JPH11241270A - Production of composite structure and composite structure produced thereby - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a composite structure bearing a functional matter thereon, enabling the functional matter such as an antimicrobial agent, deodorant or dye to adhere to a fibrous or filmy substrate as efficiently as possible and also to be sustained as long as possible, and to obtain such a composite structure by the above method. SOLUTION: This method for producing a composite structure, comprises adsorption of a functional matter 2 of ultrafine particles to a substrate 1, wherein the detailed process is as follows: the surface of the substrate 1 is previously subjected to electrification treatment so as to be electrified to opposite polarity to that of the electrified functional matter 2 being in the form of ultrafine particles made into a colloid in a solution, and the functional matter 2 is adsorbed to the substrate 1 by making use of electrostatic attractive force; otherwise, when the polarity of the ultrafine particles is identical with that of the substrate 1, an intermediate medium bearing ionic polarity opposite to those of the above is mediated, or either of the ionic polarities of the above is converted, thereby making the ultrafine particles substantially adhere to the substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a composite structure to which a functional substance is adhered, and to a composite structure produced by the production method. The present invention relates to a method for producing a composite structure to which a functional substance exhibiting the function of a substance adhered thereto while holding the composite substance is adhered, and to a composite structure produced by the production method.

[0002]

2. Description of the Related Art For example, JP-A-2-251681 discloses a fiber in which a cyclodextrin containing a deodorant is fixed to the surface of a natural fiber or a synthetic resin fiber other than wool to maintain a deodorant function. JP-A-4-200515 discloses a towel having extremely high washing fastness in which a microencapsulated moisturizing component is held together with a highly water-absorbent resin on a highly water-absorbent towel. I have. Furthermore, cyclodextrin containing squalane or squalene as a fat-soluble substance or a mixture thereof is fixed to natural fibers or synthetic resin fibers inside the cavity, and a fiber having excellent moisturizing effect and high durability is disclosed in 6-322670.

[0003] A dyeing method in which a fiber molded product is immersed in a gold hydrosol containing a cationic surfactant to adsorb gold colloid in the gold hydrosol on the fiber surface is disclosed in Japanese Patent Publication No. 63-4693. It is described in. According to this dyeing method, when the gold colloid contained in the gold hydrosol is adsorbed on the fiber, the surface is colored in purple known as "Cassius purple", and the high-grade image of gold is given to the fiber, Value is enhanced.

[0004]

SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Laid-Open No. 2-25
As disclosed in Japanese Patent No. 1681, the present invention relates to an organic deodorant in which cyclodextrin containing a deodorant is attached to the surface of a fiber to retain the deodorant function on the fiber. Above all, natural plant extract is included in natural fiber or synthetic resin fiber so that the fiber retains the deodorizing function.The fiber of the present invention is obtained by including a deodorant in cyclodextrin. For this reason, the deodorant peels off from the cyclodextrin, and the deodorant function cannot be prolonged.

As disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 4-200515, in the present invention, a microencapsulated moisturizing component is carried on a highly water-absorbing toweling together with a highly water-absorbing resin. The towel of the present invention
Although the specification states that the toweling has extremely high washing fastness, the microcapsules having a large particle size also have a disadvantage that they peel off from the toweling during use.

As disclosed in the above-mentioned Japanese Patent Application Laid-Open No. Hei 6-322670, the present invention includes the inclusion of squalane or squalene, which is a fat-soluble substance, or a mixture thereof in the cavity of cyclodextrin, Although it is fixed to natural fibers or synthetic resin fibers, since the cyclodextrin is applied to the surface of the fiber, the bond between the fiber surface and the cyclodextrin is weak. Cyclodextrin has the disadvantage of exfoliation.

As described in the above-mentioned JP-B-63-4693, the present invention relates to a dyeing method in which a gold colloid is adhered to the surface of a fiber to maintain a high-grade feeling on the fiber. In general, the technique of depositing colloidal gold on fibers is rather difficult and inefficient, and adsorption is slow, especially for fibers such as cotton. Therefore, the amount of colloidal gold remaining in the residual liquid after the dyeing treatment increases. In the case of ultrafine gold particles cationized using a surfactant or the like in a liquid as in the present invention, metal fine particles condense and become large. Therefore, when adsorbed on the fiber, the metal fine particles hardly diffuse and penetrate into the interior of the fiber, resulting in surface adsorption. In addition, the adsorption power is reduced, and the ultrafine gold particles are separated from the fiber during friction or washing. Naturally, when the metal particles condense and grow,
The surface activity of the particles becomes relatively small, and the original functionality of the metal cannot be sufficiently exhibited.

