JPH09183617A - Porous calcium carbonate-based compound and cosmetic composition containing the same - Google Patents

Abstract

(57) Abstract: [PROBLEMS] To provide a porous calcium carbonate-based compound having a specific particle size distribution, excellent dispersibility, and being transparent because it is porous, and having high oil absorption performance and moisture retention performance. SOLUTION: This is a reaction product of calcium carbonate and a phosphoric acid compound, and has an average particle diameter, a dispersion coefficient, a sharpness, and a BE.
It is composed of particles having T specific surface area, oil absorption, and water absorption as specific values.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a porous calcium carbonate compound and a cosmetic composition containing the same. More specifically, it has a specific particle size distribution, is excellent in dispersibility, has a transparent feeling because it is porous, and contains a porous calcium carbonate-based compound having high oil absorption performance and moisture retention performance, and this. The present invention relates to a cosmetic composition which has good spreadability upon application, has a natural transparent feeling, prevents shining due to excess oil in sebum, and prevents bulkiness, stickiness and the like, and has an excellent feeling of use.

[0002]

2. Description of the Related Art In general, an inorganic powder such as an extender pigment, a white pigment, a coloring pigment, and a pearl pigment is used for a foundation. For extender pigments, calcium carbonate,
Talc, kaolin, mica, titanium oxide, zinc oxide, etc. are used, but many of them have large variations in particle size.
When applied, the thickness becomes uneven, resulting in "elongation" and "stickiness".
There is a problem in usability. Further, most of these inorganic powders have a high hiding power, and there is a problem that the skin cannot have a natural transparent feeling. In addition, it is necessary to absorb excess oil and to retain moisturizing properties in order to prevent shiny, bulky, and sticky feelings, but conventional extender pigments require only a small amount to add sufficient oil absorption and moisturizing properties. Can't exert. Anhydrous silica is widely used as a thickener and scrubbing agent added to facial cleansers and massage creams.
Although it has excellent physical properties, it is not only problematic in use due to its high hardness, but also expensive in terms of dispersibility with uniform particle diameters, so there is also a problem in terms of cost. is there.

[0003]

DISCLOSURE OF THE INVENTION According to the present invention, a porous calcium carbonate compound having a specific particle size distribution, excellent dispersibility, and being porous and therefore transparent, having high oil absorption and moisturizing properties. , And containing this, it has good elongation during application, has a natural transparent feeling, and prevents shining due to excess oil in sebum, and also prevents bulkiness, stickiness, etc. In addition to the above, there is provided a cosmetic composition capable of exhibiting a thickening effect or a scrubbing effect at low cost.

[0004]

Means for Solving the Problems As a result of intensive research to solve the above problems, the present inventors have found that a porous material having a specific sharp particle size distribution, which is composed of a reaction product of calcium carbonate and a phosphoric acid compound. The calcium carbonate-based compound has good dispersibility, has high oil absorption performance and high moisturization performance because it is porous, and has a transparent feeling, and a cosmetic composition containing the same has good elongation at application, The present invention has been completed by finding that it has a natural transparency and has excellent oil absorption performance and moisturizing performance, and therefore, it prevents the glossiness and stickiness.

That is, the first aspect of the present invention relates to a reaction product of calcium carbonate and a phosphoric acid compound, which is a porous calcium carbonate compound characterized by comprising particles satisfying the following formula. (A) 0.5 ≦ dx ≦ 20 (b) 1 ≦ α ≦ 3 (c) 0 ≦ β ≦ 3 (d) 50 ≦ Sw ≦ 300 (e) 50 ≦ x ≦ 300 (f) 50 ≦ y ≦ 300 However, dx: average particle diameter (μ
m) α: dispersion coefficient α = d ₅₀ / dx d ₅₀ : 50% average particle diameter (μm) of particles measured by Microtrac FRA laser particle size distribution meter β: sharpness, the smaller the particle size distribution value, the smaller the particle size The distribution is sharp β = (d ₉₀ −d ₁₀ ) / d ₅₀ d ₉₀ : 90% cumulative total of particles passing through the sieve measured by a Microtrac FRA laser type particle size distribution particle size (μ
m) d ₁₀ : 10% cumulative total of particles passing through a sieve measured by a Microtrac FRA laser particle size analyzer (μ)
m) Sw: BET specific surface area (m ² / g) by nitrogen adsorption method x: Oil absorption (ml / 100 g) Measured according to JIS K5101. y: Water absorption (cc / 100 g) 5 g of the sample is placed on a glass plate for measuring oil absorption whose center is ground glass,
Measured by JIS K5101.19 using water The second aspect of the present invention relates to a cosmetic composition containing the above-mentioned porous calcium carbonate-based compound.

