight. In the case of a heck reaction, the monomers are reacted using a palladium catalyst in the presence of a base (eg triethylamine, etc.). The reaction is carried out at a reaction temperature of about 80 to 160 ° C. for about 1 to 100 hours using a relatively high boiling solvent (eg, N, N-dimethylformamide, N-methylpyrrolidone, etc.).
[149] In the case of Suzuki coupling reaction, palladium [tetrakis (triphenylphosphine)], palladium acetate and the like are used, for example, as catalysts, inorganic bases (such as potassium carbonate, sodium carbonate, barium hydroxide, etc.), organic Bases (e.g. triethylamine and the like) and inorganic salts (e.g. cesium fluoride and the like) are preferably added and reacted in an equivalent amount, preferably in an amount of 1 to 10 equivalents, based on the monomers. Inorganic salts are used as aqueous solutions, and reactions in a two phase system may also be acceptable. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. Depending on the solvent, temperatures of 50 to 160 ° C. are preferably used. It may also be possible to raise the temperature to near the boiling point of the solvent, causing reflux. The reaction time is about 1 to 200 hours.
[150] In the case of the Grignard reaction, the halide and the metal Mg are reacted in an ether base solvent (e.g., tetrahydrofuran, diethyl ether, dimethoxyethane, etc.) to prepare a Grignard reagent mixed with a separately prepared monomer solution. An example is a method in which a nickel or palladium catalyst is added while paying attention to a reaction, followed by raising the reaction temperature to reflux. The Grignard reagent is used in equivalents based on monomers, preferably in amounts of 1 to 1.5 equivalents and more preferably 1 to 1.2 equivalents. In addition, in the case of the polymerization by a method different from that described above, the reaction can be carried out by a known method.
[151] Next, the polymer LED of the present invention will be described. In the structure of the polymer LED of the present invention, the light emitting layer is positioned between one or more transparent or semitransparent anodes and cathodes, and the polymeric fluorescent substance of the present invention is included in the emitting layer.
[152] As the polymer LED of the present invention, a polymer LED having an electron transporting layer located between the cathode and the light emitting layer, a polymer LED having a hole transporting layer located between the anode and the light emitting layer, an electron transporting layer located between the cathode and the light emitting layer and a hole transporting layer located between the anode and the light emitting layer Polymeric LEDs are presented.
[153] For example, the following structures a) to d) are specifically illustrated.
[154] a) anode / light emitting layer / cathode
[155] b) anode / hole transport layer / light emitting layer / cathode
[156] c) anode / light emitting layer / electron transporting layer // cathode
[157] d) anode / hole transport layer / light emitting layer / electron transport layer / cathode
[158] (Where / represents the lamination of adjacent layers of layers, the same will be used later)
[159] In the present invention, 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. Here, the electron transport layer and the hole transport layer are generally called a charge transport layer.
[160] The light emitting layer, hole transporting layer and electron transporting layer may also each independently be used in two or more layers.
[161] Among the charge transport layers located adjacent to the electrodes, charge transport layers having a function of improving the charge injection efficiency from the electrodes and having the effect of reducing the driving voltage of the device are generally particularly often a charge injection layer (hole injection layer, electron injection layer). It is called).
[162] In order to improve the adhesion with the electrode and to improve the charge injection from the electrode, the above-described charge injection layer or insulating layer having a thickness of 2 nm or less can also be provided adjacent to the electrode, improving the adhesion of the interface, mixing, etc. To prevent this, a buffer thin film layer may also be inserted into the interface of the charge transport layer and the light emitting layer.
[163] The order and number of layers to be laminated and the thickness of each layer can be appropriately applied while considering light emitting efficiency and life of the device.
[164] In the present invention, a polymer LED provided with a charge injection layer (electron injection layer, hole injection layer), a polymer LED having a charge injection layer provided adjacent to the cathode and a polymer LED having a charge injection layer provided adjacent to the anode Presented.
[165] For example, the following structures e) to p) are specifically illustrated.
[166] e) anode / charge injection layer / light emitting layer / cathode
[167] f) anode / light emitting layer / charge injection layer / cathode
[168] g) anode / charge injection layer / light emitting layer / charge injection layer / cathode
[169] h) anode / charge injection layer / hole transport layer / light emitting layer / cathode
[170] i) anode / hole transport layer / light emitting layer / charge injection layer / cathode
[171] j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode
[172] k) anode / charge injection layer / light emitting layer / electron transport layer / cathode
[173] l) anode / light emitting layer / electron transport layer / charge injection layer / cathode
[174] m) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode
[175] n) anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / cathode
[176] o) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode
[177] p) anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode
[178] As a specific example of the charge injection layer, a layer containing a conductive polymer, located between the anode and the hole transport layer, and containing a material having an ionization potential that is between the ionization potential of the anode material and the ionization potential of the hole transport material contained in the hole transport layer The layer etc. which are located between a layer and a cathode, and an electron carrying layer, and which have an electron affinity between the electron affinity of an anode material and the electron affinity of the electron carrying material contained in an electron carrying layer, etc. are mentioned.
[179] When the charge injection layer described above is a layer containing a conductive polymer, the conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm to 10 ³ S / cm, and more preferably, in order to reduce the short circuit between the light emitting pixels, ^10-5 S / cm-10 ² S / cm, More preferably, it is ^10-5 S / cm-10 ¹ S / cm.
[180] In order to provide the conductivity of the conductive polymer, which is usually 10 ⁻⁵ S / cm to 10 ³ S / cm, an appropriate amount of ions are doped with the conductive polymer.
[181] In the type of doped ions, anions are used for the hole injection layer and cations are used for the electron injection layer. Examples of the anion include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and the like. Examples of cations include lithium ions, sodium ions, potassium ions, tertiary butyl ammonium ions, and the like. Can be mentioned.
[182] The thickness of the charge injection layer is, for example, 1 to 100 nm, preferably 2 to 50 nm.
[183] The material used for the charge injection layer may be appropriately selected in view of the relationship between the material of the layer adjacent to the electrode, and polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, poly (phenylene vinylene) and Derivatives thereof, poly (thienylene vinylene) and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polymers containing aromatic amine structures in the main or side chains, and metal phthalocyanines (such as copper phthalocyanine) and carbon Conductive polymers, such as these, are mentioned.
[184] The insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. As the material of the above-described insulating layer, metal fluorides, metal oxides and organic insulating materials and the like are presented. A polymer LED having an insulating layer having a thickness of 2 nm or less, wherein a polymer LED having an insulating layer having a thickness of 2 nm or less provided adjacent to a cathode and a polymer LED having an insulating layer having a thickness of 2 nm or less provided adjacent to an anode are presented. do.
[185] Specifically, the following structures q) to ab) are shown.
[186] q) Insulation layer / light emitting layer / cathode having an anode / thickness of 2 nm or less
[187] r) anode / light emitting layer / insulation layer / cathode having a thickness of 2 nm or less;
[188] s) anode / thickness of 2 nm or less insulation layer / light emitting layer / thickness of 2 nm or less insulation layer / cathode
[189] t) Insulation layer / hole transport layer / light emitting layer / cathode having an anode / thickness of 2 nm or less
[190] u) anode / hole transporting layer / light emitting layer / insulation layer / cathode having a thickness of 2 nm or less;
[191] v) Insulation layer / hole transport layer / light emitting layer / anode / thickness of 2 nm or less / insulation layer / cathode of 2 nm or less
