JPH092816A - Modified clay mineral and cosmetic containing the same - Google Patents

Abstract

PURPOSE: To obtain both an organic modified clay mineral, excellent in gelation ability and capable of imparting high thickening properties and thixotropic properties and a cosmetic, containing the organic modified clay mineral and excellent in preservation stability and usability. CONSTITUTION: This modified clay mineral is obtained by carrying out the cation exchange of a cation present between layers of a smectitic type clay mineral with a cationic surfactant containing a quaternary cationic nitrogen and has a hydrophilic-treated crystal end face thereof. The hydrophilic treatment of the crystal end face is preferably carried out with a hydrophilic agent having a polyoxyethylene chain, especially a silylating agent having the polyoxyethylene chain. The modified clay mineral is suitable for blending thereof in a cosmetic.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel modified clay mineral obtained by modifying a smectite type clay mineral and a cosmetic containing the same.

[0002]

2. Description of the Related Art Conventionally, Ca existing between layers of smectite type clay minerals, for example, montmorillonite clay minerals.
An organically modified clay mineral produced by utilizing the cation exchange ability of exchangeable cations such as ⁺⁺ , K ⁺ , Na ⁺ , and Mg ⁺⁺ and exchanging exchangeable cations existing between the layers with a cationic surfactant. Is used as an oil-based gelling agent.
The cationic surfactant for cation exchange is an ammonium type surfactant mainly containing quaternized nitrogen in its structure, and dimethyl distearyl ammonium chloride, dimethyl stearyl benzyl ammonium chloride and the like are frequently used.

In recent years, when an organically modified clay mineral is used as an oil-based gelling agent, the gelling ability and gel stability are improved by modifying it with a cationic surfactant suitable for the properties of the oil to be gelled. There are many attempts to improve the properties of the gel, for example, a technique of using an organically modified clay mineral modified with an ammonium salt modified organopolysiloxane as a gelling agent to gelate a silicone oil that is difficult to gel. It has been proposed (Japanese Patent Laid-Open No. 63-72779).

[0004]

However, when an organically modified clay mineral is blended as a gelling agent in a cosmetic composition, a large amount of the organically modified clay mineral is used because the conventional organically modified clay mineral has low thickening and gelling ability. It was necessary to blend in. When these are excessively blended, solidification due to thickening and drainage due to contraction of the gel occur, which may significantly impair usability. On the other hand, if the blending amount is reduced to improve the usability, the gelling ability is not sufficient, and problems such as separation of the system with time and precipitation of the pigment may occur.

Further, the conventional industrially established method for producing an organically modified clay mineral by cation exchange in water has a limit in improving the gelling ability of an oil agent for the following reason. That is, in order to improve the gelling ability of the oil agent, it is necessary to modify the clay mineral with a cationic surfactant having a large proportion of lipophilic moieties, but in the conventional method for producing an organically modified clay mineral, cation exchange is performed in water. Therefore, even if an attempt is made to modify with a cationic surfactant having a high proportion of lipophilic moieties, the solubility of the cationic surfactant itself in water is low, and therefore sufficient cation exchange between layers can be performed. Absent. This problem is particularly remarkable when cation exchange between layers is performed with a silicone-based cationic surfactant. That is, a cationic surfactant having a short polysiloxane chain is soluble in water and capable of sufficient cation exchange, but if the polysiloxane chain is lengthened for the purpose of improving gelation ability, the water solubility decreases, Cation exchange of cations between layers is not sufficiently performed. Although there are reports of cation exchange between solids in the absence of solvent,
It has not been applied in actual production because it cannot remove the by-product salt. Therefore, the conventional modification method using only cation exchange between layers of clay minerals has a limitation in gelling ability of the oil agent.

An object of the present invention is to provide a novel organically modified clay mineral having a higher gelling ability for oil agents. Another object is to improve the gelling ability of the organically modified clay mineral obtained by the conventional industrially established modification method by cation exchange in water.

