KR101229509B1 - Cosmetic Compositions Comprising Functional Material―Incorporating Zeolites - Google Patents

Abstract

The present invention is a cosmetic composition comprising a zeolite containing a functional material in the zeolite pores, the zeolite is surface-treated with a compound of the formula (1) to prevent the inclusion of the functional material out of the pores and to increase the dispersion It relates to a cosmetic composition characterized in that it is blocked:

Formula 1

Cosmetics, Cosmetics, Antimicrobial, Ultraviolet, Blocking, Chemical Bonding, Surface Treatment, Zeolite

Description

Cosmetic Composition Comprising Functional Material-Incorporating Zeolites

The present invention relates to a cosmetic composition having excellent discoloration resistance, dispersibility, and usability including a zeolite containing a functional material (eg, an antimicrobial or sunscreen material).

Conventionally, mica, talc, kaolin, silicic anhydride, Bengala (red oxide), for the purpose of adjusting the usability and glossiness, such as color tone preparation, elongation, adhesion, etc. of cosmetic preparations Inorganic pigments, such as iron sulfate, ultramarine blue, royal blue, titanium oxide, zinc oxide, and mica titanium, have been mix | blended.

However, in the inorganic pigments, agglomeration occurs due to the interaction between the powder particles, so that the dispersibility in the cosmetics may be lowered or precipitated in the cosmetics. In addition, depending on the type of powder and the shape particle diameter, there is a problem in feeling of roughness, inferior skin friendliness or extensibility, and it is not very preferable as a cosmetic powder.

In addition, zeolite is used as one kind of such inorganic pigments, which have been used by dispersing in cosmetics in the form of an antimicrobial zeolite containing an antimicrobial substance (Japanese Patent Laid-Open No. 63-250325). However, the contents of the patent document, when the antimicrobial zeolite is dispersed in the cosmetics, the fatal problems such as degeneration of the antimicrobial material caused by the release of the antimicrobial material out of the zeolite pores, color change of the cosmetic, deterioration of the efficacy of the antimicrobial material significantly When used in combination with cosmetics, it is difficult to disperse, coagulate, discoloration resistance is severe, and the feeling of use is rough, so there is a difficulty in actually replacing organic preservatives.

On the other hand, fine powders of various organic synthetic resins are incorporated into cosmetics for the purpose of improving the feeling of use of cosmetics, which have the advantage of being well dispersed due to the light weight of the cosmetics. The problem has been pointed out because the improvement of the world is rather hindered.

Recently, a technique has been proposed that blending polymer microparticles containing antimicrobial zeolite containing antimicrobial substances into cosmetics can improve cosmetic quality maintenance, usability, and antimicrobial activity (Korean Patent No. 0529284). Physically mixed with monomers, intermediates or fine particles of the polymer to be depressed, so that the adsorption of the antimicrobial zeolite particles attached by simple adsorption is easy and the fatal problems such as clogging of the antimicrobial zeolite pores due to the organic polymer are used. There is a difficulty in using it. Moreover, economic efficiency is a problem as antimicrobial zeolites, which are located inside the polymer fine particles and do not participate in the reaction, are used unnecessarily.

The inventors have found that when the active ingredient that imparts functionality (eg, antimicrobial or sunscreen properties) to the cosmetic composition is stably and efficiently contained in the pores of the zeolite and surface-treated and applied to the cosmetic composition, the functional provision is greatly improved. By confirming, this invention was completed.

Accordingly, it is an object of the present invention to provide a cosmetic composition having less discoloration resistance, excellent dispersibility, and excellent usability.

Another object of the present invention is to provide an antimicrobial cosmetic composition having a low discoloration resistance, excellent dispersibility and excellent usability.

Still another object of the present invention is to provide a sunscreen cosmetic composition having low discoloration resistance, excellent dispersibility, and excellent usability.

Still other objects and advantages of the present invention will become apparent from the following detailed description and claims.

According to one aspect of the present invention, the present invention is a cosmetic composition comprising a zeolite containing a functional material in the zeolite pores, wherein the zeolite is to prevent the contained functional material from coming out of the pores and to increase the dispersing power, Surface treatment with a compound of Formula 1 provides a cosmetic composition characterized in that the surface is blocked:

Formula 1

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, halogen, hydroxy, alkoxy or alkyl phosphine of C ₁ -C ₅ , alkyl, aralkyl or aryl group of C ₁ -C ₃₀ , May include a non-metallic atom or a metal atom in the middle or terminal thereof, or an organic functional group may be located at the terminal or the middle, R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different from each other, One of which has a functional group containing a hydrophilic end group or a hydrophobic end group without being bound to the zeolite and exposed to the outside; M is a Group 13, 14 or 15 element, or a transition metal element of 4, 5 or 6 cycles.

