JP3443736B2 - Novel polyfluorene, aggregate of polyfluorene and membrane containing polyfluorene - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polyfluorene represented by the general formula A (wherein R is a substituent which enhances the solubilization of the produced polymer having a hydrocarbon group in a solvent), An optically active polyfluorene aggregate produced by dissolving the polyfluorene in a good solvent and adding a poor solvent, and an optically active polyfluorene obtained by dissolving the polyfluorene in the solvent and depositing it on a substrate In a thin film, especially in the general formula A, R has 6 carbon atoms.
Novel polyfluorene, which is a hydrocarbon group of the above alkyl chain, for example, n-heptyl group, 2-methyloctyl group, 3,7-dimethyloctyl group, optically active aggregate and optical activity using the same It relates to a polyfluorene thin film.

[0002]

2. Description of the Related Art Recently, polyfluorene has been attracting attention as a functional polymer material, and examples of research aimed at applications such as polymer semiconductors, polymer conductors, electrochromic materials, electroluminescent materials, and nonlinear optical materials. Has been reported. To obtain polyfluorene having the above properties, 9
A general method is to debrominate 2,7-dibromofluorene having a substituent at the position to polymerize it by using a catalyst.
However, when bromo remains at the end of polyfluorene, it lacks thermal chemical stability, and the presence of a terminal bromo group leads to a significant decrease in the quantum efficiency of light emission, resulting in a decrease in properties as an electroluminescent material. It causes inconvenience.

Recently, especially when a chiral alkyl substituent is introduced at the 9-position to form a chiral liquid crystal structure in polyfluorene, circular dichroic absorption, circular dichroic emission, and circular dichroic electroluminescence are caused by a large asymmetry factor. It has been reported to show (M. O.
da, HG.Nothofer, G. Lieser, U. Scherf, SCJ
Meskers, and D. Neher, Advanced Materials, Vol.12,
pp. 362-365 (2000)). However, in order to form a film exhibiting the above characteristics, if the polyfluorene film is deposited only once on the substrate by the spin coating method, the asymmetry factor is extremely small. Therefore, the film is heated at a high temperature of 200 ° C. or higher for 15 hours or more. Had to handle. This means that in constructing high-performance electronic and optical functional devices using polyfluorene, in terms of characteristics such as control of conductivity, conductive carrier concentration, and mobility, as well as ease of film preparation and reproducibility. Was a big problem in terms of manufacturing.

At present, magneto-optical recording (MO) of an inorganic magnetic thin film and phase transition recording (PD) of an inorganic thin film are known as optical recording materials, and a storage device (recording material) using this principle is known. It is commercially available. The optical read storage density increases inversely with the square of the laser wavelength used. Therefore, by using a short-wavelength ultraviolet solid-state laser, for example, a GaN laser device of Nichia Corporation having an oscillation wavelength of ultraviolet 370 to 430 nm, which is said to be a next-generation light source, the current DVD-RAM (63
There is a possibility of realizing a recording medium having a capacity several times larger than that of a laser light source of 5,650 nm). Further, in the future, if a material compatible with a shorter wavelength laser light source (for example, a wavelength of 185 to 215 nm that is a harmonic of a GaN laser) is realized, it will be ten times more than that of the current DVD-RAM (a laser light source of 635 and 650 nm). High-density recording becomes possible.
BACKGROUND ART In the information communication of the 21st century, the advent of an ultra-compact recording system for recording a large amount of digital information on a lightweight medium easily, at high speed, at low cost has long been desired. In the consumer electronics industry, for full-scale commercial broadcasting of digital broadcasting,
For example, it is expected that digital information recording devices such as digital video, DVD-RAM, and hard disk magnetic recording will grow rapidly in the future.

In the MO method, since a slight change in the optical Kerr rotation angle is about 0.15 ° before and after magneto-optical writing,
In order to achieve a good contrast / noise ratio, a reflecting mirror is formed on the back surface of the medium, and a reflection mirror of 0.
It is necessary to utilize the Kerr rotation angle change amplified to about 3 °. Still, since it detects a small change in rotation angle of 0.3 °, it requires a more precise and larger detection mechanism than a magnetic head. MO system read / write speed is 30
One of the reasons that it is about 3 to 5 times slower than that of magnetic recording, which is about millisecond, is that the servo track speed becomes slow because the detection head portion including the beam splitter is heavy and large. Further, it is necessary to prepare two laser light sources and two magnetic heads, which limits the miniaturization of the entire apparatus. Therefore, if a thin film material capable of optical writing, reading, and erasing, and a change in optical rotation of more than 0.3 ° before and after writing is realized, all-optical recording using optical activity will be realized. One step closer to the realization of the system, it becomes possible to downsize the recording device and to perform high-speed writing and reading similar to a hard disk.

