RU2234912C2 - Resin-base cosmetic composition and its application in cosmetics - Google Patents

Abstract

FIELD: cosmetics and cosmetology.

SUBSTANCE: invention relates to resin-base cosmetic composition used for preparing a fixing agent for hair that consists of mainly of amphoteric urethane resin having carboxylic group and a tertiary amino-group in one molecule. The structure of amphoteric urethane group comprises a polysiloxane bond and water. The invention relating to a fixing agent for hair shows rigidity, washing out ability with shampoo, provides good external state of hair, luster, good combing and inhibits separating into layers. The fixing agent for hair elicits the excellent waterproofing with respect to neutral water and enhanced cohesion with hair surface.

EFFECT: valuable properties of composition.

5 cl, 11 tbl, 9 ex

Description

The present invention relates to a cosmetic composition based on a resin, consisting mainly of amphoteric urethane resin, and to the use of said composition based on a resin in cosmetics, in particular a cosmetic composition based on a resin used as a skin care product, a hair care product, and the like, as a hair fixative, a film forming agent, a conditioner, a viscosity controlling agent, and the like, and using the composition in cosmetics.

Typically, cationic acrylic resin, anionic acrylic resin, amphoteric or anionic / cationic acrylic resin, non-ionic polyvinylpyrrolidone resin and the like are used as the base resin for hair fixer. When this resin is used as the main resin, the hair becomes stiff, which leads to good styling ability (stiffness), but worse in appearance and worse combed, and it is possible to delaminate the hair. On the other hand, when the external condition and combing ability are in the first place, not only the styling ability becomes unsatisfactory, but also problems such as stickiness and the like can occur. Thus, it is difficult to obtain from a known base resin that it satisfies all the qualities required of a hair fixer, such as stiffness, appearance, combing ability and anti-delamination action.

The use of an anionic urethane resin as a base resin for hair fixer was then proposed, as described in Japanese Pre-Published Application TOKKAIHEI 6-321741. When using the specified anionic urethane resin, a hair retainer can be obtained having conflicting properties: with good stiffness, providing a good external condition, washed off with shampoo and having an anti-delamination effect. In this regard, the hair clip using said anionic urethane resin is superior to the hair clip using the above acrylic resin. However, the use of anionic urethane resin can cause problems such as roughness of the hair to the touch, lack of shine and poor combability.

Thus, the aim of the present invention is to create a cosmetic composition based on a resin to obtain a hair fixer having all the properties: stiffness, rinse off with shampoo, which provides good appearance, shine, good combing and has an anti-delamination effect, and in the development of the use of such cosmetics in cosmetics resin-based cosmetic composition.

According to a first aspect of the present invention, in order to achieve the aforementioned object, a resin-based cosmetic composition is provided which consists mainly of an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule, wherein the amphoteric urethane resin contains a polysiloxane bond in its structure. According to a second aspect of the present invention, there are provided cosmetic products using a resin-based cosmetic composition.

The inventors of the present invention have found that a hair retainer having rigidity, an external state, good combing and anti-delamination action and the like can be obtained by using an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule as the main resin, and a patent application has been filed for a resin composition containing substantially amphoteric urethane resin (Japanese Patent Application No. TOKUGANHEI 10-27595). The improvement in each of the properties when using amphoteric resin occurs for the following reason. Namely, the use of urethane resin as the main structure of the base resin makes it possible to combine the stiffness property with good external condition, combing and anti-delamination action - characteristics that by their nature contradict each other due to the elasticity and hardness of the urethane resin. In addition, when using an amphoteric urethane resin having a carboxyl group and a tertiary amino group, it becomes possible to obtain a hair retainer with exceptional water resistance to neutral water, since the carboxyl group and the tertiary amino group are ion-bound and also excellently washable with shampoos, since the ionic bond is shampoo torn apart. In addition, since the amphoteric urethane resin has a cationic tertiary amino group in its molecular chains that interacts with the negatively charged surface of the hair, greater adhesion can be obtained compared to the known anionic urethane resin.

Applicants have also conducted studies regarding a resin composition containing primarily amphoteric urethane resin. As a result, it was found that an additional improvement in terms of gloss, touch, combability and anti-delamination action can be obtained by introducing a polysiloxane bond into the structure of an amphoteric urethane resin. Thus, the applicants have developed the present invention.

Further, the present invention will be disclosed using a description of its options.

The resin cosmetic composition of the present invention consists mainly of an amphoteric resin having a carboxyl group and a tertiary amino group in one molecule. The main distinguishing feature of the present invention is that the amphoteric urethane resin has a polysiloxane bond in its structure. In addition, the phrase “containing mainly amphoteric urethane resin” usually means the preparation of a resin cosmetic composition in question by adding other components to an amphoteric urethane resin, but, however, includes the case where the resin cosmetic composition consists only of amphoteric urethane resin.