The present invention relates to the application or application of a zeolite to a cosmetic composition. The present inventors have found that when the active ingredient imparting the functionality to the cosmetic composition is stably and efficiently incorporated in the zeolite pores, the pores are surface treated and applied to the cosmetic composition, the functional provision is greatly improved.

The cosmetic composition of the present invention has a function of antimicrobial and sunscreen typically.

According to a preferred embodiment of the present invention, the functional material contained in the zeolite pores is an antimicrobial material, the cosmetic composition is an antimicrobial cosmetic composition.

According to a preferred embodiment of the present invention, the functional material contained in the zeolite pores is an ultraviolet absorbing material or an ultraviolet reflecting material, and the cosmetic composition is a cosmetic composition for blocking UV rays.

The antimicrobial substance contained in the zeolite pores in the antimicrobial cosmetic composition of the present invention is not particularly limited, preferably at least one cation selected from the group consisting of gold ions, silver ions, copper ions and zinc ions, most preferably Is a silver ion.

The antimicrobial cations contained in the zeolite pores can have various charges. For example, copper ions may have charges of Cu ⁺ and Cu ²⁺ , gold ions are Au ⁺ , silver ions are Ag ⁺ , and zinc ions are Zn ²⁺ .

As used herein, the term "antimicrobial" has the meaning including both sterile, antimicrobial, bacteriostatic and antifungal.

The antimicrobial material contained in the zeolite pores may themselves be stably located in the zeolite pores to some extent.

However, to make it more stable that the antimicrobial material is located in the zeolite pores, that is, to prevent the antimicrobial material from escaping the zeolite pores, the antimicrobial material contained in the pores of the zeolite is irradiated with ultraviolet rays, visible in the zeolite pores. Some or all reduction, more preferably through treatment with a light irradiation or reducing agent (e.g., hydrogen iodide, hydrogen sulfide, aluminum hydride, carbon monoxide, sulfur dioxide, sulfite, sodium sulfide, alkali metal, magnesium, zinc, aldehyde, formic acid, oxalic acid, etc.) Part is reduced. The reduced material (eg, metal cations) in the zeolite pores thus forms particles of increased size, and these particles are greatly restricted from exiting the zeolite pores.

The reduction strategy applies a so-called ship-in-bottle strategy, which allows the antimicrobial activity to be maintained for a longer time. Cosmetic composition is very important for storage stability, long-term storage stability (long-term storage stability). By using the reduction strategy, the antimicrobial substance-containing zeolite can be maintained for a long time in a cosmetic composition requiring long-term storage stability.

In the sunscreen cosmetic composition of the present invention, any of the cations, heavy molecules or nanoparticles that absorb ultraviolet rays may be any UV absorber commonly used in cosmetic compositions, preferably titanium oxide, zinc oxide, or benzoic acid. UV blockers (such as p-aminobenzoic acid (PABA), PABA monoglycerine esters and N, N'-dipropoxy PABA ethyl ester), anthranilic acid based ultraviolet absorbers (such as homomentyl-N-acetylanthranilate) ), Salicylic acid based ultraviolet absorbers (e.g. amyl salicylate, menthyl salicylate and homomentyl salicylate), cinnamic acid based ultraviolet absorbers (e.g. octyl cinnamate, ethyl-4-isopropyl cinnamate and methyl-2- 5-diisopropyl cinnamate), benzophenone ultraviolet absorbers (e.g., 2,4-dihydroxy benzophenone and 2,2-dihydroxy-4-methoxy benzophenone), 3- ( 4'-methylbenzylidene) -d, l-campo or semiconductor material, most preferably titanium oxide.

Substances used as sunscreens in cosmetic compositions generally cause side effects on the skin. Titanium oxide is widely used in cosmetics as a sunscreen, and applying a cosmetic composition comprising the same to the skin causes side effects (eg, skin troubles, skin aging, etc.). However, in the sunscreen cosmetic composition of the present invention, when the sunscreen agent contained in the zeolite pores is used, the above problem of skin side effects is overcome (see Example).

The biggest characteristic of this invention is that the zeolite used for the composition of this invention is a pore sealed. That is, the pores of the zeolite are occluded in the state in which the antimicrobial substance or the sunscreen is contained, thereby preventing the contained antimicrobial substance or the sunscreen from escaping the pores.

Preventing the outflow of the active ingredient imparting the functionality contained in the pore of the zeolite prevents one end of the pore inlet blocking molecules from binding to the oxide, sulfide, or phosphide on the surface of the porous material, and the other end of the pore opening of the zeolite surface. It consists of the effect of reducing the pore size by covering it or blocking it completely.

