JP7000009B2 - Urethane- (meth) acrylic composite resin and its aqueous dispersion - Google Patents

Description

The present invention relates to a urethane- (meth) acrylic composite resin containing a fluorine compound, an aqueous dispersion composed of the urethane- (meth) acrylic composite resin, and a cosmetic using the same. The cosmetic using the resin of the present invention has a feature that it can be widely applied to make-up cosmetics, skin care cosmetics, eye makeup cosmetics, other cosmetics and the like, including hair cosmetics. Further, the resin of the present invention can be preferably used as an industrial or household paint or a protective film (coating agent).

The urethane- (meth) acrylic composite resin is used as a cosmetic for maintaining the shape of hair and protecting the skin by utilizing its film-forming property (Patent Documents 1 and 2 below), or for industrial use (Patent Documents 1 and 2 below). (For automobiles) -Used as a paint or protective film for household use (Patent Document 3 below), but when the film to which these are applied comes into contact with an oil component, the oil resistance is insufficient and the film melts or swells. In some cases, it was not possible to fully demonstrate its performance. In addition, depending on the composition, water resistance may be insufficient, and makeup may be removed during sweating.

In order to improve this oil resistance, there are methods such as increasing the molecular weight of the resin used and increasing the content of the hard segment, but in some cases, the film becomes hard and cannot follow the substrate. Therefore, when it is peeled off at the time of bending, or when it is used as a cosmetic, it may cause stiffness and discomfort during use.
In order to improve the water resistance, it is conceivable to incorporate water-repellent and lipophilic components into the resin, but in terms of the balance with the oil resistance, satisfactory results have not been obtained so far.

As synthetic resins used in cosmetics, polymers such as acrylic, vinyl acetate, vinylpyrrolidone, and vinylmethyl ethers having various ionic properties such as anionic, cationic, nonionic, or amphoteric are widely known. ing. All of these are used for the purpose of maintaining the shape of hair and protecting the skin by utilizing the film-forming property of the resin, but there are problems such as the film being too hard or sticky depending on the resin. It was pointed out.
A urethane-acrylic composite resin composed of composite particles obtained by polymerizing a radically polymerizable monomer in the presence of polyurethane polymer particles as a cosmetic resin having improved the drawbacks such as stiffness and moisture absorption of the resin. An aqueous dispersion containing the above has been proposed (Patent Documents 1 and 2 below).

Examples of cosmetics using such cosmetic resins include "hair styling agents" for hair cosmetics, and the dosage form of this hair styling agent contains a large amount of oily components from a mist spray type aqueous formulation. There are many uses for hair styling products. In addition, the usage of cosmetic resin is not limited to hair cosmetics, such as make-up cosmetics, sun care cosmetics (sun protection agents, etc.), skin care cosmetics (skin protection, moisturizing), etc. , Has come to be used in a wide variety of ways.

Japanese Patent No. 2587801 Japanese Patent No. 5281232 Japanese Unexamined Patent Publication No. 2011-149011

When the urethane- (meth) acrylic composite resin having the film-forming property is applied in the method for improving the oil resistance as described above, it contains a large amount of oily components such as hair wax in cosmetics, for example. In the compounding, since the oily component acts as a plasticizer on the resin, the immobilization of the hair and the smooth feeling of the finish may be impaired, and there is a problem that it is difficult to fully exhibit the original function of the resin.

In addition, when used in cosmetics, with the diversification of such uses and usages, cosmetic resins are also required to exhibit functions in more diverse formulations than before.
In particular, in a formulation containing a large amount of oily component such as the hair wax, the oily component acts as a plasticizer on the resin, so that the immobilization of hair and the smooth feeling of finishing are impaired. There was a problem that the original function of the resin was not fully exhibited.
Further, when the usage environment is high temperature and high humidity, the influence of metabolites such as sweat is added, and it becomes more difficult to express the original function of the resin.

Therefore, the present invention provides a fluorine compound-containing urethane- (meth) acrylic composite resin and an aqueous dispersion thereof that can maintain the original excellent properties without damaging the film even when in contact with an oil component. In addition, the urethane- (meth) acrylic composite resin aqueous dispersion for cosmetics has both flexibility and hair conditioning (set retention) even in a hot and humid environment, and even if the set collapses, it can be easily restored. It is an object of the present invention to provide an aqueous dispersion of a cosmetic resin having a smooth feeling and a cosmetic obtained by using the aqueous dispersion.
In addition, when using cosmetics, heat source equipment such as dryers and hot eyelash curlers may be used, but cosmetics that can exhibit excellent oil resistance and water resistance even in such a usage environment are used. It is what we are trying to provide.

The gist of the present invention lies in the following [1] to [20].
[1] A polyurethane component ((A) component) and a (meth) acrylic resin ((B) component), and at least one of the components constituting the (A) component and / or the (B) component. Urethane- (meth) acrylic composite resin containing a fluorine compound as a part.
[2] The urethane- (1] according to [1], wherein the composition ratio of the component (A) and the component (B) is (A) / (B) = 80/20 to 30/70 in terms of weight ratio. Meta) Acrylic composite resin.
[3] The urethane- (meth) acrylic composite resin according to [1] or [2], wherein the fluorine compound is a compound containing an alkyl fluoride (meth) acrylic acid ester.

[4] The urethane- (meth) acrylic composite resin according to any one of [1] to [3], wherein the minimum film forming temperature of the urethane- (meth) acrylic composite resin is −20 to 40 ° C.
[5] The component (A) is a polyurethane obtained from a polyol component containing at least one of a polyether polyol and a polyester polyol, and a polyvalent isocyanate component, and the polyol component has 2 to 4 carbon atoms. It is a polyether polyol having a constituent unit derived from polyalkylene glycol as a main component and having a number average molecular weight of 400 or more and 4000 or less, or at least one selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid. The urethane- (meth) acrylic composite resin according to any one of [1] to [4], which is a polyester polyol having a structural unit derived from a species of dicarboxylic acid.
[6] The distribution of the number average molecular weight of the polyol component constituting the component (A) has a maximum value in the number average molecular weight of 1000 ± 200, and the content ratio of the polyol component in this range is 1 of the entire polyol component. % Or more. The urethane- (meth) acrylic composite resin according to [5].

[7] The polyol component in the component (A) is obtained from at least two types of polyol components and a polyhydric isocyanate component, which are polyol components having different number average molecular weights and / or polyol components having different constituent units thereof. The urethane- (meth) acrylic composite resin according to [5], which is a polyurethane.
[8] The urethane- (meth) acrylic composite resin according to [7], wherein the polyol having the smallest number average molecular weight among the plurality of types of polyols has a number average molecular weight of 400 or more and 1200 or less.
[9] The urethane- (meth) according to any one of [5] to [8], wherein the polyol component contains dimethylolalkanoic acid having an alkane moiety having a carbon atom number in the range of 1 to 6. Acrylic composite resin.
[10] The urethane- (meth) acrylic composite resin according to [9], wherein the dimethylolalkanoic acid is dimethylolpropionic acid and / or trimethylolbutanoic acid.

[11] The urethane according to [9] or [10], wherein the content of the constituent unit derived from a dicarboxylic acid composed of dimethylolalkanoic acid in the component (A) is 0.05% by weight or more and 50% by weight or less. -(Meta) acrylic composite resin.
[12] The urethane- (meth) acrylic composite resin according to any one of [1] to [7], wherein the glass transition temperature (Tg) of the component (A) is −60 ° C. or higher and 250 ° C. or lower.
[13] The urethane- (meth) acrylic composite resin according to any one of [5] to [12], wherein the acid value of the component (A) is 15 to 60 mgKOH / g.
[14] The urethane- (meth) acrylic composite resin according to any one of [5] to [13], wherein the mode (Mwp) of the component (A) is 10,000 or more and 200,000 or less.

[15] The urethane- (meth) acrylic composite according to any one of [5] to [14], wherein the carboxyl group contained in the component (A) is neutralized by 100% or more with a basic compound. resin.
[16] The urethane- (meth) acrylic composite resin according to any one of [1] to [15], wherein the glass transition temperature (Tg) of the component (B) is 0 ° C. or higher and 120 ° C. or lower.
[17] A composite resin aqueous dispersion in which the urethane- (meth) acrylic composite resin according to any one of [1] to [16] is emulsified and dispersed in an aqueous medium.
[18] The urethane- (meth) according to [17], wherein the (meth) acrylic monomer ((B') component) is emulsion-polymerized in the presence of polyurethane (component (A)). A method for producing an acrylic composite resin aqueous dispersion.

[19] The urethane- (meth) acrylic composite resin according to any one of [1] to [16], the urethane- (meth) acrylic composite resin aqueous dispersion according to [17], or [18]. A cosmetic comprising a urethane- (meth) acrylic composite resin aqueous dispersion produced by the production method described.
[20] The cosmetic according to [19], wherein the use is at least one selected from those for hair, eye makeup, skin, foundation, lipstick and nail color.

Polyurethane, which is the component (A) of the urethane- (meth) acrylic composite resin of the present invention, has excellent oil resistance so that it can be formed from a state of being mixed with an oil component. Reflected in this polyurethane-containing urethane- (meth) acrylic composite resin, it has the original characteristics of urethane- (meth) acrylic composite resin, such as flexibility, softness, and set retention, while achieving oil resistance. Will also be excellent.
Further, when the aqueous dispersion according to the present invention is used as a cosmetic for hair, it has good flexibility, a soft feeling, and good set retention.

