JPS60163809A - Cosmetic - Google Patents

Abstract

PURPOSE:A cosmetic, obtained by incorporating a hydrophobic powder obtained by reacting an organohydrogenpolysiloxane on the surface of powder in the presence of an acidic substance, and having improved cosmetic durability and moldability. CONSTITUTION:A cosmetic containing hydrophobic powder obtained by reacting an organohydrogenpolysiloxane of the formula (R1 and R2 are H, OH, CH3, C2H5 or phenyl; R3 and R4 are H, OH, alkyl, phenyl, etc.; the total of l, m and n is 5-1,000) on the surface of powder in the presence of an acidic substance, e.g. a fatty acid, lactic acid, sulfuric acid or an inorganic acid solt of an amino acid. Silicic acid, talc, mica, calcium carbonate, etc. are used as the inorganic powder, and polyamide, polyethylene, phenolic resin, celluloid, polysaccharide, protein, etc. are used as the organic powder. 0.1-20wt%, based on the powder, compound of the formula and 0.01-10wt%, based on the powder, acidic substance are used.

Description

[Detailed description of the invention] The present invention relates to cosmetics containing hydrophobic powder.

More specifically, the present invention relates to a cosmetic containing a hydrophobic powder obtained by reacting organohydrogenpolysiloxane on the surface of the powder in the presence of an acidic substance.

There have been many known methods for making hydrophilic inorganic powders hydrophobic, and in particular, it is already well known to utilize the hydrophobic properties of silicone oil.

The present inventors first homogeneously mixed and ground metal hydroxide, which is a catalyst for initiating crosslinking polymerization of reactive silicone oil, into various hydrophilic powders, and then methyl hydroxide having a predetermined amount of reaction activity. We have discovered a method for producing hydrophobic powder by mechanochemically forming hydrogen polysiloxane on the powder surface through cross-linking polymerization without any particular heat treatment. (Tokuko 56-4
3264) The powder obtained by these methods is an excellent hydrophobic powder with strong hydrophobicity that does not discolor and does not contain any silicone or resin lumps, that is, it has approximately the same particle size as the starting raw material particle size. However, in some cases, the reaction of the organohydrogenpolysiloxane on the powder is not sufficient and the reaction progresses over time, resulting in changes in hydrophobicity and poor moldability when made into a solid foundation. Cases were also observed.

As a result of intensive research to improve these drawbacks, the present inventors have discovered that by adding an acidic substance when producing hydrophobic powder by reacting organohydrogenpolysiloxane on the surface of the powder, silicone It has been found that a hydrophobic powder having a high reaction rate and without the above drawbacks can be obtained, and that this method is not limited to mechanochemical reactions and can be applied to various powder processing steps. Then, they discovered that cosmetics containing this hydrophobic powder, especially makeup cosmetics, have better long-wearing properties and moldability than those using conventional hydrophobic powders, leading to the completion of the present invention. Ta.

That is, the present invention is characterized in that organowater is formed on the surface of one or more types of powder selected from inorganic powders and organic powders in the presence of one or more types of acidic substances. It is a cosmetic.

(Left below) The powder used in the present invention includes silicic acid, silicic anhydride, magnesium silicate, talc, kaolin, mica, bentonite,
Bismuth oxychloride, zirconium oxide, magnesium oxide, zinc oxide, titanium dioxide, calcium carbonate, magnesium carbonate, iron oxide, ultramarine, deep blue, acid hyflom, chromium hydroxide, calamine, carbon black, and complex ring inorganic powders of these. body, and polyamide, polyester,
Polyethylene, polypropylene, polystyrene, polyurethane, vinyl resin, urea resin, phenol resin, fluororesin, silicon resin, acrylic acid resin, melamine resin,
Epoxy resin, polycarbonate resin, divinylbenzene, styrene copolymer, copolymer consisting of two or more monomers of the above compounds, celluloid, acetyl cellulose,
Organic powders such as polysaccharides, proteins, hard proteins, CI pigment yellow, CI pigment orange, CI pigment orange, CI pigment blue, CI pigment green, CI pigment brown, etc. Any one or two or more types may be selected and used.

