JP5281232B2 - Aqueous emulsion composition for cosmetics and hair cosmetics containing the same - Google Patents

Abstract

An aqueous emulsion composition which has sufficient water solubility, gives an excellent slippery feeling, combines softness with hair dressing properties, can optionally further have thermal hair dressing properties, and is reduced in odor emission. The composition comprises an aqueous urethane composite resin (A) emulsion obtained by: emulsifying/dispersing a liquid mixture comprising a carboxylated urethane prepolymer (a) containing an isocyanate group and a carboxy group and a polymerizable monomer (b) in an aqueous medium to prepare a first emulsion or subjecting at least part of the ingredient (a) contained in the first emulsion obtained through the emulsification/dispersion to chain extension with either a compound having active hydrogen atoms reactive with an isocyanate group or water to prepare a second emulsion; and polymerizing the ingredient (b) contained in the first emulsion or second emulsion. The resin (A) emulsion has a minimum film-forming temperature of -10 to 20°C. The amount of the ingredient (b) remaining in this aqueous emulsion is 100 ppm or smaller.

Description

  The present invention relates to an aqueous emulsion composition for use in cosmetics and hair cosmetics containing the same. The cosmetic for hair of the present invention is excellent in touch, has both flexibility and hair styling properties, and has thermal hair styling properties as necessary.

  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.

  Since these resin films are hard, brittle and lack flexibility, the hair feels hard 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 and vinyl methyl ether polymers tend to be very soft and sticky when hot and humid, and the hair-styling effect tends not to be sufficient.

  In order to improve the drawbacks of these resins, water-based polyurethane polymers having excellent film flexibility have been proposed. As such a polymer, Patent Document 1 discloses a composition using an aqueous dispersion of a polymer composed of composite particles obtained by polymerizing a radical polymerizable monomer in the presence of polyurethane polymer particles.

Japanese Patent No. 2587801

  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, so that the hair styling effect is insufficient. Since the resulting film was poorly slippery, the feel of the hair was not good.

  Furthermore, when a composition obtained by polymerizing a radical polymerizable monomer in the presence of the polyurethane emulsion described in Patent Document 1 is used for hair, the heat return property is improved to some extent, and the hair styling effect is also improved to some extent, Since the water-solubility is not sufficient, it is likely to remain on the hair more than necessary even after shampooing, and since the resulting film has poor sliding properties, the feel of the hair was not good. Moreover, the odor derived from the radical polymerizable monomer used for superposition | polymerization may remain.

  Therefore, the present invention has sufficient water solubility, is excellent in touch when fingered, has both flexibility and hair styling properties, has thermal hair styling properties as necessary, and has reduced odor. It is intended to provide an aqueous emulsion composition for cosmetics and a hair cosmetic containing the same.

  This invention is a first emulsion obtained by emulsifying and dispersing a mixed liquid containing a carboxyl group-containing urethane prepolymer (a) and a polymerizable monomer (b) containing an isocyanate group and a carboxyl group in an aqueous medium, or At least a part of the component (a) in the first emulsion is contained in the second emulsion obtained by chain extension with a compound having a plurality of active hydrogens capable of reacting with an isocyanate group or water after the emulsion dispersion. Containing an aqueous emulsion of urethane-based composite resin (A) having a minimum film-forming temperature of −10 ° C. or higher and 20 ° C. or lower obtained by polymerizing the component (b), and remaining in the aqueous emulsion ( The above problem was solved by using an aqueous emulsion composition for cosmetics in which the amount of component b) was 100 ppm or less.

  Since the carboxyl group-containing urethane prepolymer (a) or a chain-extended one thereof is used, sufficient water solubility of the resulting aqueous emulsion is ensured, and a smooth fingering feeling and heat returnability (including setability) are included. ) Can be secured. Furthermore, an odor can fully be reduced by making the quantity of the polymerizable monomer (b) which remains in an aqueous emulsion into 100 ppm or less.

  Further, the aqueous emulsion for cosmetics according to the present invention is various hair cosmetics such as hair sprays, mousses, set lotions, gels, sprays, etc., which are particularly excellent in adhesion to hair and have a good setting effect and texture. Can be provided.

The present invention will be described in detail below.
The aqueous emulsion composition for cosmetics according to the present invention comprises a urethane prepolymer (a) containing an isocyanate group and a carboxyl group (hereinafter referred to as “component (a)”), and a polymerizable monomer (b). (Hereinafter referred to as “component (b)”) A urethane-based composite resin (A) obtained by polymerizing the component (b) contained in the first emulsion obtained by emulsifying and dispersing a mixed solution in an aqueous medium. ) Aqueous emulsion.