Further, since the urethane- (meth) acrylic composite resin of the present invention contains a fluorine compound as a constituent component, it is used when the usage environment is high temperature and humidity, or when it is used as a cosmetic using a heat source device such as a dryer or hot eyelash curler. In such cases, excellent oil resistance can be exhibited, and the original functions of the resin, such as flexibility, softness, and set retention, can be accurately exhibited.
At the same time, since water repellency and water resistance based on the fluorine compound can be obtained, it is possible to suppress makeup breakage and makeup removal due to moisture and sweating.

Hereinafter, the present invention will be described in detail.
The urethane- (meth) acrylic composite resin (hereinafter sometimes abbreviated as "U / A resin") according to the present invention is a polyurethane component ((A) component) and a (meth) acrylic resin ((B) component). And / or a resin containing a fluorine compound as at least a part of the constituent components constituting the component (A) and / or the component (B). Among these, it is preferable to use a monomer constituting the component (B), that is, a fluorine compound as the component (B').
In addition, in this specification, "(meth) acrylic" means "acrylic or methacrylic".

1. 1. Polyurethane (component (A))
The polyurethane (component (A)) 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.
Hereinafter, in the present specification, the structural unit derived from the polyol component in polyurethane ((A) component) may be referred to as "polyol unit", and the structural unit derived from the dicarboxylic acid component may be referred to as "dicarboxylic acid unit". In some cases.

(Ratio of polyol unit and multivalent isocyanate compound used)
The ratio of the polyol unit to the polyhydric isocyanate compound used is preferably 1: 1.2 to 2, preferably 1: 1.5 to 1.9, in terms of equivalent ratio. If there are too many polyol units, the final coating film may become excessively soft or lack strength, resulting in insufficient setting power when used as a cosmetic. On the other hand, if the amount of the polyol unit is too small, contrary to the above, the rigidity of the coating film becomes too high, which may make the coating film brittle or give a feeling of stiffness when used as a cosmetic.

1-1. (A) Component component (1) Polyol component The polyol component that constitutes the polyol unit of the component (A) means an organic compound having two or more hydroxyl groups in one molecule, and as described above, a polyether. Examples include polyols and polyester polyols. The number average molecular weight of this polyol component is generally 400 or more and 4000 or less, and the preferable number average molecular weight is 500 or more and 3000 or less.

(Polyether polyol)
The polyether polyol is mainly composed of a structural unit derived from a polyalkylene glycol having 2 to 4 carbon atoms, and its number average molecular weight is usually 400 or more and 4000 or less as described above. The preferred number average molecular weight is 500 or more and 3000 or less.

Specific examples of such polyether polyols include ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5. -Relatively low molecular weight such as pentandiol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, trimethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, hexanediol, cyclohexanedimethanol, etc. Polyol polyols, polyethylene glycol, obtained by polycondensing polyols or at least one of them with at least one of dicarboxylic acids such as adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid, and isophthalic acid. Polyether polyols such as polypropylene glycol, polytetramethylene ether polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, and polyalkylene glycol, polycaprolactone polyol, polycarbonate polyol, polyacrylic acid ester polyol, and propylene oxide added to these polyols. Examples thereof include polyether polyols.

Among these, the above-mentioned polyether polyol containing a constituent unit derived from polyalkylene glycol as a main component is particularly preferable in that it can impart a soft texture.

The average number of carbon atoms of the polyol unit constituting the component (A) is preferably 2 to 4. By setting the average value within this range, a flexible texture can be imparted.

Further, the distribution of the number average molecular weights of the polyol components constituting the component (A) preferably has a maximum value at a number average molecular weight of 1500 ± 800, and more preferably has a maximum value at a number average molecular weight of 1000 ± 200. If the maximum value deviates from the number average molecular weight of 1500 ± 800, there may be a problem that the self-emulsifying power is lowered, and the soft feeling and the set holding power are lowered.

Further, in addition to the range of the maximum value of the distribution of the number average molecular weight described above, the content ratio of the polyol component in this range is preferably 1% or more, preferably 50% or more of the entire polyol component. If it is less than 1%, there may be a problem that the soft feeling is impaired. On the other hand, this upper limit is preferably 99%, more preferably 95%. If it is more than 99%, there may be a problem that the set retention is lowered.

Further, it is preferable that the polyether polyol has a carboxyl group because it can be expected to develop self-emulsifying power and improve the stability of the aqueous dispersion.
Examples of the method of introducing a carboxyl group into the polyether polyol include a method of using a carboxyl group-containing polyvalent hydroxy compound as a part of the polyol unit. Examples of the carboxyl group-containing multivalent hydroxy compound include dimethylol alkanoic acid as shown in the following chemical formula (1).

In the formula (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 a methyl group or an ethyl group.

Specific examples of this dimethylolalkanoic acid include dimethylolpropionic acid, trimethylolbutanoic acid, and the like, and these can also be used in combination. The amount of the carboxyl group-containing multivalent hydroxy compound used may be adjusted so that the acid value of the component (A) formed by polymerization is, for example, about 15 to 60 mgKOH / g.

The content ratio of the constituent unit derived from the dicarboxylic acid composed of dimethylolalkanoic acid in the component (A) is preferably 0.05% by weight or more, preferably 5% by weight or more. The upper limit is preferably 50% by weight, preferably 30% by weight. If it is out of this range, it may not meet the above-mentioned acid value range.

(Polyester polyol)
The polyester polyol is a compound consisting of a polyol unit and a dicarboxylic acid unit and having a hydroxyl group at both ends, and the constituent unit derived from the dicarboxylic acid is not particularly limited, but is phthalic acid, isophthalic acid and terephthalic acid. It is preferable to have a structural unit derived from at least one dicarboxylic acid selected from the group consisting of. The number average molecular weight of this polyester polyol is generally 400 or more and 4000 or less, and the preferable number average molecular weight is 500 or more and 3000 or less.

As the polyol unit, the same polyol unit as described in the section of the polyether polyol can be used.

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 preferable 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 polyurethane or urethane- (meth) acrylic composite 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 more preferable.

The content ratio of the dicarboxylic acid unit in the obtained polyurethane 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. The upper limit of the abundance is preferably 40% by weight, more preferably 35% by weight. The dicarboxylic acid unit preferably contains 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 "NumberPA" was obtained, and using these, the "dicarboxylic acid unit content (% by weight) in the polyurethane" was obtained in the same manner as described 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 obtained by performing an analysis.

As the polyester polyol, it is also preferable to use a component having a polyol and a monocarboxylic acid in addition to the polyol component.

As such a component, it is preferable to use dimethylolalkanoic acid such as dimethylolpropionic acid and dimethylolbutanoic acid, sulfonic acid-containing polyol, and the like, and dimethylolalkanoic acid is particularly preferable. In addition to this, various polyalkylene glycols, polyester polyols, polycarbonate polyols and the like other than the above can be used as the polyol component as long as the effects of the present invention are not impaired.
Such dimethylol alkanoic acid has the structure represented by the chemical formula (1). Further, the carbon number and type of the preferable alkyl group are also the same as described above.

By using dimethylol alkanoic acid as a constituent component, good copolymerizability can be obtained, and a carboxyl group can be introduced into the obtained polyurethane, so that the dispersion stability is improved when used as an aqueous dispersion, and the dispersion stability is improved. When it is used for imparting reactivity to polyurethane, especially for cosmetics, it can improve miscibility with polar components and improve adhesion to hair and skin.

The amount of the dimethylol alkanoic acid used depends on the acid value of the obtained polyurethane or the performance (dispersability in water, etc.) required for the urethane- (meth) acrylic composite resin (U / A resin) finally produced. It may be adjusted as appropriate. Specifically, it is the same as the content ratio of the constituent unit derived from the dicarboxylic acid composed of dimethylolalkanoic acid in the component (A) described in the column of the polyether polyol.

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

When this polyester polyol is used, the content ratio of polyurethane using the polyester polyol in the urethane component (component (A)) contained in the U / A resin described later is 50% by weight or more, preferably 70% by weight or more, more. It is preferably 85% by weight or more, and it is most preferable that the total amount is the polyurethane.
The urethane component other than the polyurethane having the polyurethane (component (A)) using the polyester polyol is not particularly limited as long as the object and effect of the present invention are not impaired.
Further, the U / A resin obtained by using polyurethane using a polyester polyol has a property of having good oil resistance by having a polyester polyol.

(When using multiple types of polyol units)
As the polyol component (polyether polyol or polyester polyol) constituting the polyol unit, one kind of polyol unit may be used, but the polyol component having different number average molecular weights and / or the polyol component having different constituent units thereof. At least two kinds of polyol components may be used. When two or more of these polyol units are used, it can be expected that the mechanical strength (elongation, breaking strength) of the polymer will be increased while maintaining a flexible texture.

The average number average molecular weight of the polydisperse-based polyol unit 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.), Claret polyol P-1030 (manufactured by Claret Co., Ltd.) and the like.

When a unit derived from a plurality of types of polyols is used, the difference between 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. 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 components constituting the polyurethane as a whole may be lost and the synthetic reaction may become unstable.

(2) Polyvalent Isocyanate Compound The polyisocyanate compound means an organic compound having at least two isocyanate groups in one molecule, and a polyvalent isocyanate compound such as an aliphatic, alicyclic or aromatic compound may be used. can. 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.

