KR100939674B1 - Cosmetic materials - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cosmetic materials, in particular hair cosmetic materials and external skin preparations, and aims to develop a coating agent made of a novel amphoteric urethane resin and to apply it to cosmetic materials. The means taken by the present invention is a cosmetic material characterized by blending an amphoteric urethane resin carrying a polysiloxane compound. It is preferable that the amphoteric urethane resin which comprises the amphoteric urethane resin which supported the said polysiloxane compound is an amphoteric urethane resin produced | generated by making at least the compound of following (A)-(D) react.

(A) a polyol compound,

(B) polyisocyanate compound

(C) a compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a carboxyl group

(D) Compound which has 1 or more types and tertiary amino group chosen from hydroxyl group, a primary amino group, and a secondary amino group

According to this invention, the outstanding compound material which fully exhibited the film | membrane characteristic of the novel polysiloxane carrying amphoteric urethane resin is obtained. For example, in the hair cosmetic material, particularly excellent hair elasticity is obtained, and there is no flaking in hair combing, and in the skin cosmetic material, the skin cosmetic material is particularly moist, smooth and gives the skin a moderate level of elasticity.

Description

Cosmetic Ingredients {COSMETIC MATERIALS}

This invention relates to the cosmetic material which mix | blended the amphoteric urethane resin which carried the polysiloxane compound.

Among the cosmetic materials, there are many cosmetic materials utilizing film properties such as hair cosmetic materials, manicure materials, packs, and eye cosmetic materials. For example, in the case of hair cosmetic materials, it is an important component for preparing a hairstyle, and conventionally, as the component, anionic, nonionic or amphoteric acrylic polymers, vinylpyrrolidone polymers, cationic vinylpyrrolidone polymers, cellulose polymers, etc. Is blended. Furthermore, in the manicure material, as a film forming agent and a film forming aid, nitrocellulose, an acrylic polymer, and the like pack, as a film forming agent, are used for cosmetics for eye care such as polyvinyl alcohol and polyvinyl acetate, mascara, eyeliner and the like. In the above, an acrylic polymer, polyvinyl acetate, and the like are blended as a film forming agent.

However, not all of the film forming agents have been developed to provide products that meet the needs of consumers.                         

Japanese Patent Laid-Open No. 11-228363 discloses a cosmetic resin composition containing a positive urethane resin. In addition, Japanese Patent Application Laid-Open No. 2000-191476 discloses a positive urethane resin in which a polysiloxane chain is introduced into a skeleton of a positive urethane resin using a polysiloxane compound having a functional group containing active hydrogen at the sock end or single end of the siloxane chain. have. In addition, Japanese Patent Application Laid-Open No. 2001-48735 discloses a cosmetic material in which a positive urethane resin and a silicone polymer are each formulated as a prescription ingredient. However, none of these cosmetic materials or cosmetic materials blended with resins is sufficient in terms of usability or stability.

This invention is made | formed in view of the said situation, and aims at developing the coating agent which consists of novel amphoteric urethane resin which improved the conventional urethane resin, and aims at application to cosmetics.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the present inventors discovered that the said subject was solved by developing the novel coating agent which carried the polysiloxane compound in the amphoteric urethane resin, and came to complete this invention.

That is, this invention is a cosmetic material characterized by mix | blending the amphoteric urethane resin which carried the polysiloxane compound.

The novel amphoteric urethane resin used for this invention is a big structural feature to carry the polysiloxane compound.

Here, "supporting" a polysiloxane compound means that the polysiloxane compound is "bound" by the skeleton of the amphoteric urethane resin, or that the polysiloxane compound is "entangled" in the skeleton of the amphoteric urethane resin. It does not chemically bond a polysiloxane compound to it. Therefore, in the present invention, the term "supported" is used as a meaning in which the polysiloxane compound is "bound" in the skeleton of the amphoteric urethane resin, or "tangled" in the skeleton of the amphoteric urethane resin. However, as a result, the polysiloxane compound may form part of the skeleton of the part of the amphoteric urethane resin, and as long as the desired amphoteric urethane resin is obtained, the part is not excluded from chemical bonding. Support of the polysiloxane compound on the amphoteric urethane resin can be confirmed by IR spectrum and the like.

It is preferable that the amphoteric urethane resin which comprises the amphoteric urethane resin which carry | supported the polysiloxane compound used for the cosmetics material of this invention is an amphoteric urethane resin produced | generated by making at least the compound of following (A)-(D) react.

(A) polyol compound

(B) polyisocyanate compound

(C) a compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a carboxyl group

(D) Compound which has 1 or more types and tertiary amino group chosen from hydroxyl group, a primary amino group, and a secondary amino group

Here, the presence means that the polysiloxane compound is present in the reaction system and does not mean that the polysiloxane compound is actively reacted, but a part thereof may be inevitably reacted as a result. In addition, all the terms "existence" in manufacture of the amphoteric urethane resin which carry the polysiloxane compound of this invention are used by this meaning.

The amphoteric urethane resin carrying the polysiloxane compound preferably used is an isocyanate group excess of the compounds of (A), (B) and (C) using at least the compounds of (A) to (D) and (S). And a second step of reacting the isocyanate group-containing prepolymer with the compound of (D) by reacting under the conditions of the above, and producing at least one of the first step and the second step. It can obtain by making the compound of (S) exist.

(A) polyol compound

(B) polyisocyanate compound

(C) a compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a carboxyl group

(D) Compound which has 1 or more types and tertiary amino group chosen from hydroxyl group, a primary amino group, and a secondary amino group

(S) polysiloxane compound

In addition, the amphoteric urethane resin carrying the above-mentioned polysiloxane compound preferably uses isocyanate as the compound of (A), (B) and (D) using at least the compounds of (A) to (D) and (S). A first step of producing an isocyanate group-containing prepolymer by reacting under excessive group conditions, and a second step of reacting the isocyanate group-containing prepolymer with a compound of (C), and further in the first and second steps In at least one side, you may produce | generate making the compound of (S) exist.

(A) polyol compound

(B) polyisocyanate compound

(C) a compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a carboxyl group

(D) Compound which has 1 or more types and tertiary amino group chosen from hydroxyl group, a primary amino group, and a secondary amino group

(S) polysiloxane compound

In the production of the amphoteric urethane resin carrying the polysiloxane compound of the present invention, the polysiloxane compound is present in either of the first step and the second step.

In preparing the amphoteric urethane resin carrying the polysiloxane compound of the present invention using at least the compounds of (A) to (D) and (S), after the second step, the reaction product of the second step is mixed with water. It is preferable to further include the step of performing a chain length extension reaction.

Further, in preparing the amphoteric urethane resin carrying the polysiloxane compound of the present invention using at least the compounds of (A) to (D) and (S), after the second step, the reaction product of the second step is used as the basic product. It is preferable to further include a step of performing a chain length extension reaction by mixing with or by adding a basic compound to the reaction product of the second step and then mixing with water to perform a chain length extension reaction.                     

The amphoteric urethane resin carrying the polysiloxane compound used for the cosmetic material of the present invention may be an amphoteric urethane resin produced by reacting at least the compounds of the following (A) to (E) in the presence of the polysiloxane compound.

(A) polyol compound

(B) polyisocyanate compound

(C) a compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a carboxyl group

(D) Compound which has 1 or more types and tertiary amino group chosen from hydroxyl group, a primary amino group, and a secondary amino group

(E) A compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a structural unit represented by the following general formula (1)

-(C ₂ H ₄ O) _p (C ₃ H ₆ O) _q- . (One)

(Wherein p represents an integer of 1 to 500, q represents an integer of 0 to 400.)

The amphoteric urethane resin carrying the polysiloxane compound preferably used is a compound of (A), (B), (C) and (E) using at least the compounds of (A) to (E) and (S) below. And a second step of reacting the isocyanate group-containing prepolymer with the compound of (D) to react the isocyanate group-containing prepolymer by reacting with an isocyanate group-excess condition. Further, the first step and the second step In any one of these, it can obtain by making the compound of (S) exist.                     

(A) polyol compound

(B) polyisocyanate compound

(C) a compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a carboxyl group

(D) Compound which has 1 or more types and tertiary amino group chosen from hydroxyl group, a primary amino group, and a secondary amino group

(E) A compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a structural unit represented by the following general formula (1)

-(C ₂ H ₄ O) _p (C ₃ H ₆ O) _q- . (One)

(Wherein p represents an integer of 1 to 500, q represents an integer of 0 to 400.)

(S) polysiloxane compound

In addition, the amphoteric urethane resin carrying the polysiloxane compound used preferably is (A), (B), (D) and (E) using at least the following compounds of (A)-(E) and (S). And a second step of reacting the compound of isocyanate group under excessive conditions to produce an isocyanate group-containing prepolymer, and a second step of reacting the isocyanate group-containing prepolymer with the compound of (C). In at least one of the two steps, the compound of (S) may be present and produced.

(A) polyol compound

(B) polyisocyanate compound                     

(C) a compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a carboxyl group

(D) Compound which has 1 or more types and tertiary amino group chosen from hydroxyl group, a primary amino group, and a secondary amino group

(E) A compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a structural unit represented by the following general formula (1)

-(C ₂ H ₄ O) _p (C ₃ H ₆ O) _q- . (One)

(Wherein p represents an integer of 1 to 500, q represents an integer of 0 to 400.)

(S) polysiloxane compound

In preparing the amphoteric urethane resin carrying the polysiloxane compound of the present invention using at least the compounds of (A) to (E) and (S), after the second step, the reaction product of the second step is mixed with water. It is preferable to generate | generate further by carrying out chain length extension reaction.

In the preparation of the amphoteric urethane resin carrying the polysiloxane compound of the present invention using at least the compounds of (A) to (E) and (S), after the second step, the reaction product of the second step is used as the basic product. It is preferable to produce by extending the chain length reaction by mixing with or by adding a basic compound to the reaction product of the second step and then mixing with water to perform a chain length extending reaction.

In manufacture of the amphoteric urethane resin which carried the polysiloxane compound which concerns on this invention, a polysiloxane compound is present in at least one of a 1st process and a 2nd process. Here, the polysiloxane compound may be present at any one of the first step and the second step, and the polysiloxane compound is not necessarily present from the beginning of the reaction. In addition, the polysiloxane compound may be present until the reaction product of the second step is mixed with water. Therefore, in the present invention, the "first step" means from the start of the reaction of the first step to the start of the reaction of the second step, and the "second step" refers to the step carried out after the start of the reaction of the second step (more Specifically, the reaction product of the second step described later is mixed with water).

The polysiloxane compound used in the production of the amphoteric urethane resin carrying the polysiloxane compound of the present invention is a polysiloxane compound having no at least one selected from hydroxyl group, primary amino group and secondary amino group at the sock end or single end of the siloxane. It is preferable.