[0006]

The first object of the present invention is to provide a novel optically active polyfluorene compound which does not contain a bromo group which causes the above-mentioned inconvenience at the terminal and thereby exhibits highly efficient light emission, and the compound. It is to provide an optically active product using. Another object of the present invention is to provide a novel polyfluorene compound which can eliminate the necessity of heat treatment in the production of an optically active film and the inconvenience of poor reproducibility. A second object of the present invention is to cope with a light source that emits near-ultraviolet light or violet / blue light (for example, corresponding to a 380 to 430 nm GaN laser device manufactured by Nichia Corporation), and external stimulus. Circular dichroic absorption, circular dichroic emission, circular dichroic electroluminescence change significantly in response to
It is to construct a high-performance optically active polymer optical / electronic functional device. Polyfluorene is known as a polymer having an absorption wavelength in the range of 350 to 410 nm and an emission wavelength in the range of 420 to 500 nm, stable to light, heat and redox reagents, and easy to form a thin film. Therefore, using polyfluorene having such characteristics, a transparent thin film having a function of causing a sign change of optical activity and a large signal intensity change by the optical means, and a smooth thin film without scattering can be obtained. To find out what forms.

[0007]

The first aspect of the present invention is polyfluorene containing no bromine represented by the general formula A, preferably R in the general formula A has 1 or more carbon atoms. Up to 22 straight-chain alkyl hydrocarbon groups, or alkyl hydrocarbon groups having 1 to 22 carbon atoms and containing a branched alkyl structure (provided that the branching position is from the 1 to 17th carbon atom from the fluorene ring). In at least one position and a maximum of 10 positions), in particular, a hydrocarbon group of an alkyl chain having 6 or more carbon atoms in R, for example, n-heptyl group, 2-methyloctyl group, 3,7-dimethyloctyl group. The above-mentioned novel polyfluorene is characterized in that

The second aspect of the present invention is an optically active polyfluorene aggregate produced by dissolving the polyfluorene represented by the general formula A in a good solvent and adding a poor solvent, preferably the general formula In A, R has 1 carbon atom
Or more and up to 22 straight-chain alkyl hydrocarbon groups, or alkyl hydrocarbon groups having 1 to 22 carbon atoms and containing a branched alkyl structure (provided that the branching position is from the fluorene ring to the 1 to 17th carbon atom). At least one of which is at most 10), and particularly R is a hydrocarbon group of an alkyl chain having 6 or more carbon atoms, for example, n-heptyl group, 2-methyloctyl group, 3,7-dimethyl. The optically active polyfluorene aggregate is characterized by using polyfluorene which is an octyl group.

The third aspect of the present invention is an optically active polyfluorene thin film obtained by dissolving the polyfluorene represented by the general formula A in a solvent and depositing it on a substrate, preferably the general formula A In, R is a linear alkyl hydrocarbon group having 1 to 22 carbon atoms, or
An alkyl hydrocarbon group having 1 to 22 carbon atoms and containing a branched alkyl structure (provided that the branching position is at least one of carbon atoms 1 to 17 from the fluorene ring).
The maximum number is 10 and the number of carbon atoms in R is 6
The optically active poly characterized by using the novel polyfluorene which is a hydrocarbon group of the above alkyl chain, for example, n-heptyl group, 2-methyloctyl group, 3,7-dimethyloctyl group. It is a fluorene thin film.

A third aspect of the present invention is that, in the general formula A, R is a straight-chain alkyl hydrocarbon group having 1 to 22 carbon atoms or a branched alkyl structure having 1 to 22 carbon atoms. An alkyl hydrocarbon group containing (provided that the branching position is at least 10 at at least one of the 1 to 17th carbon atoms from the fluorene ring), especially carbonization of the alkyl chain having 6 or more carbon atoms in R. A new thin film obtained by dissolving a novel polyfluorene, which is a hydrogen group such as n-heptyl group, 2-methyloctyl group, or 3,7-dimethyloctyl group, in a solvent and depositing it on a substrate is heated to a high temperature. And the sign and intensity of the optically active signal are modulated by the cooling rate, that is, by raising the temperature to a high temperature and cooling at a high speed or a low speed, characteristics such as a circular dichroic signal and optical rotation are reversed. And an optically active polyfluorene thin film characterized by being recorded / or by modulating the signal strength.