[192] w) Insulation layer / light emitting layer / electron transport layer / cathode having an anode / thickness of 2 nm or less
[193] x) anode / light emitting layer / electron transporting layer / insulation layer / cathode having a thickness of 2 nm or less
[194] y) Insulation layer / light emitting layer / electron transport layer / thickness of 2 nm or less anode / thickness / insulation layer / cathode of 2 nm or less
[195] z) Insulation layer / hole transport layer / light emitting layer / electron transport layer / cathode having an anode / thickness of 2 nm or less
[196] aa) anode / hole transport layer / light emitting layer / electron transport layer / insulation layer / cathode having a thickness of 2 nm or less
[197] ab) Insulation layer / hole transport layer / light emitting layer / electron transport layer / anode / thickness of 2 nm or less / insulation layer / cathode of 2 nm or less
[198] In the manufacture of polymer LEDs, when the film is formed from a solution using a polymer phosphor soluble in an organic solvent, the solution only needs to be dried after coating to remove the solvent, even mixing the charge transport material and the luminescent material. If so, the same method can be applied and can be quite useful in manufacturing. As film formation method from solution, spin coating, casting, micro gravure coating, micro gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen Coating methods, such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method, can be used.
[199] In the thickness of the light emitting layer, the optimum value differs depending on the material used, and may be appropriately selected so that the driving voltage and the luminous efficiency are optimal values, for example, 1 nm to 1 μm, preferably 2 To 500 nm, more preferably 5 to 200 nm.
[200] In the polymer LED of the present invention, a light emitting material other than the above-described polymeric fluorescent substance may also be mixed in the light emitting layer. Further, in the polymer LED of the present invention, a light emitting layer containing a light emitting material other than the above-described polymer phosphor may be laminated with a light emitting layer containing the above-described polymer phosphor.
[201] As the light emitting material, known materials can be used. In low molecular weight compounds, for example, naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof; Dyes such as polymethine dyes, xanthene dyes, coumarin dyes and cyanine dyes; Metal complexes of 8-hydroxyquinoline or derivatives thereof, aromatic amines, tetraphenylcyclopetane or derivatives thereof and tetraphenylbutadiene or derivatives thereof and the like can be used.
[202] Specifically, known compounds as described, for example, in JP-A 57-51781, 59-195393 and the like can be used.
[203] When the polymer LED of the present invention has a hole transporting layer, as the hole transporting material used, polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in the side chain or the main chain, a pyrazoline derivative, an aryl Amine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylenevinylene) or derivatives thereof, poly (2,5-thienylene Vinylene) or derivatives thereof, and the like.
[204] Specific examples of hole transport materials include JP-A 63-70257, 63-175860, 2-135359, 2-135361, 2-209988, 3-37992 and 3-152184. Includes those described in the heading.
[205] Among these, as the hole transporting material used in the hole transporting layer, polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in the side chain or the main chain, polyaniline or a derivative thereof, polythiophene or its Preferred are polymer hole transport materials such as derivatives, poly (p-phenylenevinylene) or derivatives thereof, poly (2,5-thienylenevinylene) or derivatives thereof, and polyvinylcarbazole or derivatives thereof, polysilane or More preferred are derivatives thereof and polysiloxane derivatives having aromatic amine compound groups in the side or main chain. In the case of low molecular weight hole transport materials, they are preferably dispersed in the polymeric binder in use.
[206] Polyvinylcarbazole or derivatives thereof are obtained, for example, by cationic polymerization or radical polymerization from vinyl monomers.
[207] As polysilanes or derivatives thereof, there are exemplified compounds described in Chem. Rev., 89 , 1359 (1989) and GB 2300196 publication specification and the like. In synthesis, the method described herein can be used, and the Kipping method can be used particularly suitably.
[208] As polysiloxanes or derivatives thereof, those having a low molecular weight structure of the above-described hole transporting material in the side chain or the main chain can be exemplified because the siloxane skeleton structure has poor hole transporting properties. In particular, what has an aromatic amine which has a hole transport characteristic in a side chain or a main chain is mentioned.
[209] The formation method of a hole transport layer is not restrict | limited, In the case of the low molecular weight hole transport layer, the method in which a layer is formed from the mixed solution with a polymeric binder is mentioned, for example. In the case of polymeric hole transport materials, a method is exemplified in which the layer is formed from a solution.
[210] The solvent used for forming the film from the solution is not particularly limited, provided that it can dissolve the hole transport material. As the solvent, chlorine solvents (e.g. chloroform, methylene chloride and dichloroethane, etc.), ether solvents (e.g. tetrahydrofuran, etc.), aromatic hydrocarbon solvents (e.g. toluene, xylene, etc.), ketone solvents (e.g. acetone, methyl ethyl Ketones and the like) and ester solvents such as ethyl acetate, butyl acetate, ethylcellosolve acetate, and the like.
[211] As film forming method from solution, spinning coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing from solution , Coating methods such as flexographic printing, offset printing and inkjet printing can be used.
[212] Polymeric mixed binders that do not significantly interfere with charge transport and do not strongly absorb visible light are preferably used as appropriate. Examples of such polymer binders include polycarbonate, polyacrylate, poly (methyl acrylate), poly (methyl methacrylate), polystyrene, poly (vinyl chloride), polysiloxane, and the like.
[213] As for the thickness of the hole transport layer, the optimum value differs depending on the material used, and can be appropriately selected such that the driving voltage and luminous efficiency are optimal values, at least a thickness in which no pinholes are generated is required, and the thickness is too thick. Larger is not preferable because the driving voltage of the device increases. Therefore, the thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 to 500 nm, and more preferably 5 to 200 nm.
[214] In the case where the polymer LED of the present invention has an electron transporting layer, a known compound is used as the electron transporting material, and oxadiazole derivatives, anthraquinonedimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, Anthraquinone or derivatives thereof, tetracyanoanthraquinomdimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline and And derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene or derivatives thereof, and the like.
[215] Specifically described in JP-A 63-70257, 63-175860, 2-135359, 2-135361, 2-209988, 3-37992 and 3-152184 For example,
[216] Among them, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinone or derivatives thereof, metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene or its derivatives Derivatives are preferred, 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum And polyquinoline are more preferred.
[217] The formation method of an electron carrying layer is not restrict | limited, In the case of the low molecular weight electron transport material, the vapor deposition method from a powder or the film formation method from a solution or a molten state is mentioned, for example, In the case of a polymer electron transport material, a solution or melting The film formation method from a state can be mentioned, respectively.
[218] The solvent used in forming the film from the solution is not particularly limited, provided that it can dissolve the electron transport material and / or the polymer binder. As the solvent, chlorine solvents (e.g. chloroform, methylene chloride and dichloroethane, etc.), ether solvents (e.g. tetrahydrofuran, etc.), aromatic hydrocarbon solvents (e.g. toluene, xylene, etc.), ketone solvents (e.g. acetone, methyl ethyl Ketones and the like) and ester solvents such as ethyl acetate, butyl acetate, ethylcellosolve acetate, and the like.
[219] As film forming method from solution or molten state, spin coating method, 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 printing method Coating methods, such as a method, a flexographic printing method, an offset printing method, and an inkjet printing method, can be used.
[220] Preferably mixed polymeric binders which do not significantly interfere with the charge transport properties and which do not strongly absorb visible light are suitably used. Such polymeric binders include poly (N-vinylcarbazole), polyaniline or derivatives thereof, polythiophene or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, poly (2,5-thienylene vinylene) Or derivatives thereof, polycarbonate, polyacrylate, poly (methyl acrylate), poly (methyl methacrylate), polystyrene, poly (vinyl chloride), polysiloxane, and the like.
