JPH11158148A - New 5-alkoxy-2-(2-pyridylazo)phenol compound and new photoresponsive lb membrane containing the same compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful as a component for photoresponsive LB membrane having a function incorporating a metal or a metal oxide ion by light irradiation. SOLUTION: This compound is represented by the formula (R is a 14-22C alkyl). The compound of the formula can be obtained by alkylating 4-(2- pyridylazo)-resorcinol with a 14-22C alkyl bromide in an inert solvent. For example, the compound of the formula (R is C18 H37 ) is synthesized by a method dissolving 4-(2-pyridylazo)resorcinol sodium salt and octadecyl bromide in dimethylformamide and stirring the mixture at room temperature for 3 day. This photoresponsive LB membrane having a function incorporating a metal or a metal oxide ion by light irradiation can be provided by including the compound of the formula. The photoresponsive LB membrane is useful as a recordable material capable of carrying out recording-erasing of information.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 5-alkoxy-2- (2-pyridylazo) phenol compound, a novel photoresponsive LB film containing the compound, and a photoresponsive LB film.
A metal or metal oxide ion-containing LB film in which metal or metal oxide ions are regularly arranged on a film, a recording material containing the photoresponsive LB film, and a metal or metal oxide using the photoresponsive LB film The present invention relates to a method for collecting and detecting ions. Photoresponsive LB of the present invention
The film captures a metal or metal oxide ion by light irradiation and dissociates the metal or metal oxide ion by contact with an acid, so that the film is useful as a recording material capable of recording and erasing information. Alternatively, it can be used for recovery and detection of metal oxide ions.

[0002]

2. Description of the Related Art Langmuir-Blodgett (LB) films are multilayer films having a structure in which molecules are regularly arranged, and various applications have been attempted. By arranging molecules regularly, the nonlinear optical response is improved, and it is possible to apply it as a non-linear optical element. There is. However, it is not easy to form a stable LB film by arranging a large number of molecules in a regular manner, and it is difficult to form a LB film, or even if the LB film can be formed, it is not stable. In order to stabilize the film, various methods have been devised such as synthesizing and using a molecule in which a long alkyl chain is connected to a relatively hydrophilic organic functional group.

[0003] Many researchers have attempted to introduce metal ions into an LB film to form a film in which ions are arranged. This is because, by arranging and assembling metal ions having magnetism at a certain density or higher, it is theoretically expected that the magnetism will be expressed, leading to the development of a new magnet. In the research examples so far, a method of first synthesizing a compound containing a metal ion and forming it on an LB film is mainly performed. Although there are some successful cases with this method, depending on the compound, it is extremely difficult to form a film, metal ions are dissociated during film formation, and the formed film can be kept stable for a long time. In many cases, it has been extremely difficult to form an LB film in which metal ions are arranged regularly and reliably with respect to various kinds of metal ions.

On the other hand, it has been attempted to introduce a photochromic material into a polymer film or the like and use it effectively as an optical recording material. If a permanent change can be made at a desired place using a laser or the like and further read out, it can be effectively used as a storage medium.
If a material containing metal ions is used in such a method,
In addition to reading by light, electrical and magnetic reading can be performed. However, there is no known example of applying an LB film containing a metal to this field.

Methods for detecting trace metal ions in a solution include atomic absorption analysis, X-ray fluorescence analysis, and ICP.
Analyzes and the like exist, but their sensitivity can be further enhanced by combining them with other separation methods. For example, pretreating a sample with a highly selective adsorbent, an ion-exchange resin, a chelating agent, or a reagent that forms a precipitate, and concentrating metal ions, can further expand the application range of the above-described high-sensitivity analysis method. it can. Such a method of separating into a solid phase has been used as a standard method in analytical chemistry since ancient times because it has a high concentration rate and can increase the detection sensitivity through a measuring method.

[0006]

The LB film having a structure in which various kinds of metal ions are regularly arranged is always stable and regularly arranged irrespective of the kind of ions, although various applications are expected. There has been no effective way to make a membrane. Further, there is not much known an example in which a complex formation reaction is introduced into the LB film and metal ions are introduced into the LB film by the complex formation reaction. However, if the introduction of metal ions into the LB film by this complexing reaction can be controlled by light, an optical recording material can be produced, and the stable metal ions once taken in can be externally processed by a certain treatment. If it can be taken out, it can be used as an optical recording material from which recorded information can be erased, and can be used as a method for collecting and detecting metal ions.