A fourth aspect of the present invention is a thin film obtained by dissolving polyfluorene in which R in the 9-position substituent in the general formula A has an achiral alkyl substituent in a solvent and depositing it on a substrate. R of the 9-position substituent has a chiral alkyl substituent, polyfluorene is dissolved in a solvent,
The multilayer thin film obtained by stacking the thin film obtained by depositing on the substrate is once heated to a high temperature, and the sign and / or intensity of the optically active signal is modulated by the cooling rate, that is, the multilayer thin film is once made. Optically active polyfluorene thin film characterized in that characteristics such as circular dichroic signal and optical rotation are inverted and / or modulated by recording the signal intensity by raising to high temperature and cooling at high speed or low speed. , R is a linear alkyl hydrocarbon group having 1 to 22 carbon atoms, or an alkyl hydrocarbon group having 1 to 22 carbon atoms and containing a branched alkyl structure (provided that the branching position is a fluorene ring. From at least one of the 1 to 17 carbon atoms, up to 10),
In particular, R is an alkyl chain hydrocarbon group having 6 or more carbon atoms, for example, n-heptyl group, 2-methyloctyl group, and 3,7-dimethyloctyl group.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail. A, Synthesis of Novel Polyfluorene Compound of the Present Invention According to reaction scheme 1, starting from 2,5-dibromofluorene as starting material, triethylbenzylammonium chloride, 50% aqueous NaOH solution, DMSO and alkyl bromide (RBr, where R is A linear alkyl hydrocarbon group having 1 to 22 carbon atoms or an alkyl hydrocarbon group containing a branched alkyl structure having 1 to 22 carbon atoms (however, the branching position is from 1 to 17 from the fluorene ring).
At most 1 in at least one of the th carbon atom
0 position), particularly R is a hydrocarbon group of an alkyl chain having 6 or more carbon atoms (selected from n-heptyl group, 2-methyloctyl group, 3,7-dimethyloctyl group) 9 , 9'-Dichiral alkyl-2,7-dibromofluorene is synthesized.

[0013]

[Chemical 2]

Then, 9,9'-dichiral alkyl-
2,7-dibromofluorene in the presence of 2-bromofluorene, Ni-based catalyst [Ni (cyclooctadiene)
₂ (Ni (COD) ₂ ] / 2,2′-bipyridinyl (1 /
1), cyclooctadiene, DMF / toluene (1 /
4) (reaction formula 2) or triphenylphosphine, Zn, 2,2′-bipyridinyl, NiCl ₂ , DM
Polycondensation in F (reaction formula 3) at 80 ° C. is carried out to produce the novel polyfluorene of the present invention.

[0015]

[Chemical 3]

By appropriately selecting the polymerization catalyst used here, polyfluorene having a number of n from 10 to a maximum of 100,000 can be obtained. The characteristic of these polyfluorene production methods is that 2,7-dibromofluorene is used as a starting material to synthesize 9,9′-disubstituted 2,7-dibromofluorene, which is synthesized in the presence of 2-bromofluorene. By carrying out polycondensation with a Ni-based catalyst, it is possible to obtain polyfluorene containing no bromine.

[0017]

EXAMPLES Specific examples of the polyfluorene of the present invention will be explained by the following examples, but the present invention is not limited to these examples. First, the synthesis of 9,9'-disubstituted 2,7-dibromofluorenes. (1), 2,7-dibromo-9,9-bis [(3S)-
3,7-Dimethyloctyl] fluorene (C ₃₃ H ₄₈ Br ₂
Exact Mass: 602.21, Molecular weight: 604.54 (Elemental analysis value C 6
5.56%, H 8.00%, Br 26.43%). 2,7-Dibromofluorene (4.85g, 14.97mmol) and a catalytic amount of triethylbenzylammonium chloride (0.1g) were added to DMS.
To a mixture of a solution of O (dimethyl sulfoxide) (30 mL) and a 50% aqueous NaOH solution prepared from NaOH (5 g) and water (5 mL) (3S).
-3,7-Dimethyloctyl bromide (9.93 g, 44.91
mmol) was added. The reaction mixture was stirred at room temperature for 3 days.
Excess ethyl acetate was added to the reaction mixture. Na generated
The OH precipitate was filtered off. The organic layer was washed with dilute hydrochloric acid and water, and dried over anhydrous MgSO ₄ . Residual (3S)-
180 in vacuum with 3,7-dimethyloctyl bromide
The pure product (7.95 g, 13.
15 mmol, 87.8%) was obtained by purification by silica gel chromatography using hexane for elution. [Α] _Nz ²⁵ = 5.3 degrees (neat), ¹ H NMR (300 MHz, CHCl ₃ , ppm) d 0.32-0.60,0.69 (d, ³ J
_HH = 6.3Hz, 6H, methyl), 0.81 (d, ³ J _HH = 6.6Hz, 12H, methy
l), 0.96-1.16,1.38-1.50 (m, 2H, methine), 1.82-2.02 (m,
4H, methylene), 7.43-7.53 (m, 6H, aromatic). ¹³ C NMR (75.4 MHz, CHCl ₃ , ppm) d 19.46,22.58,22.67,2
4.53,27.91,30.28,32.75,36.49,37.41,39.14,55.49,12
1.11,121.45,126.07,130.13,139.12,152.46.

