JPH04305515A - Emulsion-type mascara - Google Patents

Abstract

PURPOSE:To provide an emulsion-type mascara excellent in curling effect, water-resistance, curl-retaining force, storage stability and safety to the skin. CONSTITUTION:The objective mascara contains a water-soluble fibroin peptide having an average molecular weight of 300-3,500, an oily base having a melting point of 60-110 deg.C (e.g. beeswax), water and an anionic or nonionic surfactant. The mascara composition may be further incorporated with a hair-fixing vinyl resin such as polyvinyl alcohol or acrylic resin emulsion at a ratio (resin : fibroin peptide) of 1:9 to 9:1.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention protects eyelashes from dryness,
The present invention relates to an emulsified mascara that has excellent practical properties (i.e., curl-preserving ability, etc.), storage stability, and safety to the skin.

0002

2. Description of the Related Art In general, eyelashes are severely deteriorated and damaged due to heavy use of mascara and remover, resulting in dryness, fluffiness, increased hair loss, and decreased suppleness.

Conventional emulsifying mascara generally contains beeswax,
Forming a film with a high melting point oil base such as ceresin (
"Cosmetic Science" P78 Yakuji Nipposha), forming a film with acrylic resin emulsion (Japanese Patent Application Laid-Open No. 50-1
25043, Special Publication No. 61-26764, Special Publication No. 62-4
3971) or a water-soluble resin such as polyvinyl alcohol or polyvinylpyrrolidone to form a film on the eyelash surface (Japanese Patent Laid-open No. 62-224610) to increase the curling effect.

0004

[Problems to be Solved by the Invention] However, coatings formed only from high melting point oil bases or acrylic resin emulsions do not retain moisture, and are difficult for eyelashes that require a certain amount of moisture.
This caused dryness and even damage.

On the other hand, coatings formed only from water-soluble resins such as polyvinyl alcohol and polyvinylpyrrolidone do not crystallize even when dried, so they become sticky when they contain moisture, causing eyelashes to stick to each other and color transfer to the lower eyelids. There were other problems.

[0006]

[Means for Solving the Problems] The present inventors have conducted extensive research in view of the above problems.

As a result, a water-soluble fibroin peptide having an average molecular weight of 300 to 3,500 and an oily base having a melting point of 60 to 110° C. are used as a film forming agent, or in addition to the above film forming agent, the fibroin peptide is Te1:
It was discovered that an emulsified mascara prepared using a vinyl hair styling resin with a ratio of 9 to 9:1 has characteristics that eliminate all the drawbacks of the conventional ones, and the present invention was completed.

That is, an object of the present invention is to provide an emulsified mascara that has excellent practical properties (water resistance, curl-preserving ability, etc.), storage stability, and safety for the skin.

[0009] The first invention of the present invention provides the following (A) to (D)
This is an emulsified mascara characterized by containing the following four ingredients. (A) Water-soluble fibroin peptide with an average molecular weight of 300-3500 (B) Oily base with a melting point of 60-110°C (C) Water (D) Surfactant

Other inventions of the present invention include the following (A) to (
Contains 5 components of E), and the content ratio of (A) and (E) is 1
:9 to 9:1. (A) Water-soluble fibroin peptide with an average molecular weight of 300-3500 (B) Oily base with a melting point of 60-110°C (C) Water (D) Surfactant (E) Vinyl hair styling resin

The present invention will be explained in detail below. The water-soluble fibroin peptide used in the present invention is easily soluble in water,
The aqueous solution is transparent because the fibroin peptide is amorphous. When this aqueous solution is applied to the surface of a glass plate, synthetic resin sheet, eyelashes, etc. and dried, the film crystallizes, and an X-ray diffraction image confirms that this crystal is of the α type.

[0012] As a result of analysis, the amino acid composition of this fibroin peptide was found to be 43-54% glycine and 26% alanine.
~37%, serine 11-15%, tyrosine 9-12%,
Other amino acids are present in trace amounts.

[0013] The average molecular weight of fibroin peptide is 30
0-3500, preferably 1000-2500. If it is less than 300, the stability of the aqueous solution and the ability to form a film will deteriorate, and it will not crystallize even when dried, and if it contains water, it will become sticky, which is not preferable. If it is greater than 3,500, the solubility in water and the stability of the aqueous solution will deteriorate significantly, which is not preferable.