The above polysiloxane bond amphoteric urethane resin can be obtained, for example, by reacting a polyol as one compound [component (A)], a polyisocyanate compound [component (B)] having active hydrogen polysiloxane compound [component (C)] and compound [component (D) ] having active hydrogen and a carboxyl group, with each other with an excess of isocyanate groups to obtain a prepolymer containing an isocyanate group, and reacting the prepolymer with a compound [component (E)] having active hydrogen and t upmost amino group. Alternatively, a polysiloxane-bonded amphoteric urethane resin can be obtained by changing the interaction sequence (component (D) is replaced by component (E)), i.e. by the interaction of component (A), component (B), component (C) and component (E), i.e. by reacting component (A), component (B), component (C) and component (E) with an excess of isocyanate groups to obtain a prepolymer containing an isocyanate group, and reacting the prepolymer with component (D). The required amphoteric urethane resin is easier and more reliable to obtain by these methods than by known methods. In addition, if in the above methods both components, component (D) and component (E), simultaneously interact with components (A) - (C), the carboxyl group of component (E) first forms a salt that becomes insoluble in the reaction system, and interaction with the isocyanate compound may not occur even in the presence of an OH group. As a result, the desired amphoteric urethane resin may not be obtained. That is, as indicated above, a polysiloxane-bonded amphoteric urethane resin can be obtained by first reacting one of the components, component (D) or component (E), with components (A) - (C) and then reacting another component, (D) or (E).

The polyol compound of component (A) is not particularly limited and may be any polyol compound commonly used to make polyurethane. Examples of the polyol compound include polyester polyol, polyether polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, polyolefin polyol, polyacrylic ether polyol. These polyols can be used either individually or in combination with each other. Among them, polyester polyols and polyether polyes are particularly preferred. Examples of polyester polyol include products obtained by polycondensation of at least one of the dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid and the like. with at least one polyhydric alcohol, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,10-decanediol , diethylene glycol, spirogli stake, trimethylolpropane and the like, and products obtained by additive ring opening polymerization, such as ethylene oxide, propylene oxide, oxetane and tetrahydrofuran in water, a polyol, phenols such as bisphenol A, hydrogenated phenols, primary amines and secondary amines. Examples of these products include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, and products (either a block copolymer or a random copolymer, in the case of a copolymer) obtained by ring opening polymerisation of at least one of propylene oxide and ethylene oxide in bisphenol A.

The polyisocyanate compound of component (B) is not specifically limited. Examples of said compound include organic diisocyanate compounds, such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds. These compounds can be used either individually or in combination with each other. Examples of aliphatic diisocyanate compounds include ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate. Examples of alicyclic diisocyanate compounds include hydrogenated diphenylmethane-4,4′-diisocyanate, 1,4-cyclohexanediisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, norbornanediisocyanate. Examples of aromatic diisocyanate compounds include diphenylmethane-4,4′-diisocyanate, xylylenediisocyanate, toluene diisocyanate, toluene diisocyanate and naphthalenediisocyanate. Of these, 1,6-hexamethylene diisocyanate, isophorondiisocyanate, norbornanediisocyanate and the like are preferable in terms of cost.

The specific polysiloxane compound of component (C) is not specifically limited, and any compound with a polysiloxane bond, a siloxane bond chain (Si — O) that can be incorporated into the structure of an amphoteric urethane resin can be used. The polysiloxane bond introduced into the structure of the amphoteric urethane resin preferably has a repeat number n between 5 and 300, preferably between 20 and 150. This means that when the repeat number n is less than 5, the proportion of the polysiloxane bond in the amphoteric thus obtained the urethane resin becomes too low, and a sufficient effect on stiffness, combability and the like, which could initially be obtained by the introduction of a polysiloxane bond, may not be achieved. On the other hand, when the repeat number n is greater than 300, a high hydrophobic characteristic impairs compatibility with other materials and makes interaction with them more difficult. Further, since the polymer thus obtained becomes too hydrophobic, there is a fear that there will be no adhesion after combination.

The specific polysiloxane compound of component (C) is not specifically limited, and any compound with active hydrogen and a polysiloxane bond in the molecule can be used. Examples include a compound with OH groups at both ends, a compound with NH ₂ groups at both ends, a compound with OH group at one end, and a compound with NH ₂ group at one end. When a compound having OH groups at both ends or a compound having NH ₂ groups at both ends is used, an amphoteric urethane resin with a polysiloxane bond as the backbone can be obtained. When a compound having an OH group at one end or a compound having an NH ₂ group at one end is used, an amphoteric urethane resin with a polysiloxane bond as the side chain or at the end can be obtained.

Examples of said polysiloxane compound [component (C)] may include combinations, each of which has a distinct number of carbons in the alkyl groups combined with Si of each siloxane bond. Specific examples of polydialkylsiloxanediol include polydimethylsiloxanediol and polymethylethylsiloxanediol. Examples of polydialkylsiloxane monoolol include polydimethylsiloxane monoolol and polymethyl ethyl siloxane monoolol. Examples of polydialkylsiloxane diamine include polymethylethylsiloxane diamine. Examples of polydialkylsiloxane monoamine include polymethylethylsiloxane monoamine.

The compound [component (D)] with active hydrogen and a carboxyl group is not specifically limited, and it can be any compound that contains at least one active hydrogen and at least one carboxyl group in its molecule. Examples include dimethylolpropionic acid (DMPA), dimethylolbutanoic acid and polycaprolactonediol having a carboxyl group. These compounds can be used either individually or in combination.

