JP2000119171A - Collapsible particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a collapsible particle collapsing in cleansing and rinsing process and giving little skin inflammation and a cosmetic composition having remarkably excellent detergent and rinse out properties by including the same. SOLUTION: This collapsible particle comprises primary particles at least a part insoluble in water, and cohering by bonding with a water-soluble binder which includes at least one kind selected from the group comprising carboxylic acid modified polyvinyl alcohol, sulfonic acid modified polyvinyl alcohol, and a salt of carboxymethyl cellulose, and the cohesion of the collapsible particle is collapsed by the lowering of the concentration of the water-soluble salt in the aqueous solution of the water-soluble salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to disintegrating particles that cause less skin irritation due to the disintegration of the particles in the course of washing and rinsing, and contains these particles to provide extremely good detergency and washability. The present invention relates to a cosmetic composition.

[0002]

2. Description of the Related Art Skin cleansing agents (facial cleansers, body soaps, solid soaps) containing particles (scrubbing agents) are used to remove excess keratin (pores) and pores which are difficult to remove with ordinary cleaning compositions in physical cleaning. It has the characteristic that dirt and the like that have entered can be removed.

[0003] In addition, there is a high-detergency and low-irritant cleaning agent in which the size and hardness of the scrub agent are controlled in consideration of the problem of skin inflammation (Japanese Patent Application Laid-Open No. 2-151693).

On the other hand, sodium chloride particles having a solubility equal to or higher than the saturation solubility are blended in a detergent composition, and sodium chloride is present as particles so that the detergent has a detergency and a smooth skin finish (Japanese Patent Laid-Open No. 6-305951). ).

[0005]

However, a cleaning agent containing a scrub agent having a controlled particle size and hardness has problems in use such as a feeling of foreign matter at the time of massaging and a difficulty in washing off after washing. I was

[0006] Further, a detergent composition containing sodium chloride particles having a saturation solubility or higher has a problem in dispersibility because the scrubbing agent is liable to cause aggregation, sedimentation and the like. In addition, since sodium chloride is contained at a level higher than the saturation solubility, there are problems such as foaming during washing, and deterioration in washability and usability.

[0007]

Means for Solving the Problems The present inventors have formulated, in addition to a surfactant and water, disintegrating particles using a water-soluble salt having less than the saturation solubility and a specific binder.
It has high detergency and excellent feeling in use, and furthermore, the disintegrating particles are disintegrated in the washing process and the rinsing process, so that the occurrence of skin irritation is small, and the disintegrating particles are easily disintegrated by rinsing water or tears. It has been found that a cosmetic composition having extremely good washability can be obtained.

That is, the present invention provides a disintegrable particle (hereinafter, referred to as a disintegrable particle) in which primary particles at least partially insoluble in water are bound and aggregated by a water-soluble binder.
Wherein the binder contains at least one selected from the group consisting of carboxylic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol and carboxymethylcellulose salt, and has a water-soluble salt concentration in a water-soluble salt-containing aqueous solution. An object of the present invention is to provide disintegrable particles in which the aggregation of the disintegrable particles is disintegrated by the decrease.

The present invention also comprises the above-mentioned disintegrable particles, a water-soluble salt, a surfactant and water, wherein the content of the disintegrable particles is 1 to 25% by weight in the composition. It is intended to provide a cosmetic composition having a concentration of 1.0% by weight or more and less than a saturation solubility.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The average particle size of the disintegrable particles used in the present invention is preferably from 100 μm to 1000 μm from the viewpoint of discomfort when using cosmetics and skin irritation.
125 μm to 800 μm is more preferred.

The primary particles constituting the disintegrable particles of the present invention may be at least partially water-insoluble primary particles. For example, water-insoluble primary particles or a combination of water-insoluble primary particles and water-soluble primary particles may be used. preferable. These primary particles may be organic particles or inorganic particles. Here "water-insoluble"
Means that when 1 part by weight of the target particle is dissolved in 99 parts by weight of water at 25 ° C., the solubility is less than 50% by weight;
"Water-soluble" means that the solubility under the same conditions is 50% by weight or more. The solubility was determined by filtering the aqueous solution with filter paper (N
o. The solution is filtered in 2) and calculated from the solid content in the filtrate. The water-soluble primary particles preferably have a solubility of 90% by weight or more.

