JP2979159B2 - Microcapsule-containing material with photoresponsive film and method for controlling light diffusion of the material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a microcapsule-containing material using a photoresponsive composite membrane capable of controlling the diffusion permeability of a substance molecule by photostimulation, and a method for controlling the substance diffusion light thereof. The present invention relates to a microcapsule-containing material utilizing the photoresponsiveness of a conformational isomerized substance and an organic dye contained in a membrane, and a method of controlling light diffusion of the substance.

[0002]

2. Description of the Related Art In recent years, a synthetic polymer membrane having a function of separating and selectively permeating a substance at a molecular level has been attracting attention, and the substance permeability of the polymer membrane can be further controlled by an external stimulus. Things have been suggested. As a method for imparting the above-described functions to a polymer film, a method of chemically modifying a synthetic polymer film or forming some composite has been attempted. And the function control means include temperature change, light irradiation, ultrasonic irradiation, electric field, redox,
There is a pH change and the like. Specifically, "introducing a functional group or an isomerization group into the polymer side chain", "immobilizing a bimolecular film on a polymer film", "using a graft polymer as a surface treatment", There is a method such as “using a polymer gel”.

[0003] On the other hand, there is an attempt to impart the above-mentioned substance permeation function to microcapsules. Here, the microcapsule is a small container having a diameter of several microns to several hundreds of microns, and is practically used as a packaging material for ink and medicine. The substance sealed inside the container is protected from the external environment by a capsule membrane constituting the container. A capsule film of such a microcapsule is formed of a polymer film, and as in the case of the functional polymer film described above,
Attempts have been made to impart a substance permeation function by a method of chemically modifying the capsule membrane. For example, by forming a bilayer lamellar layer in a porous polymer capsule membrane or by graft-polymerizing a linear polymer onto the surface of a polymer wall membrane, the capsule internal phase substance is transmitted out of the capsule. There is an example to make it. As means for controlling the permeation rate of the capsule internal phase substance, there are temperature change, light irradiation, ultrasonic irradiation, electric field, oxidation reduction, pH change, etc., as in the case of the above-mentioned polymer membrane, and these are adjusted. Thus, it is known that the above-mentioned bimolecular film or graft polymer functions as a kind of molecular valve.

FIG. 11 schematically shows an example of a microcapsule for controlling the material permeability by light irradiation. The capsule film Cf of the microcapsule MC is made of a porous polymer material, and the bilayer film F1 forming a lamellar layer is embedded in the pores H thereof. As shown in the partial enlarged view in which the pores are enlarged, the bimolecular film F1 is made of an amphipathic compound, in which a lipid F2 containing an azobenzene group is mixed as a photoisomerizable substance. Liquid substances Mi and Mo are disposed inside (inside capsule phase) and outside (outside capsule phase) of the capsule membrane Cf, respectively.

[0005] It is known that the material permeability of the capsule membrane Cf is increased by irradiating the microcapsule-containing material having the above-mentioned structure with ultraviolet light, and is restored to the original material permeability by irradiating visible light containing no ultraviolet component. Have been. This is because the azobenzene group in the photoisomerizable substance F2 dispersed and associated with the bimolecular film F1 is changed from a linear trans form to a bent cis form by ultraviolet irradiation, and the ordered two molecules in which the molecules are arranged in an orderly manner. This is probably because the film structure of the film F1 is disturbed. By irradiation with visible light, the azobenzene group returns to the original trans form, and the bimolecular film F1 recovers an ordered film structure. In this case, the azobenzene group is formed not in the bimolecular film F1 portion,
When incorporated into the wall W portion of the capsule film Cf by covalent bond, even when irradiated with ultraviolet light and visible light in the same manner as described above,
The substance permeability hardly changes. For this reason, it is important that the photoisomerized molecule exists in the fluid bimolecular film F1.

[0006] However, the capsule film of the microcapsule is required to have such a delicate light response function as described above, and the types of photoisomerizable substances satisfying such a demand are naturally limited. Therefore, when the microcapsule-containing material is put to practical use, the types of substances that can be used as photoisomerizable substances to be dispersed and associated in the capsule membrane are limited, and the microcapsule-containing material having a desired quality is produced at low cost. It becomes difficult.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has a wide selection range of photoresponsive film materials, so that desired microcapsules can be easily manufactured with inexpensive materials. It is another object of the present invention to provide an inexpensive microcapsule-containing material capable of easily and densely controlling mutual diffusion of a substance, and a method of controlling a substance diffusion light.

[0008]

The gist of the present invention has two points. One of the points is that the above-mentioned object has a microcapsule containing a microcapsule formed of a capsule membrane which changes material permeability upon irradiation with light. Wherein the capsule film has a bimolecular film containing a conformational isomer that changes a steric structure by a redox reaction and an organic dye having spectral sensitization characteristics, and an inner phase and an outer phase of the capsule film. And disposing target materials capable of chemically reacting with each other, increasing the material permeability by irradiating the bimolecular film with light of a specific wavelength, and diffusing the target materials of the internal and external phases to each other. This is achieved by providing a microcapsule-containing material having a characteristic photoresponsive film.