The compound [component (E)] with active hydrogen and a tertiary amino group is not specifically limited, and it can be any compound that contains in its molecule at least one active hydrogen and at least one tertiary amino group. Examples include a N-alkyldialkanolamine compound such as N-methyldiethanolamine and dimethylaminoethanol. These compounds can be used either individually or in combination.

When preparing a prepolymer containing an isocyanate group by using each of the above components, it is desirable to use a chain extender. The use of a chain extender makes it possible to coordinate different characteristics of the amphoteric urethane resin obtained as a final product. The chain extension has no specific limitations. Examples include low molecular weight polyols, including glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, spiroglycol, bis (hydroxyethoxy) benzene and xylene glycol, and triols, such as trimethylolpropane and glycerin. Examples of amines include methylene (bis-o-chloroaniline).

Upon receipt of the amphoteric urethane resin, solvents may be used if necessary. For example, it is especially desirable to use solvents that can dissolve both the starting material and the resulting polyurethane. Examples include amides such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate, as well as cellosolve acetate and cellosolve ether. In addition, in the preparation of an amphoteric urethane resin, a polymerization catalyst commonly known in the field of polyurethanes can be used. Examples include a tertiary amine catalyst and an organometallic catalyst. As the tertiary amine catalyst, [2,2,2] -diazabicyclooctane (DABCO), tetramethylenediamine, N-methylmorpholine, diazabicyclooundecene (DBU) can be used. Examples of the organometallic catalyst include dibutyltin dilaurate.

Preferably, the ratio of the carboxyl group to the tertiary amino group (the ratio of the number of both groups) in the amphoteric urethane resin obtained using the above components corresponds to: carboxyl group / tertiary amino group = 1 / 10-10 / 1. Namely, when the ratio is within the specified limit, the composition can be endowed with excellent resistance to washing.

In addition, any other ingredients commonly used in cosmetics can be added to the resin-based cosmetic composition, other than a specific amphoteric urethane resin, such as pigment, colorant, coloring agent, flavoring agent, surfactant, moisturizer, preservative, antiseptic, disinfectant and antioxidant.

The resin-based cosmetic composition of the present invention is used, for example, for hair fixers, such as mousse for fixing hair, gel for fixing hair, hair fixer in the form of a spray, hair fixer in the form of a spray in a spray, as a conditioning agent for shaving cream , a film-forming agent, such as skin care lotion, powder cream, eyeliner and manicure, and as a viscosity regulator. In particular, the resin-based cosmetic composition is useful as a hair fixative.

Preferably, the particular amphoteric urethane resin is used in accordance with the above purpose after it is converted to a dispersion by dispersion in water or transferred to an aqueous solution by dissolution in water, respectively. In this case, it is preferable to disperse the amphoteric urethane resin in water containing an aliphatic polyamine. Moreover, when the polymer interacts with an aliphatic polyamine in the form of a polymer dispersed in water by the controlled polymerization reaction with an excess of isocyanate groups, the NH groups and the NH ₂ groups _{of the} aliphatic polyamide quickly interact with isocyanate groups, forming urea bonds in water, which leads to an acceleration of polymerization. Aliphatic polyamine is not specifically limited. Examples include triethylamine, ethylenediamine, propylene diamine, piperazine and diethylene triamine. In addition, a silane binder may be added to the dispersion of amphoteric urethane resin to increase adhesion to other base materials. In addition, various antibacterial agents and antifungal agents can be added to create storage stability.

The following is a description of examples and comparative examples.

Example 1

70 g of isophorondiisocyanate (IPDI), 80 g of diethylene glycol adipate (DEGA), molecular weight 2000, 20 g adduct of bisphenol A with ethylene oxide (Newpol BP3P, from Sanyo Chemical Industries Ltd., molecular weight 400), 26 g of polydimethylsiloxanediol (type of compound with OH groups at both ends, molecular weight 2000) and 16.9 g of dimethylolpropionic acid (DMPA) are placed in a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and a partial reflux condenser. Then added 50 g of ethyl acetate as a solvent and 0.02 g of dibutyltin dilaurate (DBTDL) as a catalyst, heated to 80 ° C in an oil bath, allowing to interact for 4 hours. Thereafter, 5.6 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were added and allowed to react at 80 ° C. for 2 hours to obtain a solution of a polyurethane prepolymer where NCO groups remained. Then, the polyurethane prepolymer thus obtained, where the NCO groups remain, is cooled to 50 ° C., 600 g of water containing 12.7 g of triethylamine and 3.3 g of diethanolamine are added while stirring at high speed to disperse, and then polymerized by reaction chain elongation at 50 ° C for 3 hours. Ethyl acetate is separated from the dispersion thus obtained, and a dispersion of an amphoteric urethane resin containing in its structure a dimethylsiloxane chain, substantially free of solvent, is obtained.