The polysiloxane compound used in the production of the amphoteric urethane resin carrying the polysiloxane compound of the present invention is one or two selected from the group consisting of dimethylpolysiloxane, polyether modified silicone, cyclic silicone, phenyl modified silicone, alkyl modified silicone and alkoxy modified silicone. It is preferable that it is a species or more.

It is preferable to mix | blend the amphoteric urethane resin which carried the polysiloxane compound of this invention with aqueous solution.

It is preferable that the amphoteric urethane resin of this invention is an amphoteric urethane resin which has a carboxyl group and a tertiary amino group in one molecule.                     

In the present invention, the cosmetic raw materials preferably applied are hair cosmetic materials and external skin preparations.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

The cosmetic material of this invention mix | blends the amphoteric urethane resin which carried the polysiloxane compound. Preferred amphoteric urethane resins of the present invention are amphoteric urethane resins having a carboxyl group and a tertiary amine group in one molecule.

The amphoteric urethane resin constituting the amphoteric urethane resin (hereinafter also referred to as polysiloxane-supported amphoteric urethane resin) having a carboxyl group and a tertiary amino group in one molecule of the polysiloxane compound preferably used in the present invention is at least the following (A The amphoteric urethane resin produced | generated by making the compound of (I)-(D) react is preferable.

(A) polyol compound

(B) polyisocyanate compound

(C) a compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a carboxyl group

(D) Compound which has 1 or more types and tertiary amino group chosen from hydroxyl group, a primary amino group, and a secondary amino group

It will not specifically limit, if it is a polyol compound generally used for manufacture of a urethane resin as a polyol compound (henceforth a compound (A)) used for this invention. Examples of the compound (A) include, for example, polyester polyols, polyether polyols, low molecular polyols, polycarbonate polyols, polybutadiene polyols, polyisoprene polyols, polyolepin polyols, polyacrylic acid ester polyols, and the like. Or 2 or more types together. Especially, polyester polyol, polyether polyol, and low molecular polyol are used preferably.

Examples of the polyester polyol include one or more of dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, ethylene glycol, propylene glycol, Polyvalents such as 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, spiroglycol, trimethylolpropane The polyester polyol obtained by condensation polymerization of 1 or more types of alcohol, the polyester polyol obtained by ring-opening polymerization of lactones, etc. are mentioned.

Examples of the polyether polyols include phenols such as bisphenol A and hydrides thereof, and primary amines or secondary amines, in addition to water and polyhydric alcohols used in the synthesis of the polyester polyols. And polyether polyols obtained by ring-opening addition polymerization of cyclic ethers such as oxetane and tetrahydrofuran. In addition, polyether propylene polyol, polyoxytetramethylene polyol, and polyether polyol obtained by ring-opening addition polymerization of at least one of propylene oxide and ethylene oxide to bisphenol A may be any of block copolymer and random copolymer. .) And the like.

As said low molecular polyol, 1, 4- cyclohexane dimethanol, ethylene glycol, propylene glycol, isopropylene glycol, 1, 4- butanediol, 1, 3- butanediol, butylene glycol, 1, 6- hexanediol, neo Pentyl glycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, dipropylene glycol, spiroglycol, trimethylolpropane, glycerin, diglycerine, triglycerine and the like.

Compound (A) can be used individually or in combination. In compound (A), 1, 4- cyclohexane dimethanol is preferable.

Moreover, in this invention, when overlapping with the compound (E) mentioned later in a compound (A), the compound is contained in the compound (E), and is not contained in the compound (A). In addition, in this invention, when overlapping with the compound (C) mentioned later in a compound (A), the compound is contained in a compound (C), and is not contained in a compound (A). In addition, in this invention, when overlapping with the compound (D) mentioned later in a compound (A), the compound is contained in a compound (D), and is not contained in a compound (A).

As a polyisocyanate compound (henceforth a compound (B) hereafter) used for this invention, if it is a polyisocyanate compound generally used for manufacture of a urethane resin, it will not specifically limit. As an example of a compound (B), organic diisocyanate compounds, such as an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, an aromatic diisocyanate compound, are mentioned, for example, These are used individually or in combination of 2 or more types.

Examples of the aliphatic diisocyanate compounds include ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate and the like.                     

As said alicyclic diisocyanate compound, hydrogenated 4,4'- diphenylmethane diisocyanate, 1, 4- cyclohexane diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, etc. are mentioned, for example. This is listed.

As said aromatic diisocyanate compound, 4,4'- diphenylmethane diisocyanate, xylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, etc. are mentioned, for example.

In these compounds (B), 1,6-hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, etc. are preferable at the point which is excellent in weatherability and low cost. Compound (B) can be used individually or in combination.

Compounds having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a carboxyl group (hereinafter referred to as compound (C)) used in the present invention include a hydroxyl group, a primary amino group and a second group in a molecule thereof. It will not specifically limit, if it is a compound which can obtain the target amphoteric urethane resin as a compound which has 1 or more types chosen from a class amino group, and one or more carboxyl groups. Examples of the compound (C) include carboxylic acids having 3 to 26 carbon atoms, preferably 3 to 12 carbon atoms having dialkylol groups such as dimethylol, diethanol and dipropanol. Specific examples include, for example, dimethylolpropanoic acid (DMPA), dimethylolbutanoic acid and the like. In addition, carboxyl group-containing polycaprolactone diol is also used. These are used individually or in combination of 2 or more types.

Examples of the compound (hereinafter referred to as compound (D)) having at least one kind selected from a hydroxyl group, a primary amino group and a secondary amino group and a tertiary amino group used in the present invention include a hydroxyl group and a primary amino group in a molecule thereof. And a compound having at least one kind selected from secondary amino groups and at least one tertiary amino group, as long as it is a compound capable of obtaining the target amphoteric urethane resin. Examples of the compound (D) include, for example, N-methyl diethanolamine, N-ethyl diethanolamine, N-butyl diethanolamine, N-lauryl diethanolamine, having the same dialkylol group as the compound (C). N-alkyldialkanolamine compounds, such as N-methyldipropanolamine, are mentioned. The alkyl group of the N-alkyl of the N-alkyldialkanolamine compound preferably has 1 to 24 carbon atoms, and particularly preferably 1 to 8 carbon atoms. Examples thereof include N, N-dialkylalkanolamine compounds such as N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, triethanolamine and the like. These are used individually or in combination of 2 or more types.

As the polysiloxane compound (hereinafter also referred to as compound (S)) used in the present invention, it is a polysiloxane compound that can be blended into a cosmetic material and has a hydroxyl group, a primary amino group and a secondary amino group at the end or single end of the siloxane chain. It will not specifically limit, if it is a polysiloxane compound which does not have 1 or more types chosen from, and can obtain the target amphoteric urethane resin. Examples of the polysiloxane compound include dimethylpolysiloxane, polyether modified silicone, cyclic silicone, phenyl modified silicone, alkyl modified silicone, alkoxy modified silicone and the like. 1 type (s) or 2 or more types of these polysiloxane compounds are arbitrarily selected and mix | blended.

As dimethylpolysiloxane, the compound represented, for example by General formula (2) can be mentioned.

(Wherein n represents an integer of 1 or more.)

In formula, the integer of 1-100 is preferable, the integer of 1-50 is more preferable, and the integer of 3-30 is especially preferable.

As the dimethylpolysiloxane of the present invention, a commercially available product can be used, and examples of commercially available products include, for example, the SH200 series (trade name) manufactured by Toray Dow Coating Silicone Co., Ltd. and the KF96 series (trade name) manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd. This is listed.

As polyether modified silicone, the compound represented by General formula (3) can be mentioned, for example.

(Wherein m represents an integer of 0 or more, n represents an integer of 1 or more, and R ¹ represents a group represented by the following formula (4).)

_{- (CH 2) a - (} OC 2 H 4) b (OC 3 H 6) c -OR 2 ... (4)

(Wherein R ² represents a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms, a represents an integer of 1 to 10, b represents an integer of 1 to 300, and c represents an integer of 0 to 300.)

In General formula (3), the integer of 1-300 is preferable, as for m, the integer of 1-100 is more preferable, The integer of 1-50 is especially preferable. The integer of 1-300 is preferable, the integer of 1-100 is more preferable, and, as for n, the integer of 1-50 is especially preferable. In addition, in Formula (4), 1-5 are preferable and, as for a, the integer of 2-4 is especially preferable. The integer of 2-50 is preferable, the integer of 2-40 is more preferable, and, as for b, the integer of 2-30 is especially preferable. The integer of 0-50 is preferable, the integer of 0-40 is more preferable, and the integer of 0-30 is especially preferable.

As compound (S) represented by General formula (3), in general formula (3), m is an integer of 1-300, n is an integer of 1-300, R <^1> is represented by Formula (4) As group, the compound whose a is an integer of 1-5, b is an integer of 2-50, and c is an integer of 0-50 is preferable.

As compound (S) represented by General formula (3), in general formula (3), m is an integer of 1-100, n is an integer of 1-100, R <^1> is represented by Formula (4) As group, the compound whose a is an integer of 2-4, b is an integer of 2-40 and c is an integer of 0-40 is more preferable.

As compound (S) represented by General formula (3), in general formula (3), m is an integer of 1-50, n is an integer of 1-50, R <^1> is represented by Formula (4) As the group, a compound in which a is an integer of 2 to 4, b is an integer of 2 to 30 and c is an integer of 0 to 30 is particularly preferable.

Examples of the polyether modified silicone represented by the general formula (3) include, for example, SH3746, SH3771C, SH3772C, SH3773C, SH3775C, SH3748, SH3749, SH3771M, SH3772M, SH3773M and SH3775M And KF351A, KF353A, KF945A, KF352A, KF615A, KF6011, KF6012, KF6013, KF6015, KF6016, KF6017 (trade name) of Shin-Etsu Kagaku Kogyo Co., Ltd., etc. can be mentioned.

Examples of the phenyl-modified silicones include compounds represented by the general formula (5).

(Wherein R ³ and R ⁴ represent a hydrocarbon group having 1 to 12 carbon atoms (eg, a linear or branched saturated hydrocarbon group having 1 to 12 carbon atoms), -OSi (CH ₃ ) ₃ or a phenyl group, Provided that at least one of R ³ and R ⁴ is a phenyl group, m represents an integer of 0 or greater, and n represents an integer of 1 or greater.)

In General formula (5), the integer of 0-300 is preferable, as for m, the integer of 0-100 is more preferable, The integer of 0-50 is especially preferable. The integer of 1-500 is preferable, the integer of 1-100 is more preferable, and, as for n, the integer of 1-50 is especially preferable. As the phenyl-modified silicone, methylphenylpolysiloxane of R ³ = CH ₃ or -OSi (CH ₃ ) ₃ , R ⁴ = C ₆ H ₅ , m = 0, n = 1 to 100 in the general formula (5) is particularly preferred. Do.

