A composition for hair cosmetics, a hair cosmetic containing the composition, and a method for repairing the cuticle structure of hair using the cosmetic.

Abstract

The present invention provides a hair cosmetic that does not cause the lactone ring to open even in the presence of an aqueous solvent, and that can repair the cuticle structure. [Solution] The present invention provides a hair cosmetic containing γ-dodecalactone, represented by the following formula (I), in an amount of 0.001% or more and less than 10% by weight of the hair cosmetic as an active ingredient for improving hair damage. JPEG2026062595000028.jpg2197

Description

[Technical Field]

[0001] The present invention relates to a hair cosmetic composition containing γ-dodecalactone, a hair cosmetic containing the composition, and a method for repairing the cuticle structure of hair using the cosmetic. [Background technology]

[0002] Hair consists of 80-90% protein, along with water, lipids, melanin pigment, and trace elements. The protein in hair is rich in cystine, which contributes to its properties of being hard, strong, and highly elastic. Hair is composed of three layers, from the outside inward: the cuticle layer, the cortex layer, and the medulla layer.

[0003] Here, the cuticle layer described above has a scale-like structure in which 5 to 10 layers of small pieces called cuticles overlap. The cuticle layer is a thick protective outer film, and its outermost layer, the epicuticle layer, is composed of 75% strongly crosslinked keratin protein on its surface, to which 25% fatty acids, mainly composed of 18-methyleicosanoic acid (hereinafter sometimes referred to as "18-MEA"), are bonded by thioester bonds. 18-MEA keeps the cuticle layer hydrophobic while simultaneously keeping the hair surface smooth.

[0004] Hair is naturally colorless, but it develops color when it contains melanin pigment. There are two types of melanin: eumelanin (true melanin), which is black to brownish, and pheomelanin, which is reddish-brown to yellow. The intensity of the color is determined by eumelanin, while the yellowness or redness depends on the amount of pheomelanin. Pheomelanin is chemically more stable than eumelanin, and it is known that when hair is oxidized, eumelanin is destroyed first.

[0005] Hair is known to be damaged physically by the use of hair dryers and curling irons, etc., and chemically by the use of shampoo, hair dyes and bleaches, perming agents, etc. When such damage is repeatedly inflicted, the thioester bonds on the surface of the epicuticle layer are hydrolyzed, causing the 18-MEA on the hair surface to disappear and exposing hydrophilic groups such as sulfone groups and amino groups present in the keratin protein. This exposure of hydrophilic groups makes the hair surface hydrophilic, changing the structure of the cuticle layer and causing external changes such as the cuticle peeling up. Moreover, it also leads to weakening of the hair fibers due to swelling of the cortex layer, etc. Hair that has suffered such damage is sometimes called "damaged hair."

[0006] In recent years, in order to improve or repair such hair damage, cosmetics have been proposed that contain γ-lactones having a linear or branched chain with 12 to 22 carbon atoms, instead of the quaternary ammonium salts of branched fatty acids that were conventionally used in hair cosmetics (see Patent Documents 1 and 2) (Patent Document 3, hereinafter referred to as "Prior Art 1"). Furthermore, it has been reported that when a δ-lactone derivative obtained from fatty acids derived from meadowfoam seeds is incorporated into hair mists, hair sprays, etc., it has the effect of preventing dryness and stiffness in the hair and making it easier to comb through (Patent Document 5, hereinafter referred to as "Prior Art 2").

[0007] Furthermore, in order to reduce damage to the hair when applying permanent waves, it has been proposed to use γ-lactone derivatives with 3 to 10 carbon atoms (specifically, γ-valerolactone, DL-pantoic acid-γ-lactone, and γ-hexanolactone) as pre-treatment agents for permanent waves (see Patent Document 4).

[0008] It is known that the amount of lactone mentioned above used in cosmetics is extremely low because a strong scent when applied to the hair can cause discomfort to those around the user and may trigger symptoms such as headaches, nausea, allergies, stress disorders, and chemical sensitivity.

[0009] Among various lactones, γ-dodecalactone, represented by the following formula (I), has been used in the formulation of fragrance compositions due to its peach-like aroma. Furthermore, γ-dodecalactone is known to be used as an insect attractant or repellent, a deodorant, and an intermediate in pharmaceuticals.

[0010] [ka] [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] Japanese Patent Application Publication No. 10-139620 [Patent Document 2] Japanese Patent Publication No. 2009-126851 [Patent Document 3] Japanese Patent Publication No. 2012-062250 [Patent Document 4] Japanese Patent Publication No. 2008-195633 [Patent Document 5] Japanese Patent Publication No. 2012-254946 [Overview of the project] [Problems that the invention aims to solve]

[0012] Prior art 1 is an excellent invention in that it can improve hair damage. The invention of prior art 1 chemically induces γ-elaidic lactone (also known as γ-docosanolactone, carbon number = 21) and γ-stearolactone (carbon number = 17), which are cyclic esters, from chemically synthesized elaidic acid, and formulates them into hair mists, hair essences, hair lotions, etc., and qualitatively confirms its effects in terms of four points: smoothness, feel when passing through fingers, firmness, and moistness, compared with damaged hair. However, the repair effect of the cuticle structure not included in the above evaluation items has not been considered. In addition, lactones with fewer carbon atoms than γ-docosanolactone (carbon number = 21) and γ-stearolactone (carbon number = 17) have not been produced, and naturally, their physical properties have not been confirmed. Therefore, it is also unclear whether they can be used in hair cosmetics.

[0013] In addition, prior art 2 involves formulating a δ-lactone derivative having a six-membered ring collected from meadowfoam seeds into hair cosmetics. By bonding the δ-lactone derivative to the hair by heat from a dryer or hair iron, the surface of the hair is re-hydrophobized, thereby smoothing the hair surface, imparting slipperiness, luster, and an excellent firmness improvement effect. The infrared absorption spectrum of the above lactone collected from meadowfoam seeds is shown in FIG. 5, and the IR spectrum of δ-decanolactone is shown in FIG. 8, respectively.

[0014] However, the δ-lactone derivative has a problem that when formulated in a cosmetic, the lactone ring opens during storage when an aqueous solvent is present, and the hair damage improvement effect cannot be exerted (see

[0010] of Patent Document 3). Therefore, there has been a strong social demand for finding a lactone that does not open the lactone ring even in the presence of an aqueous solvent and can repair the cuticle structure, and manufacturing it efficiently.

Means for Solving the Problems

[0015] As a result of intensive studies to solve the above problems, the inventors have found that γ-dodecalactone represented by the following formula (I), which has never been used as a hair cosmetic, has a novel property of being able to improve hair damage, and have completed the present invention.

[0016] [Chemical formula]

[0017] An object of the present invention is to provide a compound that can improve the above-described hair damage and maintain this improvement effect for a long period of time by applying it to hair at a lower concentration than γ-lactones having 16 or more carbon atoms and then performing heat treatment on the hair.

[0018] That is, a first aspect of the present invention is a hair cosmetic containing γ-dodecalactone represented by the above formula (I) in an amount of 0.001% by weight or more and less than 10% by weight of the weight of the hair cosmetic as an active ingredient for improving hair damage. Here, it is preferable that the improvement of the hair damage repairs the cuticle structure of physically or chemically damaged hair.

[0019] A second aspect of the present invention is a method for repairing the cuticle structure of hair, comprising a step of applying the hair cosmetic to physically or chemically damaged hair and a step of heat-treating the hair to which the hair cosmetic has been applied. Here, the step of heat-treating the hair is preferably a step of applying heat of 50 to 220°C for 10 to 900 seconds to the hair to which the hair cosmetic has been applied. Here, the time of 900 seconds for the heat treatment is the maximum value of the total treatment time, and it is more preferably 10 to 300 seconds.

[0020] A further aspect of the present invention is a hair cosmetic composition containing γ-dodecalactone represented by the following formula (I), which is produced by a method comprising first and second culture steps using saponified camellia oil as a raw material and microorganisms belonging to different genera in terms of biological classification. The biological classification consists of domain, kingdom, phylum, class, order, family, genus, and species.

[0021] [ka]

[0022] Here, the saponification value of the camellia oil is preferably 182 to 200, and more preferably 188 to 194. Furthermore, when the number of microorganisms used in the first step is set to 1, the number of microorganisms used in the second step is preferably 10 to 1000 times (w / w). Moreover, it is preferable to use only the culture obtained in the first step as the culture medium in the second step to produce the final product.

