JP6733326B2 - Liquid dispersion and its use - Google Patents

Description

The present invention relates to a liquid dispersion and its use. More specifically, the present invention relates to a liquid dispersion containing hydrophobized titanium oxide, a cosmetic raw material using the same, and a cosmetic.

Titanium oxide is used in various applications as a colorant, a filler, etc. Among them, pigment grade titanium oxide is preferably used as a coloring pigment in cosmetics and coating applications. It is known that inorganic powder such as titanium oxide is used in the state of a dispersion dispersed in a dispersion medium in order to promote beautiful color development (see, for example, Patent Document 1). In addition, since the surface of inorganic powder such as titanium oxide is hydrophilic, a technique for surface-treating the inorganic powder to form a dispersion has been developed in order to exhibit water resistance to moisture such as sweat and rain. (See, for example, Patent Documents 2 to 4).

JP, 2012-097259, A International publication 2013/018827 pamphlet International Publication No. 2015/125622 Pamphlet JP, 2016-74660, A

However, in the dispersion treatment of titanium oxide in a dispersion medium, equipment and personnel are required for the dispersion treatment, which is disadvantageous in terms of cost in small-scale, multi-product applications, for example, and requires advanced know-how for dispersion treatment. .. Therefore, if the raw material supplier can provide titanium oxide in the state of a liquid dispersion, the dispersion treatment in the dispersion medium is simplified, which is desirable. However, titanium oxide, which has a larger particle size (for example, a particle size of about 150 nm or more) than fine particles, tends to settle in the dispersion medium, so that the dispersion stability is not good, and caking or phase separation (color separation, etc.) However, it has been difficult to provide a stable liquid dispersion.

Patent Document 1 describes an aqueous dispersion containing a pigment having a particle size of more than 100 nm by a laser particle size analyzer and polyvinylpyrrolidone. However, there was room for improvement to further improve the dispersion stability of the pigment and form a stable liquid dispersion.

Patent Documents 2 to 4 describe dispersions in which fine particle inorganic powder having an organic surface treatment is dispersed in water. This dispersion has a good feel and handleability and can give a cosmetic having high water repellency that is strong against sweat and water, and is particularly useful as a raw material for cosmetics. However, since all the inorganic powders used are fine particles, even if pigment-grade titanium oxide having, for example, an average particle diameter of 150 nm or more is used, it is devised to make the liquid dispersion more stable. There was room for In addition, not only the O/W type cosmetics (oil-in-water type cosmetics) but also the W/O type cosmetics (water-in-oil type cosmetics) can be further enhanced by the effect of titanium oxide. There was also room for improvement.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid dispersion which can maintain a dispersed state stably for a long time and is particularly useful as a raw material for cosmetics. Moreover, it aims at providing the cosmetic raw material and cosmetics using this liquid dispersion.

The present inventors have found that a liquid dispersion containing a polyhydric alcohol, a nonionic surfactant, a hydrophobized titanium oxide (referred to as hydrophobized titanium oxide) and water has good color development, feel and handleability. While paying attention to the fact that a cosmetic having high water repellency that is strong against sweat and water can be given and further intensive studies are conducted, when water-treated and polyvalent titanium oxide having a mean particle size of 150 nm or more is used, When the content of alcohol is set to each predetermined range, the viscosity immediately after preparation of the liquid dispersion becomes appropriate, so that the dispersion state can be stably maintained for a long time, and caking or phase separation over time is sufficiently suppressed. I found a thing. Moreover, they have found that the obtained liquid dispersion also has excellent whiteness. This liquid dispersion is useful as various raw materials because it is easy to store and transport as a dispersion, and the dispersion treatment when dispersing the liquid dispersion in a dispersion medium can be simplified or omitted. It is particularly useful as a raw material, especially as a color pigment. In this way, the inventors have come to the conclusion that the above problems can be solved satisfactorily, and have completed the present invention.

