JP2979161B2 - 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 polymer substance graft-polymerized on the peripheral surface of a membrane, and a method for 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. 10 schematically shows a microcapsule MC for controlling the pH of the outer phase Op of the capsule and controlling the material permeability of the capsule membrane Cf. Micro capsule M
The capsule film Cf of C is made of a porous polymer material, and a polymer G is graft-polymerized on the outer peripheral surface thereof. Inside (capsule inner phase) and outside (capsule outer phase) of capsule membrane Cf
Are provided with liquid substances Mi and Mo, respectively.

[0005] When the environmental pH of the contents of the microcapsules, that is, the pH of the outer phase of the capsule is changed, each liquid substance Mi,
The permeability of the capsule membrane Cf to Mo increases,
It is known that returning to the original state returns to the original transparency. This is believed to depend on the degree of acid-base dissociation of the graft polymer. For example, if the graft polymer is poly4-vinylpyridine

[0006]

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In the case of (1), the outer phase of the capsule is acidic (pH <7).
In this case, the pyridine group in the side chain is protonated and hydrophilic. As a result, the graft polymer has an elongated conformation as shown in FIG. 10A due to electrostatic repulsion between side chains. Thereby, the capsule membrane Cf exhibits high substance permeability because the pores thereof are not blocked by the graft polymer G.

On the other hand, the capsule outer phase is alkaline (pH>
In the case of 8), the pyridine group in the side chain is neutral and hydrophobic, so that the graft polymer has a contracted conformation as shown in FIG. 10B. Thereby, the pores of the capsule membrane Cf are closed by the graft polymer G, and the substance permeability is reduced.

In the above-mentioned method, since the substance permeation of the graft polymerization capsule membrane is controlled by adjusting the pH, it is difficult to sharply change the substance permeability of the capsule membrane. Therefore, it becomes extremely difficult to put the contents of the graft polymerization microcapsules into practical use (for example, to apply them to a recording medium of a recording apparatus). In addition, since the means for changing the pH is naturally limited, the applicable range is narrowed.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a graft polymerized microcapsule-containing material which can control the interdiffusion of substances sharply and precisely and can secure a wide range of application, and a method for controlling the light diffusion of the substance.

[0011]

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. The capsule membrane is formed by graft polymerization of a polymer substance having a site that dissociates and ionizes by light irradiation on the peripheral surface of a wall material made of a porous material, and is formed into an inner phase and an outer phase of the capsule membrane. A target substance capable of chemically reacting is disposed, and the capsule membrane is irradiated with light of a specific wavelength to increase the substance permeability,
This is achieved by providing a microcapsule-containing material provided with a photoresponsive film, wherein the target materials of the internal and external phases are mutually diffused.

Another point of the present invention is that the above-mentioned object includes a microcapsule made of a capsule membrane which changes a substance permeability upon being irradiated with light, wherein the capsule membrane is made of a porous material. A polymer material having a site that is dissociated and ionized by light irradiation on the peripheral surface of the material is formed by graft polymerization, and target materials that can chemically react with each other are disposed in the inner phase and the outer phase of the capsule membrane, respectively, A method for controlling the substance diffusion light of a microcapsule-containing material having photoresponsiveness in which the capsule membrane increases the material permeability upon being irradiated with light of a specific wavelength, and diffuses the target substance mutually through the capsule membrane. Wherein the microcapsule-containing material provided with a photoresponsive film, wherein the irradiation intensity of the light having the specific wavelength is adjusted to control the mutual diffusion speed of the target material. By providing a substance diffused light control method is that it is achieved.

[0013]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described with reference to the first to fifth 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. 2 is a schematic explanatory view showing the concept of an apparatus for performing 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. 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 the polymer material forming the wall material 1, a general polymer material such as polyamide, polyester, polyurethane, polymethyl methacrylate, polyurea, polystyrene, polyvinyl alcohol, or the like can be suitably used.

