JPH09143275A - Eggshell membrane fine powder and various functional agents utilizing its oil absorbing ability - Google Patents

Abstract

(57) [Abstract] [Problem] To develop a new use of eggshell membrane fine powder and to effectively utilize the powder. SOLUTION: The eggshell membrane is immersed in an alcoholic solvent and subjected to at least one of stone mill type rotary grinding and ball mill type grinding to prepare a wet finely divided powder of the eggshell membrane. Due to the particular wet milling process, the eggshell membranes retain a relatively macro fiber structure. This egg shell membrane fine powder has an excellent oil absorption ability,
Alternatively, since it has the ability to stabilize an emulsion composition, it can be widely used for new applications such as an oil scavenger, a sebum remover, a pharmaceutical base, or a cosmetic base.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to egg shell membrane fine powder and various functional agents such as oil absorbents, sebum removers, pharmaceutical bases, cosmetics bases, etc., which utilize its oil absorbing ability, and impair the properties of egg shell membranes. In addition to newly providing a fine powder that effectively retains its activity, the egg shell membrane fine powder is provided as various functional agents having new uses such as oil absorption and stabilization of an emulsion composition.

[0002]

BACKGROUND OF THE INVENTION In recent years, from the viewpoint of protecting the global environment and ecosystems, there has been a strong demand for labor saving and effective utilization of resources including living organisms. However, the eggshell membrane of avian eggs (especially chicken eggs) is a protein. It is a natural material containing as a main component, and its application to the treatment of skin diseases has been attempted in the past, and most of it is currently unused and discarded.

[0003]

2. Description of the Related Art For example, Japanese Unexamined Patent Publication No. 3-190808 discloses a cosmetic using an egg shell membrane. That is, a dried eggshell membrane is solubilized in an alkaline water-containing organic solvent such as sodium hydroxide and ethanol, and mucopolysaccharide is added to the solubilized eggshell membrane to obtain a cosmetic having a skin-beautifying effect and a moisturizing effect. Is listed.

[0004]

The above-mentioned prior art is intended to effectively utilize a solubilized eggshell membrane protein obtained by dissolving an eggshell membrane in a chemical solution, but the present invention does not solubilize the eggshell membrane, It is intended to powderize this and effectively utilize it. Specifically, in addition to producing fine powder that has been successfully drawn out without impairing the properties of the eggshell membrane, we have pioneered various functional agents that have completely new uses other than the purpose of using this eggshell membrane fine powder to impart beautiful skin or moisturize. By doing so, the technical issue is to efficiently utilize the eggshell membrane, which is an organic natural product resource, and to save labor of the resource.

[0005]

Means for Solving the Problems As a result of intensive studies on the eggshell membrane and a technique for pulverizing the eggshell membrane, the present inventors have found that when the eggshell membrane is pulverized by a predetermined wet pulverization treatment method, the proteins constituting the eggshell membrane are It has been found that the activity can be effectively derived without impairing the properties. In addition, we discovered that this egg shell membrane fine powder has an excellent oil absorption function, and developed various functional agents such as oil absorbents, sebum removers, or pharmaceutical bases. It was found that the fine powder also has the ability to stabilize an emulsion as an advanced form of the oil absorption function, and was used as a cosmetic base.

That is, in the present invention 1, the eggshell membrane fine powder is wet pulverized by immersing the eggshell membrane in at least one of water and an alcohol solvent and subjecting it to at least one of stone mill rotary grinding and ball mill pulverization. It is an egg shell membrane fine powder characterized by being a powder.

The invention 2 is characterized in that the eggshell membrane fine powder of the invention 1 is brought into contact with an object to be treated so that the oil content of the object can be absorbed and removed by the eggshell membrane fine powder which is an effective main component. It is an oil-absorbing agent using a fine powder of eggshell membrane.

[0008] The present invention 3 is a sebum remover using the eggshell membrane fine powder, characterized in that the eggshell membrane fine powder of the above-mentioned invention 1 is rubbed on the skin surface to remove the sebum on the skin surface. .

[0009] The present invention 4 is characterized in that the fine powder of eggshell membrane of the present invention 1 is contained in a medicine to enable it to carry an oily medicinal ingredient in the medicine, and a pharmaceutical base using the fine powder of eggshell membrane. Is.

[0010] The present invention 5 is a cosmetic base using the eggshell membrane fine powder, which is characterized in that the eggshell membrane fine powder of the present invention 1 is blended so that a stable emulsion composition can be produced. .

The present invention 6 is a cosmetic characterized in that at least one of lecithin and a quaternary ammonium salt is added in combination to the eggshell membrane fine powder which is the cosmetic base of the above invention 5.

