JP6169372B2 - Aggregated particles and cosmetics using the same - Google Patents

Description

  The present invention relates to agglomerated particles made of a urethane-acrylic composite resin used for cosmetics.

  It is well known to fix a hair with a resin to give a desired shape. As such cosmetic resins, various types of polymers such as anionic and other ionic acrylics, vinyl acetates, vinylpyrrolidones, and vinyl methyl ethers are generally known.

  Films formed from these resins are usually hard and brittle, so that they lack flexibility, and the finish of hair is stiff and lacks a natural texture. In particular, when trying to enhance the hair styling effect, the film becomes harder and the finish of the hair is further deteriorated. Cationic acrylic polymers, vinyl pyrrolidone polymers, and vinyl methyl ether polymers tend to be very soft and sticky when hot and humid, and the hair styling effect tends to decrease.

  In order to improve the drawbacks of these resins, water-based polyurethane polymers having excellent film flexibility have been proposed. However, when a composition composed solely of polyurethane is used for hair, the shape maintenance property when heated (hereinafter referred to as “heat returnability”) is not sufficient, and the hair styling effect is insufficient. Since the resulting film was poorly slippery, the feel of the hair was not good.

Patent Document 1 describes a composition using an aqueous dispersion of a polymer composed of composite particles obtained by polymerizing radically polymerizable monomers in the presence of polyurethane polymer particles as a polymer that can improve such defects. Has been.

  Moreover, the cosmetics for hair containing the acryl-urethane emulsion of patent document 2 are known as what improved the slipperiness of the film | membrane.

Japanese Patent No. 2587801 JP 2007-001969 A

  When an aqueous emulsion containing urethane-based composite particles described in the literature as described above is made into a paste and used as a skin cosmetic, elongation may be insufficient.

  Therefore, an object of the present invention is to obtain a cosmetic material that can be sufficiently stretched and improved in touch when used as a skin cosmetic material.

The present invention solves the above problems by using aggregated particles made of urethane-acrylic composite resin having an average particle size of 10 to 200 μm.
As a method for producing the agglomerated particles, there is a method of spray drying an aqueous dispersion of urethane-acrylic composite resin having a solid content concentration of 20 to 50% by weight.

  Since the agglomerated particles obtained by spray-drying predetermined agglomerated particles, particularly a predetermined urethane-acrylic composite resin aqueous dispersion, are used, sufficient elongation can be obtained when used as cosmetics, especially skin cosmetics. And tactile sensation can be improved.

Scheme showing preferred production method of this invention Electron microscope (SEM) photograph of agglomerated particles of the aqueous emulsion obtained in Example 1

The present invention will be described in detail below.
The aggregated particles according to the present invention are aggregated particles having an average particle diameter of 10 to 200 μm made of a specific urethane-acrylic composite resin.

  The urethane-acrylic composite resin comprises a urethane prepolymer (a) containing an isocyanate group and a carboxyl group (hereinafter referred to as “(a) component”) and a polymerizable monomer (b) (hereinafter referred to as “( a composite resin obtained by polymerizing the component (b) contained in the first emulsion obtained by emulsifying and dispersing the mixed solution with the component b).

  The carboxyl group-containing urethane prepolymer (a) as the component (a) refers to a urethane prepolymer containing an isocyanate group and a carboxyl group. The component (a) may be partly chain-extended in the polymerization step of the component (b) by an aqueous medium such as water used for emulsification and dispersion. If necessary, the chain may be extended with a compound having a plurality of active hydrogens capable of reacting with an isocyanate group or with water. The water used in the emulsification dispersion and the compound or water having a plurality of active hydrogens capable of reacting with isocyanate groups, which are used for positive chain extension, are collectively referred to as “chain extender” hereinafter. Called.

  The said urethane prepolymer means the polymer which has the carboxyl group which made the diol component and the polyvalent isocyanate compound react, and has an isocyanate group at the terminal.

  As a method for introducing an isocyanate group into the component (a), the diol component and the polyvalent isocyanate compound are reacted at a ratio in which the polyvalent isocyanate compound is stoichiometrically excessive with respect to the diol component. There are methods. Thereby, the component (a) having an isocyanate group at the terminal is obtained.

  The use ratio of the diol component and the polyvalent isocyanate compound is an equivalent ratio, and diol component: polyvalent isocyanate compound = 1: 1.2-2 is preferable, and 1: 1.5-1.9 is preferable.

  The diol component refers to an organic compound having two hydroxyl groups in one molecule. Specific examples thereof include ethylene glycol, propylene glycol, 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, triethylene glycol, tetraethylene glycol, dipropylene glycol, Dicarboxylic acids such as adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid, isophthalic acid, etc., with relatively low molecular weight diols such as tripropylene glycol, hexanediol, cyclohexanedimethanol, etc. Polyester diols obtained by polycondensation with at least one acid, polyethylene glycol, polypropylene glycol, polycaprolactone diol, polytetramethylene ether diol, polycarbonate diol, polybutadiene diol, hydrogenated polybutadiene diol, polyacrylate diol, etc. can give.

  The said polyvalent isocyanate compound means the organic compound which has at least 2 isocyanate group in 1 molecule, and polyhydric isocyanate compounds, such as aliphatic, alicyclic, and aromatic, can be used. Specific examples of such polyvalent isocyanate compounds include dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 2,4-tolylene diene. Examples include isocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, and the like. Of these, aliphatic or cycloaliphatic isocyanates are preferred in that they have less yellowing.

  Moreover, the said (a) component needs to have a carboxyl group. By neutralizing the carboxyl group, it becomes a carboxylate and can exhibit surface activity, so that the obtained urethane-acrylic resin becomes a self-emulsifying resin.

