JP2000191476A - Resin composition for cosmetic and cosmetic produced by using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for cosmetic use giving a hair-dressing agent satisfying all necessary physical properties comprising setting performance, shampooing property, touch, gloss, combing easiness and flaking resistance by including a specific ampholytic urethane resin as a main component. SOLUTION: The objective resin composition for cosmetic use contains an ampholytic urethane resin containing carboxyl group and t-amino group in one molecule as a main component. The ampholytic urethane resin contains polysiloxane bond in the structure. The ampholytic urethane resin can be produced by reacting (A) a polyol compound such as polyester polyol with (B) a polyisocyanate compound such as ethylene diisocyanate, (C) a polysiloxane compound having active hydrogen such as polydialkylsiloxanediol and (D) a compound having active hydrogen and carboxyl group under a condition of excess isocyanate group and reacting the produced prepolymer with (E) a compound having active hydrogen and t-amino group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic resin composition containing an amphoteric urethane resin as a main component and a cosmetic using the same.
The present invention relates to a resin composition for cosmetics used as a film forming agent, a conditioning agent, a viscosity modifier and the like for skin care products, hair care products and the like, and a cosmetic using the same.

[0002]

2. Description of the Related Art Conventionally, as a base resin for a hairdressing agent, a cationic acrylic resin, an anionic acrylic resin, an anionic / cationic amphoteric acrylic resin, a nonionic polyvinylpyrrolidone resin and the like have been used. When these base resins are used, they are firmly finished and have good setting properties (hair styling properties), but have poor texture and combability, and have the disadvantage of causing flaking (dusting). On the other hand, if the texture and combability are prioritized, not only is the setting force insufficient, but also there are disadvantages such as stickiness. Thus, the above-mentioned conventional base resin is required as a hair styling agent, setting properties, texture,
It is difficult to satisfy all physical properties of combability and flaking resistance.

[0003]

SUMMARY OF THE INVENTION Therefore, Japanese Patent Laid-Open Publication No. Hei 6-3
As disclosed in JP-A-21741, it has been proposed to use an anionic urethane resin as a base resin for a hairdressing agent. When this anionic urethane resin is used, the acrylic resin and the like are used in that a hair setting agent having contradictory physical properties such as good setting properties, texture, hair washing properties and anti-flaking properties can be prepared. Better than if. However, when the above-mentioned anionic urethane resin is used, there is a rough feel,
There is a drawback that gloss and combability are poor.

The present invention has been made in view of such circumstances, and it is an object of the present invention to prepare a hairdressing agent having all the physical properties of setting, shampooing, texture, gloss, combability and flaking resistance. It is an object of the present invention to provide a cosmetic resin composition that can be used and cosmetics using the same.

[0005]

In order to achieve the above object, the present invention provides a resin composition for cosmetics containing, as a main component, an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule. The first gist of the amphoteric urethane resin is a cosmetic resin composition having a polysiloxane bond in its structure. In addition, a second aspect of the present invention is a cosmetic using the resin composition for cosmetics.

The present inventors have found that when an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule is used as a base resin, it has good set properties, hand feeling, combability and anti-flaking properties. We have found that a hair styling agent can be obtained, and have already filed a patent application for a resin composition containing the amphoteric urethane resin as a main component (Japanese Patent Application No. 10-27595). The use of the amphoteric urethane resin improves the physical properties for the following reasons. That is, by using a urethane resin as the main skeleton of the base resin, the elasticity and toughness possessed by the urethane resin make it possible to achieve both set properties and hand feeling, combability and flaking resistance, which are originally contradictory physical properties. Becomes possible. Moreover, by using an amphoteric urethane resin having a carboxyl group and a tertiary amino group, the carboxyl group and the tertiary amino group are ionically bonded to neutral water, resulting in excellent water resistance, such as shampoo and the like. This washing breaks the ionic bonds, and makes it possible to prepare a hair styling agent having excellent detergency. Further, the amphoteric urethane resin has a cationic tertiary amino group in its molecular chain, and this interacts with the surface of the negatively charged hair, so that it is compared with the conventional anionic urethane resin. And good adhesiveness.

The present inventors have further researched and developed a resin composition containing the amphoteric urethane resin as a main component. As a result, by introducing a polysiloxane bond into the structure of the amphoteric urethane resin, The inventors have found that gloss, touch, combability and flaking resistance can be further improved, and have reached the present invention.

[0008]

Next, an embodiment of the present invention will be described.

The cosmetic resin composition of the present invention contains, as a main component, an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule. The greatest feature of the present invention is that the amphoteric urethane resin has a polysiloxane bond in its structure. In addition, to contain an amphoteric urethane resin as a main component generally means a component of a cosmetic resin that is intended by adding other components to the amphoteric urethane resin, but also includes a case where the amphoteric urethane resin alone is used. It is the purpose.

The amphoteric urethane resin having a polysiloxane bond includes, for example, a polyol compound (component A), a polyisocyanate compound (component B), a polysiloxane compound having active hydrogen (component C), active hydrogen and a carboxyl group. Is reacted with an isocyanate group excess to produce an isocyanate group-containing prepolymer, and then the isocyanate group-containing prepolymer, a compound having active hydrogen and a tertiary amino group (component E) ) Can be produced by reacting Alternatively, in the amphoteric urethane resin having the polysiloxane bond, the reaction order of the specific D component and the E component is exchanged, that is, the A component, the B component, the C component, and the E component are reacted in excess of an isocyanate group. After the preparation of the isocyanate group-containing prepolymer, the isocyanate group-containing prepolymer is allowed to react with the above-mentioned specific D component. According to such a method, the desired amphoteric urethane resin can be manufactured more easily and safely than in the past. In the above-mentioned production method, A component, B component and C component
When simultaneously reacting both the specific D component and the specific E component together with the component, the carboxyl group in the D component and the tertiary amino group in the E component first form a salt and become insoluble in the reaction system, Even if there is an OH group, the reaction with the isocyanate compound does not occur, and the intended amphoteric urethane resin cannot be produced. That is, as described above, after reacting any one of the D component and the E component together with the A component, the B component, and the C component, the remaining D component or the E component is reacted to form a polysiloxane bond. Thus, an amphoteric urethane resin having the following formula can be produced.