A photo-responsive polymer 3 is graft-polymerized on the outer peripheral surface of the wall material 1. The photoresponsive polymer 3 is a linear polymer having a sensitive group in a side chain portion that is dissociated and ionized by irradiation with light of a specific wavelength. By the way, many compounds which dissociate ions upon irradiation with light are known, but many dissociated ions immediately recombine. As a material of the photoresponsive polymer 3, a compound having a sufficiently long life of ions generated by dissociation is preferable. Such materials include, for example,

[0015]

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[0016]

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And the like. FIG. 2 shows the dissociation change of a graft polymer in which a triphenylmethane derivative is introduced as a sensitive group into a side chain.

Since the above-mentioned graft polymer 3 is hydrophobic, it does not assume a conformation extending toward the external phase (aqueous phase) but a contracting conformation in a stable state as shown in FIG. Thus, the state is attached to the outer peripheral surface of the wall material 1 (see (ST1) in FIG. 3). In this state, the pores 2 of the wall material 1 (see FIG. 1)
Thus, the material permeability of the capsule membrane Cf decreases, and a sufficient permeability barrier property can be obtained even for a material having a small molecular weight.

In FIG. 1, a target substance 4 and its auxiliary substance 5 are arranged in the inner phase of the microcapsule MC. The target substance 4 is a substance that can diffuse through the capsule membrane Cf into the external phase, and corresponds to, for example, a dye precursor having color-forming ability. The auxiliary substance 5 is a substance that adjusts the chemical properties of the target substance 4. When the target substance 4 is, for example, a leuco dye as a dye precursor,
As the auxiliary substance 5, distilled water, which is a solvent for dissolving and dispersing the leuco dye, and organic solvents such as benzene, toluene, alkylnaphthalene, biphenyls, and paraffins are preferable. In addition, various kinds of commercially available waxes and resin polymers are mixed in order to impart appropriate viscosity to the solution of the internal phase of the capsule. Such an auxiliary substance 5 comprises a capsule membrane C
It is preferable to select a material having a molecular weight that is large enough not to pass through the pore 2 of f. When the target substance 4 is a solid, the solvent for dissolving the target substance 4 also serves as the auxiliary substance 5.

As described above, the microcapsule MC mixes one of the target materials 4 capable of chemically reacting with each other, its auxiliary material 5 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, ethylene glycol dimethacrylate is dissolved in a water and ethanol solution, and the above-mentioned microcapsule intermediate is charged into this solution. A polymerization initiator is added thereto, and the mixture is heated to introduce a vinyl group to the outer peripheral surface of the polymer material constituting the capsule wall.

Next, in a heated aqueous solution, a vinyl derivative containing a leuco-form of triphenylmethane and other vinyl monomers and ethylene are polymerized on the outer peripheral surface of the above-mentioned microcapsule intermediate by a radical initiator. As a result, the graft polymer is extended from the vinyl group introduced to the outer peripheral surface of the capsule wall. Thereafter, if the microcapsules are extracted and washed, the graft polymerization microcapsules of this example are completed.

In FIG. 1, the other target substance 6 and its auxiliary substance 7 are arranged in the external phase of the microcapsule MC. The target substance 6 is a substance capable of causing a chemical reaction with each target substance 4 in the internal phase. For example, when the target substance 4 in the inner phase is a dye precursor, the target substance 6 in the outer phase becomes a color developer capable of causing a uniform chemical reaction with the dye precursor in the inner phase of the capsule to form a color. The auxiliary substance 7 is an auxiliary substance for adjusting the physical properties of the target substance 6 like the auxiliary substance 5 in the internal phase.
The microcapsules MC produced as described above are put into a solution in which the target material 6 and the auxiliary material 7 are mixed and dispersed, thereby constituting the microcapsule-containing material of this example.

The microcapsule-containing material having the above-described structure is charged into a transparent container 8, and a light source 9 is arranged outside the container 8. The light source 9 irradiates light R including a component light having a wavelength of ν to excite a photosensitive group introduced into a side chain portion of the graft polymer 3. By adjusting the irradiation of the light R, the substance permeability of the capsule membrane cf can be controlled as described later. When the photosensitive group of the graft polymer 3 is a derivative of triphenylmethane, the wavelength ν for exciting the derivative is
Is in the ultraviolet region, and the light source 9 is an ultraviolet light source.

