Patent Grant
7951922
The present invention relates to a novel photoresponsive heterocyclic azo compound, a method for producing the same, and a rewritable optical information recording medium based thereon.
Society is in a highly information-oriented system, and therewith there have been increasing social demand and importance of technologies and materials for information processing and recording. However, conventional digital optical (or magnetic) recording methods are considered to have a limitation of about 1 TB/inch2 even allowing for future development of technologies, and there is care that the technologies reach the limit within 5 to 10 years. Thus, it has been required to find a novel very high-density recording method, thereby establishing a technology capable of overcoming the limitation.
Holographic memories have been attracting much attention as one of ultra high-density and large capacity recording methods for meeting the demand of the society. The holographic memories can, record three-dimensional information by using light interference as it is, or convert two-dimensional planar information into a recording medium three-dimensionally. Particularly, recording and regenerating methods of two-dimensional page-data are highly compatible with signal processing systems of conventional digital recording methods and show fast transfer of the recording and regeneration, and thus have great potential and can achieve very high-capacity processing with high density exceeding 1 TB/inch2.
Photorefractive materials, photopolymerizable polymers (photopolymers), and organic photochromic materials (particularly polymers) are conventionally known as optical information recording media capable for holographic memory. The pbotorefractive materials, which include inorganic crystalline materials such as barium titanate and lithium niobate as typical ones, have disadvantages of poor sensitivity, fundamental difficulty of nondestructive readout, poor selectivity for writing light wavelength, brittle, poor processabilty, difficulty for thin film fabrication, etc. Further, the photopolymers are advantageous in that they can be relatively freely designed in view of reducing the disadvantages. However, materials using the photopolymers are not rewritable and can be used only for write-once media. Known as typical examples of the organic photochromic materials are polymers having an azobenzene structure, which are capable of information recording based on various physical principles by interference exposure, multiphoton reaction, localized heat excitation, surface modification, etc., and the molecular structures and functions of the polymers have been studied For example, photo-induced birefringence, hologram recording using the same, and usability of a copolymerized macromolecule material having a photoresponsive azobenzene moiety and a highly anisotropic liquid crystalline moiety have been reported in S. Xie, A. Natansohn and P. Rochon, Chem. Rev., vol. 5 (1993) p. 403-411, “Recent Development in Aromatic Azo Polymers Research”.
Further, findings on hologram formation and relaxation dynamics in the copolymerized macromolecule material having the photoresponsive azobenzene moiety and the highly anisotropic liquid crystalline moiety have been reported in T. Bieringer, R. Wuttke, D. Haarer, U. Gesner and J. Rubner, Macromol. Chem. Phys., vol. 196 (1995) p. 1375-1390, “Relaxation of holographic gratings in liquid-crystalline side chain polymers with azo chromophores”.
Furthermore, it has been reported that, in the azobenzene polymer, the orientation of the molecules can be controlled by irradiating a linearly polarized light to utilize birefringence distribution for information recording, and the orientation can be disarranged by a circularly polarized light to erase the information. Also the effects of dipole of the highly anisotropic copolymer component on the properties have been studied in A. Natansohn and P. Rochon, ACS Symposium Series, vol. 672 (1997) p. 236-250, “Azobenzene-containing polymers: digital and holographic storage” and A. Natansohn, P. Rochon, X. Meng, C. Barrett, T. Buffeteau, S. Bonenfant and M. Pezolet, Macromolecules, vol. 31 (1998) p. 1155-1161, “Molecular addressing Selective photoinduced cooperative motion of polar ester groups in copolymers containing azobenzene groups”.
Further, a holographic recording material comprising a polymer with an azobenzene structure has been applied for a patent (WO 00/54111 (JP-T-2002-539475) and WO 00/54112 (JP-T-2002-539476), the term “JP-T” as used herein means a published Japanese translation of a PCT patent application). And compounds having an azo bond like the azobenzene structure have been studied in view of wider, various applications (JP-A-11-12242, JP-A-11-1688, JP-A-6-157511, and JP-A-11-312335).
However, a material satisfying all the various properties required for a practical application such as sensitivity, response speed, long-term storage stability, and repeatability have not found in these studies and proposals.
Under the above circumstances, an object of the present invention is to provide a novel optical information recording material or medium with improved holographic, optical information recording properties such as sensitivity, response speed, long-term storage stability, and repeatability, and a substance therefor.
As a result of intense research on materials capable of high-speed recording and regenerating high-capacity data, the inventors have found that holographic, optical information recording properties such as sensitivity, response speed, long-term storage stability, and repeatability can be improved by modifying chemical structure of azobenzene compounds, which are typical and known as substances with relatively good properties, thereby developing a novel azo compound having an aromatic ring with a heteroatom. The present invention has completed based on the finding. The inventors have found that general reason why the aromatic azo compound having a heteroatom is more excellent in the properties than conventionally known azobenzene compounds are as follows.
According to the invention, there are provided the following embodiments based on the findings.
wherein HC1 and HC2 each represent a ring structure, at least one of them being a heterocyclic structure containing 1 or more heteroatom in the ring, R1 and R2 each represent a hydrogen atom or a substituent connected to the ring structure and may be the same or different ones, s and t each represent the number thereof, and X1 and X2 each represent a terminal group or a linking group, at least one of them being a linking group connected to the main chain of the oligomer or polymer and the terminal group being a hydrogen atom or a substituent.
wherein HC1, HC2, R1, R2, s, t, X1, and X2 are as defined above, and R7 represents a hydrogen atom or a methyl group.
According to the present invention, holographic optical information recording properties such as sensitivity, response speed, long-term storage stability, and repeatability can be remarkably improved and increased, and there is provided the high-performance optical information recording material or medium.
The present invention provides the above photoresponsive heterocyclic azo compound comprising the oligomer or polymer having the building block represented by the formula (1) in at least one of the main chain and side chain, and further provides the photoresponsive heterocyclic azo compound comprising the side chain having at least one of a liquid crystalline group for promoting photo-induced molecular reorientation or a stabilizing group thereof, an optically anisotropic group, and a group for increasing the photo-induced birefringence.
