KR20210117478A - Hair cosmetics containing zinc pyrithione-polymericquaternary ammonium salt complex - Google Patents

Abstract

The present invention relates to cosmetics containing a stable zinc pyrithione (ZPT)-polyquaternium (PQ)(polymeric quaternary ammonium salt) complex. A dispersion-stabilized ZPT-PQ complex per se is very stable and a cosmetic composition containing the same is also stable without any precipitation and layer separation, and has an excellent effect of reducing dandruff and preventing itching when applied to the human scalp, and a cosmetic composition containing ZPT and PQ as a single ingredient also has a considerably stable effect.

Description

Personal care cosmetics containing zinc pyrithione-polycutanium complex composition {Hair cosmetics containing zinc pyrithione-polymericquaternary ammonium salt complex}

The present invention is stable zinc pyrithione (Zinc Pyrithione; ZPT) - polycutanium [(Polyquaternium; PQ)

(Polymeric quaternary ammonium salt; Polymeric quaternary ammonium salt)] It relates to a hair cosmetic containing a complex. More specifically, it contains a stable complex of ZPT, which is effective for preventing and removing dandruff, and PQ, which coats hair and gives hairdressing and treatment effects, so it is excellent in preventing and removing dandruff and has improved hairdressing and treatment effects. It relates to the composition.

In general, the biggest factor in the occurrence of dandruff is abnormal keratinocyte abnormality and excessive sebum secretion. In fact, more microorganisms were found on the scalp with a lot of dandruff, and in particular, a lot of proliferation of microorganisms called Pityrosporum Ovlae was found. Therefore, with the idea that dandruff symptoms will be improved when the reproduction of microorganisms is suppressed, so-called anti-dandruff agents with sterilizing action are added to shampoos and the like, and this is a dandruff treatment. Representative dandruff treatment agents include selenium disulfide, zinc pyrithione (ZPT), and pyroctonolamine. All of these substances are effective antimicrobial agents and cell division inhibitors, which can reduce dandruff in two or three uses. In particular, among the above substances, ZPT is the most commonly used drug for dandruff removal shampoo.

As an example of a hair cosmetic composition for the purpose of suppressing dandruff and itching, a shampoo composition containing ZPT as an active ingredient can be given (US Pat. No. 4,323,683, US Pat. No. 4,470,982, European Patent No. 285,388). However, since ZPT is insoluble in water, it must be dispersed in the product using a typical synthetic clay dispersant such as bentonite. This is because ZPT exhibits poor solubility in water or solvents, and it is an aromatic salt containing sulfur and zinc, and it is believed that it is because a non-bonding versus binding force is generated between O and Zn. That is, the dissolution mechanism of zinc pyrithione requires a ligand capable of coordinating a covalent bond with zinc, a heavy metal in zinc pyrithione, and suitable for this is amines having a ligand containing a lone pair of electrons. For example, EDTA (Ethylenediaminetetraacetic acid) has been mainly used as a solvent (US Patent No. 3,940,382), and recently N-acyl-EDTA chelating surfactant was used as a solvent for zinc pyrithione (Korean patent application). No. 97-9984) claiming that finer particles of ZPT can be obtained. However, amines such as EDTA have a strong alkalinity with a pH of 9 or higher, and a strong specific odor is generated. The pH of the composition cannot be neutralized, as it again forms an insoluble precipitate. On the other hand, in the case of N-acyl-EDTA chelating surfactants, for example, in the case of sodium lauroyl ethylenediamine triacetate, N having an unshared electron pair due to the steric hindrance effect of the acyl group bonded to N, that is, due to the asymmetric structure. Since the Zn of ZPT cannot be accessed efficiently, it cannot be considered that the coordination covalent bond is sufficient. On the other hand, even in dandruff removal shampoos, the use of high-molecular quaternary ammonium salts is inevitable for hair styling and treatment effects, but their use has been extremely limited because of poor compatibility with finely divided ZPT. Therefore, in the case of hair cosmetics using ZPT as a main component for dandruff removal and prevention, for example, shampoo, it has been rarely seen that the above-mentioned high molecular weight quaternary ammonium salt is sufficiently contained. Therefore, until now, the hairdressing and treatment effects of shampoos for dandruff removal and prevention using ZPT were mainly obtained using nonionic silicone emulsions. However, in the case of silicone emulsions, stabilization is difficult, so pre-emulsified emulsions must be added at a low temperature below 60°C, and since they are hydrophobic, it can lower the foaming power of the shampoo and weaken the shampoo's function. If the balance value (HLB value) and pH are not suitable, the product is easily separated, so it was quite difficult to stabilize it.