Looking at the configuration of the method of preventing the effective ingredient that provides the functionality formed inside the various zeolites to leak out in more detail as follows:

In the first method, when a compound having a functional group is covalently bonded to a hydroxyl group present on the surface of the zeolite, the bond itself blocks a pore inlet or a pore inlet of an organic or inorganic chain adjacent to the other side of the compound. In addition, the basic configuration is that the effect of reducing the size of the pore opening can be obtained.

Secondly, the opposite end of the compound covalently bonded to the surface of the zeolite was replaced with a hydrophobic or hydrophilic material according to the content of the cosmetic to be blended to promote dispersion in the cosmetic.

The pore blocking molecules that can be used in the present invention are described in Formula (1). In Formula 1, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, halogen, hydroxy, alkoxy or alkyl phosphine of C ₁ -C ₅ , an alkyl, aralkyl, or aryl group of C ₁ -C ₃₀ . It may include a non-metal or a metal atom including oxygen, nitrogen, sulfur, phosphorus, etc. in the middle or terminal thereof, and generally well-known organic functional group may be located in the terminal or the middle of the compound. In addition, R ₁ , R ₂ , R ₃ and R ₄ may be the same as or different from each other, and one of them has a functional group containing a hydrophilic end group or a hydrophobic end group without being bound to the zeolite and exposed to the outside. M includes all Group 13, 14 or 15 elements including Al, Si and P and all transition metals of 4, 5 and 6 cycles including Ti, Zr.

By the pore closure, the antimicrobial material or sunscreen contained in the zeolite may be located in the zeolite pores for a long time while maintaining nano size. That is, the antimicrobial metal substance or sunscreen agent is present for a long time in the form of particles (quantum dots) of size limited to several nanometers in the zeolite pores. The above characteristics allow the function or activity of the antimicrobial substance or the sunscreen to be sufficiently exerted, and eventually to maintain the antimicrobial or sunscreen properties of the cosmetic composition of the present invention for a long time with high activity.

As used herein, the term “zeolite” refers not only to generically minerals that are aluminum silicate hydrates of alkali or alkaline earth metals, but also to (ii) some or all of the silicon (Si) and aluminum (Al) of the zeolite as various other elements. Also included are zeotype molecular sieves which have been replaced, and broadly including all porous oxides or sulfides having hydroxyl groups on the surface. Atoms that form the backbone of molecular sieves are not only main group elements such as silicon, aluminum, gallium, boron, phosphorus, oxygen, sulfur, but also titanium, vanadium, zirconium, manganese, chromium, iron, cobalt, nickel, copper, zinc and others. Transition metals are also possible. Illustrative examples of zeolites are as follows:

1. Natural and Synthetic Zeolites

2. Zeolites and similar materials with MFI structure (ZSM-5, silicalite-1, TS-1 or metallo-silicalite-1 partially substituted with transition metals, etc.)

3. Zeolites and similar materials having a MEL structure (ZSM-11, Silicalite-2, TS-2 or Metallo-Silicalite-2 partially substituted with transition metals, etc.)

4. Zeolite A, X, Y, L, Beta, Mordenite, Ferrierite, ETS-4 or ETS-10, etc.

5. Mesoporous Silica (MCM Series, SBA Series, MSU Series, KIT Series)

6. Pseudo-molecular sieve including zeolite and mesoporous silica produced through other hydrothermal synthesis

7. Organic-inorganic composite mesoporous structures and layered materials

8. Nanoporous materials, called organic zeolites, organometallic zeolites, or coordination compound zeolites, in which metal ions and ligands combine three-dimensionally to form regular nanopores

The particle size of the zeolite used in the present invention is not limited, and considering the dispersibility and usability in the cosmetic composition, 10 nm-50 ㎛, preferably 10 nm-20 ㎛, more preferably 10 nm-10 ㎛ Most preferably have a particle size of 10 nm-1 μm (1000 nm).

The antimicrobial substance or sunscreen agent of the type contained in the zeolite described herein is independently formulated into cosmetics and has the antimicrobial and sunscreen functions as the main antimicrobial and ultraviolet ray blocking active substances, respectively. Order.

On the other hand, nanoparticle components such as nanoemulsion, nanoliposomes, etc. are widely used as a component of cosmetics, but recently, it has been reported that nanoparticles can penetrate into cells and cause cell deformation, necrosis and genetic modification. It is becoming. Therefore, according to a preferred embodiment of the present invention, the zeolite is chemically bonded on the particulate support in order to minimize the side effects caused by the nanoparticles.

If the nanoparticles of the functional substance-containing zeolite are physically adsorbed on the fine particles, there is a possibility that they are easily released and cause side effects. Therefore, it is preferable that the zeolite nanoparticles are firmly bonded to the surface of the microparticles (fine particles) by chemical bonding. This is considered to be the only method for utilizing the high reactivity of the nanoparticles, especially in the case of cosmetics applied to the surface of the human body.