In the photoresponsive heterocyclic azo compound, at least one of HC1 and HC2 in the formula (1) represents a ring structure containing at least one heteroatom as a ring atom.
One of HC1 and HC2 may be a monocyclic or polycyclic carbon ring with no heteroatom in the ring such as an aromatic ring (e.g. benzene, naphthalene, biphenyl, etc.) and an aliphatic ring (e.g. cyclohexane), the other being a monocyclic or polycyclic, heterocyclic structure containing a heteroatom in the ring. Both HC1 and HC2 may be a heterocyclic structure containing a heteroatom in the ring.
In the invention, the ring structures are preferably 5- or 6-membered ring though not restrictive. Preferred embodiments a) to f) of the ring structures are described below.
a) The ring structure of HC1 or HC2 containing a heteroatom in the ring is a 5- or 6-membered heterocyclic structure that contains 1 or more nitrogen atom, or 1 or more nitrogen atoms with a sulfur atom or an oxygen atom in the ring.
In the formula (1), R1 and R2 each represent a hydrogen atom or a substituent and are connected to HC1 and HC2 within the range of the numbers s and t. R1 and R2 may be various substituents selected from the following examples, which are equal to those of the terminal groups of X1 and X2.
The examples include halogen atoms such as —F, —Cl, —Br, and —I; —CN; —NO2; alkyl, cycloalkyl, or aryl groups such as —CH3, —C2H5, —C6H13, and —C6H6; halogenated alkyl cycloalkyl, or aryl groups such as —CF3, —CCl3, and —C6H5Cl; —N+(CH3)3; —S+(CH3)3; substituted or unsubstituted amino groups such as —NH2 and —N(CH3)2; —SH; —OH; alkoxy or acyl groups such as —OCH3, —OC6H5, and —OCOCH3; etc.
Preferred examples of the linking groups of X1 and X2 include ester groups such as —CO—O— and —O—CO—; thioester groups; —CO—; —O—; —S—; —NR3—; —CO—NR3—; —NR3—CO—; —SO2—; —SO2—O—; —SO2—NR3—; —CR4R5—; —CR4═CR5—; —C≡C—; —C(NR6)—; —CR6═N—; —CR6═N—NR3—; —CR6—NR6—NR3—NR3—; —CR6═N—CO—; —NH—NH—; —N═N—; C1 to C20 alkylene groups; C3 to C10 cycloalkylene groups; C6 to C10 arylene groups; and combinations thereof.
Herein examples of R3 and R6 include C1 to C20 alkyl groups, C3 to C10 cycloalkyl groups, C2 to C20 alkenyl groups, and C6 to C10 aryl groups, and examples of R4 and R5 include a hydrogen atom, halogen atoms, C1 to C10 alkyl groups, C1 to C20 alkoxy groups, C3 to C10 cycloalkyl groups, C2 to C20 alkenyl groups, and C6 to C10 aryl groups.
In the photoresponsive heterocyclic azo compound having the moiety represented by the formula (1), the oligomer or polymer connected to the linking group is preferably such that the main chain is a carbon chain and the side chain contains the building block of the formula (1), and the carbon chain of the main chain is preferably formed by polymerization of a monomer having the building block of the formula (1) and a polymerizable group, or by copolymerization of this monomer and another monomer having a polymerizable group.
Further, the chain may be formed by polymerization or copolymerization of the monomer represented by the formula (2).
The photoresponsive heterocyclic azo compound may be produced by one of the following two basic methods: 1) polymerization of a monomer or an oligomer and 2) polymer reaction of a polymer or an oligomer.
In the case of 1) polymerization, a polymerizable monomer of the following formula (3) having a polymerizable group M is polymerized in the presence of a polymerization initiator such as AIBN, to obtain an oligomer or polymer of the formula (4). An appropriate copolymerizable monomer may be added if necessary to obtain a copolymer having building blocks of the formulae (4) and (5). A copolymer having a number average molecular weight of 1,000 to 1,000,000, preferably 3,000 to 30,000, can be obtained in this manner.
In the formulae (3), (4), and (5), as defined in the formula (1), HC1 and HC2 each represent a ring structure, at least one of them being a heterocyclic structure containing 1 or more heteroatom in the ring, R1 and R2 each represent a hydrogen atom or a substituent connected to the ring structure and may be the same or different ones, and s and t each represent the number thereof. X1 represents a linking group connected to the main chain of the oligomer or polymer, and X2 is a terminal group of a hydrogen atom or a substituent.
M in the formula (3) may be a polycondensation-reactive, polyaddition-reactive, addition-polymerizable, isomerization-polymerizable, or ring opening-polymerizable monomer group.
Further, P1 and P2 in the formulae (4) and (5) each represent a main chain skeleton structure polymerized. n represents a copolymerization composition ratio of the monomer, which is a real number of more than 0 and at most 1.
Y is a side chain, and preferably a liquid crystalline group for efficiently promoting the photo-induced molecular reorientation of the photoresponsive copolymerization component, a functional group having a function of stabilizing the photo-induced molecular reorientation via a hydrogen bond, etc., or an optically high-anisotropic functional group. Examples thereof include groups shown in the following formulae (6), (7), and (8), and groups having 2 azo groups connected, etc. The invention is not limited to the examples.
In the case of 2) reaction, for example, a polymerizable monomer represented by the following formula (9) is polymerized in the presence of a polymerization initiator such as AIBN, to obtain an oligomer or polymer of the formula (10). An appropriate copolymerizable monomer of the formula (11) may be added if necessary to obtain a copolymer with building blocks of the formulae (10) and (11) having a number average molecular weight of 300 to 300,000, preferably 1,000 to 30,000. Then, a diazonium ion of the general formula (12) may be interacted to introduce an azo moiety to the aromatic ring HC1 containing the heteroatom via an aromatic electrophilic substitution reaction, to obtain a copolymer with the building blocks of the formulae (4) and (5) having a number average molecular weight of 1,000 to 1,000,000, preferably 3,000 to 30,000.
Signs in the formulae are as defined above.