1-2. (A) Production of components (urethane formation reaction)
The urethane production reaction for producing the component (A) 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 methylethylketone, 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, the component (B') described later, which is not reactive with the isocyanate group, that is, does not contain an active hydrogen group, may be present in the production of the component (A). In this case, the reaction system is diluted by this (B') component, and the reaction can be carried out more uniformly. The reaction for obtaining the component (A) is usually about 50 to 100 ° C. for about 0.5 to 20 hours. This makes it possible to obtain a polyurethane (component (A)) having a carboxyl group and an isocyanate group at the terminal.

As the catalyst used for producing the component (A), 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 (A) is preferably −60 ° C. or higher and 250 ° C. or lower. The glass transition temperature (Tg) can be measured by the method of JIS K 7244-4.

1-3. (A) Physical characteristics of components (weight average molecular weight)
The weight average molecular weight of the polyurethane (component (A)) 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 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.

(Acid value)
The obtained polyurethane preferably contains an acid component. For example, when a polyether polyol is used as a polyol component, a carboxyl group is contained by a method using a carboxyl group-containing polyvalent hydroxy compound or the like. When a polyester polyol is used as the polyol component, an acid component derived from a polyester polyol, dimethylolalkanoic acid, or the like is contained, and the acid value of this polyurethane is preferably 15 mgKOH / g or more, and 25 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 55 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. In addition, it may be difficult to adhere to the hair when used as a hair styling product.

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 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

(Neutralization)
It is preferable that at least a part of the carboxyl group contained in the component (A) is neutralized with one or more basic compounds. Thereby, the dispersibility of the component (A) in the aqueous medium can be improved. Examples of this basic compound include ammonia, 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.
Among them, the neutralization step is divided into two steps, the first neutralization step is performed after the production of the polyurethane, and the second neutralization step is performed after the polyurethane neutralized in the first step is dispersed in the aqueous medium. Is preferable.

As the organic amine compound, a tertiary amine compound such as trimethylamine, triethylamine, tributylamine and triethanolamine, a secondary amine compound such as aminomethylpropanol and the like are 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 possessed by the polyurethane (as a total amount used when used in a plurality of steps). 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 polyurethane 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.

2. 2. (Meta) Acrylic resin ((B) component)
2-1. Monomer constituting component (B) As an example of the (meth) acrylic acid ester monomer (component (B') which is the raw material of the component (B) in the U / A resin of the present invention, (meth). ) Acrylic acid alkyl ester 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 (B') components may be used, or a plurality of kinds may be used in combination.

This (B') component contains, if necessary, a monomer other than the (meth) acrylic monomer, for example, a single amount of an ester group-containing vinyl, as long as the object and effect of the present invention are not impaired. A body, a styrene derivative, a vinyl ether-based monomer, or 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.

2-2. (B) Glass transition temperature (Tg) of the component
(1) When composited with a polyether polyol-based polyurethane When composited with a polyurethane obtained using a polyether polyol, the glass transition temperature (Tg) of the homopolymer or copolymer composed of the component (B') is determined. It 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.

This glass transition temperature (Tg) can be measured by JIS K 7244-4 described in the section of the component (A), and can also 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 plurality of (meth) acrylic acid ester monomers are used in combination as the (B') component, 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 preferable that it is a mixture containing. As described above, by using a monomer having a different Tg of the homopolymer as the component (B'), 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.

(2) When composited with polyester polyol-based polyurethane When composited with polyurethane obtained by using polyester polyol, the glass transition temperature (Tg) of the homopolymer or copolymer containing the above component (B') as a main component. Is preferably −50 ° C. or higher, and 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.
The preferable upper limit of the glass transition temperature (Tg) and the measuring method thereof are the same as in (1) above.

(3) Combination of a plurality of (B') components In the present invention, the (meth) acrylic resin of the (B) component may be produced from a plurality of types of (meth) acrylic monomers. In that case, the flexibility of the film can be adjusted by using the monomer having a high Tg of the homopolymer and the monomer having a low Tg of the homopolymer in combination.

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.

3. 3. Urethane- (meth) acrylic composite resin (U / A resin)
(1) Production of U / A Resin The U / A resin according to the present invention is usually produced as an aqueous dispersion in an aqueous medium. Specifically, as described above, a mixed solution in which the component (A) and the component (B') are mixed is prepared, then this is emulsified and dispersed in an aqueous medium, and the component (B') in the emulsion is emulsified and dispersed. By polymerizing, an aqueous dispersion (emulsion) of U / A resin can be obtained.
Further, in the process, a chain extension reaction of the component (A) is carried out, if necessary.

In the method for obtaining a mixed solution containing the component (A) and the component (B'), the component (A) and the component (B') obtained by neutralizing at least a part of the carboxyl groups to make them water-dispersible are used. Any method may be used as long as it can be uniformly dispersed in the aqueous medium, and the timing of adding the component (B') is not particularly limited.

For example, a method of adding the component (B') before neutralizing at least a part of the carboxyl group in the component (A), or a method of adding the component (B') after neutralization can be mentioned. Further, a part or all of the component (B') is mixed with the polyol unit or the polyhydric isocyanate compound which is the raw material of the component (A), and in the presence of the component (B'), the polyol unit, many. The component (A) may be produced by reacting a valent isocyanate compound, a carboxyl group-containing polyvalent hydroxy compound, or the like. At this time, even when the remaining amount of the component (B') is added after the production of the component (A), the addition time may be any time before, simultaneously or after neutralizing the carboxyl group in the component (A). It doesn't matter.

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 (B') to obtain the component (A) is the method of obtaining the component (A) with the component (A). ') 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.

(Mixing ratio of (A) component and (B') component)
As described later, the ratio of the component (A) to the component (B) in the U / A resin is preferably (A) / (B) = 80/20 to 30/70 and 70/30 to 70 in terms of net weight ratio. 35/65 is preferable. Since almost 100% of the component (B') is a polymer, it is preferable that the mixing ratio of the component (A) and the component (B') at the time of charging is the same as described above. If the component (A) 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.

(Concentration of the mixed solution of the component (A) and the component (B'))
The concentration of the mixture of the component (A) and the component (B') 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 that the amount is 25% by weight or more, and more preferably 25% 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.

(First neutralization step)
When the carboxyl group in the component (A) is not neutralized at all, the basic compound is added to the mixed solution of the component (A) and the component (B'), and the carboxyl contained in the component (A) is added. It is preferable to neutralize at least a part of the group to obtain a neutralized product of the component (A) (hereinafter, this step is referred to as "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 (A).

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.

(Emulsification process)
Next, a mixed solution of the neutralized product of the component (A) and the component (B') 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 (A) and the component (B'), 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 the liquid 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 (A) may be denatured.

(Polymerization process)
In the emulsified dispersion obtained as described above, the component (B') is polymerized to obtain an aqueous emulsion of a urethane- (meth) acrylic composite resin (hereinafter, this step is referred to as a "polymerization step"). The polymerization reaction of the component (B') can be carried out by a general polymerization method according to the component (B') to be used, for example, by adding a radical polymerization initiator 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. And other organic peroxide-based initiators 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 sulfite-based initiator 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 (B').

The polymerization of the component (B') 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.

(Deodorizing process)
Normally, an unreacted (B') component 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, its concentration. Is preferably 100 ppm or less, preferably 70 ppm or less, and the closer the concentration is to 0, the more preferable.

Examples of the method for reducing the concentration of the component (B') include a method of heating an aqueous emulsion to volatilize the remaining component (B'), a method of circulating a gas such as air through the gas phase portion of the emulsion, and a method of circulating a gas such as air through the gas phase portion of the emulsion. Examples thereof include a method of blowing water vapor into the emulsion and a method of distilling off the component (B') 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 (B') component 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 removal of the component (B'). Since it is not preferable to release the exhaust gas containing the component (B') 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 (B') component is 100 ppm or less is used as a raw material having almost no odor for cosmetics such as hair styling products. Can be done. Further, when the urethane- (meth) acrylic composite resin aqueous dispersion according to the present invention is used, the hair styling product has good heat reversion (including settability) and a good feel such as slippage of hair. ..

(Chain extension reaction of component (A))
By the way, at any one of the above-mentioned emulsification step and the polymerization step and between the above-mentioned polymerization step and the deodorizing step, if necessary, a neutralized product of the component (A) and the component (A) is contained. . Hereinafter, the same applies), at least a part of the chain may be extended. Further, a part of the component (A) 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 component (A) may be chain-extended. Thereby, the molecular weight of the component (A) can be adjusted to a preferable range.

Since the chain extension reaction of the component (A) gradually occurs in the emulsion and also in water as a dispersion medium, a part of the chain extension reaction may occur 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. The chain extension reaction may be carried out before or after the polymerization of the (meth) acrylic monomer.

Examples of the chain extender other than water include compounds having a plurality of active hydrogens capable of reacting with isocyanate groups. 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.

(Second neutralization step)
Further, at least a part of the carboxyl group in the component (A) 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 (A). If 1 equivalent or more of the basic compound is already used in the first neutralization step, this second neutralization step may be omitted.

(Basic compounds and solvents in each neutralization step)
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. 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.

