JP6281153B2 - Hair care or nail care cosmetics - Google Patents

Description

  The present invention relates to a cosmetic product for hair care or nail care.

  In the hair, the cuticle of the outermost layer covers the cortex and medulla, which are the internal structure of the hair. To do. As a result, it is known that when the hair protecting function of the cuticle is weakened, it is easily affected by external stimuli, and further, hair internal components of the hair are damaged, dried, and the touch and gloss are reduced. Therefore, in order to reduce such hair damage and impart a hair protecting effect, cationic polymers, cationic surfactants, and the like are used in hair care cosmetics such as shampoos and conditioners.

  For example, in Patent Documents 1 and 2, a cationic polymer is used in order to enhance the adhesion of the conditioning component to the hair and scalp. Patent Document 3 discloses a preparation containing a cationic polymer, a cationic surfactant, an aminoxide, or the like as a substance that improves the combing property in a wet state.

JP 2003-503437 A JP 2002-522365 A JP 2004-67668 A

  However, conventional techniques for increasing the adhesion of conditioning ingredients to hair by blending a cationic polymer or a cationic surfactant have not yet provided a sufficient hair care effect. Further, conventional cationic polymers and cationic surfactants have a problem that they are highly irritating and damage hair and skin.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel hair care or nail cosmetic that has high protection against hair and nails and is less irritating. To do.

  In cosmetics for hair care or nail care, the present inventors have made a cationic or cationized closed endoplasmic reticulum formed by an amphiphilic substance that spontaneously forms a closed endoplasmic reticulum, or a cationic having a hydroxyl group. By forming an O / W emulsion using polycondensation polymer particles, it has been found that it has a high protective power against hair and nails and has little irritation to hair and nails, and completes the present invention. It came to. More specifically, the present invention provides the following.

  (1) Cationic polycondensation having a cationic closed endoplasmic reticulum or a hydroxyl group formed by an oil phase containing a hair care or nail care component, an aqueous phase, and an amphiphilic substance that spontaneously forms a closed endoplasmic reticulum A cosmetic for hair care or nail care comprising polymer particles and having a structure of an O / W emulsion.

  (2) The hair care product according to (1), wherein the closed endoplasmic reticulum or the polycondensation polymer particles are present at the interface between the aqueous phase and the oil phase to maintain an emulsified state and constitute an O / W type emulsion. Cosmetics for nail care.

  (3) The cosmetic for hair care or nail care according to (1) or (2), wherein the polycondensation polymer particles are sugar polymer particles.

  According to the present invention, in a cosmetic for hair care or nail care, a cationic or cationized closed vesicle (hereinafter referred to as “closed vesicle”) formed by an amphiphilic substance that spontaneously forms a closed vesicle. O / W emulsion is formed by cationic polycondensation polymer particles having a hydroxyl group (hereinafter abbreviated as “polymer particles”), and has high protection against hair and nails, and Less irritation to hair and nails.

  Hereinafter, although embodiment of this invention is described, this invention is not specifically limited to this.

  The hair care or nail care cosmetic of the present invention comprises an oil phase containing a hair care or nail care component, an aqueous phase, and cationic closed vesicles or cationic polymer particles, and has an O / W emulsion structure. It is characterized by being. In the present invention, hair care or nail care means protection of hair or nails.

  The closed vesicle or polymer particle is a particle having a hydrophilic surface, and maintains an emulsified state by being interposed at the interface between the water phase and the oil phase by van der Waals force. This emulsification mechanism is known as a three-phase emulsification mechanism using closed vesicles or polymers, and maintains the emulsified state by directing the hydrophilic part and the hydrophobic part to the aqueous phase and the oil phase, respectively, and lowering the interfacial tension between the phases. It is completely different from the emulsification mechanism of surfactants (amphiphiles).

