JPH0769855A - Cosmetic - Google Patents

Abstract

PURPOSE:To prepare a cosmetic excellent in use feeling, use property, safety and functionality as well as ultraviolet rays-blocking effect. CONSTITUTION:This cosmetic is obtained by blending an aqueous fine dispersing element of a polyester resin composed essentially of a monomer containing an ionic group-containing monomer and an aromatic polycyclic condensed ring hydrocarbon as a skeleton, e.g. 9,10-anthracenedipropionic acid.

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 A function required for cosmetics is protection of skin from ultraviolet rays. Conventionally, inorganic powders have been mainly used for imparting an ultraviolet absorbing effect to cosmetics.

[0003]

The inorganic powder is talc,
It is a fine particle of mica, titanium dioxide, iron oxide, etc., and occupies most of the powder 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.

[0004]

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 mainly relates to a polyester resin containing an ionic group in the range of 20 to 2000 eq./ton and having as an essential component a monomer having an aromatic polycyclic condensed ring hydrocarbon as a skeleton. A cosmetic product comprising a fine particle dispersion having an average particle diameter of 1.0 μm or less as a component.

The particles blended in the cosmetics of the present invention are mainly composed of polyester resin. The polyester resin is preferably used in an amount of 50 wt% or more of the total resin component, more preferably 80 wt% or more, further 90 wt% or more, and further 95%.
It is preferable that the content is at least wt%, and even more preferably at least 98 wt%. The polyester resin in the present invention is mainly composed of polyvalent carboxylic acids and polyvalent alcohols. Examples of the polyvalent carboxylic acids used for the polyester resin include: terephthalic acid, isophthalic acid, orthophthalic acid, 1,
5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, anthracene dipropionic acid, anthracene dicarboxylic acid, diphenic acid, sulfoterephthalic acid, 5
-Sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7dicarboxylic acid, 5 [4-sulfophenoxy] isophthalic acid, sulfoterephthalic acid, and / or aromatic dicarboxylic acids such as metal salts and ammonium salts thereof. Aromatic oxycarboxylic acids such as p-oxybenzoic acid and p- (hydroxyethoxy) benzoic acid, succinic acid, adipic acid, azelaic acid, sebacic acid,
Aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, aliphatic unsaturated polycarboxylic acids such as fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, and aromatic unsaturated polycarboxylic acids such as phenylenediacrylic acid Carboxylic acids-Alicyclic dicarboxylic acids such as hexahydrophthalic acid and tetrahydrophthalic acid-Trivalent or higher polycarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid

In the present invention, some of the polycarboxylic acids may be used in combination with 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, anthracenecarboxylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, salicylic acid, thiosalicylic acid, phenyl. Acetic acid and lower alkyl esters thereof, sulfobenzoic acid monoammonium salt, sulfobenzoic acid monosodium salt, cyclohexylaminocarbonylbenzoic acid, n-dodecylaminocarbonylbenzoic acid, tert-butylbenzoic acid, tert-butylnaphthalene A carboxylic acid or the like can be used, and it is more preferable to use t-butyl benzoic acid. The amount of the aromatic monocarboxylic acid used is 2 to 25 mol%, further 5 to 20 mol%, and further 8 to 1 with respect to the acid component.
The use of 6 mol% is more preferable.

In the present invention, 5 of such polyvalent carboxylic acid components are used.
It is possible to use an unsaturated aliphatic polycarboxylic acid of mol% or more. As the unsaturated polycarboxylic acid in the present invention, fumaric acid and maleic acid are preferably used, and fumaric acid is more preferably used. The use of the unsaturated polycarboxylic acid is preferably 5 mol% or more, more preferably 20 to 50 mol%, further preferably 30 to 50 mol% with respect to the acid component. Examples of polyvalent alcohols used for the polyester resin include aliphatic polyvalent alcohols, alicyclic polyvalent alcohols, aromatic polyvalent alcohols and the like. As the aliphatic polyhydric alcohols, ethylene glycol
, Propylene glycol, 1,3-propanedioe
2,3-butanediol, 1,4-butanediol
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol
, Dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, polyethylene glycol
Examples include aliphatic diols such as propylene, polypropylene glycol and polytetramethylene glycol, triols such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and tetraols. it can.