The water-insoluble organic primary particles include polyethylene, polypropylene, polyamide, polyethylene terephthalate, polystyrene and polyurethane and / or a cross-linked product thereof, sodium poly (meth) acrylate and poly (meth) acrylate and / or Ethylene rubber, propylene rubber, styrene-
Synthetic polymers such as butadiene rubber, butadiene rubber, silicone rubber and the like and / or cross-linked products thereof; natural polymers such as cellulose and / or derivatives thereof, chitosan and / or derivatives thereof, starch, fruit shells and the like; And / or derivatives thereof. Among them, polyethylene, polyamide, polystyrene, cross-linked poly (meth) acrylate, cross-linked poly (meth) acrylate,
Cellulose and / or its derivatives, starch and the like are preferably used. Here, “poly (meth) acrylic acid” means both “polyacrylic acid” and “polymethacrylic acid”.

The water-insoluble inorganic primary particles include, for example, bentonite, talc, mica, kaolin, sepiolite, silica, calcium carbonate, titanium oxide, silicic acid anhydride, hydroxy calcium apatite, and pearls. Among them, bentonite, talc, mica, kaolin, silica and the like are preferably used.

These water-insoluble primary particles may have a true spherical shape, a substantially spherical shape, a flat plate shape, a rod shape, or an irregular shape due to pulverization or the like, and hollow or porous particles may be used.
Further, these water-insoluble primary particles may be used alone or in combination of two or more, but it is more preferable to use three or more in combination.

As the water-soluble organic primary particles, polyvinyl alcohol and / or a derivative thereof, an alkali salt of poly (meth) acrylate, an alkali salt of (meth) acrylic acid / (meth) acrylate copolymer, acrylic acid / maleic Synthetic polymers such as alkali salts of acid copolymers and polyvinylpyrrolidone; methylcellulose, ethylcellulose, sodium carboxymethylcellulose, hydroxyalkylcellulose, modified starch (hydroxyalkyl-modified starch, phosphate-modified starch, etc.), sucrose, lactose, etc. Saccharides: Natural polymers such as seaweeds and proteins are used.

The water-soluble inorganic primary particles include chlorides such as sodium chloride, potassium chloride and magnesium chloride; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate and aluminum sulfate; carbonates such as sodium carbonate and sodium hydrogen carbonate. Salts. In the case of sodium chloride, salt, high-purity purified salt, natural salt and the like are used. Among them, inorganic particles such as sodium chloride, potassium chloride, magnesium chloride and sodium carbonate are preferred.

The shape of these water-soluble primary particles is not limited either, and they may be used alone or in combination of two or more.

The weight ratio of the water-insoluble primary particles to the water-soluble primary particles in the disintegrable particles of the present invention is preferably (water-insoluble primary particles) / (water-soluble primary particles) = 1/99 to 100/0, 50/50 to 100/0 is more preferred.

The average particle size of these primary particles is preferably 70 μm or less in view of the washing process of the body to be cleaned and the discomfort and washability of the primary particles when disintegrated by rinsing water or tears.

The disintegrable particles of the present invention are those in which the primary particles are bound and aggregated by the water-soluble binder. As the carboxylic acid-modified polyvinyl alcohol, modified species include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid, among which methacrylic acid,
Maleic acid and itaconic acid are preferably used. The denaturation rate is set at 0.
1 to 8 mol% (molar ratio of the monomer having the modified species in the polyvinyl alcohol composition to the total of vinyl acetate and the modified species) is preferred. 300-250 as the degree of polymerization
0 is preferable, and more preferably 500 to 2,000. Sulfonic acid-modified polyvinyl alcohol is a sulfonic acid salt-containing polymerizable monomer (for example, 2-acrylamide-2).
-Methylpropanesulfonate) incorporated into the polyvinyl alcohol skeleton. The denaturation rate is 0.1 to 8 from the viewpoint of disintegration due to a decrease in salt concentration and feeling in use.
mol% is preferred. The polymerization degree is preferably from 300 to 2500, more preferably from 500 to 2,000. In the case of a carboxymethylcellulose salt (for example, an alkali metal salt, an ammonium salt or the like as a salt), the degree of etherification (ratio of a hydroxyl group substituted with a carboxymethyl group among three hydroxyl groups present in anhydroglucose unit of cellulose: From 0 to 3.0), preferably from 0.2 to 1.2, more preferably from 0.3 to 1.1, from the viewpoint of disintegration due to a decrease in salt concentration and feeling of use. . As the water-soluble binder, a binder other than carboxylic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, and carboxymethyl cellulose may be used in combination.

