JP2001329255A - Photochromic material and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photochromic material which has good coloration and discoloration sensitivity even when a photochromic compound is added in a small amount and which has photoresponsivity as quick as in the case when dissolved in a solvent, hardly causes isomerization due to repeated reaction, is excellent in durability in repeated use, and enables various photochromic compounds to be introduced into DNA and to provide a method for producing the same. SOLUTION: This photochromic material is prepared by introducing a substance exhibiting photochromism into deoxyriboneucleic acid. Spiropyranes, spirooxazines, diarylethenes, fulgides, and fulgimides are used as substances exhibiting photochromism.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic material and a method for producing the same. More specifically, the present invention relates to a photochromic material in which a substance exhibiting photochromism is introduced into deoxyribonucleic acid, and a method for producing the same. More specifically, the present invention relates to a photochromic material having a high photoresponsiveness and a high reaction rate, and having a significantly extended durability of a photochromic reaction, and a method for producing the same.

[0002]

2. Description of the Related Art Photochromic materials have attracted attention for their characteristic color properties and have been studied for a long time.
Currently, among photoresponsive organic dyes, the development of organic compounds exhibiting photochromism is the most active, and molecular design and synthesis research on organic compounds that match the device functions required at present are being actively conducted. Photochromism is a phenomenon that a single chemical species reversibly isomerizes between two states having different absorption spectra by the action of light without changing the molecular weight, as shown in the following formula (1). Is defined.

[0003]

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[0004] That is, the photochromism means that when a certain compound is irradiated with light having a specific wavelength hν ₁ , the color of the compound changes rapidly, and the specific wavelength h
Irradiation with light of ν ₂ shows a reversible action of returning to the original color. A substance having such properties is called a photochromic substance, and various photochromic compounds have been conventionally synthesized. However, coloring-decoloring is repeated by changing the irradiation wavelength. In many cases, however, the coloring type structure B is extremely unstable thermally, and when the reversible reaction is repeatedly performed, photodegradation of the photochromic compound is reduced. It is a big problem. The photodegradation of a photochromic compound is synonymous with the loss of photochromism, and does not always correspond to the photodecomposition of the compound itself. , The light does not develop. This is believed to be due to the photodegradation blocking photochromic development.

As photochromic compounds, spiropyrans, spirooxazines, diarylethenes,
Various compounds such as fulgides and fulgimides have been synthesized, and studies have been made on improving the thermal irreversibility of the photochromic reaction and the repetition durability of the photoreaction, but none of them have been sufficiently satisfactory.

When considering the use of these photochromic compounds as a material exhibiting photochromism, such as a thin film optical memory medium or a photochromic lens, it is effective to make the photochromic material easy to process and to form a film, etc. Polymerization by introducing a photochromic compound having an addition reactivity into the side chain or the main chain of the polymer compound.However, a side reaction of the photochromic compound cannot be prevented, and repeated durability is deteriorated. I can't have it.

The photochromic compound is generally coated or kneaded in a polymer to form a film for use. As the matrix, polyvinyl alcohol (PVA), polyethylene, polypropylene, methyl methacrylate,
Resins such as polyethylene terephthalate and polycarbonate are used.

In general, a photochromic compound in a state of being dissolved in a solvent has a better color development-fading sensitivity than in a solid state. It has been found that the durability is high. This tendency depending on the polarity is the same when a solid film is used as a medium. However, since PVA, which is a highly polar medium, is hydrophilic and many of the photochromic compounds are oil-soluble, there is a problem that the compatibility is poor when kneading into a film product, and the photochromic compound bleeds out. .

Research and development of diarylethenes and the like as compounds that cause a photoreaction even in a crystalline state are proceeding, but are realized only with specific compounds and cannot be applied to many photochromic compounds. . Further, even in the case where the film is not thinned, a technique of dispersing a photochromic material in an epoxy resin or a photocuring material to form a material has been disclosed, but in this case, the photoreaction of the photochromic compound is restricted in the resin, There were problems such as reduced reactivity.

On the other hand, deoxyribonucleic acid (hereinafter abbreviated as DNA) is an organic compound possessed by all living things on the earth, and has a molecular structure in which two polynucleotide chains are spirally wound. Nucleobases that are constituent molecules of nucleotide chains include adenine, thymine, guanine, and cytosine.
There are seeds. These nucleobases protrude inward from each other in a plane perpendicular to the center, forming so-called Watson-Crick base pairs. Thus, D
NA has a characteristic chemical structure and can be said to be a functional polymer material that interacts with various substances with extremely high specificity and selectivity. Therefore, attempts have been made to apply DNA as a natural polymer material to functional materials. As an example, it has been attempted to introduce an aromatic compound such as an organic dye into DNA and use it as a functional material.
It is already known that an aromatic compound such as an organic dye is introduced into DNA.