(Mixing of fluorine compound)
It is essential that the fluorine compound is contained as at least a part of the constituent units of the component (A) and / or the component (B) as described above. Specifically, when a compound containing fluorine is used as a polyol component or a polyvalent isocyanate component constituting the component (A), or fluorine is used as the component (B') which is a monomer constituting the component (B). When the contained compound is used, a substance that does not chemically react with either the component (A) or the component (B'), that is, a compound containing fluorine as an additive component is used in combination with the component (A) or the component (B'). Examples thereof include the case where the component (A) and the component (B) are used as a constituent unit.

When a fluorine compound is used as the component (B'), an alkyl fluoride (meth) acrylic acid ester can be preferably used as the fluorine compound. Examples of this fluorinated alkyl (meth) acrylic acid ester include (meth) acrylic acid 2,2,2-trifluoroethyl, (meth) acrylic acid 2,2,3,3,3-pentafluoropropyl, ( 2- (Perfluorobutyl) ethyl (meth) acrylate 2- (perfluorohexyl) ethyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-per (meth) acrylate Fluorohexyl-2-hydroxypropyl, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylic acid, 1H, 1H, 3H-tetrafluoropropyl, (meth) acrylic acid, 1H (meth) acrylic acid , 1H, 5H-Octafluoropentyl, (meth) acrylic acid 1H, 1H, 7H-dodecafluoroheptyl, (meth) acrylic acid 1H-1- (trifluoromethyl) trifluoroethyl, (meth) acrylic acid 1H, 1H3H -Hexafluorobutyl, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl acrylate, 2- (perfluorohexyl) ethyl vinyl ether and the like can be mentioned.

The content of the structural unit composed of this fluorine compound in the component (B) is preferably 0.1% by weight or more, preferably 0.4% by weight or more. If it is less than 0.1% by weight, the effect of the fluorine compound such as oil resistance may not be sufficiently exhibited. The upper limit of the content is preferably 50% by weight, preferably 30% by weight. If it is more than 50% by weight, the original softness and setting force of the resin may be impaired.

Among the compounds containing fluorine as an additive component, examples of this fluorine compound include polyperfluoromethylisopropyl ether, polyperfluoroethoxymethoxydifluorohydroxyethyl, polyperfluoroethoxymethoxydifluoroethyl PEG phosphate, and polyperfluoro. Ethoxymethoxydifluoromethyl distea aramid, Na perfluorohexylethylphosphonate, perfluorooctyltriethoxysilane, perfluoropolymethylisopropyl, perfluorohexylethyldimethylbutyl ether, perfluoromethylcyclopentane, 2- (perfluorobutyl) ethanol , 2- (Perfluorohexyl) ethanol, 3- (perfluorohexyl) propane-1,2-diol and the like.

As an example of commercially available products, FOMBLIN HC-04, HC / 25, HC-R, FOMBLIN HC / OH-1000, FOMBLIN HC / P2-1000, FOMBLIN HC provided by Nikko Chemicals Co., Ltd. / SA-18, etc., CHEMINOX FA-4, CHEMINOX provided by Unimatec Co., Ltd.
FA-6, CHEMINOX FADO-6 and the like can be mentioned.

The fluorine compound that does not react with any of the components (A) and (B') is the component (B) at the initial stage of the reaction of the component (A), after the reaction of the component (A), before the addition or reaction of the component (B), and the component (B). The time after the reaction is considered. Among these, the initial reaction of the component (A) or the addition of the component (B) after the reaction of the component (A) or before the reaction is preferable. Further, the temperature at the time of addition is preferably 60 ° C. or lower from the viewpoint of safety.

When a fluorine compound is used as the additive component, the amount of the fluorine compound used as the additive component is preferably 30% by weight or less, preferably 20% by weight or less, based on the urethane- (meth) acrylic composite resin. If it is more than 30% by weight, the original softness and setting force of the resin may be impaired. Further, it is not necessary to use this fluorine compound that does not chemically react, and the lower limit of the content is 0% by weight.

(2) Physical characteristics of U / A resin (various average molecular weights of U / A resin)
The weight average molecular weight (Mw) of the U / A resin in the urethane- (meth) acrylic composite resin aqueous dispersion (U / A resin aqueous dispersion) obtained by the present invention 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 such a 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 U / A resin in the U / A resin aqueous dispersion is preferably 10 or more, more preferably 20 or more. .. 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.

Further, the most frequent molecular weight among the weight average molecular weights (Mw) of the polyurethane component ((A) component) contained in this U / A resin, that is, the U / A resin is gel permeation chromatograph method (GPC method). In the chart (chromatogram) obtained when Mw is measured by the above, the molecular weight at the peak position corresponding to the polymer of the polyurethane component (hereinafter, the molecular weight of the polymer of the polyurethane component is the most frequent of the polymer of the polyurethane component. The molecular weight (Mwp) is referred to as "Mwp of the urethane component"), preferably 10,000 or more, and more preferably 20,000 or more. If the Mwp of the polyurethane component is less than 10000, the long-term stability of the U / A resin is insufficient, and there is a concern that deterioration will be accelerated in an environment of, for example, above 30 ° C. in summer. On the other hand, the upper limit of Mwp of the polyurethane component is preferably 200,000, more preferably 100,000. If the Mwp of the polyurethane component is larger than 200,000, it may become hard and impair the texture, or the viscosity of the system may increase too much in the synthesis process to deteriorate the productivity.

Further, the mode molecular weight (Mwp) (hereinafter, may be referred to as "Mwp of the acrylic component") of the polymer of the acrylic component contained in this U / A resin is preferably 200,000 or more, more preferably 250,000 or more. .. If the Mwp of the acrylic component is less than 200,000, the 1,3BG resistance and the pigment dispersibility may deteriorate. On the other hand, the upper limit of Mwp of the acrylic component is preferably 20000000, more preferably 1500000. If the Mwp of the acrylic component is larger than 2000000, the texture may deteriorate.

Further, the difference ((Mwp of acrylic component)-(Mwp of urethane component)) between the most frequent molecular weight (Mwp) of the acrylic component and the most frequent molecular weight (Mwp) of the urethane component contained in this U / A resin is 200,000. The above is preferable, and 250,000 or more is more preferable. If this difference is less than 200,000, there is a possibility that the softness at the time of applying hair and the following 1,3BG resistance cannot be achieved at the same time. On the other hand, the upper limit of this difference is preferably 2000000, more preferably 1000000. If this difference is larger than 2000000, there is a possibility that the softness at the time of applying the hair and the 1,3BG resistance cannot be achieved at the same time because the difference is too large.
In addition, "1,3BG resistance" means that the sample liquid does not change even if 1,3BG (1,3-butanediol) is added to the aqueous dispersion and mixed, and the compounding stability test is performed. It is a kind of. In particular, in cosmetic applications, C.I. R. In the test, it means that the result does not change with or without 1,3BG, that is, the measurement target resin is not affected by 1,3BG.

When the (meth) acrylic acid ester monomer as the component (B') is emulsion-polymerized in an aqueous medium, the polymerization initiator, emulsifier, etc. in the aqueous medium, other polymer produced, etc. may be used during the polymerization. The chain transfer reaction 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 (A) (polyurethane having an isocyanate group and a carboxyl group) and the component (B') ((meth) acrylic acid ester monomer) are emulsified and dispersed in an aqueous medium. A urethane- (meth) acrylic composite resin aqueous dispersion (U / A resin aqueous dispersion) obtained by polymerizing the component (B') using a pre-emulsion is produced. Radical polymerization will occur with the (B') component arranged inside the component. At this time, the component (B') is protected by the component (A), and not only the chain transfer reaction during the polymerization of the component (B') is unlikely to occur, but also the polymerization termination reaction is unlikely to occur. As a result, the molecular weight of the component (B') 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 (B') tends to be larger than that of emulsion polymerization in the absence of the component (A), and the molecular weight distribution of the obtained composite resin shows two peaks.

By the way, when the most frequent molecular weight (Mwp) of the urethane component and the most frequent molecular weight (Mwp) of the acrylic component contained in the U / A resin cannot be clearly discriminated, the urethane component and the acrylic component are individually separated under the corresponding conditions. Aqueous dispersions are obtained, and Mw is measured for each by gel permeation chromatography (GPC method), and the peak position is determined by the most frequent molecular weight (Mwp) of the urethane component or the most frequent molecular weight (Mwp) of the acrylic component. ) May be used. However, in this case, in particular, Mwp of the acrylic component ((B') component) does not have the above-mentioned effect of increasing the molecular weight, so that the value is usually lower than the actual value.

(Minimum film formation temperature (MFT))
The minimum film-forming temperature (MFT) of the U / A resin in the U / A resin aqueous dispersion obtained by the present invention is −20 ° C. when measured by a method based on JIS K 6828-2, as described later. The above is good, −10 ° C. or higher is preferable, and −5 ° C. or higher is more preferable. If it is lower than -20 ° 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 40 ° C, and even more preferably 30 ° C. If the temperature is higher than 60 ° C., the flexibility of the film tends to be insufficient, 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 methods (1) to (3) of the above 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 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 (A) is brought close to 1: 1.
(3) As the component (B'), a component having a low glass transition temperature (Tg) is used.

As the relatively high molecular weight diols in (1), diols having a (weight average) molecular weight of 1000 or more such as polyester diols and polyalkylene glycols obtained by polycondensing low molecular weight diols and dicarboxylic acids. I can exemplify the kind.

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.