2,7-dibromo-9,9-bis [(2
S) -2-Methyloctyl] fluorene 2,7-dibromofluorenone (2.0 g, 5.99 mmol) and catalytic amount of triethylbenzylammonium chloride (0.1
g) in dimethylsulfamide (DMSO) solution (12 ml) and 50% N prepared from NaOH (2 g) and water (2 ml)
(S) -2-Methoxyoctyl bromide (3.73 g, 18.0 mmol) was added to the mixture of the aOH aqueous solution. The reaction mixture was stirred at room temperature for 21 hours. Excess ethyl ether was added to the reaction mixture. The formed precipitate of NaOH was filtered off. The organic layer was washed with dilute hydrochloric acid and water, dried over anhydrous MgSO
Dried on ₄ . The residual (S) -2-methyloctyl bromide was removed by distillation at 140 ° C. in vacuum,
The pure product (13.15mmol, 87.8%) was obtained by purification by silica gel chromatography using hexanes for elution. Physical properties [α] _Nz ²⁵ = 1.5 degrees (neat), ¹ H NMR (300 MHz, CHCl ₃ , ppm) d 0.28 (d, ³ J _HH = 6.6 Hz, 6
H, methyl), 0.60-1.28 (m, 26H, methyl and methylene), 1.
77-1.84 (m, xH), 2.01-2.07 (m, xH), 7.43-7.54 (m, 6H, aroma
tic). ¹³ C NMR (75.4 MHz, CHCl ₃ , ppm) d14.10,21.67,22.66,2
6.25,28.84,29.22,31.73,38.28,47.98,55.29,121.06,12
1.14,127.20,130.14,139.16,152.56

Example 1 Next, synthesis examples of two kinds of poly (9,9'-dichiral alkylfluorene-2,7-diyl) will be shown. A. Synthesis of poly [9,9-bis [(3S) -3,7-dimethyloctyl] fluorene-2,7-dil] (1) (1,5-cyclooctadiene) nickel (0) (0.19 g,
0.69 mmol), 2,2'-dipyridyl (0.11 g, 0.69 mmol) and 1,5-cyclooctadiene (0.1 ml, 0.09 g) in anhydrous DMF (2 ml) was stirred at 60 ° C for 30 minutes, and then stirred.
Monomer 2,7-dibromo-9,9-bis [(3S)-
3,7-Dimethyloctyl] fluorene (0.20g, 0.34mmo
A solution of l) in dry toluene (8 ml) was added using a syringe under an argon atmosphere. The reaction mixture was heated to 80 ° C. and stirred at that temperature for 92 hours in the dark. A solution of 2-bromofluorene (0.19 g, 0.78 mmol) in toluene (1 ml) was added to the reaction system. The mixture was allowed to react for another 4 hours. The reaction mixture was then poured into hydrochloric acid (concentrated) / methanol / acetone (1/1/1, v / v / v, 300 ml). The isolated polymer was dissolved in chloroform and reprecipitated in ethanol. Physical properties Weight average molecular weight Mw = 293000, number average molecular weight Mn = 124400, Mw / Mn = 2.36 ¹ H NMR (300 MHz, CHCl ₃ , ppm) d 0.79 (d, ³ J _HH = 6.6Hz, m
ethyl), 0.93-2.12 (br, methylene), 7.66 (br, aromatic),
7.82 (br, aromatic). ¹³ C NMR (75.4MHz, CHCl ₃ ,, ppm) d 19.58,22.60,22.69,2
4.75,27.93,30.83,32.98,36.76,37.63,39.28,55.14,11
9.96,121.58,126.22,140.14,140.64,151.74. The polymers are hexane and tetrahydrofuran (TH
F), soluble in chloroform, ether, and toluene, but insoluble in DMF.