The above-mentioned eggshell membrane fine powder is prepared by mixing the eggshell membrane with water and / or
Alternatively, it is produced by wet pulverization in an alcoholic solvent (that is, a mixed system of water and an alcoholic solvent, an alcoholic solvent, or water). The pulverization treatment may be carried out individually by stone mill type rotary grinding or ball mill type pulverization, but, for example, after the stone mortar type rotary pulverization is applied to the eggshell membrane, the ball mill type pulverization may be continuously carried out. , Both of these pulverizations can be repeated multiple times. Incidentally, it is preferable that the above-mentioned eggshell membrane fine powder is produced by prewashing a raw eggshell membrane, finely pulverizing it, and filtering and washing and drying it. In the preliminary cleaning,
It is also possible to wash with water and then with an alcoholic solvent to dissolve and remove the oil and fat adhering to the eggshell membrane, and to make the eggshell membrane an immersion product suitable for wet pulverization in the next step.

The advantage of selecting the above-mentioned alcohol cleaning is also that there is no problem of remaining water after the water cleaning, and complete replacement with alcohol is not required. The concentration of alcohol in the consistent steps from the alcohol cleaning to the next grinding and crushing can be 0.01 to 99.99%, but in practice, the bactericidal and disinfecting effect of the eggshell membrane can be exhibited at the same time. 30 to 70% is preferable. The alcohols used are saturated, unsaturated aliphatic and aromatic mono, di,
Although a wide range of polyhydric alcohols and the like can be used, ethanol and isopropanol are preferable, and those listed in the Japanese Pharmacopoeia are 70% ethanol and 30%.
%, 50% isopropanol can be used.

In the fine pulverization, the alcohol-immersed product of the eggshell membrane (or the immersed product in water) is repeatedly subjected to stone mill type rotary grinding and ball mill type pulverization to obtain a suspension of the pulverized product. The stone mill type grinding machine is composed of upper and lower special grinders, and crushes the raw material by the force such as impact, shearing, compression, and rolling friction generated between the upper grinder on the fixed side and the lower grinder on the rotating side. . As the grinder to be used, a conventional one can be used, but a ceramic material which has been developed recently and has a characteristic that it does not crack without pores is suitable. Alcohol soaked egg shell membrane
(Or immersion product in water) has an immersion ratio of 1: 0.5
It should be above (solid: dispersion medium (V / V)), actually 1: 1
Use in the range from 1 to 1:10 is preferred. In operation, continuous grinding treatment in which the material that has been ground once is repeatedly fed into the grinder is also effective. Furthermore, the cleaning effect can be further promoted by exchanging the dispersion medium during the continuous grinding process.

The ground product that has been subjected to the stone mill type grinding is put into the ball mill type crusher as it is. In the ball mill type pulverization, a method in which an object to be pulverized and a pulverization medium (for example, zirconia balls) are put in a cylinder and pulverized by rotation by the movement of a rotating shaft in the cylinder or oscillating the cylinder to pulverize is used. be able to. Also in this step, the alcohol immersion ratio of the eggshell membrane powder to be crushed is the same as in the previous step. Separation and collection of the pulverized product from this step is performed by capturing the ball through a sieve having a mesh smaller than the diameter of the ball of the pulverizing medium, and filtering the pulverized product suspension with a microfilter provided in the lower stage. . The balls are washed and the filter cake is crushed with alcohol or other volatile organic solvent.
The residual oil and fat derived from the eggshell membrane is washed and removed, and then dried to obtain an eggshell membrane fine powder (minimum particle diameter of about several microns). In this final-stage washing, the volume of the original eggshell membrane is small and, conversely, the surface area is large, so that the fats and oils can be effectively dissolved and removed. The washing solvents can be used alone or in combination, but acetone or ether can also be used.

The eggshell membrane fine powder is a wet pulverized powder which is subjected to stone mill type rotary grinding or ball mill type pulverization in water and / or alcoholic solvent as described above, and the particle size of the powder is micron unit. It is generally prepared to have various sizes centered on, but when prepared to have a size of several tens of μm to several μm, a relatively fine fiber structure derived from the organic structure originally possessed by the eggshell membrane is obtained. Can hold

The oil absorbing agent is, for example, a cleaning agent for wiping off oil stains on industrial machinery, tableware in homes and cafeterias, or an oil collecting agent for removing floating oil and spilled oil in rivers and oceans (ie , Oil catcher) etc.

The sebum remover contains fine powder of eggshell membrane as a main component, and the powder may be used as a single component, or may be combined with other powder having oil absorbing ability such as talc, feather powder, silk powder and the like. Further, the main sebum removing agent is a concept having a treating agent for removing sebum components on the skin surface as a general concept, but is also a concept including a dirt-rubbing agent for scraping off dirt and waste products on the skin surface.