(Water contact angle, hexadecane contact angle)
This U / A resin is confirmed to have a high contact angle due to the water contact angle and the hexadecane contact angle. The feature that it is possible to form a film that can confirm this high contact angle is that it is excellent in forming a film when used in cosmetics (cosmetic preparations) containing a large amount of oily components such as mascara, lipstick, lip balm, and hair wax. When used as a cosmetic, the film can improve the durability (holding) of make-up and give a firm feeling.
In addition, the effect that the function of the U / A resin is exhibited even in an environment of high temperature and high humidity such as in summer can be obtained.

In order to obtain the above effects, the water contact angle is preferably 50 ° or more, preferably 60 ° or more. Further, 180 ° or less is preferable. Similarly, the preferred hexadecane contact angle is preferably 5 ° or more, preferably 6 ° or more. Further, 180 ° or less is preferable.

(Gel content)
The gel content of the U / A 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 U / A resin in the above range.

(3) Main Applications of U / A Resin The U / A resin or U / A resin aqueous dispersion of the present invention can be suitably used for the following applications. Among them, the U / A resin or the U / A resin aqueous dispersion containing a phthalic acid-based unit, particularly an isophthalic acid unit, exhibits excellent oil resistance as described above and is composed of a self-emulsifying polyurethane. In addition, mechanical stability (emulsion stability) and pigment dispersibility are also excellent.

(3-1) Cosmetics The U / A resin or U / A resin aqueous dispersion of the present application can be suitably used as a resin for cosmetics such as for hair cosmetics and skin cosmetics. The usage thereof will be briefly described below.

[Hair cosmetics]
When used as a resin for hair cosmetics, the U / A resin or U / A resin aqueous dispersion according to the present application is added to hair cosmetics such as known shampoos, rinses, treatments, setting agents, and permanent wave liquids. do. At this time, it may be used in combination with a known polymer conventionally used. The hair cosmetic used may be in any shape such as liquid, cream, emulsion, spray, gel, mousse (cream / gel form that can be ejected in a foamy state).

The amount of the U / A resin or the U / A resin aqueous dispersion added varies depending on the form and purpose of the hair cosmetic, or the type and amount of the polymer used in combination, but the U / A for cosmetics is different from that of the hair cosmetic. The resin content of the aqueous resin dispersion is preferably added in a proportion of 0.05 to 10% by weight, more preferably 0.1 to 8% by weight.

In addition, the U / A resin or U / A resin aqueous dispersion can be used alone or in combination with a known anionic, nonionic, cationic and amphoteric set polymer. As the setting polymer to be used in combination, anionic and nonionic setting polymers are more preferable from the viewpoint of miscibility stability.

Examples of the anionic polymer used as the polymer for the set include a copolymer of (meth) acrylic acid and alkyl methacrylate (trade name: Diahold (manufactured by Mitsubishi Chemical Co., Ltd.), trade name: plus size L-. Examples thereof include 53 series (manufactured by Mutual Chemical Industry Co., Ltd.), maleic acid monoalkyl ester and methyl vinyl ether copolymer (trade name: GANTREZ AN-119 (manufactured by AISP Japan Co., Ltd.)).

Examples of the nonionic polymer used as the polymer for the set include polyvinylpyrrolidone polymer (trade name: PVP series (manufactured by AISP Japan Co., Ltd.)), vinylpyrrolidone and vinyl acetate copolymer (trade name: LUVISKOL VA series). (Manufactured by BASF Japan Ltd.)) and the like. Examples of the amphoteric polymer include a methacrylate ester copolymer (trade name: Yukaformer series (manufactured by Mitsubishi Chemical Corporation)) and the like.

Examples of the cationic polymer used as the set polymer include ethers of hydroxycellulose and glycidyltrimethylammonium chloride (trade name: Leoguard G (manufactured by Lion Co., Ltd.), trade names: Polymers JR-30M-125 and -400). (Manufactured by Union Carbide)), quaternized product of vinylpyrrolidone-dimethylaminoethyl methacrylate copolymer (trade name: GAFQUAT 734 and 755 (manufactured by ISP Japan Co., Ltd.)), dimethyldiallylammonium chloride polymer (trade name:). Examples thereof include MERQUAT 100 (manufactured by Lubrizol) and a dimethyldiallyl ammonium chloride acryloamid copolymer (trade name: MERQUAT550 (manufactured by Lubrizol)).

The cosmetics for sets in which the U / A resin or U / A resin aqueous dispersion and the polymer for setting are used include aerosol hair sprays, pump hair sprays, foam hair sprays, hair mists, set lotions, and hair creams. , Hair oils and the like, and various hair styling products containing water and / or alcohols such as ethanol and isopropanol.

When the hair styling product is a hair cosmetic (mouse) that can be ejected in a foamy state, for example, 0.01 to 10% by weight of the U / A resin or U / A resin aqueous dispersion (solid content). The composition of known setting polymers is 0 to 15% by weight, nonionic surfactant 0.1 to 5% by weight, liquefied gas 3 to 25% by weight, and water-based water-soluble solvent 60% by weight to residual. 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 the hair styling product is in the form of a gel, the U / A resin or U / A resin aqueous dispersion (solid content) is 0.01 to 10% by weight, the polymer for setting is 0 to 15% by weight, and the gel is used. Compositions such as base 0.1 to 3% by weight and water 72% by weight to residual residue are used.

In the case of a hair spray, the U / A resin or U / A resin aqueous dispersion (solid content) is 0.01 to 10% by weight, the polymer for setting is 0 to 15% by weight, the organic solvent is 30 to 80% by weight, and the spray is applied. A composition such as 10 to 70% by weight of the agent is used.

Examples of the propellant that can be used for the spray or mousse include liquefied gas such as ethanol, liquefied petroleum gas, dimethyl ether and halogenated hydrocarbon, and compressed gas such as air, carbon dioxide and nitrogen gas.

The U / A resin or U / A resin aqueous dispersion of the present invention can be used in conditioning cosmetics such as shampoos, conditioners (rinses), and permanent liquids. Such hair cosmetics often contain, for example, water and / or alcohols such as ethanol and isopropanol as a solvent, and hydrocarbons having a boiling point of 50 ° C. to 300 ° C. in addition to the alcohols. Such conditioning cosmetics, like the above-mentioned set cosmetics, are usually U / A resin or U / A resin aqueous dispersion alone, or with conventional anionic, nonionic, cationic and amphoteric conditioning polymers. It is also used. As the setting polymer to be used in combination, an anionic or nonionic setting polymer is more preferable from the viewpoint of miscibility stability.

When used for shampoo, the U / A resin or U / A resin aqueous dispersion can be added to an anionic, amphoteric or nonionic surfactant. Examples of the surfactant used here include N-coconoyl-N-methyl-β-alanine sodium, N-myristoyl-N-methyl-β-alanine sodium and the like as anionic surfactants. Examples thereof include fatty acid acyl-N-methyl-β-alanine salts.

Examples of the amphoteric surfactant include cocoasidepropyl betaine, dimethyl lauryl betaine, bis (2-hydroxyethyl) lauryl betaine, cyclohexyl lauryl amine oxide, dimethyl lauryl amine oxide, and bis (2-hydroxyethyl) lauryl amine oxide. It can be exemplified.

Examples of the nonionic surfactant include stearic acid diethanolamide, coconut oil fatty acid diethanolamide, sorbitan sesquioleate, polyoxyethylene stearyl ether and the like.

When used for rinsing, the U / A resin or U / A resin aqueous dispersion of the present application can be added to the cationic surfactant before use. Examples of such a cationic surfactant include stearyltrimethylammonium chloride, distearyldimethylammonium chloride, stearyldimethylbenzylammonium chloride and the like.

Further, when used as a permanent solution, a U / A resin or a U / A resin aqueous dispersion is added to an oxidizing agent such as bromic acid or perboronic acid, and a reducing agent such as thioglycolic acid and its salt or cysteine. And use it.

In addition to the above, for example, when used as a hair treatment, the present invention may be used in combination with or in place of a cationic surfactant and / or a cationic polymer such as a cationic polypeptide, a cationic cellulose, or a cationic polysiloxane. The U / A resin of the present invention or the aqueous dispersion of U / A resin can be used. As such a cationic surfactant, for example, those exemplified for rinsing can be used without any particular problem.

In any of the above-mentioned set cosmetics and conditioning cosmetics, in addition to the above-mentioned various ingredients, other optional ingredients may be blended, if necessary, as long as the effects of the present invention are not affected. .. Such optional components include hydrocarbons, linear alcohols, branched alcohols, higher fatty acids and their derivatives, plant-based polymers, microbial-based polymers, natural water-soluble polymers, cellulose-based polymers, and semi-synthetic. Water-soluble polymer, vinyl-based polymer, polyoxyethylene-based polymer, synthetic water-soluble polymer, inorganic water-soluble polymer, silicones, N-fatty acid acyl-L-glutamate, N-fatty acid-N-methyl Taurine salt, salt of N-fatty acid sarcosine condensate, surfactants other than the above-mentioned surfactants, emulsifiers, moisturizers, antibacterial agents, vasodilators, refreshing agents, stimulating agents, vitamins, bactericidal antiseptic Examples thereof include agents, chelating agents, pH adjusting agents, foaming agents, foaming agents, foam stabilizers and the like. Further, when these cosmetics are products 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, a metal ion scavenger, an antifungal agent, a bactericide, etc. Emulsifying agents, conditioning agents, thickening agents, antioxidants, solubilizers, rosins, hydrotropes, hair restorers, crude agents, pigments, fragrances and the like may be used.

