JP4521477B1 - Amorphous silica - Google Patents

Abstract

Disclosed is a novel amorphous silica capable of continuously imparting excellent soft focus properties when blended in a cosmetic and a method for producing the same.
The primary particle diameter measured by an X-ray small angle scattering method is 18 to 50 nm, and the circularity of each particle observed with an electron microscope is 0.70 to 0.85.
[Selection figure] None

Description

  The present invention relates to a spherical amorphous silica having a unique primary particle size and a method for producing the same, and is particularly preferably used as an additive or the like blended in cosmetics to impart soft focus properties. The present invention relates to spherical amorphous silica and a method for producing the same.

  Currently, cosmetics such as foundations, base makers, and lipsticks require a property called soft focus. This soft focus means that, for example, when a cosmetic film is formed by applying cosmetics to the skin, the skin is visible, but the surface of the skin is blurred, and the skin has spots, freckles, small wrinkles, etc. Specifically, it means that the ratio of light diffused without going straight out of the total transmitted light is large.

  As an agent for imparting such soft focus properties, inorganic powders typified by amorphous silica are used. For example, in Patent Document 1, spherical silica or the like imparts soft focus properties. Has been reported to be effective. In Patent Documents 2 and 3, spherical amorphous silica produced by using polyacrylamide or carboxymethyl cellulose as an aggregating growth agent and neutralizing an alkali silicate with an acid in the presence of the aggregating growth agent. Patent Documents 2 and 3 also describe the use of this spherical amorphous silica as a filler for cosmetics.

JP 2001-199839 A Japanese Patent Laid-Open No. 05-193927 Japanese Patent Laid-Open No. 07-232911

  However, conventionally known cosmetics have a problem in sustainability even if soft focusability is imparted by blending inorganic powders or the like. That is, when a cosmetic film is formed by applying to the skin, with time, the agent imparting soft focus due to sweat or the like changes its optical properties or falls off the skin. The focus is lost.

Accordingly, an object of the present invention is to provide a novel particle characteristic different from that of conventionally known amorphous silica, and particularly, when blended in cosmetics, it is possible to continuously provide excellent soft focus properties. It is to provide an amorphous silica .

  When the present inventors react amorphous alkali silicate with an acid in the presence of an agglomerated growth agent to produce amorphous silica, amorphous silica particles are produced by partial neutralization, and then the reaction system Conventionally known by adopting a technique of precipitating amorphous silica on the produced amorphous silica particles by gradually neutralizing the unneutralized alkali silicate remaining therein A novel amorphous silica having a primary particle size larger than that of spherical amorphous silica is obtained, and this novel amorphous silica provides excellent soft focus properties when blended in cosmetics. At the same time, the inventors have found that the sustainability is excellent, and have completed the present invention.

  According to the present invention, the primary particle diameter measured by the X-ray small angle scattering method is 18 to 50 nm, and the circularity of each secondary particle observed with an electron microscope is 0.70 to 0.85. Amorphous silica is provided.

In the amorphous silica of the present invention,
(1) The median diameter (D ₅₀ ) in terms of volume measured by the laser diffraction scattering method is in the range of 1 to 10 μm,
(2) Oil absorption is 40 ml / 100 g or more, bulk density is 0.25 to 0.70 g / cm ³ ,
Is preferred.

  In addition, the amorphous silica of the present invention is blended in cosmetics as a soft focus imparting agent, and particularly blended in cosmetics in an amount of 0.1 to 10% by weight as a soft focus imparting agent. In addition, it can be blended into various resins as a compounding agent for resins.

  Since the amorphous silica of the present invention is produced by precipitating amorphous silica by a further neutralization reaction on spherical amorphous silica particles produced by partial neutralization, X-ray small angle scattering The primary particle diameter measured by the method is in the range of 18 to 50 nm, which is larger than the conventionally known spherical amorphous silica, and is formed by bonding the primary particles, that is, an electron microscope The circularity of the secondary particles observed by the above is in the range of 0.70 to 0.85, and has a shape slightly deformed from a true sphere.

The amorphous silica of the present invention having the above characteristics generally has a median diameter of secondary particles measured by a laser diffraction scattering method in the range of 1 to 10 μm and a high oil absorption (40 ml / 100 g or more) and a low bulk density (0.25 to 0.70 g / cm ³ ). For example, when blended in a cosmetic, makeup results in multiple scattering of light as a result of the presence of many particles. Therefore, the ratio of the diffused light to the transmitted light increases, and excellent soft focus properties can be imparted. Moreover, in connection with having a high oil absorption amount, it absorbs sweat quickly, and as a result, it does not fall off the surface of the skin, exists stably in the cosmetic film, and has excellent softness. There is an advantage that it is possible to give focus.

  Furthermore, the amorphous silica of the present invention has a shape in which the primary particles are slightly larger and the secondary particles are slightly deformed from a true spherical shape, and is similar to the conventionally known spherical amorphous silica. As a compounding agent, it can also be blended with various resins (for example, resin for film formation and resin for paint).

It is a figure which shows the balance of Haze and SCOF of the polypropylene film obtained by adding predetermined amount of each amorphous silica. It is a figure which shows the balance of Clarity and blocking power of the polypropylene film obtained by adding predetermined amount of each amorphous silica. It is a figure which shows the balance of the viscosity and the 60 degree gloss value of a coating film of the coating liquid obtained by adding predetermined amount of each amorphous silica to an amino alkyd resin coating material.

<Production of amorphous silica>
The amorphous silica of the present invention is obtained by mixing a partially neutralized acid aqueous solution with a coagulant growth agent in an alkali silicate aqueous solution (reaction liquid preparation step), and leaving this mixed liquid (reaction liquid) to stand. A gel body containing silica fine particles is generated by neutralization (gelation step), the gel body is crushed to form an aqueous slurry containing the silica fine particles (slurry step), and then the obtained aqueous slurry The aqueous acid solution is gradually added to neutralize the non-neutralized alkali silicate present in the slurry, and the silica is precipitated on the fine silica particles to grow the grains (grain growth process). ), Then acid washed (acid washing step), and finally filtered, washed with water, and dried (recovery step).

1. Reaction solution preparation step;
In the reaction solution preparation step, the alkali silicate aqueous solution is used as a silica source. This alkali silicate has the following formula (1):
R ₂ O · mSiO ₂ (1)
In the formula, R is an alkali atom such as Na or K, particularly Na atom,
m is a number from 1 to 4, in particular from 2.5 to 3.5.
In general, an aqueous solution of sodium silicate is used.

The composition of the alkali silicate affects the stability of the reaction solution (mixed solution) and the yield and particle size of the produced granular material. For example, the value of m (the molar ratio of SiO ₂ ) is more than the above range. If it is too small, precipitation of the partially neutralized particles becomes difficult, the yield tends to decrease, and the particle shape and particle form tend to be uneven, and a large amount of acid is required for partial neutralization, which is not preferable. On the other hand, when the value of m is larger than the above range, there are disadvantages such as the stability of the mixed solution is lowered and the particle form is greatly deviated from the spherical shape, and the particle size distribution is not sharp. The concentration of the alkali silicate is preferably 3 to 10% by weight, particularly 4 to 8.5% by weight as SiO ₂ in the mixed solution.

