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    • 专利摘要:
    stereoisomers of methionyl-methionine and their use in cosmetics. the present invention relates to a cosmetic formulation comprising certain stereoisomers of methionyl-methionine and the use of methionyl-methionine for the treatment of nails and / or hair.
    公开号:BR102014019313B1
    申请号:R102014019313-8
    申请日:2014-08-05
    公开日:2020-09-29
    发明作者:Mike Farwick；Matthias Mentel；Andreas Seifert；Ursula MacZkiewitz
    申请人:Evonik Operations Gmbh；
    IPC主号:
    专利说明:

    Field of invention
    [001] The invention relates to cosmetic formulations comprising certain stereoisomers of methionyl-methionine and the use of methionyl-methionine for the treatment of nails and / or hair. State of the art
    [002] Methionine is a common active ingredient to improve hair properties. Thus, the use of hair care compositions comprising methionine to improve hair strength and condition is described, for example, in WOOO / 51556. The cosmetic use of dipeptides comprising at least one methionine of the formula XM or MX, in particular, L-methionyl-L-methionine, to lighten the skin is described in JP2999301.
    [003] The production and use of stereoisomeric mixtures of methionyl-methionine and its salts as an additive in the feeding of fish and crustaceans is described in W02010 / 043558. Preferably, the described dipeptide is present in the DD / LL / LD / DL mixture feed mixture, as a DL / LD or DD / LL mixture, and in a particularly preferred use, the dipeptide is present as a D- enantiomer pair. methionyl-L-methionine and L-methionyl-D-methionine.
    [004] It is an objective of the present invention to provide a substitute for methionine in cosmetics. Description of the invention
    [005] Surprisingly, it has been found that the cosmetic formulations, described below, which comprise certain stereoisomers of methionyl-methionine are capable of reaching the aforementioned object.
    [006] Surprisingly and unexpectedly, these stereoisomers have been found to have excellent and very wide application properties. These properties overshadow those of L-methionine in certain applications. Furthermore, in the specific application technology of hair, they outperform the properties of other common products on the market, such as, for example, hydrolyzed wheat proteins.
    [007] The present invention therefore provides a cosmetic formulation comprising certain stereoisomers of methionyl-methionine.
    [008] The invention also provides the use of methionyl-methionine for the treatment of nails and / or hair.
    [009] It is an advantage of the present invention that the stereoisomers of methionyl-methionine have a low cytotoxicity. It is another advantage of the present invention that the stereoisomers of methionyl-methionine have good stability in aqueous solution. Another advantage of the present invention is that the stereoisomers of methionylmethionine have a relatively low odor. Another advantage of the present invention is that methionyl-methionine is both capable of improving properties such as combability, softness, volume, formability, manageability, untangling of undamaged and damaged hair, as well as giving a beautiful shine to the hair.
    [010] For the methionyl-methionine dipeptide of the general formula (1):
    There are four different stereoisomers: D-methionyl-L-methionine, L-methionyl-D-methionine, L-methionyl-D-methionine, L-methionyl-L-methionine and D-methionyl-D-methionine:

    [011] Here, DD and LL behave like image and mirror image, that is, they are enantiomers and therefore also have the same physical properties. The same is true for the even DL and LD.
    [012] In contrast, the two pairs of DD / LL and DL / LD are diastereomeric in relation to each other, that is, they have different physical characteristics. Thus, at room temperature, for example, the DD / LL enantiomer pair has a solubility of 21 g / L in water, whereas the solubility of the DL / LD enantiomer pair is 0.4 g / L.
    [013] Therefore, the present invention provides a cosmetic formulation comprising at least one methionyl-methionine stereoisomer selected from the group D-methionyl-L-methionine, L-methionyl-D-methionine and D-methionyl-D-methionine.
    [014] In connection with the present invention, the term "D-methionyl-L-methionine" has the same meaning as "DL-methionyl-methionine". The same is true for L-methionyl-D-methionine, L-methionyl-L-methionine and D-methionyl-D-methionine. The use according to the invention, in which case it is used in a living species, is exclusively a cosmetic and non-therapeutic use.
    [015] Unless otherwise stated, all percentages mentioned (%) are percent by mass.
    [016] Preferably, in the formulation according to the invention, all stereoisomers of methionyl-methionine selected from the group of D-methionyl-L-methionine, L-methionyl-D-methionine and D-methionyl-D-methionine are present.
    [017] It may be advantageous, according to the invention, if the formulation according to the invention additionally comprises L-methionyl-L-methionine, because, for example, the presence of L-methionyl-L-methionine is required by the production process of stereoisomers. Preferably, in the formulation according to the invention, all stereoisomers of methionyl-methionine selected from the group of D-methionyl-L-methionine, L-methionyl-D-methionine, L-methionyl-L-methionine and D-methionyl -D-methionine, are therefore present.
    [018] Preferably, the total amount of L-methionyl-L-methionine based on the total weight of all stereoisomers present in the formulation of methionyl-methionine according to the invention is less than or equal to 50%, by weight, of preferably less than 35% by weight, especially preferably less than 20% by weight.
