COMPOSITION OF COSMETIC AND COSMETIC RESIN USING THEREOF DESCRIPTION OF THE INVENTION The present invention relates to a cosmetic resin composition which is essentially comprised of amphoteric urethane resin and a cosmetic which uses such a resin composition, and particularly, a composition of cosmetic resin used for a skin care product, a hair care product and the like as a hair fixative, a film forming agent, a conditioning agent, a viscosity control agent and the like, and a cosmetic which uses the same. Conventionally, a cationic acrylic resin, an anionic acrylic resin, an anionic / cationic or amphoteric acrylic resin, a nonionic polyvinyl pyrrolidone resin and the like as used as a base resin of a hair fixative. When such a resin is used as a base resin, it is left to the rigid hair, resulting in a good fixing property (stiffness), but the feeling to the touch and the combing ability are lower and peeling may also occur. On the other hand, when the sense of touch and combing ability do not first arrive, not only the fixing property becomes insufficient, but also there may be problems in rigidity and the like. In this way, it is difficult for the resin
Conventional base satisfies all the properties required for fixing hair, such as stiffness, tactile sense, combing ability and anti-scaling property. Then, an application of an anionic urethane resin as a base resin for a hair fixative is proposed as seen in Japanese Provisional Publication TKOKKAIHEI 6-321741. When such anionic urethane resin is used, a hair fixative can be prepared which has good stiffness, feel and anti-peeling properties, which are inconsistent with each other. In this view, a hair fixer which uses such a urethane resin is superior to a hair fixative which uses the acrylic resin mentioned above. However, when the anionic urethane resin is used, the ability to remove the lower shampoo may be a problem. Accordingly, it is an object of the present invention to provide a cosmetic resin composition for the preparation of a hair fixative which has all the properties of rigidity, shampoo removal ability, tactile sense, gloss, combing ability and propriety. of anti-peeling and to provide a cosmetic which uses such a cosmetic resin composition. According to a first aspect of the present invention to achieve the object described above, a cosmetic resin composition is provided which
consists essentially of an amphoteric urethane resin which has a carboxyl group and a tertiary amino group in a molecule thereof, the amphoteric urethane resin which has a polysiloxane bond in its structure. According to a second aspect of the present invention, cosmetics are provided which use the cosmetic resin composition. The inventors of the present invention found that a hair fixative which has stiffness, tactile sense, combing ability, anti-scaling property and the like can be obtained by using an amphoteric urethane resin which has a carboxyl group and a tertiary amino group in a molecule thereof as a base resin and a patent application of a resin composition consisting essentially of the amphoteric urethane resin was filed (Japanese Patent Application No. TOKUGANHEI 10-27595). The improvement of each property when the amphoteric resin is used is due to the following reason. That is, by using the urethane resin as a main skeleton of a base resin makes it possible for the stiffness to be compatible with the tactile sense, combing ability and anti-peeling property, which are originally contrary to each other, due to the elasticity and stiffness of the urethane resin. In addition, by using the amphoteric urethane resin which has a carboxyl group and a tertiary amino group,
it becomes possible to prepare a superior water-proof hair fixative against neutral water since the carboxyl group and the tertiary amino group are ion-bonded, and also superior in shampoo removal capacity since the ion bond is cut by the shampoo. In addition, since the amphoteric urethane resin has a cationic tertiary amino group, which interacts with a negatively charged hair surface, in its molecular chains, better adhesion can be obtained compared to a conventional anionic urethane resin. Thus, in the case where the amphoteric urethane resin is used as a base resin, the shampoo removal capacity can be improved compared to the case where conventional anionic urethane resin is used. However, to obtain sufficient shampoo removal capacity, there are composition restrictions, to some degree, such as adjustment of the molecular weight of the amphoteric urethane resin, choice of urethane skeleton or the like, which may be a a low degree of freedom when designing physical properties, such as hardness, flexibility or the like, important for the polymer to be used for a hair fixative. Next, the inventors have made inquiries about the composition of the resin which essentially consists of the amphoteric urethane resin. As a result, it has been found that the improvement
The further reduction in shampoo removal capacity can be obtained by the amphoteric urethane resin even with a higher molecular weight or a low vitreous transition temperature by introducing a structural unit derived from an ethylene oxide. In the structure of the amphoteric urethane resin as a nonionic hydrophilic component, and the hardness and elasticity of the base resin which contribute to the tactile sense or stiffness required for a decay fixative, can be controlled extensively. In this way, the above has been achieved in the present invention. The present invention will be described later in the present by the form of the modalities thereof. The composition of the cosmetic resin of the present invention consists essentially of an amphoteric resin which has a carboxyl group and a tertiary amino group in a molecule thereof. The most characteristic point of the present invention is that the amphoteric urethane resin has a structural unit derived from an ethylene oxide in its structure. In addition, the phrase x "consisting essentially of an amphoteric urethane resin" generally means the preparation of the cosmetic resin composition of interest by adding other components to the amphoteric urethane resin, however it includes the case where the cosmetic resin composition consists only of the amphoteric urethane resin.