The above-mentioned pharmaceutical base refers to a raw material for a drug for oral administration, application, sticking, etc., and the main medicinal components (for example, fat-soluble drugs such as fat-soluble vitamins, menthol and camphor) in the drug are It is used to ensure good drug effect of a drug by carrying or impregnating it by utilizing its oil absorbing ability.

The above-mentioned cosmetic bases are lotions, emulsions,
It is a raw material for aqueous or oily cosmetics used in the production of creams, ointments, packs, powders, shampoos, rinses, etc. Among them, it is for stably producing an emulsion composition. In addition, when various egg shell membrane fine powders and lecithin or quaternary ammonium salts are added together when formulating various emulsion compositions, the emulsion stability of the cosmetic composition is promoted. For this reason, when the eggshell membrane fine powder is used alone as a cosmetic base or in combination with lecithin or the like, it is not necessary to add other synthetic surfactants which have been widely used conventionally.

The above lecithin refers to egg yolk lecithin, soybean lecithin and the like. The quaternary ammonium salts include aliphatic ammonium salts, aromatic ammonium salts, heterocyclic ammonium salts such as pyridinium salt-based, imidazolinium salt-based, etc., cellulose-based or polyoxyalkylene adducts of.

Examples of the above-mentioned aliphatic ammonium salts include monoalkyltrimethyl or dialkyldimethylammonium salts and aliphatic amide / polyamines. Specifically, dialkyldimethylammonium chloride (ARCARD 2HT-75; Lion, etc.), lauryl trimethylammonium chloride (Cathiogen TML; manufactured by Daiichi Kogyo, etc.), cetyl trimethylammonium chloride (Cationogen TMP; manufactured by Daiichi Kogyo, etc.),
Stearyl / trimethylammonium chloride (Cationogen TMS; manufactured by Dai-ichi Kogyo Yakuhin, etc.), distearyl / dimethylammonium chloride and the like can be mentioned. Examples of the aromatic ammonium salts include benzalkonium salts and benzethonium salts, and specifically,
Benzalkonium chloride (Cation G-50 and Cation M; Sanyo Kasei, Nikkanon BZ; Nika Kagaku etc., more specifically, stearyl dimethyl benzyl ammonium chloride; Swanol CA-1485; Nippon Surfactant etc.) And so on. Examples of the above heterocyclic ammonium salts include cetyl pyridinium chloride.

The eggshell membrane may be, for example, chicken, quail,
Use eggshell membranes collected from bird eggs such as duck and duck.

[0024]

[Action and effect of the invention]

(1) The eggshell membranes, which are mostly discarded, are miniaturized and used for various purposes, so that effective use of waste materials and labor saving of resources can be achieved at the same time. In addition, since it is a fine powder that makes use of the properties of the natural egg shell membrane protein or various functional agents, it is a safe ecological product that is free from the risk of environmental pollution and has no effect on the living body when used.

(2) Since the egg shell membrane is a fine powder obtained by wet pulverizing the egg shell membrane with water and / or an alcoholic solvent by a predetermined method such as stone mill type rotary grinding, as shown in FIGS. It retains the relatively macro fiber structure originally possessed as an object, and can effectively take out the various functions of the eggshell membrane. The eggshell membrane fine powder has a new application centered on oil absorption, unlike the above-mentioned conventional uses for imparting beautiful skin or moisturizing, and has an oil scavenger, a sebum remover, a pharmaceutical base, etc. It is extremely practical as various functional agents.

(3) When the eggshell membrane fine powder is used as an oil absorbing agent, as described above, factory waste oil, floating oil of rivers and oceans, or spilled oil is quickly absorbed and removed, and the environment is well preserved. it can. In this case, as will be described later, the eggshell membrane fine powder does not have high surface hydrophobicity as compared with the feather fine powder and is relatively easy to disperse in water, so it is widely dispersed in rivers and oceans to collect oil. It is advantageous to Further, when the oil absorbing agent is applied to oil-stained machinery, tableware in homes and restaurants, or hot water baths with dross, oil contamination and dross can be satisfactorily removed to quickly clean the surface.

(4) When egg shell membrane fine powder is used as a sebum remover, sebum adhering to the skin surface such as the face and scalp can be quickly absorbed and removed, and acne, hair loss, etc. It can be prevented. In addition, since the eggshell membrane fine powder, which is a natural product, is contained as a main component, it is harmless to the human body, and it can be expected that the protein component of the eggshell membrane is supplied to the skin surface as a nutrient.