[0023] The microorganism used in the first step is preferably a lactic acid bacterium derived from camellia petals, and the microorganism used in the second step is preferably a yeast derived from camellia petals. Furthermore, the lactic acid bacterium derived from camellia petals is more preferably NITE P-03920 or NITE P03292, and the yeast derived from camellia petals is more preferably NITE P-01807.

[0024] The final product is preferably purified using a column packed with a synthetic resin and its elution solvent, and it is even more preferable that the synthetic resin is HP-20 and the elution solvent is selected from the group consisting of ethanol, propanol, and acetone. [Effects of the Invention]

[0025] The present invention provides a hair cosmetic containing γ-dodecalactone represented by formula (I) in an amount of 0.001% by weight or more and less than 10% by weight of the hair cosmetic. The invention also provides a method for repairing the cuticle structure of hair, comprising the steps of applying the hair cosmetic to physically or chemically damaged hair and heat-treating the hair to which the hair cosmetic has been applied. [Brief explanation of the drawing]

[0026] [Figure 1] Figure 1 is a schematic diagram representing the structure of hair. [Figure 2] Figure 2 shows the infrared absorption spectrum (hereinafter sometimes referred to as "IR spectrum") of γ-dodecalactone, which is commercially available as a reagent. [Figure 3] Figure 3 shows the IR spectrum of a hexane extract from saponified camellia oil.

[0027] [Figure 4] Figure 4 shows the IR spectrum of γ-docosalactone (also known as ercalactone), which is obtained by removing volatile components from commercially available ercalactone. [Figure 5] Figure 5 shows the IR spectrum of meadowlactone. [Figure 6] Figure 6 shows the IR spectrum of commercially available diethyl sebacate. [Figure 7] Figure 7 shows the IR spectrum of commercially available oleic acid.

[0028] [Figure 8] Figure 8 shows the IR spectrum of commercially available dodecanolactone. [Figure 9] Figure 9 shows a chromatogram of the results of ion chromatography of one of the hexane extracts described above. [Figure 10] Figure 10 shows a chromatogram illustrating the results of ion chromatography of another hexane extract described above.

[0029] [Figure 11] Figure 11 is a graph showing the results of an investigation into the effect of improving combability when the hair cosmetic of the present invention or the control hair cosmetic was applied to a sample made from damaged hair and then heat-treated. [Figure 12] Figure 12 is an electron microscope image (part 1) showing the improvement effect of hair cosmetic on the cuticle (treated at 180°C). [Figure 13] Figure 13 is an electron microscope image (part 2) showing the improvement effect of hair cosmetic on the cuticle (treated at 60°C). [Modes for carrying out the invention]

[0030] The γ-dodecalactone contained in the hair cosmetic mentioned above is a compound represented by the following formula (I).

[0031] [ka]

[0032] The method for producing γ-dodecalactone used in the present invention is not particularly limited, as long as it is not by chemical synthesis, and may be produced by known methods. For example, such a method is the method described in Japanese Patent No. 3479337. The method described in this patent publication is a method comprising a first step of obtaining 10-hydroxystearic acid using oleic acid as a raw material, and a second step of obtaining γ-dodecalactone from the obtained 10-hydroxystearic acid, wherein the first step uses lactic acid bacteria that have the ability to hydroxylate the carbon involved in the carbon-carbon double bond, and the second step uses yeast that has β-oxidative ability.

[0033] Here, the lactic acid bacteria are preferably lactic acid bacteria belonging to the genera Lactobacillus, Leuconostoc, or Pediococcus. Among the lactic acid bacteria, examples of lactic acid bacteria belonging to the genus Lactobacillus include Lactobacillus brevis, Lactobacillus delbruechii, Lactobacillus plantarum, Lactobacillus sanfrancisco, Lactobacillus bulgaricus, or Lactobacillus casei, and an example of lactic acid bacteria belonging to the genus Leuconostoc is Leuconostoc mesenteroides. An example of lactic acid bacteria belonging to the genus Pediococcus is Pediococcus pentosaceu.

[0034] Furthermore, it is stated that the second microorganism is preferably a member of the genera Saccharomyces, Pichia, Hansenula, or Candida. Examples of usable microorganisms are given, such as commercially available baker's yeasts belonging to the Saccharomyces genus, such as Saccharomyces cerevisiae, Saccharomyces carsbergensis, and Saccharomyces chevalieri, as well as publicly known and distributed strains such as Pichia farinosa, Candida utilis, and Hansenula anomala. In addition to these, it is stated that pressed yeast or dried yeast sold by companies such as Chuetsu Yeast Co., Ltd., Oriental Yeast Co., Ltd., Lallemand, Ltd., and Littorale Ltd. can also be used.

[0035] Furthermore, the above method states that, after completing the first step by sterilization and before starting the second step, it is preferable to add at least one nutrient source such as yeast extract, polypeptone, meat juice, malt extract, or yeast extract. In practice, yeast extract and polypeptone are added to produce γ-dodecalactone. On the other hand, the generated γ-dodecalactone is isolated, collected, and purified using general methods.

[0036] The hair cosmetic composition of the present invention comprises a first step and a second step, and is produced using microorganisms in both steps. Here, it is preferable that the microorganism used in the first step is lactic acid bacteria derived from camellia petals, and the microorganism used in the second step is yeast derived from camellia petals, because the products (compositions) produced in these steps have the effect of improving hair damage, and in particular have a high ability to close open cuticles.

[0037] Alternatively, for example, another biological manufacturing method can be used, comprising first and second steps, which uses a composition containing saponified materials obtained by processing natural materials as a raw material and employs two different types of microorganisms, as shown below.

[0038] Here, the saponified product contained in the above composition is preferably obtained by saponifying camellia oil, which is a natural material, using a solution such as sodium hydroxide or potassium hydroxide, according to a conventional method. Here, the type of camellia used to obtain the camellia oil is not particularly limited as long as the resulting camellia oil contains oleic acid, but it is preferable that it also contains linoleic acid, stearic acid, or palmitic acid in addition to oleic acid. Examples of plants of the Camellia genus mentioned above include Camellia japonica, Camellia rusticana Honda, Camellia lutchuensis, and Camellia japonica L. var. macrocarpa. Examples of places where these camellias are produced include the Goto Islands and Oshima Island in Japan. The saponified product contained in the above composition may be one that has been saponified by the above method, or a commercially available soap made from camellia, such as Camellia Soap made by Goto Camellia Co., Ltd., may be used.

[0039] First, let's explain the lactic acid bacteria derived from camellia petals used in the first step. The lactic acid bacteria derived from camellia petals used here can be obtained as follows. The petals are separated from camellia flowers collected from a camellia tree and placed in a sterile test tube containing a sterile isolation medium to create a suspension stock solution. Examples of the isolation medium include M17 broth, GYP medium, or MRS broth. However, it is preferable to use MRS broth or GYP medium containing ammonium acetate and sodium citrate, as these can suppress the growth of bacteria other than lactic acid bacteria. Adding sorbic acid to adjust the pH to approximately 5.7 can further suppress the growth of bacteria other than lactic acid bacteria.

[0040] Next, accumulation culture is performed using a large test tube containing the above-mentioned isolation medium and camellia petals. For accumulation culture, for example, the above-mentioned suspension stock solution is added to pre-sterilized and cooled MRS medium or GYP medium (hereinafter collectively referred to as "accumulation medium"), and cultured statically at approximately 30°C for approximately 24 hours to obtain the culture stock solution. The obtained culture stock solution is diluted with sterile water to the desired concentration, for example, approximately 10 times, and this operation is repeated 10 times.5 Prepare dilutions up to twice the original concentration. Then, place each of these dilutions into a petri dish, and after the dilutions have solidified, cover the surface of the solidified dilutions by layering sterile agar water on top. Incubate these petri dishes in an incubator at approximately 36°C until colonies are clearly formed. Using an agar medium containing ammonium acetate and sodium citrate can suppress the growth of bacteria other than lactic acid bacteria. Pick up the colonies formed on the agar medium and transfer them to a petri dish containing another new agar medium for incubation. Confirm the characteristics of the resulting colonies as follows: If no bubbles are generated when hydrogen peroxide is dropped onto the colonies that have appeared as described above, and the bacteria taken from these colonies are Gram-positive, then the bacteria that formed those colonies can be identified as lactic acid bacteria.