[0014] The fibroin peptide used in the present invention can be prepared, for example, as follows. Copper-ethylenediamine aqueous solution, copper hydroxide-ammonia aqueous solution,
After dissolving the refined silk raw material in at least one solvent selected from the group consisting of copper hydroxide-alkali-glycerin aqueous solution, lithium bromide aqueous solution, and calcium chloride aqueous solution,
A 0.5 to 20% by weight silk fibroin aqueous solution obtained by dialysis is hydrolyzed with an enzyme, an acid, or an alkali to obtain a fibroin peptide aqueous solution.

[0015] Enzymatic hydrolysis is usually carried out at pH 5-9,
It is carried out for about 1 to 72 hours under conditions of 20 to 50°C. As the enzyme used for hydrolysis, proteolytic enzymes such as papain and trypsin are preferred. These enzymes are
It is used in an amount of 0.1 to 5.0% by weight based on the total amount of silk fibroin aqueous solution.

[0016] Hydrolysis with acid or alkali is usually carried out at 20 to 110°C for 0.5 to 50 hours. Examples of acids used for hydrolysis include inorganic acids such as hydrochloric acid and sulfuric acid, tartaric acid, malonic acid, succinic acid, and maleic acid. The concentration used is 0.03-3N.

According to the above method, a fibroin peptide having a desired molecular weight of 300 to 3,500 and having an extremely sharp molecular weight distribution can be produced.

The above fibroin peptide aqueous solution may be powdered or the peptide may be 55% pure as a substantially pure content.
It may be used as an aqueous solution of fibroin peptide dissolved at ~10% by weight.

[0019] The substantial fibroin peptide content in the present invention is 0 based on the total amount of emulsified mascara.
．． If the amount is less than 0.05% by weight, water will not be retained and the ability to form a film will be low. Moreover, if the amount exceeds 10% by weight, the water resistance of the film will be weak, and even if a high melting point oily base is added, it will be difficult to enhance the water resistance.

[0020] Oil bases with a melting point of 60 to 110°C used in the present invention include hydrocarbons such as paraffin, ceresin, and polyethylene, animal waxes such as spermaceti wax, beeswax, and lanolin, carnauba wax, and candelilla wax. Hydrogenated natural waxes such as vegetable waxes, mineral waxes such as montan wax, and the like can be mentioned.

[0021] A base having a melting point of less than 60°C has a large temperature dependence, and the mucous membrane deteriorates in an environment of 40 to 45°C, making it undesirable for use. Further, a base having a melting point exceeding 110° C. is not preferable because it requires raising the temperature during production and causes deterioration of other base materials. This melting point is 60-11
The oily base at 0°C enhances the curling power of the mascara and strengthens the water resistance of the emulsified mascara.

The content of the oily base having a melting point of 60 to 110° C. is preferably 10 to 30% by weight; if it is less than 10% by weight, the water resistance of the film will be weak and the viscosity of the mascara will also be low, so the mascara may not be sufficiently coated. It does not adhere to the eyelashes and is not desirable in terms of effectiveness. On the other hand, if it exceeds 30% by weight, the coating will repel moisture and will not be able to retain moisture. Furthermore, the viscosity is high even as an emulsion type mascara, making it undesirable for use.

The surfactant used in the present invention may be either anionic or nonionic. Examples of the anionic surfactant include alkyl sulfates such as cetyl sulfate and lauryl sulfate. Examples include ester salts and metal salts of fatty acids such as stearic acid and myristic acid.

Examples of nonionic surfactants include polyethers such as polyoxyethylene alkyl ether and polyoxypropylene alkyl ether, and polyhydric alcohol fatty acid moieties such as sucrose fatty acid ester, glycerin monoester, and polyglycerin fatty acid ester. Examples include esters.

[0025]Also, an alkali such as triethanolamine, 2-amino-2-methyl-1-propanol, morpholine, etc. is blended into the aqueous phase, and a fatty acid is blended into the oil phase, which is then mixed to form a soap and emulsified. It is also possible to do so.

Further, the water used in the present invention includes purified water such as ion-exchanged water, and the total content thereof is preferably 30% by weight or more, and if it is less than 30% by weight, the viscosity of the mascara becomes high. , it is difficult to use and the drying speed is also slow.

