JP4660737B2 - Spiro compound and method for producing the same, photoresponsive composition and photoresponsive polymer using the same - Google Patents

Description

  The present invention relates to a technical field using a photochromic phenomenon, and relates to a photochromic compound exhibiting a reversible color change by light irradiation and a method for producing the same. The present invention also relates to a spiro compound having photochromic properties, and a photoresponsive composition and photoresponsive polymer obtained thereby.

There are compounds that change in the absorption spectrum when irradiated with ultraviolet rays or short-wavelength visible light, and are called photochromic (photoresponsive) compounds. This photochromic compound is roughly classified into an inorganic compound and an organic compound, but each has problems and advantages.
Inorganic photochromic compounds include Hg ₂ S ₂ I ₂ , ZnS, etc., but generally have poor processability, lack of abundant color tone, and are unstable to humidity, resulting in poor applicability. .
On the other hand, organic photochromic compounds have excellent properties such as good processability and various color tones. Examples of organic photochromic compounds that have been proposed so far include benzospiropyrans, spirooxazines, fulgides, diarylethenes, anthracenes and the like.

  As mentioned above, organic photochromic compounds are excellent in processability and variety of color tones. In addition, derivatives can be molecularly designed according to the purpose, and they are excellent in dispersion and homogenization in polymer films. There are many advantages such as applying various methods, using various media, and applying them to various shapes. Thus, its use is expected as various light control materials, recording materials, or display materials.

  However, organic photochromic compounds also have problems and generally have a narrow absorption wavelength range in a colored state, and few compounds can cover a visible light range of 400 to 700 nm with a single compound. A wide absorption range is indispensable for use as a light control material. As a solution, it is conceivable to mix a plurality of organic photochromic compounds to cover the visible light region. However, in this method, there is a difference in the quantum yield of the photoreaction and a difference in the return speed due to heat between the organic photochromic compounds, and the color tone changes in the process of color development and decoloration, which is a problem.

Non-Patent Document 1 reports a photochromic compound having absorption in a relatively wide wavelength range, a synthesis method thereof, and a function thereof. However, the synthesis method disclosed here is multistage and not practical. In addition, there is a problem that a mixture of a decolorant and a color former is formed due to thermal equilibrium.
To date, there are few compounds that satisfy all the required performances as various light control materials, recording materials, and display materials, and search for better compounds has been conducted.

“Chemical Review”, Minkin, V. I., 2004, 104, 2751

  The present invention relates to a spiro compound having a photochromic characteristic in which the absorption wavelength range of the color former is wide (for example, spreading over the entire visible light range), and its efficient (for example, no complicated process is required, and a short time and low cost). ) To provide a manufacturing method. Furthermore, an object of the present invention is to provide a composition and a polymer compound containing the spiro compound having the photochromic property, and a production method thereof.

（２）（１）記載のスピロ化合物を高分子化合物中に分散させたことを特徴とする光応答性組成物。
（３）１，８−ジアミノナフタレンの酸化工程を含むことを特徴とする下記化合物（Ｉ）または（II）で表されるスピロ化合物の製造方法。

The above problems have been achieved by the following means.
(1) A spiro compound represented by the following compound (I) or (II).

(2) A photoresponsive composition, wherein the spiro compound according to (1) is dispersed in a polymer compound.
(3) A process for producing a spiro compound represented by the following compound (I) or (II), which comprises an oxidation step of 1,8-diaminonaphthalene.

The spiro compound of the present invention exhibits photochromic properties, has a wide absorption wavelength range of the color former (for example, over the entire visible light range), and can be an excellent light control material. Furthermore, the spiro compound of the present invention does not require a complicated production process and can be produced efficiently (for example, in a short time and at a low cost in a one-step reaction from a commercially available compound). Is also possible.
Moreover, since the spiro compound of this invention has a primary amino group, it can introduce | transduce into a high molecular compound and another organic compound by a chemical bond. Furthermore, the spiro compound of the present invention can be dispersed in a polymer compound to form a composition. The obtained polymer compound or composition can be coated on a substrate to form a film, and can be widely used as an excellent light control material, recording material, and display material.