  As the coagulation growth agent, carboxymethyl cellulose (hereinafter sometimes referred to as CMC) is used as in the production method described in Patent Document 3 described above. That is, when CMC coexists as an aggregating growth agent in the partial neutralization of alkali silicate, the neutralized product of alkali silicate grows into shaped spherical particles with good yield.

The CMC used as a cohesive growth agent as described above should have a degree of etherification in the range of 0.5 to 2.5, especially 0.8 to 2.0. That is, CMC is a cellulose ether in which a carboxymethyl group is introduced into a hydroxyl group of cellulose, and is also called cellulose glycolic acid. Theoretically, CMC having a degree of etherification of 3 can be produced by etherifying all three hydroxyl groups per cellulose unit. Many commercially available CMCs have a degree of etherification in the range of approximately 0.5 to 1.0, and recently, those having a value of 1.0 or more are widely available. In general, CMC often refers to sodium carboxymethyl cellulose (Na-CMC), which is a sodium salt thereof. If the degree of etherification is within the above range, those having a high degree of etherification are also included in the object of the present invention. It can be used advantageously. For example, when CMC having an etherification degree outside the above range is used, it becomes difficult to recover silica particles obtained by extremely deteriorating filterability, or the particle shape becomes uneven. Inconveniences such as large variations in physical properties occur, which is the same as in Patent Document 3.
The value of the degree of etherification of CMC is a value obtained by the ash alkali method issued by the CMC Industry Association.

  The polymerization degree of CMC used is 10 to 3000, preferably 200 to 1000. When the degree of polymerization is high, it tends to be difficult to form and precipitate particulate matter and filter separation, and when the degree of polymerization is low, the function as an agglomerated growth agent is low, and fine silica of spherical silica with high yield and shape. Tends to be difficult to precipitate.

  Furthermore, since CMC is easily dissolved in water, it may be added as a powder when used. However, it is easier to handle if it is used after making it into an aqueous solution.

In the present invention, the amount of CMC added as described above varies depending on the degree of etherification, etc., but is generally 1 to 100% by weight, particularly 5 to 5% based on the weight of SiO ₂ per total silica in the alkali silicate solution. The amount is preferably 35% by weight. If the amount added is too small, sufficient cohesive growth action cannot be obtained, while if too large, the viscosity of the mixed solution tends to increase, which is economically disadvantageous. As described above, in view of the tendency for the cohesive growth property to increase in proportion to the increase in the degree of etherification, the amount of CMC added can be reduced if the degree of etherification is high. It can be said that it can be lowered.

  As the acid used for partial neutralization of alkali silicate, aqueous solutions of various inorganic acids and organic acids are used. From an economic standpoint, mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid are used. Of these, sulfuric acid is most excellent in terms of the yield of the particulate matter, the uniformity of the particle size and the form. In order to carry out a homogeneous reaction, it is preferably used in the form of a dilute aqueous solution, and an acid aqueous solution having a concentration of 1 to 15% by weight is generally preferred.

  The amount of the acid aqueous solution used here is an amount for partially neutralizing the alkali silicate, and should not be an amount for completely neutralizing. If an acid aqueous solution in an amount that completely neutralizes the alkali silicate is added to the mixed solution (reaction solution) and the alkali silicate is completely neutralized, fine particles of spherical amorphous silica can be generated. As a result, it becomes impossible to newly precipitate amorphous silica on the fine particles of the spherical amorphous silica, and as a result, the fine particles of the spherical amorphous silica cannot be grown. This is because it becomes impossible to obtain the amorphous silica of the present invention having a particle shape in which the primary particle size is reduced and the secondary particles are slightly deformed from a true spherical shape.

  Therefore, the amount of the acid aqueous solution to be used is such that the primary particle diameter of the finally obtained amorphous silica (X-ray small angle scattering method) is in the range of 18 to 50 nm, preferably 20 to 50 nm. Specifically, it is preferable to use 20 to 95%, particularly 30 to 80% of the amount of acid required for precipitating all the silicic acid contained in the alkali silicate as silica. Within this range, as the amount of the aqueous acid solution increases, the amount of silica that precipitates in the grain growth step on the fine silica particles decreases, and therefore the primary particle size of the finally obtained silica tends to decrease. On the contrary, the smaller the amount of the acid aqueous solution is, the more amorphous silica is precipitated on the fine particles of silica in the grain growth step, so that the primary particles of amorphous silica finally obtained are There is a tendency for the diameter to increase, and this can be used to adjust the primary particle diameter of the finally obtained amorphous silica.

  In the present invention, a coagulation growth aid such as a water-soluble inorganic electrolyte or a water-soluble polymer other than CMC may be used in combination with the above-mentioned CMC.

As the water-soluble inorganic electrolyte, any inorganic electrolyte can be used as long as it is water-soluble and has an aggregating action with respect to the sol or the like. Group 3 or 4 metal or other transition metal mineral or organic acid salts are used, suitable examples of which are as follows.
Alkali metal salts such as mineral salts of alkali metals such as NaCl, Na ₂ SO ₄ ;
Mineral salts such as calcium chloride, magnesium chloride, magnesium sulfate, calcium nitrate;
Other water-soluble metal salts such as zinc chloride, zinc sulfate, aluminum sulfate, aluminum chloride, titanyl sulfate;
Etc.

  Among these, an alkali metal salt is one of suitable coagulation growth aids. This is because the alkali metal salt is a by-product of partial neutralization and subsequent neutralization, and is contained in the filtrate obtained by separating the finally obtained granular silica, which can be reused. This is because it can be effectively reused together with the recovered CMC by adding to the mixed solution. On the other hand, the polyvalent metal salt has a larger aggregating action on the sol than the monovalent metal salt, and the agglomerated growth action of the partially neutralized silica even when added in a small amount as compared with the monovalent metal. Therefore, when mixing of polyvalent metal species is allowed, the use of a polyvalent metal salt is also permitted.

  Further, as water-soluble polymers other than CMC, nonionic polymers having good compatibility with CMC, such as starch, guar gum, locust bean gum, arabic gum, tragacanth gum, pretish gum, crystal gum, senegal gum, PVA, Examples thereof include polyacrylic acid soda, polyacrylamide, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, polyethylene glycol and the like.

In the present invention, by using the above-mentioned coagulation growth aid together with CMC, the gelation rate in the gelation step described later can be increased, and further, the uniformity of the generated particles can be increased. The amount of the coagulation growth aid is generally 0 to 100% by weight, particularly 0 to 20% by weight, based on the weight of SiO ₂ in the alkali silicate solution.

  When preparing the reaction liquid obtained by mixing the above-mentioned components, there is no restriction on the order of addition of each component. For example, CMC may be added after adding an acid to an aqueous alkali silicate solution, and vice versa. After adding CMC to the alkali silicate aqueous solution, an acid may be added. Of course, these may be added simultaneously. When an agglomeration aid is used, the agglomeration aid may be used as an aqueous medium for adding each component, or may be added in advance to the acid.

