JP2000239360A - Polyphenyleneethynylene having dendoron side chain, resin composition containing the same, luminescent coating, and luminescent sheet-like molded material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polyphenyleneethynylene formed by bonding polyphenyleneethynylene with a dendron through a forcal point, having both properties of a luminous power-enhancing function belonging to the dendoron side chain and excellent solvent-dissolvable and film-forming properties belonging to the polyphenyleneethynylene, and useful as a luminescent material. SOLUTION: This polyphenyleneethynylene compound is obtained by bonding polyphenyleneethynylene with a dendron having repeating units including aromatic rings through forcal points. The polyphenyleneethynylene preferably has a chemical structure expressed by formula I (L is a dendron). The dendron preferably has a polybenzyl ether structure, wherein the polybenzyl ether structure preferably comprises 3,5-dioxybenzyl groups of formula II as repeating units. The polyphenyleneethynylene comprises any of phenyleneetynylene units expressed by formulae III, IV and V (R1, R2, R3 and R4 are each H, methyl or the like).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyphenyleneethynylene having a dendron side chain, a resin composition containing the same, a luminescent paint, and a luminescent sheet-like molded product. Specifically, high luminous ability, excellent solvent solubility,
Also, the present invention relates to a novel material which is very useful as a light-emitting material that can be applied in a solution because it has excellent film-forming properties.

[0002]

2. Description of the Related Art Polyphenyleneethynylene has properties such as light absorption, light emission, and conductivity because of its long π-electron conjugated system, so that it can only be used as a light emitter or a wiring means in nanoelectronics. Rather, it is a material that is expected to exhibit unique physical properties such as liquid crystallinity due to its rigid chemical structure. For example, Devadoss, C.A.
J. et al. Am. Chem. Soc. , 118, 963
5 (1996), or Go Ikeda et al .; Polym. P
repr. , Japan, Vol. 47, No. 3, p. 403 (19
98) describes the use of optical properties of this structure.

On the other hand, dendrons sterically crowded as side chains of a π-electron conjugated system (a term used in the meaning of a molecular building part having a dendrimer structure having dendritic regular branches; for example, GR Newkome et al.) Book; D
endric Molecules, Concep
ts ・ Synthesis ・ Perspectives
(VCH Verlagsgesellschaft
mbH; Weinheim, Germany; 199
6, ISBN: 3-527-29325-6))
By introducing "Molecular wiring (Molecular
Attempts to coat wire) have been published by Schening,
A. P. H. J. Chem. Commun. , 10
13 (1998). However, the π-electron conjugated system of the substance reported here has a polyethynylene structure, the number of repeating units is as small as 5 at most, and it cannot be said that the material has excellent coating properties. Further, the effect of enhancing the light emission by the aromatic dendron used was not known.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a luminescent material which has high luminous ability, excellent solvent solubility, and excellent film-forming properties, and which can be applied in a solution. An object of the present invention is to provide a paint and a luminescent sheet-like molded product.

[0005]

The present inventors have conducted intensive studies to achieve the above object, and as a result, a novel material comprising a dendron side chain and polyphenylene ethynylene has been described as having a light emitting ability of the dendron side chain. It has been found that it has both the enhancing function and the excellent solvent solubility and coating properties of polyphenyleneethynylene, and can be used extremely usefully as a luminescent material.In particular, the systematic study of the synthesis and polycondensation of bisethynyl compounds with dendrons As a result of careful studies, the present invention has been completed.

That is, the gist of the present invention resides in the following nine items. 1. A polyphenylene ethynylene having a dendron side chain, wherein a dendron having a repeating unit containing an aromatic ring is bonded to polyphenylene ethynylene at its focal point. 2. A polyphenyleneethynylene having a dendron side chain, whose chemical structure is represented by the following general formula (1) (in the formula (1), L represents a dendron which may be different from each other).

[0007]

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[0008] 3. A polyphenyleneethynylene having a dendron side chain, wherein the dendron has a polybenzyl ether structure. 4. A polyphenyleneethynylene having a dendron side chain, wherein the polybenzyl ether structure has a 3,5-dioxybenzyl group represented by the following general formula (2) as a repeating unit.