First, Japanese Patent Application Laid-Open No. 61-6885 discloses that
It is stated that a DNA aqueous solution is put in a mortar, and a solid, water-insoluble pigment is added thereto and then ground, whereby the aqueous solution is colored, and a complex is obtained by separating the colored solution.

Further, J. J. Am. Chem. Soc. , 1
18 (44), 1067 (1996);
No. 1-119270 discloses that a DNA-Na salt aqueous solution is mixed with an aqueous solution of a quaternary ammonium salt having a long-chain alkyl group, and the resulting precipitate is centrifuged and freeze-dried to obtain the obtained DNA-quaternary ammonium salt. Dissolve the salt complex in a non-aqueous organic solvent and cast to produce a film,
This film is added to an aqueous solution of dye or methanol solution.
A method for obtaining a film in which a dye is introduced into DNA by immersion for 4 hours is described.

[0013] Further, Polymer Preprin
ts, Japan, 48 (3), 368 (1999),
And JP-A-11-119270, DNA-
An aqueous solution of a Na salt and an aqueous solution of a quaternary ammonium salt having a long-chain alkyl group are mixed, and the generated precipitate is separated by filtration and dried.
A method is described in which the obtained DNA-quaternary ammonium salt complex is dissolved in a non-aqueous solvent, a dye is added thereto, the mixture is allowed to stand overnight, and then a film is obtained by casting the dye into the DNA.

[0014] As described above, conventionally, the purpose is to study the mode of introduction of aromatic compounds such as dyes and the like and to study the expression of limited functions, and to study materials using DNA as a matrix. Has few examples,
In particular, there is no example of studying a photochromic compound as a matrix or studying application to a photochromic material.

[0015]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a color-discoloration sensitivity which is good even with a small addition amount of a photochromic compound, and has a light response as fast as that when dissolved in a solvent. It is another object of the present invention to provide a photochromic material and a method for producing the same, wherein various photochromic compounds can be introduced into DNA, in which isomerization due to repetitive reactions is less likely to occur and which has excellent repetitive durability.

[0016]

Means for Solving the Problems As a result of intensive studies, the present inventors have introduced a photochromic substance into deoxyribonucleic acid to obtain a photochromic substance having excellent photochromic reactivity, stability and repetition durability. A material and its manufacturing method have been found.

That is, the present invention provides a photochromic material in which a substance exhibiting photochromism is introduced into deoxyribonucleic acid.

Further, the present invention provides the photochromic material, wherein the substance exhibiting photochromism is one or more selected from the group consisting of spiropyrans, spirooxazines, diarylethenes, fulgides and fulgimides. Things.

The present invention also provides the photochromic material, wherein the substance exhibiting photochromism has a colored structure.

Further, the present invention provides a method for producing the photochromic material, which comprises a step of introducing a substance exhibiting photochromism into deoxyribonucleic acid.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Substance exhibiting photochromism The substance exhibiting photochromism used in the present invention is not particularly limited as long as it is a photochromic compound having photoreactivity. In addition, substances that exhibit photochromism (hereinafter referred to as photochromic compounds) include spiropyrans, spirooxazines,
It is selected from diarylethenes, fulgides, and fulgimides, and may be used alone, but depending on the purpose of use, two or more kinds may be used in combination, and the combination is not particularly limited. Hereinafter, examples of the photochromic compound will be described.

Photochromic compounds 1) Spiropyrans Spiropyrans are compounds represented by the following general formula (2).

[0023]

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(Wherein, R ₁ , R ₂ and R ₃ are each a hydrogen atom, an alkyl group or an alkoxyl group (preferably having 18 or less carbon atoms), W is a hetero atom, and X is A hydrogen atom, an alkyl group or an alkoxyl group (preferably having 18 or less carbon atoms), a nitro group, an amine group, a substituted or unsubstituted aromatic group, a condensed ring or a heterocyclic ring, wherein X is substituted or unsubstituted; When it is a substituted aromatic group, a condensed ring or a hetero ring, it has a structure sharing one carbon-carbon bond of an adjacent aromatic ring), and specific examples thereof are represented by the following formula (3). Is mentioned. When X has a substituent in the aromatic group, the substituent is preferably an alkyl group or an alkoxyl group having 18 or less carbon atoms, and the hetero atom of W is preferably O, S or N.

[0025]

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The spiropyrans, as represented by the following formula (4), open their rings by irradiation with ultraviolet light of a specific wavelength hν ₁ , and undergo reversible changes that return to the original state by irradiation with visible light of a specific wavelength hν _2. I do. This reversible change is due to the heat energy T
Can be said to be thermoreversible.

[0027]

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2) Spirooxazines Spirooxazines are compounds represented by the following general formula (5).