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. 3, a transparent container 8 contains a microcapsule MC containing one target material 4 and a microcapsule-containing material of the present example obtained by mixing the other target material 6 and its auxiliary material and the like. ing. In the thermally stable initial state stage (ST1), as shown in FIG. 10B, the graft polymer 3 polymerized and implanted on the outer peripheral surface of the capsule membrane Cf is in a stable state showing hydrophobicity. Therefore, the graft polymer 3 takes a contracted conformation without affinity for the external phase (water) and adheres to the outer peripheral surface of the wall material 1 to close the pores (see FIG. 1). as a result,
The material permeability of the capsule membrane Cf is low, and the target materials 4 and 6 in the capsule and the external phase are isolated by the capsule membrane Cf.

The microcapsule-containing material in the initial state is irradiated with light R by a light source 9 installed outside the transparent container 8 shown in FIG. 1 (ST2). The light R is light containing spectral component light having a wavelength of ν, and the photosensitive group of the graft polymer 3 absorbs the component light having a wavelength of ν to be in an excited state, dissociated and ionized. Among the generated ions, the ion dissociated from the polymer, for example, the graft polymer 3 is a triphenylmethane derivative (see Chemical formula 2 or Chemical formula 3).
In the case of (1), an anion such as OH (-) or CN (-) is dispersed in the solvent (external phase liquid). Thereby, the graft polymer 3
The triphenylmethane cation remains, and the graft polymer 3 adopts a radially extending conformation as shown in FIG. 1 due to the electrostatic repulsion between the cations.
As a result, there are no obstacles blocking the pores 2 of the capsule membrane Cf, and each of the target substances 4 and 6 in the capsule and in the external phase can easily pass through the capsule membrane Cf through the pores 2. That is,
The substance permeability of the capsule membrane Cf increases.

Here, by controlling the intensity or time of light irradiation, it is possible to control the amount of sensitive group molecules that actually cause photodissociation. That is, by controlling the intensity and irradiation time of the light R, the substance permeability of the capsule membrane Cf based on the degree of dissociation of the graft polymer 3 can be controlled. This makes it possible to control the interdiffusion speed of the target materials 4 and 6 in the capsule and the external phase through the capsule film Cf, as described later.

In FIG. 3, after starting irradiation of light R,
When this light irradiation is continued, the material permeability of the capsule membrane Cf increases, and the target materials 4 and 6 in the capsule inner and outer phases are increased.
Begin to spread to each other (ST3). Then, as time elapses, the amount of the target materials 4 and 6 that diffuse mutually increases (ST4). When the target substances 4 and 6 of the inner and outer phases are a dye precursor and a developer, respectively, they are mixed with each other to start a color forming reaction.

The amount of diffusion of each of the target materials 4 and 6 in the inner and outer phases varies depending on the size of molecules passing through the capsule membrane, the pressure value inside and outside the capsule, and the like, but also varies depending on the degree of dissociation of the graft polymer 3 as described above. . 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 occurring when the target materials 4 and 6 are mixed. In FIG. 3, the case where light R is strongly irradiated is shown in the upper part, and the case where light R is weakly irradiated is shown in the lower part. The states at the same stage are arranged vertically and compared. 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 the light R is stopped (ST5). As a result, the photodissociated ions are recombined and stabilized, and the graft polymer 3 loses its electrostatic repulsion and returns to the original conformation attached to the capsule membrane Cf. As a result, the pores of the capsule membrane Cf are closed by the graft polymer 3 to lower the material permeability, and the interdiffusion of the target materials 4 and 6 is prevented.

As described above, the microcapsule-containing material of this example and the method of controlling the substance diffusion light thereof can precisely control the mutual diffusion of the substance only by controlling the irradiation time or irradiation intensity of the light. It can be put to practical use in a range.

