JP2003104719A - Clay composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial and mildew-proofing agent, an anti- oxidizing agent or an ultraviolet rays absorbing agent whose safety for a human body is high and being good for environment. SOLUTION: A clay composite contains swelling clay having a base exchanging function, an oil soluble antibacterial and mildew-proofing agent, an oil soluble anti-oxidizing agent or an oil soluble ultraviolet rays absorbing agent and a basic substance.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to clay composites. More specifically, it relates to a clay composite used as an antibacterial and antifungal agent, an antioxidizing agent or an ultraviolet absorber.

[0002]

2. Description of the Related Art In the present world, many antibacterial and antifungal agents, antioxidizing agents, and ultraviolet absorbers are used in large quantities based on chemical synthesis technology. While these are low-priced and highly functional, they have come to be pointed out to be harmful to the human body or environment such as side effects and residual toxicity. On the other hand, extracts from natural materials (including those whose chemical structure is manufactured by chemical synthesis) are inferior to the above-mentioned chemical synthetic products in terms of price or robustness, but they are less harmful to the human body. It also has the feature of being environmentally friendly. The price is largely dependent on the production scale or production technology and can be dealt with as it is, but it is very difficult to improve the robustness because it is the essence of the product. In addition, many of these functional materials are oil-soluble, but in order to use them in an aqueous system, it is necessary to make these oil-soluble materials aqueous using an emulsifier, etc. There are many technical problems such as safety and emulsion stability. Further, even when these oil-soluble materials are used in an oil-based system such as oil or fat or a polyolefin material, it is difficult to uniformly mix them in the system as they are, the robustness is deteriorated, and the bleeding is deteriorated. There is a problem that migration problems such as blooming and blooming are likely to occur.

[0003]

DISCLOSURE OF THE INVENTION The present invention improves the fastness of oil-soluble, antibacterial and antifungal agents, antioxidants or ultraviolet absorbers, which are derived from natural materials which are less harmful to the human body and are environmentally friendly. At the same time, it is an object to provide a material that is easily compatible with the use atmosphere.
Examples of oil-soluble antibacterial and antifungal agents include hinokitiol and flavonoids. Hinokitiol was originally extracted from Taiwan cypress and Aomori Hiba, but since it has become possible to produce it by chemical synthesis in recent years, there is a possibility that it can be reduced in price. Functionally, it is said that it is effective against a wide range of bacteria and yeast, and that it is hardly resistant to bacteria, and that it is effective for addition to foods and preservation of fresh foods. On the other hand, because of its high sublimability,
It has the drawbacks that the effect is not persistent and the light resistance is poor. Flavonoids also have the drawback of poor light resistance. Similarly, substances such as carotenoids are effective as antioxidants, but they also have poor light resistance. Further, flavone-based, flavonol-based or diketone-based substances are effective as the ultraviolet absorber, but they also have poor light resistance.

[0004]

Means for Solving the Problems The present inventor is derived from a swelling clay having a base exchange ability and a natural material, and contains an oil-soluble antibacterial and antifungal agent, an antioxidant or an ultraviolet absorber and a basic substance. It was found that the clay composite is excellent in various fastnesses such as sublimation resistance, light resistance and migration resistance while maintaining its original function and has a high affinity with the atmosphere in which these materials are used. It was

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. Examples of the swelling clay having a base exchange ability used in the present invention include smectite, montmorillonite, bentonite,
Examples include vermiculite, muscovite or phlogopite. Specifically, products commercially available from Coop Chemical Co., Ltd., Tomita Pharmaceutical Co., Ltd., Kunimine Industry Co., Ltd., etc. can be used. It is considered that these clays can adsorb an oil-soluble substance on the surface thereof, and by adsorbing the clay, the robustness is improved, although the reason is not clear. Further, the alkali metal cations existing between the layers of clay are relatively easily exchanged with other cation substances (referred to as base exchange ability). It is considered that this property can be utilized to complex a basic substance with clay to adjust the complex to be hydrophilic or lipophilic, and to prevent easy migration.