[0009]

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[0010] 5. A resin composition comprising the polyphenyleneethynylene having a dendron side chain according to any one of the above 1 to 4, and an amorphous resin. 6. A resin composition wherein the amorphous resin according to the above item 5 is any one of a styrene resin, an acrylic resin, and an aromatic polycarbonate resin. 7. 5. A luminescent coating, comprising the polyphenyleneethynylene having a dendron side chain according to any one of the above 1 to 4. 8. A luminescent coating, comprising the resin composition according to the above 5 or 6. 9. A luminescent sheet-like molded product obtained by applying and drying the luminescent paint according to the above item 7 or 8.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. <Dendron> Dendron (Dendr) in the present invention
The term “on)” is a term widely used in the research of dendrimers (dendrimer: a generic name of polymer structures having dendritic branches), which has become very popular in recent years, in the sense of molecular building parts having such structural units. Yes, for example, it is used in the compendium of Newcome et al., Supra. The starting point of the branch structure (corresponding to the pivot of the fan when the dendron is schematically considered to be a sector) is called a focal point, and the order of the branch is referred to as “generation (Gen).
eration) (see FIG. 1). The number of branches at the branch point of the dendron in the present invention is not limited, but is usually two (in the case of FIG. 1) or three, and preferably two. In the present invention, a structure having one branch point (that is, the first generation) is also regarded as a dendron.

The dendron used in the present invention needs to have an aromatic ring in the repeating unit of its chemical structure. This is because the dendron absorbs ultraviolet light or visible light to cause the polyphenyleneethynylene of the present invention to emit light more strongly. Here, the aromatic ring is, for example,
It means a hydrocarbon aromatic ring such as a benzene ring, a naphthalene ring and an anthracene ring, and a nitrogen-containing aromatic ring such as a pyridine ring and a quinoline ring. As a structural example of the dendron suitable for the present invention, specifically, aromatic polyethers such as polybenzyl ether, aromatic polyesters such as polyhydroxybenzoic acid, aromatic or semi-aromatic polyamide, aromatic polycarbonate, aromatic polycarbonate Polyester carbonate, aromatic polysulfide such as polyphenylene sulfide, aromatic polyimide including aromatic polyimide, aromatic polyamide imide and other elements other than carbon in the polymer main chain, aromatic polymer structure, polyphenylene, polyphenylene ethynylene, carbon such as polyphenylene ethylene -Aromatic conjugated polymer structures in which the main chain is composed of carbon bonds, among which aromatic polyethers such as polybenzyl ether, aromatic polyesters such as polyhydroxybenzoic acid and the like are preferable, and Aromatic polyethers such as benzyl ether More preferably ethers, structure a repeating unit of 3,5-dioxy benzyl group represented by the following general formula (2) (C.J.Hawke
R et al. Chem. Soc. Chem. Commu
n. Pp. 1010-1013 (1990)). It is to be noted that these plural kinds of structures may coexist in one dendron residue, and plural kinds of dendron residues may be bonded to one polyphenyleneethynylene chain.

[0013]

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The generation of the dendron used in the present invention is not particularly limited, but is usually 1 to 6, preferably 1 to 4 from the viewpoint of easiness of synthesis, more preferably 2 to 4 in terms of luminous effect, and most preferably 3 to 4. Or 4. The dendron used in the present invention must bind to polyphenyleneethynylene at its focal point. The bonding mode is not particularly limited, but specific bonding structures include, for example, an ether bond, an ester bond, an amide bond, a carbon-carbon bond, and a carbon-nitrogen bond. The number of dendrons bonded to the polyphenyleneethynylene main chain is not particularly limited, and varies depending on the desired light emission behavior.
The ratio of the number of dendrons to the number of phenylene rings in one repeating unit is usually 2: 1 to 1:10, preferably 2: 1 to 1: 8, and more preferably 2: 1 in terms of luminous efficiency and solvent solubility.
１ ： 1: 6, most preferably 2: 1 to 1: 4.

<Polyphenyleneethynylene> The polyphenyleneethynylene in the present invention is specifically composed of any of phenyleneethynylene units represented by the following general formulas (3) to (5). Is a polymer containing at a copolymerization ratio of However, in the general formulas (3) to (5), R ₁ , R ₂ , R ₃ and R ₄ are each independently:
Hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, ter
hydrocarbon groups having 10 or less carbon atoms such as t-butyl group, isobutyl group, hexyl group, octyl group and decyl group, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, sec- It means a structure arbitrarily selected from the group consisting of an alkoxy group having 6 or less carbon atoms such as a butyloxy group, an isobutyloxy group and a hexyloxy group, and the above-mentioned dendron.

