JP6377447B2 - Polyurethane and urethane- (meth) acrylic composite resin - Google Patents

Description

The present invention relates to a urethane- (meth) acrylic composite resin and a polyurethane as a raw material thereof.
The urethane- (meth) acrylic composite resin of the present invention is widely applicable to hair cosmetics, eye makeup cosmetics, makeup cosmetics, skin care cosmetics, other cosmetics, and the like as raw materials for cosmetics. Moreover, it can be preferably used as industrial and household paints and protective films (coating agents).

  The urethane- (meth) acrylic composite resin is used as a cosmetic for maintaining the shape of the hair, protecting the skin, etc. by utilizing its film forming property (Patent Documents 1 and 2), or industrial (automobile) Used for household paints and protective coatings (Patent Document 3), but when a coating to which these are applied comes into contact with an oily component, the oil resistance is insufficient and the coating dissolves or swells. In some cases, the performance cannot be fully exhibited.

  In order to improve this oil resistance, there are methods such as increasing the molecular weight of the resin used or increasing the hard segment content, but in some cases the film becomes hard and the followability to the substrate is lost In some cases, it peels off when bent, or when it is used as a cosmetic, it may become irritated or uncomfortable when used.

Japanese Patent No. 2587801 Japanese Patent No. 5281232 JP 2011-149011 A

In the method for improving oil resistance as described above, when the urethane- (meth) acrylic composite resin having the film-forming property is applied to various uses, for example, an oily oil represented by hair wax among cosmetics. In the formulation containing many components, the oily component acts as a plasticizer for the resin, so that the fixation of the hair and the smooth feel of the finish may be impaired, and the original function of the resin may not be sufficiently exhibited. there were.

  An object of the present invention is to provide a urethane- (meth) acrylic composite resin and an aqueous dispersion thereof that can maintain the original excellent characteristics without being damaged by the film even when contacted with an oily component, and its It is to provide a specific polyurethane as a raw material.

  The gist of the present invention is a polyurethane obtained from a polyol component containing a polyester polyol and a polyvalent isocyanate component, wherein the polyester polyol is at least one dicarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid. A polyurethane having an acid-derived structural unit and capable of being casted at 23 ° C. from a mixed solution (weight ratio 50/50) of silicone oil and the polyurethane.

  Another gist of the present invention is a urethane- (meth) acrylic composite resin obtained by combining the polyurethane and the (meth) acrylic resin, wherein a solution mixed with a silicone oil at a weight ratio of 50/50 is provided. The urethane- (meth) acrylic composite resin that can be cast at 23 ° C. also exists.

  Another aspect of the present invention is to use an aqueous composite resin dispersion in which the urethane- (meth) acrylic composite resin is emulsified and dispersed in an aqueous medium, and the urethane- (meth) acrylic composite resin. It also exists in cosmetics.

  The polyurethane of the present invention is so excellent in oil resistance that the film can be formed from a state where it is mixed with an oily component, and this feature is characteristic of the urethane- (meth) acrylic composite resin containing this polyurethane. As a result, the oil resistance is excellent while having the original characteristics of flexibility, softness and set retention.

The example of the graph which shows the result of having measured the weight average molecular weight of the urethane- (meth) acrylic composite resin of this invention

Hereinafter, the present invention will be described in detail separately for polyurethane and urethane- (meth) acrylic composite resin (hereinafter sometimes abbreviated as “U / A resin”) obtained by using this polyurethane.
In the present specification, “(meth) acryl” means “acryl or methacryl”.

<1. Polyurethane of the present invention>
The polyurethane of the present invention is a polyurethane obtained from a polyol component and a polyvalent isocyanate component.
This polyurethane is characterized in that cast film formation is possible at 23 ° C. from a mixed solution (weight ratio 50/50) of silicone oil and this polyurethane.

  The polyol component which is a raw material of the polyurethane of the present invention contains a porester polyol. This polyester polyol is composed of a structural unit derived from a polyol component (hereinafter sometimes referred to as “polyol unit”) and a structural unit derived from a dicarboxylic acid component (hereinafter sometimes referred to as “dicarboxylic acid unit”). Is a compound.

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

  The dicarboxylic acid unit is a unit composed of an organic compound having two or more carboxyl groups in one molecule. In the present invention, the dicarboxylic acid unit is selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid. It is important to use a structural unit derived from at least one dicarboxylic acid component (hereinafter sometimes referred to collectively as a “phthalic acid unit”). By using a polyester polyol having such 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 a phthalic acid-based unit, examples of the polyester polyol having a structural unit derived from isophthalic acid include Kuraray polyol P-1012, 2012, 530, 1030, 2030, etc. (manufactured by Kuraray Co., Ltd. Name), Teslac 2474 (manufactured by Nippon Kasei Polymer Co., Ltd., trade name), OD-X-2560 (manufactured by DIC Corporation, trade name), HS2F-136P (manufactured by Toyokuni Oil Co., Ltd., trade name), etc. Examples of polyester polyols having structural units derived from terephthalic acid include, for example, Kuraray polyols P-1011, 2011, 2013, 520, 1020, 2020, etc. (trade name, manufactured by Kuraray Co., Ltd.). Can do.

  Among the polyester polyols having phthalic acid units, polyester polyols having a structural unit derived from isophthalic acid (hereinafter sometimes referred to as “isophthalic acid unit”) are preferred.

  The content ratio of dicarboxylic acid units 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, an oil resistance improvement effect can be obtained. On the other hand, by setting the content of the dicarboxylic acid unit to 50% by weight or less, it becomes 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 resulting film may become brittle. The dicarboxylic acid unit is preferably present in an amount of 0.08% by weight or more, and more preferably 0.1% by weight or more. Further, it is preferably present at 40% by weight or less, and more preferably at 35% by weight or less. The dicarboxylic acid unit needs to contain a phthalic acid-based unit, and particularly preferably an isophthalic acid unit. By including an isophthalic acid unit, an effect of improving oil resistance while maintaining flexibility can be obtained.

The content of the phthalic acid unit (PA unit) (C ₈ H ₄ O ₃ = formula 148) in the polyester polyol and the content of the phthalic acid unit in the polyurethane are calculated as follows. Can do. The polyester polyol is referred to as “PEsPO”, the phthalic acid 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 units is referred to as “NumberPA”.
In the polyester polyol, since the (both) ends are always diol ends, the following relational expression is established.
1) Number of phthalic acid units (PA units) in polyester polyol (PEsPO) = (molecular weight of PEsPO-terminal DOL molecular weight) / (PA unit formula weight + DOL unit formula weight)
= NumberPA
(In the above formula, “PA unit formula amount + DOL unit formula amount” is the formula amount of ester units in PEsPO formed by PA and DOL units.)
2) PA unit content in PEsPO (wtPA (weight fraction))
= (Number PA × PA unit formula amount) / PEsPO molecular weight 3) PA unit content (weight) in PEsPO charge (F)
= F x wtPA
4) PA unit content (% by weight) in polyurethane
= (F × wtPA) × 100 / total polyurethane amount (= total charge of urethane raw material)

When dicarboxylic acids other than phthalic acid units are used in combination as the acid component, in the above calculation, instead of the “PA unit formula amount” of 1), formula amounts of other dicarboxylic acids used together (− OC-X-CO-O-, where "X" is a divalent hydrocarbon group other than the benzene nucleus) and the formula weight of the PA unit multiplied by the respective mole fractions of each component. The “dicarboxylic acid average formula amount” was used to determine the “total number of dicarboxylic acid units” corresponding to the above “NumberPA”, and using these, the “dicarboxylic acid unit content in polyurethane (wt%) was determined in the same manner as described above. ), And this amount is apportioned using the molar fraction and the formula weight of both to obtain the “PA unit content in polyurethane”.
The same applies when a plurality of diol components are used.
In addition, when the composition is not clarified such as a commercial product, the composition can be determined by using a method capable of analyzing a high molecular substance such as nuclear magnetic resonance spectrum analysis (NMR) or gel permeation chromatography (GPC). It can also be determined through analysis.