[0029]

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Wherein R ₄ , R ₅ and R ₆ are each a hydrogen atom, an alkyl group or an alkoxyl group (preferably having 18 or less carbon atoms), and X is a hydrogen atom, an alkyl group or an alkoxyl group. A group (preferably having 18 or less carbon atoms), a nitro group, an amine group, a substituted or unsubstituted aromatic group, a condensed ring or a heterocyclic ring, wherein X is a substituted or unsubstituted aromatic group, When the ring is a condensed ring or a hetero ring, one carbon-
Having a structure sharing a carbon bond), and specific examples thereof include those represented by the following formula (6). In addition,
When X has a substituent on the aromatic group, the substituent is preferably an alkyl group or an alkoxyl group having 18 or less carbon atoms.

[0031]

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The spirooxazines are represented by the following formula (7)
, A specific wavelength hν _ThreeUV irradiation
Ring opening and a specific wavelength hν_FourOf visible light
Make a reversible change back. This reversible change is caused by heat energy
-It is also said that it is thermoreversible because it is also caused by T
Can be. When this is used, compared to spiropyrans
It is preferable because the durability is high.

[0033]

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3) Diarylethenes Diarylethenes are, for example, compounds represented by the following general formula (8-1) or (8-2).

[0035]

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(8-1) (wherein R ₇ and R _{7 ′} are an alkyl group, an alkoxy group, a halogen atom, a cyano group, or a cyclic hydrocarbon starting from R ₇ and R _{7 ′} ) R ₈ and R ₉ each represent a hydrogen atom, an alkyl group or an alkoxyl group (preferably having 18 or less carbon atoms), a group, a cyclic hydrocarbon group containing a hetero atom, and a cyclic hydrocarbon group having a halogen substituent. X ₁ and X ₂ each represent a hydrogen atom, an alkyl group or an alkoxyl group (preferably having 18 or less carbon atoms), a nitro group, an amine group, a substituted or unsubstituted aromatic group, a condensed ring or a hetero ring. Is.)

(8-2) wherein R ₇ and R _{7 ′} are an alkyl group, an alkoxy group, a halogen atom, a cyano group, or a cyclic hydrocarbon starting from R ₇ and R _{7 ′} R ₈ and R ₉ each represent a hydrogen atom, an alkyl group or an alkoxyl group (preferably having 18 or less carbon atoms), a group, a cyclic hydrocarbon group containing a hetero atom, and a cyclic hydrocarbon group having a halogen substituent. X ₁ and X ₂ each represent a hydrogen atom, an alkyl group or an alkoxyl group (preferably having 18 or less carbon atoms), a nitro group, an amine group, a substituted or unsubstituted aromatic group, a condensed ring or a hetero ring. Z ₁ and Z ₂ are hetero atoms, and when it has three or more valences, a hydrogen atom, an alkyl group or an alkoxyl group may be added.)

Specific examples thereof include those represented by the following formula (9). When X ₁ has a substituent on the aromatic group, the substituent has 18 carbon atoms.
The following alkyl groups or alkoxyl groups are preferred, and Z
The heteroatoms ₁ and Z ₂ are preferably O, S or N.

[0039]

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The above diarylethenes are represented by the following formula (10)
-1) and (as represented by 10-2), ring closure by ultraviolet irradiation of a particular wavelength hv _5, also a reversible change of returning to the original by visible light irradiation of a particular wavelength hv _6. This reversible change is not irreversible because it does not occur with thermal energy.

[0041]

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4) Fulgides Fulgides are represented by the following general formula (11-1) or (11-)
A compound represented by 2)

[0043]

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(Wherein R ₁₀ , R ₁₁ , R ₁₂ and R
₁₃ is a hydrogen atom, an alkyl group or an alkoxyl group (preferably having 18 or less carbon atoms);
₁ is a hydrogen atom, an alkyl group or an alkoxyl group (preferably having 18 or less carbon atoms), a nitro group, an amine group, a substituted or unsubstituted aromatic group, a condensed ring or a hetero ring, wherein X ₁ Is a substituted or unsubstituted aromatic group, a condensed ring or a heterocyclic ring, has a structure sharing one carbon-carbon bond of a five-membered ring containing the atom Z,
Z is a hetero atom, and when it is trivalent or more, a hydrogen atom;
An alkyl group or an alkoxyl group may be added),
Specific examples thereof include those represented by the following formula (12). When X ₁ has a substituent on the aromatic group, the substituent is preferably an alkyl group or an alkoxyl group having 18 or less carbon atoms, and the hetero atom of Z is
O, S or N are preferred.

[0045]

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As shown by the following formula (13), the above-mentioned fulgites are reversibly changed such that they are closed by irradiation with ultraviolet light having a specific wavelength hν ₇ and return to the original state by irradiation with visible light having a specific wavelength hν _8. do. This reversible change is not irreversible because it does not occur with thermal energy.