  The acid value of the component (a) is preferably 15 mgKOH / g or more, and more preferably 20 mgKOH / g or more. If it is less than 15 mgKOH / g, the state of dispersion in water in the subsequent step is deteriorated and an aqueous dispersion cannot be obtained. On the other hand, the upper limit is preferably 100 mgKOH / g, more preferably 80 mgKOH / g or less. If it exceeds 100 mgKOH / g, it may become hard and lose its elasticity.

  Examples of the method for introducing a carboxyl group into the component (a) include a method using a carboxyl group-containing polyvalent hydroxy compound as a part of the diol component. As this carboxyl group-containing polyvalent hydroxy compound, dimethylolalkanoic acid as shown in the following chemical formula (1) is preferable.

  In the above formula (1), R represents an alkyl group having 1 to 20 carbon atoms, preferably a methyl group or an ethyl group.

  Specific examples of the dimethylolalkanoic acid include dimethylolpropionic acid and dimethylolbutanoic acid. What is necessary is just to adjust the usage-amount of the said carboxyl group containing polyhydric hydroxy compound so that the acid value of the said (a) component formed by superposition | polymerization may become the above-mentioned range.

  In producing the component (a) by polymerization, a desirable use ratio of the carboxyl group-containing polyvalent hydroxy compound used as a part of the diol component is the total of the diol component and the carboxyl group-containing polyvalent hydroxy compound. 30 mol% or more, and more preferably 50 mol% or more. On the other hand, it is good that it is 90 mol% or less, and it is more preferable that it is 80 mol% or less. By setting it within this range, the above acid value range can be satisfied.

  The urethane formation reaction for producing the component (a) can be carried out in the absence of a solvent, but in order to carry out the reaction uniformly, ethers such as dioxane, ketones such as acetone and methyl ethyl ketone, dimethylformamide, Amides such as dimethylacetamide and N-methyl-2-pyrrolidone, and other organic solvents which are inert to isocyanate groups and have a high affinity for water may be used. Moreover, the said (b) component which is not reactive with an isocyanate group, ie, does not contain an active hydrogen group, may exist at the time of manufacture of this (a) component. In this case, the reaction system is diluted by the component (b), and the reaction can be performed uniformly. The reaction for obtaining the component (a) may be performed at about 50 to 100 ° C. for about 0.5 to 20 hours. Thereby, (a) component which contains an isocyanate group in a carboxyl group and the terminal can be obtained.

  As a catalyst used for manufacture of the said (a) component, the catalyst generally used for a urethanation reaction can be used. Specific examples include dibutyltin dilaurate.

  The number average molecular weight of the component (a) is preferably 800 to 10,000, more preferably 1000 to 9000. When the number average molecular weight is less than 800, the resulting film becomes hard, and problems such as a feeling of stickiness may occur when used as a cosmetic. On the other hand, if it is greater than 10,000, the viscosity of the prepolymer itself becomes high, and gelation may occur or a stable emulsion may not be obtained.

  It is preferable that at least a part of the carboxyl group contained in the component (a) is neutralized with a basic compound. By doing in this way, the dispersibility in the aqueous medium of (a) component 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 component (a) is produced and before being dispersed in the aqueous medium. Among these, it is preferable to perform in the 1st neutralization process mentioned later and the 2nd neutralization process mentioned later as needed.

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

  The total amount of these basic compounds used is, for example, as a total amount used in the first neutralization step and the second neutralization step, which will be described later, with respect to the carboxyl group amount of the component (a). It is preferably 8 equivalents or more, more preferably 1 equivalent or more. If it is less than 0.8 equivalent, neutralization becomes insufficient, and 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 component (a) 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 chain extension reaction of the component (a) is performed using the chain extender, that is, a compound having a plurality of active hydrogens capable of reacting with an isocyanate group or water (including water as the aqueous medium). .

  Examples of the compound having a plurality of active hydrogens capable of reacting with an isocyanate group which is a kind of chain extender include polyfunctional alcohols having 1 to 8 carbon atoms and polyamine compounds. Examples of the polyfunctional alcohol include ethylene glycol and diethylene glycol. Examples of polyamine compounds include diamines such as ethylene diamine, hexamethylene diamine, and isophorone diamine.

  In the chain elongation reaction, when the first emulsion obtained by emulsifying and dispersing the mixed solution containing the component (a) and the polymerizable monomer (b) in the aqueous medium is obtained, water is used as the aqueous medium. When this is used, the water may cause a part of the chain elongation reaction of the component (a) in the polymerization step of the component (b). Moreover, when performing chain | strand extension reaction positively, the said chain | strand extender can be added and the chain | strand extension reaction can be performed after the emulsification dispersion | distribution which obtains this 1st emulsion. And the chain | strand extension reaction should just occur about at least one part of (a) component contained in a 1st emulsion. Also, after polymerizing the component (b) contained in the first emulsion or the second emulsion obtained by subjecting at least a part of the component (a) contained in the first emulsion to a chain extension reaction In addition, at least a part of the component (a) or the component derived from the component (a) contained in these emulsions may be positively chain extended. In addition, although said (a) component was chain extended | stretched with water or the active hydrogen containing compound in the chain extension process during emulsion polymerization, a part of isocyanate group may remain unreacted. is there. This remaining component was referred to as “the component derived from the component (a)”.

  The polymerizable monomer (b) as the component (b) is a monomer having a polymerizable double bond, and among them, a polymerizable monomer that is not reactive with an isocyanate group, that is, an active monomer. A polymerizable monomer containing no hydrogen group is preferred.