The polyol compound as the component A is not particularly limited as long as it is generally used in the production of polyurethane, and examples thereof include polyester polyols, polyether polyols, polycarbonate polyols, polybutadiene polyols, and polyisoprene polyols. , Polyolefin polyols, polyacrylate polyols, and the like, which may be used alone or in combination of two or more. Among them, polyester polyols and polyether polyols are particularly preferred. As the polyester polyol, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, at least one of dicarboxylic acids such as terephthalic acid, ethylene glycol, propylene glycol, 1, 4-butanediol,
1,3-butanediol, 1,6-hexanediol,
Neopentyl glycol, 1,8-octanediol,
Examples thereof include those obtained by condensation polymerization of at least one polyhydric alcohol such as 1,10-decanediol, diethylene glycol, spiro glycol, and trimethylolpropane, and those obtained by ring-opening polymerization of lactones. Further, as the polyether polyol,
In addition to water and the polyhydric alcohol used in the synthesis of the polyester polyol, phenols such as bisphenol A and hydrogenated products thereof, or primary amines and secondary amines, ethylene oxide, propylene oxide, oxetane, Those obtained by ring-opening addition polymerization of a cyclic ether such as tetrahydrofuran can be used, and polyoxyethylene polyol, polyoxypropylene polyol,
Polyoxytetramethylene polyol, bisphenol A obtained by ring-opening addition polymerization of at least one of propylene oxide and ethylene oxide (in the case of a copolymer, any of a block copolymer and a random copolymer may be used) and the like. can give.

The polyisocyanate compound as the component B is not particularly limited, and examples thereof include organic diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds. Or 2
Used in combination of more than one species. Examples of the aliphatic diisocyanate compound include ethylene diisocyanate,
2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate and the like can be mentioned. Examples of the alicyclic diisocyanate compound include hydrogenated 4,4'-diphenylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, and norbornane diisocyanate. Examples of the aromatic diisocyanate compound include 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, toluene diisocyanate, and naphthalene diisocyanate. Among these, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate and the like are preferable in consideration of performance and price.

The specific polysiloxane compound as the component C is not particularly limited as long as it can introduce a polysiloxane bond in which a siloxane bond (Si—O) is linked into the structure of the amphoteric urethane resin. Not something. The polysiloxane bond to be introduced into the structure of the amphoteric urethane resin is preferably one in which the number of repeating siloxane bonds (Si—O) is in the range of n = 5 to 300, particularly preferably n = 20 to 150. is there. That is, when n is less than 5, the ratio of polysiloxane bonds in the resulting amphoteric urethane resin is too small, and it is difficult to obtain sufficient effects on the texture, combability and the like originally obtained by introducing polysiloxane bonds. Because it becomes. Conversely, if n exceeds 300, the compatibility with other raw materials becomes poor due to its high hydrophobicity, and the reaction becomes difficult. Also, the resulting polymer becomes too hydrophobic,
This is because adhesion to hair may be impaired.

The polysiloxane compound (component C) is not particularly limited as long as it has an active hydrogen and a polysiloxane bond in its molecule.
Both terminal OH group introduction type, both terminal NH ₂ group introduction type,
One-terminal OH group introduction type, one-terminal NH ₂ group introduction type and the like can be mentioned. When the above-mentioned OH group-introduced type or NH ₂ group-introduced type is used, an amphoteric urethane resin having a polysiloxane bond in the main chain can be obtained. In addition, one end OH group introduction type or one end NH ₂
When the group introduction type is used, an amphoteric urethane resin having a polysiloxane bond at a side chain or at a terminal can be obtained.

Examples of the polysiloxane compound (component C) include polydialkylsiloxane diol, polydialkylsiloxane monool, polydialkylsiloxane diamine, and polydialkylsiloxane monoamine. These may be used alone or in combination of two or more. Used together. The alkyl group bonded to Si of each siloxane bond such as the above polydialkylsiloxane diol preferably has 1 to 10 carbon atoms, and particularly preferably has 1 to 5 carbon atoms. The polysiloxane compound (component C) may be a mixture of compounds having different carbon numbers in the alkyl group bonded to Si in each siloxane bond. Specifically, examples of the polydialkylsiloxane diol include polydimethylsiloxane diol and polymethylethylsiloxane diol. Examples of the polydialkylsiloxane monool include polydimethylsiloxane monool and polymethylethylsiloxane monool. Examples of the polydialkylsiloxane diamine include polydimethylsiloxane diamine and polymethylethylsiloxane diamine. Examples of the polydialkylsiloxane monoamine include polydimethylsiloxane monoamine and polymethylethylsiloxane monoamine.

The compound having active hydrogen and a carboxyl group as the component D is not particularly limited as long as it has at least one active hydrogen and at least one carboxyl group in the molecule. Methylol propionic acid (DMPA), dimethylol butanoic acid, carboxyl group-containing polycaprolactone diol, and the like. These may be used alone or in combination of two or more.

