JP2573007B2 - Modified animal hair powder - Google Patents

Description

The present invention relates to a modification obtained by reacting a finely pulverized animal hair powder with a mercaptan containing a higher hydrocarbon group in its structural formula or a mercapto-modified silicone oil. Related animal hair powder.

[Conventional technology]

Animal hair, such as animal hair, human hair, bird feathers and feathers, has keratin protein as a main component, but has a high content of cystine as a constituent amino acid, so the degree of cross-linking of peptide chains is high and the natural state Are insoluble in water and oily solvents and also resistant to ordinary protein hydrolases. Therefore, an attempt to utilize such characteristics based on keratin protein to powder wool or the like and apply it to cosmetics has been made in JP-A-49-132247, JP-A-54-70435, and JP-A-55-27120. It is disclosed in gazettes and the like.

[Problems to be solved by the invention]

However, the wool powder disclosed in these publications,
It is merely a mechanically crushed wool and has not been chemically modified, so it has no special features other than powder. In addition, all of them have a large particle size, so that when incorporated into cosmetics, the properties of keratin protein, which is a constituent component thereof, cannot be sufficiently exhibited, which is not satisfactory.

Therefore, the present invention modifies animal hair powder without losing its properties based on its constituents, and expands its application range.For example, when blended in cosmetics, it becomes familiar with the skin and provides a stable and excellent feel. The purpose is to be able to give.

[Means for solving the problem]

The present inventors have focused on the fact that animal hair such as wool contains a large amount of cystine as a constituent amino acid, and are keen to modify the properties of animal hair powder using disulfide (SS) bonds possessed by the cystine. As a result of repeated studies, modified animal hair powders obtained by reacting mercaptans or mercapto-modified silicone oils containing higher hydrocarbon groups in the structural formula with finely pulverized animal hair powders have higher hydrocarbon groups. Has a disulfide bond with animal hair powder in the cystine side chain in animal hair powder, and has a higher affinity for oil than unmodified animal hair powder. It has the property of absorbing oil well and also absorbing water, so it has very good emulsifying and dispersing properties. When incorporated into, familiar well to the skin, found to impart excellent texture stability, they have accomplished the present invention.

That is, the present invention relates to a mercaptan or a mercapto-modified silicone in which a mercaptan or a mercapto-modified silicone oil containing a higher hydrocarbon group in a structural formula reacts with a cystine side chain in animal hair powder. The invention relates to animal hair powders that have been modified by the oil forming disulfide bonds with the animal hair powder.

Hereinafter, the configuration of the present invention is described as (1) the type of animal hair, (2)
A method for producing animal hair powder, (3) a method for modifying animal hair powder (that is, a reaction between animal hair powder and a mercaptan or mercapto-modified silicone oil containing a higher hydrocarbon group in the structural formula), and a method for forming a disulfide bond with animal hair powder. Determination of mercaptans or mercapto-modified silicone oils containing higher hydrocarbon groups formed in the structural formula, (4) Reagents used for modification, (5) Application range of modified animal hair powder,
And (6) Specific description will be made sequentially in accordance with the degree of modification.

(1) Types of animal hair In this specification, “animal hair” means animal hair, human hair, bird feathers, and bird feathers. Examples of animal hair include wool, mink hair, ordinary goat hair, mohair hair, Tibetan hair, camel hair, cashmere hair, llama hair, alpaca hair, gusinako hair, Angora rabbit hair, cow hair, normal rabbit hair, horse hair, and cat. Hair, pig hair, etc. Bird feathers and bird feathers include, for example, feathers and feathers of moth birds, ducks, other water birds, chickens and the like.

(2) Production method of animal hair powder Animal hair powder can be prepared, for example, by subjecting the above-mentioned “animal hair” to circulating vacuum pulverization. The circulating vacuum pulverization is carried out using a circulating vacuum pulverizer obtained by further improving a known vacuum pulverizer (Japanese Patent Publication No. 52-11787), which is invented by the present inventor. As described in the above-mentioned Japanese Patent Publication No. 52-11787, the above-mentioned known vacuum pulverizing apparatus comprises: (a) a pulverized material container for loading a raw material to be processed;
(B) a pulverizer equipped with a hammer and a ridge, (c) a pulverized material container for collecting products, (d) a connecting and transferring means interposed therebetween, and (e) a storage of the above-mentioned pulverized material. It is mainly composed of a vacuum pump connected to the vessel (a) and the pulverized material container (c). The inventor has improved the vacuum pulverizer, replacing the hammer and the ridges in the pulverizer (b) with rotary blades and fixed blades, and connecting the outlet of the pulverized material container (c) with the pulverized material. It was connected to the inlet of the container (a) so that the circulating pulverization could be performed under vacuum. When the animal hair is circulated and vacuum-pulverized using this improved apparatus, the animal hair is pulverized much more finely than conventional ones.