    [019] Preferred formulations according to the invention have a weight ratio of DL- and LD-methionyl-methionine to DD- and LL-methionyl-methionine from 9: 1 to 2: 3, preferably 8: 2 to 1: 1, in particular, 7: 3 to 3: 2, in which the sum of the individual enantiomers per enantiomer pair, in each case, is taken into account. The above formulation does not exclude the possibility that only one of the enantiomers of a pair of enantiomers is present in the formulation.
    [020] In an alternative preferred use, DL- and LD- methionyl-methionine and DD- and LL-methionyl-methionine are in the ratio of 10: 90-0.01: 99.99.
    [021] The formulations according to the invention can comprise, for example, at least one additional component selected from the group of emollients, emulsifiers, thickeners / viscosity regulators / stabilizers, UV protection filters, antioxidants, hydrotropes ( or polyols) solids and fillers, film-forming, pearl-shine additives, deodorant and antiperspirant active ingredients, insect repellents, anti-tanning agents, preservatives, conditioners, perfumes, dyes, odor absorbers, cosmetic active ingredients, treatment additives, agents super greasers, solvents.
    [022] Substances that can be used as exemplary representatives of individual groups are known to those skilled in the art and can be found, for example, in German Order DE 102008001788.4. This patent application is hereby incorporated by reference and is therefore part of the disclosure.
    [023] Regarding the optional components and quantities of these components used, reference is made expressly to the relevant manuals known to those skilled in the art, for example, K. Schrader, "Grundiagen und der Rezepturen Kosmetika [Fundamentals and Formulations of Cosmetics] ", 2nd edition, pages 329 to 341, Hüthig Buch Verlag Heidelberg.
    [024] The quantities of particular additives are governed by the intended use. Typical guide formulations for the respective applications are known from the state of the art and are included, for example, in the manufacturers' brochures on particular basic materials and active ingredients. These existing formulations can generally be adopted unchanged. If necessary, the desired modifications can, however, be carried out without complications, through simple experiments for the purpose of adaptation and optimization.
    [025] The present invention also provides the use of methionyl-methionine for the treatment of nails and / or hair, especially hair, for hair conditioning, to increase hair shine, to increase the tensile strength of the hair. hair, to increase hair volume, to increase the intensity of hair color, to increase the carrying capacity of hair, to protect hair against UV damage, to protect hair against oxidative damage, to protect hair against thermal damage, to protect the hair from chemical damage, such as, for example, for alkaline treatment or treatment with reducing agents, and / or to improve the mechanical properties of nails.
    [026] Preferably, at least one methionyl-methionine stereoisomer selected from the group of D-methionyl-L-methionine, L-methionyl-D-methionine and D-methionyl-D-methionine is used according to the invention .
    [027] According to the invention, in particular, the above-mentioned formulations according to the invention can be used, with preferred formulations according to the invention, being preferably used according to the invention.
    [028] The examples listed below describe the present invention, by way of example, without any intention of restricting the invention, the scope of application of which is apparent from the entirety of the description and the claims, for the modalities specified in the examples.
    [029] The following figures are a component of the examples:
    [030] Figure 1. Ability of methionyl-methionine stereoisomers to be washed after conditioning treatment, for 30 minutes.
    [031] Figure 2. Ability of methionylmethionine stereoisomers to be washed after conditioning treatment for 24 hours.
    [032] Figure 3. Repair of bleached hair. Improvements after hair treatment with a simple hair conditioner (Table 3) with Load parameter determined using a 15% elongation tensile tester are shown. The values shown are in millinewtons (mN).
    [033] Figure 4: Repair of bleached hair. Improvements after hair treatment with a simple hair conditioner (Table 3) with the Work parameter determined by means of a Traction Tester of up to 15% elongation are shown. The values shown are in microjoules (pJ).
    [034] Figure 5: Repair of bleached hair. Improvements after treating the hair with an expanded hair conditioner (Table 4) with the Load parameter determined using a 15% elongation tensile tester are shown. The values shown are in millinewtons (mN).
    [035] Figure 6: Repair of bleached hair. Improvements after treating the hair with an expanded hair conditioner (Table 4) of the Parameter Work determined by means of a Tensile Tester greater than 15% elongation are shown. The values shown are in microjoules (pj).
    [036] Figure 7: Repair of bleached hair. The improvements after shampooing the hair (Table 5) with the Load parameter determined using a 15% elongation tensile tester are shown. The values shown are in millinewtons (mN).
    [037] Figure 8: Repair of bleached hair. The characteristic of a life span a, determined by means of an Automatic Cycle Tester, after treating the hair with a simple hair conditioner (Table 3) is shown. The values shown are number of cycles during which 63.2% of all hair fibers break.
    [038] Figure 9: Repair of straightened hair with alkaline product. Improvements after hair treatment with a simple hair conditioner (Table 8) with the Load parameter determined using a 15% elongation tensile tester are shown. The values shown are in millinewtons (mN).
    [039] Figure 10: Repair of straightened hair reductively. Improvements after treating the hair with a simple hair conditioner (Table 9) with the Load parameter determined by means of a Tensile Tester in relation to the 15% elongation vehicle are shown. The values shown are in millinewtons (mN).