The compound having the active hydrogen and the tertiary amino group as the component E is not particularly limited as long as it has at least one active hydrogen and at least one tertiary amino group in the molecule. Not something like N
-Methyldiethanolamine (NMDEtA), N-alkyldialkanolamine compounds such as N-butyldiethanolamine, and dimethylaminoethanol. These may be used alone or in combination of two or more.

In preparing an isocyanate group-containing prepolymer using the above components, it is preferable to use a chain extender. By using this chain extender, it becomes possible to adjust various properties of the amphoteric urethane resin obtained as a final product. The chain extender is not particularly limited, and examples thereof include low molecular polyols and amines. Examples of the low-molecular polyol include ethylene glycol, propylene glycol, 1,
4-butanediol, diethylene glycol, 1,6-
Glycols such as hexanediol, spiroglycol, bis (β-hydroxyethoxy) benzene, and xylylene glycol; and triols such as trimethylolpropane and glycerin. Examples of the amines include methylene (bis-o-chloroaniline).

In producing the amphoteric urethane resin,
A solvent can be used if necessary. For example, it is particularly preferable to use an organic solvent that dissolves both the raw material and the produced polyurethane. As the organic solvent, N-methylpyrrolidone, dimethylformamide, amides such as dimethylacetamide, acetone, ketones such as methyl ethyl ketone, esters such as ethyl acetate,
Other examples include cellosolve acetate and cellosolve ether. When producing the amphoteric urethane resin, a polymerization catalyst known in the field of polyurethane can be used, and for example, a tertiary amine catalyst, an organometallic catalyst and the like can be used. Examples of the tertiary amine catalyst include [2,2,2] diazabicyclooctane (DABC
O), tetramethylenediamine, N-methylmorpholine, diazabicycloundecene (DBU) and the like. Examples of the organometallic catalyst include dibutyltin (tin) dilaurate.

The amphoteric urethane resin obtained using each of the above components has a ratio of carboxyl group to tertiary amino group (ratio of the number of both functional groups) of carboxyl group / tertiary amino group =
Those set in the range of 1/10 to 10/1 are preferable. That is, by setting the ratio of the carboxyl group to the tertiary amino group in the amphoteric urethane resin within the above range, excellent washing properties can be provided.

The cosmetic resin composition of the present invention includes:
In addition to the above specific amphoteric urethane resin, any other components normally used in cosmetics such as pigments, dyes, colorants, fragrances, surfactants, humectants, preservatives, preservatives, bactericides, antioxidants, etc. Can also be contained.

Then, the cosmetic resin composition of the present invention comprises:
For example, hair styling agents such as foam hair styling agents, gel hair styling agents, spray hair styling agents, pump spray hair styling agents, conditioning shaving cream agents, skin care lotion agents, foundations, film forming agents such as eyeliners and nail polish; It can be used as a viscosity modifier and the like, and is particularly useful as a hairdressing agent.

The above specific amphoteric urethane resin is preferably dispersed in water to form an aqueous dispersion or solubilized to form an aqueous solution, and then used for the above applications. In this case, the amphoteric urethane resin is preferably dispersed in water containing an aliphatic polyamine. That is, when the degree of polymerization is suppressed by making the isocyanate group excessive, and the polymer is reacted with the aliphatic polyamine while being dispersed in water, the NH group and the NH ₂ group in the aliphatic polyamine rapidly react with the isocyanate group, and This causes a urea bond to be formed and the polymerization to proceed. As the aliphatic polyamine,
There is no particular limitation, and examples include triethylamine, ethylenediamine, propylenediamine, piperazine, diethylenetriamine, and the like. In addition, it is also possible to add a silane coupling agent as an additive to the aqueous dispersion of the amphoteric urethane resin to improve the adhesiveness with another base material. In addition, various additives can be freely added to impart storage stability, and examples thereof include a protective colloid agent, an antibacterial agent and a fungicide.

Next, examples will be described together with comparative examples.

[0025]

Example 1 70 g of isophorone diisocyanate (IPDI) and 80 of diethylene glycol adipate (DEGA, molecular weight 2000) were placed in a glass four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser.
g, ethylene oxide adduct of bisphenol A (Newpol BP3P, manufactured by Sanyo Chemical Industries, Ltd., molecular weight 40)
0) 20 g, 26 g of polydimethylsiloxanediol (both terminal OH group-introduced type, molecular weight 2000) and 16.9 g of dimethylolpropionic acid (DMPA) were added.
50 g of ethyl acetate as a solvent and 0.02 g of dibutyltin dilaurate (DBTDL) as a catalyst were added, and the mixture was heated to 80 ° C. using an oil bath and reacted for 4 hours. Then, N-methyldiethanolamine (NMDEtA)
5.6 g and 60 g of ethyl acetate were added, and the mixture was further reacted at 80 ° C. for 2 hours to obtain a solution of a polyurethane prepolymer having NCO groups remaining. After cooling the polyurethane prepolymer having the NCO groups remaining to 50 ° C., 600 g of water containing 12.7 g of triethylamine and 3.3 g of diethanolamine was added thereto under high-speed stirring and dispersed, and the chain was further extended at 50 ° C. for 3 hours. The reaction was performed to increase the molecular weight. The ethyl acetate was recovered from the obtained aqueous dispersion to obtain an aqueous dispersion of an amphoteric urethane resin having a dimethylsiloxane chain substantially free of a solvent in the structure.