[0041] The lactic acid bacteria used in the first step are not limited to those derived from camellia petals, as long as they can produce lactones, but it is preferable that they belong to the genera Lactobacillus, Leuconostoc, or Pediococcus. Among these, it is preferable that they belong to the genus Leuconostoc, and even more preferable that they be Leuconostoc mesenteroides. An example of such lactic acid bacteria is NITE accession number P-03920. Using such lactic acid bacteria makes it possible to obtain a primary culture that can produce more of the target lactone when yeast is used in the second step, as described later. Furthermore, while a single species of lactic acid bacteria may be used, multiple species of lactic acid bacteria may be mixed as appropriate.

[0042] The primary culture in the first step is a step of converting at least the oleates contained in the above-mentioned composition to 10-hydroxystearic acid, and this conversion is carried out by the lactic acid bacteria described above. The lactic acid bacteria described above consume the oleates contained in the culture medium used here during cultivation and produce 10-hydroxystearic acid. Furthermore, this production reaction is not necessarily carried out in a single step. Note that the composition used for the primary culture may also contain compounds other than oleates, such as linoleic acid, stearic acid, or palmitic acid, so their metabolites may also be produced during the primary culture. The IR spectrum of oleic acid is shown in Figure 7.

[0043] Primary culture can be carried out according to conventional methods and is not particularly limited as long as the conditions are suitable for the lactic acid bacteria used. For example, primary culture of lactic acid bacteria can be cultured in a buffer containing oleic acid, oleates, and / or surfactants. Examples of such buffers include phosphate buffer (pH 6.0-8.0), HEPES buffer, and Tris buffer. Examples of surfactants include nonionic surfactants, particularly Tween® 20, Tween 40, Tween 60, and Tween 80. Adding such surfactants has the effect of promoting the formation of thick-walled spores of yeast-like fungi (e.g., fungi belonging to the genus Candida), uniform dispersion in the culture medium, promotion of fatty acid supply, and promotion of nutrient uptake, thereby improving the yield of the target product, γ-dodecalactone.

[0044] Adding a surfactant to the liquid culture medium described above promotes the dispersion of lactic acid bacteria and oleates in the medium; however, using oleates allows for a reduction in the amount of surfactant added. Furthermore, in the purification process of the secondary culture described later, oleic acid can be removed by adsorption onto the solid phase, thus obtaining a good composition that does not contain oleic acid. For this reason, it is preferable to use a composition containing oleates rather than oleic acid as a raw material for production. As the oleic acid used here, sodium oleate is preferred, for example.

[0045] The ratio (by weight) of the saponified product, surfactant, and lactic acid bacteria (inoculation amount) in the composition used for the primary culture is preferably 1-10:0.1-1:0.05-1. Needless to say, to avoid contamination by bacteria other than lactic acid bacteria, the culture medium used for the primary culture should be sterilized before adding the lactic acid bacteria. Adding the saponified camellia oil mentioned above slightly increases the pH, but the pH of the culture medium used for the primary culture is preferably about 6.0-7. Note that there is no need to add nutrients during the primary culture.

[0046] The primary culture is generally carried out under anaerobic conditions. The culture temperature is preferably around 20-40°C, and more preferably 25-35°C. The culture period can be set appropriately according to the composition of the culture medium and the temperature conditions, and is often 24-96 hours. The primary culture may be carried out by static culture, or by gently stirring the culture medium to raise the settling lactic acid bacteria. This primary culture can be completed by sterilization, for example, by autoclaving. Note that even if the primary culture obtained in the primary culture is used as a raw material for the secondary culture, which is the second step, without sterilization, it will not have any particular effect on the completion of the target product.

[0047] In the second step, yeast derived from camellia petals is added to the primary culture obtained in the first step and cultured to produce the target product, γ-dodecalactone, represented by the following formula (I). The IR spectrum of commercially available γ-dodecalactone is shown in Figure 1.

[0048] [ka]

[0049] The yeast derived from camellia petals used in the second step described above can be obtained as follows. The petals are separated from camellia flowers collected from a camellia tree and placed in a large, sterile test tube containing a sterile isolation medium. For yeast isolation, for example, koji extract or YMA medium can be used. When using koji extract as an isolation medium, first place the desired weight of rice koji in a cloth bag, add 4 to 5 times the weight of the rice koji in water, and hold at a predetermined temperature for a predetermined time, for example, at approximately 50 to 63°C for approximately 4 to 6 hours. Next, take a small amount of liquid from the bag and check the starch reaction using an iodine-potassium iodide solution. Once the starch reaction has disappeared, lift the bag and squeeze lightly, then boil the extracted liquid. If the extracted liquid is not clear, add egg white, stir well, squeeze lightly, and boil this extracted liquid. After boiling, filter all boiled liquids using filter paper or similar.

[0050] Next, water is added using a sugar analyzer to adjust the Balling reading to a predetermined value, for example, around 10, to obtain the koji extract. Here, the Balling reading represents the number of grams of sucrose contained in 100 g of sucrose aqueous solution at 17.5°C. Note that the Balling reading is sometimes abbreviated as Ballg. reading. To prevent bacterial contamination, it is preferable to add, for example, chloramphenicol or other antibiotics to the above culture medium in accordance with conventional methods.

[0051] Next, the koji extract (isolation medium) prepared as described above and the camellia petals are placed in a large test tube and cultured at approximately 30°C for about 3 to 4 days. Here, "cultivation" refers to a culture method used to isolate a target microorganism from a sample containing multiple microorganisms, by controlling various growth environmental factors to ensure that only the target microorganism can grow, thereby eliminating other microorganisms. After culturing, the koji extract is appropriately diluted and spread onto an agar plate in a petri dish. The agar plate used here is, for example, YMA agar plate (NBRC medium No. 108), which is then cultured at a predetermined temperature for a predetermined period, for example, at approximately 30°C for about 3 to 4 days, until colonies appear. From the resulting colonies, those with different morphologies are selected and spread onto a new agar plate to obtain yeast as single colonies. These colonies are then inoculated onto, for example, V8 agar plate, cultured at approximately 30°C for about two weeks, and examined under a microscope to obtain the desired yeast. The yeast thus isolated can then be used in the second step of secondary culture.

[0052] In the second step described above, it is preferable to use yeast belonging to the genera Saccharomyces, Pichia, Hansenula, or Candida as the camellia petal-derived yeast, because it is possible to produce a large amount of the target lactone from the primary culture. The target lactone here is γ-dodecalactone, represented by formula (I) above.

[0053] In the secondary culture performed in the second step described above, it is preferable to use yeast at a wet weight ratio of approximately 100 to 1,000 times the amount of lactic acid bacteria used in the primary culture, and more preferably at 300 to 800 times the amount. In this secondary culture, yeast extract, polypeptone, and other nitrogen-producing nutrients may be added to the primary culture as appropriate. In that case, it goes without saying that these nutrients should be sterilized before adding the yeast to be used for the secondary culture. Lactones will still be produced even if the above nutrients are added to the culture medium used for the secondary culture, i.e., the primary culture. On the other hand, when a large amount of yeast is added, the amount of lactone produced will be higher if nutrients are not added. Therefore, the addition of nutrients in the secondary culture should be appropriately determined in relation to the amount of yeast used. If the above nutrients are not added at the start of the secondary culture, sterilization of the primary culture is unnecessary, and the yeast can be added immediately after the end of the primary culture to start the secondary culture, thereby improving production efficiency.

[0054] The secondary culture using the above yeast is preferably carried out under aerobic conditions, unlike the primary culture. The culture temperature is preferably about 20 to 40°C, and more preferably about 25 to 35°C. The culture period can be set appropriately depending on the composition of the culture medium and the temperature conditions, but for example, it is generally about 24 to 72 hours. The culture may be carried out by standing or by slow shaking. This secondary culture can be terminated, for example, by performing a sterilization procedure.