The porous calcium carbonate-based compound of the present invention is a reaction product of calcium carbonate and a phosphoric acid-based compound as described above, and is characterized in that it comprises particles satisfying the following formula. (A) 0.5 ≦ dx ≦ 20 (b) 1 ≦ α ≦ 3 (c) 0 ≦ β ≦ 3 (d) 50 ≦ Sw ≦ 300 (e) 50 ≦ x ≦ 300 (f) 50 ≦ y ≦ 300 In the above, when dx is less than 0.5, the elongation when applied is poor, and when it exceeds 20, the feeling of roughness becomes strong and the adhesiveness is low. Further, when α exceeds 3, many particles are aggregated to form secondary particles and become amorphous particles, so that the elongation when applied is poor and the adhesiveness is low. On the other hand, when β exceeds 3, variation in particle size is large and the thickness of the coating film becomes uneven, which causes color unevenness. Furthermore, if Sw is less than 50,
Transparency is reduced because there are few voids, and both oil absorption and water absorption are less than 50, causing stickiness and glazing. When it exceeds 300, both oil absorption and water absorption exceed 300 and a suitable oil absorption. For the purpose of imparting the property and water absorbency, the addition amount becomes extremely small, and therefore, it does not contribute to the elongation upon application and the physical properties in the feeling of use such as adhesiveness. The same applies to x and y.

The porous calcium carbonate-based compound of the present invention is preferably one which satisfies the following formula because it gives a good feeling when used on the skin. (G) 1 ≦ dx ≦ 15 (b) 1 ≦ α ≦ 3 (c) 0 ≦ β ≦ 3 (d) 50 ≦ Sw ≦ 300 (e) 50 ≦ x ≦ 300 (f) 50 ≦ y ≦ 300

The porous calcium carbonate-based compound used in the present invention can be easily obtained by reacting calcium carbonate with a phosphoric acid-based compound as described in JP-A-7-223813. The calcium carbonate used is not particularly limited and may be either heavy calcium carbonate or synthetic calcium carbonate. Further, the size of particles, the shape of particles, the dispersed state of particles, the crystal form, the degree of impurities in calcium carbonate, etc. are not particularly limited.

Various types of phosphoric acid compounds can be used, but soluble phosphoric acid compounds are preferable in terms of reactivity with calcium carbonate. Soluble phosphate compound, for example _{H 3 PO 4, K 3 PO} 4, KH 2 PO 4, Na 2 HPO 4 · 1
2H ₂ O, (NH ₄ ) PO ₃ , 3H ₂ O and the like can be mentioned. Of course, these may be used alone or in combination of two or more. The reaction amount of the phosphoric acid compound is preferably about 1 to 55% by weight with respect to calcium carbonate. Of course, it may be more than this depending on the application. Generally, as the reaction amount of the phosphoric acid compound increases, the BET specific surface area increases under the same reaction conditions, that is, the porosity progresses. However, there is an inflection point, and when reacted over a certain amount, the particles agglomerate with each other, and the BET specific surface area does not increase any further.
In addition, the holes are slightly distorted. On the other hand, under the same reaction conditions, generally, the smaller the reaction amount of the phosphoric acid compound,
The pore diameter is small. The larger the amount of reaction, the larger the diameter and the petal shape. As a general method of the porous calcium carbonate-based compound of the present invention, a method of adding a phosphoric acid-based compound to an aqueous slurry of calcium carbonate is preferable.