[0047]

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5) Flugimides The fulgimides are represented by the following general formula (14-1) or (14)
A compound represented by -2)

[0049]

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(Wherein R ₁₄ , R ₁₅ , R ₁₆ and R
₁₇ is a hydrogen atom, an alkyl group or an alkoxyl group (preferably having 18 or less carbon atoms);
₁ is a hydrogen atom, an alkyl group or an alkoxyl group (preferably having 18 or less carbon atoms), a nitro group, an amine group, a substituted or unsubstituted aromatic group, a condensed ring or a hetero ring, wherein X ₁ Is a substituted or unsubstituted aromatic group, a condensed ring or a heterocyclic ring, has a structure sharing one carbon-carbon bond of a five-membered ring containing the atom Z,
X ₂ is a substituted or unsubstituted aromatic group, a condensed ring or a hetero ring, Z is a hetero atom, and when it has three or more valences, a hydrogen atom, an alkyl group or an alkoxyl group may be added ), As a specific example, the following formula (15)
Are represented by Note that X ₁ and X ₂
Has a substituent on the aromatic group, the substituent is preferably an alkyl group or an alkoxyl group having 18 or less carbon atoms, and the hetero atom of Z is preferably O, S or N.

[0051]

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As shown in the following formula (16), the above-mentioned fulgimides are reversibly changed in such a manner that they are closed by irradiation with ultraviolet light having a specific wavelength hν ₉ and return to the original state by irradiation with visible light having a specific wavelength hν _10. do. This reversible change is not irreversible because it does not occur with thermal energy.

[0053]

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The photochromic compound introduced into the deoxyribonucleic acid in the present invention preferably has a colored structure. This is because the colored structure has a planar structure as compared with the decolored body, and therefore, the colored body is more easily introduced into the deoxyribonucleic acid than the decolored body. Note that the colored structure referred to in the present invention, by structural isomers obtained by irradiating a specific wavelength hv ₁ as shown in equation (1) is irradiated with a specific wavelength hv ₂ Shoirotai An isomer structure that develops a color when it changes into a structure. In addition, the photochromic compound, in addition to the photoisomerization reaction is a reversible reaction,
In some cases, a side reaction occurs to convert to a compound that does not cause photoisomerization. When a colored structure is introduced into deoxyribonucleic acid, the conversion to a compound that does not undergo photoisomerization due to this side reaction can be significantly reduced.
In the case of spiropyrans and spirooxazines,
The introduction of the colored structure has an effect of suppressing light deterioration, and thus the durability is improved.

In the case of fulgides, fulgimides and diarylethenes, the decolorized structure may have structural isomers not involved in the photochromic reaction. However, when a colored structure is introduced into deoxyribonucleic acid, this side reaction may occur. Is less likely to occur, thereby improving the durability.

Deoxyribonucleic acid (DNA) The DNA used in the present invention is not particularly limited.
Raw materials include, for example, salmon, trout, herring, mackerel, cod, and other fish milt (sperm), and bovine mammary gland. The molecular weight and the purity may be appropriately selected according to the use and the target physical properties.

Method for Producing a Photochromic Material The method for producing a photochromic material of the present invention can be achieved by introducing the above-mentioned substance exhibiting photochromism into DNA. The method of introduction may be a method of mixing DNA and a substance exhibiting photochromism, and the mixing method is not particularly limited. For example, a method of mixing and complexing DNA and a photochromic compound as they are without using a solvent, A method in which DNA prepared in a film is immersed in a solution in which a photochromic compound is dissolved in a solvent to form a complex, a method in which DNA and a photochromic compound are mixed and formed in a polar solvent without forming a precipitate,
A method in which an aqueous DNA solution and a photochromic compound are mixed in an organic solvent that separates from water, and the resulting complex is extracted into an organic solvent. The aqueous DNA solution and the photochromic compound are mixed in an organic solvent, and the resulting complex is mixed. And a method of separating a substance as a precipitate.

In the present invention, when mixing the DNA and the photochromic compound, it is preferable to use a solvent. As a step after the complexation, the used solvent may be removed, or the precipitate may be used as a solvent. It may be redissolved. Examples of the solvent used include alcohols such as methanol, ethanol, propanol, 1-butanol and 1-pentanol, ethers such as diethyl ether, dipropyl ether, benzyl ethyl ether, dioxane and tetrahydrofuran, acetone and methyl ethyl ketone. , Ketones such as cyclohexanone, ethyl formate, methyl acetate,
Examples include esters such as ethyl acetate, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, trichloroethane, tetrachloroethane, dichloroethylene, trichloroethylene, and tetrachloroethylene, and hydrocarbons such as hexane, heptane, cyclohexane, toluene, and xylene. The amount of the photochromic compound is not particularly limited,
The photochromic compound is preferably used in an amount of 0.01 to 1.5 mol per one phosphorus atom in DNA.