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

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

  In the formula (1), R is, for example, an alkyl group having 1 to 10 carbon atoms, and among them, those having 1 to 6 carbon atoms are preferable. Particularly preferred is one in which R is a methyl group or an ethyl group, and in particular, when R is a methyl group, that is, dimethylolalkanoic acid is preferably dimethylolpropionic acid.

  By using dimethylolalkanoic acid as described above, good copolymerizability can be obtained, and carboxyl groups can be introduced into the resulting polyurethane, which improves dispersion stability when used as an aqueous dispersion. When the polyurethane is made reactive, particularly when used for cosmetics, the miscibility with polar components can be improved, and the adhesion to hair and skin can be increased.

  The amount of the dimethylolalkanoic acid used depends on the acid value of the resulting polyurethane or the performance (dispersibility in water, etc.) required for the urethane- (meth) acrylic composite resin (U / A resin) to be finally produced. What is necessary is just to adjust suitably according to.

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

  The number average molecular weight of the polyol component is preferably 300 or more, and preferably 600 or more. If it is less than 300, the flexibility tends to decrease. On the other hand, the upper limit is preferably 3000 and 2500 is preferable. If it exceeds 3000, the self-emulsifying power may be reduced, or depending on the type of the polyol component, it may become excessively flexible.

  The polyisocyanate used for producing polyurethane refers to an organic compound having at least two isocyanate groups in one molecule, and uses aliphatic, alicyclic, aromatic and other polyvalent isocyanate compounds. be able to.

  Specific examples of such polyvalent isocyanate compounds include dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 2,4-tolylene diene. Examples thereof include isocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,2′-diphenylmethane diisocyanate. Of these, aliphatic or cycloaliphatic isocyanates are preferred in that they are less susceptible to yellowing over time.

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

The acid value can be measured according to a potentiometric titration method (JIS-K-0070) using potassium hydroxide. At this time, “amount of polyurethane” is used as the mass of the sample.
In addition, for example, when potassium hydroxide is used for neutralization in the production of polyurethane, salt exchange hardly occurs, and thus measurement by the JIS method may be 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) = Mole number of acid-containing raw material charged × 56.1 (KOH molecular weight) / polyurethane amount (g) × 1000

  The production of the polyurethane of the present invention can be carried out in the absence of a solvent. However, in order to carry out the reaction uniformly, ethers such as dioxane, ketones such as acetone and methyl ethyl ketone, dimethylformamide, dimethylacetamide, N-methyl- Amides such as 2-pyrrolidone and other organic solvents which are inert to isocyanate groups and have a high affinity for water may be used. In addition, solvents other than those described above can also be used as organic solvents that are not reactive with isocyanate groups, that is, do not contain active hydrogen groups.

  The ratio of the polyester polyol and the polyvalent isocyanate compound used in the production of the polyurethane of the present invention is the equivalent ratio of the hydroxyl group of the polyester polyol and the isocyanate group of the polyvalent isocyanate compound. = 1: 1.2-2 is preferable, and 1: 1.5-1.9 is preferable.

  In addition, when producing a urethane- (meth) acrylic composite resin following the production of polyurethane, a (meth) acrylic monomer having no active hydrogen may coexist at the time of producing the polyurethane. The reaction for obtaining this polyurethane may be carried out at about 50 to 100 ° C. for about 0.5 to 20 hours. Thereby, the polyurethane which has an isocyanate group in a carboxyl group and the terminal can be obtained.

  As a catalyst used for the production of the polyurethane, a catalyst generally used for a urethanization reaction can be used. Specific examples include dibutyltin dilaurate.

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

The glass transition temperature (Tg) of the polyurethane is preferably −60 ° C. or higher and 250 ° C. or lower. Moreover, a plurality of glass transition temperatures may be manifested by the glass transition temperature of the polyurethane soft segment (derived from the polyol unit) and the glass transition temperature of the hard segment (derived from the isocyanate unit). The low temperature side (soft segment side) glass transition temperature at this time is preferably −60 ° C. or higher, and more preferably −50 ° C. or higher. When it is lower than −60 ° C., the resulting film may be excessively soft. On the other hand, the low-temperature side glass transition temperature is preferably 0 ° C. or lower, and more preferably −5 ° C. or lower. If it exceeds 0 ° C, the flexibility of the film tends to be insufficient. Further, the glass transition temperature on the high temperature side (hard segment side) is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, although the influence on the physical properties of the coating film is not as great as the lower temperature side. If it is less than 30 degreeC, the toughness of a film | membrane may be inferior. On the other hand, the upper limit is preferably 250 ° C. or lower, and more preferably 200 ° C. or lower. If it exceeds 250 ° C., the film may become hard and the texture may be poor.
The glass transition temperature can be measured by the method of JIS K7244-4.

The carboxyl group contained in the polyurethane is preferably at least partially neutralized with one or more basic compounds. Thereby, the dispersibility in the aqueous medium of a polyurethane can be improved. Examples of the basic compound include organic amine compounds and alkali metal hydroxides. This neutralization reaction can be performed at any time after the polyurethane is produced, and may be performed in one step or divided into two or more steps. Moreover, the basic compound used for this neutralization reaction may use a different kind for every process.
In particular, the neutralization step is divided into two steps, the first neutralization step is performed after the production of polyurethane, and the second neutralization step is performed after the polyurethane neutralized in the first step is dispersed in an aqueous medium. Is preferred.

  As the organic amine compound, tertiary amine compounds such as trimethylamine, triethylamine, tributylamine, and triethanolamine 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 of the polyurethane (as the total amount used in the first neutralization step and the second neutralization step). That is, it is preferable that the carboxyl group in the polyurethane is neutralized by 100% or more with a basic compound. If it is less than 1 equivalent, a good dispersion 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 problems when used for cosmetics.

  Examples of the aqueous medium in which the polyurethane is dispersed include water and a mixed solution of water and an organic solvent compatible with water such as methanol and ethanol. Among these, water is more preferable from the environmental aspect.

  The polyurethane can be adjusted within the range of the weight average molecular weight by performing a chain extension reaction as necessary. Examples of the chain extender used at this time include a compound having a plurality of active hydrogens capable of reacting with an isocyanate group, water (including water as the aqueous medium), and the like.

  Examples of the compound having a plurality of active hydrogens capable of reacting with the isocyanate group include C1-C8 polyols and polyamine compounds. Examples of the polyol include ethylene glycol and diethylene glycol. Examples of polyamine compounds include diamines such as ethylene diamine, hexamethylene diamine, and isophorone diamine.

  This polyurethane can be cast and formed at 23 ° C. from a solution mixed with silicone oil in a weight ratio of 50/50. “Cast film can be formed” means that after casting, the film is allowed to stand at 23 ° C. for 6 hours, and when the part of the film is picked up with tweezers or the like, the film is not damaged. Say that it will be raised. Examples of the silicone oil that can be used here include cyclopentasiloxane (for example, KF-995 (manufactured by Shin-Etsu Chemical Co., Ltd .: volatile cyclic silicone)) and the like.