In addition, in the case of a cationized ultrafine metal (gold) described in JP-B-63-4693,
Since the colloidal stability of the solution is originally unstable, it is susceptible to impurities in the solution and drugs used in combination, and has a disadvantage that the colloidal stability is easily destroyed. Especially in the early stage of adsorption to the fiber, the cationic surfactant in the gold sol is first adsorbed to the fiber, the concentration in the sol decreases, and as a result the unstable gold colloid is adsorbed in the next stage Therefore, the gold colloid in the residual liquid after the treatment becomes extremely unstable.

Further, instead of using the gold of the cationized ultrafine metal of the invention described in Japanese Patent Publication No. 63-4693, for example, if the method described in the present invention is used to convert copper into a colloid, Does not change. Although silver can be formed into a colloid by using the method of the present invention, metals that can be practically used are limited, such as poor adsorption ability to fibers. In addition, when the metal concentration is increased, the colloid becomes unstable, so that usually only those having a concentration of 100 to 200 ppm can be produced, which has a drawback that the used concentration is low.

An object of the present invention is to improve the above-mentioned conventional disadvantages, and an object of the present invention is to provide a support formed in a fibrous body, a film, or the like, with an antibacterial agent, a deodorant, a dye, or the like. When attaching the functional substance, it is possible to attach the functional substance to the support as efficiently as possible.
In addition, a method for producing a composite structure to which a functional substance capable of retaining the functional substance adhered to these holders for as long a life as possible, and a composite structure produced by the production method are to be obtained. is there.

[0011]

In order to achieve the object of the present invention as described above, according to the first aspect of the present invention, there is provided a composite structure in which a functional substance comprising ultrafine particles is adsorbed on a support. In the manufacturing method, after the surface of the holding body is subjected to a charging treatment in advance so as to be charged to the opposite polarity to the charging polarity of the functional material that has been turned into a colloid in a solution and turned into ultrafine particles,
There is provided a method for producing a composite structure, characterized in that the finely divided functional substance is adsorbed in a solution by electrostatic attraction.

According to a second aspect of the present invention, in the method for producing a composite structure in which a functional substance composed of ultrafine particles is adsorbed on a support, the charge polarity of the functional substance which is colloidalized into ultrafine particles in a solution is opposite to that of the charged substance. The intermediate medium, which has been adsorbed in advance by an electrostatic attraction to an intermediate medium composed of polar charged ultrafine particles, and further adsorbed the ultrafine particles in a solution,
There is provided a method for producing a composite structure, characterized in that it is made to adhere to a surface of a holding member which has been subjected to charging treatment in advance by electrostatic attraction in a solution.

According to a third aspect of the present invention, in the method for producing a composite structure in which a functional substance composed of ultrafine particles is adsorbed on a support, a surfactant is used to remove either the surface of the support or the surface of the ultrafine particles. By converting one of the charging polarities to make the charging polarities of the surface of the holder and the surface of the ultrafine particles different from each other,
There is provided a method for producing a composite structure, characterized in that the ultrafinely divided functional substance is adsorbed on the surface of a holder by electrostatic attraction in a solution. According to a fourth aspect of the present invention, the holding body is a film or a plate formed in a flat shape, and the composite structure is selected from one of the first to third aspects. A body recipe is provided.

According to the fifth aspect of the present invention, the holder is a fibrous structure.
A method is provided for making a composite structure of any one of the following: According to a sixth aspect of the present invention, there is provided a method of manufacturing any one of the first to third composite structures, wherein the holder is a porous ceramic.

According to the present invention, in the composite structure in which the functional substance composed of ultrafine particles is adsorbed on the holder, the surface of the holder whose surface is forcibly charged is charged with the charged electrode on the surface. Provided is a composite structure characterized in that ultrafine particles charged to the opposite polarity charge are attached thereto.

According to the present invention, in a composite structure in which a functional material composed of ultrafine particles is adsorbed on a holder, the surface of the holder whose surface is forcibly charged is charged with a charged electrode on the surface. The composite structure is characterized by comprising an intermediate medium charged to a polarity opposite to that of the intermediate medium and adsorbing the ultrafine particles.

