JPH0725722A - Cosmetic - Google Patents

Abstract

PURPOSE:To obtain a cosmetic excellent in UV rays shielding effects, etc., by blending cross-linked polyester spherical grains prepared by cross-linking a polyester resin containing an aromatic monomer as a part of constituent components with a vinylic monomer and having a specific grain diameter. CONSTITUTION:This cosmetic is obtained by comprising 5-99wt.% vinylic monomer in 1-95wt.% polyester resin containing an aromatic monomer as a part of constituent components, then carrying out the polymerization, providing a cross-linked resin, converting this cross-linked resin into spherical grains having 5-100mum volume-average grain diameter (D) and blending the resultant spherical grains. The cosmetic is excellent in the feeling of use, usability, safety and functional properties and further UV rays shielding effects. The polyester grains are blended in a cleansing cream, a wiping-off cosmetic, a face washing preparation, toilet water, a milky lotion, face powder, a foundation, a rouge, an eye shadow, a lipstick, an eye liner, a mascara, an eyebrow powder, an eyebrow pencil, a pack, a massage cream, a ground cream, a lotion, etc., to afford excellent effects.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic product which is excellent in usability, usability, safety and functionality and has an excellent ultraviolet ray shielding effect.

[0002]

2. Description of the Related Art Powders have been used in many cosmetic products. The powders used in these cosmetics are roughly classified into inorganic powders and organic powders. Inorganic powders are fine particles of talc, mica, titanium dioxide, etc., and make up the majority of powders used in cosmetics. These inorganic particles have a granular shape, a needle shape, a plate shape, an amorphous shape, or the like, and are unsatisfactory in the feeling of use, particularly the elongation on the skin, the feeling, and the like. Further, the inorganic powder generally has a high specific gravity, and liquid cosmetics tend to settle when left standing for a long time. Also, in the case of solid or powdery cosmetics, there may be a problem in blending with other ingredients.

Organic powders, that is, polymer particles, solve the above problems, and at the same time, have functionalities such as encapsulation or adsorption / sustained release of liquid components such as oil component, fragrance component, and moisture, and coloring property by coloring material. In recent years, attention has been paid to the fact that it has been used in cosmetics, and in particular, it is becoming an indispensable raw material for make-up cosmetics such as foundation and white powder. Polymer particles used in cosmetics are mainly polyamide type polymers such as nylon 6 and nylon 12, vinyl type polymers represented by styrene, polymethylmethacrylate and copolymers thereof. It is used. All of these are spherical in shape, so when blended into cosmetics, they have excellent feeling on use, such as elongation on the skin and feel, and usability. In addition, they do not cause sedimentation in liquid cosmetics due to their low specific gravity. It shows the dispersion stability.

[0004]

However, these polymer particles have the following drawbacks. Polyamide-based polymers are inferior in ultraviolet ray shielding effect and inferior in particle productivity, so that mass product-like production is difficult and extremely expensive. Some vinyl polymers have a certain degree of ultraviolet shielding effect depending on the copolymerization components and the like. However, in these vinyl polymers, unreacted monomers remain during the polymerization, and there are many cases in which there are problems such as odor and safety.

[0005]

In view of the above situation, the inventors of the present invention have conducted earnest studies to realize a cosmetic product which is excellent in usability, usability, safety and functionality and is also excellent in ultraviolet ray shielding effect. As a result, they have reached the next invention. That is, the present invention comprises a cross-linking resin obtained by adding 5 to 99% by weight of a vinyl monomer to 1 to 95% by weight of a polyester resin containing at least an aromatic monomer as a constituent and then polymerizing the mixture. , The volume average particle diameter D is 0.5 to 10
It is a cosmetic product containing crosslinked polyester spherical particles of 0 μm.

The polyester resin in the present invention is mainly obtained by a condensation reaction of a polyvalent carboxylic acid and a polyvalent alcohol. In the present invention, it is essential to use 5 mol% or more of such a polycarboxylic acid component as an unsaturated aliphatic polycarboxylic acid. Examples of the unsaturated polycarboxylic acid in the present invention include fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, and other aliphatic unsaturated polycarboxylic acids, and phenylenediacrylic acid and other aromatic unsaturated polycarboxylic acids. An acid or the like can be used. As the unsaturated polycarboxylic acid, fumaric acid or maleic acid is preferably used, and fumaric acid is more preferably used. The use of unsaturated polycarboxylic acid is required to be 5 mol% or more with respect to the acid component, and 20 to 50
mol% is preferable, and 30 to 50 mol% is more preferable.