Example 2

70 g of isophorondiisocyanate (IPDI), 56 g of polytetraoxymethylene glycol (PTMG), molecular weight 2000, 20 g adduct of bisphenol A with ethylene oxide (ADK polyether BPX21 from Asahi Denka Koduo KK, molecular weight 400), 26 g of polyethylene glycol (PEG), molecular weight 26 g of polydimethylsiloxanediol (type of compound with OH groups at both ends, molecular weight 2000) and 16.9 g of dimethylolpropionic acid (DMPA) are placed in a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and a partial reflux condenser. Then added 50 g of ethyl acetate as a solvent and 0.02 g of dibutyltin dilaurate (DBTDL) as a catalyst, heated to 80 ° C in an oil bath, allowing to interact for 4 hours. Thereafter, 5.6 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were added and allowed to react at 80 ° C. for 2 hours to obtain a solution of a polyurethane prepolymer where NCO groups remained. Then, the polyurethane prepolymer thus obtained, where the NCO groups remain, is cooled to 50 ° C., 600 g of water containing 12.7 g of triethylamine and 3.3 g of diethanolamine are added while stirring at high speed to disperse, and then polymerized by reaction chain elongation at 50 ° C for 3 hours. Ethyl acetate is separated from the dispersion thus obtained, and a dispersion of an amphoteric urethane resin containing in its structure a dimethylsiloxane chain, substantially free of solvent, is obtained.

Example 3

70 g of isophorondiisocyanate (IPDI), 70 g of diethylene glycol adipate (DEGA), a molecular weight of 2000, 26 g of polydimethylsiloxanediol (a type of compound with an OH group at one end, a molecular weight of 2000) and 16.9 g of dimethylolpropionic acid (DMPA) were placed in a four-necked flask, equipped with a stirrer, a thermometer, a tube for introducing nitrogen and a partial condenser of hot irrigation. Then added 50 g of ethyl acetate as a solvent and 0.02 g of dibutyltin dilaurate (DBTDL) as a catalyst, heated to 80 ° C in an oil bath, allowing to interact for 4 hours. Thereafter, 5.6 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were added and allowed to react at 80 ° C. for 2 hours to obtain a solution of a polyurethane prepolymer where NCO groups remained. Then, the polyurethane prepolymer thus obtained, where the NCO groups remain, is cooled to 50 ° C., 600 g of water containing 18.4 g of triethanolamine and 6.6 g of diethanolamine are added with stirring at high speed to disperse, and then polymerized by reaction chain elongation at 50 ° C for 3 hours. Ethyl acetate is separated from the dispersion thus obtained, and a dispersion of an amphoteric urethane resin, mainly not containing an organic solvent, and having in its structure a dimethylsiloxane chain as a side chain, is obtained.

Example 4

70 g of isophorondiisocyanate (IPDI), 80 g of diethylene glycol adipate (DEGA), molecular weight 2000, 20 g adduct of bisphenol A with ethylene oxide (Newpol BP3P, from Sanyo Chemical Industries Ltd., molecular weight 400), 10 g of polydimethylsiloxanediol (type of compound with OH groups at both ends, molecular weight 800) and 16.9 g of dimethylolpropionic acid (DMPA) are placed in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a partial hot irrigation condenser. Then added 50 g of ethyl acetate as a solvent and 0.02 g of dibutyltin dilaurate (DBTDL) as a catalyst, heated to 80 ° C in an oil bath, allowing to interact for 4 hours. Thereafter, 5.6 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were added and allowed to react at 80 ° C. for 2 hours to obtain a solution of a polyurethane prepolymer where NCO groups remained. Then, the polyurethane prepolymer thus obtained, where the NCO groups remain, is cooled to 50 ° C., 600 g of water containing 12.7 g of triethylamine and 3.3 g of diethanolamine are added while stirring at high speed to disperse, and then polymerized by reaction chain elongation at 50 ° C for 3 hours. Ethyl acetate is separated from the dispersion thus obtained, and a dispersion of an amphoteric urethane resin containing in its structure a dimethylsiloxane chain, substantially free of solvent, is obtained.

Example 5

70 g of isophorondiisocyanate (IPDI), 80 g of diethylene glycol adipate (DEGA, molecular weight 2000), 20 g adduct of bisphenol A with ethylene oxide (Newpol BP3P, from Sanyo Chemical Industries Ltd., molecular weight 400), 26 g of polydimethylsiloxanediol (type of compound with OH groups at both ends, molecular weight 5000) and 16.9 g of dimethylolpropionic acid (DMPA) are placed in a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and a partial hot irrigation condenser. Then added 50 g of ethyl acetate as a solvent and 0.02 g of dibutyltin dilaurate (DBTDL) as a catalyst, heated to 80 ° C in an oil bath, allowing to interact for 4 hours. Thereafter, 5.6 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were added and allowed to react at 80 ° C. for 2 hours to obtain a solution of a polyurethane prepolymer where NCO groups remained. Then, the polyurethane prepolymer thus obtained, where the NCO groups remain, is cooled to 50 °, 600 g of water containing 12.7 g of triethylamine and 3.3 g of diethanolamine are added with stirring at high speed to disperse, and then polymerized by extension reaction chain at 50 ° C for 3 hours. Ethyl acetate is separated from the dispersion thus obtained, and a dispersion of an amphoteric urethane resin containing in its structure a dimethylsiloxane chain, substantially free of solvent, is obtained.