    [040] Figure 11: Protection of hair against thermal stress (straightening treatment with iron) by preventive treatment with the active ingredient solution. The characteristic α life span, determined by means of an Automatic Cyclic Tester, at 33%, 20% and 10% probability of survival is shown.
    [041] Figure 12: Protection of hair against thermal stress (straightening treatment with a board) by preventive protection treatment with the active ingredient solution. The improvement in the temperature of hair denaturation determined by differential scanning calorimetry is shown. Examples: Example 1: Improved washing behavior as a result of treatment with stereoisomers of methionyl-methionine
    [042] Sections of curls of Euro-Natural human hair, Remis, of double collection with a length of 23 cm and a width of 2.0 cm, with a weight of 2.0 cm and dark brown color were moistened under running water tap for 10 seconds. 8 g of an aqueous solution of hydrogen peroxide at 30% strength, were mixed with 4 g of bleaching powder Basler Blond Claire, 2 ml of an aqueous solution of ammonia at 25% strength, were added, and combined again and 8 g of resulting paste were massaged into the curl sections with the help of a comb and with protected hands. After a contact time of 30 minutes at room temperature, the curl sections were washed for 2 minutes with running tap water at about 35 ° C and then dried using an electronic hair dryer, for 3 minutes combing at the same time. The entire procedure was repeated once starting from the moistened curls section.
    [043] Then, the curl sections were either covered with hair conditioner containing 2% LL-methionyl-methionine or with hair conditioner containing 2% DD / LL / LD / DL-methionyl-methionine (Table 1) in a plastic dish. The two different conditioning treatments were performed in each case, for a contact time of 30 minutes and 24 hours. Then, washing was carried out under a stream of water at about 35 ° C for 2 minutes and then dried by means of an electronic hair dryer for 3 minutes, combing at the same time.
    Table 1. Test formulations of simple hair conditioners. Mass percentage data. DD / LL / LD / DL weight ratio = 1: 1: 1: 1. Usual formulation processes known to the person skilled in the art were used to produce the formulations.
    [044] The bunch sections were cut in half and part of it was subjected to quantitative analysis by means of HPLC in order to determine the content of methionyl-methionine; the other part was first washed with shampoo. For the treatment with shampoo, the curl section, after drying, was moistened under the tap with running water and then 2 ml of shampoo was applied (Table 2) and massaged with the hands for about 2 minutes. . Then, the bunch section was washed under a stream of running water at about 35 ° C for 2 minutes. The curl section was dried using an electronic hair dryer for 3 minutes and the shampoo treatment was repeated four times.
    Table 2. Shampoo formulation. Mass percentage data. Usual formulation processes known to the person skilled in the art were used to produce the formulations.
    [045] From the curl sections treated (in each case with the hair conditioner containing 2% LL-methionyl-methionine or with hair conditioner containing 2% DD / LL / LD / DL-methionyl-methionine ( weight ratio of DD / LL / LD / DL = 1: 1: 1: 1)), both with and without shampoo treatment) about 100-200 mg of hair were taken in each case in order to determine the content of methionyl-methionine. The hair sample is cut into sections of 1-3 mm in length and extraction with methionyl-methionine was carried out in a screw cap container by means of duplicate extraction with a 20 mM aqueous solution of NaOH (pH ~ 13) with vigorous stirring for 2 hours at room temperature. The extraction solutions were combined and covered to 25 mL with 20 mM NaOH solution. 1 ml of this solution was made neutral with acid by adding about 50 pL of an aqueous solution of H3PO4 (0.2 ml of 85% H3PO4 per 10 ml) and analyzed by means of HPLC.
    [046] Quantitative analysis was performed using HPLC-UV with an Agilent 1100 system with Inertsil ODS-3 column (250 mm, 4.6 mm internal diameter (ID), 5 pm). The mobile phases used were Phase A (870 ml H2O, 5 ml MeCN, 125 ml 0.2 M H3PO4) and Phase B (400 ml H2O, 475 ml MeCN, 125 ml 0.2 M H3PO4 ) at 1 ml / min and 30 ° C, after injection of 20 pl of analyte solution. The gradient was 10% B (0-6 min), then linear to 55% B (6-30 min), again linear to 10% B (30-32 min) and still with 10% B (32-35 min). Detection was performed at 205 nm.
    [047] To produce a calibration solution, about 20 mg of reference substances to be quantified were weighed in a 100 mL measuring flask and filled to the mark with mobile phase A. The solution was treated for about 5 minutes in the ultrasound bath.
    [048] Figures 1 and 2 show in each case that the results were obtained after treatment with conditioner for 30 minutes (Figure 1) or 24 hours (Figure 2). The remaining fraction of stereoisomers of methionyl-methionine (in percent) on or in the hair after shampoo treatment has occurred, compared to unwashed hair, is shown.
    [049] After treatment with conditioner with 2% LL-methionyl-methionine for 30 minutes, still 68.0% DD, LL-methionyl-methionine (sum of the enantiomers of D-methionyl-D-methionine and L -methionyl-L-methionine) remain after shampoo treatment, whereas this fraction, after conditioning treatment with 2% DD / LL / LD / DL-methionyl-methionine for 30 minutes was 80.3%. As a result, treatment with 2% DD / LL / LD / DL-methionyl-methionine for 30 minutes, after treatment with shampoo in addition to a 50.0% DL, LD-methionyl-methionine (sum of the pair of enantiomers D-methionyl-L-methionine and L-methionyl-D-methionine) were recovered. After treatment with conditioner with LL-methionyl-methionine, as expected, no DL, LD-methionyl-methionine was detected after hair extraction.