In the present invention, it is preferable to use an aromatic polycarboxylic acid as the other polycarboxylic acid component. Examples of the aromatic polycarboxylic acid in the present invention include terephthalic acid, isophthalic acid, sulfoisophthalic acid and / or ammonium salts or alkali metal salts thereof, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6
-Naphthalenedicarboxylic acid, diphenic acid, 4-4 'diphenyldicarboxylic acid and the like can be used. In the present invention, 30 to 90 mol% of aromatic dicarboxylic acid is added to the acid component.
It is preferable to use in the range of 50 to 90 mol
%, More preferably 70 to 90 mol%. In the present invention, as polyvalent carboxylic acid, terephthalic acid 10 to 80 mol%, isophthalic acid 10 to 50 mol%,
Further, the total amount of terephthalic acid and isophthalic acid is preferably 60 mol% or more. The content rate of terephthalic acid is 30
˜80 mol%, more preferably 50 to 80 mol%, and the total sum of terephthalic acid and isophthalic acid is more preferably 70 mol% or more.

In the present invention, trimellitic acid, trimesic acid, pyromellitic acid and the like can be used as the trivalent or higher polycarboxylic acid. Trivalent or higher polycarboxylic acid can be used in the range of 0 to 8 mol%. Again 1
It is more preferable to use about 6 to 6 mol%, and further about 3 to 5 mol%. Other polycarboxylic acids include p-oxybenzoic acid,
aromatic oxycarboxylic acids such as p- (hydroxyethoxy) benzoic acid, succinic acid, adipic acid, azelaic acid,
Sebacic acid, aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid,
Alicyclic dicarboxylic acid and the like can be used.

In the present invention, a part of the polycarboxylic acids may be used together with the monocarboxylic acids. Aromatic monocarboxylic acids are preferred as the monocarboxylic acids. Examples of the aromatic monocarboxylic acid include benzoic acid, chlorobenzoic acid, bromobenzoic acid, parahydroxybenzoic acid, naphthalenecarboxylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, salicylic acid, thiosalicylic acid, phenylacetic acid,
And lower alkyl esters thereof, sulfobenzoic acid monoammonium salt, sulfobenzoic acid monosodium salt, cyclohexylaminocarbonylbenzoic acid, n-dodecylaminocarbonylbenzoic acid, tert-butylbenzoic acid, tert-butylnaphthalenecarboxylic acid, etc. It is possible to use, and it is more preferable to use especially tertiary benzoic acid. The amount of the aromatic monocarboxylic acid used is 2 to 25 mol% based on the acid component, and further 5 to 20 mol%.
More preferred is the use of mol%, or even 8-16 mol%.

As the polyvalent alcohol component in the present invention, aliphatic polyvalent alcohol, alicyclic polyvalent alcohol, aromatic polyvalent alcohol and the like can be used. Examples of the aliphatic polyvalent alcohol in the present invention include ethylene glycol
, Propylene glycol, 1,3-propanedioe
2,3-butanediol, 1,4-butanediol
Alkylene glycols such as 1,2,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and 2,2,4-trimethyl-1,3-pentanediol.
, Diethylene glycol, dipropylene glycol,
Polyethylene glycol, polypropylene glycol,
Polyoxyalkylene glycol such as polytetramethylene glycol can be used. Further, as trivalent or higher alcohols, trimethylolethane, trimethylol-
It is possible to use triol and tetraol such as propane, glycerin and pentaerythritol. Further, as the aliphatic polyhydric alcohol, ethylene glycol,
The use of propylene glycol or 2,3-butanediol is particularly preferred.

In the present invention, as the alicyclic polyvalent alcohol, 1,4-cyclohexane diol, 1,4-cyclohexane dimethanol, tricyclodecane dimethanol and tricyclodecane diol are used. Hydrogenated biphenol,
Hydrogenated bisphenol A or the like can be used. The alicyclic polyvalent alcohol is 0 to 80 mol% based on the alcohol component.
It can be used in the range of. As the alicyclic diols, tricyclodecane dimethanol, cyclohexane diol and hydrogenated biphenol are particularly preferably used.