Another point of the present invention is that the above-described object is to change the material permeability by receiving light of a specific wavelength.
A microcapsule comprising a capsule membrane provided with a molecular membrane, wherein a target substance capable of chemically reacting with each other is disposed in an inner phase and an outer phase of the capsule membrane, and the bimolecular membrane has a three-dimensional structure by a redox reaction. Contains microcapsules that contain a conformational isomer to be changed and an organic dye with spectral sensitization properties, and have photoresponsiveness that changes the three-dimensional structure of the molecule upon irradiation with light of a specific wavelength and increases material permeability A method for controlling the substance diffusion light of a substance, wherein the irradiation amount of the light of the specific wavelength is increased when irradiating the capsule membrane in a state of low substance permeability with light of the specific wavelength to increase the substance permeability. And controlling the interdiffusion rate of the target material by providing a method of controlling the material diffusion light of the microcapsule-containing material provided with the photoresponsive film. In that is it.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described with reference to the first to fourth embodiments.
A specific description will be given based on examples. <First Embodiment> FIG. 1 shows a structure of a photoresponsive polymer microcapsule-containing material as a first embodiment and a method of controlling material diffusion through the capsule membrane by light irradiation (hereinafter, material diffusion light control). FIG. 4 is a schematic explanatory view showing the concept of the method. The wall material 1 constituting the capsule membrane Cf of the microcapsule MC is made of a porous material and has a large number of fine pores 2.
have. In this embodiment, a porous sponge-like wall material 1 is formed by using a synthetic polymer material as the material of the wall material 1. The film thickness of the wall material 1 is set to about several tens of microns (μm) to several tens of nanometers (nm). As a polymer material forming the wall material 1, polyamide, polyester,
General polymer materials such as polyurethane, polymethyl methacrylate, polyurea, polystyrene, and polyvinyl alcohol can be suitably used.

In the pores 2 of the wall material 1, a bimolecular cumulative film 3 made of an amphiphilic compound is embedded. This bimolecular cumulative film 3 can be produced by a simple method by deposition described later, and the layer structure obtained at this time is a lamellar layer having a multilayer structure as shown in FIG. Further, the bimolecular cumulative film 3 of the present example is set to have a low phase transition temperature at which a transition from a liquid crystal state to a crystalline state occurs so that the liquid crystal state has a certain degree of fluidity at room temperature. As described above, when the micropores 2 of the microcapsules MC are covered with the bimolecular cumulative film 3, a high permeability barrier property can be provided even for a substance having a low molecular weight.

The molecules constituting the bimolecular cumulative film 3 include:
For example, phospholipids

[0013]

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[0014]

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For example, dialkyl compounds such as

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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For example, trialkyl compounds such as

[0022]

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Examples of the liquid crystal type monoalkyl compound include:

[0024]

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Examples of fluorocarbon compounds include:

[0026]

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Various amphiphilic compounds can be used.

As shown in FIG. 2, the bimolecular cumulative film 3 contains
The conformational isomer 4 is dispersed and associated.
The conformational isomer 4 is a substance that changes the three-dimensional structure of a molecular chain by a redox reaction. As the conformational isomerization substance 4, a ferrocene compound shown in FIG. 3 is preferably used. In FIG. 3, when the ferrocene compound is oxidized, the alkyl long-chain portion having a ferrocene group undergoes a large conformational change, and the alkyl long-chain portion becomes a bent molecular form. When the ferrocene compound in the bent conformation is reduced, the ferrocene compound returns to the original linear conformation. In addition, as the conformational isomerization substance 4, various substances having the same conformational isomerization characteristics can be used without being limited to the above-mentioned ferrocene compound.

As shown in [a] of FIG.
The conformational isomerized substance 4 dispersed in the compound has a linear conformation under the influence of the regular molecular arrangement state of the bimolecular cumulative film 3 forming the lamellar layer, and the bimolecular cumulative film 3 as a whole It has a dense layer structure.

As shown in FIG. 2, an organic dye 5 having spectral sensitization characteristics is dispersed and associated with the bimolecular cumulative film 3. As a result, the bimolecular cumulative film 3 is irradiated with light of a specific wavelength to which the organic dye 5 is sensitive, and its electrical characteristics are greatly changed, thereby enabling electron transfer. In addition, the organic dye 5 is 2
Association with a specific regularity in the molecular accumulation film 3 (for example, J
It is known that, when the association is performed, the spectral absorption spectrum of the entire two-molecule accumulation film 3 is significantly shifted to the longer wavelength side.

As the organic dye 5 as described above,

[0032]

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[0033]

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[0034]

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Preference is given to cyanine dyes such as When a cyanine dye is associated with the bimolecular cumulative film 3 as the organic dye 5, the cyanine dye 5 has a tendency to associate between the hydrophilic groups in the bimolecular cumulative film 3 as shown in FIG. is there.

Returning to FIG. 1, the capsule membrane Cf of the microcapsule MC is, as described above, an amphiphile in which a conformational isomer is dispersed and associated within the micropores 2 of the wall material 1 made of a polymer substance. A bimolecular cumulative film 3 made of a conductive compound is embedded therein to form a composite structure. This capsule membrane Cf
Is as thin as tens of microns to tens of nanometers,
In addition, the capsule film Cf becomes substantially transparent by sufficiently bringing the optical refractive indices of the polymer material wall material 1 forming the skeleton of the film and the amphiphilic compound forming the bimolecular cumulative film 3 close to each other.
Therefore, the color of the microcapsules MC is the same as that of the capsule membrane Cf.
It looks like the color of the capsule inner phase material (core material) present in the inner phase (inner phase).

In the inner phase of the microcapsule MC, a target material 6 and its auxiliary material 7 are arranged. The target material 6 is a material that permeates through the capsule film Cf and diffuses into the external phase, and corresponds to, for example, a dye precursor having color-forming ability. The auxiliary substance 7 is a substance that adjusts the chemical properties of the target substance 6. When the target substance 6 is, for example, a leuco dye as a dye precursor, the auxiliary substance 7 may be distilled water, a solvent for dissolving or dispersing the leuco dye, benzene, toluene, alkylnaphthalene, biphenyls, paraffins, etc. Are preferred. In addition, in order to give appropriate viscosity to the solution of the internal phase of the capsule,
Various commercially available waxes and resin polymers are mixed. It is preferable to select such an auxiliary substance 7 having a molecular weight that is large enough not to be able to permeate the bimolecular cumulative membrane 3 of the capsule membrane Cf. When the target material 6 is solid,
The solvent for dissolving this also becomes the auxiliary substance 7.