The amphoteric urethane resin mentioned above which has a structural unit derived from an ethylene oxide can be obtained, for example, by reacting a polyol compound ([component (A)], a polyisocyanate compound [component (B)], a polyethylene oxide derivative [component (C)] which has an active hydrogen and a compound [D () component which has an active hydrogen and a carboxyl group with each other in excess of the isocyanate groups to thereby produce a prepolymer which contains an isocyanate group and reacts the prepolymer with a compound [component (E)] which has an active hydrogen and a tertiary amino group.Alternatively, the amphoteric urethane resin which has a structural unit derived the order of the reaction of the component (D) by the component (E) in excess of the isocyanate groups to produce a prepolymer which contains an isocyanate group and react the prepolymer with the comp (D) The amphoteric urethane resin of interest can be produced more easily and more safely by such methods than the conventional method. further, if both the component (D) and the component (E) are reacted simultaneously with each other with the components (A) to (C) in the above methods, a carboxyl group of the component (D) and a tertiary amino group of the component ( E) initially form a salt which becomes insoluble to the reaction system and a reaction with the isocyanate compound can not occur even in the presence of an OH group. As a result, the amphoteric urethane resin of interest; it can not be produced. That is, as mentioned above, the amphoteric urethane resin which has a structural unit derived from an ethylene oxide can be produced by first reacting one of the component (D) and the component (E) together with the components (A) < ? (C) and then reacting the other component (D) or (E). The polyol compound of component (A) is not specifically limited, but any of the polyol compounds are generally used to produce the polyurethane. Examples of the polyol compound include the polyester polyol, polyether polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, polyolefin polyol, polyacrylic polyol ester. These can be used either alone or in combination thereof. Among all, polyester polyol and polyether polyol are especially preferred. Examples of the polyester polyol include the products obtained by condensation polymerization 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 of the polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol,
i,?,?, and 1, 6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, spiroglycol, trimethylolpropane and like, and products obtained by addition polymerization of open e ring cyclics such as ethylene oxide, propylene oxide oxetane and tetrahydrofuran in water, polyol, phenols such as bisphenol A, hydrogenated phenols, primary amines and secondary amines. Examples of such products include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene glycol and products (both a block copolymer or a random copolymer in case of a copolymer) obtained by open ring polymerization lactones. In addition, examples of polye polyol can be obtained by polymerizing by addition of cyclic e open rings such as ethylene oxide, propylene oxide oxetane and tetrahydrofuran in water, polyhydric alcohols to synize polyester polyol, phenols such as bisphenol A, hydrogenated phenols, primary amines and secondary amines. Examples of such products include polyoxyethylene glycol, polyoxypropylene polyol, polyoxytetramethyl polyol and products (both a blocked copolymer or a random copolymer in case of a copolymer) obtained by addition polymerization of open ring of at least one propylene oxide and oxide of ethylene in bisphenol A.
polyisocyanate compound of component (B) is not specifically limited. Examples eof include organic diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds and aromatic diisocyanate compounds. e can be used ei alone or in combination of migmos. Examples of aliphatic diisocyanate compounds include ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate. Examples of alicyclic diisocyanate compounds include methane-, 4'-hydrogenated diphenyl diisocyanate, cyclohexane diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate. Examples of aromatic diisocyanate compounds include methane-4, '-diphenyl diisocyanate, xylylene diisocyanate, toluene diisocyanate and naphthalene diisocyanate. Among all, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate and like are preferred in behavioral cost viewpoints. specific polyethylene oxide derivative of component (c) is not specifically limited, but any of compounds may be used wherein a structural unit derived from an ethylene oxide (abbreviated as "EO", hereinafter present) may be introduced. ) in structure of amphoteric urethane resin. structural unit derived from EO introduced into structure of amphoteric urethane resin includes an EO unit represented by following general formula (1) and a propylene oxide unit (abbreviated as "PO" hereinafter) represented by following general formula (2), among which EO unit is preferred. amphoteric urethane resin can have both EO unit and PO unit. ratio of unit EO to unit PO is preferably within a range of unit EO / unit PO = 10/0 to 2/8 on a basis by weight, more preferably unit EO / unit PO = 10/0 to 4/6. A repeating number "n" of EO unit in above general formula (1) is preferably within a range of N = 3 to 300, more preferably n = 20 to 120. When number "n" is less than 3, amount of EO unit introduced into amphoteric urethane resin is very small, so that sufficient hydrophilic property can not be imparted, efore sufficient capacity of elimination with shampoo can not be obtained. On o hand, when number "n" exceeds 300, the hydrophilic property of the same amphoteric urethane resin becomes very strong to thus have bad effects on moisture resistance and the like. Also, a repetitive number "m" of the unit PO in the above general formula (2) is preferably within the same range as the previous EO unit. In addition, when both the unit EO and the unit PO are had, it is preferred that an amount of "n" and "m" be within the above range. That is, the total amount is within the range of n + m = 3 to 300, more preferably n + m = 20 to 120. Examples of the ethylene oxide derivative [component (c)] include polyethylene glycol (PEG and polyoxyethylene) polyoxypropylene glycol (EOPO blocked copolymer), among which polyoxyethylene glycol is preferred The above polyethylene oxide derivative [component (c)] can be either of a type which has the OH groups on both terminals, a type having the NH2 groups in both terminals, a type having an OH group in a terminal and a type having an NH2 in a terminal When the type having the OH groups in both terminals is used, the amphoteric urethane resin can be obtained has the EO unit as a main chain When the type having the OH group is used in a terminal or the type having NH2 in a terminal, the amphoteric urethane resin having the EO unit can be obtained as a side chain or in a termin The above specific polyethylene oxide derivative [component (C)] preferably has a molecular weight of 200 to 20,000, more preferably 2,000 to
-, - afeÍÉfcÍ.