  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. The acid value of the component (a) is preferably 15 mgKOH / g or more, 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 70 mgKOH / g, and more preferably 60 mgKOH / g or less. If it exceeds 70 mgKOH / g, the elasticity may be insufficient, or it may be difficult to adhere to the hair when used in a hairdressing material.

  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. Examples of this carboxyl group-containing polyvalent hydroxy compound include dimethylol alkanoic acid as shown in the following chemical formula (1).

In the above formula (1), R represents an alkyl group, 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 above 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 it is 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 component (b), particularly a polymerizable monomer containing no active hydrogen group, are (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, the component (b) is preferably a homopolymer when it is a single type, and preferably has a glass transition temperature of 1 ° C. or higher when it is composed of a plurality of types. More preferably, the temperature is higher than or equal to ° C. If it is less than 1 ° C., the heat returnability (including setability) of the resulting cosmetic may be deteriorated. On the other hand, the glass transition temperature is preferably 70 ° C. or lower, and more preferably 60 ° C. or lower. If it exceeds 70 ° C., the minimum film-forming temperature increases, and a uniform film may not be formed.

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 aqueous emulsion composition for cosmetics concerning this invention is demonstrated.
As described above, the aqueous emulsion composition for cosmetics according to the present invention is prepared by preparing a mixed solution obtained by mixing the component (a) and the component (b), and then emulsifying and dispersing the mixture in an aqueous medium. It can be obtained by producing an aqueous emulsion of the urethane-based composite resin (A) by polymerizing the component (b) in the emulsion. 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, heat returnability (including setability) when used as a hair styling agent may be deteriorated.

  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) (hereinafter, this step is referred to as “first neutralization step”).

  The amount of the carboxyl group neutralized in the first neutralization step is preferably 0.5 equivalents or more and preferably 0.55 equivalents or more based on the total carboxyl groups in the component (a).

  When the amount of the carboxyl group neutralized by the first neutralization step is 0.8 equivalent or more, the 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.

  The minimum film-forming temperature of the urethane-based composite resin (A) obtained in the polymerization step is + 20 ° C. or lower, preferably + 15 ° C. or lower. If it exceeds + 20 ° C., defects such as cracks are likely to occur in the resulting film. On the other hand, the minimum film forming temperature is −10 ° C. or higher, and preferably 0 ° C. or higher. If it is less than -10 degreeC, the heat return property (including set property) of the film obtained may deteriorate.

  In the present invention, various methods can be exemplified to control the minimum film-forming temperature of the urethane-based composite resin (A) within the above-mentioned preferable range. For example, as a method for lowering the minimum film-forming temperature, There are the methods (1) to (3). In general, in order to increase the minimum film forming temperature, a method reverse to the following method may be used.

(1) As a diol component used as a raw material for the component (a), the amount of a relatively high molecular weight diol having a molecular weight exceeding 1000 is increased.
(2) The equivalent ratio of the diol component and the polyvalent isocyanate compound used when producing the component (a) is made close to 1: 1.
(3) A component having a low glass transition temperature (Tg) is used as the component (b) used when the urethane-based composite resin (A) is produced.

  Examples of the relatively high molecular weight diol of (1) above include polyester diols obtained by condensation polymerization of relatively low molecular weight diols and dicarboxylic acids, polyalkylene glycols, and polyesters having hydroxyl groups at both ends. Examples thereof include diols having a (weight average) molecular weight of 500 or more, such as system polymers.

  Specific examples of the relatively low molecular weight diols include diols having a molecular weight of less than 500, such as ethylene glycol and propylene glycol. Specific examples of the polyalkylene glycols include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, (hydrogenated) polybutadiene diol, and the like. Furthermore, specific examples of the above-mentioned polyester polymers having hydroxyl groups at both ends include polycaprolactone diol, polycarbonate diol, polyacrylate diol and the like.

  In the aqueous emulsion of the urethane-based composite resin (A) obtained by the polymerization step, the unreacted component (b) remains, and the concentration thereof is set to 100 ppm or less in order to suppress the odor derived therefrom. It is necessary, more preferably 70 ppm or less, and closer to 0 is more preferable.

  As a method for reducing the concentration of the component (b), for example, a method of volatilizing and removing the component (b) remaining by heating the aqueous emulsion, or a method of circulating a gas such as air in the gas phase part of the emulsion. And a method of blowing water vapor into the emulsion, a method of distilling off the component (b) under reduced pressure, and the like (hereinafter, this step is referred to as “deodorizing step”).