  A feature of being capable of being cast at 23 ° C. from a solution mixed with this silicone oil at a weight ratio of 50/50 is that cosmetics containing a large amount of oily components such as mascara, lipstick, lip balm and hair wax (makeup) When used in a preparation, the film exhibits excellent film-forming properties, and when used as a cosmetic, effects such as improvement in the sustainability (holding) of makeup and imparting a firm feeling can be obtained.

<2. Urethane- (meth) acrylic composite resin obtained using the polyurethane>
(1) Method for producing urethane- (meth) acrylic composite resin (U / A resin) By polymerizing a (meth) acrylic monomer in the presence of the polyurethane, polyurethane and (meth) acrylic resin are produced. A composite urethane- (meth) acrylic composite resin (U / A resin) can be obtained.

  In order to produce such a U / A resin, for example, in the emulsion formed by emulsifying and dispersing the polyurethane and the (meth) acrylic monomer in an aqueous medium, the (meth) acrylic resin is used. A method of emulsion polymerization of monomers can be used, and at this time, a urethane- (meth) acrylic composite resin (U / A resin) is obtained as an aqueous dispersion.

  In parallel with the polymerization of the (meth) acrylic monomer, water in the emulsion may cause a chain elongation reaction of polyurethane.

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

  Examples of the polymerization reaction include azo initiators such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyanovaleric acid, and persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate. Organic peroxides such as initiators, t-butyl hydroperoxide, dilauroyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, di (2-ethylhexyl) peroxydicarbonate A radical polymerization initiator of an oxide-based initiator can be used without particular limitation.

  Moreover, you may use as a redox type | system | group polymerization initiator which combined organic peroxide type initiators and persulfate type | system | group initiators, and reducing agents, such as ascorbic acid, Rongalite, or a sulfite metal salt. 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 (meth) acrylic monomer.

  Moreover, polymerization temperature is 10-80 degreeC normally, and it is preferable to carry out at 30-60 degreeC. After completion of heat generation, the polymerization is almost completed by maintaining at 40 to 90 ° C. for about 30 minutes to 3 hours. Thereby, the aqueous emulsion of U / A resin is obtained.

(2) Urethane component of U / A resin The urethane component of the U / A resin of the present invention includes a polyurethane having a component derived from a polyester polyol having the above-mentioned phthalic acid unit, and is contained in the U / A resin. The content ratio of the polyurethane in the urethane component contained in is not less than 50% by weight, preferably not less than 70% by weight, more preferably not less than 85% by weight, and it is most preferable that the total amount is the polyurethane.
The urethane component other than the polyurethane having a component derived from the polyester polyol having the phthalic acid unit is not particularly limited as long as the object and effect of the present invention are not impaired.

Furthermore, in the present invention, the content of the dicarboxylic acid-derived structural unit (dicarboxylic acid unit) contained in the polyurethane among the constituent components of the U / A resin is 0.05% by weight or more and 50% by weight as described above. The content is preferably 0.08% by weight or more and 40% by weight or less, more preferably 0.1% by weight or more and 35% by weight or less. By making content of a dicarboxylic acid unit into the said range, the outstanding softness | flexibility, intensity | strength, and oil resistance of the U / A resin of this invention can be made especially favorable.
In addition, the content of the structural unit derived from the dicarboxylic acid (dicarboxylic acid unit) contained in the polyol component in the polyurethane described above is also preferably in the same range for the same reason.
This is because in the U / A resin, the component that affects oil resistance is a component derived from polyurethane, so increasing the oil resistance of the polyurethane will improve the oil resistance of the entire U / A resin. is there.

The dicarboxylic acid unit is at least one selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid, and an isophthalic acid unit is particularly preferred from the viewpoint of oil resistance.
The content of the dicarboxylic acid unit should be calculated from the composition of the U / A resin and the content of the unit in the urethane in accordance with the above-described method for calculating the content of the phthalic acid component in the polyester polyol. Can do.

(3) (Meth) acrylic component of U / A resin Examples of the (meth) acrylic monomer used in the U / A resin include (meth) acrylic acid alkyl esters. 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, (Meth) acrylic acid isopentyl, (meth) acrylic acid t-pentyl, (meth) acrylic acid 3-methylbutyl, (meth) acrylic acid neopentyl, (meth) acrylic acid hexyl, (meth) acrylic acid 2-methylpentyl, ( 4-methylpentyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, (meth) acryl Cyclopentyl, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, 2-heptyl (meth) acrylate, 3-heptyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylic acid 2-octyl, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, 3,3,5-trimethylhexyl (meth) acrylate, decyl (meth) acrylate, (meth ) Undecyl acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, tetracosyl (meth) acrylate, (meth) Methylcyclohexyl acrylate, isobornyl (meth) acrylate, (meta Norbornyl acrylate, (meth) acrylate, benzyl (meth) phenethyl acrylate are exemplified. Among these, (meth) acrylic acid alkyl esters having 1 to 24 carbon atoms in the alkyl group are preferable, and those having 1 to 8 carbon atoms in the alkyl group are particularly preferable.
Only one kind of these (meth) acrylic monomers may be used, or a plurality of kinds may be mixed and used.

  In the U / A resin of the present invention, in addition to the (meth) acrylic monomer, an ester group-containing vinyl other than the (meth) acrylic monomer, as long as the purpose and effect of the present invention are not impaired. A monomer, a styrene derivative, a vinyl ether monomer, a radically polymerizable unsaturated group-containing silicon macromonomer, or the like may be used in combination. Examples of the ester group-containing vinyl monomer include vinyl acetate, diethyl maleate, dibutyl maleate and the like.

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

  The glass transition temperature (Tg) of the homopolymer or copolymer having the (meth) acrylic monomer as a main component is preferably −50 ° C. or higher, and more preferably −40 ° C. or higher. When Tg is lower than −50 ° C., stickiness may appear in the feel of the resulting cosmetic, and the touch may be deteriorated.

  On the other hand, the glass transition temperature (Tg) is preferably 120 ° C. or lower, and more preferably 110 ° C. or lower. When it exceeds 120 ° C., the minimum film-forming temperature increases, and a uniform film may not be formed. By setting the glass transition temperature within this range, the plasticization of the polymer due to the oil can be suppressed even in the blending with a large amount of the oil without greatly deteriorating the performance as a cosmetic.

The glass transition temperature (Tg) can also be measured by the above-mentioned JIS method. In the case of a copolymer, it can also be calculated by the following formula (1) (FOX formula).
1 / Tg = (Wa / Tga) + (Wb / Tgb) + (Wc / Tgc) + (1)
Where Tg is the glass transition temperature (K) of the copolymer, Tga, Tgb, Tgc, etc. are the glass transition temperatures (K) of the homopolymers of the constituent monomers a, b, c, etc. Wa, Wb , Wc, etc. are the weight fractions of the constituent monomers a, b, c in the copolymer.
In order to express Tg as “° C.”, “273” may be subtracted from the numerical value of Tg obtained by the above formula.

  In addition, when using several types of (meth) acrylic-type monomer, the softness | flexibility of a film | membrane is used by using together the monomer with high Tg of a homopolymer, and the monomer with low Tg of a homopolymer. Can be adjusted.

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

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

(4) Features of U / A resin Next, the U / A resin of the present invention will be described.
The U / A resin of the present invention contains a polyester polyol as a polyol component in the urethane component, and the polyester polyol is derived from at least one dicarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid. By having a component having a structural unit, that is, a structural component derived from a phthalic acid-based polyester component, particularly an isophthalic acid-based polyester component, the property of having good oil resistance is exhibited.