[0007]

In view of the above situation, the present inventors have conducted diligent research on organically modified clay minerals produced by cation exchange of cations existing between layers with a cationic surfactant, and as a result, Cation exchange of the cations between the layers of smectite-type clay minerals with a cationic surfactant containing quaternary cationic nitrogen, and hydrophilization of the crystal end faces of the cation-exchanged organically modified clay minerals results in the conventional high water-soluble cation The organically modified clay minerals that have undergone cation exchange between layers with a water-soluble surfactant also have high structural viscosity,
The inventors have found that an excellent gelling agent having thixotropy can be obtained, and that cosmetics containing it have good temperature stability and excellent usability, and have completed the present invention.

That is, according to the present invention, the cations existing between the layers of the smectite type clay mineral are cation-exchanged with a cationic surfactant containing a quaternary cationic nitrogen, and the crystal end faces thereof are hydrophilized. A modified clay mineral characterized by the above and a cosmetic containing the same.

The details will be described below. Examples of the smectite-type clay mineral used in the present invention include natural or synthetic clay minerals such as montmorillonite, beidellite, nontronite, saponite, and hectorite. As the raw material of the modified clay mineral of the present invention, one kind or two or more kinds of these smectite type clay minerals can be appropriately selected and used. The smectite-type clay mineral has a crystal structure of a layered structure, oxygen atoms bonded to silicon exist on the surface of the layer, and exchangeable cations such as Ca ⁺⁺ , K ⁺ , Na ⁺ , and Mg ⁺⁺ are present between the layers. Exist, and hydroxyl groups are present on the crystal end face, that is, the side face of the layer structure.

In the modified clay mineral of the present invention, the cations existing between the layers of the smectite type clay mineral are cation-exchanged with a cationic surfactant containing a quaternary cationic nitrogen, and the crystal end face of the smectite type clay mineral is It is essential that the modified cations are hydrophilized.This modified clay mineral is an organically modified clay in which the cations existing between the layers of smectite-type clay minerals are cation-exchanged with a cationic surfactant containing quaternary cationic nitrogen. The mineral may be hydrophilized, or the cation existing between the layers of the hydrophilized smectite clay mineral may be cation-exchanged with a cationic surfactant containing a quaternary cationic nitrogen. In the present invention, the modifying agent used for the cation exchange of the cation between the layers of the smectite-type clay mineral,
An ionic surfactant containing a quaternary cationic nitrogen, which has at least one ammonium salt in one molecule, and examples thereof include compounds represented by the following general formulas (1) and (2).

[0011]

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[Wherein R ¹ is an alkyl group having 10 to 22 carbon atoms or a benzyl group, R ² is an alkyl group having 1 to 22 carbon atoms, R ³ is the same or different, an alkyl group having 1 to 3 carbon atoms or a hydroxy group. The alkyl group, X is a halogen atom or a methylsulfate residue. ]

[0013]

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[In the formula, R ⁴ is an alkyl group having 1 to 12 carbon atoms, a phenyl group or a fluorine-substituted alkyl group, and R ⁵ is [C _a
H _2a (OCH ₂ CH (OH) CH ₂ ) _b N (R ⁷ ) ₃ ] ⁺ X
~ Or [C _a H _2a O (C ₂ H ₄ O) _p (C ₃ H ₆ O) _q CH ₂ C
H (OH) CH ₂ N (R ⁷ ) ₃ ] ⁺ X ~, R ⁶ is R ⁴ or R ⁵
And n is 0, at least one of R ⁶ is R ⁵ . R ⁷ has the same or different carbon number 1 to 1
An alkyl group of 0, a phenyl group, a benzyl group or a hydroxyethyl group, X is a halogen atom, a is an integer of 2 to 5, b
Is 0 or 1, m is an integer of 0 to 200, n is an integer of 0 to 10, p is an integer of 2 to 200, q is an integer of 0 to 200, p
+ Q is an integer of 3 to 200, and p / q is 1 or more. ]

Examples of the compound represented by the general formula (1) include dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetyldimethylethylammonium chloride, stearyldimethylethylammonium chloride, myristyl. Diethylmethylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzylmethylethylstearylammonium chloride, stearyldimethylhydroxypropylammonium chloride, benzylbehenyldihydroxyethylammonium chloride and corresponding bromide salt, methyl Rufeto salts and the like. Further, as the one represented by the general formula (2), for example,