[0026]

Example 2 70 g of isophorone diisocyanate (IPDI) and polytetraoxymethylene glycol (PTMG, molecular weight 2000) were placed in a glass four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser.
56 g, 20 g of ethylene oxide adduct of bisphenol A (ADEKA polyether BPX21, manufactured by Asahi Denka Co., molecular weight 400), 26 g of polyethylene glycol (PEG, molecular weight 2000), polydimethylsiloxane diol (both terminal OH group introduction type, molecular weight 2000) 26g
And dimethylolpropionic acid (DMPA) 16.9
g, 50 g of ethyl acetate as a solvent and 0.02 g of dibutyltin dilaurate (DBTDL) as a catalyst were heated to 80 ° C. using an oil bath, and reacted for 4 hours. Then, N-methyldiethanolamine (NM
5.6 g of DEtA) and 60 g of ethyl acetate were added, and the mixture was further reacted at 80 ° C. for 2 hours to obtain a solution of a polyurethane prepolymer in which NCO groups remained. This NC
After cooling the polyurethane prepolymer having the remaining O groups to 50 ° C., 600 g of water containing 12.7 g of triethylamine and 3.3 g of diethanolamine was added thereto under high-speed stirring and dispersed, and the chain extension reaction was further performed at 50 ° C. for 3 hours. To increase the molecular weight. The ethyl acetate was recovered from the obtained aqueous dispersion to obtain an aqueous dispersion of an amphoteric urethane resin having a dimethylsiloxane chain substantially free of a solvent in the structure.

[0027]

EXAMPLE 3 70 g of isophorone diisocyanate (IPDI) and 70 g of diethylene glycol adipate (DEGA, molecular weight 2000) were placed in a glass four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser.
g, 26 g of polydimethylsiloxanediol (one terminal OH group introduction type, molecular weight 2000) and 16.9 g of dimethylolpropionic acid (DMPA), 50 g of ethyl acetate as a solvent, and 0.02 g of dibutyltin dilaurate (DBTDL) as a catalyst. In addition, the mixture was heated to 80 ° C. using an oil bath and reacted for 4 hours. Then N
-5.6 g of methyldiethanolamine (NMDEtA)
Further, 60 g of ethyl acetate was added, and the mixture was further reacted at 80 ° C. for 2 hours to obtain a solution of a polyurethane prepolymer in which NCO groups remained. After cooling the polyurethane prepolymer having the NCO groups remaining to 50 ° C., 600 g of water containing 18.4 g of triethanolamine and 6.6 g of diethanolamine was added thereto under high-speed stirring to disperse the mixture. A chain extension reaction was performed to increase the molecular weight. The ethyl acetate was recovered from the resulting aqueous dispersion to obtain an aqueous dispersion of an amphoteric urethane resin having a dimethylsiloxane chain substantially free of a solvent as a side chain in the structure.

[0028]

Example 4 70 g of isophorone diisocyanate (IPDI) and 80 g of diethylene glycol adipate (DEGA, molecular weight 2000) were placed in a glass four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser.
g, ethylene oxide adduct of bisphenol A (Newpol BP3P, manufactured by Sanyo Chemical Industries, Ltd., molecular weight 40)
0) 20 g, 10 g of polydimethylsiloxanediol (both terminal OH group-introduced type, molecular weight 800) and 16.9 g of dimethylolpropionic acid (DMPA) were added, 50 g of ethyl acetate was used as a solvent, and dibutyltin dilaurate (DBTDL) was used as a catalyst. After adding 02 g, the mixture was heated to 80 ° C. using an oil bath and reacted for 4 hours. Then, N-methyldiethanolamine (NMDEtA)
5.6 g and 60 g of ethyl acetate were added, and the mixture was further reacted at 80 ° C. for 2 hours to obtain a solution of a polyurethane prepolymer having NCO groups remaining. After cooling the polyurethane prepolymer having the NCO groups remaining to 50 ° C., 600 g of water containing 12.7 g of triethylamine and 3.3 g of diethanolamine was added thereto under high-speed stirring and dispersed, and the chain was further extended at 50 ° C. for 3 hours. The reaction was performed to increase the molecular weight. The ethyl acetate was recovered from the obtained aqueous dispersion to obtain an aqueous dispersion of an amphoteric urethane resin having a dimethylsiloxane chain substantially free of a solvent in the structure.

[0029]

Example 5 70 g of isophorone diisocyanate (IPDI) and 80 of diethylene glycol adipate (DEGA, molecular weight 2000) were placed in a glass four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser.
g, ethylene oxide adduct of bisphenol A (Newpol BP3P, manufactured by Sanyo Chemical Industries, Ltd., molecular weight 40)
0) 20 g, 26 g of polydimethylsiloxane diol (both terminal OH group-introduced type, molecular weight 5000) and 16.9 g of dimethylolpropionic acid (DMPA) were added.
50 g of ethyl acetate as a solvent and 0.02 g of dibutyltin dilaurate (DBTDL) as a catalyst were added, and the mixture was heated to 80 ° C. using an oil bath and reacted for 4 hours. Then, N-methyldiethanolamine (NMDEtA)
5.6 g and 60 g of ethyl acetate were added, and the mixture was further reacted at 80 ° C. for 2 hours to obtain a solution of a polyurethane prepolymer having NCO groups remaining. After cooling the polyurethane prepolymer having the NCO groups remaining to 50 ° C., 600 g of water containing 12.7 g of triethylamine and 3.3 g of diethanolamine was added thereto under high-speed stirring and dispersed, and the chain was further extended at 50 ° C. for 3 hours. The reaction was performed to increase the molecular weight. The ethyl acetate was recovered from the obtained aqueous dispersion to obtain an aqueous dispersion of an amphoteric urethane resin having a dimethylsiloxane chain substantially free of a solvent in the structure.