(5) Generally, in the case of producing a tablet-shaped pharmaceutical product, leaching of the oily medicinal component is often caused during tableting. For example, in the case of vitamin preparations, vitamin A and fat-soluble vitamins such as tocopherol acetate may exude from tablets during tableting, but when eggshell membrane fine powder is used as a pharmaceutical base (that is, excipient), As shown in the test examples below, it effectively carries a fat-soluble vitamin due to its oil absorption capacity,
Alternatively, since it is impregnated, the above-mentioned adverse effects can be promptly eliminated. Also, vitamin K, vitamin D, etc. are solid oils different from the above vitamin A, etc., but since the solid oils are also dissolved in an oil agent and then made into functional agents, the eggshell membrane fine powder having high oil absorption ability is shaped into that shape. It is suitable as an agent.

Further, peppermint oil, methyl salicylate, eucalyptus oil and the like are used as oily medicinal components of drug-containing adhesive coated articles (patches), but the eggshell membrane fine powder is impregnated with these agents due to its oil absorbing ability. Because of the high value, the drug retention amount per unit surface area of poultice can be increased.
Therefore, even when applying a poultice of the same size as an existing product, the amount of the drug increases and the effect of the poultice can be maintained for a long time. From this point as well, the eggshell membrane fine powder is advantageous. In addition, menthol, which is the main component of the peppermint oil, or camphor, etc. is poorly soluble in water and easily separated from the paste, and easily vaporized due to the high vapor pressure, but the eggshell membrane fine powder has an effect of retaining these components. Is excellent. As described above, when the eggshell membrane fine powder is used as the drug base, the oily drug effect component in the drug can be surely supported, the loss of the component at the time of production can be prevented, and the drug effect can be favorably maintained.

(6) The prior art mentioned above is a cosmetic using a solubilized egg shell membrane protein. For example, in the production example of the cream (see the left upper column on page 3 of the conventional publication), squalane and cetanol are used. The above-mentioned solubilized eggshell membrane protein is added to a cosmetic raw material such as, and polyoxyethylene sorbitan, which is a surfactant, is further added to emulsify the whole.

On the other hand, although the eggshell membrane fine powder of the present invention has a high oil absorbing ability, it has a higher surface hydrophobicity as compared with the feather fine powder composed of the same keratin protein as shown in the test examples described later. Rather, it can be presumed to have the property of a fibrous hydrophobic substance covered with a hydrophilic shell.
Therefore, moisturizers such as oil, water, glycosaminoglycans, etc.
(Or collagen), coloring agents, and fragrances, when the eggshell membrane fine powder is mixed with the powder, the eggshell membrane fine powder is adsorbed around the oil particles, or the capsule is emulsified like oil containing oil inside the powder. It can be presumed that a stable emulsion system can be formed by the action. At this time, the fact that the surface of the eggshell membrane fine powder is not so hydrophobic and is relatively hydrophilic is considered to contribute to the stabilization of the system. Therefore, when the eggshell membrane fine powder is used, a sufficiently practical emulsion composition can be obtained by formulating it with other agents. It is not necessary to mix the agent (incidentally, as shown in the test example described later, the eggshell membrane fine powder has greater emulsion stability than lecithin alone which is a constituent of egg yolk). That is, above (1)
In (5), the application focusing on the oil absorbing ability of the eggshell membrane fine powder was mentioned, but the egg shell membrane fine powder has a function of stabilizing the emulsion composition as a further development of the oil absorbing ability, and therefore, as a cosmetic base. Has excellent uses. However, when lecithin or a quaternary ammonium salt is added together to the eggshell membrane fine powder, the emulsion composition, which is a mixed system of cosmetic raw materials, can be further stabilized.

In addition, the cosmetics containing the fine powder of eggshell membrane spread widely and thinly and evenly on the skin surface due to the oil absorption function of the eggshell membrane and the like, so that it spreads well with sebum and does not leave a white residue. Highly effective for preventing makeup from falling off. In particular, the present cosmetic composition also has a function as a makeup removing agent and is promising for removing sebum and removing makeup. In addition to the above functions, the eggshell membrane fine powder has a moisturizing ability of the powder itself,
Either alone or in synergy with a moisturizer added separately, it greatly contributes to the moisturizing effect of the cosmetic itself.

(7) In the above (5), the use of the eggshell membrane fine powder as a pharmaceutical base was described from the viewpoint of the supporting action of the oily medicinal component based on the oil absorption ability. From the viewpoint of the stabilizing effect, the eggshell membrane fine powder is suitable as a drug base when various emulsion-type drugs are produced.

(8) Since the present eggshell membrane fine powder exhibits an effective oil absorbing ability, it can be widely used in various applications including antiperspirants in addition to the above-mentioned various functional agents. The antiperspirant is a subordinate use of cosmetics, but when the eggshell membrane fine powder is attached to the armpit or palm, the perspiration component can be absorbed and the antiperspirant ability can be effectively exhibited. Moreover, although similar to the removal of sebum, if the eggshell membrane fine powder is rubbed on the skin surface as a scrubbing agent, it is possible to satisfactorily scrape off the plaque and waste products.