According to the invention, by using the above polymer or oligomer, there is provided the optical information recording material that can record an optical information utilizing change of an optical absorption property or refractive index caused by light irradiation or localized heating, the building block represented by the formula (1) being used as a photoresponsive moiety. For example, the optical information recording material may be used as a rewritable volume hologram memory or a rewritable surface relief memory. The methods of producing and using the material may be selected from various known methods such as spin coating onto a substrate.
The invention will be described in more detail below with reference to Examples.
The invention is not limited to Examples.
<A> Synthesis of Methacrylate Copolymer Having Aromatic Heterocycle-Containing Azo Moiety in Side Chain
4.96 g (30 mmol) of N-hydroxyethyl-N-ethylaniline and 6.27 ml (45 mmol) of triethylamine were dissolved in tetrahydrofuran, and 4.36 ml (40 mmol) of methacryloyl chloride was slowly added thereto dropwise while stirring the mixture in an ice bath. After 3 hours of stirring, the reaction solution was filtered to remove salts, transferred to a separatory funnel, and washed with an aqueous potassium carbonate solution, a saturated sodium chloride solution, and distilled water, and the dichloromethane phase was extracted. The solvent was distilled off under reduced pressure to obtain 15.906 g of Molecule 1 of the following formula as an yellow oil with 83% yield.
Then, 0.274 g (2.06 mmol) of 2-aminoimidazole-4,5-dicarbonitrile was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.142 g (2.06 mmol) of sodium nitrite in distilled water dropwise. To this was slowly added a solution of 10.4 g (1.71 mmol) of Molecule 1 dissolved in a 4 N aqueous sodium hydroxide solution dropwise, stirred at 0° C. for 2 hours and at the room temperature for 3 hours, and filtered to obtain red precipitates. Further, the precipitates were subjected to recrystallization from u-hexane, to obtain 20.43 g of Molecule 2 of the following formula having an azo group sandwiched between 4,5-dicyanoimidazole and N-ethylaniline with a yield of 55%. The 1H-NMR data of the obtained molecule were as shown in Table 1, and the IR spectrum thereof was as shown in
0.344 g (3.42 mmol) of methyl methacrylate, 20.8 g (3.42 mmol) of Molecule 2, and 0.045 g (0.27 mmol) of 2,2′-azobisisobutyronitrile were dissolved in 35 ml of tetrahydrofuran. The resultant solution was added to a 150-ml flask and subjected to deaeration using liquid nitrogen, the reaction system was sealed, and polymerization was carried out at 65° C. After 24 hours, the polymerization product was isolated and purified by repeating reprecipitation in methanol twice. As a result, a 1:1 random copolymer of methyl methacrylate and Molecule 2 represented by the following formula was obtained as red powder with a number average molecular weight of 12,000. The glass transition temperature of the obtained copolymer determined by DSC analysis was 175° C., and the absorption spectrum thereof (5×10−5 mol/L in THF) was as shown in
Molecule 1 was synthesized in the same manner as Example 1. 0.429 g (4.29 mmol) of methyl methacrylate, 1.0 g (4.29 mmol) of Molecule 1, and 0.028 g (0.172 mmol) of 2,2′-azobisisobutyronitrile were dissolved in 40 ml of tetrahydrofuran. The resultant solution was added to a 150-ml flask and subjected to deaeration using liquid nitrogen, the reaction system was sealed, and polymerization was carried out at 65° C. After 24 hours, the polymerization product was isolated and purified by repeating reprecipitation in methanol twice. As a result, 0.83 g of a 1:1 copolymer of methyl methacrylate and Molecule 1 was obtained as white powder with a yield of 58%.
Then, 0.05 g (0.376 mmol) of 2-aminoimidazole-4,5-dicarbonitrile was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.026 g (0.376 mmol) of sodium sulfite in distilled water dropwise. To this was slowly added an acetic acid solution of 0.055 g (0.25 mmol, based on the unit average molecular weight) of the 1:1 random copolymer of methyl methacrylate and Molecule 1 of N-methacryloyloxyethyl-N-ethylaniline dropwise, stirred at 0° C. for 2 hours and at the room temperature for 3 hours, and filtered to obtain red precipitates. Further, the precipitates were purified by reprecipitation in methanol, to obtain 0.013 g of a random copolymer of methyl methacrylate and Molecule 2 as red powder with a copolymerization ratio of 1:1 (x=y=0.5). The glass transition temperature and the absorption spectrum of the obtained copolymer were the same as the case of Example 1.
Molecule 1 was synthesized in the same manner as Example 1. 0.161 g (1.61 mmol) of methyl methacrylate, 1.5 g (6.43 mmol) of Molecule 1, and 0.053 g (0.322 mmol) of 2,2′-azobisisobutyronitrile were dissolved in 40 ml of tetrahydrofuran. The resultant solution was added to a 150-ml flask and subjected to deaeration using liquid nitrogen, the reaction system was sealed, and polymerization was carried out at 65° C. After 24 hours, the polymerization product was isolated and purified by repeating reprecipitation in methanol twice. As a result, 1.05 g of a 1:4 random copolymer of methyl methacrylate and Molecule 1 was obtained as white powder with a yield of 63%.
Then, 0.048 g (0.36 mmol) of 2-aminoimidazole-4,5-dicarbonitrile was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.025 g (0.36 mmol) of sodium sulfite in distilled water dropwise. To this was slowly added an acetic acid solution of 0.05 g (0.24 mmol, based on the unit average molecular weight) of the 1:4 random copolymer of methyl methacrylate and Molecule 1 dropwise, stirred at 0° C. for 2 hours and at the room temperature for 3 hours, and filtered to obtain red precipitates Further, the precipitates were purified by reprecipitation in methanol, to obtain 0.062 g of a random copolymer of methyl methacrylate and Molecule 2 as red powder with a copolymerization ratio of 1:4 (x=0.2, y=0.8) with a yield of 53%.