The circulation vacuum pulverization is 2 to 30 mmHg, preferably 2 to 10 mmHg.
Performed under mmHg vacuum. The circulation is carried out two to ten times, preferably three times. Before performing the above-mentioned circulating vacuum pulverization, animal hair as a raw material can be degreased with an organic solvent such as diethyl ether, acetone, chloroform or trichloroethane, or can be degreased and washed with various surfactants. In addition, a commercially available product after the degreasing / washing treatment can be used as it is.

After circulating vacuum milling, the product is classified. As a classification method, a method known per se, for example, sieving, wet classification or dry classification can be used.
It is preferable to use a dry classifier, for example, a gravity classifier, an inertial classifier, particularly a centrifugal classifier, and it is particularly preferable to use a forced vortex centrifugal classifier. By employing an appropriate classification means, a fine powder mainly composed of a cuticle (hair skin) forming the outermost layer of animal hair [in this case, for example, a forced vortex centrifugal classification device (separation diameter 0.5 to 50 μm)
m, preferably 0.5 to 30 μm], or a fine powder containing a large amount of other parts, that is, cortex and cortex.

Dyeing, bleaching, UV (ultraviolet irradiation) treatment, electrostatic treatment, water repellent treatment, insect repellent treatment, antiseptic treatment, antifungal treatment, and other surface treatments of the obtained animal hair are performed before or after circulating vacuum pulverization or classification. It can be performed either before or after the treatment or modification of the present invention, but is most preferably performed before the modification of the present invention.

For dyeing, for example, Red No. 3, Red No. 104, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1, Blue No. 2, Red
227, red 230, orange 206, orange 207, yellow 202
No. 201, green No. 201, green No. 204, green No. 205, etc., tar dyes, carminic acid, laccaic acid, calsamine, bradylin, crocin, annatto, anthocyanins, safrole yellow, red ball dyes and other natural dyes are stained according to a conventional method. be able to. As for the UV treatment, for example, an ultraviolet absorbent such as salicylic acid, paraaminobenzoic acid, and urocanic acid can be adsorbed according to a conventional method, but such treatment is preferably performed after the modification of the present invention.

By the above-mentioned circulating vacuum pulverization and classification, an average major axis of 30
A fine powder having a size of 4 μm or less and an aspect ratio of 4 or more is obtained. The obtained fine powder is mainly composed of adjacent flake-like (flat) fine powder, and there is no change in the size of the fine powder before and after the modification of the present invention.

In the present specification, the size of the fine powder is measured as follows. The obtained fine powder is suspended in a dispersion medium such as acetone, placed on an aluminum sample table, dried, and subjected to gold deposition to obtain a sample. Take electron micrographs.

Since the image of the fine powder is indefinite, the longest diameter is defined as the `` major axis '', and the major axis is measured for at least 50, preferably 100 or more fine powders, and the average value is referred to as `` average major axis ''. I do. In addition, the longest diameter in the direction perpendicular to the above “major axis” is defined as “minor axis”, and the biaxial average of each fine powder, that is, (“major axis” + “minor axis”) × 1/2 is obtained. The average value calculated and obtained from the individual biaxial averages in the same manner as above is referred to as “average biaxial average”. On the other hand, a sample was prepared from the fine powder in the same manner as described above, the sample stage was tilted at about 45 °, an electron micrograph was taken of the adjacent piece of fine powder viewed from the side, and the longest thickness of the image figure was determined. The “average thickness” is determined in the same manner as described above with the “thickness” of the fine powder. Next, “average biaxial average” / “average thickness” was calculated, and this was calculated as “aspect ratio”.
And

The fine powder pulverized by the circulating vacuum pulverizer is, when measured by the above-described measuring method, an average major axis of 30 μm or less, preferably 1 to 20 μm, more preferably 2 to 10 μm, and an average biaxial average of 1 to 20 μm, preferably 2 to 10 μm. And an average thickness of 5 μm or less, preferably 0.2 to 10 μm, and an aspect ratio of 4 or more, preferably 7 to 100.

As measured by the BET method the surface area of the powder the fine and the 0.1 m ² / g or more, especially from 0.5 to 5 m ² / g.

When the fine powder pulverized by the circulating vacuum pulverizer is observed with an electron microscope, a large number of adjacent flaky powders can be seen. Also,
In the amino acid composition of the fine powder before the modification of the present invention, since the amount of serine, proline and cystine is large, it is considered that cuticle is the main component. Therefore, the above-mentioned circulating vacuum pulverization processing is performed to pulverize individual cuticles. And since the crushing is performed to the unit of each cuticle,
Animal hair cortex and cortex
It is considered that pulverization is also performed at least partially in each of the parts.