  Examples of such a polymerizable monomer not containing component (b), particularly an active hydrogen group, include (meth) acrylic monomers such as (meth) acrylic acid alkyl esters having 1 to 24 carbon atoms. , Ester group-containing vinyl monomers, styrene derivatives, vinyl ether monomers, and the like.

  Examples of the (meth) acrylic acid alkyl ester having 1 to 24 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, ( (Meth) butyl acrylate, (meth) acrylate isobutyl, (meth) acrylate s-butyl, (meth) acrylate t-butyl, (meth) acrylate pentyl, (meth) acrylate s-pentyl, (meth) 1-ethylpropyl acrylate, 2-methylbutyl (meth) acrylate, isopentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, neopentyl (meth) acrylate, (meta ) Hexyl acrylate, 2-methylpentyl (meth) acrylate, 4-methylpentyl (meth) acrylate Ruthel, 2-ethylbutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-heptyl (meth) acrylate, 3-heptyl (meth) acrylate, Octyl (meth) acrylate, 2-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, (3,3,5-acrylic acid) Trimethylhexyl, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) acrylate, (meth) acrylic acid Docosyl, Tetracosyl (meth) acrylate, Methylsic (meth) acrylate Hexyl, (meth) acrylic acid isobornyl (meth) norbornyl acrylate, (meth) acrylate, benzyl (meth) phenethyl acrylate are exemplified. Among these, (meth) acrylic acid alkyl esters having 1 to 24 carbon atoms, particularly (meth) acrylic acid alkyl esters having 1 to 8 carbon atoms are preferable. “(Meth) acryl” means “acryl or methacryl”.

  Specific examples of the ester group-containing vinyl monomer include (meth) acrylic acid lower alkyl esters having 1 to 8 carbon atoms, vinyl acetate, diethyl maleate, dibutyl maleate, vinyl (meth) acrylate, and the like. And a hydrophobic vinyl monomer, a fluoroalkyl ester of (meth) acrylic acid, an unsaturated group-containing macromonomer such as a radically polymerizable unsaturated group-containing silicon macromonomer, and the like.

  Examples of the styrene derivative include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene and the like.

  Specific examples of the vinyl ether monomer include vinyl methyl ether and vinyl cyclohexyl ether.

  Only one type of these (b) components may be used, or a plurality of types may be mixed and used.

In addition, when it is a copolymer, the calculation method of the glass transition temperature is based on following formula (1). Here, 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 respective monomers a, b, c, etc. Wa, Wb, Wc, etc. indicate the weight fraction of each monomer a, b, c in the copolymer.
1 / Tg = (Wa / Tga) + (Wb / Tgb) + (Wc / Tgc) + (1)

Next, the manufacturing method of the said urethane-acrylic composite resin is demonstrated.
The urethane-acrylic composite resin can be obtained by first producing an aqueous emulsion of a urethane-acrylic composite resin and then spray drying.

  The aqueous emulsion of the urethane-acrylic composite resin is prepared by preparing a mixed liquid obtained by mixing the component (a) and the component (b), and then emulsifying and dispersing the mixed liquid in an aqueous medium. It is obtained by polymerizing the component (b) to produce an aqueous emulsion of the urethane composite resin (A). In the middle of the process, the chain extension reaction of the component (a) is performed as necessary.

  First, a method of obtaining a mixed solution containing the component (a) and the component (b) is finally obtained by neutralizing at least a part of the carboxyl group to make it water-dispersible (a) component and (b) Any method may be used as long as the components are uniformly dispersed in the aqueous medium, and the addition timing of the component (b) is not particularly limited.

  Examples thereof include a method of adding the component (b) before neutralizing at least a part of the carboxyl groups in the component (a) and a method of adding the component after neutralization. Further, a part or all of the component (b) is mixed with the diol component or the polyvalent isocyanate compound which is the raw material of the component (a), and the diol component, the polyvalent isocyanate is added in the presence of the component (b). The component (a) may be produced by reacting a compound, a carboxyl group-containing polyvalent hydroxy compound and the like. At this time, when the remaining amount of the component (b) is added after the production of the component (a), the remaining component (b) is added before, simultaneously with or after neutralizing the carboxyl group in the component (a). It may be added at any time.

  Among them, the method of obtaining the component (a) by reacting the diol component, the carboxyl group-containing polyvalent hydroxy compound and the polyvalent isocyanate in the presence of the component (b) includes the components (a) and ( This is preferable because a mixed liquid in which the component b) is well mixed is obtained (hereinafter, this step is referred to as a “prepolymerization step”).

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

  The mixing ratio of the component (a) and the component (b) in the above-mentioned mixed solution is preferably (a) :( b) = 10: 90 to 90:10, and 30:70 to 80: 20 is preferred. When the component (a) is less than 10% by weight, emulsification becomes insufficient during synthesis, causing gelation during water dispersion or forming a non-uniform water dispersion. On the other hand, if it exceeds 90% by weight, the number of unreacted isocyanate groups increases, and the reaction between the isocyanate groups and water occurs frequently during emulsification, which may cause poor phase inversion.

  The concentration of the liquid mixture of the component (a) and the component (b) is not particularly limited, but the amount of nonvolatile components in the finally obtained aqueous emulsion composition is 20% by weight or more. It is preferable to make it 30% by weight or more. 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, more preferably 60% by weight or less. If it exceeds 70% by weight, preparation of water dispersibility may be difficult.

  Next, when the carboxyl group in the component (a) is not neutralized at all, the basic compound is added to the liquid mixture of the component (a) and the component (b), and the component (a) is contained. It is preferable to neutralize at least a part of the carboxyl group to be obtained to obtain a neutralized product of component (a) (first neutralization step).