[0030]

Example 6 70 g of isophorone diisocyanate (IPDI) and 80 g of diethylene glycol adipate (DEGA, molecular weight 2000) were placed in a glass four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser.
g, ethylene oxide adduct of bisphenol A (Newpol BP3P, manufactured by Sanyo Chemical Industries, Ltd., molecular weight 40)
0) 20 g, 52 g of polydialkylsiloxane diol (both terminal OH group introduction type, alkyl chain length = 8 to 10, molecular weight 5000) and dimethylolpropionic acid (D
MPA) was added, and ethyl acetate 50 was used as a solvent.
g, dibutyltin dilaurate (DBTD) as a catalyst
L) 0.02 g was added, and the mixture was heated to 80 ° C. using an oil bath and reacted for 4 hours. Thereafter, 5.6 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were added, and the mixture was further reacted at 80 ° C. for 2 hours to obtain a solution of a polyurethane prepolymer in which NCO groups remained. After cooling the polyurethane prepolymer having the NCO group remaining to 50 ° C., 600 g of water containing 12.7 g of triethylamine and 3.3 g of diethanolamine was added thereto under high-speed stirring and dispersed.
For 3 hours to increase the molecular weight. The ethyl acetate was recovered from the obtained aqueous dispersion to obtain an aqueous dispersion of an amphoteric urethane resin having a dimethylsiloxane chain substantially free of a solvent in the structure.

[0031]

Comparative Example 1 70 g of isophorone diisocyanate (IPDI) and 10 g of diethylene glycol adipate (DEGA, molecular weight 2000) were placed in a glass four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser.
6 g, bisphenol A ethylene oxide adduct (Newpol BP3P, manufactured by Sanyo Chemical Industries, molecular weight 4
00) 20 g and dimethylolpropionic acid (DMP
A) 16.9 g, and 50 g of ethyl acetate as a solvent;
Dibutyltin dilaurate (DBTDL) as catalyst
0.02 g was added, and the mixture was heated to 80 ° C. using an oil bath and reacted for 4 hours. Thereafter, 5.6 g of N-methyldiethanolamine (NMDEtA) and 60 g of ethyl acetate were added, and the mixture was further reacted at 80 ° C. for 2 hours.
A solution of a polyurethane prepolymer in which NCO groups remained was obtained. After cooling the polyurethane prepolymer having the remaining NCO groups to 50 ° C., it is added with triethylamine 1
Water 6 containing 2.7 g and 3.3 g of diethanolamine
00g was added under high-speed stirring to disperse, and a chain extension reaction was performed at 50 ° C. for 3 hours to increase the molecular weight. The ethyl acetate was recovered from the obtained aqueous dispersion to obtain an aqueous dispersion of an amphoteric urethane resin substantially containing no solvent.

[0032]

Comparative Example 2 70 g of isophorone diisocyanate (IPDI) and 10 g of diethylene glycol adipate (DEGA, molecular weight 2000) were placed in a glass four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser.
6 g, bisphenol A ethylene oxide adduct (Newpol BP3P, manufactured by Sanyo Chemical Industries, molecular weight 4
00) 20 g and dimethylolpropionic acid (DMP
A) 16.9 g, and 50 g of ethyl acetate as a solvent;
Dibutyltin dilaurate (DBTDL) as catalyst
0.02 g was added, and the mixture was heated to 80 ° C. using an oil bath and reacted for 6 hours to obtain a solution of a polyurethane prepolymer in which NCO groups remained. After cooling the polyurethane prepolymer having the NCO groups remaining to 50 ° C., 600 g of water containing 12.7 g of triethylamine and 3.3 g of diethanolamine was added thereto under high-speed stirring and dispersed, and the chain was further extended at 50 ° C. for 3 hours. The reaction was performed to increase the molecular weight. The ethyl acetate was recovered from the obtained aqueous dispersion to obtain an aqueous dispersion of an anionic urethane resin substantially containing no solvent.

[0033]

Comparative Example 3 Aqueous dispersion of amphoteric urethane resin obtained in Comparative Example 1 was added to dimethyl silicone emulsion FZ-4160.
An aqueous dispersion of an amphoteric urethane resin containing polydimethylsiloxane not chemically bonded to the amphoteric urethane resin (not covalently bonded) was obtained by blending 65 g of an active ingredient (manufactured by Nippon Unicar, 45%). Was.

Using the aqueous dispersions of the examples and comparative examples thus obtained, foaming hair styling agents a to i were prepared in the following proportions.

<Foam hairdressing agent a> The components shown in Table 1 below were blended in the blending ratios shown in the same table and mixed until homogeneous to obtain component X. Subsequently, the Y component shown in the following Table 1 was added to the X component to prepare a foaming hair styling agent a.

[0036]

[Table 1]

<Foam hair fixatives b, c, d, e, f> In place of the aqueous dispersion of Example 1, which is the X component shown in Table 1, the aqueous dispersion of Examples 2, 3, 4, 5, and 6 was used. An aqueous dispersion was used. Other than that, in the same manner as the foaming hair styling a, the foaming hair styling b,
c, d, e, and f were produced, respectively.

<Foam hair fixatives g, h, i> Comparative examples 1 and 2 were used in place of the aqueous dispersion of Example 1 as the X component shown in Table 1 above.
A few aqueous dispersions were used. Except for that, foamed hair styling agents g, h, and i were prepared in the same manner as foamed hair styling agent a.