Examples of the oil-soluble antibacterial and antifungal agent derived from natural materials used in the present invention include hinokitiol and flavonoids. Specific examples include hinokitiol, catechin, epicatechin, epigallocatechin or epicatechin gallate. The amount used is 0.01 to 2, preferably 0.1 to 1.5 weight ratio with respect to the clay. If it is less than 0.01, the function of antibacterial and antifungal is insufficient, and if it is more than 2, the robustness is poor.

Examples of the oil-soluble antioxidant derived from a natural material used in the present invention include beta carotene. Specific examples include tocopherol, beta carotene, capsanthin, lycopene, canthaxanthin and the like. The amount used is 0.01 to 2, preferably 0.1 to 1.5 weight ratio with respect to the clay. If it is less than 0.01, the antioxidant function is insufficient, and if it is more than 2, the robustness is poor.

Examples of the oil-soluble ultraviolet absorber derived from natural products used in the present invention include flavonols and diketomethanes. Specific examples include quercetin, curcumin, oryzanol and rice germ oil. The amount used is 0.01 to 2 with respect to clay,
Preferably, the weight ratio is 0.1 to 1.5. 0.0
If it is less than 1, the ultraviolet absorption function is insufficient, and if it is more than 2, the robustness is poor.

The basic substance used in the present invention is a hydrophilic substance derived from a natural product, and specific examples of amine-type substances include glucosamine, oligoglucosamine, chitosan berberine, betacyanin and betaxanthine. . On the other hand, specific examples of the oxonium type include shisonin, rubrobrassin, enine, and beonin. Examples include marbin and cyanidin. Examples of the lipophilic substance include amines and ammoniums substituted with long-chain alkyl groups or alkenyl groups. Specific examples thereof include dimethylstearylamine, trimethyldodecylammonium, dimethyldidecylammonium and the like. That is, the clay and the adsorbed functional agent can be made hydrophilic or lipophilic by selectively adjusting the basic substance, and can be adjusted to the medium. The amount used is 0.1 to 2 weight ratio with respect to clay. If it is less than 0.1, the affinity for the medium will be insufficient regardless of whether it is hydrophilic or lipophilic.
There is no need for more.

The clay composite prepared in the present invention is
For example, it is used by being dispersed or dissolved in an aqueous recording liquid for inkjet printers, cosmetics, juices, foods, etc., or dispersed or dissolved in an oily medium such as fats and oils, or adsorbed on a textile product. I use it.

[0011]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. The parts mean the meanings of parts by weight.

[Example 1] (Preparation of clay composite for antibacterial and antifungal agent) 10 parts of hinokitiol was dissolved in 500 parts of methanol, and Lucentite SWN (synthetic smectite; manufactured by Coop Chemical Co., Ltd.) was added to the solution.
100 parts and chitosan oligosaccharide (Kai Kasei Co., Ltd.)
(Manufactured by Mitsui Chemical Co., Ltd.) and stirred at room temperature for 48 hours, and then methanol was distilled off to obtain 129 parts of powder. The obtained powder was added to 1000 parts of distilled water and stirred for 24 hours while applying ultrasonic waves to obtain a uniform slurry. (Evaluation) As a recording liquid for inkjet printers,
20 parts of diethylene glycol, 10 parts of glycerin, CI
10 parts of Food Black-2 was dissolved in distilled water to make the total amount 295 parts. When 5 parts of the slurry was added to 95 parts of the mixture and stirred for 3 hours, they were uniformly mixed. This was placed in a 200 mL beaker and left indoors. Hinokithiol 0.
4 parts were added. Although it could not be mixed uniformly, it was placed in a beaker as it was and left in the same manner. The remaining 10
About 0 part, it was put in a beaker as it was and left in the same manner. While supplying distilled water according to the amount of evaporation of water, 2
When left for a month, no mold was found in the ink containing the clay complex, but mold was found in the ink containing hinokitiol itself or the ink containing no hinokitiol.