2. Gelation step;
After sufficiently mixing and homogenizing each component as described above (usually about 0.5 to 20 minutes), the reaction solution is allowed to stand to neutralize part of the alkali silicate ( Partially neutralized), the neutralized product (amorphous silica) precipitates in a tuft-like shape along the coagulation growth agent, and the reaction liquid becomes a yogurt-like gel. The particulate matter precipitated in the gel body is a particulate matter (secondary particle) in which primary particles of amorphous silica, which is a neutralized product of alkali silicate, are cross-linked, and the primary particles are It is extremely fine and the secondary particles are homogeneous particles that are nearly spherical.

  As the gelation conditions, it is generally suitable to leave at a temperature of 0 to 100 ° C., particularly 10 to 40 ° C. for 1 to 50 hours, preferably 3 to 20 hours. In general, the lower the temperature, the smaller the primary particle size of the precipitated particles, and the higher the temperature, the larger the primary particle size of the precipitated particles.

3. Slurrying step;
In the present invention, the gel body as described above is produced and then crushed to obtain an aqueous slurry in which the fine particles of the amorphous silica are dispersed and containing an unneutralized alkali silicate. In other words, the yogurt-like gel body cannot uniformly react the unneutralized alkali silicate present in the gel body with the acid.

The degree of crushing may be performed so that the yogurt-like gel body exhibits fluidity, for example, by applying a shearing force by stirring with a stirring blade or the like, and usually by stirring for several minutes at room temperature. Good. If the degree of crushing (shearing force) is too strong, the secondary particles are broken, which is not preferable.
In addition, although pH (25 degreeC) of this aqueous slurry changes with the grades of partial neutralization, generally it is about 11-12.

4). Grain growth process;
In the present invention, an aqueous acid solution is further added to the aqueous slurry obtained as described above to neutralize the non-neutralized alkali silicate present in the slurry. Here, an important point is that by gradually adding an aqueous acid solution, silica is precipitated on the fine particles of spherical amorphous silica contained in the slurry, thereby causing grain growth. The primary particle diameter by the small-angle scattering method is increased, the circularity of the secondary particles is lowered, and silica particles having a shape slightly deformed from the true sphere can be obtained.

  For example, in Example 12 (corresponding to Comparative Production Example 7 described later) and Comparative Production Example 1 of Patent Document 3 described above, a gel body is generated once, and the gel body is crushed by stirring and dispersing to obtain an aqueous slurry. Although an acid aqueous solution is added all at once, in such a means, unneutralized alkali silicate contained in the aqueous slurry is neutralized to precipitate silica as the neutralized product. Due to the fact that elution occurs at the same time, this silica does not precipitate on the silica fine particles that have been produced in advance and is produced independently. It is only possible to obtain a form in which uniform fine silica particles are mixed with uniform spherical silica particles. That is, uniform silica particles having a desired large primary particle diameter and slightly deformed from a true spherical shape cannot be obtained.

  However, in the present invention, the silica fine particles in which the silica is previously formed by gradually adding the acid aqueous solution to the aqueous slurry and slowly depositing silica that is a neutralized product of the unreacted alkali silicate. The particles can be deposited on the surface of the particles and allowed to grow, whereby silica particles having a desired primary particle size and circularity can be obtained.

In the present invention, the amount of the aqueous acid solution used at this stage is an amount obtained by subtracting the amount used for partial neutralization from the amount necessary for precipitating the total amount of silicic acid in the used alkali silicate. Specifically, it is 5 to 80%, particularly 20 to 70%, of the amount necessary for precipitating the entire amount of silicic acid.
The addition rate of the acid aqueous solution as described above can be set to an appropriate range depending on the primary particle diameter and circularity of the silica particles to be finally obtained. It should be added over 25 hours, and the addition rate should be set so that the addition is completed in 0.25 to 30 hours, particularly 0.5 to 15 hours. In addition, the temperature of the aqueous slurry at this time is preferably adjusted to a range of about 10 to 100 ° C., particularly about 10 to 40 ° C., and the addition of the acid aqueous solution is performed under stirring to obtain uniform silica particles. It is preferable in obtaining.

  As the acid aqueous solution to be used, the same acid aqueous solution as that used for preparing the reaction solution described above can be used, and an acid aqueous solution having a concentration of 1 to 15% by weight, particularly sulfuric acid is preferably used.

As described above, the acid aqueous solution is gradually added, and almost simultaneously with the addition of the acid aqueous solution, silicic acid contained in the remaining alkali silicate is precipitated as silica, and the grain growth step is completed. Further, after completion of the addition, if necessary, the reaction solution may be aged by allowing it to stand at a temperature of about 10 to 40 ° C. for about 1 hour.
The slurry pH when the silica deposition is completed is about 10 to 11. This is because even when all the silicic acid is precipitated by neutralization with an acid, the alkali component in the alkali silicate used for the preparation of the reaction solution is neutralized only by 60 to 80%, especially 60 to 75%. This is because unneutralized alkali ions are present in the slurry.

5). Acid cleaning step;
After the silica is completely precipitated in this way, an acid aqueous solution in an amount that neutralizes the unneutralized alkali remaining in the slurry is added again with stirring, and the generated silica particles are acid washed. That is, by this acid cleaning, alkali metal ions such as Na ions adhering to the surface of the silica particles are eluted and separated from the silica particles together with the CMC and the coagulation growth aid contained in the silica particles. Therefore, in this step, the aqueous acid solution does not need to be gradually added, and may be added all at once.

  The acid aqueous solution used for the acid cleaning may be the same type as the acid aqueous solution used for neutralizing the alkali silicate described above, and this addition amount is usually 2.5 pH of the slurry containing the silica particles grown. The amount may be about 4 to 4, and the stirring time is about 0.5 to 120 minutes. When the pH is lower than 2.5, CMC is precipitated, and filtration is difficult. On the other hand, if the pH is higher than 4, alkali removal during filtration will be insufficient.

6). Recovery process;
After acid cleaning, filtration, washing and drying are carried out according to conventional methods, and further, if necessary, firing is performed, moisture is completely removed, and then adjusted to a predetermined particle size by dry grinding using a jet mill or the like. The amorphous silica particles of the present invention can be obtained. Since the filtrate contains acid, CMC, and further a coagulant aid, this filtrate can be reused as it is for the preparation of the reaction solution.

<Amorphous silica>
In the amorphous silica obtained as described above, silica produced by neutralization of unneutralized alkali silicate is deposited on fine particles of spherical amorphous silica precipitated by partial neutralization. Therefore, the primary particle diameter of the silica particles is increased by the grain growth, and each secondary particle is an aggregate of fine primary particles and has a shape slightly deformed from a true spherical shape. Yes. Therefore, an amorphous silica having a primary particle diameter of 18 to 50 nm measured by the X-ray small angle scattering method and a primary particle diameter in such a range has not been synthesized so far. Furthermore, the circularity of individual secondary particles observed with an electron microscope is in the range of 0.70 to 0.85 on average, and the circularity is slightly lower than 1.