Molecule 1 was synthesized in the same manner as Example 1. 1.03 g (10 mmol) of methyl methacrylate, 0.6 g (257 mmol) of Molecule 1 of N-methacryloyl oxyethyl-N-ethylaniline, and 0.053 g (0.50 mmol) of 2,2′-azobisisobutyronitrile were dissolved in 60 ml of tetrahydrofuran. The resultant solution was added to a 150-ml flask and subjected to deaeration using liquid nitrogen, the reaction system was sealed, and polymerization was carried out at 65° C. After 24 hours, the polymerization product was isolated and purified by repeating reprecipitation in methanol twice. As a result, 1.1 g of a 4:1 random copolymer of methyl methacrylate and Molecule 1 was obtained as white powder with a yield of 69%.
Then, 0.079 g (0.59 mmol) of 2-aminoimidazole-4,5-dicarbonitrile was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.041 g (0.59 mmol) of sodium nitrite in distilled water dropwise. To this was slowly added an acetic acid solution of 0.05 g (0.39 mmol, based on the unit average molecular weight) of the 4:1 copolymer of methyl methacrylate and Molecule 1 dropwise, stirred at 0° C. for 2 hours and at the room temperature for 3 hours, and filtered to obtain red precipitates. Further, the precipitates were purified by reprecipitation in methanol, to obtain 0.021 g of a random copolymer of methyl methacrylate and Molecule 2 as red powder with a copolymerization ratio of 4:1 (x=0.8, y=0.2) with a yield of 35%
1.23 g (10 mmol) of 4-aminobenzyl alcohol was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.69 g (10 mmol) of sodium nitrite in a small amount of distilled water dropwise. The mixture was stirred for about 30 minutes, 0.921 g (10 mmol) of 2-cyanopyrrole dissolved in a 1 M aqueous sodium hydroxide solution was slowly added dropwise, and the resultant was stirred for about 5 hours. The mixture was filtrated after completion of the reaction, and the obtained orange-yellow powder washed with water twice and subjected to recrystallization from a water/ethanol mixed solvent, to obtain 0.191 g of Molecule 3 of the following formula as orange powder with a yield of 8.4%.
0.1 g (0.44 mmol) of Molecule 3 dissolved in chloroform and 0.049 g (0.49 mmol) of triethylamine were stirred in an ice bath, and 0.051 g (0.49 mmol) of methacryloyl chloride was slowly added thereto dropwise and stirred overnight. After completion of the reaction, the resultant mixture washed with an aqueous potassium carbonate solution, a saturated sodium chloride solution, and distilled water, and extracted with chloroform. The solvent was distilled off under reduced pressure, to obtain orange powder of Molecule 4 of the following formula having an azo group sandwiched between 2-cyanopyrrole and benzyl ester.
A desired random copolymer of thus synthesized Molecule 4 and methyl methacrylate was produced in the same manner as Examples 1 to 4, and the obtained copolymer had a number average molecular weight of 8,000.
The following formula shows the structure of the copolymer.
0.238 g (2 mmol) of 5-amino-2-cyanopyridine was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.16 g (2.3 mmol) of sodium nitrite in a small amount of distilled water dropwise. The mixture was stirred for about 30 minutes, thereto was added 0.4 g (10 mmol) of sodium hydroxide, and a solution prepared by dissolving 0.33 g (2 mmol) of N-hydroxyethyl-N-ethylaniline in 40 ml of distilled water and 40 ml of methanol was slowly added dropwise and stirred. The mixture was filtrated after completion of the reaction, and the obtained red powder washed with water twice and subjected to recrystallization from a water/ethanol mixed solvent, to obtain Molecule 5 of the following formula as red powder.
0.1 g (0.34 mmol) of Molecule 5 dissolved in chloroform and 0.038 g (0.38 mmol) of triethylamine were stirred in an ice bath, and 0.040 g (0.38 mmol) of methacryloyl chloride was slowly added thereto dropwise and stirred overnight. After completion of the reaction, the resultant mixture washed with an aqueous potassium carbonate solution, a saturated sodium chloride solution, and distilled water, and extracted with chloroform. The solvent was distilled off under reduced pressure, to obtain red powder of Molecule 6 of the following formula having an azo group sandwiched between 2-cyanopyridine and N-ethylaniline. The 1H-NMR data and elementary analysis values of the obtained molecule were as shown in Table 2.
A desired random copolymer of thus synthesized Molecule 6 and methyl methacrylate was produced in the same manner as Examples 1 to 4, and the obtained copolymer had a number average molecular weight of 16,000.
The following formula shows the structure of the copolymer. The glass transition temperature of the obtained copolymer determined by DSC analysis was 125° C., and the absorption spectrum thereof (1×10−4 mol/L in CHCl3) was as shown in
In the same manner as Example 6, a molecular compound of the following formula having a similar structure to that of the above Molecule 6 was obtained.
The 1H-NMR data of the obtained molecule were as shown in Table 3.
1H NMR Data: 1H-NMR, δ (ppm): 1.97 (s, 3H), 4.34 (t, 2H), 4.58 (t, 2H),
Further, a random copolymer of this molecular compound and methyl methacrylate was obtained. The obtained copolymer had the structure represented by the following formula and the absorption spectrum thereof was as shown in
1.08 g (10 mmol) of 2-methylaminopyridine, 1.6 g (20 mmol) of 2-chloroethanol, 3.32 g (20 mmol) of potassium iodide, and 2.76 g (20 mmol) of potassium carbonate were dissolved in 100 ml of dimethylformamide, and reacted at 120° C. for 2 hours. Then, the reaction mixture was stirred at the room temperature for 48 hours, thereto were added a 10% aqueous sodium hydroxide solution and distilled water in the appropriate amounts, to obtain precipitates. The precipitates were isolated by filtration, and the obtained crystal washed with water twice to obtain N-hydroxyethyl-N-methylaminopyridine.
0.238 g (2 mmol) of 5-amino-2-cyanopyridine was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.16 g (2.3 mmol) of sodium nitrite in a small amount of distilled water dropwise. The mixture was stirred for about 30 minutes, thereto was added 0.4 g (10 mmol) of sodium hydroxide, and a solution prepared by dissolving 0.304 g (2 mmol) of N-hydroxyethyl-N-methylaminopyridine in 40 ml of distilled water and 40 ml of methanol was slowly added dropwise and stirred. The mixture was filtrated after completion of the reaction, and the obtained red powder washed with water twice and subjected to recrystallization from a water/ethanol mixed solvent, to obtain a red crystal of Molecule 7 of the following formula having an azo group sandwiched between 2-cyanopyridine and N-methylaminopyridine.