Examples of the phenyl-modified silicone represented by the general formula (5) include, for example, SH556, SF557, SF558, SH559 (trade name) manufactured by Toray Dow Coating Silicon, and KF50-100cs manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd .; KF53, KF54, KF56 (brand name), etc. can be mentioned.

As alkyl modified silicone, the compound represented by General formula (6) can be mentioned, for example.

(In formula, R <^5> -R <^7> represents a C1-C50 hydrocarbon group and may mutually be same. However, at least 1 of R <^5> -R <^7> is a C5-C30 hydrocarbon group. M is one or more An integer, and n represents an integer of 1 or more.)

In general formula (6), as R <^5> -R <^7> , a linear or branched saturated hydrocarbon group can be illustrated as a C1-C50 hydrocarbon group. It is preferable that carbon number of a hydrocarbon group is 5-30, It is more preferable that it is 5-20, It is especially preferable that it is 10-20. Moreover, it is preferable that m is an integer of 10-300, It is more preferable that it is an integer of 1-100, It is especially preferable that it is an integer of 1-50. It is preferable that n is an integer of 1-300, It is more preferable that it is an integer of 1-100, It is especially preferable that it is an integer of 1-50.

Examples of the alkyl-modified silicone represented by the general formula (6) include SF8416 (trade name) manufactured by Toray Dow Coating Silicone Co., Ltd. and KF-412, KF-413, KF- manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd. 414 (brand name) etc. can be mentioned.

As an alkoxy modified silicone, the compound represented by General formula (7) can be mentioned, for example.

(In formula, R <^8> -R <^10> may represent a C1-C12 hydrocarbon group or a C1-C50 alkoxy group, and may mutually be the same. However, one or more of R <^8> -R <^10> may be C1-C50. M represents an integer of 0 or more, and n represents an integer of 1 or more.)

In general formula (7), although R <^8> -R <^10> is a C1-C12 hydrocarbon group or a C1-C50 alkoxy group, it is a C1-C12 hydrocarbon group and can illustrate a linear or branched saturated hydrocarbon group. A straight or branched alkoxy group can be illustrated as a C1-C50 alkoxy group. As for carbon number, it is preferable that carbon number of the 1-50 alkoxy group is 1-30, It is more preferable that it is 1-25, It is especially preferable that it is 1-20. Moreover, it is preferable that m is an integer of 1-500, It is more preferable that it is an integer of 1-100, It is especially preferable that it is an integer of 1-50. It is preferable that n is an integer of 1-100, It is more preferable that it is an integer of 1-80, It is especially preferable that it is an integer of 1-50.

As alkoxy modified silicone represented by General formula (7), KF-851, X-22-801B (brand name) etc. of Shin-Etsu Kagaku Kogyo Co., Ltd. can be mentioned, for example.

As cyclic silicone, the compound represented by General formula (8) can be mentioned, for example.

In the formula, R ¹¹ represents a hydrocarbon group having 2 to 12 carbon atoms, but may be the same as or different from each other in each repeating unit. M represents an integer of 1 or more, n represents an integer of 0 or more, and m + n = 3 ~ 10)

In General formula (8), R <^11> is a C1-C12 hydrocarbon group and can illustrate a linear or branched saturated hydrocarbon group. It is preferable that R <^11> has 2-10 carbon atoms, It is more preferable that it is 2-8, It is especially preferable that it is 2-5. Moreover, it is preferable that m is an integer of 3-8, It is more preferable that it is an integer of 4-8, It is especially preferable that it is an integer of 4-6. It is preferable that n is an integer of 0-7, It is more preferable that it is an integer of 0-5, It is especially preferable that it is an integer of 0-3. It is preferable that m + n is 3-8, It is more preferable that it is 4-8, It is especially preferable that it is 4-6.

Examples of the cyclic silicone represented by the general formula (8) include, for example, SH244, SH344, SH245, DC345, DC246 (trade name) manufactured by Toray Dow Coating Silicone Co., Ltd., and KF994, KF995 manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd. , KF9937 (brand name), etc. can be mentioned.

The repeating unit moiety of the compounds represented by the general formulas (3) and (5) to (8) may be any one of polymerization forms such as random polymerization and block polymerization.

The viscosity (kinematic viscosity) at 25 ℃ of the compound (S) is both 1~5000mm ² / s is particularly preferred that the preferred, and, 1~2000mm and more preferably ² / s in 1~1000mm ² / s. As compound (S), dimethylpolysiloxane and polyether modified silicone are preferable. Compound S can be used alone or in combination.

Preferred polysiloxane-carrying amphoteric urethane resin in this invention is amphoteric urethane resin produced | generated by making at least the said compound (A)-(D) react in presence of the said compound (S). In the production of the polysiloxane-supported amphoteric urethane resin according to the present invention, at least the compounds (A) to (D) and (S) are used, and the compounds (A), (B) and (C) are excessive in isocyanate groups. 1st process of making isocyanate group containing prepolymer by making it react on condition of, and the 2nd process of making this isocyanate group containing prepolymer react with compound (D), Furthermore, in at least one of a 1st process and a 2nd process, And compound (S) can be produced. Moreover, it can also manufacture by alternating the reaction order of the said compound (C) and a compound (D).

The weight ratio of compound (S) and compounds (A), (B), (C) and (D), i.e., (S) / ((A) + (B) + (C) + (D)) is 0.1 / It is preferable that it is 100-30 / 100, It is more preferable that it is 0.5 / 100-25 / 100, It is especially preferable that it is 1 / 100-20 / 100.

In addition, the molar ratio of compound (B) and compound (A), (C) and (D), namely (B) / ((A) + (C) + (D)), is 2.0 / 1.8 to 2.0 / 0.8. It is preferable, it is more preferable that it is 2.0 / 1.8-2.0 / 1.0, and it is especially preferable that it is 2.0 / 1.8-2.0 / 1.2.

Reaction of the said 1st process and a 2nd process can be performed using reaction conditions normally used at the time of manufacturing a polyurethane, using a suitable polymerization catalyst. As the polymerization catalyst, a polymerization catalyst usually used for producing a urethane resin can be used. The polymerization catalyst is not particularly limited as long as the target amphoteric urethane resin can be obtained. As the polymerization catalyst, for example, a tertiary amine catalyst, an organometallic catalyst, or the like can be used. Examples of the tertiary amine catalysts include [2,2,2] diazabicyclooctane (DABCO), tetramethylenediamine, N-methylmorpholine, diazabicycloundecene (DBU), and the like. Examples of the organometallic catalysts include dibutyl tin (tin) dilaurate and the like.

When producing the amphoteric urethane resin, an organic solvent may be used as necessary for the reaction of the first step and the second step, and for example, an organic solvent that dissolves both of the compounds (A) to (D) and the resulting amphoteric urethane resin. It is preferable to use a solvent. Such organic solvents include, for example, amides such as N, N-methylpyrrolidone, dimethylformamide and dimethylacetamide, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and other cellosolve acetates. And cellosolve ethers.

Further, after the second step, it is preferable to perform the chain length extension reaction by mixing the reaction product of the second step with water. After the second step, the reaction product of the second step is mixed with basic water to carry out the chain length extension reaction. Or after adding a basic compound to the reaction product of a 2nd process, it is more preferable to mix with water and to perform chain length extension reaction. Among these, it is particularly preferable to carry out the chain length extension reaction by mixing the reaction product of the second step with the basic water after the second step. In the present invention, after the reaction of the first step and the second step in the organic solvent, it is preferable to mix the reaction mixture of the second step with basic water, and then further perform the chain length extension reaction in water. Thus, the form which mixes the reaction mixture after a 2nd process with basic water, and then performs a chain length extension reaction in water is preferable because it can obtain a high molecular weighted amphoteric urethane resin easily. In this manufacturing method, it is preferable to set the production conditions so that the reaction mixture after the second step is a prepolymer containing an isocyanate group at the terminal.

The basic water refers to water in which a basic substance is dissolved in water and shows basicity. For example, triethylamine, triethanolamine, ammonia, potassium hydroxide, sodium hydroxide, 2-amino-2-methyl-1-propanol, and the like The dissolved water can be illustrated.

In addition, a chain length extension agent can be used for the chain length extension reaction at the time of manufacturing the polysiloxane supported urethane resin in this invention, and the characteristic of the polysiloxane supported amphoteric resin finally obtained by a chain length extension agent can be adjusted. have. As the chain length extender, examples of the compound used in the chain length extension reaction include low molecular polyols, amines, water and the like. Examples of the low molecular polyols include glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, spiroglycol, bis (β-hydroxyethoxy) benzene, and xylene glycol. And triols such as trimethylolpropane and glycerin. Examples of the amines include methylene (bis-o-chloraniline) and the like.

In the present invention, it is preferable to use a polysiloxane-supported amphoteric urethane resin having a structural unit derived from alkylene oxide (hereinafter referred to as RO) in the structure of the resin in terms of improving the stability and properties of the cosmetic material. Do. Examples of the structural unit derived from RO include ethylene oxide (hereinafter referred to as EO) units, propylene oxide (hereinafter referred to as PO) units, and the like, and preferably EO units.                     

The compound having a structural unit derived from RO in the structure is not particularly limited as long as it can introduce a structural unit derived from RO into the structure of the polysiloxane-supported amphoteric urethane resin.

As a preferable compound which has a structural unit derived from RO in a structure, the compound which has at least 1 sort (s) chosen from a hydroxyl group, a primary amino group, and a secondary amino group, and a structural unit represented by following General formula (1) (following) , Compound (E).).

-(C ₂ H ₄ O) _p (C ₃ H ₆ O) _q- . (One)

(Wherein p represents an integer of 1 to 500, q represents an integer of 0 to 400.)

In the formula (1), when q is 0, a polymer (polyoxyethylene) of C ₂ H ₄ O, if q is not 0, C is a copolymer of ₂ H ₄ O and C ₃ H ₆ O . In the case of this copolymer, a random copolymer or a block copolymer may be sufficient.

In General formula (1), p is an integer of 1-500. Moreover, even when q is not 0, even when it is 0, p is preferable from 3-250, 3-120 are more preferable, and 3-50 are especially preferable. If p is less than 1, since there are too few EO units to be introduced into the amphoteric urethane resin, sufficient hydrophilicity cannot be imparted, and when the amphoteric urethane resin is used, for example, in a barbering agent, the hydrophilicity of the barbering agent is insufficient, resulting in hair trituration. This gets worse. On the other hand, when n exceeds 500, the hydrophilicity of the amphoteric urethane resin itself is excessively strengthened, which adversely affects moisture resistance and the like.

In general formula (1), the repeating number q of PO unit is an integer of 0-400, Preferably q = 0. When q is not 0, it is preferable to set q to the range of 3-200, More preferably, it is 3-100. Especially preferably, it is 3-40. In addition, even if q is not 0 and 0, it is preferable to set in the range of p + q = 3-300, More preferably, it is p + q = 10-120. Especially preferably, it is p + q = 3-50.