[0035]

Example: Egg shell membrane fine powder
Powder) preparation examples, along with a test example of oil absorption rate and sebum removal ability by the eggshell membrane fine powder, a test example of absorption rate of oily drug substance by the eggshell membrane fine powder, surface hydrophobicity test of eggshell membrane fine powder Examples, and cosmetics containing eggshell membrane fine powder and examples of the emulsion stability test thereof will be sequentially described. However, the present invention is not limited to the following examples.

<< Production Example of Eggshell Membrane Fine Powder >> A raw eggshell membrane obtained from chicken eggs was washed with water and immersed in water. Then, the water immersion product of the eggshell membrane is crushed by a stone mill (mass colloider MK
ZA6-5; manufactured by Masuyuki Sangyo Co., Ltd., was circulated three times for grinding treatment, and then filtered, washed with water, and filtered again to obtain a first-stage ground product. Then, water is added to the first-stage ground product to prepare a slurry, which is then ground with an alumina medium having a rod diameter of 1/2 inch using a vibrating ball mill grinder (SWECO vibration mill M-18L; manufactured by Shinko Pantec Co., Ltd.). It was crushed to obtain a second-stage ground product.

A part of this second-stage ground product was crushed by air flow using a crusher (Current Jet CJ25; manufactured by Nisshin Engineering Co., Ltd.) and then a classifier (turbo classifier TC1).
5; manufactured by Nisshin Engineering Co., Ltd.) and air classified to obtain a finely ground fraction ESMP-A and a coarsely ground fraction ESMP-C.

On the other hand, water was added to the step portion of the second-stage ground product to prepare a slurry, and this slurry was further added to a zirconia ball having a diameter of 3 mm by using a planetary ball mill grinder (Hisie BX254; manufactured by Kurimoto Iron Works). After trituration with the above, washing with water, washing with an organic solvent, and drying, the third-stage ground product ESMP-B was recovered.

The relationship between the type of the eggshell membrane fine powder obtained by the above wet pulverization treatment and the average particle diameter is as follows. ESMP-A: Particle size 6.36 μm ESMP-B: Particle size 2.71 μm ESMP-C: Particle size 41.85 μm

6A and 6B are eggshell membranes before wet crushing treatment, FIG. 5A is an egg shell membrane fine powder ESMP-A obtained by wet crushing treatment, and FIG. 5B is a micrograph showing ESMP-C. Is. As shown in FIGS. 5A and 5B, the eggshell membrane fine powder has a relatively macroscopic fiber structure.

<< Test Example of Oil Absorption Rate >> Eggshell membrane fine powder ESMP-A, B and C obtained in the above-mentioned production example of the wet pulverization method
Is selected as a sample and the oil absorption rate of linseed oil is measured by the following method based on a general pigment test method, and commercially available talc (manufactured by Kanto Kagaku), polyethylene powder (manufactured by Sumitomo Seika), defatted wheat flour (commercially available) The same measurement was performed using a product that was degreased and adjusted by hexane treatment) as a comparative example. In the measurement method, a certain amount of fine eggshell membrane powder was weighed in a tray, and the linseed oil collected in a burette was dropped into the powder in the tray drop by drop. Repeating the kneading operation, when the eggshell membrane fine powder has a paste-like shape and the spatula has a tail (i.e., when the eggshell membrane fine powder reaches a saturated oil absorption state), the end point is the total of linseed oil at that time point. The consumed amount was divided by the weighed amount of eggshell membrane fine powder, and converted into% to obtain the oil absorption rate.

FIG. 1 shows the test results. The egg shell membrane fine powders ESMP-A to C showed a high oil absorption rate compared with talc, which is an inorganic substance, and defatted wheat flour and polyethylene powder having high surface hydrophobicity. . In particular, ESMP-C, which has the largest particle size among the eggshell membrane fine powders, has an extremely high oil absorption rate of more than 400%, and is four times as strong as that of wheat flour which has been conventionally known as having a high oil absorption rate. Excellent oil absorption capacity was observed. In addition, when compared relatively among the eggshell membrane fine powders, 40
ESMP-C having a coarse particle diameter centered on the order of μm exhibited a higher oil absorption. From this, when the eggshell membrane fine powder is used as an oil absorbent, it is sufficient to control the particle diameter of the eggshell membrane fine powder to be blended depending on the application and the functional agent form, and only adjust the particle diameter according to the purpose of use. Therefore, the processing is simple and rational.

ND in the wheat flour column of FIG. 1 indicates that when the wheat flour was treated with hexane, it became almost pasty and the particle diameter could not be measured.