0.1 g (0.35 mmol) of Molecule 7 dissolved in chloroform and 0.039 g (0.39 mmol) of triethylamine were stirred in an ice bath, aid 0.041 g (0.39 mmol) of methacryloyl chloride was slowly added thereto dropwise and stirred overnight. After completion of the reaction, the resultant mixture washed with an aqueous potassium carbonate solution, a saturated sodium chloride solution, and distilled water, and extracted with chloroform. The solvent was distilled off under reduced pressure, to obtain red powder of Molecule 8 of the following formula.
A desired random copolymer of Molecule 8 and methyl methacrylate was produced in the same manner as Examples 1 to 4, and the obtained copolymer had a number average molecular weight of 7,000.
The following formula shows the structure of the copolymer.
<B> Synthesis of Compound Having Azo Group Sandwiched Between Heterocycles
In Examples 8 to 15, synthesis examples of compounds with an azo group sandwiched between heterocycles are described. The synthesized compounds are converted to monomers having a methacrylo group, and copolymerized with eg. methyl methacrylate to produce random copolymers in the same manner as Examples 1 to 7.
0338 g (2 mmol) of 2-amino-5-trifluoromethyl-1,3,4-thiadiazole was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.16 g (2.3 mmol) of sodium nitrite in a small amount of distilled water dropwise. The mixture was stirred for about 30 minutes, thereto was added 0.4 g (10 mmol) of sodium hydroxide, and a solution prepared by dissolving 0.304 g (2 mmol) of N-hydroxyethyl-N-methylaminopyridine in 40 ml of distilled water and 40 ml of methanol was slowly added dropwise and stirred. The mixture was filtrated after completion of the reaction, and the obtained red powder washed with water twice and subjected to recrystallization from a water/ethanol mixed solvent, to obtain a red crystal of a compound having an azo group sandwiched between 5-trifluoromethylthiadiazole and N-methylaminopyridine. Then, in the same manner as Examples 1 to 8, the obtained compound was reacted with methacryloyl chloride and converted to a monomer connected to a methacryloyl group. The monomer compound has the structure represented by the following formula.
0.20 g (2 mmol) of 2-aminothiazole was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.16 g (2.3 mmol) of sodium nitrite in a small amount of distilled water dropwise. The mixture was stirred for about 30 minutes, thereto was added 0.4 g (10 mmol) of sodium hydroxide, and a solution prepared by dissolving 0304 g (2 mmol) of N-hydroxyethyl-N-methylaminopyridine in 40 ml of distilled water and 40 ml of methanol was slowly added dropwise and stirred. The mixture was filtrated after completion of the reaction, and the obtained orange powder washed with water twice and subjected to recrystallization from a water/ethanol mixed solvent, to obtain an orange crystal of a compound having an azo group sandwiched between thiazole and N-methylaminopyridine. Then, in the same manner as Examples 1 to 8, the obtained compound was reacted with methacryloyl chloride and converted to a monomer connected to a methacryloyl group. The monomer compound has the structure represented by the following formula
58.7 mg (0.58 mmol) of 2-aminothiazole was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 80.5 mg (0.12 mmol) of sodium nitrite in a small amount of distilled water dropwise. After the mixture was stirred for about 15 minutes, an aqueous solution containing 0.612 g of phenol was slowly added dropwise thereto and stirred. After completion of the reaction, the resultant solution was adjusted to about pH 7 and subjected to extraction using methylene chloride. The solvent was removed from the resultant solution to obtain a crude product. The obtained crude product was purified using a silica gel column to obtain a molecule of the following formula as a red solid.
The mass spectrum data of the obtained molecule were as shown in Table 4.
0.168 g (2 mmol) of 3-amino-1,2,4-triazole was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.16 g (2.3 mmol) of sodium nitrite in a small amount of distilled water dropwise. The mixture was stirred for about 30 minutes, thereto was added 0.4 g (10 mmol) of sodium hydroxide, and a solution prepared by dissolving 0.304 g (2 mmol) of N-hydroxyethyl-N-methylaminopyridine in 40 ml of distilled water and 40 ml of methanol was slowly added dropwise and stirred. The mixture was filtrated after completion of the reaction, and the obtained red powder washed with water twice and subjected to recrystallization from a water/ethanol mixed solvent, to obtain a red crystal of a compound having an azo group sandwiched between triazole and N-methylaminopyridine. Then, in the same manner as Examples 1 to 8, the obtained compound was reacted with methacryloyl chloride and converted to a monomer connected to a methacryloyl group. The monomer compound has the structure represented by the following formula.
0.192 g (2 mmol) of 2-amino-1,2,4-triazine was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.16 g (2.3 mmol) of sodium nitrite in a small amount of distilled water dropwise. The mixture was stirred for about 30 minutes, thereto was added 0.4 g (10 mmol) of sodium hydroxide, and a solution prepared by dissolving 0304 g (2 mmol) of N-hydroxyethyl-N-methylaminopyridine in 40 ml of distilled water and 40 ml of methanol was slowly added dropwise and stirred. The mixture was filtrated after completion of the reaction, and the obtained red powder washed with water twice and subjected to recrystallization from a water/ethanol mixed solvent, to obtain a red crystal of a compound having an azo group sandwiched between triazine and N-methylaminopyridine. Then, in the same manner as Examples 1 to 8, the obtained compound was reacted with methacryloyl chloride and converted to a monomer connected to a methacryloyl group. The monomer compound has the structure represented by the following formula.
0.166 g (2 mmol) of 2-amino-oxazole was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.16 g (23 mmol) of sodium nitrite in a small amount of distilled water dropwise. The mixture was stirred for about 30 minutes, thereto was added 0.4 g (10 mmol) of sodium hydroxide, and a solution prepared by dissolving 0.304 g (2 mmol) of N-hydroxyethyl-N-methylaminopyridine in 40 ml of distilled water and 40 ml of methanol was slowly added dropwise and stirred. The mixture was filtrated after completion of the reaction, and the obtained red powder washed with water twice and subjected to recrystallization from a water/ethanol mixed solvent, to obtain a red crystal of a compound having an azo group sandwiched between oxazole and N-methylaminopyridine. Then, in the same manner as Examples 1 to 8, the obtained compound was reacted with methacryloyl chloride and converted to a monomer connected to a methacryloyl group. The monomer compound has the structure represented by the following formula.
