JP2003160693A - Organic and inorganic composite composition, resin composition and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve dispersion of a functional organic compound when the functional organic compound is mixed with a resin, and to control the elution rate of a functional organic compound. <P>SOLUTION: The composition is prepared by sintering a functional organic compound, an inorganic aggregate and an inorganic flocculant. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organic-inorganic composite composition, a resin composition, and a molded article.

[0002]

2. Description of the Related Art As a method for imparting the function of a functional organic compound to various base materials, addition, adhesion, or spreading to the base material together with the compound alone or other compound that improves the functionality is performed. The method of wearing is common.

[0003]

[Problems to be Solved by the Invention]
A functional organic compound soluble in a solvent, regardless of whether it is a non-aqueous system, may elute upon contact with the solvent, resulting in a decrease in the functionality. Further, when the functional organic compound has polarity, the compatibility with the non-polar resin is poor, and when the compound is non-polar, the compatibility with the polar resin is poor. In some cases, it was not possible to localize and evenly impart the functionality. In order to solve such a problem, for example, JP-A No. 11-60804 discloses a resin composition to which a filler carrying ε-polylysine is added, but sufficient functionality is obtained depending on the application. In some cases, it was difficult to control the elution amount and the elution time.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies in view of the above-mentioned problems of the prior art. As a result, the functional organic compound is mixed with the inorganic aggregate and the inorganic coagulant and sintered to form an organic-inorganic composite composition, and when this is added to the resin, the dispersibility of the functional organic compound in the resin is improved. By further selecting or adjusting the type, particle size and mixing ratio of the aggregate and / or the aggregating agent,
It was found that the elution amount and elution time of the compound contained in the composite composition can be controlled, and the present invention was completed based on this finding.

The present invention has the following configurations (1) to (19). (1) An organic-inorganic composite composition obtained by sintering a functional organic compound, an inorganic aggregate, and an inorganic coagulant.

(2) An organic-inorganic composite composition obtained by further pulverizing the organic-inorganic composite composition according to the above item 1.

(3) The functional organic compound is one or more selected from ε-polylysine, protamine, chitosan, sorbic acid, hyaluronic acid, ascorbic acid derivatives, kojic acid, and salts thereof. The organic-inorganic composite composition described.

(4) The organic-inorganic composite composition according to the above item 1, wherein the functional organic compound is ε-polylysine and / or a salt thereof.

(5) The organic-inorganic composite composition according to the above item 1, wherein the functional organic compound is L-ascorbic acid 2-sodium phosphate and / or L-ascorbic acid 2-magnesium phosphate.

(6) The organic-inorganic composite composition according to item 1, wherein the inorganic aggregate is one or more selected from talc, silica, zeolite, alumina, titania, zirconia, and diatomaceous earth.

(7) The organic-inorganic composite composition according to the above item 1, wherein the inorganic coagulant is at least one selected from colloidal silica and organosilica.

(8) The organic-inorganic composite composition according to any one of items 1 to 7, wherein the functional organic compound is selected or adjusted by selecting or adjusting at least one of the following A to D. An organic-inorganic composite composition in which the elution rate of a compound is controlled. A: Properties of functional organic compound B: Kind and particle size of inorganic aggregate C: Kind and particle size of inorganic coagulant D: Mixing ratio of functional organic compound, inorganic aggregate, and inorganic coagulant

(9) A resin composition containing the organic-inorganic composite composition according to any one of the above items 1 to 8 and a resin.

(10) A molded product comprising the resin composition according to the above item 9.

(11) A molded article obtained by adhering and / or spreading the organic-inorganic composite composition according to any one of the above items 1 to 8.

(12) A packaging material containing the organic-inorganic composite composition according to any one of the above items 1 to 8 and / or the resin composition according to the above item 9.

(13) A medical device containing the organic-inorganic composite composition according to any one of the above items 1 to 8 and / or the resin composition according to the above item 9.

(14) A fiber containing the organic-inorganic composite composition according to any one of the above items 1 to 8 and / or the resin composition according to the above item 9.

(15) A fabric containing the organic-inorganic composite composition according to any one of the above items 1 to 8 and / or the resin composition according to the above item 9.

(16) A paint containing the organic-inorganic composite composition according to any one of the above items 1 to 8 and / or the resin composition according to the above item 9.

(17) An adhesive containing the organic-inorganic composite composition according to any one of the above items 1 to 8 and / or the resin composition according to the above item 9.