(3) A method for modifying animal hair powder and a method for quantifying mercaptans or mercapto-modified silicone oils containing a higher hydrocarbon group forming a disulfide bond with animal hair powder in a structural formula of animal hair powder obtained as described above. Modification is performed as follows.

In the simplest case, animal hair powder is dispersed in a liquid, and a mercaptan or a mercapto-modified silicone oil containing a higher hydrocarbon group in the structural formula is added to the dispersion to contain the animal hair powder and the higher hydrocarbon group in the structural formula. A modified animal hair powder is obtained by reacting with a mercaptan or a mercapto-modified silicone oil. That is, a disulfide bond (SS) bond of cystine (Cys-SS-Cys) in animal hair powder is combined with a mercaptan or a mercapto-modified silicone oil (hereinafter referred to as A-SH) containing a higher hydrocarbon group in the structural formula. By performing such a reaction, a higher hydrocarbon group or a group constituting a silicone oil is introduced into the animal hair powder.

Cys-SS-Cys + A-SH → Cys-SS-A + Cys-SH In the above reaction, it is considered that the SS part of Cys-SS-Cys is cleaved and the AS part of A-SH is replaced with S-Cys. Can be Therefore, it is not mercaptans or mercapto-modified silicone oils themselves containing higher hydrocarbon groups in the structural formula that form disulfide bonds (SS bonds) with animal hair powder, but H (hydrogen) in SH groups is removed therefrom. However, in the present invention, for convenience, it is expressed that a mercaptan or a mercapto-modified silicone oil containing a higher hydrocarbon group in the structural formula forms a disulfide bond with animal hair powder.

Further, as shown in the above reaction formula, cystine becomes a form having a mercapto group, that is, cysteine, which is further combined with a mercaptan or a mercapto-modified silicone oil containing a higher hydrocarbon group in the structural formula as shown in the following reaction formula. It is preferable to use an oxidizing agent in order to cause the reaction.

In the reaction of Cys-SH with A-SH, H and A-SH of Cys-SH also displace, so that the formation of a disulfide bond with animal hair powder is due to the removal of H in the SH group of A-SH. According to the present invention, in this case, too, it is described that mercaptans or mercapto-modified silicone oils containing higher hydrocarbon groups in the structural formula form disulfide bonds with animal hair powder.

The reaction between Cys-SH and A-SH proceeds in the presence of trace amounts of oxygen and heavy metal ions such as iron ions (spontaneous oxidation) without the use of an oxidizing agent. The reaction can be terminated.

Also, a reducing agent can be used before or at the time of contacting a mercaptan or a mercapto-modified silicone oil containing a higher hydrocarbon group in the structural formula with animal hair powder. In this case, the cystine in the animal hair powder is converted into a form having a mercapto group, ie, cysteine, by the action of the reducing agent, and then a mercaptan or a mercapto-modified silicone containing cysteine and a higher hydrocarbon group in the structural formula using an oxidizing agent. It is preferable to employ a method of promoting a disulfide bond formation reaction with oil.

As the reducing agent used for reducing the animal hair powder, for example, thioglycolic acid, thioglycolate such as ammonium thioglycolate, thiomalic acid or a salt thereof,
Low molecular weight organic mercaptan compounds such as thiolactic acid or a salt thereof, thioglycerol, and 2-mercaptoethanol;
Examples thereof include sulfites such as sodium sulfite, sodium bisulfite, potassium sulfite, ammonium sulfite, and ammonium bisulfite; sulfides such as sodium sulfide, potassium sulfide, and ammonium sulfide; and metal hydrides such as sodium borohydride. Examples of the oxidizing agent include inorganic peroxides such as hydrogen peroxide, bromates such as sodium bromate and potassium bromate, and organic peroxides such as benzoyl peroxide, peracetic acid and lauroyl peroxide. Can be mentioned. In addition, mercaptans and mercapto-modified silicone oils containing a higher hydrocarbon group in the structural formula are hardly soluble in water, so that it is usually preferable to carry out the reaction in an organic solvent. In addition, a mercaptan or a mercapto-modified silicone oil containing a higher hydrocarbon group in a structural formula with a surfactant or an emulsifier can be dispersed as an emulsion and reacted in water or a mixture of water and an organic solvent. . After the reaction is completed, the reaction product is thoroughly washed with an organic solvent, a surfactant or an emulsifier to remove mercaptans or mercapto-modified silicone oil containing higher hydrocarbon groups, which are merely attached, in the structural formula. Only mercaptans or mercapto-modified silicone oils containing a higher hydrocarbon group forming a disulfide bond with the hair powder in the structural formula remain in the animal hair powder. The process is terminated by drying it. As long as the animal hair powder modified in this way is not subjected to a treatment such as reduction again, mercaptans or mercapto-modified silicone oil containing a higher hydrocarbon group forming a disulfide bond with the animal hair powder in the structural formula is used. It does not deviate from animal hair powder. Although washing after the reaction may not always be necessary, mercaptans or mercapto-modified silicone oils containing a higher hydrocarbon group used in the reaction in the structural formula usually have a mercapto odor,
In order to remove such an unpleasant odor, it is preferable to perform washing. In addition, when a reducing agent or an oxidizing agent is used, it is preferable to sufficiently remove them by washing.