0.168 g (2 mmol) of 2-aminoimidazole was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.16 g (23 mmol) of sodium nitrite in a small amount of distilled water dropwise. The mixture was stirred for about 30 minutes, thereto was added 0.4 g (10 mmol) of sodium hydroxide, and a solution prepared by dissolving 0.304 g (2 mmol) of N-hydroxyethyl-N-methylaminopyridine in 40 ml of distilled water and 40 ml of methanol was slowly added dropwise and stirred. The mixture was filtrated after completion of the reaction, and the obtained red powder washed with water twice and subjected to recrystallization from a water/ethanol mixed solvent, to obtain a red crystal of a compound having an azo group sandwiched between imidazole and N-methylaminopyridine. Then, in the same manner as Examples 1 to 8, the obtained compound was reacted with methacryloyl chloride and converted to a monomer connected to a methacryloyl group. The monomer compound has the structure represented by the following formula.
1.20 g (10.1 mmol) of S-amino-2-cyanopyridine was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.70 g (10.2 mmol) of sodium nitrite in a small amount of distilled water dropwise. The mixture was stirred for about 30 minutes, and was slowly added dropwise to a solution prepared by dissolving 0.60 g (5.99 mmol) of 2(5H)thiophene in 20 ml of a 10% aqueous potassium hydroxide solution, and stirred. After completion of the reaction, 2 M hydrochloric acid was added to the resultant solution until the pH thereof reached about 4. The mixture was filtrated to obtain a crude product. The mixture was separated and purified using a silica gel column to obtain 0.20 g of an ocherous solid.
0.12 g (0.35 mmol) of the obtained molecule dissolved in chloroform and 0.039 g (0.39 mmol) of triethylamine were stirred in an ice bath, and 0.041 g (0.38 mmol) of methacryloyl chloride was slowly added dropwise thereto and stirred overnight. After completion of the reaction, the resultant mixture washed with an aqueous potassium carbonate solution, a saturated sodium chloride solution, and distilled water, and extracted with chloroform. The solvent was distilled off under reduced pressure, to obtain a molecule of the following formula as ocherous powder.
The 1H-NMR data of the obtained molecule were as shown in Table 5.
1H NMR Data: 1H-NMR in Acetone-D6, δ (ppm): 1.97 (s, 3H), 4.34 (t, 2H),
1.18 g (10.0 mmol) of 4-cyanoaniline was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 0.70 g (10.2 mmol) of sodium nitrite in a small amount of distilled water dropwise. The mixture was stirred for about 30 minutes, and was slowly added dropwise to a solution prepared by dissolving 0.60 g (6.00 mmol) of 2(5H)thiophene in 20 ml of a 10% aqueous potassium hydroxide solution, and stirred. After completion of the reaction, 2 M hydrochloric acid was added to the resultant solution until the pH thereof reached about 4. The mixture was filtrated to obtain a crude product. The mixture was separated and purified using a silica gel column to obtain 0.29 g of an ocherous solid.
0.12 g (0.35 mmol) of the obtained molecule dissolved in chloroform and 0.039 g (0.39 mmol) of triethylamine were stirred in an ice bath, and 0.041 g (0.39 mmol) of methacryloyl chloride was slowly added dropwise thereto and stirred overnight. After completion of the reaction, the resultant mixture washed with an aqueous potassium carbonate solution, a saturated sodium chloride solution, and distilled water, and extracted with chloroform. The solvent was distilled off under reduced pressure, to obtain a molecule of the following formula as ocherous powder.
The 1H-NMR data of the obtained molecule were as shown in Table 6.
1H NMR Data: 1H-NMR. δ(ppm): 1.97 (s, 3H). 4.34 (t, 2H), 4.58 (t, 2H),
In the same manner as Example 10, a compound represented by the following formula having an azo group sandwiched between cyanopyridine and N-methylaminopyridine or N-methylamino-methylpyridine was obtained.
In the same manner as Example 11, 52.2 mg (0.57 mmol) of 3-aminopyridine was dissolved in 2 M hydrochloric acid, and stirred in an ice bath. Thereto was slowly added a solution prepared by dissolving 78.2 mg (0.11 mmol) of sodium nitrite in a small amount of distilled water dropwise. After the mixture was stirred for about 15 minutes, an aqueous solution containing 0.608 g of phenol was slowly added dropwise thereto and stirred. After completion of the reaction, the resulting solution was adjusted to about pH 7 and subjected to extraction using methylene chloride. The solvent was removed from the resultant solution to obtain a crude product. The obtained crude product was purified using a silica gel column to obtain 28.4 mg of a molecule represented by the following formula as an orange solid.
The mass spectrum data of the obtained molecule were as shown in Table 7.
<C> Evaluation of Photo-Induced Birefringence Property
Comparison Between Cyanoazobenzene and Dicyanoimidazole
Polymers 1 and 2 of the following formulae were compared with respect to properties.
Each sample was obtained by spin-coating a 1-mm-thick glass substrate with a chloroform-tetrahydrofuran solution of each Polymer (10 wt %) at 700 revolutions/minute. As shown in
In the same manner as Example 20, the homopolymer of the invention represented by the following formula and the homopolymer of cyanoazobenzene were compared and evaluated with respect to photoresponsive properties.
From
A copolymer represented by the following formula of the monomer constituting the homopolymer of the invention in Example 21 and a monotolan monomer (copolymerization ratio of 1:1 and 2:1) was evaluated with respect to photoresponsive properties.
The optical system for evaluation and measurement conditions were the same as Example 20.
The absorption spectrum of the 2:1 copolymer (3.3×10−6 mol/L in CHCl3) is shown in
Each sample was obtained by spin-coating a 1-mm-thick glass substrate with a dichloromethane solution of each copolymer (5 wt %) at 700 revolutions/minute.