The foam hair styling compositions a to i thus obtained
Was used to evaluate curl retention and hair washability according to the following criteria. The results are shown in Table 2 below.

[Curl Retention] 0.6 g of each foam hair styling agent was applied to black virgin hair (length 15 cm, weight 3 g).
Each sample was applied to form five curls, which were dried at 50 ° C. overnight. Next, the dried hair bundle was hung on a board with a memory and placed in a thermo-hygrostat at a temperature of 30 ° C. and a humidity of 90% RH. Then, the initial curl length (a) and the curl length after 5 hours were measured for (b), and the curl retention was evaluated according to the following equation. The closer this curl retention is to 100%, the stronger the curl holding power. In the following formula, L represents the length of the hair bundle when fully extended.

[0041]

## EQU1 ## Curl retention (%) = ｛(L−b) /
(L-a)｝ × 100

[Shamwashing property] Each foamy hair styling agent was applied to black virgin hair (length 15 cm, weight 3 g) by 0.6 g each.
A hair bundle which was dried at room temperature and trimmed was produced. Next,
After gently loosening the hair bundle with warm water of 40 ° C for 30 seconds,
0.4 g of a 10% shampoo solution was applied and washed for 30 seconds. Thereafter, the shampoo solution was rinsed again with warm water at 40 ° C., and the set of the hair bundle after being sufficiently dried at 50 ° C. was evaluated. The evaluation was that the hair bundle after drying had no settability and the hair washability was very good. ◎ The hair bundle after drying had little settability.
Good hair washability was indicated by し た, and hair washability was slightly poor was indicated by Δ.

Using the foaming hair styling compositions a to i, the feeling, the setting property, the gloss, the touch, the combability and the anti-flaking property were evaluated. That is, 0.8 g was applied to one bundle of black virgin hair (length 25 cm, weight 5.0 g), dried at room temperature, and evaluated according to the following criteria. The results are shown in Table 2 below.

[Hand] After drying, the hair bundle is not disturbed.
◎ indicates that the elasticity was very good, ○ indicates that the elasticity was excellent, and △ indicates that the texture was slightly inferior.

[Setting property] The hair bundle was not disturbed after drying and the hair setting property was excellent, and the hair setting property was indicated by ◎, the hair setting property was indicated by ○, and the setting property was slightly inferior by Δ.

[Gloss] The hair bundles with excellent gloss and gloss after drying were marked with ◎, those with excellent gloss as ○, and those with slightly poor gloss as Δ.

[Hand] The hair bundle has a smooth feel or a very good feel after drying. ◎ indicates that the hair bundle is excellent, ○ indicates that the feel is excellent, and Δ indicates that the feel is slightly rough.
Displayed as

[Combability] A hair bundle having excellent combability after drying is marked with ◎, a hair bundle with excellent combability is marked with ○, and a comb with slightly poor combability is marked with △. Is indicated as x when the result is poor.

[Flaking resistance] ◎ indicates that the hair did not powder at all after passing the comb 10 times through the dried hair bundle, ○ indicates that the hair was hardly generated, and 、 indicates that the hair was hardly wiped. What occurred was indicated as △.

[0050]

[Table 2]

From the results shown in Table 2 above, the foaming hair styling agents a to f
Is curl retention, hair wash, texture, set,
It can be seen that all the physical properties such as luster, touch, combability and flaking resistance are excellent. And since the said foamy hair-fixing agent a-f uses the amphoteric urethane resin which has a dimethylsiloxane chain in a structure, it becomes the foamy hair-dressing agent g which used the amphoteric urethane resin which does not have a dimethylsiloxane chain in a structure. In comparison, the gloss, the touch, the combability, and the flaking resistance are far superior. Further, it can be seen that since the foamy hair styling agent b has an ethylene oxide chain as a nonionic hydrophilic component in the structure of the amphoteric urethane resin, the hair washing property, the feeling and the setting property are very good.

On the other hand, since the foamy hair styling agent g uses an amphoteric urethane resin, it has good curl retention, shampooing properties, texture, and setability, but the structure of the amphoteric urethane resin contains dimethylsiloxane. It can be seen that, since there is no chain, gloss, touch, combability and flaking resistance are inferior. In addition, since the foamy hair styling h uses an anionic urethane resin, it can be seen that the combability is remarkably inferior, and other physical properties except for the setting property are also inferior. And
Since the foam hairdressing agent i uses an aqueous dispersion containing an amphoteric urethane resin and dimethylsiloxane, the gloss, the touch,
Combability and anti-flaking properties are improved over the foamed hair fixative g and the foamed hair fixative h. However, since the dimethylsiloxane is not bonded to the amphoteric urethane resin, the foamed hair fixative a It can be seen that the above physical properties are inferior to those of f.

Next, using the aqueous dispersions of the above Examples and Comparative Examples, the gel-like hair styling agent a
To i.

<Gel-like hair styling agent a> The components shown in Table 3 below were mixed in the mixing ratio shown in the same table, and mixed until a viscous gel was formed to obtain an X component. Next, the Y component obtained by blending the components shown in Table 3 below at the blending ratio shown in the same table was added to the X component, and mixed until homogeneous,
A gel hair styling a was prepared.

[0055]

[Table 3]

<Gel-like hair styling agents b, c, d, e, and f> In place of the aqueous dispersion of Example 1, which is the Y component shown in Table 3, the hair styling agents of Examples 2, 3, 4, 5, and 6 were used. An aqueous dispersion was used. Other than that, the gel-shaped hairdressing agents b, c, d, e, and f were respectively prepared in the same manner as the gel-shaped hairdressing agent a.