  The spiro compound (I) or (II) represented by the following chemical formula of the present invention will be described in detail below.

Compound (I) or (II) has two states (first colored state and second colored state) that change reversibly. The two colored states have different absorption wavelengths, and can be alternately changed by light irradiation or the like. It is preferable that the range of the absorption wavelength in any one of the two colored states is wide.
In a colored state showing a wide absorption wavelength range, the absorption wavelength extends in the range of 400 nm to 700 nm.
The absorption wavelength of light can be measured by, for example, a common visible / ultraviolet absorption spectrum measuring apparatus, and the range of absorption wavelength (spread) is continued by a range in which absorption is recognized (for example, the absorbance is 0.1 or more). ) Can be determined.

The change from the first colored state to the second colored state can be performed by light irradiation, and is preferably performed by light irradiation with a wavelength of 360 nm to 440 nm. The time (response) required for the state change by light irradiation is preferably 10 to 300 seconds. Although there is no restriction | limiting in particular in the conditions to change a state (light irradiation), It is preferable to carry out at the temperature of 0-80 degreeC. The apparatus for irradiating light is not particularly limited as long as light having a preferable wavelength can be obtained. For example, a mercury lamp can be used.
The change from the second colored state to the first colored state can be performed by light irradiation or standing. In the case of light irradiation, it is preferably performed by light irradiation with a wavelength of 440 nm to 750 nm. The time (response) required for the state change by light irradiation is preferably 10 seconds to 3 hours. Although there is no restriction | limiting in particular in the conditions to change a state (light irradiation), It is preferable to carry out at the temperature of 0-80 degreeC. The apparatus for irradiating light is not particularly limited as long as light having a preferable wavelength can be obtained. For example, a laser irradiation apparatus can be used.
When changing the state by standing still, there are no particular restrictions on the conditions, but it may be left in a dark place in order to distinguish it from light irradiation. As for the temperature to stand still, 20-100 degreeC is preferable. The standing time is preferably 0.5 to 20 hours.

In the spiro compound of the present invention, it is preferable that a reversible change between two colored states can be repeated, and that there is no substantial change in the isosbestic point in the absorption spectra of the two states. Moreover, although one change can be performed by light irradiation and the other (reverse) change can be left stationary, bidirectional changes can also be performed by light irradiation of different wavelengths. Repeated changes may be made by appropriately combining these.
The color of the spiro compound of the present invention is determined by the absorption wavelength of light. However, in the state of absorption in a narrow wavelength range, the color dissolved in an organic solvent such as toluene is a pale color, for example, a pale yellow It can be said. On the other hand, in a state where the absorption wavelength is shown in a wide range, it shows a dark color, for example, dark brown or dark blue.

The spiro compound of the present invention can be produced as follows.
1,8-diaminonaphthalene can be synthesized by oxidation in an organic solvent containing an oxidizing agent. More specifically, 1,8-diaminonaphthalene can be obtained by coupling (dimerization) while partially oxidizing and dehydrogenating with an oxidizing agent.
Although there is no restriction | limiting in particular in an oxidizing agent, For example, manganese dioxide, potassium permanganate, sodium hypochlorite, potassium t-butoxy / oxygen, cuprous chloride / oxygen etc. are mentioned. Among these, manganese dioxide is preferable in that a good yield can be obtained. The amount of the oxidizing agent is preferably 100 to 1000 parts by mass with respect to 100 parts by mass of 1,8-diaminonaphthalene.

The organic solvent can be appropriately selected depending on the type of oxidizing agent, and examples thereof include benzene, toluene, t-butanol, dimethyl sulfoxide, and pyridine. The reaction temperature can be 0 ° C. to the boiling point of the solvent, and 20 to 40 ° C. is particularly preferable. If it is too high, there will be many by-products, and if it is too low, the reaction time will be long. The reaction time varies depending on the temperature and the type of oxidizing agent, but is preferably about 1 hour to 5 days. The amount of the organic solvent is preferably 20 to 500 parts by mass with respect to 100 parts by mass of 1,8-diaminonaphthalene.
In the method for producing a spiro compound of the present invention, other compounds may be added in addition to the organic solvent or the oxidizing agent as long as the yield is not impaired.