<< Sebum Removal Test Example 1 Using Eggshell Membrane Fine Powder >> Eggshell membrane fine powder ESMP-A was used as it is as a sebum remover, and 10 persons with polylipidemia or those with a strong tendency were arbitrarily selected as subjects. Then, about half a teaspoon (0.3 to 0.5 g) of fine powder of eggshell membrane is strongly rubbed on the palm of each subject to scrape off the sebum on the surface of the palm, and after about 5 minutes, the palm oil removal effect after use Was subjected to a sensory test as compared with before use.

First, as a primary test, the presence / absence of a "sticky" feeling was tested. As a result, 10 people answered "no" and 0 people answered "present". That is, it is understood that the sebum removing effect is effective for each test subject and the stickiness is no longer felt. Therefore, in order to determine the degree of sebum removal as a secondary test for the 10 people, the ratio of "smoothness" and "roughness" of the skin was tested, but those who answered "smooth" 8 people, 2 "Crispy"
Was a person. 20% of "dryness" indicates the high oil-absorbing ability of the eggshell membrane fine powder. By adjusting the amount used and diluting with other materials such as talc, the feeling of use can be improved. Seem. Further, due to its high oil absorption ability, it is advantageous depending on the application of makeup such as when the applied cosmetic is once completely removed with the eggshell membrane fine powder and then reapplied with a useful cosmetic.

<< Sebum Removal Test Example 2 Using Eggshell Membrane Fine Powder >> The sebum removal ability was measured by a method different from that of Test Example 1 above. That is, after selecting 10 subjects (those who have a normal skin surface, unlike the above-mentioned polylipidemia) and evenly applying 1 ml of vegetable oil such as olive oil or soybean oil to the hands, In the same manner as in Test Example 1 above, about 1 teaspoon of the eggshell membrane fine powder was picked up by hands, and both hands were rubbed to bring it into contact with oil, and the attached oil film was scraped off. Next, the eggshell membrane fine powder was washed off by exposing to running water, and the state of water drops adhering to the hands was observed.

As a result, fine water droplets were not observed in all of the 10 subjects, and the water adhesion state similar to that of a normal skin surface was exhibited. It is considered that this is because the egg shell membrane fine powder effectively removed the oil film of the vegetable oil adhering to the hand, and showed the same wetness as the hand before applying the oil component. However, when the dents such as wrinkles on the hands and palm prints were examined in detail, fine water droplets were observed in a plurality of the above subjects. This is probably because the scraping effect of the eggshell membrane fine powder was not reached in the recessed portion, and the oil film of vegetable oil remained, so the water repellency of the oil repelled water and caused water droplets. . That is, this test result should take into consideration individual differences such as the shape of the hand.

<Example of Retention Test of Oily Medicinal Component> The suitability of the powder as a pharmaceutical base was examined by testing the ability of the eggshell membrane fine powder to carry or impregnate the oily medicinal component. That is, the absorption rate of the eggshell membrane fine powder ESMP-A and C for various oily medicinal components was measured by using the same method as in the above oil absorption rate test example of linseed oil. Oily medicinal ingredients include tocopherol acetate, fat-soluble vitamin A, and peppermint oil, which is a medicinal ingredient in poultices.
Methyl salicylate and eucalyptus oil were selected. Further, talc, crystalline cellulose, and starch, which are commonly used as pharmaceutical excipients, were used as comparative examples.

FIG. 2 shows the results. In the fat-soluble vitamin, the absorption rate of the comparative example is 100 to 200%, whereas that of the eggshell membrane fine powder shows 218 to 403%.
In particular, ESMP-C had a high absorption rate of about 400%. This tendency was almost the same for the poultice ingredients. In addition, it is considered that the absorption rate of the eggshell membrane fine powder changes for each oil-based medicinal ingredient, because the viscosity of each medicinal ingredient is also affected. As described above, the eggshell membrane fine powder is excellent in the ability to carry or impregnate the oily medicinal component, and it is recognized that it is suitable as a drug base such as a drug excipient.

Example of Surface Hydrophobicity Test The degree of surface hydrophobic environment (amount of hydrophobic groups on the surface) of the eggshell membrane fine powder was measured using 8-anilinonaphthalenesulfonic acid (ANS) as a fluorescent probe. That is, ANS-Na salt was adjusted to a final concentration of 10 ^-5 M in a 1 mg / ml aqueous suspension of eggshell membrane fine powder, and excitation wavelength was 377 nm and fluorescence wavelength was 463 nm.
The relative fluorescence intensity in was measured. On the other hand, as a comparative example, the surface hydrophobicity of fine powder of feathers, which is a natural protein similar to eggshell membranes, was measured. The eggshell membrane fine powder used had a particle diameter of about 27 μm. In addition, the feather fine powder was produced by a wet pulverization treatment method similar to that of the eggshell membrane fine powder, and the surface hydrophobicity of various powders having different particle diameters was measured.