[0016]

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[0017]

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[0018]

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A particularly preferred structure of polyphenyleneethynylene is represented by the following general formula (1):
Represents the above-mentioned dendron which may be different from each other)
Are represented.

[0020]

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In the polyphenyleneethynylene of the present invention, the number of repeating phenyleneethynylene units (degree of polymerization) represented by any of the general formulas (3) to (5) is not particularly limited. The weight average degree of polymerization is usually from 5 to 1,000, preferably from 10 to 700, more preferably from 15 to 500, and most preferably from 20 to 400, from the viewpoint of coating properties and solvent solubility. The molecular weight distribution at this time is not particularly limited, but the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC).
And the number average molecular weight (Mn) as Mw / Mn is usually 2.0 to 20, preferably 2.2 to 15, more preferably 2.3 to 13, and most preferably 2.3 to 13, from the viewpoint of coating properties and solvent solubility. Preferably, it is set to 2.3 to 10.

<Resin Composition> The present invention provides a resin composition comprising polyphenyleneethynylene and a non-crystalline resin, wherein the above-mentioned dendron is bonded as a side chain. The amorphous resin referred to here is a polymer that gives a transparent amorphous molded body in a visible region by a melt molding means generally used in the resin molding industry, and includes, for example, polystyrene, styrene / α- Styrene resins such as methyl styrene copolymer, styrene / maleic anhydride copolymer, styrene / methyl methacrylate copolymer, styrene glycidyl methacrylate copolymer, polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polyethyl acrylate Acrylic resins such as polytert-butyl methacrylate, polyphenyl methacrylate, polybenzyl methacrylate, polyadamantyl acrylate, polymethacrylic acid, polyacrylic acid, polyacrylamide, methyl methacrylate / methacrylic acid copolymer, Polycarbonate starting from 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A); polycarbonate starting from 2,2-bis (3-methyl-4-hydroxyphenyl) propane (commonly known as bisphenol C); Aromatic polycarbonate resin such as polycarbonate made from 2,2-bis (4-hydroxyphenyl) phenylethane (commonly called bisphenol P), hydrogenated polystyrene, poly (3-methylbutene-
Examples thereof include amorphous polyolefins such as 1). Among them, polystyrene, styrene / α-methylstyrene copolymer, styrene / maleic anhydride copolymer, and styrene are preferable in terms of light transmittance and molding temperature. Styrene resins such as glycidyl methacrylate copolymer, acrylic resins such as polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polyethyl acrylate, polyadamantyl acrylate, polymethacrylic acid, methyl methacrylate / methacrylic acid copolymer, and Aromatic polycarbonate resins such as bisphenol A polycarbonate, bisphenol C polycarbonate and bisphenol P polycarbonate, among which styrene resins such as polystyrene, polymethyl methacrylate, polymethyl alcohol Relate, methyl methacrylate /
Acrylic resins such as methacrylic acid copolymers and aromatic polycarbonate resins such as bisphenol A polycarbonate and bisphenol P polycarbonate are more preferred.

The method for producing such a resin composition is not particularly limited. For example, tetrahydrofuran (THF),
General-purpose means such as solution mixing in a solvent such as toluene, methylene chloride, and chloroform, or melt mixing using a single-screw extruder, a twin-screw extruder, a Brabender, a roll mixer, or the like is possible. In the resin composition of the present invention, the weight percentage of the polyphenylene ethynylene having a dendron side chain of the present invention is usually 0.1% to 95%, preferably 1% to 95% from the luminous ability of the resin composition. Preferably 3%
To 95%, more preferably 3% to 80%, most preferably 5% to 70% from the viewpoint of the mechanical strength of the resin composition. Incidentally, such a resin composition, as long as the effect is not significantly impaired, glass fiber, glass flakes, glass beads, mica, talc, montmorillonite, smectite, synthetic mica, synthetic fillers such as inorganic smectite, polyethylene, polypropylene, polyester,
Thermoplastic resins such as polyamide, rubber components such as styrene-based thermoplastic elastomers and acrylic rubber, resin beads, hollow beads, heat stabilizers, antioxidants, ultraviolet absorbers, flame retardants, plasticizers such as petrolatum and glycerin esters, Lubricant,
Arbitrary additives such as metal powder, semiconductor powder, graphite, resin powder, pigment, dye, fluorescent dye, pigment, and compatibilizer may be added.