The respective photo-induced birefringence dynamics thereof are shown in
From
In the same manner, a copolymer represented by the following formula of the monomer constituting the homopolymer of the invention in Example 21 and a bistolan monomer (copolymerization ratio of 1:1) was evaluated with respect to photoresponsive properties.
The photo-induced birefringence dynamics of the copolymer are shown in
A copolymer represented by the following formula (x:y:z 1:1:1) was evaluated in the same manner with respect to photoresponsive properties.
The photo-induced birefringence dynamics of the copolymer are shown in
It was found that the copolymer showed a large photo-induced birefringence value of about 0.059 per 1 μm-thick film and a slight relaxation (although a little signal change was observed immediately after the light was blocked). It is considered that these results are attributable to the pasticization effect of the system due to the introduction of a methylmethacrylate monomer. On the contrary, from the viewpoint of introduction amount of dye, by introducing a methylmethacrylate monomer unit, the copolymer exerted equivalent photo-induced birefringence with a smaller introduction amount of dye than that of the monotolan copolymer, therefore, it is also an extremely preferable property from the viewpoint of application thereof to memory for practical purposes.
Synthesis examples of the compounds with a tolan structure and a bistolan structure to be used in Examples 22 to 24 are described.
1) Synthesis of Methacrylate Monomer with Tolan Structure
1.10 g (5 mmol) of 4-iodophenol, 0.935 g (5.5 mmol) of 4-ethynyl-α,α,α-rifluorotoluene, 0.019 g of copper iodide, 0.289 g of a palladium catalyst (Pd(PPh3)4) were dissolved in a mixed solvent of 200 ml of triethylamine and 10 ml of THF and reacted at room temperature for 10 hours or more. The reaction product was extracted with ether and subjected to separation and purification by column chromatography to obtain 1.31 g of a product.
To 1.31 g (5 mmol of the obtained product and 1.25 g (10 mmol) of 2-bromoethanol, 138 g (10 mmol) of potassium carbonate was added, and the mixture was refluxed in acetone for 72 hours. The reaction product was extracted with ether and subjected to separation and purification by column chromatography to obtain 0.82 g of a compound with a structure represented by the following formula as a white solid.
0.755 g (2.5 mmol) of the resultant white solid was reacted with 0.523 g (5 mmol) of methacryloyl chloride in the presence of 0.506 g (5 mmol) of triethylamine. After completion of the reaction, the resultant solution was subjected to extraction using chloroform, and recrystallization from methanol to obtain 0.61 g of a white solid.
The obtained white solid is a monomer with a structure of the following structure and the 1H-NMR spectrum and absorption spectrum of the monomer are shown in
The polymerization method for obtaining a random copolymer of this monomer and a methacrylate monomer of a heterocyclic azo compound is in accordance with the method described above.
2) Synthesis of Methacrylate Monomer with Bistolan Structure
1.10 g (5 mmol) of 4-iodophenol, 0.996 g (5.5 mmol) of 1-bromo-4-ethynylbenzene, 0.019 g of copper Iodide, 0.289 g of a palladium catalyst (Pd(PPh3)4) were dissolved in a mixed solvent of 200 ml of triethylamine and 10 ml or THF and reacted at room temperature for 10 hours or more. The reaction product was extracted with ether and subjected to separation and purification by column chromatography to obtain 1.27 g of a product of the following formula.
0.68 g (2.5 mmol) of the above compound, 0.45 mlg (2.76 mmol) of 4-ethynyl-α,α,α-trifluorotoluene, 0.009 g of copper iodide, 0.145 g of a palladium catalyst (Pd(PPh3)4) were dissolved in 100 ml of triethylamine and reacted at 90° C. for 2 hours or more. The reaction product was extracted with ether and subjected to separation and purification by column chromatography to obtain 0.79 g of a compound of the following formula.
To 0.995 g (2.64 mmol) of the above compound and 0.55 ml (7.76 mmol) of 2-bromoethanol, 0.725 g (5.25 mmol) of potassium carbonate was added, and the mixture was refluxed in butanone for 72 hours. The reaction product was extracted with ether and subjected to separation and purification by column chromatography to obtain 0.50 g of a compound of the following formula as a white solid.
0.354 g (0.87 mmol) of the obtained white solid was reacted with 0.135 g (1.29 mmol) of methacryloyl chloride in the presence of 0.36 ml (2.85 mmol) of triethylamine. After completion of the reaction, the resultant solution was subjected to extraction using chloroform, and recrystallization from methanol to obtain 0.21 g of a compound of the following formula as a white solid.
A 1:1 copolymer with a cyanobiphenyl monomer represented by the following formula was evaluated in the same manner with respect to photoresponsive properties.
It was found that the copolymer showed a photo-induced birefringence value (about 0.035/μm) about 3 times as large as that of Polymer (2) (1:1 copolymer) in Example 20. Also, it was found that the relaxation immediately after the light was blocked was improved by about 4 times, i.e., from about 23% to about 5%. It is considered that this is attributable to the effect on stabilization of orientation based on the liquid crystallinity of the cyanobiphenyl group introduced as a copolymerization component. Further, from the viewpoint of introduction amount of dye, the copolymer exerted about 3 times photo-induced birefringence with a smaller introduction amount of dye than that of the 1:1 copolymer (the above Polymer 2) of Molecule (2) and a methylmethacrylate monomer, therefore, it is also an extremely preferable property from the viewpoint of application thereof to memory for practical purposes.
In the same manner, polymers 3, 4 and 5 represented by the following formulae were compared and effects of the introduction of a copolymerization component with large birefringence on properties were examined. The results are shown in
As shown in
The comonomers as the copolymerization components for increasing the photo-induced birefringence may be synthesized by, for example, the following steps.