10,000. The compound [component (D)] having an active hydrogen and a carboxyl group is not specifically limited, but also any of the compounds which may have at least one active hydrogen and at least one carboxyl group in its molecule. Examples include dimethylol propionic acid (DMPA), dimethylolbutanoic acid and the polycaprolactone diol having a carboxyl group. These can be used either alone or in combination thereof. The compound [component (E)] having an active hydrogen and a tertiary amino group is not specifically limited, but also any of the compounds which have at least one active hydrogen and at least one tertiary amino group in their molecule. Examples include the compound N-alkyldialkanolamine such as N-methyldiethanolamine and dimethylaminoethanol. These can be used either alone or in combination thereof. In the preparation of the prepolymer which contains an isocyanate group by using each of the above components, it is preferred to use a chain extender. The use of the chain extender makes it possible to adjust various properties of the obtained amphoteric urethane resin as a final product. The chain extender is not specifically limited. Examples include low molecular weight polyols and amines. In the preparation of the amphoteric urethane resin, the solvents may be used, as required. For example, it is specifically preferred to use the solvents which can solubilize both a raw material and the obtained 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 the amphoteric urethane resin, a polymerization catalyst conventionally known in the field of polyurethane can be used. Examples include the tertiary amine catalyst and the organometallic catalyst. As the tertiary amine catalyst, [2, 2, 2] diazabicyclooctane (DABCO), tetramethylenediamine, N-methylmorpholine, diazbicyclo undecene (DBU) can be used. As the organometallic catalyst, examples include dibutyltin dilaurate. It is preferred that the proportion of the carboxyl group and the tertiary amino group (the ratio of the numbers of both groups in the amphoteric urethane resin obtained by using each of the above components is the carboxyl group / tertiary group = 1/10 to 10 / That is, when the ratio is within the above range, excellent washing ability can be imparted.Also, any other ingredients generally used in cosmetics other than the specific amphoteric urethane resin, such as pigments, coloring matter can be added. dye, fragrance, surfactant, humectant, preservative, antiseptic, disinfectant and antioxidant to the cosmetic resin composition The cosmetic resin composition of the present invention is used for, for example, hair fixatives such as a mousse hair fixative , a gel hair fixative, a hair spray fixative and a spray spray hair fixative ba, a conditioner shaving cream agent, a film forming agent such as a skin care lotion, make-up base, eyeliner and manicure, and viscosity adjuster. Especially, the cosmetic resin composition is useful for a hair fixative. It is preferred that the specific amphoteric urethane resin be applied for the above use after being dispersed as a dispersion by the dispersion thereof in water or solubilized as an aqueous solution by solubilization thereof in water, respectively. In this case, it is preferred that the amphoteric urethane resin be dispersed in water containing aliphatic polyamine. That is to saywhen the polymer is reacted with the aliphatic polyamine as soon as the polymer is dispersed in water by controlling the excess polymerization of the isocyanate groups, NH groups and NH2 groups of the aliphatic polyamide reacts rapidly with the isocyanate groups to generate the linkages of the polyamide. urea in water, which results in the acceleration of the polymerization. The aliphatic polyamine is not specifically limited. Examples include triethylamine, ethylene diamine, propylene diamine, piperazine and diethylenetriamine. In addition, it is possible that the silane coupling agent may be added in the dispersion of the amphoteric urethane resin for improvement of the adhesive property with other base materials. Still further, various additives such as the protective colloid agent, an antibacterial agent and an antifungal agent can be added to give preservation stability. The examples will be described immediately together with the comparative examples Example 1 70 grams of isofan diisocyanate are placed
(IPDI), 80 grams of diethylene glycol adipate (DEGA, molecular weight 2,000), 20 grams of a bisphenol A adduct with ethylene oxide (Ne pol BP3P, available from Sanyo Chemical
Industries Ltd., molecular weight 400, repetitive numbers of the EO unit, n + n = 3), 26 grams of polyoxyethylene glycol (PEG,
ji-nÁaA J: Á £ Írl¿itt-i¿a;
molecular weight 2,000, a repeating number of unit EO, n = 50) and 16.9 grams of dimethylolpropionic acid (DMPA) in a four-necked flask provided with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser . Then, 50 grams of the ethyl acetate is added as a solvent and 0.02 grams of dibutyltin dilaurate (DBTL) as a catalyst thereto is heated to 80 by an oil bath so that it is allowed to react for 4 hours. After this, 5.6 grams of N-methyldiethanolamine (NMDEtA) and 60 grams of ethyl acetate are added thereto and allowed to react at 80 for 2 hours, to obtain a polyurethane prepolymer solution in which the NCO groups remain. After the polyurethane prepolymer obtained in this way where the NCO groups remain, it is cooled to 50, 600 grams of water containing 12.7 grams of triethylamine and 3.3 grams of diethanolamine are added thereto under high speed agitation to be dispersed, and then it is polymerized by chain elongation reaction in 50 for 3 hours. The ethylene acetate is extracted from the dispersion obtained in this way and an amphoteric urethane resin dispersion which does not substantially include a solvent and which has an ethylene oxide chain in its structure. Example 2. 70 grams of isophorone diisocyanate are placed