[221] As for the thickness of the electron transporting layer, the optimum value differs depending on the material used, and can be appropriately selected such that the driving voltage and luminous efficiency are optimal values, at least a thickness in which no pinholes are generated is required, and the thickness is too thick. Larger is not preferable because the driving voltage of the device increases. Therefore, the thickness of the electron transporting layer is, for example, 1 nm to 1 m, preferably 2 to 500 nm, and more preferably 5 to 200 nm.
[222] The substrate forming the polymer LED of the present invention may preferably be one that does not change when forming the electrode and the organic material layer, and examples thereof include glass, plastic, polymer film, and silicon substrate. In the case of an opaque substrate, the counter electrode is preferably transparent or translucent.
[223] In the present invention, it is preferable that the anode is transparent or semitransparent, and as the material of such an anode, an electron conductive metal oxide film, a semitransparent metal thin film, and the like are used. Specifically, a film (NESA, etc.) manufactured using an electronic conductive glass composed of indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO) and indium zinc oxide, which are metal oxide complexes, is used. , Gold, platinum, silver, copper and the like are used, and among these, ITO, indium zinc oxide and tin oxide are preferable. As the manufacturing method, a vacuum vapor deposition method, sputtering method, ion plating method, plating method and the like are used. As the anode, organic transparent conductive films such as polyaniline or derivatives thereof and polythiophene or derivatives thereof and the like can also be used.
[224] The thickness of the anode can be appropriately selected in consideration of light transmittance and conductivity, and is, for example, 10 nm to 10 m, preferably 20 nm to 1 m, and more preferably 50 to 500 nm.
[225] In addition, for easy charge injection, a layer including a phthalocyanine derivative conductive polymer and carbon or the like or a layer having an average film thickness of 2 nm or less including a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided on the anode. .
[226] As the cathode material used in the polymer LED of the present invention, one having a low function of 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 and ytterbium, or Alloys comprising two or more thereof, one or more of them and an alloy comprising one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin, graphite or graphite intercalation compounds, and the like. Used. Examples of alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys and calcium-aluminum alloys. The cathode may be formed of a laminated structure of two or more layers.
[227] The thickness of the cathode can be appropriately selected in consideration of light transmittance and conductivity, and is, for example, 10 nm to 10 m, preferably 20 nm to 1 m, and more preferably 50 to 500 nm.
[228] As the method for producing the cathode, a vacuum vapor deposition method, a sputtering method, a lamination method in which a metal thin film is adhered under heat and pressure, and the like are used. In addition, between the cathode and the organic layer, a layer containing a conductive polymer or a layer containing a metal oxide, a metal fluoride, an organic insulating material, and the like and having an average film thickness of 2 nm or less can also be provided, A protective layer protecting the polymer LED may also be provided. For stable use of polymer LEDs for long periods of time, it is desirable to provide a protective layer and / or protective cover to protect the device to prevent external damage.
[229] As the protective layer, a high molecular compound, a metal oxide, a metal fluoride and a metal borate can be used. As the protective cover, a glass plate and a plastic plate having a low-water-permeation surface can be used, and a method of attaching the cover to the element substrate by thermosetting resin or photocurable resin for sealing is suitably used. . In the case where the space is maintained using the spacer, it is easy to prevent the element from being damaged. When the internal gases (e.g. nitrogen and argon) are sealed in this space, it is possible to prevent oxidation of the cathode and also to place moisture (e.g. barium oxide, etc.) in the above-described spaces, It is easy to suppress the damage of the device. Of these, one or more methods are preferably adopted.
[230] In order to emit light in a planar shape using the polymer LED of the present invention, the planar anode and cathode may be appropriately arranged so that they are stacked on each other. Also, in order to emit light in the form of a pattern, a method of placing a mask with a window in the form of a pattern on the above-described planar light emitting element, a method of forming an organic layer of the non-light emitting portion to obtain a substantially large thickness which provides substantially non-light emission. And a positive electrode or a negative electrode, or a method of forming both of them in a pattern. By forming a pattern by any of these methods and arranging some electrodes so that independent on / off is possible, a display apparatus in the form of segments capable of displaying numbers, letters, simple marks, and the like is obtained. In addition, to form a dot matrix device, it may be useful to make the anode and cathode in the form of strips and to arrange them so that they cross at right angles. Area color display and multi-color display are obtained by a method of separately disposing various kinds of polymer phosphors emitting light in different colors or by using a color filter or a luminescence conversion filter. The dot matrix display can be driven by passive driving or by active driving combined with TFT or the like. These display devices can be used as a display of a computer, a television, a portable terminal, a portable telephone, a car cover, and a finder of a video camera.
[231] In addition, the above-described flat light emitting element is a thin layer of self-light emitting element, and can be suitably used as a flat light source for back light of a liquid crystal display or as a flat light source for illumination. In addition, if a flexible plate is used, it can be used as a curved light source or a display.
[232] Example
[233] The following examples further illustrate the invention but do not limit the scope thereof.
[234] Here, in weight average molecular weight and number average molecular weight, polystyrene conversion average molecular weight is obtained by gel permeation chromatography (GPC) using chloroform as a solvent.
[235] Example 1
[236] <Synthesis of Polymer Phosphor 1>
[237] 0.62 g (1.13 mmol) of 1,4-dibromo-2,5-di (3,7-dimethyloctyloxy) benzene, N, N'-diphenyl-N, N'-di (3-methyl-4 0.25 g (0.37 mmol) of bromophenyl) benzidine and 0.55 g of 2,2'-bipyridyl are added to the reaction vessel, and then the atmosphere of the reaction system is purged with argon gas. To this was added 40 ml of toluene (dehydrated solvent) degassed by bubbling argon gas in advance. Subsequently, 0.96 g of bis (1,5-cyclooctadiene) nickel (0) is added to the mixed solution, and the mixture is stirred at room temperature for 10 minutes, and then they are reacted at 60 ° C. for 7 hours. The reaction is carried out under argon gas atmosphere. After the reaction, the solution is cooled, poured into a mixed solution of 10 ml of 25% aqueous ammonia / 150 ml of methanol / 50 ml of ion-exchanged water, and then the mixture is stirred for about 1 hour. Then, the mixed solution is left to separate into two layers. The top layer is recovered and the solution is poured into methanol to reprecipitate and the resulting precipitate is recovered. This precipitate is dried and then dissolved in chloroform. The solution is filtered to remove insoluble material, then the solution is poured into methanol to reprecipitate and the resulting precipitate is recovered. This precipitate is dried under reduced pressure to give 0.22 g of a polymer. The resulting polymer is referred to as Polymeric Phosphor 1.
[238] Polymeric fluorescent substance 1 has a polystyrene reduced number average molecular weight of 1.7 × 10 ⁴ and a polystyrene reduced weight average molecular weight of 1.3 × 10 ⁵ . The structure of the polymer expected from the charged monomers is a random copolymer and the molar ratio of repeat units is described below.
[239]
[240] Example 2
[241] <Synthesis of Polymeric Phosphor 2>
[242] The polymer is obtained in the same manner as in Example 1 except that 1,4-dibromo-2,5-di (3,7-dimethyloctyloxy) benzene to N, N'-diphenyl-N, N'- The filling ratio of di (3-methyl-4-bromophenyl) benzidine is 1: 1. This polymer is referred to as polymeric fluorescent substance 2.
[243] Polymeric fluorescent substance 2 has a polystyrene reduced number average molecular weight of 1.6 x 10 ⁴ and a polystyrene reduced weight average molecular weight of 4.2 x 10 ⁴ . The structure of the polymer expected from the charged monomers is a random copolymer and the molar ratio of repeat units is described below.
[244]
[245] Example 3
[246] <Synthesis of Polymeric Phosphor 3>