<Second Embodiment> FIG. 4 is a schematic explanatory view showing the structure of a microcapsule-containing material according to a second embodiment and the concept of an apparatus for implementing a method of controlling the material diffusion light.
Note that the same components as those in the above embodiment are denoted by the same reference numerals, and description thereof will be omitted.

In this embodiment, the graft polymer 3 is polymerized and implanted on the inner peripheral surface of the capsule wall material 1 to form the microcapsules MC '.
Is formed. Other configurations are the same as those of the first embodiment. By implanting the graft polymer 3 of the microcapsules MC 'on the inner peripheral surface of the wall material 1 as described above, even when the external phase of the capsule is a solid type, the same light-responsive substance diffusion effect as that of the liquid type is obtained. Can be. When the capsule outer phase is a solid phase, if the graft polymer 3 is implanted on the outer peripheral surface of the wall material 1 as in the first embodiment, even if the graft polymer 3 is photodissociated, it is regulated by the solid external phase. As shown in FIG. 1, it is not possible to sufficiently expand radially. Therefore, even if the light R is irradiated, the material permeability of the capsule film Cf does not sharply increase. On the other hand, if the graft polymer 3 is implanted on the inner peripheral surface of the wall material 1 as in this example, if the outer phase is a solid system, but if the capsule inner phase is a liquid system, the graft polymer 3 will
As shown in (1), it can be photodissociated and extend sufficiently toward the center of the capsule. Therefore, even in the case where the external phase is a solid system, it is possible to obtain a sharp photoresponsive substance permeation effect as in the case of the first embodiment.

Next, a method of manufacturing the microcapsules MC 'of this embodiment will be described. First, a microcapsule intermediate including a target material and a water / ethanol solution of ethylene glycol dimethacrylate in a shell-shaped wall material is manufactured. As an intermediate production method, an interfacial polymerization method,
An in-situ (in-situ) polymerization method, a coacervation method, or the like can be used.

Next, the above-mentioned microcapsule intermediate is charged into an aqueous solution, a polymerization initiator is added thereto, and the mixture is heated to introduce a vinyl group into the inner peripheral surface of the polymer material constituting the capsule wall.

Next, after the capsule is sufficiently dialyzed in an aqueous solution, the capsule is transferred into an aqueous solution of a vinyl derivative containing a leuco-form of triphenylmethane and other vinyl monomers or ethylene, and these substances are converted into an inner phase of the capsule. Spread.

Next, the obtained capsule is placed in an aqueous solution and polymerized by a radical initiator. As a result, the graft polymer is extended from the vinyl group introduced into the inner peripheral surface of the capsule wall. Thereafter, if the microcapsules are extracted and washed, the graft polymerization microcapsules of this example are completed.

As shown in FIG. 5, the procedure of the method for controlling the material diffusion light of the microcapsule-containing material is the same as the method for controlling the material diffusion light of the first embodiment shown in FIG. In this case, the only difference is that the graft polymer 3 implanted on the inner peripheral surface of the wall material 1 extends toward the center of the capsule.

<Third Embodiment> As shown in FIG. 6, three types of microcapsules M
Contains C1, MC2 and MC3. The number of types of microcapsules MC to be contained is plural, and therefore, four or more types may be used. Thus, the photoresponsiveness of these three types of microcapsules MC1, MC2, and MC3, that is, the wavelength of the irradiation light at which the material permeability of each of the capsule films Cf1, Cf2, and Cf3 changes is made different. In order to make the response light wavelength of each capsule film different, the photoresponsiveness of the graft polymers 10a, 10b, 10c implanted on the outer peripheral surface of each capsule wall material 1 is made different. That is, each of the graft polymers 10a, 10
In b and 10c, photodissociating groups having different wavelengths of irradiation light upon dissociation are introduced, respectively.

In each of the internal phases of the microcapsules MC1, MC2 and MC3, an auxiliary substance 12 identical to one of the target substances 11a, 11b and 11c of a different kind is arranged. And these microcapsules MC1, MC
2. In the outer phase of MC3, the other target substance 13 capable of chemically reacting with the target substance 11a, 11b, 11c of each capsule inner phase and its auxiliary substance 14 are arranged. still,
As the specific materials used for the wall materials constituting the capsule films Cf1, Cf2, and Cf3, and the auxiliary materials 12 and 14 in the capsule and in the external phase, those suitable for the materials described in the first embodiment are selected. Can be used.