According to a preferred embodiment of the present invention, the zeolite containing the functional material is bonded using a known chemical bond on the surface of the organic material fine particles (polymer bead) or inorganic material fine particles (silica, alumina, zeolite, clay, etc.). This greatly increases the dispersibility of the zeolite in the cosmetics, and serves to significantly improve the usability of the cosmetics.

The antimicrobial active substance or the sunscreen active substance-containing zeolite is a compound selected from the group consisting of compounds of the following Chemical Formulas 2 to 8 and is firmly bonded to the outer surface of the microparticles by chemical bonding, and At the same time, it is possible to solve the problems such as the release of the active substance from the surface of the particulate, the inclusion of unnecessary active substance contained in the particulate, economic efficiency, and the risk of nanoparticles.

(2)

Z-L1-X

(3)

MR ' ₄

Formula 4

R ₃ Si-L1-Y

Formula 5

HS-L1-X

6

HS-L1-SiR ₃

Formula 7

HS-L1-Y

Formula 8

Z-L2 (+) L3 (-)-Y or Z-L3 (-) L2 (+)-Y

In the above formula, Z is R ₃ Si or an isocyanate group (-NCO); Wherein R represents a halogen group, an alkoxy group of C ₁ -C ₄ or an alkyl group of C ₁ -C ₄ and at least one of the three Rs is a halogen group or an alkoxy group; L 1 is a substituted or unsubstituted C ₁ -C ₁₇ alkyl, aralkyl or aryl group and may include one or more oxygen, nitrogen or sulfur atoms; X is a halogen group, an isocyanate (-NCO) group, a tosyl group or an azide group; R 'has the same meaning as R and at least two of the four R's are halogen or alkoxy groups; M is silicon, titanium or zirconium; Y is a hydroxy group, thiol group, amine group, ammonium group, sulfone group and salts thereof, carboxylic acid and salts thereof, acid anhydride, epoxy group, aldehyde group, ester group, acrylic group, isocyanate group (-NCO), sugar residues, A coordination compound capable of double bonds, triple bonds, dienes, diynes, alkyl phosphines, alkyl amines or ligand exchanges, Y may be located at the terminal as well as in the middle of the linking compound; L 2 (+) is a functional group having at least one positive charge (+) at the terminal, straight chain or side chain of a substituted or unsubstituted C ₁ -C ₁₇ hydrocarbon compound which may include one or more oxygen, nitrogen or sulfur atoms. Represent; L 3 (-) is a functional group having at least one negative charge (-) at the terminal, straight or side chain of a substituted or unsubstituted C ₁ -C ₁₇ hydrocarbon compound which may include one or more oxygen, nitrogen or sulfur atoms. Indicates.

The size of the organic or inorganic particulate support used in the present invention is not limited, and considering the dispersibility and usability in the cosmetic composition, it is 100 nm-100 ㎛, preferably 100 nm-50 ㎛, more preferably 100 nm Have a particle size of 10 μm, most preferably 10 nm-5 μm.

According to a preferred embodiment of the present invention, the content of the antimicrobial substance or sunscreen-containing zeolite is 0.0001-10% by weight, more preferably 0.001-5% by weight, based on the total weight of the cosmetic composition.

The components included in the cosmetic composition of the present invention include components commonly used in cosmetic compositions in addition to the antimicrobial substance or sunscreen-containing zeolite, and include, for example, conventional agents such as antioxidants, stabilizers, solubilizers, vitamins, pigments and flavorings. Phosphorus aids, and carriers.

Cosmetic compositions of the present invention may be prepared in any formulation conventionally prepared in the art and include, for example, solutions, suspensions, emulsions, pastes, gels, creams, lotions, powders, soaps, surfactant-containing cleansing , Oils, powder foundations, emulsion foundations, wax foundations and sprays, and the like, but are not limited thereto. More specifically, it may be prepared in the form of a flexible lotion (skin), nourishing lotion (milk lotion), nourishing cream, massage cream, essence, eye cream, cleansing cream, cleansing foam, cleansing water, pack, spray or powder. .

When the formulation of the present invention is a paste, cream or gel, an animal oil, vegetable oil, wax, paraffin, starch, tracant, cellulose derivative, polyethylene glycol, silicone, bentonite, silica, talc or zinc oxide may be used as the carrier component .

In the case where the formulation of the present invention is a powder or a spray, lactose, talc, silica, aluminum hydroxide, calcium silicate or polyamide powder may be used as a carrier component. Especially, in the case of a spray, a mixture of chlorofluorohydrocarbons, propane / Propane or dimethyl ether.

When the formulation of the present invention is a solution or emulsion, a solvent, solubilizer or emulsifier is used as the carrier component, such as water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1 Fatty acid esters of, 3-butyl glycol oil, glycerol aliphatic ester, polyethylene glycol or sorbitan.