· 1,4 as the alicyclic polyvalent alcohols
-Cyclohexanediol, 1,4-cyclohexanedimethanol, spiroglycol, hydrogenated bisphenol A, ethylene oxide adduct and propylene oxide adduct of hydrogenated bisphenol A, tricyclodecanediol , Tricyclodecane dimethanol, and the like. .As the aromatic polyhydric alcohols, ethylene oxide addition of para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, and 1,4-phenylene glycol Examples thereof include bisphenol A, bisphenol A, ethylene oxide adduct of bisphenol A, and propylene oxide adduct. Further, as the polyester polyol, lactone type polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone can be exemplified. Further, like the carboxylic acids, monoalcohols such as aliphatic alcohols, aromatic alcohols and alicyclic alcohols can be used.

An essential requirement of the polyester resin of the present invention is to use a monomer having an aromatic polycyclic condensed ring hydrocarbon as a skeleton as an essential component. As the aromatic polycyclic condensed ring hydrocarbon, indene, naphthalene, fluorene, phenanthrene, anthracene, pyrene, chrysene, naphthacene, benzophenanthrone, dibenzophenanthrene,
2H-indene, 3H-fluorene, 1,4-dihydronaphthalene, etc. can be exemplified, and in the present invention, monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and / or polycarboxylic acids derived from these skeletons are used. Carboxylic acid, monoalcohol, glycol, trio
It is possible to use polyhydric alcohol, tetraol, and / or polyalcohol having a higher content. In addition to such polycyclic fused ring hydrocarbon carboxylic acid and alcohol, other substituents may be present as long as they do not hinder polyester polymerization.
The monomer having an aromatic polycyclic condensed ring hydrocarbon as a skeleton used in the present invention is preferably one having naphthalene or anthracene as a skeleton, and more preferable specific compound is 2,6-naphthalenedicarboxylic acid. ,
1,5-naphthalenedicarboxylic acid, naphthalene methano-
And anthracene dipropionic acid, anthracene dipropionic acid, anthracene carboxylic acid, anthracene methanol, anthracene dimethanol, and the like. The amount of the monomer having an aromatic polycyclic condensed ring hydrocarbon as a skeleton is 1 mol% or more, preferably 1 mol% or more, with respect to one of the components of the carboxylic acid or the alcohol constituting the polyester. Two
It is preferable to use mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, still more 20 mol% or more, still further 30 mol% or more, even more preferably 50 mol% or more. Further, it is preferable to add a monomer having a naphthalene skeleton in a range exceeding 10 mol%. If the amount added is less than this range, a sufficient ultraviolet absorbing effect may not be obtained.

In the present invention, in addition to these, a monocyclic hydrocarbon,
A heteromonocyclic compound and / or a monomer having a condensed heterocyclic compound as a skeleton can be used. Cyclohexene is a monocyclic hydrocarbon that can serve as a monomer skeleton,
Examples thereof include cyclohexadiene, cyclopentene, cyclopentadiene, cyclopentylidene, and the like. Examples of the heteromonocyclic compound that can serve as a skeleton of the monomer include furan, thiophene, pyrrole, 2H-pyrrole, 2-pyrroline, pyrrolidine, oxazole, isoxazole and thiazo-
, Isothiazole, imidazole, 2H-imidazole
2-imidazoline, imidazolidine, pyrazole,
3-pyrazoline, pyrazolidine, 1H-1,2,3-triazol, 2H-1,2,3-triazol, 2H-
1,2,4-triazole, furazan, 1H-tetrazole, 2H-pyran, 4H-pyran, 4H-thiine, pyridine, piperidine, 4H-1,4-oxazine, morpholine, 4H-1,4- Examples thereof include thiazine, pyridazine, pyrimidine, pyrazine, piperazine, 1,3,5-triazine and the like.