FIG. 4 shows the results. In FIG. 4, the higher the relative fluorescence intensity is, the higher the surface hydrophobicity is. According to this measurement result, it was confirmed that the eggshell membrane fine powder was not so high in surface hydrophobicity as the feather fine powder and was relatively hydrophilic. Then, the Example of the cosmetics which uses egg shell membrane fine powder as the cosmetics base is described.

<< Example of Manufacturing Emulsion >> 1. Example 1 (A) Squalane 10.0 %% Stearic acid 0.50% Behenyl alcohol 0.50% Butylparaben 0.10% (B) Xanthan gum 0.20% Methylparaben 0.10% Purified water (A) to (C). The rest (C) Eggshell membrane fine powder ESMP-A 1.20% Dipropylene glycol 5.00% Purified water 15.00%

E of the above-mentioned production example as an egg shell membrane fine powder
SMP-A was used. First, 60 parts of each component of (B) above
Dissolve at 0 ° C., disperse each component of (C) above with a homomixer for 2 minutes, mix the aqueous solution of (B) with the dispersion of (C), and add this mixture to 60 ° C. of the above (A). Each component is dissolved and emulsified with a homomixer for 3 minutes to obtain an o / w type emulsion composition,
The emulsion of Example 1 was used. However, the mixing ratio of the above components was wt% with respect to the total amount of the emulsion, and the mixing ratio of the purified water (B) was adjusted so that 100% was obtained when all the components were mixed.

2. Example 2 Based on Example 1 above, 0.13% of lecithin was additionally added to the component (A), and ESMP-A and lecithin were used in combination (mixing conditions for other components were the same as those in Example 1). The same applies to the cases of Comparative Examples 1 and 2). 3. Comparative Example 1 Based on the above-mentioned Example 1, from the component (C), the ESMP-
A is omitted, and 0.13% of lecithin is additionally added to the component (A). 4. Comparative Example 2 Based on Example 1 above, from the component (C), the ESMP-
A is omitted, and sorbitan monostearate is additionally added to the component (A) in an amount of 0.60%. As the above lecithin, soybean lecithin was used.

<Emulsion Emulsion Stability Test Example> As shown in FIG. 3A, the prepared emulsion was immediately placed in a test tube and the degree to which the emulsion was separated into oil layer, cream layer and water layer was visually observed with time. It was measured at. The degree of separation was calculated by the following formula. Separation degree = (total length of separated oil, water and cream layers / total length of liquid layer) x 100

FIG. 3B shows the results. In Example 1, the degree of separation of the liquid layer was lower than in Comparative Examples 1 and 2, and it was recognized that the eggshell membrane fine powder contributed greatly to the stability of the emulsion.
In particular, lecithin is also a constituent of egg yolk, but the eggshell membrane fine powder has a greater effect of stabilizing the emulsion than this lecithin (used alone). Further, as can be seen from the comparison between Examples 2 and 1, when lecithin was added to the eggshell membrane fine powder in combination, the stability of the emulsion was increased more than when the eggshell membrane fine powder was used alone.
That is, when the eggshell membrane fine powder is formulated in combination with lecithin, dipropylene glycol, etc., it is useful for the production of a cosmetic emulsion composition having extremely high stability and good feeling due to the excellent action of the combination.

<< Example of Cream Rinse Production >> First, the eggshell membrane fine powder ESMP-A was put in water to prepare suspension water with various surfactants, and the eggshell membrane fine powder was dispersed in the suspension water. , Or the degree of swelling was tested. The dispersing conditions are as follows: eggshell membrane fine powder is added at 2% by weight, surfactant is added at a predetermined ratio of 0.002 to 0.6% by weight, and the rest is adjusted with purified water to 100% by weight, and 600 with a homomixer.
The mixture was stirred at 0 rpm for 3 minutes.

The surfactant used is (1)
To (6) cationic surfactants (specifically, quaternary ammonium salts) and (7) to (12) nonionic surfactants. (1) Benzalkonium chloride (manufactured by Kanto Chemical) (2) Benzethonium chloride (manufactured by Kanto Chemical) (3) Dialkyldimethylammonium chloride (ARCARD 2HT-75; manufactured by Lion) (4) Lauryltrimethylammonium chloride (catiogen)
(TML; manufactured by Dai-ichi Kogyo Yakuhin) (5) Cetyltrimethylammonium chloride (CationogenTM)
P; manufactured by Dai-ichi Kogyo) (6) Stearyl trimethyl ammonium chloride (Cathogen TMS; manufactured by Dai-ichi Kogyo) (7) Polyoxyethylene nonylphenyl ether (Neugen EA-170; manufactured by Dai-ichi Kogyo) (8) Poly Oxyethylene dodecyl phenyl ether (Neugen EA-73; manufactured by Daiichi Pure Chemicals) (9) Polyoxyethylene lauryl ether (Neugen ET-1
70; manufactured by Daiichi Kogyo Yakuhin) (10) Polyoxyethylene oleyl ether (Neugen ET-
80; Dai-ichi Kogyo KK) (11) Polyoxyethylene (EO6) sorbitan monooleate (Nikko TS-106; Nikko Chemicals) (12) Polyoxyethylene (EO20) sorbitan monooleate (Nikko TS-10) (Manufactured by Nikko Chemicals)