[Example 2] (Preparation of clay complex for antioxidizing agent) 10 parts of tocopherol was dissolved in 500 parts of methanol, and 100 parts of the synthetic smectite used in Example 1 and 10 parts of glucosamine were added thereto, and the mixture was allowed to stand at room temperature. After stirring for 48 hours, methanol was distilled off to obtain 118 parts of powder. The obtained powder was added to 1000 parts of distilled water and stirred for 24 hours while applying ultrasonic waves to obtain a uniform slurry. (Evaluation) 10 parts of green tea leaves were added to 295 parts of hot water at 80 ° C., left standing for 3 minutes for extraction, and then allowed to cool to room temperature. When 5 parts of the slurry was added to 95 parts of the mixture and stirred for 3 hours, they were uniformly mixed. This was placed in a 200 mL beaker and left indoors. To the remaining 100 parts was added 0.4 parts of tocopherol. Although it could not be mixed uniformly, it was placed in a beaker as it was and left in the same manner. The remaining 100 parts were placed in a beaker as they were and left in the same manner. When left for 2 days,
No starch was found in the green tea extract containing the clay complex, but it was found in the extract containing tocopherol itself and the extract containing no tocopherol. The starch is assumed to be an oxidative polymerization product of tannin.

[Example 3] (Preparation of clay complex for ultraviolet absorbent) 10 parts of rice germ oil was dissolved in 500 parts of ethanol, and then 100 parts of Kunipia F (bentonite; Kunimine Industry Co., Ltd.) and oligochitosan. 20 parts were added and a clay composite slurry was prepared in the same manner as in Example 1. (Evaluation) 145 parts of polyglycerin and 145 parts of water were mixed. To 90 parts of this mucus, 10 parts of the slurry was added and mixed uniformly with a homomixer. 0.5 part of rice germ oil was added to the remaining 100 parts, but could not be mixed uniformly. Apply mucus containing clay complex, mucus containing rice germ oil itself non-uniformly and additive-free mucus to each upper arm, and after exposing to direct sunlight for 3 hours, rinse mucus and visually check the degree of sunburn. It was judged. Almost no sunburn was observed in the area to which the clay complex was applied, but clear sunburn was observed in the area to which the other mucus was applied.

[Example 4] (Preparation of antibacterial and antifungal clay complex) The same as Example 1 except that epigallocatechin was used instead of hinokitiol and betacyanine was used instead of chitosan oligosaccharide. To prepare a slurry of clay composite. (Evaluation) Instead of the ink-jet ink in Example 1, orange juice squeezed with raw orange was used, and it was checked whether or not mold was generated when left for 1 week. As in Example 1, no mold was found in the juice containing the clay complex, but mold was found in the other juices.

Example 5 (Evaluation of Stability of Clay Composite for Antioxidant) The clay complex of tocopherol prepared in Example 2 was added to chicken feed in an amount of 3% by weight. The feed was left at 50 degrees for 1 week, but the residual rate as tocopherol was 85%. On the other hand, when the same evaluation was carried out with the tocopherol as it was, the residual rate was 62%, which was low.

Example 6 (Preparation of Clay Complex for Antioxidant) In the same manner as in Example 2 except that beta-carotene was used instead of tocopherol in Example 2 and anthocyanin was used instead of glucosamine, A clay composite slurry was prepared. (Evaluation) 29 parts of ethanol and 261 parts of water were mixed.
Using this ethanol solution, in the same manner as in Example 2,
It was evaluated by a sensory test. A little sourness was felt in the system in which the beta-carotene was added as it was and in the system in which the clay complex was not added, as compared with the system in which the clay complex was added.

[Example 7] (Preparation and evaluation of clay composite for ultraviolet absorber) Example 3
A slurry was prepared and evaluated in the same manner as in Example 3 except that curcumin was used instead of rice germ oil in. As in Example 3, it was effective in preventing sunburn.