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

  When the polyurethane component is more than 80/20, heat returnability (including setability) when used as a hair styling agent may be deteriorated. On the other hand, when it is less than 30/70, the emulsion stability during the production of the U / A resin may be insufficient, or the aqueous emulsion to be produced may become non-uniform.

  When the U / A resin is used as an aqueous emulsion, the concentration thereof is not particularly limited, but the amount of nonvolatile components is preferably 20% by weight or more, and preferably 30% by weight or more. More preferably. If it is less than 20% by weight, drying may take time. On the other hand, the upper limit is preferably 70% by weight or less, and more preferably 60% by weight or less. If it exceeds 70% by weight, the emulsion may become unstable.

  Further, the minimum film forming temperature of the U / A resin is preferably 10 ° C. or less, and preferably 5 ° C. or less. When it exceeds 10 ° C., the flexibility of the film may be insufficient. On the other hand, the minimum film forming temperature is preferably −20 ° C. or higher, and preferably −10 ° C. or higher. If it is less than -20 degreeC, the heat return property (a setting property is included) of the film obtained may deteriorate.

  Various methods are used to bring the minimum film-forming temperature of the U / A resin into the preferred range. For example, the following methods (a) to (c) ) Method. In general, in order to increase the minimum film-forming temperature, a method opposite to this method may be used.

(A) As the polyol unit, use a relatively high molecular weight polyol having a molecular weight exceeding 1000, for example, or increase the amount used.
(B) The equivalent ratio of the polyol unit in the polyurethane to the polyvalent isocyanate compound is brought close to 1: 1.
(C) A (meth) acrylic monomer component having a low glass transition temperature (Tg) is used.

  In addition, the unreacted (meth) acrylic monomer component usually remains in the aqueous emulsion of the U / A resin immediately after the polymerization of the (meth) acrylic monomer. May be. Therefore, the residual monomer concentration should be 100 ppm by weight or less, preferably 70 ppm by weight or less. The residual monomer concentration is preferably closer to 0.

  As a method of reducing the residual monomer concentration, for example, a method of volatilizing the residual monomer by heating the aqueous emulsion to about 60 to 100 ° C., or a gas such as air is circulated in the gas phase part of the emulsion. Examples thereof include a method, a method of blowing water vapor into an emulsion, a method of distilling off a (meth) acrylic monomer component under reduced pressure, and the like.

  Thus, the aqueous dispersion of U / A resin in which the residual amount of the (meth) acrylic monomer component is 100 ppm by weight or less has almost no odor when used for cosmetics such as hairdressing. It can be preferably used as a raw material.

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

The weight average molecular weight (Mw) of the U / A resin is preferably 100,000 or more and preferably 150,000 or more. Further, the upper limit of the weight average molecular weight is preferably 2000000, preferably 1000000, and more preferably 800000. By satisfying this range, the mechanical stability and the pigment stability when a pigment is added are excellent.
On the other hand, if the weight average molecular weight is less than 100,000, the pigment dispersibility may be inferior. On the other hand, if the weight average molecular weight is larger than 2,000,000, the film tends to be hard and brittle and the texture may be deteriorated. By setting the weight average molecular weight (Mw) in such a range, particularly good oil resistance (cast film forming property) can be obtained.

Moreover, the molecular weight distribution (Mw / Mn) of the U / A resin is usually 1.5 or more and 2.5 or less, and preferably 1.7 or more and 2 or less.
By making the molecular weight distribution within this range, it is possible to reduce the stickiness due to low molecular weight components and the wrinkle due to high molecular weight components of the resulting product, and particularly to improve the feeling of use when used in skin cosmetics. it can.

  Furthermore, the most frequent molecular weight among the weight average molecular weights (Mw) of the urethane component contained in the U / A composite resin, that is, the U / A composite resin as shown in FIG. In the chart (chromatogram) obtained when Mw is measured by the GPC method), the molecular weight (hereinafter referred to as urethane component) of the peak position corresponding to the urethane component polymer (the portion indicated by (A) in FIG. 1). This molecular weight of the polymer is referred to as the mode molecular weight (Mwp) of the polymer of the urethane component, and may be referred to as “Mwp of the urethane component”) is preferably 30000 or more, and more preferably 40000 or more. If the Mwp of the urethane component is smaller than 30000, the long-term stability of the U / A resin is insufficient, and there is a concern that the deterioration will be accelerated, for example, in an environment exceeding 30 ° C. in summer. On the other hand, the upper limit of Mwp of the urethane component is preferably 200000 and more preferably 150,000. If the Mwp of the urethane component is greater than 200000, it may become hard and the texture may be impaired, or the viscosity of the system may increase excessively in the synthesis process, and productivity may deteriorate.

  Further, the mode molecular weight (Mwp) of the polymer of the acrylic component contained in the U / A composite resin (refers to the portion indicated by (B) in FIG. .) Is preferably 200000 or more, more preferably 300000 or more. If the Mwp of the acrylic component is less than 200,000, the 1,3-BG resistance and pigment dispersibility may deteriorate. On the other hand, the upper limit of Mwp of the acrylic component is preferably 2000000 and more preferably 1000000. When the Mwp of the acrylic component is larger than 2000000, the film tends to be hard and brittle and the texture may be deteriorated.

In addition, the difference between the mode molecular weight (Mwp) of the acrylic component contained in the U / A composite resin and the mode molecular weight (Mwp) of the urethane component ((Mwp of the acrylic component) − (Mwp of the urethane component)) is It is desirable that the distance is moderate, preferably 200000 or more, more preferably 250,000 or more. If this difference is smaller than 200000, the mechanical stability may be insufficient. On the other hand, the upper limit of this difference is preferably 2000000 and more preferably 1000000. When this difference is larger than 2000000, the high molecular weight side affects the film, and the film tends to be hard and brittle, and the texture may be deteriorated.
In addition, “1,3BG resistance” generally means that even if 1,3BG (1,3-butanediol) is added to an aqueous dispersion and mixed, the sample solution does not change. It is a kind of blending stability test. 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.

In addition, when the (B) component (meth) acrylic acid ester-based polymerizable monomer is emulsion-polymerized in an aqueous medium, a polymerization initiator, an emulsifier, etc. in the aqueous medium in the middle of the polymerization or other polymer produced A chain transfer reaction to the polymer tends to occur, and the molecular weight of the resulting polymer may be low.
On the other hand, in this application, (A) component (polyurethane having an isocyanate group and a carboxyl group) and (B) component ((meth) acrylic acid ester-based polymerizable monomer) are emulsified and dispersed in an aqueous medium. In the emulsion droplet, (A) urethane- (meth) acrylic composite resin aqueous dispersion (U / A resin aqueous dispersion) obtained by polymerizing the component (B) is used. Radical polymerization occurs in the state where the component (B) is 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) hardly occurs, but also the polymerization proceeds in a state where the termination reaction of the polymerization hardly occurs. Therefore, the molecular weight of the component (B) tends to increase. The urethane resin constitutes the shell portion, and the (meth) acrylic resin constitutes the core portion. At this time, the molecular weight of the component (B) tends to be larger than that of the emulsion polymerization in the absence of the component (A), and the molecular weight distribution of the resulting composite resin has two peaks as shown in FIG. Will be shown. The horizontal axis (RT _min ) in FIG. 1 means the retention time (minutes), and the shorter the RT, the higher the molecular weight.
An example of this molecular weight distribution is as shown in FIG. 1, and the relationship between each peak position, that is, the Mwp of the acrylic component and the Mwp of the urethane component is as described above.