As the organic solvent used in the reaction, for example, methanol, ethanol, propanol, isopropanol,
Examples include acetone, methyl acetate, ethyl acetate, benzene, toluene, hexane, heptane, pentane, butane, ethyl ether, propyl ether, isopropyl ether, chloroform, carbon tetrachloride, and 1,1,1-trichloroethane.

In the modified animal hair powder thus obtained, the amount of the mercaptan or mercapto-modified silicone oil containing a higher hydrocarbon group forming a disulfide bond with the animal hair powder in the structural formula is determined by the amount of the modified animal hair. A mercaptan or a mercapto-modified silicone oil containing a higher hydrocarbon group in the structural formula is removed from the animal hair powder by causing a reducing agent to act on the powder, and then extracted and concentrated to dryness with the organic solvent described above. Can be determined by measuring the weight of the sample and taking the difference between the sample and the control product treated in the same manner except that the reducing agent is not used. In addition to the above,
A disulfide bond is formed with the animal hair powder in the modified animal hair powder also by quantifying the component extracted from the modified animal hair powder into an organic solvent by liquid chromatography, gas chromatography, or the like. The amount of a mercaptan or a mercapto-modified silicone oil containing a higher hydrocarbon group in the structural formula can be determined.

(4) Reagents that can be used for modification Mercaptans or mercapto-modified silicone oils containing a higher hydrocarbon group in the structural formula include mercapto groups (thiol groups) and hydrophobic (lipophilic) moieties in their structures. The chemical structure is not particularly limited as long as it can form a disulfide (SS) bond with the hair powder and can thereby introduce a hydrophobic structure into the animal hair powder. In order to exert the effect, it is preferable that the mercaptans having a higher hydrocarbon group in the structural formula contain at least one hydrocarbon structure having 10 or more carbon atoms, and that the mercapto-modified silicone oil has at least one polycarbon having 5 or more silicon atoms. Those containing a (hydrocarbon-modified siloxane) structure are preferred. Further, in addition to these structures, the effects of the present invention are not impaired, and in some cases, the solubility in an organic solvent is improved upon modification of the present invention, or the reactivity with animal hair powder or the modified animal It may have a structure further containing various functional groups for the purpose of improving the feel of the hair powder. Such functional groups include, for example, hydroxyl groups, amides, ethers, esters,
Examples include amines, imines, and quaternary ammoniums.

As mercaptans containing a higher hydrocarbon group in the structural formula that can be used in the present invention, for example, higher hydrocarbons such as n-decyl mercaptan, lauryl mercaptan, myristyl mercaptan, palmityl mercaptan, stearyl mercaptan, eicosanthiol, tert-lauryl mercaptan, etc. Mercaptans, N- (2-mercaptoethyl) lauroylamide, N- (2-mercaptoethyl) decanoylamide, N- (2-mercaptoethyl) myristoylamide, N- (2-mercaptoethyl) palmitoylamide, N- (2-mercaptoethyl) eicosanoylamide, N- (2-mercaptoethyl) triacontanoylamide, N- (2-mercaptoethyl) undecylenoylamide, N- (2-mercaptoethyl) oleoylamide, N − (2- Higher hydrocarbon fatty acids 2 such as mercaptoethyl) isostearoylamide, N- (2-mercaptoethyl) avietoylamide, N- (2-mercaptoethyl) palm oil fatty acid amide, N- (2-mercaptoethyl) bovine fatty acid amide -Mercaptoethylamide and the like.

Examples of the mercapto-modified silicone oil include mercapto-modified silicone oils having a mercapto group introduced therein, such as 3-mercaptopropyl-modified dimethylpolysiloxane, 2-mercaptoethyl-modified dimethylpolysiloxane, and 3-mercaptopropyl-modified methylphenylpolysiloxane. Can be mentioned. However, mercaptans containing a higher hydrocarbon group in the structural formula, and mercapto-modified silicone oils, are not limited to those exemplified, and are similar to those having at least one mercapto group and at least a hydrophobic structural part. Any similar compounds that can exert an effect can be used.