[0055] To recover γ-dodecalactone from the secondary culture obtained as described above, methods for isolating substances from conventional microbial cultures can be applied. For example, after separating the microbial cells from the culture medium by centrifugation or filtration, the target substance, γ-dodecalactone, can be extracted from the supernatant or filtrate. This extraction can be performed by solution partitioning, chromatography utilizing differences in affinity to various solid phases, etc. γ-dodecalactone is practically insoluble in water and has a relatively high boiling point. Therefore, it can also be obtained by solvent extraction followed by evaporation, and the crude product obtained in this way can be further purified using chromatography or other separation methods. These purification methods can be used in appropriate combinations as needed.

[0056] The present invention employs a purification method that does not use hexane, an organic solvent. First, the secondary culture obtained in the secondary culture is adsorbed onto a suitable solid phase. Examples of such solid phases include styrene-divinylbenzene synthetic resins and alkyl-modified silica resins. Examples of the styrene-divinylbenzene synthetic resins include Diaion HP-20 and Diaion HP-21, which have hydrophobic interactions, and examples of the alkyl-modified silica resins include octadecyl silica (hereinafter sometimes abbreviated as "ODS") which has a C18 alkyl difference. γ-dodecalactone is adsorbed onto such resins, and then eluted with an eluent such as ethanol to obtain a fraction containing γ-dodecalactone. Then, by distilling off the solvent of this fraction under reduced pressure, a composition containing γ-dodecalactone without unpleasant odor can be obtained.

[0057] Furthermore, in the hair cosmetic composition of the present invention, no nutrients are added after the completion of the first step described above, and it is preferable that the amount of yeast used in the second step is 10 to 1,000 times (w / w) the amount of lactic acid bacteria used in the first step, as this increases the amount of γ-dodecalactone produced. When using microorganisms to produce a compound, in order to obtain the compound with a certain degree of reproducibility, it is necessary to specify the culture conditions and other factors in addition to the microorganisms used and describe it as a product-by-process claim, and it is extremely impractical to describe it as a composition that specifies the content of other components. This is because, even if other components are included in a certain amount, it takes a considerable amount of time to purify the compound from the culture and determine its structure, and even if trace components are purified, they are likely to fall below the detection limit, in which case it is not only impossible to determine the structure, but it is also impossible to even detect the presence of the compound, as is well known to those skilled in the art.

[0058] Furthermore, it is preferable that the hair cosmetic of the present invention uses the above-mentioned saponified camellia oil as a raw material, as this allows for the development of new uses for camellia oil. It is preferable that the camellia oil used here is obtained from camellia fruits by the following procedure, in order to ensure high quality. First, the harvested camellia fruits are dried slowly in the sun for 5 to 6 days to open the skins and extract the black seeds from inside. These black seeds are then dried in the sun for another 5 to 6 days and sorted to remove immature seeds. The sorted camellia fruits are then put into a grinder to finely grind them, and the ground fruits are steamed for about 20 minutes. The ground fruits, while still hot after steaming, are packed into a ball press and slowly pressed to extract the oil. A ball press is used because it prevents the extraction of excess components, thus yielding high-quality camellia oil.

[0059] The protein that forms hair is called keratin, and it is synthesized in the hair follicle. Keratin is harder than skin keratin, and is sometimes called hard keratin. Normally, the binding structure of skin proteins is the cross-linking of e-(γ-glutamyl)lysine by transglutaminase, but in keratin, in addition to these lysine cross-links, there are many SS cross-links formed by sulfhydryl oxidase, and hydrogen bonds between amino acids, so hair is a harder tissue than skin. In the hair follicle, the upper part of the hair follicle is hard tissue with many SS cross-links, with the central part of the hair bulb (keratinization zone) being the boundary, but the lower part of the hair follicle is relatively soft tissue because the SH groups remain intact.

[0060] As mentioned above, hair is composed of three layers from the outside inward: the cuticle layer, the cortex layer, and the medulla layer (see Figure 1). The cuticle layer accounts for approximately 10-15% of the hair. The cuticles that make up the cuticle layer are made up of transparent cells without pigment, and each cuticle is about 0.5 μm thick and about 45 μm long. In healthy hair, 6-8 cuticles overlap and are tightly packed together on a single strand of hair (see Figure 1). As mentioned above, the cuticle layer is hard but weak against friction and is a brittle tissue. Therefore, rough brushing or washing hair roughly without lathering the shampoo sufficiently can damage or easily peel off the cuticles.

[0061] When observed with a transmission electron microscope, the cuticle layer can be divided into three layers. These three layers, from the outermost layer toward the cortex, are called the epicuticle (sometimes abbreviated as "Epi"), the exocuticle (sometimes abbreviated as "Ex"), and the endocuticle (sometimes abbreviated as "En").

[0062] (1) Epicuticle (Epi) layer The outermost layer of the cuticle is composed of lipids and keratin proteins, and its thickness is approximately 10 nm. The epicuticle has stronger resistance to chemical irritants such as stratum corneum-dissolving or protein-dissolving drugs than the following two layers, but it is hard and brittle, making it vulnerable to physical irritation.

[0063] (2) Exocuticle (Ex) layer The exocuticle is an amorphous keratin layer with a high cystine content, containing approximately 20% cystine as the total amino acid, and a thickness of about 100-300 nm. The exocuticle can be further divided into two layers based on the difference in cystine content; the outer (upper) layer is called the a-layer and has an even higher cystine content than the entire exocuticle. The a-layer has a relatively consistent thickness and is therefore uniformly distributed within the exocuticle. The inner (lower) part of the a-layer has an irregular shape and is in contact with the endocuticle. This layer as a whole has strong resistance to protein-soluble chemicals, but weak resistance to chemicals that break SS bonds, such as permanent wave lotion 1, and is easily damaged. Note that sometimes only the inner part of the a-layer is referred to as the "exocuticle."

[0064] (3) Endocuticle (En) layer This layer is located in the innermost part of the cuticle layer, and its thickness varies considerably, ranging from approximately 50 to 300 nm. The endocuticle layer has irregular contact with the exocuticle on its outer (upper) side, while its inner (lower) side has relatively uniform contact with the cell membrane complex (hereinafter sometimes abbreviated as "CMC"). In contrast to the Ex layer, this layer has a low cystine content and a higher content of acidic or basic amino acids than other layers that make up the cuticle, so it has the property of swelling when it absorbs water. It is resistant to chemicals that break the disulfide bonds of cystine, but it is not resistant to protein-soluble chemicals, and is therefore susceptible to damage from such chemicals.

[0065] The cell membrane complex (CMC) located between adjacent cuticles has the function of bonding them together. CMC is formed by the fusion of two unit cell membranes between cells, and has a structure in which a δ-layer composed of protein with a thickness of approximately 10 nm is sandwiched between a β-layer composed of lipids. CMC is found not only between adjacent cuticles but also in the internal structure of the cortex, bonding cells within the cortex. Furthermore, it is said to have the function of creating a route for the elution of water and proteins from within the cortex, and for the penetration of water, perming agents, hair colorants, and other chemicals from the outside into the hair.

[0066] Therefore, as mentioned above, rough brushing and harsh shampooing can cause physical damage to the hair, and the use of perming agents and hair coloring agents can cause chemical damage. For this reason, the hair damage improvement described above is preferable because it involves repairing the cuticle structure of physically or chemically damaged hair, as this yields a high level of damage improvement.

[0067] The γ-dodecalactone of the present invention is not obtained through chemical synthesis, but by processing a saponified product obtained from a natural material called camellia oil in first and second steps using different microorganisms. In the first step, camellia oil or commercially available camellia oil saponified by adding water and sodium hydroxide while heating and stirring the camellia oil in a saponification kettle is used. The saponification value of this camellia oil is preferably 182 to 200, and more preferably 188 to 194, in relation to the molecular weight of the fatty acids that make up the camellia oil. The saponification value represents the amount of potassium hydroxide (mg) required to saponify 1 g of oil.

[0068] Furthermore, in the first step described above, it is preferable to use lactic acid bacteria derived from camellia petals, and it is preferable to use NITE P-03920 or NITE P-03292 because it allows for efficient processing in the second step described later. 2 x 10⁶ per gram of saponified product using the above lactic acid bacteria. 7 pieces~2x108 After adding the cells, the culture is incubated statically in a designated container at approximately 35°C to 40°C for approximately 12 to 96 hours to obtain the primary culture.