As described above, the microcapsule MC mixes one of the target materials 6 capable of chemically reacting with each other, its auxiliary material 7 and other materials (capsule internal phase material) to form the capsule film Cf. The structure is sealed in the internal phase.

Here, a method for manufacturing the above-described microcapsules MC will be described. First, a microcapsule intermediate in which a capsule inner phase material containing a target material is enclosed in a shell-shaped wall material is manufactured. As a method for producing this intermediate, an interfacial polymerization method, in-situ (in-situ)
A polymerization method, a coacervation method, or the like can be used.

Next, the alkane solution in which the amphiphilic compound of the bimolecular cumulative film material and the conformational isomer are dissolved is heated, and the above-mentioned microcapsule intermediate is put into this solution. When left for a few minutes and allowed to cool naturally, a bimolecular film was deposited at the interface between the aqueous phase containing the phase material in the capsule inside the wall material and the alkane phase outside the wall material, and accumulated on the micropores of the wall material. The molecular film is embedded. It is to be noted that a bimolecular cumulative film is formed in advance in the micropores of the wall material with an amphiphilic compound, and a bimolecular cumulative film is similarly formed by adsorbing a conformational isomerized substance onto the micropores. Can be embedded in

Next, the microcapsules in which the above-described bimolecular cumulative film is embedded are immersed in an aqueous solution in which an organic dye is dispersed and mixed, and the organic dye is adsorbed on the bimolecular cumulative film. Is completed.

In FIG. 1, the other target substance 8 and its auxiliary substance 9 are arranged in the external phase of the microcapsule MC. The target substance 8 is a substance capable of causing a chemical reaction with each target substance 6 in the internal phase. For example, when the target material 6 in the inner phase is a dye precursor, the target material 8 in the outer phase becomes a color developer capable of causing a uniform chemical reaction with the dye precursor in the capsule inner phase to develop a color. The auxiliary substance 9 is an auxiliary substance for adjusting the physical properties of the target substance 8 like the auxiliary substance in the internal phase. The microcapsules M produced as described above are mixed in a solution in which the target substance 8 and the auxiliary substance 9 are mixed and dispersed.
C was added to constitute the microcapsule-containing material of this example.

The microcapsule-containing material having the above-described structure is charged into a transparent container 10 and the first container is placed outside the container 10.
The light source 11 and the second light source 12 are arranged respectively. The first light source 11 irradiates a first light R1 including a component light having a wavelength ν1 to which the organic dye in the bimolecular accumulation film 3 is sensitive. Therefore, by controlling the irradiation of the first light R1, the electron mobility in the bimolecular cumulative film 3 can be controlled. The second light source 12 emits a second light R2 including a component light having a wavelength of ν2 for exciting the conformational isomerization substance 4 in the bimolecular accumulation film 3.
Preferably, each of the lights R1 and R2 is a monochromatic light.

Next, the operation of controlling the substance diffusion light in the microcapsule-containing material configured as described above will be described with reference to FIG. In FIG. 5, a transparent container 10 is charged with a microcapsule MC containing one target material 6 and a microcapsule content of the present example obtained by mixing the other target material 8 and its auxiliary material and the like. ing.
In the thermally stabilized initial state stage (ST1), as shown in FIG. 4A, the conformationally isomerized substance 4 dispersed and associated in the bimolecular cumulative film 3 contains the bimolecular cumulative film 3.
Is stable in a molecular form that relieves the surface pressure. In this example, a ferrocene compound is used as the conformational isomerization substance 4. This ferrocene compound is stable in a molecular form in a reduced state shown in FIG. doing. As described above, in the initial state, the bimolecular cumulative film 3 is in a liquid crystal state, so that the surface pressure is relatively low, and the ferrocene compound of the conformational isomerization substance 4 is in the above-described reduced state. Thus, everywhere in the bimolecular cumulative film 3 has a dense film structure on average. Accordingly, the substance permeability of the bimolecular cumulative membrane 3 in the initial state is low, and the target substances 6 and 8 in the capsule and the external phase are formed in the capsule membrane Cf.
Is isolated through.

However, the bimolecular cumulative film 3 generally has a phase transition characteristic, and is in a liquid crystal state having a fluidity at a temperature higher than the phase transition temperature Tc, whereas a gel (crystal) is formed at a temperature lower than the phase transition temperature Tc. State. Therefore, the bimolecular cumulative film 3 shows a higher barrier property against permeation at a temperature lower than the phase transition temperature Tc. In this example, the phase transition temperature T is such that the bimolecular cumulative film 3 is in a liquid crystal state under a normal temperature environment.
c is set lower than the ambient temperature. Therefore, since the bimolecular accumulation film 3 is always in a liquid crystal state and has a low barrier property against substance permeation, it exhibits a small substance permeability even in an initial state (ST1) where light is not irradiated. The phase transition temperature Tc of the bimolecular cumulative film 3 made of an amphiphilic compound is 15 ° C. to 6 ° C.
0 ° C.

The first light R 1 and the second light R 2 are applied to the microcapsule contents in the initial state by the first light source 11 and the second light source 12 installed outside the transparent container 10 shown in FIG.
(ST2). The first light R1 has a wavelength of ν1.
And the organic dye in the two-molecule cumulative film absorbs component light having a wavelength of ν1 to increase its electron mobility. In the case of the cyanine dye used in this example, the light corresponding to the wavelength ν1 is light in the visible region. The second light R2 is light containing spectral component light having a wavelength of ν2, and the conformational isomer in the two-molecule cumulative film absorbs and excites the component light having a wavelength of ν2 to emit electrons. It will be cheap. When the conformational isomer is a ferrocene compound, light corresponding to the wavelength ν2 is in the ultraviolet region.