(18) A cosmetic containing the organic-inorganic composite composition according to any one of the above items 1 to 8 and / or the resin composition according to the above item 9.

(19) An electric appliance coated with the paint according to the above item 16.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the present invention, the functional organic compound does not react with the inorganic aggregate or the inorganic flocculant, does not decompose at the sintering temperature, and has an antibacterial effect, an antistatic effect, or an antioxidant effect. If it is, it will not be specifically limited.

Examples of the functional organic compound having an antibacterial effect include food preservatives such as ε-polylysine, protamine, chitosan, sorbic acid and salts thereof. Examples of the functional organic compound having an antistatic effect include cosmetic raw materials such as hyaluronic acid and / or salts thereof. Examples of the functional organic compound having an antioxidant effect include cosmetic raw materials such as ascorbic acid derivatives, kojic acid and salts thereof.

Of these, ε-polylysine and salts thereof, L-ascorbic acid 2-magnesium phosphate and sodium L-ascorbic acid 2-phosphate are preferably used in the present invention because they are highly safe for the human body. You can

The inorganic aggregate used in the present invention is not particularly limited, and examples thereof include talc, silica, zeolite, alumina, titania, zirconia, diatomaceous earth and the like.

The inorganic flocculant used in the present invention is not particularly limited, but colloidal silica, organosilica and the like are preferably used. Furthermore, if necessary, a polyvalent metal salt of phosphoric acid typified by aluminum phosphate may be used in combination as an inorganic sintering aid.

In the present invention, the mixing ratio of the properties of the functional organic compound and the inorganic substance, the kind of the inorganic aggregate, the particle size, the kind of the inorganic coagulant, the particle size, and the mixing ratio of the inorganic aggregate and the inorganic coagulant. Is especially important.

In the present invention, the property of the functional organic compound is not particularly limited, but when the solution-type functional organic compound is used in the present invention, it is The functional organic compound is advantageous in that it is easily finely dispersed in the organic-inorganic composite composition, the initial elution amount thereof is small, and a long elution period is easily obtained. Further, by increasing the mixing ratio of the functional organic compound to the inorganic substance, the initial elution amount is increased, and
The elution period can be extended.

The type, particle size and mixing ratio of the inorganic aggregate and / or the inorganic flocculant in the present invention are not particularly limited. For example, when colloidal silica is used as the inorganic coagulant, the elution amount of the functional organic compound is very small when silica is used as the inorganic aggregate, but the elution amount increases when silica is appropriately replaced with talc, When the solid content of colloidal silica is replaced by silica as an aggregate, the amount of elution decreases. In this way, a desired elution rate can be obtained by adjusting the type and particle size of the inorganic aggregate, the type and particle size of the inorganic coagulant, and the mixing ratio of the inorganic aggregate and the inorganic coagulant.

The resin composition of the present invention contains the organic-inorganic composite composition of the present invention and a resin, and the resin composition may be one in which the composition and the resin are integrated. The resin composition may be adhered to the surface of the resin, or the resin composition may be laminated on the sheet-shaped resin composition, and the composition and the resin may be simply mixed. It may be in a closed state. When the resin composition is one in which the composition and the resin are integrated, the resin composition can be easily molded into a desired shape.

The following resins can be used in the resin composition of the present invention. Polypropylene and binary or terpolymers of propylene and other α-olefins, low density polyethylene, linear low density polyethylene, and polyolefin resins such as high density polyethylene, polyethylene terephthalate, polybutylene terephthalate,
And thermoplastic polyester resins such as copolyester, polyamide resins such as nylon 6 and nylon 66, polystyrene, and acrylonitrile-
Polystyrene resin such as butadiene-styrene copolymer,

Thermoplastic resins such as polyvinyl chloride, thermoplastic elastomers such as ethylene-propylene-rubber copolymers and styrene-butadiene-rubber copolymers,
Furthermore, a mixture of one or more selected from these thermoplastic resins, an unsaturated polyester resin, a diallyl phthalate resin, a phenol resin, an epoxy resin, and a melamine-
Thermosetting resin such as formaldehyde resin, biodegradable resin such as polylactic acid and starch.

The resin composition of the present invention contains a filler, an antistatic agent, and an antistatic agent as long as the effects of the present invention are not impaired.
Stabilizer, slip agent, weather resistance agent, light resistance agent, functional additive,
It may contain other additives such as fillers, oils and fats, pigments, dyes, natural resins, synthetic resins, metals, glasses, and surfactants.