Example 6

70 g of isophorondiisocyanate (IPDI), 80 g of diethylene glycol adipate (DEGA, molecular weight 2000), 20 g adduct of bisphenol A with ethylene oxide (Newpol BP3P, from Sanyo Chemical Industries Ltd., molecular weight 400), 52 g of polydialkylsiloxanediol (type of compound with OH groups at both ends, the length of the alkyl chain = 8-10, molecular weight 5000) and 16.9 g of dimethylolpropionic acid (DMPA) are placed in a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and a partial reflux condenser. Then add 50 g of ethyl acetate as a solvent and 0.02 g of dibutyltin dilaurate (DBTDL) as a catalyst, heated to 80 ° C in an oil bath, allowing to interact for 4 hours. Thereafter, 5.6 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were added and allowed to react at 80 ° C. for 2 hours to obtain a solution of a polyurethane prepolymer where NCO groups remained. Then, the polyurethane prepolymer thus obtained, where the NCO groups remain, is cooled to 50 ° C., 600 g of water containing 12.7 g of triethylamine and 3.3 g of diethanolamine are added with stirring at high speed to disperse, and then polymerized by reaction chain elongation ^at 50 ° C within 3 hours. Ethyl acetate is separated from the dispersion thus obtained, and a dispersion of an amphoteric urethane resin containing in its structure a dimethylsiloxane chain, substantially free of solvent, is obtained.

Comparative Example 1

70 g of isophorondiisocyanate (IPDI), 106 g of diethylene glycol adipate (DEGA, molecular weight 2000), 20 g of adduct bisphenol A with ethylene oxide (Newpol BP3P, from Sanyo Chemical Industries Ltd., molecular weight 400) and 16.9 g of dimethylolpropionic acid (DMPA) placed in a four-necked flask equipped with a stirrer, thermometer, a tube for introducing nitrogen and a partial condenser of hot irrigation. Then added 50 g of ethyl acetate as a solvent and 0.02 g of dibutyltin dilaurate (DBTDL) as a catalyst, heated to 80 ° C in an oil bath, allowing to interact for 4 hours. Thereafter, 5.6 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were added and allowed to react at 80 ° C. for 2 hours to obtain a solution of a polyurethane prepolymer where NCO groups remained. Then, the polyurethane prepolymer thus obtained, where the NCO groups remain, is cooled to 50 ° C., 600 g of water containing 12.7 g of triethylamine and 3.3 g of diethanolamine are added while stirring at high speed to disperse, and then polymerized by reaction chain elongation at 50 ° C for 3 hours. Ethyl acetate is separated from the dispersion thus obtained, and a dispersion of an amphoteric urethane resin is obtained, essentially not including a solvent.

Reference Example 2

70 g of isophorondiisocyanate (IPDI), 106 g of diethylene glycol adipate (DEGA, molecular weight 2000), 20 g of adduct bisphenol A with ethylene oxide (Newpol BP3P, from Sanyo Chemical Industries Ltd., molecular weight 400) and 16.9 g of dimethylolpropionic acid (DMPA) placed in a four-necked flask equipped with a stirrer, thermometer, a tube for introducing nitrogen and a partial condenser of hot irrigation. Then, 50 g of ethyl acetate as a solvent and 0.02 g of dibutyltin dilaurate (DBTDL) as a catalyst are added, heated to 80 ° C in an oil bath, allowing to interact for 6 hours, obtaining a solution of a polyurethane prepolymer where NCO groups remain. Then the polyurethane prepolymer thus obtained, where the NCO groups remain, is cooled to 50 ° C, 600 g of water containing 12.7 g of triethylamine and 3.3 g of diethanolamine are added, carrying out a chain extension reaction with stirring at high speed at 50 ° C. within 3 hours. Ethyl acetate is separated from the dispersion thus obtained, and a dispersion of amphoteric urethane resin is obtained which is substantially free of solvent.

Reference Example 3

65 g of dimethylsilicone emulsion FZ-4160 (from Nippon Unicar Co. Ltd., active ingredient 45%) was added to a dispersion of amphoteric urethane resin obtained in comparative example 1 to obtain a dispersion of amphoteric urethane resin with polydimethylsiloxane chemically unrelated to amphoteric urethane resin (i.e., not covalently linked to it).

Mousses for hair fixation a-i are obtained using the dispersions thus obtained from the examples and comparative examples with the following ratios of the components of the mixtures.

Mousse for fixing hair a.

The ingredients shown in table 1 are mixed in the proportions indicated in the same table and mixed until the resulting mixture becomes homogeneous, obtaining component X. Then, component Y indicated in the same table is added to component X, obtaining mousse for fixing hair a.

Mousses for fixing hair b, c, d, e and f

Instead of the dispersion obtained in Example 1, for the component X shown in Table 1, each of the dispersions in Examples 2, 3, 4, 5, and 6 is used. Other than this, mousses for fixing hair b, c, d, e, and f receive in the same way as a mousse for fixing hair a.

Mousses for fixing hair g, h and i

Instead of the dispersion obtained in Example 1 shown in Table 1, each of the dispersions in comparative examples 1, 2 and 3 is used. Other than this, mousses for fixing hair g, h and i are obtained in the same way as mousse for fixing hair a.