  When the amount of the carboxyl group neutralized by the first neutralization step is 0.8 equivalent or more, the second neutralization step (second neutralization step) described later may not be performed. On the other hand, when it is less than 0.8 equivalent, the second neutralization step described later is performed as necessary.

  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 “emulsification step”). As a method of adding an aqueous medium to the mixed liquid of the neutralized product of the component (a) and the component (b), a method in which the aqueous medium is dropped into the mixed liquid and dispersed, and the mixed liquid is added to the aqueous medium. Either method of dropping and dispersing may be used. The temperature at the time of dispersion can employ the same temperature as the temperature at which the component (a) is dispersed in the aqueous medium.

  The temperature during emulsification dispersion is preferably 0 ° C. or higher, and preferably 10 ° C. or higher. On the other hand, 80 degrees C or less is good and 60 degrees C or less is preferable. This is because the component (a) may be denatured if the temperature is too high.

  Next, in the emulsified and dispersed dispersion obtained as described above, the emulsified and dispersed component (b) is polymerized to obtain an aqueous emulsion of the urethane-based composite resin (A) (hereinafter, this step is referred to as “step”). Referred to as "polymerization step"). The polymerization reaction during the polymerization of the component (b) can be performed by a general polymerization method according to the component (b), for example, by adding a radical polymerization initiator to the mixed solution. it can.

  As the radical polymerization initiator, a conventional radical polymerization initiator may be used. For example, azo initiators such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyanovaleric acid, and persulfuric acid. Persulfate initiators such as sodium, potassium persulfate, ammonium persulfate, t-butyl hydroperoxide, dilauroyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, etc. An organic peroxide-based initiator can be used. A redox polymerization initiator in which an organic peroxide initiator or persulfate initiator is combined with a reducing agent such as ascorbic acid, Rongalite or metal sulfite 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 performed at a polymerization temperature of 10 to 80 ° C, more preferably 30 to 60 ° C. This polymerization is usually almost completed by maintaining the temperature at about 40 to 90 ° C. for about 30 minutes to 3 hours after the end of heat generation. Thereby, the aqueous emulsion of urethane type composite resin (A) is obtained.

  By the way, in any one place between said emulsification process and a polymerization process and between the said polymerization process and a deodorizing process, (a) component (The neutralized product of (a) component is included as needed. Hereinafter, the same applies) or at least a part of the component derived from component (a) may be chain-extended. Further, part of the component (a) is chain-extended between the emulsification step and the polymerization step, and chain extension is performed between the polymerization step and the deodorization step by the chain extension step. Alternatively, at least a part of the component (a) remaining or the component derived from the component (a) may be chain extended.

  Since the chain extension reaction of component (a) occurs gradually in the emulsion and also with water as the dispersion medium, part of the chain extension reaction may occur during the polymerization process. However, since chain extension with water is usually slow in reaction rate, in order to perform chain extension more effectively and reliably, a chain extension reaction other than the above-described chain extension agent should be used actively. Is good. By the chain extension reaction, a urethane polymer having a chain extended more quickly can be obtained, and a flexible and elastic coating can be obtained.

  Moreover, after said emulsification process or polymerization process, you may further neutralize at least one part of the carboxyl group which (a) component contains using the said basic compound (2nd neutralization). Process). By advancing the degree of neutralization to a predetermined range, it is possible to obtain effects such as improving the storage stability of the resulting emulsion and improving the film-forming property.

  In the second neutralization step, among the carboxyl groups derived from the component (a), when there is a carboxyl group remaining without being neutralized in the first neutralization step, the urethane prepolymer (a) is derived. The total amount of the basic compound used is preferably 0.8 equivalents or more, more preferably 1 equivalent or more based on the total carboxyl groups. In addition, when 0.8 equivalent or more of a basic compound is already used in the first neutralization step, this second neutralization step may be omitted.

  The basic compound used in the neutralization step is preferably used as an aqueous solution or an aqueous dispersion in order to facilitate addition and mixing. The neutralized urethane-based composite resin (A) is dissolved or dispersed in only water as a solvent, a mixed solvent of a polar organic solvent and water, or an organic solvent alone. Examples of the organic solvent include alcohols, ketones, and other organic solvents. Examples of alcohols include alcohols containing 1 to 8 carbon atoms including ethanol, propanol, isopropanol, butanol, benzyl alcohol, phenylethyl alcohol, polyalcohols such as alkylene glycols such as glycerin, ethylene glycol, and propylene glycol. Can be given. Examples of ketones include acetone and methyl ethyl ketone. 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 give.

  The urethane-acrylic resin is preferably a self-emulsifying resin. Self-emulsifying urethane resin can be emulsified and dispersed in water without using an emulsifier, etc., by having “hydrophilic” functional groups such as carboxyl groups and sulfonic acid groups and hydrophilic segments in the urethane polymer molecule. Resin. For example, commercially available urethane resins such as Superflex (Daiichi Kogyo Seiyaku Co., Ltd.) and Takelac W (Mitsui Chemicals Co., Ltd.) can be exemplified, but the present invention is not limited thereto. After synthesizing using a diol having a carboxyl group (for example, dimethylolpropionic acid or dimethylolbutanoic acid) or having a sulfonic acid group, at least a part of the acidic groups in the obtained polyurethane It can also be manufactured by adding.

  Aggregated particles according to the present invention can be produced by spray drying the aqueous emulsion of urethane-acrylic composite resin obtained by the above production method.

  The urethane-acrylic composite resin obtained by the above production method preferably has a weight average molecular weight of 100,000 or more, and preferably 700,000 or more. If it is smaller than 100,000, solvent resistance and heat resistance may be lowered. On the other hand, the upper limit of the weight average molecular weight is preferably 7 million, and preferably 6 million. If it is larger than 7 million, the resin tends to become hard as a whole.