(5) Application Range of Modified Animal Hair Powder The modified animal hair powder of the present invention is characterized in that the keratin protein constituting the animal hair has a high cystine content and contains cystine residues and other functional side chains. Since it has a large amount, it is highly reactive with metals and the like, and a hydrophobic structure is introduced, so utilizing such properties, as it is or after performing an appropriate treatment, a heavy metal adsorbent, heavy metal It can be used as a chromatographic carrier for separation, feed, medical polymer, immobilizing carrier for enzymes, etc., carrier for affinity chromatography, pharmaceutical base, cosmetic base and the like. Further, the modified animal hair powder of the present invention exhibits an excellent emulsifying action, and thus can be used as an emulsifier. Further, among the modified animal hair powders of the present invention, the colored animal hair powder that contains the pigment itself is in its original form, and the pigment that does not itself contain the pigment or does not have the desired color is suitable. After dyeing, the colored or colored products can be used as pigments or dyes. Such pigments or dyes are light and excellent in dispersibility, and are based on natural proteins.For example, when formulated in cosmetics for skin, etc., they are easily adapted to hair and skin and have little irritation to the skin. .

In particular, the modified animal hair powder of the present invention is very compatible with the oily component due to the introduction of a lipophilic higher hydrocarbon group or a polysiloxane structure. The amount of liquid absorption is several steps larger than before the modification. Therefore, when used on the skin as a cosmetic composition together with these oily components, it spreads well on the skin and has an action of keeping the oily components on the skin for a long time, so it is particularly useful as a cosmetic base, Foundations such as creamy, liquid, solid, cream paste, powder paste, powder paste, talcum powder, paste paste, baby powder, body powder, white powder such as water paste, powdered powder,
Lipstick, lip balm, eye shadow, eye liner,
It has great value as a powder raw material such as blusher, mascara, eyebrows, powdered perfume, etc. Further, the modified animal hair powder of the present invention obtained by absorbing an oily component can also be used.
The oil-absorbed oily component is excellent as a cosmetic compounding agent, because it is easy to mix, for example, when compounded in cosmetics, and does not cause rapid separation of the oily component and gradually releases the oily component. . As the oily component to be absorbed into the animal hair powder modified as described above, for example, liquid paraffin, vaseline, paraffin, microcrystalline wax, ceresin, squalane, hydrocarbons such as pristane, lauric acid, myristic acid, palmitic acid, Natural or synthetic higher fatty acids such as stearic acid, behenic acid, oleic acid, linoleic acid, linoleic acid, lanolinic acid, isostearic acid, isopalmitic acid, lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, lanolin alcohol, cholesterol, Natural or synthetic higher alcohols such as 2-hexyldecanol and 2-octyldodecanol, hexyldecyl stearate, hexyldecyl isostearate, 2-ethylhexyl palmitate, isopalmi Phosphate 2-
Ethylhexyl, isopropyl isostearate, di (2-ethylhexyl) succinate, isopropyl palmitate, isopropyl myristate, diisopropyl sebacate, diisobutyl adipate, diisopropyl adipate, myristyl lactate, cetyl lactate, diisostearyl malate, dimethyloctanoic acid Fatty acid esters such as hexyldecyl, hexyl laurate, octyldodecyl myristate, butyl stearate, and decyl oleate; animal and plant waxes such as carnauba wax, candelilla wax, whale wax, beeswax, and lanolin; animal and vegetable fats or oils or workpiece water添等, synthetic glycerides, higher fatty acid amides, Vita with silicone oil, vitamin _{a 1, B 2, D,} E , or those similar structure Down-like substance, a variety of fragrances, and the like can be given. When the fragrance is absorbed, there is an effect that the fragrance of the fragrance is retained for a long period of time.

(6) Degree of Modification By the modification of the present invention, the amount of mercaptans or mercapto-modified silicone oil containing a higher hydrocarbon group forming a disulfide bond with animal hair powder in the structural formula is determined in the modified animal hair powder. , 0.05 to 5.0% by weight. If the content is less than 0.05% by weight, the modified effect is not sufficiently exhibited, and if the content is more than 5.0% by weight, severe conditions are required for the modification, and the animal hair powder is damaged and modified. Animal hair powder has a poor feel and value.

〔The invention's effect〕

Since the modified animal hair powder of the present invention contains a higher hydrocarbon or siloxane structure in its chemical structure, it is easily compatible with the oily component, and therefore, when formulated in a cosmetic composition together with the oily component, it can form on the skin. It spreads well and keeps oily components on the skin for a long time. Therefore, as described above, it is excellent as a cosmetic base, especially creamy, liquid, and solid foundations, cream paste, solid paste, powder paste, talcum powder, paste paste, baby powder, body powder, water paste. , Lipstick, lip balm, eye shadow, eyeliner, blusher,
It can be suitably used as a powder raw material for mascara, eyebrows, powdered perfumes and the like. Also, the modified animal hair powder of the present invention,
Since it has an excellent emulsifying action, it can be used as an emulsifier. Further, the modified animal hair powder of the present invention is dyed as it is if it itself contains a pigment, and appropriately dyed if it does not itself contain a pigment or does not have a desired color. Later, their color or color can be used as pigments or dyes.