  Cationic closed vesicles or polymer particles and cationic surfactants have an action of adsorbing to hair and nails. In order to develop an emulsifying effect, a conventional surfactant must have an activator molecule oriented on the surface of the oil droplet and an activator molecule present free in the aqueous phase in an equilibrium state, And they are repeating adsorption / desorption with each other. Therefore, if the surfactant in the free state is particularly cationic, it is adsorbed and taken away exclusively by the hair and nails, and the emulsifying ability tends to be insufficient. Moreover, although the cationic amphiphile which is not made into the closed endoplasmic reticulum and the cationic polymer which is not made into particles are adsorbed to hair or the like, the above-described three-phase emulsifying action is not exhibited on the oily component. In contrast, the cationic closed endoplasmic reticulum or the cationic polymer particles constituting the present invention exhibit a three-phase emulsifying action and can form a stable O / W type emulsion with respect to the oil component in the aqueous system. . By the way, three-phase emulsification is different from emulsification with surfactant molecules, and because the emulsified state is maintained by the inclusion of closed vesicles or polymer particles at the oil-water interface, free closed vesicles that do not contribute to emulsification in the aqueous phase Or polymer particles need not be present. Then, the cationic closed vesicles or polymer particles having an adsorbing action are integrally adsorbed to the hair and nails in a state of adhering to the oil phase surface, and the inner components are eluted from the hair and nails in order to cover uniformly. Suppress. As a result, the present invention can obtain a high protection against hair and nails.

  Cationic closed endoplasmic reticulum or polymer particles and cationic surfactants have an adsorption action on hair and nails, as described above, while denaturing proteins such as keratin present on the hair and nails by adsorption. And give a stimulus. According to the conventional cationic surfactant, as described above, the free cationic surfactant present in the aqueous phase is adsorbed on the skin, so that the irritation is high. In addition, amphiphiles that are not closed endoplasmic reticulum and non-particulate cationic polymers exist independently of the oil component and are not closed endoplasmic reticulum or particles, so the contact area with the contacted surface is wide. The irritation is high accordingly. On the other hand, the cationic closed endoplasmic reticulum or polymer particles constituting the present invention are in the form of particles, so that the contact area with the contacted surface is relatively narrow and the irritation to hair and nails is expected to be reduced accordingly. Is done.

  In order to obtain a three-phase emulsifying action, when a closed vesicle of a nonionic amphiphile is used, a method of adding a cationic surfactant to the vesicle and making it cationized as a whole can be employed. In this case, it is cationized by chemical action. On the other hand, the cationic polymer particles have a cationic group or the like at a site constituting the polymer molecule.

  The hair care or nail care component is not particularly limited, for example, isononyl isononanoate, isopropyl palmitate, isopropyl myristate, triisodecyl isononanoate, stearyl stearate, diglyceryl monoisostearate, hydrogenated didecene, hydrogenated tridecene, hydrogenated Examples include tetradecene, hydrogenated pentadecene, methyl heptyl laurate, and the like. These may be used alone or in combination of two or more. Moreover, you may use oil agents other than these as needed.

  Cationic closed vesicles or polymer particles are extremely excellent in emulsifying performance. For this reason, the amount of the hair care or nail care component in the cosmetic can be selected from a range of 0.1 to 95% by mass and may be appropriately selected according to the purpose of use.

  Cationic closed vesicles or polymer particles are extremely excellent in emulsifying performance. For this reason, the amount of water in cosmetics can be widely selected from the range of 0.1 to 95% by mass, and may be appropriately selected according to the type and amount of hair care or nail care ingredients, the purpose of use, etc. .

  In the present invention, in addition to cationic closed vesicles or polymer particles, a surfactant or an emulsifier may or may not be included in the usage mode. However, the cationic surfactant, the cationic closed endoplasmic reticulum or the polymer is irritating to hair and nails as described above. Therefore, in the case of containing a cationic surfactant, a cationic non-endoplasmic amphiphile or a non-particulate cationic polymer, these cosmetics are more effective in terms of reducing irritation. % By weight is preferably 5% by weight or less, more preferably 3% by weight or less, still more preferably 1% by weight or less, and most preferably none.

  As the amphiphilic substance in the present invention, a polyoxyethylene hydrogenated castor oil derivative represented by the following general formula 1 or a dialkylammonium derivative represented by the general formula 2, a trialkylammonium derivative, a tetraalkylammonium derivative, A halogenated derivative of a dialkenyl ammonium derivative, a trialkenyl ammonium derivative, or a tetraalkenyl ammonium derivative may be employed.