The present invention provides a novel 5-alkoxy-2-
An object of the present invention is to provide a (2-pyridylazo) phenol compound and a photoresponsive LB film containing the compound and having a function of taking in a metal or metal oxide ion by light irradiation. By using the photoresponsive LB film of the present invention,
After a stable LB film is first formed, a method of introducing a metal or metal oxide ion by a complex formation reaction can be adopted. Therefore, an LB film in which a wide range of metal or metal oxide ions is stably and regularly arranged. It is possible to obtain In addition, the photoresponsive LB film of the present invention not only captures metal or metal oxide ions, but also dissociates the captured metal or metal oxide ions by contact with an acid. It is useful as a possible recording material and can be used for recovery of metal or metal oxide ions and high-sensitivity detection.

[0008]

That is, the present invention provides a compound of the formula (I)

[0009]

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(Wherein R represents an alkyl chain having 14 to 22 carbon atoms).

The present invention also relates to a photoresponsive LB film containing the compound of the formula (I).

The present invention further provides a metal- or metal-oxide ion-containing LB in which metal or metal oxide ions are regularly arranged in the photoresponsive LB film.
Forming a photoresponsive LB film from a film and a compound having the formula (I), and then introducing a metal or metal oxide ion into the LB film by light irradiation. The present invention also relates to a method for manufacturing an LB film. Light irradiation is preferably performed with light of 300 to 400 nm.

The present invention is further characterized in that a recording material comprising the photoresponsive LB film, and information is recorded by introducing a metal or metal oxide ion into the recording material by light irradiation. A method for recording information on a recording material, wherein the recording material on which the information is recorded is contacted with an acid to dissociate a metal or metal oxide ion, thereby erasing the information. It also relates to a method of erasing the information.

Further, the present invention is directed to a method of collecting a metal or metal oxide ion by irradiating light onto the photoresponsive LB film and then contacting the photoresponsive LB film with an acid to collect the metal or metal oxide ion. In which metal or metal oxide ions are recovered.

The present invention further provides a method for collecting metal or metal oxide ions on the photoresponsive LB film by irradiating light, and bringing the metal or metal oxide ions collected on the LB film into contact with an acid. The present invention also relates to a method for detecting a low-concentration metal or metal oxide ion, which comprises dissociating and then analyzing the dissociated metal or metal oxide ion.

The metal or metal oxide ions introduced and recovered in the present invention include Ag ⁺ , Hg ²⁺ , Ni ²⁺ , Z
n ²⁺ , Cu ²⁺ , VO ²⁺ , Cd ²⁺ , Pb ²⁺ , Fe ³⁺ , Eu
Metal or metal oxide ions such as ³⁺ and UO ₂ ²⁺ are included, and Cu ²⁺ and UO ₂ ²⁺ are particularly preferable.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The 5- (5)
The alkoxy-2- (2-pyridylazo) phenol compound has a pyridine ring adjacent to the diazo group, has a trans-type structure, and has an absorption maximum near 330 nm.
Further, it has a long alkyl chain in order to form an LB film. This compound can be prepared, for example, by adding 4- (2
-Pyridylazo) resorcinol is obtained by alkylation with an alkyl bromide having 14 to 22 carbon atoms such as octadecyl bromide. Examples of the inert solvent include dimethylformamide. The reaction is performed at room temperature or under heating, and a reaction accelerator such as a catalyst may be optionally used. The compound (I) thus obtained is desirably acidified with dilute hydrochloric acid or the like, precipitated, recrystallized with acetone or the like, and purified before use.

The LB film is obtained by fixing this compound on a substrate. The substrate for forming the LB film may be any of those conventionally used, such as quartz, glass, vinyl chloride plate,
Examples thereof include a polymethyl methacrylate plate and a polyethylene terephthalate plate, and quartz, glass, and a polymethyl methacrylate plate are preferable. This LB film can be formed by any conventional method, for example, by spreading a chloroform solution of compound (I) on the surface of ion-exchanged water and accumulating it on a substrate such as quartz or a glass plate. can get.