This circularity is calculated from the following formula:
Circularity = 4π × (area) / (perimeter) ²
Is calculated by When this value is 1, the particles are perfectly spherical. Therefore, an average circularity of 0.70 to 0.85 means that this particle is close to a true sphere, but is slightly deformed from a true sphere.

Further, the amorphous silica of the present invention obtained as described above has voids in the secondary particles, which are aggregates of primary particles, because CMC is used as an aggregating growth agent. It also has the property of high oil absorption and low bulk density. The oil absorption and bulk density can be adjusted according to the application while maintaining the secondary particle size and circularity by changing the amount balance of the acid aqueous solution used for neutralization in the gelation step and the grain growth step. . For example, as the amount of the acid aqueous solution used in the gelation process is increased, the amount of silica precipitated in the grain growth process on the fine particles of silica is decreased. The amount is large and the bulk density is small. Conversely, the smaller the amount of the acid aqueous solution used in the gelation step, the more amorphous silica precipitates in the grain growth step on the fine silica particles, and thus the amorphous material finally obtained. The amount of oil absorption of the fine silica is small and the bulk density is large. By utilizing this, it is possible to adjust the oil absorption and bulk density of the finally obtained amorphous silica. Generally, the oil absorption is adjusted to 40 ml / 100 g or more, particularly 60 to 250 ml / 100 g, and the bulk density is 0.25 to 0.70 g / cm ³ , especially 0.30 to 0.65 g / cm. ³ is adjusted.

Further, the amorphous silica of the present invention is porous as understood from the large amount of oil absorption as described above. For example, the pore volume as the volume of nitrogen adsorbed at a specific pressure of 0.96 is In general, it is in the range of 0.1 cm ³ / g or more, especially 0.1 to 1.5 cm ³ / g. Furthermore, the BET specific surface area is in the range of 50 to 500 m ² / g, in particular 80 to 400 m ² / g.

When the amorphous silica of the present invention having the above properties is used by being dispersed and blended in various base materials (for example, resins), it is usually in terms of volume measured by a laser diffraction scattering method. The particle size is preferably adjusted to such an extent that the median diameter (D ₅₀ ) is in the range of 1 to 10 μm, and in particular, the particle size is adjusted so that a coarse particle having a particle size of 10 μm or more is 2% or less. Is preferred.

<Application>
Since the amorphous silica of the present invention produced by the above-described method has a slightly large primary particle diameter and low circularity, is slightly deformed from a spherical shape, and has a low bulk density, a soft focus imparting agent As such, it can be blended into various cosmetics to enhance the soft focus property. That is, when blended in cosmetics, as a result of the presence of a large number of particles, light is transmitted through the cosmetic film while being scattered multiple times. Therefore, the ratio of diffused light to the transmitted light increases, and excellent soft focus. Sex can be imparted.

  The optical characteristics of the amorphous silica of the present invention can be evaluated by the total light transmittance (Tt) and the diffuse transmittance (Td) as shown in Examples described later. For example, the amorphous silica of the present invention has a high total light transmittance of 93% or higher and a diffuse transmittance of 45% or higher. This is because the amorphous silica of the present invention improves the soft focus property. It is extremely useful.

  In addition, the amorphous silica of the present invention is not only slightly deformed from a spherical shape, but also has a high oil absorption, and therefore has a property of quickly absorbing sweat and the like. As a result, it does not fall off from the surface of the skin, is stably present in the cosmetic film, and has the advantage of continuously providing excellent soft focus properties. For example, in the case of true spherical silica whose particle circularity is higher than the aforementioned range, it is easy to fall off when applied to the skin, while in the case of amorphous silica lower than the aforementioned range, the elongation when applied to the skin is increased. Worsens and deteriorates the properties of cosmetics.

  Since the above-described amorphous silica has a spherical shape with a high degree of circularity compared to the plate-like body, there is an advantage that, when blended in cosmetics, it can impart higher slipperiness than the plate-like body.

  When blending the amorphous silica of the present invention in a cosmetic as a soft focus imparting agent, it is blended in the cosmetic in an amount of at least 0.1 to 10% by weight, depending on the type of cosmetic to be blended. Thus, the desired soft focus property can be imparted, and the soft focus property can be continuously expressed when applied to the skin.

  That is, cosmetics are used in the form of liquids, emulsions or creams, powders, solids, etc. Among such cosmetics, makeup cosmetics, foundations, and the like that particularly require soft focus properties. In the lipstick and the like, the amorphous silica of the present invention is blended as a soft focus imparting agent. These cosmetics generally have a water-repellent oil component such as a film-forming polymer, a surfactant, a thickener, water, a moisturizer, a fragrance, a pigment or dye, or a silicone oil, depending on the application or use form. Cosmetic ingredients such as ultraviolet absorbers are contained in an appropriate amount, and the amorphous silica of the present invention can be blended in the above amount to enhance the soft focus property.

The amorphous silica of the present invention can be used for various applications in the same manner as conventionally known amorphous silica, in addition to the use of blending in the cosmetic as described above as a soft focus imparting agent.
For example, by taking advantage of the low bulk density, it can be blended with various thermoplastic resins or thermosetting resins as a compounding agent for resins to improve the properties of molded products and resin coating films formed from the resins. .

That is, since the amorphous silica of the present invention has a low bulk density and can be close-packed, for example, it is 0.01 to 10% by weight, particularly 0.02 to 2% by weight in a resin for film formation. By blending, the resin film molded from the resin is excellent in balance between anti-blocking properties and transparency (see Experimental Example 5 described later).
In addition, in the case of a master batch in which the compounding agent for resin is blended at a high concentration in the resin, the blending amount may be larger than the above.
In addition, by blending as a matting agent in the coating resin used to form the coating film, not only can the matting effect of the resin coating film formed be imparted, it is the same as a commercially available matting agent. Since the viscosity of the coating liquid is lower than when the number of added parts is blended, the matte property can be enhanced because it can be added at a high concentration (see Experimental Example 6 described later). The matting agent can be added in an amount of 1 to 15 parts by weight per 100 parts by weight of the resin.

  When the amorphous silica of the present invention is used as a compounding agent for a resin, surface treatment may be performed as necessary. Although it does not limit to this as a surface treating agent, it can carry out using the following organic or inorganic adjuvant.

  Examples of organic auxiliaries include stearic acid, palmitic acid, lauric acid, etc., and metal soaps such as calcium salts, zinc salts, magnesium salts, and barium salts, silane coupling agents, aluminum coupling agents, and titanium based cups. Examples thereof include ring agents, zirconium coupling agents, various waxes, silicone oil, various unmodified or modified resins (for example, rosin, petroleum resin, etc.). The surface treatment amount (coating amount) is preferably in the range of 0.01 to 20% by weight, particularly 0.1 to 10% by weight, per untreated resin compounding agent.