B. Poly [9,9-bis [(3S) -3,
Synthesis of 7-dimethyloctyl] fluorene-2,7-dil] (2) (1,5-Cyclooctadiene) nickel (0) (2.04 g, 7.4
2 mmol), 2,2'-dipyridyl (1.16 g, 7.42 mmol), and 1,5-cyclooctadiene (1.1 ml, 0.97 g) anhydrous D
The mixture of the MF (21.5 ml) solution was stirred at 60 ° C. for 30 minutes, and the monomer 2,7-dibromo-9,9-bis [(3
S) -3,7-Dimethyloctyl] fluorene (2.19 g,
A solution of 3.62 mmol) in dry toluene (86 ml) was added with a syringe under argon atmosphere. The reaction mixture was heated to 80 ° C. and stirred at that temperature for 89 hours in the dark.
2-Bromofluorene (1.9 g, 7.75 mmol) in toluene (10 m
l) The solution was added to the reaction system. The mixture was allowed to react for another 7 hours. The reaction mixture was then poured into hydrochloric acid (concentrated) / methanol / acetone (1/1/1, v / v / v, 600 ml). The isolated polymer was dissolved in chloroform and reprecipitated in ethanol. Finally, pure polymer (5.84mg, 0.36%,
Mw = 152,400, Mn = 63,200, Mw / Mn = 2.41) was centrifuged.
Pure polymer (1.05g, Mw = 179,000, Mn = 58,700, Mw / Mn = 3.0
5) could not be obtained by centrifugation, but was obtained by reprecipitation from THF solution in DMF.

Example 2 Poly [9,9-bis [(2S) -2-methyloctyl]
Fluorene-2,7-diyl] synthesis (1,5-cyclooctadiene) nickel (0) (2.04 g, 7.4
2 mmol), 2,2′-dipyridyl (1.16 g, 7.42 mmol), and a mixture of 1,5-cyclooctadiene (1.1 ml, 0.97 g) in anhydrous DMF (21.5 ml) after stirring at 60 ° C. for 30 minutes , Monomer 2,7-dibromo-9,9-bis [(2
S) -2-Methyloctyl] fluorene (2.19g, 3.62mmo
A solution of l) in dry toluene (86 ml) was added using a syringe under an argon atmosphere. The reaction mixture is heated to 80 ° C,
Then, the mixture was stirred at the temperature for 89 hours in the dark. A solution of 2-bromofluorene (1.9 g, 7.75 mmol) in toluene (10 ml) was added to the reaction system. The mixture was allowed to react for another 7 hours.
The reaction mixture was then poured into hydrochloric acid (concentrated) / methanol / acetone (1/1/1, v / v / v, 600 ml). The isolated polymer is dissolved in chloroform, reprecipitated in ethanol and then reprecipitated in methanol. Finally, pure polymer (5.84 mg, 0.37%, Mw = 153,400, Mn = 64,200,200, Mw
/Mn=2.41) was centrifuged. Pure polymer (1.05g, Mw = 1
78,000, Mn = 58,600, Mw / Mn = 3.05) Not obtained by centrifugation, but obtained by reprecipitation from a THF solution in a DMF solution. The characteristic values of the obtained polyfluorene are shown in Table 1, which shows the physical properties of the polymer, and Table 2 shows the fluorescence quantum yield, which is an optical characteristic. Table 3 shows the quantum yield when bromine is contained at the end.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3]

From Tables 2 and 3, it is understood that the polyfluorene of the present invention has improved optical properties (fluorescence quantum yield).

Example 3 Formation of optically active poly (9,9'-dikiralalkylfluorene-2,7-diyl) aggregates. Optically active poly (9,9'-bis {(S3,7) -dimethyloctyl} fluorene-2,7-diyl) (1 in Table 1
The optically active aggregate was formed by dissolving -1) in chloroform and adding n-octanol.
The circular dichroic intensity largely changes depending on the ratio of chloroform / n-octanol mixed solvent. For example, in a pure solvent of chloroform 100% or a mixed solvent of 60% or less,
The circular dichroic intensity could hardly be observed with a Δε value of 1 or less.
A large cotton effect was observed for the first time when the ratio of n-octanol was 60% or more, and at 80%, the Δε value reached −60, which was extremely large. Figure 1 shows chloroform / n-
1-of Table 1 above in different compositions of octanol
1 shows the UV / visible and circular dichroism spectra of one polymer.