Other polyhydric alcohols include spiroglycol, paraxyleneglycol, metaxyleneglycol, orthoxyleneglycol, 1,4-phenyleneglycol and 1,4-phenyleneglycol. -Ethylene oxide adduct, diol such as bisphenol A,
Ethylene oxide adducts and propylene oxide adducts of bisphenol A, hydrogenated bisphenol A ethylene oxide adducts and propylene oxide adducts, and as polyester polyols, lactones such as ε-caprolactone are subjected to ring-opening polymerization. The lactone-based polyester polyols and the like obtained as described above can be used.

In the present invention, it is essential to use at least an aromatic monomer as a constituent component. The content of the aromatic monomer is preferably 5 mol% or more, more preferably 10 to 70 mol%, and further preferably 30 to 50 mol% with respect to all the constituent components. When the composition ratio of such an aromatic monomer is small, the ultraviolet shielding effect may not be improved. Further, excessive use of the aromatic monomer tends to raise the glass transition temperature of the polyester resin too much. As the aromatic monomer, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc. can be preferably used as the acidic component, and the bisphenol monomer can be preferably used as the alcohol component. In the present invention, it is preferable to use a polyester resin mainly containing an aromatic monomer as an acid component and an aliphatic monomer or polyoxyalkylene glycol as an alcohol component.

The glass transition point of the polyester resin in the present invention is preferably 40 ° C. or higher, 45 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher. If the glass transition point is lower than this, blocking tends to occur during handling or storage, and it may be difficult to handle the resulting powder. The number average molecular weight of the polyester resin of the present invention is preferably in the range of 1,000 to 20,000. Further, the range of 2000 or more and 5000 or less is preferable, and the range of 3000 or more and 4000 or less is more preferable.

In the present invention, the ionic group is 20 to 50.
0 eq. It is essential to contain the polyester resin in the range of / ton. As the ionic group, a sulfonic acid group, a carboxyl group, a sulfuric acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group or an ammonium salt thereof,
It is an anionic group such as a metal salt or a cationic group such as a primary to tertiary amine group, and preferably an alkali metal sulfonate group or an ammonium carboxylate group can be used. It is preferable that these ionic groups are contained in a form copolymerized with polyester or introduced into the polymer terminal. Examples of the polyvalent carboxylic acid containing a metal sulfonate copolymerizable with polyester include sulfoterephthalic acid, 5-sulfoisophthalic acid,
4-sulfophthalic acid, 4-sulfonaphthalene-2,7 dicarboxylic acid, 5 [4-sulfophenoxy] isophthalic acid, and / or salts thereof can be exemplified.
Further, by using a metal salt of sulfobenzoic acid together, a metal sulfonate base can be introduced at the polymer terminal. As salts, ammonium-based ions, Li, Na,
Examples thereof include salts of K, Mg, Ca, Cu, Fe and the like, and particularly preferred are K salt or Na salt. The carboxyl group can be added to the polymer terminal by introducing a polyvalent carboxylic acid such as trimellitic acid into the system at the final stage of polymerization of polyester. Further, by neutralizing this with ammonia, sodium hydroxide or the like, the carboxylate group can be exchanged. The content of these ionic groups is
20 to 500 eq. With respect to the polyester resin. / To
The range of n is essential, and more preferably 50 to 200e.
q. / Ton.

When the polyester resin of the present invention contains an ionic group, it exhibits water dispersibility. Water dispersibility means a state generally called emulsion or colloidal dispersion. The ionic group dissociates in the aqueous medium and forms an electric double layer at the interface between the polyester resin and water. When the polyester resin is present as fine microparticles in the water system, an electrostatic repulsive force is generated between the microparticles due to the action of the electric double layer, and the microparticles are stably dispersed in the water system. The resin particles in the invention are prepared by, for example, dispersing an ionic group-containing polyester resin in water to prepare a polyester emulsion (or polyester dispersion), and releasing the water-dispersed polyester microparticles into a plasticized state. It can be obtained by aggregating.