The thus obtained LB film has a thickness of 300 to
Irradiation with light of 400 nm, preferably 330-350 nm, causes a cis-trans tautomerization reaction, resulting in a structure in which the three coordination atoms readily form a complex with a metal or metal oxide ion. FIG. 1 shows the structural change of the compound induced by light irradiation. FIG. 1 shows the case of a divalent metal or metal oxide ion. In the case of monovalent or trivalent ions, electrical neutralization is maintained by anions and cations in the solution, but basically divalent. The same structural change as in the case of is shown. When the film substrate is immersed in a metal or metal oxide ion solution, the LB film is in a state 2 in which the LB film is complexed with the metal or metal oxide ions because a gap where ions easily enter due to a change in the film structure of the LB film occurs. Become. In this state, the wavelength of the absorption maximum changes according to the type of the complexed metal or metal oxide ion. For example, in the case of uranyl ions, around 580 nm, in the case of copper ions, around 560 nm,
In the case of nickel ions, a new absorption maximum is observed around 595 nm. This photoresponsiveness is not observed in a compound released in a solution, and is a function newly developed after LB film formation.

In the LB film complexed with the metal or metal oxide ion, the compound which is a constituent molecule of the LB film is determined from the measurement of polarized UV spectrum and electron spin resonance.
It has been confirmed that (I) and the metal or metal oxide ions in the film are regularly arranged. Since the metal or metal oxide ions are regularly arranged, the metal or metal oxide ion-containing LB film of the present invention has a possibility as a magnetic material such as a magnetic tape.

In the present invention, a metal or metal oxide ion is introduced by light irradiation after preparing an LB film in advance, so that a metal or metal oxide ion-containing LB film having a uniform arrangement can be easily formed. . As a result, the range of applicable metal or metal oxide ions expands,
The resulting film is also excellent in stability.

Next, when the LB film complexed with the metal or metal oxide ion is transferred to an acid solution, the metal or metal oxide ion is dissociated into the solution with a half life of about several minutes to one day depending on conditions. , The compound changes to protonated state 3. This compound has an absorption maximum near 400 nm. At this time, the acid solution may be an acid having a concentration that does not break the LB film, and for example, hydrochloric acid, nitric acid, sulfuric acid, or the like can be used. The concentration of the acid solution is about 1N to about 3
N, preferably about 1N to about 2N. Thus, by bringing the LB film that has collected the metal or metal oxide ion into contact with the acid, the metal or metal oxide ion that has been collected in the LB film can be recovered.

The ions dissociated in the acid solution are converted to IP
C. Since the ions present in the mother liquor can be identified by analyzing by X-ray fluorescence measurement or the like, this method can also be used as a method for detecting metal or metal oxide ions. When detecting uranyl ions, the present inventors have confirmed that the photoresponsive LB film of the present invention also responds to uranyl ions at a low concentration of about 5 × 10 ⁻⁵ M.

Further, in the photoresponsive LB film of the present invention, light-irradiation is performed in a solution containing metal or metal oxide ions, and the operation of immersion in an acid solution is repeated, so that recording-erasing in the LB film is performed. It is possible to repeat the operation. That is, information can be recorded in the LB film by light irradiation (introduction of metal or metal oxide ions), and the information can be erased by contact with an acid (dissociation of metal or metal oxide ions). . Therefore, the photoresponsive LB film of the present invention is useful as a recording material capable of recording and erasing information. Furthermore, it is also possible to create an erasable pattern such as embedding metal or metal oxide ions in a linear manner in the LB film using a laser or the like.

[0025]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention does not limit the technical scope to these examples. Example 1 Synthesis of Compound (I) (R = C ₁₈ H ₃₇ ) 1.2 g of 4- (2-pyridylazo) resorcinol sodium salt, 1.6 g of octadecyl bromide were dissolved in 30 ml of dimethylformamide, and the mixture was dissolved at room temperature. Stir for 3 days. The mixture was concentrated to 10 ml, poured into 100 ml of ion-exchanged water, acidified with dilute hydrochloric acid and precipitated, and the resulting orange crystals were collected by filtration. This was recrystallized twice with acetone to obtain 0.15 g of crystals (yield 16%). Melting point 67-68 ° C ¹ H-NMR (270 MHz, CDCl ₃ ) δ 0.88 (t, 3H, CH ₃ ), 1.25 (m,
30H), 1.83 (m, 2H ), 4.01 (t, J = 6.60Hz, 2H, OCH 2), 6.
30 (d, J = 2.31Hz, 1H), 6.53 (dd, J 1 = 2.31Hz, J 2 = 9.24H
z, 1H), 7.17 (m, 1H), 7.54 (d, J = 9.42Hz, 1H), 7.83
(m, 2H), 8.58 ( d, J = 4.2Hz, 1H) Anal:. C 29 H 45 N 3 calculated as O ₂ value C: 74.48, H: 9.70, N: 8.98 Found C: 74.28, H: 9.82, N: 8.69

Example 2 Formation of LB film Compound (I) obtained in Example 1 was dissolved in chloroform, and then spread on the surface of ion-exchanged water, and the temperature was 20 ° C. and the pressure was 30 mN / m using a Lauda film balance. Pulling speed 2 under the condition of
By repeating up and down 20 times at a rate of 4 mm / min at a rate of 4 mm / min, 40 LB films were formed on the quartz substrate.