<Light-Emitting Paint and Light-Emitting Sheet-Shaped Molded Article> The present invention provides a light-emitting paint containing the polyphenyleneethynylene having a dendron side chain of the present invention or the above resin composition of the present invention, and coating the same. Provided is a luminescent sheet-like molded product obtained by drying. Such a paint can be obtained by dissolving the polyphenyleneethynylene of the present invention or the resin composition of the present invention in a suitable solvent. The solvent used is not particularly limited as long as it has the necessary solubility. Examples thereof include tetrahydrofuran (THF), toluene, methylene chloride, chloroform and the like, as long as the effects of the present invention are not significantly impaired. The above-mentioned optional additives may be added.

In the luminescent coating of the present invention, the amount of the polyphenyleneethynylene of the present invention to be used is usually 0.1 to 80 parts by weight, preferably 1 to 80 parts by weight from the viewpoint of luminous ability, based on 100 parts by weight of the solvent used. Parts by weight, more preferably 5 to 80 parts by weight, still more preferably 5 to 60 parts by weight, and most preferably 5 to 50 parts by weight from the viewpoint of the handleability of the solution. When the resin composition of the present invention is used, the amount of the composition relative to 100 parts by weight of the solvent used is usually 1 to 70 parts by weight, preferably 5 to 70 parts by weight from the viewpoint of luminous ability, The amount is more preferably 7 to 70 parts by weight, still more preferably 7 to 60 parts by weight, most preferably 10 to 50 parts by weight from the viewpoint of handleability of the solution.

The luminescent sheet-like molded product obtained by applying and drying the luminescent coating of the present invention can be obtained as a three-dimensional structure of any shape such as a particle, a film, a film, a sheet, and the like. In particular, when it is formed as a film or a film, it has high practical value. There is no particular limitation on the method for obtaining such a molded body, and for example, a general-purpose method of applying and drying the luminescent coating material of the present invention on a substrate (optionally performing any steps such as heating and deformation if necessary). ) Can be suitably manufactured.

The substrate used is not particularly limited, but examples thereof include inorganic substances such as metals, metal oxides, ceramics, and compound semiconductors, and organic substances such as various polymers and paper. For example, an LB film can be obtained using a liquid surface such as alcohols. As a method of applying to the substrate, a general method such as a spin coating method, a dip coating method, a wetting film method, and a spray coating method can be used.

In addition to the method described above, when the polyphenyleneethynylene of the present invention or the resin composition of the present invention has thermoplasticity, a general-purpose method such as heat extrusion film formation is also possible. The thickness, size, shape, and surface properties (e.g., flat, spherical,
Attributes such as a curved surface, a concave surface, a convex surface, a porous surface, smoothness, and a thickness distribution are not particularly limited, but for example, the thickness is usually 1 to 100,000 nm, preferably 1 to 100 nm.
It is preferably about 000 nm, more preferably about 1 to 1,000 nm.

Further, optional additives such as various stabilizers such as an antioxidant, a heat stabilizer or a light stabilizer, glass fiber, glass beads, mica, talc, kaolin, clay mineral, Various fillers such as carbon fibers, carbon black, graphite, metal fibers, metal powders, antistatic agents, release agents, plasticizers, pigments and dyes, rubbers and elastomers, thermoplastic resins, etc., as required. It is also possible to mix things.

<Light Emitting Method and Principle> There is no limitation on the method of emitting light from any of the polyphenyleneethynylene, the resin composition, the luminescent paint, and the luminescent sheet-shaped molded product of the present invention. It is possible by irradiation with ultraviolet light or visible light that is absorbed by the main chain of polyphenyleneethynylene or polyphenyleneethynylene.

Although it is known that the polyphenyleneethynylene structure itself emits light, one of the natural phenomena necessary for the completion of the present invention is that the dendron itself substantially emits light by irradiation with light absorbed by the side chains of the dendron. The polyphenyleneethynylene main chain emits strong light without emitting light. This is M. Kawa et al .; Chem. Mate
r. 10, pp. 286-296 (1998), which is nothing but the discovery of the new fact that the sensitizing effect (antenna effect) of the lanthanoid cation emission of an aromatic dendron also occurs in an organic luminescent material. The present inventors have already demonstrated that by controlling the chemical structure of the dendron side chain, energy transfer from the dendron to the polyphenyleneethynylene main chain occurs with almost 100% efficiency. It is possible for the first time to control the chemical structure of such dendrons, which can achieve extremely intense light emission, which cannot be achieved by the technology for emitting light. It is pointed out that the light emission characteristics may be further improved by optimizing the molecular structure.