In addition, even if q is not 0 and 0, the ratio of EO unit and PO unit is preferably in the range of EO unit / PO unit = 10/0 to 2/8 by weight, more preferably EO Unit / PO unit = 10/0 to 3/7. Especially preferably, it is EO unit / PO unit = 10/0-4/6.

Furthermore, compound (E) is preferably a sock end OH group introduction type, a sock end NH ₂ group introduction type, a one end OH group introduction type, and a one end NH ₂ group introduction type. In the case where the sock end OH group introduction type or the sock end NH ₂ group introduction type is used, an amphoteric urethane resin having a structural unit represented by the general formula (1) in the main chain is obtained. In addition, when the single-terminal OH group introduction type or single-terminal NH ₂ group introduction type is used, the amphoteric urethane resin which has a structural unit represented by General formula (1) in a side chain or a terminal is obtained.

The weight average molecular weight of the compound (E) is preferably in the range of 200 to 20000, more preferably 200 to 5000. Especially preferably, it is 500-2000.

Examples of the compound (E) include polyethylene glycol (PEG), polyethylene polypropylene glycol, polyethylene polypropylene block copolymers, and the like. Especially, polyethylene glycol is preferable. Compound (E) can be used alone or in combination.

The polysiloxane-supported amphoteric urethane resin in the case of adding the compound (E) is preferably an amphoteric urethane resin produced by reacting the compounds (A) to (E) at least in the presence of the compound (S).

In manufacture of this resin, it can carry out similarly to the manufacturing method in the case of not adding a compound (E). That is, the compound (A), (B), (C) and (E) are reacted under an isocyanate group excess condition using at least the compounds (A) to (E) and (S) to form an isocyanate group-containing prepolymer. And a second step of reacting the isocyanate group-containing prepolymer with the compound (D), and at least one of the first step and the second step produces the compound (S). can do. Moreover, you may manufacture by alternating the reaction order of the said compound (C) and a compound (D).

The weight ratio of compound (S) and compounds (A), (B), (C), (D) and (E), i.e., (S) / ((A) + (B) + (C) + (D) It is preferable that + (E)) is 0.1 / 100-30 / 100, It is more preferable that it is 0.5 / 100-25 / 100, It is especially preferable that it is 1 / 100-20 / 100.

In addition, the molar ratio of compound (B) and compound (A), (C), (D) and (E), namely (B) / ((A) + (C) + (D) + (E)), is 2.0. It is preferable that it is /1.8-2.0/0.8, It is more preferable that it is 2.0 / 1.8-2.0 / 1.0, It is especially preferable that it is 2.0 / 1.8-2.0 / 1.2.

Further, the reaction of the first step and the second step can be carried out using the appropriate polymerization catalyst, using the reaction conditions usually used when producing the urethane resin, as in the case where the compound (E) is not added. The polymerization catalyst, organic solvent, chain length extension reaction and the like are also the same as above. Moreover, as mentioned above, also when compound (E) is added, it is more preferable to perform the said 1st process and a 2nd process in an organic catalyst, and to perform chain length extension reaction in water.

The polysiloxane-carrying amphoteric urethane resin of the present invention has a carboxyl group and a tertiary amino group in one molecule. The ratio (the ratio of the number of both functional groups) of the carboxyl group and the tertiary amino group, the carboxyl group / tertiary amino group are preferably 1/50 to 50/1, more preferably 1/1 to 50/1, more preferably 1/1 to 1 25/1 is particularly preferred. When the ratio of the carboxyl group and the tertiary amino group in the polysiloxane-supported urethane resin is 1/50 to 50/1, the hair will have more excellent hair when using a barber compound containing the polysiloxane-supported amphoteric urethane resin. In addition, 1 / 50-50 / 1 is preferable and, as for the ratio (molar ratio) of a compound (C) and a compound (D), and a compound (C) / compound (D) on the reaction, More preferably, 1 / 1-25 / 1 are especially preferable.

The polysiloxane-supported amphoteric urethane resin according to the present invention does not necessarily contain the polysiloxane chain of the polysiloxane compound through covalent bonds in the skeleton thereof, and the skeleton of the amphoteric urethane resin "constrains" the polysiloxane compound or the skeleton of the amphoteric urethane resin. By physically intertwining with the polysiloxane chain of the polysiloxane compound, the polysiloxane chain is contained. This restraint or entanglement is further complicated by the progress of the polymerization reaction of the amphoteric polyurethane, and it is considered that it is difficult to separate the polysiloxane compound from the obtained amphoteric urethane resin.

In this invention, the frame | skeleton of the amphoteric urethane resin and the entangled state of the polysiloxane compound are called the state in which the skeleton of the amphoteric urethane resin "supports" a polysiloxane compound. Here, the "support" differs in the form of an aqueous urethane resin in the form of an aqueous solution or in the form of an aqueous dispersion. The skeleton of the amphoteric urethane resin is usually a straight chain structure, but may have a branched structure and a crosslinked structure, and in the case where the amphoteric urethane resin is in the form of an "aqueous solution", it is considered that the polysiloxane chain enters between the skeletons of the amphoteric urethane resin.

On the other hand, when the amphoteric urethane resin is in the form of "water dispersion", it is considered that the amphoteric urethane resin is in the form of particles dispersed in water, and some forms are considered as a form of restraint of polysiloxane chains to the particles. First, the first form is a form in which all or part of the polysiloxane chain is surrounded by the particles. In the second form, the ends of the polysiloxane chains are surrounded by the particles. The third aspect is a form in which the polysiloxane chain is attached to the surface of the particles. All of the first to third forms correspond to "constraints", and it is considered that the first to third forms are present in a mixture.

As described above, the skeleton of the amphoteric urethane resin according to the present invention carries a polysiloxane compound. For this reason, while polysiloxane chains have the property of being relatively mobile, it is thought that it is difficult to separate a polysiloxane compound from an amphoteric urethane resin.

Below, the manufacture example of the polysiloxane carrying amphoteric urethane resin used for this invention and another urethane resin as a comparison is listed.

Production Example 1 Polysiloxane-supported amphoteric urethane resin (A)]

In a four-necked flask equipped with a stirring device, a thermometer, a nitrogen introducing tube and a reflux condenser, 70 g of isophorone diisocyanate (IPDI), 63 g of polypropylene glycol (PPG, weight average molecular weight 1000), 1,4-cyclohexanedimethanol ( CHDM) 7 g, dimethyl polysiloxane (viscosity at 25 ° C is 10 mm 2 / s, 8 g of SH200C-10cs (trade name) manufactured by Toray Dow Corning Silicon Co., Ltd.) and 20 g of dimethylolbutanoic acid (DMBA) were added as a solvent. 50 g of ethyl acetate was added, the mixture was heated to 80 ° C using an oil bath, and reacted for 3 hours. Then, 2 g of N-methyl diethanolamine (NMDEtA) and 60 g of ethyl acetate were added, and it reacted further at 80 degreeC for 3 hours, and the prepolymer in which an isocyanate group remained was obtained. After cooling the prepolymer in which this isocyanate group remained to 50 degreeC, it was made to disperse | distribute by high speed stirring to 700g of water containing 10g of potassium hydroxide, and it extended | reacted high molecular weight by carrying out chain length extension reaction at 50 degreeC for 3 hours. The said ethyl acetate was collect | recovered from the obtained aqueous liquid, and the aqueous liquid of the polysiloxane carrying amphoteric urethane resin (A) which does not contain a solvent substantially was obtained.

Production Example 2; Polysiloxane-supported amphoteric urethane resin (B)]

In the production method described in Production Example 1, instead of 8 g of dimethylpolysiloxane, 8 g of polyether-modified silicone (viscosity at 25 ° C was 1600 mm 2 / s, manufactured by Toray Dow Corning Silicon Co., Ltd.) 8 g Aqueous liquid of polysiloxane carrying amphoteric urethane resin (B) was obtained using the method similar to manufacture example 1 except having used.

Production Example 3; Polysiloxane-supported amphoteric urethane resin (C)]

In the production method described in Production Example 1, instead of 8 g of dimethylpolysiloxane, 8 g of cyclic silicone (viscosity at 25 ° C was 4 mm 2 / s, manufactured by Toray Dow Corning Silicone Co., Ltd.) 8 g Was prepared in the same manner as in Production Example 1 to obtain an aqueous solution of the polysiloxane-supported amphoteric urethane resin (C).                     

Production Example 4 Polysiloxane-supported amphoteric urethane resin (D)]

In the production method described in Production Example 1, instead of 8 g of dimethylpolysiloxane, 8 g of phenyl-modified silicone (22 mm2 / s in viscosity at 25 ° C. and SH556 (trade name) manufactured by Toray Dow Corning Silicon Co., Ltd.) was used. Aqueous liquid of polysiloxane carrying amphoteric urethane resin (D) was obtained using the method similar to manufacture example 1 except this.

Production Example 5 Polysiloxane-supported amphoteric urethane resin (E)]

In the manufacturing method of manufacture example 1, instead of 8 g of dimethylpolysiloxane, 8 g of alkyl modified silicone (500 mm <2> / s in viscosity at 25 degreeC, KF-412 (brand name) by Shin-Etsu Kagaku Kogyo Co., Ltd. product) was used. Aqueous liquid of polysiloxane carrying amphoteric urethane resin (E) was obtained using the method similar to manufacture example 1 except this.

Production Example 6 Polysiloxane-supported amphoteric urethane resin (F)]

In the manufacturing method of manufacture example 1, instead of 8 g of dimethylpolysiloxanes, 8 g of alkoxy modified silicone (80 mm <2> / s of viscosity in 25 degreeC, KF-851 (brand name) by Shin-Etsu Kagaku Kogyo Co., Ltd. product) was used. Aqueous liquid of polysiloxane carrying amphoteric urethane resin (F) was obtained except using the same method as the manufacturing example 1.

Production Example 7 Polysiloxane-supported amphoteric urethane resin (G)]

In the manufacturing method of manufacture example 1, instead of 8 g of dimethyl polysiloxanes, 20 g of dimethyl polysiloxanes (10 mm <2> / s of viscosity in 25 degreeC, SH200C-10cs (brand name) of Toray Dow Corning Silicone Co., Ltd. product) were prepared. Aqueous liquid of polysiloxane carrying amphoteric urethane resin (G) was obtained using the method similar to manufacture example 1 except having used.                     

Production Example 8 Polysiloxane-supported amphoteric urethane resin (H)]

In the production method described in Production Example 1, 20 g of a polyether-modified silicone (1600 mm 2 / s of viscosity at 25 ° C, SH3775C (trade name) manufactured by Toray Dow Corning Silicon Co., Ltd.) was used instead of 8 g of dimethylpolysiloxane. Aqueous liquid of polysiloxane carrying amphoteric urethane resin (H) was obtained using the method similar to manufacture example 1 except having used.