The above object of the present invention is to form a ZPT-PQ (Zinc Pyrithione-Polymeric quaternary ammonium salt) complex by adding ZPT to polycutternium (PQ) and stirring while heating, and it is a homomixer, dispenser, ball mill, colloid mill, and ultrasonic wave. After dispersion and stabilization with a vibrator, the dispersion stability of the stabilized ZPT-PQ composite was investigated in comparison with the ZPT aqueous solution, the ZPT aqueous solution dissolved with EDTA, and the ZPT-PQ composite without redispersion. Then, a hair cosmetic composition containing the dispersion-stabilized ZPT-PQ complex and a silicone emulsion was prepared, and the stability of the hair cosmetic composition was investigated by observing the formation of precipitation over time. The effect of reducing dandruff and preventing itching by applying the hair cosmetic composition was confirmed through clinical trials.

As described above through the above examples and experimental examples, the dispersion-stabilized ZPT-PQ complex itself is very stable and the hair cosmetic composition containing it is also stable, so there is no precipitation, no layer separation, and dandruff when applied to the human body. It has an excellent effect of reducing and preventing itching. Also, a hair cosmetic composition containing ZPT and PQ as a single component has a fairly stable effect, so it is a very useful invention in the hair cosmetic industry.

The present invention is a ZPT-PQ (Zinc Pyrithione-Polymeric quaternary ammonium salt) complex by mixing ZPT in a PQ aqueous solution in which various types of PQ including PQ-10 and PQ-11 are respectively dissolved in water at 80°C and stirring with a high-speed stirrer preparing water and dispersing and stabilizing it with a ball mill, a homomixer, a colloid mill, a super-lymphatic vibrator, etc.; Preparing a ZPT-GHTC complex by mixing JPT in an aqueous solution of guar hydroxypropyltrimonium chloride (GHTC) in the same manner as above and stabilizing dispersion in the same manner; Visually observe the dispersion state of the fine particles of the dispersion-stabilized ZPT-PQ-10 composite, and in the same way, 2 weight ZPT aqueous solution, 2.0 weight ZPT aqueous solution dissolved with 0.5 EDTA, and 2.8 weight ZPT-PQ-10 without redispersion Investigating the dispersion stability of the dispersion-stabilized ZPT-PQ composite by observing and comparing the dispersion state of the composite, and comparing the particle size after drying the materials to examine whether it is suitable when applied as a hair cosmetic composition ; preparing a hair cosmetic composition containing a dispersion-stabilized ZPT-PQ-10 and ZPT-PQ-11 complex and a silicone emulsion, and a hair cosmetic composition containing ZPT and PQ single components and a silicone emulsion; Comparing the stability of the hair cosmetic composition of the present invention by observing the generation of precipitation under a microscope while keeping the prepared hair cosmetic composition and visually observing the layer separation of the silicone emulsion; After applying the hair cosmetic composition of the present invention to men with a lot of dandruff, it consists of a clinical trial stage to investigate the effect of reducing dandruff and preventing itching.

ZPT, which is used as an anti-dandruff agent in the present invention, is a divalent aromatic salt with very low solubility in water. Industrially used, the particle size of ZPT is 0.3-10 μ, and its structure is represented by the following formula (I). same as it has been

In the present invention, ZPT and PQ, which makes the composite, are polymeric quaternary ammonium salts and are mainly used in hair cosmetics to give hairdressing and treatment effects, thereby preventing static electricity, giving gloss, and preventing damage to hair. PQ's solubility in water and properties as a polymer are determined according to the molecular weight, the number of substituted quaternary ammonium groups in the molecule, and the properties of an alkyl group substituted with the ammonium group. PQ used in the present invention has an appropriate molecular weight and water solubility, and is industrially used PQ-1, PQ-2, PQ-4, PQ-5, PQ-8, PQ-9, PQ-10, PQ. -11, PQ-12, PQ-13, PQ-14, PQ-15, PQ-17, PQ-18, GHTC, and the like, and the structure is as generally shown in the following formula (II).

where R 1 , R 2 , R 3 , and R 4 are an alkyl, acyl, alkylamine, or alkylester group substituted with N, and X is a quaternary ammo

It is the counter anion of nium, and n is the degree of polymerization.