Examples of hydrocarbons include liquid paraffin, petrolatum, solid paraffin, 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, octyldodecanol and the like.

Higher fatty acids and their derivatives include lauric acid, myristic acid, palmitic acid, stearic acid, behen (behenyl) acid, oleic acid, 1,2-hydroxystearic acid, undecylenic acid, tollic acid, lanolin fatty acid, isostearic acid, etc. Examples thereof include linoleic acid, linoleic acid, γ-linolenic acid, and eicosapentaenoic acid.

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 and the like, and examples of the N-fatty acid acyl-L-glutamate include N-lauryl-L-monosodium glutamate and N. -Palm oil fatty acid-L-monotriethanolamine glutamate, acyl N-myristylate-L-monosodium glutamate, N-mixed fatty acid acyl-L-monosodium glutamate and the like can be mentioned.

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 include sodium acylsarcosine, acylglutamate, sodium acyl-β-alanine, acyltaurate, lauryl sulfate, betaine lauryldimethylaminoacetate, alkyltrimethylammonium chloride, polyoxyethylene hydrogenated castor oil and the like. Can be mentioned.

Examples of the emulsifier include glyceryl monostearate, sorbitan monopalmitate, polyoxyethylene cetyl ether, polyoxyethylene sorbitan monolaurate and the like.

Moisturizers include (poly) ethylene glycol, (poly) propylene glycol, glycerin, 1,3-butylene glycol, maltitol, sorbitol, chondroitin sulfate, hyaluronic acid, atelocollagen, cholesteryl-1,2-hydroxystearate, lactic acid. Examples thereof include sodium, 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 and the like. Examples of the chelating agent include protein hydrolysates, amino acids, plant extracts, EDTA-Na and the like. Examples of the pH adjuster include succinic acid, sodium succinate, triethanolamine and the like.

Next, skin cosmetics and makeup cosmetics, which are other uses of the U / A resin or the U / A resin aqueous dispersion according to the present application, will be described.
[Skin cosmetics]
When used as a resin for skin cosmetics, the U / A resin or U / A resin aqueous dispersion according to the present application is additionally used in skin cosmetics such as skin cream, lotion, and milky lotion.

[Makeup cosmetics]
Examples of make-up cosmetics include eye make-up cosmetics such as mascara, eye liner, and eye shadow, lipstick, lip gloss, foundation, make-up apple rouge, and the like, and these make-up cosmetics are the present invention. U / A resin or U / A resin aqueous dispersion, usually used for oils such as solid oils, fats and oils, waxes, silicone oils, powder components such as pigments, and cosmetics such as solvents such as liquid alcohols. It is obtained by adding and mixing the materials to be used according to the intended use and purpose.

When a U / A resin or a U / A resin aqueous dispersion using polyurethane using a polyether polyol is used, the following can be exemplified as the powder component of the pigment or the like.
(A) Dyes such as Red 104, Red 102, Red 226, Red 201, Red 202, Yellow 4, Black 401, etc.
(B) Lake dyes such as Blue No. 1 Aluminum Lake, Yellow No. 4 Aluminum Lake, Yellow No. 5 Aluminum Lake, Yellow No. 203 Barium Lake, etc.

(C) Nylon powder, silk powder, urethane powder, Teflon (registered trademark) powder, silicone powder, polymethyl methacrylate powder, cellulose powder, silicone elastomer spherical powder, powdery polymer such as polyethylene powder,
(D) Colored pigments such as yellow iron oxide, red iron oxide, black iron oxide, chromium oxide, carbon black, ultramarine, and dark blue.

(E) White pigments such as zinc oxide, titanium oxide and cerium oxide, extender pigments such as talc, mica, serisite, kaolin and barium plate sulfate,
(F) Pearl pigments such as mica titanium, red iron oxide-coated mica titanium, carmine-coated mica titanium, navy blue-coated mica titanium, and black iron oxide-coated mica titanium.

(G) Metal salts such as barium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate, magnesium silicate, etc.
(H) Inorganic powders such as silica and alumina,
(I) Bentonite, smectite, boron nitride, lauroyl lysine, fine particle titanium oxide, fine particle zinc oxide and the like.

The size of these powders is preferably in the range of 5 nm to 100 μm, more preferably 10 nm to 50 μm. Further, the shape (spherical shape, rod shape, needle shape, plate shape, indefinite shape, fluffy shape, spindle shape, etc.) is not particularly limited.

The various powders exemplified above may be individually blended or may be blended after being premixed as a mixture of powder blending agents.

Further, a mixture whose color is adjusted to a desired color such as skin color may be used, and further, an ultraviolet scattering component such as fine particle titanium oxide or fine particle zinc oxide is added to impart an ultraviolet protection function to the formulation. You can also do it.

Examples of the oil component such as the solid oil include volatile or non-volatile oils, solvents, and resins usually used in cosmetics, and may be liquid, paste, or solid at room temperature.

Examples of the oil component that can be used in the present invention include, for example, the following.
(A) Fatty acids such as isostearic acid, undecylenic acid, and oleic acid,
(B) Fatty acid esters such as myristyl myristate, hexyl laurate, decyl oleate, isopropyl myristate, hexyl decyl dimethyl octanate, glycerin monostearate, diethyl phthalate, ethylene glycol monostearate, octyl oxystearate,

(C) Higher hydrocarbons such as liquid paraffin, paraffin, petrolatum, squalane, so-called waxes such as lanolin, reduced lanolin, carnauba wax, candelilla wax, selecin, ozokelite, microcrystallin wax, minced oil, coconut oil, palm oil, etc. Oils and fats such as palm kernel oil, camellia oil, sesame oil, paraffin oil, and olive oil,
(D) Medium to low molecular weight synthetic polymers such as polyethylene wax, ethylene / α-olefin / co-oligomer, ethylene propylene, copolymer, etc.

(E) Cyclic silicone, dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, polyether-modified organopolysiloxane, alkyl-modified organopolysiloxane, terminal-modified organopolysiloxane, polyglyceryl-modified silicone, amodimethicone, amino-modified organopoly Silicone oils and silicone compounds such as siloxane, silicone gel, acrylic silicone, trimethylsiloxysilicic acid,
(F) Fluorine compounds such as perfluoropolyether, fluorocarbon and fluoroalcohol.

Examples of the solvent such as the liquid alcohol include the following.
(A) Lower alcohol: ethanol, isopropyl alcohol, etc.
(B) Higher alcohols: cetyl alcohol, isostearyl alcohol, lauryl alcohol, hexadecyl alcohol, octyldodecanol, etc.

(C) Polyhydric alcohol: Polyhydric alcohol such as glycerin, sorbitol, ethylene glycol, propylene glycol, 1.3 butylene glycol, polyethylene glycol, etc.
(D) Other solvents: water, light liquid isoparaffin, ethers, LPG, fluorocarbon, N-methylpyrrolidone, fluoroalcohol, volatile linear silicone, various chlorofluorocarbons and the like.

In addition to the above-mentioned components, the cosmetic of the present invention includes fluorine compounds, various resins, surfactants, viscosity-imparting agents, preservatives, fragrances, and ultraviolet absorbers (organic) that are usually used in cosmetics. Ingredients such as UV-A and B), physiologically active ingredients, salts, antioxidants, chelating agents, neutralizing agents, pH adjusters, etc. As long as the purpose and effect of the invention are not impaired, they can be appropriately blended.

When using a U / A resin or a U / A resin aqueous dispersion using polyurethane using a polyether polyol, a hair spray, mousse, set lotion, gel, or spray having a good setting effect and texture. Etc., various hair cosmetics can be provided.

On the other hand, when a U / A resin or a U / A resin aqueous dispersion using polyurethane using a polyester polyol is used, these U / A resins can also be used as skin lotions because the obtained film is flexible. It can be preferably used and can also be used, for example, in liquid foundations, skin creams, UV care creams, skin lotions and the like.

Further, since it has excellent oil resistance, it exhibits good film forming ability even in cosmetics containing a large amount of oily components, and is therefore suitable for applications such as mascara and eyeliner.

The U / A resin of the present invention can also be used for cosmetics other than the above, such as nail color. In that case, a fluorine compound for cosmetics and various resins are used according to their respective purposes and uses. , Surface active agents, viscosity-imparting agents, preservatives, fragrances, organic / inorganic UV absorbers, physiologically active ingredients, salts, antioxidants, chelating agents, neutralizers, pH adjusters, etc. As long as the purpose and effect of the invention are not impaired, they can be appropriately blended.

(3-2) Other Applications The U / A resin or U / A resin aqueous dispersion of the present invention utilizes its features such as oil resistance, flexibility, adhesion, substrate followability, and abrasion resistance. It can be used for industrial paints (particularly automobile paints), paints for household paints, coating agents, protective film forming agents, and 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.

1. 1. Raw materials First, the raw materials used will be described.

