JPH0827186A - New silk fibroin peptide, its production and cosmetic and detergent composition containing the same - Google Patents

Abstract

PURPOSE:To obtain a new silk fibroin peptide excellent in film formability, water holding ability, solubility and long-term preservability, useful for cosmetics having of high humectancy and safety or detergent having high foaming power and detergency, by treating silk fibroin at high temperatures and pressures to effect its hydrolysis. CONSTITUTION:This new fibroin peptide of the formula (R and R' are each side chain of the various amino acids constituting the silk fibroin; (n) is an integer of 0-20) is easily and industrially obtained at low cost by the following process: silk fibroin powder and distilled water are put into a pressure vessel and treated in the presence of a <=0.1N acid or <=0.1N alkali in a nitrogen atmosphere in a high-pressure water at 150-250 deg.C for 16hr to effect its hydrolysis followed by cooling and then filtering off minute amounts of insolubles to collect a filtrate which is then concentrated. This fibroin peptide is excellent in film formability, water-holding ability, solubility and long-term preservability, therefore being useful for cosmetics of high humectancy, film formability and safety, and detergent compositions of good foaming power, detergency, foam properties and safety.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silk fibroin peptide excellent in film forming ability, water retention ability, solubility, and long-term storage ability, and an industrially easy and inexpensive production method thereof. Furthermore, the present invention relates to a cosmetic composition containing the silk fibroin peptide and having excellent moisturizing properties, film-forming ability and safety, and a detergent composition having excellent foaming power, detergency, foam quality and safety.

[0002]

2. Description of the Related Art Peptides obtained by hydrolyzing proteins derived from natural products such as animals and plants have little irritation to the skin and hair, and have excellent moisturizing properties. Was used for. Specific examples include collagen peptide (gelatin), keratin peptide, soy protein peptide and the like. However, these peptides contain sulfur-containing amino acids such as cysteine and methionine among the constituent amino acids, and thus have a problem of having a sulfur odor.

In recent years, in addition to the above-mentioned peptides, silk fibroin peptides have been used. Since the silk fibroin peptide is derived from a natural protein, it is known that it does not have an irritating effect on skin and hair and has a film-forming ability. In addition, many amino acids that compose fibroin are neutral amino acids such as glycine and alanine, which are similar to the amino acids that compose skin tissue, and their involvement with natural moisturizing factor (NMF) has been extensively studied. Furthermore, the high-class feeling of silk has come to match the consumer's intention, and silk fibroin peptides have come to be used in the form of being added to cosmetics and detergents.

However, since the silk fibroin peptide has a high content of inorganic salts, it has been stored for a long period of time due to a formulation problem such as salt deposition or silk peptide deposition in the formulation of cosmetics and the like. Silk fibroin peptide had problems such as turbidity, sediment, and precipitation, which reduced its commercial value.

There are roughly two types of known methods for producing conventional silk fibroin peptides. One is a method of directly hydrolyzing silk fibroin with an acid or an alkali. In this method, since fibroin had to be reacted as a solid, a large amount of fibroin remained in a fibrous state, and the reaction yield was as low as about 50%.

Another method is disclosed in JP-A-55-124.
This is a method represented by the manufacturing method disclosed in Japanese Patent No. 743. This method facilitates the hydrolysis reaction,
In this method, silk fibroin is once dissolved in a concentrated solution such as calcium chloride or copper-ethylenediamine, desalted by a method such as dialysis, and then hydrolyzed with an acid / alkali or an enzyme. According to this method, a silk peptide having a relatively narrow molecular weight distribution can be obtained.

However, in the latter method, since an inorganic salt such as calcium chloride is used for solubilizing silk fibers, a desalting step such as dialysis is indispensable before the subsequent hydrolysis reaction. Further, when an acid or an alkali is used in the hydrolysis reaction, it is necessary to neutralize after the reaction, and a considerable amount of salt was also generated there.

When a silk fibroin peptide having a high content of inorganic salts is used, the formulation problems such as salt precipitation and silk peptide precipitation in the formulation of cosmetics and the like, and silk fibroin stored for a long time Peptides had problems such as turbidity, sediment, and precipitation, which reduced their commercial value.

Further, when the silk fibroin is hydrolyzed and then desalted by a method such as dialysis, the low molecular weight peptide is removed together with the inorganic salt, resulting in a decrease in the silk fibroin yield.

When a large amount of silk fibroin peptide is to be produced on an industrial scale, the desalting step is not an easy treatment step because a large amount of waste water is produced, the dialysis membrane is clogged, and the operation becomes complicated. It was

Therefore, the conventional method is not suitable for an industrial and inexpensive manufacturing method. Further, the silk fiber solubilizing agent such as calcium chloride and the corrosion of the reaction device due to acid or alkali during hydrolysis have also been a problem.
Further, when a copper-ethylenediamine complex was used as a solubilizing agent, heavy metal contamination in the product was a problem. Further, in the case of hydrolyzing silk fibroin with an enzyme such as protease, it was not suitable for industrialization because an expensive enzyme was used. In this way, in the conventional method, the product obtained is expensive due to the low reaction yield, the large amount of auxiliary raw materials in the manufacturing process, and the long reaction process. The range was limited. As described above, the conventional methods for producing silk fibroin peptide have many problems.

There is also an example in which after solubilizing silk fibroin, it is not hydrolyzed and dried as it is to be incorporated into cosmetics as silk fibroin, but its solubility is poor and a dispersant is required, so that the range of use is limited. It had been.

In addition, when the silk fibroin peptide produced by the conventional method was incorporated into a cosmetic, there were some problems. That is, when it was used as a cosmetic, it was not satisfactory in terms of moderate film forming property and moisturizing property due to insufficient film forming ability.

Regarding detergent compositions, general surfactants currently used in shampoos and kitchen detergents have a considerable amount of skin irritant, and if used frequently, they cause itching of the scalp and rough hands. It was. In addition, since the foam quality is often scattered, a fine-textured cleansing agent has been desired. Therefore, it has been desired that the detergent composition has a high foaming power / cleansing power, a foamy quality, and a low skin irritation.

[0015]

The problems to be solved and used by the present invention are to solve the drawbacks of the prior art and to have excellent film-forming ability, water retention ability, solubility, and long-term storability. An inexpensive silk fibroin peptide and a method for producing the same. Furthermore, the present invention relates to a cosmetic composition containing the silk fibroin peptide and having excellent moisturizing properties, film-forming ability and safety, and a detergent composition having excellent foaming power, detergency, foam quality and safety.

[0016]

[Means for Solving the Problems] For the purpose of obtaining silk fibroin powder, a method of swelling silk fibers by heating with steam is already known (Japanese Patent Laid-Open No. 45232/1983).
JP-A-58-46097). However, these methods were not intended to obtain silk fibroin peptide by hydrolyzing silk, but the purpose was simply to swell and swell the fiber. In fact, in this method, silk fibroin was hardly hydrolyzed, and the silk fiber was shortened.

The present inventors have discovered that silk fibroin is completely dissolved and the peptide bond is cleaved to form silk fibroin peptide when it is sufficiently heated and steamed for a longer period of time. In view of this result, further investigation was conducted, and it was found that by treating silk fibroin with high-temperature high-pressure water under a certain condition, hydrolysis easily proceeds to form a silk fibroin peptide, and the present invention was completed.