[0069] The obtained primary culture is sterilized by autoclaving the container for approximately 10 to 20 minutes. Then, microorganisms are added to the container and cultured in the second step to obtain a secondary culture. The microorganism added in the second step is preferably a yeast derived from camellia petals, and NITE P-01807 is preferred because it produces a large amount of γ-dodecalactone in the secondary culture.

[0070] The amount of microorganisms added in the second step described above is preferably about 10 to 1,000 times (w / w) the amount of microorganisms used in the first step described above, as this results in a large production of γ-dodecalactone. Furthermore, it is preferable not to add peptone, yeast extract, or other nutrients when subjecting the material to the second step described above, as this results in a secondary culture that does not have an off-odor, and thereby simplifies the process of producing γ-dodecalactone from the secondary culture.

[0071] Specifically, the saponified product used is prepared by heating and stirring camellia oil in a saponification oven while adding water and sodium hydroxide to react with it. Alternatively, it can be purchased as saponified camellia oil from a supplier that handles camellia oil, for example, a cosmetics manufacturer in the Goto Islands. This saponified mixture is mixed with 0.05 M phosphate buffer (pH 6.8) in a weight ratio of approximately 5:1 to 15:1. Then, the lactic acid bacteria used in the first step (accession number NITE P-03920 or NITE P-03292) are added to this mixture at a rate of approximately 2 x 10⁶ per gram of the saponified mixture used. 7 pieces ~ approx. 2x10 8 Add the cells and culture at approximately 35°C to 40°C for approximately 12 to 96 hours to obtain the primary culture.

[0072] Next, the obtained primary culture is autoclaved for approximately 10-25 minutes to kill the lactic acid bacteria and obtain a sterile primary culture. Without adding the above nutrients to the sterile primary culture, approximately 4.8 x 10 per 1 g of saponified material used 7 pcs ~ approx. 1.6x10 9 Add one yeast cell (accession number NITE P-01807) and culture with shaking at approximately 35°C to 40°C for approximately 24 to 72 hours to obtain a secondary culture.

[0073] The bacterial cells are separated from the secondary culture obtained as described above by centrifugation or filtration, the supernatant is extracted with a polar or nonpolar organic solvent, and the crude product is obtained by distilling off the organic solvent.

[0074] When the crude product obtained as described above is analyzed using gas chromatography or other analytical instruments, peaks for γ-dodecalactone and its derivatives (hereinafter collectively referred to as "γ-dodecalactone") are detected, just as when nutrients are added, but peaks for components generated when nutrients are added are not detected. When the γ-dodecalactone content is determined by the peak area ratio method, a content of approximately 0.001 to 10% (w / v) is preferable from the viewpoint of improving damaged hair. Furthermore, the γ-dodecalactone obtained as described above can be chemically bonded to the hair's proteins by applying it to the hair and then subjecting it to heat treatment, thereby improving the aforementioned hair damage.

[0075] Due to these properties of γ-dodecalactone, the crude product obtained as described above can be incorporated in small amounts into the hair cosmetic product described later to produce a hair cosmetic product. The amount of γ-dodecalactone incorporated into the hair cosmetic of the present invention is not particularly limited, but it is preferably in the range of 0.0001 to 20% by weight, as this does not result in an overly strong peach-like fragrance of γ-dodecalactone, and more preferably in the range of 0.002 to 5% by weight.

[0076] Furthermore, the γ-dodecalactone of the present invention can be used by dispersing it in an aqueous medium. This is because, unlike the δ-lactone described above, it can exist stably even in an aqueous medium. In this specification, "aqueous medium" means a liquid medium mainly composed of water, and may also contain water-soluble inorganic or organic substances as components other than water. When dispersing the γ-dodecalactone of the present invention in an aqueous medium, it is preferable to use a suspending agent to enable the preparation of a stable suspension. Here, "suspending agent" is an additive added to make the suspended particles into a stable suspension, and can be divided into thickeners and dispersants. Examples of thickeners that increase the viscosity of the suspension include sucrose and gum arabic, and examples of dispersants that disperse the secondary particles of the suspended particles into primary particles include calcium hexametaphosphate, sodium citrate, and surfactants.

[0077] Surfactants can be classified into anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and polymeric surfactants. Here, anionic surfactants have a lipophilic group consisting of hydrocarbon residues and hydrophilic groups such as carboxyl groups and sulfone groups in their molecules, while cationic surfactants have the above lipophilic group and a hydrophilic group such as an amino group. Nonionic surfactants have the above lipophilic group and a hydrophilic group such as an ester or hydroxyl group. Furthermore, amphoteric surfactants are surfactants that, when dissolved in water, exhibit the properties of anionic surfactants in alkaline regions and cationic surfactants in acidic regions. This is because they contain both a group that becomes a cation and a group that becomes anion in the same molecule. Amphoteric surfactants have resistance to hard water and can be mixed with other surfactants as desired. Polymeric surfactants are generally those with a molecular weight of several thousand or more that have surfactant functions, and specific examples include polyoxypropylene, polyoxyethylene block copolymers, and polyacrylic acid derivatives in which alkyl chains are introduced into polyacrylic chains.

[0078] These surfactants are preferably quaternary ammonium salts, as this allows for the production of hair cosmetic products with stable quality, and it is even more preferable to mainly use long-chain dialkyl quaternary ammonium salts. Furthermore, the use of polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan oleate, polyglyceryl-10 oleate, other sterols and / or polyether polyols and other polyols in combination is preferable as it can further stabilize the dispersibility of γ-dodecalactone and the like.

[0079] Examples of hair cosmetic products of the present invention include oil shampoos, cream shampoos, conditioning shampoos, anti-dandruff shampoos, hair color shampoos, rinse-integrated shampoos and other shampoos; rinses, treatments, hair packs, etc.; hair foams, hair mousses, hair sprays, hair mists, hair waxes, hair gels, water greases, setting lotions, color lotions, hair tonics, hair liquids, pomades, sticks, hair creams, etc.; hair blow dryers, split end coats, hair oils; perm-related agents such as permanent wave agents, straight perm agents, perm pre-treatments, and perm after-treatments; coloring-related agents such as oxidative hair dyes, hair bleaches, hair color pre-treatments, hair color after-treatments, and hair manicures; and hair growth agents.

[0080] Examples of the hair cosmetic formulations of the present invention include emulsified cosmetic formulations such as oil-in-water (O / W) type, water-in-oil (W / O) type, W / O / W type, and O / W / O type, as well as oily cosmetic formulations, solid cosmetic formulations, liquid cosmetic formulations, paste cosmetic formulations, stick cosmetic formulations, volatile oil type cosmetic formulations, powder cosmetic formulations, jelly type cosmetic formulations, gel type cosmetic formulations, paste type cosmetic formulations, emulsified polymer type cosmetic formulations, sheet type cosmetic formulations, mist type cosmetic formulations, spray type cosmetic formulations, and the like.

[0081] The hair cosmetic composition of the present invention can be manufactured according to conventional methods. For example, a hair oil can be manufactured by mixing 95% by weight of camellia oil, 0.1% by weight of ethylhexylglycerin, 3.9% by weight of squalene, and 1.0% by weight of camellia leaf wax.

[0082] Furthermore, the hair cosmetic composition containing γ-dodecalactone of the present invention may optionally contain additives commonly used in hair cosmetics, such as oily bases, humectants, texture enhancers, surfactants, polymers, thickeners / gelling agents, solvents, propellants, antioxidants, reducing agents, oxidizing agents, preservatives, antibacterial agents, chelating agents, pH adjusters, acids, alkalis, powders, inorganic salts, vitamins and their derivatives, hair growth agents, blood circulation promoters, stimulants, plant / animal / microbial extracts, fragrances, pigments, colorants, dyes, pigments, water, etc., in desired proportions.

[0083] In addition to these, it is possible to include known cosmetic ingredients, pharmaceutical ingredients, food ingredients, etc., in known combinations, formulation ratios, and amounts, such as ingredients listed in the Cosmetic Raw Material Standards, Cosmetic Ingredient Formulation Standards, Japan Cosmetic Industry Association Ingredient Labeling Name List, INCI Dictionary (The International Cosmetic Ingredient Dictionary and Handbook), Quasi-drug Raw Material Standards, Japanese Pharmacopoeia, Pharmaceutical Additives Standards, Food Additives Compendium, etc., as well as ingredients listed in Japanese and foreign patent gazettes and patent publications (including published and republished gazettes) belonging to the International Patent Classification IPC A61K7 and A61K8 classifications.