The content ratio of the organic-inorganic composite composition in the resin composition of the present invention is not particularly limited because it depends on the desired function and the environment and conditions under which it is used.

The molded article of the present invention is obtained by molding the resin composition of the present invention using various ordinary molding machines. When the resin used in the resin composition is a thermoplastic resin, a mixture of the organic-inorganic composite composition of the present invention and the thermoplastic resin is heated and kneaded by a heating and kneading device such as an extruder or a roll. After that, it may be formed into a desired shape.

When the resin used in the resin composition is a thermosetting resin, a mixture of the prepolymer before curing and the organic-inorganic composite composition of the present invention is formed into a mold having a desired shape. It may be put and molded.

When the molded product of the present invention is a film, sheet, tube or the like, the structure thereof may be a single layer structure formed of the resin composition of the present invention alone, and the resin composition and other resin compositions. It may be a multi-layered structure formed by
Further, it may have a sponge structure. When the molded product has a multi-layer structure, it is preferable from the viewpoint of cost to use the resin composition only in the layer (site) where the function is desired to be exhibited.

The molded article of the present invention can also be obtained by depositing and / or spreading the organic-inorganic hybrid composition of the present invention on a molded article which is previously molded without containing the organic-inorganic hybrid composition of the present invention. Can be obtained. As a method of attaching and / or spreading, a method of coating or spraying the organic-inorganic composite composition with a binder, or a method of spreading the organic-inorganic composite composition on a molded product using a rolling roll or a press are used. be able to.

The purpose and use of the molded article of the present invention are not particularly limited, but civil engineering materials, building materials, agricultural materials, automobile materials, electric equipment, medical supplies, sanitary products, toiletry products, sanitary materials, interior materials, furniture, It can be suitably used for clothes, bedding, general packaging materials, food packaging materials, containers, toys, stationery, ornaments, binding tools, and the like. Among them, the molded article of the present invention using the above-mentioned food preservative as a functional organic compound has a high frequency of direct contact with food such as food packaging materials, medical products such as infusion packs, catheters and syringes. It can be particularly preferably used for applications such as equipment.

As long as the fiber of the present invention contains the organic-inorganic composite composition of the present invention or the resin composition of the present invention, its composition, form and manufacturing method are not particularly limited.

As the method for producing the fiber, for example, a prepolymer prepared by suspending the organic-inorganic composite composition of the present invention in a suitable solvent or plasticizing it by a suitable method, or the resin composition of the present invention is used. A wet spinning method, a dry spinning method, a gel spinning method, or the like to form a fibrous material, or an appropriate amount of the organic-inorganic composite composition of the present invention is attached to a previously spun fiber by an attachment method. Methods and the like. Further, the fiber of the present invention can form a mixed fiber with other materials.

Textile products using the fiber of the present invention include:
Examples thereof include spun yarn obtained by spinning the fiber alone or the other fiber, string, woven fabric, non-woven fabric, and processed products thereof.

As the method for producing the woven fabric, the fibers alone,
Alternatively, a method such as a single weaving method, a double weaving method or a multiple weaving method using the fibers and other fibers, or a woven cloth not containing the organic-inorganic composite composition of the present invention is attached to the organic-inorganic Examples include a method of depositing the composite composition in appropriate amounts.

As the method for producing the non-woven fabric, a method such as a dry method, a wet method, a needle punch method or a felt method which is a known fiber processing method using the fiber alone or the fiber and other fibers, Examples include a spunbond method using the resin composition of the invention and a method of adhering the organic-inorganic composite composition by an appropriate amount to a nonwoven fabric that does not contain the organic-inorganic composite composition of the present invention. it can.

The purpose and use of the fiber are not particularly limited, but include civil engineering materials, construction materials, agricultural materials, automobile materials, electrical equipment, medical supplies, sanitary products, toiletry products, sanitary materials, interior materials, furniture, clothing, It can be suitably used for bedding, general packaging materials, food packaging materials, containers, toys, stationery, ornaments, binding tools and the like. Among them, the fiber of the present invention, which uses the above-mentioned food preservative or cosmetic raw material as the functional organic compound, can be particularly preferably used for applications such as clothing which are frequently in direct contact with human skin.

The coating composition of the present invention is not particularly limited in its composition, form and production method as long as it contains the organic-inorganic composite composition of the present invention or the resin composition of the present invention.

As the method for producing the paint, for example, a method of adding a composition liquid obtained by suspending the organic-inorganic hybrid composition of the present invention in a suitable solvent to a known paint, or Examples thereof include a method of adding the powder of the organic-inorganic composite composition and / or the powder of the resin composition of the present invention.

