JP7096647B2 - Composition and hair cosmetics using it - Google Patents

Description

The present invention relates to hair cosmetics and compositions used therein.

There are various dosage forms such as waxes, gels, creams, foams, sprays and lotions as hair cosmetics for adjusting hairstyles. These hair cosmetics are often prepared using polymer compounds, but if the amount of polymer compounds is increased in order to enhance the effect, there will be problems with the texture such as stiffness and stickiness, or the appearance problems such as flaking. It may occur, and it has become an issue to achieve both a hair conditioning effect and a feel at the time of use.

Until now, the combination of resin that imparts setting power and other components has been devised to achieve both keeping power and conditioning effect, but if the conditioning effect is emphasized, the resin is affected by the ingredients blended to obtain the conditioning effect. Was affected by the plasticizing effect, and in some cases, sufficient keeping power was not exhibited. On the other hand, if the keeping power is emphasized, the hair feels stiff and resiny due to the influence of the resin blended in a large amount, so that the conditioning effect is not always satisfactory.

Furthermore, the resin that imparts keeping force often has a high film-forming ability as its characteristic, and the hairstyle made of such a resin may not return once the style is broken by an external factor, and the hairstyle may not be restored. There has been a demand for a styling agent having a hair styling property. Hair wax is an example of a conventional styling agent that has hair styling properties, but it is suitable for creating light hairstyles, which is a trend in recent years, because of the weight and stickiness caused by the oil contained in the formulation. I wasn't. Therefore, amine oxide group-containing resins (see, for example, Patent Document 1, Patent Document 2, and Non-Patent Document 1) have been developed as resins having both settability and keeping power. As an example of applying this amine oxide group-containing resin, a hair cosmetic (for example, see Patent Document 3), which is a combination of an amine oxide group-containing resin and a silicone compound and has excellent keeping power, settability, and conditioning effect, and amine oxide. Cosmetics with excellent settability and keeping power (see, for example, Patent Document 4), which are a combination of a group-containing resin and a compound having a plurality of OH groups such as a polyhydric alcohol, an amine oxide group-containing resin and a propylene oxide copolymer. Examples thereof include hair cosmetics having a settability and a conditioning effect (see, for example, Patent Document 5) in which a polyhydric alcohol and a polyether-modified silicone are combined.

Japanese Patent No. 3520674 Japanese Unexamined Patent Publication No. 2001-310915 Japanese Unexamined Patent Publication No. 2000-336018 Japanese Unexamined Patent Publication No. 2000-327522 Japanese Unexamined Patent Publication No. 2007-31307

The Cosmetic Toiletries and Fragrance Association, "International Cosmetic Ingredient Dictionary and Handbook 9th Edition", 2002, volume 1, p. 31

However, when the polymers or emulsions described in the above documents are used as hair cosmetics, the flexibility can be improved, but the moisture resistance and the hardness of the hair when set may not be sufficient. ..

Therefore, an object of the present invention is to obtain a hair cosmetic and a composition used therein, which retains moisture resistance and sufficient hair hardness when set, in addition to flexibility.

The gist of the present invention lies in the following [1] to [11].
[1] A composition containing the following components (1), (2), and (3).
(1) A resin containing at least one of a repeating unit selected from a repeating unit derived from an unsaturated monomer having a betaine structural group and a repeating unit derived from an unsaturated monomer having an amine oxide group, or a carboxyl group or a sulfonic acid. It contains a repeating unit derived from an unsaturated monomer having an anionic group selected from the group consisting of a group and a phosphoric acid group, and further a repeating unit derived from an unsaturated monomer having a tertiary amino group and a quaternary ammonium. A resin containing at least one of the repeating units derived from an unsaturated monomer having a group. (2) Polyurethane (P) or the polyurethane (P) and (meth) acrylic resin (Q) obtained from a polyol component containing at least one selected from a polyether polyol and a polyester polyol and a polyvalent isocyanate component. A composite urethane- (meth) acrylic composite resin, the polyester polyol of the polyol component contains a structural unit derived from a polyalkylene glycol having 2 to 4 carbon atoms as a main component and has a number average molecular weight of 400. The polyester polyol is 4000 or less, or the polyester polyol as the polyol component has a constituent unit derived from at least one dicarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid. Polyurethane or urethane- (meth) acrylic composite resin.
(3) At least one selected from (t-1) oils, (t-2) alcohols, (t-3) surfactants, (t-4) protein hydrolysates, amino acids and derivatives thereof, ( t-5) A compounding ingredient containing any one or more of water.

[2] The component (1) contains at least one selected from a repeating unit derived from an unsaturated monomer having a betaine structural group and a repeating unit derived from an unsaturated monomer having an amine oxide group [1]. Hair cosmetics using the described composition.
[3] The component (1) contains a repeating unit derived from an unsaturated monomer having an anionic group selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and further contains a tertiary amino group. A hair cosmetic using the composition according to [1], which contains at least one of a repeating unit derived from an unsaturated monomer having a quaternary ammonium group and a repeating unit derived from an unsaturated monomer having a quaternary ammonium group.

[4] The polyol component constituting the component (P) has at least two types of polyol components in which the number average molecular weights are different and / or the constituent units thereof are different. [2] or [ 3] The hair cosmetic according to.
[5] The item according to any one of [2] to [4], wherein the weight ratio ((P) / (Q)) of the component (P) to the component (Q) is 80/20 to 30/70. Hair cosmetics.
[6] Any of [2] to [5], wherein a polyether polyol is used as the polyol component constituting the component (P), and the average value of the carbon atoms of the constituent units constituting the polyether polyol is 2 to 4. The hair cosmetic according to item 1.

[7] The hair cosmetic according to [6], wherein the polyether polyol has a number average molecular weight of 500 or more and 3000 or less.
[8] A plurality of types of polyether polyols having different number average molecular weights are used as the polyol component, and among the plurality of types of polyether polyols, the polyether polyol having the smallest number average molecular weight has a number average molecular weight of 400 or more. The hair cosmetic according to [6] or [7], which is 1200 or less.
[9] A polyester polyol is used as the polyol component constituting the component (P), and the dicarboxylic acid-derived structural unit in the polyester polyol is any one of [2] to [5], which is an isophthalic acid-derived structural unit. Hair cosmetics listed in section.
[10] The hair cosmetic according to [9], wherein the content ratio of the constituent unit derived from the dicarboxylic acid is 0.05% by weight or more and 50% by weight or less.
[11] The hair cosmetic according to any one of [2] to [10], wherein the pH of the composition is 3 to 11.

Since the hair cosmetic according to the present invention contains the above-mentioned components (1) to (3), it maintains flexibility, moisture resistance, and sufficient hair hardness when set. It can demonstrate the feature of being able to do it.

Hereinafter, the present invention will be described in detail.
The hair cosmetic according to the present invention comprises the following specific biionic polymer ((1) component), a predetermined urethane or urethane- (meth) acrylic composite resin ((2) component), and the above-mentioned (3) component. , (T-1) oils, (t-2) alcohols, (t-3) surfactants, (t-4) protein hydrolysates, amino acids and at least one selected from their derivatives, (t- 5) A cosmetic containing a composition containing a compounding component ((3) component) containing any one or more of water, particularly a cosmetic for hair.

The composition containing the above components (1) to (3) is diluted with water or the like, if necessary, and neutralized by adding an alkaline agent to thicken the composition. Therefore, the pH of the hair cosmetic of the present invention is preferably in the range of 3 to 11. The alkaline agent for neutralization is not particularly limited, and an inorganic base such as sodium hydroxide or potassium hydroxide, or an organic base such as triethanolamine, isopropanolamine or a basic amino acid can be used.

In the hair cosmetic of the present invention, it is preferable to adjust the blending amount so that the pH of the hair cosmetic is 3 to 11, preferably 6 to 9, and more preferably 7 to 8. When the pH is within this range, the safety of the product becomes better and the formulation becomes smoother. The pH of the composition in the present invention is a value directly measured without diluting the pharmaceutical product using a commercially available pH measuring meter with a pH glass electrode.

<Resin made of a specific zwitterionic polymer (component (1))>
The resin (1) made of an amphoteric polymer of the present invention is made of an amphoteric polymer (A) having both a cation and an anion in the polymer. Having an anion in the polymer makes it possible to develop a setting force and a keeping force, and having a cation in the polymer makes it possible to improve the affinity for hair.
That is, the zwitterionic polymer (A) of the present invention has both a cation and an anion in the polymer, so that it has sufficient setting power and keeping power, but has good affinity for hair. can do. By using this zwitterionic polymer (A) as a shell portion, it is possible to directly exert the characteristics of the zwitterionic polymer (A) on the hair.

The amphoteric polymer (A) includes, for example, an unsaturated unit having an amine oxide group and a repeating unit derived from an unsaturated monomer containing a betaine structural group such as a carboxybetaine group, a sulfobetaine group or a phoshobetaine group. A repeating unit derived from a monomer, a repeating unit derived from an unsaturated monomer having an anionic group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group, and a group having a quaternary ammonium salt (hereinafter, also referred to as a quaternary ammonium group). A polymer containing at least one of a repeating unit derived from an unsaturated monomer having a tertiary amino group and a repeating unit derived from an unsaturated monomer having a tertiary amino group can be mentioned.

The polymer having a repeating unit (carboxybetaine group-containing resin) derived from the unsaturated monomer having a betaine structural group is used.
(A-1) One kind of betaine group-containing monomer,
(A-2) Two or more types of betaine group-containing monomers,
(A-3) Betaine group-containing monomer and other hydrophilic monomers,
(A-4) (A-1) to (A-3) and hydrophobic monomers,
It is obtained by polymerizing or copolymerizing any of the above. Preferably, the proportion of the betaine group-containing monomer in all the monomers used for the water-soluble resin of the present invention is 30% by weight or more.

In the case of (A-4) above, the hydrophobic monomer is copolymerized as long as the water solubility of the resin is not impaired. It can also be obtained by using a nitrogen-containing precursor monomer instead of the betaine group-containing monomer, polymerizing or copolymerizing the monomer, and then quaternizing the monomer. Further, it can also be obtained by polymerizing a monomer having a reactive functional group and then reacting with a compound having both an active group and a betaine group capable of reacting with the functional group. In the present specification, the "repeating unit derived from an unsaturated monomer having a betaine structural group" is a repeating unit obtained by using a betaine group-containing ethylenically unsaturated monomer for polymerization, and a betaine group-free ethylene property. Both means that an unsaturated monomer is used for polymerization, and then the obtained polymer is modified to contain a betaine group in a repeating unit derived from this monomer.

Specific examples of the polymer having a repeating unit derived from the unsaturated monomer having a betaine structural group include Yukaformer 205S, Yukaformer SM, AMPHOSET, Yukaformer 301, Yukaformer 104D, Yukaformer 202, Yukaformer 510, Yukaformer FH, Yukaformer 204WL and Examples thereof include a methacrylic carboxybetaine polymer which is a monohaloacetate modified product of a dimethylaminoethyl methacrylate / methacrylic acid alkyl ester copolymer such as Yukaformer 204WL-2 (manufactured by Mitsubishi Chemical Corporation). These polymers are disclosed in, for example, JP-A-51-9732, JP-A-55-104209, JP-A-61-258804, JP-A-7-285832, and the like.

The polymer having a repeating unit (amine oxide group-containing resin) derived from the unsaturated monomer having an amine oxide group is used.
(A-5) One kind of amine oxide group-containing monomer,
(A-6) Two or more kinds of amine oxide group-containing monomers,
(A-7) Amine oxide group-containing monomer and other hydrophilic monomers,
It is obtained by polymerizing or copolymerizing (A-8) (A-5) to (A-7) with any of the hydrophobic monomers. Preferably, the ratio of the amine oxide group-containing monomer to all the monomers used in the water-soluble resin of the present invention is 30% by weight or more.

In the case of (A-8) above, the hydrophobic monomer is copolymerized as long as the water solubility of the resin is not impaired. It can also be obtained by using a nitrogen-containing precursor monomer instead of the amine oxide group-containing monomer, polymerizing or copolymerizing the monomer, and then oxidizing the monomer. Further, it can also be obtained by polymerizing a monomer having a reactive functional group and then reacting with a compound having both an active group and an amine oxide group capable of reacting with the functional group. In the present specification, the "amine oxide group-containing repeating unit corresponding to that derived from the amine oxide group-containing ethylenically unsaturated monomer" is obtained by using the amine oxide group-containing ethylenically unsaturated monomer for polymerization. The repeating unit to be used and the amine oxide group-free ethylenically unsaturated monomer were used for the polymerization, and then the obtained polymer was modified to contain an amine oxide group in the repeating unit derived from this monomer. Means both.