Production Example 9; Polysiloxane-supported amphoteric urethane resin (I)]

In a four-necked flask equipped with a stirring device, a thermometer, a nitrogen introduction tube and a reflux condenser, 70 g of isophorone diisocyanate (IPDI), 55 g of polypropylene glycol (PPG, weight average molecular weight 1000), polyethylene glycol (PEG, weight average molecular weight 1000) ) 8 g, 1 g of 1,4-cyclohexanedimethanol (CHDM), 8 g of dimethyl polysiloxane (viscosity at 25 ° C. at 10 mm 2 / s, Toray Dow Corning Silicone Co., Ltd.) 20 g of dimethylol butanoic acid (DMBA) was added, 50 g of ethyl acetate was added as a solvent, and the mixture was heated to 80 DEG C using an oil bath for 3 hours. Then, 2 g of N-methyl diethanolamine (NMDEtA) and 60 g of ethyl acetate were added, and it reacted further at 80 degreeC for 3 hours, and the prepolymer in which an isocyanate group remained was obtained. After cooling the prepolymer in which this isocyanate group remained to 50 degreeC, it was made to disperse | distribute by high speed stirring to 700g of water containing 10g of potassium hydroxide, and it extended | reacted high molecular weight by carrying out chain length extension reaction at 50 degreeC for 3 hours. The said ethyl acetate was collect | recovered from the obtained aqueous liquid, and the aqueous liquid of polysiloxane carrying amphoteric urethane resin (I) which does not contain a solvent substantially was obtained.

Production Example 10; Polysiloxane-supported amphoteric urethane resin (J)]                     

In the production method described in Production Example 9, instead of 8 g of dimethylpolysiloxane, 8 g of polyether-modified silicone (viscosity at 25 ° C was 1600 mm 2 / s, manufactured by Toray Dow Corning Silicon Co., Ltd.) 8 g Except for the use, the aqueous solution of the polysiloxane-supported amphoteric urethane resin (J) was obtained in the same manner as in Production Example 9.

Production Example 11 Polysiloxane-supported amphoteric urethane resin (K)]

In the production method described in Production Example 9, instead of 8 g of dimethylpolysiloxane, 20 g of dimethyl polysiloxane (viscosity at 25 ° C was 10 mm 2 / s and manufactured by Toray Dow Corning Silicon Co., Ltd.) was 20 g. Aqueous liquid of polysiloxane carrying amphoteric urethane resin (K) was obtained using the method similar to manufacture example 9 except having used.

Production Example 12; Polysiloxane-supported amphoteric urethane resin (L)]

In the manufacturing method of manufacture example 9, instead of 8 g of dimethylpolysiloxanes, 20 g of polyether modified silicones (viscosity at 25 degreeC is 1600 mm <2> / s and SH3775C (brand name) of Toray Dow Corning Silicone Co., Ltd. product) Aqueous liquid of polysiloxane carrying amphoteric urethane resin (L) was obtained using the method similar to manufacture example 9 except having used.

[Comparative Preparation Example 1; Amphoteric urethane resin (M)]

In the manufacturing method of manufacture example 1, the aqueous solution of amphoteric urethane resin (M) was obtained using the method similar to manufacture example 1 except not having used all the dimethylpolysiloxane.

[Comparative Preparation Example 2; Amphoteric urethane resin (N)]

In a four-necked flask equipped with a stirring device, a thermometer, a nitrogen introducing tube and a reflux condenser, 70 g of this phophorone diisocyanate (IPDI), 63 g of polypropylene glycol (PPG, weight average molecular weight 1000), 1,4-cyclohexanedimethanol ( 7 g of CHDM) and 20 g of dimethylol butanoic acid (DMBA) were added, 50 g of ethyl acetate was added as a solvent, and the mixture was heated to 80 DEG C using an oil bath for 3 hours. Then, 2 g of N-methyl diethanolamine (NMDEtA) and 60 g of ethyl acetate were added, and it reacted further at 80 degreeC for 3 hours, and the prepolymer in which an isocyanate group remained was obtained. After cooling the prepolymer in which this isocyanate group remained to 50 degreeC, it was made to disperse | distribute by high speed stirring to 700g of water containing 10g of potassium hydroxide, and it extended | reacted high molecular weight by carrying out chain length extension reaction at 50 degreeC for 3 hours. After recovering the ethyl acetate from the obtained aqueous solution and obtaining an aqueous solution of an amphoteric urethane resin substantially free of a solvent, dimethylpolysiloxane (viscosity at 25 ° C was 10 mm 2 / s, Toray Dow Corning Silicon Co., Ltd.) 8g of SH200C-10cs (brand name) of the product) was added, and the aqueous liquid of the amphoteric urethane resin (N) was obtained.

[Comparative Preparation Example 3; Amphoteric urethane resin (O)]

In the production method described in Comparative Production Example 2, 8 g of polyether-modified silicone (viscosity at 25 ° C is 1600 mm 2 / s, SH3775C (trade name) manufactured by Toray Dow Corning Silicon Co., Ltd.) instead of 8 g of dimethylpolysiloxane. Aqueous liquid of amphoteric urethane resin (O) was obtained using the method similar to the comparative manufacture example 2 except having used this.

[Comparative Preparation Example 4; Positive urethane resin (P)]

In the production method described in Comparative Production Example 2, instead of 8 g of dimethylpolysiloxane, 8 g of cyclic silicone (viscosity at 25 ° C was 4 mm 2 / s, manufactured by Toray Dow Corning Silicone Co., Ltd.) 8 g Except for the aqueous solution of the amphoteric urethane resin (P) using the same method as in Comparative Production Example 2.

[Comparative Preparation Example 5; Positive urethane resin (Q)]

In the production method described in Comparative Production Example 2, instead of 8 g of dimethylpolysiloxane, 8 g of phenyl-modified silicone (22 mm2 / s in viscosity at 25 ° C. and SH556 (trade name) of Toray Dow Corning Silicon Co., Ltd.) was used. Aqueous liquid of amphoteric urethane resin (Q) was obtained using the method similar to the comparative manufacture example 2 except having used.

[Comparative Preparation Example 6; Amphoteric urethane resin (R)]

In the production method described in Comparative Production Example 2, 8 g of alkyl-modified silicone (500 mm 2 / s in viscosity at 25 ° C., KF-412 (trade name) manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.) was substituted for 8 g of dimethylpolysiloxane. Aqueous liquid of amphoteric urethane resin (R) was obtained using the method similar to the comparative manufacture example except having used.

[Comparative Preparation Example 7; Positive urethane resin (S)]

In the manufacturing method of the comparative manufacturing example 2, instead of 8 g of dimethylpolysiloxane, 8 g of alkoxy modified silicone (80 mm <2> / s of viscosity in 25 degreeC, KF-851 (brand name) of Shin-Etsu Kagaku Kogyo Co., Ltd. product)) Aqueous liquid of amphoteric urethane resin (S) was obtained using the method similar to the comparative manufacture example except having used.

[Comparative Preparation Example 8; Positive urethane resin (T)]

In the production method described in Production Example 1, in place of 8 g of dimethylpolysiloxane, dimethyl polysiloxane diol (both end OH group introduction type, viscosity at 25 ° C. is 62 mm 2 / s, manufactured by Shin-Etsu Kagaku Kogyo KK-6002) (Brand name) Using the same method as Preparation Example 1, except that 8 g was used and 55 g of polypropylene glycol (PPG, weight average molecular weight 1000) was used instead of 63 g of polypropylene glycol (PPG, weight average molecular weight 1000). An aqueous liquid of amphoteric urethane resin (T) was obtained.

[Comparative Preparation Example 9; Positive urethane resin (U)]

In the production method described in Production Example 1, in place of 8 g of dimethylpolysiloxane, dimethyl polysiloxane diol (single-terminal OH group introduction type, viscosity at 25 ° C. is 88 mm 2 / s, manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.) X-22 The same method as Preparation Example 1 was carried out except that 8 g of -176B (trade name) was used and 55 g of polypropylene glycol (PPG, weight average molecular weight 1000) was used instead of 63 g of polypropylene glycol (PPG, weight average molecular weight 1000). To obtain an aqueous liquid of the amphoteric urethane resin (U).

Next, the cosmetic material containing a polysiloxane carrying amphoteric urethane resin is explained in full detail.

In the cosmetic material of the present invention, it is preferable to use a polysiloxane-supported amphoteric urethane resin in the form of an aqueous liquid, and the polysiloxane-supported amphoteric urethane resin according to the present invention is preferably mixed with water to form an aqueous solution. In the present invention, the aqueous solution is an aqueous dispersion and / or water suspension in which a polysiloxane-supported urethane resin is added to an aqueous solution completely dissolved in water, and the polysiloxane-supported urethane resin is dispersed and / or suspended in water. Means status. However, you may use the resin powder of the polysiloxane carrying amphoteric urethane resin obtained by substantially removing solvents, such as water. In addition, a crosslinking agent such as a silane binder may be added to the aqueous solution of the polysiloxane-carrying amphoteric urethane resin to impart crosslinking properties. In addition, it is also free to add various additives to impart storage stability, and examples thereof include protective colloids, antibacterial agents, antifungal agents and the like.

The cosmetic material of the present invention can be obtained by a conventional method by blending the polysiloxane-carrying amphoteric urethane resin as one component of the cosmetic material. In particular, the present invention provides an excellent cosmetic material exhibiting the functional coating properties of the polysiloxane-supported amphoteric urethane resin. It does not specifically limit as a cosmetic ash, For example, Hair barbers, such as a foam barber, a gel barber, an aerosol spray barber, a pump spray barber, hair cosmetics, such as hair conditioning, mascara, eyeliner, manicure, foundation, lipstick It can be widely applied as a cosmetic preparation such as makeup cosmetics, packs / masks, shaving agents, creams, emulsions, lotions, skin external preparations such as essences (cosmetics), fragrance cosmetics, body cosmetics and the like.

In addition, the formulations of cosmetic materials are also based on solution, solubilization, emulsification, foam, powder, powder dispersion, emulsion, gel, ointment, aerosol, spray, pump spray, water-oil two-layer, water- Oil-powder trilayers, a wide range of formulations can be employed.

Although the compounding quantity of the said polysiloxane carrying amphoteric urethane resin in this invention changes with cosmetics materials, 0.1-25.0 weight% is preferable in the cosmetics whole quantity. For example, in order to be used as a film forming agent of hair cosmetics, 0.1-10.0 weight% is preferable in the total amount of cosmetics materials. More preferably, it is 0.5 to 8.0 weight%. In the case of makeup cosmetic materials such as mascara, eyeliner, manicure, foundation, and lipstick, 0.1 to 25.0% by weight of the total amount of the cosmetic material is preferable. Moreover, in the case of a pack mask agent, 0.1-25.0 weight% is preferable in the cosmetics whole quantity. Moreover, in the case of external skin preparations, such as a shaving agent, cream, milky lotion, essence (cosmetic liquid), 0.1-15.0 weight% is preferable in the total amount of cosmetics materials.