According to a ninth aspect of the present invention, the holding member is a film or a plate formed in a flat plate shape. Two composite structures are provided. According to a tenth aspect of the present invention, there is provided any one of the composite structures selected from the seventh and eighth aspects, wherein the holder is a fiber structure. According to an eleventh aspect of the present invention, there is provided a composite structure according to any one of the seventh and eighth aspects, wherein the holder is a porous ceramic.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, an embodiment of the present invention will be described in detail with reference to the drawings. Generally, ultrafine particles dispersed in water have a constant positive or negative charge when they are in a colloidal state, which prevents condensation between the ultrafine particles (colloidal particles) and stabilizes the colloidal material.
Here, the ultrafine particles have a diameter (d) in the range of about 1 nm <d <100 nm and have a surface area of several tens of square meters or more per gram. It has a thin uniform interface layer consisting of a thin film, has an atomic level step surface, can be uniformly dispersed and mixed in gas, liquid and solid, and can be chain ultrafine particles.
It has special properties such as discrete electron energy levels in particles, particle size on the order of the mean free path of electrons in solids, and easy transport, penetration, rejection or incorporation anywhere in living organisms. . On the other hand, a carrier to which ultrafine particles are to be attached, for example, a fiber, tends to be negatively charged in water. However, the charge of the fiber itself is weak, and even if a support such as a fiber is immersed in a colloid solution in which colloid particles are dispersed, the electrostatic attraction between the charged ultrafine particles and the support is weak, and the The ultrafine particles are not adsorbed well.

Therefore, in the present invention, the surface of the support to which the ultrafine particles in the colloidal state are adhered in the liquid is positively charged in the colloidal liquid to the polarity opposite to the charge of the ultrafine particles. The ultrafine particles are adsorbed on the holder without waste. The adsorption of the ultrafine particles to the support is performed by immersing the support in a colloidal solution of the ultrafine particles, but the higher the temperature, the greater the adsorption of the ultrafine particles to the support. In addition, as the diameter of the ultrafine particles decreases, the surface area increases, the adsorptivity increases, and the intrinsic functions (eg, antibacterial properties, deodorant properties, catalytic functions, etc.) of the substances constituting the ultrafine particles significantly increase. At the same time, it can be penetrated into the inside of the holding body at the time of adsorption to the holding body.

In the case where the substance to be adsorbed on the carrier becomes ultrafine particles in the colloid solution and the surface of the carrier has the same charged electrode property, in the present invention, the ultrafine particles or the carrier may be used. A pre-treatment is performed in advance to convert either one of the charged electrode properties to make the charges on the ultrafine particles and the surface of the carrier opposite to each other, thereby facilitating the adsorption of the ultrafine particles on the carrier.

In the above, when it is not possible to change the polarity of either the carrier or the ultrafine particles to make the charged electrode properties of the carrier and the ultrafine particles different, in the present invention, the carrier and the ultrafine particles are used. In between, an intermediate medium material charged to a polarity different from these polarities is interposed, and the ultrafine particles are substantially attached to the support.

FIG. 1 shows a model structure diagram of the composite structure according to the present invention. In FIG. 1, a model (a) is obtained by ion-bonding cationized, for example, copper ultrafine particles 2 to an anionized support 1. Model (b) is
The cationized silver and copper ultrafine particles 12 and 13 are ion-bonded to the cationized support 11 through an intermediate medium 14 such as anionized TiO _{2 in} which the ionization is performed. The model (c) is obtained by ion-bonding ultrafine particles 22 such as anionized TiO ₂ to the cationized support 11.

As the physical shape of the holder, a fibrous body,
Examples include films, fixed shapes, and porous bodies made of ceramics. In addition, examples of the substance of the ultrafine particles include metals such as gold, copper, and nickel.In addition to ceramics such as titanium oxide and aluminum oxide, some polymer compounds can be included. .

In the present invention, in order to adsorb the ultrafine particles or the intermediate medium having the ultrafine particles adsorbed thereon, the electrostatic polarity opposite to the ultrafine particles or the intermediate medium to be adsorbed is preliminarily applied to the support. To be charged. That is, when the ultrafine particles or the intermediate are anionized immediately before being adsorbed, the support is cationized. When the ultrafine particles or the intermediate are cationized immediately before being adsorbed, the support is anionized. For example, when the support is a natural fiber such as cotton, chemicals generally used as a cationizing agent include a nitrogen-based cationic surfactant and a cationic water-soluble polymer compound (including a polymer flocculant). Yes, roughly, as shown in FIG. 2, it is composed of primary to tertiary amine salts and quaternary ammonium salts.
As an aqueous solution of a cationic surfactant, in an aqueous solution, a hydrophilic group has such a property that a hydrophilic group is charged to a cation and repels ions of the same kind, and is neutralized with other kinds of anions to bind the particles ionically.