Examples of the condensed heterocyclic compound which can be the skeleton of the monomer include benzofuran, isobenzofuran, benzothiophene, indol 3H-indole, indoline, isoindole, benzoxazole, benzothiazole, 1H. -Indazole, benzimidazole, 2
H-chromene, 4H-chromencoumarone, isocumalone, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, dibenzofuran, carbazol, xanthene, acridine, phenanthridine, 1,10-phenanthroline, phenazine, phenoxazine, thianthrene. , Indolizine, 4H-quinolidine, quinuclidine, 1,8-naphthyridine, purine,
Examples thereof include pteridine.

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 20.
00eq. 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 2000 eq./ton with respect to the polyester resin
Is essential, and is preferably 20 to 500 eq./to
n, more preferably 50 to 200 eq./ton.

It is essential that the average particle size of the fine particle dispersion in the present invention is 1.0 μm or less, preferably 0.5 μm or less, more preferably 0.2 μm or less, and further preferably 0.1 μm or less. is there. If the particle system of the fine particle dispersion exceeds this range, the dispersion stability may deteriorate.

A fine particle dispersion of the polyester resin can be obtained by the method described below. That is, when it contains an ionic group, the polyester resin of the present invention 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 aqueous dispersion of the ionic group-containing polyester resin is prepared by previously mixing the ionic group-containing polyester resin and the water-soluble organic compound, and then adding water, 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 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 building bath dye, a vat dye, a slene dye, a basic dye or the like can be used. In the cosmetics of the present invention, in addition to polyester particles which are an essential component, white, constitution, color pigments, pallets, natural minerals, organic powders, oils, metal soaps, which are usually used as cosmetic components depending on the product type, purpose, etc., 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,
Excellent effects can be obtained by blending with foundation, blusher, eye shadow, lipstick, eyeliner, mascara, eyebrow, eyebrow, pack, massage cream, foundation cream, lotion, etc. .

The polyester fine particle dispersion blended in the cosmetics of the present invention has a low specific gravity as compared with the inorganic particles and thus exhibits good dispersion stability and does not cause sedimentation even after long-term storage. Although it is a condensation type polymer, the unreacted monomer
It 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 a monomer having an aromatic polycyclic condensed ring hydrocarbon as a skeleton as an essential component, and therefore has a particularly excellent ultraviolet ray shielding effect. Due to the above actions, the cosmetic of the present invention inherits all the characteristics of the cosmetics using known polymer particles in terms of usability, feeling of use, and the like, in addition to conventional cosmetics mainly using inorganic particles. In terms of UV shielding effect, odor, safety, and degree of freedom in product design, it is more effective.

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

【Example】

[Polymerization of polyester resin] 1,5 naphthalenedicarboxylic acid dimethyl ester 171 parts by weight Isophthalic acid dimethyl ester 49 parts by weight 5-sodium sulfoisophthalic acid dimethyl ester 3 parts by weight in an autoclave equipped with a thermometer and a stirrer Parts 68 parts by weight of ethylene glycol, 114 parts by weight of neopentyl glycol, and 0.1 parts by weight of tetrabutoxytitanate were charged and the transesterification reaction was carried out by heating at 150 to 220 ° C. for 180 minutes. Next, the temperature of the reaction system is lowered to 180 ° C., 8 parts by weight of maleic anhydride and 0.1 part by weight of tert-butyl catechol are added, the reaction is continued at 200 ° C. for 60 minutes, and then the temperature of the reaction system is set to 220 ° C. After raising the temperature to ˜240 ° C., the system pressure 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 (A1). 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. Shown in. The composition of the polyester is NMR analysis, the glass transition temperature is DSC, the acid value is titrated, the molecular weight is GPC,
The sodium sulfonate group equivalent was determined by quantitative determination of S.
Thereafter, the raw materials were changed and the same polymerization was carried out. To obtain polyester resins (A2) to (A6).