The ratio of ZPT and PQ used in the preparation of the ZPT-PQ composite in the present invention may vary depending on the nature of PQ.

However, the weight ratio is preferably 1: 0.05 to 1: 10.

The production of the ZPT-PQ complex of the present invention can be viewed as possible by a hydrogen bond between ZPT and PQ as a medium and a van der Waals bond between the hydrophobic groups of both ZPT and PQ. Originally, the solubility of ZPT itself is due to the bonding force between electronegative O and electronegative Zn in water, which has low solubility and weak reactivity. The ZPT-PQ complex of the present invention improves the dispersion efficiency of ZPT by binding ZPT to the reaction site of PQ in a molecular unit, and also maintains the hairstyling and treatment effect of PQ by maintaining the film-forming properties of PQ. In particular, as the ZPT-PQ complex has surface activity, it adsorbs well to the scalp and hair and forms a flexible thin film. It can prevent hair roughness and has the effect of more stabilizing the hair cosmetic composition containing the silicone emulsion due to the surface activity of ZPT-PQ, which is more hydrophobic than PQ.

In the present invention, the ZPT-PQ complex has anti-dandruff effect, antiseptic sterilization effect, hair styling and treatment

It has effects, foaming power, dispersing power, film forming power, etc., and has a dispersion stabilizing action in a composition used as a silicone emulsion.

In the present invention, the ZPT-PQ composite makes a suspended solution even at a fairly low concentration because the hydrophilicity is lower than that of the transparently dissolving polymer quaternary ammonium salt. The ZPT-PQ complex thus formed is more stably dispersed because the probability of forming a complex with an anion is reduced rather than with PQ itself in the anionic shampoo composition due to the reduced cation of PQ. When using the ZPT-PQ composite with silicone emulsions, the hydrophobic part has good compatibility with the hydrophobic silicone, so it exists at the interface of the silicone emulsion in the shampoo base, and the cationic polymer part, which is the hydrophilic part, is hydrophilic in trauma. Due to the effect, the stability of the silicone emulsion is improved. In addition, since ZPT-PQ complex has surface activity, it is more uniformly adsorbed to the scalp and hair, and although the overall cationicity is weakened, it is absorbed more efficiently by the scalp than ZPT itself due to the cationicity of the partially unbound part. It can be washed off and it can be used more efficiently because it is not easily washed off even by shampoo's detergent than when ZPT is contained alone. In the detection test of residual ZPT after actual shampoo use using iron chloride (FeCl 2 ), the residual components of the ZPT-PQ complex were confirmed even after rinsing 4 times. was found to have been removed.

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Since the ZPT-PQ complex can bind Mg , Zn and Ca to its unreacted quaternary ammonium group, EDTA (ethylenediaminetetraacetic acid), which is a commonly known chelate, may not be used, but the effect is effective when used in combination. can be higher

As described above, the ZPT-PQ composite is a cationic polymer and has surface activity, so it is more uniformly and

By binding to the scalp and hair more strongly, the anti-dandruff effect can be increased.

Specific examples of the ZPT-PQ complex include ZPT-PQ-1, ZPT-PQ-2, ZPT-PQ-4, ZPT-PQ-5, ZPT-PQ-6, ZPT-PQ-8, ZPT-PQ-9, ZPT-PQ-10, ZPT-PQ-11, ZPT-PQ-12, ZPT-PQ-13, ZPT-PQ-14, ZPT-PQ-15, ZPT-PQ-18, ZPT-GHTC, etc. These ZPT-PQ composites form an entangled opaque gel at high PQ concentrations and a mixture of homogeneous opaque gels and fine ZPT particles at low PQ concentrations.

The hair cosmetic composition of the present invention containing the dispersion-stabilized ZPT-PQ complex may have a conventional formulation. For example, it may be formulated into shampoo, hair conditioner, hair conditioner, hair cream, hair tonic, hair treatment cream, hair treatment pack, hair spray, hair gel, hair cream, and the like. The compositions of each of these formulations contain the ZPT-PQ complex of the present invention and contain various components necessary for the commercialization of each formulation, and the types and amounts of these various components can be appropriately selected as needed, and the ZPT-PQ complex of the present invention In general, it can be used in an amount of 0.01-20 weight, preferably 1-10 weight, based on the total weight of the composition.