For example, when the support is a natural fiber such as cotton, there are various methods of anionizing the support.
For example, there are those utilizing an esterification reaction with an acid anhydride or an etherification reaction with a halogen compound,
Representative examples are shown below. 1) Anionization treatment of cotton by esterification reaction with acid anhydride According to the reaction formula shown in FIG. 3 (a), when the esterification reaction is performed using fluorinated acetic anhydride as a catalyst, the cotton fiber as a support is anionized. 2) Anionization treatment of cotton by etherification with a halogen compound As shown in FIG. 3 (b), it reacts with monochloroacetic acid to form carboxymethyl ether in the presence of a basic catalyst. In addition, for example, the surface of silicon oxide serving as a support can be ionized using a surfactant (silane coupling material) such as 3-aminopropyltriethoxysilane.

[0026]

EXAMPLE 1 Silver in an aqueous silver oxide solution was reduced by a chemical reduction method to form ultrafine cationized silver metal particles having a diameter of 5 nm in the aqueous solution. A solution prepared by reducing copper and mixing 50 parts of a solution in which cationized copper ultrafine particles having a diameter of 5 nm is formed in an aqueous solution is produced by, for example, a chemical vapor phase method or a liquid phase method. Ultrafine titanium oxide particles having a diameter of about 50 nm, which is an intermediate medium substance, are put into the mixed solution, and the mixture is thoroughly stirred to form silver and copper ultrafine particles on the surface of the titanium oxide ultrafine particles having a diameter of about 50 nm, which is an intermediate medium substance. To adhere. Then, the titanium oxide ultrafine particles having silver and copper ultrafine particles adsorbed and fixed on the surface are further anionized using a surfactant. Ag / Cu / Ti with silver and copper immobilized on titanium colloid as described above
Two kinds of aqueous dispersion solutions whose concentrations have been adjusted to 2 g / liter and 5 g / liter with O ₂ are prepared.

Separately, after performing a scouring treatment on a cloth made of a 48th-count double-thread knit (100% cotton),
Using a well-known cationizing agent, cationization treatment is performed,
The fibers were immersed in the aqueous dispersion solution prepared as described above, and the titanium oxide ultrafine particles having silver / copper ultrafine particles adsorbed thereon were adsorbed on the surface of the cloth serving as a holder by a padding method.

To examine the degree of adsorption of Ag / Cu / TiO ₂ on the holder, the dough was taken out of the colloid solution, and the remaining amount of Ag / Cu / TiO ₂ in the solution was measured. The concentration was reduced to 2 g / liter. The result is that TiO ₂ is 0.1pp
m or less, Ag ₂ O ₃ is 0.1 ppm or less, CuO is 0.1 ppm or less.
ppm or less. When the concentration was set to 5 g / liter, TiO ₂ was 0.1 ppm or less and Ag ₂ O ₃ was 0.1 ppm.
The content of CuO was 1 ppm or less, and the content of CuO was 0.1 ppm or less.

In order to compare the degree of adsorption, the same scouring treatment as that of the above-mentioned dough was performed (the one without the cationization treatment).
And Ag / Cu / Ti is added thereto in the same manner as described above.
O ₂ was adsorbed. And Ag / Cu / T in the residual liquid
When the iO ₂ concentration was checked, the concentration of 2 g / liter was 42 ppm for TiO _{2 and} 0.4 pp for Ag ₂ O ₃ .
m and CuO were 1.5 ppm. Further, when the concentration is 5
g / liter, 148 ppm of TiO ₂ , Ag ₂
O ₃ was 1.1 ppm and CuO was 6.9 ppm. Further, antibacterial performance, which is one of the performances of this fiber, was measured.
The measuring method followed the processing shake evaluation method of the antibacterial deodorized processed product manual shake flask method. 0.75 g of a test piece 1 (treated at a concentration of 2 g / liter) was placed in 75 ml of the test bacterium Staphylococcus aureus suspension, and after shaking for 1 hour, the number of viable cells was measured. The number was 10 or less, and the antibacterial effect was remarkable. On the other hand, the sample to which Ag / Cu / TiO ₂ was adhered without performing the cationization treatment could not be sterilized. Test piece 2
A similar test was also performed for (treated at a concentration of 5 g / liter), but the sterilization rate was almost the same as above, and the antibacterial effect was remarkable.

Example 2 A solution in which silver in an aqueous copper oxide solution was reduced by a chemical reduction method to form ultra-fine particles of cationized silver metal having a diameter of 5 nm in the aqueous solution, and a copper solution in a copper oxide solution Is reduced, and a solution is prepared by mixing 50 parts of a solution obtained by forming ultra-fine particles of cationized copper metal having a diameter of 5 nm in an aqueous solution.