Example 4 Optically active poly (9,9'-bis {(S3,7) -dimethyloctyl} fluorene-2,7-diyl) (1 in Table 1)
Polymer of No. 4) was dissolved in chloroform, and n-octanol was added thereto to form an optically active aggregate. The circular dichroic intensity in the chloroform / n-octanol mixed solvent changed greatly. For example, in the mixed solvent in which n-octanol was 60% or less, the cotton effect was hardly observed with the Δε value of 1 or less. FIG. 2 shows the UV / visible and circular dichroism spectra of 1-4 of Table 1 above in different compositions of chloroform / n-octanol.

Example 5 Optically active poly (9,9'-bis {(S3,7) -dimethyloctyl} fluorene-2,7-diyl) (1 in Table 1)
-2 polymer) was dissolved in chloroform and n-octanol was added to form optically active aggregates. Circular dichroic dichroic intensity is greatly increased just by leaving it in a mixed solvent of chloroform / n-octanol (ratio = 10/90) at 20 ° C., for example, Δε immediately after the formation of aggregates.
Although the value was +200, the cotton effect was reversed after 2 hours, and the Δε value reached −450 after 24 hours. In this case, the asymmetry factor represented by Δε / ε is 1 × 10 ^-2
And became very big. This value was comparable to an asymmetry factor almost equal to that of polyfluorene heated at 200 ° C. or higher for 15 hours or longer, and a high asymmetry factor could be easily realized at room temperature. Examples of the good solvent used to form the optically active aggregate include hydrocarbons such as hexane which dissolves the polymer of the present invention, tetrahydrofuran (T
HF), chloroform, ether, toluene and the like, and examples of the poor solvent for aggregation include n-
Examples include higher alcohols such as octanol, DMF, and the like. FIG. 3 shows UV / visible and circular dichroism spectra of polymer 1-2 of Table 1 at different times (0 to 1440 minutes) in chloroform / n-octanol 10/90, temperature 20 ° C.

Example 6 Optically active poly [9,9'-bis {(S3,7) -dimethyloctyl} fluorene-2, obtained in Example 5,
7-diyl] (polymer of 1-2 in Table 1) aggregates were further annealed at + 50 ° C. for 1 hour and returned to room temperature, the asymmetry factor was further increased by 50%, and a very good chiral self-assembly was obtained. Formed. Figure 4 shows chloroform / n-
Chiral 1-2 in octanol (10/90) mixture
Circular dichroism asymmetry factor of (g _CD = Δε / ε, 413n
m) is shown. The polymer 1-2 mixture in Table 1 used above was annealed at 20 ° C. for 1 day or more. It was heated to 50 ° C. and annealed at that temperature for several hours. The mixture was cooled to 20 ° C. and a circular dichroism spectrum was recorded. Repeat the annealing process (5
Annealing at 0 ° C. and cooling to −10 ° C.) were performed.

Example 7 The optically active poly (9,9'-bis {(S3,7) dimethyloctyl} fluorene-2,7 obtained in Example 5
-Diyl) (polymer of 1-2 in Table 1) Aggregates were examined for temperature change (heat run only). The asymmetry factor is -10
Although the temperature was slightly decreased by increasing the temperature from 0 ° C to 50 ° C, there was no significant change in the size. FIG. 5 shows a mixed solvent of chloroform / n-octanol (ratio = 10/90) ([c] ₀ = 3.21).
XM, d = 1 cm), the temperature is from −10 ° C. to 5
G _CD (= Δε of chiral 1-2 when changed to 0 ° C.)
/ Ε, 413 nm).