  The gel fraction of the urethane-acrylic composite resin obtained by the above production method is preferably 10% by weight or more, and preferably 15% by weight or more. If it is less than 10% by weight, the solvent resistance and heat resistance may decrease. On the other hand, the upper limit of the gel fraction amount is preferably 99% by weight, and preferably 95% by weight. When it is larger than 99% by weight, the flexibility tends to be insufficient.

  The loss coefficient (tan δ) of the urethane-acrylic composite resin used in the present invention is preferably in the range of −50 or more and 20 or less. When this value is in the above range, when used as a cosmetic, moderate flexibility and elasticity can be imparted to the hair and skin. In particular, when the aggregated particles of the present invention are blended in a cosmetic containing a large amount of oily components to improve the sticky feeling due to the oily components, the cosmetics become rough when tan δ exceeds the above range. A feeling may come out and usability may be impaired. On the other hand, if tan δ is less than the above range, the particles are too soft and the effect of addition is not sufficiently obtained.

  The solid concentration in the aqueous emulsion of the urethane-acrylic composite resin subjected to spray drying is preferably 20% by weight or more, and preferably 25% by weight or more. If it is 20% by weight or less, the concentration of the active ingredient is low, and as a result, the amount of water to be evaporated increases, so that much energy for heating is consumed. On the other hand, the upper limit of the solid content concentration is preferably 50% by weight, and preferably 45% by weight. If it is larger than 50% by weight, the viscosity of the spray liquid becomes so high that good droplets cannot be obtained, or adhesion to the inner surface of the sprayer or dryer may occur.

  The spray drying can be performed using a spray dryer such as a rotary disk (rotary disc) spray dryer or a two-fluid nozzle spray dryer.

  The spray drying conditions for producing the agglomerated particles of the present invention are adjusted according to the physical properties of the raw material resin and the properties of the produced agglomerated particles (resin composition, glass transition temperature and particle size, target particle size of the agglomerated particles, etc.). do it. Items that can be adjusted as drying conditions include drying temperature (dryer air inlet / outlet temperature), spray conditions (rotary disk dryer for disk rotation, two-fluid nozzle dryer for gas-liquid flow rate) Ratio, supply liquid flow rate, dry gas flow rate, etc.).

Although the urethane-acrylic composite resin particles are formed by the spray drying, the particles are not primary particles in an emulsified state but are aggregated particles in which the primary particles are aggregated. The average particle diameter of the aggregated particles needs to be 10 μm or more, and preferably 50 μm or more. If it is smaller than 10 μm, the tactile sensation as particles may not be obtained when used as a cosmetic. On the other hand, the upper limit of the average particle diameter needs to be 200 μm, and preferably 160 μm. When it is larger than 200 μm, the feeling of use may be deteriorated due to roughness.
The particle diameter of the agglomerated particles can be controlled by adjusting the spraying conditions (disk rotational speed, gas-liquid flow rate ratio, etc.) in consideration of the properties (concentration, viscosity, etc.) of the resin dispersion supplied.

  In addition, the scheme of the preferable manufacturing method of the aggregated particle concerning this application is shown in FIG.

  The agglomerated particles according to the present application can be used as cosmetics, particularly cosmetics applied to the skin, by making a paste. In this paste, materials usually used in cosmetics such as oil agents such as solid oil agents, powder components such as pigments, solvents such as liquid alcohols, and the like are added to and mixed with the above aggregated particles according to the purpose and purpose. Can be obtained.

Examples of powder components such as pigments that can be used in the present invention include the following.
(1) Dyes such as Red No. 104, Red No. 102, Red No. 226, Red No. 201, Red No. 202, Yellow No. 4, Black No. 401,
(2) Lake No. 1 aluminum lake, yellow No. 4 aluminum lake, yellow No. 5 aluminum lake, yellow No. 203 barium lake and other lake dyes,

(3) Powdered polymers such as nylon powder, silk powder, urethane powder, Teflon (registered trademark) powder, silicone powder, polymethyl methacrylate powder, cellulose powder, silicone elastomer spherical powder, polyethylene powder,
(4) Colored pigments such as yellow iron oxide, red iron oxide, black iron oxide, chromium oxide, carbon black, ultramarine and bitumen,

(5) White pigments such as zinc oxide, titanium oxide, cerium oxide, extender pigments such as talc, mica, sericite, kaolin, plate-like barium sulfate,
(6) Pearl pigments such as titanium mica, bengara-coated mica titanium, carmine-coated mica titanium, bitumen-coated mica titanium, black iron oxide-coated mica titanium,

(7) Metal salts such as barium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate, magnesium silicate,
(8) Inorganic powders such as silica and alumina,
(9) 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. The shape (spherical, rod-like, needle-like, plate-like, indefinite shape, flake-like shape, spindle-like shape) is not particularly limited.

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

  In addition, it is also possible to use a mixture color that is adjusted to a desired color such as skin color, and further to use UV scattering components such as fine particle titanium oxide and fine particle zinc oxide to protect the compound from ultraviolet rays. It is also possible to add functions.

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

Examples of oil agent components that can be used in the present invention include the following.
(1) Fatty acids such as isostearic acid, undecylenic acid, oleic acid,
(2) Fatty acid esters such as myristyl myristate, hexyl laurate, decyl oleate, isopropyl myristate, hexyl decyl dimethyloctanoate, glyceryl monostearate, diethyl phthalate, ethylene glycol monostearate, octyl oxystearate,

(3) Higher hydrocarbons such as liquid paraffin, paraffin, petrolatum, squalane, lanolin, reduced lanolin, carnauba wax, candelilla wax, ceresin, ozokerite, microcrystalline wax and so-called wax, mink oil, cocoa butter, coconut oil, Oils and fats such as palm kernel oil, camellia oil, sesame oil, castor oil, olive oil,
(4) Polyethylene wax, ethylene / α-olefin / co-oligomer, medium to low molecular weight synthetic polymer in ethylene propylene,

(5) 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,
(6) Fluorine compounds such as perfluoropolyether, fluorocarbon, and fluoroalcohol.