According to this reaction method, an inorganic salt is not used for solubilizing the silk fiber, and an acid / alkali /
Since no enzymatic reaction is performed, there is no need to neutralize after hydrolysis. Therefore, it is not necessary to perform the desalting step which is a problem in the conventional method. Moreover, since no acid or alkali is used for hydrolysis, there is no concern about corrosion of the equipment. Further, since it is not necessary to use an expensive enzyme, it is possible to manufacture at low cost.
According to the production method of the present invention, the silk fibroin peptide can be obtained simply by placing silk fiber and water in a pressure vessel and heating, so that the process is very short and the operation is simple. Therefore, it can be said that the manufacturing method is industrially easier to carry out and less expensive than the conventional method.

Surprisingly, the silk fibroin peptide obtained by this method was superior to the silk fibroin peptide produced by the conventional method in film forming ability and water retaining ability. In addition to being water-soluble, the solubility in lower alcohol aqueous solutions such as ethanol was also high. Furthermore, it was discovered that the long-term storage precipitation and turbidity found in conventional products are eliminated, and that the product has excellent long-term storage stability.

Furthermore, when used in skin cosmetics and hair cosmetics, it was more excellent in moisturizing property, film forming ability and safety as compared with conventional silk fibroin peptides. In addition, when used as a detergent, it not only improves foaming power and detergency, but also has a creamy foam quality and is low in irritation, and also has the effect of relaxing the irritation of conventional surfactants. Had.

That is, the present invention provides silk fibroin with 1
The following general formula (1) obtained by treating in 50-250 ° C. high-pressure water and hydrolyzing

[0022]

[Chemical 7]

(In the formula (1), R and R ′ are side chains of various amino acids constituting silk fibroin, and n is 0 to 0).
Is an integer of 20).

A second aspect of the present invention is a silk fibroin peptide represented by the above general formula (1) characterized by treating silk fibroin in high-pressure water at 150 to 250 ° C. for hydrolysis. The present invention relates to a manufacturing method.

As the silk fibroin used in the present invention, those commercially available as silk fibroin powder are most suitable, but raw silk, raw silk scraps, auxiliary silkworm threads such as cocoon brim, carrier, burette, noil, etc. are used. You can also Silk fibers consist of fibroin and sericin surrounding fibroin, but silk without sericin can also be used. These sub-silk yarns and the like are scraps at the time of scouring, and are inexpensive and can secure a sufficient amount, so they are suitable for industrial production.

The production of the silk fibroin peptide of the present invention is accomplished by placing silk fibroin in a pressure-resistant container, further adding water, heating to 150 to 250 ° C., and stirring for 1 to 48 hours. Water can be used in an amount of 1 to 100 times, and preferably 5 to 30 times, the weight of silk fiber. If the amount of water is small, it becomes difficult to stir, and silk fibers may stick to the wall surface of the pressure vessel.
On the other hand, if the amount of water is too large, there is no problem in the reaction, but the concentration of silk fibroin peptide becomes low and the economical efficiency decreases.

If the reaction temperature is lower than 150 ° C., the silk fiber cannot be completely hydrolyzed even if the reaction time is extended, and the fiber remains, resulting in a low yield. Again 250
At a reaction temperature exceeding ℃, although the reaction rate is fast, the obtained silk fibroin peptide is colored brown,
It is not preferable because sometimes a burnt odor is obtained.
In addition, the pressure during the reaction increases and the risk of explosion increases, which is not preferable. The reaction temperature is preferably 170-
It is 200 ° C. At this temperature the pressure is usually 7-12 kg
It is about f / cm ² . In terms of coloring in the reaction,
It is preferable to start the heating after nitrogen replacement.

When producing the silk fibroin peptide of the present invention, hydrolysis may be carried out in the presence of a constant concentration of acid or alkali. When the hydrolysis is carried out in the presence of acid or alkali, the reaction time can be shortened as compared with the case where the reaction is carried out only with water. However, if the acid or alkali used is not dilute, silk fibroin may be hydrolyzed to silk amino acid. Specifically, 0.1 for both acid and alkali
Hydrolysis is performed at a concentration of N or less. Preferably 0.05N
The concentrations are as follows. When the concentration exceeds 0.1 N, the silk amino acid content in the obtained silk fibroin peptide is 80.
Since it exceeds the weight percentage, a silk fibroin peptide having the desired properties cannot be obtained.

Examples of the acid used in the method of the present invention include acids such as hydrochloric acid, sulfuric acid, nitric acid and acetic acid. Examples of the alkali include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, and carbonate salts such as sodium carbonate and potassium carbonate. When diluted acid or diluted alkaline water is used, it is necessary to neutralize after the reaction,
Since the amount of acid or alkali used originally is small, the salt produced by neutralization is small, and the irritation does not pose a problem when the obtained silk fibroin peptide is used in a cosmetic or cleaning composition.

Further, in the production method of the present invention, activated carbon, activated clay, activated alumina, porous inorganic compounds such as silica gel, hydrogen peroxide, hydrosulfite,
Reducing agents such as sodium bisulfite and sodium sulfite, Raney Ni, Raney Co, Pd carbon and the like may be added to prevent coloring and deodorize during hydrolysis. The degree of polymerization of the silk fibroin peptide thus obtained can be measured by the method disclosed in JP-A-55-124793 (nitrogen content by Kjeldahl method and terminal amino group number by formol titration). The obtained silk fibroin peptide is a mixture of peptides having different degrees of polymerization, and its molecular weight distribution can be easily measured by analysis such as GPC. The average degree of polymerization of the silk fibroin peptide of the present invention can be adjusted to a desired average degree of polymerization by changing the reaction temperature and the reaction time. To give a concrete example,
When the reaction solvent is water alone and the reaction temperature is 200 ° C. and the reaction time is 1 hour, a peptide having an average degree of polymerization of 2 is obtained. Similarly, when the reaction temperature is 170 ° C. and the reaction time is 6 hours, a peptide having an average degree of polymerization of 6 is obtained.

The silk fibroin peptide thus obtained is usually a pale yellow to pale brown aqueous solution, but when the silk fiber is not completely dissolved, the unreacted fiber can be easily removed by filtering the reaction solution. . Further, when used as a cosmetic or a cleaning agent, when slight coloring or odor is concerned, activated carbon treatment may be performed. Alternatively, treatment with hydrogen peroxide is also effective.

The silk fibroin peptide obtained by the method of the present invention does not have an unpleasant odor derived from a sulfur-containing amino acid found in keratin hydrolysates and has an extremely low inorganic salt content. In addition, it is extremely excellent in film forming ability and water retention ability, and when added to cosmetics and cleaning agents, it showed remarkable effects. The silk fibroin peptide obtained by the conventional method did not have sufficient solubility and long-term storage stability, and had moderate moisturizing properties and film-forming ability.Therefore, it was not satisfactory when incorporated into cosmetics or detergents. There wasn't. Therefore, the silk fibroin peptide of the present invention and the conventional product are clearly distinguished. A third invention of the present invention is, as described above, a silk fibroin peptide represented by the above general formula (1), which is obtained by treating silk fibroin with high-pressure water at 150 to 250 ° C. and hydrolyzing it. It is a cosmetic material characterized by containing. The content of the silk fibroin peptide used in the cosmetic of the present invention is preferably 0.001 to 10% by weight, and more preferably 0.005 to 5% by weight, based on the cosmetic. If it is less than 0.001% by weight, its effect is small, and if it exceeds 10% by weight, the stickiness during use becomes strong, which is not preferable.