In the present invention, when ZPT and PQ are added to the hair cosmetic composition, respectively, ZPT is 0.01 to 5 weight, preferably 0.1 to 2 weight, and PQ is 0.01 to 20 weight, preferably 1 to 10 weight. can Taking a representative shampoo composition as an example of the hair cosmetic composition of the present invention containing the dispersion-stabilized ZPT-PQ complex, looking at the components, the shampoo formulation can be divided into a detergent, a surfactant, and an additive. The choice of surfactant in shampoo is very important as it predominantly influences the properties of the product. The most commonly used surfactants are anionic surfactants, followed by amphoteric surfactants and nonionic surfactants as auxiliary surfactants. Shampoo additives play an auxiliary role and play a role that surfactants cannot perform, increasing the added value of products. These include thickeners, foam enhancers, inorganic electrolytes, water-soluble polymers, pearlizing agents, hydrotropes. Conditioning agent, antiseptic disinfectant, metal sequestrant, UV absorber, dandruff treatment agent, color and fragrance, etc.

The surfactant used in the present invention is mainly an anionic surfactant, and amphoteric and nonionic surfactants are also used, and it is 40 to 80 weight, preferably 50 to 60 weight of the composition. Hereinafter, the additive component is 10 to 50 weight, and may preferably contain 20 to 30 weight.

Synthetic anionic surfactants that can be used in the present invention are lactic acid ester salts, such as ether lactate and alkyl oil.

It is an acid salt and an alkylamido lactate, and is as represented by the following formulas (III), (IV) and (V). RO(CH 2 CH 2 O) n SO 3 M ... Formula (III) ROSO 3 M ... Formula (IV)

RCONHOSO 3 M ... formula (V)

In the above formula, R is an alkyl group having 10 to 20 carbon atoms, n is 0 to 7, and M is a counter ion of an anionic surfactant selected from water-soluble cations such as sodium, potassium, ammonium, diethanolamine, and triethanolamine. . Preferably, R is an anionic surfactant having 12 to 16 carbon atoms and n is 3.

The higher alcohol used in the present invention is preferably derived from palm oil or palm oil, but is preferably a straight-chain alcohol obtained from petroleum. In the case of ether lactate, the alcohol is reacted with an average of 3 moles of ethylene oxide, followed by sulfur oxidation and neutralization. Specific examples thereof include glycerin monoalkyl ester monolactate, monoalkylsulfosuccinic acid ester, sodium lauryl sulfate, lauryl sulfate triethanolamine, lauryl sulfate diethanolamine salt, lauryl sulfate ammonium salt, polyoxyethylene ( 3EO) sodium lauryl sulfate, polyoxyethylene (3EO) lauryl ammonium sulfate, etc.

all.

Examples of the amphoteric surfactant used in the present invention include imidazoline type, alkylbetaine type, alkylamidopropylbetaine and sulfobetaine type, and specific examples thereof include cocoamphodiacetate, cocoyldimethylcarboxymethylbetaine, dimethylcarboxy methylcocamidopropylbetaine, laurylamidopropyldimethylsulfobetaine, and the like.

Synthetic nonionic surfactants used in the present invention include alkanolamide and amine oxide, and specific examples include lauric acid diethanolamide, palm oil fatty acid diethanolamide, polyethoxylated lauric acid diethanolamide, lauryl di Ethylamine oxide, N-coco amidopropyl- dimethyl amine oxide, etc. are mentioned. The surfactants mentioned above are widely used in shampoo cosmetics in the hair cosmetic composition of the present invention.

It can be used alone, but in general, it can be used in combination by taking advantage of each characteristic.

The composition of shampoo cosmetics among hair cosmetics according to the present invention can be made by changing its components according to the purpose of the product. Usage and frequency can be different.

Hereinafter, the specific method of the present invention will be described in detail with examples, but the scope of the present invention

is not limited only to these examples. Example 1: Preparation of dispersion-stabilized ZPT-PQ composite