Examples of the solvents such as the liquid alcohol include the following.
(1) Lower alcohol: ethanol, isopropyl alcohol, etc.
(2) Higher alcohol: cetyl alcohol, isostearyl alcohol, lauryl alcohol, hexadecyl alcohol, octyldodecanol, etc.

(3) Polyhydric alcohol: Polyhydric alcohol such as glycerin, sorbitol, ethylene glycol, propylene glycol, 1.3 butylene glycol, polyethylene glycol, etc.
(4) 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 components, the cosmetics of the present invention include fluorine compounds, various resins, surfactants, surfactants, preservatives, perfumes, ultraviolet absorbers (organic) that are commonly used in cosmetics. System, inorganic system (which may correspond to UV-A or B), physiologically active ingredients, salts, antioxidants, chelating agents, neutralizing agents, pH adjusting agents, etc. As long as the object and effect of the invention are not impaired, they can be appropriately blended.

  The content ratio of the aggregated particles in the paste is usually 0.5% by weight to 99% by weight, and preferably 5% by weight to 95% by weight. If the amount is less than 0.5% by weight, the effect due to the blending of the aggregated particles may not be sufficiently obtained. On the other hand, if the amount exceeds 99% by weight, the feeling of use may be deteriorated or the cosmetic composition as a blend may be deteriorated. The fluidity may deteriorate, and the extensibility may be impaired when applied to the skin or hair.

  The content ratio of the pigment in the paste is generally 0.1% by weight to 20% by weight, preferably 0.2% by weight to 7% by weight. If it is less than 0.1% by weight, color control properties due to addition of pigments such as coloring and hiding may be insufficient. On the other hand, when the pigment or the like is blended in excess of 20% by weight, the coloring may be unfavorable as a cosmetic, or the blending ratio of other raw materials may be lowered, resulting in insufficient basic performance.

  The content of the oil agent such as the solid oil agent in the paste is generally 1% by weight to 95% by weight, and the preferable content is 2% by weight to 60% by weight. If it is less than 1% by weight, the familiarity to the skin at the time of application or immediately after application may be deteriorated. On the other hand, if it is added in excess of 95% by weight, the sticky feeling becomes remarkable and the feeling of use tends to deteriorate.

  The content of the solvent such as the liquid alcohol in the paste is generally 1% by weight to 95% by weight, and preferably 2% by weight to 70% by weight. If it is less than 1% by weight, the familiarity with the skin may be insufficient, and the effects of moisturizing and other additions may not be obtained. On the other hand, if it is blended in a large amount exceeding 95% by weight, the relative content of other blended components decreases, and for example, the adhesion and fixation of the powder component to the skin and hair is inhibited, and the effect as a cosmetic is obtained. There may be a shortage.

  In addition to the various components described above, other optional components may be added to the paste as necessary within a range that does not affect the effects of the present invention. These optional components include hydrocarbons, linear alcohols, higher alcohols, higher fatty acids and derivatives thereof, plant polymers, microbial polymers, natural water-soluble polymers, cellulose polymers, semi-synthetic water-soluble compounds. Polymer, vinyl polymer, polyoxyethylene polymer, synthetic water-soluble polymer, inorganic water-soluble polymer, silicone, N-fatty acid acyl-L-glutamate, N-fatty acid-N-methyltaurine salt , N-fatty acid sarcosine condensate salts, surfactants other than the above-mentioned surfactants, emulsifiers, moisturizers, antibacterial agents, vasodilators, refreshing agents, stimulating agents, vitamins, bactericidal and antiseptics Agents, chelating agents, pH adjusting agents, foam increasing agents, foaming agents, foam stabilizers and the like. Furthermore, when the set product or the product with the conditioning function is an aerosol product, a propellant such as liquefied petroleum gas or dimethyl ether, a metal ion scavenger, a fungicide, a disinfectant, an emulsion, a conditioning agent, an increase Examples include stickiness agents, antioxidants, solubilizers, rosin, hydrotropes, hair nourishing agents, herbal medicines, pigments, and fragrances.

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

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

  Examples of the higher fatty acids and derivatives thereof include lauric acid, myristic acid, palmitic acid, stearic acid, behen (behenyl) acid, oleic acid, 1,2-hydroxystearic acid, undecylenic acid, tallic acid, lanolin fatty acid, isostearic acid Linoleic acid, α-linolenic acid, γ-linolenic acid, eicosapentaenoic acid and the like.

  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, 40,000, 60,000 and the like. Examples of the synthetic water-soluble polymer include polyethyleneimine. Examples of the inorganic water-soluble polymer include bentonite, AlMg silicate (beegum), labonite, hectorite, and silicic anhydride.

  Examples of the silicones include volatile silicone oil, silicone resin, silicone gum, and alkyl-modified silicone. Examples of the N-fatty acid acyl-L-glutamate include N-lauryl-L-glutamate monosodium, N-coconut oil fatty acid-L-glutamate monotriethanolamine, N-myristylate acyl-L-glutamate monosodium, N -Mixed fatty acid acyl-monosodium L-glutamate and the like.

  Examples of the N-fatty acid-N-methyl taurate include methyl taurine sodium laurate 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.

  Examples of the 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, etc. Can be given.