When the first light R1 and the second light R2 are simultaneously irradiated as described above, the conformationally isomerized substance is
When the first light R1 is received, the electrons of the conformational isomer move through an organic dye having increased electron mobility. The conformational isomer that has released electrons changes the steric structure of the molecule. In the case where the conformational isomer is a ferrocene compound, in FIG. 3, the ferrocene site loses electrons (is oxidized), so that the site becomes conformationally isomerized and changes from a linear molecular form to a bent molecular form. Change. The emitted electrons move through a channel formed by association of the organic dye 5 (see FIG. 2), and then recombine with another conformational isomer 4 in an oxidized (emitted) state. . As a result, the conformational isomer 4 in the oxidized state is reduced and returns to the original three-dimensional structure.

In FIG. 5, the first light R1 and the second light R2
, The conformational isomer in the bimolecular cumulative film repeats electron emission and recombination. As a result, the conformational isomerization substance as a whole is maintained in a state where a certain percentage of the conformational isomerization substance is oxidized and assumes a bent molecular form. In the case of a ferrocene compound, as shown in FIG. 4B, when the conformational isomer 4 takes a bent molecular form (oxidized state), the space occupied in the two-molecule accumulation film 3 increases, Is compressed, and the surface pressure of the bimolecular cumulative film 3 increases. As a result, the film structure of the bimolecular cumulative film 3 is greatly disturbed around the ferrocene compound 4. As a result, the permeability of the two-molecule cumulative film 3 for the substance molecules in the inner and outer phases of the capsule is increased. It is considered that this is because the substance molecules easily pass through the portion where the film structure is disordered, that is, around the ferrocene compound 4.

Here, by controlling the intensity or time of light irradiation, the amount of the molecule that actually causes conformational isomerization among all the conformational isomerization molecules contained in the two-molecule cumulative film 3 is determined. Can be controlled. That is,
By controlling the intensity and time of light irradiation, the degree of turbulence of the bimolecular cumulative film 3 can be controlled, and the material permeability of the bimolecular cumulative film 3 can be freely controlled. As a result, as described below,
It is possible to control the interdiffusion speed of the target materials 6 and 8 in the capsule and the external phase through the capsule film Cf.
In the case of single irradiation of the first light R1 or the single irradiation of the second light R2, electrons do not move, and the molecular three-dimensional structure of the conformational isomer does not change. If the wavelength is ν1 or ν2
The above-mentioned conformational isomerization does not proceed even if the light which does not contain the component light of the above is irradiated. Therefore, even under the illumination of the light which does not contain the component light of the wavelengths ν1 and ν2, the material permeation by the above-mentioned light irradiation Control can be carried out smartly.

In FIG. 5, when the irradiation of the first and second lights R1 and R2 is started and the light irradiation is continued, the material permeability of the capsule film Cf is increased, and each of the target materials 6 in the inner and outer phases of the capsule is increased. 8 begin to spread each other (ST3). Then, as time elapses, the amount of the target materials 6 and 8 that diffuse mutually increases (ST4). When the target substances 6, 8 of the inner and outer phases are a dye precursor and a developer, respectively,
The two are mixed with each other to start the color reaction.

Here, each target material of the inner and outer phases 6,
The amount of diffusion of 8 varies depending on the size of molecules passing through the two-molecule accumulation film, the pressure value inside and outside the capsule, and the like, but also varies depending on the degree of turbulence of the two-molecule accumulation film. Therefore, by changing the intensity or time of light irradiation, it is possible to control not only the interdiffusion speed of the target material but also the speed of the chemical reaction caused by mixing the target materials 6 and 8.
In FIG. 5, the case where the first and second lights R1 and R2 are strongly irradiated is shown in the upper part, and the case where the first and second lights R1 and R2 are weakly irradiated is shown in the lower part. From this, it can be seen that, at the stage of material interdiffusion progression (ST4), the amount of target material diffused more in the case of intensely irradiating the upper stage light.

When the mutual diffusion of the substance contained in the microcapsules progresses to a desired degree, the irradiation of both the first light R1 and the second light R2 is stopped (ST5). This allows
The electrons that have begun to transfer are donated to the conformational isomers (in the oxidation state), which have already excited and released electrons, without being newly excited by the conformational isomers. The isomerized substance returns to its original molecular steric structure (reduced state). In the case of a ferrocene compound, FIG.
In the above, the molecular form in the bent state in the oxidized state is reduced to a linear molecular form. As a result, in FIG. 4, the two-molecule accumulation film 3 returns to a dense layer structure without disorder, in which the original molecules are arranged in order as a whole. As a result, the material permeability of the capsule membrane Cf decreases, and the mutual diffusion of the target materials 6 and 8 in the inner and outer phases stops.

<Second Embodiment> FIG. 6 is a schematic explanatory view showing the concept of an apparatus for implementing the substance diffusion light control method as the second embodiment and the structure of the microcapsule contents used in this method. In this example, three types of microcapsules MC
1, MC2 and MC3 are used. The number of types of the microcapsules MC to be used is plural, and therefore four or more types may be used. Thus, these three types of microcapsules MC
1, MC2, MC3 photo-response, that is, each capsule film Cf
The wavelengths of irradiation light at which the material permeability of 1, Cf2 and Cf3 change are made different. In order to make the response light wavelength of each capsule film different, irradiation is performed to change the photoresponsiveness of the organic dye molecules introduced into the two-molecule cumulative film of each capsule film, that is, the electron mobility of each organic dye molecule. The wavelengths of light may be made different as follows.

In general, it is known that the absorption spectrum of an organic dye molecule in a two-molecule cumulative film has a sharper (narrower) peak than an ordinary absorption spectrum. For example, the absorption spectrum of a dye-dispersed solution or cast film shows a broad absorption spectrum because the dye molecules are aggregated in various association states, but when the dye is introduced into a two-molecule cumulative film. The absorption spectrum of
This shows a sharp peak with a narrower absorption wavelength region.
This is because the dye molecules are affected by the regular orientation of the two-molecule cumulative film and associate with a certain orientation.