Example 8 Preparation of Clay Complex for Antibacterial and Antifungal Agent A clay complex was prepared in the same manner as in Example 1 except that dimethyl distearyl ammonium chloride was used in place of the chitosan oligosaccharide. Was formed to obtain a powder. 5 parts of the powder was kneaded with 95 parts of polypropylene (abbreviated as PP) resin using a three-roll mill for 180 degrees and 30 minutes, and then a thickness of 5 mm
The PP resin plate was molded. Separately, hinokitiol 0.5
Part and 99.5 parts of PP resin were kneaded in the same manner, and a PP resin plate having a thickness of 5 mm was molded in the same manner for the PP resin without addition. These resin plates were immersed in water after breeding ornamental fish for 3 months. In the plate in which the viscosity composite was kneaded, the surface had a slight amount of null, but in the other plates, slime adhered to the surface.

Example 10 (Preparation of Clay Complex for Antibacterial and Antifungal Agent) Example 1 was repeated except that the chitosan oligosaccharide in Example 1 was replaced by polyethylene-polypropylene glycol terminated with amino groups at both ends. In the same manner as above, a clay complex was formed to obtain a powder. 5 parts of the powder was kneaded into 95 parts of polyethylene terephthalate (abbreviated as PET) resin using a three-roll mill for 180 degrees and 30 minutes, and then a thickness of 0.5 mm
PET film was molded. Separately, 0.5 part of hinokitiol and 99.5 parts of PET resin were kneaded in the same manner, and a PET film having a thickness of 0.5 mm was molded in the same manner for the additive-free PET resin. These films were immersed in the cooling water of the cooling tower for 3 months. In the film in which the viscosity composite was kneaded, the surface had a slight amount of null, but in other films, slime was attached to the surface.

[0021]

Industrial Applicability The clay composite of the present invention is suitable as an antibacterial and antifungal agent, an antioxidizing agent, or an ultraviolet absorber, and is highly safe to the human body and environmentally friendly.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09K 15/06 C09K 15/06

Claims (14)

[Claims] 1. A clay composite containing a swelling clay having a base exchange ability and an oil-soluble substance and a basic substance. 2. The clay composite according to claim 1, wherein the oil-soluble substance is an antibacterial and antifungal agent. 3. The clay composite according to claim 1, wherein the oil-soluble substance is an antioxidant. 4. The oil-soluble substance is an ultraviolet absorber.
The described clay composite. 5. The clay composite according to any one of claims 1, 2, 3 and 4, wherein the swelling clay having a base exchange ability is smectite, montmorillonite bentonite or vermiculite. 6. The basic substance is an amine-based substance, an ammonium-based substance or an oxonium-based substance,
Clay composites according to 2, 3, 4 and 5. 7. The clay composite according to claim 12, 5 or 6, wherein the antibacterial and antifungal agent is hinokitiol or flavonoid. 8. The clay composite according to claim 1, wherein the antioxidizing agent is tocopherol, beta carotene, capsanthin, lycopene, canthaxanthin. 9. The ultraviolet absorber is quercetin, curcumin,
Oryzanol or rice germ oil.
And a clay composite according to item 6. 10. The clay composite according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9, wherein the basic substance is hydrophilic or water-soluble. 11. The basic substance is glucosamine, oligoglucosamine, chitosan, berberine, betacyanin or betaxanthin, which is 1, 2, 3, 4, 5, 5.
Clay composites according to 6, 7, 8, 9 and 10. 12. The basic substance is shisonin, rubrobrassin, enine, and beonin. Malvin or cyanidin, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 1
Clay composite according to 0. 13. The clay composite according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8 and 9, wherein the basic substance is lipophilic or fat-soluble. 14. The basic substance is a substance containing a long-chain alkyl or alkenyl group, 1, 2, 3, 4,
Clay composites according to 5, 6, 7, 8, 9 and 13.