The aqueous dispersion of the ionic group-containing polyester resin is prepared by mixing the ionic group-containing polyester resin and the water-soluble organic compound in advance and then adding water, and the ionic group-containing polyester resin, the water-soluble organic compound and water. Can be obtained by a method of mixing and heating all at once. At that time, a surfactant or the like can be used together. As the water-soluble organic compound, ethanol, isopropanol,
Butanol, ethylene glycol, propylene glycol
, Methyl cellosolve, ethyl cellosolve, butyl cellosolve, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane and the like can be used. The water-soluble organic compound is preferably one that can be removed by azeotropic distillation after the ionic group-containing polyester resin is dispersed in water.

The polyester seed particles obtained by slowly agglomerating the microdispersion are substantially spherical and have a sharp particle size distribution, and high temperature dispersion dyeing is possible. The volume average particle diameter D of the polyester particles thus obtained can be freely controlled in the range of 1 to 100 μm (depending on the electrolyte concentration, temperature and time), and the particle diameter distribution is in the range of 0.5D to 2.0D. 80% by weight of all particles
It becomes a sharp particle having a coefficient of variation of 30% or less and a substantially spherical polyester particle having an average sphericity (minor axis / major axis) of 0.8 or more. The specificity of the particles of the present invention with respect to the particles of vinyl polymer obtained by suspension polymerization or the like is exhibited not only in the variety of physical properties of the polyester resin but also in the shape and particle size distribution of such polyester particles. In general, suspension-polymerized particles have a broad particle size distribution and only a coefficient of variation of about 30% or more can be obtained. In the present invention, the particle size is adjusted to 0.
80% by weight or more of particles in the range of 5D to 2.0D,
It is preferably 85% by weight or more, more preferably 90% by weight or more, and even more preferably 95% by weight or more. The coefficient of variation is 30% or less, preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, still more preferably 7%.
It can be: The average sphericity (minor axis / major axis) can be 0.8 or more, preferably 0.85 or more, more preferably 0.9 or more, still more preferably 0.95 or more. Here, the coefficient of variation means a value obtained by dividing the standard deviation by the average value. Such a sharp particle size distribution is maintained even if the seed polymerization described later is performed.

Different kinds of aqueous dispersions can be incorporated into the polyester particles of the present invention during the particle growth process.
The heterogeneous water dispersion includes, for example, known organic and inorganic dyes and pigments such as phthalocyanine pigments, quinacridone pigments, azo pigments, lake pigments, benzidine pigments, anthraquinone pigments, carbon black, and the like. Talc, titanium oxide,
Alumina, silica, and other metal oxides, ferrite, chromium oxide, cobalt oxide, and other magnetic powders, other acrylics,
Examples thereof include styrene-based organic polymer particles and water-dispersible waxes. Further, since the polyester particles of the present invention ensure stable dispersibility at the time of completion of particle growth, dyeing by post-processing, surface treatment, etc. are easy, and known disperse dyes, vat dyes, basic dyes, acid dyes are known. It can be dyed at a high density with a reactive dye, a reactive disperse dye, or the like.

In the present invention, the polyester particles thus obtained are used as seed particles, and the polyester particles are dispersed in an aqueous medium, and the vinyl monomer is used in an amount of 1 to 95% by weight of a polyester resin and a vinyl resin. Monomer-5-9
The desired crosslinked resin particles are obtained by swelling so as to be 9% by weight and further polymerizing and crosslinking. Examples of the vinyl-based monomer used in the present invention include alkyl (meth) acrylate in which the alkyl group has 1 to 10 carbon atoms, methoxyethyl (meth) acrylate, and (meth).
(Meth) acrylic acid esters such as hydroxyethyl acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, methyl vinyl ketone, phenyl vinyl ketone, methyl isopropenyl ketone, etc. Unsaturated ketones, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate vinyl butanoate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, vinyl halides and halogenated compounds. Vinylidenes, acrylamide and its alkyl-substituted products, styrene, styrene alkyl-substituted products, styrene halogen-substituted products, allyl alcohol and its esters or ethers, acrolein, vinyl aldehydes such as methacrolein, Vinyl monomers such as acrylonitrile, methacrylonitrile and vinylidene cyanide, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid and itaconic acid and salts thereof, vinyl sulfonic acid, acrylic sulfonic acid, para Unsaturated hydrocarbon sulfonic acids such as styrene sulfonic acid and salts thereof, phosphates having a double bond, and salts thereof, pyridine, vinylpyrrolidone, vinylimidazo-
, Vinylcarbazol, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (methacrylate, etc. can be used. In addition to these, ring-opening polymerization of siloxanes, lactones, lactams, epoxy compounds, etc. You may use together a system monomer.