Example 3 Preparation of LB Film Containing Metal or Metal Oxide Ions FIG. 2 shows an experimental apparatus used for light irradiation in this example. 50
Collimates the light from the 0W ultra-high pressure mercury lamp (1)
(2) Light is irradiated through a bandpass glass filter (4) of 330 nm. From the compound (I) obtained in Example 1, a photoresponsive LB film was formed on a 4 × 1 cm quartz substrate, and this was introduced into a 1 cm square cell (7) for measuring an absorption spectrum.
The total amount of compound (I) in the LB film was about 5 × 10 ⁻⁸ mol. A 0.5 mM UO ₂ (NO ₂ ) ₃ aqueous solution and a 0.5 mM NiCl ₂ aqueous solution were introduced into the square cells containing the LB film substrate (5), respectively, and light irradiation was performed.

FIG. 3 shows the measurement results of the absorption spectrum.
FIGS. 3A and 3B show changes in absorption spectra when uranyl ions and nickel ions are introduced, respectively. 33 before irradiation
It is in a state having an absorption maximum near 0 nm, but when this LB film is introduced into a 0.5 mM metal or metal oxide aqueous solution and irradiated with light, the absorption spectrum gradually changes as shown in FIG. It can be seen that the state changed to a complexed state.

FIG. 4 shows L in a state of complex formation with copper ions.
3 shows an electron spin resonance (ESR) spectrum of a B film.
The measurement was performed while changing the angle of the magnetic field with respect to the LB film. FIG. 5 shows the polarization U of the LB film complexed with zinc ions.
5 shows a V spectrum. FIG. 4 shows that the angle dependence of the ESR signal indicates out-of-plane anisotropy, and that the metal ions in the metal ion-containing LB film are regularly arranged in the normal direction of the substrate. From the polarized UV spectrum of FIG.
As in SR, it can be seen that metal ions are regularly arranged in the normal direction of the substrate.

Example 4 Recovery of Metal Ions The LB film from which metal ions were collected in Example 3 was transferred to a 1N aqueous hydrochloric acid solution and left without irradiation. FIG. 6 shows the result of dissociation of copper ions. From FIG. 6, it was confirmed that approximately 100% of the copper ions were dissociated into the aqueous hydrochloric acid solution in about 30 minutes. Of recovery immediately Chi, the metal ion is hydrochloric acid water volume solution
Was.

[0031] Place the LB film obtained by use EXAMPLE 2 Example 5 As a recording material 0.5MMCuCl ₂ aqueous solution, in 0.5MMNiCl ₂ aqueous solution, as shown in FIG. 7, "Cu" or "Ni" When light irradiation was performed on the LB film for 60 minutes through a light-shielding sheet cut out from the characters,
The letters "Cu" or "Ni" were recorded on the LB film. The result is shown in FIG. FIG. 8A shows 0.5 mM Cu.
When using Cl ₂ solution, (b) is a case of using 0.5MMNiCl ₂ solution. This character is very stable even when the LB film is taken out of the aqueous solution containing metal ions.
No change was seen for more than two months. By immersing the LB film on which the characters were recorded again in a 1N or more aqueous hydrochloric acid solution, the characters "Cu" or "Ni" could be erased.

[0032]

According to the present invention, a novel 5-alkoxy-2- (2-pyridylazo) phenol compound and a novel photoresponsive LB film containing the compound are provided. Further, by using the photoresponsive LB film, it is possible to adopt a method in which a stable LB film is first generated and then a metal or a metal oxide ion is introduced by a complex formation reaction. It is possible to obtain an LB film in which metal oxide ions are arranged stably and regularly. In addition, the photoresponsive LB film of the present invention not only captures metal or metal oxide ions, but also dissociates the captured metal or metal oxide ions by contact with an acid. It is useful as a possible recording material, and can be used for recovery of metal or metal oxide ions and high-sensitivity detection.

[Brief description of the drawings]

FIG. 1 is a diagram showing a compound used in the present invention and a change in its state.

FIG. 2 is a diagram showing an arrangement of a light irradiation experiment apparatus according to a third embodiment of the present invention.