The modified animal hair powder of the present invention has a high cystine content in the keratin protein constituting the animal hair and has a large amount of cystine residues and other functional side chains, so that it has low reactivity with metals and the like. Utilizing the rich nature, immobilize heavy metals (mercury, copper, cadmium, chromium, etc.) adsorbents, chromatography carriers for separating heavy metals, feed, medical polymers, enzymes, etc. , A carrier for affinity chromatography, a carrier for affinity chromatography, and a pharmaceutical base.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples. In describing the examples, a method for preparing animal hair powder used in the examples will be described first as a reference example.

(1) Reference Example [Preparation of animal hair (wool) powder] 50 kg of Merino wool, which has been degreased, washed, and minced in advance by an ordinary method, is taken using a vacuum pulverizer (Seiwa Kasei: SWM-48 type). After loading into the crushed material container of the circulation type improvement device and evacuating the system (5 mmHg), 5.5 KWh and 300
Grinding was performed by operating for 6 hours at 0 rpm. In addition, when the pulverization was similarly performed without circulating this apparatus, the required time was 2 hours, and this processing means that the pulverization processing was repeated three times on average.

Subsequently, classification was performed using a forced vortex centrifugal classifier [Nisshin Engineering: TC-15N (separation diameter: 20 μm)] to obtain 4.5 kg of fine powder having a size of 20 μm or less.

It is considered that the fine powder thus obtained has a cuticle as a main component substantially. The reason is as follows.

(A) The fine powder has an amino acid composition that is in good agreement with the amino acid composition of the cuticle of wool as a raw material (see the section on amino acid analysis below).

(B) Observation of the obtained fine powder with a scanning electron microscope (JEOL: JSMM-T100 type) shows that the shape of the fine powder is adjacent to each other and matches the shape of the cuticle.

(C) The yield of the fine powder is almost equal to the weight ratio of cuticle in wool (about 10%).

Amino acid analysis 10 mg of Merino wool as a starting material of wool powder and 10 mg of fine powder as a product were precisely weighed into a test tube for hydrolysis, 2 ml of 6N hydrochloric acid was added, and the tube was evacuated and sealed. Subsequently, the mixture was completely hydrolyzed at 110 ° C. for 24 hours. The obtained decomposed liquid was concentrated under reduced pressure to remove hydrochloric acid, and then diluted to prepare a sample for amino acid analysis. These samples were analyzed with a fully automatic high-speed amino acid analyzer JLC-300 (JEOL). Data processing is data processing unit 7000B (System Instruments)
Made by. The results obtained are shown in Table 1.

As is clear from Table 1, the fine powder (wool powder) of the reference example contains a large amount of serine, cystine, and proline, and when compared with literature values, it can be seen that the cuticle content is large.

(2) Example (Modification of Wool Powder) Using the wool powder obtained in Reference Example, the following modified wool powder was prepared.

Example 1 10 g of wool powder was dispersed by stirring in 250 ml of isopropyl alcohol, and 1 g of lauryl mercaptan was added. twenty four
After stirring at room temperature for a period of time, the wool powder is collected on filter paper by vacuum filtration, washed with 100 ml of isopropyl alcohol, and dried, and the modified wool powder, that is, lauryl mercaptan, forms a disulfide bond with the wool powder. A modified wool powder was obtained by forming.

Example 2 Modified wool powder, i.e. N-lauroyl-2, in the same manner as in Example 1 except that methanol was used instead of isopropyl alcohol and (2-mercaptoethyl) lauroylamide was used instead of lauryl mercaptan. -A wool powder modified by aminoethyl mercaptan forming a disulfide bond with the wool powder is obtained.

Example 3 10 g of wool powder was dispersed by stirring in 250 ml of isopropyl alcohol, and 2 g of a 50% (wt%, hereinafter the same) aqueous solution of ammonium thioglycolate was added thereto, followed by stirring for 1 hour. Next, 2 g of stearyl mercaptan was added, and the mixture was further stirred for 2 hours. Then, 0.5 g of a 35% aqueous hydrogen peroxide solution was added, and the mixture was stirred for 2 hours. The wool powder is collected on a filter paper by vacuum filtration, washed with 100 ml of isopropyl alcohol, and then dried to obtain a modified wool powder, that is, a wool powder modified by forming stearyl mercaptan into a disulfide bond with the wool powder. I got

Example 4 Example 3 except that methanol was used in place of isopropyl alcohol and (2-mercaptoethyl) myristoylamide was used in place of stearyl mercaptan.
In the same manner as described above, a modified wool powder, that is, a wool powder modified by forming a disulfide bond with N-myristoyl-2-aminoethylmercaptan and wool powder was obtained.