[0016]

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[Chemical 6]

And the like. The clay mineral in which the cations present between the layers of the smectite-type clay mineral in the present invention are cation-exchanged with a cationic surfactant containing a quaternary cationic nitrogen, that is, an organically modified clay mineral, is a smectite-type clay mineral obtained by modifying the above-mentioned modification. It can be obtained by treating the agent with an ionic surfactant containing a quaternary cationic nitrogen by a conventional method. For example, it can be obtained by dispersing a smectite type clay mineral in water, adding an aqueous solution of a modifier to the dispersion under stirring, removing water by filtering, drying, and pulverizing.

In the present invention, a commercially available organic modified clay mineral may be used as the cation-exchanged organic modified clay mineral. Examples of commercially available organically modified clay minerals include, for example, Sven, Organite (manufactured by Toyonyo Corp., trade name), Clayton (Southern Clay Co., trade name), Benton (NL Industry Co., Ltd.,
Trademark name) and the like.

The hydrophilization of the present invention is carried out by utilizing the hydroxyl groups present on the crystal end faces of the smectite type clay mineral as reaction sites. Smectite-type clay mineral, since there is a hydroxyl group on the crystal end face, originally has a hydrophilic bond between the crystal end faces, but the present invention further hydrophilizes this crystal end face,
It further strengthens the hydrophilic bond between the crystal end faces of the smectite type clay mineral, and thereby imparts a gelling ability which is superior to that of the conventional modified clay mineral, that is, high thickening property and thixotropic property.

The hydrophilization treatment of the crystal end face is performed by attaching a hydrophilic compound to the crystal end face. By introducing a hydrophilic organic group into the crystal end face, the hydrophilic treatment of the present invention is performed. A polyoxyethylene chain is preferred as the hydrophilic organic group. In introducing the hydrophilic organic group, a method of reacting a glycidyl compound having a polyoxyethylene chain under an appropriate catalyst or after treating a crystal end face with an intermediate such as a silane coupling agent, an organic compound having a hydrophilic group is introduced. A method of treating with a compound may be adopted. Specifically, for example, a method of reacting a water-soluble compound having a hydroxyl group or an amino group in the presence of a catalyst such as boron trifluoride after introducing an epoxide group on a crystal end surface with an epoxide group-containing silane coupling agent, a radical Method of introducing a radical polymerizable group to a crystal end face with a polymerizable group-containing silane coupling agent and then polymerizing an ionic and / or nonionic water-soluble radical monomer to introduce a hydrophilic chain, silane having an amino group A method of introducing a polyoxyethylene chain by adding ethylene oxide after introducing an amino group on the crystal end face with a coupling agent, similarly reacting a glycidyl compound having a polyoxyethylene chain under a suitable catalyst Examples of the method include introducing an oxyethylene chain, but the present invention is not limited thereto.

In the present invention, a more preferable hydrophilic treatment is a method using a silylating agent having a polyoxyethylene chain. A preferable silylating agent is represented by the following general formula (3). _{^{(R 8 O) e R 9}} f SiR 10 O (C 2 H 4 O) r (C 3 H 6 O) t R 11 (3) [ wherein, R ⁸ is an alkyl group having 1 to 10 carbon atoms, R ⁹ is an alkyl group having 1 to 10 carbon atoms or a phenyl group, R ¹⁰ is a divalent hydrocarbon group having 2 to 5 carbon atoms, R ¹¹ is hydrogen or 1 to 1 carbon atoms
An alkyl group of 0, e is an integer of 1 to 3, f is an integer of 0 to 2, and e + f is 3. r is an integer of 2 to 200, t
Is an integer of 0 to 200, and r + t is an integer of 3 to 200. Moreover, r / t is 1 or more. ]