(1: Example of Compound Having Connected Two Azo Groups)
71.0 g (3.16 mmol) of Disperse Yellow, 0.79 g (632 mmol) of 2-bromoethanol, and 0.87 g (6.32 mmol) of potassium carbonate were dissolved in 50 ml of acetone, and reacted at 50° C. for 72 hours. Then, the mixture was air-cooled to the room temperature, extracted using 100 ml of chloroform and 100 ml of a saturated aqueous potassium carbonate solution, and extracted using 200 ml of chloroform and 200 ml of aqueous sodium chloride solution. The resultant solution washed with distilled water twice, and subjected to a filtration. The obtained powder was subjected to recrystallization from ethanol to obtain Molecule (9) of the following formula with a yield of 74%
0.288 g (0.8 mmol) of the obtained Molecule (9) and 0.162 g (1.6 mmol) of triethylamine were dissolved in dichloromethane and stirred in an ice bath. 0.167 g (1.6 mmol) of methacryloyl chloride was slowly added dropwise thereto and stirred overnight. After completion of the reaction, the mixture washed with an aqueous potassium carbonate solution, a saturated sodium chloride solution, and distilled water, and extracted with chloroform. The solvent was distilled off under reduced pressure to obtain Molecule (10) of the following formula as brown powder.
The NMR spectrum and ultraviolet-visible absorption spectrum of Molecule (10) are shown in
The thus synthesized Molecule (10) was copolymerized with Molecule 2 described in Example 1 in the same manner as Example 1, to obtain a copolymer with increased photo-induced birefringence using Molecule (10) as an optically anisotropic group.
(2: Example of Compound Having Cyanobiphenyl Group)
35 ml of ethanol was added to 13.8 g (100 mmol of 4-hydroxybenzoic acid, and thereto was further added a solution prepared by dissolving 15.0 g (270 mmol) of potassium hydroxide and 1.0 g of potassium iodide in 15 ml of water. 14.6 ml (110 mmol) of 6-chloro-1-hexanol was added to the mixture dropwise and refluxed overnight. After the solvent was removed, the residue was dissolved in water, and hydrochloric acid was added thereto, and then, the resulting precipitates were isolated and washed with water. The precipitates were subjected to recrystallization from ethanol to obtain a white solid with a yield of 62.2%.
40 ml of 1,4-dioxane, 1.0 ml (7.7 mmol) of N,N-dimethylaniline, and a small amount of 2,6-di-tert-butyl-p-cresol were added to 1.67 g (7 mmol) of the obtained white solid. The mixture was kept at 60° C., and 0.6 ml (7.7 mmol) of acryloyl chloride was slowly added dropwise thereto and stirred for 2 hours. After completion of the reaction, the mixture was subjected to extraction using chloroform and recrystallization from a tetrahydrofuran/hexane mixed solvent, to obtain a white solid with a yield of 27.3%.
To 0.75 g (2.6 mmol) of the white solid were added a drop of dimethylformamide, 9.1 ml (130 mmol) of thionyl chloride, and a small amount of 2,6-di-tert-butyl-p-cresol. After the mixture was stirred for 30 minutes in a water bath, 30 ml of tetrahydrofuran was added to the mixture. Then, a solution prepared by dissolving 0.5 g (2.6 mmol) of 4-hydroxy-4′-cyanobiphenyl and 1.8 ml (12.8 mmol) of triethylamine in 10 ml of tetrahydrofuran was added dropwise, and the resulting mixture was stirred overnight. The tetrahydrofuran was removed, and the residue was purified by column chromatography using a chloroform/ethyl acetate mixed solvent, to obtain white solid of Molecule (11) with a yield of 59%. The polymerization method for obtaining a random copolymer of Molecule 11 and a methacrylate monomer of an azo compound is in accordance with the method described above.
The NMR data of Molecule 11 are shown in
Further, the following example of synthesizing a compound having a cyanobiphenyl group is described.
That is, first, to 3.0 g (15 mmol) of 4-hydroxy(1,1′-biphenyl)-4-carbonitrile and 18.74 g (150 mmol) of 2-bromoethanol, 20.73 g (150 mmol) of potassium carbonate was added, and the mixture was refluxed in acetone for 48 hours. After the solvent was removed, the residue washed and dried to obtain 2.45 g of a light yellow solid.
2.0 g (8.36 mmol) of the obtained white solid was reacted with 1.06 ml (11 mmol) of methacryloyl chloride in the presence of 1.8 ml (13 mmol) of triethylamine. After completion of the reaction, the resultant solution was subjected to extraction using chloroform, and recrystallization from methanol to obtain 0.85 g of a white solid.
The 1H-NMR data of the obtained solid were as shown in Table 8.
1H NMR (δ[ppm], CDCl3): 1.96 (t, 3H), 4.28 (t, 2H), 453 (t, 2H),
A 1:1 copolymer represented by the following formula of the methacrylate monomer of Molecule (6) of the above Example 6 and Molecule (10) was evaluated with respect to photoresponsive properties.
The optical system for evaluation and measurement conditions were the same as Example 20.
As shown in
A 1:1 copolymer represented by the following formula was evaluated in the same manner as above with respect to photoresponsive properties.
As shown in
A 1:1 copolymer represented by the following formula of the above Molecule (2) and Molecule 10 was evaluated in the same manner with respect to photoresponsive properties.
This copolymer showed a photo-induced birefringence value (about 0.061/μm) about 5 times as large as that of the 1:1 copolymer (Polymer 2) of Molecule (2) and the methylmethacrylate monomer. Even if it is compared with the photo-induced birefringence value of the 1:1 copolymer of Molecule 2 and the cyanobiphenyl methylmethacrylate monomer, about 1.7 times improvement was achieved. Further, also the relaxation immediately after the light was blocked was about 7%, which showed that the improvement was achieved. However, it was found that the responsiveness was slightly delayed. It is considered that thus was attributable to the large molecular birefringence and motility of Molecule (10) introduced as a copolymerization component.
According to the present invention as described above, compared with the prior art, various holographic optical information recording properties such as sensitivity, response speed, long-term storage stability, and repeatability can be significantly improved and increased, and there is provided the high-performance optical information recording material or medium.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2004-235687 | Aug 2004 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2005/015105 | 8/12/2005 | WO | 00 | 5/18/2007 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2006/016725 | 2/16/2006 | WO | A |
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| Number | Date | Country | |
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| 20070242322 A1 | Oct 2007 | US |