Further, at the time of mixing, an organic cationic substance or the like may be used in combination. The organic cationic substance used in the present invention is not particularly limited, but is preferably an amine or a quaternary ammonium salt, and can impart the required physical properties of the composition obtained by the type of the quaternary ammonium salt. Become. Specifically, benzylammonium salts such as trimethylbenzylammonium salt, triethylbenzylammonium salt, benzalkonium salt and benzethonium chloride; alkylpyridinium salts such as laurylpyridinium salt and laurylpicolinium salt; imidazolinium salts; tetramethylammonium Aliphatic quaternary ammonium salts such as salts, tetraethylammonium salts, tetrabutylammonium salts, lauryltrimethylammonium salts, myristyltrimethylammonium salts, oleyltrimethylammonium salts, stearyltrimethylammonium salts, dilauryldimethylammonium salts; trimethylphenylammonium salts; Polymethyl such as trimethyl (tetraoxadocosyl) ammonium salt and polyoxypropylenemethyldiethylammonium salt Xyalkylene ammonium salt; amphoteric surfactant such as carboxybetaine, aminocarboxylate, imidazolinium betaine, alkylamine oxide; high-molecular cationic compound such as polydimethyldiallylammonium salt, copolymer of dimethyldiallylammonium salt and acrylamide And the like. In the present invention, the amount of the organic cationic substance added is not particularly limited.
Organic cationic substance is added to one phosphorus atom in A.
It is preferred that the amount be 1 to 1.5 mol.

In the present invention, it is preferable to heat and stir the DNA and the photochromic compound at the time of mixing, since the rate and rate of introduction of the photochromic compound into the DNA are improved. The temperature during mixing is preferably from 0 to 100 ° C, more preferably from 30 to 80 ° C. If the temperature is higher than this, the DNA may be denatured.

In the present invention, the photochromic compound can be introduced into the DNA by a complex formation between a phosphate residue of the DNA and a cationic group of the photochromic compound based on the structure of the DNA. This may be due to insertion of a compound (called intercalation), and high-function expression is expected by controlling the mode of introduction. Intercalation is preferable in order to prevent a side reaction of the photochromic compound, because even if the complexed photochromic compound causes a side reaction, the intercalated photochromic compound is hardly affected. Organic cationic substances are suitable for preferential introduction into phosphate residues. When introducing a photochromic compound into DNA, the photochromic compound may be used alone or as a mixture of two or more compounds, and is not particularly limited. By using two or more types of photochromic compounds, each photochromic compound has a specific light absorption wavelength and has a specific wavelength of coloring → fading, fading → coloring, so it can be used for multi-step recording etc. It becomes possible.

When a step of removing the solvent after mixing the DNA and the photochromic compound in a polar solvent, the method of introducing the photochromic compound includes compox formation with a phosphate residue of DNA, and nucleobase of DNA. In addition to intercalation between pairs, it is conceivable that the DNA containing the photochromic compound is not dissolved, and that the DNA mixed with the photochromic compound is not dissolved. It is desirable to wash the solid obtained by removing the solvent with acetone (such as acetone or cyclohexane). The solvent used for this washing varies depending on the state of the DNA used and the photochromic compound, and is not particularly limited.

According to the present invention, by introducing a photochromic compound between nucleic acid base pairs of DNA, it is possible to suppress a side reaction which is one of the major factors for shortening the life of a photochromic material. Further, the stereoisomer which does not perform the photoreaction originally contained in the photochromic compound can be efficiently removed, and only the compound which performs the photoreaction can be effectively used. In addition, by forming the photochromic compound into a complex with a phosphate residue of DNA, it is possible to arrange the compound regularly and to make it difficult to receive interaction between molecules.

The form of the photochromic material obtained in the present invention is not particularly limited. The powder may be used as it is, or the powder may be dissolved in a solvent and subjected to processing such as coating before use. Further, since it can be easily formed into a film or a fiber, it may be used after being formed into a film or a fiber. When forming a film, for example, the obtained solid content is dissolved in a solvent (for example, water or ethanol) and the casting is performed. At this time, if the solvent is removed by reducing the pressure and / or heating, a film can be efficiently formed, and a transparent film can be easily obtained. The heating temperature is desirably 100 ° C. or less to prevent denaturation of the film. In the case of fiberization, the solid content obtained in the same manner as ordinary synthetic fibers may be melt-spun. The melting temperature varies depending on the type and amount of the introduced photochromic compound and the used quaternary ammonium salt, but is preferably from 60 to 150 ° C.

The use of the photochromic material obtained in the present invention is not limited and can be used in a wide range. For example, it can be used as various storage materials such as various photosensitive materials in place of silver salt photosensitive agents, copying materials, photoreceptors for printing, storage materials for cathode ray tubes, photosensitive materials for lasers, photosensitive agents for photography, and optical memories. In addition, it can be used as an optical material such as a photochromic lens material and an optical filter material, a display material, a light meter, and a decoration material.