The cosmetic material of the present invention can be blended with other ingredients usually used in cosmetics, pharmaceuticals and the like in addition to the above ingredients in a range that does not impair the effects of the present invention. For example, oil, powder components, surfactants, moisturizers, water-soluble polymers, thickeners, coatings, ultraviolet absorbers, metal ion blockers, sugars, amino acids, organic amines, pH regulators, skin nutrients, vitamins, antioxidants, fragrances, water, etc. This is listed.

The present invention will be described in detail with reference to the following Examples. The compounding quantity is weight%. In addition, it is% by weight unless it is specifically limited. Prior to the description of the Examples will be described the effect test method used in the present invention.

(Elasticity; curl memory method)

0.5 g of the prepared style link rim was applied to the black virgin hair (length 20 cm, weight 4 g), five curls were prepared per sample, and the resultant was dried at 50 ° C for 1 hour. The length of the hair strand to which this curl was added is measured, and it is set as the initial value (c). Then, a load of 60 g is applied to the hair tip for 15 minutes, the load is released after 15 minutes, and the scale of the hair tip is read (d). According to the following formula, the curl memory value was calculated.

Curl memory value (%) = {(20-d) / (20-c)} × 100

The closer the curl memory value is to 100%, the stronger the curl retention is and the better the elasticity is. In addition, evaluation criteria were set as follows.

◎: more than 90%

O: less than 70 to 90%

△: less than 50 to 70%

X: less than 50%

(Flaking)

To the black virgin hair (length 20cm, weight 4g), 0.5 g of the prepared style link rim was applied, and this was dried at 50 ° C for 1 hour. Subsequently, it was left to stand in a constant temperature and humidity container with a temperature of 25 ° C. and a humidity of 60% RH for 30 minutes. The state of flaking when the comb was passed through this hair strand five times was visually observed.

Evaluation criteria were set as follows.

◎: no flaking was found at all

O flaking not found

△: slightly flaking found

X: Flaked

(stability)

Thirty styling mousses are prepared in a transparent container, and cycle temperature tests (50 ° C to -10 ° C, 2 cycles / day, 1 month) are performed, and a professional researcher visually observes separation, creaming, and coagulation. It evaluated according to the following evaluation methods.

(Double-circle): 0 samples with which separation | segmentation, creaming, and aggregation were found.                     

O: One sample in which separation, creaming, agglomeration, or the like is found.

(Triangle | delta): Two samples in which separation | separation, creaming, and aggregation were found.

X: Three samples in which separation, creaming, agglomeration and the like are found.

(Examples 1 to 6)

First, in order to show the characteristic of the cosmetic material of this invention, the evaluation test was done using the styling mousse which is a hair cosmetic material as an example. The styling mousse of Examples 1-6 was produced with the prescription shown in Table 1, and the elasticity, flaking, and emulsion stability were evaluated. The results are also shown in Table 1. In addition, the polysiloxane carrying amphoteric urethane resin was mix | blended as an aqueous liquid.

(quite)

The emulsifying unit adds (1) to (2), (3), (4) and part of (16), and emulsifies with a homomixer. Subsequently, part of (15) is added to form an emulsifying unit. The ethanol portion is stirred and dissolved in (5) and (12) to (14). The water phase part adds (6) to (11) and the remaining (15) to the remainder (16), stirs and makes it uniform. As a mousse stock solution, the said 3 parts are mixed and obtained suitably. 92 parts of the obtained mousse stock solution were put into an aerosol can, a valve was put, and 8 parts of liquefied petroleum gas (LPG) was filled, and each styling mousse was obtained.

Example One 2 3 4 5 6 One Dimethyl Polysiloxane (6 mPas) 5.0 5.0 5.0 5.0 5.0 5.0 2 1,3-butylene glycol 5.0 5.0 5.0 5.0 5.0 5.0 3 glycerin 5.0 5.0 5.0 5.0 5.0 5.0 4 Polyoxyethylene Cured Castor Oil (40EO) 2.0 2.0 2.0 2.0 2.0 2.0 5 ethanol 10.0 10.0 10.0 10.0 10.0 10.0 6 Polysiloxane-supported amphoteric urethane resin (A) (resin concentration 20%) 15.0 - - - - - 7 Polysiloxane-supported amphoteric urethane resin (B) (resin concentration 20%) - 15.0 - - - - 8 Polysiloxane-supported positive urethane resin (C) (resin concentration 20%) - - 15.0 - - - 9 Polysiloxane-supported positive urethane resin (D) (resin concentration 20%) - - - 15.0 - - 10 Polysiloxane-supported amphoteric urethane resin (E) (resin concentration 20%) - - - - 15.0 - 11 Polysiloxane-supported positive urethane resin (F) (resin concentration 20%) - - - - 15.0 12 Specialty lauric acid diethanolamide (1: 1 form) 0.2 0.2 0.2 0.2 0.2 0.2 13 Alkyltrimethylammonium chloride 0.1 0.1 0.1 0.1 0.1 0.1 14 Parabens 0.1 0.1 0.1 0.1 0.1 0.1 15 Polyoxyethylene lauryl ether (12EO) 0.4 0.4 0.4 0.4 0.4 0.4 16 Ion exchange water Remainder Remainder Remainder Remainder Remainder Remainder Elasticity ◎ ◎ ◎ O ◎ O Flaking ◎ ◎ O ◎ O O stability O ◎ O O O O

As can be seen from Examples 1 to 6 of Table 1, the styling mousse of Examples 1 to 6 containing the polysiloxane-supported amphoteric urethane resins (A) to (F) according to the present invention were evaluated for the results of elasticity, flaking and stability. All proved to be excellent.

(Examples 7-12)

The styling mousse of Examples 7-12 was manufactured by the prescription shown in Table 2, and it carried out similarly to the method of Table 1, and evaluated the elasticity, flaking, and emulsion stability. The results are also shown in Table 2. In addition, polysiloxane carrying amphoteric urethane resin was mix | blended in the form of an aqueous liquid similarly to Table 1.                     

Example 7 8 9 10 11 12 One Dimethyl Polysiloxane (6 mPas) 5.0 5.0 5.0 5.0 5.0 5.0 2 1,3-butylene glycol 5.0 5.0 5.0 5.0 5.0 5.0 3 glycerin 5.0 5.0 5.0 5.0 5.0 5.0 4 Polyoxyethylene Cured Castor Oil (40EO) 2.0 2.0 2.0 2.0 2.0 2.0 5 ethanol 10.0 10.0 10.0 10.0 10.0 10.0 6 Polysiloxane-supported amphoteric urethane resin (G) (resin concentration 20%) 15.0 - - - - - 7 Polysiloxane-supported positive urethane resin (H) (resin concentration 20%) - 15.0 - - - - 8 Polysiloxane-supported amphoteric urethane resin (I) (resin concentration 20%) - - 15.0 - - - 9 Polysiloxane-supported positive urethane resin (J) (resin concentration 20%) - - - 15.0 - - 10 Polysiloxane-supported amphoteric urethane resin (K) (resin concentration 20%) - - - - 15.0 - 11 Polysiloxane-supported amphoteric urethane resin (L) (resin concentration 20%) - - - - - 15.0 12 Specialty lauric acid diethanolamide (1: 1 form) 0.2 0.2 0.2 0.2 0.2 0.2 13 Alkyltrimethylammonium chloride 0.1 0.1 0.1 0.1 0.1 0.1 14 Parabens 0.1 0.1 0.1 0.1 0.1 0.1 15 Polyoxyethylene lauryl ether (12EO) 0.4 0.4 0.4 0.4 0.4 0.4 16 Ion exchange water Remainder Remainder Remainder Remainder Remainder Remainder Elasticity ◎ ◎ ◎ ◎ ◎ ◎ Flaking O ◎ ◎ ◎ O ◎ stability O ◎ O ◎ O ◎

As can be seen from Examples 7 to 12 of Table 2, the styling mousse of Examples 7 to 12 containing the polysiloxane-supported amphoteric urethane resins (G) to (L) according to the present invention were evaluated for the results of elasticity, flaking and stability. All proved to be excellent.

(Comparative Examples 1 to 5)

The styling mousse of Comparative Examples 1-5 was manufactured with the prescription shown in Table 3, and the elasticity, flaking, and emulsion stability were evaluated. The results are also shown in Table 3. In addition, the amphoteric urethane resin was mix | blended in the form of the aqueous liquid.

(quite)                     

An emulsifying part adds (1) to (2), (3), (4) and some (15), and emulsifies with a homomixer. Subsequently, part (14) is added to form an emulsifying unit. The ethanol portion is stirred and dissolved in (5) and (11) to (13). The water phase part adds (6) to (10) and the remaining (14) to the remaining (15), stirs and makes it uniform. As a mousse stock solution, the said 3 parts are mixed and obtained suitably. 92 parts of the obtained mousse stock solution were put in an aerosol can, a valve was put, 8 parts of liquefied petroleum gas (LPG) was filled, and each styling mousse was obtained.

Comparative example One 2 3 4 5 One Dimethyl Polysiloxane (6 mPas) 5.0 5.0 5.0 5.0 5.0 2 1,3-butylene glycol 5.0 5.0 5.0 5.0 5.0 3 glycerin 5.0 5.0 5.0 5.0 5.0 4 Polyoxyethylene Cured Castor Oil (40EO) 2.0 2.0 2.0 2.0 2.0 5 ethanol 10.0 10.0 10.0 10.0 10.0 6 Amphoteric urethane resin (M) (resin concentration 20%) 15.0 - - - - 7 Amphoteric urethane resin (N) (resin concentration 20%) - 15.0 - - - 8 Amphoteric urethane resin (O) (resin concentration 20%) - - 15.0 - - 9 Amphoteric urethane resin (P) (resin concentration 20%) - - - 15.0 - 10 Amphoteric urethane resin (Q) (resin concentration 20%) - - - - 15.0 11 Specialty lauric acid diethanolamide (1: 1 form) 0.2 0.2 0.2 0.2 0.2 12 Alkyltrimethylammonium chloride 0.1 0.1 0.1 0.1 0.1 13 Parabens 0.1 0.1 0.1 0.1 0.1 14 Polyoxyethylene lauryl ether (12EO) 0.4 0.4 0.4 0.4 0.4 15 Ion exchange water Remainder Remainder Remainder Remainder Remainder Elasticity △ △ △ O △ Flaking O O △ X X stability X X X X X

As can be seen from Comparative Examples 1 to 5 of Table 3, all of the styling mousses of Comparative Examples 1 to 5 containing the positive urethane resins (M) to (Q) outside the scope of the present invention are all the results of the evaluation of elasticity, flaking and stability. It turns out that it does not satisfy.