In addition, inorganic auxiliary agents include fine particle silica such as aerosil and hydrophobically treated aerosil, silicates such as calcium silicate and magnesium silicate, metal oxides such as calcia, magnesia and titania, magnesium hydroxide, aluminum hydroxide The above-mentioned compounding agent for untreated resin comprising shaped particles comprising a metal hydroxide such as calcium carbonate, a metal carbonate such as calcium carbonate, a synthetic zeolite such as A-type or P-type, and an acid-treated product thereof or a metal ion-exchange product thereof. It can also be used in a blend or mabushi. A silane-based, titanium-based, or zirconium-based coupling agent can also be used.
These inorganic auxiliaries are preferably used in an amount of 0.01 to 20% by weight, particularly 0.1 to 10% by weight, based on the untreated resin compounding agent.

  Such compounding agents for resins can be used alone or in combination with various compounding agents. Regarding the blending method, the blending agents may be blended separately or may be blended in one pack in advance.

  Although it is not limited to this as a compounding agent used together, a plasticizer, a lubricant, an antistatic agent, an antifogging agent / antifogging agent, an ultraviolet absorber, a light stabilizer (hindered amine type, etc.), an antioxidant (phenol) System, sulfur system, phosphite system, etc.), fatty acids and their metal salts, amides / amines (erucic acid amides, etc.), monohydric / polyhydric alcohol fatty acid esters, low melting point resins, flame retardants, reinforcing materials, reinforcing materials, etc. Each can be used as needed. Insect repellents, insect repellents, deodorants, fungicides, fungicides, fragrances, medicinal ingredients and the like can also be used.

  Furthermore, in the case of paint resins, pigments, wetting agents, dispersants, thickeners, anti-settling agents, emulsifiers, anti-skinning agents, antifoaming agents, antiseptics, anti-sagging agents, drying agents, anti-coloring agents Coloring agents, antifouling agents, and the like can also be used.

  In addition to the above uses, the amorphous silica of the present invention is a fluidity improver such as an electrophotographic toner, a high-grade abrasive, a chromatographic carrier, a fragrance carrier, a putty filler, an adsorbent, a release agent, and rubber. It can also be used as a filler.

  The excellent effects of the present invention will be described in the following experimental examples. Various physical properties of amorphous silica were measured by the following methods.

(1) Primary particle size (X-ray small angle scattering method)
Using Rigaku RINT-Ultima III,
Transmission small angle scattering optical system selection slit;
DS: 1.0 mm,
SS: 0.2 mm,
RS: 0.1 mm,
Cu tube,
40kV,
40 mA,
Scan axis 2θ / θ (continuous);
Scanning range: 0.1 ° -8 °
Scanning speed (step): 0.02 ° / min
Measured with

(2) Circularity From the two-dimensional photographic image obtained with a scanning electron microscope (S-570 manufactured by Hitachi), the circularity defined by the following formula was obtained using image analysis software (WinROOF manufactured by Mitani Corporation). .
Circularity = 4π × (area) / (perimeter) ²

(3) Median diameter (D ₅₀ )
A median diameter (D ₅₀ ) on a volume basis was measured by a laser diffraction scattering method using a master maker 2000 manufactured by Malvern and using water as a solvent.

(4) Oil absorption JIS. K. It was measured according to 5101-13-1: 2004.

(5) Bulk density JIS. K. Measurement was performed according to 6220-1 7.7: 2001.

(6) Pore volume and specific surface area Measurement was performed by a nitrogen adsorption method using TriStar 300 manufactured by Micromeritics.
The pore volume was the volume of nitrogen adsorbed at a specific pressure of 0.96, and the specific surface area was analyzed by the BET method from the adsorption branch side nitrogen adsorption isotherm with a specific pressure of 0.05 to 0.35 or less.

(7) Silica yield (%)
The total weight (W0) of the reaction solution and the weight (W1) collected in a small amount were determined. After leaving still for 20 hours, unreacted sodium silicate and CMC were removed by filtering what was crushed and slurried by stirring the gel.
The obtained filter cake was redispersed in an appropriate amount of water, and 13.6% sulfuric acid sufficient to neutralize the total amount of Na ₂ O in No. 3 sodium silicate used was poured over 30 seconds with stirring. And acid cleaning was performed. Next, filtration and washing were performed, and the acid-washed filter cake was baked at 750 ° C. to determine the weight (W2) of the amorphous silica. The SiO ₂ base yield was calculated from the following formula, assuming that the weight of SiO ₂ in the total amount of No. 3 sodium silicate used was W3.
Silica yield (%) = (W2 / W3) × (W0 / W1) × 100

<Production of amorphous silica>
In the following production examples, No. 3 sodium silicate (SiO ₂ : 22.8 wt%, Na ₂ O: 7.21 wt%, balance: water) was used as the alkali silicate.

(Production Example 1)
Carboxymethylcellulose (CMC-A) having a degree of etherification of 1.2, a 1% aqueous solution viscosity of 70 cP / 25 ° C. and a pure content of 93% by weight was prepared in a 2 L stainless steel container,
698 g of water,
No. 3 sodium silicate 219g,
10.0 g of sodium chloride (20% based on ₂ weight of SiO),
6.45 g CMC-A (12% based on SiO ₂ weight)
And this mixed solution was kept at 30 ° C. with stirring to prepare a reaction solution (reaction solution preparation step).
To this reaction solution, 66.2 g of 13.6% sulfuric acid (an amount that neutralizes 36 mol% of Na ₂ O) was added over 90 seconds.
After the addition, the mixture was further stirred for 30 seconds, and then the stirring was stopped and the mixture was left to gel to obtain a yogurt-like gel (gelation step).

The obtained gel was allowed to stand for 20 hours, and then the gel was crushed by stirring to form a slurry. (At this stage, about half of the silicic acid content in the sodium silicate was precipitated as silica.)
To this slurry, 47.5 g of 13.6% sulfuric acid (amount to be neutralized to 61.8 mol% of Na ₂ O in No. 3 sodium silicate used) was stirred in an environment of 30 ° C. While slowly dropping over 7 hours, the silica was completely precipitated (grain growth step).

Next, 70.3 g of 13.6% sulfuric acid (the amount by which the total amount of Na ₂ O in No. 3 sodium silicate used was neutralized) was added over 30 seconds with stirring in a 30 ° C. environment. Acid cleaning was performed (acid cleaning step).
The acid washed slurry was filtered and washed with water, and the resulting cake was placed in a crucible and baked at 750 ° C. for 1 hour. Next, fine grinding was performed to obtain amorphous silica (E1). The production conditions and various physical properties are shown in Table 1.

(Production Examples 2 to 5)
Amorphous silica (E2 to E5) was obtained in the same manner as in Production Example 1, except that the addition time of sulfuric acid in the grain growth step was changed as shown in Table 1. Various physical properties of the obtained amorphous silica are shown in Table 1 together with the production conditions.

(Production Example 6)
In the same manner as in Production Example 2, except that the pouring time of sulfuric acid in the grain growth step was set to 2.7 hours, and the cake obtained by filtering and washing the slurry after acid washing was dried at 110 ° C. Silica (E6) was obtained. Various physical properties of the obtained amorphous silica are shown in Table 1 together with the production conditions.