Separately, after performing a scouring treatment on a cloth made of a 48th twin yarn knit (100% cotton),
Anionization treatment is performed using a well-known anionizing agent.
In this anionization treatment, the cloth is immersed in a 10% monochloroacetic acid solution, squeezed to 80%, reacted in a 50% caustic soda solution, carboxymethylated, and adjusted to have a substitution degree of 0.1. The anionization treatment is performed by the following reaction. CellOH + ClCH ₂ COOH → Cell-OCH
₂ COONa + NaCl + 2H ₂ O The fiber thus treated was immersed in the aqueous dispersion solution prepared as described above, and the silver / copper ultrafine particles were adsorbed on the surface of the cloth serving as a holder by a padding method.

In order to examine the degree of adsorption of Ag / Cu on the holder, the dough was taken out of the colloid solution, and the A
When the g / Cu remaining amount was measured, the amount of Ag ₂ O ₃ was 0.1 pp.
m or less, and CuO was 0.1 ppm or less.

In order to compare the degree of adsorption, the same scouring treatment as that of the above-mentioned dough was performed (the one without the cationization treatment)
Was prepared, and Ag / Cu 2 was adsorbed on it in the same manner as described above. Then, when the Ag / Cu concentration in the residual liquid was examined, 0.4 ppm for Ag ₂ O _{3 and} 1.5 ppm for CuO
Met. The sterilization effect was the same as in Example 1.

Example 3 Silver in an aqueous silver oxide solution was reduced by a chemical reduction method to form ultra-fine cationized silver metal particles having a diameter of 5 nm in the aqueous solution. Is prepared by mixing, for example, a chemical vapor phase method or a liquid phase method in a solution prepared by mixing 50 parts of a solution obtained by forming ultra-fine particles of cationized copper metal having a diameter of 5 nm in an aqueous solution. Ultrafine titanium oxide particles having a diameter of about 50 nm, which is an intermediate medium substance, are put into the mixed solution, and the mixture is thoroughly stirred to form silver and copper ultrafine particles on the surface of the titanium oxide ultrafine particles having a diameter of about 50 nm, which is an intermediate medium substance. To adhere. Then, titanium oxide ultrafine particles with silver and copper ultrafine particles adsorbed and fixed on the surface,
Further anionization is performed using a surfactant. Ag / Cu / with silver and copper immobilized on titanium colloid in this way
An aqueous dispersion solution whose concentration is adjusted to 2 g / liter with TiO ₂ is prepared.

Separately, an acrylic resin film previously subjected to a cationization treatment under the following conditions is prepared as a support, which is immersed in the above aqueous dispersion solution, and immersed in the above-mentioned aqueous dispersion solution to obtain a support as described above. Ultrafine particles of titanium oxide with ultrafine silver / copper particles adsorbed on the surface of the dough. The method of the cationization treatment uses a guanidine-based condensed polyamine-type cation-based polymer compound having a structure shown in FIG. 4 as the cationization agent, and 1 g of the cationization agent is used.
Per liter of a solution, which is warmed to 70 degrees Celsius, and immersed in the solution for 30 minutes to cationize the surface of the support.

In order to examine the adsorption of Ag / Cu / TiO _{2 on the} support, after removing the support from the colloid solution,
When the remaining amount of Ag / Cu / TiO ₂ in the solution was measured,
TiO ₂ was 0.1 ppm or less, Ag ₂ O ₃ was 0.1 ppm or less, and CuO was 0.1 ppm or less.

For comparison of the degree of adsorption, an acrylic resin film not subjected to a cationization treatment was prepared, and Ag / Cu / TiO ₂ was adsorbed on the acrylic resin film in the same manner as described above. When the concentration of Ag / Cu / TiO ₂ in the remaining liquid was examined, TiO ₂ was 30 ppm, Ag ₂ O ₃ was 0.3 ppm, and C
uO was 1.0 ppm.

Example 4 Silver in an aqueous silver oxide solution was reduced by a chemical reduction method, and ultrafine cationized silver metal particles having a diameter of 5 nm were used as an intermediate medium substance in the aqueous solution, and the surface was anionized. It is attached to the surface of titanium oxide ultrafine particles having a diameter of about 50 nm. The ultrafine titanium oxide particles having the ultrafine silver particles adsorbed and fixed on the surface are further anionized using a surfactant. An aqueous dispersion in which the Ag / TiO ₂ concentration in which silver is immobilized on the titanium colloid is adjusted to 50 g / liter is prepared in advance.