The polymer having a repeating unit (amine oxide group-containing resin) derived from the unsaturated monomer having an amine oxide group is a fatty acid acrylic ester having 1 to 24 carbon atoms, ethylamine methacrylate oxide, acrylic acid and methacrylic acid. It is a polymer having at least one of them as a constituent component, and contains an amine oxide group as a structural unit. Specific examples thereof include Diaformer Z-711, Diaformer Z-712, Diaformer Z-631, Diaformer Z-632, and Diaformer Z-732.
Examples thereof include diaformer Z-651, diaformer Z-731, and diaformer Z-772 (all manufactured by Mitsubishi Chemical Corporation).

It has a repeating unit derived from an unsaturated monomer having an anionic group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group, a repeating unit derived from an unsaturated monomer having a quaternary ammonium group, and a tertiary amino group. Specific examples of the polymer containing at least one of the repeating units derived from the unsaturated monomer include Unformer 28-4910, Unformer LV-71 and Unformer LV-47 (all manufactured by Axonobel). A polymer containing an unsaturated monomer having a carboxyl group, which is a hydroxypropyl methacrylate / butylaminoethyl methacrylate / octylamide acrylate copolymer, and an unsaturated monomer having a tertiary amino group as essential components; A carboxyl group which is a diallyldimethylammonium chloride / acrylic acid copolymer such as Marcourt 295 (manufactured by Lubrizol) and a diallyldimethylammonium chloride / acrylic acid / acrylamide copolymer such as Marcourt Plus 3330 (manufactured by Lubrizol). Examples thereof include a polymer containing an unsaturated monomer having a quaternary ammonium group and an unsaturated monomer having a quaternary ammonium group as essential components.

The zwitterionic polymer (A) contains a repeating unit derived from an unsaturated monomer having a betaine structural group from the viewpoint of improving the affinity for hair and particularly improving the hair conditioning effect under high temperature and humidity. It is preferable to do so.

Further, from the viewpoint that the affinity for hair can be improved and the irritation to the skin can be further reduced, the amphoteric polymer (A) is a repeating unit derived from an unsaturated monomer having an amine oxide group. Is preferably contained.

<Polyurethane or urethane- (meth) acrylic composite resin (component (2))>
The component (2) is a polyurethane (P) obtained from a polyol component containing at least one selected from a polyether polyol and a polyester polyol and a polyvalent isocyanate component, or the polyurethane (P) and a (meth) acrylic resin. It is a urethane-based resin component composed of at least one of a urethane- (meth) acrylic composite resin formed by compounding (Q).

The polyurethane ((P) component) of the present invention is a polyurethane obtained from a polyol component and a polyhydric isocyanate component, and specifically, a polyol component containing at least one of a polyether polyol and a polyester polyol, and many. It is a polyurethane obtained from a valent isocyanate component.
In the following, polyurethane using a polyol component containing a polyether polyol is the first polyurethane ((P1) component), U / A resin and U / A resin aqueous dispersion using the first polyurethane are the first U / A resin and It is referred to as a first U / A resin aqueous dispersion. Further, the polyurethane using the polyol component containing the polyester polyol is the second polyurethane ((P2) component), and the U / A resin and the U / A resin aqueous dispersion using the second polyurethane are the second U / A resin and the second U / A resin. It is called a 2U / A resin aqueous dispersion.
In addition, "U / A resin" means "urethane- (meth) acrylic composite resin".

<First polyurethane ((P1) component)>
Next, the polyether polyol used in the first polyurethane (component (P1)) has a constituent unit derived from a polyalkylene glycol having 2 to 4 carbon atoms as a main component and has a number average molecular weight of 400 or more and 4000 or less. It is characterized by being a certain polyether polyol.

The ratio of the polyol unit to the polyhydric isocyanate compound in the component (P1) is preferably 1: 1.2 to 2 and 1: 1.5 to 1.9 in terms of equivalent ratio. Is preferable.

The polyol unit constituting the component (P1) means a unit composed of an organic compound having two or more hydroxyl groups in one molecule, and specific examples thereof include ethylene glycol, 1,3-propanediol, and 1. , 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, trimethylene glycol, triethylene Relatively low molecular weight polyols such as glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, hexanediol, cyclohexanedimethanol, or at least one of these, and adipic acid, sebacic acid, itaconic acid, maleic anhydride, Polyester polyols obtained by polycondensation with at least one dicarboxylic acid such as terephthalic acid and isophthalic acid, polyethylene glycol, polypropylene glycol, polytetramethylene ether polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyalkylene glycol and the like. Examples thereof include ether polyols, polycaprolactone polyols, polycarbonate polyols, polyacrylic acid ester polyols, and polyether polyols obtained by adding propylene oxide to these polyols.

Among these, the polyether polyol whose main component is a structural unit derived from polyalkylene glycol as described above constitutes an essential component because it can impart a flexible texture.

As the above-mentioned polyol component, one kind of polyol component may be used, but at least two kinds of polyol components having different number average molecular weights and / or different constituent units thereof are used. , The polyol unit used is a polydisperse unit having at least two mountain distributions in the molecular weight distribution. By using such a polyol unit, it is possible to increase the mechanical strength (elongation, breaking strength) of the polymer while maintaining a flexible texture.

The average value of the carbon number of the units of the plurality of types of polyols used for the polyol unit of the polydispersion system is preferably 2 to 4. By setting the average value within this range, a flexible texture can be imparted.

The average number average molecular weight of the polyol units of the polydispersion system is preferably 300 or more, preferably 400 or more, more preferably 500 or more, and particularly preferably 600 or more. If the number average molecular weight is too small, the flexibility tends to decrease. On the other hand, the upper limit is preferably 4000, preferably 3000, and more preferably 2500. If the number average molecular weight is too large, the self-emulsifying power may decrease or, depending on the type of polyol unit, it may become excessively flexible.

As described above, when a unit derived from a plurality of types of polyols is used, the number average molecular weight of the polyol having the smallest number average molecular weight among the plurality of types of polyols used is preferably 400 or more, preferably 500 or more. If the number average molecular weight is too small, the resulting film may become stiff and impair flexibility. On the other hand, the upper limit is preferably 1200, preferably 1500. If the number average molecular weight is too large, the self-emulsifying power may decrease or the effect of using the low molecular weight diol may be insufficient.

Specific examples of the above-mentioned polyol having the smallest number average molecular weight include PTMG650 (manufactured by Mitsubishi Chemical Corporation), Hiflex D1000 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and Sanniks PP1000 (manufactured by Sanyo Kasei Kogyo Co., Ltd.). ), Polyether P-1000 (manufactured by ADEKA Corporation), PEG1000 (manufactured by Nichiyu Co., Ltd.) and the like.

As described above, when a unit derived from a plurality of types of polyols is used, the number average molecular weight of the polyol having the smallest number average molecular weight and the number average molecular weight of the polyol having the largest number average molecular weight among the plurality of types of polyols used are used. The difference, that is, the difference in number average molecular weight is preferably 100 or more, preferably 500 or more. If the difference in number average molecular weight is too small, the effect of using a plurality of types of polyols may be insufficient. On the other hand, the upper limit is preferably 2000, preferably 1000. If the difference in number average molecular weight is too large, the balance of the component (P) as a whole may be lost and the synthetic reaction may become unstable.

Further, the component (P1) has a carboxyl group. The acid value of the component (P) is preferably 15 mgKOH / g or more, and more preferably 20 mgKOH / g or more. If it is less than 15 mgKOH / g, the state of dispersion in water in a subsequent step may deteriorate and an aqueous dispersion may not be obtained. On the other hand, the upper limit thereof is preferably 60 mgKOH / g, more preferably 50 mgKOH / g or less. If it exceeds 60 mgKOH / g, the elasticity may be insufficient or it may be difficult to adhere to the hair when used as a hair styling product.

Examples of the method for introducing a carboxyl group into the component (P1) include a method using a carboxyl group-containing multivalent hydroxy compound as a part of the polyol unit. Examples of this carboxyl group-containing multivalent hydroxy compound include dimethylolalkanoic acid as shown in the following chemical formula (p1-1).

In the above formula (p1-1), R represents, for example, an alkyl group having 1 to 10 carbon atoms, and is preferably a methyl group or an ethyl group.

Specific examples of this dimethylol alkanoic acid include dimethylol propionic acid and dimethylol butanoic acid. The amount of the carboxyl group-containing polyvalent hydroxy compound used may be adjusted so that the acid value of the component (P1) formed by polymerization is within the above range.

In producing the component (P) by polymerization, the preferable ratio of the carboxyl group-containing polyvalent hydroxy compound to be used is 30 mol% or more of the total of the polyol unit and the carboxyl group-containing polyvalent hydroxy compound. It is more preferable that the content is 50 mol% or more. On the other hand, 90 mol% or less is preferable, and 80 mol% or less is more preferable. By setting it within this range, the above-mentioned acid value range can be satisfied.

The polyvalent isocyanate compound used for producing the component (P1) means an organic compound having at least two isocyanate groups in one molecule, and is an aliphatic, alicyclic, aromatic or other polyvalent isocyanate compound. Can be used. Specific examples of such polyvalent isocyanate compounds include dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, and 2,4-tolylene diisocyanate. Examples thereof include isocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate. Of these, aliphatic or alicyclic isocyanates are suitable because they cause less yellowing over time.

The urethane production reaction for producing the component (P1) can be carried out without a solvent, but in order to carry out the reaction uniformly, ethers such as dioxane, ketones such as acetone and methyl ethyl ketone, dimethylformamide, etc. An organic solvent that is inert to amides such as dimethylacetamide and N-methyl-2-pyrrolidone and other isocyanate groups and has a high affinity with water may be used. Further, as a solvent other than the above, an organic solvent that is not reactive with the isocyanate group, that is, does not contain an active hydrogen group can also be used. Further, a component (Q) that is not reactive with an isocyanate group, that is, does not contain an active hydrogen group, may be present during the production of the component (P). In this case, the reaction system is diluted by the component (Q), and the reaction can be carried out more uniformly. The reaction for obtaining the component (P) is usually about 50 to 100 ° C. for about 0.5 to 20 hours. This makes it possible to obtain a (P1) component having a carboxyl group and an isocyanate group at the terminal.

As the catalyst used for producing the component (P1), a catalyst generally used for the urethanization reaction can be used. Specific examples include dibutyl tin dilaurate and the like.

The glass transition temperature (Tg) of the component (P1) is preferably −60 ° C. or higher and 250 ° C. or lower. Further, a plurality of glass transition temperatures may occur depending on the glass transition temperature of the soft segment (derived from the polyol unit) of the component (P1) and the glass transition temperature of the hard segment (derived from the isocyanate unit). The low temperature side (soft segment side) glass transition temperature at this time is preferably −60 ° C. or higher, more preferably −50 ° C. or higher. Below -60 ° C, the resulting film may become overly flexible. On the other hand, the glass transition temperature on the low temperature side is preferably 0 ° C. or lower, more preferably −5 ° C. or lower. If the temperature exceeds 0 ° C., the flexibility of the film tends to be insufficient. The glass transition temperature on the high temperature side (hard segment side) is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, although the effect on the physical characteristics of the coating film is not as great as on the low temperature side. Below 30 ° C, the toughness of the film may be inferior. On the other hand, the upper limit is preferably 250 ° C. or lower, more preferably 200 ° C. or lower. If the temperature exceeds 250 ° C., the film may become hard and the texture may be inferior.
The glass transition temperature (Tg) can be measured by the method of JIS K7424-4.

It is preferable that at least a part of the carboxyl group contained in the component (P1) is neutralized by a basic compound. Thereby, the dispersibility of the component (P1) in the aqueous medium can be improved. Examples of this basic compound include organic amine compounds and alkali metal hydroxides. This neutralization reaction can be carried out at any time after the component (P1) is produced and before it is dispersed in the aqueous medium. Among them, it is preferable that the first neutralization step described later and, if necessary, the second neutralization step described later are performed.

As the above-mentioned organic amine compound, a tertiary amine compound such as trimethylamine, triethylamine, tributylamine and triethanolamine is preferably used. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.

The total amount of these basic compounds used is one equivalent or more with respect to the amount of the carboxyl group of the component (P1) as the total amount used in the first neutralization step and the second neutralization step described later. preferable. That is, it is preferable that the carboxyl group in the component (P1) is neutralized by 100% or more with the basic compound. If it is less than 1 equivalent, a good dispersed state may not be obtained in an aqueous medium. On the other hand, the upper limit is preferably 2.0 equivalents, more preferably 1.5 equivalents. If it exceeds 2.0 equivalents, the basic compound remains in the emulsion, which may cause a problem when used for cosmetics.

Examples of the aqueous medium for dispersing the component (P1) include water and a mixed solution of water and an organic solvent compatible with water such as methanol and ethanol. Of these, water is more preferable from the environmental aspect.

Examples of the compound having a plurality of active hydrogens capable of reacting with the isocyanate group include polyols having 1 to 8 carbon atoms and polyamine compounds. Examples of the polyol include ethylene glycol and diethylene glycol. Further, examples of the polyamine compound include diamines such as ethylenediamine, hexamethylenediamine and isophoronediamine.