  By the way, when the mode molecular weight (Mwp) of the urethane component and the mode molecular weight (Mwp) of the acrylic component contained in the U / A composite resin cannot be clearly distinguished, that is, as shown in FIG. In the gel permeation chromatographic method (GPC method) chart (chromatogram) of composite resin, if two peaks do not appear clearly, the urethane component and the acrylic component are individually polymerized under the corresponding conditions and dispersed in water. A liquid is obtained, Mw is measured for each by gel permeation chromatography (GPC method), and the peak position may be the mode molecular weight (Mwp) of the urethane component or the mode molecular weight (Mwp) of the acrylic component. In this case, however, the Mwp of the acrylic component (component (B)) is usually a lower value than actual because there is no effect of increasing the molecular weight as described above.

The U / A resin preferably contains a component (gel content) that does not dissolve in THF (tetrahydrofuran). The preferred gel content is preferably 10% by weight or more, more preferably 30% by weight or more. If the gel fraction is too small, blending stability and oil resistance may be inferior.
The upper limit of the gel content is not particularly limited, and may be 100% by weight, but is preferably 99% by weight or less. By setting it as such a gel part, the above-mentioned oil resistance (cast film forming property) improves more. 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 uses of U / A resin>
The U / A resin of the present invention contains a phthalic acid unit, particularly an isophthalic acid unit, and thus exhibits excellent oil resistance as described above and is composed of a self-emulsifying polyurethane. (Emulsion stability) and pigment dispersibility are also excellent and can be suitably used for the following applications.

(1) Cosmetics The urethane- (meth) acrylic composite resin (U / A resin) and its aqueous dispersion (U / A resin aqueous dispersion) of the present invention are cosmetics for hair cosmetics and skin cosmetics. It can be suitably used as a resin for use. The usage will be briefly described below.

[Hair cosmetics]
When used as a hair cosmetic resin, an aqueous dispersion of the U / A resin of the present application is added and used in hair cosmetics such as shampoos, rinses, treatments, setting agents, and permanent wave solutions. At this time, a conventionally used polymer or the like may be used in combination.

  The form of such a hair cosmetic may be adjusted according to its use and usage, such as liquid, cream, emulsion, spray, gel, mousse (can be ejected in a foam state), and is not particularly limited.

  The amount of the U / A resin 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 ratio of the U / A resin is 0.05 to 10% by weight with respect to the hair cosmetic. It is preferable to add at a ratio of 0.1 to 8% by weight.

  The U / A resin can be used alone or in combination with conventional anionic, nonionic, cationic and amphoteric setting polymers. The set polymer used in combination is more preferably an anionic or nonionic set polymer from the standpoint of mixing stability.

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

  Nonionic polymers used as the set polymer include, for example, polyvinylpyrrolidone polymer (trade name: PVP series (manufactured by ASP Japan)), vinylpyrrolidone-vinyl acetate copolymer (trade name: LUVISKOL VA series). (BASF Japan Co., Ltd.)). Examples of amphoteric polymers include methacrylate ester copolymers (trade name: Yucaformer series (manufactured by Mitsubishi Chemical Corporation)).

  Examples of the cationic polymer used as the set polymer include ethers of hydroxycellulose and glycidyltrimethylammonium chloride (trade name: Leogard G (manufactured by Lion Corporation), trade names: polymers JR-30M-125 and -400. (Manufactured by Union Carbide)), quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymer (trade name: GAFQUAT 734 and 755 (manufactured by ASP Japan Co., Ltd.)), dimethyldiallylammonium chloride polymer (trade name: MERQUAT 100 (manufactured by Lubrizol)), dimethyldiallylammonium chloride acrylic amide copolymer (trade name: MERQUAT550 (manufactured by Lubrizol)) and the like.

  Cosmetics for set in which the U / A resin and the set polymer are used include aerosol hair spray, pump hair spray, foam hair spray, hair mist, set lotion, hair cream, hair oil, Various hair styling agents containing alcohols such as ethanol and isopropanol are included.

  When the hair styling material is a hair cosmetic (mousse) that can be ejected in a foam state, for example, the U / A resin is 0.01 to 10% by weight, the set polymer is 0 to 15% by weight, and a nonionic surfactant. A composition such as 0.1 to 5% by weight of an agent, 3 to 25% by weight of a liquefied gas, and 60% by weight or more of an aqueous solvent mainly composed of water is used.

  Nonionic surfactants used in the above include, for example, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene Castor oil, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamide and the like can be mentioned.

  Moreover, when it is set as a gel (gel) hair-styling agent, generally U / A resin 0.01 to 10 weight%, set polymer 0 to 15 weight%, gel base 0.1 to 3 weight%, water 72 weight% -A composition such as a residue is used.

  In the case of a hair spray, a composition such as 0.01 to 10% by weight of a U / A resin, 0 to 15% by weight of a setting polymer, 30 to 80% by weight of an organic solvent, and 10 to 70% by weight of a propellant is used. .

  Examples of the propellant that can be used for the spray and 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 of the present invention can be used in conditioning cosmetics such as shampoos, conditioners (rinse), 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 thereto. Such conditioning cosmetics are used as U / A resins alone or in combination with conventional anionic, nonionic, cationic and amphoteric conditioning polymers in the same manner as the above-described cosmetics for sets. The conditioning polymer used in combination is more preferably an anionic or nonionic set polymer from the standpoint of stability of mixing.

  Moreover, when using for a shampoo, the said U / A resin can be added and used for anionic, amphoteric, or nonionic surfactant. Examples of the surfactant used herein include N-coconoyl-N-methyl-β-alanine sodium, N-myristoyl-N-methyl-β-alanine sodium and the like as anionic surfactants. And fatty acid acyl-N-methyl-β-alanine salts.

  Examples of amphoteric surfactants include cocoaside propyl 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 illustrated.

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

  Moreover, when using for rinse, the U / A resin of this invention can be added and used for a cationic surfactant. Examples of such cationic surfactants include stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, and the like.

  Further, when used as a permanent liquid, a U / A resin is added to an oxidizing agent such as bromates and perboric acids, and a reducing agent such as thioglycolic acid and salts thereof and cysteine.

  In addition to the above, for example, when used as a hair treatment, this is used in combination with or in place of a cationic surfactant and / or a cationic polymer such as cationic polypeptide, cationic cellulose, cationic polysiloxane, etc. The U / A resin of the invention 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-described cosmetics for conditioning and conditioning cosmetics, in addition to the various components described above, other optional components may be blended if necessary within a range that does not affect the effects of the present invention. . Such optional components include hydrocarbons, linear alcohols, branched alcohols, higher fatty acids and derivatives thereof, plant polymers, microbial polymers, natural water-soluble polymers, cellulose polymers, semi-synthetics. Water-soluble polymer, vinyl polymer, polyoxyethylene 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, surfactant other than the above-mentioned surfactant, emulsifier, moisturizer, antibacterial agent, vasodilator, refresher, stimulant, vitamins, bactericidal and antiseptic Agents, chelating agents, pH adjusting agents, foam increasing agents, foaming agents, foam stabilizers and the like. Furthermore, when these cosmetics are aerosol products, a propellant such as liquefied petroleum gas or dimethyl ether is used in combination, and other metal ion scavengers, fungicides, bactericides, Emulsifiers, conditioning agents, thickeners, antioxidants, solubilizers, rosin, hydrotropes, hair nourishing agents, herbal medicines, pigments, fragrances and the like may be used.

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

  Examples of branched alcohols include monostearyl glycerin ether, 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, octyldodecanol and the like.

  Higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, 1,2-hydroxystearic acid, undecylenic acid, tolic acid, lanolin fatty acid, isostearic acid, linoleic acid, Linolenic acid, γ-linolenic acid, eicosapentaenoic acid and the like can be mentioned.