General formula 1

  In the formula, E, which is the average added mole number of ethylene oxide, is 3 to 100. If E is excessive, the type of good solvent that dissolves the amphiphilic substance is limited, and thus the degree of freedom in producing hydrophilic nanoparticles is narrowed. The upper limit of E is preferably 50, more preferably 40, and the lower limit of E is preferably 5.

General formula 2

  In the formula, R 1 and R 2 are each independently an alkyl group or alkenyl group having 8 to 22 carbon atoms, R 3 and R 4 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and X is F, Cl, Br, I or CH3COO.

  Alternatively, phospholipids, phospholipid derivatives, and the like may be employed. As the phospholipid, among the structures represented by the following general formula 3, DLPC (1,2-Dilauroyl-sn-glycero-3-phospho-rac-1-choline) having a carbon chain length of 12, DMPC (1,2-Dimyristol-sn-glycero-3-phospho-rac-1-choline), DPPC with a carbon chain length of 16 (1,2-Dipalmitoyyl-sn-glycero-3-phospho-rac-1-choline) Can be adopted.

General formula 3

  In addition, among the structures represented by the following general formula 4, DLPG (1,2-Diilauroyl-sn-glycero-3-phospho-rac-1-glycerol) Na salt or NH4 salt, carbon chain of carbon chain length 12 Na or NH4 salt of DMPG having a length of 14 (1,2-Dimyristol-sn-glycero-3-phospho-rac-1-glycerol), DPPG having a carbon chain length of 16 (1,2-Dipalmitoyyl-sn-glycero-3) -Phospho-rac-1-glycerol) Na salt or NH4 salt may be employed.

Formula 4

  These are cationized by treatment with a cationic surfactant or the like. More specifically, the following method can be employed.

  When polyoxyethylene hydrogenated castor oil (HCO-10) known as an amphiphilic substance is cationized with a cationic surfactant (CTAB cetyltrimethylammonium bromide, etc.), the cationic surfactant having 14 or more carbon atoms and HCO-10 is used. After mixing and stirring the agent so that the molar fraction XS = 0.1 or less, distilled water is added and stirred so that HCO-10 has a predetermined concentration to obtain a cationized closed endoplasmic reticulum. Can do. Even when a cationic surfactant is added in a molar fraction of 0.1 or more, the zeta potential of the closed endoplasmic reticulum does not change any more, and the cationic surfactant is not only solubilized in the closed endoplasmic reticulum but also eluted in water. Therefore, it is considered that a molar fraction of 0.1 is the best.

  The method for preparing the cationized closed endoplasmic reticulum is the same when the substance forming the closed endoplasmic reticulum is changed to phospholipid. However, in the case of phospholipids, it may take time to solubilize the cationic surfactant. Therefore, it is recommended to take the method of adding the following mixed crystals to water. A good solvent such as Ethanol is added to the phospholipid, stirred with Vortex, and uniformly dissolved. On the other hand, the cationic surfactant also prepares an Ethanol solution. The phospholipid / Ethanol solution and the cationic surfactant / Ethanol solution are mixed so as to have a predetermined mixed composition and stirred sufficiently. Ethanol is completely removed by drying to produce a mixed solid of phospholipid and cationic surfactant. Next, cationized closed endoplasmic reticulum can be obtained by adding water to the mixed crystal so that the phospholipid has a predetermined concentration and dispersing it.

  The cationic polymer is not particularly limited, and examples thereof include cationized guar gum such as guar hydroxypropyltrimonium chloride, and cationized cellulose such as hydroxyethylcellulose hydroxypropyltrimethylammonium chloride ether. The particles include both single particles of the polycondensation polymer and those in which the single particles are connected, but do not include aggregates (having a network structure) before being formed into single particles.

  The cationic closed vesicles or polymer particles have an average particle size of about 8 nm to 800 nm before the formation of the emulsion, but have an average particle size of about 8 nm to 500 nm in the O / W emulsion structure. Since these preparation methods are conventionally known as disclosed in Japanese Patent No. 3855203, etc., they are omitted.