    [050] The condition is similar after treatment with conditioner for 24 hours. In the case of treatment with 2% LL-methionyl-methionine, after treatment with shampoo, still 63.8% of DD, LL-methionyl-methionine remain in or on the hair, whereas this fraction after treatment with conditioner with DD / LL / LD / DL-methionyl-methionine was 66.7%. Here too, after shampoo treatment, still an additional 68.3% of LD, LD-methionyl-methionine were recovered.
    [051] The results of this experiment impressively demonstrate the advantages of a hair treatment with DD / LL / LD / DL-methionyl-methionine, particularly, compared to a hair treatment with LL-methionyl-methionine. First, it was shown that the most soluble enantiomer pair of DD / LL-methionyl-methionine (21 g / L in water at room temperature), as the pure enantiomer LL-methionyl-methionine, has a substantivity for the hair since even after a shampoo treatment five times still clearly detectable amounts were found after hair extraction. The relatively recovered amounts were increased when the hair was treated with DD / LL / LD / DL-methionyl-methionine, compared to treatment with LL-methionyl-methionine.
    [052] Yet another aspect similarly demonstrates the advantage of a hair treatment with DD / LL / LD / DL-methionyl-methionine. Although the solubility of the DL / LD-methionyl-methionine enantiomer pair is only 0.4 g / L, surprisingly substantial amounts of it are absorbed by the hair, and the relative recovery is still very high, even after shampoo treatment. five times. In the case of treatment with conditioner for 24 hours, the relatively recovered fraction of DL / LD-methionyl-methionine is still mostly, compared to the relatively recovered fraction of DD / LL-methionyl-methionine.
    [053] This surprisingly improved unexpected substantivity clearly shows the advantage of DD / LL / LD / DL-methionyl-methionine hair treatment, and explains the excellent properties, shown below, of DD / LL / LD hair treatment / DL-methionyl-methionine on the mechanical properties of damaged hair. Example 2: Improvement in the mechanical properties of hair damaged by bleaching treatment, as a result of treatment with methionyl-methionine.
    [054] A section of double collection of Euro-Natural human hair, Remis, 23 cm long and 2.0 cm wide, with a weight of 2.0 g and dark brown color was moistened under running water tap for 10 seconds. 8 g of a 30% strength aqueous hydrogen peroxide solution was mixed with 4 g of Basler Blond Claire bleaching powder, 2 ml of a 25% strength ammonia aqueous solution was added, and combined again and 8 g of The resulting paste was massaged into the curl section with the help of a comb and protected by hand. After a contact time of 30 minutes at room temperature, the bunch section was washed for 2 minutes under running tap water at about 35 ° C and then dried using an electronic hair dryer for 3 minutes, combing at the same time. The entire procedure was repeated once after moistening the bunch section.
    [055] After that, by treatment method 40 the hair was removed from the curl section and in each case, the middle part of a hair with a length of 3 cm was folded between two metal gloves with plastic coating inside. The average area of each individual hair was measured using a three-dimensional fiber system Dia-stron FDAS760 and application software UvWin PC. The hair samples were then transferred to the sample cassette of a Diaston Tensile Tester MTT 670 and mixed in each case with demineralized water at pH 7 using citric acid. A measurement of individual hair strands with the Single Fiber Method (20% Extension, 20 mm / min rate, Gauge Force 2, Maximum Force 200, Break Limit 5, Sample size 30 mm) was initiated. The hair samples were then removed from the sample cassette and covered with demineralized water in a plastic bowl.
    [056] For treatment with the hair conditioner, the water was removed after 30 minutes and the hair samples were covered with hair conditioner. After a contact time of 30 minutes, each individual hair sample was washed under a stream of water at about 35 ° C for 6 seconds. The hair samples were dried overnight at 22 ° C and 50% relative atmospheric humidity.
    Table 3. Test formulations of simple hair conditioners. Mass percentage data. DD / LL / LD / DL weight ratio = 1: 1: 1: 1. Usual formulation processes known to the person skilled in the art have been used to produce the formulations.

    Table 4. Test formulations of expanded hair conditioners. Mass percentage data. DD / LL / LD / DL weight ratio = 35: 35: 65: 65. Usual formulation processes known to the person skilled in the art were used to produce the formulations.
    [057] For the shampoo treatment, the water was removed after 30 minutes and the hair samples were covered with shampoo. After a contact time of 5 minutes, each individual hair sample was washed under a stream of running water at about 35 ° C for 6 seconds. The hair samples were briefly dried using an electronic hair dryer and the shampoo treatment was repeated four times.

    Table 5. Shampoo Test Formulations. Mass percentage data. DD / LL / LD / DL weight ratio = 35: 35: 65: 65. Usual formulation processes known to the person skilled in the art were used to produce the formulations.