The microcapsule-containing material having the above-described configuration is charged into a transparent container 15, and three light sources 16a, 16b, and 16c are arranged outside the container 15. Each of the light sources 16a, 16b, 16c is provided with a capsule film Cf1, Cf.
2, Cf3 graft polymers 10a, 10b, 10c
Are irradiated with light Ra, Rb, and Rc, respectively, including component light of wavelengths νa, νb, and νc for exciting the respective light.

Next, a method for controlling the substance diffusion light in the microcapsule-containing material having the above configuration will be described.
FIG. 7 shows that the above three types of light are irradiated simultaneously and the light R
FIG. 9 is a schematic explanatory view showing step by step the substance diffusion operation when the irradiation intensity of a, Rb, and Rc is changed. By controlling the irradiation intensity of the light R in this manner, the amount of the group that is actually dissociated among the photodissociable groups introduced into the graft polymer 10 can be controlled. Therefore, by controlling the intensity of the irradiation light, the graft polymer 10 of each microcapsule can be controlled.
From the material permeability of each of the capsule membranes Cf1, Cf2, Cf3 based on the degree of dissociation of a, 10b, 10c, the interdiffusion speed of each of the target materials 11a, 11b, 11c, and 12 in the capsule and the external phase is precisely and easily controlled. be able to.
In this example, the intensity of the light Rc, which is responsive to the graft polymer 10c and controls the material permeability of the capsule membrane Cf3, is the strongest,
Similarly, the light R controlling the material permeability of the capsule membrane Cf2
The intensity of b is set the weakest.

Irradiation of light Ra, Rb, Rc to the microcapsule contents in the initial state (ST1) is started (ST2), and this light irradiation operation is continued. Thereby, each capsule film Cf1, Cf2, Cf of the microcapsules MC1, MC2, MC3.
3, the material permeability of the target material 11a, 11b, 11c of the inner phase of each capsule and the target material 1 of the outer phase are increased.
3 begin to diffuse through each capsule film Cf1, Cf2, Cf3 (ST3).

When the light irradiation is continued, the target materials 11a, 11b, 1
The amount of mutually diffused molecules of 1c and 13 increases (ST4). At this time, each microcapsule MC1, MC2,
The molecular weight of the interdiffusion material in MC3 is determined by light Ra, Rb,
The amount of interdiffusion related to the microcapsules MC3 responding to the light Rc having the highest irradiation intensity is the largest, and the amount of interdiffusion related to the microcapsules MC2 responding to the light R2 is the smallest. . When the interdiffusion of the target substances 11a, 11b, 11c and 13 in the capsule inner and outer phases has progressed to the desired degree at the respective speeds, the irradiation of the light Ra, Rb and Rc is stopped. Thereby, the dissociated ions of the respective graft polymers 10a, 10b, 10c of the microcapsules MC1, MC2, MC3 are recombined, and the respective graft polymers 10a, 10b,
10c loses the electrostatic repulsion and returns to the original conformation attached to the outer peripheral surface of the wall material. As a result, the pores of each of the capsule membranes Cf1, Cf2, Cf3 are closed, and the material permeability is reduced to the same extent as the initial state, and the interdiffusion of each of the target materials 11a, 11b, 11c and 13 in the capsule and in the external phase is performed. Is blocked (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.

<Fourth Embodiment> FIG. 8 is a schematic explanatory view showing the structure of a microcapsule-containing material according to a fourth embodiment and the concept of an apparatus for implementing a method for controlling the material diffusion light.
In this example, a plurality of types of microcapsules MC'1, M
Graft polymer 1 on inner peripheral surface of each wall material 1 of C'2, MC'3
0a, 10b, and 10c are respectively polymerized and planted. Other configurations are the same as in the third embodiment.