Separately, after performing a scouring treatment on a cloth made of a 48th twin yarn knit (100% cotton),
Using a well-known cationizing agent, cationization treatment is performed,
The fibers were immersed in the aqueous dispersion solution prepared as described above, and titanium oxide ultrafine particles having silver ultrafine particles adsorbed thereon were adsorbed on the surface of the cloth as a support by a padding method.

[0040] To investigate the Ag / TiO ₂ adsorption degree to the holding body, after removal of the fabric from a colloidal solution, where the Ag / TiO ₂ remaining in the solution was measured, TiO ₂ is 47
5 ppm and Ag ₂ O ₃ were 32 ppm.

In order to compare the degree of adsorption, a cloth subjected to the same scouring treatment as that of the above-mentioned dough was prepared, and Ag / TiO ₂ was adsorbed thereto in the same manner as described above. And A in the remaining liquid
When the g / TiO ₂ concentration was examined, TiO ₂ was found to be 529 pp.
m and Ag ₂ O ₃ were 35 ppm.

Example 5 Silver in an aqueous silver oxide solution was reduced by a chemical reduction method, and ultra-fine cationized silver metal particles having a diameter of 5 nm were added to the aqueous solution. It is attached to the surface of titanium oxide ultrafine particles of about 5 nm to 10 nm. The ultrafine titanium oxide particles having the ultrafine silver particles adsorbed and fixed on the surface are further anionized using a surfactant. Ag / TiO ₂ concentration of 5 g in which silver is immobilized on titanium colloid is 5 g.
Prepare an aqueous dispersion solution adjusted to 1 / liter.

Separately, after performing a scouring process on a cloth made of a 48th twin yarn knit (100% cotton),
Using a well-known cationizing agent, cationization treatment is performed,
This fiber is immersed in the aqueous dispersion solution prepared as described above, and the ultrafine titanium oxide particles obtained by adsorbing the ultrafine silver particles on the surface of the cloth serving as the support by the immersion exhaust method are adsorbed on the surface of the support. I let it.

[0044] To investigate the Ag / TiO ₂ adsorption degree to the holding body, after removal of the fabric from a colloidal solution, where the Ag / TiO ₂ remaining in the solution was measured, TiO ₂ is 5.
3 ppm and Ag ₂ O ₃ were 0.5 ppm or less.

In order to compare the degree of adsorption, a cloth subjected to the same scouring treatment as that of the above-mentioned dough was prepared, and Ag / TiO ₂ was adsorbed thereto in the same manner as described above. And A in the remaining liquid
Examination of the g / TiO ₂ concentration, TiO ₂ is 67ppm
, Ag ₂ O ₃ was 2.1 ppm.

Embodiment 6 After silicon oxide SiO ₂ powder is kneaded with a polyvinyl alcohol liquid as a binder, the mixture is compressed in a mold to form a predetermined shape, and dried to sufficiently diffuse internal moisture. After drying, the binder is preliminarily fired at a temperature of about 900 degrees Celsius in a nitrogen atmosphere to sufficiently disperse the binder. After the binder is sufficiently scattered, it is fired at a temperature of about 1150 degrees Celsius for about 1 hour in the same nitrogen atmosphere to form a porous body of silicon oxide SiO ₂ .

On the other hand, copper in the copper oxide liquid is reduced by a chemical reduction method, and a diameter of 5 nm to 10 n
Ultra-fine particles of cationized copper metal of m are precipitated. The porous sintered body of silicon oxide SiO ₂ formed by the above calcination is anionized by using a well-known anionizing agent, and then immersed in an aqueous solution in which the ultrafine copper particles are deposited, and the aqueous solution is vacuumed. Transfer to the chamber, soak the aqueous solution in which the copper ultrafine particles are precipitated in the porous body sufficiently,
In addition, the ultrafine copper particles were attached to the surface of the porous body that had been anionized.

To examine the degree of adsorption of Cu on the support, the porous body was taken out of the colloid solution, and the remaining amount of Cu in the solution was measured. As a result, Cu was 10 ppm or less.

In order to compare the degree of adsorption, a porous sintered body of silicon oxide SiO ₂ not subjected to anionization treatment was prepared, and it was tried to adsorb cationized Cu ultrafine particles. The ultrafine metal particles could not be attached to the porous sintered body of silicon oxide SiO ₂ .

The ultrafine silver colloid dispersion of Example 7,60nm diameter (aq) i.e., Ag ₂₀₃ 2% / purified water 98
% Liquid is previously subjected to coarse dispersion using a disperser mixer, and then ultrafine particles are prepared by an ultrahigh pressure (pressure 1000 kg / square cm) homogenizer treatment.
This is called diluted solution 7.