iAi iámi ....... ..,. *. ».-«. N - • idßttm - "- '" "-" * - (IPDI), 70 grams of diethylene glycol adipate (DEGA, molecular weight 2,000), 26 grams of polyoxyethylene glycol (PEG, molecular weight 2,000, a repeating unit number EO, n = 50) and 16.9 grams of dimethylolpropionic acid (DMPA) in a four-necked flask provided with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser. Then, 50 grams of ethyl acetate are added thereto as a solvent and 0.02 grams of dibutyltin dilaurate (DBTDL) as a catalyst, heated to 80 by an oil bath and allowed to react for four hours. After this, 5.6 grams of N-methyldiethanolamine (NMDEtA) and 60 grams of ethyl acetate are added thereto and allowed to react at 80 for 2 hours, to obtain a polyurethane prepolymer solution wherein the NCO groups remain cooled to 50, 600 grams of water containing 12.7 grams of triethylamine and 3.3 grams of diethanolamine under high-speed stirring are added thereto to be dispersed, and then polymerized by chain-lengthening reaction at 50 for 3 hours. The ethyl acetate is extracted from this dispersion thus obtained and an amphoteric urethane resin dispersion is obtained which does not include substantially solvent and which has an ethylene oxide chain in its structure. Example 3. 70 grams of isophorone diisocyanate are placed
(IPDI), 80 grams of diethylene glycol adipate (DEGA, molecular weight 2,000), 10 grams of an adduct of bisphenol A with ethylene oxide (Newpol BP3P, available from Sanyo Chemical Industries Ltd., molecular weight 400, repeating numbers of the unit EO, n + n = 3), 11 grams of polyethylene glycol (PEG, molecular weight 200, a repeating number of unit EO, n = 250) and 16.9 grams of dimethylolpropionic acid (DMPA) in a four-necked flask provided with an agitator, a thermometer, a nitrogen inlet tube and a reflux condenser. Then, 50 grams of the ethyl acetate is added as a solvent and 0.02 grams of dibutyltindilaurate (DBTDL) as a catalyst thereto is heated to 80 by an oil bath to allow it to react for four hours. After this, 5.6 grams of N-methyldiethanolamine (NMDEtA) and 60 grams of ethyl acetate are added and allowed to react at 80 for 2 hours., to obtain the solution of the polyurethane prepolymer where the NCO groups remain. Then the polyurethane prepolymer obtained in this way where the NCO groups remain is cooled to 50, 600 grams of water containing 12.7 grams of triethylamine and 3.3 grams of diethanolamine are added thereto under high speed agitation to be dispersed, and then it is polymerized by chain elongation reaction in 50 for 3 hours. The ethyl acetate is extracted from the dispersion obtained from this
fc & ^ > A dispersion of amphoteric urethane resin is obtained which does not substantially include an organic solvent and which has an ethylene oxide chain in its structure. Example 4 70 grams of isophorone diisocyanate are placed
(IPDI), 80 grams of diethylene glycol adipate (DEGA, molecular weight 2,000), 20 grams of an adduct of bisphenol A with ethylene oxide (Ne pol BP3P, available from Sanyo Chemical Industries Ltd., molecular weight 400, repeating numbers of unit EO, n + n = 3), 52 grams of polyethylene glycol (PEG, molecular weight 10,000, a repeating number of unit EO, n = 250) and 16.9 grams of dimethylolpropionic acid (DMPA) in a four-necked flask provided with an agitator, a thermometer, a nitrogen inlet tube and a reflux condenser. Then, 50 grams of the ethyl acetate is added as a solvent and 0.02 grams of dibutyltindilaurate (DBTDL) as a catalyst thereto is heated to 80 by an oil bath to allow it to react for four hours. After this, 5.6 grams of N-methyldiethanolamine (NMDEtA) and 60 grams of ethyl acetate are added thereto and allowed to react at 80 for 2 hours, to obtain the solution of the polyurethane prepolymer where the NCO groups remain. Then the polyurethane prepolymer obtained in this way where the NCO groups remain is cooled to 50, 600 grams of water containing 12.7 grams of triethylamipa and 3.3 grams of diethanolamine are added thereto under high speed agitation to be dispersed, and then it is polymerized by chain elongation reaction in 50 for 3 hours. The ethyl acetate is extracted from the dispersion obtained in this way and an amphoteric urethane resin dispersion is obtained which does not substantially include an organic solvent and which has an ethylene oxide chain and its structure. Example 5 70 grams of isophorone diisocyanate (IPDI), 80 grams of diethylene glycol adipate (DEGA, molecular weight 2,000), 20 grams of a bisphenol A adduct with ethylene oxide (Newpol BP3P, available from Sanyo Chemical Industries Ltd are placed. ., molecular weight 400, repetitive numbers of the EO unit, n + n = 3), 26 grams of polyoxypropylene glycol (blocked EOPO copolymer, molecular weight 2,000, a repeating number of the EO unit, n = 20, a repetitive number of the unit PO, m = 21) and 16.9 grams of dimethylolpropionic acid (DMPA) in a four-necked flask provided with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser. Then, 50 grams of ethyl acetate is added as a solvent and 0.02 grams of dibutyltin dilaurate (DBTDL) as a catalyst thereto,
It is heated to 80 by an oil bath to allow it to react for four hours. After this, 5.6 grams of N-methyldiethanolamine (NMDEtA) and 60 grams of ethyl acetate are added thereto and allowed to react at 80 for 2 hours, to obtain the polyurethane prepolymer solution where the NCO groups remain. Then the polyurethane prepolymer obtained in this way where the NCO groups remain is cooled to 50, 600 grams of water containing 12.7 grams of triethylamine and 3.3 grams of diethanolamine are added thereto under high speed agitation to be dispersed, and then it is polymerized by chain elongation reaction in 50 for 3 hours. The ethyl acetate is extracted from the dispersion obtained in this way and an amphoteric urethane resin dispersion is obtained which does not substantially include an organic solvent and which has an ethylene oxide chain in its structure. Example 6 70 grams of isophorone diisocyanate (IPDI), 80 grams of diethylene glycol adipate (DEGA, molecular weight 2,000), 20 grams of a bisphenol A adduct with ethylene oxide (Newpol BP3P, available from Sanyo Chemical Industries Ltd are placed. ., molecular weight 400, repetitive numbers of unit EO, n = 50), and 16.9 grams of dimethylolpropionic acid (DMPA) in a four-necked flask