[0084] The hair cosmetic composition containing γ-dodecalactone of the present invention can improve hair damage even when used in the usual manner, such as by taking an appropriate amount in the palm of the hand and applying it to the hair. After using it as described above, by applying heat treatment to the hair, the hair damage improvement effect can be exerted for a longer period than when using γ-lactones with 16 or more carbon atoms in the side chain (hereinafter sometimes referred to as "long-chain γ-lactones"). In this case, the amount of γ-dodecalactone of the present invention can be at a lower concentration than that of the long-chain γ-lactones mentioned above.

[0085] Here, for the heat treatment of hair described above, hair irons, combs, dryers and other devices can be used. For example, when using a hair iron or a comb, the set temperature of these devices can be set to about 60 to about 180°C and used about 1 to 10 times. In the case of a digital perm, it can be treated at about 60 to about 120°C for about 1 to 60 minutes, and in the case of a dryer, it can be treated with hot air for about 30 seconds to about 10 minutes.

Example

[0086] Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

[0087] (Example 1) Generation of γ-dodecalactone Add 200 mL of phosphate buffer (0.05 M, pH 6.8) to a 500 mL Erlenmeyer flask, and add 0.5 g of the saponified product of camellia oil obtained from Tsubaki Camellia Co., Ltd. and 50 mg of Tween 80 (manufactured by Yoneyama Pharmaceutical Co., Ltd.) as a surfactant. This was autoclaved at 121°C for 15 minutes for sterilization and used as a raw material for the first culture. Take out the above raw material from the autoclave and cool it to room temperature, and then inoculate about 0.1 g (about 1x10 9 cells / g) of the wet cells of lactic acid bacteria (Leuconostoc mesenteroides, accession number NITE P-03920, Tsubaki Camellia Co., Ltd.) obtained from camellia petals, and hold it in a constant temperature machine at 30°C for 72 hours to obtain a primary culture.

[0088] Sterilize a 500 mL Erlenmeyer flask containing the above primary culture by autoclaving at 121°C for 15 minutes. Take out the sterilized Erlenmeyer flask from the autoclave and cool it to room temperature, and add 0.3 g (1.6 x 10 8 cells / g) of pressed yeast (Saccharomyces cerevisiae, accession number NITE P-01807, Tsubaki Camellia Co., Ltd.) obtained from camellia petals, and culture it at 30°C for 48 hours while shaking at 100 rpm to obtain a secondary culture.

[0089] Next, the concentration of γ-dodecalactone contained in the secondary culture obtained as described above was measured. For the measurement sample, 200 mL of the above secondary culture was placed in a 500 mL round-bottom flask, 100 mL of hexane (manufactured by Yoneyama Pharmaceutical Co., Ltd.) was added, the flask was covered and shaken, and after standing, the separated oil phase (hexane layer) was removed. Hexane was removed from the oil phase using a rotary evaporator under reduced pressure, and 6 mL of hexane was added to the resulting oil phase residue to dissolve it and prepare the solution. 0.3 mL of this solution was taken into a test tube, and 0.6 mL of hexane was added to it to prepare the measurement sample solution.

[0090] In the examples described herein, IRAffinity-1 (Shimadzu Corporation) was used to measure infrared absorption spectra. The IR spectra of commercially available γ-dodecalactone and the hexane extract from the above secondary culture are shown in Figures 2 and 3, respectively. Also, 1 For the measurement of the 1H-NMR spectrum, deuterated methanol was used as the solvent, and the measurement was performed using a JNM-AL (300 MHz, JEOL Ltd.). The primary and secondary cultures obtained as described above were subjected to analysis using a gas chromatograph-mass spectrometer at the Tokyo Metropolitan Industrial Technology Research Center, and it was confirmed that γ-dodecalactone was present as the main component. The analysis results are shown in Figures 9 and 10.

[0091] (Comparative Example 1) Synthesis of γ-docosalactone (γ-4-hydroxydocosanoate γ-lactone) In a 200 mL reaction vessel equipped with a stirrer, thermometer, and gas inlet tube, 16.9 g (0.05 M) of erucic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10.1 g (0.1 M) of concentrated sulfuric acid (manufactured by Fujifilm Wako Co., Ltd.) were charged and reacted at 85°C for 6 hours under a nitrogen atmosphere to obtain a reaction solution. To the obtained reaction solution, 50 g of deionized water and 118 g of heptane were added, and 1 M sodium hydroxide was added to a final concentration of 4%, and the mixture was shaken to extract the target product into the heptane phase.

[0092] The heptane phase containing the target compound obtained as described above was neutralized with 2% sodium hydroxide solution, and then the heptane phase was washed three times with deionized water. The washed heptane phase was concentrated under reduced pressure using a rotary evaporator to obtain 3.4 g of the target compound as a white solid. This white solid was made into tablets using the KBr tablet method, and its infrared absorption spectrum was measured, yielding 2918, 2851, 1753, 1468, and 1188 cm⁻¹. -1 This is what happened. 1 The H-NMR spectrum was assigned and its structure confirmed that the white solid was γ-docosalactone. The IR spectrum is shown in Figure 4. This white solid, γ-docosalactone, was used in the example.

[0093] (Comparative Example 2) Synthesis of γ-stearolactone (4-hydroxyoctadecanoic acid γ-lactone) In a 200 mL reactor equipped with a stirrer, thermometer, and gas inlet tube, 14.1 g (0.0500 mol) of oleic acid (Kao Corporation, product name: Lunac O-LL-V) and 10.1 g (0.100 mol) of concentrated sulfuric acid were charged, and the reaction was carried out at 85°C for 6 hours under a nitrogen atmosphere. 50 g of deionized water, 99 g of heptane, and 4% sodium hydroxide were charged into the resulting reaction solution, and the target product was extracted into the heptane phase. The heptane phase containing the target substance obtained as described above was neutralized with 2% sodium hydroxide solution, and then washed three times with deionized water. The heptane phase was concentrated under reduced pressure, and 2.6 g of the target compound was obtained as a white solid. This white solid was made into tablets by the KBr tablet method, and its infrared absorption spectrum was measured, yielding 2920, 2851, 1753, 1470, and 1190 cm⁻¹. -1 This was the case. 1 Structural confirmation using 1H-NMR spectroscopy confirmed that the compound is represented by the following general formula: The white solid described above is a compound represented by the following formula (II)(C 22 H 42 The compound had the structure represented by O2). In the following examples, this white solid γ-stearolactone will be used.

[0094] [ka]

[0095] (Example 2) Sensory evaluation of hair (Preparation of hair cosmetic products) By mixing each component according to the component ratios shown in Table 1 below, hair cosmetic formulations containing the compounds of Example 1, Comparative Example 1, or Comparative Example 2 were prepared, and these were designated as Example, Comparative Example 1, or Comparative Example 2 hair cosmetic formulations, respectively.

[0096] The details of the components listed in Table 1 are as follows: butylene glycol (manufactured by Fuyuho Alcohol Kogyo Co., Ltd.), PEG-40 hydrogenated castor oil (manufactured by Nikko Chemical Co., Ltd.), cetanol (manufactured by Fuyuho Alcohol Kogyo Co., Ltd.), and diethyl sebacate (hereinafter sometimes abbreviated as "DES"; manufactured by Nippon Seika Co., Ltd.). The ratios of each component in Table 1 are shown in weight percent. The IR data of diethyl sebacate is shown in Figure 6, and the IR spectrum data of the product from Example 1 is shown in Figure 3. We evaluated the effectiveness of these hair cosmetic products in improving the perceived damage to hair. The test method was as follows:

[0097] [Table 1]

[0098] (Test method) Hair bundles of damaged hair were prepared by impregnating healthy black human hair (hereinafter sometimes referred to as "healthy hair") in a bleaching agent made by mixing 6% hydrogen peroxide and 2% ammonia water in a 1:1 ratio for 30 minutes, followed by rinsing with water, and repeating this process three times. Next, 3g of each damaged hair bundle was immersed in 1.5g of various hair cosmetics prepared according to Table 1, applied uniformly, and then air-dried. These bundles were designated as hair bundles A1 to A4. A portion of hair bundles A1 to A4 was subjected to heat treatment at 180°C for 5 seconds five times using a hair iron, and designated as hair bundles B1 to B4. Additionally, a portion of hair bundles A1 to A4 was air-dried at 60°C for 60 seconds, and designated as hair bundles C1 to C4. After that, hair bundles A1, B1, and C1 were washed with a shampoo (MTG ReFa Ion Care Shampoo) and air-dried again. Each hair bundle prepared was evaluated for its effectiveness in improving hair damage through sensory evaluation (by 7 panelists). The evaluation was conducted by comparing four points—smoothness, manageability, firmness, and moisture—with untreated hair bundles (damaged hair). The results are shown in Table 2. The state of the cuticle is shown in Figures 12 and 13.