  The amount of the cationic closed vesicle or polymer particle may be appropriately set according to the amount of the oil phase, and is not particularly limited, but may be 0.0001 to 5% by mass in total. Thereby, the emulsified state before use of cosmetics can be maintained favorably. Unlike conventional surfactants, cationic closed vesicles or polymer particles have excellent emulsifying properties, and therefore 5% by mass or less (specifically, 4% by mass or less, 3% by mass or less, 2% by mass or less) Even a small amount of 1.0 mass% or less and 0.75 mass% or less) can provide sufficient protection to hair or nails. Thus, giving sufficient protective power to cosmetics in a small amount is preferable in that it can suppress irritation to hair and nails by excess cationic sugar polymer. In addition, all the said amounts are solid content.

  In order to maximize the properties of hair care or nail care ingredients, the emulsion particles are sufficiently broken by the external force during application, etc., and the oil phase hair care or nail care ingredients are spread evenly on the application target (hair, nails) Is desirable. If the particle size of the oil phase is too small, the external force is not sufficiently applied to the emulsion particles, and it is difficult to sufficiently break the emulsion particles. Therefore, the average particle size of the oil phase is preferably 0.5 μm or more, more preferably 0.7 μm or more, and most preferably 1.0 μm or more. Thereby, the spread (use feeling) to an application object improves. Further, from the viewpoint of balance between ease of production and the above effect, the average particle diameter of the oil phase is not particularly limited, but may be 20 μm or less, 15 μm or less, and 10 μm or less. The average particle size of the oil phase is measured by a laser diffraction scattering type particle size distribution analyzer (SALD2100, Shimadzu Corporation) in a state where the viscosity of the emulsion is sufficiently low (diluted as necessary).

  The zeta potential of the O / W emulsion is used as an index of adsorptivity to hair and nails. When an O / W type emulsion is formed, a high zeta potential is required to provide a protective effect. On the other hand, if the zeta potential is too high, irritation to the hair and nails by the cationic substance increases. According to the conventional cationic surfactant, a large amount of the cationic surfactant is required to require the emulsifying action, and as a result, the zeta potential is higher than the zeta potential required for the adsorption action. The stimulus becomes stronger. However, according to the present invention, a stable O / W emulsion can be formed with a small amount of cationic closed vesicles or polymer particles. Therefore, the degree of cationization can be suppressed as compared with conventional cationic surfactants, and the zeta potential can be set to such an extent that an adsorption action can be achieved, so that irritation to hair and nails can be suppressed. The zeta potential of the O / W emulsion is preferably 50 mV or less, more preferably 30 mV or less, and most preferably 20 mV or less in that the stimulation is less.

  Note that the above zeta potential does not indicate a value in the state of a cosmetic product as a final product. This is because the final product contains various components as shown in [Table 2], and most of them are anions, so the zeta electrons in the product state are anions as shown in [Table 2]. Because it becomes. These anionic components do not adsorb on the hair surface (the hair surface is an anion). In the product, anion particles and cation particles coexist, but agglomeration and precipitation do not occur, and they are stably dispersed.

  That is, the value of the zeta electron is obtained by emulsifying liquid paraffin as an oil phase in an aqueous system and measuring the zeta potential as shown in [Table 1]. The emulsification employed in the present invention does not depend on the surface-active action using closed vesicles or polymer particles other than emulsification with a surfactant.

  The zeta potential of the O / W type emulsion is measured by ELS-Z (manufactured by Otsuka Electronics Co., Ltd.).

  Hair care cosmetics are not particularly limited, for example, shampoo, rinse-in shampoo, conditioner, treatment, hair restorer, hair spray, foam styling agent, gel styling agent, hair liquid, hair tonic, hair gel, hair color, hair cream , Bleaching agents, permanent agents and the like. The nail care cosmetics are not particularly limited, and examples thereof include nail enamels such as manicure and pedicure, nail coats, under nails, and nail top coats.