[247] The polymer is obtained in the same manner as in Example 2, except that 1,4-dibromo-2,5-di (3,7-dimethyloctyloxy) benzene is added to 1,4-dibromo-2- (3, Replace with 7-dimethyloctyloxy) benzene. This polymer is referred to as polymeric fluorescent substance 3.
[248] Polymeric fluorescent substance 3 has a polystyrene reduced number average molecular weight of 1.6 × 10 ⁴ and a polystyrene reduced weight average molecular weight of 5.0 × 10 ⁴ . The structure of the polymer expected from the charged monomers is a random copolymer and the molar ratio of repeat units is described below.
[249]
[250] Example 4
[251] <Synthesis of Polymeric Phosphor 4>
[252] 0.41 g (0.75 mmol) of 1,4-dibromo-2,5-di (3,7-dimethyloctyloxy) benzene, 2,5-bis (4-bromophenyl) -1-oxa-3,4 0.285 g (0.75 mmol) of diazole and 0.55 g of 2,2'-bipyridyl are added to the reaction vessel, and then the atmosphere of the reaction system is purged with argon gas. To this was added 40 ml of tetrahydrofuran (dehydrated solvent) degassed by bubbling argon gas in advance. Subsequently, 0.96 g of bis (1,5-cyclooctadiene) nickel (0) is added to the mixed solution, and the mixture is stirred at room temperature for 10 minutes, and then they are reacted at 60 ° C. for 7 hours. The reaction is carried out under argon gas atmosphere. After the reaction, the solution is cooled, poured into a mixed solution of 10 ml of 25% aqueous ammonia / 150 ml of methanol / 50 ml of ion-exchanged water, and then the mixture is stirred for about 1 hour. Then, the mixed solution is left to separate into two layers. The top layer is recovered and the solution is poured into methanol to reprecipitate and the resulting precipitate is recovered. This precipitate is dried and then dissolved in chloroform. The solution is filtered to remove insoluble material, then the solution is poured into methanol to reprecipitate and the resulting precipitate is recovered. This precipitate is dried under reduced pressure to yield 0.19 g of a polymer. The resulting polymer is referred to as Polymeric Phosphor 4.
[253] Polymeric fluorescent substance 4 has a polystyrene reduced number average molecular weight of 1.8 × 10 ⁴ and a polystyrene reduced weight average molecular weight of 4.5 × 10 ⁴ . The structure of the polymer expected from the charged monomers is a random copolymer and the molar ratio of repeat units is described below.
[254]
[255] Example 5
[256] <Synthesis of Polymeric Phosphor 5>
[257] 0.41 g (0.75 mmol) of 1,4-dibromo-2,5-di (3,7-dimethyloctyloxy) benzene, 4,4'-dibromo-2,5-di (3,7-dimethyl 0.488 g (0.75 mmol) of octyloxy) stilbene and 0.55 g of 2,2'-bipyridyl are added to the reaction vessel, and then the atmosphere of the reaction system is purged with argon gas. To this was added 40 ml of tetrahydrofuran (dehydrated solvent) degassed by bubbling argon gas in advance. Subsequently, 0.96 g of bis (1,5-cyclooctadiene) nickel (0) was added to the mixed solution, and the mixture was stirred at room temperature for 10 minutes, and then they were reacted at 60 ° C. for 7 hours. The reaction is carried out under argon gas atmosphere. After the reaction, the solution is cooled, poured into a mixed solution of 10 ml of 25% aqueous ammonia / 150 ml of methanol / 50 ml of ion-exchanged water, and then the mixture is stirred for about 1 hour. Then, the mixed solution is left to separate into two layers. The top layer is recovered and the solution is poured into methanol to reprecipitate and the resulting precipitate is recovered. This precipitate is dried and then dissolved in chloroform. The solution is filtered to remove insoluble material, then the solution is poured into methanol to reprecipitate and the resulting precipitate is recovered. This precipitate is dried under reduced pressure to yield 0.24 g of polymer. The resulting polymer is called polymeric fluorescent substance 5.
[258] Polymeric fluorescent substance 5 has a polystyrene reduced number average molecular weight of 7.3 × 10 ⁴ and a polystyrene reduced weight average molecular weight of 2.1 × 10 ⁵ . The structure of the polymer expected from the charged monomers is a random copolymer and the molar ratio of repeat units is described below.
[259]
[260] Example 6
[261] <Synthesis of Polymeric Phosphor 6>
[262] 0.41 g (0.75 mmol) of 1,4-dibromo-2,5-di (3,7-dimethyloctyloxy) benzene, 1,4-dibromo-2- (2- (4-diphenylaminophenyl 0.379 g (0.75 mmol) of 2) ethenyl) benzene and 0.55 g of 2,2'-bipyridyl are added to the reaction vessel, and then the atmosphere of the reaction system is purged with argon gas. To this was added 40 ml of tetrahydrofuran (dehydrated solvent) degassed by bubbling argon gas in advance. Subsequently, 0.96 g of bis (1,5-cyclooctadiene) nickel (0) is added to the mixed solution, and the mixture is stirred at room temperature for 10 minutes, and then they are reacted at 60 ° C. for 7 hours. The reaction is carried out under argon gas atmosphere. After the reaction, the solution is cooled, poured into a mixed solution of 10 ml of 25% aqueous ammonia / 150 ml of methanol / 50 ml of ion-exchanged water, and then the mixture is stirred for about 1 hour. This mixed solution is then left until it is separated into two layers. The top layer is recovered and the solution is poured into methanol to reprecipitate and the resulting precipitate is recovered. This precipitate is dried and then dissolved in chloroform. The solution is filtered to remove insoluble material, then the solution is poured into methanol to reprecipitate and the resulting precipitate is recovered. This precipitate is dried under reduced pressure to yield 0.05 g of a polymer. The resulting polymer is referred to as Polymeric Phosphor 6.
[263] Polymeric fluorescent substance 6 has a polystyrene reduced number average molecular weight of 1.1 × 10 ⁵ and a polystyrene reduced weight average molecular weight of 4.6 × 10 ⁵ . The structure of the polymer expected from the charged monomers is a random copolymer and the molar ratio of repeat units is described below.
[264]
[265] Example 7
[266] <Synthesis of Polymeric Phosphor 7>
[267] 0.41 g (0.75 mmol) of 1,4-dibromo-2,5-di (3,7-dimethyloctyloxy) benzene, 2,6-dibromo-1,5-di (3,7-dimethyloctyl 0.365 g (0.75 mmol) of oxy) naphthalene and 0.55 g of 2,2'-bipyridyl are added to the reaction vessel, and then the atmosphere of the reaction system is purged with argon gas. To this was added 40 ml of tetrahydrofuran (dehydrated solvent) degassed by bubbling argon gas in advance. Subsequently, 0.96 g of bis (1,5-cyclooctadiene) nickel (0) is added to the mixed solution, and the mixture is stirred at room temperature for 10 minutes, and then they are reacted at 60 ° C. for 7 hours. The reaction is carried out under argon gas atmosphere. After the reaction, the solution is cooled, poured into a mixed solution of 10 ml of 25% aqueous ammonia / 150 ml of methanol / 50 ml of ion-exchanged water, and then the mixture is stirred for about 1 hour. Then, the mixed solution is left to separate into two layers. The top layer is recovered and the solution is poured into methanol to reprecipitate and the resulting precipitate is recovered. This precipitate is dried and then dissolved in chloroform. The solution is filtered to remove insoluble material, then the solution is poured into methanol to reprecipitate and the resulting precipitate is recovered. This precipitate is dried under reduced pressure to yield 0.12 g of polymer. The resulting polymer is referred to as Polymeric Phosphor 7.
[268] Polymeric fluorescent substance 7 has the polystyrene reduced number average molecular weight of 1.1 × 10 ⁴ , and the polystyrene reduced weight average molecular weight of 5.3 × 10 ⁴ . The structure of the polymer expected from the charged monomers is a random copolymer and the molar ratio of repeat units is described below.
[269]
[270] Example 8
[271] <Synthesis of Polymeric Phosphor 8>
[272] 1,4-dibromo-2,5-di (3,7-dimethyloctyloxy) benzene 1.65 g (3.00 mmol), 4,4'-di (trifluoromethylsulfoxy) -3,3'- 1.69 g (3.00 mmol) of diethoxytilbene and 2.2 g of 2,2'-bipyridyl are added to the reaction vessel, and then the atmosphere of the reaction system is purged with argon gas. To this was added 160 ml of tetrahydrofuran (dehydrated solvent) degassed by bubbling argon gas in advance. Subsequently, 3.84 g of bis (1,5-cyclooctadiene) nickel (0) is added to this mixed solution, and the mixture is stirred at room temperature for 10 minutes, and then they are reacted at 60 ° C. for 7 hours. The reaction is carried out under argon gas atmosphere. After the reaction, the solution is cooled, poured into a mixed solution of 40% of 25% aqueous ammonia / 600ml of methanol / 200ml of ion-exchanged water, and then the mixture is stirred for about 1 hour. Then, the mixed solution is left to separate into two layers. The top layer is recovered and the solution is poured into methanol to reprecipitate and the resulting precipitate is recovered. This precipitate is dried and then dissolved in chloroform. The solution is filtered to remove insoluble material, then the solution is poured into methanol to reprecipitate and the resulting precipitate is recovered. This precipitate is dried under reduced pressure to yield 0.14 g of polymer. The resulting polymer is referred to as Polymeric Phosphor 8.
[273] Polymeric fluorescent substance 8 has a polystyrene reduced number average molecular weight of 1.8 × 10 ⁴ and a polystyrene reduced weight average molecular weight of 1.0 × 10 ⁵ . The structure of the polymer expected from the charged monomers is a random copolymer and the molar ratio of repeat units is described below.
[274]
[275] Example 9