The organohydrogen polysiloxane used in the present invention is selected from one or more compounds represented by the following general formula. Among these, Si! has an active hydrogen group that directly bonds to silicon. (Equivalent (001N NaOH aqueous solution 1
The number of grams of organohydrogenpolysiloxane required to generate 1 mole of hydrogen gas at 00° C. is preferably 550 or less, particularly 30 to 550.

(In the formula, R7 may be the same or different, and represents a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, or a phenyl group,
R2 represents a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, or a phenyl group, and R3 may be the same or different, and represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 22 carbon atoms, a phenyl group, or Alkoxy group or carbon number 1-4
R4 may be the same or different from each other, and R4 may be the same or different, and may be a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 22 carbon atoms, a phenyl group, an alkoxy group having 1 to 22 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
indicates a cyanoalkyl group, and j! , m, , n represent an integer of 5 to 1000 in total. The respective constituent units of β, m, and n may be bonded regularly or irregularly,
A collection of several of each structural unit may be bonded regularly or irregularly. ) SiH equivalent is an important factor that determines the degree of crosslinking polymerization of organohydrogenpolysiloxane; if the 5ill equivalent is small, a hard coating, that is, a polymer with a high degree of crosslinking, and if the 5ill equivalent is large, a viscous coating, that is, a crosslinked polymer is produced. Forms low-grade polymers.

(Leaving space below) JP-A-1999-3809 (4) When the SiH equivalent is less than I, an extremely hard film is formed, and although hydrophobization progresses, it tends to differ from the usage characteristics of the starting powder, and silicone alone It is difficult to prevent resin lumps unless a polymerization intermediate (oligo) is created. When the SiH equivalent exceeds 550, a soft film is formed and hydrophobization is relatively difficult to proceed.

The amount of organohydrogenpolysiloxane added may range from 0.1 to % (wt/wt) based on the starting powder, and is preferably determined based on the specific surface area of the starting powder. Since the powder surface characteristics differ depending on each powder, it cannot be said that it is uniform, but in general, 10 m9 of organohydrogenpolysiloxane per 1 m' is sufficient.

Acidic substances used in the present invention include fatty acids, polybasic acids, % acids, malic acid, tartronic acid, citric acid, isocitric acid, tartaric acid, ascorbic acid, vitamin A acid, aromatic acids, urocanic acid, and pyrrolidone carboxylic acid. , acidic amino acids, neutral amino acids, acylamino acids, Dalcono-δ-
Examples include lactone, sulfuric acid, hydrochloric acid monophosphate, boric acid, inorganic acid salts of amino acids, organic acid salts of amino acids, inorganic acid salts of acylamino acids, organic acid salts of tri-acyl amino acids, metal salts of inorganic acids, etc. , one or more types are selected from these.

Conventionally, alkaline substances and organic acid salts of various metals have been used as reaction accelerators for organohydrogenpolysiloxanes. In particular, hydrophobic powders using metal hydroxides as reaction accelerators do not discolor and have excellent hydrophobicity, as described above, and are close to ideal as powders for cosmetics (Japanese Patent Publication No. 56-43264). . However, there remained room for improvement in terms of the reaction rate of the organohydrogen polysiloxane used. This only problem was also solved by the addition of acidic substances according to the present invention, but the amount of these acidic substances added was 0.01 to 10% (wt/wt) based on the starting powder.
From the viewpoint of hydrophobicity, it may be 0.01 to 5% (w
t/wt, ) is preferred.

Various processes can be adopted for producing the hydrophobic powder. When adding organohydrogenpolysiloxane to the powder, it may be diluted in a solvent, added directly, or sprayed in the form of a gas. These operations may be performed while mixing and stirring, or mixing and stirring may be performed after addition. The mixing and stirring method may be a commonly used method, and no special equipment is required.

Mechanochemical method for mixing and stirring, specifically ball mill,
Hodgersite ball mills, vibrating ball mills, vibrating rod mills, vibrating mills, attritors, bot mills, rod mills, pan mills, crushers, etc. can also be used. The mechanochemical method is a particularly excellent method for mixing powders, acidic substances, and organohydrogenpolysiloxane t-q-.