(Comparative Examples 6 to 10)                     

In the formulation shown in Table 4, the styling mousse of Comparative Examples 6 to 10 was prepared in the same manner as in Table 3, and the elasticity, flaking, and emulsion stability were evaluated. The results are also shown in Table 4. In addition, the amphoteric urethane resin mix | blended is an aqueous liquid similarly to Table 3.

Comparative example 6 7 8 9 10 One Dimethyl Polysiloxane (6 mPas) 5.0 5.0 5.0 5.0 5.0 2 1,3-butylene glycol 5.0 5.0 5.0 5.0 5.0 3 glycerin 5.0 5.0 5.0 5.0 5.0 4 Polyoxyethylene Cured Castor Oil (40EO) 2.0 2.0 2.0 2.0 2.0 5 ethanol 10.0 10.0 10.0 10.0 10.0 6 Amphoteric urethane resin (R) (resin concentration 20%) 15.0 - - - - 7 Amphoteric urethane resin (S) (resin concentration 20%) - 15.0 - - - 8 Amphoteric urethane resin (T) (resin concentration 20%) - - 15.0 - - 9 Amphoteric urethane resin (U) (resin concentration 20%) - - - 15.0 - 10 Cationic polymer (resin concentration 30%) - - - - 15.0 11 Specialty lauric acid diethanolamide (1: 1 form) 0.2 0.2 0.2 0.2 0.2 12 Alkyltrimethylammonium chloride 0.1 0.1 0.1 0.1 0.1 13 Parabens 0.1 0.1 0.1 0.1 0.1 14 Polyoxyethylene lauryl ether (12EO) 0.4 0.4 0.4 0.4 0.4 15 Ion exchange water Remainder Remainder Remainder Remainder Remainder Elasticity △ △ O O X Flaking X X X X O stability X X X X △

Yukaformer SM manufactured by Mitsubishi Kagaku Co., Ltd. (ethanol solution of N-methacryloyloxy-N, N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate copolymer)

As can be seen from Comparative Examples 6 to 10 of Table 4, all of the styling mousses of Comparative Examples 6 to 9 containing the positive urethane resins (R) to (U) outside the scope of the present invention were evaluated for elasticity, flaking, and stability. It turns out that it is not satisfying. Moreover, it turns out that the comparative example 10 which mix | blended the amphoteric polymer other than the amphoteric urethane resin similarly does not satisfy all evaluation of elasticity, flaking, and stability.                     

In addition, examples of the present invention are listed below. The blended polysiloxane-supported amphoteric urethane resins are all aqueous liquids. Moreover, about the following, although the evaluation test is not specifically demonstrated individually, the characteristic of the polysiloxane carrying amphoteric urethane resin of this invention was fully exhibited.

Example 13 Pack (Jelly Shape Peel Off Type)

Compounding amount (% by weight)

(1) polyvinyl alcohol 10.0

(2) Polysiloxane-supported amphoteric urethane resin (A) 2.5

    (20% aqueous solution) (0.5% as amount of resin)

(3) polysiloxane-supported amphoteric urethane resin (J) 2.5

    (20% aqueous solution) (0.5% as amount of resin)

(4) Carboxymethylcellulose 5.0

(5) 1,3-butylene glycol 5.0

(6) Ethanol 12.0

(7) appropriate amount of spices

(8) Methylparaben 0.2

(9) Buffer (Quenoic Acid, Cuenoic Acid Na) appropriate amount

(10) polyoxyethylene oleyl alcohol ether 0.5

(11) rest of ion exchange water

(quite)                     

(9), (5), (2) and (3) are added to (11), and it heats at 70-80 degreeC. Here, (4) and (1) are added and stirring and dissolution are performed. After dissolving (7), (8), and (10) in (6), it is added to the said water phase, and is degassed, filtered, and cooled. The skin using this product was moist, smooth and gives the skin a firm feeling.

[Example 14] O / W Emulsion Type Foundation

Compounding amount (% by weight)

(1) talc 3.0

(2) titanium dioxide 5.0

(3) Bengala 0.5

(4) iron sulfate 1.4

(5) iron oxide black 0.1

(6) bentonite 0.5

(7) monostearic acid polyoxyethylene sorbitan 0.9

(8) Triethanolamine 1.0

(9) Propylene Glycol 10.0

(10) Polysiloxane Supported Amphoteric Urethane Resin (B) 10.0

     (20% aqueous solution) (2% by amount of resin)

(11) rest of ion exchange water

(12) stearic acid 2.2

(13) Isohexadecyl alcohol 7.0                     

(14) glycerin monostearate 2.0

(15) Liquid Lanolin 2.0

(16) Paraffin 8.0

(17) ethyl paraffin 0.1

(18) appropriate amount of perfume

(quite)

(9) in which (6) is dispersed is added to (11), and after homomixing at 70 ° C, the remaining water phase components (7), (8), and (10) are added and sufficiently stirred. To this, the powder part which was sufficiently mixed and pulverized was added while stirring, and homomixed at 70 ° C. Then, oil phases (12) to (16) and (17) heated and dissolved at 70 to 80 ° C are gradually added and homogenized at 70 ° C. It cools with stirring, (18) is added at 45 degreeC, and it cools to room temperature. Finally, it is degassed and filled into the container. The obtained emulsion foundation was moist, smooth, and had good makeup lasting properties.

[Example 15] Eyeliner

Compounding amount (% by weight)

(1) Iron oxide (black) 14.0

(2) Polysiloxane Supported Amphoteric Urethane Resin (C) 45.0

    (20% aqueous solution) (9.0% as amount of resin)

(3) glycerin 5.0

(4) polyoxyethylene sorbitan monooleic acid ester 1.0                     

(5) Carboxymethylcellulose 1.5

(6) Acetyl Tributyl Cuene 1.0

(7) rest of ion exchange water

(8) Methylparaben 0.1

(9) appropriate amount of spices

(quite)

(2), (3) and (4) are added to (7), and after heating and melting, (1) is added and treated with a colloid mill (pigment part). The remaining ingredients are mixed and heated to 70 ° C. A pigment part is added to this and it disperse | distributes uniformly with a homomixer. The obtained eyeliner had a moderate degree of elasticity and a good usability.

Example 16 Lotion

Compounding amount (% by weight)

(1) 1,3-butylene glycol 6.0

(2) glycerin 5.0

(3) polyethylene glycol 400 3.0

(4) Olive Oil 0.5

(5) polyoxyethylene (20) sorbitan monostearic acid ester 1.5

(6) polyoxyethylene (5) oleyl alcohol ether 0.3

(7) Ethanol 10.0

(8) appropriate amount of spices                     

(9) appropriate amount of colorant

(10) phenoxyethanol appropriate amount

(11) quenic acid

(12) appropriate amount of soda

(13) Proper amount of brown inhibitor

(14) proper amount of ion-exchanged water

(15) polysiloxane supported amphoteric urethane resin (D) 0.5

           (20% aqueous solution) (0.1% as amount of resin)

(16) polysiloxane supported amphoteric urethane resin (L) 0.5

           (20% aqueous solution) (0.1% as amount of resin)

(quite)

(1), (2), (3), (11), (12), (15), and (16) are added to (14), and it melt | dissolves at room temperature. On the other hand, (4), (5), (6), (10), and (8) are added to (7), and it melt | dissolves at room temperature. This alcohol phase is added to the aqueous phase, and (9) and (13) are further added to adjust the microemulsion. The obtained lotion was moist, smooth, and gives skin a firm feeling.

Example 17 Latex

Compounding amount (% by weight)

(1) cetyl alcohol 1.0

(2) yellow wax 0.5                     

(3) Vaseline 2.0

(4) squalene 6.0

(5) Dimethylpolysiloxane (viscosity 20 MpaS) 2.0

(6) Ethanol 4.0

(7) glycerin 4.0

(8) 1,3-butylene glycol 4.0

(9) Polyoxyethylene (10) monooleic acid ester 1.0

(10) Glycerol Monostearic Acid Ester 1.0

(11) Chinese quince seed extract (5% aqueous solution) 10.0

(12) Polysiloxane Supported Ammonium Urethane Resin (E) 10.0

     (20% aqueous solution) (2% as amount of resin)

(13) Methyl paraben appropriate amount

(14) Solvent (dye) appropriate amount

(15) appropriate amount of spices

(16) rest of ion exchange water

(quite)

(7), (8), (12) and (14) were added to (16), and heating was adjusted to 70 ° C. (9) and (10) are added to (1)-(5), and it heat-adjusts to 70 degreeC. This is added to the water phase and preliminary emulsification is performed. (6) which melt | dissolved (11) and (13) was added here, and after emulsifying particle | grains by making it uniform with stirring and a homomixer, after degassing and filtration, (15) is added and cooling is performed. The feeling of use of the obtained emulsion was moist, smooth, and it gave elasticity to skin.

Example 18 Cream

Compounding amount (% by weight)

(1) stearyl alcohol 6.0

(2) stearic acid 2.0

(3) hydrogenated lanolin 4.0

(4) squalene 9.0

(5) Octyldodecanol 10.0

(6) 1,3-butylene glycol 6.0

(7) polyethylene glycol 1500 4.0

(8) polysiloxane supported amphoteric urethane resin (F) 3.0

    (20% aqueous solution) (0.6% as amount of resin)

(9) Polyoxyethylene (25) cetyl alcohol ether 3.0

(10) glycerin monostearate 2.0

(11) methylparaben

(12) Vitamin E

(13) appropriate amount of spices

(14) rest of ion exchange water

(quite)

(6), (7), (8) is added to (14), and it heat-adjusts to 70 degreeC. After (1)-(5) is melt | dissolved by heating, (9), (10), (11), (12), and (13) are added, and it heat-adjusts to 70 degreeC. This is added to the previous water phase, the emulsion particles are uniformed in a homomix, degassed, filtered and cooled. The obtained cream was moist and smooth, and also gave elasticity to skin.

Example 19 Whitening Essence

Compounding amount (% by weight)

(1) dipropylene glycol 5.0

(2) polyethylene glycol 400 5.0

(3) Ethanol 10.0

(4) Carboxyvinyl Polymer 0.3

(5) Alginic acid Na 0.3

(6) potassium hydroxide 0.15

(7) polyoxyethylene sorbitan monostearic acid ester 1.0

(8) Sorbitan monooleic acid ester 0.5

(9) polysiloxane-supported amphoteric urethane resin (G) 0.5

    (20% aqueous solution) (0.1% as amount of resin)

(10) oleyl alcohol 0.5

(11) Pracent Extract 0.2

(12) Vitamin E Acetate 0.2

(13) appropriate amount of spices

(14) Methyl paraben appropriate amount                     

(15) appropriate amount of trisodium edite

(16) rest of ion exchange water

(quite)

After dissolving (4) and (5) in some (16), (1), (2), and (15) are dissolved sequentially. (3), (7), (8), (10), (11), (12), (13), and (14) are sequentially dissolved in (3), added to the aqueous phase, and microemulsified. Finally, (6) is melt | dissolved and added to some (16), and (9) is then added, and it stirred, degassed, and filtered. The obtained whitening essence was moist and smooth, and also gave elasticity to skin.