The cosmetics of the present invention may contain polyhydric alcohols such as glycerin, propylene glycol, 1,3-butylene glycol and sorbitol, hyaluronic acid, carboxymethyl chitin, elastin, chondroitin sulfate, dermatanic acid, if necessary. Water-soluble polymeric substances such as fibronectin and ceramides, cell activating agents such as aloe extract and placenta extract, anti-inflammatory agents such as allantoin and glycyrrhizinate, chelating agents such as edetate, citric acid, malic acid and gluconic acid , Benzoate, salicylate, sorbate, dehydroacetate, paraoxybenzoate, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 3,4,4'-trichlorocarbanilide, benzal chloride Preservatives such as ruconium, hinokitiol, resorcin, Antibacterial agents, antibacterial agents, antioxidants such as dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, and ascorbic acid, and ultraviolet absorbers such as oxybenzone, 4-tert-butyl-4′-methoxybenzoylmethane, and 2-ethylhexylparadimethylaminobenzoate , Silicone compounds such as amino-modified silicone and polyether-modified silicone, and fragrances and dyes can be appropriately used.

The cosmetic composition of the present invention may have any shape, such as a solubilized system, an emulsified system, a powder dispersion system, or a water-oil two-layer system. To produce the cosmetic of the present invention,
A compounding method generally used by those skilled in the art may be used.

Although the use is optional, typical examples are skin cosmetics such as lotion, emulsion, cream, pack, cleansing, beauty essence and foundation,
Examples include hair conditioners, hair treatments, hair conditioners, hair brushing agents, hair tonics, permanent wave agents, hair bleaching agents, hair cosmetics such as hair dyes, cosmetic soaps, and bath agents.

The fourth invention of the present invention is, as described above, the silk represented by the general formula (1) obtained by treating silk fibroin with high-pressure water at 150 to 250 ° C. and hydrolyzing it. A detergent composition comprising a fibroin peptide.

The detergent composition of the present invention comprises the silk fibroin peptide represented by the general formula (1) and at least one surfactant selected from anionic surfactants, amphoteric surfactants and nonionic surfactants. It is obtained by blending.

As the anionic surfactant used in the detergent composition of the present invention, fatty acid soaps such as sodium laurate and triethanolamine laurate, alkylbenzene sulfonates, α-olefin sulfonates, sodium lauryl sulfate, Lauryl sulfate triethanolamine and other lauryl sulfates, polyoxyethylene (3) sodium lauryl ether sulfate and other ether sulfates, polyoxyethylene (3) coconut oil fatty acid amide amide sulfate and other amide ether sulfates, monododecyl phosphate trioxide Phosphate esters such as ethanol, sodium polyoxyethylene dodecyl ether phosphate,
Acylmethyl taurine salts such as sodium cocoyl methyl taurine and sodium lauroyl methyl taurine, acyl isethionates such as sodium lauroyl isethionate, disodium lauryl sulfosuccinate, POE
(1-4) Disodium lauryl sulfosuccinate, polyoxyethylene (5) lauric acid monoethanolamide Disodium sulfosuccinate such as disodium sulfosuccinate, alkyl ether carboxylates, cellulose derivatives such as carboxymethyl cellulose, cocoyl sarcosine N-acyl sarcosine salts such as sodium, sodium lauroyl sarcosine, sodium myristoyl sarcosine, potassium lauroyl sarcosine, and triethanolamine, cocoyl-N
-Methyl-β-alanine sodium, lauroyl-N-
Methyl-β-alanine sodium, myristoyl-N-
Methyl-β-alanine sodium, palmitoyl-N-
Methyl-β-alanine sodium, stearoyl-N-
N-acyl-β-alanine salts such as sodium methyl-β-alanine, lauroyl-N-methyl-β-alanine potassium, lauroyl-N-methyl-β-alanine triethanolamine, sodium N-lauroyl aspartate, N- Triethanolamine lauroyl aspartate, N-acyl aspartates such as sodium N-myristoyl aspartate, sodium N-lauroyl glutamate, triethanolamine N-lauroyl glutamate, sodium N-cocoyl glutamate, triethanol amine N-cocoyl glutamate, etc. N-acyl glutamate, N-2-hydroxyethyl-N-2-lauric acid amidoethylglycine, N-
2-Hydroxyethyl-N-2-coconut oil fatty acid amide ethylglycine, N-2-hydroxyethyl-N-2-lauric acid amide ethyl-β-alanine, N-2-hydroxyethyl-N-2-coconut oil fatty acid amide ethyl -Β-
Alanine, N-carboxymethyl-N- {2- [N'-
(2-Hydroxyethyl) lauric acid amide] ethyl}
Glycine, N-carboxymethyl-N- {2- [N'-
(2-Hydroxyethyl) coconut oil fatty acid amide] ethyl} glycine, N- {2- [N- (2-hydroxyethyl) lauric acid amide] ethyl} glycine, N- {2-
[N- (2-hydroxyethyl) coconut oil fatty acid amide]
Examples thereof include amidocarboxylic acid type surfactants such as ethyl} glycine.

Examples of the amphoteric surfactant used in the detergent composition of the present invention include alkyl betaine type amphoteric surfactants such as lauryl betaine, amido betaine type amphoteric surfactants such as lauroyl amidopropyl betaine, and 2-alkyl- Imidazoline-type amphoteric surfactants such as N-carboxymethylimidazolinium betaine and 2-alkyl-N-carboxyethylimidazolinium betaine, alkylsulfobetaine-type amphoteric surfactants, coconut oil fatty acid amide dimethylhydroxypropylsulfobetaine, etc. Amidosulfobetaine type amphoteric surfactants and the like.

Examples of the nonionic surfactant used in the detergent composition of the present invention include fatty acid diethanolamides such as coconut oil fatty acid diethanolamide and lauric acid diethanolamide, coconut oil fatty acid monoethanolamide and lauric acid monoethanolamide. Fatty acid monoethanolamides, coconut oil fatty acid diglycolamides, fatty acid diglycolamides such as lauric acid diglycolamide, fatty acid isopropanolamides such as lauric acid isopropanolamide, polyoxyethylene (2) lauric acid monoethanolamide, polyoxyethylene (5) Polyoxyethylene fatty acid monoethanolamide such as coconut oil fatty acid monoethanolamide, fatty acid ester, alkylamine oxide such as lauryldimethylamine oxide, OE higher alcohol ether,
Examples include nonionic surfactants such as POE alkyl phenyl ethers and alkyl glucosides such as decyl glucoside.

Among the above-mentioned anionic surfactants, the cleaning agent of the present invention has the following general formula (2):

[0042]

Embedded image

(In the formula (2), R ¹ represents an alkyl group or an alkenyl group having 7 to 19 carbon atoms, and M 1
Represents an alkali metal atom, an alkaline earth metal atom, an ammonium group, a cationic residue of a basic amino acid or a cationic residue of an alkanolamine, and m is an integer equal to the valence of the atom or group represented by M. And R ² is
Structural formulas of the following formulas (a) to (h)

[0044]

[Chemical 9]

Represents one member selected from The use of the amidocarboxylic acid salt shown in)) has extremely excellent foaming power and detergency, and also gives a creamy foam with a fine texture and further reduces the slight irritation originally possessed by the amidocarboxylic acid salt, resulting in almost irritation. An extremely excellent detergent composition having no properties is obtained.