Example 5 Instead of lauryl mercaptan, 3-mercaptopropyl-modified dimethylpolysiloxane (trade name: X-22-98)
Example 1 except that 2 g of Shin-Etsu Silicone Co., Ltd. was used.
In the same manner as described above, a modified wool powder, that is, a wool powder modified by forming a disulfide bond with 3- (dimethylpolysiloxane) propylmercaptan to obtain wool powder was obtained.

Example 6 Instead of stearyl mercaptan, 3-mercaptopropyl-modified dimethylpolysiloxane (trade name: X-22-98)
Example 3 except that 2 g of Shin-Etsu Silicone Co., Ltd. was used.
In the same manner as described above, a modified wool powder, that is, a wool powder modified by forming a disulfide bond with 3- (dimethylpolysiloxane) propylmercaptan to obtain wool powder was obtained.

(3) Measurement of the content The content of mercaptans or mercapto-modified silicone oil in the modified wool powder containing a higher hydrocarbon machine in the structural formula, that is, the formation of disulfide bonds with the wool powder in the modified wool powder The amount (%) of the mercaptan or mercapto-modified silicone oil containing higher hydrocarbon groups in the structural formula was determined by the following method.

1 g of each wool powder modified according to Examples 1 to 6,
The mixture was dispersed in a solution obtained by adding 0.2 g of 50% ammonium thioglycolate to a mixed solution of 40 ml of chloroform and 10 ml of methanol, followed by stirring for 1 hour. By allowing the reducing agent to act in this way, mercaptans or mercapto-modified silicone oil containing higher hydrocarbon groups introduced into the wool powder in the structural formula are extracted from the wool powder, and the extract is filtered to obtain wool. The powder was separated by filtration and further washed with 20 ml of chloroform.
The filtrate was transferred to a separating funnel, washed three times with 30 ml of 1% aqueous sodium hydrogen carbonate solution, and finally washed with 30 ml of water to remove ammonium thioglycolate. This liquid
After dehydration using 1 g of anhydrous magnesium sulfate, the solution was concentrated under reduced pressure, and further dried under vacuum to determine the dry residue. From the results, a disulfide bond was formed with the wool powder in the modified wool powder by subtracting the result of quantifying the dry residue except that 0.2 g of 50% ammonium thioglycolate was not separately added. The amount (%) of a mercaptan or a mercapto-modified silicone oil containing a higher hydrocarbon group in the structural formula was determined. The result is
It is shown in the table.

As shown in Table 2, from the wool powders modified in Examples 1 to 6, either mercaptans containing a higher hydrocarbon group in the structural formula or mercapto-modified silicone oil were determined. In Examples 3 to 4 and Example 6 in which a 35% aqueous solution of hydrogen peroxide was used as an oxidizing agent using an aqueous solution of ammonium thioglycolate at a concentration of 35%, the content was confirmed to be large.

(4) Measurement of Particle Size The particle size of the wool powder of the reference example and the wool powder modified in Examples 1 to 6 was measured by the method described above. Table 3 shows the results.

As shown in Table 3, the wool powder of the reference example was also obtained in Example 1.
The wool powder modified with No. 6 also did not change the average major axis, the average biaxial average, the average thickness, and the aspect ratio so much, and there was almost no change in the particle size even by the chemical modification.

(5) Measurement of oil absorption and water absorption The limit of the amount of powder that can absorb liquid is usually called the amount of liquid absorption. A point that forms one soul from the dispersed state is found, and the weight (g) of the liquid added up to that point is defined as the liquid absorption of the powder. The amount of liquid absorption varies greatly depending on the properties of the surface of the liquid, but the influence of the size of the particles is particularly large. It is said that the smaller the particle size, the larger the amount of liquid absorption.

As the liquid absorption, the water absorption was measured using distilled water,
The results of oil absorption measured using liquid paraffin and isopropyl myristate as oils are shown in Table 4 below.
For comparison, the results for talc and titanium oxide commonly used in cosmetics are also shown.

As shown in Table 4, the oil absorption of the modified wool powders of Examples 1 to 6 (the liquid absorption of liquid paraffin and isopropyl myristate) is larger than the wool powder of the reference example. The water absorption of the modified wool powders of Examples 1 to 6 was slightly reduced as compared with the wool powder of the reference example, but was larger than that of talc or titanium oxide. Thus, it was confirmed that the modified wool powders of Examples 1 to 6 had a large liquid absorption (oil absorption and water absorption) and were excellent as powder materials for cosmetics.