  Examples of the plant polymer include carrageenan, pectin, agar, quince seed (malmello), algae colloid (gypsum extract), starch (rice, corn, potato, wheat), glycyrrhizic 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 polymers such as collagen and gelatin. Examples of the cellulose polymer include methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, cellulose sodium sulfate, hydroxypropyl cellulose, sodium carboxymethyl cellulose (CMC), crystalline cellulose, and cellulose powder.

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

  Examples of the polyoxyethylene polymer include polyethylene glycol 20,000, 4,0000, 60,000 and the like. Examples of the synthetic water-soluble polymer include polyethyleneimine. Examples of the inorganic water-soluble polymer include bentonite, aluminum magnesium silicate (beegum), labonite, hectorite, and anhydrous silicic acid.

  Examples of silicones include volatile silicone oils, silicone resins, silicone gums, alkyl-modified silicones, and the N-fatty acid acyl-L-glutamate salts include monosodium N-lauryl-L-glutamate, N -Palm oil fatty acid-L-glutamate monotriethanolamine, N-myristylate acyl-L-glutamate monosodium, N-mixed fatty acid acyl-L-glutamate monosodium, and the like.

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

  Other surfactants include acyl sarcosine sodium, acyl glutamate, acyl-β-alanine sodium, acyl taurate, lauryl sulfate, lauryl dimethylaminoacetic acid betaine, 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.

  As humectants, (poly) ethylene glycol, (poly) propylene glycol, glycerin, 1,3-butylene glycol, maltitol, sorbitol, chondroitin sulfate, hyaluronic acid, atelocollagen, cholesteryl-1,2-hydroxystearate, lactic acid Sodium, bile salt, dl-pyrrolidone carboxylate, short chain soluble collagen and the like can be mentioned.

  Examples of the antibacterial agent include hinokitiol, hexachlorophene, benzalkonium chloride, trichlorocarbanilide, and pithionol. Examples of the vasodilator include carpronium chloride. Examples of the refreshing sensation agent include menthols. Examples of the irritation imparting agent include benzyl nicotinate. Examples of vitamins include vitamins A, B, C, D, E and the like.

  Examples of the bactericidal / preservative include chlorhexidine gluconate, isopropylmethylphenol, and p-hydroxybenzoate. Examples of chelating agents include protein hydrolysates, amino acids, plant extracts, EDTA-Na (ethylenediaminetetraacetic acid sodium salt), and the like. Examples of the pH adjuster include succinic acid, sodium succinate, triethanolamine and the like.

[Skin cosmetics]
When the U / A resin of the present invention is used as a resin for skin cosmetics, it is usually added and used in skin cosmetics such as skin creams, skin lotions, and emulsions.

[Make-up cosmetics]
Examples of makeup cosmetics include mascara, eyeliner, eye shadow, lipstick, lip gloss, foundation, and makeup applege. These makeup cosmetics include the U / A resin of the present invention. Applications and purposes of materials commonly used in cosmetics such as solid oils, oils, waxes, oils such as silicone oil, powder components such as pigments and resin powders, or solvents such as water and liquid alcohol in aqueous dispersions It is obtained by adding and mixing depending on the condition.

  In addition, since the obtained film is flexible, the U / A resin of the present invention can be preferably used as a cosmetic for skin, for example, liquid foundation, skin cream, UV care cream, and skin lotion. it can.

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

  The U / A resin of the present invention can also be used in cosmetics other than those described above. In that case, the fluorine compound for cosmetics, various resins, and surfactants are used according to the respective purposes and applications. Ingredients such as viscosity imparting agents, preservatives, perfumes, organic / inorganic ultraviolet absorbers, physiologically active ingredients, salts, antioxidants, chelating agents, neutralizing agents, pH adjusters, etc. As long as the effect is not impaired, it can mix | blend suitably.

(2) Other uses The U / A resin of the present invention uses industrial paints (particularly paints for automobiles), taking advantage of its oil resistance, flexibility, adhesion, substrate followability, wear resistance, etc. It can be used for paints such as household paints, coating agents, protective film forming agents, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely using an Example, this invention is not limited by a following example.

<< 1. Raw materials >>
<Polyol unit>
-N4073 ... Nippon Polyurethane Industry Co., Ltd. product name: NIPPOLAN 4073, polyester polyol (1,6HD-AA) of 1,6-hexanediol and adipic acid, number average molecular weight (Mn) = 2000.
-P-2012 ... manufactured by Kuraray Co., Ltd .: trade name Kuraray polyol P-2012, mixed polyester polyol of methylpentanediol and adipic acid / isophthalic acid (MPD-AA-IP) (molar ratio of adipic acid / isophthalic acid = 1 / 1), number average molecular weight (Mn) = 2000.

-P-1030 ... Kuraray Co., Ltd. product name: Kuraray polyol P-1030, polyester polyol of methylpentanediol and isophthalic acid (MPD-IP), number average molecular weight (Mn) = 1000.
-P-2030 ... Kuraray Co., Ltd. product name: Kuraray polyol P-2030, polyester polyol of methylpentanediol and isophthalic acid, number average molecular weight (Mn) = 2000.

<Polyisocyanate compound>
・ IPDI: Degussa Japan Co., Ltd .: Brand name VESTANAT IPDI (isophorone diisocyanate)
<Carboxyl group-containing polyvalent hydroxy compound>
DMPA: Perstop Co., Ltd .: dimethylolpropionic acid (carboxylic acid-containing polyol).

<Polymerization inhibitor>
MEHQ: Wako Pure Chemical Industries, Ltd .: 2-methoxyhydroquinone <polymerizable monomer>
MMA: Mitsubishi Rayon Co., Ltd., methyl methacrylate BA: Mitsubishi Chemical Co., Ltd., n-butyl acrylate

<Radical polymerization initiator>
TBPO: Kayaku Akzo Co., Ltd .: di-tert-butyl peroxide <reducing agent>
AsA: Wako Pure Chemical Industries, Ltd .: L-ascorbic acid (reagent special grade)
<Basic compound>
-KOH: Potassium hydroxide ... Wako Pure Chemical Industries, Ltd. (reagent)
-TEA: Triethanolamine: Shell Chemicals Japan Co., Ltd .: TEA99

<< 2. Evaluation method >>
(1) Oil resistance Cast from a solution in which silicone oil (KF-995 manufactured by Shin-Etsu Chemical Co., Ltd.) and polyurethane or U / A resin are mixed at a weight ratio of 50/50 onto a plate made of polypropylene resin at 23 ° C. To do. After standing for 6 hours, a part of the film is pulled up with tweezers and the film formation state is observed.
◎: The thin film can be pulled up stably with tweezers. ○: The thin film can be pulled up with tweezers without breaking in the middle. △: A film is formed on the resin sheet. Break along the way.
×: No film is formed

(2) Mechanical stability Using a paint shaker (5400-H3 type) manufactured by RED DEVIL, 15 parts by weight of pigment (Pigment Blue 15 (trade name), manufactured by Tokyo Chemical Industry Co., Ltd.), polymer (of the present invention) Polyurethane or U / A resin aqueous dispersion) 20 parts by weight (in terms of solid content), isopropanol (reagent grade 1, manufactured by Wako Pure Chemical Industries, Ltd.) and ion-exchanged water will be 100 parts by weight. The mixture was stirred and mixed for 1 hour, filtered through a 100 mesh nylon net, and the residue remaining on the net was visually observed.
◎: There is little or no residue. ○: Residue remains as if the nylon mesh is lightly colored, but there is no problem with filterability. △: Residue remains on the nylon mesh and the filterability is poor. Gelled and cannot be filtered