Known coating materials include phenol resin, alkyd resin, melamine-alkyd resin, polyester resin, epoxy resin, polyurethane resin, vinyl acetate resin, styrene resin, acrylic resin, methacrylic resin, acrylic silicone resin, fluororesin, polyvinylpyrrolidone. Resin, polyacetal resin, lacquer, boil oil, oil varnish, oil enamel and the like can be mentioned.

The use of the coating material of the present invention is not particularly limited, but civil engineering materials, construction materials, agricultural materials, automobile materials, electric equipment, medical supplies, sanitary products, toiletry products,
Examples include coatings for sanitary materials, interior materials, furniture, general packaging materials, food packaging materials, containers, toys, stationery, labels, binding products, buildings, appliances, and the like.

Further, the application of the paint of the present invention includes hospitals, schools, scientific laboratories, animal husbandry houses, food factories, department stores,
Painting of buildings such as shopping centers, condominiums, office buildings, halls, and detached houses, refrigerators, washing machines, vacuum cleaners, rice cookers, mobile phones, handsets, automatic dishwashers, air conditioners, dehumidifiers, humidifiers, fans ,microwave,
Rice mill, water purifier, shaving machine, electric therapy device, blood pressure monitor,

Body fat meter, various mixers, water heaters, electric toothbrushes, various dryers, wireless devices, radar, global positioning system (GPS), fax machines, personal computers, televisions, radios, CD players, MD players, LP players. ,video,
Mention may be made of painting appliances such as cameras, DVDs, and earphones. Among them, particularly, the coating containing the organic-inorganic composite composition of the present invention using the above-mentioned food preservative or cosmetic raw material as the functional organic compound is preferably used for coating of those that frequently come into direct contact with human skin. can do.

As long as the adhesive of the present invention contains the organic-inorganic composite composition of the present invention or the resin composition of the present invention, its composition, form and manufacturing method are not particularly limited.

As a method for producing the adhesive, for example, a liquid obtained by dissolving or suspending the organic-inorganic hybrid composition of the present invention or the resin composition of the present invention in a suitable solvent is added to a known adhesive. Examples thereof include a method and a method of adding the powder of the organic-inorganic composite composition and / or the powder of the resin composition of the present invention to a known adhesive.

The use of the adhesive is not particularly limited, but civil engineering materials, construction materials, agricultural materials, automobile materials, electric equipment,
Examples thereof include medical supplies, sanitary products, toiletry products, hygiene materials, interior materials, furniture, general packaging materials, food packaging materials, containers, toys, stationery, labels, binding products and the like.

The cosmetic composition of the present invention is not particularly limited in its composition, form and manufacturing method as long as it contains the organic-inorganic hybrid composition of the present invention or the resin composition of the present invention.

Examples of the method for producing the cosmetic material include a method of adding a powdery material of the organic-inorganic composite composition of the present invention or the resin composition of the present invention to a known cosmetic material.

Since the organic-inorganic hybrid composition of the present invention or the resin composition of the present invention can exhibit the function of the functional organic compound contained therein for a long period of time, the above-mentioned food preservative as a functional organic compound. The cosmetics containing the organic-inorganic composite composition of the present invention, which has the antibacterial effect, suppresses the growth of microorganisms for a long period of time and exhibits high storage stability. Further, the cosmetic containing the organic-inorganic composite composition of the present invention using the cosmetic raw material such as the ascorbic acid derivative or kojic acid as the functional organic compound stably exhibits their antioxidant effect for a long period of time. be able to.

[0060]

EXAMPLES The present invention will be further described with reference to examples, but the examples do not limit the present invention.
In the following, "%" is expressed on a weight basis. In this example, ε-polylysine is a 25% aqueous solution or 100% of ε-polylysine manufactured by Chisso Corporation.
As the powder, L-ascorbic acid 2-magnesium phosphate used was L-ascorbyl magnesium phosphate, which was easily soluble by Chisso Corporation.

<Preparation of Sample 1 and Sample 2> Sample 1 Fine talc having an average particle size of 1 μm (HTPu manufactured by Tomoe Kogyo Co., Ltd.)
ltra5C) 1.5 g and ε-polylysine (hereinafter EP
2.5 g of 100% powder (referred to as L) was dry mixed. Colloidal colloidal silica solution (Adelite AT-40 manufactured by Asahi Denka Co., Ltd., solid content 40%) was added to the dry mixture.
5 g was added dropwise to form a slurry. Since the slurry gradually aggregated, it was transferred to an evaporation dish while it could be handled, dehydrated for 12 hours at 105 ° C. using an electric furnace, and subsequently cured at 150 ° C. for 8 hours. As a result, a hard agglomerate was obtained, which was finely pulverized in an agate mortar to obtain Sample 1 which was an organic-inorganic composite composition.