As a specific example of the amidocarboxylic acid salt represented by the general formula (2), the partial structural formula (a) includes N-cocoylsarcosine sodium and N-lauroylsarcosine sodium. The N-acyl sarcosine salt, represented by (b), is N-cocoyl-N-methyl-β-alanine sodium or N-lauroyl-N-.
N-acyl-N such as methyl-β-alanine sodium
-Methyl-β-alanine salt, represented by (c) is N
-N-acyl aspartates such as sodium lauroyl aspartate and triethanolamine N-stearoyl aspartate, and (d) is represented by N- such as sodium N-cocoyl glutamate and triethanolamine N-lauroyl glutamate. The acylglutamates (e) to (h) are so-called imidazolinium betaine type surfactants which are ring-opening type amidoaminocarboxylic acid salts.

The content of the silk fibroin peptide of the present invention in the detergent composition is preferably 0.001 to 10% by weight, more preferably 0.005 to 5% by weight, based on the detergent.
Is. If less than 0.001% by weight, the effect is small and 10
If it is blended in excess of wt%, the sticky feeling during use and after use will become strong and the foaming power and detergency will tend to be suppressed, such being undesirable.

The amount of at least one surfactant selected from anionic surfactants, amphoteric surfactants and nonionic surfactants used in the cleaning agent of the present invention varies depending on the purpose of use, but is 1 per cleaning agent. -80 wt% is suitable.

The detergent composition of the present invention may contain the following additional components, if desired. Examples of the additional component include quaternary ammonium salt type cationic surfactants such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride and distearyl dimethyl ammonium chloride, cationized polymers and cationized guar gum.

The following additional components can also be used if necessary. Examples of these additional components include polyhydric alcohols such as glycerin, propylene glycol, 1,3-butylene glycol and sorbitol, silicones such as methylpolysiloxane and oxyalkylene-modified organopolysiloxane, zinc pyrithione and piroctone olamine. Antidandruff agents, hyaluronic acid, collagen, elastin chondroitin sulfate, dermatanic acid, water-soluble polymer substances such as fibronectin, ceramides, chitin, chitosan, cell activating agents such as aloe extract, placenta extract, allantoin, glycyrrhizinate, etc. Anti-inflammatory agent, edetate, pyrophosphate, hexametaphosphate, citric acid, malic acid, chelating agent such as gluconic acid, benzoate, salicylate, sorbate, dehydroacetate, paraoxybenzoate, 2 4,4'-trichloro-2'-hydroxy-diphenyl ether, 3,
Preservatives such as 4,4'-trichlorocarbanito, benzalkonium chloride, hinokitiol and resorcin, bactericides, antioxidants such as dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate and ascorbic acid, fragrances and pigments Can be mentioned.

The shape of the detergent composition of the present invention is arbitrary and may be any shape such as liquid, paste, gel, powder and solid. The appearance is generally transparent, pearly, or emulsified, but is not limited thereto. In order to produce the detergent composition of the present invention, a compounding method generally used by those skilled in the art may be used.
Although the use is optional, typical examples include kitchen detergents, hard surface cleaners, face cleansers, cleansing foams,
Examples include detergents such as shampoo, body shampoo, and solid detergent.

[0052]

The reason why the silk fibroin peptide of the present invention is superior to the conventional silk fibroin peptide in moisturizing property, film forming ability, solubility and long-term storage stability is not clear, but the silk fibroin peptide is not clear. It is thought that this is because the molecular weight distribution of is properly dispersed.
The conventional product is a silk fibroin peptide with a certain degree of polymerization, and although it has excellent solubility, suppleness, and tough film-forming ability, its water-retaining ability and film-forming ability are moderate, and turbidity or precipitation can occur during long-term storage. There was a drawback that occurred. Silk amino acid obtained by thoroughly hydrolyzing silk fibroin has good moisturizing properties and film-forming properties, and is highly water-soluble, but its solubility in lower alcohols is somewhat difficult. In the product of the present invention, it is considered that the silk fibroin peptide having a certain degree of polymerization, the silk fibroin peptide having a low degree of polymerization and the silk amino acid are present in an appropriate ratio. As a result, while retaining the solubility and tough film-forming ability of peptides with a high degree of polymerization, they impart the moisturizing properties and film-forming properties of silk amino acids, and at the same time compensate for the short-term storage stability and other disadvantages. It is considered that these characteristics are exhibited. The appropriate molecular weight distribution can be achieved only by treating silk fibroin with high-pressure heated water and hydrolyzing it, which cannot be realized by a conventional method.

When the silk fibroin peptide of the present invention is blended in a cosmetic composition or a cleaning composition, it is possible to obtain a remarkable effect which could not be expected in the case of using a conventional product. It is considered to be due to outstanding properties such as forming ability, water retention ability, good solubility, and long-term storage stability.

[0054]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 100 g of silk fibroin powder and 1500 g of distilled water were placed in a pressure-resistant container of 2 liter, and after substituting with nitrogen, the mixture was heated and stirred at 180 ° C. for 16 hours. The pressure at this time is 12 kg / cm
^{Was 2} . After cooling, a trace amount of insoluble matter was filtered and the mother liquor was concentrated. The obtained silk fibroin peptide was a light brown transparent liquid. The average degree of polymerization was 2.3 from formol titration and nitrogen content. HPLC using GPC column
As a result of analysis, the average molecular weight was 200 (yield:
96%. Ash: 0.01%).

Example 2 100 g of silk fibroin (silk noil) and 0.01 N
Hydrochloric acid (1500 g) was placed in a 2 liter Hastelloy autoclave, and after nitrogen substitution, the mixture was heated and stirred at 160 ° C. for 1 hour for hydrolysis. The pressure at this time is 20 kg / cm ^2.
Met. After cooling, no insoluble matter was observed. The average degree of polymerization was 4.6 from the formol titration and the nitrogen content. From the HPLC analysis using the GPC column, the average molecular weight was 450 (yield: 100%. Ash content: 0.5).
%).

Example 3 100 g of silk fiber (Mayukeba) and 1500 g of 0.001 N caustic soda were put into a 2 liter autoclave, and after substituting with nitrogen, heated and stirred at 150 ° C. for 2 days for hydrolysis. After cooling, the insoluble matter was filtered to concentrate the mother liquor. The silk fibroin peptide obtained was a brown liquid. To this, 5 g of activated carbon (Shirasagi A) was added, and the mixture was heated and stirred at 70 ° C. for 1 hour for decolorization / deodorization treatment, then the activated carbon was filtered off and concentrated to obtain silk fibroin peptide (pale yellow transparent solution). . Average degree of polymerization is 7.8, average molecular weight is 730
(Yield: 86%, Ash: 0.1%).

As shown in Examples 1 to 3 above, the silk fibroin peptide could be obtained in a high yield by a simple operation. Further, the obtained silk fibroin peptide contained almost no inorganic salt. Furthermore, the obtained silk fibroin peptide had no unpleasant odor due to sulfur.

Comparative Example 1 100 g of silk fiber (silk noil) and 1500 g of distilled water were placed in a pressure-resistant container of 2 liters and the atmosphere was replaced with nitrogen.
The mixture was heated and stirred at 48 ° C for 48 hours. The pressure at this time is 3 kg / c
m ² . After cooling, the fibrous insoluble matter was filtered, dried and weighed to find that it was 96 g. Therefore, it can be said that the hydrolysis reaction hardly proceeds at this reaction temperature.

Comparative Example 2 100 g of silk fiber (Kisoso) and 1500 g of distilled water were placed in a pressure-resistant container of 2 liters, and the atmosphere was replaced with nitrogen.
It was hydrolyzed by heating and stirring for an hour. The pressure at this time is 32k
It was g / cm ² . After cooling, the obtained silk fibroin peptide had a blackish brown color and had a strong burning odor.