[0027] The emulsified mascara of the present invention contains the water-soluble fibroin peptide described above, an oily base with a melting point of 60 to 110°C, water, and a surfactant, so it can provide excellent effects. Furthermore, depending on the desired quality, properties such as adhesion to the eyelashes and strength of the film can be improved by adding a specific amount of a known vinyl hair styling resin such as polyvinyl alcohol, polyvinylpyrrolidone, or acrylic resin emulsion. can do.

When fibroin peptide and vinyl hair styling resin are used together, the total content is at most 20% by weight, preferably within 10% by weight, and the ratio is fibroin peptide:vinyl hair styling resin=1: The ratio is 9 to 9:1.

When an acrylic resin emulsion is used in combination, it is preferably blended as an emulsion with a resin content of 30 to 60% by weight, and up to about 30% by weight can be blended.

[0030] In addition, pigments, dyes, emulsifiers, preservatives, bactericidal agents, oils, gels, sequestrants, and the like may be appropriately blended as necessary.

The emulsified mascara of the present invention is extremely stable even after long-term storage, and dissolved fibroin peptides do not precipitate, coagulate, or precipitate. In addition, since fibroin peptide is a peptide derived from silk fibroin, it gives the eyelashes the good luster, luster, and supple texture characteristic of silk, and also provides the amino acid component that is nutritious.
Eyelash repair and cosmetic effects can be further improved.

These useful and remarkable effects are not found in collagen peptides derived from collagen or keratin peptides derived from keratin, and the specificity of the effects of the present invention is remarkable.

[0033]

[Example] Examples will be described below. Example 1,
According to the formulation and preparation method described in 2 and Comparative Examples 1 to 4,
Emulsified mascara was manufactured and tested for practical properties, storage stability, and safety on the skin.

Example 1 An emulsified mascara is prepared according to the recipe in Table 1.

[0035]

[Table 1]

The preparation method is as follows. (Oil phase) Beeswax, stearic acid, and butyl paraoxybenzoate are uniformly dissolved at 100°C. (Aqueous phase) Dipropylene glycol, 2-amino-2-methyl-1-propanol, fibroin peptide aqueous solution, and methyl paraoxybenzoate are uniformly mixed and dissolved in purified water at 60°C, and then black iron oxide is mixed and dispersed. . The oil phase is added to the water phase and emulsified using a homomixer, then ethanol is added, cooled to room temperature, and filled into mascara containers.

Example 2 The content of the fibroin peptide aqueous solution of Example 1 was reduced to 10
Polyvinylpyrrolidone aqueous solution (purity 7%)
The same as Example 1 except that 40% by weight was added.

Comparative Example 1 This was the same as Example 1 except that the fibroin peptide aqueous solution in Example 1 was replaced with a polyvinyl alcohol aqueous solution (purity 7%).

Comparative Example 2 This was the same as Example 1 except that the fibroin peptide aqueous solution in Example 1 was replaced with a polyvinylpyrrolidone aqueous solution (purity 7%).

Comparative Example 3 This was the same as Example 1 except that the fibroin peptide aqueous solution in Example 1 was replaced with a keratin peptide aqueous solution (purity 7%).

Comparative Example 4 This was the same as Example 1 except that the fibroin peptide aqueous solution in Example 1 was replaced with a collagen peptide aqueous solution (purity 7%).

Comparative Example 5 The same as Example 1 except that beeswax (melting point 62-67°C) in Example 1 was replaced with spermaceti wax (melting point 42-50°C).

Comparative Example 6 The beeswax of Example 1 (melting point 62-67°C) was mixed with lanolin (
The procedure is the same as in Example 1 except that the melting point is 36 to 42°C).

Comparative Example 7 The same as Example 1 except that beeswax (melting point 62-67°C) in Example 1 was replaced with cetanol (melting point 46-55°C).

(Practical Characteristic Test) A set of samples of the comparative example and the sample of the working example were applied to each side of the eyelashes of 30 female test subjects to compare and evaluate the comparative example and the working example. The five evaluation items were ``stickiness'', ``curling effect'', ``gloss'', ``water resistance'', and ``makeup retention (durability of makeup effect)'', and the evaluation was ``excellent''. "○" if there are 20 or more people, "△" if there are 10 to 19 people
, if there are fewer than 9 people, it is indicated with an "x". The results are shown in Table 2.