[276] <Synthesis of Polymeric Phosphor 9>
[277] Under argon atmosphere, 1,4-bis (propylene boronate) -2,5-di (3,7-dimethyloctyloxy) (321 mg, 0.575 mmol), 4,7-dibromo-benzothiadiazole ( 161 mg, 0.547 mmol) and aliquat ^R 336 (Aldrich, 221 mg, 0.547 mmol) are dissolved in toluene (30 mL), and 30 mL of an aqueous solution of potassium carbonate (238 mg, 1.73 mmol) is added thereto. Tetrakis (triphenylphosphine) palladium (1.27 mg, 1.09 × 10 ⁻⁶ mmol) is also added and the mixture is heated at reflux for 20 hours. After cooling, the solution is separated and the organic layer is washed with water. This organic layer is added dropwise to methanol (300 ml), and the precipitate precipitate is filtered off. The precipitate is purified by silica gel chromatography (toluene) to give a polymer. The resulting polymer is then dissolved in toluene to prepare a solution. This solution and 25% aqueous ammonia are mixed in a sealed bottle and stirred at room temperature for 3 hours. After leaving to separate with toluene and water, the toluene layer is recovered. The solution is poured into methanol and stirred to filter the resulting precipitate. After washing with methanol, drying was carried out at 50 ° C. for 2 hours under reduced pressure to give 231 mg of the polymer. The resulting polymer is referred to as Polymeric Phosphor 9.
[278] The polymeric fluorescent substance 9 has a polystyrene reduced number average molecular weight of 2.6 × 10 ⁴ and a polystyrene reduced weight average molecular weight of 7.6 × 10 ⁴ . The structure of the polymer expected from the charged monomers is an alternating copolymer, and the molar ratio of the repeating units is as follows.
[279]
[280] Example 10
[281] <Evaluation of fluorescence characteristics>
[282] A 0.2 wt% solution of polymeric fluorescent substance 1 in chloroform was spin-coated on a quartz plate to prepare a thin film of polymeric fluorescent substance 1. The fluorescence spectrum of this thin film is measured using a fluorescence spectrophotometer (Hitachi Ltd .; 850). In the same manner, the fluorescence spectra of the polymeric phosphors 2 to 9 are measured.
[283] Polymeric phosphors 1 to 9 all have strong fluorescence and exhibit fluorescence peak wavelengths shown in Table 1 below.
[284] Polymer phosphorFluorescence peak wavelength (nm) Polymeric fluorescent substance 1416 Polymer Phosphor 2418 Polymeric Phosphors 3422 Polymeric Phosphors 4450 Polymeric Phosphors 5472 Polymeric Phosphors 6456 Polymeric Phosphors 7416 Polymeric Phosphors 8452 Polymeric Phosphors 9570
[285] Comparative Example 1
[286] <Synthesis of Polymeric Phosphor 10>
[287] The polymer is obtained in the same manner as in Example 5 except that 1,4-dibromo-2,5-di (3,7-dimethyloctyloxy) benzene is substituted with 2,7-dibromo-9,9-di Replace with octyl-fluorene. This polymer is referred to as polymeric fluorescent substance 10.
[288] The polymeric fluorescent substance 10 has a polystyrene reduced number average molecular weight of 1.3 × 10 ⁵ and a polystyrene reduced weight average molecular weight of 4.5 × 10 ⁵ . The structure of the polymer expected from the charged monomers is a random copolymer and the molar ratio of repeat units is as described below.
[289]
[290] Example 11
[291] <Evaluation of fluorescence characteristics>
[292] A 0.2 wt% chloroform solution of polymeric fluorescent substance 5 was spin-coated on a quartz plate to form a thin film of polymeric fluorescent substance 5. A thin film of polymeric fluorescent substance 10 is formed in the same manner. Ultraviolet absorption spectra and fluorescence spectra of these thin films are measured using an ultraviolet visible absorption spectrophotometer (Hitachi, Ltd .; UV3500) and a fluorescence spectrophotometer (Hitachi Ltd .; 850), respectively. For the calculation of fluorescence intensity, the fluorescence spectrum excited at 350 nm is used. The relative area of fluorescence intensity is obtained by dividing the area of the fluorescence spectra shown for the wave number of abscissa by the absorption of 350 nm.
[293] The relative value of the fluorescence intensity of the polymeric fluorescent substance 5 obtained in Example 5 is 8.8, and the relative value of the fluorescence intensity of the polymeric fluorescent substance 10 obtained in Comparative Example 1 is 6.0.
[294] Example 12
[295] Synthesis of Poly (9,9-dioctylfluorene)
[296] Poly (9,9-dioctylfluorene) was obtained in the same manner as in Example 5 except using only 2,7-dibromo-9,9-dioctyl-fluorene as monomer.
[297] The poly (9,9-dioctylfluorene) obtained had a polystyrene reduced number average molecular weight of 4.3 × 10 ⁴ and a polystyrene reduced weight average molecular weight of 1.1 × 10 ⁵ .
[298] <Manufacture and Evaluation of Devices>
[299] On a glass substrate having a thickness of 150 nm according to the sputtering method, a film having a thickness of 50 nm was coated with a solution of poly (ethylenedioxythiophene) / polystyrenesulfonic acid (Baytron, Bayer) by spinning coating. Form and the film is dried on a hot plate at 120 ° C. for 10 minutes. Subsequently, poly (9,9-dioctylfluorene) and polymeric fluorescent substance 1 were mixed at a weight ratio of 50:50, and spin-coated using a toluene solution prepared so that the total amount was 1.5% by weight to have a thickness of about 100 nm. Form a film. In addition, the film was dried at 80 DEG C under reduced pressure for 1 hour, and lithium fluoride was deposited at 0.4 nm as a cathode buffer layer, calcium was deposited at 25 nm as a cathode, and aluminum was deposited at 40 nm to produce a polymer LED. Manufacture. In the deposition, the degree of vacuum is 1 to 8 x 10 ^-6 Torr. Voltage was applied to the resulting device to obtain EL light emission from polymeric fluorescent substance 1. The intensity of EL light emission is approximately proportional to the current density.
[300] The luminance of this device reaches 1 mW / m 2 or more at about 3.1 V. The device exhibits a maximum EL efficiency of 0.94 mW / A and a maximum luminance of 6920 mW / m 2.
[301] Example 13
[302] <Manufacture and Evaluation of Devices>
[303] Polymer LEDs were prepared in the same manner as in Example 12 except that instead of using poly (9,9-dioctylfluorene) and polymeric fluorescent substance 1, poly (9,9-dioctylfluorene), polymeric fluorescent substance 10 and The polymeric fluorescent substance 5 is mixed and used by the weight ratio of 63:27:10. Voltage was applied to the resulting device to obtain EL luminescence from polymeric phosphor 3. The intensity of EL light emission is approximately proportional to the current density.
[304] The luminance of this device reaches 1 mW / m 2 or more at about 4.2 V. The device has a maximum EL efficiency of 1.71 mW / A and a maximum luminance of 6087 mW / m 2.
[305] Example 14
[306] <Synthesis of poly (9,9-diisoamylfluorene-co-9,9-dioctylfluorene>
[307] Poly (9,9-diisoamylfluorene-co-9,9-dioctylfluorene was prepared in the same manner as in Example 5 except that as monomer, 2,7-dibromo-9,9-di Isoamyl-fluorene and 2,7-dibromo-9,9-dioctyl-fluorene are used in a molar ratio of 1: 1.
[308] The poly (9,9-diisoamylfluorene-co-9,9-dioctylfluorene) obtained had a polystyrene reduced number average molecular weight of 1.7 × 10 ⁵ and a polystyrene reduced weight average molecular weight of 6.5 × 10 ⁵ .
[309] <Manufacture and Evaluation of Devices>
[310] Polymer LEDs were prepared in the same manner as in Example 12 except that instead of the use of poly (9,9-dioctylfluorene) and polymeric phosphor 1, poly (9,9-diisoamylfluorene-co-9, 9-dioctylfluorene), polymeric fluorescent substance 2 and polymeric fluorescent substance 8 are mixed and used at a weight ratio of 63:27:10. Voltage was applied to the resulting device to obtain EL luminescence from polymeric phosphor 8. The intensity of EL light emission is approximately proportional to the current density.
[311] The luminance of this device reaches 1 mW / m 2 or more at about 3.9 V. The device has a maximum EL efficiency of 0.93 mW / A and a maximum luminance of 6234 mW / m 2.
[312] Comparative Example 2
[313] <Manufacture and Evaluation of Devices>
[314] Polymer LEDs were prepared in the same manner as in Example 12 except that only poly (9,9-dioctylfluorene) was used instead of poly (9,9-dioctylfluorene) and polymeric fluorescent substance 1. Voltage is applied to the resulting device to obtain EL luminescence from poly (9,9-dioctylfluorene). The intensity of EL light emission is approximately proportional to the current density.
[315] The luminance of this device reaches 1 GHz / m 2 or more at about 4.6 V. The device has a maximum EL efficiency of 0.09 mW / A and a maximum luminance of 749 mW / m 2.
[316] The polymeric fluorescent substance of the present invention exhibits strong fluorescence and / or excellent charge transport properties, and can be suitably used as a light emitting material and / or charge transport material for polymer LEDs. The polymeric fluorescent substance of the present invention can also be used as a dye for lasers, materials for organic solar cells, organic semiconductors for organic transistors, and materials for conductive thin film. In addition, polymer LEDs obtained using such polymeric phosphors exhibit lower voltage and higher electroluminescence efficiency. Therefore, the polymer LED can be suitably applied as a back light of a liquid crystal display device or as a display device such as a curved or flat light source for illumination and a flat panel display of a segment type or dot matrix.