<Polyol>
-D1000 ... Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: Product name Highflex D1000, polypropylene glycol (C3 polyol), number average molecular weight (Mn) = 1000, OHV = 111
-D2000 ... Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: Product name Highflex D2000, Polypropylene glycol (C3 polyol) number average molecular weight (Mn) = 2000, OHV = 55.8
N4073: Made by Nippon Polyurethane Industry Co., Ltd .: Trade name: Nippon Polyurethane Industry Co., Ltd .: Polyester polyol (1,6HD-AA) containing 1,6-hexanediol and adipic acid, number average molecular weight (Mn) = 2000, OHV = 56. 5
-P2012 ... Made by Kuraray Co., Ltd .: Brand name Kuraray polyol P-2012, mixed polyester polyol (MPD-AA-IP) of methylpentanediol and adipic acid / isophthalic acid (molar ratio of adipic acid / isophthalic acid = 1/1) ), Number average molecular weight (Mn) = 2000, OHV = 55.8
-P1030 ... Made by Kuraray Co., Ltd .: Brand name Kuraray polyol P-1030, polyester polyol (MPD-IP) of methylpentanediol and isophthalic acid, number average molecular weight (Mn) = 1000, OHV = 111.3
In the above, "OHV" means a hydroxyl value (OH Value), and the unit is "mgKOH / g".

<Multivalent isocyanate compound>
・ IPDI… Made by Degussa Japan Co., Ltd .: Product name VESTANAT IPDI (isophorone diisocyanate)

<Carboxyl group-containing multivalent hydroxy compound>
-Bis-MPA ... Manufactured by Pascal Co., Ltd .: Dimethylolpropionic acid (carboxylic acid-containing diol)
・ DMBA… Huzhou Changsheng Chemical Co., Ltd .: 2,2-bis (hydroxymethyl) butanoic acid <polymerization inhibitor>
・ MEHQ: Wako Pure Chemical Industries, Ltd .: 2-Methoxyhydroquinone

<Polymerizable monomer>
・ MMA: manufactured by Mitsubishi Rayon Co., Ltd., methyl methacrylate ・ BA: manufactured by Mitsubishi Chemical Co., Ltd., n-butyl acrylate <fluorine compound>
Fluorine compound 1 ... Perfluorohexyl ethyl methacrylate, manufactured by Daikin Industries, Ltd .: C6SFMA monomer, in the theoretical calculation of Tg, the Tg of the homopolymer thereof was set to 30 ° C.
-Fluorine compound 2: Polyperfluoroethoxymethoxydifluoromethyldistearamid, manufactured by Nikko Chemicals Co., Ltd .: FOMBLIN HC / SA-18

<Radical polymerization initiator>
tBPO ... Chemical agent Axo Co., Ltd .: Di-tert-butyl peroxide <Reducing agent>
AsA ... Wako Pure Chemical Industries, Ltd .: L-ascorbic acid (special grade reagent)
<Basic compound>
・ KOH: Potassium hydroxide ... Wako Pure Chemical Industries, Ltd. (reagent)

2. 2. Test method Each test method will be described below.
<Number average molecular weight of polyol>
The number average molecular weight was calculated from the hydroxyl value (OHV: unit mgKOH / g) according to the following formula.
Polyol Mn = potassium hydroxide formula amount (56.1) / raw material OHV × 2 × 1000
The hydroxyl value (OHV) was measured by JIS K 1557-1.

<Content ratio in which the number average molecular weight (Mn) in the polyol component is in the range of 1000 ± 200 (hereinafter referred to as "Mn1000 ratio")>
The Mn1000 ratio can be calculated according to the following formula.
Mn1000 ratio (%) = Mn1000 charge amount / charge amount of all polyol components × 100
Here, the "Mn1000 charging amount" is the charging amount of the polyol component having a number average molecular weight (Mn) in the range of 1000 ± 200.

<Acid value measurement method and calculation method>
It was measured according to the potentiometric titration method (JIS K 0070) using potassium hydroxide. At this time, the "polyurethane amount" was 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 JIS method difficult. In such a case, the "theoretical acid value" per 1 g of polyurethane was 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 formula amount) / polyurethane amount (g) x 1000

<MFT measurement method and calculation method>
With reference to JIS K 6828-2, after the aqueous dispersion was dried, the lowest temperature at which a uniform film without cracks was formed was measured as the film forming temperature (MFT).
Specifically, using a thermal gradient tester manufactured by Nichiri Shoji Co., Ltd .: the obtained aqueous dispersion is applied using an applicator so as to have a thickness of 0.2 to 0.3 mm. After the moisture was dried, the temperature corresponding to the boundary line between the continuous film and the discontinuous film was defined as MFT.

<Neutralization degree>
The degree of neutralization of the obtained polyurethane or urethane-acrylic resin contains carboxyl based on the component (A) used for the preparation, as shown in the description of the first neutralization step and the second neutralization step of the present specification. It was calculated from the number of moles and the number of equivalents of the neutralizing agent (KOH, etc.) used for neutralization.
It is also possible to experimentally obtain the content of the acid component by neutralization titration, which is usually used, and the amount of the component (A) charged.

<Glass transition temperature (Tg)>
[(A) component]
Measured according to JIS K 7244-4.
[(B') component]
According to the following formula (1) (FOX formula), the Tg of the polymer was calculated from the Tg and the weight fraction of each homopolymer of the polymerizable monomer used.
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.
As described above, when it is desired to express Tg in "° C", "273" may be subtracted from the value of Tg obtained by the above formula.
As another measurement method, measurement can be performed according to JIS K 7121.

<Physical characteristics of the film>
[Stress-Strain (SS)]
・ SS of resin alone
(1) Preparation of test piece A sample (aqueous dispersion) is applied on a polypropylene plate so that the thickness of the dry film is 200 μm, and the sample (aqueous dispersion) is left at room temperature overnight to form a film. The obtained film is peeled off and dried in a vacuum dryer for 6 hours.
(2) Evaluation method The dry film obtained above was cut into strips with a width of 0.5 cm and used with an Autocom C-type universal testing machine (manufactured by KSE Co., Ltd.) at a constant temperature of 23 ° C and 50% RH. In a wet chamber, 100% modulus, maximum strength, and maximum elongation were measured under the conditions of a chuck interval of 2 cm and a tensile speed of 200 mm / min.

・ SS when a plasticizer (glycerin) is added
(1) Preparation of test piece The above-mentioned "resin alone" except that the sample (aqueous dispersion) before application is mixed with 10% glycerin with respect to the resin and the obtained film is not vacuum-dried. It was created in the same manner as (1) of "SS".
(2) Evaluation method Evaluation was carried out in the same manner as in (2) of the above-mentioned "SS of resin alone".

<Coating film contact angle>
Using an applicator, the obtained resin was applied to a thickness of 100 μm and dried at room temperature for 24 hours to prepare a test piece.
With reference to JIS R 3257, 2 μL of water or hexadecane was added dropwise, and the measurement was performed by the θ / 2 method with a waiting time of 1 second.
The measurement was carried out using Drop Master DM-500 (manufactured by Kyowa Surface Chemistry Co., Ltd.).

<Applied physical properties>
[C. R. : Curl retention]
・ C.I. under high temperature and high humidity. R.
The sample is applied to the hair sample, dried in a curled state, and the morphological retention state is observed after 3 hours have passed under the following predetermined temperature and humidity conditions.
As a sample solution, the obtained aqueous solution was diluted with water so as to have a solid content of 5% by weight, and this was applied to a hair bundle having a length of 23 cm and a weight of 2 g so as to have a coating amount of 0.7 g. This hair bundle was wrapped around a cold rod having a diameter of 1 cm, dried at 50 ° C. × 2 hours, and the obtained curled hair bundle was removed from the rod and suspended in an environment of 30 ° C. × 90% RH after 3 hours. The length of the curl hair bundle was measured, and the curl retention rate was calculated from the following formula.
Curl retention rate (%) = (23- "length after 3 hours") x 100 / (23- "initial length")
However, the "length" means the length of the hair bundle in the curled state.

・ C. after soaking in water. R.
A curl hair bundle was prepared in the same manner as in the above-mentioned "CR under high temperature and high humidity", removed from the rod, and then immersed in water for 8 seconds. After pulling it out of the water and lightly wiping off excess water on the surface of the curl hair bundle, it was hung at room temperature. Immediately after and 30 minutes later, the length of the curl hair bundle was measured, and the curl retention rate was calculated.

[Water absorption, quick-drying]
The sample solution was applied to the hair sample, dried in a curled state, then immersed in water, and the water absorption and quick-drying property were evaluated from the weight immediately after pulling up and 15 minutes later, respectively.
A curl hair bundle was prepared in the same manner as in the above-mentioned "CR under high temperature and high humidity", removed from the rod, and then immersed in water for 3 seconds. Immediately after pulling it out of the water, excess water on the surface of the curl hair bundle was lightly wiped off and the weight was measured. The weight change rate was calculated from the following formula to evaluate the water absorption.
Weight change rate (%) = {(weight immediately after withdrawal from water)-(initial weight)} x 100 / initial weight Then, after leaving at room temperature for 15 minutes, the weight of the curl hair bundle was measured. The water retention rate was calculated from the following formula, and the quick-drying property was evaluated.
Moisture retention rate (%) = {(weight 15 minutes after pulling up from water)-(initial weight)} x 100 / initial weight

[Curl elasticity]
The sample solution was applied to the hair sample, dried in a curled state, and the elasticity of the curl was confirmed by finger touch.
As the sample solution, the obtained aqueous dispersion was diluted with water so that the solid content content was 1% by weight, and this was applied to a hair bundle having a length of 23 cm and a weight of 2 g so as to have a coating amount of 0.7 g.
This hair bundle was wrapped around a cold rod having a diameter of 1 cm, dried at 50 ° C. for 2 hours, and the obtained curled hair bundle was removed from the rod to prepare a hair sample. This hair sample was checked by touch to see if there was a difference in feel, and evaluated according to the following criteria.
○: Elasticity is felt.
Δ: Some elasticity is felt.
×: No elasticity is felt.