The reaction conditions include (1) the reaction temperature of the system,
(2) Charge time of phosphoric acid compound, (3) stirring conditions,
(4) The time of standing with stirring (aging) after mixing both, (5) the concentration of the reaction system, etc. are involved as the reaction conditions for making the material porous.

With respect to the above (1), it is preferable to react in the range of 15 to 30 ° C. If the reaction does not proceed satisfactorily with this, after mixing both, the temperature may be further raised by about 15 to 20 ° C. If the reaction is performed at a temperature of 50 ° C. or higher from the beginning, the pores are likely to become distorted.

As for the above (2), as described above,
In general, a method of adding the phosphoric acid compound to the calcium carbonate water slurry is preferable, but in this case, a method of charging the phosphoric acid compound for 30 to 60 minutes or more is preferable, instead of charging all at once. If it is thrown in at a stretch, the particles tend to aggregate and the pores become distorted.

With regard to (3), it is desirable to stir with a strong stirring force of a certain level or more. If the stirring power is weak, uniform pores cannot be formed in the whole particles, and good dispersibility and sharp particle size distribution cannot be obtained. The stirring power of a certain level or more means that the entire suspension system can be uniformly stirred, and a paddle, a turbine, a propeller, and a high-speed impeller disperser can be used as the stirring mechanism. It is preferable to attach a baffle plate to the container. Stirring power is 0.2-50 kW /
Power of m ³ is preferred, dispersibility is less than 0.2 kw / m ³ ,
The particle size distribution becomes worse, and when it exceeds 50 kw / m ³ , it becomes difficult to increase the size of the reactor and the production efficiency remarkably decreases.

With regard to the above (4), it is desirable that after the two are mixed, they are aged with stirring for preferably 5 hours or more, more preferably 20 hours or more.

Regarding the above (5), considering the production efficiency of calcium carbonate, it is preferable that the amount of calcium carbonate is 50 to 200 g CaCO ₃ / liter, more preferably about 60 to 150 g CaCO ₃ / liter.

The above (1) to (5) assume a method of adding a soluble phosphoric acid compound to an aqueous slurry of calcium carbonate. Such a porous material generally has a BET specific surface area of about 3 to 10 times that of the initial calcium carbonate. The size of the holes generated in the present invention is about 0.01 to 1.0 μm on average. Generally, when the both are slowly reacted with each other over time, the pores are small and the porosity is uniform. However, the above reaction temperature, stirring force, etc. also act in a complicated manner. On the other hand, colloidal calcium carbonate with a primary particle size of 1 μm or less or several μm
The light calcium carbonate (1) has agglomerated particles when it is made porous by the above method, and the single particles tend to be considerably larger than the original calcium carbonate.

The reason why the calcium carbonate is made porous is not always clear, but it is considered that calcium phosphate is fixed to the surface of the calcium carbonate to form a porous state.

The porous calcium carbonate-based compound of the present invention obtained as described above has the above-mentioned sharp particle size distribution, is excellent in dispersibility, has good elongation at the time of coating, and is porous. It has a natural transparency, high oil absorption and moisturizing properties, and when incorporated into cosmetics, it prevents excess oil in the sebum from shining and prevents bulkiness and stickiness, resulting in an excellent feeling of use. A cosmetic composition having is provided. Further, since the porous calcium carbonate-based compound of the present invention has a high thickening effect, by blending it with the water phase or oil phase of creams, it is possible to prevent separation of water and oil,
It is also possible to carry a fragrance or the like. Furthermore, since the porous calcium carbonate-based compound of the present invention is spherical and has a controllable particle size, it can be used as a scrubbing agent that does not damage the skin, such as a facial cleanser or a massage cream.