The chain extension reaction is carried out when a mixed solution containing the component (P1) and the polymerizable monomer (q) described later is emulsified and dispersed in the aqueous medium to obtain a first emulsion. When water is used as the liquid, the water may partially cause a chain extension reaction of the component (P1) during the polymerization step of the component (q). Further, when the chain extension reaction is positively carried out, the chain extension reaction can be carried out by adding the chain extension agent after the emulsification and dispersion to obtain the first emulsified solution. The chain extension reaction may occur for at least a part of the (P1) component contained in the first emulsion. Further, after polymerizing the component (q) contained in the first emulsion or the second emulsion obtained by carrying out a chain extension reaction of at least a part of the component (P1) in the first emulsion, the component (q) is polymerized. At least a part of the component (P1) in the emulsion may be positively chain-extended.

<Second polyurethane ((P2) component)>
The polyester polyol used in the second polyurethane (component (P2)) is characterized by being a polyester polyol having a structural unit derived from at least one dicarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid. be.

Further, this polyurethane is characterized in that a cast film can be formed at 23 ° C. from a mixed solution of silicone oil and this polyurethane (weight ratio 50/50).

The polyol component which is the raw material of the polyurethane of the present invention contains a porester polyol. This polyester polyol is composed of a constituent unit derived from a polyol component (hereinafter, may be referred to as a "polyol unit") and a constituent unit derived from a dicarboxylic acid component (hereinafter, may be referred to as a "dicarboxylic acid unit"). It is a compound.

The polyol unit is a unit composed of an organic compound having two or more hydroxyl groups in one molecule, and specific examples of the polyol constituting the polyol unit include ethylene glycol, propylene glycol, and 1,3-propanediol. , 1,3-Butanediol, 1,4-Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, trimethylene glycol, Relatively low molecular weight diols such as triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexanedimethanol, or at least one of these, adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid. Polyester polyols obtained by polycondensation with at least one dicarboxylic acid such as acid and isophthalic acid, polyethylene glycol, polypropylene glycol, polycaprolactone diol, polytetramethylene ether diol, polycarbonate diol, polybutadiene diol, hydrogenated polybutadiene diol, Examples thereof include poly (meth) acrylic acid ester diols, dialkylene glycols, and polyether polyols obtained by adding propylene oxide to these polyols.

The dicarboxylic acid unit is a unit composed of an organic compound having two or more carboxyl groups in one molecule, and in the present invention, the dicarboxylic acid unit is derived from phthalic acid, isophthalic acid and terephthalic acid as described above. It is important to use a structural unit derived from at least one dicarboxylic acid component selected from the group (hereinafter, may be collectively referred to as "phthalic acid-based unit"). By using such a polyester polyol having a phthalic acid-based unit, oil resistance can be imparted to the obtained (P2) component and the second U / A resin.

Among the polyester polyols having such phthalic acid-based units, examples of the polyester polyol having a constituent unit derived from isophthalic acid include Kuraray polyols P-1012, 2012, 530, 1030, 2030 and the like, manufactured by Kuraray Co., Ltd. Name), Teslac 2474 (manufactured by Nihon Kasei Polymer Co., Ltd., trade name), OD-X-2560 (manufactured by DIC Co., Ltd., trade name), HS2F-136P (manufactured by Toyokuni Oil Co., Ltd., trade name), etc. Examples of the polyester polyol having a structural unit derived from terephthalic acid include Kuraray polyols P-1011, 2011, 2013, 520, 1020, 2020 and the like (trade name manufactured by Kuraray Co., Ltd.). Can be done.

Among the polyester polyols having phthalic acid-based units, polyester polyols having isophthalic acid-derived structural units (hereinafter, may be referred to as “isophthalic acid units”) are preferable.

The content ratio of the dicarboxylic acid unit in the obtained (P2) component is preferably 0.05% by weight or more and 50% by weight or less. When the dicarboxylic acid unit is present in an amount of 0.05% by weight or more, the effect of improving oil resistance can be obtained. On the other hand, by setting the content of the dicarboxylic acid unit to 50% by weight or less, it is possible to increase the strength of the film while maintaining sufficient oil resistance. If it is out of this range, the effect of improving oil resistance may be insufficient or the obtained film may become brittle. The dicarboxylic acid unit is preferably present in an amount of 0.08% by weight or more, more preferably 0.1% by weight or more. Further, it is preferably present in an amount of 40% by weight or less, and more preferably 35% by weight or less. The dicarboxylic acid unit needs to contain a phthalic acid-based unit, and particularly preferably contains an isophthalic acid unit. By containing the isophthalic acid unit, the effect of improving the oil resistance while maintaining the flexibility can be obtained.

The content of the phthalic acid-based unit (PA unit) (C _{8H 4 O 3} = formula amount 148) in the polyester polyol and the content of the phthalic acid-based unit in the polyurethane shall be calculated as follows. Can be done. The polyester polyol is referred to as "PEsPO", the phthalic acid-based unit is referred to as "PA", the diol is referred to as "DOL" (in the case of a diol unit, referred to as "DOL unit"), and the number of phthalic acid-based units is referred to as "NumberPA".
In polyester polyols, the (both) ends are always diol ends, so the following relational expression holds.
1) Number of phthalic acid-based units (PA units) in polyester polyol (PEsPO) = (molecular weight of PEsPO-terminal DOL molecular weight) / (PA unit formula amount + DOL unit formula amount)
= NumberPA
(In the above formula, "PA unit formula amount + DOL unit formula amount" is the formula amount of the ester unit in PEsPO formed by PA and DOL units.)
2) PA unit content in PEsPO (wtPA (weight fraction))
= (Number PA x PA unit formula amount) / PEsPO molecular weight 3) PA unit content (weight) in the PEsPO charge amount (F)
= F × wtPA
4) PA unit content (% by weight) in polyurethane
= (F x wtPA) x 100 / total amount of polyurethane (= total amount of urethane raw material charged)

When a dicarboxylic acid other than a phthalic acid-based unit is used in combination as an acid component, the formula amount (-) of other dicarboxylic acids used in combination is replaced with the "PA unit formula amount" in 1) in the above calculation. OC-X-CO-O-, where "X" is a divalent hydrocarbon group other than the benzene nucleus) and the formula amount in PA units are totaled after multiplying by the molar fraction of each component. Using the "dicarboxylic acid average formula amount", the "total number of dicarboxylic acid units" corresponding to the above "NumberPA" was obtained, and using these, the "dicarboxylic acid unit content (% by weight) in the polyurethane" was obtained in the same manner as above. ) Is calculated, and this amount can be prorated using the molar fraction and the formula amount of both to obtain the "PA unit content in polyurethane".
The same applies when a plurality of diol components are used.
If the composition of a commercially available product has not been clarified, use a method capable of analyzing a polymer substance such as nuclear magnetic resonance spectrum analysis (NMR) or gel permeation chromatography (GPC). It can also be calculated by performing an analysis.

As the polyol component of the polyurethane of the present invention, it is also preferable to use a component having a polyol and a monocarboxylic acid in addition to the above-mentioned polyol component.

As such a component, it is preferable to use dimethylol alkanoic acid such as dimethylol propionic acid and dimethylol butanoic acid, a sulfonic acid-containing polyol, and the like, and dimethylol alkanoic acid is particularly preferable. In addition to this, as the polyol component, various polyalkylene glycols, polyester polyols, polycarbonate polyols and the like other than the above can be used as long as the effects of the present invention are not impaired.
Such dimethylol alkanoic acid has a structure represented by the above chemical formula (p1-1).

In the above formula (p1-1), R is, for example, an alkyl group having 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Particularly preferred is one in which R is a methyl group or an ethyl group, and in particular, when R is a methyl group, that is, dimethylol alkanoic acid is preferably dimethylol propionic acid.

By using the above-mentioned dimethylol alkanoic acid, good miscibility can be obtained, and a carboxyl group can be introduced into the obtained polyurethane, and the dispersion stability is improved when used as an aqueous dispersion. , Polyurethane can be made reactive, and especially when used for cosmetics, the miscibility with polar components can be improved and the adhesion to hair and skin can be improved.

The amount of dimethylol alkanoic acid used may be appropriately adjusted according to the acid value of the obtained polyurethane or the performance (dispersability in water, etc.) required for the finally produced second U / A resin.

As such a polyol component, one kind of polyol component may be used, or a component derived from a plurality of kinds of polyols may be used.

As the polyol component constituting the above-mentioned polyol unit, one kind of polyol unit may be used, but at least two kinds of polyols having different number average molecular weights and / or polyol components having different constituent units thereof. When the component is used, the polyol unit used becomes a multidispersion unit having at least two mountain distributions in the molecular weight distribution. By using such a polyol unit, it is possible to increase the mechanical strength (elongation, breaking strength) of the polymer while maintaining a flexible texture.

The average value of the carbon number of the units of the plurality of types of polyols used for the polyol unit of the polydispersion system is preferably 2 to 4. By setting the average value within this range, a flexible texture can be imparted.

The average number average molecular weight of the polyol units of the polydispersion system is preferably 300 or more, preferably 400 or more, more preferably 500 or more, and particularly preferably 600 or more. If the number average molecular weight is too small, the flexibility tends to decrease. On the other hand, the upper limit is preferably 4000, preferably 3000, and more preferably 2500. If the number average molecular weight is too large, the self-emulsifying power may decrease or, depending on the type of polyol unit, it may become excessively flexible.

As described above, when a unit derived from a plurality of types of polyols is used, the number average molecular weight of the polyol having the smallest number average molecular weight among the plurality of types of polyols used is preferably 400 or more, preferably 500 or more. If the number average molecular weight is too small, the resulting film may become stiff and impair flexibility. On the other hand, the upper limit is preferably 1200, preferably 1500. If the number average molecular weight is too large, the self-emulsifying power may decrease or the effect of using the low molecular weight diol may be insufficient.

As described above, when a unit derived from a plurality of types of polyols is used, the number average molecular weight of the polyol having the smallest number average molecular weight and the number average molecular weight of the polyol having the largest number average molecular weight among the multiple types of polyols used are used. The difference, that is, the difference in number average molecular weight is preferably 100 or more, preferably 500 or more. If the difference in number average molecular weight is too small, the effect of using a plurality of types of polyols may be insufficient. On the other hand, the upper limit is preferably 2000, preferably 1000. If the difference in number average molecular weight is too large, the balance of the (P2) component as a whole may be lost and the synthesis reaction may become unstable.

Further, as the polyvalent isocyanate used for producing the component (P2), the polyvalent isocyanate described above can be used.

The obtained (P2) component includes the above-mentioned diol component, particularly an acid component derived from polyester polyol, dimethylolalkanoic acid, etc., and the acid value of this polyurethane is preferably 15 mgKOH / g or more. , 20 mgKOH / g or more is more preferable. If it is less than 15 mgKOH / g, the dispersibility in water is deteriorated, and in an extreme case, an aqueous dispersion may not be obtained. On the other hand, the upper limit thereof is preferably 60 mgKOH / g, more preferably 50 mgKOH / g or less. If it exceeds 60 mgKOH / g, the elasticity becomes insufficient or the polymer becomes too hard, and when it is used for hair cosmetics, it causes stiffening or becomes white powder during use, which is insufficient as a cosmetic. It can be a thing.

The acid value can be measured according to the potentiometric titration method (JIS-K-0070) using potassium hydroxide. At this time, the "polyurethane amount" is used as the mass of the sample.
Further, for example, when potassium hydroxide is used for neutralization in the production of polyurethane, salt exchange is less likely to occur, which may make measurement by the above JIS method difficult. In such a case, the "theoretical acid value" per 1 g of polyurethane may be calculated and used according to the following formula.
Theoretical acid value (mgKOH / g-polyurethane) = number of moles charged with acid-containing raw materials x 56.1 (KOH molecular weight) / polyurethane amount (g) x 1000

The conditions relating to the solvent for the polyurethane formation reaction for producing the component (P2), the presence of the component (q), the reaction temperature, the reaction time, the catalyst, the chain extension reaction, etc. are for producing the component (P1). It can be carried out under the same conditions as the reaction for producing polyurethane.

The ratio of the polyester polyol to the polyhydric isocyanate compound used in producing the component (P2) is the equivalent ratio of the hydroxyl group of the polyester polyol to the isocyanate group of the polyhydric isocyanate compound, and the polyester polyol: polyhydric isocyanate. The compound = 1: 1.2 to 2 is preferable, and 1: 1.5 to 1.9 is preferable.

The weight average molecular weight of the component (P2) is preferably 1000 or more, more preferably 2000 or more. If the weight average molecular weight is less than 1000, the obtained film becomes hard, and when used as a hair cosmetic, problems such as a feeling of stiffness may occur. On the other hand, the upper limit of the weight average molecular weight is usually about 150,000, preferably 100,000, more preferably 70,000. If it is larger than 150,000, the viscosity of the prepolymer itself becomes high, and gelation may occur or a stable emulsion may not be obtained.