Separately, after a scouring treatment is performed on a cloth made of a 48th-count double yarn knit (smooth knitting, 100% cotton), an anionizing treatment is performed using a well-known anionizing agent. In this anionization treatment, the cloth is immersed in a 10% monochloroacetic acid solution, squeezed to 80%, reacted in a 50% caustic soda solution, carboxymethylated, and adjusted to have a substitution degree of 0.1. The anionization treatment is performed by the following reaction. CellOH + ClCH ₂ COOH → Cell-OCH
₂ COONa + NaCl + 2H ₂ O The fiber subjected to such treatment was immersed in the aqueous dispersion solution prepared as described above, and the ultrafine silver particles were adsorbed on the surface of the cloth serving as a holder by a padding method.

[0052] To examine the Ag adsorption degree to the holding body, after removal of the fabric from a colloidal solution, where the Ag remaining in the solution was measured, Ag ₂ O ₃ by way of 2 g / l of a dilute solution 7 0 0.1 ppm or less. The concentration of Ag ₂ O ₃ in the diluted solution 7 of 5 g / liter was 8.5 ppm.

In order to compare the degree of adsorption, a cloth subjected to the same scouring treatment as the above-mentioned cloth was prepared, and Ag was adsorbed on the cloth in the same manner as described above. Then, when the Ag concentration in the residual solution was examined, it was found that the dilute solution 7 having a concentration of 2 g / liter
₂ O ₃ was 35 ppm. The concentration of Ag ₂ O ₃ in the diluted solution 7 of 5 g / liter was 98 ppm.

Example 8 Using a chemical reduction method, silver in an aqueous silver oxide solution was reduced to form ultra-fine cationized silver metal particles having a diameter of 5 nm in the aqueous solution. Ultrafine particles of titanium oxide having a diameter of about 50 nm, which is an intermediate medium material produced by a phase method or a liquid phase method and having an anionized surface, are introduced into the mixed solution, and the mixture is thoroughly stirred to obtain the intermediate medium substance having a diameter of about 50 nm. Silver ultrafine particles are adhered to the surface of the titanium oxide ultrafine particles. The ultrafine titanium oxide particles having the ultrafine silver particles adsorbed and fixed on the surface are further anionized using a surfactant.
A thus obtained by immobilizing silver and copper on titanium colloid
An aqueous dispersion solution whose concentration has been adjusted to 2 g / liter with g / Cu / TiO ₂ is prepared.

Separately, an ABS resin film which has been subjected to a cationization treatment in advance under the following conditions is prepared as a support, which is immersed in the above aqueous dispersion solution, and immersed in the above-mentioned aqueous dispersion solution. Ultrafine titanium oxide particles having fine silver particles adsorbed thereon were adsorbed on the surface of the fabric. The method of the cationization treatment uses a guanidine-based condensed polyamine-type cation-based high molecular compound having a structure shown in FIG. 4 as a cationization agent, and the cationization agent is converted into a 1 g / liter solution. With this heated to 70 degrees Celsius, the holder is immersed in the solution for 30 minutes to cationize the surface of the holder.

[0056] To examine the Ag / TiO ₂ adsorption degree to the holding body, after removal of the holder from a colloidal solution, where the Ag / TiO ₂ remaining in the solution was measured, TiO ₂ is 0.1ppm or less, Ag ₂ O ₃ was 0.1 ppm or less.

For comparison of the degree of adsorption, an ABS resin film not subjected to a cationization treatment was prepared, and Ag / TiO ₂ was adsorbed on the ABS resin film in the same manner as described above. When the concentration of Ag / TiO ₂ in the remaining liquid was examined, it was found that TiO ₂ was 35 ppm and Ag ₂ O ₃ was 0.4 ppm.

Although the present invention has been described with reference to the above embodiment, various modifications and applications are possible within the scope of the present invention, and these modifications and applications are excluded from the scope of the present invention. is not.

[0059]

As described in detail above, claim 1 is as follows.
In the invention according to the present invention, after the surface of the holding body is subjected to a pre-charging treatment so as to be charged to the opposite polarity to the charging polarity of the functional substance that has been turned into a colloid in a solution and turned into ultra-fine particles, the ultra-fine particles are turned into a solution. Since the composite structure is composed by adsorbing the functional materials that are present by electrostatic attraction, the ultrafine particles are more strongly attracted and adhered to the holder compared to the conventional structure, and distortion such as washing is added. Also, the ultrafine particles do not peel off.

When the support is preliminarily cationized or anionized and the ultrafine particles are adhered to the support,
An extremely large amount of ultrafine particles adhere to the support, and very little remains in the colloid solution. For this reason,
The functional substance composed of ultrafine particles can be made to adhere to the holder as efficiently as possible.