The porous calcium carbonate compound can be widely applied to cosmetics containing powder, and can be used in cosmetics by the same compounding method as conventional pigments. For example, foundation, lipstick, eye shadow, eyeliner,
Examples include makeup cosmetics such as dusting powder and face powder. Further, by applying the thickening effect and the scrubbing effect, it can be used for massage cream, cleansing cream, face washing soap, body soap and the like.
The amount of the porous calcium carbonate compound compounded in the cosmetic composition can be selected according to the purpose, but is generally 2 to 95% by weight, preferably 10 to 90% by weight. If it is less than 2% by weight, no sufficient effect can be expected, and 9
If it exceeds 0% by weight, water absorption and oil absorption will be too high,
It reduces usability.

[0020]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

Example 1 Preparation of Porous Calcium Carbonate Compound (Small Particle Size) Cubic calcium carbonate having a primary particle diameter of 0.07 μm, solid concentration of 10% by weight of water slurry was prepared and agitated. After the temperature was set to 30 ° C., 55% by weight of phosphoric acid with respect to calcium carbonate was added dropwise with stirring so as to have a pH of 5 to 6.5. After the dropping, the slurry temperature is set to 50 ° C.
The temperature was raised to 10 minutes and aged for 10 hours. 25kw / stirring
It was carried out by the power of m ^3. After the completion of the reaction, the slurry was dehydrated, dried and pulverized to obtain a spherical porous calcium carbonate-based compound having a single particle of 2.0 μm and good dispersion. Table 1 shows the powder properties of the obtained porous calcium carbonate compound (Sample No.).

Example 2 Production of Porous Calcium Carbonate Compound (Medium Particle Size Product) Commercially available heavy calcium carbonate having a primary particle size of 3.36 μm (trade name “Super SSS”, manufactured by Maruo Calcium Co., Ltd.) A water slurry having a solid content concentration of 15% by weight was prepared, the slurry temperature was adjusted to 30 ° C. with stirring, and then 40% by weight phosphoric acid was added dropwise to calcium carbonate with stirring so as to have a pH of 5 to 6.5. After the completion of dropping, the slurry temperature was raised to 50 ° C. and aged for 15 hours. Agitation 2
It was performed with a power of 5 kw / m ³ . After the completion of the reaction, the slurry was dehydrated, dried, and pulverized to obtain a spherical porous calcium carbonate-based compound in which single particles were dispersed at 5.5 μm. Table 1 shows the powder properties of the obtained porous calcium carbonate compound (Sample No.).

Example 3 Production of Porous Calcium Carbonate Compound (Large Particle Size) Phosphoric acid 30% by weight with respect to calcium carbonate
A spherical porous calcium carbonate-based compound in which single particles were dispersed at 12.5 μm was obtained by the same method as in Example 2 except that kw / m ³ was used. Table 1 shows the powder properties of the obtained porous calcium carbonate compound (Sample No.).

Comparative Example 1 By the same method as in Example 1 except that stirring was carried out at 0.1 kw / m ³ , an amorphous porous calcium carbonate compound in which single particles were aggregated at 2.1 μm was obtained. Table 1 shows the powder properties of the obtained porous calcium carbonate compound (Sample No.).

Comparative Example 2 For comparison, Table 1 shows the powder physical properties of commercially available heavy calcium carbonate (trade name "Super SSS", manufactured by Maruo Calcium Co., Ltd.) (Sample No.).

[0026]

[Table 1]

However, dx: average particle diameter (μ
m) α: dispersion coefficient α = d ₅₀ / dx d ₅₀ : 50% average particle diameter (μm) of particles measured by Microtrac FRA laser particle size distribution meter β: sharpness, the smaller the particle size distribution value, the smaller the particle size The distribution is sharp β = (d ₉₀ −d ₁₀ ) / d ₅₀ d ₉₀ : 90% cumulative total of particles passing through the sieve measured by a Microtrac FRA laser type particle size distribution particle size (μ
m) d ₁₀ : 10% cumulative total of particles passing through a sieve measured by a Microtrac FRA laser particle size analyzer (μ)
m) Sw: BET specific surface area (m ² / g) by nitrogen adsorption method x: Oil absorption (ml / 100g) Measurement according to JIS K5101 y: Water absorption (cc / 100g) 5g sample, oil absorption with ground glass Take it on a glass plate dedicated to quantity measurement,
Measured according to JIS K5101.19 using water