<Gel-like hair styling agents g, h, i> The aqueous dispersions of Comparative Examples 1, 2, and 3 were used in place of the aqueous dispersion of Example 1, which is the Y component shown in Table 3 above. Other than that, in the same manner as the gel-like hair styling agent a, the gel-like hair styling agents g, h, i
Were prepared respectively.

The gel-like hair styling thus obtained a
Using ~ i, according to the above criteria, curl retention,
Evaluation of hair washing property, texture, setting property, gloss, touch, combability and flaking resistance was performed. As a result, almost the same evaluation was obtained as in the case of using the foam hair styling agents a to i.

Using the aqueous dispersions of the above Examples and Comparative Examples, a spray-shaped hairdressing a
To i.

<Spray-like hair dressing agent a> The components shown in Table 4 below were blended in the mixing ratio shown in the same table, and mixed until homogeneous to obtain component X. Subsequently, the Y component shown in the following Table 4 was added to the X component to prepare a spray-shaped hair styling agent a.

[0061]

[Table 4]

<Spray hair styling agents b, c, d, e, f>
The aqueous dispersions of Examples 2, 3, 4, 5, and 6 were used in place of the aqueous dispersion of Example 1, which is the X component shown in Table 4 above. Other than that, the spray-shaped hair styling agents b, c, d, e, and f were respectively prepared in the same manner as the spray-shaped hair styling agent a.

<Spray hair styling agents g, h, i> Table 4 above
The aqueous dispersions of Comparative Examples 1, 2, and 3 were used in place of the aqueous dispersion of Example 1 which is the X component shown in (1). Otherwise, in the same manner as in the above-mentioned spray-shaped hair styling agent a, spray-shaped hair styling agents g,
h and i were prepared respectively.

Using the spray-shaped hair stylings a to i thus obtained, evaluation of curl retention, shampooing, texture, setting, gloss, touch, combability and flaking resistance was carried out in accordance with the above criteria. Was done. As a result, almost the same evaluation was obtained as in the case of using the foam hair styling agents a to i.

Further, using each of the aqueous dispersions of the above Examples and Comparative Examples, pump spray hair styling agents a to i were prepared in the following proportions.

<Pump spray type hair styling agent a>
Were mixed in the mixing ratio shown in the same table and mixed until the mixture became homogeneous to prepare a pump spray hairdressing agent a.

[0067]

[Table 5]

<Pump spray hair styling agents b, c, d,
e, f> Instead of the aqueous dispersion of Example 1 shown in Table 5 above,
The aqueous dispersions of Examples 2, 3, 4, 5, and 6 were used. Except for that, pump spray-type hair styling agents b, c, d, e, and f were respectively prepared in the same manner as the above-mentioned pump spray-type hair styling agent a.

<Pump spray hair styling agents g, h, i> Comparative examples 1 and 2 were used in place of the aqueous dispersion of Example 1 shown in Table 5 above.
A few aqueous dispersions were used. Except for this, pump spray-type hair styling agents g, h, and i were respectively prepared in the same manner as the above-mentioned pump spray-type hair styling agent a.

Using the thus obtained pump spray hair styling compositions a to i, curl retention, shampooing properties, texture, setting properties, gloss, touch, combability and flaking resistance, according to the above criteria. An evaluation was performed. As a result, almost the same evaluation was obtained as in the case of using the foam hair styling agents a to i.

The cosmetic resin composition of the present invention may contain, in addition to the above-mentioned hair styling agent, the following conditioning, shaving cream, skin care lotion, emulsion foundation, cream foundation, eyeliner, nail polish, etc. It can be used as a forming agent and the like.

<Conditioning, shaving and cream formulation> The components shown in Table 6 below were mixed in the proportions shown in the same table, and heated to 80 ° C to obtain Component X. Then, the components shown in Table 6 below were mixed at the ratio shown in the same table,
To obtain a Y component. Then, the above-mentioned X component and Y component were mixed at 80 ° C., and after cooling to 40 ° C., an appropriate amount of a preservative and a fragrance were added to prepare a desired conditioning shaving cream.

[0073]

[Table 6]

<Skin care lotion> The components shown in Table 7 below were mixed in the proportions shown in the same table, and heated to 80 ° C. to obtain Component X. Subsequently, the components shown in Table 7 below were mixed in the proportions shown in the same table, and heated to 80 ° C. to obtain a Y component. Then, the X component and the Y component are mixed and stirred at 80 ° C. for 30 minutes, and then a 2% aqueous solution of Carbopol 940 is added.
0.00% by weight was added and stirred until uniform. Thereafter, the mixture was cooled to 40 ° C. to prepare a desired skin care lotion.

[0075]

[Table 7]

<Emulsion foundation> (1) Preparation of pigment Each component shown in Table 8 below was mixed at the ratio shown in the table, and then pulverized through a pulverizer to prepare a pigment. (2) Preparation of aqueous phase After heating the deionized water to 70 ° C, bentonite was added to swell. Next, sodium carboxymethylcellulose preliminarily dispersed in propylene glycol was added thereto and dissolved. Then, triethanolamine and methyl paraoxybenzoate were added thereto and dissolved to prepare an aqueous phase. (3) Preparation of Oil Phase Each component shown in Table 8 below was mixed at a ratio shown in the table, and then heated and melted at 70 to 80 ° C. to prepare an oil phase. (4) Preparation of Pigment Dispersion After the pigment was added to the aqueous phase with stirring, a pigment dispersion was prepared through a colloid mill. (5) Emulsification After heating the pigment dispersion at 75 ° C. and the oil phase at 80 ° C., add the oil phase to the pigment dispersion while stirring, cool, add perfume at 45 ° C., and bring to room temperature. Stirring and cooling were continued until the desired emulsion liquid foundation was obtained.