Comparative Example 3 32 g of silk fibroin powder was added to 150 g of a 50% by weight calcium chloride aqueous solution, and heated and stirred at 120 ° C. for 5 hours to be dissolved. The insoluble matter was filtered off, and the mother liquor was dialyzed against a cellulose tube to desalt. The obtained silk fibroin solution was concentrated under reduced pressure to a concentration of 20% by weight. Hydrochloric acid was added thereto in an amount of 0.2 N, and the mixture was heated and stirred at 94 ° C. for 4 hours for hydrolysis. After the reaction was completed, it was neutralized with 6N sodium hydroxide. The silk fibroin peptide obtained by concentration under reduced pressure was a yellowish brown solution, and the average degree of polymerization was 6.3 from the results of nitrogen content and formol titration (yield: 86.
%. Ash: 6.7%).

Comparative Example 4 Silknoyl 10 was added to 200 g of 0.5N sodium hydroxide.
g was added and the mixture was heated and stirred at 80 ° C. for 4 hours for hydrolysis.
After cooling, a large amount of unreacted silknoyl remained, so this was filtered off. The mother liquor was neutralized with 2N hydrochloric acid and then concentrated under reduced pressure to obtain a yellow-brown silk fibroin peptide. The average degree of polymerization was 2.9 from the results of nitrogen content and formol titration.
(Yield: 45%, Ash: 16.7%).

Comparative Example 5 Silknoyl 10 was added to 200 g of 0.5N sodium hydroxide.
g was added, and the mixture was heated and stirred at 110 ° C. for 48 hours for thorough hydrolysis. After cooling, the reaction liquid was brown. 2N hydrochloric acid was added dropwise to the reaction solution for neutralization, and the mixture was concentrated under reduced pressure to obtain a yellowish brown silk fibroin peptide. From the nitrogen content and the results of formol titration, the average degree of polymerization was 1.1, indicating that the product was silk amino acid (yield: 98.
%, Ash content: 14.6%).

The silk fibroin peptides of the present invention obtained in Examples 1 to 3, the silk fibroin peptides and silk amino acids obtained in Comparative Examples 3 to 5 and commercial silk fibroin peptides were subjected to a film characteristic test, a skin water content test, and dissolution. A sex test and a stability test with long-term storage were performed. The test method is as follows.

<Film characteristic test> A sample solution is applied on Japanese paper to form a film, and a breaking stress (g) is measured by a tensile tester.
Was measured. The evaluation was carried out by the average value of the results of three times.
The larger the breaking stress, the stronger the film formed.

<Skin water content test> 15 μl of silk fibroin peptide (concentration: 1% by weight) was placed on the skin of the inner part of the upper arm, allowed to absorb water for 10 seconds and then wiped off, and the conductance after 60 seconds was measured. The evaluation was performed by the conductance ratio.

[0067]

[Equation 1]

The evaluation was performed by the average value of three tests. A larger conductance ratio means that more water is retained.

<Solubility test> 10 ml of silk fibroin peptide (concentration: 10% by weight) was placed in 10 ml of 50% by weight ethanol water, and after stirring, the mixture was allowed to stand at 20 ° C. for 24 hours to examine whether or not a precipitate appeared. The criteria for judgment were set as follows. ◯: No turbidity Δ: There is turbidity x: A precipitate is formed.

<Long-term storage stability> Silk fibroin peptide (concentration: 10% by weight, methylparaben 0.1% by weight was added) was placed in a thermostatic chamber at 5 ° C. and stored for 6 months, and then the presence or absence of precipitation was examined. ◯: No turbidity Δ: Turbidity ×: Precipitate formation The test results are shown in Table 1.

[0071]

[Table 1]

From Table 1, it can be seen that the product of the present invention is extremely excellent in film forming ability and water retention ability as compared with the conventional product.
Furthermore, the solubility in ethanol, which was a problem with conventional products, was improved, and no turbidity was observed even after long-term storage, and the stability was excellent. Further, even when compared with silk amino acid, the product of the present invention was extremely excellent in film forming ability.

Examples 4-10 and Comparative Examples 6-10 Lotions shown in Table 2 were prepared using the silk fibroin peptides obtained in Examples 1-3 and Comparative Examples 3-4.
The obtained lotion was subjected to the following moisturizing test / safety test. The results are shown in Table 2.

<Formulation of lotion> Ethanol 10.0 wt% Glycerin 3.0 Silk fibroin peptide Amount shown in Table 2 POE (50) oleyl ether 0.5 Methylparaben 0.2 Purified water balance.

<Humidity test> A sensory test was conducted by actually using a sample prepared by 10 professional panelists. The evaluation results are shown in the following display. ∘: 8 or more out of 10 answered that they were good. ○: 6 or more out of 10 answered that they were good. B: 4 or more out of 10 answered that they were good. ×: Less than 4 out of 10 respondents answered good.

<Safety test> After removing hair from the ventral back side of the guinea pig, a double patch for patch test, to which the sample (2% by weight, 0.1 ml) was applied, was applied for 24 hours. The state of the sticking site was observed every 3, 24, and 48 hours after the sticking was removed, and a score was given based on the following criteria. Judgment Criteria and Scores No Red Scarlet ・ ・ ・ ・ 0 points Very mild red scarlet (barely distinguishable) ・ 1 point Mild scarlet red ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 2 points, clear erythema ・ ・ ・ ・ 3 points, strong erythema ・ ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ 4 points Red erythema with mild edema ・ ・ ・ ・ ・ ・ ・ ・ 5 Points Red erythema with strong edema ・ ・ ・ ・ ・ ・6 points Partial crusting: 7 points Full crusting or necrosis: 8 points Safety evaluation: 3, An average score of 24 and 48 hours was used.
In general, the safety evaluation categories derived from the average score are as follows.

Average score Safety evaluation category 0.0 to 1.0 ... No irritation 1.1 to 3.0・ ・ ・ Mild stimulus 3.1 to 5.0 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Moderate stimulus 5.1 to 7.0 ・ ・ ・ ・・ ・ ・ Strength stimulation 7.1-8.0 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Table 2 shows the corrosion test results.

[0078]

[Table 2]

From the results of Table 2, the lotion of the present invention had excellent moisturizing properties. Regarding the safety, neither the lotion of the present invention nor the lotion of Comparative Example was judged as non-irritating,
Since no erythema was observed in the product of the present invention,
It can be seen that it is superior to conventional products.

Examples 9 to 13 and Comparative Examples 10 to 13 Using the silk fibroin peptides obtained in Examples 1 to 3 and Comparative Examples 3 to 4 and the silk amino acid obtained in Comparative Example 5, the formulations shown in Table 3 were used. A hair conditioner having the composition was prepared. The obtained conditioner was subjected to a sensory test after use (presence of moistness, gloss, and gloss), state of cuticle of the hair after use with an electron microscope, and safety test.

<Hair Conditioner Formulation> POE (24) Cholesterol 1.0 wt% Polyvinylpyrrolidone 2.0 Silk fibroin peptide Amount shown in Table 3 Ethanol 5.0 Purified water balance.