[0046]

[Table 2]

A curl retention test was conducted to confirm the difference in curling effect between the examples and comparative examples. In the curl retention test, hair bundles of length 20 cm and 1.3 g were tested with fibroin peptide aqueous solution (purity 7%), keratin peptide aqueous solution (purity 7%), collagen peptide aqueous solution (purity 7%), and purified water as a blank. After soaking in each of the four types of liquid, squeezing with a certain pressure, winding it around a rod with a diameter of about 1 cm,
Dry in a dryer at 45°C for 24 hours and use as a sample. These samples are attached to the top of a scale plate and left under conditions of 25° C. and 70% RH, and the lowered position of the curl tip is read from the scale plate and calculated using the following formula.

[0048] L: Length when the test hair is fully extended LO: Position of the tip of the curl before being left LT: Position of the tip of the curl after being left for a certain period of time (T) The results measured as above are shown in Table 3.
Shown below.

[0049]

[Table 3]

(Storage stability test) In order to compare the storage stability between the example and the comparative example, the
The viscosity of the mascara when left in each thermostat at 5°C for 3 days was measured using a bismetron type viscometer (rotor No. 4).
, 6 rpm). The results are shown in Table 4. The unit is cp
It is s.

[0051]

[Table 4]

[0052] From these results, it can be seen that the comparative example has a large temperature dependence, while the example has a small temperature dependence and is excellent in storage stability.

(Skin safety test) In order to compare the skin safety of Examples and Comparative Examples 1 to 4, 20
A practical test was conducted by a panel of experts, and evaluation was made using the following criteria.

◎: If 18 or more people answered that it was good without feeling any stinging around the eyes ○: 〃
If 〃 is 14 to 17 people △: 〃
If 〃 is 8 to 13 people ×: 〃
Table 5 shows the results when 〃 is 7 or less.

[0055]

[Table 5]

Example 3 An emulsified mascara is prepared according to the recipe in Table 6.

[0057]

[Table 6]

The preparation method is as follows. (Oil phase) Beeswax, ceresin, stearic acid, and butyl paraoxybenzoate are uniformly dissolved at 100°C. (Aqueous phase) Dipropylene glycol, 2-amino-2-methyl-1-propanol, fibroin peptide solution, and methyl paraoxybenzoate are uniformly mixed and dissolved in purified water at 60°C, and then black iron oxide is mixed and dispersed. . The oil phase is added to the water phase and emulsified using a homomixer, then ethanol and acrylic resin emulsion are added, cooled to room temperature, and filled into mascara containers.

Example 4 An emulsified mascara having the formulation shown in Table 7 is prepared.

[0060]

[Table 7]

The preparation method is as follows. (Oil phase) Microcrystalline wax, ceresin, stearic acid, and butyl paraoxybenzoate are uniformly dissolved at 100°C. (Aqueous phase) Dipropylene glycol, 2-amino-2-methyl-1-propanol, fibroin peptide aqueous solution, polyvinyl alcohol, and methyl paraoxybenzoate were uniformly mixed and dissolved in purified water at 60°C, and then black iron oxide was added. Mix and disperse. The oil phase is added to the water phase and emulsified using a homomixer, then cooled to room temperature and filled into mascara containers.

In Examples 3 and 4, practical property tests, storage stability tests, and skin safety tests were conducted in the same manner as in Example 1, and excellent evaluations were obtained.

[0063]

Effects of the Invention As described above, the present invention has an average molecular weight of 30
0-3500 water-soluble fibroin peptide, melting point 60
Practical properties (curl effect, water resistance, makeup retention, etc.) and storage stability are improved by blending an oily base at ~110°C, water, and a surfactant, and by further blending a vinyl hair styling resin. It is clear that an emulsified mascara that has excellent properties and is highly safe for the skin is provided.

Claims (2)

[Claims] 1. An emulsified mascara characterized by containing the following four components (A) to (D). (A) Water-soluble fibroin peptide with an average molecular weight of 300-3500 (B) Oily base with a melting point of 60-110°C (C) Water (D) Surfactant 2. An emulsified mascara comprising the following five components (A) to (E), and the content ratio of (A) to (E) is 1:9 to 9:1. (A) Water-soluble fibroin peptide with an average molecular weight of 300-3500 (B) Oily base with a melting point of 60-110°C (C) Water (D) Surfactant (E) Vinyl hair styling resin