When the formulation of the present invention is a suspension, liquid carrier diluents such as water, ethanol or propylene glycol, suspending agents such as ethoxylated isostearyl alcohol, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, and microcrystals are used as carrier components. Soluble cellulose, aluminum metahydroxy, bentonite, agar or tracant and the like can be used.

When the formulation of the present invention is an interfacial active agent-containing cleansing, the carrier component is selected from aliphatic alcohol sulfate, aliphatic alcohol ether sulfate, sulfosuccinic acid monoester, isethionate, imidazolinium derivative, methyltaurate, sarcosinate, fatty acid amide Ether sulfates, alkylamidobetaines, aliphatic alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable oils, lanolin derivatives, or ethoxylated glycerol fatty acid esters.

In summary, the features and advantages of the present invention are as follows:

(Iii) In functional materials used in the cosmetic compositions of the invention, in particular antimicrobial metals or sunscreen-containing zeolites, since the antimicrobial or sunscreens are located in the pores of the zeolite, they do not increase in size anymore and do not increase in nanoscale size. I can keep it.

(Ii) The nano-sized antimicrobial material or sunscreen agent located in the zeolite pores has a very high antimicrobial and UV blocking ability as compared to the micro-sized counterpart.

(Iii) Therefore, the cosmetic composition of the present invention comprising an antimicrobial substance or a sunscreen-containing zeolite can exhibit a very good antimicrobial or ultraviolet blocking ability while being stable to the human body.

(Iii) The antimicrobial cosmetic composition of the present invention effectively inhibits the cosmetic composition from being deteriorated by microorganisms for a long time without using a separate preservative necessarily included in a conventional cosmetic composition.

(Iii) The sunscreen cosmetic composition of the present invention can provide a very safe cosmetic to the skin by greatly inhibiting the skin irritation caused by the sunscreen.

(Iii) In the cosmetic composition of the present invention, in the case of closing the pores of the zeolite, the antimicrobial substance or the sunscreen is suppressed from escaping out of the zeolite pores for a long time.

(Iii) In the cosmetic composition of the present invention, when the antimicrobial substance or the sunscreen-containing zeolite is firmly bonded to the outer surface of the organic or inorganic particulate support by chemical bonding, the dispersing force and the feeling of use are increased and the efficiency of the function is economically improved. Function.

(Iii) Therefore, the cosmetic composition of the present invention can exert antimicrobial activity or ultraviolet ray blocking ability even when stored for a long time.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

Example

Example 1 Preparation of Metal Ion-Containing Zeolites

The antimicrobial zeolite of the present invention is prepared by contacting a zeolite with a mixed aqueous solution prepared in advance to contain silver ions, copper ions, zinc ions, and other antimicrobial metal ions, and causing substitution between the ion exchangeable ions in the zeolite and the ions. Manufacture. Ion exchange may be performed at 10 to 70 ^° C., preferably 40 to 60 ^° C., 3 to 24 hours, preferably 10 to 24 hours in a light-blocked dark room. The pH of the mixed aqueous solution is appropriately adjusted to 3 to 10 and 5 to 7 is preferable.

In addition, the ions of the mixed aqueous solution are usually all supplied in salt form. For example, silver ions may include silver nitrate, silver sulfate, silver perchlorate, silver acetate, diamine nitrate, diamine sulfate and the like, and copper ions include (II) copper nitrate, copper perflate, Copper acetate, potassium tetracyano diphosphate, copper sulfate, and the like may be used, and zinc ions may be used as (II) zinc nitrate, zinc sulfate, zinc perchlorate, zinc thiocyanate, zinc acetate, and the like. Mercury ions may be used as mercury perchlorate, mercury nitrate and mercury acetate, tin ions as tin ions, lead sulphate and lead nitrate as lead ions, and bismuth chloride as bismuth ions. Odide, etc. may be used, and cadmium ions include cadmium perchlorate, Chromium sulphate, cadmium nitrate and cadmium acetate can be used, and chromium ions can be used as chromium perchlorate, chromium sulphate, ammonium chromium sulphate, chromium nitrate, etc. Thallium nitrate, thallium acetate and the like can be used.

In the present invention, the content of the antimicrobial substance in the antimicrobial zeolite may be determined according to the ion concentration and the ion exchange conditions of the antimicrobial substance in the mixed aqueous solution.

After the ion exchange is completed, the zeolite is thoroughly wiped with water containing no ions, dried at 100-200 ^° C. under vacuum, and stored in a dark room.