(7) Application example (7) -1 Powder foundation A powder foundation having the following formulation was prepared using the modified wool powder of the present invention (Example 1).

Modified wool powder (Example 1) 33.0 Talc 25.0 Titanium oxide 10.0 Muscovite 20.0 Red iron oxide 0.4 Yellow iron oxide 1.2 Black iron oxide 0.1 2-Ethylhexyl isopalmitate 7.8 Silicone oil 1.2 Sorbitan sesquistearate 1.0 Propylparaben 0.3 Perfume Appropriate amount The powder foundation consisting of the above formulation has better spread and adhesion than the control product prepared by adding 33.0% of the wool powder of the reference example instead of the modified wool powder (Example 1). There was little makeup loss.

(7) -2 Powder paste A powder paste having the following formulation was prepared using the modified wool powder of the present invention (Example 2).

(% By weight) Modified wool powder (Example 2) 33.0 Talc 40.0 Kaolin 21.0 Titanium oxide 1.0 Zinc stearate 2.0 Magnesium carbonate 3.0 Colorant Appropriate amount Flavor Appropriate amount Compared with a control product prepared by adding the same amount of wool powder of Reference Example instead of 2), the product had excellent spreadability and adhesion, was easily adapted to the skin, and had a clean skin.

(8) -3 Stick lipstick A stick lipstick having the following formulation was prepared using the modified wool powder of the present invention (Example 3).

(% By weight) Modified wool powder (Example 3) 5.0 Carnauba wax 10.0 Celesin 12.0 Beeswax 20.0 Lanolin 8.0 Hydrogenated castor oil 28.0 2-Ethylhexyl stearate 10.0 Cetanol 4.0 Red iron oxide 2.0 Yellow iron oxide 0.5 Red 204 No. 0.4 Dibutylhydroxytoluene 0.1 Perfume Appropriate amount The stick-like lipstick having the above formulation has a longer spread and a feeling of adhesion than a control product prepared by adding the same amount of the wool powder of the reference example instead of the modified wool powder (Example 3). Excellent,
Even when the makeup was lost and no oil droplets were formed on the surface even after long-term storage, the product stability was excellent.

(8) -4 Paste-like blush A paste-like blush having the following formulation was prepared using the modified wool powder of the present invention (Example 4).

(% By weight) Modified wool powder (Example 4) 5 Vaseline 60 Lanolin 15 Ozokerite 5 Talc 10 Pigment 5 Antioxidant Appropriate amount Fragrance Appropriate amount The mixed blush that has the above formulation is a modified wool powder (Example 4). In comparison with the control product prepared by adding the same amount of wool powder of the reference example, it has better spreadability, close fit, does not lose makeup, and does not generate oil droplets on the surface even after long-term storage, and is stable as a product The character was excellent.

(8) -5 Mascara Using the modified wool powder of the present invention (Example 5), a mascara having the following formulation was prepared.

(% By weight) Modified wool powder (Example 5) 4 Triethanolamine stearate 40 Carnauba wax 15 Paraffin 10 Lanolin 8 Isopropyl isostearate 3 Black iron oxide 20 Mascara composed of the above formulation is modified wool powder ( Compared to the control product prepared by adding the same amount of wool powder of the reference example instead of Example 5), it had an excellent adhesion, was easily adapted to the skin, and had little makeup loss.

(8) -6 Stick Eye Shadow A stick eye shadow having the following formulation was prepared using the modified wool powder of the present invention (Example 6).

(% By weight) Modified wool powder (Example 6) 4 Ozokerite 38 Liquid paraffin 38 Candelilla wax 8 Cetanol 9 Isopropyl stearate 3 Pigment Appropriate amount Preservative Appropriate amount Fragrance Appropriate amount The stick-shaped eye shadow composed of the above formulation was modified. Compared to a control product prepared by adding the same amount of wool powder of Reference Example instead of wool powder (Example 6), it had excellent adhesion, was easily adapted to the skin, and had little makeup loss.

Claims (3)

(57) [Claims] 1. A mercaptan or a mercapto-modified silicone oil containing a higher hydrocarbon group in its structural formula reacts with a cystine side chain in animal hair powder to produce a mercaptan or a mercapto-modified silicone oil containing a higher hydrocarbon group in its structural formula. Animal hair powder modified by forming a disulfide bond with the animal hair powder. 2. An average major axis of 30 μm or less and an aspect ratio of 4
The modified animal hair powder according to claim 1, which is as described above. 3. The amount of mercaptan or mercapto-modified silicone oil containing a higher hydrocarbon group forming a disulfide bond with animal hair powder in the modified animal hair powder is 0.05 to 5.0% by weight. A modified animal hair powder according to claim 1.