  Specifically, a method of directly heating a container containing an aqueous emulsion, or removing residual polymerizable monomer (b) while blowing water vapor and / or gas into the aqueous emulsion while stirring as necessary. There is a way. Moreover, the concentration of the component (b) can be more effectively reduced by blowing water vapor and / or gas while heating the aqueous emulsion, or by allowing gas to flow through the gas phase.

  When the container containing the aqueous emulsion is heated, the liquid temperature of the aqueous emulsion is preferably 40 ° C. or higher, and more preferably 60 ° C. or higher. On the other hand, the liquid temperature needs to be below the boiling point of an aqueous medium, and it is preferable in it being 100 degrees C or less. In addition, when the gas is blown or circulated, the temperature of the gas is preferably 20 ° C. or higher and 100 ° C. or lower, and more preferably 60 ° C. or higher and 95 ° C. or lower. In addition, also when injecting water vapor | steam, it is preferable that the liquid temperature of aqueous emulsion satisfy | fills said conditions.

  When the gas is circulated, the flow rate (volume / time under the above gas use conditions) is not particularly limited, but it is preferably 2 to 100 times volume / min of the volume of the gas phase of the container. -80 volume times / minute is preferable. If it is less than 2 times volume / minute, the removal of component (b) tends to be insufficient. On the other hand, when the volume is more than 100 vol./min, the aqueous emulsion is scattered, a deposit film is stretched on the liquid surface, and deposits are generated on the container wall, or the (b) component removal efficiency is lowered. Sometimes.

  Moisture evaporated by heating can be supplemented as necessary after the removal of component (b). In addition, since it is not preferable to discharge the component (b) to be evaporated to the atmosphere as it is, it is preferable to collect the condensate obtained by cooling the released gases together in a tank or the like and perform wastewater treatment.

  As described above, the aqueous emulsion composition in which the residual amount of the component (b) is 100 ppm or less can be used as a cosmetic having almost no odor when used in cosmetics such as hairdressing. Furthermore, the aqueous emulsion composition for cosmetics according to the present invention has a good heat return property (including setability) when used for hair styling, and a good feel such as slipping of the hair. .

  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, at least one part of the carboxyl group which (a) component contains in at least 1 place chosen from between the said emulsification process and a polymerization process, between the said polymerization process and a deodorization process, and after the said deodorization process. May be further neutralized using the above basic compound (hereinafter, this step is referred to as “second neutralization step”). By advancing the degree of neutralization to a predetermined range, it is possible to obtain effects such as improving the storage stability of the 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 first neutralization step and the second neutralization step is preferably used as an aqueous solution or an aqueous dispersion in order to facilitate addition and mixing. The neutralized urethane-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.

  In addition, the scheme of the preferable manufacturing method of the aqueous emulsion composition for cosmetics concerning this application is shown in FIG.

  The aqueous emulsion composition for cosmetics according to the present application is added and used as a hair cosmetic resin in hair cosmetics such as known shampoos, rinses, treatments, setting agents, and permanent wave solutions. At this time, you may use together with the well-known polymer currently used conventionally. The hair cosmetic used for addition may have any shape such as liquid, cream, emulsion, spray, gel, mousse (can be ejected in a foam state).

  The amount of the aqueous emulsion composition for cosmetics added varies depending on the form and purpose of the hair cosmetic, or the type and amount of the polymer used in combination. It is preferable to add at a ratio of 0.05 to 10% by weight, and more preferable to add at a ratio of 0.1 to 8% by weight.

  The aqueous emulsion composition for cosmetics can be used alone or in combination with conventional anionic, nonionic, cationic and amphoteric known set polymers. As the set polymer used in combination, anionic and nonionic known set polymers are more preferable in terms of mixing stability.

  Examples of the anionic polymer used as the set polymer include a copolymer of (meth) acrylic acid and alkyl methacrylate (trade name: Diamond Hold (manufactured by Mitsubishi Chemical Corporation), trade name: plus size. (Manufactured by Interactive Chemical Co., Ltd.), maleic acid monoalkyl ester and methyl vinyl ether copolymer (trade name: GANTREZ (manufactured by ISP)) and the like.

  Nonionic polymers used as the above set polymer include, for example, polyvinylpyrrolidone polymer (trade name: PVP (manufactured by ISP)), vinylpyrrolidone and vinyl acetate copolymer (trade name: LUVISKOL (manufactured by BASF)), and the like. Can be given. Examples of amphoteric polymers include methacrylic acid ester copolymers (trade name: Yucaformer-AM-75W (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), trade names: polymers JR-30M-125 and -400 (union). Carbide)), quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymer (trade name: GAFQUAT 734 and 755 (manufactured by GAF)), dimethyldiallylammonium chloride polymer (trade name: MERQUAT 100 (Merck) And dimethyl diallylammonium chloride acryloamide copolymer (trade name: MERQUAT550 (manufactured by Merck & Co., Inc.)).