(Production Example 7)
A polyacrylamide (PAA) aqueous solution (concentration: 10% by weight) having an average molecular weight of 700,000 to 1,000,000 was prepared.
In the reaction solution preparation step, the amount of water to be mixed was changed to 644 g and CMC was changed to the above PAA aqueous solution 60.0 g (12% based on SiO ₂ weight), and the same as in Production Example 1 Silica (E7) was obtained. Various physical properties of the obtained amorphous silica are shown in Table 1 together with the production conditions.

(Production Example 8)
Carboxymethyl cellulose (CMC-B) having a degree of etherification of 1.42, 1%, an aqueous solution viscosity of 135 cP / 25 ° C., and a pure content of 88% was prepared.
In Production Example 1, CMC in the reaction liquid preparation step was changed to 14.2 g of CMC-B (25% based on SiO ₂ weight), and the amount of sulfuric acid in the gelation step was 58.9 g (No. 3 silica). change in the amount) to neutralize 32 mol% of Na ₂ O in the sodium, medium is the amount of sulfuric acid in the grain growth process to 70 mol% of Na ₂ O of 69.9 g (silicate in sodium using The amount of sulfuric acid in the acid washing step was changed to 64.4 g (corresponding to the amount by which up to 105 mol% of Na ₂ O in the sodium silicate used was neutralized).
Amorphous silica (E8) was obtained in the same manner as in Production Example 1 except that the above changes were made. Various physical properties of the obtained amorphous silica are shown in Table 1 together with the production conditions.

(Production Example 9)
In Production Example 1, the formulation of each component to be charged into a 2 L stainless steel container in the reaction liquid preparation step was changed as follows.
585 g of water,
No. 3 sodium silicate 307g,
3.50 g of sodium chloride (5% based on SiO ₂ weight)
CMC-B 5.57 g (7% based on SiO ₂ weight),
Furthermore, the amount of sulfuric acid in the gelation step was changed to 99.2 g (amount that neutralizes 38.5 mol% of Na ₂ O), and the amount of sulfuric acid in the grain growth step was 81.1 g (sodium silicate used) Na ₂ amounts to 70 mol% of O is neutralized), the amount of sulfuric acid in the acid washing step to 98 mol% of Na ₂ O of 72.1 g (silicate in soda used is neutralized in Each).
Amorphous silica (E9) was obtained in the same manner as in Production Example 1 except that the above changes were made. Various physical properties of the obtained amorphous silica are shown in Table 1 together with the production conditions.

(Production Example 10)
In Production Example 1, the formulation of each component (not using sodium chloride) to be charged into a 2 L stainless steel container in the reaction liquid preparation step was changed as follows.
505 g of water,
No. 3 sodium silicate 373g,
6.28 g of CMC-B (6.5% based on SiO ₂ weight),
Further, by changing the amount of sulfuric acid gelling step 116 g (an amount to neutralize 37 mol% of Na ₂ O), the amount of sulfuric acid in the grain growth process 77.6 g (silicate in sodium using _Na 2 O The amount of sulfuric acid in the acid washing step was changed to 110 g (the amount by which up to 97 mol% of Na ₂ O in the sodium silicate used was neutralized). did.
Amorphous silica (E10) was obtained in the same manner as in Production Example 1 except that the above changes were made. Various physical properties of the obtained amorphous silica are shown in Table 1 together with the production conditions.

(Comparative Production Example 1)
Amorphous silica (H1) was obtained in the same manner as in Production Example 1 except that the pouring time of sulfuric acid in the grain growth step was changed to 0.01 hours. Various physical properties of the obtained amorphous silica are shown in Table 2 together with the production conditions.

(Comparative Production Example 2)
In order to contrast with Production Examples 1 to 5, an amorphous silica was produced by omitting the grain growth step.
That is, the steps up to the gelation step were carried out in the same manner as in Production Example 1, and the gel obtained was allowed to stand for 20 hours, then the gel was crushed by stirring and slurried, and the unreacted sodium silicate was filtered. And CMC were removed.
The obtained filter cake was redispersed in 500 g of water, and 70.3 g of 13.6% sulfuric acid was added over 30 seconds with stirring to perform acid washing. Subsequently, filtration and water washing were performed in the same manner as in Production Example 1, and the acid-washed filter cake was baked and finely pulverized at 750 ° C. to obtain amorphous silica (H2). The production conditions and various physical properties are shown in Table 2.

(Comparative Production Example 3)
Comparative Production Example 2 except that the amount of water input in the reaction liquid preparation step was changed to 644 g and CMC-A was changed to 60.0 g of PAA aqueous solution (see Production Example 7) (6% of SiO ₂ weight). In the same manner as above, the grain growth step was omitted to obtain amorphous silica (H3). Various physical properties of the obtained amorphous silica are shown in Table 2 together with the production conditions.

(Comparative Production Example 4)
CMC having a degree of etherification of 1.44, a 1% aqueous solution viscosity of 230 cP / 25 ° C., and a pure content of 89% (CMC-C) was prepared.
Amorphous silica (H4) was obtained by omitting the grain growth step in the same manner as in Comparative Production Example 2, except that CMC used in the reaction preparation step was changed to 6.74 g of the above CMC-C. Various physical properties of the obtained amorphous silica are shown in Table 2 together with the production conditions.

(Comparative Production Example 5)
In Production Example 1 (Comparative Production Example 2), the formulation of each component to be charged into a 2 L stainless steel container in the reaction liquid preparation step was changed as follows.
650 g of water,
No. 3 sodium silicate 253g,
6.0 g of anhydrous sodium sulfate (10.4% based on SiO ₂ weight),
9.93 g CMC-A (16% based on SiO ₂ weight),
Further, neutralization with acid in the gelation step is the same as in Production Example 1 (Comparative Production Example 2) by changing 80.7 g of 13.6% sulfuric acid (amount that neutralizes 38 mol% of Na ₂ O). Gelation was performed to obtain a yogurt-like gel (gelation step).
Next, the amorphous silica (H5) was obtained by omitting the grain growth step in the same manner as in Comparative Production Example 2 except that the amount of sulfuric acid in the acid washing step was changed to 81.1 g. The production conditions and various physical properties are shown in Table 2.

(Comparative Production Example 6)
In Comparative Production Example 5, the calcination for 1 hour at 750 ° C. was changed to the drying at 110 ° C. to obtain amorphous silica (H6). The production conditions and various physical properties are shown in Table 2.

(Comparative Production Example 7)
In this example, amorphous silica was produced in the same manner as in Example 12 of Patent Document 3.
That is, the reaction liquid was prepared in the same manner as in Production Example 1 with the following prescription of the reaction liquid prepared in the reaction liquid preparation step.
659 g of water,
No. 3 sodium silicate 219g,
CMC-A 11.3 g (21% based on SiO ₂ weight),
To this reaction solution, 110.4 g of 13.6% sulfuric acid (an amount that neutralizes 60% mol% of Na ₂ O) was added over 90 seconds with stirring in a 30 ° C. environment. After further stirring for 30 seconds, the stirring was stopped and the mixture was allowed to stand to obtain a pudding gel (gelation step).
This gel was allowed to stand for 3 hours, and then crushed by stirring to form a slurry. To this slurry, 73.6 g of 13.6% sulfuric acid (amount to neutralize Na ₂ O to 100 mol%) was added over 30 seconds with stirring.
The obtained slurry was filtered and washed with water, and the obtained cake was put in a crucible and baked at 500 ° C. for 2 hours. Next, finely pulverized to obtain amorphous silica (H7). The production conditions and various physical properties are shown in Table 2.