Example 2 Method of Blocking Pore of Metal Ion-Containing Zeolite

In order not to expose the metal ion-containing zeolite prepared in Example 1 to light and moisture, the zeolite dried in the dark was placed in a flask, and 50 mL of a non-polar solvent (normal nucleic acid or toluene, etc.) from which moisture was removed was added. Stir with a rod magnet. When the zeolite is sufficiently released, while stirring, C ₁₈ H ₃₇ Si (OMe) ₃ , C ₁₈ H ₃₇ SiCl ₃ , H ₃ NC ₃ H ₆ Si (OMe) ₃ , Si (OEt) ₄ , Zr (OEt) _4, etc. Add organic and inorganic compounds. When the reactants are sufficiently uniform, the reaction is performed at room temperature or 60 ° C. for 3-6 hours. (At this time, only organic and inorganic compounds can be reacted without using a solvent such as normal nucleic acid or toluene.) When the reaction is completed, the sample is centrifuged or filtered, and wiped several times with a non-polar solvent. Eliminate excess organic and inorganic compounds (pore blocker molecules). (See the section on 'Blocking Molecules' in Claims.)

Example 3: Physical / chemical characterization of metal ion-containing zeolites

In order to examine the physical and chemical properties of the ultraviolet-rays or visible light of the metal ion-containing zeolite powder prepared in Example 1, a zeolite powder to which a large amount of silver ions were added and a zeolite powder to which a small amount of silver ions were added were fluorescent lamps. And placed on an ultraviolet lamp and examined the color 24 hours later.

As a result, when a large amount of silver ions were added, the white powder turned into a dark gray powder regardless of the fluorescent lamp or ultraviolet lamp, and when a small amount of silver ions was added, the color was irrespective of the fluorescent lamp or the UV lamp. There was no change in white. This means that the ion-exchanged silver ions are reduced to ultraviolet light or visible light and take electrons out of the zeolite skeleton and change into a metal material constrained by the pore size. Unlike the case where a large amount of silver ions is present, In the case of a small amount of substitution, it is understood that the change of color does not occur because the size of the reduced metal is so small that it does not have a distinctive color.

Example 4 Preparation of Cosmetic Composition Comprising Pore-Blocked Metal Ion-Containing Zeolites

Example 4-1 Preparation of Nutritional Cream

An example of the composition of the nutrient cream in the cosmetic composition containing the silver ion-containing zeolite with blocked pores is as follows. No preservatives were included in the nourishing cream composition of the present invention.

ingredient Content (unit: weight%) Silver-Ion Containing Zeolites
Lipophilic monostearate
Cetearyl Alcohol
Stearic acid
Wax
Polysorbate 60
Sorbitan stearate
Cured Vegetable Oil
Squalane
Mineral oil
Trioctanoine
Dimethicone
Sodium magnesium silicate
glycerin
Betaine
Triethanolamine
Sodium hyaluronate
Incense
Distilled water .0
2.0
2.2
1.5
1.0
1.5
0.6
1.0
3.0
5.0
5.0
1.0
0.1
5.0
3.0
1.0
4.0
a very small amount
Balance Sum 100

Example 4-2 Preparation of Soft Cosmetics

Examples of the composition of the flexible longevity in the cosmetic composition containing the silver ion-containing zeolite blocked pores are as follows. No preservatives were included in the flexible cosmetic composition of the present invention.

ingredient Content (unit: weight%) Silver-Ion Containing Zeolites
glycerin
1.3-butylene glycol
PEG 1500
Allantoin
DL-Panthenol
EDTA-2NA
Benzophenone-9
Sodium hyaluronate
ethanol
Octicdodeceth-16
Polysorbate 20
Incense
Distilled water 1.0
5.0
3.0
1.0
0.1
0.3
0.02
0.04
5.0
10.0
0.2
0.2
a very small amount
Balance Sum 100

Example 4-3 Preparation of Packs

The compositional example of the pack in the cosmetics containing the pore-blocked silver ion containing zeolite is as follows. No preservatives were included in the pack composition of the present invention.

ingredient Content (unit: weight%) Silver-Ion Containing Zeolites
Polyvinyl alcohol
Cellulose gum
glycerin
Fiji 1500
Cyclodextrin
DL-Panthenol
Allantoin
Monoammonium glycyrrhizin acid
Nicotinamide
ethanol
PEG 40 Cured Castor Oil
Incense, pigment, preservative
Distilled water 3.0
15.0
0.15
3.0
2.0
0.15
0.4
0.1
0.3
0.5
6.0
0.3
a very small amount
Balance Sum 100

Example 5 Preparation of Cosmetic Composition Comprising Pore-Blocking Sunscreen-Including Zeolite

In order to prepare a sunscreen cosmetic composition, a sunscreen agent was used instead of the antimicrobial metal ion and the procedure of Example 1-2 was applied. A sunscreen cream and a softening lotion were prepared in the same composition and content as those described in Example 4, except that a pore-blocked sunscreen (TiO ₂ ) -containing zeolite was used.