Example 8 Synthesis example of optically active poly (9,9'-dichiral alkylfluorene-2,7-diyl) thin film. Optically active poly (9,9'-bis {(S3,7) -dimethyloctyl} fluorene-2,7-diyl) (Table 1 above)
1-3 polymer) in chloroform (concentration 1.2)
6 × 10 ⁻² M) was prepared, and the film thickness was adjusted to 0.1 by spin coating (rotation speed 3000 rpm, 30 seconds) on a smooth quartz substrate at room temperature.
A 05 μm thin film was deposited. FIG. 6 shows an ultraviolet-visible absorption spectrum and a circularly polarized dichroic spectrum of the obtained thin film. The polyfluorene thin film is a slightly yellowish transparent film, and scatterers are not generated due to generation of microcrystals. This film has an absorption wavelength at 350-410 nm corresponding to a 380-430 nm GaN laser, and shows the possibility of laser recording by a heat mode. The circular dichroic intensity at 400 nm is weak at +6 m °. No in-plane anisotropy was observed. This polyfluorene thin film has a wavelength of 1
There is also a second strong ultraviolet absorption band at 90-240 nm and a weak circular dichroic signal (+2 m °), which has a wavelength of 185-21.
Sufficiently compatible with 5 nm short wavelength UV lasers. Figure 6
Figure 3 is the visible / ultraviolet and circular dichroism spectra of films obtained from polymers 1-3 in Table 1. The membrane is prepared from a chloroform solution (c = 1.26 × 10 ^-2 M) by spin coating (3000 rpm for 30 seconds).

Example 9 The optically active poly [9,9′-bis {(S3,7) -dimethyloctyl} fluorene-2 obtained in Example 8 above,
7-diyl] (1-3 in Table 1) In order to clarify the possibility of laser recording of a thin film in the heat mode, the thin film substrate was heated at 200 ° C. in the atmosphere for 3 hours. It is considered that heating by the heat mode of the laser reaches this temperature instantaneously. The thin film was immersed in ice water, and the ultraviolet-visible absorption spectrum and circular dichroic spectrum change of the thin film were measured under rapid cooling conditions (about 200 ° / sec) and under slow cooling (about 10 ° / hour). The results are shown in Fig. 7. Regarding the UV-visible absorption spectrum, no significant changes were observed in the absorption wavelength, intensity, and half width before and after the heat treatment. However, the circular dichroic spectrum changed significantly. The circular dichroic intensity at 390 nm before heat treatment showed a weak positive circular dichroic signal of +6 m ° at 390 nm, but the circular dichroic intensity of the heat-treated and quenched film was conversely -500 m °. It showed a strong negative circular dichroic signal. That is, the circular dichroic signal is inverted by the heating / quenching operation of the thin film, and the relative signal intensity change reaches 0.5 °. This is twice the intensity change of the current MO recording. Even if the circular dichroic signal is replaced with optical rotation dispersion (wavelength dependence of optical rotation), almost the same signal intensity change can be obtained. On the other hand, the circular dichroic intensity of the heat-treated and slowly cooled film was −1300 m °, which was a negative circular dichroic signal about 2.5 times stronger than that of the rapidly cooled film. That is, the circular dichroic signal is inverted by the heating / slow cooling operation of the thin film, and the relative signal intensity change reaches 1.3 °. This is the current MO record 4
It is a double intensity change. Even if the circular dichroic signal is replaced with optical rotation dispersion (wavelength dependence of optical rotation), almost the same signal intensity change can be obtained. Even in the wavelength range of 190-240 nm, the change in signal intensity is slightly small, but it is 200 m at 215 nm.
It shows a practical change of 350 m ° at 200 °. From this fact, recording using a short wavelength ultraviolet laser having a wavelength of 185 to 215 nm is sufficiently applicable. Thus, by only controlling the heating / cooling conditions of the transparent optically active polyfluorene thin film, it is possible to obtain a media material showing a large sign and intensity change of the circular two-color (and optical rotation) signal. The most realistic method for this media material is write once (WR
ITE ONCE) information record. This is a method in which a linearly polarized GaN laser with an oscillation wavelength of 380 nm is written in a heat mode to a polyfluorene thin film spin-coated at room temperature, and a change in optical rotation is read out from the linearly polarized GaN laser in a photon mode. By optimizing the writing power and the modulation method, it is possible to select three states (+2 m °, −500 m ° and −1300 m °) with different optical rotation intensities corresponding to the slow cooling and the rapid cooling. That is, polarization multiplexing recording.

[0033]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, a novel optically active polyfluorene compound exhibiting more efficient light emission and an optically active recording material using the compound are provided with activation. Without the need for heat treatment
Highly optically active polymer light with high reproducibility and high performance
The remarkable effect that an electronic functional device can be built is brought about.

[Brief description of drawings]

FIG. 1 shows UV / visible and circular dichroism spectra of 1-1 polymers of Table 1 above in different compositions of chloroform / n-octanol.

FIG. 2 shows UV / visible and circular dichroism spectra of 1-4 in Table 1 above in different compositions of chloroform / n-octanol.