The order of addition of the raw material powder, acidic substance, and organohydrogenpolysiloxane is not particularly limited. The organohydrogen polysiloxane may be added after mixing the raw material powder and the acidic substance, or a mixture of the acidic substance and the organohydrogen polysiloxane may be added to the raw material powder. Further, an acidic substance may be added to the mixture of raw material powder and organohydrogenpolysiloxane.

(Left below) 15 If the second production method is carried out under heating, the reaction will proceed more quickly.

Reference Example 1 98 parts by weight of mica, 1 part by weight of citric acid, 1 part by weight of methylhydrogen polysiloxane with SiH equivalent of 65, 2 parts by weight of dichloromethane
00 parts by weight of the mixture was heated under reflux at 50° C. with stirring, and then heated and stirred at 100° C. for 2 hours to distill off dichloromethane. The reaction rate of the methylhydrogen polysiloxane at this time was 62%.

Reference Example 2 When treated in exactly the same manner as in Reference Example 1 without adding citric acid, the reaction rate of methylhydrogen polysiloxane was 10%.

Reference Example 3 After mixing and grinding a mixed powder of 50 parts by weight of titanium dioxide and 468 parts by weight of talc with 02 parts by weight of phosphoric acid in a vibrating ball mill (Chuo Kakokiko type, 1°5-#) for 10 minutes, S
: Methylhydrogen polysiloxa with LH equivalent of 145 JP-A Show G
3 parts by weight of O-I G 3809 (5) were added and mixed and ground for 70 minutes in the vibrating ball mill. The reaction rate of the methylhydrogen polysiloxane at this time was 58%.

Reference Example 4 When treated in exactly the same manner as Reference Example 3 except that calcium hydroxide was used instead of phosphoric acid, the reaction rate of methylhydrogen polysiloxane was 19%.

Reference example 5 Titanium dioxide, kaolin, magnesium oxide, silicic acid,
85 parts by weight of a powder mixture of equal amounts of titanium-coated mica, 5 parts by weight of glutamic acid, and 10 parts by weight of methylhydrogen polysiloxane having an SiH equivalent of 550 were mixed and ground in a bot mill for 5 hours. The reaction rate of methylhydrogen polysiloxane at this time is 6
It was 7%.

Reference Example 6 When treated in the same manner as in Reference Example 5 without adding glutamic acid, the reaction rate of methylhydrogen polysiloxane was 12%.

(Left below) 7 Reference Example 7 895 parts by weight of black iron oxide, 5 parts by weight of nylon powder,
05 parts by weight of zinc sulfate and 5 parts by weight of methylhydrogen polysiloxane having an SiH equivalent of 252 were mixed and ground in a bot mill for 5 hours. The reaction rate of the methylhydrogen polysiloxane at this time was 49%.

Reference Example 8 Using aluminum hydroxide instead of zinc sulfate, Reference Example 7
When treated in exactly the same manner as above, the reaction rate of methylhydrogen polysiloxane was 16%.

Reference Example 9 50 parts by weight of red iron oxide, 489 parts by weight of talc, 1 part by weight of lactic acid, and 1 part by weight of ethylhydrogen polysiloxane having an SiH equivalent of 35 were mixed and ground in a bot mill for 5 hours. The reaction rate of the ethyl hydrogen polysiloxane at this time was 42%.

Reference Example 10 When treated in exactly the same manner as Reference Example 9 using magnesium hydroxide instead of lactic acid, the reaction rate of ethylhydrogen polysiloxane was 18%.

8 Reference example] 1 925 parts by weight of yellow iron oxide, 5 parts by weight of kaolin, 0 parts by weight of tartaric acid
．． 5 parts by weight, si. Two parts by weight of methylethylhydrogen polysiloxane having a H equivalent of 79 were mixed and ground in a bot mill for 5 hours. At this time, the reaction rate of methylethylhydrogen polysiloxane was 51%.

The reaction rate of methylethylhydrogenpolysiloxane was 9% when treated in exactly the same manner as in Example 1].

Reference Example 13 3 parts by weight of yellow iron oxide 9L, 5 parts by weight of t IJ, 0.2 parts by weight of adipic acid, 05 parts by weight of malic acid, 2 parts by weight of methylhydrogen polysiloxane with an SiH equivalent of 145, and S
iH/M127 methylphenylhydrogen polysiloxane 1
The weight parts were mixed and milled in a bot mill for 5 hours. The reaction rate of methylphenyl hydrogen polysiloxane at this time was 57%.
Met.