[0099] [Table 2]

[0100] In Table 2 above, ○ indicates improvement compared to untreated hair bundles (damaged hair), △ indicates slight improvement compared to untreated hair bundles (damaged hair), and × indicates no change compared to untreated hair bundles (damaged hair).

[0101] As shown in Table 2, the hair cosmetic compositions of Comparative Examples 1 and 2, which did not contain γ-dodecalactone of the present invention, showed little damage improvement effect, whereas the hair cosmetic compositions of the present invention (Example 1 (primary culture) and Example 1 (secondary culture)) containing γ-dodecalactone showed a significant improvement in the perceived damage. This effect was greater when heat treatment was applied. Furthermore, compared to the hair cosmetic compositions of Comparative Examples 1 and 2, the hair damage improvement effect was observed even at lower concentrations. Therefore, it has been shown that the hair cosmetic composition containing γ-dodecalactone of the present invention has the effect of improving hair damage even at low temperatures and low concentrations.

[0102] (Example 3) Evaluation of reactivity with hair The reactivity of the γ-dodecalactone of the present invention with hair was tested. The test was conducted as follows, and the results are shown in Table 3.

[0103] (Test method) A sample of hair cosmetic was prepared by dissolving γ-dodecalactone, produced in Example 1, in diethyl sebacate to a concentration of 0.0025% (w / w). The sample was then applied to each bundle of damaged hair prepared in the same manner as in Example 2, and the applied hair bundles were subjected to the heat treatments shown in Table 3. The 140°C and 180°C treatments were performed using a hair iron (MTG, product name ReFa Straight Iron Pro), with five 5-second heat treatments. The 60°C treatment was performed using a hair dryer (MTG, product name ReFa BEAUTECH Dryer Pro), with a 60-second heat treatment. After heat treatment, the hair bundles were washed with a shampoo (ReFa Ion Care Shampoo, MTG) and air-dried. The infrared absorption spectra (ATR method) of the hair bundles before and after heat treatment were measured using FTIR, and the lactone-derived 1750 cm⁻¹ was identified. -1 The presence or absence of a nearby peak (hereinafter referred to as the "lactone peak") was checked. Note that no lactone peak was observed in the hair strands before the sample was applied.

[0104] [Table 3]

[0105] As shown in the results in Table 3, a lactone peak was observed when the γ-dodecalactone of the present invention was applied to hair, but it was confirmed that this peak disappeared after heat treatment. In other words, it is thought that the γ-dodecalactone of the present invention chemically bonded with the hair and changed its structure when applied to hair and subjected to heat treatment, causing the lactone peak to disappear. This chemical bond was confirmed to be an amide bond. This result suggests that the γ-dodecalactone formed an amide bond with amino groups exposed on the hair surface due to damage.

[0106] (Example 4) Test of the effect of improving combability The comb-shape improving effect of γ-dodecalactone in the present invention was tested. The test was conducted as follows, and the results are shown in Figure 11.

[0107] (Evaluation method) Test samples 1 and 2 were obtained by applying the damaged hair prepared in Example 2 to the hair cosmetic composition 1 (Sample 1) of the present invention, which contains 0.005% γ-dodecalactone in diethyl sebacate, and the hair cosmetic composition of the present invention (Sample 2), which contains 0.0025% γ-dodecalactone. Control sample 1 was prepared by applying control hair cosmetic 1, which contained diethyl sebacate with γ-docosalactone at a concentration of 0.005%, and control sample 2 was prepared by applying control hair cosmetic 2, which contained γ-docosalactone at a concentration of 0.0025%.

[0108] Both control samples 1 and 2, and test samples 1 and 2, were subjected to heat treatment at 180°C or 60°C. For the 180°C treatment, a hair iron (MTG Corporation, product name: ReFa Straight Iron Pro) was used, and strands of hair were clamped between plates heated to 180°C for 5 seconds, repeated 5 times. For the 60°C treatment, a hair dryer (MTG Corporation, product name: ReFa BEAUTECH Dryer Pro) was used, and each sample was treated with hot air for 60 seconds in MOIST mode. After that, each heat-treated sample was washed with a hair wash (MTG Corporation, product name: ReFa Ion Care Shampoo) and air-dried at room temperature.

[0109] Next, a combability test was performed on each sample after natural drying using a multi-purpose hair testing machine (manufactured by Diastron Co., Ltd.) (N=3). The results of measuring the force (J) applied when combing are shown in Figure 11. From the results in Figure 11, in test samples 1 or 2 to which hair cosmetic composition 1 or 2 of the present invention was applied, the combability effect was significantly improved compared to damaged hair in all samples (Figure 11). This indicates that even when a trace amount of the hair cosmetic composition of the present invention is included, such as 0.0025% to 0.005%, the combability effect is significantly improved compared to damaged hair. In particular, the combability of the test sample to which test sample 2 was applied and heat-treated at 180°C was improved to a level comparable to healthy hair.

[0110] In contrast, among the control samples that did not contain γ-dodecalactone but did contain γ-docosalactone, only the control sample treated with control sample 1 and then heated at 180°C showed a slight improvement in combability. However, the other control samples showed no significant difference in combability on damaged hair. Furthermore, scanning electron microscopy examination of the hair surfaces of control samples 1 and 2, as well as test samples 1 and 2, revealed that the cuticles were open in the hair surfaces of control samples 1 and 2, regardless of whether high-temperature or low-temperature treatment was applied, indicating that there was no cuticle repair effect. In contrast, in the test samples treated with hair cosmetic compositions 1 and 2 of the present invention, the cuticles were closed, and it was confirmed that the hair was in a state close to that of healthy hair. This indicates that the hair cosmetic compositions of the present invention have a cuticle repair effect (Figures 12 and 13). The results above demonstrate that incorporating γ-dodecalactone at low concentrations into hair cosmetics provides superior combability improvement at lower concentrations than other γ-lactones.

[0111] (Example 5) Hair Improvement Effect Test The hair-improving effect of γ-dodecalactone of the present invention was tested. The test was conducted as follows, and the results are shown in Figures 12 and 13.

[0112] (Evaluation method) The damaged hair prepared in Example 2 was coated with the sample prepared in Example 3, and the hair bundles were then heat-treated. The 180°C treatment involved using a hair iron (MTG, product name: ReFa Straight Iron Pro) to heat the hair bundles by clamping them between plates heated to 180°C for 5 seconds, repeating this process five times. The 60°C treatment involved using a hair dryer (MTG, product name: ReFa BEAUTECH Dryer Pro) to heat the hair bundles for 60 seconds. After heat treatment, the hair bundles were washed with shampoo and air-dried. The surface of the treated hair samples was observed using a scanning electron microscope (SEM) (Figures 12 and 13).

[0113] The results shown in Figures 12 and 13 indicate that incorporating γ-dodecalactone of the present invention improves the hair cuticle. γ-dodecalactone exhibits its hair-improving effect when heat is applied, and this effect was confirmed even with heat treatment at 60°C.

[0114] (Example 6) Hair mist The hair mist was prepared by adding each component to a container in the composition ratio shown in Table 4 below and stirring until uniform. Damaged hair to which this hair mist was applied and air-dried (60°C) was given a non-sticky, smooth, and pleasant feel, and was easy to comb through.

[0115] [Table 4]

[0116] (Example 7) Hair Essence The components of parts A and B were added to separate containers to achieve the composition ratios shown in Table 5 below, and the mixture was heated to approximately 80°C to dissolve the components. Then, part B was gradually added to part A and mixed uniformly to prepare the hair essence. Damaged hair that had been impregnated with this hair essence and air-dried (60°C) felt refreshed, non-greasy, and had been given moisture and a smooth feel.