FIG. 3: Chloroform / n-octanol 10/90,
1 shows the UV / visible and circular dichroism spectra of polymer 1-2 of Table 1 at different times (0 to 1440 minutes) at a temperature of 20 ° C.

FIG. 4 Chloroform / n-octanol (10/9
0) Circular dichroism asymmetry factor of chiral 1-2 in mixture (g _CD = Δε / ε, 413 nm)

FIG. 5: Chloroform / n-octanol mixed solvent (ratio
Rate = 10/90) ([c] ₀= 3.21 × M, d = 1 cm)
In the case of changing the temperature from −10 ° C. to 50 ° C.
Chi chi 1-2 g_CD(= Δε / ε, 413 nm)

FIG. 6 is the visible / ultraviolet and circular dichroism spectra of the films obtained from polymers 1-3 in Table 1.

FIG. 7 shows 20 membranes obtained from the polymers of 1-3 in Table 1.
The visible / ultraviolet and circular dichroism spectra of annealed at 0 ° C. for 3 hours.

FIG. 8 is a visible / ultraviolet and circular dichroism spectrum of films obtained from polymers 1-3 of Table 1 and 2 after annealing at 200 ° C. for 3 hours.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-3-28220 (JP, A) Special table 2002-539287 (JP, A) Special table 2002-527553 (JP, A) (58) Fields investigated ( Int.Cl. ⁷ , DB name) C08G 61/00-61/12

Claims (8)

(57) [Claims] 1. The following general formula A: Wherein R is a substituent that enhances the solubilization of the resulting polymer composed of a hydrocarbon group in a solvent, the substituted polyfluorene ring is a repeating unit, and the terminal group is a fluorene ring.
Is an integer from 10 to 100000, polyfluorene. 2. In the general formula A, R is a linear alkyl hydrocarbon group having 1 to 22 carbon atoms or an alkyl hydrocarbon group containing a branched alkyl structure having 1 to 22 carbon atoms. (However, the branching position is at least 10 positions at least at any one of the 1 to 17th carbon atoms from the fluorene ring) and the novel polyfluorene according to claim 1. 3. An optically active polyfluorene aggregate produced by dissolving the polyfluorene represented by the general formula A in a good solvent and adding a poor solvent. 4. In the general formula A, R is a linear alkyl hydrocarbon group having 1 to 22 carbon atoms or an alkyl hydrocarbon group having a branched alkyl structure having 1 to 22 carbon atoms. (However, the branching position is at least 10 positions at least at any one of the 1 to 17th carbon atoms from the fluorene ring.) A novel polyfluorene is dissolved in a good solvent to obtain a poor solvent. An optically active polyfluorene aggregate produced by adding a. 5. An optically active polyfluorene thin film comprising fluorene obtained by dissolving the polyfluorene represented by the general formula A in a solvent and depositing it on a substrate. 6. In the general formula A, R is a linear alkyl hydrocarbon group having 1 to 22 carbon atoms or an alkyl hydrocarbon group containing a branched alkyl structure having 1 to 22 carbon atoms. (However, the branch position is at least 10 positions at least at any one of the 1 to 17th carbon atoms from the fluorene ring). A novel polyfluorene is used. Item 6. The optically active polyfluorene thin film according to item 5. 7. In the general formula A, R is a linear alkyl hydrocarbon group having 1 to 22 carbon atoms or an alkyl hydrocarbon group containing a branched alkyl structure having 1 to 22 carbon atoms. (However, the branch position is at least 10 positions at least at any one of the 1 to 17th carbon atoms from the fluorene ring.) A new polyfluorene is dissolved in a solvent and deposited on a substrate. An optically active polyfluorene thin film obtained by raising the temperature of the thin film thus obtained to a high temperature and modulating the sign and intensity of the optically active signal according to the cooling rate. 8. A thin film obtained by dissolving polyfluorene in which R of the 9-position substituent R has an achiral alkyl substituent in a solvent and depositing it on a substrate, and a 9-position substituent R is a polyfluorene having a chiral alkyl substituent dissolved in a solvent and laminated with a thin film obtained by depositing it on a substrate to raise a multilayer thin film to a high temperature once Optically active polyfluorene thin film characterized by modulating the sign and intensity of a signal, where R is a linear alkyl hydrocarbon group having 1 to 22 carbon atoms, or 1 to 22 carbon atoms An alkyl hydrocarbon group containing a branched alkyl structure (provided that the branching position is at least 10 positions at least at any one of carbon atoms 1 to 17 from the fluorene ring). It