As a concrete example, for example, (CH ₃ O) ₃
SiC ₃ H ₆ O (C ₂ H ₄ O) ₁₀ H, (CH ₃ O) ₃ SiC ₃ H ₆ O
(C ₂ H ₄ O) ₁₀ CH ₃ , (CH ₃ CH ₂ O) ₃ SiC ₃ H ₆ O (C ₂
H ₄ O) ₂₀ (C ₃ H ₆ O) ₁₀ CH ₃ , (CH ₃ O) ₃ SiC ₃ H ₆ O
_{(C 2 H 4 O) 30} C 2 H 5, (CH 3) (CH 3 O) 2 SiC 3 H 6 O
_{(C 2 H 4 O) 5} C 3 H 7, (CH 3 O) 3 SiC 4 H 8 O (C 2 H
₄ O) ₁₀ C ₄ H ₉ , (C ₄ H ₉ O) (CH ₃ ) ₂ SiC ₅ H ₁₀ O (C ₂
H ₄ O) ₂₀ CH _{3 and the} like.

The method of hydrophilizing the crystal end face of the smectite-type clay mineral by using the above-mentioned silylating agent having a polyoxyethylene chain is a method in which the smectite-type clay mineral is dispersed in water or alcohol or a mixture thereof. A silylating agent is added to this dispersion liquid by adding a silylating agent dissolved in water or alcohol or a mixture thereof, stirring treatment or ball milling treatment to remove water, drying and crushing, smectite type clay minerals. A conventionally known method such as a dry method of spraying and drying can be adopted. The amount of the hydrophilic treatment agent for the smectite-type clay mineral varies depending on the type of the hydrophilic treatment agent used and the hydrophilic treatment method,
Although not particularly limited, it is preferably 0.1 to 10 of clay minerals.
It is 20% by weight (hereinafter, simply indicated by "%"), and more preferably 0.3 to 10%. The method for producing the modified clay mineral of the present invention may be either a method of hydrophilizing a cation-exchanged organic modified clay mineral or a method of hydrophilizing a smectite-type clay mineral and then organically modifying it. Absent.

When the modified clay mineral obtained as described above is blended in a cosmetic composition, its blending amount is not particularly limited, but preferably 0.1 to 15% by weight, more preferably 0.1.
2 to 10% by weight. As cosmetics, foundation, eye shadow, lipstick, mascara, eyeliner,
Examples include nail enamel, lotion, emulsion, cream, pack and the like. In the cosmetics of the present invention, other components commonly used in ordinary cosmetics, for example, oils, surfactants, film-forming agents, humectants, water-soluble polymers, powders, pigments, dyes, preservatives. , Fragrances and the like can be appropriately added within a range that does not impair the effects of the present invention.

[0025]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Production Example 1 30 g of dimethyl distearyl ammonium modified montmorillonite (Esben 74: trade name, manufactured by Toyojun Yoko) was dispersed in 100 g of methanol to obtain a uniform slurry. An aqueous solution of a silylating agent having a polyoxyethylene chain having the structure shown below (1.2 g of silylating agent, 10 g of water) was added to this slurry, and the mixture was stirred with a ball mill for 10 minutes. The treated slurry was dried under reduced pressure, heat-treated at 100 ° C. for 20 minutes, pulverized, washed with ethanol, and then dried to obtain a modified clay mineral whose crystal end faces were hydrophilized. _{(CH 3 O) 3 SiCH 2} CH 2 CH 2 O (C 2 H 4 O) u (C 3 H 6
O) _w CH ₃ [wherein u / w = 2.5 to 3.5, u + w = 25 to 35]
It is. ]

Production Example 2 40 g of dimethylbenzylstearyl ammonium-modified hectorite (Benton 27: trade name, manufactured by NL Industry Co., Ltd.) was dispersed in 80 g of methanol to obtain a uniform slurry. To this slurry, an aqueous solution of a silylating agent having a polyoxyethylene chain having the structure shown below (1.6 g of silylating agent, 10 g of water) was added, and pulverized in a mortar for 30 minutes. After drying and heat treating at 100 ° C. for 20 minutes,
The powder was re-ground, washed with methanol, and dried to obtain a modified clay mineral whose crystal end faces were hydrophilized. _{(CH 3 O) 3 SiCH 2} CH 2 CH 2 O (C 2 H 4 O) k CH 3 [ where a k = 30 to 34. ]