Sample 2 Sample 2 which was an organic-inorganic composite composition was obtained according to the method of sample 1 except that the amount of EPL100% powder was 0.25 g. The compositions of Sample 1 and Sample 2 are as follows.
EPL as an active ingredient of the obtained samples 1 and 2
The amount of the sample 1 was 46.3% and that of the sample 2 was 7.9%. Sample 1 composition EPL: talc: silica = 25: 15: 1
4 Sample 2 composition EPL: talc: silica = 2.5: 15:
14

<Preparation of Sample 3> As a comparative sample,
A silica gel support of EPL was prepared. Sample is EP
L 25% aqueous solution 0.8 g (0.2% as EPL component)
g) silica gel (SYLY manufactured by Fuji Silysia Chemical Ltd.)
SIA250, 0.8 g of average particle diameter 2.7 μm) was suspended, stirred and mixed for 24 hours, and then dried under reduced pressure at 40 ° C. to prepare Sample 3 as a silica gel carrier of EPL. The composition of sample 3 is as follows. The amount of EPL as an active ingredient of the obtained sample 3 was 20%. Sample 3 composition E
PL: silica gel = 2: 8

<Antibacterial Test 1-1> Samples 1 and 2 above
With respect to Sample 3 and Sample 3, the antibacterial effect test was carried out by the following test method for those that were washed under the following washing conditions and those that were not washed.

<Washing conditions> 25 g of a solution in which 1 g of each of Samples 1 to 3 was adjusted to pH 7 with 14 mM phosphate buffer.
It was suspended in 1 l, stirred for 48 hours, filtered, and then kept at 30 ° C. for 24 hours.
It was dried under reduced pressure for an hour.

<Antibacterial Test Method> A predetermined amount of the above sample was put into a 10 ml sterilized spitz, and 5 m of ordinary broth medium was added.
E. coli (Escherichia coli, IF
O13500) has a viable cell count of 5.0 × 10 ⁴ /
Adjust to a concentration of ml and 48 at 30 ± 1 ℃.
The culture was shaken for a period of time. The spitz was laid horizontally and shaken so that the sample in the medium did not aggregate on the bottom of the spitz. After the completion of the culture, the growth state of the bacteria was confirmed with Petri film (Sumitomo 3M Co., Ltd.). Regarding the growth state of the fungus, the one in which the fungus was not observed was marked with ◯, and the one in which the fungus was recognized was marked with x. The results are shown in Table 1.

[0067]

[Table 1]

As is clear from Table 1, the samples 1 and 2 shown in Examples 1 to 10 of the present invention were not washed with the sample 3 of Comparative Examples 1 to 5 simply supported on the inorganic filler. It can be seen that at times, EPL shows an antibacterial effect at a low concentration, and also has an antibacterial effect even after washing the sample.

<Antibacterial Test 1-2> The above Sample 1, Sample 2, Sample 3 and, for comparison, a film prepared by kneading EPL with polypropylene was prepared, and the antibacterial property of the film was evaluated.

<Production conditions of film> Polypropylene powder (manufactured by Chisso Corporation, MFR 10.9 g / 10 minutes,
230 ° C., 21.18 N), Sample 1, Sample 2, Sample 3,
And EPL 100% powdered product was added and mixed in a predetermined amount,
Press molding under conditions of 200 ° C. and 10 MPa, thickness 10
A 0 μm film was made.

<Antibacterial Test Method (Film Adhesion Method)>
An antibacterial property test was conducted according to the "film adhesion method", which is a synthetic resin antibacterial property test method defined in "Silver Inorganic Antibacterial Research Group: Antibacterial Evaluation Method of Silver Inorganic Antibacterial Products (1995)". .

<Preparation of Test Bacteria Solution> Ordinary broth medium was diluted 500 times with sterilized purified water, and E. coli (Escherichia coli) was diluted with 1/500 medium adjusted to pH 7.0 ± 0.2 with a sterilized pipette. , IFO1350
0) was prepared so that the number of viable cells in the medium was 5.0 × 10 ⁵ cells / ml.