Example 6: Analysis of Antimicrobial Activity

The bacteria to be tested were suspended in physiological saline at a concentration of about 100 million birds per physiological saline. This was dispersed in medium using a Conrad rod (0.1 mL). Mueller Hinton culture medium was used for bacteria other than Eumictes, and Sabourand agar medium was used for Yumaicites. The nourishing cream of the present invention prepared in Example 4-1 was applied to a filter paper having a diameter of 8 mm. This disc was placed in medium and maintained at 37 ^° C. for 18 hours for most bacteria. For Yumaicites, it was maintained at 30 ^o C for a week. Antibacterial activity was assessed when an inhibition zone was formed along the circumference of the disc. As a result of investigating the activity according to such a method, the cosmetic composition comprising the antimicrobial metal ion-containing zeolite of the present invention is antimicrobial to bacteria such as Eumycetes , Escherichia coli , Pseudomonas aeruginosa , Staphylococcus aureus , Candida albicans , Aspergillus flavus It was investigated.

Although the cosmetic composition of the present invention does not contain a preservative, it can be seen that exhibits excellent antimicrobial properties through the antimicrobial metal ion-containing zeolite.

Example 7 UV Protection

In order to investigate the sunscreen protection of the sunscreen of the present invention prepared in Example 5, the SPF (sun protection factor) value was measured using an SPF 290 instrument (Optometrics Corporation, UK). The experimental results are shown in Table 4.

Item Example 5 Comparative example SPF 25.4 20.2

In Table 4, the comparative example is a cosmetic composition containing titanium oxide instead of TiO ₂ -containing zeolite blocked pores.

As can be seen in Table 4, it is understood that the sunscreen cosmetic composition of the present invention comprising the TiO ₂ -containing zeolite blocked pores exhibits a superior sunscreen effect than the sunscreen composition containing a titanium oxide. Can be.

Example 8: Skin irritation test

In order to find out the skin irritation of the sunscreen cosmetic composition of the present invention prepared in Example 5, 0.1 g of sunscreen at 5 ㅧ 20 cm in the lower part of both arms for 50 healthy adults male / female Applied once. Subsequently, after 10 days and 30 days, the skin condition change was read visually, and the stimulation rate was calculated by the following equation. The results are shown in Table 5.

Prescription Tested embroidery Judgment result Stimulus
(%)      ++ + +-- Example 5 50 - - 2 48 1.3 Comparative example 50 - One 6 43 5.3

In Table 5, the comparative example is a cosmetic composition containing titanium oxide instead of TiO ₂ -containing zeolite blocked pores.

Criteria

-: No erythema or unusual phenomenon

+ -: slightly reddish from the surroundings

+: Significantly reddened than surrounding

++: Severe reddening and swelling around

As can be seen in Table 5, the UV-protective cosmetic composition of the present invention comprising a TiO ₂ -containing zeolite blocked pores exhibited a very low irritation, the UV-protective composition comprising a conventional titanium oxide is relatively High skin irritation was shown.

Therefore, it can be seen that the sunscreen cosmetic composition of the present invention has a very low skin irritation and does not cause skin trouble and is a very safe composition for the skin.

As described in detail above, in the functional material blocked pores used in the cosmetic composition of the present invention, such as antimicrobial material or sunscreen-containing zeolite, the antimicrobial material or sunscreen is no longer sized because it is located in the pores of the zeolite It can maintain nano-scale size without increasing, and it can be used for a long time with very good antimicrobial or UV blocking ability. In addition, the sunscreen cosmetic composition of the present invention can provide a very safe cosmetics to the skin by greatly inhibiting the skin irritation caused by the sunscreen.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (12)

In the cosmetic composition comprising a zeolite containing a functional material in the zeolite pores, the zeolite is surface-treated with a compound of the formula (1) to prevent the encapsulated functional material from escaping out of the pores and increase dispersibility Blocked, the functional material is a cosmetic composition, characterized in that the antimicrobial material, ultraviolet absorbing material or ultraviolet reflecting material: Formula 1