In the disintegrable particles of the present invention, the water-soluble primary particles and the water-soluble binder may use the same type of material or different materials.

The water-soluble binder is preferably used in an amount of 0.5 to 30% by weight, more preferably 0.75 to 25% by weight, based on the weight of the primary particles. In this case, the amount of the water-soluble binder used is preferable from the viewpoint of the disintegration of the particles and the workability during the production of the disintegrable particles or the cosmetic composition containing the same.

The method for producing the disintegrable particles of the present invention is not particularly limited. For example, while mixing and / or mixing the primary particles and a water-soluble binder, tumbling granulation, tumbling fluidized granulation, fluidized bed granulation are performed. It is preferably produced by a granulation method such as granulation, stirring tumbling granulation, melt granulation, extrusion granulation method, spray drying granulation and / or a coating method such as spray drying.

The disintegrable particles of the present invention thus obtained are
As described above, in an aqueous solution containing a water-soluble salt, the water-soluble salt has a characteristic that the disintegration rate increases due to a decrease in the water-soluble salt concentration. Therefore, when the disintegrating particles are incorporated into a cosmetic composition, the disintegrating particles are stably dispersed without disintegration in the cosmetic composition, and the concentration of the water-soluble salts in the washing step and the rinsing step is reduced. The disintegrable particles disintegrate with the decrease. Taking into account the incorporation into such a cosmetic composition, the disintegration properties of the disintegrable particles of the present invention can be determined in an aqueous solution having a water-soluble salt concentration of less than 1.0% by weight, more preferably less than 1.5% by weight. It is preferable to design at least a part to collapse, and from the viewpoint of rinsing water and tearability,
Furthermore, it is designed such that 70% by weight or more of the disintegrable particles before washing (that is, before disintegration) disintegrates in an aqueous solution having a water-soluble salt concentration of less than 1.0% by weight, more preferably less than 1.5% by weight. More preferably. Further, it is preferable that the collapsed particles at this time have an average particle diameter of 74 μm or less.

The cosmetic composition of the present invention contains the above-mentioned disintegrable particles, a water-soluble salt, a surfactant and water, and the content of the disintegrable particles is determined from the viewpoint of feel and physical (mechanical) detergency. It is 1 to 25% by weight, preferably 2 to 20% by weight in the composition.

The water-soluble salts used in the cosmetic composition of the present invention include water-soluble inorganic salts and water-soluble organic salts, with water-soluble inorganic salts being preferred.

Examples of the water-soluble inorganic salt include chlorides such as sodium chloride, potassium chloride and magnesium chloride; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate and aluminum sulfate; carbonates such as sodium carbonate and sodium hydrogen carbonate. Is mentioned. In the case of sodium chloride, salt, high-purity purified salt, natural salt and the like are used.
Among them, sodium chloride, potassium chloride, magnesium chloride, sodium sulfate and sodium carbonate are particularly preferably used.

Examples of the water-soluble organic salt include citrate, succinate, maleate, fumarate, malate, etc., fatty acid soaps, ester phosphates, acylated amino acid salts, sulfosuccinates, and the like. Anionic surfactants such as taurate-based surfactants and amphoteric surfactants such as betaine stearyldimethylaminoacetate, trimethylglycine and laurylhydroxysulfobetaine are used. These water-soluble inorganic salts and water-soluble organic salts can be used in combination. In such a case, the weight ratio (water-soluble inorganic salt)
// (water-soluble organic salt) = 100/0 to 5/95 is preferable in view of improvement in detergency, and 90/10 to 10/90 is more preferable.