[Slip feeling]
The sample solution was applied to the hair sample, dried in a curled state, and the slipperiness (smoothness) of the surface was evaluated by touch.
The hair bundle prepared in the same manner as in the above "curl elasticity" was wound around a cold rod having a diameter of 1 cm, dried at 50 ° C. for 30 minutes, and the obtained curled hair bundle was removed from the rod to prepare a hair sample.
○: It feels smooth and flexible.
Δ: A little smoothness is felt.
×: There is a squeaky feeling.

[soft]
The sample solution was applied to the hair sample, dried in a curled state, and the softness of the hair bundle was evaluated by touch.
The hair bundle prepared in the same manner as in the above "curl elasticity" was wound around a cold rod having a diameter of 1 cm, dried at 50 ° C. for 30 minutes, and the obtained curled hair bundle was removed from the rod to prepare a hair sample.
⊚: Especially soft and natural texture.
○: It feels soft.
Δ: There is a slightly hard feeling.

[Quick-drying (feeling to the touch)]
The hair sample sample solution was applied and dried in a curled state, and the dry state of the surface was evaluated by touch.
The hair bundle prepared in the same manner as the procedure in the above "curl elasticity" was wound around a cold rod having a diameter of 1 cm, dried at 50 ° C. for 20 minutes, and then the dry state when the hair bundle was removed from the rod was evaluated by finger touch.
◯: It is dry.
×: Insufficient drying and a damp feeling.

3. 3. Examples, Comparative Examples (Examples 1 to 15)
A predetermined amount of the urethane raw material, acrylic raw material, fluorine compound 1, fluorine compound 2 and polymerization inhibitor shown in the table are added to a four-necked flask equipped with a thermometer, a stirrer and a reflux cooling tube, and the internal temperature is set to 50 ° C. After mixing, the temperature was raised to 90 ° C., and the mixture was reacted at this temperature for 5 hours to disperse in the (meth) acrylic polymerizable monomer. Obtained a polymer.
Subsequently, the liquid temperature was maintained at 50 ° C., and a predetermined amount of the neutralizing agent (basic compound) shown in Tables 1 and 2 was added to medium all or part of the carboxyl groups in the carboxyl group-containing urethane prepolymer. It was harmonized.
Next, the phase inversion water (pure water: DW) is added dropwise in the amounts shown in Tables 1 and 2 over 15 minutes while keeping the internal temperature at 50 ° C. to invert the emulsion, and the emulsion is milky white and transparent. A dispersion was obtained.
This dispersion is kept at 50 ° C., and a predetermined amount of the acrylic polymerization catalyst (polymerization initiator and reducing agent) shown in Tables 1 and 2 is added to polymerize the (meth) acrylic polymerizable monomer. It started. After the heat generation due to the polymerization is completed, the temperature is further raised to 70 ° C. and maintained for 3 hours, and the urethane- (meth) acrylic composite resin containing the urethane- (meth) acrylic composite resin and the unreacted polymerizable monomer is contained. An aqueous dispersion was obtained. The results are shown in Tables 1 and 2.

(Comparative Examples 1 and 2)
The synthesis was carried out in the same procedure as in Examples 1 and 4 except that the fluorine compound was not added at the time of initial charging. The results are shown in Tables 1 and 2.

(result)
In Examples 1, 2, 4, 6 to 8, 12 to 15, the curl retention immediately after being soaked in water and immediately after being pulled up is 95% or more, and is excellent in water resistance. It is considered to be particularly effective when you want to prevent makeup from coming off due to rain or sweating.
Examples 1, 9 to 12 and 14 are considered to be particularly effective when the feel of the hair bundle is particularly soft and a natural texture is required by a hair styling agent or the like.
Example 12 has both water resistance and softness, and has high curl retention under high temperature and high humidity. Furthermore, since a tough film is formed even when a plasticizer is blended, it is considered that the original function of the resin can be exhibited even when a blend containing a large amount of oil component is used.
In Examples 1 to 4, 6 to 8, 13, and 14, the maximum elongation of SS is 100% or more, the obtained film is sufficiently flexible, can follow hair and skin, and is used for cosmetics. It was possible.
On the other hand, in Comparative Example 2, the maximum elongation of SS was less than 100%, and the obtained film was too hard and brittle.
The contact angle was improved in Examples 1 to 4 and 13 by using the fluorine compound. Further, in particular, Examples 1, 6 and 13 to 15 are considered to be particularly effective for cosmetics in which the contact angle is further improved by heating and a scene using a heat source such as a dryer / hot eyelash curler is assumed. Be done.

Claims (19)

It is composed of a polyurethane component ((A) component) and a (meth) acrylic resin ((B) component), and
The component (A) is a polyurethane obtained from a polyol component and a multivalent isocyanate component, and has a carboxyl group-containing multivalent hydroxy compound as a part of the polyol component.
The component (A) is a polyurethane obtained from a polyol component containing at least one of a polyether polyol and a polyester polyol, and a polyhydric isocyanate component.
The polyether polyol is a polyether polyol having a constituent unit derived from a polyalkylene glycol having 2 to 4 carbon atoms as a main component and having a number average molecular weight of 400 or more and 4000 or less.
The polyester polyol 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.
A fluorine compound is contained as at least a part of the constituent units constituting the component (B).
The content of the structural unit composed of the fluorine compound in the component (B) is 0.1% by weight or more and 30% by weight.
A urethane- (meth) acrylic composite resin that does not use a polydimethylsiloxane group-containing ethylenically unsaturated monomer as a constituent unit constituting the component (B). The urethane- (meth) acrylic according to claim 1, wherein the composition ratio of the component (A) and the component (B) is (A) / (B) = 80/20 to 30/70 in terms of weight ratio. Composite resin. The urethane- (meth) acrylic composite resin according to claim 1 or 2, wherein the fluorine compound is a compound containing an alkyl fluoride (meth) acrylic acid ester. The urethane- (meth) acrylic composite resin according to any one of claims 1 to 3, wherein the minimum film forming temperature of the urethane- (meth) acrylic composite resin is −20 to 40 ° C. The distribution of the number average molecular weight of the polyol component constituting the component (A) has a maximum value in the number average molecular weight of 1000 ± 200, and the content ratio of the polyol component in this range is 1% or more of the total polyol component. The urethane- (meth) acrylic composite resin according to any one of claims 1 to 4 . A polyurethane obtained from at least two types of polyol components and a polyhydric isocyanate component, wherein the polyol component in the component (A) is a polyol component having a different number average molecular weight and / or a polyol component having a different constituent unit thereof. The urethane- (meth) acrylic composite resin according to any one of claims 1 to 4 . The urethane- (meth) acrylic composite resin according to claim 6 , wherein the polyol having the smallest number average molecular weight among the plurality of types of polyols has a number average molecular weight of 400 or more and 1200 or less. The urethane- (meth) acrylic composite resin according to any one of claims 1 to 7 , wherein the polyol component contains dimethylolalkanoic acid having an alkane portion having a carbon atom number in the range of 1 to 6. The urethane- (meth) acrylic composite resin according to claim 8 , wherein the dimethylolalkanoic acid is dimethylolpropionic acid and / or dimethylolbutanoic acid. The urethane- (meth) acrylic according to claim 8 or 9 , wherein the content ratio of the constituent unit derived from a dicarboxylic acid composed of dimethylol alkanoic acid in the component (A) is 0.05% by weight or more and 50% by weight or less. Composite resin. The urethane- (meth) acrylic composite resin according to any one of claims 1 to 6 , wherein the glass transition temperature (Tg) of the component (A) is −60 ° C. or higher and 250 ° C. or lower. The urethane- (meth) acrylic composite resin according to any one of claims 1 to 11 , wherein the acid value of the component (A) is 15 to 60 mgKOH / g. The urethane- (meth) acrylic composite resin according to any one of claims 1 to 12 , wherein the mode (Mwp) of the component (A) is 10,000 or more and 200,000 or less. The urethane- (meth) acrylic composite resin according to any one of claims 1 to 13 , wherein the carboxyl group contained in the component (A) is neutralized by 100% or more with a basic compound. The urethane- (meth) acrylic composite resin according to any one of claims 1 to 14 , wherein the glass transition temperature (Tg) of the component (B) is 0 ° C. or higher and 120 ° C. or lower. A composite resin aqueous dispersion obtained by emulsifying and dispersing the urethane- (meth) acrylic composite resin according to any one of claims 1 to 15 in an aqueous medium. The urethane- (meth) acrylic composite resin according to claim 16 , wherein the (meth) acrylic monomer ((B') component) is emulsion-polymerized in the presence of polyurethane (component (A)). A method for producing an aqueous dispersion. A cosmetic comprising the urethane- (meth) acrylic composite resin according to any one of claims 1 to 15 or the urethane- (meth) acrylic composite resin aqueous dispersion according to claim 16 . .. The cosmetic according to claim 18 , wherein the use is at least one selected from those for hair, eye makeup, skin, foundation, lipstick and nail color.