The reaction initiator is not particularly limited, and a known initiator may be used. For example, benzoylperoxide, parachlorobenzoylperoxide, 2,4-dichlorobenzoylperoxide, caprylylperoxide, laurylperoxide, acetylperoxide, methylethylketoneperoxide, cyclohexanoneperoxide, bis (1-hydroxycyclohexyl). Peroxide), hydroxyheptylperoxide, t-butylhydroperoxide, p-menthanperoxide, cumenehydro, 2,5-dimethylhexyl-2,5-dihydroper
Oxide, di-t-butylperoxide, dicumylperoxide, 2,5-dimethyl-2,5-di (per)
Oxybenzoate), t-butylperbenzoate,
t-butyl peracetate, t-butyl per octet
, T-butyl peroxy oxyisobutyrate, di-t-butyl di-per phthalate, organic peroxide initiators such as peroxysuccinic acid, azoisobutyl nitrile, disoxybenzoyl, phenylacetaldehyde, phenylpyroglucose, An initiator such as a pinaconic acid derivative can be used. As the reaction accelerator, cobalt-based, vanadium-based, manganese-based, tertiary amine-based, quaternary ammonium salt-based,
A reaction promoter such as a mercaptan type can be used.
The crosslinked resin particles thus obtained maintain the particle size distribution of the polyester seed particles, and the particles having a particle size in the range of 0.5D to 2.0D are 80% by weight or more, preferably 85% by weight of the whole particles.
Or more, more preferably 90% by weight or more, even more preferably 95% by weight or more, and the coefficient of variation is 30%.
Or less, preferably 20% or less, more preferably 15%
It can be below, more preferably 10% or less, and even more preferably 7% or less.

The polyester resin of the present invention has good light fastness even when colored with a dye. As the dye, a disperse dye, an oil-soluble dye, a construction bath dye, a vat dye, a slene dye, a basic dye, a cationic dye, an acid dye, a reactive dye, a reactive disperse dye and the like can be used. Specific examples of the disperse dye and the oil-soluble dye include C.I. I. Disperse Yellow 198 C.I. I. Disperse Yellow 42 C.I. I. Solvent Yellow 162 C.I. I. Disperse Red 92 C.I. I. Solvent Red 49 C.I. I. Solvent Red 52 C.I. I. Disperse Violet 26 C.I. I. Disperse Violet 35 C.I. I. Disperse Blue 60 C.I. I. Disperse Blue 87 C.I. I. Solvent Blue 70 C.I. I. At least one dye selected from Solvent Black 3 is preferably used. Specific examples of the basic dye include: C.I. I. Basic Yellow 11 C.I. I. Basic Yellow 13 C.I. I. Basic Yellow 21 C.I. I. Basic Red 14 C.I. I. Basic Red 15 C.I. I. Basic Red 39 C.I. I. Basic Violet 7 C.I. I. Basic Violet 11 C.I. I. Basic Violet 28 C.I. I. Basic Violet 40 C.I. I. Basic Violet C.I. I. Basic Blue 3 C.I. I. At least one dye selected from Basic Blue 75 is preferably used. When such a basic dye is used, it is preferable that the binder resin contains an anionic group to serve as a dyeing seat, and the dye is present in the side chain and / or the end of the binder resin polymer chain. The cation moiety of the basic dye is contained in the form of forming a salt with the anionic group, and the anion (mainly halogen ion, generally chlorine ion) which is a counter ion of the basic dye is substantially not contained. preferable. More specifically, the content of halogen ions (in the form of a salt with a halogen acid or an alkali metal ion or an alkaline earth metal ion) is preferably 2 eq./ton or less. Such a preferable state is realized by dyeing the anionic group-containing resin in an aqueous medium. As a pigment, C.I. I. Pigment Yellow 14 C.I. I. Pigment Yellow 17 C.I. I. Pigment Red 48 C.I. I. Pigment Red 57 C.I. I. Pigment Red 81 C.I. I. Pigment Red 122 C.I. I. Pigment Blue 15 C.I. I. Pigment Blue 16 / carbon black or the like can be used.