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

  Examples of the humectant include (poly) ethylene glycol, (poly) propylene glycol, glycerin, 1,3-butylene glycol, maltitol, sorbitol, chondroitin sulfate, hyaluronic acid, atelocollagen, cholesteryl-1,2-hydroxystearate, Examples thereof include sodium lactate, bile salt, dl-pyrrolidone carboxylate, short chain soluble collagen and the like.

  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 stimulus imparting agent include benzyl nicotinate. Examples of the vitamins include vitamins A, B, C, D, E and the like.

  Examples of the antiseptic preservative include chlorhexidine gluconate, isopropylmethylphenol, p-hydroxybenzoate 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 adjusting agent include succinic acid, sodium succinate, triethanolamine and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely using an Example, this invention is not limited by a following example. First, raw materials to be used will be described.

<Diol component>
Teslac 2461: manufactured by Hitachi Chemical Polymer Co., Ltd .: hexanediol adipate, hydroxyl value: 56 mgKOH / g (hereinafter referred to as “TL2461”)
Plaxel CD220: manufactured by Daicel Chemical Industries, Ltd .: 1.6 hexanediol carbonate diol, hydroxyl value: 56 mg KOH / g (hereinafter referred to as “CD220”)
PTMG2000: manufactured by Mitsubishi Chemical Corporation: polytetramethylene ether glycol, hydroxyl value 56 mgKOH / g (hereinafter referred to as “PTMG2000”)
Highflex D2000 manufactured by Daiichi Pharmaceutical Co., Ltd .: Polypropylene glycol, hydroxyl value 56 mgKOH / g (hereinafter referred to as “D2000”)

<Polyisocyanate compound>
Isophorone diisocyanate: manufactured by Degussa-Huls: VESTANAT IPDI (hereinafter referred to as “VES”)
Isophorone diisocyanate: Sumika Bayer Urethane Co., Ltd .: Death Module W (hereinafter referred to as “D-W”)

<Carboxyl group-containing polyvalent hydroxy compound (self-emulsifying group raw material)>
・ Dimethylolpropionic acid: Guangei Perstorp Co., Ltd. (hereinafter referred to as “DMPA”)
Dimethylolbutanoic acid: manufactured by Nippon Kasei Co., Ltd. (hereinafter referred to as “DMBA”)

<Polymerizable monomer>
・ Methyl methacrylate: Mitsubishi Rayon Co., Ltd. (hereinafter referred to as “MMA”)
N-butyl acrylate: manufactured by Mitsubishi Chemical Corporation (hereinafter referred to as “BA”)

<Neutralizing agent>
Triethanolamine: Shell Chemicals Japan: TEA99 (hereinafter referred to as “TEA”)
-Potassium hydroxide ... Wako Pure Chemical Industries, Ltd .: Reagents-Triethylamine ... Daicel Chemical Industries, Ltd.

<Radical polymerization initiator>
T-Butyl hydroperoxide with a purity of 70% by weight: Kayaku Akzo Co., Ltd .: Kayabutyl H-70 (hereinafter referred to as “tBPO”).
Ascorbic acid: Takeda Pharmaceutical Co., Ltd .: Vitamin C (indicated in the table as “VC”)

(Test method)
Hereinafter, each test method will be described.
<Glass transition temperature (Tg)>
According to the formula (1), the Tg of the polymer was calculated from the Tg and weight fraction of each polymerizable monomer used.

<Acid value of component (a)>
About 1 g of sample is dissolved in 40 ml of THF.
Then, using an automatic titrator (COM-555 (manufactured by Hiranuma Sangyo Co., Ltd.)), 0.1 mol / l potassium hydroxide solution (methanolic) (N / 10) was continuously added to change the pH to the maximum. The local point is found, and the acid value of the sample is calculated according to the following formula.
Acid value = concentration of KOH used (mol / l) x molecular weight of KOH (g / mol) x factor x titer (ml) / (sample amount (g) x non-volatile content (%) / 100)

<Emulsion solids ratio>
Spread 1 g of sample on an aluminum foil pan and weigh accurately. After weighing, leave at room temperature for 12 hours or more, then dry in the center of a thermostatic chamber maintained at 105 ± 2 ° C for 180 ± 5 minutes, let cool in a desiccator, weigh its mass, To calculate the solid content.
N = Wd / Ws × 100
(N: non-volatile content (%), Wd: mass of sample after drying (g), Ws: mass of sample before drying (g))

<Weight average molecular weight>
20 mg of the aggregated particles are made up to 10 ml with THF and dissolved (room temperature / 24 hrs). The sample is filtered through a filter, 1 μl is injected, and measurement is performed using the following conditions and apparatus. The peak area obtained on the chromatogram is converted into PMMA, and the weight average molecular weight is obtained.
Filter: GL chromatodisc 13N pore size 0.45 μl (GL Science)
・ Device: LC-20AD (manufactured by Shimadzu Corporation)
・ Column: PLgel MIXED-B (manufactured by Polymer Laboratory)
-Column temperature: 40 ° C
・ Flow rate: 1 ml / min
-Mobile phase: THF
・ Detector: RI
Standard: PMMA (polymethyl methacrylate, standard molecular weight sample (commercially available))

<Particle size of particles after spray drying>
It was measured with a laser diffraction particle size distribution analyzer (dry type, SALD-2200 (manufactured by Shimadzu Corporation)). The median diameter is treated as the average particle diameter of the sample.