[0117] [Table 5]

[0118] (Example 8) Hair lotion According to the composition ratios in Table 6 below, each component of Part A and each component of Part B were added to separate containers and mixed. The mixed Part B was then added to the mixed Part A and mixed uniformly to prepare the hair lotion. When this hair lotion was placed in the palm of the hand and sprayed onto healthy and damaged hair, the refreshing sensation of menthol lasted and the scalp felt refreshed.

[0119] [Table 6]

[0120] (Example 9) Fixing bedhead The hair styling product was prepared by adding each component to a container according to the composition ratio shown in Table 7 below, stirring, and dissolving each component uniformly. When this hair styling product was sprayed on both healthy and damaged hair, it improved smoothness and manageability, and provided a moist and resilient feel.

[0121] [Table 7]

[0122] (Example 10) Hair cream According to the ingredient ratios in Table 8 below, parts A and C were added to separate containers and heated to approximately 80°C to dissolve. Then, part C was added to part A and stirred, and part B was added to prepare the hair cream. When this hair cream was used as a finishing touch for hair styling, it provided shine, was non-greasy, retained moisture in the hair, and gave it a smooth feel.

[0123] [Table 8]

[0124] (Example 11) Hair wax According to the composition ratios in Table 9 below, parts A and B were placed in separate containers, heated to approximately 80°C, and mixed uniformly. Then, part B was gradually added to part A while stirring, mixed uniformly, and then cooled (part D). Part C was added to part D and the pH was adjusted to 6 to prepare the hair wax. When this hair wax was placed on the palm and spread on the hair, it was not sticky, adhered well to the hair, and had excellent setting properties. Furthermore, with continued use, it suppressed hair damage and split ends in both healthy and damaged hair.

[0125] [Table 9]

[0126] (Example 12) Hair Mist Wax The hair wax was prepared by adding each component to a container according to the composition ratio shown in Table 10 below, stirring and mixing uniformly, and adjusting the pH to 6. When this hair mist wax was used by spraying it onto the hair like a spray at the end of styling, it was non-greasy, adhered well to the hair, and provided excellent hold. Furthermore, continued use suppressed the feeling of hair damage in both healthy and damaged hair.

[0127] [Table 10]

[0128] (Example 13) Mousse The mousse concentrate was prepared by adding each component to a container and mixing it uniformly according to the composition ratios shown in Table 11 below. Then, the mousse concentrate and liquefied petroleum gas were mixed in a ratio of 92:8 to create a spray-type mousse. This mousse had a smooth, pleasant feel and a lightweight styling finish.

[0129] [Table 11]

[0130] (Example 14) Hair spray According to the composition ratios in Table 12 below, part B was added to a container mixed with part A (part D). Then, part C was added to part D and mixed. After filling a can with 55% by weight of this stock solution, 45% by weight of liquefied petroleum gas was added to prepare the hairspray. This hairspray had a good feel and hold, and showed the effect of improving the feel of the hair, such as shine and moisture.

[0131] [Table 12]

[0132] (Example 15) Shampoo According to the composition ratios in Table 13 below, parts A and B were placed in separate containers, heated to approximately 80°C, and mixed uniformly. Then, part A was added to part B and mixed uniformly, and then cooled (part D). Part C was added to part D to adjust the pH to 6-6.5, thereby preparing the shampoo. This shampoo, when air-dried (60°C) after use, suppresses frizz in both healthy and damaged hair, provides moisture to the hair, and leaves it smooth to the touch.

[0133] [Table 13]

[0134] (Example 16) Rinse-in shampoo According to the composition ratios in Table 14 below, parts A and B were placed in separate containers, heated to approximately 80°C, and mixed uniformly. Then, part A was added to part B, mixed uniformly, and cooled to prepare a rinse-in shampoo. This rinse-in shampoo, when air-dried (60°C) after use, provides a moisturizing effect and smooth feel to both healthy and damaged hair.

[0135] [Table 14]

[0136] (Example 17) Shampoo for hair color A hair color shampoo was prepared by taking all the ingredients into a container according to the composition ratio shown in Table 15 below, heating to 80°C, stirring and mixing until uniform, and then cooling. This hair color shampoo suppresses hair color fading and provides improved texture and lasting effects, such as adding shine and moisture to the hair.

[0137] [Table 15]

[0138] (Example 18) Treatment According to the composition ratios in Table 16 below, parts A and B were placed in separate containers, heated to approximately 80°C, and mixed until uniform. Then, part B was gradually added to part A while stirring, mixed uniformly, and then cooled (part D). Furthermore, part C was added to part D to adjust the pH to 5.2-5.7, thereby preparing the treatment. This treatment, when air-dried (60°C) after use, can provide moisture and body to both healthy and damaged hair.

[0139] [Table 16]

[0140] (Example 19) Treatment According to the composition ratios shown in Table 17 below, parts A and B were added to separate containers, heated, and dissolved. Then, while stirring, part A was gradually added to part B and mixed uniformly. After stirring for 1 minute, the mixture was rapidly cooled to prepare the treatment. This treatment provided hair with a supple and smooth feel.

[0141] [Table 17]

[0142] (Example 20) Leave-in hair treatment According to the composition ratios in Table 18 below, parts A and C were added to separate containers and heated to approximately 80°C to dissolve. Then, part C was added to part A while stirring, and after uniform mixing, it was cooled to approximately 40°C. Next, part B was added and uniformly mixed to prepare a leave-in hair treatment. This hair treatment is used on wet hair after showering, and after air-drying (60°C), it improves the smoothness, manageability, manageability, and moisturizing effect on both healthy and damaged hair.

[0143] [Table 18]

[0144] (Example 21) Hair oil The hair oil was prepared by uniformly stirring and mixing each component according to the composition ratio shown in Table 19 of the formulation below. This hair oil, used as a leave-in treatment and air-dried (60°C) after use, provided a moist feel to both healthy and damaged hair, giving it moisture, shine, and hydration. It also exhibited good stability.

[0145] [Table 19] [Industrial applicability]

[0146] This invention is useful in the field of cosmetics technology.

Claims

1. A hair cosmetic containing γ-dodecalactone, represented by the following formula (I), in an amount of 0.001% or more and less than 10% by weight of the hair cosmetic as an active ingredient for improving hair damage. 【Chemistry 1】

2. The hair cosmetic according to claim 1, characterized in that the improvement of hair damage is achieved by repairing the cuticle structure of physically or chemically damaged hair.

3. A method for repairing the cuticle structure of hair, comprising the steps of applying the hair cosmetic according to claim 1 or 2 to hair, and heat-treating the hair to which the hair cosmetic has been applied.

4. The method for repairing the cuticle structure of hair according to claim 3, characterized in that the step of heat-treating the hair is a step of applying heat of 50 to 220°C to the hair to which the hair cosmetic has been applied for 10 to 900 seconds.

5. A hair cosmetic composition containing γ-dodecalactone represented by the following formula (I), manufactured using saponified camellia oil as a raw material and comprising a method comprising first and second culture steps using multiple microorganisms belonging to different genera in biological classification. 【Chemistry 2】

6. The hair cosmetic composition according to claim 5, characterized in that, when the number of microorganisms used in the first culture step is set to 1, the number of microorganisms used in the second culture step is 10 to 1,000 times (w / w).

7. The hair cosmetic composition according to claim 6, characterized in that only the culture and microorganisms obtained in the first culture step are used in the culture in the second culture step to produce the final product.

8. The hair cosmetic composition according to any one of claims 5 to 7, characterized in that the microorganism used in the first step is a lactic acid bacterium derived from camellia petals, and the microorganism used in the second step is a yeast derived from camellia petals.

9. The hair cosmetic composition according to claim 8, characterized in that the lactic acid bacteria derived from camellia petals is Leuconostoc mesenteroides.

10. The hair cosmetic composition according to claim 8, characterized in that the yeast derived from camellia petals is Saccharomyces cerevisiae.

11. The hair cosmetic composition according to claim 5, characterized in that the method comprising the first and second culture steps further comprises a purification step for producing the final product.

12. The hair cosmetic composition according to claim 11, characterized in that the purification step involves purifying the final product using a column packed with synthetic resin and its elution solvent.

13. The hair cosmetic composition according to claim 12, characterized in that the synthetic resin is HP-20 and the eluting solvent is at least one selected from the group consisting of ethanol, propanol, and acetone.

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