The content of these water-soluble salts is less than the saturation solubility in water in the cosmetic composition, but the stability of the disintegratable particles in the composition, the disintegration by rinsing or tearing, and the cosmetic From the viewpoint of the foaming property of the mixture, the solubility is preferably 1.0% by weight or more and less than the saturation solubility, more preferably 1.5% by weight or more and less than the saturation solubility, and particularly preferably 2% by weight or more and 0.8 times or less the saturation solubility. preferable.

The surfactants (except those used as the water-soluble organic salts) used in the cosmetic composition of the present invention are not particularly limited. Examples thereof include fatty acid soaps, phosphates, acylated amino acids, and sulfosuccinic acids. , Anionic surfactants such as taurate surfactants and polyoxyethylene alkyl sulfates; and nonionic surfactants such as alkyl saccharides and EO addition surfactants. Among them, phosphoric esters, acylated amino acids, alkyl saccharides and the like are preferred because they cause less skin irritation.

Although the surfactant and the water-soluble organic salt used in the cosmetic of the present invention partially overlap, an ionic surfactant which functions as a salt should be used as a water-soluble salt. Can be. The amount of the surfactant is not particularly limited, but is 60 to 90% by weight when the detergent is a solid, 40 to 70% by weight when a detergent is used, 40 to 70% by weight when a detergent is used, and when the detergent is a liquid. It is preferable to mix 10 to 50% by weight. Further, it is also preferable to use an amine oxide, an imidazoline-based surfactant, or a betaine-based surfactant as a foaming property improver.

In addition to the above components, components commonly used in cosmetics,
For example, oils, thickeners, wetting agents, coloring agents, preservatives, feel improvers, fragrances, anti-inflammatory agents, bactericides, ultraviolet absorbers, humectants, etc. may be used as long as the effects of the present invention are not impaired. it can.

The disintegrating particles of the present invention include face wash, whole body cleanser, skin cleanser such as solid soap, shampoo, scalp cleanser, dishwashing cleanser, contact lens cleanser, toothpaste, hair restorer and the like. It can be widely used for massage agents.

[0034]

EXAMPLES The parts described below refer to parts by weight.

Production Example 1 of Disintegrable Particles 200 g of W-400G as primary particles was placed in an LFS-GS-2J high speed mixer (manufactured by Fukae Kogyo KK).
After premixing, 267 g of PVA-1 having an effective content of 15% was gradually added as a binder while rotating to granulate. The granulated product was dried at 70 ° C. for 24 hours, and 20 g of disintegrated particles (1) having an average particle size of 400 μm were obtained using a sieve.

Preparation Examples 2-4 of Disintegrable Particles The types and amounts of primary particles and the types and amounts of binders are shown in Table 1.
The disintegrable particles (2) to (4) were produced in the same manner as in Production Example 1 except that the particles were changed as shown in (1). The ratios in the tables represent parts by weight of the effective components.

Production Example 5 of Disintegrable Particles SPRAY DRYER SD-1 (manufactured by EYELA)
And 200% kaolin as the primary particle, 2% CM
800 g of C-1 was added and spray dried. The obtained particles are further dried at 70 ° C. for 24 hours, and the average particle size is 350 μm through a sieve.
Thus, 42 g of m disintegrable particles (5) were obtained.

Test Example The average particle size of the disintegrable particles obtained in Production Example and the disintegration rate in a salt solution were measured. Table 1 shows the obtained results.

(1) Method for Measuring Average Particle Size The average particle size was measured by a laser diffraction / scattering type particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.). The median diameter was used as the average particle diameter.