Production Example 3 40 g of a smectite type clay mineral (Bengel A: trade name, manufactured by Toyojun Yoko) was dispersed in 1460 g of water, and a 4% aqueous solution of dodecyltrimethylammonium chloride 1
000 g was gradually added with stirring. Next, water was removed by filtration, followed by drying and pulverization to obtain dodecyltrimethylammonium chloride modified clay mineral. This clay mineral 30
g was dispersed in 110 g of methanol, and an aqueous solution of a silylating agent having a polyoxyethylene chain having the same structure as in Production Example 2 (3 g of silylating agent, 10 g of water) was added to this slurry,
The mixture was stirred for 10 minutes with a ball mill. This was dried under reduced pressure, heat-treated at 100 ° C. for 20 minutes, pulverized, washed with methanol, and then dried to obtain a modified clay mineral whose crystal end faces were hydrophilized.

Production Example 4 30 g of smectite type clay mineral (Bengel A: trade name, manufactured by Toyojun Yoko) was dispersed in 1470 g of water, and 30 g of organopolysiloxane having the structure shown below was added to 670 of water.
g, dissolved in 300 g of ethanol were gradually added with stirring. Next, water was removed by filtration, followed by drying and pulverization to obtain a silicone-modified clay mineral. 20g of this clay mineral
Was dispersed in 60 g of methanol, and the aqueous solution of the silylating agent having a polyoxyethylene chain used in Production Example 2 (2 g of silylating agent, 10 g of water) was added to obtain a uniform slurry. The slurry was crushed in a mortar for 30 minutes, dried, and then heat-treated at 100 ° C. for 20 minutes. Then, it was re-ground, washed with ethanol, and dried to obtain a modified clay mineral whose crystal end faces were hydrophilized.

[0029]

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Production Comparative Example 1 30 g of dimethyl distearyl ammonium-modified montmorillonite (Esben 74: trade name, manufactured by Toyojun Yoko) was dispersed in 100 g of methanol to obtain a uniform slurry. This slurry was stirred for 10 minutes with a ball mill. The treated slurry was dried under reduced pressure, heat-treated at 100 ° C. for 20 minutes, and then pulverized to obtain Production Comparative Example 1.

Example 1 and Comparative Example 1 A gel composition having the following composition was prepared. The modified clay mineral produced in Production Example 1 was used in Example 1, and the modified clay mineral produced in Production Comparative Example 1 was used in Comparative Example 1. Their temporal stability and viscosity were evaluated. (Component) Example 1 Comparative Example 1 1. Decamethylcyclopentasiloxane 54 (wt%) 54 (wt%) 1. Polyether-modified silicone 3 3 3. Modified Clay Mineral (Production Example 1) 3-4. Modified Clay Mineral (Comparative Production Example 1) -3 5. Purified water 40 40 (Preparation method) Components 1 to 4 were uniformly mixed and dispersed with a Dispers mill, and then component 5 was added while mixing to obtain a gel composition.

1. Stability with time The obtained gel composition was set in a constant temperature bath at 0 ° C, 30 ° C, and 40 ° C, and the state after 1 month was visually observed. 2. Viscosity After preparation of the gel composition, the gel composition was set in a constant temperature bath at 30 ° C., and the viscosity of the next day was measured by a vibrating viscometer CJV5000 (manufactured by Chichibu Cement Co.).

The results are shown below. Example 1 Comparative Example 1 Stability over time 0 ° C. ΔΔ 30 ° C. ○ × 40 ° C. ○ × Viscosity (mPas) 398 91 As is clear from the above results, the modified clay mineral according to the present invention exhibits excellent gel stability. It also had a good thickening property.

Example 2 Manicure (component) (wt%) 1. Nitrified cotton 20.0 2. Butyl acetate remaining 3. Ethyl acetate 10.0 4. Isopropyl alcohol 8.0 5. Alkyd resin 7.0 6. Acetyltributyl citrate 5.0 7. Benzoic acid sucrose ester 8.0 8. Suitable amount of pigment 9. Modified clay mineral (Production Example 2) 6.0 (Production method) Component 1 was added to Components 2 to 4 and dissolved, and Components 5 to 9 were further added and uniformly mixed to obtain a nail polish.
Example 2 had good stability, had smooth elongation, and was excellent in usability.