(Contrast product)
As commercially available amorphous silica, Asahi Glass Sunsphere H-122 (H8), Catalytic Chemical Silica P-1500 (H9), Asahi Chemical Chemicelene (H10), Fuji Silysia Cyrossphere C-1504 (H11) ), Micron spherical silica (H12) and Shin-Etsu Chemical spherical silica (H13) were prepared.
In addition, SYLOBLOC45 (H14) manufactured by Grace Davison was used as a reference product for evaluation as an anti-blocking agent for polypropylene film, which will be described later, and Mizukasil P-73 (manufactured by Mizusawa Chemical Co., Ltd.) was used as a reference product for evaluation as a matting agent for aminoalkyd resin coatings. H15) was prepared.
Various physical properties of these control products are shown in Table 3.

<Evaluation as a soft focus agent>
In the following experimental examples, the amorphous silicas E1, E8, and E10 produced in the production examples described above and the control amorphous silicas H8, H9, and H10 described above were prepared as soft focus imparting agents.

The total light transmittance (Tt) and diffuse transmittance (Td) of the various soft focus imparting agents prepared above were measured as follows.
Various kinds of amorphous silica and silicone oil (KF-96-1000cS manufactured by Shin-Etsu Chemical Co., Ltd., refractive index: 1.40) are blended at a ratio of 4 g in total, and Hoover Mara manufactured by Toyo Seiki Seisakusho Co., Ltd. Kneaded.
The paste obtained by kneading was applied to an OHP sheet with a 50 μm applicator manufactured by Taiho Kikai Co., Ltd., and the total transmittance (Tt) and haze (H) were measured at three locations using a haze meter (manufactured by Toyo Seiki Seisakusho). Furthermore, the following formula:
Td = Tt × H / 100
Thus, diffuse transmittance (Td) was calculated, and an average value was obtained for each.
The results are shown in Table 4 together with various physical properties of each amorphous silica.

(Experimental Example 1-1)
Using amorphous silica (E1), a powder foundation was obtained according to the following formulation.

(Powder foundation)
Ingredient Amount (wt%)
(1) Silicone-treated talc 15.00
(2) Silicone-treated sericite 32.80
(3) Silicone-treated synthetic phlogopite 10.00
(4) Silicone-treated titanium oxide 15.00
(5) Silicone-treated iron oxide 3.00
(6) Silicone-treated zinc oxide 2.00
(7) Polymethyl methacrylate 7.00
(8) Boron nitride 3.00
(9) Methylparaben 0.20
(10) Amorphous silica (E1) 1.00
(11) Methyl polysiloxane 4.90
(12) Dioctyl succinate 4.00
(13) Squalane 2.00
(14) Fragrance 0.10
Total 100.00

  Specifically, the above components (1) to (10) are uniformly mixed with a Henschel mixer, and the remaining binder components (11) to (14) are added and mixed, and then pulverized again. And passed through the sieve. This was compression molded into a metal pan to obtain a powder foundation.

  The powder foundation obtained as described above was applied to 10 female panelists, and the effect of hiding fine lines immediately after application and after 3 hours was evaluated by the following method. The results are shown in Table 5 together with the type of amorphous silica used in the formulation.

<Effect to hide fine lines>
Sensory evaluation was performed by 10 professional panelists, and the evaluation was made in 7 stages using the following evaluation criteria, and the average value was evaluated.
(Evaluation criteria)
7 points: The effect of hiding fine lines is very high 6 points: The effect of hiding fine lines is high 5 points: The effect of hiding fine lines is slightly high 4 points: Normal 3 points: The effect of hiding fine lines is slightly low 2 points: The fine lines are hidden Low effect 1 point: Very low effect of hiding fine lines

  In Table 5, ◎ indicates that the average value of the above-mentioned scores is 6 points or more, ○ indicates that the average value is 4 points or more and less than 6 points, Δ indicates 3 points or more and less than 4 points, and X indicates less than 3 points. .

(Experimental example 1-2)
In the formulation adopted in Experimental Example 1-1, the blending amount of the component (10) which is amorphous silica (E1) is 5% by weight, and the total component is adjusted to 100% by weight in the component (2). A powder foundation was produced and evaluated in exactly the same manner as in Experimental Example 1-1 except that the formulation was changed. The results are shown in Table 5.

(Experimental Example 1-3)
In the formulation adopted in Experimental Example 1-1, the blending amount of the component (10) which is amorphous silica (E1) is 10% by weight, and the total component is adjusted to 100% by weight in the component (2). A powder foundation was produced and evaluated in exactly the same manner as in Experimental Example 1-1 except that the formulation was changed. The results are shown in Table 5.

(Experimental Example 1-4)
A powder foundation was produced and evaluated in exactly the same manner as in Experimental Example 1-2 except that E8 was used instead of amorphous silica. The results are shown in Table 5.

(Experimental example 1-5)
A powder foundation was produced and evaluated in exactly the same manner as in Experimental Example 1-2, except that E10 was used instead of amorphous silica. The results are shown in Table 5.

(Experimental Examples 1-6, 1-7 and 1-8)
A powder foundation was produced and evaluated in exactly the same manner as in Experimental Example 1-2, except that the amorphous silica was replaced with the control products H8, H9 and H10. The results are shown in Table 5.

As is clear from Table 5, the powder foundation (Experimental Examples 1-1 to 1-5) containing the amorphous silica of the present invention had a very high effect of hiding fine lines immediately after coating. In addition, even after 3 hours of application, the effect did not change, and it became clear that the effect of hiding fine lines was not lowered even if sweat or sebum occurred on the skin over time.
On the other hand, the powder foundations of Experimental Examples 1-6 and 1-7 prepared using the control product (commercial product) amorphous silica have a high effect of hiding fine lines immediately after coating, but after 3 hours. The effect was low, and it became clear that the powder foundation was wetted by sweat and sebum produced on the skin, and the effect of hiding fine lines was reduced.
In addition, the powder foundation of Experimental Example 1-8 prepared using a control product (commercial product) amorphous silica was insufficient in the effect of hiding fine lines both after application and after 3 hours.

(Experimental example 2)
Using amorphous silica (E1), a makeup base was prepared according to the following formulation.