^ || ^. ^ toA ^^ a.j ^ J.a »^ * tt > .Tjr, --- > > . - -. ....... * - ».--- provided with an agitator, a thermometer, a nitrogen inlet tube and a reflux condenser. Then, 50 grams of the ethyl acetate is added as a solvent and 0.02 grams of dibutyltindilaurate (DBTDL) as a catalyst thereto is heated to 80 by an oil bath to allow it to react for four hours. After this, 5.6 grams of N-methyldiethanolamine (NMDEtA) and 60 grams of ethyl acetate are added thereto and allowed to react at 80 for 2 hours, to obtain the solution of the polyurethane prepolymer where the NCO groups remain. Then the polyurethane prepolymer obtained in this way where the NCO groups remain is cooled to 50, 600 grams of water containing 12.7 grams of triethylamine and 3.3 grams of diethanolamine are added thereto under high speed agitation to be dispersed, and then it is polymerized by chain elongation reaction in 50 for 3 hours. The ethyl acetate is extracted from the dispersion obtained in this way and an amphoteric urethane resin dispersion is obtained which does not substantially include an organic solvent and which has an ethylene oxide chain in its structure. Comparative Example 1 70 grams of isophorone diisocyanate (IPDI), 106 grams of diethylene glycol adipate (DEGA, molecular weight 2,000), 20 grams of a bisphenol A adduct with ethylene oxide (Newpol BP3P, available from Sanyo Chemical Industries) are placed. Ltd., molecular weight 400, repetitive numbers of the EO unit, n + n = 3), 16.9 grams of dimethylolpropionic acid (DMPA) in a four-necked flask provided with a stirrer, a thermometer, an inlet tube for nitrogen and a reflux condenser. Then, 50 grams of the ethyl acetate is added as a solvent and 0.02 grams of dibutyltindilaurate (DBTDL) as a catalyst thereto is heated to 80 by an oil bath to allow it to react for four hours. After this, 5.6 grams of N-methyldiethanolamine (NMDEtA) and 60 grams of ethyl acetate are added thereto and allowed to react at 80 for 2 hours, to obtain the solution of the polyurethane prepolymer where the NCO groups remain. Then the polyurethane prepolymer obtained in this way where the NCO groups remain is cooled to 50, 600 grams of water containing 12.7 grams of triethylamine and 3.3 grams of diethanolamine are added thereto under high speed agitation to be dispersed, and then it is polymerized by chain elongation reaction in 50 for 3 hours. The ethyl acetate is extracted from the dispersion obtained in this way and an amphoteric urethane resin dispersion is obtained which does not substantially include a solvent. Comparative example 2
70 grams of isophorone diisocyanate (IPDI), 106 grams of diethylene glycol adipate (DEGA, molecular weight 2,000), 20 grams of a bisphenol A adduct with ethylene oxide (Newpol BP3P, available from Sanyo Chemical Industries Ltd., molecular weight 400, repetitive numbers of the EO unit, n + n = 3), and 16.9 grams of dimethylolpropionic acid (DMPA) in a four-necked flask provided with a stirrer, a thermometer, a nitrogen inlet tube and a condenser of reflux. Then, 50 grams of the ethyl acetate is added as a solvent and 0.02 grams of dibutyltindilaurate (DBTDL) as a catalyst thereto, heated to 80 by an oil bath to allow it to react for six hours, to obtain a solution of the prepolymer. of polyurethane where the NCO groups remain. After obtaining thus the polyurethane prepolymer in which the NCO groups remain, it is cooled to 50, 600 grams of water containing 12.7 grams of triethylamine and 3.3 grams of diethanolamine are added thereto under high speed agitation to be dispersed, and then polymerized by chain elongation reaction at 50 for 3 hours. The ethyl acetate is extracted from the dispersion obtained in this way and an amphoteric urethane resin dispersion is obtained which does not substantially include a solvent. Comparative example 3 70 grams of isophorone diisocyanate (IPDI) are placed, 80 grams of diethylene glycol adipate (DEGA, molecular weight 2,000), 20 grams of a bisphenol A adduct with ethylene oxide (Newpol BP3P, available from Sanyo Chemical Industries Ltd., molecular weight 400, repetitive numbers of the EO unit, n = 50), and 16.9 grams of dimethylolpropionic acid (DMPA) in a four-necked flask provided with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser. Then, 50 grams of the ethyl acetate is added as a solvent and 0.02 grams of dibutyltindilaurate (DBTDL) as a catalyst thereto, heated to 80 by an oil bath to allow it to react for six hours, to obtain the prepolymer solution of polyurethane where the NCO groups remain. After obtaining thus the polyurethane prepolymer where the NCO groups remain, it is cooled to 50, 600 grams of water containing 12.7 grams of triethylamine and 3.3 grams of diethanolamine are added thereto under high speed agitation to be dispersed, and then polymerizes by chain elongation reaction in 50 for 3 hours. The ethyl acetate is extracted from the dispersion obtained in this way and an amphoteric urethane resin dispersion is obtained which does not substantially include a solvent. Fixers for hair in mousse are prepared
t. When using the dispersions obtained in this way, the Examples and the Comparative Examples in the mixing ratios as follows: A fixative for mousse hair a The ingredients shown in the following are mixed Table 1 in proportions shown in the same table, and mix until the obtained mixture becomes homogeneous, to obtain the component X. Then, the component shown in the same table is added in the component X, to obtain a fixer for mousse hair a Table 1
1: NIKKOL BS-20 available from Nikko Chemicals Co,
Ltd.