Further, in the invention according to claim 2, in addition to the effect of the invention according to claim 1, even if the ionization polarity of the ultrafine particles as the functional substance and the carrier is the same, an intermediate medium is interposed. This allows the ultrafine particles to adhere to the holder.

According to the invention of claim 3, in addition to the effect of the invention of claim 1, even if the ionization polarity of the ultrafine particles as the functional substance and the holder is the same, either one of them is converted. Therefore, the ultrafine particles can be adhered to the holder.

In the invention according to the fourth aspect, the application can be extended to a plate-like body and a film as the holding body.

[0064] In the invention according to claim 5, as the holding body,
Applications can be extended to fiber structures.

In the invention according to claim 6, as the holding body,
Applications can be extended to porous structures.

In the invention according to claims 7 and 8,
Compared with the conventional one, the ultrafine particles are firmly attached to the holder by suction, and the ultrafine particles do not peel off even if a strain such as washing is applied. In addition, since the support is previously cationized or anionized, an extremely large amount of ultrafine particles are attached to the support, and the ultrafine particles are firmly attached to the support by suction as compared with conventional ones. Even when distortion such as washing is applied, the ultrafine particles do not peel off. In addition, it becomes possible to freely adsorb the ultrafine particles and the holder, which have not been able to be attached.

In the invention according to the ninth, tenth and eleventh aspects, the present invention can be applied to a film or a plate, a fibrous structure, and a porous ceramic as a support.

[Brief description of the drawings]

FIG. 1 is a model structure diagram showing a structure according to the present invention.

FIG. 2 is a chemical structural diagram showing a cationization treatment of a support.

FIG. 3 is a chemical structural diagram showing anionization treatment of a support.

FIG. 4 is a chemical structural formula of a condensed polyamine type cationic polymer compound.

[Explanation of symbols]

 1, 11, 21 ... Holder 14 ... Intermediate 2, 12, 13, 22 ... Ultrafine particles

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masatake Masuda 780 Shinjuku-cho, Ashikaga-city, Tochigi Pref. Person Hirofumi Shimada 24 Suehirocho, Ashikaga City, Tochigi Prefecture

Claims (11)

[Claims] 1. A method for producing a composite structure in which a functional material composed of ultrafine particles is adsorbed on a support, wherein the functional material is colloidalized in a solution and charged so as to have a polarity opposite to that of the charged functional material. A method for producing a composite structure, comprising: subjecting a surface of a body to a charging treatment in advance, and then adsorbing the ultrafinely divided functional substance in a solution by electrostatic attraction. 2. A method for producing a composite structure in which a functional substance comprising ultrafine particles is adsorbed on a support, comprising: a method of forming ultrafine particles by colloidalization in a solution; The intermediate medium which has been adsorbed in advance by an electrostatic attraction to the intermediate medium, and the ultrafine particles are adsorbed in the solution, is adsorbed by the electrostatic attraction in the solution to the surface of the pre-charged holding body in the solution. A method for producing a composite structure, comprising: 3. A method for producing a composite structure in which a functional material composed of ultrafine particles is adsorbed on a support, wherein a surfactant is used to convert the charging polarity of either the surface of the support or the surface of the ultrafine particles. Wherein the charged material on the surface of the carrier and the surface of the ultrafine particles are made different from each other, and the functional material, which has been turned into ultrafine particles, is adsorbed on the surface of the carrier by electrostatic attraction in a solution. Recipe. 4. A method according to claim 1, wherein said holder is a film or a plate formed in a flat plate shape. 5. The method according to claim 1, wherein said holding body is a fiber structure.
Of two composite structures. 6. A method according to claim 1, wherein said holding body is a porous ceramic. 7. A composite structure in which a functional material composed of ultrafine particles is adsorbed on a carrier, wherein the surface of the carrier whose surface is forcibly charged is charged to a polarity opposite to that of a charged electrode on the surface. A composite structure, characterized in that the coated ultrafine particles are attached to the composite structure. 8. A composite structure in which a functional material composed of ultrafine particles is adsorbed on a holder, wherein the surface of the holder whose surface is forcibly charged is charged to a polarity opposite to that of a charging electrode on the surface. Characterized in that the intermediate structure is adsorbed and the ultrafine particles are adsorbed by the intermediate medium. 9. The composite structure according to claim 7, wherein said holding body is a film or a plate formed in a flat plate shape. 10. The composite structure according to claim 7, wherein said holding body is a fibrous structure. 11. The composite structure according to claim 7, wherein said holder is a porous ceramic.