(3) Pigment dispersibility The compounded liquid containing the U / A resin prepared for the mechanical stability evaluation is applied on a glass plate using a bar (No. 4) and dried at room temperature for 30 minutes. The surface was observed and evaluated according to the following criteria.
◎: Glossy and uniform hue ○: Inferior to ◎, but glossy and uniform hue △: The coated surface is uniform, but there is uneven color ×: The coated surface is uneven And / or significant color irregularities

<< 3. Evaluation of urethane- (meth) acrylic composite resin >>
(Test method)
Hereinafter, each test method will be described.
<Glass transition temperature (Tg)>
[(A) component]
It measured according to JIS K 7244-4.
[Component (B)]
According to the following formula (1) (FOX formula), the Tg of the polymer was calculated from the Tg and weight fraction of each homopolymer of the polymerizable monomer to be used.
1 / Tg = (Wa / Tga) + (Wb / Tgb) + (Wc / Tgc) + (1)
Where Tg is the glass transition temperature (K) of the (co) polymer, Tga, Tgb, Tgc, etc. are the glass transition temperatures (K) of the homopolymers of the constituent monomers a, b, c, etc. Wa , Wb, Wc, etc. indicate the weight fraction of each constituent monomer a, b, c in the copolymer.
As described above, when Tg is expressed as “° C.”, “273” may be subtracted from the numerical value of Tg obtained by the above formula.

<Weight average molecular weight and molecular weight distribution>
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured using gel permeation chromatography (GPC method) under the following conditions.
Moreover, in U / A resin, the mode molecular weight (Mwp) of (A) component and the mode molecular weight (Mwp) of (B) component were measured from the said GPC chart.
・ Measurement device: LC-20AD (manufactured by Shimadzu Corporation)
・ Detector: RI (refractive index)
-Column: PLgel Mixed B (manufactured by Agilent Technologies)
・ Developing solvent: THF (tetrahydrofuran)
・ Developing solvent flow rate: 1 ml / min
・ Measurement sample injection volume: 100 μL
Measurement sample: A dry sample is prepared from the obtained urethane- (meth) acrylic composite resin dispersion under the following drying conditions, and a 0.2 wt% solution is prepared using THF. This solution was filtered with the following filter, and the obtained filtrate was used as a measurement sample.
・ Drying conditions: After drying at 40 ° C. × 12 hours, vacuum drying at room temperature × 6 hours ・ Filter for measurement sample preparation: GL Chromatodisc (pore size 0.45 μm) (manufactured by GL Sciences Inc.)
-Calibration curve: PMMA (polymethyl methacrylate) conversion

<Gel content>
40 mg of the dried sample obtained above is dissolved in 20 mL of THF and filtered through a gel fraction filter (manufactured by ADVANTEC, PF-100: pore size 100 μm).
The filter for gel content after filtration is dried at 105 ° C. for 3 hours, the residual solid content is determined from the weight of the unused filter dried in the same manner, and the gel content is calculated by the following formula.
Gel content (% by weight) = (filter weight after drying (mg) −filter weight before use (mg)) / 40 (mg) × 100

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

<Liquid properties>
[Compounding stability]
The obtained aqueous dispersion was mixed so that the solid content was 5% by weight, ethanol 10% by weight, and 1,3-butanediol 5% by weight (the remainder was water), and stored at room temperature. The state of the liquid was visually evaluated.
A: No change.
○: Viscosity changes to some extent after blending, but then stabilizes.
Δ: Some concentration gradient, sedimentation, aggregate generation, viscosity change, etc.
X: Concentration gradient, sedimentation, and aggregate generation can be clearly confirmed.

<Applied physical properties>
[C. R. : Curl retention]
-Resin alone C.I. R.
A sample is applied to a hair sample, dried in a curled state, and the state of shape retention after 3 hours is observed 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 30% by weight, and this was applied to a hair bundle having a length of 23 cm × weight of 2 g to a coating amount of 0.7 g. This hair bundle was wound around a cold rod having a diameter of 1 cm, dried at 50 ° C. for 2 hours, and the curled hair bundle obtained was removed from the rod and suspended in an environment of 30 ° C. × 90% RH, and after 3 hours. The length of the curled hair bundle was measured, and the curl retention was calculated from the following formula.
Curl retention (%) = (length after 23-3 hours) × 100 / (23−initial length)
However, “length” means the length in a curled state.
-C. when 1,3BG (1,3-butanediol) is blended. R.
The sample solution was the same as “CR of resin alone” except that the solid content was 5% by weight, 1,3-butanediol was 5% by weight, and the residue was diluted to be water. And evaluated.

<< 4. Examples and Comparative Examples >>
(Examples 1 and 2, Comparative Example 2: Production of urethane)
To a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, a predetermined amount of the urethane raw material and the reaction solvent shown in Table 1 are added, mixed at an internal temperature of 50 ° C., and then heated to 90 ° C. Then, the reaction was carried out at this temperature for 5 hours to obtain a carboxyl group-containing urethane prepolymer containing an isocyanate group and a carboxyl group.
Subsequently, the liquid temperature was kept at 50 ° C., and a predetermined amount of the neutralizing agent (basic compound) shown in Table 1 was added to neutralize all or part of the carboxyl groups in the carboxyl group-containing urethane prepolymer. .
Next, phase inversion water (pure water: DW) is added in the amount shown in Table 1 and dripped over 15 minutes while maintaining the internal temperature at 50 ° C., and the emulsion is phase-inverted, milky white and transparent. A dispersion was obtained.
This dispersion was heated to 80 ° C., and the reaction solvents (methyl ethyl ketone (MEK) and ethanol (EtOH)) used during the production of the urethane prepolymer were collected to obtain a polyurethane dispersion (dispersion).

The content of the isophthalic acid unit in Example 1 is calculated as follows according to the above description.
Here, “P-1030” has an acid component of isophthalic acid alone, a diol component of methylpentanediol alone, and a molecular weight (PEsPO) of 1,000.
From this, the formula weight of PA unit is 148, the formula weight of DOL unit is 100, and the molecular weight of terminal diol is 101, so the PA unit content in polyurethane can be calculated as follows.
1) Number of PA units Number of PA units (NumberPA) = (1000-101) / (100 + 148) = 4 (rounded off to the nearest decimal place)
2) The content of isophthalic acid unit (wtPA) in PEsPO is from 1) above.
wtPA = (NumberPA) x PA unit formula amount / (PA unit formula amount + DOL unit formula amount)
= 4 × 148/1000 = 0.59
3) The PA unit content during charging can be calculated as follows from the above result and “Polyol charging amount” (0.23) in Table 1.
PA unit content during preparation = 0.23 × 0.59 = 0.14
4) The isophthalic acid unit content% in the polyurethane can be calculated as follows based on the above results and the charged amounts of the respective components serving as the urethane raw materials in Table 1.
PA unit content (wt%) = (0.23 × 059) / (60.8 + 0.2 + 7.8 + 31.2) × 100 = 0.1% by weight
This value is “isophthalic acid (IP) content (wt%) in polyurethane” in Table 1.
The PA unit content in the polyurethane can be calculated in the same manner in Examples 2 to 6, 8, 9 and Comparative Example 1 using P-1030 as the diol component.