<Moisture Feeling> Ten professional panelists actually used it, and a sensory test was conducted on the feel of the hair after washing. The evaluation criteria were set as follows. ◎ ... Responded that 8 or more people were moist ○ ... Responded that 6 to 8 people were moist △ ... Responded that 4 to 5 people were moist × ... Responded to 3 or less people moist

<Gloss / luster> Ten professional panelists actually used it to perform a sensory test on the gloss and gloss of the hair after washing. The evaluation standard was set as follows. ◎ ... More than 8 people answered that they had gloss / luster. ○ ... 6-8 people answered that they had gloss / luster. △ ... 4-5 people answered that they had gloss / luster. I answered that.

<Condition of Cuticle> 1000 healthy hairs of a 12-year-old woman were bundled, immersed in a test solution at 30 ° C. for 1 hour, rinsed lightly, and then dried. This was brushed 1000 times from the tip of the hair toward the root. The state of the cuticle was visually observed using a scanning electron microscope. The evaluation criteria were set as follows. Cuticles for healthy hair: 5 points Some cuticles are detached 4 points About half of the cuticles are detached. 3 points A large proportion of the cuticles detached ........ 2 points Almost all cuticles detached ........ 1 point When immersed only in water, damage equivalent to 1 point in the above score. I got hair. The evaluation was carried out by observing 10 randomly selected hairs after the test conducted for each test and averaging the respective scores. The larger the average value is, the less the hair is damaged. Therefore, it is considered that a strong film is formed on the hair surface.

<Safety test> After removing hair from the ventral back side of the guinea pig, a sample (2% by weight, 0.1 ml) applied to a double patch for a patch test was stuck for 24 hours. The state of the sticking site was observed every 3, 24, and 48 hours after the sticking was removed, and a score was given based on the following criteria. Judgment Criteria and Scores No Red Scarlet ・ ・ ・ ・ 0 points Very mild red scarlet (barely distinguishable) ・ 1 point Mild scarlet red ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 2 points, clear erythema ・ ・ ・ ・ 3 points, strong erythema ・ ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ 4 points Red erythema with mild edema ・ ・ ・ ・ ・ ・ ・ ・ 5 Points Red erythema with strong edema ・ ・ ・ ・ ・ ・6 points Partial crusting: 7 points Full crusting or necrosis: 8 points Safety evaluation: 3, An average score of 24 and 48 hours was used.
In general, the safety evaluation categories derived from the average score are as follows.

Average score Safety evaluation category 0.0 to 1.0 ... No irritation 1.1 to 3.0・ ・ ・ Mild stimulus 3.1 to 5.0 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Moderate stimulus 5.1 to 7.0 ・ ・ ・ ・・ ・ ・ Strength stimulation 7.1-8.0 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Table 3 shows the corrosion test results.

[0087]

[Table 3]

From Table 3, the hair conditioner containing the silk fibroin peptide of the present invention has a function of imparting a moist feeling, gloss and luster after use and protecting hair from being damaged by brushing. It was also excellent in safety. On the other hand, as is clear from Comparative Examples 10 to 13, the conventional products were not satisfactory.

Example 14 An emulsion having the following composition was prepared by a usual method and subjected to the same test as in Example 4. Ingredients% by weight • Polyoxyethylene sorbitan monostearate (20EO) 1.0 • Polyoxyethylene sorbitate tetraoleate (60EO) 0.5 • Lipophilic glyceryl monostearate 1.0 • Stearic acid 0.5 • Behenyl alcohol 0 Avocado oil 3.0 Glyceryl trioctanoate 5.0 1,3-butylene glycol 5.0 Xanthan gum 0.1 Disodium edetate 0.2 Silk fibroin peptide of Example 0.01 0.01 Preservative 0.1 / Purified water The balance test results are shown in Table 4.

Example 15 A cream having the following composition was prepared by a usual method and subjected to the same test as in Example 4. Ingredients wt% Polyethylene glycol monostearate (40EO) 1.0 Self-emulsifying glyceryl monostearate 5.0 Stearic acid 5.0 Behenyl alcohol 1.0 Liquid paraffin 10.0 Cetyl octanoate 10.0 -Ethyl paraoxybenzoate 0.2-Glycerin 5.0-Silk fibroin peptide of Example 1 0.1-Loofah extract 1.0-Preservative 0.5-Purified water balance The test results are shown in Table 4.

Example 16 A lotion having the following composition was prepared by an ordinary method, and Example 4 was used.
The same test was performed. Ingredients wt% -Polyoxyethylene hydrogenated castor oil (60EO) 8.0-Ethanol 15.0-Behenyl alcohol 1.0-Methyl paraoxybenzoate 0.1-Glycerin 5.0-Silk fibroin peptide of Example 2 0.006 -Purified water The balance test results are shown in Table 4.

Example 17 A poultice of the following composition was prepared by a usual method and subjected to the same test as in Example 4. Ingredients wt% -Polyacrylic acid 30.0-Crotamiton 1.0-Sodium polyacrylate 7.0-Aluminum chloride 0.3-Glycerin 20.0-Sorbitan monooleate 1.0-Titanium oxide 5.0-Implementation Silk fibroin peptide of Example 3 0.01 Purified water balance Table 4 shows the test results.

[0093]

[Table 4]

As is clear from Table 4, the skin cosmetic of the present invention was extremely excellent in moisturizing property and also excellent in safety.

Example 18 A hair brushing agent having the following composition was prepared by a usual method and subjected to the same tests as in Example 9. Ingredient wt% -Cocoyl arginine ethyl ester-PCA salt 0.5-Silk fibroin peptide of Example 1-0.3-Ethanol 5.0-Methylparaben 0.1-Perfume 0.1-Purified water The balance The test results are shown in Table 5. Show.

Example 19 A hair cream having the following composition was prepared by a usual method,
The same test as in Example 9 was performed. Ingredients wt% Liquid paraffin 10.0 Squalane 7.0 Jojoba oil 3.0 Solid paraffin 3.0 Polyoxyethylene cetyl ether 1.5 Sorbitan sesquioleate 0.8 Silk fibroin peptide of Example 1 1.0-preservative 0.3-purified water balance Table 5 shows the test results.

Example 20 A hair treatment cream having the following composition was prepared by a usual method and subjected to the same tests as in Example 9. Ingredients wt% -Avocado oil 5.0-Squalane 7.0-Liquid paraffin 10.0-Stearic acid 3.0-Glycerin monostearate 3.0-Lanolin alcohol 5.0-Silk fibroin peptide of Example 1 6-Sodium edetate 0.1-Preservative 0.2-Purified water balance Table 5 shows the test results.

Example 21 A hair rinse having the following composition was prepared by a usual method and subjected to the same tests as in Example 9. Ingredients wt% -Cetyl alcohol 3.0-Liquid paraffin 3.0-Cetyl octanoate 8.0-Stearyl trimethyl ammonium chloride 3.0-Silk fibroin peptide of Example 1 1.0-Methyl paraoxybenzoate 0.1- Table 5 shows the test results of the purified water balance.

[0099]

[Table 5]

As is clear from Table 5, the cosmetic for hair of the present invention imparted a moist feel and gloss / gloss to the hair after use. Further, there was an effect of preventing the cuticle from being peeled off. Furthermore, it was excellent in safety.

Example 22 A bath agent having the following composition was prepared by a usual method and its performance was evaluated. As a result, an excellent moisturizing sensation on the skin after bathing was shown. Ingredients wt% -sodium sulfate 55.0-sodium hydrogencarbonate 10.0-sodium carbonate 5.0-sodium chloride 29.5-silk fibroin peptide 0.5 from Example 1.