<Preparation of Test Piece> The film to be subjected to the antibacterial test was wiped lightly for 2 to 3 times with pharmacopoeia gauze impregnated with ethanol, and dried again at room temperature to obtain a test piece.

<Antibacterial Test> Each test piece was put in a sterile petri dish, and 0.5 ml of the inoculum bacterial solution was inoculated on the test surface,
After covering with a sterilized polyethylene coating film and covering with a lid, the temperature was 35 ° C ± 1 ° C and the relative humidity was 90.
The culture was performed for 24 hours under the condition of not less than%. After completion of the culture, the bacteria attached to each test piece and the culture film are SCDL
Sufficiently wash out into a sterile petri dish using 10 ml of P medium, and 1 ml of the washed out liquid is added to Petrifilm (Sumitomo 3
(Manufactured by M Co.) and the viable cell count was measured. After the test was completed, the difference in increase / decrease value was calculated by the following formula. The results are shown in Table 2.

Calculation method of increase / decrease value difference [A]: Number of viable bacteria immediately after inoculation of antibacterial unprocessed sample [B]: Number of viable bacteria after culture operation of antibacterial unprocessed sample [C]: Culture operation of antibacterial processed sample Subsequent increase / decrease difference in viable cell count = Log ₁₀ (B / A) −Log ₁₀ (C /
A)

[0076]

[Table 2]

As is clear from Table 2, Examples 11 to 14 using Sample 1 and Sample 2 of the present invention are Comparative Examples 7 and 8 using Sample 3, and Comparative Example 9 containing EPL as it is. Compared with No. 10, the dispersibility of the sample in the film was improved, and thus the sample exhibited high antibacterial property even if the EPL concentration in the film was the same. Further, the higher the EPL concentration in the sample, the smaller the amount of the sample added in order to make the EPL concentration in the film the same, and thus the density of the sample in the film is reduced. , And 14, even if the EPL concentration in the sample is increased and the amount of the sample added to the film is reduced, the antibacterial performance is not affected.

<Preparation of Sample 4> 1.5 g of fine powder talc (HTPtra5C manufactured by Tomoe Kogyo Co., Ltd.) having an average particle size of 1 μm
And L-ascorbic acid 2-magnesium phosphate (hereinafter,
1 g of PAM) was dry mixed. 3.5 g of colloidal colloidal silica solution (Adelite AT-40 manufactured by Asahi Denka Kogyo Co., Ltd., solid content 40%) was added dropwise to this dry mixture to form a slurry. Since the slurry gradually aggregated, it was transferred to an evaporation dish while it could be handled, dehydrated for 12 hours at 105 ° C. using an electric furnace, and subsequently cured at 150 ° C. for 8 hours. This gave a hard agglomerate, so pulverize it in an agate mortar,
Sample 4 which is an organic-inorganic composite composition was obtained. The composition of sample 4 is as follows. PAM as an active ingredient of sample 4
The amount was 25.6%. Sample 4 composition PAM: talc: silica = 10: 15: 14

<Preparation of Sample 5> As a comparative sample,
A silica gel carrier of PAM was prepared. Sample is PA
To 10 g of a 10% aqueous solution of M (1 g as a PAM component), silica gel (SYLYSIA2 manufactured by Fuji Silysia Chemical Ltd.)
50 g, average particle diameter 2.7 μm) (3 g) were suspended, mixed with stirring for 24 hours, and then dried under reduced pressure at 40 ° C. to obtain a sample 5 as a silica gel carrier of PAM. The composition of sample 5 is as follows. The amount of PAM as an active ingredient of sample 5 is 25%
Met. Sample 5 composition PAM: silica gel = 1: 3

<Preparation of Foundations 1 and 2> Foundation 1 as the cosmetic of the present invention was prepared according to the following formulation. Foundation 1 Compounding ingredients wt% 1. Stearic acid 4.0 2. Glycerin monostearate 3.0 3. Cetanol 1.5 4. Isopropyl myristate 7.0 5. Liquid paraffin 10.0 6. White beeswax 3.0 7. Dihydroxybenzophenone 8.0 8. Triethanolamine 1.5 9. Glycerin 3.0 10. Bentonite 1.0 11. Titanium oxide 8.0 12. Mica titanium 3.0 13. Kaolin 3.0 14. Talc 3.0 15. Sample 4 4.0 16. Coloring pigment (yellow iron oxide) 1.0 17. Coloring pigment (red iron oxide) 1.0 18. Preservative (paraben) appropriate amount 19. Perfume (sandalwood water) Suitable amount 20. The remaining blending components 1 to 7 to be purified water 100 were mixed, stirred and heated to prepare a mixture 1 at 70 ° C. Next, mix the ingredients 8, 9, 18, 20 and
The mixture was stirred and heated to prepare a mixture 2 at 70 ° C. Mixing components 10 to 17 were dispersed in mixture 1 under stirring at 70 ° C., then, mixture 2 was gradually added to emulsify, and after cooling with stirring, mixing component 19 was added to obtain foundation 1.