Compounds (I) and (II) are usually synthesized simultaneously. Compound (I) and compound (II) which are in a mixed state at the time of synthesis can be isolated and recovered by a purification operation. At this time, by-products (for example, 8,8′-diamino-1,1′-azonaphthalene) and the like contained at the same time are also removed by a purification operation, and the compound (I) or (II) is isolated, respectively. Is preferred.
The purification operation can be performed by column chromatography, recrystallization from a solution, or a combination thereof. As column chromatography used for isolation and purification of compound (I) or (II), it is preferable to use neutral silica gel as a stationary phase. As the mobile phase, hexane, ethyl acetate or the like can be used.
The purity of the isolation and purification is not particularly limited as long as the photoresponsiveness is not impaired, but 95 to 100% by mass is practical.

The spiro compound of the present invention can be a composition dispersed in a polymer, or can be a solid thin film of a polymer compound having photochromic properties by chemical bonding in the polymer compound.
Polystyrene, polymethyl methacrylate, or the like can be used as the polymer compound to be dispersed to form a composition, but a polymer compound having a low polarity is preferable because of high coloring efficiency. The content of the spiro compound of the present invention is preferably 0.5 to 30 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polymer compound. If the amount of the spiro compound of the present invention is too small, the color density is low, and if it is too large, a non-uniform film tends to be formed.
The method for bonding the spiro compound of the present invention to the polymer compound is not particularly limited, and a conventional method can be used. However, compound (I) or (II) is added to a polymerizable monomer having reactivity with an amino group. It is preferable to obtain a polymerizable photochromic monomer by chemical bonding. Thereafter, a photochromic (photoresponsive) polymer can be obtained by heat or photopolymerization. Examples of the polymerizable monomer having reactivity with an amino group include methacrylic acid chloride, acrylic acid chloride, polyfunctional isocyanate and the like.

  There is no restriction | limiting in particular in the thickness of the film | membrane formed with the high molecular compound or composition containing the spiro compound of this invention, Although it determines suitably according to a use, 0.0002-2 mm is preferable, for example. Although there is no restriction | limiting in particular in the board | substrate which forms a film | membrane, For example, a glass substrate etc. are mentioned. In addition to the polymer compound layer containing the spiro compound of the present invention, a protective layer or the like may be added on the substrate.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

Example 1
Synthesis of Compound (I) and Compound (II) 2.5 g of 1,8-diaminonaphthalene was dissolved in 250 ml of dry benzene, and 13 g of activated manganese dioxide and 1 g of molecular sieve 4A were added to this solution at room temperature ( (27 ° C.) for 3 hours. The reaction mixture was filtered and the solvent was removed from the filtrate under reduced pressure. The obtained product was isolated and purified by column chromatography using silica gel 60 as a stationary phase and hexane / ethyl acetate (4/1 volume ratio) as a mobile phase. The structure was confirmed from the analysis results shown below.

Compound (I): Yield 3%, yellow solid, ¹ H NMR ((CD ₃ ) ₂ CO, 300 MHz) 6.09 (br, 2H, NH ₂ ), 6.16 (d, J = 9.87 Hz, 1H), 6.40 -6.46 (m, 2H), 6.64 (d, J = 7.41 Hz, 2H), 6.75 (d, J = 9.33 Hz, 2H), 7.12-7.16 (m, 3H), 7.23 (t, 2H) 7.70 (br , 2H, NH), 10.79 (s, 1H, NH); ¹³ C NMR (150 MHz, CDCl ₃ ) 65.44, 106.18, 109.00, 111.42, 115.80, 116.47, 117.23, 126.94, 126.98, 129.90, 131.92, 134.03, 134.32, 139.16, 150.13, 174.73, mass spectrometry ESIMS (m / z) [M + H] ⁺ calculated value (C ₂₀ H ₁₇ N ₄ ) 313.15, measured 313.23, calculated elemental analysis (C ₂₀ H ₁₆ N ₄ ): C 76.90, H 5.16 N 17.94%, measured C 76.38, H 5.00, N17.78%.