That is, the present invention provides a liquid dispersion containing a polyhydric alcohol (A), a nonionic surfactant (B), a hydrophobized titanium oxide (C), and water (D). The content of (A) is less than 10% by mass based on 100% by mass of the liquid dispersion, the average particle diameter of the hydrophobized titanium oxide (C) is 150 to 700 nm, and the water (D). The content of the liquid dispersion is less than 300 parts by mass based on 100 parts by mass of the total amount of the polyhydric alcohol (A) and the nonionic surfactant (B).

The liquid dispersion preferably further contains lecithin and/or hydrogenated lecithin (E). As a result, for example, the adhesion of the hydrophobized titanium oxide (C) to the skin when used in cosmetics is improved, and the usability is further improved, such as improvement in makeup retention.

The content of the hydrophobized titanium oxide (C) is preferably 60% by mass or more based on 100% by mass of the liquid dispersion. This is preferable because when a liquid dispersion is used as a raw material for various purposes, a small amount can exert a sufficient effect.

The hydrophobized titanium oxide (C) is titanium oxide surface-treated with at least one selected from the group consisting of silicone, alkylsilane, fatty acid (salt), amino acid (salt) and alkylphosphoric acid (salt). It is preferable to have. As a result, the hydrophilic portion of the titanium oxide to be surface-treated is sufficiently blocked, and when it is blended with, for example, a cosmetic containing a water-soluble polymer, gel formation between the titanium oxide (C) and the water-soluble polymer occurs. In addition to being suppressed, the tingling sensation during use is sufficiently reduced and water resistance is also improved.

The polyhydric alcohol (A) is at least one selected from the group consisting of ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, pentylene glycol, glycerin, diglycerin, triglycerin and polyglycerin. Is preferred. Thereby, the nonionic surfactant (B) can be more uniformly oriented on the surface of the hydrophobized titanium oxide (C), and the liquid dispersion is further stabilized.

The nonionic surfactant (B) is preferably a polyether-modified silicone. This further improves the stability of the liquid dispersion and the feeling of use when used in cosmetics. Polyether-modified silicone is also suitable in terms of high safety and thermal stability.

The liquid dispersion preferably has a viscosity at 25° C. of 1000 mPa·s or more. As a result, the hydrophobized titanium oxide (C) becomes harder to move (that is, harder to settle), so that the dispersion stability is further improved.

The present invention is also a cosmetic raw material comprising the above liquid dispersion.
The present invention is also a cosmetic containing the above liquid dispersion.

The liquid dispersion of the present invention can stably maintain a dispersed state for a long time. Therefore, the dispersion process for the dispersion medium can be simplified or omitted, and the cost required for the dispersion process can be reduced. In addition, this liquid dispersion is particularly useful as a raw material for cosmetics, especially as a coloring pigment, since it can give a cosmetic having good color development, touch and handleability and having high water repellency against sweat and water.

Hereinafter, one example of the present invention will be specifically described, but the present invention is not limited only to the following description, and can be appropriately modified and applied without changing the gist of the present invention.

[Liquid dispersion]
The liquid dispersion of the present invention contains a polyhydric alcohol (A), a nonionic surfactant (B), a hydrophobized titanium oxide (C) and water (D). The total content of these essential components is preferably 80% by mass or more based on 100% by mass of the total amount of the liquid dispersion. It is more preferably 85% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 97% by mass or more. If necessary, other components may be contained, and each contained component may be used alone or in combination of two or more.
Hereinafter, each contained component will be described.

-Polyhydric alcohol (A)-
The polyhydric alcohol (A) is not particularly limited as long as it is a dihydric or higher alcohol, but for example, a polyhydric alcohol having 1 to 20 carbon atoms is preferable. More preferably, it is at least one selected from the group consisting of ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, pentylene glycol, glycerin, diglycerin, triglycerin and polyglycerin. Thereby, the nonionic surfactant (B) can be more uniformly oriented on the surface of the hydrophobized titanium oxide (C), and the liquid dispersion is further stabilized. Among them, it is particularly preferable to use 1,3-butylene glycol. In the case of 1,3-butylene glycol, when blended in a cosmetic, it is particularly preferable in that it is highly safe for the human body.