The absorption spectrum of the organic dye molecules having the sharp peaks described above depends not only on whether the phase state of the bimolecular cumulative film is in a gel state or a liquid crystal state, but also on the association state of the organic dye molecules in the bimolecular cumulative film. The absorption spectrum also significantly changes (shifts) to both the long and short wavelength sides depending on the amount of the associated molecule which affects the wavelength. Therefore, if the associated molecular weight of the organic dye molecules introduced into the two-molecule accumulation film is changed in three ways, the photoresponsiveness when changing the material permeability is sharp, and the wavelengths of the response light are different from each other. Capsule membranes Cf1, Cf2,
Cf3 can be configured. In this example, three kinds of ferrocene compounds having different wavelengths of light that respond to each other as conformational isomers are dispersed and associated in a bimolecular cumulative film of each capsule film Cf1, Cf2, and Cf3, and cyanine as an organic dye is formed. The dyes are associated with each other by changing the amount of the introduced dye, and the wavelengths of the respective response lights of the capsule films Cf1, Cf2, and Cf3 are different from each other. In addition, each capsule membrane Cf1, Cf2,
Even when the same conformational isomerized substance and the organic dye are introduced into the two-molecule cumulative film of Cf3 such that the photoresponsiveness differs from each other, the photoresponsiveness of each of the capsule films Cf1, Cf2, and Cf3 is made different. be able to. In this example, the substances that can be used as a conformational isomerization substance or an organic dye are not limited to those described above.

In each of the internal phases of the microcapsules MC1, MC2 and MC3, an auxiliary substance 14 identical to one of the target substances 13a, 13b and 13c of a different kind is disposed. And these microcapsules MC1, MC
2. In the outer phase of MC3, the other target substance 15 capable of chemically reacting with the target substance 13a, 13b, 13c of each capsule inner phase and its auxiliary substance 16 are arranged. still,
As the specific substances used for the bimolecular cumulative membranes constituting the capsule membranes Cf1, Cf2, Cf3, and the auxiliary substances 14, 16 in the capsule and in the external phase, those preferred in the first embodiment can be used. Can be selected and used.

The microcapsule-containing material having the above-described structure is charged into a transparent container 17, and outside the container 17, 3
The first light sources 18a, 18b, 18c and the second light source 19
a, 19b and 19c are arranged respectively. Each first light source 1
8a, 18b and 18c are capsule membranes Cf1, Cf2 and Cf3.
The first lights R1a, R1b, and R1c containing the component lights of the wavelengths a1a, b1b, and c1c, which respectively excite the three types of conformational isomers contained therein, are emitted. The second light sources 19a, 19b, and 19c respectively irradiate second lights R2a, R2b, and R2c including component lights of wavelengths ν2a, ν2b, and ν2c that respectively increase the electron mobility of the three types of organic dyes. I do.
Preferably, each of the lights R1 and R2 is a monochromatic light.

Next, a method for controlling the substance diffusion light in the microcapsule-containing material having the above-described structure will be described.
In the method of the present example, it is possible to select microcapsules for performing substance diffusion and to control the amount of substance diffusion in each microcapsule. FIG. 7 shows a method of selecting microcapsules for performing substance diffusion. In the figure, the first embodiment (FIG. 5)
2), the two stages of the material diffusion start stage and the progress stage in the material diffusion stage (ST3). Therefore, the method of the present example has a thermally stable initial stage (ST
1), a light irradiation step (ST2), a substance diffusion step (ST3), and a substance diffusion stop step (ST4). Initial stage (ST
The state of the microcapsule-containing material in 1) is the same as the case of the first embodiment, and the microcapsule MC
Each of the two-molecule cumulative films of MC1, MC2 and MC3 is in a liquid crystal state.

When only the first light R1a and the second light R2a of the three types of first light R1a, R1b, R1c and the second light R2a, R2b, R2c are irradiated on the microcapsule-containing material, Only the capsule membrane Cf1 of the microcapsule MC1 of the three types of microcapsules MC1, MC2, and MC3 is disturbed in the membrane structure of the two-molecule accumulation membrane, and the substance permeability is increased (lower stage of ST2). That is, the cyanine dye dispersed and associated with the two-molecule accumulation film in the capsule film Cf1 absorbs light having the wavelength ν1a to increase the electron mobility, and the ferrocene compound similarly associated with the two-molecule accumulation film. Absorbs light of the wavelength ν2a and excites it to emit electrons easily, and emits electrons through the above-mentioned cyanine dye. As a result, the ferrocene compound undergoes conformational isomerization to take the oxidized molecular three-dimensional structure shown in FIG. Thereby, the film structure of the bimolecular cumulative film is disturbed, and the material permeability increases.

When the above light irradiation is continued, the capsule film C
The material permeability of f1 increases, and the target materials 13a and 15 in the capsule inner and outer phases begin to diffuse into each other via the capsule membrane Cf1 (ST3).

As time elapses, the target material 13a,
Once the 15 interdiffusions have progressed to the desired degree, the first,
The irradiation of the second lights R1a and R2a is stopped. As a result, the film structure of the capsule film Cf1 that has been disturbed returns to the original layer structure (the reduced state shown in FIG. 4A), and the material permeability of the capsule film Cf1 decreases to the same level as the initial stage (ST1). As a result, the mutual diffusion of the target substances 13a and 15 in the capsule inner and outer phases stops (ST4).

A case where only the first light R1b and the second light R2b are irradiated (middle stage of ST2 to ST4), and a case where only the first light R1c and the second light R2c are irradiated (upper stage of ST2 to ST4) In the same manner as in the case where only the first light R1a and the second light R2a are radiated, only the microcapsules MC2 and MC3 selectively increase the material permeability, and increase the internal phase. The target material 13b, 13c and the target material 15 in the external phase are mutually diffused through the respective capsule films Cf2, Cf3.