(2) Method of measuring the disintegration rate of disintegrable particles (0.9% saline disintegration rate A (%), 10% saline disintegration rate B (%)) 0.9% saline solution in 29.7 g 0.3 g of each disintegrable particle was added and stored in a thermostat at 35 ° C. for 15 hours. Next, 6 g of this sample was weighed on artificial leather, and one more
Cover with a piece of artificial leather and apply 5 g / cm ² load before and after
After reciprocating, the mixture is filtered through a 200-mesh (sieve diameter 74 μm) sieve, and the dry weight of the residue is measured. At this time, the ratio by which the disintegrable particles passed through a 200-mesh sieve was expressed as a percentage by weight, and was defined as a 0.9% saline solution disintegration rate A (%). The same operation was performed using 10% saline, and the 10% saline water disintegration rate B (%)
And

[0041]

[Table 1]

* 1: Mixing ratio in primary particles * 2 [(binder weight) / (primary particle weight)] × 10
0 W-400G: Cellulose powder, Nippon Paper Industries Co., Ltd. PVA-1: Itaconic acid-modified polyvinyl alcohol, product name KL-506, Kuraray Co., Ltd. Sodium chloride: Special grade salt, Naikai Salt Industry Co., Ltd. PVA-2 : Sulfonic acid-modified polyvinyl alcohol, corn starch manufactured by Kuraray Co., Ltd .: Corn starch: Japanese Pharmacopoeia, Matsutani Chemical Industry Co., Ltd. PVA-3: Maleic acid-modified polyvinyl alcohol, product name SPC-20A, Shin-Etsu Chemical Co., Ltd., PE -1080: Polyethylene beads, Sumitomo Seika Co., Ltd.
MK-100: Synthetic mica, Corp Chemical Co., Ltd. PVA / CMC: Maleic acid-modified polyvinyl alcohol, product name Gosenal T-330, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., sodium carboxymethylcellulose, degree of etherification 0.80 A binder obtained by mixing FT-3, manufactured by Nippon Paper Industries Co., Ltd., at a weight ratio of 90:10. Kaolin: CMC-1 manufactured by Wako Pure Chemical Industries, Ltd .: sodium carboxymethylcellulose,
Degree of etherification 0.44, product name L-3600, manufactured by Nippon Paper Industries Co., Ltd.

As can be seen from Table 1, the disintegrable particles of the present invention have a lower disintegration rate of the disintegrable particles when the salt concentration is lower in the aqueous solution containing the water-soluble salts than when the salt concentration is higher. Is found to rise.

Examples 1 to 6 and Comparative Examples 1 to 2 Disintegrable particles 1 to 5 and powdery silica (average particle size 210 μm)
m) or CL-5007 (average particle size: 360 μm, polyethylene beads, manufactured by Sumitomo Seika Co., Ltd.) to prepare a cosmetic composition having the composition shown in Table 2. Using these cosmetic compositions, the disintegration rate, washing rate, foaming property, massage feeling, and washability were evaluated for Examples 1 to 6 and Comparative Examples 1 and 2, respectively, by the following measurement methods. Table 3 shows the results.

(A) Method for Measuring Disintegration Rate of Disintegrable Particles in Cosmetic Composition (Disintegration Rate (%)) 3 g of the cosmetic composition and 3 g of tap water are weighed on artificial leather, and another sheet is taken. After covering with artificial leather and applying a load of 5 g / cm ² and reciprocating 5 times back and forth, 200 mesh (particle size 74)
(μm), and the dry weight of the residue is measured. The decay rate conforms to the above-mentioned measuring method (2). (B) Washing rate (%) 1-[(p-phenylazo) -phenyl] on artificial leather
Solid fat dyed with azo [2-naphthol] is 15m in diameter
m, applied to a thickness of 0.1 mm and washed with cosmetics of Examples and Comparative Examples containing collapsible particles or other particles, or cosmetics containing purified water instead of collapsible particles or other particles The remaining solid fat was dissolved in an organic solvent, the absorbance was measured, and the measured value was compared with the measured absorbance of the solid fat of the unwashed product to determine the washing rate. These were put into the following equation to determine the cleaning rate.