[0032]

EXAMPLES Specific examples of the present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist of the present invention.
The reagents and resins used in the examples were supplied from Aldrich unless otherwise noted.

[Measurement Apparatus and Conditions, etc.] (1) ¹ H-NMR GSX-270 type FT-NMR (270M) manufactured by JEOL
Hz), solvent: CDCl _3. Room temperature measurement. The standard is CDC
It was the signal of 7.28ppm of l _3. (2) Mass spectrum: Protei manufactured by Bruker
nTof type MALDI-TOF-MS was used. 9-Nitroanthracene was used as matrix material. (3) GPC: Tosoh Corporation HLC-8020 is used,
Solvent is tetrahydrofuran (THF), Inlet temperature 35 ° C, oven temperature 40 ° C, flow rate: 1mL / min 1mL /
The measurement was performed at a pressure of 76 kgf / cm ² and an absorption of 432 nm. The molecular weight was determined by a calibration curve using a plurality of types of monodisperse polystyrenes having known molecular weights. (4) Absorption spectrum: V560 absorption spectrophotometer manufactured by JASCO (using a 1 cm quartz cell). Room temperature measurement. (5) Emission spectrum: FP-777W manufactured by JASCO
Fluorometer (using 1 cm quartz cell). Room temperature measurement.

1. Synthesis of dendrons Jiang, D .; -L. J. et al. Am. Chem. So
c. , 120, 10895, according to the method described in
A dendron having a 3,5-dimethoxybenzyl group, having a repeating unit of a 3,5-dioxybenzyl structure, and having a benzyl bromide structure at a focal point was obtained (hereinafter, this dendron is referred to as [G-n] Br Abbreviated.
Here, n is a natural number and represents the number of dendron generations. However,
[Gn] corresponds to L (n-1) in the display in the document. ). The structure and purity were 3.7 p in ¹ H-NMR.
It was confirmed from the ratio of the integrated value of the signal of the methoxy group of pm to the benzyl-position proton and the fact that a signal corresponding to the theoretical molecular weight was obtained in the mass spectrum.

2. Synthesis of diethylene benzene [G-n] 2E2 bound to dendron First, chloride was added to 1,4-dihydroxy-2,5-diiodobenzene (compound 1: 1.0 equivalent in FIG. 2) while stirring. Copper (0.05 equivalent) and dichlorobis (triphenylphosphine) palladium (II) (0.05 equivalent) were sequentially added at room temperature, and the evacuation and nitrogen replacement in the vessel were repeated. Here, trimethylsilylacetylene (3.0 equivalents)
And diisopropylamine (3.0 equivalents) in that order.
After reacting at 0 ° C. for 4 hours, the mixture was diluted with toluene and filtered to remove solids. This was purified by silica gel column chromatography to obtain 1,4-dihydroxy-2,5-bis (trimethylsilylethynyl) benzene (compound 2 in FIG. 2). Then, this was stirred in methanol at room temperature for 24 hours with an excess amount of anhydrous potassium carbonate, and purified by silica gel column chromatography using methanol / methylene chloride as an eluent to give 1,4-dihydroxy-.
2,5-diethynylbenzene was obtained (compound 3 in FIG. 2). The chemical structures of these products were confirmed by ¹ H-NMR. Furthermore, a dendron [G-n] B having a benzyl bromide structure at the focal point synthesized above.
r (2.1 equivalents) and 1,4-dihydroxy-2,5-diethynylbenzene (compound 3: 1.0 equivalents in FIG. 2),
Vacuuming and replacement with nitrogen in a vessel mixed with anhydrous potassium carbonate (5.0 equivalents) were repeated, and dried N, N-
5. Add dimethylformamide (DMF) at 60 ° C.
Stir for 5 hours. The reaction solution was poured into a large excess of water while stirring, and the resulting solid was separated by filtration and purified by silica gel column chromatography to obtain the desired dendron-bound diethynylenebenzene [G-n] 2E2 (FIG. Final product in 2). The structure of this product is such that signals derived from dendron (methoxy group, benzyl position and benzene ring), ethynyl group and benzene ring to which ethynyl group are bonded were clearly observed in ¹ H-NMR. , And their integral values were confirmed. 3. Synthesis and evaluation of polyphenyleneethynylene with dendron attached to side chain