  Set products that use the above aqueous emulsion composition for cosmetics and set polymer include aerosol hair spray, pump hair spray, foam hair spray, hair mist, set lotion, hair styling, hair cream, hair oil, etc. In addition, known hair styling agents using water and / or alcohols such as ethanol and isopropanol as a solvent are included.

  In the case where a hair cosmetic (mousse) that can be ejected in a foam state is used as the set product, the composition is 0.01 to 10% by weight as a resin content of the cosmetic aqueous emulsion composition. Examples include 0 to 15% by weight of a polymer, 0.1 to 5% by weight of a nonionic surfactant, 3 to 25% by weight of a liquefied gas, and 60% by weight to the balance of a water-soluble solvent mainly composed of water. (However, water is contained in the hair cosmetic by 60% by weight or more).

  When gel (gel) is used as the set product, the composition is 0.01 to 10% by weight as the resin content of the cosmetic aqueous emulsion composition, 0 to 15% by weight of the known set polymer, and gel base 0 .1-3 wt%, water 72 wt% -residue.

  When a hair spray is used as the set product, the composition is 0.01 to 10% by weight as the resin content of the cosmetic aqueous emulsion composition, 0 to 15% by weight of the known set polymer, and 30 to 80% of the solvent. %, Propellant 10 to 70% by weight.

  In the mousse, a nonionic surfactant is used. Examples of the nonionic surfactant that can be used include sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, Examples thereof include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, and fatty acid alkanolamide.

  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 gas, and nitrogen gas.

  The aqueous emulsion composition for cosmetics can be used for a product with a conditioning function. In this case, the hair cosmetic intended for imparting the conditioning function has a solvent such as shampoo, rinse, permanent liquid, etc., and the solvent is water and / or alcohol such as ethanol, isopropanol, or hair treatment, or hair treatment. Examples thereof include hair cosmetics comprising water and / or alcohols such as ethanol and isopropanol, or alcohols and / or hydrocarbons having a boiling point of 50 ° C to 300 ° C. This conditioning function-imparted product is used as an aqueous emulsion composition for cosmetics alone or in combination with conventional anionic, nonionic, cationic and amphoteric known conditioning polymers in the same manner as the set products described above. . As the combination set polymer, a known anionic and nonionic set polymer is more preferable from the viewpoint of mixing stability.

  For example, when used as a shampoo, the above-mentioned aqueous emulsion composition for cosmetics can be added to a known anionic, amphoteric or nonionic surfactant base material. Examples of the surfactant base material used here include anionic surfactants such as N-coconoyl-N-methyl-β-alanine sodium, N-myristoyl-N-methyl-β-alanine sodium, and the like. N-fatty acid acyl-N-methyl-β-alanine salts and the like.

  The amphoteric surfactant base material includes 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. And oxides.

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

  Moreover, when using as rinse, an amine oxide group containing water-soluble resin can be added and used for a well-known cationic surfactant. Examples of the cationic surfactant base material include stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, and the like.

  Furthermore, when used as a permanent liquid, an amine oxide group-containing water-soluble resin is added to a known oxidizing agent such as bromates and perboric acids, and a reducing agent such as thioglycolic acid and its salts and cysteine. be able to.

  Furthermore, when used as a hair treatment, it is used together with or in place of a known cationic surfactant base material and / or a cationic polymer such as a cationic polypeptide, cationic cellulose, cationic polysiloxane or the like. An aqueous emulsion composition for cosmetics can be added and used. As this cationic surfactant base material, for example, those exemplified as being usable for rinsing can also be used for hair treatment.

  In any case of the above set product and conditioning function-provided product, in addition to the various components described above, other optional components may be blended 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 glycerin ether, 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, and octyldodecanol.