[0020]

[Table 1] In addition, Table 1. Medium AMC is 9-anthracenecarboxylic acid ADC is 9,10-anthracene dipropionic acid NDC is 1,5-naphthalene dicarboxylic acid TPA is terephthalic acid IPA is isophthalic acid SIP is 5-sodium sulfoisophthalic acid TMA is trimellitic acid AM is 9-anthracene methanol EG is ethylene glycol NPG is neopentyl glycol BPP is propylene oxide adduct of bisphenol A (average molecular weight 350) Tg is glass transition temperature.

[Preparation of Polyester Water Fine Dispersion] To 200 parts of polyester resin (A1), 100 parts of butanol was added and dissolved at 90 ° C., and then cooled to 80 ° C. Further, a 1N aqueous ammonia solution was added so that the acid value was equal to the acid value of the polyester resin, and the mixture was stirred at 80 ° C. for 30 minutes and then 500 parts of water at 80 ° C. was added to obtain an aqueous polyester dispersion. 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, and a polyester fine particle water dispersion having a solid content concentration of 30% ( B1) was obtained. Similarly, from the polyester resin (A6) to the fine particle water dispersion (B6)
Got Polyester resin (A2) 200 parts by weight, methyl ethyl ketone 100 parts by weight, tetrahydrofuran 50
After dissolving 20 parts by weight of ethanol and 80 parts by weight of ethanol at 80 ° C., 500 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. The resulting water-based microdispersion was placed in a distillation flask,
Distillation was carried out until the distillate temperature reached 100 ° C., and water was added after cooling to obtain a polyester fine particle water dispersion (B1) having a solid content concentration of 30%. , The same as the following polyester resin (A
3) to (A5) were used to obtain polyester fine particle water dispersions (B3) to (B5).

[Evaluation of UV shielding effect] 70 parts by weight of the obtained polyester resin fine particle water dispersion, glycerin 30
The emulsion was prepared by mixing 1 part by weight and emulsified, and the resulting emulsion was applied on a quartz plate with an applicator to a coating film thickness of about 20 μm to prepare a sample for measuring the ultraviolet shielding effect. With respect to the above materials, the ultraviolet shielding rate was determined using Hitachi Spectrophotometer U-3210 type. The measurement wavelength is 320 to 400 n in the A region.
The m and B regions were set to 290 to 320 nm, and the average value of each region was obtained. The results are shown in Table 2. Shown in. The fine particle dispersion P
The average particle size was determined by the laser scattering method.

[Table 2]

[0023]

Comparative Example Using a fine particle water dispersion of a polymer obtained by emulsion polymerization of styrene and PMMA, the ultraviolet shielding effect was measured in the same manner as in the example. The results are shown in Table 3. Shown in.

[0024]

[Table 3] (Solid powder foundation) 40 parts by weight of polyester fine particle dispersion, 30 parts by weight of talc, 2 parts by weight of titanium oxide, 6 parts by weight of color pigment, 20 parts by weight of mica were uniformly mixed into a blender, and 2 parts by weight of vaseline. Part, squalane 8 parts by weight, liquid paraffin 2 parts by weight, and the mixture was further mixed by heating. Then, the obtained mixture was press-molded to obtain a solid powder foundation. Similarly, the particle dispersion was changed in the same manner as described above to manufacture a foundation. The obtained foundation can be easily removed to the mat regardless of which polyester particles, crosslinked polyester particles, or nylon particles are used, and the elongation at the time of application is good, and a uniform and natural cosmetic film with a feeling of adhesion is formed. However, it was excellent in the ultraviolet shielding effect.

[0025]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yozo Yamada 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd.

Claims (1)

[Claims] 1. A polyester resin containing an ionic group in the range of 20 to 2000 eq./ton and containing as an essential component a monomer having an aromatic polycyclic condensed ring hydrocarbon as a skeleton. A cosmetic comprising a fine particle dispersion having an average particle diameter of 1.0 μm or less as a component.