The “curl retention” and “shampoo wash-off” of the a-i hair fixation mousses thus obtained are evaluated in accordance with the standards indicated below. The results are shown in table 2.

Curl holding

0.6 g of the thus obtained mousse for fixing hair is applied to a separate strand of black natural hair (15 cm long, weight 3 g), respectively, and for each of the examples and comparative examples, 5 samples are obtained and dried at 50 ° C in overnight. Then the dried samples are suspended on graduated boards and placed in a thermohydrostat, where the temperature is 30 ° C and humidity 90% RH. Measure each length (a) of curls at the beginning and each length (b) of curls after 5 hours and evaluate each amount of curl retention according to the above formula. Curl retention close to 100% indicates that curl retention is stronger. In the formula 1, L means the length of the fully elongated sample.

Formula 1

Curl Hold (%) = {(L-b), (L-a)} × 100

Shampoo washability

0.6 g of the thus obtained mousse for fixing hair is applied to a separate strand of black natural hair (15 cm long, weight 3 g), respectively, and the sample is dried at room temperature to obtain a sample of combed hair. Then each sample is slightly dissolved in warm water at 40 ° C for 30 seconds, 0.4 g of a 10% solution of shampoo is applied to it and washed for 30 seconds. After that, each sample is washed with warm water at 40 ° C to rinse everything, and then dried, as required, at 50 ° C. The sample thus obtained is evaluated for stiffness. Evaluation shows that the dried sample is not hard, due to its excellent washability with shampoo; that the dried sample is generally not stiff due to good shampoo washability; and shows insufficient washability with shampoo.

The external state, stiffness, shine, feeling of touch, combing and anti-delamination action for mousses for fixing hair a-i obtained in this way were also evaluated. 0.8 g of the thus obtained mousse for fixing hair is applied to a separate strand of black natural hair (25 cm long, weight 5 g), respectively, and the hair sample is dried at room temperature. A hair sample is evaluated in accordance with the standards given below. The results are also shown in table 2.

External condition

Shows the absence of tattered hair created on the sample after drying, and excellent elasticity; shows that elasticity is good; and shows that the external condition has slightly worsened.

Rigidity

Shows the absence of tattered hair created on the sample after drying, and excellent stiffness; shows rigidity is good; and shows that the stiffness is a little insufficient.

Shine

Shows that the brightness and gloss of the sample after drying are excellent; shows that the gloss is good; and shows that the gloss is slightly insufficient.

Touch feeling

Indicates that the sample, after drying, is smooth to the touch or very pleasant to the touch; shows a good feeling to the touch; and shows a slightly rude feeling to the touch.

Combable

It shows that the combability of the sample after drying is excellent; shows that combability is good; shows that combing is slightly difficult; and shows that combability has worsened.

Anti-delamination action

Indicates that delamination of the specimen after 10-fold combing is not caused; shows that almost no delamination of the sample is caused; indicates that slight delamination is being caused.

From the results of table 2 it is seen that mousses for a-f hair fixation are excellent in all properties: retention of curls, rinse off with shampoo, the appearance of the hair, stiffness, shine, feel to the touch, combability and anti-delamination effect. It was also found that mousses for fixing hair af additionally surpass mousse for fixing hair g, which uses an amphoteric urethane resin that does not have a dimethylsiloxane chain in its structure, in shine, touch, combability and anti-delamination action, because in mousses for AF hair fixation uses an amphoteric urethane resin with a dimethylsiloxane chain in its structure. In addition, it was found that the mousse for fixing hair b is excellent in rinse off with shampoo, ensuring the external state and rigidity due to the presence of an ethylene oxide chain as a nonionic hydrophilic component in the structure of amphoteric urethane resin.

On the other hand, it was found that mousse for fixing hair g is good from the point of view of holding the curl, rinse off with shampoo, appearance, stiffness due to gloss, touch feeling, combability and anti-delamination action, since the amphoteric urethane resin used in it does not have in its structure dimethylsiloxane chain. In addition, mousse for fixing hair h is much worse in terms of combability, since it uses anionic urethane resin, and also much worse in other properties, except for stiffness. In addition, it was found that the mousse for fixing hair i is improved in. with respect to shine, touch, combability and anti-delamination action compared to hair fixation mousses g and h, since hair dispersion mousse i uses a dispersion containing amphoteric urethane resin and dimethylsiloxane, but worse than af hair fixation mousses properties because the above dimethylsiloxane is not chemically bound to the amphoteric urethane resin.

Then gels were obtained for fixing hair a-i using each of the dispersions of the examples and comparative examples in accordance with the following proportions.

Gel for fixing hair a

The ingredients shown in table 3 are mixed in the proportions indicated in the same table and mixed until a viscous gel is formed to obtain component X. Then, the ingredients shown in table 3 are mixed in the proportions indicated in the same table yielding component Y. Component Y thus obtained is added to component X thus obtained and mixed until the mixture becomes homogeneous, obtaining a gel for fixing the hair a.

Gels for fixing hair b, c, d, e and f

Instead of the dispersion obtained in Example 1, each of the dispersions of Examples 2, 3, 4, 5, and 6 is used for the Y component shown in Table 3. Other than this, hair fixation gels b, c, d, e, and f receive in the same way as a gel for fixing hair a.