  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, 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, 4,000,000, 600,000 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”)
C2050: manufactured by Kuraray Co., Ltd .: poly (methylpentanediol / 1,6-hexanediol carbonate) (hereinafter referred to as “C2050”)

<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>
・ Dimethylolpropionic acid: manufactured by Marincklot Chemicals, Inc. (hereinafter referred to as “DMPA”)
<Urethane polymerization catalyst>
Dibutyltin dilaurate (dibutyltin dilaurate): Wako Pure Chemical Industries, Ltd .: Reagent (denoted as “DBT” in the table)
<Polymerization inhibitor>
Hydroquinone: a reagent manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter referred to as “HQ”)

<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”)

<Basic compound>
Triethanolamine: manufactured by Shell Chemicals Japan: TEA99 (denoted as “TEA” in the table)
・ Potassium hydroxide: Wako Pure Chemical Industries, Ltd .: Reagent

<Radical polymerization initiator>
-70% by weight of t-butyl hydroperoxide (manufactured by Kayaku Akzo Co., Ltd .: Kayabutyl H-70) was diluted 10 times with water to give a 7% by weight aqueous solution (indicated as “PO” in the table) To do.)
Ascorbic acid (manufactured by Takeda Pharmaceutical Co., Ltd .: Vitamin C) was dissolved in water to give a 1% by weight aqueous solution (denoted as “VC” in the table).

<Reaction solvent>
・ Methyl ethyl ketone: Wako Pure Chemical Industries, Ltd. (denoted as “MEK” in the table)
<Chain extender>
・ 80% hydrated hydrazine: Wako Pure Chemical Industries, Ltd. (in the table, indicated as “HD”)

(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.

<Water-soluble evaluation>
A 20% by weight aqueous emulsion composition was coated on a glass plate with a 0.1 mm applicator, and then immediately put in a constant temperature dryer at 50 ° C. and dried for 2 hours. Next, it was cured for 24 hours in an environment of 23 ° C. and 50% RH. Then, the state after being immersed in 40 degreeC warm water for 2 hours was observed visually, and it evaluated according to the following references | standards.
○: Complete dissolution Δ: Emulsion dissolution by rubbing by hand ×: Maintaining the film state without dissolving or maintaining the film shape

<Acid value of component (a)>
Based on the molar fraction of the monomer having a carboxyl group calculated corresponding to the charged composition, the carboxyl group equivalent (mol / g) was determined, and the acid value was calculated by the following formula. (Unit: mgKOH / g)
Acid value = (carboxyl group equivalent × 56.1 × 1000) / (weight of urethane prepolymer (a))

<Minimum film-forming temperature (abbreviated as “MFT” in the table)>
Using a thermal gradient test apparatus (ASTM D2354-65T manufactured by Nikkei Shoji Co., Ltd.), a 20% by weight aqueous emulsion composition was applied with a 0.2 mm applicator.
Measured according to K 6828-2.

<Evaluation of heat return (set property)>
A 20% by weight aqueous emulsion composition coated on a Teflon sheet (manufactured by DuPont, trade name) so as to have a thickness of 0.1 mm was left to dry at room temperature for 3 days. After that, hot air was applied to the film cut out to 5 cm square with a 1200 W dryer for 30 seconds, immediately folded in two, observed after 20 minutes at room temperature, the returned angle was measured and evaluated as follows. .
○: 0 to 45 degrees Δ: 45 to 90 degrees ×: 90 to 180 degrees

<Slip evaluation>
A 20% by weight aqueous emulsion composition was coated on a glass plate with a 0.1 mm applicator, and then immediately put in a constant temperature dryer at 50 ° C. and dried for 2 hours. Next, it was cured for 24 hours in an environment of 23 ° C. and 50% RH. The surface was traced with a finger, and the slipperiness was evaluated by its tactile sensation.
○: No catching △: Slightly stuck but no stickiness ×: Sticking with stickiness

<Evaluation of monomer-derived odor>
50 g of the aqueous emulsion composition was sampled in a 200 ml Erlenmeyer flask, put on a stopper, held in an oven at 40 ° C. for 30 minutes, then immediately removed, and the odor when the stopper was removed was determined by the following criteria in the sensory test. evaluated.
○: Almost no odor △: Slight odor ×: Strong odor

<Residual polymerizable monomer amount>
40 g (exact balance) of the resulting aqueous emulsion composition was collected in a round bottom flask, 125 g of distilled water, 4 ml of toluene (exact balance), and appropriate amounts of a polymerization inhibitor and an antifoaming agent were added thereto, and the mixture was sufficiently stirred. Then, it sets to a distillation apparatus and performs azeotropic distillation of water / toluene at bath temperature 110-120 degreeC. The distillate is phase-separated to obtain a toluene layer.

  The obtained toluene solution was injected into a gas chromatograph under the following conditions, using the peak area of the retention time corresponding to the target polymerizable monomer, and a calibration curve created separately using a standard sample, The amount of the residual polymerizable monomer was calculated, and the concentration in the aqueous emulsion was determined from this.