A * &J ^ * y.L.
* 2: Amicor CDE-1, available from Mlyoshl Oil Fixators for mousse hair b, c, d, e and f Instead of the dispersion obtained by Example 1 for component X shown in Table 1, each of the dispersion of Examples 2, 3, 4, 5 and 6. Except that mousse hair fixatives b, c, d, e and f are prepared in the same manner as the hair mousse a fixative. The fixatives for mousse hair g, h and I Instead of the dispersion obtained by example 1 shown in Table 1, each of the dispersions of Comparative Examples 1, 2 and 3 is used. Except that fixatives for mousse hair g, h and I are prepared in the same way as the mousse a hair fixative. The "curl retention" and "shampoo removal capacity" are determined for mousse hair fixatives obtained in this manner in accordance with the following standards. The results are shown in the following Ta, bla 2. CURL RETENTION Each one of the mousse hair fixers obtained in this way is applied to a sample of virgin black hair of separated hair (15 cm in length, 3 grams in weight). ), respectively, and each of the 5 samples for each Example and comparative examples are prepared and
l-dry at 50 during the night. Afterwards, the dry samples are suspended in graduated boards and placed in a thermohydrostat, where the temperature is 30 and the humidity is 90% of RH. Each length (a) of the initial loops and each length (b) of the locks after 5 hours is measured and each loop retention is evaluated according to the following formula. As soon as the curl retention is almost 100%, this shows that the retention of the curl is stronger. In formula 1, L is a length of the sample set fully extended. Formula 1 Retention of the curl (%) =. { (L-b) / (L-a)} x 100 Removal capacity per shampoo Each of the 0.6 grams of the
15 fixators for mousse hair obtained in this way in a sample book for hair separated from virgin black hair
(15 cm in length, 3 grams in weight), respectively, and the hair sample is dried at room temperature, to obtain each prepared hair sample. After every
20 samples are loosened slightly with hot water of 40
30 seconds, 0.4 grams of 10% shampoo solution is applied and washed for 30 seconds. After this, each sample is rinsed in hot water of 40 to be washed like this, and then it is dried sufficiently in 50.
25 evaluates the sample obtained in this way for rigidity. In
¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^. r. .y ^ ¡üyy. . Y.. . ytX »* l & MI ** *** evaluation, it is indicated that the dry sample does not have rigidity due to the elimination capacity with excellent shampoo, which indicates that the dry sample does not have substantial rigidity due to the good elimination capacity with shampoo and indicates Elimination capacity with insufficient shampoo. Also, the tactile sense, brightness, tactile property, combing ability and anti-toweling property of the mousse hair fixers obtained thus a a i are evaluated. Each 0.8 grams of the mousse hair fixers obtained in this way is applied in a sample book for separate hair of black virgin hair (25 cm in length), 5.0 grams by weight), respectively, and the hair sample is dried at room temperature. The hair sample is determined according to the following standards. The results are also shown in the following Table 2. Direction to the touch Indicates that it does not cause disheveled in the sample after being dried and the elasticity is excellent, indicates that the elasticity is good and indicates that the sensation to the touch is slightly lower. RIGIDITY Indicates that it does not cause dishevelment in a sample after drying and the stiffness is excellent, indicates that the stiffness is good and indicates that the stiffness is slightly lower. HAIR CAPACITY Indicates that the combing capacity of a sample after drying is excellent, indicates that the combing ability is good; indicates that the combing capacity is slightly lower and X indicates that the styling capacity is lower. ANTIDESCARAPLED PROPERTY Indicates that it does not cause flakes in a sample after being dried with ten times combing, it indicates that the flakes are not provoked and indicates that they provoke slightly flakes. Table 2
From the results in Table 2, it is found that mousse aaf hair fixatives are superior in all properties of curl retention, shampoo removal ability, tactile sense, stiffness, combing ability and anti-scaling properties. . It is also found that the fixatives for mousse hair a to f are especially excellent in shampoo and tactile removal capacity since an amphoteric urethane resin having the EO unit in its structure is used. On the other hand, it is found that a fixative for hair of mousse g is superior to a hair fixative of mousse h, which uses an anionic urethane resin, in the capacity of elimination with shampoo, rigidity and combing ability, since mousse g hair fixative uses amphoteric urethane resin. However, the hair fixative g is inferior to the hair fixatives a to f, which have the EO unit in the structure of the amphoteric urethane resin. In addition, a mousse hair fixative h is remarkably inferior in combing ability since the mousse hair fixer h uses an anionic urethane resin, and is also inferior in other properties except for the tactile sense. A fixative for mousse hair contains the urethane resin which, although it has the EO unit in the structure thereof, is not an amphoteric but anionic. Therefore, it is found that the mousse hair fixer i is inferior in capacity