Reference Example 14 When treated in exactly the same manner as in Reference Example 19] 3 without adding adipic acid and malic acid, the reaction rate of methylphenylhydrogen polysiloxane was 6%.

The reaction rates of organohydrogen polysiloxanes in Reference Examples 1 to 14 were calculated by the following method.

Example 1 Powder White Powder Weight % Hydrophobized talc (obtained in the same manner as Reference Example 1) 7
6.3 Powder of Reference Example 5 20.0 Powder of Reference Example 11 0.2 Powder of Reference Example 9 05 Squalane zO Propylene Glycol 1.0 Preservative Appropriate amount Flavor Appropriate amount (the following margins) Reference Example 1 and Hydrophobized talc obtained in the same manner, Reference Example 5
．． Mix the powders in Steps 11 and 9 well using a blender. This was sprayed with an oil in which squalane, propylene glycol, and a preservative were evenly dissolved, and then a fragrance was sprayed on it, and the powder was crushed and filled into containers.

Comparative Example 1 Hydrophobized talc (obtained in the same manner as Reference Example 2) instead of hydrophobized talc (obtained in the same manner as Reference Example 1). Reference Example in place of the powder in Reference Example 5. White powder obtained in the same manner as in Example 1 using the powder of Reference Example 6, the powder of Reference Example 12 instead of the powder of Reference Example 11, and the powder of Reference 1o instead of the powder of Reference Example 9. The make-up retention was inferior to that of the white powder of Example 1.

(Leaving space below) 1 Example 2 Solid foundation for summer Powder of Reference Example 1 500% by weight Powder of Reference Example 7 0.1 Powder of Reference Example 13 4.0 Powder of Reference Example 9 1.3 Stearin Acid 1.5 Lanolin 50 Squalane 5.0 Sorbitan Nasquioleate 2゜Triethanolamine 10 Fragrance appropriate amount Preservative appropriate amount Stir (powder part). Add triethanolamine to 50% equivalent amount of purified water and keep at 70℃ (
aqueous phase). Mix other ingredients except fragrance, heat and dissolve.7
Keep at 0'C (oil phase). Add the oil phase to the water phase and uniformly emulsify with a homomixer, add this to the powder 2 and knead with a kneader, then evaporate the water.
Process in a crusher. Further, while stirring the mixture well, the fragrance is evenly sprayed and compression molded.

The obtained foundation had very good makeup retention and excellent moldability.

Comparative example? Hydrophobized talc (obtained in the same manner as in Reference Example 2) was used instead of hydrophobized talc (obtained in the same manner as in Reference Example 1), and powder in Reference Example 2 was used in place of the powder in Reference Example 1. powder of Reference Example 8 instead of the powder of Reference Example 7; powder of Reference Example 1o instead of the powder of Reference Example 9; powder of Reference Example 4 instead of the powder of Reference Example 13; The makeup retention and moldability of the foundation obtained in the same manner as in Example 2 using the same method as in Example 2 were inferior to those of the foundation in Example 2.

Example 3 Kohoku 23 Powder of Reference Example 9 2-0 Squalane 5.0 Lanolin 3.0 Sorbitan trioleate zO Preservative Appropriate amount Fragrance Appropriate amount Hydrophobized talc, Powder of Reference Example 1.11.9 Mix well in a render. Heat the lanolin, squalane, preservative, and sorbitan trioleide-1 to completely dissolve the preservative, then sprinkle it on the powder section, then sprinkle on the fragrance and mix. It is processed in a crusher and then molded.

The resulting blusher had very good makeup retention and excellent moldability.

Comparative Example 3 Hydrophobized talc (obtained in the same manner as Reference Example 2) was used instead of hydrophobized talc (obtained in the same manner as Reference Example 1), and Reference Example was used in place of the powder in Reference Example 1. [Reference Example 2] Powder of Reference Example 1 was obtained in the same manner as in Example 3 using the powder of Reference Example 10 instead of the powder of Reference Example 9. The makeup retention and moldability of Tahoohoku were inferior to the foundation of Example 3.