权利要求:
Claims (19)
[1" claim-type="Currently amended] Exhibits fluorescence in the solid state, has a polystyrene reduced number average molecular weight of 10 ³ to 10 ⁸ , contains at least one repeating unit of formula (1) and at least one repeating unit of formula (2), and the total amount of repeating units of formula (1) And 10 mol% to 90 mol% based on the total amount of the repeat units of 2.
Formula 1

Formula 2
-Ar _1-
In Chemical Formulas 1 and 2,
R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a substituent, at least one of R ₁ , R ₂ , R ₃ and R ₄ is an alkoxy group, an aryl group substituted by an alkoxy group, aryl A group selected from an oxy group and an arylalkoxy group,
Ar ₁ represents a group different from that of Formula 1, substituted phenylene groups (having one or more substituents other than alkoxy groups, aryl groups substituted by alkoxy groups, aryloxy groups and arylalkoxy groups), substituted stilbenes Groups (having at least one group selected from an alkoxy group, an aryl group substituted by an alkoxy group, an aryloxy group and an arylalkoxy group in the benzene ring), a distilbene group, a condensed polycyclic aromatic compound group, a condensed poly A cyclic heterocyclic compound group, an aromatic amine compound group and a group selected from the group of formula (3):
Formula 3
-Ar ₂ -Ar ₃ -Ar _4-
(In Formula 3, Ar ₂ , Ar ₃ and Ar ₄ are different groups from those of Formula 1, and each independently represent an arylene group or a divalent heterocyclic compound group).
[2" claim-type="Currently amended] The polymeric fluorescent substance of claim 1, wherein the repeating unit of Formula 1 is selected from repeating units of Formulas 4 and 5.
Formula 4