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, halogen, hydroxy, alkoxy or alkyl phosphine of C ₁ -C ₅ , alkyl, aralkyl or aryl group of C ₁ -C ₃₀ , May include a non-metallic atom or a metal atom in the middle or terminal thereof, or an organic functional group may be located at the terminal or the middle, R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different from each other, One of which has a functional group containing a hydrophilic end group or a hydrophobic end group without being bound to the zeolite and exposed to the outside; M is a Group 13, 14 or 15 element, or a transition metal element of 4, 5 or 6 cycles. The cosmetic composition according to claim 1, wherein the functional material contained in the zeolite pores is an antimicrobial substance, and the cosmetic composition is an antimicrobial cosmetic composition. The cosmetic composition according to claim 1, wherein the functional material contained in the zeolite pores is an ultraviolet absorbing material or an ultraviolet reflecting material, and the cosmetic composition is a cosmetic composition for blocking ultraviolet rays. The cosmetic composition according to claim 2, wherein the antimicrobial material is at least one cation selected from the group consisting of gold ions, silver ions, copper ions, and zinc ions. The method of claim 3, wherein the ultraviolet absorbing material is titanium oxide, zinc oxide, p-aminobenzoic acid (PABA), PABA monoglycerine esters, N, N'- dipropoxy PABA ethyl ester, homomentyl-N- Cosmetic composition, characterized in that acetylanthranilate, amyl salicylate, octyl cinnamate, 2,4-dihydroxy benzophenone, 3- (4'-methylbenzylidene) -d, l-campo or semiconductor material . The composition of claim 1 wherein the cosmetic composition consists of a solution, suspension, emulsion, paste, gel, cream, lotion, powder, soap, surfactant-containing cleansing, oil, powder foundation, emulsion foundation, wax foundation and spray Cosmetic composition, characterized in that it has a formulation selected from the group. The cosmetic composition according to claim 2, wherein the antimicrobial substance contained in the pores of the zeolite is partially or totally reduced through ultraviolet irradiation, visible light irradiation, or reducing agent treatment in the state of the zeolite pores. The compound of claim 1, wherein the zeolite is selected from the group consisting of the compounds of the following Chemical Formulas 2 to 8 on the surface of the organic particulate support or the inorganic particulate support in order to promote dispersion in cosmetics and to improve the feeling of use. Cosmetic composition, characterized in that chemically bonded to: (2) Z-L1-X (3) MR ' ₄ Formula 4 R ₃ Si-L1-Y Formula 5 HS-L1-X 6 HS-L1-SiR ₃ Formula 7 HS-L1-Y Formula 8 Z-L2 (+) L3 (-)-Y or Z-L3 (-) L2 (+)-Y In the above formula, Z is R ₃ Si or an isocyanate group (-NCO); Wherein R represents a halogen group, an alkoxy group of C ₁ -C ₄ or an alkyl group of C ₁ -C ₄ and at least one of the three Rs is a halogen group or an alkoxy group; L 1 is a substituted or unsubstituted C ₁ -C ₁₇ alkyl, aralkyl or aryl group and may include one or more oxygen, nitrogen or sulfur atoms; X is a halogen group, an isocyanate (-NCO) group, a tosyl group or an azide group; R 'has the same meaning as R and at least two of the four R's are halogen or alkoxy groups; M is silicon, titanium or zirconium; Y is a hydroxy group, thiol group, amine group, ammonium group, sulfone group and salts thereof, carboxylic acid and salts thereof, acid anhydride, epoxy group, aldehyde group, ester group, acrylic group, isocyanate group (-NCO), sugar residues, A coordination compound capable of double bonds, triple bonds, dienes, diynes, alkyl phosphines, alkyl amines or ligand exchanges, Y may be located at the terminal as well as in the middle of the linking compound; L 2 (+) is a functional group having at least one positive charge (+) at the terminal, straight chain or side chain of a substituted or unsubstituted C ₁ -C ₁₇ hydrocarbon compound which may include one or more oxygen, nitrogen or sulfur atoms. Represent; L 3 (-) is a functional group having at least one negative charge (-) at the terminal, straight or side chain of a substituted or unsubstituted C ₁ -C ₁₇ hydrocarbon compound which may include one or more oxygen, nitrogen or sulfur atoms. Indicates. The cosmetic composition according to claim 8, wherein the organic particulate support or inorganic particulate support to which the zeolite is bonded is one of the following supports: (a) a substance having a hydroxy group on its surface as an oxide containing only one or two or more metal and nonmetal elements; (b) a metal bonded to a thiol group (-SH) or an amine group (-NH ₂ ); (c) an organic polymer having a functional group on its surface; (d) semiconductor compounds; (e) zeolite or its pseudomolecules; And (f) Natural polymer which has a hydroxyl group on the surface. The cosmetic composition according to claim 1, wherein the zeolite is one of the following zeolites: (a) natural and synthetic zeolites; (b) zeolites and similar materials having an MFI structure; (c) zeolites and similar materials having a MEL structure; (d) zeolite A, X, Y, L, beta, mordenite or ferrierite; (e) mesoporous silica; (f) a pseudomolecular body comprising zeolite and mesoporous silica produced through hydrothermal synthesis; (g) organic-inorganic composite mesoporous structures and layered materials; And (h) Nanoporous materials called organic zeolites, organometallic zeolites, or coordination compound zeolites in which metal ions and ligands combine three-dimensionally to form regular nanopores. The cosmetic composition of claim 1, wherein the zeolite has a particle size of 10 nm-50 µm. The cosmetic composition according to claim 8, wherein the organic particulate support or the inorganic particulate support has a particle size of 100 nm-100 μm.