Gels for fixing hair g, h and i

Instead of the dispersion of Example 1 for component Y shown in Table 3, each of the dispersions of Comparative Examples 1, 2 and 3 is used. Other than this, gels for fixing hair g, h and i are obtained in the same way as the gel for fixing hair a.

Curl retention, shampoo rinse, appearance, stiffness, shine, touch, comb and anti-delamination effects provided by the a-i hair-fixation gels thus obtained are evaluated in accordance with the standards set forth above for them. In general, the same results were obtained as in the case of using mousses to fix hair a-i.

In addition, hair fixers were obtained in the form of a-i spray using dispersions of the examples and comparative examples with the following ratios of the components of the mixtures.

Hair lock in the form of a spray a

The ingredients shown in table 4 are mixed in the proportions indicated in the same table and mixed until the mixture becomes homogeneous, obtaining component X. Then, the ingredients shown in table 4 are mixed in the proportions indicated in the same table to obtain the component Y. The component Y thus obtained is added to component X to obtain a hair fixer in the form of a spray a.

Hair fixers in the form of a spray b, c, d, e and. f

Instead of the dispersion of Example 1 for component X shown in Table 4, each of the dispersions of Examples 2, 3, 4, 5, and 6 is used. Other than this, hair fixers in the form of a spray b, c, d, e, and f are obtained by in the same way as the hair fixer in the form of a spray a.

Hair clips in the form of a spray g, h and i.

Instead of the dispersion of Example 1 for component X shown in Table 4, each of the dispersions of Comparative Examples 1, 2 and 3 is used. Other than this, hair fixers in the form of a spray g, h and i are obtained in the same way as a hair fixer in the form of a spray a.

Curl retention, shampoo rinse, appearance, stiffness, shine, touch, comb and anti-delamination action provided by hair fixers obtained in this way in the form of a-i spray are evaluated in accordance with the standards mentioned above. In general, the same results were obtained as in the case of using mousses to fix hair a-i.

In addition, hair fixers were obtained in the form of a spray in the spray a-i using dispersions according to the examples and comparative examples with the following ratios of the components of the mixtures.

Hair clip in the form of a spray in a spray bottle a.

The ingredients shown in table 5 are mixed in the proportions indicated in the same table and mixed until the mixture becomes homogeneous, getting a hair lock in the form of a spray in a spray bottle a.

Hair clips in the form of a spray in the spray b, c, d, e and f

Instead of the dispersion of Example 1 indicated in Table 5, each of the dispersions of Examples 2, 3, 4, 5, and 6 is used. Other than this, hair fixers in the form of a spray in the spray b, c, d, e, and f get the same in the way that the hair fixer in the form of a spray in the spray gun a.

Hair clips in the form of a spray in the spray gun g, h and i

Instead of the dispersion of Example 1 shown in Table 5, each of the dispersions of Comparative Examples 1, 2 and 3 is used. Other than this, hair fixers in the form of a spray in the spray gun g, h and i are obtained in the same manner as the hair fixer in spray form a.

Curl retention, shampoo rinse, appearance, stiffness, gloss, touch feeling, combability and anti-delamination action provided by the thus obtained hair fixers in the form of a spray in the spray a-i are evaluated in accordance with the standards specified above for them. In general, the same results were obtained as in the case of using mousses to fix hair a-i.

In addition, the resin-based cosmetic compositions of the present invention can be used as a conditioning agent for shaving cream, a film-forming agent, such as skin care lotion, emulsified base, cream powder, eyeliner and manicure, as shown below.

Shaving Cream Conditioner

The ingredients shown in table 6 are mixed in the proportions indicated in the same table and heated to 80 ° C to obtain component X. After that, the ingredients shown in the same table are mixed in the proportions indicated in the same table and heated to 80 ° C, obtaining component Y. Then component X and component Y are mixed at 80 ° C, the resulting mixture is cooled to 40 ° C and antiseptic and flavoring agent are added in suitable amounts to obtain the required conditioning agent for shaving cream.

Skin care lotion

The ingredients shown in table 7 are mixed in the proportions indicated in the same table and heated to 80 ° C to obtain component X. After that, the ingredients listed in the same table are mixed in the proportions indicated in the same table and heated to 80 ° C, obtaining component Y. Then component X and component Y are mixed and stirred at 80 ° C for 30 minutes. To the resulting mixture was added 20.00 wt.% 2% aqueous solution of Carbopol 940 and stirred until the mixture became homogeneous. After that, it is cooled to 40 ° C, obtaining the required skin care lotion.

Emulsified base

(1) Obtaining pigment

The ingredients shown in table 8 are mixed in the proportions indicated in the same table, and the resulting mixture is ground into powder on a grinding machine, obtaining a pigment.

(2) Preparation of the aqueous phase

After heating deionized water to 70 ° C, bentonite is added to it and left to swell. Then, a previously prepared dispersion is added to the mixture, where sodium carboxymethyl cellulose is dispersed in propylene glycol to form a solution. Then, triethanolamine and methyl paraben are added to the mixture to dissolve, to obtain the aqueous phase.