Column: 20% (w / w) silicon DC710AW-DMCS ChromosorbW, 60/80 mesh, Glass 2.6 mmφ (inner diameter) × 3 m (length)
Carrier gas: Nitrogen (flow rate 10 ml / min)
-Column temperature: 110 ° C
Inlet / detector temperature: 190 ° C / 190 ° C
・ Gas pressure: hydrogen 0.6kg / cm2, air 0.5kg / cm2
・ Detector: FID
-Sample volume: 2 μl

Example 1
To a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, TL2461 and DMPA are added in amounts as described in the column of prepolymerization step in Table 1 to an internal temperature of 50 ° C., and then VES and DBT are added. The amount described in the column of prepolymerization step in Table 1 is added, heated to 90 ° C., and reacted at this temperature for 5 hours to obtain a carboxyl group-containing urethane prepolymer (a) containing an isocyanate group and a carboxyl group. It was.

  While maintaining the obtained carboxyl group-containing urethane prepolymer (a) solution at 50 ° C., the basic compound described in the column of the first neutralization step in Table 1 was added in an amount described in Table 1, and this carboxyl group was added. All or some of the carboxyl groups in the containing urethane prepolymer (a) were neutralized. Subsequently, the aqueous medium described in the column of the emulsification step in Table 1 was dropped into this solution in an amount shown in Table 1 at 50 ° C. over 15 minutes to obtain a milky white transparent dispersion.

  Thereafter, the dispersion was kept at 50 ° C., and at this temperature, the radical polymerization catalyst described in the column of the polymerization step in Table 1 was added in an amount shown in Table 1 to start polymerization of the polymerizable monomer. did. After completion of heat generation, the mixture was further heated to 70 ° C. and maintained for 3 hours to obtain an aqueous emulsion containing the urethane composite resin (A) and the unreacted polymerizable monomer (b).

  Subsequently, as shown in the column of the deodorization step in Table 1, dry air was supplied to the gas phase part (volume: 0.2 liter) of this reaction vessel at a rate of 1.5 liter / minute at 75 ° C. for 6 hours. Blew in. After 6 hours from the start of blowing, the sample was cooled to room temperature and sampled, the solid content was measured in accordance with the provisions described in JIS K 6833, water was calculated from the measurement result to be 40% solid content, and water was added. An aqueous emulsion composition having a reduced amount of the polymerizable monomer (b) was obtained.

  The above measurement / evaluation was performed on this aqueous emulsion composition. The results are shown in Table 1.

  In Example 1, a chain extension reaction was performed during the polymerization step with water, which is an aqueous medium added in the emulsification step. Then, in addition to the aqueous medium in the emulsification step, the chain elongation reaction was not performed by positively adding a chain extender. For this reason, the operation method of Example 1 was not described as “chain extension step”. This is the same for each of the following Examples and Comparative Examples (except for Example 5).

(Comparative Example 1)
In the procedure of Example 1, MMA, BA, and HQ were not added in the prepolymerization step. Instead, 63.7 parts by weight of methyl ethyl ketone was added as a reaction solvent, and distilled water added after neutralization was 493. The amount was changed from 3 parts by weight to 242.3 parts by weight. Moreover, after obtaining a dispersion liquid, it heated up to 80 degreeC, and after removing methyl ethyl ketone, it cooled to 50 degreeC, and the polymerization monomer (b) was carried out by the quantity of Table 1 at a subsequent polymerization process. In addition, the mixture was well stirred and polymerized, and then 252.1 parts by weight of distilled water was added.
Moreover, the addition amount of ascorbic acid which is a radical polymerization catalyst in the polymerization step was changed from 53.5 parts by weight to 53.9 parts by weight. Except for these, an aqueous emulsion was obtained by the same procedure as in Example 1.

  This urethane seed polymerization method corresponds to the conventional method for producing an aqueous emulsion described in Japanese Patent No. 2587801. The results are shown in Table 1. There was a problem with slipperiness, and water solubility and heat returnability (setting property) were not sufficient.

(Comparative Example 2)
In Example 1, MMA, BA and HQ were not added. Instead, 63.7 parts by weight of methyl ethyl ketone was added as a reaction solvent, and distilled water added after neutralization was changed from 493.3 parts by weight to 242.3 parts by weight. The urethanization reaction was carried out with modification. After adding distilled water, the temperature was raised to 80 ° C. to remove methyl ethyl ketone to produce an emulsion of urethane alone, and the above-described measurement and evaluation were performed. The results are shown in Table 1. The slipperiness was not sufficient, and there was a problem in heat returnability (setability).