Example 3 Hand Cream (Component) (wt%) 1. Acrylic-silicone graft copolymer 6.0 (KP-504, manufactured by Shin-Etsu Chemical Co., Ltd.) 2. Polyether-modified silicone 3.0 3. Ethanol 10.0 4. Dimethyl polysiloxane 40.0 5. Modified clay mineral (Production Example 3) 3.0 6. Preservative proper amount 7. Purified water Remaining amount (Production method) While mixing and dispersing Components 1 to 5, Component 6 to
7 was added to obtain a hand cream. Example 3 had good stability, had smooth elongation, and was excellent in usability.

Example 4 Eyeliner (Component) (wt%) 1. Acrylic-silicone graft copolymer 8.0 (Shin-Etsu Chemical Co., Ltd .: KP-504) 2. Trimethylsiloxysilicic acid 4.0 3. Decamethylcyclopentasiloxane 40.0 4. Polyether-modified silicone 4.0 5. Modified clay mineral (Production Example 1) 2.0 6. Appropriate amount of pigment 7. Preservative appropriate amount 8. Purified water Remaining amount (Production method) While mixing and dispersing components 1 to 6, component 7 to
8 was added to obtain an eyeliner. Example 4 had good stability, had smooth elongation, and was excellent in usability.

Example 5 Oily foundation (component) (% by weight) Carnauba Blow 3.0 2. Paraffin wax 2.0 3. Microcrystalline wax 2.0 4. Dextrin fatty acid ester 2.0 5.2 Cetyl 2-ethylhexanoate residual amount 6. Dimethyl polysiloxane 13.0 7. Glyceryl tri-2-ethylhexanoate 4.0 8. Squalane 5.0 9. Suitable amount of pigment 10. Modified Clay Mineral (Production Example 3) 8.0 (Production Method) Components 1 to 10 were dissolved under heating and mixed and dispersed with a three-roll to obtain an oily foundation. Example 5
Had good stability, had smooth elongation, and was excellent in usability.

Example 6 Mascara (component) (wt%) 1. Carnauba wax 5.0 2. Microcrystalline wax 4.0 3. Rosinic acid Penteeri slit 10.0 4. Dextrin fatty acid ester 5.0 5. Modified clay mineral (Production Example 3) 2.0 6. Propylene carbonate 0.6 7. Silicic anhydride 1.0 8. Suitable amount of pigment 9. Light liquid paraffin Remaining amount (manufacturing method) Components 1 to 9 were dissolved by heating and mixed and dispersed with a three-roll to obtain a mascara. Example 6 had good stability, had smooth elongation, and was excellent in usability.

Example 7 Sun-Cut Agent (Component) (wt%) 1. Fine particle titanium oxide 8.0 2. Acrylic-silicone type graft copolymer 4.0 (KP-504, manufactured by Shin-Etsu Chemical Co., Ltd.) 3. Decamethylcyclopentasiloxane remaining amount 4. Modified clay mineral (Production Example 4) 5.0 5. Polyether modified silicone 2.0 6. Ethanol 15.0 7. Ultraviolet absorbent Proper amount (manufacturing method) Components 1 to 7 were uniformly mixed and dispersed to obtain a suncut agent. Example 7 had good stability, smooth elongation, and excellent feeling in use.

[0040]

INDUSTRIAL APPLICABILITY The modified clay mineral of the present invention has an excellent gelling ability with respect to an oil agent, and can impart high viscosity and thixotropy. The cosmetic containing the modified clay mineral of the present invention has excellent storage stability and usability. For example, when the modified clay mineral of the present invention is blended with a water-in-oil emulsion, the outer oil phase gels (has a network-like structure), so that it has a high viscosity when standing, and the inner water phase coalesces. And creaming are prevented, and temperature stability and temporal stability are improved. In addition, when an external force is applied to the skin at the time of use, the network structure of the gel is broken and the viscosity is lowered, so that there is an effect that it has good elongation and is easy to apply. It should be noted that this network structure is restored by leaving it stationary.