[0066]

According to the present invention, a photochromic compound having a wide range of properties from water-soluble to oil-soluble can be introduced into DNA, and the stability of the photochromic compound introduced into DNA is improved, as in a polar solvent. Behavior. Although the mechanism is not clear, photochromic compounds
Since it is introduced by interaction with nucleic acid residues in addition to interaction with phosphate residues in DNA, it is possible to introduce photochromic compounds with a wide range of physical properties, and to exhibit the same behavior as in polar solvents . Furthermore, inclusion is generally known to be useful for preventing oxidation, but in this case, it is presumed that it has an effect of dispersing the photochromic compound in molecules and has an effect of suppressing photodegradation.

[0067]

EXAMPLES The present invention will now be described specifically with reference to examples, but these do not limit the scope of the present invention. (Example 1) Salmon milt-derived DNA (P content: 7.7%, the same is used in the following Examples and Comparative Examples) 7
8 mg was dissolved in 10 ml of distilled water to obtain a DNA aqueous solution. Separately, as a spiropyran compound, 0.1 mmol (32.2 mg) of the following compound 1 was added to 10 m of chloroform.
and mixed with the aqueous DNA solution. After stirring at 40 ° C. for 30 minutes, a mixed solvent of water-chloroform was removed to obtain a solid content. The obtained solid was washed by immersion in 10 ml of acetone in order to simply remove the spiropyran compound 1 attached thereto. The solid content was separated by filtration, dried under reduced pressure, and mixed with water-ethanol (2: 1 vol.).
Ratio) and cast film formation to obtain a photochromic material into which spiropyran compound 1 was introduced.

[0068]

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Example 2 78 mg of DNA was added to 10 parts of distilled water.
The resulting solution was dissolved in the resulting solution to give an aqueous DNA solution. Separately, 0.05 mmol of the following compound 2 as a spirooxazine compound
(16.4 mg) was dissolved in 10 ml of ethanol and mixed with the aqueous DNA solution. After stirring at 40 ° C for 1 hour,
The solution was evaporated under reduced pressure to obtain a solid. The obtained solid content was immersed and washed in 20 ml of acetone to simply remove the spirooxazine compound 2 attached thereto. Water to solids
It was dissolved in a mixed solvent of ethanol (2: 1 vol ratio) and cast into a film to obtain a photochromic material into which spirooxazine compound 2 was introduced.

[0070]

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(Example 3) 78 mg of DNA was added to distilled water 10
The resulting solution was dissolved in the resulting solution to give an aqueous DNA solution. Separately, as a spiropyran compound, 0.3 mmol (160
mg) was dissolved in 10 ml of ethanol and mixed with the aqueous DNA solution. After stirring at 40 ° C. for 2 hours, the solution was distilled off under reduced pressure to obtain a solid content. The obtained solid content is simply acetone 2 in order to remove the spiropyran compound 3 attached thereto.
It was immersed and washed with 0 ml. The solid was separated by filtration, dried under reduced pressure, dissolved in a mixed solvent of water and ethanol (2: 1 vol ratio), and cast into a film to obtain a photochromic material into which spiropyran compound 3 was introduced.

[0072]

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Example 4 78 mg of DNA was added to 10 parts of distilled water.
The resulting solution was dissolved in the resulting solution to give an aqueous DNA solution. 53 mg of monostearyltrimethylammonium chloride was added to the aqueous DNA solution.
(0.2 mmol) was added to prepare a turbid solution containing the DNA-lipid complex. Separately, 0.1 mmol (38.7) of the following compound 4 as a diarylethene compound
mg) was dissolved in 10 ml of chloroform and added to a turbid solution containing the DNA-lipid complex. This mixed solution was stirred at 50 ° C. for 30 minutes. The obtained solid is filtered, and ethanol-chloroform (3: 1 vol ratio) is used.
The resultant was dissolved in a mixed solvent and cast into a film to obtain a photochromic material into which diarylethene compound 4 was introduced.

[0074]

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(Example 5) 78 mg of DNA was added to distilled water 10
The resulting solution was dissolved in the resulting solution to give an aqueous DNA solution. 53 mg of monolauryltrimethylammonium chloride was added to the aqueous DNA solution.
(0.2 mmol) was added to prepare a turbid solution containing the DNA-lipid complex. Separately, 0.04 mmol of the following compound 5 (14.
9 mg) was dissolved in 10 ml of chloroform and added to a turbid solution containing a DNA-lipid complex. This mixed solution was stirred and mixed at room temperature for 3 hours. The obtained solid was filtered and dried to obtain a powder of a photochromic material into which spirooxazine compound 5 was introduced.