    [058] After the particular treatment, the measurement of the individual hair samples starting with the transfer to the Dia-stron Tensile Tester MTT 670 sample cassette was repeated.
    [059] Data evaluation occurs by reference to elasticity parameter modules (module E), Load and / or Work. If a hair is pulled, the elongation is initially proportional to the applied force (Hooke band). The modulus of elasticity describes the force applied by stretching (in Newton / mm2) in the Flooke range and therefore represents the tensile strength of a hair fiber. Once the hair has been stretched to a length of about 2%, it deforms very quickly to about 25 to 30% of its original length, where the increase in the strength required for this is minimal (Yield Range). The Load parameter corresponds to the force (in Newton) that is needed to lengthen the hair up to 15% and the Work parameter indicates the work required to lengthen the hair 0-15% (in Joule).
    [060] In order to measure the breakdown of hair fatigue, the hair samples were transferred to the sample cassette of a Dia-stron Automatic Cyclic Tester tester (CYC800) and air-conditioned at 22 ° C and 50-55% humidity relative atmospheric. The measurement of individual hair curls occurs with the Constant Stress Method (0.015 g / pm2, max 10,000 cycles, Load Trigger 10 gmf). The characteristic life span of a hair fiber is calculated using Weibull analysis. Parameter a represents the number of cycles in which 63.2% of all hair fibers break.
    [061] As can be seen in Figures 3 and 4, treatment with a simple hair conditioner has already had a mild repair effect on hair damaged by discoloration determined by measuring the tensile elongation forces using a Tensile Tester , at a 2.65 mN level (15% load) and 11.0 pj (15% work). This repair effect cannot yet be increased, either by adding hydrolyzed wheat proteins or by adding L-methionine to the hair conditioner. As a result of treatment with a hair conditioner comprising DD / LL / LD / DL-methionyl-methionine, however, the Charge value of 15% could be increased to 4.14 mN and for Work from 15% to 19.4 pJ . Consequently, DD / LL / LD / DL-methionyl-methionine had a surprising and considerable notable repair effect on hair damaged by bleaching.
    [062] Figures 5 and 6 show the effect of treating an expanded hair conditioner on hair damaged by discoloration, determined by measuring the tensile elongation forces using a Tensile Tester, at a Level 1 level, 28 mN (15% load) and 3.51 pj (15% work). This repair effect was able to be increased by adding hydrolyzed wheat protein to the hair conditioner to 2.87 mN (15% load) and 13.0 pj (15% work). As a result of treatment with a hair conditioner comprising DD / LL / LD / DL-methionyl-methionine, however, the value of 15% of the Load was further increased to 4.85 mN and for work from 15% to 18, 2 pJ. Consequently, treatment with DD / LL / LD / DL-methionyl-methionine had a significantly more notable repair effect on hair damaged by bleaching than treatment with hydrolyzed wheat protein.
    [063] The effect of shampooing on hair damaged by discoloration, determined by measuring the tensile elongation forces using a Tensile Tester, is shown in Figure 7. The vehicle's effect had an influence on the forces of tensile elongation at a level of 0.46 mN (15% load) and 2.46 pj (15% work). This repair effect cannot be increased by adding hydrolyzed wheat protein to the hair conditioner; in the case of the Working parameter of 15%, a reduction in the uniform repair effect occurred. As a result of treatment with hair conditioner comprising DD / LL / LD / DL-methionyl-methionine, however, the value for the 15% load has been increased to 1.33 mN and for the Work by 15%, slightly to 2 , 58 pJ. Consequently, it has been shown that treatment of hair damaged by bleaching with DD / LL / LD / DL-methionyl-methionine has a remarkable repair effect not only from applications that are left in the hair (leavein), but also from applications with rinses. This repair effect is valuable since the residence time of a hair shampoo is significantly shorter than the residence time of a leave-in hair conditioner and cannot be achieved by treatment with usual commercial active ingredients, such as, for example, hydrolyzed wheat protein.
    [064] Figure 8 shows the improvement in the breakdown of hair fatigue from hair damaged by discoloration after treatment with a simple hair conditioner. The cycles measured by an Automatic Cyclic Tester in which 63.2% of the hair fibers break is 14 190 after treatment with the vehicle. This value was increased as a result of treatment with hydrolyzed wheat protein at 27,490 cycles, but was even more notable after treatment with DD / LL / LD / DL-methionyl-methionine at a level of 33,980 cycles. Thus, DD / LL / LD / DL-methionyl-methionine leads to a further reduction in hair fatigue breakage that can be achieved with the usual commercial standards.
    [065] In summary, it can be said that the effect of a treatment with DD / LL / LD / DL-methionyl-methionine on hair damaged by bleaching is noticeably more noticeable, and unexpectedly far outweighs the treatment effect with commercial standards usual. Example 3: Improvement in the mechanical properties of hair damaged by alkaline straightening treatments as a result of treatment with methionyl-methionine
    [066] A section of double collection of Euro-Natural human hair, Remis, with a length of 23 cm and a width of 2.0 cm, with a weight of 2.0 g and dark brown color was moistened under the tap running water for 10 seconds. 8 g of a Relaxing Cream were mixed with 2 g of Relaxing Activator and the resulting paste was applied to the curl section with the help of a brush. After a contact time of 15 minutes at room temperature, the bunch section was washed for 2 minutes under running tap water at about 35 ° C and then dried using an electronic hairdryer. for 3 minutes, combing at the same time.