The glass transition temperature (Tg) of the component (P2) can take the same value for the same reason as the glass transition temperature (Tg) of the component (P1) described above.

It is preferable that at least a part of the carboxyl group contained in the component (P2) is neutralized with one or more basic compounds. This makes it possible to improve the dispersibility of polyurethane in an aqueous medium. Examples of this basic compound include organic amine compounds and alkali metal hydroxides. This neutralization reaction can be carried out at any time after the polyurethane is produced, and may be carried out in one step or may be carried out in two or more steps. Further, the basic compound used for this neutralization reaction may also be a different kind for each step.
Above all, the neutralization step is divided into two steps, the first neutralization step is carried out after the production of polyurethane, and the second neutralization step is carried out after the polyurethane neutralized in the first step is dispersed in an aqueous medium. Is preferable.

As the organic amine compound, a tertiary amine compound such as trimethylamine, triethylamine, tributylamine and triethanolamine is preferably used. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.

The total amount of these basic compounds used is preferably 1 equivalent or more with respect to the amount of carboxyl groups contained in the polyurethane (as the total amount used in the first neutralization step and the second neutralization step). That is, it is preferable that the carboxyl group in the polyurethane is neutralized by 100% or more with the basic compound. If it is less than 1 equivalent, a good dispersed state may not be obtained in an aqueous medium. On the other hand, the upper limit is preferably 2.0 equivalents, more preferably 1.5 equivalents. If it exceeds 2.0 equivalents, the basic compound remains in the emulsion, which may cause a problem when used for cosmetics.

Examples of the aqueous medium for dispersing the component (P2) include water and a mixed solution of water and an organic solvent compatible with water such as methanol and ethanol. Of these, water is more preferable from the environmental aspect.

This component (P2) can be cast into a film at 23 ° C. from a solution mixed with silicone oil in a weight ratio of 50/50. In addition, "cast film formation is possible" means that after casting, the film is allowed to stand at 23 ° C for 6 hours, and then when a part of the film is picked up with tweezers or the like, the film is integrated without being damaged. Say it will be pulled up. Examples of the silicone oil that can be used here include cyclopentasiloxane (for example, KF-995 (manufactured by Shin-Etsu Chemical Co., Ltd .: volatile cyclic silicone)).

The feature that cast film formation is possible at 23 ° C from a solution mixed with this silicone oil in a weight ratio of 50/50 is that cosmetics containing a large amount of oily components such as mascara, lipstick, lip balm, and hair wax (makeup). When used in a pharmaceutical product), it exhibits excellent film-forming properties, and when used as a cosmetic, it is possible to obtain effects such as improvement of make-up durability (holding) and imparting a firm feeling due to the film.

<1st U / A resin and 1st U / A resin aqueous dispersion>
The first U / A resin according to the present invention comprises a (meth) acrylic acid ester-based polymerizable monomer ((q) component) which is a constituent unit of the (Q) component in the presence of the (P) component. By polymerization, a first U / A resin obtained by combining the component (P1) and the component (Q) can be obtained.

In order to produce such a first U / A resin, for example, in a pre-emulsion formed by emulsion-dispersing the component (P1) and the component (q) in an aqueous medium, the component (q) is mixed. A method of emulsion polymerization can be used, at which time the first U / A resin is obtained as the first U / A resin aqueous dispersion.

Examples of the (meth) acrylic acid ester-based polymerizable monomer of the component (q) include (meth) acrylic acid alkyl esters and the like. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth). S-butyl acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, s-pentyl (meth) acrylate, 1-ethylpropyl (meth) acrylate, 2-methylbutyl (meth) acrylate, Isopentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, 2-methylpentyl (meth) acrylate, ( 4-Methylpentyl acrylate, 2-ethylbutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-heptyl (meth) acrylate, (meth) ) 3-Heptyl Acrylic Acid, (Meta) Octyl Acrylic Acid, (Meta) 2-octyl Acrylic Acid, (Meta) 2-Ethylhexyl Acrylic Acid, (Meta) Isooctyl Acrylic Acid, (Meta) Nonyl Acrylic Acid, (Meta) Acrylic Acids 3,3,5-trimethylhexyl, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Eikosyl, docosyl (meth) acrylate, tetracosyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, benzyl (meth) acrylate, benzyl (meth) acrylate Phenethyl and the like are exemplified. Among these, (meth) acrylic acid alkyl esters having an alkyl group having 1 to 24 carbon atoms are preferable, and those having an alkyl group having 1 to 8 carbon atoms are particularly preferable.

Only one kind of these components (q) may be used, or a plurality of kinds thereof may be mixed and used.

The component (q) may contain other monomers other than the (meth) acrylic monomer, for example, an ester group-containing vinyl monomer, if necessary, as long as the object and effect of the present invention are not impaired. , Styrene derivatives, vinyl ether monomers and the like may be used in combination. Examples of the ester group-containing vinyl monomer include hydrophobic vinyl monomers such as vinyl acetate, diethyl maleate, and dibutyl maleate, and unsaturated group-containing macromonomers such as radically polymerizable unsaturated group-containing silicon macromonomers. Illustrated.

Examples of the styrene derivative include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene and the like. Further, specific examples of the vinyl ether-based monomer include vinyl methyl ether, vinyl cyclohexyl ether and the like.

The glass transition temperature (Tg) of the homopolymer or copolymer composed of the component (q), that is, the copolymer in the composition ratio of the homopolymer if it is composed of one kind, or the copolymer in the composition ratio of the homopolymer if it is composed of multiple kinds. The glass transition temperature of the above is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, further preferably 40 ° C. or higher, and particularly preferably 60 ° C. or higher. If the temperature is lower than 0 ° C., the heat-returning property (including settability) of the obtained cosmetic may be deteriorated. On the other hand, the glass transition temperature is preferably 120 ° C. or lower, more preferably 110 ° C. or lower. If it exceeds 120 ° C., the minimum film forming temperature becomes high, and a uniform film may not be formed. By setting the glass transition temperature in this range, it is possible to suppress the plasticization of the polymer due to the oil content even in the case of cosmetics containing a large amount of oil.

The glass transition temperature (Tg) can be measured by the JIS method described in the section of the component (P1), or can be calculated by the following formula (1) (FOX formula).

1 / Tg = (Wa / Tga) + (Wb / Tgb) + (Wc / Tgc) + ... (1)
However, Tg is the glass transition temperature (K) of the (co) polymer, and Tga, Tgb, Tgc and the like are the glass transition temperatures (K) of the homopolymers such as the constituent monomers a, b and c, and Wa. , Wb, Wc and the like indicate the weight fraction of each constituent monomer a, b, c in the copolymer.
If Tg is to be expressed in "° C", "273" may be subtracted from the value of Tg obtained by the above formula.

When a mixture of a plurality of (meth) acrylic acid ester-based polymerizable monomers is used as the component (q), the first monomer having a high Tg of the homopolymer and the second monomer having a low Tg of the homopolymer are used. It is preferably a mixture containing a polymer. As described above, by using a monomer having a different Tg of the homopolymer as the component (q), the flexibility of the suitable film can be adjusted.

The Tg of the homopolymer of the first monomer is preferably 95 ° C. or higher, preferably 100 ° C. or higher. If the temperature is lower than 95 ° C., the adjustment range of the film flexibility becomes small. The upper limit of Tg is usually about 150 ° C.

The Tg of the homopolymer of the second monomer is preferably 30 ° C. or lower, preferably 10 ° C. or lower. If the temperature is higher than 30 ° C., the flexibility will be insufficient or the adjustment range of the film flexibility will be small. On the other hand, the lower limit of Tg is preferably −70 ° C., preferably −60 ° C. If the temperature is lower than −70 ° C., stickiness of the film may occur.

Next, a method for producing the first U / A resin aqueous dispersion for cosmetics according to the present invention will be described. As the first U / A resin aqueous dispersion for cosmetics according to the present invention, as described above, a mixed solution in which the component (P) and the component (q) are mixed is prepared, and then this is emulsified and dispersed in an aqueous medium. By polymerizing the component (q) in the emulsion, an aqueous emulsion of a urethane- (meth) acrylic composite resin can be obtained. Further, in the process, a chain extension reaction of the component (P) is carried out, if necessary.

In the method for obtaining a mixed solution containing the component (P1) and the component (q), the component (P1) and the component (q), which are made water-dispersible by neutralizing at least a part of the carboxyl group, are an aqueous medium. Any method may be used as long as it can be uniformly dispersed therein, and the timing of addition of the component (q) is not particularly limited.

For example, a method of adding the component (q) before neutralizing at least a part of the carboxyl group in the component (P1) and a method of adding the component (q) after the neutralization can be mentioned. Further, a part or all of the component (q) is mixed with the polyol unit or the polyhydric isocyanate compound which is the raw material of the component (P1), and in the presence of the component (q), the polyol unit or the polyhydric isocyanate is mixed. The component (P1) may be produced by reacting a compound, a polyhydric hydroxy compound containing a carboxyl group, or the like. At this time, even when the remaining amount of the component (q) is added after the production of the component (P1), the addition time may be any time before, simultaneously or after neutralizing the carboxyl group in the component (P1). I do not care.

Above all, the method of reacting the polyol unit, the carboxyl group-containing polyvalent hydroxy compound and the polyhydric isocyanate in the presence of the component (q) to obtain the component (P1) is the method of obtaining the component (P1) with the component (P). It is preferable because the components can be mixed more uniformly (hereinafter, this step is referred to as "prepolymerization step").

Examples of the reaction method of the polyol unit, the carboxyl group-containing polyvalent hydroxy compound and the polyhydric isocyanate include a method of polymerizing in the presence of a urethane polymerization catalyst such as dibutyltin dilaurate.

The mixing ratio of the component (P1) and the component (q) in the above-mentioned mixed solution is preferably (P1) / (q) = 80/20 to 30/70 and 70/30 to 35 / in terms of pure weight ratio. 65 is preferable. If the component (P) exceeds 80% by weight, the heat return property (including settability) when used as a hair styling product may deteriorate. On the other hand, if it is less than 20% by weight, emulsification may be insufficient at the time of synthesis, gelation may occur at the time of water dispersion, or a non-uniform water dispersion may be formed.

The concentration of the mixture of the component (P1) and the component (q) is not particularly limited, but the amount of the non-volatile component in the finally obtained aqueous emulsion composition is 20% by weight or more. It is preferable to make it 30% by weight or more, and it is more preferable to make it 30% by weight or more. If it is less than 20% by weight, it may take time to dry. On the other hand, the upper limit thereof is preferably an amount of 70% by weight or less, more preferably 60% by weight or less. If it exceeds 70% by weight, it may be difficult to prepare water dispersibility or the dispersion stability may be lowered.

When the carboxyl group in the component (P1) is not neutralized at all, the basic compound is added to the mixed solution of the component (P1) and the component (q), and the carboxyl group contained in the component (P1) is added. It is preferable to neutralize at least a part of the above to obtain a neutralized product of the component (P1) (hereinafter, this step is referred to as a “first neutralization step”).

The amount of the carboxyl group neutralized by the first neutralization step is preferably 0.5 equivalent or more, preferably 0.55 equivalent or more, with respect to all the carboxyl groups in the component (P1).

When the amount of the carboxyl group neutralized by the first neutralization step is 1 equivalent or more, the second neutralization step described later may not be performed. On the other hand, if the amount is less than 1 equivalent, the second neutralization step described later is performed as necessary.

Next, a mixed solution of the neutralized product of the component (P1) and the component (q) is emulsified and dispersed in the aqueous medium (hereinafter, this step is referred to as an "emulsification step"). As a method of adding an aqueous medium to the mixed solution of the neutralized product of the component (P1) and the component (q), a method of dropping and dispersing the aqueous medium in the mixed solution, and the mixed solution in the aqueous medium. The method of dropping and dispersing is not particularly limited.

The temperature at the time of emulsification and dispersion is preferably 0 ° C. or higher, preferably 10 ° C. or higher. On the other hand, 80 ° C. or lower is preferable, and 60 ° C. or lower is preferable. If the temperature is too high, the component (P1) may be denatured.

In the emulsified dispersion obtained as described above, the component (q) is polymerized to obtain an aqueous emulsion of the first urethane- (meth) acrylic composite resin (hereinafter, this step is referred to as "polymerization step"). .. The polymerization reaction of the component (q) can be carried out by a general polymerization method according to the component (q) to be used, and for example, the radical polymerization initiator can be added to the mixed solution.

As the radical polymerization initiator, a conventional radical polymerization initiator can be used, for example, an azo-based initiator such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyanovaleric acid, etc. Persulfate-based initiators such as sodium sulfate, potassium persulfate, ammonium persulfate, t-butylhydroperoxide, dilauroyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate. Organic peroxide-based initiators such as the above can be used. Further, a redox-based polymerization initiator in which an organic peroxide-based initiator or a persulfate-based initiator is combined with a reducing agent such as ascorbic acid, longalit or a metal sulfate salt is also preferably used. The amount of the radical polymerization initiator used may be about 0.1 to 5% by weight, preferably about 0.5 to 2% by weight, based on the polymerizable monomer (q).

