JPH09151114A - Clathrate crosslinked compound and composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic excellent in messy makeup preventive effect and makeup sustainability. SOLUTION: This clathrate crosslinked compound is obtained by clathrate crosslinking an olefinimine such as ethyleneimine with a metal phosphate lamellar structure 5-70Å in interlamellar spacing (where, the metal is at least one kind of metal selected from the groups IVa and IVb, lanthanoid series and actinoid series, such as titanium, zirconium, cerium or tin). The objective cosmetic such as a messy makeup preventive cosmetic is obtained by formulating a cosmetic base with 0.1-50wt.%, based on the whole cosmetic, of this compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cosmetic composition suitable for cosmetics.
It is a compound obtained by inclusion-crosslinking an olefinimine with a layered structure of a metal phosphate containing at least one metal selected from the group consisting of Va, IVb, lanthanoid series and actinoid series metals.

[0002]

2. Description of the Related Art In cosmetics, prevention of makeup breakdown is a very important factor. Even if the makeup is made cleanly, the makeup will be destroyed over time, and the makeup will be ruined. Therefore, women often had to carry cosmetics for makeup correction. From such a viewpoint, many of such cosmetics for remake-up have a dosage form in which portability is prioritized. Therefore, there is a difference between the original makeup and the makeup after make-up due to the difference in dosage form. Occasionally, there was a problem.

Reflecting such a situation, various cosmetics having a long lasting makeup and cosmetics for preventing makeup collapse have been developed. For example, for the purpose of preventing makeup collapse, cosmetics for finishing such as foundation, white powder, etc. A volatile silicone oil (Unexamined Japanese Patent Publication No. 62-298512, Japanese Unexamined Patent Publication No.
6-72824), melamine cyanurate (Japanese Patent Publication No. 63-
12442), a fluorinated oil agent (Japanese Patent Laid-Open No. 06-6502).
8) Water-repellent oil agents such as 8) and anhydrous fine particle silica (Japanese Patent Laid-Open No.
1-204112), hydroquinone glycosides (JP-A-6-206
1-207309), a fluorine compound-treated powder (Japanese Patent Laid-Open No.
Water-repellent and / or oil-repellent powders such as 6-321725 and JP-A-03-246210, or apatite composite particles (JP-A-06-321748), and porous spherical magnesium carbonate (JP-A-63-159306). There is an example in which an absorbing powder is blended.

However, although these methods have dramatically improved the makeup lasting, they do not eliminate the makeup repairing operation, and the number of operations 5 or 6 times a day is reduced to about 2 or 3 times at most. It was only possible.

On the other hand, a compound obtained by inclusion-crosslinking an olefinimine with a layered structure of a metal phosphate containing a group IVa group, a group IVb group, a lanthanoid series metal, or an actinoid series metal has not been known so far. However, it has not been known that such a compound also has an effect of preventing makeup loss. As an approximate compound, a compound obtained by inclusion-crosslinking ethylene oxide with a zirconium phosphate is known, but this compound has no known effect of preventing makeup deterioration.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of such a situation, and is a cosmetic raw material having an action of preventing makeup loss, and a cosmetic having excellent makeup retention and being resistant to makeup loss. The challenge is to provide.

[0007]

In view of such circumstances, the inventors of the present invention have conducted diligent research for a substance having an effect of preventing makeup disintegration, and as a result, have identified olefinimine with a specific layered metal phosphate. We found such a property in a compound formed by inclusion cladding and completed the invention.

That is, the compounds of the present invention are group IVa,
It is a clathrate cross-linking compound obtained by clathrating and cross-linking an olefinimine with a layered structure of a metal phosphate containing at least one metal selected from Group IVb, lanthanoid series and actinoid series metals.

The clathrate-crosslinking compound of the present invention has an excellent effect of preventing makeup loss and can be used by being blended in cosmetics. The cosmetic of the present invention contains the above-mentioned clathrate-crosslinking compound, and is a cosmetic that has excellent makeup retention and does not easily lose makeup.

[0010]

Embodiments of the present invention will be described below in detail.