Example 4 Powder of oil-based foundation Stinoku Reference Example 5 44.5% by weight Powder of Reference Example 7 01 Powder of Reference Example 11 40 Powder of Reference Example 9 1.4 Squalane 340 Sorbitan Sesquioleate 3.0 Solid paraffin 50 - 15゛ Carna crystal wax 30 Isopropyl myristate 50 Flavor Appropriate amount Preservative Appropriate amount DeReference Example 5, '7.11 and 9 powders are thoroughly mixed in 4 renders (powder section) . Add 15 parts of squalane and sorbitan sesquioleate to the powder part, disperse uniformly with a homomixer, and then add solid paraffin, 5 carnauba wax, 19 parts of squalane, isopropyl myristate, and a preservative by heating and dissolving them, Add flavoring and stir well. Pour this into a container and cool it.

The resulting oil-based foundation makeup had excellent makeup retention.

Comparative Example 4 Powder of Reference Example 6 was used instead of the powder of Reference Example 5. Powder of Reference Example 8 was used instead of the powder of Reference Example 7. Powder of Reference Side Stop was used instead of the powder of Reference Example 11. An oil-based foundation stick obtained in the same manner as in Example 4 using the powder of Reference Example 10 instead of the powder of Reference Example 9 had poor makeup retention compared to the oil-based foundation stick of Example 11.

(Leaving space below) G Example 5 Group Blue 100 Navy Blue 150 Squalane 30 Vaseline 2+0 Sorbitan trinylene) 20 Fragrance Appropriate amount Preservative Appropriate amount - Oil portion in which squalane, petrolatum, sorbitan trioleate, and preservatives are uniformly dissolved. The product is sprayed with a fragrance, then crushed with a crusher, and then filled and molded.

The resulting solid eyeshadow had very good makeup retention and excellent moldability.

Comparative Example 5 The powder of Reference Example 6 was used instead of the powder of Reference Example 5.27 The makeup retention and moldability of the solid eye shadow obtained in the same manner as in Example 5 were similar to those of the solid eye shadow of Example 5. It was inferior in comparison.

Example 6 Dual use solid foundation Powder of Reference Example 1 48.5% by weight Powder of Reference Example 5 35. O Powder of Reference Example 9 13 Powder of Reference Example 11 37 Powder of Reference Example 7 0.2 Magnesium aluminum silicate 0.3 Squalane
4゜Lanolin 5.0 Sorbitan Trioleate 2+O Preservative Appropriate amount Fragrance Appropriate amount Mix the powder of Reference Example 1.5.9.11.7 and magnesium aluminum silicate well in a blender (powder part)
.

Next, an oil part in which squalane, lanolin, sorbitan trioletate, and a preservative are uniformly dissolved is added to the powder part, and then the fragrance is added, mixed uniformly, and processed in a pulverizer. Compression mold.

The resulting dual-use solid foundation had very good makeup retention and excellent moldability.

By the way, dual-use solid foundation refers to foundation that can be used with or without using a sponge.

Comparative Example 6 Powder of Reference Example 2 instead of powder of Reference Example 1, powder of Reference Example 6 instead of powder of Reference Example 5, powder of Reference Example 10 instead of powder of Reference Example 9 , obtained in the same manner as in Example 6 using the powder of Reference Example 2 instead of the powder of Reference Example H and the powder of Reference Example 8 instead of the powder of Reference Example 7. Company Shiseido (Volunteer to write procedural amendments) March g, 19801, Indication of the case, 1982 Patent Application No. 20434, 2, Name of invention cosmetics 3, Person making the amendment 4, Specification subject to amendment Column 5 of Detailed Description of the Invention, Contents of Amendment (1) On page 3, line 5 of the specification, "Number of charcoal plants" is amended to read "Number of carbons."

(2) On page 17, line 12 of the specification, "parts by weight, lactic acid" should be corrected to "1M parts, lactic acid."

(3) “Methylphenyl” on page 18 of the specification, line 4 from the bottom
Correct the wording to "organo".

(4) In the first line of page 19 of the specification, the word "methylphenyl" has been amended to read "organo."