  The cosmetics of the present invention may contain any known ingredients contained in conventional hair care or nail care cosmetics. For example, a fragrance, a pH adjuster, a preservative, a thickener, a stabilizer, a colorant, an antioxidant, a fragrance and the like may be included. However, the present invention is not particularly limited to this and may not be included.

  Cosmetics can be prepared by mixing a dispersion containing cationic closed vesicles or polymer particles with an oily ingredient containing a hair care or nail care ingredient to form an O / W emulsion. The water-soluble optional component may be added to the dispersion before mixing, or may be added to the emulsion after mixing.

  The technology of the present invention can be applied to cosmetics other than hair care or nail care cosmetics. Specific forms are not particularly limited, but may be cosmetics such as facial cleansers, cleansings, body soaps, peeling agents, sunscreens, foundations, etc., and liquids, emulsions, ointments, creams, gels, aerosols, etc. It may be a dosage form.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples.

<Test Example 1>
When hair is immersed in water, its cuticle opens and amino acids, proteins, lipids and the like flow out, which causes hair damage, drying, loss of gloss, deterioration of touch, and the like. Here, when the hair is protected, the opening of the cuticle is suppressed, and proteins and the like inside the hair are retained. On the other hand, if the hair is not protected when the hair is immersed in water, the turbidity of water (OD (turbidity according to the known Lambert-Beer law)) increases due to the outflow of proteins and the like inside the hair. . In other words, when there is a protective power, the outflow of protein or the like is suppressed, so that no change is observed in turbidity compared to the case without the protective power. Utilizing this property of hair, the effect of protecting hair was evaluated by the following method.

A 30 ml storage bottle was prepared, and 10 ml of the aqueous solutions of Example 1 and Comparative Examples 1 to 3 having the formulations shown in Table 2 were added to separate storage bottles. In addition, the composition component employ | adopted what comprises a standard hair care cosmetics. Two storage bottles to which each aqueous solution was added were prepared, and one bundle of hair (1.0 g human hair) was placed in only one, and no hair was placed in the other. These were allowed to stand at 40 ° C. for 24 hours, and after 24 hours, the elution amount of internal components from each hair was measured as turbidity (OD ₆₀₀ : turbidity detected with light having a wavelength of 600 nm). The results are shown in Table 3. In addition, the zeta potential of the O / W type emulsion was measured by ELS-Z (manufactured by Otsuka Electronics Co., Ltd.).

  A negative difference in turbidity (B)-(A) between the presence of hair (A) and the absence of hair (B) suggests elution of hair internal components, and means that the prescription protection power is low. Although the change rate of the comparative example 1 was low compared with the comparative example 3 (purified water), it was a negative value. In Comparative Example 2, there was no difference between the presence of hair (A) and the absence of hair (B). On the other hand, in Example 1, it was confirmed that (B)-(A) was a positive value.

  From this result, it is considered that Comparative Example 1 (using a cationic surfactant) was insufficient even if it had some hair protection effect as compared with Comparative Example 3 (purified water). Further, in Comparative Example 2 (using a non-particulate cationic polymer), it is considered that elution of hair internal components was prevented, or the elution amount and the adsorption amount of the conditioning component in the formulation were comparable. . On the other hand, in Example 1 (using cationic polymer particles), the three-phase emulsification action and the adsorption action of the cationic polymer, the oil phase containing the cationic polymer particles and the conditioning component are integrated into the hair and As a result of suppressing the elution of internal components from the hair by uniformly adsorbing to the nails and coating the whole, and exerting a hair protecting effect, the difference in turbidity between the presence of hair (A) and the absence of hair (B) (B)-(A) seems to be positive.