Foundation 2 Foundation 2 was obtained according to the method of Foundation 1 except that Sample 5 which was the component 15 was mixed.

<Improvement test for dullness, stains and freckles> Foundations 1 and 2 were stored at room temperature for 1 month, 6 months and 12 months after preparation for 50 panelists, and continuously used for 1 month (morning and evening). (Apply to the face once)
Then, an evaluation test was performed on the effect of improving dullness, stains, and freckles on the face. Table 3 shows the number of respondents who evaluated themselves as self-assessment and had an improvement effect.

[0083]

[Table 3]

As is clear from Table 3, Sample 4 of the present invention
It can be seen that the foundation 1 using No. 1 has a stable effect of improving the functions of PAM, such as dullness, spots, and freckles, over a long period of time as compared to Foundation 2 using Sample 5 as a comparative sample.

<Production of Sample 6 and Sample 7> Sample 6 Fine talc having an average particle size of 1 μm (HTPu manufactured by Tomoe Kogyo Co., Ltd.)
ltra5C) 2.1 g and ε-polylysine (hereinafter EP
2.5 g of 100% powder (referred to as L) was dry mixed. 2 g of colloidal colloidal silica solution (Adelite AT-40 manufactured by Asahi Denka Co., Ltd., solid content 40%) was added to the dry mixture.
Was added dropwise to form a slurry. Since the slurry gradually aggregated, it was transferred to an evaporation dish while it could be handled, dehydrated for 12 hours at 105 ° C. using an electric furnace, and subsequently cured at 150 ° C. for 8 hours. As a result, a hard agglomerate was obtained, which was finely pulverized in an agate mortar to obtain Sample 6 which was an organic-inorganic composite composition.

Sample 7 An organic-inorganic composite composition sample 7 was obtained according to the method of sample 6 except that the amount of fine powder talc was 0.9 g and the amount of colloidal silica colloid solution was 5 g. The compositions of Sample 6 and Sample 7 are as follows. The amount of EPL as an active ingredient of the obtained sample 6 and sample 7 was 4 in both cases.
It was 6.3%. Sample 6 composition EPL: talc: silica = 25: 21: 8 Sample 7 composition EPL: talc: silica = 25: 9: 20

<Dissolution Test> 0.1 g of each of Samples 1, 6 and 7 was placed in a 200 ml screw cap bottle, 100 ml of purified water was poured, the lid was placed, and the mixture was stirred with a stirrer at 200 rpm at room temperature. After 24 hours and 48 hours from the start of stirring, 7
After 2 hours, 0.1 ml of water was sampled from each screw cap bottle, and the eluted EPL was quantified by high performance liquid chromatography. The quantification was performed by using 0.1 ml of 0.0463% aqueous solution of EPL, which has the same concentration as the total amount of EPL in each sample eluted, with the peak area of the chromatogram measured by high performance liquid chromatography as 100%. It was The quantification results are shown in Table 4.

[0088]

[Table 4]

As is apparent from Table 4, the organic-inorganic composite composition of the present invention contains the functional organic compound by adjusting the mixing ratio of talc which is an inorganic aggregate and colloidal silica which is an inorganic aggregate. It can be seen that the elution rate of can be controlled.

[0090]

When the organic-inorganic hybrid composition of the present invention is dispersed in a resin, the dispersibility of the functional organic compound contained in the organic-inorganic hybrid composition in the resin is good. The organic-inorganic hybrid composition and the resin composition of the present invention can control the elution rate of the functional organic compound contained therein. Further, the organic-inorganic composite composition and the resin composition can be suitably used for resin molded products, films, sheets, packaging materials, medical equipments, fibers, paints, adhesives, cosmetics and the like.