Example 20 Sunscreen Essence

Compounding amount (% by weight)

(1) stearic acid 3.0

(2) cetanol 1.0

(3) Lanolin derivative 3.0

(4) floating paraffin 5.0

(5) 2-ethylhexyl stearate 3.0

(6) 1,3-butylene glycol 6.0

(7) polysiloxane supported amphoteric urethane resin (H) 4.0

    (20% aqueous solution) (0.8% as amount of resin)

(8) polyoxyethylene cetyl alcohol ether 2.0

(9) glycerin monostearate 2.0                     

(10) Triethanolamine 1.0

(11) 2-hydroxy-4-methoxybenzophenone 4.0

(12) dibenzoylmethane derivative 4.0

(13) sorbic acid 0.2

(14) appropriate amount of spices

(15) rest of ion exchange water

(quite)

(6), (7), and (10) are dissolved in (15), heated, and maintained at 70 ° C. After dissolving (1)-(5) at 70-80 degreeC, (8), (9), (11), (12), (13), and (14) are melt | dissolved sequentially and it is made into the temperature of 70 degreeC. . The oil phase is added while stirring the said water phase, and emulsification is performed. After homogeneously adjusting the emulsion particles with a homomixer, degassing and cooling. The obtained ultraviolet blocking essence was moist and smooth, and also gave elasticity to skin.

Example 21 Hair Styling Gel

Compounding amount (% by weight)

(1) Carboxyvinyl Polymer 0.7

(2) polysiloxane-supported amphoteric urethane resin (I) 5.0

    (20% aqueous solution) (1.0% as amount of resin)

(3) polysiloxane supported amphoteric urethane resin (K) 5.0

    (20% aqueous solution) (1.0% as amount of resin)

(4) glycerin 2.5                     

(5) 1,3-butylene glycol 2.5

(6) Polyoxyethylene Cured Castor Oil (40EO) 0.5

(7) Dimethylpolysiloxane 100cs 5.0

(8) polyether modified silicone 1.0

   (Brand name: KF6011, Shin-Etsukagaku Bridge)

(9) sodium hydroxide appropriate amount

(Prepared at pH 7.5)

(10) Ethanol 20.0

(11) polyoxyethylene octyldodecyl ether 0.1

12.Fragrance 0.1

(13) trisodium edetic acid 0.03

(14) rest of ion exchange water

(quite)

(7) is mixed with (4), (5), (6), (8), and some (14), and it emulsifies with a homomixer. Next, part of (14) is added to form an emulsifying unit. On the other hand, (1), (2), (3), (9), (10), (11), (12), and (13) were uniformly dissolved in the remaining (14), and the preceding emulsification part was added thereto. Thus, an oil-like hair styling gel was obtained.

Example 22 Manicure

Compounding amount (% by weight)

(1) ethylcarbitol 2.5                     

(2) 1,3-butylene glycol 1.0

(3) Polysiloxane Supported Amphoteric Urethane Resin (B) 45.0

    (20% aqueous solution) (9.0% as amount of resin)

(4) Polysiloxane Supported Ammonium Urethane Resin (A) 40.0

    (20% aqueous solution) (8.0% as amount of resin)

(5) clay minerals 0.2

(6) Polyoxyethylene Cured Castor Oil (40EO) 0.3

(7) appropriate amount of color materials

(8) rest of ion exchange water

(quite)

After dissolving (6) in (8), (7) was mixed and fully dispersed. Then, (1)-(5) was stirred and mixed uniformly, and the manicure was obtained.

Example 23 Mascara

Compounding amount (% by weight)

(1) Iron oxide (black) 10.0

(2) Polysiloxane-supported amphoteric urethane resin (C) 20.0

    (30% aqueous solution) (6.0% as amount of resin)

(3) polysiloxane-supported amphoteric urethane resin (G) 10.0

    (30% aqueous solution) (3.0% as amount of resin)

(4) Solid Paraffin 8.0                     

(5) Lanolin Wax 8.0

(6) hard isoparaffin 30.0

(7) sesquioleic acid sorbitan 4.0

(8) rest of ion exchange water

(9) appropriate amount of preservative

(10) appropriate amount of spices

(quite)

(1) is added to (8), and it disperse | distributes with a homomixer, (2) and (3) are added, it heats, and it maintains at 70 degreeC (water phase). The other components are mixed, heated and kept at 70 ° C (oil phase). The oil phase is uniformly emulsified and dispersed in a homomixer.

Example 24 Lipstick

Compounding amount (% by weight)

(1) titanium dioxide 4.5

(2) Red 201 2.5

(3) Selesin 4.0

(4) candellila wax 8.0

(5) carnauba wax 2.0

(6) Castor oil 30.0

(7) isostearic acid diglycelide 40.0

(8) Polyoxyethylene Cured Castor Oil (20EO) 1.0                     

(9) rest of ion exchange water

(10) polysiloxane supported amphoteric urethane resin (D) 2.0

    (30% aqueous solution) (0.6% as amount of resin)

(11) polysiloxane supported amphoteric urethane resin (E) 3.0

    (30% aqueous solution) (0.9% as amount of resin)

12 Glycerin 2.0

(13) appropriate amount of spices

(14) appropriate amount of antioxidant

(quite)

(1) and (2) were added to a part of (6) and processed with a roller (pigment part). (9)-(12) are mixed (water phase). After a part of (3)-(5), (6), (7), (8), and (14) is mixed and heat-fused, a pigment part is added at 80 degreeC, and it mixes uniformly by a homomixer. Thereafter, an aqueous phase is added, the emulsion is dispersed with a homomixer, and then (13) is added to flow into the mold.

According to this invention, the outstanding cosmetic material which fully exhibited the film | membrane characteristic of the novel polysiloxane carrying amphoteric urethane resin is obtained. For example, in the hair cosmetic material, particularly excellent hair elasticity is obtained, there is no flaking in combing, and the emulsion stability of the product is excellent. In the makeup cosmetics material, there is a particularly moist feeling, and the makeup persistence such as wear resistance is good. In skin cosmetic materials, it is particularly moist and smooth and gives the skin a moderate level of elasticity.

Claims (15)

delete  A cosmetic material comprising an amphoteric urethane resin carrying a polysiloxane compound, The amphoteric urethane resin is produced by reacting at least the compounds of the following (A) to (D) in the presence of the following compound (S). (A) at least one polyol compound selected from polyester polyols, polyether polyols, low molecular weight polyols, polycarbonate polyols, polybutadiene polyols, polyisoprene polyols, polyolefin polyols, and polyacrylic acid ester polyols (B) at least one polyisocyanate compound selected from aliphatic diisocyanate compounds, alicyclic diisocyanate compounds and aromatic diisocyanate compounds (C) at least one compound selected from carboxylic acids having 3 to 26 carbon atoms having a dialkylol group and a carboxyl group-containing polycaprolactone diol (D) at least one compound selected from N-alkyldialkanolamine, N, N-dialkylalkanolamine, triethanolamine (S) A polysiloxane compound which is not chemically bonded to the amphoteric urethane resin backbone through a covalent bond, and is at least one polysiloxane compound selected from dimethylpolysiloxane, polyether modified silicone, cyclic silicone, phenyl modified silicone, alkyl modified silicone and alkoxy modified silicone. . The method of claim 2, The amphoteric urethane resin, A first step of producing the isocyanate group-containing prepolymer by reacting the compounds of (A), (B) and (C) under conditions of excess isocyanate group, and Positive which is produced by the method of making the compound of (S) exist in at least one of a 1st process and a 2nd process including the 2nd process of making the said isocyanate group containing prepolymer react with the compound of said (D). Cosmetic material characterized by the urethane resin. The method of claim 2, The amphoteric urethane resin, A first step of reacting the compounds of (A), (B) and (D) under conditions of excess isocyanate group to produce an isocyanate group-containing prepolymer, and Positive which is produced by the method of making the compound of (S) exist in at least one of a 1st process and a 2nd process including the 2nd process of making the said isocyanate group containing prepolymer react with the compound of said (C). Cosmetic material characterized by the urethane resin. The method of claim 2, The amphoteric urethane resin is produced by further reacting the following compound (E) in addition to the compounds (A) to (D) at least in the presence of the compound (S). (E) A compound having at least one selected from a hydroxyl group, a primary amino group and a secondary amino group and a structural unit represented by the following general formula (1) -(C ₂ H ₄ O) _p (C ₃ H ₆ O) _q- . (One) (Wherein p represents an integer of 1 to 500, q represents an integer of 0 to 400.) The method of claim 5, wherein The amphoteric urethane resin, A first step of producing the isocyanate group-containing prepolymer by reacting the compounds of (A), (B), (C) and (E) under conditions of excess isocyanate group, and Positive which is produced by the method of making the compound of (S) exist in at least one of a 1st process and a 2nd process including the 2nd process of making the said isocyanate group containing prepolymer react with the compound of said (D). Cosmetic material characterized by the urethane resin. The method of claim 5, wherein The amphoteric urethane resin, A first step of producing the isocyanate group-containing prepolymer by reacting the compounds of (A), (B), (D) and (E) under conditions of excess isocyanate group, and Positive which is produced by the method of making the compound of (S) exist in at least one of a 1st process and a 2nd process including the 2nd process of making the said isocyanate group containing prepolymer react with the compound of said (C). Cosmetic material characterized by the urethane resin. 8. The method according to any one of claims 3, 4, 6 and 7, further comprising a step of performing a chain length extension reaction by mixing the reaction product of the second step with water after the second step. Cosmetic material characterized by the above. 8. The chain length extension reaction according to any one of claims 3, 4, 6 and 7, wherein after the second step, the reaction product of the second step is mixed with basic water to perform a chain length extension reaction, or A cosmetic material comprising the step of adding a basic compound to the reaction product of the step and then mixing with water to effect a chain length extension reaction. The polysiloxane compound according to any one of claims 2 to 7, wherein the polysiloxane compound is a polysiloxane compound having no at least one selected from a hydroxyl group, a primary amino group and a secondary amino group at the sock end or single end of the siloxane. Cosmetic ingredients. delete The cosmetic material according to any one of claims 2 to 7, wherein the amphoteric urethane resin carrying the polysiloxane compound is blended as the amphoteric urethane resin aqueous solution. The cosmetic material according to any one of claims 2 to 7, wherein the amphoteric urethane resin is an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule. The cosmetic material according to any one of claims 2 to 7, wherein the cosmetic material is a hair cosmetic material. The cosmetic material according to any one of claims 2 to 7, wherein the cosmetic material is an external skin preparation.