    Table 6. Formulation of Relaxing Cream. Mass percentage data. Usual formulation processes known to the person skilled in the art were used to produce the formulations.
    Table 7. Formulation of Relaxing Activator. Mass percentage data.
    [067] Then the hairs 40 were removed from a section of curl and measured as described in Example 1. The repair treatment by means of hair conditioner and the repeated measurements by means of a Dia-stron Tensile Tester MTT 670 tester were done.
    Table 8. Test formulations of simple hair conditioners. Mass percentage data. DD / LL weight ratio = 1: 1. Usual formulation processes known to the person skilled in the art were used to produce the formulations.
    [068] Figure 9 shows the effect of a treatment with a simple hair conditioner on hair damaged by alkaline straightening, determined by measuring the tensile elongation forces, using a Tensile Tester. Considering that the vehicle treatment constituted only a slight repair effect at the level of 0.43 mN (15% load), the repair effect can be increased by the addition of hydrolyzed wheat protein of 1.91 mN and by adding 2.73 mN L-methionine. Using DD / LL-methionyl-methionine, however, the value for the 15% load can be increased to 3.76 mN.
    [069] Consequently, DD / LL-methionyl-methionine has a surprising and very remarkable repairing effect on hair damaged by alkaline straightening treatments, which cannot be obtained to this extent with usual commercial active ingredients. Example 4: Improvement in the mechanical properties of hair damaged by treatment with reductive straightening as a result of treatment with methionyl-methionine
    [070] A section of Euro-Natural, remis, double collection human hair with a length of 23 cm and a width of 2.0 cm, with a weight of 2.0 g and dark brown color was moistened under the tap running water for 10 seconds. Then, 10 g of Basler hair straightening cream (for strong hair) was applied to the curl section with the help of a brush. During a contact time of 30 minutes, at room temperature, combing is carried out regularly, and then the bunch section is washed for 2 minutes with running tap water at about 35 ° C. A hand towel is used to dry the hair, and Basler fixative cream (specifically for hair straightening cream) is applied to the curl section with the help of a brush. During a contact time of 10 minutes at room temperature, combing is carried out regularly, and then the bunch section is washed for 2 minutes under running tap water at about 35 ° C.
    [071] Then the hairs 40 were removed from the curl section and measured as described in Example 1. The repair treatment by means of hair conditioner and the repeated measurement by means of a Dia-stron Tensile Tester MTT 670 tester were performed.
    Table 9. Test formulations of simple hair conditioners. Mass percentage data. DD / LL weight ratio = 1: 1. Usual formulation processes known to the person skilled in the art were used to produce the formulations.
    [072] Figure 10 shows the effect of a treatment with a simple hair conditioner on hair damaged by reductive straightening, determined by measuring the tensile elongation forces, using a Tensile Tester. Although treatment with hydrolyzed wheat protein was only a slight repair effect compared to vehicle treatment, at a level of 0.07 mN (15% load), the effect can be increased to 0.96 mN using DD / LL-methionyl-methionine.
    [073] Consequently, DD / LL-methionyl-methionine has a surprising and very remarkable repairing effect on hair damaged by reducing straightening treatments, which cannot be achieved with hydrolyzed wheat protein as the usual commercial standard. Example 5: Protection of hair against thermal stress by treatment with methionyl-methionine
    [074] A section of double-collected Euro-Natural human hair remis, with a length of 23 cm and a width of 2.0 cm, with a weight of 2.0 g and dark brown color was moistened under the tap running water for 10 seconds. Then, 2 mL of shampoo (28.6% Texapon NSO in distilled water) was massaged into the hair for 30 seconds, washed for another 30 seconds under running water at about 35 ° C, and the curl of hair was squeezed between two fingers and combed six times. The curl of hair is immersed for 1 minute in 300 mL of active ingredient solution (active ingredient, demineralized water, lactic acid, pH 5.5), squeezed between two fingers and washed for 30 seconds in running water at about 35 ° C and hairstyle. The hair was dried using an electronic hair dryer for 3 minutes with simultaneous combing and then stored overnight in a climate controlled chamber (37 ° C, 50% relative atmospheric humidity). The curl section is modeled four times in each case for 30 seconds using a straightening board (~ 210 ° C), which is pressed into the curl, using a weight of 630 g. This treatment is repeated a total of five times from the wetting of the hair and treatment with shampoo (a total of 20 models using the straightening board).
    [075] Next, the 50 hairs were removed from the curl section and, in each case, the middle section of a 3 cm long hair was folded between two metal gloves with plastic coating on the inside. The average area of each individual hair was measured using a three-dimensional fiber system Dia-stron FDAS760 and application software UvWin PC.
    [076] The hair samples were then transferred to the sample on a Dia-stron Automatic Cycle Tester cassette (CYC800) and air-conditioned at 22 ° C and 50-55% relative atmospheric humidity. The measurement of individual hair curls occurs with the Constant Stress Method (0.015 g / pm2, maximum 100000 cycles, Load Trigger 10 gmf). The probability of survival and the life span α characteristic of a hair fiber are calculated using Weibull's analysis.