(3) Obtaining an oil phase

After mixing the ingredients indicated in table 8 in the proportions indicated in the same table, the resulting mixture is heated to 70-80 ° C until dissolved, thereby obtaining an oil phase.

(4) Obtaining pigment dispersion

After the above pigment was added to the above aqueous phase with stirring, the resulting mixture was passed through a colloidal mill to obtain a pigment dispersion.

(5) Emulsification

After heating the pigment dispersion and the oil phase to 75 ° C and 80 ° C, respectively, the oil phase is added to the pigment dispersion with stirring. Then the resulting mixture is cooled and, when the temperature reaches 45 ° C, flavor is added. The resulting mixture was further cooled with stirring to room temperature, obtaining the desired emulsified base.

Cream powder

(1) Obtaining pigment

The ingredients shown in table 9 are mixed in the proportions indicated in the same table, and the resulting mixture is ground into powder on a grinding machine, obtaining a pigment.

(2) Preparation of the aqueous phase

The ingredients shown in table 9 are mixed in the proportions indicated in the same table, obtaining the aqueous phase.

(3) Obtaining an oil phase

After adding the ingredients indicated in table 9 in the proportions indicated in the same table, the resulting mixture was heated to 70-80 ° C until dissolved, thus obtaining an oil phase.

(4) Obtaining pigment dispersion

After the above pigment was added to the above aqueous phase with stirring, the resulting mixture was passed through a colloidal mill to obtain a pigment dispersion.

(5) Emulsification

After heating the pigment dispersion and the oil phase to 75 ° C and 80 ° C, respectively, the oil phase is added to the pigment dispersion with stirring. Then the resulting mixture is cooled and, when the temperature reaches 50 ° C, add flavoring. The resulting mixture was further cooled with stirring to room temperature, obtaining the desired emulsified base.

Eyeliner

After mixing the ingredients shown in table 10, in the proportions indicated in the same table, the resulting mixture is heated to 70-80 ° C until dissolved, obtaining the oil phase. Then, the ingredients shown in table 10 are mixed in the proportions indicated in the same table to obtain the aqueous phase. After that, the heated aqueous phase is added with stirring to the oil phase for emulsification. A dispersion of pre-soaked bentonite, a pigment and a flavor are added to the emulsion thus obtained. The resulting mixture is passed through a colloidal mill for dispersion and cooling, obtaining the desired composition for eyeliner.

Manicure

After dispersing the pigment in the water passed through the ion exchanger, the dispersion of Example 1 and the other ingredients listed in Table 11 are added to it in the proportions indicated in the same table. The resulting mixture is stirred with shaking until it becomes homogeneous, and finally deaerated, obtaining the desired tool for manicure.

SUMMARY OF THE INVENTION

As indicated above, the resin-based cosmetic composition of the present invention consists mainly of an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule. So, the use of urethane resin as the main structure of the base resin [in hair care products] makes it possible, due to the elasticity and hardness of the urethane resin, to combine the stiffness property with good external hair condition, combing and anti-delamination action - characteristics that are inherently contradictory . In addition, when using an amphoteric urethane resin having a carboxyl group and a tertiary amino group, it becomes possible to obtain a hair retainer with exceptional water resistance to neutral water, since the carboxyl group and tertiary amino group are ion-bound and also excellently rinse-off with shampoos; since the amphoteric urethane resin has a cationic tertiary amino group in its molecular chain that interacts with the negatively charged surface of the hair, greater adhesion can be obtained compared to the known anionic urethane resin. In addition, an additional improvement in gloss, touch, combability and anti-delamination action can be obtained by introducing a polysiloxane bond into the structure of an amphoteric urethane resin.

Claims (5)

1. A cosmetic composition based on a resin, consisting mainly of an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule, the amphoteric urethane resin having a polysiloxane bond in its structure, wherein the amphoteric urethane resin is obtained by the interaction of the following components (A) - ( D) with an excess of isocyanate groups to obtain a prepolymer containing isocyanate groups, and the interaction of the prepolymer with the following component (E): (A) a polyol compound; (B) a polyisocyanate compound; (C) a polysiloxane compound with active hydrogen; (D) a compound with active hydrogen and a carboxyl group; (E) a compound with active hydrogen and a tertiary amino group, or by reacting the following components (A), (B), (C) and (E) with an excess of isocyanate groups to obtain a prepolymer containing isocyanate groups, and reacting the prepolymer with the following component (D ): (A) a polyol as one compound; (B) a polyisocyanate compound; (C) a polysiloxane compound with active hydrogen; (D) a compound with active hydrogen and a carboxyl group; (E) a compound with active hydrogen and a tertiary amino group, and water. 2. The resin-based cosmetic composition according to claim 1, wherein the resin-based cosmetic composition is used as a hair fixative. 3. The resin-based cosmetic composition according to claim 1 or 2, wherein the amphoteric urethane resin is dispersed or dissolved in water. 4. A cosmetic product containing a resin-based cosmetic composition according to any one of claims 1 to 3. 5. The cosmetic product according to claim 4, which is at least one selected from the group including mousse for fixing hair, gel for fixing hair, hair lock in the form of a spray, hair lock in the form of a spray in a spray, conditioning agent cream shaving and film forming agent.