Example 1 Diethynylenebenzene [G-3] 2E2 (96.8 mg; 1.D) bound with the third-generation dendron synthesized above.
0 eq), p-diiodobenzene (15.27 mg;
1.0 equivalent), tetrakis (triphenylphosphine) palladium (0) (2.68 mg; 0.05 equivalent)
, And the vessel was repeatedly evacuated and replaced with nitrogen. Then, 3 mL of dry tetrahydrofuran (THF) was added as a solvent, and 2.75 mmol of cuprous iodide was added to 10 mL of the solvent.
A solution dissolved in 00 mL of diisopropylamine was added with stirring so as to obtain 0.05 equivalent of cuprous iodide. After stirring at 50 ° C. for 26 hours, 2 drops of ethynylbenzene were added, and the reaction was continued for another 13 hours. The reaction solution was concentrated under reduced pressure, and purified by a reprecipitation method in which a chloroform-soluble component was poured into methanol. This product was analyzed by GPC with a number average molecular weight (Mn) of 43900 and a weight average molecular weight (Mw) of 2
77600, 150,000 as peak top molecular weight
(Corresponding to about 70-mers based on the expected structure shown in FIG. 3). This product is soluble in tetrahydrofuran,
In the absorption spectrum measurement of this solution, an absorption band derived from a dendron was observed around 280 nm, and an absorption band derived from a polyphenyleneethynylene main chain was observed around 432 nm.
Then, when ultraviolet light of 280 nm was irradiated to excite the dendron structure, the emission band (31
(Near 0 nm) was not observed, and only the emission band (around 454 nm) derived from the polyphenylene ethynylene main chain was observed. Thus, it was confirmed that light was emitted by energy transfer from the dendron side chain to the polyphenylene ethynylene main chain. Was. Furthermore, a comparison of the absorption spectrum and the excitation spectrum confirmed that this energy transfer occurred at an efficiency of almost 100%. In addition, a good film was obtained by spin casting of this solution, and the same emission band as that of the above solution system was given by irradiation with ultraviolet light of 280 nm. Therefore, it was confirmed that the film of this substance also had excellent luminescence ability. Was done.

Example 2 The same operation was carried out by using [G-2] 2E2 which is a corresponding compound to which a second-generation dendron was bound instead of [G-3] 2E2 of Example 1, and the same was performed by GPC. The production of nylene was confirmed. Example 3 The same operation was performed using [G-4] 2E2 which is a corresponding compound to which a fourth-generation dendron was bound instead of [G-3] 2E2 of Example 1, and the production of pophenyleneethynylene was performed by GPC. It was confirmed. 4. Preparation and evaluation of a composition of polyphenyleneethynylene with dendron attached to the side chain and amorphous resin

Example 4 Polystyrene (weight average molecular weight: about 35,000) was added to a solution of polyphenyleneethynylene in the tetrahydrofuran having the third-generation dendron synthesized in Example 1 bonded to a side chain. The mixing ratio of the polyphenylene ethynylene and the polystyrene was 10:90 by weight. A good film was obtained by spin casting of this solution, and the same emission as the emission band described in Example 1 was given by irradiation with ultraviolet light of 280 nm. Therefore, this polystyrene resin composition film also has excellent emission ability. It was confirmed that.

Example 5 A similar film was obtained in the same manner as in Example 4 except that the mixing ratio of polyphenyleneethynylene in which the third generation dendron was bonded to the side chain and polystyrene was 80:20 by weight. The resulting polystyrene resin composition film was confirmed to have excellent luminous ability, since the same luminescence as in the luminescence band described in Example 1 was obtained by irradiation with ultraviolet light of 280 nm.

Example 6 Polymethylene methacrylate (weight average molecular weight of about 15%) was added to a tetraphenylfuran solution of polyphenyleneethynylene in which the third generation dendron synthesized in Example 1 was bonded to the side chain.
000) was added. The mixing ratio of the polyphenylene ethynylene and the polymethyl methacrylate was 10:90 by weight. A good film was obtained by spin-casting this solution, and the same emission as in the emission band described in Example 1 was given by irradiation with ultraviolet light of 280 nm. Therefore, this polymethyl methacrylate resin composition film also has excellent light emission ability. Was confirmed to have.