(Examples 3-8, Comparative Example 3: Production of U / A resin)
To a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, a predetermined amount of the urethane raw material, acrylic raw material, and polymerization inhibitor listed in Table 1 were added and mixed at an internal temperature of 50 ° C. The mixture was heated to 90 ° C. and reacted at this temperature for 5 hours to obtain a carboxyl group-containing urethane prepolymer containing an isocyanate group and a carboxyl group dispersed in a (meth) acrylic polymerizable monomer.
Subsequently, the liquid temperature was kept at 50 ° C., and a predetermined amount of a neutralizing agent (basic compound) shown in Table 1 was added to neutralize all or part of the carboxyl groups in the carboxyl group-containing urethane prepolymer.
Next, phase inversion water (pure water: DW) is added in the amount shown in Table 1 dropwise over 15 minutes while maintaining the internal temperature at 50 ° C., phase inversion of the emulsion, and milky white and transparent dispersion A liquid was obtained.
While maintaining this dispersion at 50 ° C., a predetermined amount of an acrylic polymerization catalyst (polymerization initiator and reducing agent) described in Table 1 was added to initiate polymerization of the (meth) acrylic polymerizable monomer. After the heat generation by polymerization is completed, the temperature is further raised to 70 ° C. and maintained for 3 hours, and a urethane- (meth) acrylic composite resin containing a urethane- (meth) acrylic composite resin and an unreacted polymerizable monomer An aqueous dispersion was obtained.

In Example 7, P-2012, which is a mixed polyester polyol of adipic acid and isophthalic acid, is used as the polyol of the urethane raw material (the diol component is methylpentanediol alone). In this case, “PA unit content in polyurethane” can be calculated as follows.
1) Multiply the formula amount of the dicarboxylic acid used by each usage ratio (molar fraction) and add up the total number, and use the “average formula amount of dicarboxylic acid” to obtain the “NumberPA” when the dicarboxylic acid is used alone. "Number of dicarboxylic acid units" corresponding to "."
The molecular weight and molar fraction of P-2012 and its raw materials are as follows.
P-2012: PEsPO molecular weight = 2000, terminal DOL molecular weight = 101
Methylpentanediol: DOL unit formula amount = 100
Adipic acid: adipic acid unit formula amount = 128, molar fraction = 0.5
Isophthalic acid: PA unit formula amount = 148, molar fraction = 0.5
From the above,
Average formula amount of dicarboxylic acid = (128 × 0.5) + (148 × 0.5) = 138
Number of dicarboxylic acid units = (2000-101) / (100 + 138) = 8 (rounded off after the decimal point)
2) From the above results, the dicarboxylic acid unit content in PEsPO is as follows.
Dicarboxylic acid unit content in PEsPO = 7.98 x 138/2000 = 0.55
3) The content of the dicarboxylic acid unit in the feed is from PEsPO charge = 54.52 (Table 1).
Dicarboxylic acid unit content in feed (%) = 54.52 × 0.55 = 29.99
4) The dicarboxylic acid unit content in the polyurethane can be calculated from the raw material charge shown in Table 1 as follows.
Dicarboxylic acid unit content (wt%) = 29.99 / (54.52 + 9.14 + 36.34) × 100 = 29.99 wt%
5) From the above results, the PA unit content in the polyurethane is calculated from the formula amount of PA units and the molar fraction of PA.
PA unit content (wt%) = 29.99 × (148/138) × 0.5 = 16.08 wt%
This value is shown as “IP content in polyurethane (wt%)” in Table 1.

(Example 9: Example of performing the first and second neutralization steps)
After synthesizing a carboxyl group-containing urethane prepolymer containing an isocyanate group and a carboxyl group in the same manner as in Examples 3 to 8 except that the raw materials shown in Table 1 were used, the liquid temperature was subsequently kept at 50 ° C. In the state maintained, among the neutralizing agents listed in Table 1, TEA (triethanolamine) was used to neutralize a part of the carboxyl groups in the carboxyl group-containing urethane prepolymer (first neutralization step) ).
Thereafter, in the same manner as in Example 1 above, phase inversion was performed using phase inversion water (pure water: DW) to obtain a milky white transparent dispersion.
To this dispersion, an acrylic raw material (monomer) of the type and amount shown in Table 1 and a polymerization catalyst (initiator and reducing agent) were added, and polymerization and aging were carried out in the same manner as in Examples 3 to 8 above ( The temperature was increased and maintained after completion of the polymerization heat generation) to obtain a urethane- (meth) acrylic composite resin aqueous dispersion containing a urethane- (meth) acrylic composite resin and an unreacted polymerizable monomer.
After cooling the obtained aqueous dispersion to 30 ° C., a second neutralization step is performed using the amount of potassium hydroxide shown in Table 1, and a part of the carboxyl groups in the urethane- (meth) acrylic composite resin. Was neutralized to prepare an aqueous U / A resin dispersion.

(Comparative Example 1)
Carboxyl group containing isocyanate group and carboxyl group in the same manner as in Example 1 except that a predetermined amount of the urethane raw material shown in Table 1 was used and MEK was used as the reaction solvent in the amount shown in Table 1. A urethane prepolymer was obtained.
Subsequently, a predetermined amount of ethanol (EtOH) described in the reaction solvent column of Table 1 was added dropwise at 50 ° C. over 15 minutes to obtain a transparent solution.
The above-described measurement and evaluation were performed on the obtained aqueous emulsion (MEK / ethanol solution in Comparative Example 1). The results are also shown in Table 1.

Since Examples 1-9 contain a predetermined amount of dicarboxylic acid units (particularly phthalic acid units) in the polyurethane or U / A resin, the oil resistance (film formation from silicone oil) is good.
On the other hand, in a comparative example, since it does not contain a dicarboxylic acid unit or does not contain a predetermined amount even if it contains, oil resistance is inferior.

Claims (10)

A cosmetic comprising a urethane- (meth) acrylic composite resin obtained by combining the following polyurethane and a (meth) acrylic resin.
(Polyurethane)
A polyurethane obtained from a polyol component containing a polyester polyol and a polyvalent isocyanate component,
The polyester polyol has a structural unit derived from at least one dicarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid and terephthalic acid, and
Polyurethane that can be cast into a film at 23 ° C. from a mixed solution of silicone oil and polyurethane (weight ratio 50/50).   The cosmetic according to claim 1, wherein the structural unit derived from dicarboxylic acid is a structural unit derived from isophthalic acid.   The cosmetic according to claim 1 or 2, wherein the polyol component contains dimethylolalkanoic acid.   The cosmetic according to claim 3, wherein the alkane portion of the dimethylolalkanoic acid has 1 to 6 carbon atoms.   The cosmetic according to claim 4, wherein the dimethylolalkanoic acid is dimethylolpropionic acid.   The cosmetic according to any one of claims 1 to 5, wherein a content ratio of the structural unit derived from the dicarboxylic acid is 0.05% by weight or more and 50% by weight or less.   The cosmetic according to any one of claims 1 to 6, wherein a solution obtained by mixing the urethane- (meth) acrylic composite resin with a silicone oil in a weight ratio of 50/50 can be cast at 23 ° C. . The content ratio of the polyurethane component and the (meth) acrylic component in the urethane- (meth) acrylic composite resin is in the range of 30/70 or more and 80/20 or less (weight ratio, where the sum of both is 100). Cosmetics given in any 1 paragraph of Claims 1-7.   The content rate of the structural unit derived from dicarboxylic acid in the polyurethane which is a structural component of the urethane- (meth) acrylic composite resin is 0.05% by weight or more and 50% by weight or less. Cosmetics described. The cosmetic according to any one of claims 1 to 9, wherein the urethane- (meth) acrylic composite resin has a weight average molecular weight (Mw) of 100,000 to 2,000,000 and a gel content of 10% by weight or more. .

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