    [077] In addition, the hair of the curl section is pricked with scissors and differential scanning calorimetry (Thermo Instruments Q 1000; temperature range 50-180 ° C, heating rate 10 ° C / min) to determine the denaturation temperature (TD).
    [078] Figure 11 shows the protection of the hair, determined by means of hair fatigue break measures, against thermal stress (straightening treatment with a straightener) as a result of pretreatment with the active ingredient. The range of life α survival is given. Thus, the number of cycles in which 20% of the hair remains intact is 5500 after the protective treatment with the vehicle. The addition of hydrolyzed wheat protein cannot increase this value, but, using DD / LL-methionyl-methionine, the DD / LL weight ratio = 1: 1, 20% of the hair was still intact even at 10,000 cycles. This trend is also evident for a 33% probability of survival. The protective effect becomes more noticeable if the number of cycles is considered when 10% of the hair does not break. Thus, in this case, the number of cycles can be increased from 8000 after vehicle treatment using wheat protein easily hydrolyzed to 11000, while the use of DD / LL-methionyl-methionine led to 10% of the hair still surviving up to 22000 cycles.
    [079] Treatment with DD / LL-methionyl-methionine thus leads to an unexpected, impressive reduction in hair fatigue breakage, as it cannot be achieved with hydrolyzed wheat protein as the usual market standard.
    [080] Figure 12 shows the protection of the hair, determined by differential calorimetry scanning, against thermal stress (straightening treatment with a board), as a result of pretreatment with the active ingredient. The denaturation temperature in the case of vehicle treated hair is 137.9 ° C and can be increased to 138.9 ° C by adding hydrolyzed wheat protein. The use of DD / LL-methionyl-methionine resulted in an additional increase in the denaturation temperature to 139.9 ° C.
    [081] As a result of protective treatment with DD / LL-methionyl-methionine, the structure of a hair can therefore be greatly strengthened, which is not possible with this measure, as a result of treatment with a market standard usual, such as hydrolyzed wheat protein. Example 6: Hair tonic
    Example 7: Deluxe hair tonic
    Example 8: Mousse Basic Hair Conditioner Leave-In

    Example 9: Mousse Hair Conditioner Leave-In Clear Special
    Example 10: Hair Repair Leave-In Hair Conditioner Spray
    Example 11: Mousse Leave-In Hair Conditioner
    Example 12: Repair Leave-In Hair Conditioner
    Example 13: Leave-In hair conditioner with brittle tip repair

    Example 14: Leave-In Style & Relax hair conditioner
    Example 15: Mousse "HPP" Leave-In Light Hair Conditioner

    Example 16: Rich, Creamy Hair Conditioner
    Example 17: Shine cream for short hair

    Example 18: Body and Basic Shampoo
    Example 19: Sulfate and PEG-Free Hair Conditioner Shampoo
    Example 20: Light Hair Shampoo with UV Protection Properties

    Example 21: Pearl & Protect Hair Conditioner Shampoo
    Example 22: Light Hair Body Shampoo with Ceramide
    Example 23: Dandruff Shampoo
    Example 24: 2inl shampoo
    Example 25: Hair Conditioner Gel

    Example 26: Solar Protection Touch Gel Wax with Mica
    Example 27: Rinse hair conditioner with UV protection properties, free from PEG
    Example 28: Combination Light Combination Shampoo (Combi-Mix)
    Example 29: Pearly Hair Conditioner and Repair Shampoo
    权利要求:
    Claims (15)
    [0001]
    1. Cosmetic formulation characterized by comprising at least one stereoisomer of methionyl-methionine selected from the group consisting of D-methionyl-L-methionine, L-methionyl-D-methionine and D-methionyl-D-methionine, in which all stereoisomers of methionyl-methionine are contained in an amount of 0.5 to 4.0% by weight based on the total formulation.
    [0002]
    Cosmetic formulation according to claim 1, characterized in that it further comprises L-methionyl-L-methionine.
    [0003]
    3. Cosmetic formulation, according to claim 2, characterized by the fact that the total amount of L-methionyl-L-methionine, based on the total weight of all stereoisomers of methionyl-methionine present in the formulation according to the invention , is less than 50% by weight.
    [0004]
    Cosmetic formulation according to any one of claims 1 to 3, characterized in that it has a weight ratio of DL- and LD-methionyl-methionine to DD- and LL-methionyl-methionine from 9: 1 to 2 : 3.
    [0005]
    5. Use of methionyl-methionine characterized for being for the treatment of nails and hair.
    [0006]
    6. Use of methionyl-methionine characterized for being for hair conditioning.
    [0007]
    7. Use of methionyl-methionine characterized to increase hair shine.
    [0008]
    8. Use of methionyl-methionine, characterized by increasing the tensile strength of the hair.
    [0009]
    9. Use of methionyl-methionine, characterized by increasing the volume of hair.
    [0010]
    10. Use of methionyl-methionine, characterized by increasing the intensity of hair color.
    [0011]
    11. Use of methionyl-methionine characterized by being for the increase of the hair carrying capacity.
    [0012]
    12. Use of methionyl-methionine characterized to protect the hair from UV damage.
    [0013]
    13. Use of methionyl-methionine characterized to protect hair against oxidative damage and / or to protect hair against thermal damage and / or to protect hair against chemical damage.