[0077]

[Table 8]

<Cream Foundation> (1) Preparation of Pigment The components shown in Table 9 below were mixed in the proportions shown in the table, and then pulverized through a pulverizer to prepare a pigment. (2) Preparation of aqueous phase Each component shown in Table 9 below was mixed at a ratio shown in the same table,
An aqueous phase was prepared. (3) Preparation of Oil Phase Each component shown in Table 9 below was mixed at a ratio shown in the table, and then heated and melted at 70 to 80 ° C. to prepare an oil phase. (4) Preparation of Pigment Dispersion After the pigment was added to the aqueous phase with stirring, a pigment dispersion was prepared through a colloid mill. (5) Emulsification After heating the pigment dispersion at 75 ° C. and the oil phase at 80 ° C., add the oil phase to the pigment dispersion with stirring, cool, add a fragrance at 50 ° C., and bring the mixture to room temperature. Stirring and cooling were continued until the cream foundation was obtained.

[0079]

[Table 9]

<Eyeliner> The components shown in Table 10 below were mixed at the ratio shown in the same table, and then mixed at 70 to 80 ° C.
To prepare an oil phase. Table 10 below
Were mixed in proportions shown in the same table to prepare an aqueous phase. Then, the heated aqueous phase was added to the oil phase while stirring, and emulsified. A bentonite dispersion, a pigment and a fragrance, which had been swollen in advance, were added to this emulsion, dispersed through a colloid mill, and then cooled to produce a target eyeliner.

[0081]

[Table 10]

<Manicure> After the pigment was dispersed in ion-exchanged water, the aqueous dispersion of Example 1 and other components shown in Table 11 below were added in the proportions shown in the same table. Then, the mixture was uniformly stirred and mixed, and finally degassed to prepare a target nail polish.

[0083]

[Table 11]

[0084]

As described above, the cosmetic resin composition of the present invention contains, as a main component, an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule.
In this way, by setting the main skeleton of the base resin to the urethane resin, the elasticity and toughness of the urethane resin cause the original contradictory physical properties, setting property and texture,
Combability and flaking resistance can both be achieved. Moreover, by using an amphoteric urethane resin having a carboxyl group and a tertiary amino group, the carboxyl group and the tertiary amino group are ionically bonded to neutral water, resulting in excellent water resistance, such as shampoo and the like. This washing breaks the ionic bonds, and makes it possible to prepare a hair styling agent having excellent detergency. Further, the amphoteric urethane resin has a cationic tertiary amino group in its molecular chain, and this interacts with the surface of the negatively charged hair, so that it is compared with the conventional anionic urethane resin. And good adhesiveness. In addition, since the amphoteric urethane resin has a polysiloxane bond in its structure, gloss, touch, combability and flaking resistance can be further improved.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Katsuya Koyama 5-4-1-202 Senmon, Itami-shi, Hyogo F-term (reference) 4C083 AA082 AA122 AB242 AB432 AB442 AC012 AC022 AC072 AC102 AC112 AC122 AC132 AC182 AC242 AC342 AC352 AC392 AC402 AC422 AC482 AC542 AC642 AC792 AD092 AD132 AD152 AD161 AD162 AD242 AD512 CC01 CC12 CC14 CC21 CC28 CC32 CC33 DD08 DD27 DD31 DD38 DD39 DD41 EE06 EE07 EE28 FF01 FF05

Claims (7)

[Claims] 1. A cosmetic resin composition containing, as a main component, an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule, wherein the amphoteric urethane resin has a polysiloxane bond in its structure. A resin composition for cosmetics, characterized by having: 2. The resin composition for cosmetics according to claim 1, wherein the resin composition for cosmetics is a resin composition for hair styling. 3. The amphoteric urethane resin includes the following (A) to
The component (D) is obtained by reacting the isocyanate group-containing prepolymer by reacting the isocyanate group excess in an isocyanate group excess, and then reacting the isocyanate group-containing prepolymer with the following component (E). Or the resin composition for cosmetics according to 2. (A) a polyol compound. (B) a polyisocyanate compound. (C) A polysiloxane compound having active hydrogen. (D) a compound having active hydrogen and a carboxyl group. (E) a compound having active hydrogen and a tertiary amino group. 4. The amphoteric urethane resin includes the following (A),
The components (B), (C) and (E) are reacted in excess of an isocyanate group to produce an isocyanate group-containing prepolymer, and the isocyanate group-containing prepolymer is reacted with the following component (D) to obtain a prepolymer. The cosmetic resin composition according to claim 1 or 2, wherein (A) a polyol compound. (B) a polyisocyanate compound. (C) A polysiloxane compound having active hydrogen. (D) a compound having active hydrogen and a carboxyl group. (E) a compound having active hydrogen and a tertiary amino group. 5. The cosmetic resin composition according to claim 1, wherein the amphoteric urethane resin is dispersed or solubilized in water. 6. A cosmetic comprising the resin composition for cosmetics according to claim 1. 7. The cosmetic product is at least one selected from the group consisting of a foam hair styling agent, a gel hair styling agent, a spray hair styling agent, a pump spray hair styling agent, a conditioning shaving cream agent and a film forming agent. 7. The cosmetic product according to claim 6, wherein