Compound (II): Yield 7%, yellow solid, ¹ H NMR ((CD ₃ ) ₂ CO, 300 MHz) 6.06 (d, J = 10.14 Hz, 1H), 6.17 (br, 2H, NH ₂ ), 6.62 (d, J = 7.14 Hz, 2H), 6.82 (d, J = 9.33 Hz, 1H), 6.96 (d, J = 10.17 Hz, 1H), 7.11-7.26 (m, 5H), 7.34 (t, 1H) , Mass spectrometry ESIMS (m / z) [M + H] ⁺ calculated value (C ₂₀ H ₁₆ N ₃ O) 314.13, measured value 314.13, elemental analysis calculated value (C ₂₀ H ₁₅ N ₃ O): C 76.66, H 4.82 N 13.41%, measured value C 76.12, H 4.60, N 13.44%.

(Example 2)
Compound (I) was dissolved in toluene at a concentration of 3 × 10 ⁻⁵ M, and the visible / ultraviolet absorption spectrum was measured with 8453 manufactured by Hewlett-Packard Company. As a result, the absorption maximum was shown at 410 nm (first state).
When this solution was irradiated with 405 nm light extracted from a mercury lamp, the intensity of the absorption band having a maximum at 410 nm decreased, and at the same time, the maximum was 490 nm, the shoulder was near 580 nm, and the long wavelength end of absorption was 700 nm. A new absorption band appeared (second state). The response was about 120 seconds. In this state, the absorption wavelength spread over 400 to 700 nm.
When it was allowed to stand at 27 ° C. in the dark, it returned to the original absorption spectrum (first state) having a maximum at 490 nm with a life of 5.4 hours (1 / k).

(Example 3)
Compound (I) was brought into the second state by the method described in Example 2. When this sample was irradiated with 532 nm laser light, it returned to the original spectrum having the absorption band at 490 nm (first state) in about 3 hours.
Furthermore, although 10 cycles of reversible photoreaction were performed by alternately irradiating 405 nm light and 532 nm light, the isosbestic point was not changed and high repetitive stability was exhibited.

Example 4
Compound (II) was dissolved in toluene at a concentration of 1.7 × 10 ⁻⁵ M, and a visible / ultraviolet absorption spectrum was measured in the same manner as in Example 2. As a result, an absorption maximum was shown at 398 nm (first state).
When this solution was irradiated with 405 nm light extracted from a mercury lamp, the intensity of the absorption band having a maximum at 398 nm decreased, and at the same time, a new absorption band having a maximum at 520 nm and 595 nm and a long wavelength end of absorption of 750 nm was obtained. Appeared (second state). The response was about 120 seconds. In this state, the absorption wavelength was spread over 400 to 750 nm.
When it was allowed to stand at 27 ° C. in the dark, it returned to the original absorption spectrum (first state) having an absorption band at 490 nm with a lifetime of 26 minutes (1 / k).

(Example 5)
Compound (II) was brought into the second state by the method described in Example 4. When this sample was irradiated with a laser beam of 532 nm, it returned to the original spectrum (first state) having an absorption band at 398 nm in about 1 hour.
Furthermore, although 6 cycles of reversible photoreactions were carried out by alternately irradiating 405 nm light and 532 nm light, the isoabsorption point did not change and high repetition stability was exhibited.

(Example 6)
1 part by mass of Compound (I) and 40 parts by mass of polystyrene were dissolved in 200 parts by mass of chloroform, about 100 parts by mass of chloroform was removed under reduced pressure, the solution was concentrated, and then coated on a glass substrate with a spin coater. The thin film obtained after drying was pale yellow and showed an absorption maximum at 410 nm (first state).
When irradiated with 405 nm light extracted from a mercury lamp, the thin film turned dark brown (second state), and then changed to the original light yellow color when left at room temperature for 10 minutes (first state). This reversible change was repeated 10 times or more.

Claims (3)

A spiro compound represented by the following compound (I) or (II).

  A photoresponsive composition, wherein the spiro compound according to claim 1 is dispersed in a polymer compound. The manufacturing method of the spiro compound represented by the following compound (I) or (II) characterized by including the oxidation process of 1, 8- diamino naphthalene.