(1) Inclusion cross-linking compound of the present invention The compound of the present invention is a layered structure of a metal phosphate containing at least one metal selected from the group consisting of IVa group, IVb group, lanthanoid series and actinoid series metals. It is an inclusion-crosslinking compound obtained by inclusion-crosslinking an olefinimine in the body. The inclusion cross-linking compound of the present invention is a compound in which molecules of olefinimine are inserted (intercalated) in the crystal lattice of the layered structure at an arbitrary composition ratio, and at least a part of the olefinimine is the metal Cleavage by reaction with phosphate, forming a P-O-C bond to form a phosphate ester,
A crosslinked structure is formed between the metal phosphate and the olefinimine.

The clathrate compound of the present invention has at least such a cross-linking structure, but in addition, olefin imines may react with each other to form a bond in the clathrate cross-linking compound. The cleaved primary ammonium salt of olefinimine may form an ionic bond with PO ₄ ⁻ . Therefore, the inclusion cross-linking compound of the present invention,
It may be substantially a mixture of these reaction products.

Examples of the IVa group metal include titanium, zirconium, hafnium, lanthanum and actinium. Examples of the group IVb metal include tin and the like. Examples of the lanthanoid series metal include lanthanum and cerium. Of these, preferred are titanium, zirconium, cerium or tin, and most preferred is zirconium.

Examples of metal phosphates containing these metals include zirconium phosphate, titanium phosphate, tin phosphate,
Examples include cerium phosphate. Of these, used in the present invention is a layered metal phosphate crystal structure,
The crystal structure may be any structure, but is preferably α type, β type, or γ type. The layer spacing is preferably about 5 to 70Å.

The olefin imine has 2 to 6 carbon atoms.
The degree of olefin imine is preferable, and for example, ethylene imine, propylene imine, butene imine and the like can be illustrated. Of these, ethyleneimine is most preferable in terms of reactivity, availability, and economy. All of these olefin imines are known compounds, and their production methods are already known. That is, α-amino-β-
Desulfate cyclization of sulfoolefin using alkali,
It can be an olefin imine.

The inclusion cross-linking compound of the present invention can be easily obtained by mixing the olefinimine thus obtained with the metal phosphate under heating and reacting them. The reaction temperature is preferably about 10 to 200 ° C, more preferably 30 to 100 ° C. Reaction time is 5 to 1
It is preferably about 00 hours.

The formation of the inclusion cross-linking compound of the present invention can be known by monitoring the chemical shifts of phosphorus and nitrogen by solid-state NMR.
In the inclusion cross-linking compound of the present invention, the preferable molar ratio of the phosphoric acid group and the olefinimine is phosphoric acid group: olefinimine = 20: 1 to 1: 1 and more preferably 10: 1 to 5: 1. : 1.

(2) Cosmetic of the present invention The cosmetic of the present invention is characterized by containing the above-mentioned inclusion cross-linking compound of the present invention. In this case, the clathrate compound of the present invention may contain only one kind or may contain two or more kinds in combination.

The dosage form of the cosmetic of the present invention can be used without particular limitation as long as it is a dosage form which is usually used in cosmetics, but the most preferred are finish powder and undermake-up. Is. In addition, foundations, basic cosmetics, point makeup cosmetics, etc. are also possible.

The cosmetic composition of the present invention may contain, in addition to the clathrate-crosslinking compound of the present invention, optional components usually used in cosmetic compositions. As an optional component, hydrocarbons such as petrolatum and squalane; esters such as jojoba oil and gayleu; triglycerides such as beef tallow and olive oil; surface active agents such as nonionic surfactants, anionic surfactants and cationic surfactants Agents; polyhydric alcohols such as glycerin, 1,3-butanediol, PEG; preservatives; fatty acids such as stearic acid and oleic acid; antioxidants; ultraviolet absorbers; powders; pigments; hyaluronic acid, carbopol , Water-soluble polymers such as guar gum; and the like.

The content of the clathrate-crosslinking compound of the present invention is preferably 0.1 to 50% by weight, more preferably 1 to 20% by weight, based on the total amount of these cosmetics. The cosmetic of the present invention can be produced according to a usual method for producing cosmetics.

[0022]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

<Example 1: Production example of ethyleneimine> 5
6.4 g of β-aminoethylsulfuric acid was weighed and 176 g of 40% aqueous sodium hydroxide solution was added dropwise while cooling with water.
The reaction was started by heating gradually. When the reaction starts,
The temperature was maintained for 20 minutes so that the reaction product would boil, and the reaction was allowed to proceed. Subsequently, heating was continued and volatile matter was taken out by distillation. The distilled fraction was taken out with 500 ml of ethyl acetate and 3 parts of water.
Liquid-liquid extraction was performed with 00 ml, the organic layer was taken out, and potassium hydroxide pellets were added for dehydration. Distill this, 1
3.1 g of ethyleneimine was obtained.