A ZPT-PQ-10 complex was prepared by mixing 100 g of ZPT (48), which is a spherical shape with a particle size of 0.3-10 μ, with 1 kg of PQ-10 prepared as a 2 aqueous solution. At this time, the preparation reaction was mainly performed using a high-speed stirrer of 2000 to 4000 RPM at 70 ~ 100 ℃. Since the ZPT-PQ-10 composite prepared in this way is entangled in a gel state, use a homomixer, disperser, ball mill, colloid mill, ultrasonic vibrator, etc. with strong dispersing power so that ZPT is bound to PQ-10 in molecular units from 70 to 100. Dispersion stabilization was carried out at ℃ for 1 to 2 hours. The dispersion stabilization was determined according to the binding state of the composite and the performance of the dispersion device. In addition, the ZPT-PQ composite is prepared in the same manner as above, but the ZPT used is the same, but PQ is PQ-1, PQ-2, PQ-4, PQ-5, PQ-8, PQ-9, PQ-11, PQ. Final ZPT-PQ-1, ZPT-PQ-2, ZPT-PQ-4, ZPT using -12, PQ-13, PQ-14, PQ-15, PQ-16, PQ-17, PQ-18 respectively -PQ-5, ZPT-PQ-8, ZPT-PQ-9, ZPT-PQ-11, ZPT-PQ-12, ZPT-PQ-13, ZPT-PQ-14, ZPT-PQ-15, ZPT-PQ -16, ZPT-PQ-17, and ZPT-PQ-18 were prepared and

It was also dispersed and stabilized in the same way.

Example 2: Preparation of dispersion-stabilized ZPT-GHTC composite

In this example, the ZPT-PQ composite was prepared in the same manner as in Example 1, but the ZPT used was the same, but the final ZPT-GHTC was prepared using GHTC for PQ, and the dispersion was stabilized in the same way. At this time, the GHTC used is Jaguar C13S, a product of Celanse. Experimental Example 1: Dispersion stability of ZPT-PQ composite

In this experimental example, the dispersion stability of the dispersion-stabilized 2.8wtZPT-PQ-10 composite (Sample 4) prepared in Example 1 was finely dissolved with 2.0 wtZPT solution itself (Sample 1) and 0.5EDTA to improve stability. The dispersion stability of the solution (Sample 2) and the 2.8wtZPT-PQ-10 composite (Sample 3) without redispersion was compared, and the adhesion and particle state during drying were investigated and compared. As for the method, the microscopic state was observed with the naked eye, and all of the ZPT microdissolution-stabilized with ZPT or EDTA used in the ZPT solution itself were fine particles of about 0.3 to 10μ. As a result of the experiment, in the aqueous solution state, samples 1, 2, and 4 were all observed to form a fine, stable dispersion state in the case of the supernatant, but as can be seen in Table 1, samples 1 and 2 were found to have solid insoluble masses at the base. On the other hand, in the case of Sample 4 of the present invention, solid lumps could not be found. On the other hand, when comparing the state after the sample solution was dried, samples 1 and 2 were fairly non-uniform and formed large and coarse dry particles, and powder was blown out after complete drying. In Sample 3, large lumps of undispersed ZPT-PQ complexes were observed in aqueous solution, and white undispersed aggregates were observed even after drying. On the other hand, in the dispersion-stabilized ZPT-PQ-10 composite sample 4 of the present invention, after drying, coarse particles could not be found with the naked eye, and a uniform smooth film with good adhesion was formed. This is because the dispersion-stabilized ZPT-PQ-10 complex of the present invention is more uniformly present in the solution, and when used as a cosmetic composition, it is more uniformly attached to the scalp and hair, so that the anti-dandruff effect of ZPT and hairdressing and treatment effect of PQ are at the same time. indicates that it can be improved.

Claims (4)

A hair cosmetic comprising zinc pyrithione and polycutternium as active ingredients.
With respect to the total raw material composition 100, as an active ingredient, 0.1 to 20.0 of a complex of zinc pyrithione and polycutanium

Hair cosmetic composition, characterized in that it contains an amount.
With respect to the total raw material composition 100, zinc pyrithione and polycutternium as active ingredients were each added with 0.01 to 5 weight and

Hair cosmetic composition, characterized in that it contains 0.01 to 20 weight. [Claim 4] The polycutternium according to claim 1 to 3, wherein the polycutternium is polycutternium-1 (PQ-1), polycutternium-2 (PQ-2), polycutternium-4 (PQ-4), polycutternium. -5(PQ-5), Polycutternium-8(PQ-8), Polycutternium-9(PQ-9), Polycutternium-10(PQ-10), Polycutternium-11(PQ-11) ), polycutternium-12(PQ-12), polycutternium-13(PQ-13), polycutternium-14(PQ-14), polycutternium-15(PQ-15), polycutternium- 17 (PQ-17), polycutternium-18 (PQ-18), guarhydroxypropyltrimonium chloride

(GHTC) hair cosmetic composition, characterized in that.