Example 23 A solid detergent having the following composition was prepared by a usual mechanical kneading method,
When the performance was evaluated, it showed an excellent moist feeling on the skin after use. Ingredients% by weight • Base material for soap (beef tallow: coconut oil = 7: 3, water content 15%) 92.9 • Cetanol 7.0 • Silk fibroin peptide 0.1 of Example 3.

Example 24 A solid detergent having the following composition was prepared by a usual mechanical kneading method,
When the performance was evaluated, it showed an excellent moist feeling on the skin after use. Ingredients wt% -N-lauroyl-L-glutamate monosodium 50.0-N-oleoyl-L-glutamate monosodium 41.999-Myristyl alcohol 8.0-Silk fibroin peptide 0.001 of Example 1. Example 25 A blow dry conditioner having the following composition was prepared and its performance was evaluated. As a result, the hair after blowing showed excellent moist feeling and gloss. Ingredients wt% ・ Quaternized polyvinylpyrrolidone 2.0 ・ Oleyldimethylbenzylammonium chloride 0.6 ・ POE (20) sorbitan monolaurate 0.2 ・ Silk fibroin peptide of Example 2 0.5 ・ Ethanol 3.0 ・The rest of purified water.

Example 26 A first agent for permanent wave having the following composition was prepared and its performance was evaluated. As a result, excellent set persistence was shown. In addition, the hair had little damage after use and exhibited excellent moisturizing feeling and gloss. Ingredients wt% Cetyltrimethylammonium chloride 4.0 Polyether-modified silicone 1.5 Ammonium thioglycolate (50%) 12.0 Silk fibroin peptide of Example 1 0.5 Monoethanolamine 0.8 Emulsifier 1.0-Lauric acid diethanolamide 0.3-Dipotassium glycyrrhizinate 0.05-EDTA 0.1-Ammonia water (25%) pH = 9 amount-Purified water balance.

As is clear from the above examples, the cosmetics containing the silk fibroin peptide of the present invention had not only excellent safety but also excellent moisturizing properties.
When used on hair, it had the effect of giving a moist feel and also giving the hair gloss and luster.

Examples 27 to 36 and Comparative Examples 14 to 19 The silk fibroin peptides shown in Examples 1 to 3 and Comparative Examples 3 to 4 and the silk amino acid shown in Comparative Example 5 were used, and the blending composition shown in Table 6 was used. A detergent was prepared. The obtained detergent was subjected to the following foaming power test, detergency test, foam creamy feeling and protein denaturation test. The test methods were as follows.

1) Foaming power test The cleaning agent was diluted with distilled water so that the pure content of the active agent was 0.2%, and the foaming power was measured according to the method described in JIS K3362. The evaluation criteria were set as follows. ∘: Very good foaming, foaming power of 200 mm or more ◯: Good foaming, foaming power of 170 mm or more, 200 mm
Less than Δ: Foaming is normal, foaming power is 130 mm or more, 170 mm
Less than × ... Poor foaming, foaming power less than 130 mm.

2) Detergency test 0.1% Sudan III as an indicator was added to beef tallow, and 5% of this was applied to a porcelain dish (diameter 25 cm), and 30 g of a 10% by weight cleaning solution was impregnated with the solution. The washing power was defined as the number of dishes that were washed by rubbing with a sponge and washed until the tallow could no longer be washed from the dishes.

3) Foam creamy sensation Each sample was subjected to a sensory evaluation using 20 male and female panelists to examine the foamy creamy sensation. The evaluation criteria were set as follows. ⊚: 16 or more were good ○: 12-15 were good △: 8-11 were good ×: 7 or less were good.

4) Protein Denaturation Rate Test The ovalbumin denaturation rate when the sample was added to the ovalbumin pH7 buffer solution at a sample concentration of 1% using aqueous gel filtration high performance liquid chromatography was 220%.
It measured using the absorption peak of nm. Denaturation rate (%) = [(H 2 _O −H _s ) / H _o ] × 100 H 2 _O : 220 nm absorption peak height of ovalbumin H _S : 2 when the sample is added to the ovalbumin buffer solution
The height evaluation standard for the 20 nm absorption peak was set as follows. ◎ Ovalbumin denaturation rate less than 10% ○ Ovalbumin denaturation rate 10-19% △ Ovalbumin denaturation rate 20-49% × Ovalbumin denaturation rate 50% or more The test results are shown in Table 6.

[0111]

[Table 6]

As is clear from the results shown in Table 6, the detergents of Examples 27 to 36 containing the silk fibroin peptide of the present invention have excellent foaming power / detergency, foam quality and creamy skin irritation. It was low and very suitable as a cleaning agent. On the other hand, those containing no silk fibroin peptide and those containing the silk fibroin peptide produced by the conventional method lacked foaming ability and detergency, and the foam quality was not satisfactory. In the protein denaturation test, the detergent containing no silk fibroin peptide was judged to be irritating, but the silk fibroin peptide-containing detergent had its irritation alleviated.

Example 37 A rinse-inclusive shampoo having the following composition was prepared, and Example 2 was used.
It used for the same test as 7. Ingredient wt% N-carboxymethyl-N- {2- [2-hydroxy-ethyl) coconut oil fatty acid amide] ethyl} glycine (30%) 20.0 N-cocoyl-L-glutamic acid triethanolamine (30% ) 5.0-2-coconut oil alkyl-N-carboxyethyl-N-hydroxyethyl imidazolinium betaine (30%) 10.0-lauric acid diethanolamide 1.0-silk fibroin peptide of Example 1 0.01 Stearyl trimethyl ammonium chloride 1.5 Cetyl octanoate 0.5 Carboxymethyl chitin 0.1 Hyaluronic acid 0.1 Sodium edetate 0.1 Preservative 0.1 Purified water balance Test results are shown in Table 7. Shown in.

Example 38 A conditioning shampoo having the following composition was prepared and subjected to the same test as in Example 27. Ingredients wt% -Polyoxyethylene (3) sodium lauryl sulfate 10.0-Lauroylmethyl-β-alanine sodium (30%) 20.0-Polyoxyethylene (3) coconut oil fatty acid monoethanol sodium amide sulfate (30%) 2.0-cationized guar gum 0.3-lauric acid diethanolamide 2.0-silk fibroin peptide of Example 1 1.0-glycerin 3.0-sodium edetate 0.1-citric acid pH = 6.5 Amount to be used ・ Purified water The balance test results are shown in Table 7.

Example 39 A pearly shampoo having the following composition was prepared and subjected to the same test as in Example 27. Ingredients wt% N-2-hydroxyethyl-N-2-coconut oil fatty acid amide ethylglycine (30%) 15.0 2-coconut oil alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine (30 %) 10.0-coconut oil fatty acid amide propyl betaine (30%) 5.0-sodium lauroylmethyltaurine (30%) 5.0-silk fibroin peptide of Example 1 1.0-lauric acid diethanolamide 2.0 -Coconut oil fatty acid monoethanolamide 1.5-caustic soda pH = 6 amount-methylparaben 0.1-perfume proper amount-purified water balance Table 7 shows the test results.

Example 40 A face cleanser having the following composition was prepared and subjected to the same test as in Example 27. Ingredient wt% N-2-hydroxyethyl-N-2-coconut oil fatty acid amide Ethyl-β-alanine (30%) 60.0 Lauric acid diethanolamide 7.0 ・ 2-Alkyl-N-carboxymethyl-N -Hydroxy-ethylimidazolinium betaine (30%) 5.0-Monylammonium glycyrrhizinate 0.2-Silk fibroin peptide of Example 1 3.0-Allantoin 0.5-Methylparaben 0.1-Citric acid pH = 6 Amount to be 0.5. Purified water Table 7 shows the balance test results.