The polymerization of the component (q) is preferably carried out at a polymerization temperature of 10 to 80 ° C, more preferably 30 to 60 ° C. Further, after the heat generation is completed, the polymerization is almost completed by maintaining the temperature at about 40 to 90 ° C. for about 30 minutes to 3 hours. As a result, an aqueous emulsion of urethane- (meth) acrylic composite resin is obtained.

Examples of the relatively high molecular weight diols include polyester diols obtained by shrink-polymerizing a low molecular weight diol and a dicarboxylic acid, polyalkylene glycols, and other diols having a (weight average) molecular weight of 1000 or more. can.

Specific examples of the low molecular weight diols include diols having a molecular weight of less than 500, such as ethylene glycol and propylene glycol. Specific examples of the polyalkylene glycols include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, (hydrogenated) polybutadiene diol and the like. In addition, polycaprolactone diol, polycarbonate diol, polyacrylic acid ester diol and the like can also be used.

Normally, an unreacted component (q) remains in the aqueous emulsion of the urethane- (meth) acrylic composite resin obtained in the polymerization step, but in order to suppress the odor derived from this, for example, the concentration thereof should be adjusted. It is preferably 100 ppm or less, preferably 70 ppm or less, and the closer the concentration is to 0, the more preferable.

As a method for reducing the concentration of the component (q), for example, a method of heating an aqueous emulsion to volatilize the remaining component (q), a method of circulating a gas such as air through the gas phase portion of the emulsion, or an emulsion. Examples thereof include a method of blowing water vapor and a method of distilling off the component (q) under reduced pressure, and these may be combined as necessary (hereinafter, this step is referred to as a “deodorizing step”).

When the aqueous emulsion is heated, the liquid temperature of the aqueous emulsion is preferably 40 ° C. or higher, more preferably 60 ° C. or higher. On the other hand, the liquid temperature is preferably not less than the boiling point of the aqueous medium, preferably 100 ° C. or less. When a gas is blown or circulated, the gas temperature is preferably 20 ° C. or higher and 100 ° C. or lower, and more preferably 60 ° C. or higher and 95 ° C. or lower. Even when steam is blown in, it is preferable that the liquid temperature of the aqueous emulsion satisfies the above conditions.

The flow rate (volume / hour under the conditions of using the gas) when the gas is circulated is not particularly limited, but is preferably 2 to 100 volumes / minute, preferably 5 to 80 volumes / minute of the volume of the gas phase portion of the container. .. If it is less than 2 volumes / minute, the removal of the component (q) tends to be insufficient. On the other hand, if the volume is more than 100 times / minute, deposits may be formed on the container wall due to the scattering of the aqueous emulsion or the filming on the liquid surface, which is not preferable.

The water evaporated by the heating can be replenished as needed after the component (q) is removed. Since it is not preferable to release the exhaust gas containing the component (q) into the atmosphere, it is preferable to collect the condensed liquid obtained by cooling the exhaust gas in a tank or the like and perform wastewater treatment.

As described above, the aqueous dispersion of the urethane- (meth) acrylic composite resin in which the residual amount of the component (q) is 100 ppm or less can be used as a raw material having almost no odor for cosmetics such as hair styling products. can. Further, when the urethane- (meth) acrylic composite resin aqueous dispersion according to the present invention is used, the heat return property (including settability) is good as a hair styling product, and the feel such as slipping of hair is also good. ..

By the way, at any one place between the emulsification step and the polymerization step and between the polymerization step and the deodorizing step, if necessary, a neutralized product of the component (P1) ((P1) component is contained. . Hereinafter, the same applies), at least a part of the chain may be extended. Further, a part of the component (P1) is chain-extended between the emulsification step and the polymerization step, and the chain is extended by the chain extension step between the polymerization step and the deodorizing step. At least a part of the remaining (P1) component may be chain-extended.

Since the chain extension reaction of the component (P1) gradually occurs in the emulsified solution and in water as a dispersion medium, a part of the chain extension reaction may occur even during the polymerization step. However, since the reaction rate of chain extension by water is usually slow, in order to carry out chain extension more effectively and reliably, it is necessary to positively carry out the chain extension reaction using a chain extension agent other than the above-mentioned water. good. As a result, the chain-extended urethane polymer can be obtained more quickly, and a flexible and elastic film can be obtained.

Further, at least a part of the carboxyl group in the component (P1) is placed in at least one place selected between the emulsification step and the polymerization step, between the polymerization step and the deodorization step, and after the deodorization step. , The basic compound may be used for further neutralization (hereinafter, this step is referred to as "second neutralization step"). By advancing the degree of neutralization to a predetermined range, it is possible to obtain effects such as improving the storage stability of the obtained emulsion and improving the film-forming property.

The amount of the basic compound used in the second neutralization step is preferably 1 equivalent or more as the sum of the amount used in the first neutralization step with respect to the carboxyl group in the component (P1). If 1 equivalent or more of the basic compound is already used in the first neutralization step, this second neutralization step may be omitted.

The basic compound used in the first neutralization step and the second neutralization step is preferably used as an aqueous solution or an aqueous dispersion in order to facilitate addition and mixing. The neutralized urethane- (meth) acrylic composite resin is dissolved or dispersed in water alone, a mixed solvent of a polar organic solvent and water, or an organic solvent. Examples of this organic solvent include alcohols, ketones, and other organic solvents. Alcohols include alcohols containing 1 to 8 carbon atoms such as ethanol, propanol, isopropanol, butanol, benzyl alcohol, and phenylethyl alcohol, and divalent or higher hydrates such as alkylene glycols such as glycerin, ethylene glycol, and propylene glycol. Alcohol and the like can be mentioned. Moreover, examples of ketones include acetone, methyl ethyl ketone and the like. Examples of other organic solvents include low boiling hydrocarbons such as pentane, ethers such as dimethyl ether and dimethoxymethane, glycol ethers such as mono-, di-, or tri-ethylene glycol monoalkyl ether, and esters such as methyl acetate. Can be mentioned.

The weight average molecular weight (Mw) of the first U / A composite resin in the obtained first U / A composite resin aqueous dispersion is preferably 180,000 or more, more preferably 200,000 or more. If the weight average molecular weight (Mw) is too small, the pigment dispersibility may be inferior. On the other hand, the upper limit of the weight average molecular weight (Mw) is preferably 1,000,000, more preferably 800,000. If the weight average molecular weight (Mw) is too large, the softness when applied to hair may be inferior. By setting the weight average molecular weight (Mw) in the range, particularly good oil resistance (cast film forming property from a mixed solution with silicone oil) can be obtained.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the first U / A composite resin in the first U / A composite resin aqueous dispersion is preferably 10 or more, preferably 20 or more. The above is more preferable. If Mw / Mn is too small, it tends to be difficult to achieve both the two characteristics of flexibility and high setting force (high CR value). On the other hand, the upper limit of Mw / Mn is preferably 70, more preferably 60. If Mw / Mn is too large, the texture of the film may be impaired by the polymer on either the low molecular weight side or the high molecular weight side or both.

In the case of emulsion polymerization of the (meth) acrylic acid ester-based polymerizable monomer which is the component (q) in an aqueous medium, a polymerization initiator, an emulsifier, etc. in the aqueous medium during the polymerization and other polymers produced are used. The chain transfer reaction to the above is likely to occur, and the molecular weight of the obtained polymer may be low.
On the other hand, in the present application, the component (P1) (polyurethane having an isocyanate group and a carboxyl group) and the component (q) ((meth) acrylic acid ester-based polymerizable monomer) are emulsified and dispersed in an aqueous medium. A urethane- (meth) acrylic composite resin aqueous dispersion (first U / A resin aqueous dispersion) obtained by polymerizing the component (q) is produced by using the pre-emulsion. Radical polymerization will occur in the state where the component (q) is arranged inside the P1) component. At this time, the component (q) is protected by the component (P1), and not only the chain transfer reaction during the polymerization of the component (q) is unlikely to occur, but also the polymerization proceeds in a state where the polymerization termination reaction is unlikely to occur. Therefore, the molecular weight of the component (q) tends to increase. Then, the urethane resin constitutes the shell portion, and the (meth) acrylic resin constitutes the core portion, and becomes a composite resin having a core-shell structure. At this time, the molecular weight of the component (q) tends to be larger than that of emulsion polymerization in the absence of the component (P1), and the molecular weight distribution of the obtained composite resin may show two peaks. ..

The minimum film-forming temperature (MFT) of the first U / A composite resin aqueous dispersion obtained by the present invention is preferably −10 ° C. or higher when measured by a method based on JIS K6828-2, as described later. 5 ° C or higher is preferable. If it is lower than -10 ° C, it may become too soft and the settability and heat reversion of the formed film may be insufficient. On the other hand, the upper limit of MFT is preferably 60 ° C, preferably 50 ° C, more preferably 30 ° C, and even more preferably 20 ° C. If the temperature is higher than 60 ° C., the temperature becomes too hard, and it is difficult to form a film in a living environment, which may be unsuitable for cosmetic applications.

In the present invention, various methods are used to set the minimum film-forming temperature of the urethane- (meth) acrylic composite resin within the above-mentioned preferable range. For example, the following methods are used to lower the minimum film-forming temperature. The method of <1> to <3> can be mentioned. In addition, in order to raise the minimum film-forming temperature, generally, a method opposite to this method may be used.

<1> As the above-mentioned polyol unit, the amount of relatively high molecular weight diols having a molecular weight exceeding 1000, for example, is increased.
<2> The equivalent ratio of the polyol unit and the polyhydric isocyanate compound when producing the component (P1) is brought close to 1: 1.
<3> As the component (q), one having a low glass transition temperature (Tg) is used.

The gel content of the first U / A composite resin aqueous dispersion obtained in the present invention is preferably 50% by weight or more, preferably 60% by weight or more. If it is less than 50% by weight, the hardness is insufficient, and the compounding stability and the dispersion stability tend to be inferior. On the other hand, the upper limit of the gel content is preferably 99% by weight, preferably 95% by weight. If it is more than 99% by weight, it may become too hard or may become stiff in cosmetic applications. By using such a gel component, the above-mentioned oil resistance (cast film forming property) is further improved. This characteristic can be obtained particularly effectively by setting the weight average molecular weight (Mw) of the first U / A resin in the above range.

<Second U / A resin and second U / A resin aqueous dispersion>
(1) Method for Producing Second Urethane- (Meta) Acrylic Composite Resin (Second U / A Resin) Polymerize a (meth) acrylic monomer ((q) component) in the presence of the above (P2) component. Thereby, a second U / A resin obtained by combining the component (P2) and the component (Q) can be obtained.

In order to produce such a second U / A resin, for example, the component (q) is mixed in an emulsion formed by emulsion-dispersing the component (P2) and the component (q) in an aqueous medium. A method of emulsion polymerization can be used, at which time the second U / A resin is obtained as an aqueous dispersion.

In parallel with the polymerization of the component (q), the water in the emulsion may cause a chain extension reaction of polyurethane.

Further, the chain extension reaction can be carried out by adding the chain extender to the emulsion. The chain extension reaction may be carried out before the polymerization of the component (q) or after the polymerization.

As the radical polymerization initiator used in the above-mentioned polymerization reaction, the same radical polymerization initiators used in the first U / A resin and the first U / A resin aqueous dispersion can be used.

The polymerization temperature is usually 10 to 80 ° C, preferably 30 to 60 ° C. After the heat generation is completed, the polymerization is almost completed by maintaining the temperature at 40 to 90 ° C. for about 30 minutes to 3 hours. As a result, an aqueous emulsion of the second U / A resin is obtained.

<Urethane component ((P2) component) of the second U / A resin and the second U / A resin aqueous dispersion liquid>
The urethane component ((P2) component) of the second U / A resin and the second U / A resin aqueous dispersion contains polyurethane having a component derived from the polyester polyol having the above-mentioned phthalic acid-based unit, and is the second U. The content ratio of the polyurethane in the urethane component contained in the / A resin is 50% by weight or more, preferably 70% by weight or more, more preferably 85% by weight or more, and the total amount thereof is most preferably the polyurethane. ..
The urethane component other than polyurethane having a component derived from the polyester polyol having a phthalic acid-based unit is not particularly limited as long as the object and effect of the present invention are not impaired.

Further, in the present invention, the content of the dicarboxylic acid-derived structural unit (dicarboxylic acid unit) contained in the polyurethane ((P2) component) among the constituents of the second U / A resin is 0. It is preferably 05% by weight or more and 50% by weight or less, more preferably 0.08% by weight or more and 40% by weight or less, and particularly preferably 0.1% by weight or more and 35% by weight or less. By setting the content of the dicarboxylic acid unit in the above range, the excellent flexibility, strength and oil resistance of the second U / A resin of the present invention can be made particularly good.