In addition to polyester particles, which is an essential component of the cosmetics of the present invention, white, constitution, coloring pigments, pallets, natural minerals, organic powders, oils, etc. which are usually used as cosmetic components depending on the product type, purpose, etc. Metal soaps, surfactants, moisturizers, preservatives, fragrances, and other additives may be added. The cosmetics of the present invention may take any product form and shape such as powder, press, liquid, stick, emulsion, oil and cream. More specifically, in the present invention, the characteristic polyester particles are cleansing cream, wiping lotion, face wash, lotion, milky lotion, white powder, foundation, blusher, eye shadow, lipstick, eye liner, mascara. , Eyebrow, eyebrow, pack, massage cream, foundation cream, roll
It is possible to obtain an excellent effect by blending it with a solution or the like.

The polyester particles blended in the cosmetic of the present invention have a low specific gravity as compared with the inorganic particles and thus exhibit good dispersion stability, and no sedimentation occurs even after long-term storage. In addition, the main component is a condensation polymer, but the unreacted monomer
Has little residual and is excellent in terms of odor and safety. In addition, the hydrophilicity / hydrophobicity can be freely controlled by copolymerization of the hydrophilic component, and the characteristics according to the purpose can be obtained. Further, the polyester resin in the present invention contains an aromatic monomer as an essential component, and therefore has a particularly excellent ultraviolet ray shielding effect. Due to the above action, the cosmetic of the present invention has usability as compared with conventional cosmetics mainly using inorganic particles.
Inheriting all the characteristics of cosmetics using known polymer particles in terms of usability, etc., and in addition to showing superior effects in terms of UV shielding effect, odor, safety, freedom of product design, etc. Is.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto.

【Example】

[Polyester resins (A1) to (A4),
Polymerization of (A7)] An autoclave equipped with a thermometer and a stirrer
87 parts by weight of terephthalic acid dimethyl ester, 87 parts by weight of isophthalic acid dimethyl ester, 6 parts by weight of 5-sodium sulfoisophthalic acid dimethyl ester, 68 parts by weight of ethylene glycol, 114 parts by weight of neopentyl glycol, and tetra 0.1 part by weight of butoxy titanate was charged and heated at 120 to 220 ° C. for 120 minutes to carry out a transesterification reaction. Then, set the temperature of the reaction system to 180 ° C.
And then fumaric acid (9 parts by weight) and hydroquinone (0.1 parts by weight) were added, and the reaction was continued at 200 ° C. for 60 minutes.
As a result of continuing the reaction at 0 mmHg for 60 minutes, a copolyester resin (A1) was obtained. The composition, glass transition temperature, acid value, molecular weight and sodium sulfonate group equivalent of the obtained copolyester resin (A1) are shown in Table 1 below. Shown in. The composition of the polyester was determined by NMR analysis, the glass transition temperature was determined by DSC, the acid value was determined by titration, the molecular weight was determined by GPC, and the sodium sulfonate group equivalent was determined by S. Thereafter, the raw materials were changed and the same polymerization was carried out. To obtain polyester resins (A2) to (A4) and (A7). [Polymerization of polyester resin (A5)] In an autoclave equipped with a thermometer and a stirrer, 128 parts by weight of dimethyl terephthalate, 45 parts by weight of ethylene glycol, and propylene oxide addition of bisphenol A. 270 parts by weight of the product, 0.1 parts by weight of tetrabutoxy titanate were charged and heated at 150 to 220 ° C. for 180 minutes to carry out a transesterification reaction. Then, the temperature of the reaction system is lowered to 180 ° C., 29 parts by weight of maleic anhydride and 0.1 part by weight of hydroquinone are added, the reaction is continued at 200 ° C. for 60 minutes, and then the temperature of the reaction system is raised to 220 to 240 ° C. Then, the pressure of the system was gradually reduced to 10 mmHg after 30 minutes, and the reaction was continued for 60 minutes. After that, the atmosphere in the autoclave was replaced with nitrogen gas and the pressure was adjusted to atmospheric pressure. The temperature was kept at 200 ° C., 8 parts by weight of trimellitic anhydride was added, and the reaction was carried out for 60 minutes. To obtain a copolyester resin (A5).
[Polymerization of polyester resin (A6)] 700 parts by weight of a propylene oxide adduct of bisphenol A and maleic anhydride 1 were placed in an autoclave equipped with a thermometer and a stirrer.
96 parts by weight and 1 part by weight of hydroquinone were charged, nitrogen gas was introduced into the reaction system to maintain an inert atmosphere, 0.05 part by weight of dibutyltin oxide was added, and the reaction was carried out at 200 ° C. To obtain a polyester resin (A6). In addition, Table 1. Medium NDC is 1,5-naphthalenedicarboxylic acid TPA is terephthalic acid IPA is isophthalic acid SIP is 5-sodium sulfoisophthalic acid FA is fumaric acid MA is maleic acid TMA is trimellitic acid EG is ethylene glycol NPG is neopentyl glycol CHDM is cyclohexanedimethanol BPP is propylene oxide adduct of bisphenol A (average molecular weight 350) Tg is glass transition temperature.