As a result, the quaternary ammonium salt (1)
In the case of (6)-(6), the cake layer was formed on the uppermost layer at the compounding rate of 0.2% or more, but in the case of 0.1% or less, the nonionic type (7)-(1
In comparison with 2), the formation interface of precipitates was not clear in all cases, and only a small water layer was seen from the top.
That is, the egg shell membrane fine powder showed an extremely high swelling state due to the incorporation of the quaternary ammonium salt, and good dispersibility was observed. The appropriate concentrations of the above quaternary ammonium salts (1) to (6) were as follows. (1) ~ (2) = 0.01% (3) = 0.05% (4) ~ (6) = 0.02%

Then, paying attention to the dispersing effect of the quaternary ammonium salt in the above suspension test, an egg shell membrane fine powder and
A production example of a cream rinse using the quaternary ammonium salts of the above (3) and (6) together will be described. ARCARD 2HT-75 2.0% Cationogen TMS 3.0% Methylparaben 0.1% Behenyl alcohol 2.5% Silicone oil 0.2% Eggshell membrane fine powder ESMP-A 2.0% 1,3-Butylene glycol 3.0 % Purified water balance

First, the above-mentioned items 1 to 3 are dissolved in purified water in advance,
And were separately dissolved by heating at 60 ° C. Also,
And were thoroughly kneaded, and these were combined with dissolved water of ~, and the above was added to the place where it was heated to 50 ° C, and the mixture was stirred with a homomixer at 6000 rpm for 5 minutes to prepare a cream rinse. However, the mixing ratio of the above components was wt% with respect to the entire rinse, and was adjusted by the mixing amount of purified water so as to be 100% when all the components were mixed.

As a result, the resulting emulsion composition had a smooth and uniform feel, and when the eggshell membrane fine powder was formulated in combination with quaternary ammonium salts, it was found that a cream rinse or the like with a good dispersion / swelling condition was obtained. It was found to be suitable for manufacturing.

[Brief description of the drawings]

FIG. 1 is a table showing the test results of oil absorption by eggshell membrane fine powder and other agents.

FIG. 2 is a table showing the test results of the absorption rate of oily medicinal components by eggshell membrane fine powder and other agents.

FIG. 3A is an explanatory diagram of a stability test of an emulsion containing an egg shell membrane fine powder, and FIG. 3B is a time-dependent change diagram of the degree of separation showing the results of the stability test.

FIG. 4 is a view showing test results of surface hydrophobicity of eggshell membrane fine powder and feather fine powder.

FIG. 5A is a magnification 5 of the eggshell membrane fine powder ESMP-A.
Microscope photograph at 000 times, Fig. 5B shows 1 of the same ESMP-C.
It is a microscope photograph at a magnification of 000.

FIG. 6A is a micrograph of an eggshell membrane before pulverization at a magnification of 1000 times, and FIG. 6B is a micrograph at a magnification of 5000 times.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C09K 3/32 C09K 3/32 K

Claims (6)

[Claims] 1. The eggshell membrane fine powder is a wet pulverized powder obtained by immersing the eggshell membrane in at least one of water and an alcoholic solvent and subjecting it to at least one of stone mill rotary milling and ball mill pulverization. Characterized eggshell membrane fine powder. 2. The eggshell membrane fine powder according to claim 1 is brought into contact with a substance to be treated, and the eggshell membrane fine powder which is an effective main component enables absorption and removal of oil content of the substance to be treated. An oil absorbing agent that uses fine powder of eggshell membranes. 3. A sebum-removing agent using egg shell membrane fine powder, characterized by rubbing the egg shell membrane fine powder according to claim 1 on a skin surface to enable removal of sebum on the skin surface. 4. A drug base using the egg shell membrane fine powder, which comprises the egg shell membrane fine powder according to claim 1 in a medicine so that an oily medicinal component in the medicine can be supported. 5. A cosmetic base using eggshell membrane fine powder, which comprises blending the eggshell membrane fine powder according to claim 1 to enable production of a stable emulsion composition. 6. A cosmetic, comprising at least one of lecithin and a quaternary ammonium salt used in combination with the eggshell membrane fine powder as the cosmetic base according to claim 5.