(Makeup base)
Ingredient Amount (wt%)
(1) Methyl glucoside sesquistearate 1.00
(2) Sodium stearoyl lactate 0.20
(3) Hardened rapeseed oil alcohol 3.50
(4) Squalane 6.00
(5) Octyldodecyl myristate 6.00
(6) Methylphenylpolysiloxane 6.00
(7) Macadamia nut oil fatty acid phytosteryl 2.00
(8) Polyglyceryl triisostearate 1.00
(9) Butylparaben 0.10
(10) Purified water 52.94
(11) Synthetic sodium silicate / magnesium 1.00
(12) Hydroxyethane diphosphonic acid 0.06
(13) Xanthan gum 0.20
(14) 1,3-butylene glycol 10.00
(15) Methylparaben 0.20
(16) Diglycerin 5.00
(17) Amorphous silica (E1) 4.00
(18) Methyl polysiloxane 0.50
Total 100.00

  Specifically, in the above formulation, the water phase components (10) to (13) are stirred and mixed and heated to 85 ° C. Oil phase components (1) to (9) are mixed and dissolved by heating to 80 ° C. Then, after adding the above-mentioned aqueous phase component to this oil phase component and pre-emulsifying it, and emulsifying uniformly with a homomixer, the component (14)-( Add the mixture up to 17). Subsequently, cooling was started, component (18) was added at about 70 ° C., and further cooled to 35 ° C. to obtain a makeup base.

  The obtained makeup base contained a lot of oil and polyhydric alcohol and formed a coating film in a moist and wet state. However, since the amorphous silica of the present invention was blended as the component (17), soft focus It was excellent in performance and had a high function of preparing the skin while hiding fine lines.

(Experimental example 3)
Using amorphous silica (E1), an oily foundation was prepared according to the following formulation.

(Oil foundation)
Ingredient Amount (wt%)
(1) Liquid paraffin 18.00
(2) Isopropyl palmitate 15.00
(3) Liquid lanolin 4.50
(4) Microcrystalline wax 4.50
(5) Ceresin 10.00
(6) Carnavalou 2.00
(7) Sorbitan sesquioleate 1.00
(8) Paraben 0.20
(9) Titanium oxide 15.00
(10) Kaolin 8.50
(11) Talc 13.00
(12) Iron oxide 5.00
(13) Amorphous silica (E1) 3.00
(14) Fragrance 0.30
Total 100.00

  Specifically, in the above formulation, the components (1) to (8) are heated and melted at 80 ° C., and the mixture of (9) to (12) is added thereto. The mixture is kneaded with a roll mill, heated and melted again, and (13) is added thereto and mixed uniformly. After defoaming this, (14) was added, poured into an inner dish and cooled to obtain an oily foundation.

  The obtained oily foundation was a foundation with a high function of hiding fine lines despite the fact that it contained a lot of oil.

(Experimental example 4)
Using amorphous silica (E1), a lipstick was prepared according to the following formulation.

(Lipstick prescription)
Ingredient Amount (wt%)
(1) Ceresin 10.00
(2) Microcrystalline wax 2.00
(3) Carnauba 1.00
(4) Synthetic hydrocarbon wax 2.00
(5) Isopropyl dimer acid 15.00
(6) Tri (capryl / capric acid) glycerin 33.85
(7) Dipentaerythritol fatty acid ester 3.50
(8) Vitamin E 0.10
(9) Polyglyceryl triisostearate 12.00
(10) Coloring agent 6.50
(11) Synthetic phlogopite 9.00
(12) Amorphous silica (E1) 5.00
(13) Fragrance 0.05
Total 100.00

  Specifically, the components (9) to (12) of the above prescription are dispersed with a roller mill. Thereafter, components (1) to (8) are heated and melted, and the mixture of components (9) to (12) and component (13) are added and mixed well. Filtered, poured into a mold at high temperature, cooled and molded into a container to obtain a lipstick.

  The obtained lipstick had excellent soft focus properties even when the powder was blended in a state of being wet with oil, and made it difficult to see the vertical lines of the lips.

<Evaluation as anti-blocking agent>
(Experimental examples 5-1 to 5-9)
Amorphous silica E1, E9 or H14 is added to polypropylene resin (random PP, MFR = 7 g / 10 min) to a concentration of 5% by weight and melt-mixed at 220 ° C. using a twin screw extruder (φ37 mm). Got a masterbatch. Components other than amorphous silica are not added.
The polypropylene resin was melt-mixed with each of the master batches so as to have the concentrations shown in Table 6, and a 30-micron-thick PP film was prepared using a φ40 mm water-cooled inflation molding machine.
About the produced film, Haze was measured based on ASTMD1003-95. The smaller the value of Haze, the better the transparency.
Further, the clarity was measured with a measuring apparatus described in ASTM D 1044-94. The greater the value of Clarity, the better the clarity. As the measuring device, a haze-gard plus manufactured by Gardner was used.
Furthermore, about the produced film, based on ASTMD1894-95, the coefficient of friction (COF) of film outer surfaces was evaluated. DCOF represents the dynamic friction coefficient, and SCOF represents the static friction coefficient. The lower the value, the better the slipperiness. The measuring device used was Toyo Seiki's friction measuring machine TR-2.
Furthermore, the blocking power of the film was measured by the method based on ISO 11502-1995 method B about the produced film. However, the thermocompression bonding conditions between the films were 6 kPa, 45 ° C., and 120 hours. As a measuring apparatus, an autograph AGS-H 20N manufactured by Shimadzu Corporation was used.
Table 6 shows the results of measurement of haze, clarity, friction coefficient, and blocking force. The balance between Haze and SCOF is shown in FIG. 1, and the balance between Clarity and blocking force is shown in FIG.

<Evaluation as matting agent>
(Experimental examples 6-1 to 6-6)
Amorphous silica E9 or H15 was added to 100 parts by weight of amino alkyd resin paint so as to have a predetermined part by weight, and dispersed at 2500 rpm for 5 minutes using a homodisper. About the said coating material, the viscosity in 30 rpm and 1 minute value was measured using the Toki Sangyo B-type viscosity meter TVB-10M.
Next, the paint was applied onto a tin plate (JIS G 3301) using an applicator and dried at 140 ° C. for 2 hours to form a coating film having a thickness of about 30 microns. About the created coating film glossiness, the 60 degree gloss value was measured based on JISZ8741 (1997). The smaller the gloss value, the higher the matte performance. For the measurement, a gloss meter VG2000 manufactured by Nippon Denshoku Industries Co., Ltd. was used. The results of the viscosity of the coating liquid and the 60 ° gloss value of the coating film are shown in Table 7, and the balance between them is shown in FIG.

Claims (6)

  Amorphous silica characterized in that the primary particle diameter measured by the X-ray small angle scattering method is 18 to 50 nm, and the circularity of each secondary particle observed with an electron microscope is 0.70 to 0.85 . The amorphous silica according to claim 1, wherein the median diameter (D ₅₀ ) in terms of volume measured by a laser diffraction scattering method is in the range of 1 to 10 µm. The amorphous silica according to claim 1, wherein the oil absorption is 40 ml / 100 g or more and the bulk density is 0.25 to 0.70 g / cm ³ .   The amorphous silica according to claim 3, which is blended in cosmetics as a soft focus imparting agent.   A cosmetic comprising 0.1 to 10% by weight of the amorphous silica according to claim 3 as a soft focus imparting agent.   A compounding agent for resin comprising the amorphous silica according to claim 1.

Images