[Production of polyester seed particles] 340 parts by weight of polyester resin (A1), methyl ethyl ketone 15
After dissolving 0 parts by weight and 140 parts by weight of tetrahydrofuran at 80 ° C., 680 parts of water at 80 ° C. was added to obtain an aqueous microdispersion of a copolyester resin having a particle diameter of about 0.1 μm. Further, the obtained water-based microdispersion was placed in a distillation flask and distilled until the distillation temperature reached 100 ° C. After cooling, water was added to make the solid content concentration 30%. To a four-necked 1-liter separable flask equipped with a thermometer, a condenser, and a stirring blade, 300 parts by weight of the aqueous copolymer polyester dispersion was charged and the temperature was raised to 80 ° C. Then, 40 parts by weight of a 20% by weight aqueous solution of dimethylaminoethyl methacrylate (DAM) was added over 60 minutes (0.2
mol / l), and the stirring was continued while maintaining the temperature at 80 ° C. for 300 minutes. The conductivity in the system increased from about 1 mS to 25 mS, and the pH decreased from 10.8 to 6.7. From this, it was confirmed that the added dimethylaminoethyl methacrylate was almost completely hydrolyzed afterward to form a salt of dimethylaminoethanol and methacrylic acid. Submicron existing in polyester aqueous microdispersion
Copolymers having a particle size of dart grow as coalesced particles over time. Polyester spherical particles shown in (B1)
Got Table 2. Medium, average particle diameter, particle diameter distribution, and coefficient of variation were measured using a corter counter TA2.
The sphericity was measured by processing a scanning electron micrograph of the particles with an image processing device Image Analyzer V1 [manufactured by Toyobo Co., Ltd.]. Experiments were performed in the same manner, except that the raw materials and conditions were changed, and Table 2. To obtain polyester particles (B2) to (B4) and (B7). To 34 parts of copolyester (A5), 10 parts of butanol was added and the temperature was 90 ° C.
After being dissolved in, the mixture was cooled to 80 ° C. Further, 1N aqueous ammonia solution was added so that the acid value of the copolyester becomes equal to the acid value, and the mixture was stirred at 80 ° C for 30 minutes and then 80 ° C.
56 parts of water was added to obtain an aqueous dispersion of copolyester. Further, 1000 parts of the obtained water dispersion was placed in a distillation flask, distilled until the distillation temperature reached 100 ° C., then cooled, and finally desolvated. An aqueous dispersion of a copolyester having a solid content concentration of 33%. Got 4. In a four-liter 1-liter separable flask equipped with a thermometer, a condenser, and a stirring blade, 300 parts by weight of the aqueous dispersion of copolymerized polyester, and dimethylaminoethyl methacrylate 5.
0 parts by weight was added and the temperature was raised to 70 ° C. The reaction was continued for another 180 minutes at 70 ° C. As a result, the copolymer having the particle size of submicron order, which was present in the aqueous dispersion of the copolymerized polyester, grows into particles, and the copolymer shown in Table 2. To obtain polyester particles (B5). In the same manner, polyester particles (B6) were obtained from the polyester resin (A6).