The content of the dicarboxylic acid-derived structural unit (dicarboxylic acid unit) contained in the polyol component of the above-mentioned polyurethane is also preferably in the same range for the same reason.
This is because, in the second U / A resin, the component that affects the oil resistance is a component derived from polyurethane, so that increasing the oil resistance of polyurethane improves the oil resistance of the entire second U / A resin. Because.

Further, the dicarboxylic acid unit is at least one selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid, and an isophthalic acid unit is particularly preferable from the viewpoint of oil resistance.
The content of this dicarboxylic acid unit is calculated from the composition of the second U / A resin and the content of the unit in urethane according to the above-mentioned method for calculating the content of phthalic acid-based constituents in the polyester polyol. be able to.

The (q) component and other monomers other than the (q) component used in this reaction are the (q) component and (q) used in the above-mentioned first U / A resin and first U / A resin aqueous dispersion. ) The same components as other monomers other than the components can be used.

The glass transition temperature (Tg) of the homopolymer or copolymer containing the component (q) as a main component is preferably −50 ° C. or higher, more preferably −40 ° C. or higher. When the Tg is lower than −50 ° C., the obtained cosmetic may become sticky to the touch, and the tactile sensation may be deteriorated.

On the other hand, the glass transition temperature (Tg) is preferably 120 ° C. or lower, more preferably 110 ° C. or lower. If it exceeds 120 ° C., the minimum film forming temperature becomes high, and a uniform film may not be formed. By setting the glass transition temperature within this range, it is possible to suppress the plasticization of the polymer due to the oil content even when the amount of the oil content is large, without significantly deteriorating the performance of the hair cosmetic according to the present invention. .. The glass transition temperature (Tg) can be measured or calculated using the method for measuring or calculating the glass transition temperature (Tg) described in the above-mentioned first U / A resin and first U / A resin aqueous dispersion. can.

When a plurality of types of (meth) acrylic monomers are used, the flexibility of the film is obtained by using a monomer having a high Tg of the homopolymer and a monomer having a low Tg of the homopolymer in combination. Can be adjusted.

In this case, the Tg of the homopolymer of one monomer is preferably 95 ° C. or higher and 150 ° C. or lower, preferably 100 ° C. or higher and 140 ° C. or lower, and the Tg of the homopolymer of the other monomer is −. 70 ° C. or higher and 30 ° C. or lower are preferable, and −60 ° C. or higher and 10 ° C. or lower are preferable.

If the Tg of the monomer on the high Tg side is too high, the film may become too hard, and if the Tg of the monomer on the low Tg side is too low, it may become sticky.

<Characteristics of 2nd U / A resin and 2nd U / A resin aqueous dispersion>
Next, the second U / A resin and the second U / A resin aqueous dispersion will be described.
The second U / A resin contains a polyester polyol as a polyol component in the urethane component, and the polyester polyol is derived from at least one dicarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid. By having a component having a constituent unit, that is, a component derived from a phthalic acid-based polyester component, particularly an isophthalic acid-based polyester component, the property of having good oil resistance is exhibited.

The composition ratio of the polyurethane component and the (meth) acrylic component in the second U / A resin is preferably 80/20 to 30/70 and 70/30 to 35/70 as the polyurethane component / (meth) acrylic component in terms of weight ratio. 65 is preferable. The total amount of both the polyurethane component and the (meth) acrylic component is 100.

If the polyurethane component is more than 80/20, the heat return property (including settability) when used as a hair styling product may deteriorate. On the other hand, if it is less than 30/70, the emulsion stability during the production of the second U / A resin may be insufficient, or the produced aqueous emulsion may become non-uniform.

When the second U / A resin is used as an aqueous emulsion, its concentration is not particularly limited, but it is preferable that the amount of the non-volatile component is 20% by weight or more, and it is 30% by weight or more. Is more preferable. If it is less than 20% by weight, it may take time to dry. On the other hand, the upper limit is preferably 70% by weight or less, more preferably 60% by weight or less. If it exceeds 70% by weight, the emulsion may become unstable.

The minimum film forming temperature of the second U / A resin is preferably 10 ° C. or lower, preferably 5 ° C. or lower. If the temperature exceeds 10 ° C., the flexibility of the film may be insufficient. On the other hand, the minimum film forming temperature is preferably −20 ° C. or higher, preferably −10 ° C. or higher. If the temperature is lower than -20 ° C, the heat return property (including settability) of the obtained film may deteriorate.

Various methods are used to set the minimum film-forming temperature of the second U / A resin within the above-mentioned preferable range. For example, as a method for lowering the minimum film-forming temperature, the following <a> to < The method of c> can be mentioned. In addition, in order to raise the minimum film-forming temperature, generally, a method opposite to this method may be used.

<a> As the polyol unit, relatively high molecular weight polyols having a molecular weight of, for example, exceeding 1000 are used, or the amount used thereof is increased.
<B> The equivalent ratio of the polyol unit in polyurethane to the polyhydric isocyanate compound is brought close to 1: 1.
<c> As the (meth) acrylic monomer component, one having a low glass transition temperature (Tg) is used.

Further, for the deodorizing step of the second U / A resin and the second U / A resin aqueous dispersion, the same method as the deodorizing step of the first U / A resin and the first U / A resin aqueous dispersion may be used. preferable.

In this way, the aqueous dispersion of the second U / A resin having the residual amount of the (meth) acrylic monomer component set to 100% by weight ppm or less has almost no odor when used for cosmetics such as hair styling products. Therefore, it can be preferably used as a raw material.

As described above, this second U / A resin can be cast into a film at 23 ° C. from a solution mixed with a silicone oil such as cyclopentasiloxane at a weight ratio of 50/50.

The weight average molecular weight (Mw) of the second U / A resin is preferably 100,000 or more, preferably 150,000 or more. The upper limit of the weight average molecular weight is preferably 2000000, preferably 1,000,000, and more preferably 800,000. By satisfying this range, the mechanical stability and the pigment stability when a pigment is added are excellent.
On the other hand, if the weight average molecular weight is less than 100,000, the pigment dispersibility may be inferior. On the other hand, if the weight average molecular weight is larger than 2000000, the film tends to be hard and brittle, and the texture may be deteriorated. By setting the weight average molecular weight (Mw) in the range, particularly good oil resistance (cast film forming property) can be obtained.

The molecular weight distribution (Mw / Mn) of the second U / A resin is usually 1.5 or more and 2.5 or less, and preferably 1.7 or more and 2 or less.
By setting the molecular weight distribution within this range, it is possible to reduce the stickiness of the obtained product due to the low molecular weight component and the stickiness due to the high molecular weight component, and it is possible to improve the usability especially when used in skin cosmetics. can.

In the case of emulsion polymerization of the (meth) acrylic acid ester-based polymerizable monomer which is the component (q) in an aqueous medium, a polymerization initiator, an emulsifier, etc. in the aqueous medium during the polymerization and other polymers produced are used. The chain transfer reaction to the above is likely to occur, and the molecular weight of the obtained polymer may be low.
On the other hand, in the present application, the component (P2) (polyurethane having an isocyanate group and a carboxyl group) and the component (q) ((meth) acrylic acid ester-based polymerizable monomer) are emulsified and dispersed in an aqueous medium. A urethane- (meth) acrylic composite resin aqueous dispersion (second U / A resin aqueous dispersion) obtained by polymerizing the component (q) is produced by using the pre-emulsion. Radical polymerization will occur in the state where the component (q) is arranged inside the P2) component. At this time, the component (q) is protected by the component (P2), and not only the chain transfer reaction during the polymerization of the component (q) is unlikely to occur, but also the polymerization proceeds in a state where the polymerization termination reaction is unlikely to occur. Therefore, the molecular weight of the component (q) tends to increase. Then, the urethane resin constitutes the shell portion, and the (meth) acrylic resin constitutes the core portion, and becomes a composite resin having a core-shell structure. At this time, the molecular weight of the component (q) tends to be larger than that of emulsion polymerization in the absence of the component (P2), and the molecular weight distribution of the obtained composite resin shows two peaks.

The second U / A resin preferably contains a component (gel component) that is insoluble in THF (tetrahydrofuran). The preferred gel content is preferably 10% by weight or more, preferably 30% by weight or more. Therefore, if the gel fraction is too small, the compounding stability and oil resistance may be inferior.
The upper limit of the gel content is not particularly limited and may be 100% by weight, but 99% by weight or less is preferable. By using such a gel component, the above-mentioned oil resistance (cast film forming property) is further improved. This characteristic can be obtained particularly effectively by setting the weight average molecular weight (Mw) of the second U / A resin in the above range.

<(3) Ingredient>
The component (3) is selected from (t-1) oils, (t-2) alcohols, (t-3) surfactants, (t-4) protein hydrolysates, amino acids and derivatives thereof. It is a compounding component containing at least one of (t-5) water and at least one of them.

The oil agent in the component (t-1) is liquid, pasty or solid at 20 ° C., and examples of these (t-1) include liquid paraffin, hydrocarbons such as vaseline, castor oil and sunflower oil. , Olive oil, vegetable oils such as alkantree kernel oil, oleyl alcohol, stearyl alcohol, octyldodecanol, lauryl alcohol, cetostearyl alcohol, cetanol, higher alcohols such as cholesterol, isopropyl myristate, refined lanolin, octyldodecyl myristate, myristic acid. Fatty acid esters such as isopropyl, natural waxes such as candelilla wax, carnauba wax, whale wax, and honey wax, synthetic hydrocarbon waxes such as paraffin wax and microcrystallin wax, waxes such as mineral waxes such as ceresin and ozokerite, and laurin. Examples thereof include saturated higher fatty acids such as acid, myristic acid, stearic acid and isostearic acid, unsaturated higher fatty acids such as oleic acid and undecylenic acid, and silicones. Specific examples of silicone include cyclopentasiloxane, dimethicone, dimethylpolysiloxane, decamethylcyclopentasiloxane, phenyltrimethicone, dimethiconol, methylpolysiloxane, methylphenylpolysiloxane, and polyoxyethylene / methylpolysiloxane copolymers. , Decamethylcyclopentasiloxane, polyoxyethylene / perfluoropolysiloxane, amino-modified silicones other than (aminoethylaminopropylmethicone / dimethicone) copolymers (aminopropylphenyltrimethicone, etc.), (hydrolyzed silk / PG-propylmethylsilane) Examples thereof include diol) crosspolymer (PG is an abbreviation for propylene glycol), (dihydroxymethylsilylpropoxy) hydroxypropyl hydrolyzed keratin and the like.

The content of the component (t-1) in the hair cosmetic of the present invention is not particularly limited, but preferably the lower limit is 0.01% or more, preferably 0.1% or more, based on the total amount of the hair cosmetic. Is more preferable, and 0.3% or more is further preferable. The upper limit thereof is preferably 90% or less, more preferably 80% or less, still more preferably 50% or less. As a specific range, it is preferably 0.01 to 90%, more preferably 0.1 to 80%, and even more preferably 0.3 to 50%. Within these ranges, it can be blended without impairing the function as a cosmetic.

The alcohols in the component (t-2) include lower alcohols having 2 to 7 carbon atoms such as ethanol, glycerin, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 3-methyl-1,3-butane. Diol, hexylene glycol, diglycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, 3-methyl-1,3-butanediol, neopentyl glycol dicaprate Examples thereof include polyhydric alcohols such as sorbitol, martitol, and sugar alcohols such as xylitol. In the present invention, 1,3-butylene glycol, glycerin, propylene glycol, dipropylene glycol, ethylene glycol, and diethylene glycol are used in the present invention. , Triethylene glycol and polyethylene glycol 200 to 600 are preferable, and 1,3-butylene glycol is more preferably used. In addition, the use of sugar alcohol is particularly excellent in terms of imparting suppleness to hair.

The content of the component (t-2) in the hair cosmetic of the present invention is not particularly limited, but preferably the lower limit is 0.01% or more, preferably 0.1% or more, based on the total amount of the hair cosmetic. Is more preferable, and 0.3% or more is further preferable. The upper limit thereof is preferably 90% or less, more preferably 80% or less, still more preferably 50% or less. As a specific range, it is preferably 0.01 to 90%, more preferably 0.1 to 80%, and even more preferably 0.3 to 50%. Within these ranges, it is possible to impart smoothness and moistness to the hair without stickiness.

The surfactant in the component (t-3) is not particularly limited, but a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant should be used. Can be done.
Specific examples of the above-mentioned nonionic surfactant include ether-type nonionic surfactants such as polyoxyethylene hydrogenated castor oil, polyethylene glycol monostearate, polyoxyethylene sorbit honey wax, and polyoxyethylene cetyl ether, and self-emulsifying type. Examples thereof include ester-type nonionic surfactants such as glycerin monostearate and sorbitan sesquioleate.