Using Examples 4 to 6 and Comparative Examples 3 and 4 and the samples shown in Table 1, solid foundations having the following compositions were produced. Composition: (A) Sample 56.5% by weight Mica 16.0% by weight Titanium oxide 13.5% by weight Red iron oxide 0.8% by weight Yellow iron oxide 2.0% by weight Black iron oxide 0.2% by weight Para benzoin Methyl acid 0.2% by weight (B) Squalane 10.5% by weight Perfume 0.3% by weight Production method: The above (A) was uniformly mixed with a Henschel mixer and pulverized with a pulverizer. The obtained pulverized product was again mixed with (B) in a Henschel mixer uniformly, pulverized with a pulverizer,
The product was pressed with a metal dish.

The feeling of use of the obtained solid foundation was evaluated by 10 female panelists. With respect to the evaluation items of the feeling of use, seven items of spread, moisturizing feeling, transparency feeling, bulk feeling, adhesion to skin, sticky feeling, and shiny feeling were evaluated according to the following evaluation criteria. Table 2 shows the evaluation results.
From Table 2, it was confirmed that the cosmetic compositions of Examples 4 to 6 of the present invention were excellent in all evaluation items.

[0030]

[0031]

[Table 2]

[0032]

EFFECT OF THE INVENTION The porous calcium carbonate compound of the present invention is excellent in dispersibility, oil absorption performance, and moisturizing performance. By using this compound in cosmetics, elongation, moisturizing feeling, transparency feeling when used on skin, Provided is a cosmetic composition which is good in all respects such as bulkiness, adhesiveness, stickiness, and glossiness, and has an excellent feeling in use.

Claims (3)

[Claims] 1. A porous calcium carbonate-based compound, which is a reaction product of calcium carbonate and a phosphoric acid-based compound, and is composed of particles satisfying the following formula. (A) 0.5 ≦ dx ≦ 20 (b) 1 ≦ α ≦ 3 (c) 0 ≦ β ≦ 3 (d) 50 ≦ Sw ≦ 300 (e) 50 ≦ x ≦ 300 (f) 50 ≦ y ≦ 300 However, dx: average particle diameter (μ
m) α: dispersion coefficient α = d ₅₀ / dx d ₅₀ : 50% average particle diameter (μm) of particles measured by Microtrac FRA laser particle size distribution meter β: sharpness, the smaller the particle size distribution value, the smaller the particle size The distribution is sharp β = (d ₉₀ −d ₁₀ ) / d ₅₀ d ₉₀ : 90% cumulative total of particles passing through the sieve measured by a Microtrac FRA laser type particle size distribution particle size (μ
m) d ₁₀ : 10% cumulative total of particles passing through a sieve measured by a Microtrac FRA laser particle size analyzer (μ)
m) Sw: BET specific surface area (m ² / g) by nitrogen adsorption method x: Oil absorption (ml / 100g) Measurement according to JIS K5101 y: Water absorption (cc / 100g) 5g sample, oil absorption with ground glass Take it on a glass plate dedicated to quantity measurement,
Measured according to JIS K5101.19 using water 2. The porous calcium carbonate-based compound according to claim 1, wherein the particles satisfy the following formula. (G) 1 ≦ dx ≦ 15 (b) 1 ≦ α ≦ 3 (c) 0 ≦ β ≦ 3 (d) 50 ≦ Sw ≦ 300 (e) 50 ≦ x ≦ 300 (f) 50 ≦ y ≦ 300 3. A cosmetic composition comprising the porous calcium-based compound according to claim 1 or 2.