[Preparation of crosslinked particles] Polyester particles (B
Dilute the water dispersion of 1) with deionized water to adjust the solid content to 5
% To prepare an aqueous dispersion of polyester particles. 1000 parts by weight of the polyester aqueous dispersion was placed in a separable flask and gently stirred, and 1 part by weight of sodium chloride,
Distilled styrene 50 in which 1% by weight of benzoyl peroxide is dissolved
After adding a weight part and continuing stirring for 30 minutes, the temperature of the system was raised to 80 ° C. and the reaction was continued for 300 minutes. After cooling the system to room temperature, the obtained particles were dehydrated and washed with a suction funnel and vacuum dried to obtain crosslinked polyester dried particles (C1). The average particle size, particle size distribution, coefficient of variation, and sphericity of the obtained particles were measured by the same method. The results are shown in Table 3 below. Shown in. The obtained particles were immersed in ethyl alcohol, and solvent resistance was evaluated by whether or not the particle shape could be retained. Further, the particles were placed on a hot plate at 100 ° C., and heat resistance was evaluated by whether or not the particle shape could be maintained. The results are shown in Table 3. Shown in. It can be seen that the particles using the unsaturated polyester resin copolymerized with maleic acid or fumaric acid show good heat resistance and solvent resistance. The particles (C7) made of the saturated polyester (A7) are inferior in heat resistance and solvent resistance.

[Evaluation of UV-shielding effect] 5 parts by weight of the obtained polyester particles were mixed with 95 parts by weight of glass beads having an average particle diameter of 0.5 mm. The polyester particles and the glass beads are negatively contacted by the contact frictional electrification.
The glass beads were positively charged. The mixture of polyester particles and glass beads was dropped onto a quartz plate whose surface was positively charged by positive corona treatment, and the polyester particles were attached to the quartz plate by electrostatic force. The potential of the quartz plate was adjusted according to the corona treatment conditions, and the amount of polyester particles adhered was standardized to 10 mg / cm ^{2, which} was used as the material for measuring the ultraviolet shielding ratio. Further, as a comparative example, commercially available nylon 6 particles and PMMA particles were used and the same data were obtained. With respect to the above materials, the ultraviolet shielding rate was determined using Hitachi Spectrophotometer U-3210 type. The measurement wavelength is 32 in A area
The average value of each region was obtained by setting 0 to 400 nm and the B region to 290 to 320 nm. The results are shown in Table 4 below. Shown in. It can be seen that the polyester particles have a high ultraviolet ray shielding rate, and in particular, almost completely shield the B region. In comparison, nylon 6 or PMMA particles have a low shielding effect.
This result is derived from the fact that the aromatic component contained in the polyester particles has absorption in the ultraviolet region, and shows that the polyester particles have properties that are difficult to obtain with conventional nylon-based or PMMA-based particles. .

(Solid powder foundation) Blender was charged with 10 parts by weight of crosslinked polyester particles C1, 30 parts by weight of talc, 2 parts by weight of titanium oxide, 6 parts by weight of color pigment, 40 parts by weight of mica, and uniformly mixed. 2 parts by weight of petrolatum, 8 parts by weight of squalane, and 2 parts by weight of liquid paraffin were added to the heat-melted mixture and further mixed. Then, the obtained mixture was press-molded to obtain a solid powder foundation. The obtained foundation can be easily removed to the mat regardless of which polyester particles are used, has good elongation at the time of application, forms a uniform and uniform cosmetic film, and is excellent in the ultraviolet shielding effect. It was

[0031]

As described above, the cosmetics containing the crosslinked polyester particles of the present invention are excellent in usability and feeling, and have a high ultraviolet ray shielding effect.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

Front page continuation (72) Inventor Taiji Horita 2-1-1 Katata, Otsu City, Shiga Toyobo Co., Ltd. (72) Inventor Goji Maeda 2-1-1 Katata, Otsu, Shiga Prefecture Toyobo Inside Research Institute Co., Ltd. (72) Inventor Yozo Yamada 1-1-1 Katata, Otsu City, Shiga Prefecture Inside Toyobo Research Co., Ltd.

Claims (1)

[Claims] 1. A cross-linked resin obtained by adding 5 to 99% by weight of a vinyl monomer to 1 to 95% by weight of a polyester resin containing at least an aromatic monomer as a constituent, and then polymerizing the mixture. , And the volume average particle diameter D is 0.
Cosmetics containing cross-linked polyester spherical particles of 5 to 100 μm.