Specific examples of the above-mentioned cationic surfactant include, for example, alkyltrimethylammonium chloride (lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, etc.), alkyltrimethylammonium bromide (flammation). Haloalkane trimethylammonium such as lauryltrimethylammonium, cetyltrimethylammonium bromide, stearyltrimethylammonium bromide, behenyltrimethylammonium bromide, etc.; Oil alkyl dimethylammonium, dialkyl chloride (C12-18) dimethylammonium (the number in parentheses after alkyl means the carbon number of the alkyl group. The same applies to each of the following materials)] and the like. Haloalkane dialkyldimethylammonium; alkyltrimethylammonium metosulfate such as cetyltrimethylammonium metosulfate, behenyltrimethylammonium metosulfate; isoalkyl (C10-40) amidopropylethyldimethylammonium etosulfate; and the like. The blending amount of the cationic surfactant in the hair cosmetic is preferably, for example, 1 to 5% by mass.

Examples of the counter ion of the cationic residue include a halide ion such as a chloride ion, a bromide ion, and an iodide ion, a metosulfate ion, and a saccharide ion.
In addition, these cationic surfactants may contain a trace amount of solvent (ethanol, isopropanol, etc.). Therefore, the hair cosmetic of the present invention may contain the above-mentioned solvent contained in the cationic surfactant.

Examples of the anionic surfactant include alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylic acids. Examples thereof include salts, α-sulfonic acid fatty acid salts, N-acylamino acid type surfactants, phosphoric acid mono or diester type surfactants, sulfosuccinic acid esters and the like. Examples of the counter ion of the anionic residue of the surfactant include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; alkanol group having 2 or 3 carbon atoms. Examples thereof include alkanolamines having 1 to 3 alkanolamines (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

Examples of the amphoteric tenside include imidazoline-based, carbobetaine-based, amide betaine-based, sulfobetaine-based, hydroxysulfobetaine-based, and amide sulfobetaine-based.

In the present invention, one or more of these surfactants can be appropriately selected and used. The blending amount of these surfactants is usually 0.1 to 20.0%, preferably 0.3 to 10.0%, based on the total amount of hair cosmetics. If it is less than 0.1%, stability may be impaired, and if it exceeds 20.0%, stickiness may occur.

Specific examples of the protein hydrolyzate and its derivative in the component (t-4) include a hydrolyzate of a protein such as collagen, keratin, soybean protein, silk, pea protein, and rice protein; and a derivative of the hydrolyzate. Trimethyl quaternary ammonium compound, higher alkyl quaternary ammonium compound, acylated product, etc.);

Specific examples of the amino acid and its derivative in the component (t-4) include, for example, glycine, alanine, valine, leucine, isoleucine, serine, threonine, phenylalanine, tyrosine, tryptophan, cystine, cysteine, methionine, proline, hydroxyproline. , Aspartic acid, glutamic acid, arginine, histidine, lysine, pyrrolidone carboxylic acid or its salt, acylated amino acid or its salt, N-lauroyl-L-glutamic acid di (phytosteryl 2-octyldodecyl), N-lauroyl-L-glutamic acid Examples thereof include di2-octyldodecyl, di2-hexyldecyl N-lauroyl-L-glutamate, and di-di2-lauroyl-L-glutamic acid (cholesteryl 2-octyldodecyl). The blending amount of the amino acid and its derivative in the hair cosmetic is preferably, for example, 0.001 to 3% by mass.

The content of the component (3) in the hair cosmetic of the present invention is not particularly limited, but preferably the lower limit is 0.01% by mass (hereinafter abbreviated as%) or more based on the total amount of the hair cosmetic. 0.02% or more is more preferable, and 0.05% or more is further preferable. The upper limit thereof is preferably 95% or less, more preferably 90% or less, still more preferably 85% or less. As a specific range, 0.01 to 95% is preferable, 0.02 to 90% is more preferable, and 0.05 to 85% is more preferable. Within these ranges, more excellent effects can be obtained in terms of conditioning property, set property, keeping power, and hair reshaping property.

In addition to the above-mentioned components, various components contained in conventionally known hair cosmetics can be added to the hair cosmetics of the present invention, if necessary. Examples of such additive components include aromatic alcohols, preservatives, pH adjusters, viscosity regulators, fragrances and the like.

Specific examples of the aromatic alcohol include phenoxyethanol, phenoxyisopropanol, benzyl alcohol and the like. The blending amount of the aromatic alcohol in the hair cosmetic is preferably, for example, 0.1 to 2% by mass.

Specific examples of the preservatives include, for example, benzoic acid and salts thereof (sodium salt, etc.); paraoxybenzoic acid esters such as methyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, and salts thereof (sodium salt, etc.). ); Salicylic acid and its salt; sorbic acid and its salt; phenoxyethanol; methylisothiazolinone; methylchloroisothiazolinone, methylisothiazolinone; and the like.

Specific examples of the pH adjuster include acids such as glycolic acid, citric acid, phosphoric acid, malic acid, tartaric acid and lactic acid; ammonia, sodium hydroxide, monoethanolamine and amino-2-methyl-1-. Alkali such as propanol;
Specific examples of the viscosity modifier include alkaline thickeners such as carbonmer, hydroxyethyl cellulose, xanthan gum and the like.

<Mixing amount of (1) component to (3) component>
The blending amount of (1) with respect to 100 parts by weight of the component (3) is not particularly limited, but preferably the lower limit is 0.01% by mass (hereinafter abbreviated as%) or more based on the total amount of hair cosmetics. , 0.02% or more is more preferable, and 0.05% or more is further preferable. The upper limit thereof is preferably 10% or less, more preferably 9% or less, still more preferably 7% or less. As a specific range, 0.01 to 10% is preferable, 0.02 to 9% is more preferable, and 0.05 to 7% is more preferable. Within these ranges, more excellent effects can be obtained in terms of conditioning property, set property, keeping power, and hair reshaping property. If it is more than 10%, the hair feels stiff and resiny due to the influence of the resin blended in a large amount, which may cause a problem that a sufficient effect cannot be obtained in the conditioning effect. On the other hand, if it is less than 0.01%, the resin may be affected by the plasticizing effect due to the influence of the components blended to obtain the conditioning effect, and sufficient keeping power may not be exhibited.

The amount of the component (2) to be blended with respect to 100 parts by weight of the component (3) is not particularly limited, but preferably the lower limit is 0.01% by mass (hereinafter abbreviated as%) based on the total amount of hair cosmetics. The above is preferable, 0.02% or more is more preferable, and 0.05% or more is further preferable. The upper limit is preferably 30% or less, more preferably 10% or less. If it is more than 30%, there may be a problem that the hair feels stiff and the resin feeling becomes too strong. On the other hand, if it is less than 0.01%, the continuity of the film becomes insufficient, the keeping force and the adhesion to the hair become insufficient, and the effect of the addition may not appear.

Further, the compounding ratio of the component (1) and the component (2) is (1) / (2), preferably 1/1 or more, preferably 2/1 or more. If it is smaller than 1/1, no difference from the case where only one of (1) and (2) is added to (3) is seen, and a sufficient synergistic effect may not be obtained. On the other hand, the upper limit of the compounding ratio is preferably 10/1. If it is larger than 10/1, the effect of the component (2) may not be obtained.

<Hair cosmetics>
Furthermore, when these cosmetics are in the form of an aerosol, a propellant such as liquefied petroleum gas or dimethyl ether is used in combination, and depending on other uses and purposes, metal ion scavengers, fungicides, bactericides, etc. Emulsifying agents, conditioning agents, thickening agents, antioxidants, solubilizers, rosins, hydrotropes, hair restorers, crude drugs, pigments, fragrances and the like may be used.

Examples of the hydrocarbons include liquid paraffin, petrolatum, solid paraffin, isoparaffin, squalane, olefin oligomer and the like. Examples of the linear alcohol include lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, and cetostearyl alcohol.

Examples of the branched alcohols include monostearyl glycerin ether, 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol and lauryl alcohol. And 2-octyldodecanol and the like.

Examples of the higher fatty acids and derivatives thereof include lauric acid, myristic acid, palmitic acid, stearic acid, behen (behenyl) acid, oleic acid, 1,2-hydroxystearic acid, undecylenic acid, toll acid, lanolin fatty acid and isostearic acid. Acids, linoleic acid, linoleic acid, γ-linolenic acid, eikosapentaenoic acid and the like can be mentioned.

Examples of the plant-based polymer include carrageenan, pectin, canten, quince seed (quince), algae colloid (quince extract), starch (rice, corn, potato, wheat), glycyrrhizinic acid and the like.

Examples of the microbial polymer include xanthan gum, dextran, pullulan and the like. Examples of the natural water-soluble polymer include animal-based polymers such as collagen and gelatin. Examples of the cellulosic polymer include methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, sodium carboxymethyl cellulose (CMC), crystalline cellulose, cellulose powder and the like.

Examples of the semi-synthetic water-soluble polymer include alginic acid-based polymers such as sodium alginate and propylene glycol alginate. Examples of the vinyl-based polymer include polyvinyl alcohol, polyvinylmethyl ether, polyvinylpyrrolidone, and carboxyvinyl polymer (carbopol).

Examples of the polyoxyethylene polymer include polyethylene glycol 20,000, 40,000, 60,000 and the like. Examples of the synthetic water-soluble polymer include polyethyleneimine and the like. Examples of the inorganic water-soluble polymer include bentonite, magnesium aluminum silicate (beagum), labonite, hectorite, silicic acid anhydride and the like.

Examples of the silicones include volatile silicone oils, silicone resins, silicone gums, alkyl-modified silicones, dimethylpolysiloxanes, methylphenylpolysiloxanes, polyether-modified silicones, amino-modified silicones and the like, and the N-fatty acid acyls. As L-glutamate, N-lauryl-L-monosodium glutamate, N-palm oil fatty acid-L-monotriethanolamine glutamate, acyl N-myristylate-monosodium L-glutamate, N-mixed fatty acid acyl- Examples thereof include monosodium L-glutamate.

Examples of the N-fatty acid-N-methyl taurine salt include sodium methyl taurine laurate, sodium coconut oil fatty acid methyl taurine and the like. Examples of the salt of the N-fatty acid sarcosine condensate include sodium lauroyl sarcosine and sodium cocoyl sarcosine.

Other surfactants mentioned above include sodium acylsarcosine, acylglutamate, sodium acyl-β-alanine, acyltaurate, lauryl sulfate, betaine lauryldimethylaminoacetate, alkyltrimethylammonium chloride, polyoxyethylene hydrogenated castor oil. And so on. Also, cationic surfactants such as stearyltrimethylammonium chloride, distearyldimethylammonium chloride and lauryltrimethylammonium chloride, anionic surfactants such as polyoxyethylene lauryl ether sulfate and polyoxyethylene laurylsulfosuccinate, laurylhydroxysulfobetaine and Examples thereof include amphoteric surfactants such as lauryldimethylcarboxybetaine.

Examples of the emulsifier include glyceryl monostearate, sorbitan monopalmitate, polyoxyethylene cetyl ether, polyoxyethylene sorbitan monolaurate and the like.
Examples of the moisturizing agent include (poly) ethylene glycol, (poly) propylene glycol, glycerin, 1,3-butylene glycol, martitol, sorbitol, chondroitin sulfate, hyaluronic acid, atelocollagen, and cholesteryl-1,2-hydroxystearate. Examples thereof include sodium lactate, bile acid salt, dl-pyrrolidone carboxylate, short chain soluble collagen and the like.

Examples of the antibacterial agent include hinokitiol, hexachlorophene, benzalkonium chloride, trichlorocarbanilide, pithionol and the like. Examples of the vasodilator include carpronium chloride. Examples of the refreshing sensation imparting agent include menthols and the like. Examples of the stimulant-imparting agent include benzyl nicotinate and the like. Examples of vitamins include vitamins A, B, C, D and E.
Examples of the bactericidal / preservative include chlorhexidine gluconate, isopropylmethylphenol, paraoxybenzoic acid ester, paraben and the like. Examples of the chelating agent include protein hydrolysates, amino acids, plant extracts, EDTA-Na and the like. pH
Examples of the adjusting agent include succinic acid, sodium succinate, triethanolamine and the like.

Examples of the glyceride include camellia oil, castor oil, cacao oil, mink oil, avocado oil, jojoba oil, macadamian nut oil, olive oil and the like. Examples of the waxes include beeswax and lanolin. Examples of the polyhydric alcohols include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin and sorbitol.
Examples of the ethylene oxide and / or propylene oxide adduct of the higher alcohol include polyoxyethylene lauryl ether, polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene stearyl ether and the like.

Examples of the amides include esters such as isopropyl myristate, octyldodecyl myristate, hexyl laurate and cetyl lactate; oleic acid diethanolamide and lauric acid diethanolamide.
Examples of the protein derivative or amino acid derivative include collagen hydrolyzate, keratin hydrolyzate, polyamino acid and the like. Examples of the ultraviolet absorber include oxybenzene and the like.