Example 41 A solid detergent having the following composition was prepared and subjected to the same test as in Example 27. Ingredients wt% -Soap substrate (beef tallow: coconut = 8: 2) 93.3-N-lauroyl-L-sodium aspartate 2.0-Titanium oxide 0.1-Edetate 0.1-Example 1 Silk Fibroin Peptide 4.5 The test results are shown in Table 7.

Example 42 A kitchen detergent having the following composition was prepared and subjected to the same test as in Example 27. Ingredients wt% -sodium α-olefin sulfonate 15.0-laurylamide dimethylhydroxypropyl sulfobetaine (30%) 5.0-lauryl glucoside 3.0-POE (2) lauric acid monoethanolamide 2.0-edetic acid Salt 0.1-Silk Fibroin Peptide of Example 1-Purified Water Remainder Table 7 shows the test results.

Example 43 A gel shampoo having the following composition was prepared and subjected to the same test as in Example 27. Ingredients% by weight Silk fibroin peptide of Example 1 1.0 Silk fibroin peptide of Example 2 1.0 Polyoxyethylene (3) lauric acid monoethanolamide sodium sulfate (30%) 25.0 Lauric acid isopropanol Amide 8.0-Carboxymethyl chitin 0.1-Methylparaben 0.1-EDTA 0.1-Citric acid pH = 7.0 Amount-Purified water Residual test results are shown in Table 7.

Example 44 A body shampoo having the following composition was prepared and subjected to the same test as in Example 27. Ingredients wt% 2-lauryl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine (30%) 20.0 Silk fibroin peptide of Example 2 2.0 Sodium monododecyl phosphate 5.0 Laurin Acid diethanolamide 3.0-Lauric acid triethanolamine 7.0-Methylparaben 0.1-EDTA 0.1-Purified water balance Table 7 shows the test results.

Example 45 A shampoo having the following composition was prepared and subjected to the same test as in Example 27. Ingredient Weight% & Example 1 Silk fibroin peptide 1.0-C _{14-.alpha.-olefin} sulfonate sodium 5.0 - sodium cocoyl isethionate 5.0-polyoxyalkylene-modified organopolysiloxane (a 20% denaturing polyoxyethylene 20% by weight) 1.0-Lauric acid diethanolamide 5.0-Lauric acid monoethanolamide 2.0-Methylparaben 0.1-EDTA 0.1-Purified water Residual test results are shown in Table 7.

Example 46 A shampoo having the following composition was prepared and subjected to the same test as in Example 27. Ingredients wt% -Sodium lauryl sulfate 15.0-Silk fibroin peptide of Example 0.1-Mono (polyoxyethylene (6) lauric acid amide) Sodium phosphate 4.0-Lauric acid diethanolamide 3.0-Methylparaben 0.1-EDTA 0.1-Purified water The balance test results are shown in Table 7.

Example 47 A kitchen detergent having the following composition was prepared and subjected to the same tests as in Example 27. Ingredients wt% -Polyoxyethylene (3) lauric acid monoethanolamide sodium sulfate (30%) 10.0-Polyoxyethylene (5) lauric acid monoethanolamide disodium sulfosuccinate (30%) 5.0-Example No. 1 silk fibroin peptide 1.0-lauryl dimethylamine oxide 4.0-lauric acid diethanolamide 3.0-ethanol 2.0-purified water Residual test results are shown in Table 7.

[0124]

[Table 7]

As is clear from the results in Table 7, the detergents of Examples 37 to 47 containing the silk fibroin peptide of the present invention were excellent in foaming power, detergency and foam quality, and had little protein denaturation. . In particular, the effect was remarkable when compounded with an amidocarboxylic acid type anionic surfactant.

[0126]

Industrial Applicability The silk fibroin peptide obtained by treating and hydrolyzing silk fibroin in high-pressure heated water at 150 to 250 ° C., high-pressure heated dilute acid water or high-pressure heated dilute alkaline water does not have an unpleasant odor and is an inorganic salt. The content is also very low. Furthermore, compared with conventional silk fibroin peptide, it has extremely excellent film forming ability, water retention ability, solubility, and long-term storage stability. The method of the present invention is a very simple treatment of heating only with silk fibroin and water, and does not require the desalting step which was necessary in the past. Further, since no enzyme is used, it is an industrially easy and inexpensive production method.

The cosmetic and detergent composition containing the silk fibroin peptide of the present invention exhibits remarkable effects. That is, when blended in cosmetics, not only is it highly safe, but it also has excellent moisturizing properties, moisturizing sensation, and
Adds luster and gloss to hair. When used in a detergent composition, not only the foaming power and cleaning power are improved, but also the foam quality is fine and creamy. Further, it also has a function of alleviating the irritation of conventional surfactants. In particular, when it is blended with an amidocarboxylic acid salt, its effect is remarkable, so that it is suitable as a detergent composition.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location // A61K 7/50 (72) Inventor Fumihiko Kondo 2835 Imafuku Kawagoe City, Saitama Kawaken Fine Chemicals Saitama Project In-house

Claims (8)

[Claims] 1. The following general formula (1): embedded image obtained by treating silk fibroin in high-pressure water at 150 to 250 ° C. for hydrolysis. (In the formula (1), R and R ′ are side chains of various amino acids constituting silk fibroin, and n is an integer of 0 to 20). 2. Silk fibroin is treated in high-pressure water at 150 to 250 ° C. to be hydrolyzed, and is represented by the following general formula (1): (In the formula (1), R and R ′ are side chains of various amino acids constituting silk fibroin, and n is an integer of 0 to 20). 3. The method for producing a silk fibroin peptide according to claim 2, which comprises hydrolyzing in the presence of an acid of 0.1 N or less. 4. The method for producing a silk fibroin peptide according to claim 2, which comprises hydrolyzing in the presence of an alkali of 0.1 N or less. 5. The following general formula (1): embedded image obtained by treating silk fibroin with high-pressure water at 150 to 250 ° C. and hydrolyzing it. (In the formula (1), R and R ′ are side chains of various amino acids constituting silk fibroin, and n is an integer of 0 to 20), and the silk fibroin peptide is contained. Cosmetics. 6. Silk fibroin is treated with high-pressure water at 150 to 250 ° C. and hydrolyzed to obtain the following general formula (1): (In the formula (1), R and R ′ are side chains of various amino acids constituting silk fibroin, and n is an integer of 0 to 20), and the silk fibroin peptide is contained. Cleaning composition. 7. The silk fibroin peptide according to claim 6, which contains at least one surfactant selected from anionic surfactants, amphoteric surfactants and nonionic surfactants, and the silk fibroin peptide represented by the general formula (1). A cleaning composition comprising: 8. The anionic surfactant according to claim 6, wherein the anionic surfactant is represented by the following general formula (2): (In the formula (2), R ¹ represents an alkyl group or an alkenyl group having 7 to 19 carbon atoms, M represents an alkali metal atom, an alkaline earth metal atom, an ammonium group, or a cationic residue of a basic amino acid. Represents a group or a cationic residue of an alkanolamine, m represents an integer equal to the valence of the atom or group represented by M, and R ² represents the following formula (a):
~ (H) structural formula: Represents one member selected from. ) A detergent composition which is an amidocarboxylic acid type surfactant represented by