The wavelength of light to which each of the capsule films Cf1, Cf2, and Cf3 responds is unique to the capsule film. For example, the capsule film that responds to the first light R1a having the wavelength ν1a is C
When only f1 is irradiated on the other capsule films Cf2 and Cf3, there is no response. Therefore, even when the first light R1a, R1b, R1c and the second light R2a, R2b, R2c are simultaneously irradiated, the material permeability of each of the capsule films Cf1, Cf2, Cf3 is independently controlled. Can control.

FIG. 8 is a schematic explanatory view showing stepwise the material diffusion operation when the above-mentioned six types of light are simultaneously irradiated and the irradiation intensity of the first light R1a, R1b, R1c is changed. is there. By controlling the light irradiation intensity in this manner, it is possible to control the amount of the molecule that actually causes conformational isomerization among all the conformational isomerization substance molecules contained in the two-molecule cumulative film. it can. That is, by controlling the intensity of the irradiation light, the degree of disturbance of each of the bimolecular cumulative films is controlled, and each of the target substances 13a, 1 in the capsule and the external phase based on the substance permeability of each of the capsule films Cf1, Cf2, Cf3.
The interdiffusion speed of 3b, 13c and 15 can be easily controlled. In this example, the electron mobility of the organic dye associated with the capsule film Cf3 is changed, and as a result, the conformational isomerization material is oxidized to thereby change the capsule film Cf3.
The intensity of the first light R1c for controlling the material permeability of the capsule film Cf2 is set to be the strongest, and the intensity of the first light R1b for controlling the material permeability of the capsule film Cf2 is similarly set to the weakest. The second light R2a, R2 that excites the conformational isomer
The irradiation intensities of 2b and R2c are all set to be the same.

The first light R1a, R1b, R1c and the second light R2 are applied to the microcapsule contents in the initial state (ST1).
The irradiation of a, R2b, and R2c is started (ST2), and the light irradiation operation is continued (ST3). Thereby, the material permeability of the bimolecular cumulative membrane in each of the microcapsules MC1 to MC3 is increased, and the target materials 13a and 13
b, 13c and the target substance 15 in the external phase permeate through the two-molecule cumulative film of each of the capsule films Cf1, Cf2, Cf3 and begin to diffuse into each other (ST3).

When the light irradiation is continued, each of the target materials 13a, 13b, 1
The amount of mutually diffused molecules of 3c and 15 increases (ST
Four). At this time, each microcapsule MC1, MC2, MC3
The molecular weight of the interdiffusion substance in the first light R1a, R1b,
The amount of substance interdiffusion related to the microcapsules MC3 responding to the first light R1c having the highest irradiation intensity differs according to the irradiation intensity of R1c, and is related to the microcapsules MC2 responding to the first light R2. The least amount of material interdiffusion.

Each target substance 13 in the capsule internal phase and external phase
When the interdiffusion of a, 13b, 13c and 15 progresses to the desired degree at the respective speeds, the first light R1a, R1b, R1c
Then, all light irradiation of the second lights R2a, R2b, and R2c is stopped. Thereby, each microcapsule MC1, MC2, M
The conformational isomers dispersedly associated with the C3 bimolecular cumulative film are reduced and return to the original molecular steric structure. As a result, each two-molecule cumulative film returns to its original orderly and dense film structure, and the mutual diffusion of each substance in the inner and outer phases of the capsule stops (ST5). In this way, it is possible to easily and accurately obtain the contents of the microcapsules in which the respective target substances are mutually diffused to a desired degree.

<Third Embodiment> In the method of the first embodiment (see FIG. 5), the two-molecule accumulation film is already in the liquid crystal state from the initial state. The molecular accumulation film is in a crystalline state at an initial stage. For this purpose, as described above, the phase transition temperature Tc of the amphiphilic compound constituting the bimolecular cumulative film may be set higher than the ambient temperature. Other configurations of the microcapsules are the same as those of the first embodiment. As a result, the bimolecular cumulative film becomes a gel state (crystal state) from the initial stage and exhibits a higher barrier property against molecular permeation, and as shown in FIG. 9, the capsule film Cf in the initial state stage (ST1). Has a very low material permeability. Therefore, the target material 6 existing in the inner phase of the capsule membrane Cf and the target material 8 existing in the outer phase of the capsule film Cf
Can be more reliably isolated, and a chemical reaction due to “leakage” in which a small amount of substance molecules permeate through each capsule membrane Cf in the initial state stage without light irradiation can be more reliably prevented.

The first light R1 is applied to the microcapsules MC having the crystalline bimolecular accumulation film in the same manner as in the first embodiment.
Is irradiated with the second light R2 (ST2). By this light irradiation,
The conformational isomers dispersed and associated in the two-molecule cumulative film are oxidized (emit electrons) and try to change the molecular three-dimensional structure, but are regulated by the two-molecule cumulative film in a crystalline state. Disturbance of the film structure does not occur sufficiently. Therefore, the substance permeability of the two-molecule accumulation membrane hardly increases, and the target substances 6 and 8 in the inner and outer phases do not pass through the capsule membrane Cf. This state does not substantially change even if the respective intensities of the first light R1 and the second light R2 are increased.

Next, the material contained in the microcapsules is heated to a temperature equal to or higher than the phase transition temperature Tc of the bimolecular cumulative film, and the bimolecular cumulative film undergoes a phase transition to a liquid crystal state. As a result, the regulatory force of the two-molecule cumulative film disappears, the three-dimensional structure of the conformational isomer changes into a bent shape (see FIG. 3), and the film structure of the two-molecule cumulative film is disturbed (ST3). . As a result, the material permeability of the capsule film Cf increases, and the target material 6 existing in the capsule internal phase and the target material 8 existing in the external phase begin to diffuse through each other through the capsule film Cf (ST
Four). Thereafter, if the irradiation of the first and second lights R1 and R2 is continued and the heating of the microcapsule contents is continued to maintain the system temperature at or above the phase transition temperature Tc, mutual diffusion of the substance proceeds. (ST5).