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) A61K 7/00 A61K 7/00 K 4J037 7/48 7/48 4J038 B32B 27/20 B32B 27/20 Z 4J040 C08J 3 / 12 CEP C08J 3/12 CEPA 5/00 5/00 C08K 3/00 C08K 3/00 C08L 5/00 C08L 5/00 101/00 101/00 C09C 1/00 C09C 1/00 3/08 3/08 C09D 7/12 C09D 7/12 201/00 201/00 C09J 11/02 C09J 11/02 201/00 201/00 F-term (reference) 4C083 AA081 AA082 AB171 AB172 AB211 AB221 AB232 AB241 AB242 AB431 AB432 AB441 AC022 AC072 AC122 AC242 AC271 AC352 AC392 AC472 AC482 AC542 AC841 AD321 AD331 AD411 AD641 AD642 CC12 DD23 EE12 EE17 4F070 AA01 AA11 AA41 AA71 AB11 AC13 AC14 AC15 AC22 AC23 AE22 DA01 DA41 DC05 DC11 DC12 DC13 DC16 4F071 AA01 AA08 AA20 AE100A20AB17A18 AB17 AB26 AF18 AB26 AF18 AB26 AF18 AB26 AF18 AB26 AB18 AF26 AB18 AF26 AB18 AB26 AA20H AA21A AA21H AA27A AA27H AC10A AC10H AH02A AH02H AH03A AH0 3H AT00B BA02 BA10A BA10B CC00A EJ48A GB23 GB48 GB66 GB81 JC00 JG03 4J002 AA01X AB05W BB03X BB05X BB12X BB14X BC03X BN15X CF06X CF07X CL01A29A30A22 CB021 CB091 CE051 DA041 DA141 DA161 DB001 DD181 HA146 HA216 HA436 HA446 HA526 HA536 JA35 KA02 KA08 4J040 BA101 CA041 CA071 CA081 DA021 DA091 DA101 DB031 DC021 DD051 EB031 EB111 EB131 ED011 ED041 ED42 EG03 EG03

Claims (19)

[Claims] 1. An organic-inorganic composite composition obtained by sintering a functional organic compound, an inorganic aggregate, and an inorganic coagulant. 2. An organic-inorganic composite composition obtained by further pulverizing the organic-inorganic composite composition according to claim 1. 3. The functional organic compound is ε-polylysine,
The organic-inorganic hybrid composition according to claim 1, which is one or more selected from protamine, chitosan, sorbic acid, hyaluronic acid, ascorbic acid derivatives, kojic acid, and salts thereof. 4. The organic-inorganic hybrid composition according to claim 1, wherein the functional organic compound is ε-polylysine and / or a salt thereof. 5. The organic-inorganic composite composition according to claim 1, wherein the functional organic compound is L-ascorbic acid 2-sodium phosphate and / or L-ascorbic acid 2-magnesium phosphate. 6. The organic-inorganic composite composition according to claim 1, wherein the inorganic aggregate is one or more selected from talc, silica, zeolite, alumina, titania, zirconia, and diatomaceous earth. 7. The inorganic coagulant is one or more selected from colloidal silica and organosilica.
The organic-inorganic composite composition described. 8. The organic-inorganic composite composition according to any one of claims 1 to 7, wherein the elution rate of the functional organic compound is selected or adjusted by selecting or adjusting one or more of the following A to D. A controlled organic-inorganic composite composition. A: Properties of functional organic compound B: Kind and particle size of inorganic aggregate C: Kind and particle size of inorganic coagulant D: Mixing ratio of functional organic compound, inorganic aggregate, and inorganic coagulant 9. A resin composition containing the organic-inorganic composite composition according to claim 1 and a resin. 10. A molded product comprising the resin composition according to claim 9. 11. A molded product obtained by adhering and / or spreading the organic-inorganic composite composition according to any one of claims 1 to 8. 12. A packaging material containing the organic-inorganic composite composition according to claim 1 and / or the resin composition according to claim 9. 13. A medical device containing the organic-inorganic composite composition according to any one of claims 1 to 8 and / or the resin composition according to claim 9. 14. A fiber containing the organic-inorganic composite composition according to any one of claims 1 to 8 and / or the resin composition according to claim 9. 15. A fabric containing the organic-inorganic composite composition according to any one of claims 1 to 8 and / or the resin composition according to claim 9. 16. A coating material containing the organic-inorganic composite composition according to claim 1 and / or the resin composition according to claim 9. 17. An adhesive containing the organic-inorganic composite composition according to any one of claims 1 to 8 and / or the resin composition according to claim 9. 18. A cosmetic containing the organic-inorganic composite composition according to any one of claims 1 to 8 and / or the resin composition according to claim 9. 19. An electric appliance coated with the paint according to claim 16.