(5) On the third line from the bottom of page 20 of the specification, the text "Reference 10" should be corrected to "Reference Example 10."

5 (6) On the second line from the bottom of the first page of the specification, "Example 11" should be corrected to "Example 4."

(7) In the 8th line of page 26 of the specification, the phrase ``1-lieleate'' has been corrected to [trioleate-1-J.

that's all

Claims (1)

[Scope of Claims] (1) In the presence of one or more acidic substances, organohydrogenpolysiloxane is formed on the surface of one or more powders selected from inorganic powders and organic powders. Cosmetics. (2) The inorganic powder is silicic acid, silicic anhydride, magnesium silicate, talc, kaolin, mica, bentonite, titanium-coated mica, bismuth oxychloride, zirconium oxide,
The cosmetic according to claim (1), which is any one of magnesium oxide, zinc oxide, titanium dioxide/calcium carbonate/magnesium carbonate, iron oxide, ultramarine, deep blue, chromium oxide, chromium hydroxide, calamine, and carbon black. fee. (3) If the organic powder is polyamide, polyester, polyethylene, polypropylene, polystyrene, polyurethane, vinyl resin, urea resin, phenol resin, fluororesin, silicone resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, divinylbenzene, Styrene copolymer, copolymer consisting of two or more monomers of the above compounds, celluloid, acetyl cellulose, polysaccharide, protein, hard protein, o epigment yellow, CI pigment orange, C epigment red, C
Epigment Violet, 0 Epigment Blue, 0
The cosmetic according to claim (1), which is either Epigment Green or CI Pigment Brown. (4) Claim No. 1 in which the organohydrogen polysiloxane is any of the compounds represented by the following general formula.
Cosmetics according to any one of paragraphs ) to (3). (In the formula, RI may be the same or different, and represents a hydrogen atom, hydroxyl group, methyl group, ethyl group or) phenyl group,
R2 is a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, or
A phenyl group, R3 may be the same or different from each other,
A hydrogen atom, a hydroxyl group, a group with a carbon number of 1, R, may be the same or different from each other - a hydrogen atom, a hydroxyl group, a group with a carbon number of 1 to 2
2 alkyl group, phenyl group, alkoxy group having 1 to 22 carbon atoms, or cyanoalkyl group having 1 to 4 carbon atoms,
l, m·le represent an integer of 5 to 1000 in total. l%
In m y n, each constituent unit may be bonded regularly or irregularly, or any number of each constituent unit may be bonded regularly or irregularly. ) (5) A patent claim in which the organohydrogenpolysiloxane has a 5i)1 equivalent (the number of grams of the organohydrogenpolysiloxane necessary to generate 1 mole of hydrogen gas in a 0,01N NaOH aqueous solution at 100°C) from 31,111 to 550. Cosmetics according to scope (4). (6) Claim No. 1, wherein the amount of organohydrogenpolysiloxane added is 01 to 20% by weight based on the powder.
Cosmetics according to any one of paragraphs to (5). (7) Acidic substances include fatty acids, polybasic acids, lactic acid, malic acid, tartronic acid, citric acid, isocitric acid, tartaric acid, ascorbic acid, vitamin A acid, aromatic acids, urocanic acid, pyrrolidone carboxylic acid, acidic amino acids, medium amino acids, acylamino acids, glycono-δ-lactone/sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, inorganic acid salts of amino acids, organic acid salts of amino acids, inorganic m salts of acylamino acids, organic acid salts and inorganic acids of acylamino acids The cosmetic according to any one of claims (1) to (6), which is any one of the metal salts. (8) The amount of acidic substance added is 001 to 10 per powder.
Claims (1) to (7) which are weight %
Cosmetics described in any of the paragraphs. (The following is a blank space) (9) Claim No. 1 characterized in that the organohydrogenpolysiloxane is reacted mechanochemically.
) to (8). (10) A cosmetic according to claim 9, characterized in that the reaction is carried out under heating. (11) The cosmetic according to any one of claims (1) to (1o), which is a makeup cosmetic. (1no) A patent application in which the cosmetic is a solid foundation;
Cosmetic composition according to any one of claims (1) to (10). Cosmetics described in any of Items 1 to 1. (Hereinafter referred to as blank space)