Formula 5

In Chemical Formulas 4 and 5,
R ₅ represents a group selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms and a monovalent heterocyclic compound group having 4 to 60 carbon atoms,
n represents an integer of 1 to 4, when n is 2 or more, a plurality of OR ₅ may be the same or different,
R ₆ and R ₇ are each independently selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms and a monovalent heterocyclic compound group having 4 to 60 carbon atoms. Represents a group,
l represents an integer of 1 to 5,
m represents an integer of 1 to 3, and when l is 2 or more, the number of OR ₆ may be the same or different, and when m is 2 or more, the number of OR ₇ may be the same or different.
[3" claim-type="Currently amended] The polymeric fluorescent substance of claim 1 or 2, wherein the repeating unit of formula (2) is selected from repeating units of formula (6).
Formula 6

In Chemical Formula 6,
R ₈ , R ₉ and R ₁₀ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, or 1 to 20 carbon atoms. 40 alkylamino groups, aryl groups of 6 to 60 carbon atoms, aryloxy groups of 6 to 60 carbon atoms, arylsilyl groups of 6 to 60 carbon atoms, arylamino groups of 6 to 60 carbon atoms, arylalkyl groups of 7 to 60 carbon atoms, Arylalkoxy group having 7 to 60 carbon atoms, arylalkylsilyl group having 7 to 60 carbon atoms, arylalkylamino group having 7 to 60 carbon atoms, arylalkenyl group having 8 to 60 carbon atoms, arylalkynyl group having 8 to 60 carbon atoms A monovalent heterocyclic compound group of 4 to 60 and a group selected from cyano group,
i and j each independently represent an integer of 0 to 4,
k represents an integer of 0 to 5,
h represents an integer of 1 or 2, and when i is 2 or more, a plurality of R ₈ may be the same or different; when j is 2 or more, a plurality of R ₉ may be the same or different, and k is 2 or more; If multiple R ₁₀ may be the same or different,
R ₈ to R ₁₀ may be bonded to form a ring, and when R ₈ to R ₁₀ are a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a hetero atom. It may be substituted by a group containing.
[4" claim-type="Currently amended] The polymeric fluorescent substance of claim 1 or 2, wherein the repeating unit of formula (2) is selected from repeating units of formula (7).
Formula 7

In Chemical Formula 7,
R ₁₁ and R ₁₂ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, and an alkyl having 1 to 40 carbon atoms. Amino group, aryl group of 6 to 60 carbon atoms, aryloxy group of 6 to 60 carbon atoms, arylsilyl group of 6 to 60 carbon atoms, arylamino group of 6 to 60 carbon atoms, arylalkyl group of 7 to 60 carbon atoms, 7 to 6 carbon atoms Arylalkoxy group of 60, arylalkylsilyl group of 7 to 60 carbon atoms, arylalkylamino group of 7 to 60 carbon atoms, arylalkenyl group of 8 to 60 carbon atoms, arylalkynyl group of 8 to 60 carbon atoms, 4 to 60 carbon atoms Represents a group selected from a monovalent heterocyclic compound group and a cyano group,
a and b each independently represent an integer of 0 to 3, and when a is 2 or more, a plurality of R ₁₁ may be the same or different, and when b is 2 or more, a plurality of R ₁₂ may be identical or different. There is,
R ₁₁ and R ₁₂ may be bonded to form a ring, and when R ₁₁ and R ₁₂ are a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a hetero atom. It may be substituted by a group containing.
[5" claim-type="Currently amended] The polymeric fluorescent substance of claim 1 or 2, wherein the repeating unit of formula (2) is selected from repeating units of formula (8).
Formula 8

In Chemical Formula 8,
R ₁₃ and R ₁₆ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, and an alkyl having 1 to 40 carbon atoms. Amino group, aryl group of 6 to 60 carbon atoms, aryloxy group of 6 to 60 carbon atoms, arylsilyl group of 6 to 60 carbon atoms, arylamino group of 6 to 60 carbon atoms, arylalkyl group of 7 to 60 carbon atoms, 7 to 6 carbon atoms Arylalkoxy group of 60, arylalkylsilyl group of 7 to 60 carbon atoms, arylalkylamino group of 7 to 60 carbon atoms, arylalkenyl group of 8 to 60 carbon atoms, arylalkynyl group of 8 to 60 carbon atoms, 4 to 60 carbon atoms Represents a group selected from a monovalent heterocyclic compound group and a cyano group,
c and d each independently represent an integer of 0 to 4, and when c is 2 or more, a plurality of R ₁₃ may be the same or different, and when d is 2 or more, a plurality of R ₁₆ may be the same or different. There is,
One or two substituents of the benzene ring is a group selected from the group consisting of an alkoxy group, an aryl group substituted by an alkoxy group, an aryloxy group and an arylalkoxy group,
R ₁₄ and R ₁₅ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, or a monovalent heterocyclic compound group having 4 to 60 carbon atoms. And a cyano group,
R ₁₃ to R ₁₆ may be bonded to form a ring, and when R ₁₃ to R ₁₆ are a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a hetero atom. It may be substituted by a group containing.
[6" claim-type="Currently amended] The polymeric fluorescent substance of claim 1 or 2, wherein the repeating unit of formula (2) is selected from repeating units of formula (9).
Formula 9

In Chemical Formula 9,
R ₁₇ and R ₂₀ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, and an alkyl having 1 to 40 carbon atoms. Amino group, aryl group of 6 to 60 carbon atoms, aryloxy group of 6 to 60 carbon atoms, arylsilyl group of 6 to 60 carbon atoms, arylamino group of 6 to 60 carbon atoms, arylalkyl group of 7 to 60 carbon atoms, 7 to 6 carbon atoms Arylalkoxy group of 60, arylalkylsilyl group of 7 to 60 carbon atoms, arylalkylamino group of 7 to 60 carbon atoms, arylalkenyl group of 8 to 60 carbon atoms, arylalkynyl group of 8 to 60 carbon atoms, 4 to 60 carbon atoms Represents a group selected from a monovalent heterocyclic compound group and a cyano group,
e represents an integer of 0 to 5,
f represents an integer of 0 to 3, when e is 2 or more, a plurality of R ₁₇ may be the same or different, and if f is 2 or more, a plurality of R ₂₀ may be the same or different,
R ₁₈ and R ₁₉ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, or a monovalent heterocyclic compound group having 4 to 60 carbon atoms. And a cyano group,
R ₁₇ to R ₂₀ may be bonded to form a ring, and when R ₁₇ to R ₂₀ are a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a hetero atom. It may be substituted by a group containing.
[7" claim-type="Currently amended] The polymeric fluorescent substance of claim 1 or 2, wherein the repeating unit of formula (2) is selected from repeating units of formula (10).
Formula 10