<Example 2: Preparation example of clathrate compound> 32 g
[Alpha] -type zirconium phosphate (manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.) and 2 g of ethyleneimine produced in Example 1 above were mixed and heated at 50 [deg.] C. for 3 hours to obtain the inclusion cladding compound 1 of the present invention. Manufactured. This product showed a P--O-- between the metal phosphate and the olefinimine by solid-state NMR changes in chemical shifts of phosphorus and nitrogen, and X-ray analysis.
It was confirmed that a C bond was formed.

<Example 3: Preparation example of clathrate compound> 32 g
[Alpha] -type zirconium phosphate (manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.) and 1 g of ethyleneimine produced in Example 1 above were mixed and heated at 50 [deg.] C. for 3 hours to obtain the inclusion cladding compound 2 of the present invention. Manufactured. This product showed a P--O-- between the metal phosphate and the olefinimine by solid-state NMR changes in chemical shifts of phosphorus and nitrogen, and X-ray analysis.
It was confirmed that a C bond was formed.

<Example 4: Production example of clathrate compound> 32 g
Γ-type zirconium phosphate (manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.) and 1 g of the ethyleneimine produced in Example 1 above were mixed and heated at 50 ° C. for 3 hours to obtain the inclusion cross-linking compound 3 of the present invention. Manufactured. This product showed a P--O-- between the metal phosphate and the olefinimine by solid-state NMR changes in chemical shifts of phosphorus and nitrogen, and X-ray analysis.
It was confirmed that a C bond was formed.

<Example 5: Production example of clathrate compound> 28 g
Γ-type titanium phosphate (manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.) and 1 g of ethyleneimine produced in Example 1 above were mixed and heated at 50 ° C. for 3 hours to obtain the inclusion clathrate cross-linking compound 4 of the present invention. Manufactured. This product showed solid-state NMR changes in phosphorus and nitrogen chemical shifts and X-ray analysis.
It was confirmed that a P—O—C bond was formed between the metal phosphate and the olefin imine.

<Example 6: Preparation example of cosmetics> A base cosmetics was prepared according to the following formulation. That is, part A was mixed at low speed with a Henschel mixer, and part B was added thereto while mixing at high speed. This product was crushed with a pulverizer equipped with a 1 mm herringbone screen, then filled in a gold plate and pressure-molded to obtain a base cosmetic 1.

(Part A) Iron oxide baked talc: 30 parts by weight Sericite: 30 parts by weight Titanium mica: 20 parts by weight Inclusion cross-linking compound 1:10 parts by weight (Part B) Squalane: 5 parts by weight Dimethylpolysiloxane: 5 Parts by weight

<Example 7: Blending Example of Cosmetics> A finishing cosmetic was prepared according to the following formulation. That is, part A was mixed at low speed with a Henschel mixer, and part B was added thereto while mixing at high speed. This product was crushed with a pulverizer equipped with a 1 mm herringbone screen, then filled in a gold plate and pressure-molded to obtain a finishing cosmetic material 2.

(Part A) Talc: 20 parts by weight Sericite: 30 parts by weight Titanium mica: 10 parts by weight Titanium oxide: 14 parts by weight Yellow iron oxide: 5 parts by weight Red iron oxide: 1 part by weight Inclusion cross-linking compound 2:10 parts by weight Part (B part) Squalane: 1 part by weight Dimethylpolysiloxane: 9 parts by weight

<Example 8: Blending example of cosmetics> A finishing cosmetic was prepared according to the following formulation. That is, part A was mixed at low speed with a Henschel mixer, and part B was added thereto while mixing at high speed. This product was crushed with a pulsarizer equipped with a 1 mm herringbone screen, then filled in a gold plate and pressure-molded to obtain a finishing cosmetic material 3.