of elimination with shampoo, sense of touch, combing ability and anti-peeling property for mousse hair fixatives a to f which contain the amphoteric urethane resin that has the EO unit in the structure thereof. Next, fixators for gel hair a a i are prepared using each dispersion of the Examples and comparative examples according to the following proportions. Fixators for gel hair a The ingredients shown in the following Table 3 are mixed in proportions shown in the same table and mixed until a viscous gel is formed, to obtain component X. Then, the ingredients shown in the Table are mixed. 3 in proportions shown in the table rriLsma, to obtain the component Y. The component Y obtained in this way is added in the component X obtained in this way and mixed until it becomes homogeneous, to obtain a fixative for gel hair to. Table 3
* 2001 structure available from National Starch and Chemical Company. Fixators for gel hair b, c, d, e and f Instead of the dispersion of Example 1 for component Y shown in Table 3 above, each dispersion of Examples 2, 3, 4, 5 and 6 is used. Except that , fixators for gel hair b, c, d, e and f are prepared in the same way as the gel hair fixative a. Fixers for gel hair g, h and i. Instead of the dispersion of Example 1 for the component Y shown in Table 3 above, each dispersion of comparative examples 1, 2 and 3 is used. Except that, the fixatives for gel hair, g, hyi are prepared in the same way as the gel hair fixative a. The curl retention, shampoo removal capacity, tactile sense, stiffness, combing ability, and anti-peeling property of the gel hair fixers obtained in this manner are determined in accordance with the standards mentioned above for them. The same results are generally obtained as in the case where the fixatives for mousse hair a a i
• la-rf tf ifiiH »- *" -are used.Also, fixators for aai spray hair are prepared using the dispersions of Examples and Comparative Examples in mixing ratios as follows. the ingredients shown in the following Table 4 in proportions shown in the same table and mixed until it becomes homogeneous, to obtain component X. Afterwards, the ingredients shown in Table 4 are mixed in proportions shown in the same table, for obtain component Y. Add component Y obtained in this way in component X, to obtain a fixative for spray hair a.Table 4 (% by weight)
rMO-70E monawet available from Mona Industries Inc.
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Hair spray fixatives b, c, d, e and f Instead of the dispersion of example 1 for component X shown in Table 4 above, each dispersion of Examples 2, 3, 4, 5 and 6 is used. Except that , spray hair fixatives b, c, d, e and f are prepared in the same way as the hair spray fixative a. Fixators for spray hair g, h and i. Instead of the dispersion of example 1 for component X shown in Table 4 above, each dispersion of comparative examples 1, 2 and 3 is used. Except that, the fixatives for spray hair g, hyi are prepared therein. way as the hair spray fixative a. The curl retention, elimination capacity with shampoo, tactile sense, rigidity, combing ability and anti-scaling property of the hair spray fixatives obtained in this way a a i in accordance with the standards mentioned above for them is determined. The same results are obtained generally as in the case where mousse hair fixers a to i are used. In addition, fixators for pump spray hair a a i are prepared by using the dispersions of Examples and Comparative Examples in mixing ratios as follows. Fixer for hair spray of rope
u ^ £ j3 ^^ | ^^ Are the ingredients shown in the following Table 5 mixed in proportions shown in the same table and mixed and blended until it becomes homogeneous, to obtain a pump spray hair fixative? . Table 5
* Monawet M0-70E available from Mona Industries Inc. Fixators for pump spray hair b, c, d, e and f Instead of the dispersion of Example 1 shown in Table 5 above, each dispersion of Examples 2, 3 is used. , 4, 5 and 6. Except that, fixators for pump spray hair b, c, d, e and f are prepared in the same way as the pump spray hair fixative a. Fixators for pump spray hair g, hei Instead of the dispersion of Example 1 shown in Table 5 above, each dispersion of Comparative Examples 1, 2 and 3 is used. Except that, fixers for pump spray hair g, hei are prepared in the same way as the pump spray hair fixative a. The retention of the curl, capacity of
. iíyi ti-Á-l elimination with shampoo, tactile sense, rigidity, combing ability and anti-toweling property of the fixators, for pump spray hair obtained in this way a a i in accordance with the standards mentioned above for them. The same results are obtained generally as in the case where the fixatives for mousse hair a a i are used. In addition, the composition of the cosmetic resin of the present invention can be used for a conditioning shaving cream agent, a film forming agent such as a skin care lotion, emulsified make-up base, cream makeup base , eyeliner and manicure, as mentioned later. Conditioning shaving cream agent The ingredients shown in the following Table 6 are mixed in the proportions as shown in the same table and heated to 80, to obtain component X. Then, the ingredients shown in the same table are mixed in the same table. the proportions shown in the same table and heated up to 80, to obtain the component Y. Then, the component X and the component Y are mixed in 80, the resulting mixture is cooled to 40 and the antiseptic and the fragrance are added in each adequate amount, to obtain the conditioner shaving cream of interest.