In the case of the material diffusion light control method of this embodiment,
As in the third embodiment, the graft polymers 10a, 10b,
10c are sensitive to three types of light R having different wavelengths from each other.
By individually controlling the irradiation intensity of a, Rb, and Rc,
The mutual diffusion of substances in each of the microcapsules MC'1, MC'2, MC'3 can be selected and controlled precisely.

<Fifth Embodiment> In this embodiment, a polymer resin or wax whose viscosity rapidly decreases with an increase in environmental temperature is used as a viscosity adjusting substance in a capsule. Then, the temperature at which the viscosity of the viscosity adjusting substance rapidly decreases is set to a level higher than room temperature. FIG. 9 shows a case where a viscosity adjusting substance is arranged in the internal phase of the microcapsule MC of the first embodiment. Note that the configuration of the present embodiment is not limited to the first embodiment, and can be applied to the second to fourth embodiments, respectively. Further, the same viscosity adjusting substance may be provided not only in the capsule inner phase but also in the capsule outer phase.

In FIG. 9, under normal environmental temperature (ST1
In ST2), since the viscosity of the capsule internal phase is high, the target substance 4 contained therein is extremely difficult to diffuse into the external phase, and the target substance 6 included in the external phase is also extremely dispersed into the internal phase having a high viscosity. Difficult to spread. For this reason, the target materials 4 and 6 in the capsule and the external phase are separated more reliably than in the first to fourth embodiments. 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 irradiation with light R (ST2), the contents of the microcapsules are heated to a temperature at which the viscosity of the above-mentioned viscosity adjusting substance decreases (ST3). As a result, the viscosity of the viscosity adjusting substance contained in the capsule internal phase sharply decreases.
As a result, the target material 4 in the inner phase and the target material 6 in the outer phase begin to diffuse into each other as in the first embodiment. When the mutual diffusion of the inner and outer phase target materials 4 and 6 progresses to a desired degree (ST4), the irradiation of the light R is stopped,
And lower the temperature to the same temperature as the initial state (ST1) (ST
Five). As a result, the state of the microcapsule-containing substance returns to the initial state (ST1), and the mutual diffusion of the substance is prevented. That is, the internal phase of the capsule becomes the original high viscosity and suppresses the diffusion and transfer of the substance. It should be noted that mutual diffusion of the substance can be prevented only by performing either the temperature reduction or the stop of the light irradiation.

As described above, according to the present embodiment, the interdiffusion of substances can be easily controlled not only by light but also by temperature, and the "leakage" transmission of substance molecules in the initial stage can be more completely prevented. Is obtained.

Although the present invention has been described in detail based on five 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 third embodiment, different target substances are respectively arranged on a plurality of types of microcapsules having different photoresponsiveness.
The same target substance may be provided on different types of microcapsules. That is, in FIG. 6, the same target substance 11a may be arranged in each internal phase of the microcapsules MC1 and MC2.

[0053]

As described above in detail, according to the present invention, a graft polymer which dissociates in response to light is polymerized and implanted on the peripheral surface of a capsule wall material formed of a porous material. By constructing a photo-responsive capsule membrane that changes the material permeability in response to irradiation, and by allowing a chemically reactable target substance to be isolated and present in the inner and outer phases of the capsule membrane to form microcapsule-containing materials By merely irradiating the microcapsule-containing material with light having a specific wavelength capable of dissociating the graft polymer, the degree of mutual diffusion of the internal and external phase target materials can be easily and precisely controlled. 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. . In this case, the graft polymer is not dissociated by light having a wavelength other than the specific wavelength, and thus the material permeability of the capsule membrane does not change.For example, the mutual diffusion of the material can be precisely controlled even under normal light illumination. Above is very convenient. or,
Since the light irradiation requires only a very short time of irradiating pulse light, high-speed light control of interdiffusion of substances is possible, and the application to which the present invention can be applied is widened.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view showing a configuration of a microcapsule-containing material as a first embodiment of the present invention and a concept of an apparatus for implementing a method for controlling a substance diffusion light thereof.