[Procedure amendment]

[Submission date] February 22, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction contents]

[0002]

2. Description of the Related Art Conventionally, Ca existing between layers of smectite type clay minerals, for example, montmorillonite clay minerals.
An organically modified clay mineral produced by utilizing the cation exchange ability of exchangeable cations such as ²⁺ , K ⁺ , Na ⁺ , Mg2 ^+, etc., and exchanging exchangeable cations existing between the layers with a cationic surfactant. Is used as an oil-based gelling agent.
The cationic surfactant for cation exchange is an ammonium type surfactant mainly containing quaternized nitrogen in its structure, and dimethyl distearyl ammonium chloride, dimethyl stearyl benzyl ammonium chloride and the like are frequently used.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

The details will be described below. Examples of the smectite-type clay mineral used in the present invention include natural or synthetic clay minerals such as montmorillonite, beidellite, nontronite, saponite, and hectorite. As the raw material of the modified clay mineral of the present invention, one kind or two or more kinds of these smectite type clay minerals can be appropriately selected and used. The smectite-type clay mineral has a layered structure in its crystal structure, has oxygen atoms bonded to silicon on the surface of the layer, and exchangeable cations such as Ca ²⁺ , K ⁺ , Na ⁺ , and Mg ²⁺ between the layers. Exist, and hydroxyl groups are present on the crystal end face, that is, the side face of the layer structure.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction contents]

[0016]

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[Chemical 6]

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction contents]

[0029]

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[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction contents]

Example 1 and Comparative Example 1 A gel composition having the following composition was prepared. The modified clay mineral produced in Production Example 1 was used in Example 1, and the modified clay mineral produced in Production Comparative Example 1 was used in Comparative Example 1. Their temporal stability and viscosity were evaluated. (Component) Example 1 Comparative Example 1 1. Decamethylcyclopentasiloxane 54 (wt%) 54 (wt%) 1. Polyether-modified silicone 3 3 3. Modified Clay Mineral (Production Example 1) 3-4. Modified Clay Mineral ( Production Comparative Example 1) -3 5. Purified water 40 40 (Preparation method) Components 1 to 4 were uniformly mixed and dispersed with a Dispers mill, and then component 5 was added while mixing to obtain a gel composition.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction contents]

Example 6 Mascara (component) (wt%) 1. Carnauba wax 5.0 2. Microcrystalline wax 4.0 3. Rosinic acid pentaerythrit 10.0 4. Dextrin fatty acid ester 5.0 5. Modified clay mineral (Production Example 3) 2.0 6. Propylene carbonate 0.6 7. Silicic anhydride 1.0 8. Suitable amount of pigment 9. Light liquid paraffin Remaining amount (manufacturing method) Components 1 to 9 were dissolved by heating and mixed and dispersed with a three-roll to obtain a mascara. Example 6 had good stability, had smooth elongation, and was excellent in usability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsuyoshi Yakuda 48-18 Sakaemachi, Kita-ku, Tokyo Inside Kose Research Institute (72) Inventor Koji Sakuta 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Shin-Etsu Gaku Kogyo Co., Ltd. Silicon Electronic Materials Research Laboratory (72) Inventor Shoji Ichinohe 1-10 Hitomi Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicon Electronic Materials Research Laboratory (72) Inventor Ogata Masanobu 143-1 Hara, Annaka-shi, Gunma Toyonjun Mining Co., Ltd.

Claims (4)

[Claims] 1. A cation existing between layers of a smectite-type clay mineral is cation-exchanged with a cationic surfactant containing a quaternary cationic nitrogen, and its crystal end face is subjected to a hydrophilic treatment. Modified clay mineral to be used. 2. The modified clay mineral according to claim 1, wherein the crystal end face is hydrophilized by a hydrophilizing agent having a polyoxyethylene chain. 3. The modified clay mineral according to claim 1, wherein the crystal end surface is hydrophilized with a silylating agent having a polyoxyethylene chain. 4. A cosmetic comprising the modified clay mineral according to claim 1, 2 or 3.