FIG. 3 is a diagram showing a measurement result of an absorption spectrum in Example 3 of the present invention.

FIG. 4 is a diagram showing a measurement result of electron spin resonance in Example 3 of the present invention.

FIG. 5 is a diagram showing a measurement result of a polarized UV spectrum in Example 3 of the present invention.

FIG. 6 is a diagram showing a measurement result of an absorption spectrum in Example 4 of the present invention.

FIG. 7 is a diagram illustrating an apparatus used for a recording test according to a fifth embodiment of the present invention.

FIG. 8 is a diagram showing the results of a recording test in Example 5 of the present invention.

[Explanation of symbols]

Reference Signs List 1 500 W ultra-high pressure mercury lamp 2 Collimating optical system 3 Shutter 4 Band pass filter 5 LB film substrate 6 0.5 mM metal or metal oxide ion-containing aqueous solution 7 1 cm square cell 11 Mercury lamp 12 LB film substrate 13 0.5 mM metal ion-containing aqueous solution 14 Shading sheet

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G11B 7/24 522 G11B 7/24 522A (72) Inventor Hiroo Nakahara 3-5-27 Minami Oizumi, Nerima-ku, Tokyo (72) Invention Yoshinobu Izumi 3-18-30-603 Yamadahigashi, Suita-shi, Osaka

Claims (16)

[Claims] 1. A compound of the formula (I) (Wherein, R represents an alkyl chain having 14 to 22 carbon atoms). 2. Photoresponsive L containing the compound according to claim 1.
B film. 3. An LB film containing metal or metal oxide ions, wherein the LB film according to claim 2 contains metal or metal oxide ions in a regularly arranged manner. 4. The method according to claim 1, wherein the metal or metal oxide ion is
Ag ⁺ , Hg ²⁺ , Ni ²⁺ , Zn ²⁺ , Cu ²⁺ , VO ²⁺ , C
^{d 2+, Pb 2+, Fe 3+} , is selected from the group consisting of Eu ³⁺ and UO ₂ ^2+, claim 3, wherein the metal or metal oxide ion-containing LB film. 5. The metal according to claim 3, wherein the photoresponsive LB film according to claim 2 is formed, and then a metal or metal oxide ion is introduced into the LB film by light irradiation. Alternatively, a method for producing a metal oxide ion-containing LB film. 6. The method according to claim 5, wherein the light irradiation is performed with light of 300 to 400 nm. 7. A recording material comprising the LB film according to claim 2. 8. A method for recording information on a recording material according to claim 7, wherein information is recorded on the recording material by introducing a metal or metal oxide ion by light irradiation. 9. The recording method according to claim 8, wherein the light irradiation is performed with light of 300 to 400 nm. 10. A method of erasing a recording material on which information has been recorded by the method of claim 8 or 9 by contacting the recording material with an acid to dissociate metal or metal oxide ions. A method for erasing information recorded on the recording material. 11. A metal or metal oxide ion is collected on the photoresponsive LB film according to claim 2 by light irradiation,
Next, a metal or metal oxide ion collected on the LB film is dissociated by contact with an acid to recover the metal or metal oxide ion. 12. The method according to claim 12, wherein said metal or metal oxide ion is Ag ⁺ , Hg ²⁺ , Ni ²⁺ , Zn ²⁺ , Cu ²⁺ , V
^{O 2+, Cd 2+, Pb 2+} , Fe 3+, it is selected from the group consisting of Eu ³⁺ and UO ₂ ^2+, recovery method of claim 11, wherein. 13. The recovery method according to claim 11, wherein the light irradiation is performed with light of 300 to 400 nm. 14. A metal or metal oxide ion is collected on the photoresponsive LB film according to claim 2 by light irradiation,
A metal or metal oxide ion having a low concentration, wherein the metal or metal oxide ion trapped on the LB film is dissociated by contact with an acid, and then the dissociated metal or metal oxide ion is analyzed. How to detect. 15. The method according to claim 15, wherein the metal or metal oxide ion is Ag ⁺ , Hg ²⁺ , Ni ²⁺ , Zn ²⁺ , Cu ²⁺ , V
^{O 2+, Cd 2+, Pb 2+} , Fe 3+, it is selected from the group consisting of Eu ³⁺ and UO ₂ ^2+, detection method of claim 14, wherein. 16. The detection method according to claim 14, wherein the light irradiation is performed with light having a wavelength of 300 to 400 nm.