In Chemical Formula 10,
R ₂₁ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, or 6 to 60 carbon atoms. Aryl group, aryloxy group having 6 to 60 carbon atoms, arylsilyl group having 6 to 60 carbon atoms, arylamino group having 6 to 60 carbon atoms, arylalkyl group having 7 to 60 carbon atoms, arylalkoxy group having 7 to 60 carbon atoms, carbon atom Arylalkylsilyl group having 7 to 60, arylalkylamino group having 7 to 60 carbon atoms, arylalkenyl group having 8 to 60 carbon atoms, arylalkynyl group having 8 to 60 carbon atoms, monovalent heterocyclic compound having 4 to 60 carbon atoms Group selected from the group and cyano group,
g represents an integer of 0 to 2, and if g is 2, a plurality of R ₂₁ may be the same or different,
A plurality of R ₂₁ may be bonded to form a ring, and when R ₂₁ is a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a group containing a hetero atom. May be substituted by
X ₁ is selected from O and S.
[8" claim-type="Currently amended] The polymeric fluorescent substance of claim 1 or 2, wherein the repeating unit of formula (2) is selected from repeating units of formula (11).
Formula 11

In Chemical Formula 11,
R ₂₂ and R ₂₃ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, and an alkyl having 1 to 40 carbon atoms. Amino group, aryl group of 6 to 60 carbon atoms, aryloxy group of 6 to 60 carbon atoms, arylsilyl group of 6 to 60 carbon atoms, arylamino group of 6 to 60 carbon atoms, arylalkyl group of 7 to 60 carbon atoms, 7 to 6 carbon atoms Arylalkoxy group of 60, arylalkylsilyl group of 7 to 60 carbon atoms, arylalkylamino group of 7 to 60 carbon atoms, arylalkenyl group of 8 to 60 carbon atoms, arylalkynyl group of 8 to 60 carbon atoms, 4 to 60 carbon atoms Represents a group selected from a monovalent heterocyclic compound group and a cyano group,
o and p each independently represent an integer of 0 to 4, when o is 2, a plurality of R ₂₂ may be the same or different, and if p is 2, a plurality of R ₂₃ may be the same or different,
R ₂₂ and R ₂₃ may be bonded to form a ring, and when R ₂₂ and R ₂₃ are a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a hetero atom. May be substituted by a group containing
X ₂ represents a group selected from O, S, NR ₂₄ and SiR ₂₅ R ₂₆ ,
X ₃ and X ₄ each independently represent a group selected from N and CR ₂₇ ,
R ₂₄ to R ₂₇ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms and a monovalent heterocyclic compound group having 4 to 60 carbon atoms. Group selected from.
[9" claim-type="Currently amended] The polymeric fluorescent substance of claim 1 or 2, wherein the repeating unit of formula (2) is selected from repeating units of formula (12).
Formula 12

In Chemical Formula 12,
Ar ₅ represents an arylene group or a divalent heterocyclic compound group,
R ₂₄ and R ₂₉ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 60 carbon atoms, and an alkyl having 1 to 40 carbon atoms. Amino group, aryl group of 6 to 60 carbon atoms, aryloxy group of 6 to 60 carbon atoms, arylsilyl group of 6 to 60 carbon atoms, arylamino group of 6 to 60 carbon atoms, arylalkyl group of 7 to 60 carbon atoms, 7 to 6 carbon atoms Arylalkoxy group of 60, arylalkylsilyl group of 7 to 60 carbon atoms, arylalkylamino group of 7 to 60 carbon atoms, arylalkenyl group of 8 to 60 carbon atoms, arylalkynyl group of 8 to 60 carbon atoms, 4 to 60 carbon atoms Represents a group selected from a monovalent heterocyclic compound group and a cyano group,
q and r each independently represent an integer of 0 to 4, and if q is 2 or more, a plurality of R ₂₄ may be the same or different, and if r is 2 or more, a plurality of R ₂₉ may be the same or different. There is,
R ₂₅ to R ₂₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, or a monovalent heterocyclic compound group having 4 to 60 carbon atoms. And a cyano group,
R ₂₄ to R ₂₉ may be bonded to form a ring, and when R ₂₄ to R ₂₉ are a group containing an alkyl chain, at least one methyl group, methylene group and methine group constituting the alkyl chain may be a hetero atom. It may be substituted by a group containing.
[10" claim-type="Currently amended] A polymer light emitting device comprising at least one light emitting layer comprising a pair of electrodes composed of one or more transparent or translucent anodes and cathodes and the polymer phosphor according to any one of claims 1 to 9.
[11" claim-type="Currently amended] The polymer light emitting device of claim 10, wherein the layer including the conductive polymer is at least positioned between the one electrode and the light emitting layer so as to be adjacent to the electrode.
[12" claim-type="Currently amended] The polymer light emitting device according to claim 10, wherein an insulating layer having a thickness of 2 nm or less is at least positioned between one electrode and the light emitting layer so as to be adjacent to the electrode.
[13" claim-type="Currently amended] The polymer light emitting device according to any one of claims 10 to 12, wherein the layer including the electron transport compound is positioned between the cathode and the light emitting layer so as to be adjacent to the light emitting layer.
[14" claim-type="Currently amended] The polymer light emitting device according to any one of claims 10 to 12, wherein the layer including the hole transport compound is positioned between the anode and the light emitting layer so as to be adjacent to the light emitting layer.
[15" claim-type="Currently amended] The method according to any one of claims 10 to 12, wherein the layer containing the electron transport compound is positioned between the cathode and the light emitting layer so as to be adjacent to the light emitting layer, and between the anode and the light emitting layer such that the layer containing the hole transport compound is adjacent to the light emitting layer. Located polymer light emitting device.
[16" claim-type="Currently amended] A planar light source comprising the polymer light emitting device according to any one of claims 10 to 15.
[17" claim-type="Currently amended] Segment display comprising the polymer light emitting device according to any one of claims 10 to 15.
[18" claim-type="Currently amended] A dot matrix display comprising the polymer light emitting device according to any one of claims 10 to 15.
[19" claim-type="Currently amended] A liquid crystal display comprising the polymer light emitting device according to any one of claims 10 to 15 as back light.

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DE60237259D1|2010-09-23|

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SG121712A1|2006-05-26|

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EP2264124A1|2010-12-22|

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EP2221353A3|2010-09-15|

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EP1253180A2|2002-10-30|

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TW541855B|2003-07-11|

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KR101000728B1|2010-12-14|

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EP2221353A2|2010-08-25|

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KR101031992B1|2011-05-02|

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EP1253180B1|2010-08-11|

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SG147309A1|2008-11-28|

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EP2221354A2|2010-08-25|

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EP1253180A3|2003-01-22|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2001-04-27|Priority to JPJP-P-2001-00132423

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2001-04-27|Priority to JP2001132423

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2002-04-26|Application filed by 스미또모 가가꾸 고교 가부시끼가이샤

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2002-11-02|Publication of KR20020083494A

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2010-12-14|Application granted

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2010-12-14|Publication of KR101000728B1

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-2001-00132423|2001-04-27|

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JP2001132423|2001-04-27|