When the interdiffusion of the substance contained in the microcapsules progresses to a desired degree, the irradiation of the first and second lights R1 and R2 is stopped. As a result, the conformational isomer in the bimolecular cumulative film is reduced and returns to the linear molecular three-dimensional structure (see FIG. 3), and the bimolecular cumulative film returns to the original layer structure. As a result, the material permeability of the capsule film Cf is reduced to about the initial stage (ST1) of the first embodiment shown in FIG. The mutual diffusion of the substances 6 and 8 stops (ST6). The interdiffusion of substances can be stopped by stopping the light irradiation or by lowering the environmental temperature to the layer transition temperature of the bimolecular cumulative film or lower. As described above, according to the method of the present example, the substance diffusion in the microcapsule-containing material can be controlled not only by light irradiation but also by adjusting the environmental temperature, so that more precise control of the substance diffusion can be easily performed. Is possible.

In the above-described second embodiment containing a plurality of types of microcapsules, as in this embodiment, by controlling the temperature of the contents of the microcapsules, the substance diffusion due to "leakage" in the initial state can be ensured. Thus, a more precise substance diffusion control effect can be easily obtained.

<Fourth Embodiment> FIG. 10 is a schematic explanatory view showing a method for controlling a substance diffusion light in a microcapsule-containing material as a fourth embodiment. The method of the present example is based on the structure of the third example, and further includes a polymer resin whose viscosity sharply decreases with an increase in environmental temperature, as a viscosity adjusting substance among the auxiliary substances disposed in the capsule and the external phase. Wax is used. Here, a case where a viscosity adjusting substance is arranged in the capsule inner phase will be described as an example. Then, the temperature at which the viscosity of the viscosity adjusting substance rapidly decreases is set near the phase transition temperature Tc of the two-molecule cumulative film.

Thus, under normal environmental temperature (from ST1 to ST2), the bimolecular cumulative film of the capsule film Cf is in a crystalline state and the internal phase of the capsule has a high viscosity. Substance 6 hardly diffuses into the external phase,
Further, the target substance 8 contained in the outer phase is in a state where it is extremely difficult to diffuse into the high-viscosity inner phase. For this reason, the target materials 6 and 8 in the capsule and the external phase are separated more reliably than in the third embodiment. Therefore, it is possible to more completely prevent substance diffusion due to "leakage" in which a small amount of substance molecules permeate the capsule film Cf in the initial stage (ST1) in which light is not irradiated.

After irradiating the first and second lights R 1 and R 2 (ST 2), the microcapsule-containing material is immersed in the same manner as in the third embodiment.
The film is heated to a temperature equal to or higher than the phase transition temperature Tc of the molecular accumulation film (ST3). As a result, the two-molecule cumulative film transitions to a liquid crystal state,
The viscosity of the above-mentioned viscosity adjusting substance contained in the internal phase of the capsule rapidly decreases. As a result, the target material 6 in the inner phase and the target material 8 in the outer phase begin to diffuse into each other as in the first embodiment (ST4). Then, when the mutual diffusion of the inner and outer phase target materials 6 and 8 progresses to a desired degree (ST5), the irradiation of the first and second lights R1 and R2 is stopped and the temperature is set to the same as the initial state (ST1). Lower to temperature (ST
6). Thereby, the state of the microcapsule-containing material returns to the initial state (ST1). That is, the internal phase of the capsule becomes the original high viscosity, and the bimolecular cumulative film returns to the crystalline state.
It should be noted that mutual diffusion of the substance is stopped only by performing either the temperature reduction or the stop of the light irradiation.

As described above, according to this embodiment, the interdiffusion of the substance can be easily controlled not only by the light but also by the temperature as in the third embodiment, and the “leakage” transmission of the substance molecules in the initial stage can be achieved. Can be more completely prevented. still,
The same effect can be obtained by disposing the same viscosity adjusting substance as the capsule external phase substance. Further, the same method as in the present embodiment can be applied to the case where a plurality of types of microcapsules are contained as in the second embodiment.

Although the present invention has been described in detail based on four embodiments, the present invention is not limited to these specific embodiments and the like, and various modifications may be made within the technical scope of the present invention. Is of course possible. For example, in the second embodiment, as shown in FIG. 8, the second light R2a,
The intensity of R2b, R2c is kept constant, and the first light R1a, R1b, R
By changing only the strength of 1c, each microcapsule MC1, MC
2. The material diffusion rate of MC3 is controlled, but not limited to this. Conversely, by making the intensity of the first light R1a, R1b, R1c constant and changing the intensity of the second light R2a, R2b, R2c, each of the microcapsules MC1, MC2, MC
3. Material diffusion can be controlled independently. Further, in the second embodiment, different target materials are provided for a plurality of types of microcapsules having different light responsiveness, but the same target material may be provided for different types of microcapsules.
That is, in FIG. 6, the same target substance 13a is used for each internal phase of the microcapsules MC1 and MC2.
May be arranged.

[0078]

As described above in detail, according to the present invention, a conformational isomer and an organic dye are contained as photo-responsive substances in micropores of a capsule film formed of a porous material. A two-molecule cumulative film is embedded to form a light-responsive capsule film that changes the material permeability in response to light irradiation, and a target material that can chemically react is isolated and present in the inner and outer phases of the capsule film. By structuring the microcapsule content, the microcapsule content is irradiated with light of a specific wavelength capable of redoxing a conformational isomerized substance and light of a specific wavelength that changes the electron mobility of an organic dye. The degree of interdiffusion of each target material in the internal and external phases can be easily and precisely controlled by only the above. In this case, since two types of photoresponsive substances are contained in the bimolecular accumulation film, the selection range of the bimolecular accumulation film material is widened, and the production of microcapsules having a desired photoresponsive property becomes easy. By adjusting the intensity of the irradiation light, it becomes possible to more precisely control the degree of progress of the chemical reaction caused by the target substance, extending from the permeation and diffusion rate at which the target substance of the internal and external phases permeates the capsule membrane. . Further, since light having a wavelength other than the above-mentioned specific wavelength does not change the material permeability of the two-molecule accumulation film, the mutual diffusion of the material can be precisely controlled even under normal light illumination, which is extremely convenient in practice. Furthermore, light irradiation requires only a very short period of time to irradiate pulsed light, so that high-speed light control of interdiffusion of substances is possible.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view showing a configuration of a microcapsule-containing material as one embodiment of the present invention and a concept of a light control method thereof.