FIG. 2 is an explanatory view showing a dissociation reaction of a graft polymer in the microcapsule-containing material.

FIG. 3 is a schematic explanatory view showing an example of a substance diffusion light control method using the microcapsule-containing material.

FIG. 4 is a schematic explanatory view showing the concept of an apparatus for implementing a method for controlling a substance-diffused light according to a second embodiment of the present invention.

FIG. 5 is a schematic explanatory view showing a material diffusion light control method according to the second embodiment.

FIG. 6 is a schematic explanatory view showing the concept of an apparatus for implementing a substance containing microcapsules and a method for controlling a substance diffusion light using the same as a third embodiment of the present invention.

FIG. 7 is a schematic explanatory view showing a method for controlling material diffusion light according to the third embodiment.

FIG. 8 is a schematic explanatory view showing a microcapsule-containing material as a fourth embodiment of the present invention and a method of controlling a substance diffusion light using the same.

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

FIG. 10 is a schematic explanatory view showing a change in material permeability of a microcapsule obtained by polymerizing a graft polymer.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Wall material 2 Porous 3,10a, 10b, 10c Graft polymer 4,11a, 11b, 11c Target substance (inner phase) 5,7,12,14 Auxiliary substance 6,13 Target substance (outer phase) 8,15 Container 9, 16a, 16b, 16c Light source Cf, Cf1, Cf2, Cf3 Capsule film MC, MC ', MC1, MC2, MC3 MC'1, MC'2, MC'3 Microcapsule R, Ra, Rb, Rc Light R2, R2a, R2b, R2c Second light

Claims (10)

(57) [Claims] 1. A microcapsule-containing material comprising a microcapsule comprising a capsule membrane which changes a substance permeability upon being irradiated with light, wherein the capsule membrane is provided on a peripheral surface of a wall material made of a porous material. A polymer material having a site that is dissociated and ionized by light irradiation is formed by graft polymerization, target materials capable of chemically reacting with each other are disposed in an inner phase and an outer phase of the capsule film, and the capsule film has a specific wavelength of light. A microcapsule-containing material provided with a photoresponsive film, characterized in that the material permeability is increased by irradiation with the light, and the respective target materials of the internal and external phases are mutually diffused. 2. The microcapsule-containing material according to claim 1, wherein the polymer material is graft-polymerized on the outer peripheral surface of the wall material. 3. The microcapsule-containing material according to claim 1, wherein the polymer material is graft-polymerized on an inner peripheral surface of the wall material. 4. The microcapsule-containing material according to claim 1, which comprises a plurality of types of microcapsules in which the specific wavelength to which the capsule membrane responds is different from each other. 5. The microcapsule content according to claim 1, wherein a substance whose viscosity sharply decreases with an increase in temperature is added to the internal phase or the external phase of the microcapsule. 6. A microcapsule comprising a capsule film which changes substance permeability upon receiving light irradiation, wherein the capsule film is dissociated and ionized by light irradiation on a peripheral surface of a wall material made of a porous material. A polymer material having a site is formed by graft polymerization, target materials capable of chemically reacting with each other are disposed separately in an inner phase and an outer phase of the capsule film, and the capsule film is irradiated with light of a specific wavelength. Is a material diffusion light control method of the microcapsule-containing material having photoresponsiveness to increase the material permeability and mutually diffuse the target material through the capsule membrane, wherein the irradiation intensity of the light of the specific wavelength is increased. Controlling the interdiffusion rate of the target substance by controlling the diffusion rate of the target substance. 7. The method according to claim 6, wherein the polymer material is graft-polymerized on the outer peripheral surface of the wall material. 8. The method according to claim 6, wherein the polymer is graft-polymerized on the inner peripheral surface of the wall material. 9. The method according to claim 6, wherein a microcapsule containing a plurality of types of microcapsules having different specific wavelengths to which the capsule film responds is used. 10. The method according to claim 6, wherein a substance whose viscosity rapidly decreases with increasing temperature is added to the internal phase or the external phase of each of the microcapsules.