[Effect of glass transition temperature of polymer on heat return property (set property) and slip property]
( Reference Example 1 )
In Example 1, the amount of the polymerizable monomer (b) used was the ratio shown in Table 1, and the glass transition temperature of the polymer was 48 ° C. Neutralization was carried out using 20.9 parts by weight of triethanolamine in place of the aqueous potassium hydroxide solution, and the same procedure as in Example 1 was carried out except that the amount of distilled water added dropwise was changed as shown in Table 1. An aqueous emulsion was obtained and subjected to the above measurement and evaluation. The results are shown in Table 1. Although the slipping property was sufficient, the heat return property (setting property) was slightly insufficient.

( Reference Example 2 )
In Example 1, 20.9 parts by weight of triethanolamine was used instead of 79 parts by weight of aqueous potassium hydroxide during neutralization, and the amount of distilled water to be added next was changed as shown in Table 1. In the same manner as in Example 1, an aqueous emulsion was obtained, and the above measurement and evaluation were performed. The glass transition temperature of the polymer was 6 ° C. The results are shown in Table 1. Both slipping property and heat return property (setting property) were slightly insufficient.

(Comparative Example 3)
In Example 2, the types and amounts of TL2461 and polymerizable monomer (b) used were changed as shown in Table 1, and the glass transition temperature of the polymer was -52 ° C. The amount of distilled water dropped after neutralization was also changed as shown in Table 1 to obtain an aqueous emulsion. An aqueous emulsion composition was obtained in the same manner as in Example 2 except that dry air was not blown into the aqueous emulsion, and the above measurement and evaluation were performed. The results are shown in Table 1. The odor was strong, and there was a problem with heat returnability (setting property) and water solubility.

(Comparative Example 4)
In Example 2, the types and amounts of TL2461 and polymerizable monomer (b) used were changed as shown in Table 1, and the glass transition temperature of the polymer was 105 ° C. An aqueous emulsion composition was obtained in the same manner as in Example 2 except that the amount of distilled water dropped after neutralization was changed to the amount shown in Table 1, and the above measurement and evaluation were performed. The results are shown in Table 1. When an attempt was made to evaluate heat returnability (setting property) and water solubility, film formation could not be performed.

[Residual amount of polymerizable monomer]
(Comparative Example 5)
In Example 1, an aqueous emulsion was obtained by the same procedure as in Example 1 except that dry air was not blown, and the above measurement was performed. The results are shown in Table 1.

[Reaction system for performing the second neutralization step]
(Example 2 )
In Example 1, the kind and amount of the raw material used were changed as shown in Table 1, and the glass transition temperature of the polymer was 48 ° C. In addition, as a 1st neutralization process, the basic compound of Table 1 is added only by the quantity of Table 1, and the addition amount of the basic compound in a 1st neutralization process is equivalent to 0.6 equivalent. did. Moreover, after completion | finish of a deodorizing process, the basic compound of Table 1 is added only by the quantity of Table 1 as a 2nd neutralization process, and the addition amount of a basic compound is 0.6 by the 2nd neutralization process. The basic compound corresponding to 1.2 equivalents was added together with the first neutralization step. The results are shown in Table 1.

[Reaction system for performing a chain extension step using a chain extender other than water]
( Reference Example 3 )
In the procedure of Example 1, C2050 is used as the polyol instead of TL2461, D-W is used instead of VES as the diisocyanate, TEA is used instead of KOH, and HD is used to chain before the polymerization step. An elongation process was performed, and the same procedure as in Example 1 was performed except that the amount of each component used was changed to the amount shown in Table 1, and an aqueous emulsion was obtained. The above measurement / evaluation was performed on this aqueous emulsion composition. The results are shown in Table 1.

[Evaluation method for hair cosmetics]
(Composition 1)
The aqueous emulsion composition for cosmetics of Example 1 was diluted with pure water so that the resin content would be 5 (% by weight) to obtain a composition 1.
(Composition composition 2)
Except for using the aqueous emulsion composition for cosmetics of Example 2, everything was carried out in the same manner as Formulation Composition 1 to obtain Formulation Composition 2.
(Comparative formulation 1)
A comparative blending composition 1 was obtained in the same manner as in the blending composition 1 except that the cosmetic aqueous emulsion composition of Comparative Example 1 was used.
(Comparative composition 2)
A comparative blending composition 2 was obtained in the same manner as the blending composition 1 except that the cosmetic aqueous emulsion composition of Comparative Example 2 was used.