    [0014]
    14. Use of methionyl-methionine characterized to improve the mechanical properties of nails.
    [0015]
    15. Use according to any one of claims 5 to 14, characterized in that a formulation, as defined in any one of claims 1 to 4, is used.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE2251877C3|1972-10-23|1981-01-08|Degussa Ag, 6000 Frankfurt|Food and feed additive|
    DE2261926C3|1972-12-18|1978-11-30|Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt|Process for the production of DL-methionyl-DL-methionine|
    JP2999301B2|1991-07-25|2000-01-17|協和醗酵工業株式会社|Cosmetics|
    ES2101263T3|1993-02-19|1997-07-01|Howard Green|COMPOSITIONS CONTAINING CORNEOCYTE PROTEINS.|
    GB9913765D0|1999-06-14|1999-08-11|Procter & Gamble|Hair care compoaitions|
    DE602005004139T2|2005-06-30|2009-01-02|Evonik Goldschmidt Gmbh|Use of salicyloyl sphingoid base for the treatment or prevention of cellulitis|
    AU2006326361B2|2005-12-16|2010-08-26|Unilever Plc|Hair treatment compositions|
    EP2001460A4|2006-03-28|2011-01-12|Novus Int Inc|Compositions for promoting hair growth|
    DE102006047529A1|2006-10-07|2008-04-10|Evonik Goldschmidt Gmbh|Dermatological composition contains an oligopeptide as an agent for increasing skin sensitivity|
    PL2065029T3|2007-11-30|2013-09-30|Evonik Degussa Gmbh|Personal care and cosmetic composition containing tetrapeptides with the motifs GX1X2G, PX1X2P, or PX1X2K|
    DE102008001788A1|2008-05-15|2009-11-26|Evonik Goldschmidt Gmbh|Use of organomodified siloxane block copolymers for the preparation of cosmetic or pharmaceutical compositions|
    DE102008042932A1|2008-10-17|2010-04-22|Evonik Degussa Gmbh|Production and use of methionylmethionine as a feed additive for fish and crustaceans|
    US8287845B2|2008-12-18|2012-10-16|E I Du Pont De Nemours And Company|Hair-binding peptides|
    DE102010032983A1|2010-07-31|2012-02-02|Vag-Armaturen Gmbh|connector|
    FR2964967A1|2010-09-17|2012-03-23|Exsymol Sa|PEPTIDOMIMETICS DERIVED FROM METHIONINE AND THEIR USE IN THE PROTECTION OF MITOCHONDRIA OF SKIN CELLS|DE102014225218A1|2014-12-09|2016-06-09|Henkel Ag & Co. Kgaa|Powerful color protection hair treatment products with a dipetid|
    DE102014225211A1|2014-12-09|2016-06-09|Henkel Ag & Co. Kgaa|Powerful cosmetic products with proteolipid and a dipeptide|
    DE102015203825A1|2015-03-04|2016-09-08|Henkel Ag & Co. Kgaa|"Keratin fiber coloring agent containing a dipeptide and a substantive dye"|
    DE102015203826A1|2015-03-04|2016-09-08|Henkel Ag & Co. Kgaa|Hair treatment agent containing a dipeptide III|
    DE102015203827A1|2015-03-04|2016-09-08|Henkel Ag & Co. Kgaa|Keratin fiber deforming agent with dipeptide and hair shaping method II|
    DE102015203820A1|2015-03-04|2016-09-08|Henkel Ag & Co. Kgaa|Blonding agent with a dipeptide|
    DE102015203823A1|2015-03-04|2016-09-08|Henkel Ag & Co. Kgaa|"Oxidation Dye Having a Dipeptide and a Pyrazole-Based Oxidation Pre-dye"|
    DE102015203824A1|2015-03-04|2016-09-08|Henkel Ag & Co. Kgaa|Hair treatment agent containing a dipeptide IV|
    DE102015203818A1|2015-03-04|2016-09-08|Henkel Ag & Co. Kgaa|"Cosmetics with Bio-Active and a Dipeptide"|
    DE102015203821A1|2015-03-04|2016-09-08|Henkel Ag & Co. Kgaa|"Oxidation Dye with Dipeptide and Aromatic Diamine"|
    JP6896381B2|2015-07-10|2021-06-30|花王株式会社|Hair cosmetics|
    CN108939139B|2018-08-04|2021-02-02|浙江派菲特新材料科技有限公司|Preparation method of medical adhesive with efficient anti-inflammatory and hemostatic functions|
    法律状态:
    2015-12-01| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2017-08-15| B25A| Requested transfer of rights approved|Owner name: EVONIK DEGUSSA GMBH (DE) |
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-02-27| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |
    2020-05-19| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-08-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-09-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/08/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102013215434.8A|DE102013215434A1|2013-08-06|2013-08-06|Methionyl-methionine stereoisomers and their use in cosmetics|
    DE102013215434.8|2013-08-06|
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