[0076]

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(Example 6) 1) Preparation of DNA complex 10 g of DNA was dissolved in 800 ml of distilled water to prepare an aqueous DNA solution. Adecamine 4DAC80 is added to this aqueous DNA solution.
17.8g (0.025mo) made by Asahi Denka Kogyo Co., Ltd.
l) was added to prepare a DNA-lipid complex. After centrifuging the turbid liquid to separate solids,
After drying, 20.5 g of the DNA-lipid complex was obtained. 2) Preparation of photochromic material into which photochromic compound was introduced 170 mg of DNA-lipid complex prepared in 1)
Was dissolved in 10 ml of ethanol. 0.05 mmol (17.6 mg) of the following compound 6 as a fulgide compound
Was dissolved in ethanol, added to an ethanol solution of the DNA-lipid complex, and mixed by stirring to form a cast film. The surface of the obtained film was washed with a small amount of cyclohexane to simply remove the attached photochromic compound. The solid content was dried to obtain fulgide compound 6
To obtain a photochromic material.

[0078]

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(Example 7) 79 mg of DNA was added to distilled water 10
Dissolved in ml. Separately, 0.1 mmol (24.4 m
g) was dissolved or dispersed in 10 ml of chloroform and mixed with the aqueous DNA solution. After stirring at 40 ° C. for 30 minutes, a mixed solvent of water-chloroform was removed to obtain a solid content. The obtained solid content is simply acetone 1 in order to remove the attached diarylethene colored structure compound 7.
It was immersed and washed with 0 ml. The solid content was separated by filtration, dried under reduced pressure, dissolved in a water-ethanol mixed solvent (2: 1 vol ratio), cast-formed to form a diarylethene-colored structure compound 7
To obtain a photochromic material.

[0080]

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Example 8 78 mg of DNA was added to 10 parts of distilled water.
The resulting solution was dissolved in the resulting solution to give an aqueous DNA solution. 53 mg of monostearyltrimethylammonium chloride was added to the aqueous DNA solution.
(0.2 mmol) was added to prepare a turbid solution containing the DNA-lipid complex. Separately, 0.1 mmol of the following compound 8 as a diarylethene colored structure compound
(46.8 mg) was dissolved in 10 ml of chloroform.
It was added to the turbid solution containing the NA-lipid complex. This mixed solution was stirred at 50 ° C. for 30 minutes.
The obtained solid was filtered, dissolved in a mixed solvent of ethanol-chloroform (3: 1 vol ratio), and cast to form a film, thereby obtaining a photochromic material into which the diarylethene-colored structure compound 8 was introduced.

[0082]

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Example 9 79 mg of DNA was added to 10 parts of distilled water.
The resulting solution was dissolved in the resulting solution to give an aqueous DNA solution. 53 mg of monolauryltrimethylammonium chloride was added to the aqueous DNA solution.
(0.2 mmol) was added to prepare a turbid solution containing the DNA-lipid complex. Separately, 0.2 mmol of the following compound 9 as a diarylethene colored compound
(65.2 mg) was dissolved in 10 ml of chloroform.
It was added to the turbid solution containing the NA-lipid complex. This mixed solution was stirred and mixed at room temperature for 1 hour. The obtained solid was filtered and dried to obtain a powder of a photochromic material into which the colored compound of the diarylethene-colored structure 9 was introduced.

[0084]

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Example 10 78 mg of DNA was added to distilled water 1
The DNA was dissolved in 0 ml to obtain a DNA aqueous solution. Distearyl dimethyl ammonium chloride 110 mg in the DNA aqueous solution
(0.2 mmol) was added to prepare a turbid solution containing the DNA-lipid complex. Separately, 0.1 mmol (3
4.1 mg) in 10 ml of chloroform
-Added into the turbid solution containing the lipid complex. The mixed solution was stirred at room temperature for 30 minutes. The obtained solid was filtered, dissolved in chloroform, and cast into a film to obtain a photochromic material into which the fulgide compound 10 was introduced.

[0086]

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Example 11 1) Preparation of DNA Complex 10 g of DNA was dissolved in 800 ml of distilled water to prepare an aqueous DNA solution. Adecamine 4DAC80 is added to this aqueous DNA solution.
17.8g (0.025mo) made by Asahi Denka Kogyo Co., Ltd.
l) was added to prepare a DNA-lipid complex. After centrifuging the turbid liquid to separate solids,
After drying, 20.5 g of the DNA-lipid complex was obtained. 2) Preparation of photochromic material into which photochromic compound was introduced 170 mg of DNA-lipid complex prepared in 1)
Was dissolved in 10 ml of chloroform. 0.05 mmol of the following compound 11 as a colored compound of fulgides
(19.7 mg) was dissolved in chloroform, added to a chloroform solution of the DNA-lipid complex, mixed with stirring, and cast to form a film. Thus, a photochromic material into which the fulgide-based colored structure compound 11 was introduced was obtained.