Further, in addition to the above, metal sequestering agents such as disodium edetate, trisodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, caffeine, tannin, verapamil, tranexamic acid and its derivatives, various types. Raw medicine, tocopherol acetate, glycyrrhizinic acid and its derivatives or salts thereof, glycyrrhetinic acid derivatives, salicylic acid derivatives, lysophosphatidylcholine and lysophosphatidic acid, laminose 5 production promoters such as soybean preparations, glucose, fructose, mannose, Sugars such as sucrose and trehalose, whitening agents such as arbutine and kodiic acid, nonyl acid valenylamide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingeron, cantalistinki, ictamol, tannic acid, α-borneol , Tocopherol nicotinate, inositol hexanicotinate, cyclanderate, cinnaridine, trazoline, acetylcholine, cepharanthin, γ-orizanol and other blood circulation promoters, sulfur, thiantoll and other antilipolytic agents, hinokithiol, zinc oxide for various purposes , Silica-coated zinc oxide, allantin, turmeric extract, beech bud extract, hydrolyzed casein, rice extract hydrolyzate, rice bran extract, tounin extract, clara extract, thiotaurine, hipotaurin, majorum extract, ichiyakuso Extracts, xylitol, arginine and its hydrochlorides, serine, Oubaku extract, Ouren extract, Kakkon extract, Shikon extract, Shakuyaku extract, Senburi extract, Birch extract, Sage extract, Biwa extract, Carrot Extract component, Aloe extract component, Zenia oi extract component, Iris extract component, Grape extract component, Yokuinin extract component, Hechima extract component, Yuri extract component, Saffron extract component, Senkyu extract component, Shokyo extract component, Otogirisou extract component, Rosemary Extract components, garlic extract components, pepper extract components, plant extracts such as crackle extract components, vitamin A such as chimpi, touki, retinol, retinol acetate, riboflavin, riboflavin butyrate, flavin adenine nucleotides and other vitamin B2, pyridoxin Vitamin B6s such as hydrochloride, pyridoxin dioctanoate, L-ascorbic acid, L-ascorbic acid dipalmitic acid ester, L-ascorbic acid-2-sodium sulfate, L-ascorbic acid phosphorus Vitamin C such as acid ester, DL-α-tocopherol-L-ascorbic acid phosphate diester dipotassium, pantothenic acid such as calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether, acetylpantotenyl ethyl ether, ergocalci Vitamin Ds such as ferrol and cholecalciferol, nicotinic acids such as nicotinic acid, nicotinic acid amide and benzyl nicotinate, α-tocopherol, tocopherol acetate, DL-α-tocopherol nicotinate, DL-α-tocopherol succinate and the like Vitamin E, vitamin P, vitamins such as biotin and the like can also be appropriately blended.

Furthermore, anti-aging agents, moisturizers, antioxidants, oily ingredients, ultraviolet absorbers, surfactants, thickeners, preservatives, alcohols, pH adjusters, detergents, desiccants, emulsifiers, other than the above, Powder components, coloring materials, aqueous components, water, various hair nutrients, fragrances, plant extracts and the like can be appropriately blended as needed.

<Specific uses of hair cosmetics>
The use of the hair cosmetic of the present invention is used as a hair styling agent such as a hair styling emulsion, a setting agent, and the like.
The usage form of the hair cosmetic of the present invention is not particularly limited, and can be used as, for example, an aerosol hair spray, a pump hair spray, a foam hair spray, a hair mist, a set lotion, a hair gel, a hair cream, a hair oil, and the like. ..

In the hair cosmetic of the present invention, as a propellant, chlorfluoroalkane such as trichlormonofluoromethane or dichlorodifluoromethane; halogenated hydrocarbons; liquefied petroleum gas composed of alkanes; dimethyl ether; carbon dioxide gas, nitrogen gas and the like. It is also possible to use a compressed gas of the above or a mixed gas thereof to form an aerosol formulation according to a conventional method.

Next, examples of usage and the like will be shown for use as hair styling products and setting agents.
When the hair cosmetic (mouse) that can be ejected in a foamy state is used as the hair conditioner or set agent, for example, the hair cosmetic (solid content) of the present invention has a nonionic interface of 0.01 to 25% by weight. Compositions such as 0.1 to 5% by weight of the activator, 3 to 25% by weight of the liquefied gas, and 60% by weight to the residual amount of the water-soluble solvent mainly composed of water are used. (However, water is contained in hair cosmetics in an amount of 60% by weight or more).

Examples of the nonionic surfactant used here include sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene. Examples thereof include castor oil, polyoxyethylene hydrogenated castor oil, and fatty acid alkanolamide.

When a gel-like hair styling product is used, the hair cosmetic (solid content) of the present invention is 0.01 to 25% by weight, gel base 0.1 to 3% by weight, and water 72% by weight. -A composition such as residual residue is used.

In the case of a hair spray, the hair cosmetic (solid content) of the present invention has a composition of 0.01 to 25% by weight, an organic solvent of 30 to 80% by weight, a propellant of 10 to 70% by weight, or the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

<Raw materials>
[(1) Ingredient]
-Z631 ... Made by Mitsubishi Chemical Corporation: Z-631. Specifically, this component is Acrylates / Lauril Acrylate / Steanyl Acrylate / Ethylamine Oxide Methacrylate Copolymer, and these amine oxide group-containing resins are The Cosmetic Toiletry.
It is described in "International Cosmetic Ingredient Dictionary and Handbook" published by Fragrance Association.

[(2) Ingredient]
・ FS1000 ... Japan Coating Resin Co., Ltd .: Ricabond FS-1000. This is a composite of polyurethane and a (meth) acrylic resin, which is a polyester polyol having a structural unit derived from at least one dicarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid. Urethane- (meth) acrylic composite resin.

[(3) Ingredient]
・ S24… Elastine It Style 24 Curling Styling Elastinesence LG Household & Health Care: Water, modified alcohol, cyclopentasiloxane, glycerin, dipropylene glycol, mineral oil, ceteares-30, neopentylglycol dicaprate, alkane tree kernel oil , Hydrolyzed keratin, dimethicone oil, ceteares-3, polyacrylamide, 13-14 isoparaffin, laureth-7, maltitol, dimethicone, (dimethicone / vinyl dimethicone) crosspolymer, (acrylics / dimethicone) copolymer, carbonomer, tromethamine, 3 -A composition containing octyloxy-1,2-propanediol, (acrylate / stearyl acrylate / dimethicone methacrylate) copolymer, acrylates copolymer, isopropyl myristate, ethylenediamine tetraacetic acid, butylene glycol, phenoxyethanol, and a fragrance.

<Evaluation>
[Hardness]
Hair having a film formed by using the composition obtained in Examples and the like was evaluated by performing a three-point bending test according to JIS K 7171 (2008).
Specifically, first, 0.4 g of each of the samples prepared in Example 1 and Comparative Examples 1 to 3 was applied to a hair bundle having a length of 15 cm and a weight of 1.3 g. Next, the hair bundle was combed into a flat plate having a width of 2 cm, and the hair bundle was dried at 50 ° C. for 2 hours to form a film. In this way, flat hair having a film formed on the surface was obtained. Then, the hair was allowed to stand for 24 hours under the conditions of 23 ° C. and 60% relative humidity.
Then, the flat plate-shaped hair was placed on a support base having a distance between fulcrums of 65 mm, and the central portion of the hair was pressed with an indenter at a speed of 2 cm / min (3-point bending test). Then, the maximum load (bending strength) at the time when the central portion of the hair was bent to a depth of 2 cm was measured and evaluated according to the following criteria.
◯: The bending strength was 100 g or more.
Δ: The bending strength was 20 g or more and less than 100 g.
X: The bending strength was less than 20 g.

[Curl holding power]
The curl holding power was evaluated by measuring the curl retention of the hair on which the film was formed. To black virgin hair (length: 23 cm, weight: 2 g), 0.7 g of the samples prepared in Example 1 and Comparative Examples 1 to 3 was applied, and immediately curled using a curler with a curl diameter of 1.2 cm. Was prepared and dried at 50 ° C. for 2 hours.
The length of the curled hair strand is measured, and this length is set as the initial value (L0). Next, the dried hair strands were hung on a board with a memory, placed in a high-temperature humidifier having a temperature of 30 ° C. and a relative humidity of 90% for 3 hours, and then the length of the hair strands was measured and this length was measured. Is the length after humidification (L1). The length of the hair strand is the maximum diameter of the curl when it is curled, and the maximum length from the end on the root side when the curl is partially or wholly unwound (for example, the root side). The length from the end of the hair to the end on the tip side of the hair). Next, the curl retention value was calculated according to the following equation (2). The closer the curl retention value is to 100%, the stronger the curl retention rate, the better the moisture resistance, and the better the style retention.
Curl retention value (%) = 100 × (23-L1) / (23-L0) ... (2)

〇: The curl retention value was 50% or more.
Δ: The curl retention value was 20% or more and less than 50%.
X: The curl retention value was less than 20%.

[viscosity]
(Change in viscosity after storage for 1 month)
Using the samples (cream of oil-in-water emulsified composition) obtained in Examples and Comparative Examples, the viscosity changes after storage at 5 ° C, 23 ° C, and 50 ° C for 1 day after production and 1 month after production ( B-type viscometer, 25 ° C.) was measured.
◯: The value obtained by dividing the viscosity of the sample after storage by the viscosity of the sample immediately after preparation is 0.9 or more and less than 1.1.
Δ: The value obtained by dividing the viscosity of the sample after storage by the viscosity of the sample immediately after preparation is 0.7 or more and less than 0.9, or 1.1 or more and less than 1.3.
X: The value obtained by dividing the viscosity of the sample after storage by the viscosity of the sample immediately after preparation is less than 0.7 or more than 1.3.

[Appearance stability]
Using the samples (cream of oil-in-water emulsified composition) obtained in Examples and Comparative Examples, visually observe the appearance after storage at 5 ° C, 23 ° C, and 50 ° C for 1 day after production and 1 month after production. Confirmed at.
◯: There is no change in appearance.
Δ: A slight change is seen in the appearance.
X: The appearance is changed, and the viscosity is clearly decreased or increased.

(Examples 1 to 4, comparative examples 1 to 3)
Each component shown in Table 1 was blended in the amount shown in Table 1 to prepare a composition, and the pH was adjusted.
Then, the above evaluation was performed. The results are shown in Table 1.

Claims (8)

A hair cosmetic consisting of a composition containing each of the following components (1), (2), and (3).
(1) A resin containing at least one of a component selected from a repeating unit derived from an unsaturated monomer having a betaine structural group and a repeating unit derived from an unsaturated monomer having an amine oxide group.
Alternatively, it contains a repeating unit derived from an unsaturated monomer having an anionic group selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and further derived from an unsaturated monomer having a tertiary amino group. A resin containing at least one of a repeating unit derived from an unsaturated monomer having a unit and a quaternary ammonium group.
(2) A urethane- (meth) acrylic composite resin obtained by using a polyester polyol as a polyol component and combining polyurethane (P ) obtained from this with a polyhydric isocyanate component and a (meth) acrylic resin (Q). And,
A urethane- (meth) acrylic composite resin, wherein the polyester polyol as a polyol component has a structural unit derived from at least one dicarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid.
(3) At least one selected from (t-1) oil, (t-2) alcohols shown below, (t-3) surfactant, (t-4) protein hydrolyzate, amino acids and derivatives thereof. A compounding ingredient containing one or more of seeds and (t-5) water.
(T-2) Alcohols include ethanol, glycerin, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 3-methyl-1,3-butanediol, hexylene glycol, diglycerin, ethylene glycol, and the like. With a polyhydric alcohol selected from the group consisting of diethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, 3-methyl-1,3-butanediol, and neopentyl glycol dicaprate . , Sorbitol, Martinol , and Glycol selected from the group consisting of xylitol. The hair according to claim 1, wherein the component (1) contains at least one selected from a repeating unit derived from an unsaturated monomer having a betaine structural group and a repeating unit derived from an unsaturated monomer having an amine oxide group. Cosmetics. The component (1) contains a repeating unit derived from an unsaturated monomer having an anionic group selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and further has a tertiary amino group. The hair cosmetic according to claim 1, which contains at least one of a repeating unit derived from a saturated monomer and a repeating unit derived from an unsaturated monomer having a quaternary ammonium group. The second or third claim, wherein the polyol component constituting the component (P) has at least two types of polyol components in which the number average molecular weights are different and / or the constituent units thereof are different. Hair cosmetics. The hair cosmetic according to any one of claims 2 to 4, wherein the weight ratio ((P) / (Q)) of the component (P) to the component (Q) is 80/20 to 30/70. A polyester polyol is used as the polyol component constituting the component (P).
The hair cosmetic according to any one of claims 2 to 5, wherein the constituent unit derived from dicarboxylic acid in the polyester polyol is the constituent unit derived from isophthalic acid. The hair cosmetic according to claim 6, wherein the content ratio of the constituent unit derived from the dicarboxylic acid is 0.05% by weight or more and 50% by weight or less. The hair cosmetic according to any one of claims 2 to 7, wherein the pH of the composition is 3 to 11.