<Test Example 2>
Using the hair of Example 1 and Comparative Examples 1 to 3 after holding at 40 ° C. for 24 hours in Test Example 1, the amount of the protective component adsorbed on the hair was evaluated. When the hair is immersed in water, the cuticle opens and the hair internal components and external penetrating / replenishing components are eluted. Utilizing this property, specifically, the hair bundle was rinsed with running water and the prescription components adhering to the hair surface were removed by drying with a drier, and then immersed in 10 ml of purified water at 40 ° C. for 24 hours. Then, the internal component elution amount from each hair was measured as turbidity (OD ₆₀₀ ). The results are shown in Table 4. This Test Example 2 confirms that the more the protective component is adsorbed, the longer the hair cuticle can be prevented from swelling for a longer time and the elution of protein from the hair can be prevented. That is, in this Test Example 2, the protein that could not be eluted in the previous Test Example 1 is positioned as a test for forcibly eluting the protein by applying more severe conditions. From the results of Test Example 1, since the turbidity change when most of the hair internal components are eluted is on the order of 0.01, a positive value of 0.1 order or more is penetrating / supplementing from outside, that is, protection. This is considered to indicate the adsorption of components.

  From this result, it was confirmed that the protective component of Example 1 was adsorbed as compared with Comparative Example 1. This suggests that the hair care component emulsified with the cationic polymer particles is superior in hair protection and adsorbability compared to the hair care component emulsified with the cationic surfactant. It was. Moreover, it was suggested that Example 1 and Comparative Example 2 have the same amount of adsorption. However, in Test Example 1, Example 1 was superior to Comparative Example 2 in the protective effect, so that the cationic polymer and the hair care component that were not emulsified in Comparative Example 2 were partially adsorbed, and the protective action was It is thought that it was because it was not fully demonstrated. This is probably because the hair care component was adsorbed on a part of the hair by the cationic polymer, and the amount of protein elution was larger than that in Example 1.

<Test Example 3>
Protein denaturation in the human body is a cause of damage to the hair, skin, nails, etc. (rough skin, eczema, hair crackling, etc.). Therefore, in order to replace the human body with egg white, investigate the effects of cationic polymers and cationic surfactants on the protein in egg white, and perform protein denaturation evaluation tests by the following methods in order to predict the risk to the human body. It was. As a test sample, in addition to Example 1, Comparative Example 1 and Comparative Example 2 in Table 2, the same as Example 1, Comparative Example 1 and 2 except that the cationic polymer and the cationic surfactant are not included. Evaluation was carried out using the formulation of Comparative Example 4 (Comparative Example 4) as a control.

  5 g of each aqueous solution of Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 4 and 5 g of egg white were mixed and held at room temperature for 1 hour. Thereafter, the mixture is centrifuged at 200 g for 10 minutes. Among the solid substances produced, the oil content in the formulation is separated upward, the amount of denatured protein is separated as a downward precipitate, and the degree of precipitation is determined by the short and long sides of the precipitate in the centrifuge tube. It was quantified by visual confirmation and calculated based on Comparative Example 4. The results are shown in Table 5.

  In Example 1, compared with Comparative Example 1 and Comparative Example 2, since there was little protein modification | denaturation, it was guessed that irritation | stimulation to hair, skin, a nail, etc. was low. Comparative Example 1 and Comparative Example 2 are the results of denaturation of proteins by free cationic polymers and cationic surfactants, and irritation due to adsorption to the skin was presumed. On the other hand, Example 1 is considered that the irritation | stimulation with respect to hair and a nail | claw became low as a result of many of cationic polymer particles adhering to the oil phase and stabilizing by three-phase emulsification.

Claims (3)

Comprising an oil phase containing a hair care or nail care ingredients, and an aqueous phase, the cationic polycondensation polymer particles having a water group,
A cosmetic for hair care or nail care that maintains an emulsified state by interposing the polycondensation polymer particles at the interface between the aqueous phase and the oil phase, and constitutes an O / W emulsion .   The cosmetic for hair care or nail care according to claim 1, wherein the polycondensation polymer particles are sugar polymer particles. Comprising an oil phase containing a hair care or nail care ingredients, and an aqueous phase, spontaneously closed vesicle amphiphile by forming a cationic closed vesicle body forming a
The closed endoplasmic reticulum is formed of an amphipathic substance formed by adding a cationic surfactant to a molar fraction of 0.1 or less,
A cosmetic for hair care or nail care that maintains an emulsified state by interposing the closed endoplasmic reticulum at the interface between the aqueous phase and the oil phase to constitute an O / W emulsion .