[0088]

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Example 12 170 g of the DNA-lipid complex prepared in 1) of Example 11 was dissolved in 10 ml of chloroform. 0.15 mmol (50.9 mg) of the following compound 12 as a fulgide-colored compound is dissolved in chloroform, added to a chloroform solution of a DNA-lipid complex, mixed with stirring, and cast to form a film. Thus, a photochromic material into which No. 12 was introduced was obtained.

[0090]

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(Example 13) 78 mg of DNA was added to distilled water 1
The DNA was dissolved in 0 ml to obtain a DNA aqueous solution. 0.1 mmol of the following compound 13 as a colored compound of spiropyrans
(32.2 mg) was dissolved or dispersed in 10 ml of chloroform and mixed with an aqueous DNA solution. After stirring at 40 ° C. for 30 minutes, a mixed solvent of water-chloroform was removed to obtain a solid content. The obtained solid content was immersed and washed in 10 ml of acetone in order to simply remove the spiropyran-colored compound 13 attached thereto. After filtering the solid content under reduced pressure and drying,
Dissolved in a water-ethanol mixed solvent (2: 1 vol ratio),
A photochromic material into which a spiropyran colored compound 13 was introduced by casting was obtained.

[0092]

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Example 14 78 mg of DNA was added to distilled water 1
The DNA was dissolved in 0 ml to obtain an aqueous DNA solution. As a spirooxazine colored compound, 0.05 mmol of the following compound 14
1 (16.4 mg) was dissolved in ethanol (10 ml) and mixed with the DNA aqueous solution. After stirring at 40 ° C. for 1 minute, the solution was distilled under reduced pressure to obtain a solid content. The obtained solid content is simply the attached spirooxazine colored compound 1.
In order to remove No. 4, immersion washing was carried out with 20 ml of acetone. The solid content was mixed with a water-ethanol mixed solvent (2: 1 vol.
Ratio) and cast film formation to obtain a photochromic material into which spirooxazine coloring compound 14 was introduced.

[0094]

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(Comparative Examples 1 to 12) Polystyrene 110 m
g of chloroform were added and dissolved, and the photochromic compounds used in Examples 1 to 6 were mixed in the same amounts as in the Examples to uniformly dissolve, cast-film-formed and kneaded with the photochromic compounds (polystyrene). Comparative Examples 1 to 6 were prepared. Further, Examples 1 to
Solutions prepared by dissolving 5 mg of the photochromic compound used in 6 in 1 ml of ethanol were used as Comparative Examples 7 to 12.

(Test Example 1) The photochromic materials obtained in Examples 1 to 6, the compositions prepared in Comparative Examples 1 to 6, and the ethanol solutions obtained in Comparative Examples 7 to 12 were irradiated with ultraviolet rays for 30 seconds. And the color change was observed. Examples 7 to
The photochromic material obtained in 14 was irradiated with visible light for 30 seconds, and the color change was observed. Table 1 shows the results.

[0097]

[Table 1]

From the results in Table 1, it can be seen that Examples 1 to 5 of the present invention were used.
The photochromic materials obtained in No. 14 were Comparative Examples 1 to 6.
It was found that the photo-response was faster than that of the composition (polystyrene thin film) prepared as above, and the photo-response was as fast as the ethanol solutions of Comparative Examples 7 to 12.

(Test Example 2) Durability of the photochromic materials obtained in Examples 1 to 14 and the compositions prepared in Comparative Examples 1 to 6 by alternate irradiation of ultraviolet light and visible light under the following conditions (the number of cycles) ) Was observed. Table 2 shows the results. Durability test conditions UV lamp: wavelength 365 nm, 20 mW / cm ² , 3
0 second irradiation Visible light lamp: 600 nm wavelength, 30 second irradiation

[0100]

[Table 2]

From the results shown in Table 2, it can be seen that the photochromic material of the present invention has superior durability as compared with a conventional photochromic compound kneaded in polystyrene. Furthermore, those into which the photochromic compound having a colored structure was introduced exhibited high repetition durability, and retained the photochromic properties even after 10,000 repetition tests.

[0102]

According to the present invention, even if the addition amount of the photochromic compound is small, the color development-fading sensitivity is good, the photoresponsiveness is as fast as that when dissolved in a solvent, and the reaction is repeated. A photochromic material and a method for producing the same are provided, in which isomerization is hardly caused, and the photochromic compound is excellent in repeated durability and can introduce various photochromic compounds into DNA.

Claims (4)

[Claims] 1. A photochromic material in which a substance exhibiting photochromism is introduced into deoxyribonucleic acid. 2. A substance exhibiting photochromism includes spiropyrans, spirooxazines, diarylethenes,
The photochromic material according to claim 1, wherein the photochromic material is at least one member selected from the group consisting of fulgides and fulgimides. 3. The photochromic material according to claim 1, wherein the substance exhibiting photochromism has a colored structure. 4. A method for producing a photochromic material, comprising a step of introducing a substance exhibiting photochromism into deoxyribonucleic acid.