FIG. 2 is a schematic cross-sectional view showing a detailed configuration of a capsule membrane in the microcapsule-containing material.

FIG. 3 is an explanatory diagram showing an isomerization reaction of a conformationally isomerized substance in the capsule membrane.

FIG. 4 is an explanatory diagram showing a transition of a bimolecular cumulative film containing the isomerized substance.

FIG. 5 is a schematic explanatory view showing an example of a flow of a substance diffusion light control method using the microcapsule-containing material.

FIG. 6 is a schematic explanatory view showing the concept of a microcapsule-containing material and a method of controlling a substance diffusion light using the same as another embodiment of the present invention.

FIG. 7 is a schematic explanatory view showing another embodiment of the substance diffusion light control method using the microcapsule-containing material of FIG.

FIG. 8 is a schematic explanatory view showing a modification of the method for controlling material diffusion light in FIG. 7;

FIG. 9 is a schematic explanatory view showing still another embodiment of the material diffusion light control method of the present invention.

FIG. 10 is a schematic explanatory view showing still another embodiment of the material diffusion light control method of the present invention.

FIG. 11 is a schematic sectional view showing a conventional microcapsule-containing material.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Wall material 2 Pore 3 2 molecule accumulation film 4 Conformation isomerized substance 5 Organic dye 6,13a, 13b, 13c Target substance (internal phase) 7,9,14,16 Auxiliary substance 8,15 Target substance ( External phase) 10, 17 Vessel 11, 18a, 18b, 18c First light source 12, 19a, 19b, 19c Second light source Cf, Cf1, Cf2, Cf3 Capsule film MC, MC1, MC2, MC3 Microcapsule R1, R1a, R1b, R1c first light R2, R2a, R2b, R2c second light

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification symbol FI // B01J 13/02 B01J 13/02 Z (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/73 G01J 1/00 G01J 1/50 G01N 21/78 B01J 13/02

Claims (10)

(57) [Claims] 1. A microcapsule-containing material containing microcapsules comprising a capsule membrane that changes material permeability upon irradiation with light, wherein the capsule membrane changes a three-dimensional structure by an oxidation-reduction reaction. A bimolecular film containing an isomer and an organic dye having spectral sensitization characteristics, wherein a target material capable of chemically reacting with each other is disposed in an inner phase and an outer phase of the capsule film, and the bimolecular film is Increased material permeability by receiving irradiation of light of a specific wavelength,
A microcapsule-containing material provided with a photoresponsive film, wherein the target substances of the internal and external phases are mutually diffused. 2. The microcapsule-containing material according to claim 1, comprising a plurality of types of microcapsules in which the specific wavelength to which the bilayer film responds is different from each other. 3. The microcapsule-containing material according to claim 1, wherein a material having a phase transition temperature at which a liquid crystal state is formed at room temperature is selected as a material of each of the bimolecular films. 4. A material having a phase transition temperature at which it becomes a crystalline state at room temperature is selected as a material of each of said bimolecular films, and each of said bimolecular films is irradiated with light of said specific wavelength and heated. 3. The method according to claim 1, wherein the substance permeability is increased.
The microcapsule-containing material according to the above. 5. The microcapsule according to claim 4, wherein a substance at which the temperature at which the viscosity sharply decreases with increasing temperature is sufficiently close to the phase transition temperature of each bilayer is added to the internal phase or the external phase of each microcapsule. Capsule contents. 6. A target material comprising a microcapsule comprising a capsule film provided with a bimolecular film for changing the material permeability upon receiving light of a specific wavelength, wherein an internal phase and an external phase of the capsule film are capable of chemically reacting with each other. Are arranged in isolation, and
The molecular film contains a conformational isomer that changes the three-dimensional structure by oxidation-reduction reaction and an organic dye with spectral sensitization properties, and receives light of a specific wavelength to change the three-dimensional structure of the molecule and increase material permeability A method for controlling a substance diffusion light of a microcapsule-containing substance having a photoresponsive property, wherein the method comprises irradiating light of the specific wavelength to the capsule membrane in a state of low substance permeability to increase the substance permeability. A method of controlling a substance diffusion light of a microcapsule-containing substance having a photoresponsive film, wherein a light irradiation amount of the specific wavelength light is adjusted to control a mutual diffusion speed of the target substance. 7. A method according to claim 6, wherein the specific molecular wavelength responding to the bimolecular film contains a plurality of types of microcapsules different from each other. 8. The material diffusion light control method according to claim 6, wherein a material having a phase transition temperature at which a liquid crystal state is formed at room temperature is selected as a material of each of the bimolecular films. 9. A material having a phase transition temperature at which it becomes a crystalline state at room temperature is selected as a material of each of said bimolecular films, and said bimolecular film is irradiated with light of said specific wavelength and heated. 8. The material according to claim 6, wherein the material permeability is increased.
The method of controlling a substance diffusion light according to the above. 10. The substance according to claim 9, wherein a substance whose temperature at which the viscosity sharply decreases with increasing temperature is sufficiently close to the phase transition temperature of each bilayer is added to the internal phase or the external phase of each microcapsule. Diffuse light control method.