Example 7 The same operation as in Example 4 was carried out except that the mixing ratio of polyphenyleneethynylene in which the third-generation dendron was bonded to the side chain and polymethyl methacrylate was changed to 80:20 by weight, and the result was good. A film was obtained, and the same emission as the emission band described in Example 1 was given by irradiation with ultraviolet light of 280 nm, confirming that this polymethyl methacrylate resin composition film also has excellent light emission ability.

Example 8 Bisphenol A polycarbonate (ASTM-D1) was added to a tetrahydrofuran solution of polyphenylene ethynylene having the third-generation dendron synthesized in Example 1 bonded to a side chain.
238 standard (melt index at 300 ° C./1.2 kg load: 8-10 g / 10 min) was added. The mixing ratio of the polyphenyleneethynylene and the bisphenol A polycarbonate was 10:90 by weight. A good film was obtained by spin-casting this solution, and the same emission as the emission band described in Example 1 was given by irradiation with ultraviolet light of 280 nm. Therefore, this bisphenol A polycarbonate resin composition film also has excellent light emission ability. Was confirmed to have.

Example 9 The same operation as in Example 4 was carried out, except that the mixing ratio of polyphenyleneethynylene in which the third-generation dendron was bonded to the side chain and bisphenol A polycarbonate was changed to 80:20 by weight, the result was good. A film is obtained, 28
Irradiation with ultraviolet light of 0 nm gave the same light emission as the light emission band described in Example 1, confirming that this bisphenol A polycarbonate resin composition film also had excellent light emission ability.

[0044]

According to the present invention, polyphenyleneethynylene having a dendron having an aromatic ring in the repeating unit in the side chain, which is newly found in the present invention, has excellent solvent solubility, coating film forming property, and high luminous ability. It can be used as a luminescent paint or a luminescent sheet-like molded product obtained by applying the paint to a film or the like. Further, since it has compatibility with an amorphous resin such as a styrene-based resin, an acrylic-based resin, or an aromatic polycarbonate resin, it can be used as a composition with the resin, and such a resin composition also has the same characteristics and uses as described above. Have.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing dendrimer generations and focal points.

FIG. 2 is an explanatory diagram showing a synthesis route of polyphenyleneethynylene having a dendron of the present invention in a side chain.

FIG. 3 is a schematic diagram showing the chemical structure of the product obtained in Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 69/00 C08L 69/00 C09D 5/22 C09D 5/22 C09K 11/06 C09K 11/06 (72) Inventor Manabu Kawa 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa F-term in Yokohama Research Laboratory, Mitsubishi Chemical Corporation 4F006 AA01 AA11 AA31 AB16 AB24 AB32 AB35 AB38 AB52 BA15 CA05 4J002 AC085 BB035 BB125 BB17X BC03X BC04X BC07X BC09X BC13 BG01X BG04X BG05X BG06X BG13X BM00W BN17W BN23W CE00W CF005 CF18W CG00W CG01X CG04W CG045 CH07W CL005 CL06W CM04W CN02W FA040 FA100 FD010 FD020 FD050 FD060 FD01 CC04 CB010 FD010 FD01 FD090 FD130 FD090 FD01

Claims (9)

[Claims] 1. A polyphenylene ethynylene having a dendron side chain, wherein a dendron having a repeating unit containing an aromatic ring is bonded to polyphenylene ethynylene at its focal point. 2. The dendron side chain according to claim 1, wherein the chemical structure is represented by the following general formula (1) (in the formula (1), L represents a dendron which may be different from each other). A polyphenyleneethynylene having the formula: Embedded image 3. The polyphenylene ethynylene having a dendron side chain according to claim 1, wherein the dendron has a polybenzyl ether structure. 4. The polyphenylene ether having a dendron side chain according to claim 3, wherein the polybenzyl ether structure has a repeating unit of a 3,5-dioxybenzyl group represented by the following general formula (2). Niren. Embedded image 5. A resin composition comprising the polyphenyleneethynylene having a dendron side chain according to claim 1 and an amorphous resin. 6. The resin composition according to claim 5, wherein the amorphous resin is any one of a styrene resin, an acrylic resin, and an aromatic polycarbonate resin. 7. A luminescent coating material comprising the polyphenyleneethynylene having a dendron side chain according to claim 1. Description: 8. A luminescent coating comprising the resin composition according to claim 5 or 6. 9. A luminescent sheet-like molded product obtained by applying and drying the luminescent coating according to claim 7 or 8.