(Part A) Talc: 20 parts by weight Sericite: 30 parts by weight Titanium mica: 10 parts by weight Titanium oxide: 14 parts by weight Yellow iron oxide: 5 parts by weight Red iron oxide: 1 part by weight Inclusion cross-linking compound 3:10 parts by weight Part (B part) Squalane: 1 part by weight Dimethylpolysiloxane: 9 parts by weight

<Example 9: Blending example of cosmetics> A finishing cosmetic was prepared according to the following formulation. That is, part A was mixed at low speed with a Henschel mixer, and part B was added thereto while mixing at high speed. This product was crushed with a pulsarizer equipped with a 1 mm herringbone screen, then filled in a gold plate and pressure-molded to obtain a finishing cosmetic material 4.

(Part A) Talc: 24 parts by weight Sericite: 30 parts by weight Titanium mica: 10 parts by weight Titanium oxide: 10 parts by weight Yellow iron oxide: 5 parts by weight Red iron oxide: 1 part by weight Inclusion cross-linking compound 4:10 parts by weight Part (B part) Squalane: 1 part by weight Dimethylpolysiloxane: 9 parts by weight

<Example 10: Makeup holding test> A makeup holding test was carried out on the above-mentioned base cosmetic 1 with the inclusion cross-linking compound 1 of the base cosmetic 1 replaced with titanium oxide (Comparative Example 1) as a control. It was That is, for 10 panelists, one half of the half-face was applied to the base cosmetic material 1 and the other half-face was applied to Comparative Example 1 to form the base, and normal makeup was applied on the makeup, and after 5 hours, the makeup retention was judged. . Table 1 shows the results. Than this,
It can be seen that the base cosmetics of the present invention have excellent makeup retention. The numbers in the figure indicate the number of panelists who made the judgment for each evaluation item.

[0037]

[Table 1]

<Example 11: Makeup holding test> For the finishing cosmetic 2, a makeup holding test was carried out with reference to the finishing cosmetic 2 in which the inclusion cross-linking compound 2 was replaced with titanium oxide (Comparative Example 2). . That is, about 10 panelists, normal makeup was applied, a half face was finished with the makeup 2, the remaining half face was finished with the comparative example 2, and the makeup retention was judged after 5 hours. Table 2 shows the results. From this, it is understood that the finish cosmetic composition of the present invention is excellent in makeup retention.

[0039]

[Table 2]

<Example 12: Makeup holding test> A makeup holding test was carried out on the finish cosmetic composition 3 with reference to the finish cosmetic composition 3 in which the inclusion cross-linking compound 3 was replaced by titanium oxide (Comparative Example 3). . That is, about 10 panelists, normal makeup was applied, a half face was finished with makeup 3, the remaining half face was finished with Comparative Example 3, and the makeup lasting was judged after 5 hours. Table 3 shows the results. From this, it is understood that the finish cosmetic composition of the present invention is excellent in makeup retention.

[0041]

[Table 3]

<Example 13: Makeup holding test> A makeup holding test was carried out on the finish cosmetics 4 with reference to the finish cosmetics 4 in which the inclusion cross-linking compound 4 was replaced by titanium oxide (Comparative Example 4). . That is, about 10 panelists, normal makeup was applied, a half face was finished with makeup 4, and the other half face was finished with Comparative Example 4, and after 5 hours, the makeup retention was judged. Table 4 shows the results. From this, it is understood that the finish cosmetic composition of the present invention is excellent in makeup retention.

[0043]

[Table 4]

[0044]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a cosmetic raw material having an excellent effect of preventing makeup collapse and a cosmetic material having excellent makeup retention and being resistant to collapse.

Claims (7)

[Claims] 1. A clathrate bridge formed by clathrating an olefinimine with a layered structure of a metal phosphate containing at least one metal selected from IVa group, IVb group, lanthanoid series and actinoid series metals. Compound. 2. The clathrate cross-linking compound according to claim 1, wherein the at least one metal selected from the IVa group, the IVb group, the lanthanoid series, and the actinoid series metal is titanium, zirconium, cerium, or tin. 3. The clathrate-crosslinking compound according to claim 1, wherein the olefinimine is ethyleneimine. 4. A metal phosphate layered structure having a layer spacing of 5
The inclusion cross-linking compound according to claim 1, which is a layered crystal of about 70Å. 5. A cosmetic containing the clathrate-crosslinking compound according to any one of claims 1 to 4. 6. The cosmetic according to claim 5, wherein the content of the inclusion cross-linking compound is 0.1 to 50% by weight based on the whole cosmetic. 7. A cosmetic for preventing makeup loss.
Or the cosmetic according to 6.