i-8 - * - • * - * - * "" - "* - '-'-- -" > .- •, -, A ....,. T.fcJ Table 6 by weight),
Skin care lotion The ingredients shown in the following table 7 are mixed in the proportions shown in the same table and heated to 80, to obtain the component X. They are mixed immediately, the ingredients shown in the same table in the proportions mixed in the same table and heated up to 80, to obtain the component Y. Then, the component X and the component Y are mixed and they shake at 80 for 30 minutes. 20.00% by weight of the aqueous carbopol 940 2% solution is added to the resulting mixture and stirred until it becomes homogeneous. After this, it would go to 40, to obtain the lotion for the care of the skin of interest. Table 7
^ y ^^ £ ^ u ^. t | lMMtMlfctj.,. .MHi? ßÉk? Kidiiiitttkün makeup emulsified base (1) Preparation of pigment the following ingredients are mixed in the following Table 8 in proportions shown in the same table and the resulting mixture by a comminuting machine is sprayed to obtain a pigment. (2) Preparation of an aqueous phase The deionized water is then heated to 70,
ba4A ^ j - »* - '- *" "» "*, ..." ^ "a, *,".? fc * add to the same bentonite and swell, then add to it a dispersion preliminarily prepared where the carboxymethyl cellulose is dispersed in propylene glycol to be solubilized. Furthermore, adding thereto triethanolamine and methylparaben to be solubilized to obtain an aqueous phase. (3) Preparation of oil phase are mixed after the ingredients shown in Following Table 8 in proportions shown in the following table, the resulting mixture is heated to 70 to 80 to be solubilized, to obtain an oil phase. (4) Preparation of a pigment dispersion The above pigment is then added in the aqueous phase thereto with stirring, the resulting mixture through a colloid mill to obtain a pigment dispersion is passed. (5) Emulsification After the pigment dispersion and the oil phase to 75 and 80 respectively is heated, add the F Add oil to the pigment dispersion with agitation. Then, the resulting mixture is cooled and fragrance is added thereto when the temperature thereof is 45. The resulting mixture is further cooled with stirring at room temperature to obtain the emulsified make-up base of interest. Table 8
s¿ Cream base cream * < - * - * • '• (1) Preparation of pigment The ingredients shown in the following table 9 are mixed in proportions shown in the same table and the resulting mixture is pulverized by a grinding machine to obtain a pigment. (2) Preparation of an aqueous phase The ingredients shown in the following Table 9 are mixed in proportions shown in the same table to obtain an aqueous phase. l'O (3) Preparation of an oil phase After the ingredients shown in the following table 9 are added in proportions shown in the same table, the resulting mixture is heated to 70 to 80 to be solubilized, to obtain an oil phase . 15 (4) Preparation of a pigment dispersion After the above pigment is added in the above aqueous phase with stirring, the resulting mixture is passed through a colloid mill to obtain a pigment dispersion. 0 (5) emulsification After the pigment dispersion is heated and the oil phase is heated to 75 and 80, respectively, the oil phase is added to the pigment dispersion with stirring. Then, the resulting mixture is cooled, and the fragrance is added to the same when the temperature of the same is 50. It colds
also the resulting mixture with stirring at room temperature, to obtain the cream makeup base of interest. Table 9
Fragrance Fragrance Adequate Amount Sheet Eyelin All the ingredients shown in the following table 10 are mixed in proportions shown in the same table, the resulting mixture is heated to 70 to 80 to be solubilized to obtain an oil phase. Then, the ingredients shown in Table 10 are mixed in proportions shown in the same table to obtain an aqueous phase. In addition, the hot aqueous phase is added to the oil phase with stirring for emulsification. A dispersion of preliminarily swollen bentonite, pigment and fragrance in the emulsion obtained in this way is added. The resulting mixture is passed through a colloid grind to be dispersed and cooled, to obtain the eyeliner of interest. Table 10
Manicure After the pigment is dispersed in ion exchange water, the dispersion of Example 1 and other ingredients shown in the following Table 11 are added thereto in proportions shown in the same table. The resulting mixture is mixed with agitation until it becomes homogeneous and finally deaerated to obtain the manicure of interest. Table 11
.., HUAA ~ i ~ au Effect of the invention As described above, the cosmetic resin composition of the present invention consists essentially of amphoteric urethane resin which has a carboxyl group and a tertiary amino group in a molecule Of the same. In this way, using the urethane resin as a main skeleton of a base resin makes it possible due to the elasticity and rigidity of the urethane resin that the stiffness is compatible with the tactile sensation, combing ability and an anti-scaling property. , which are originally contrary to each other. In addition, by using the amphoteric urethane resin which has a carboxyl group and a tertiary amino group. It becomes possible to prepare a fixative for superior hair for water proof against neutral water since the carboxyl group and the tertiary wreck group are bound by ions, and also superior in shampoo removal capacity since the ion bond is cut off by the shampoo, in addition, since the amphoteric urethane resin has a cationic tertiary arrhythmic group, which interacts with a negatively charged hair surface, in its molecular chain, better adhesion can be obtained compared with the conventional anionic urethane resin. In addition, the amphoteric urethane resin, although it has a high molecular weight, or a low vitreous transition temperature, also improves the shampoo removal capacity since it has a structural unit derived from an ethylene oxide in it. as a non-ionic hydrophilic component and makes it possible to widely control the hardness and elasticity of the base resin which contributes to the feel to the touch or stiffness required for a hair fixative.
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