<Tanσ>
The raw material emulsion is formed into a film so as to have a thickness of about 1 mm. The film is cut into 30 × 5 mm strips, which are used as test pieces.
The test piece is mounted on the apparatus, measured in the following temperature-dependent mode, and the peak top of tan δ is detected.
(Temperature-dependent mode conditions)
Temperature: -100 to 200 ° C
Temperature increase rate: 5 ° C / min
Frequency: 11Hz
Test apparatus: Rheogel-E4000 (manufactured by UBM)

<Productivity>
The suitability of aggregated particle production by spray drying based on the test sample was evaluated by observing the operating conditions and adhesion after operation when spray drying the aqueous emulsion with a spray dryer.
(Evaluation 1)
Those satisfying the following two items are judged by "Evaluation 2". Those that do not satisfy are marked with “x”.
1) The pump can be continuously supplied to the dryer by pump for more than 1 hour. 2) The adhesion to the inside of the device and the adhesion to the disk after 2 hours of operation are almost not observed by visual observation (Evaluation 2).
100 g of the obtained agglomerated particles were sieved with a 2 mm gold cage, the amount of particles remaining on the sieve was measured, and evaluated according to the following criteria.
More than 30g (30% by weight) on sieve: x
Sieving amount 10 g or more and less than 30 g (10 wt% or more, less than 30 wt%): Δ
Less than 10 g on sieve (less than 10% by weight): ○

<Feel>
A sample in which 3% of aggregated particles were added to 1,3-butanediol (manufactured by Wako Pure Chemical Industries, Ltd., special grade) was prepared. The sample was blended with the back of the hand to confirm the feel and evaluated according to the following criteria.
○: The absence of stickiness can be remarkably confirmed as compared with the case of no addition.
Δ: Same as unadded product.
X: It is more sticky than the non-added product.

<Compounding stability>
After the sample used in the touch evaluation was stored at room temperature for 1 week, the presence or absence of a change from the initial state was visually confirmed.
○: Initial and no change.
X: Changes such as thickening and aggregation are confirmed.

(Examples 1-5, Comparative Example 1)
To a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, add the diol component, the self-emulsifiable base material, and the polymerizable monomer shown in Table 1 in the amounts shown in the above to an internal temperature of 50 ° C. Then, the polyisocyanate compound was added in the amounts shown in Table 1, 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.

  Next, while maintaining the obtained carboxyl group-containing urethane prepolymer solution at 50 ° C., the neutralizing agent shown in Table 1 was added to neutralize all or part of the carboxyl groups in the carboxyl group-containing urethane prepolymer. did. Subsequently, ion-exchanged water as described above was added dropwise to this solution so that the final emulsion nonvolatile content was 30% at 50 ° C. over 15 minutes to obtain a milky white transparent dispersion.

Thereafter, this dispersion was kept at 50 ° C., and at this temperature, radical polymerization catalysts (tBPO and VC) were added in the stated amounts to initiate polymerization of the polymerizable monomer. After completion of heat generation, the temperature was further raised to 70 ° C. and maintained for 3 hours to obtain an aqueous emulsion containing a urethane composite resin and an unreacted polymerizable monomer.
FIG. 2 shows an electron microscope (SEM) photograph of the aggregated particles of the aqueous emulsion obtained by the method of Example 1 among the obtained aqueous emulsion.
The observation with an electron microscope was performed at a magnification of 350 times and a voltage of 20 kV using aggregated particles previously coated with platinum as a sample.

The obtained aqueous emulsion was pulverized with a rotary disk (rotating disk) type spray dryer (Okawara Chemical Co., Ltd., CL-8 type) under the following conditions (excluding Comparative Example 1). Said evaluation was performed using the obtained aqueous | water-based emulsion and powder. The results are shown in Table 1.
・ Inlet temperature: 150 ℃
・ Outlet temperature: 60 ℃
・ Rotation speed: 20000 rpm (disk diameter: 50 mm)
・ Supply amount: 80ml / min

Claims (8)

Aggregated particles made of urethane-acrylic composite resin having an average particle size of 10 to 200 μm ,
The urethane-acrylic composite resin comprises a urethane prepolymer (a) containing an isocyanate group and a carboxyl group (hereinafter referred to as “(a) component”) and a polymerizable monomer (b) (hereinafter referred to as “( b) component ”))), and obtained by polymerizing the component (b) contained in the first emulsion obtained by emulsifying and dispersing the mixture in an aqueous medium.
The component (b) is at least one unit selected from the group consisting of (meth) acrylic acid alkyl esters having 1 to 24 carbon atoms, ester group-containing vinyl monomers, styrene derivatives, and vinyl ether monomers. Agglomerated particles that are masses .   The aggregated particle according to claim 1, wherein the urethane-acrylic composite resin is a self-emulsifying resin.   The aggregated particles according to claim 1 or 2, wherein the urethane-acrylic composite resin has a weight average molecular weight of 100,000 or more and 7 million or less. The acid value of the urethane resin in the urethane-acrylic composite resin is 15 mgKOH / g or more and 100 mgKOH / g or less, and the number average molecular weight is 800 to 10,000,
The aggregated particle according to any one of claims 1 to 3 , wherein the component (b) is a (meth) acrylic acid alkyl ester having 1 to 24 carbon atoms . The carboxyl group-containing urethane prepolymer (a) is obtained by reacting a polyvalent isocyanate compound, a diol component, and a carboxyl group-containing polyvalent hydroxy compound according to any one of claims 1 to 4. The agglomerated particles described. A cosmetic comprising the aggregated particles according to any one of claims 1 to 5 and containing an oil agent and a cosmetic base material. The method for producing agglomerated particles, wherein the agglomerated particles according to any one of claims 1 to 5 are produced by spray-drying an aqueous dispersion of a urethane-acrylic composite resin having a solid content concentration of 20 to 50% by weight. . The said spray drying is a manufacturing method of the aggregated particle of Claim 7 performed using a rotary disk type spray dryer or a two fluid nozzle type spray dryer.