(Evaluation of curl retention (setting force))
0.7 g of each of Formulation Compositions 1 and 2 and Comparative Formulation Compositions 1 and 2 was applied to 2.0 g of a hair bundle having a length of 25 cm, wound around a rod having a diameter of 3.0 cm and dried at 50 ° C. for 2 hours. After cooling to room temperature, the hair bundle was removed from the rod to obtain a curled one.
The curl retention was evaluated according to the following criteria based on the elongation of the hair bundle after the hair bundle was suspended for 1 hour in a constant temperature and humidity chamber which was previously conditioned at 30 ° C. and 90% humidity. The results are shown in Table 2.
○: Almost no change.
Δ: Slight elongation is observed.
X: Elongation is clearly recognized.

(Softness evaluation)
0.7 g of each of Formulation Compositions 1 and 2 and Comparative Formulation Compositions 1 and 2 was applied to 2.0 g of a hair bundle having a length of 25 cm, wound around a rod having a diameter of 3.0 cm and dried at 50 ° C. for 2 hours. After cooling to room temperature, the hair bundle was removed from the rod to obtain a curled one.
Using this, the softness (elasticity) was evaluated by the following criteria based on finger erosion. The results are shown in Table 2.
○: Soft feeling and flexibility △: Soft feeling but lacks some flexibility ×: Hard and brittle without soft feeling

Scheme showing preferred production method of this invention

Claims (7)

Contains an aqueous emulsion of urethane-based composite resin (A) having a minimum film-forming temperature of −10 ° C. or higher and 20 ° C. or lower, which is obtained by sequentially performing the following steps (1) to (5). An aqueous emulsion composition for cosmetics.
(1) A polymerizable monomer containing an ester group-containing vinyl monomer and / or a styrene derivative, and a polymer obtained by polymerizing the monomer has a glass transition temperature of 1 ° C. or higher and 70 ° C. or lower. In the presence of the component (b) which is a polymerizable monomer, a diol component consisting of polyester diol or polyalkylene glycol, dimethylol alkanoic acid, and an aliphatic or alicyclic polyvalent isocyanate are reacted to produce an isocyanate group and a carboxyl. A step of obtaining a carboxyl group-containing urethane prepolymer (component (a)) containing a group,
(2) A step of neutralizing the carboxyl group contained in component (a) obtained in (1) with a basic compound to obtain a neutralized product of component (a),
(3) The obtained neutralized product of component (a) and component (b) are emulsified and dispersed in an aqueous medium, and the ratio of component (a) to component (b) is A step of obtaining a first emulsion of component (b) (pure weight ratio) = 30: 70 to 80:20,
(4) A step of polymerizing the component (b) in the emulsion to obtain an aqueous emulsion of the urethane-based composite resin (A),
(5) A step of heat-treating the aqueous emulsion obtained in (4) to obtain an aqueous emulsion composition in which the amount of the component (b) remaining in the aqueous emulsion is reduced to 100 ppm or less.
However, when the basic compound used in the step (2) is a tertiary amine or potassium hydroxide, and the basic compound used here is potassium hydroxide, in the step (2), neutralize all the carboxyl groups, on the other hand, if the salt group compound is a tertiary amine is additionally performs the following step (6).
(6) The component (a) is present at least at one position selected between the steps (3) and (4), between the steps (4) and (5), and after the step (5). A step of further neutralizing all the carboxyl groups remaining as unneutralized in the step (2) to be contained using potassium hydroxide as a basic compound.   The aqueous emulsion composition for cosmetics according to claim 1, wherein the acid value of the component (a) is 15 mgKOH / g or more and 70 mgKOH / g or less.   At least part of the component (a) or the component derived from the component (a) is isocyanate between the steps (3) and (4) or between the steps (4) and (5). The aqueous emulsion composition for cosmetics according to claim 1, further comprising a step of chain extension with water or a compound having a plurality of active hydrogens capable of reacting with a group.   A step of chain extending a part of the component (a) with a compound having a plurality of active hydrogens capable of reacting with an isocyanate group or water between the steps (3) and (4); and In addition, at least part of the component (a) or the component derived from the component (a) remaining without being chain-extended by the chain extension step between the steps (4) and (5) is converted to an isocyanate. The aqueous emulsion composition for cosmetics according to claim 1, further comprising a step of chain extension with water or a compound having a plurality of active hydrogens capable of reacting with a group.   A cosmetic for hair containing the aqueous emulsion composition for cosmetics according to any one of claims 1 to 4.   The cosmetic for hair according to claim 5, comprising 0.05 to 10% by weight of the aqueous emulsion composition for cosmetics as a solid content thereof.   A hair cosmetic for sprays, wherein the hair cosmetic according to claim 5 or 6 contains at least one propellant selected from the group consisting of ethanol, liquefied petroleum gas, and dimethyl ether.

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