[0046]

(Equation 1)

Where W = detergency W ₁ = absorbance of cosmetic containing collapsible particles or other particles W _O = absorbance of cosmetic containing purified water

(C) Foaming property 20 g of the cosmetic composition and 20 g of tap water were placed in a 120 ml glass container (40 mm in diameter), shaken 20 times, and then allowed to stand.
From the height (mm) of the foam after 0 seconds and 5 minutes, the foamability was checked.

(D) Massage Feeling Ten female professional panelists performed face washing, and the sensory evaluation of the massage feeling was carried out and judged according to the following criteria.

◎: 8 to 10 persons evaluated good. ：: 6 to 7 persons evaluated it as good. B: Five or less evaluated as good. X: Even one person was evaluated as feeling discomfort and irritation.

(E) Rinse-off properties Ten female panelists were subjected to face-washing, and the sensory evaluation of the wash-off property was made based on the presence of particles during face-washing and rinsing, and the following criteria were used.

◎: 8 to 10 persons evaluated good. ：: 6 to 7 persons evaluated it as good. B: Five or less evaluated as good. X: Even one person was evaluated that the particles remained.

[0053]

[Table 2]

[0054]

[Table 3]

As can be seen from Table 3, it is clear that the disintegrating particles in the cosmetic composition of the present invention disintegrate in the washing step and the rinsing step, and are excellent in washability.
Further, when the cosmetic composition of the present invention was used, the washing rate was high and the massage feeling was good. There is no skin irritation. Furthermore, since the concentration of the water-soluble salts in the cosmetic composition of the present invention is less than the concentration of the saturated salt, extremely high foaming properties are maintained, and the washing properties and the feeling upon use are excellent. The disintegrable particles in the cosmetic composition of the present invention were all favorable in the blending stability of the cosmetic composition in a storage test at 50 ° C.

[0056]

Industrial Applicability The cosmetic composition of the present invention is particularly excellent in physical (mechanical) detergency, excellent in stability over time, and has a good feeling in use. Furthermore, since the disintegrating particles are disintegrated in the washing step and the rinsing step, there is no skin irritation, and the disintegrating particles are easily disintegrated by rinsing water or tears, so that the washability is extremely good.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yoshihiro Hasebe 1334 Minato, Wakayama-shi, Wakayama Prefecture F-term in Kao Corporation Research Institute 4C083 AB332 AB432 AB442 AC122 AC242 AC482 AC542 AC562 AC902 AD022 AD111 AD112 AD242 AD262 AD271 BB25 BB36 CC23 EE01 EE06 EE12 4H003 AB03 AB46 BA10 BA12 BA28 DA02 EA19 EA27 EB05 EB07 EB09 EB14 EB28 EB29 EB33 EB41 EB42 ED02 FA15 FA21 FA33

Claims (5)

[Claims] Claims: 1. Disintegrating particles comprising at least a part of water-insoluble primary particles bonded and aggregated by a water-soluble binder, wherein the binder is a carboxylic acid-modified polyvinyl alcohol, a sulfonic acid-modified polyvinyl alcohol, Disintegrable particles containing at least one selected from the group consisting of carboxymethylcellulose salts, wherein the aggregation of the disintegrable particles is disintegrated due to a decrease in the concentration of the water-soluble salts in the aqueous solution containing the water-soluble salts. 2. The disintegrable particles according to claim 1, wherein the carboxylic acid-modified polyvinyl alcohol is itaconic acid-modified polyvinyl alcohol and / or maleic acid-modified polyvinyl alcohol. 3. The disintegrable particles according to claim 1, wherein the carboxymethyl cellulose salt has a degree of etherification of 0.2 to 1.2. 4. A composition comprising the disintegrable particles according to claim 1, a water-soluble salt, a surfactant and water, wherein the content of the disintegrable particles is 1 to 25% by weight in the composition. A cosmetic composition having a salt concentration of 1.0% by weight or more and less than the saturation solubility. 5. The disintegrable particles are at least partially disintegrated in a washing step and a rinsing step of the object to be washed, and the disintegration rate at which the disintegrable particles become particles of 74 μm or less is determined by the disintegration rate before washing. The cosmetic composition according to claim 4, wherein the amount is 70% by weight or more based on the particles.