The content of the polyhydric alcohol (A) is less than 10% by mass based on 100% by mass of the total amount of the liquid dispersion. This further improves the dispersion stability of the liquid dispersion. It is preferably 9.9% by mass or less, more preferably 9% by mass or less, further preferably 8.5% by mass or less, particularly preferably 8% by mass or less, and most preferably 7.5% by mass or less. The lower limit is not particularly limited, but is preferably 1% by mass or more in order to enhance the effect of the polyhydric alcohol. It is more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 4% by mass or more.

-Nonionic surfactant (B)-
The nonionic surfactant (B) is not particularly limited as long as it is a compound usually used as a nonionic (nonionic) surfactant, and examples thereof include polyether or its derivative, polyether alkyl ether, and poly(ether alkyl ether). Oxyalkylene alkenyl phenyl ether, polyether fatty acid ester, sorbitan fatty acid ester, polyether sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyether castor oil, polyether hardened castor oil, polyether modified silicone , Polyglycerin-modified silicone and the like. Among them, it is preferable to use polyether fatty acid ester, polyether sorbitan fatty acid ester and/or polyether modified silicone. It is more preferable to use at least a polyether-modified silicone, which further improves the stability of the liquid dispersion and the feeling of use when used in cosmetics. Polyether-modified silicone is also suitable in terms of high safety and thermal stability.

The nonionic surfactant (B) is also a compound that dissolves or becomes cloudy at 35° C. when mixed with 1,3-butylene glycol at a concentration of 20% by mass (the nonionic surfactant is at room temperature). In the case of paste-like to solid, it is preferable that the mixture is heated to homogenize and then heated to 35° C.). As a result, a layer of the nonionic surfactant can be efficiently formed on the surface of the hydrophobized titanium oxide (C), so that the dispersion stability of the liquid dispersion is further improved.
When two or more kinds of nonionic surfactants are used in combination, when the nonionic surfactants mixed in the liquid dispersion at the mixing ratio are subjected to the above-mentioned test, they are transparently dissolved. Alternatively, it is preferably slightly turbid.

The nonionic surfactant (B) is a compound which becomes insoluble or cloudy at 35° C. when mixed in water at a concentration of 20% by mass (when the nonionic surfactant is paste-like to solid at room temperature, It is also preferable that the temperature is set to 35° C. after heating to make it uniform). As a result, when blended into a cosmetic as a cosmetic raw material, the water resistance of the resulting cosmetic becomes more excellent without impairing the dispersibility in water.
When two or more kinds of nonionic surfactants are used in combination, they are insoluble or insoluble when the above-mentioned test is performed on the nonionic surfactants mixed in the liquid dispersion at the mixing ratio. It is preferably cloudy.

In the present specification, “transparent dissolution” means that the haze value of the obtained mixed solution at an optical path length of 10 mm at 35° C. is less than 10, and “fine turbidity” means that the obtained mixed solution has a haze value of 35. This means that the haze value at an optical path length of 10 mm at 10° C. is 10 or more and the total light transmittance is 30% or more. Further, "insoluble" means that undissolved residue occurs even if mixed, or even if it seems turbid at first glance, phase separation occurs after 1 hour, and "white turbidity" means It means that the haze value at an optical path length of 10 mm at 35° C. of the obtained mixed liquid is 10 or more and the total light transmittance is less than 30%.

The HLB (hydrophilic/lipophilic balance) of the nonionic surfactant (B) is preferably 6 to 12, for example. When the HLB is within this range, the dispersibility of the hydrophobized titanium oxide (C) is further enhanced, and, for example, when this liquid dispersion is blended with an O/W type cosmetic (oil-in-water type cosmetic), it is hydrophobic. Adsorption of the chemically treated titanium oxide (C) to the skin is improved, and water resistance is also improved.
When two or more nonionic surfactants (B) are used, the HLB of the mixture is preferably within the above range.

In the present specification, HLB refers to W. C. It is obtained by the following equation (1) defined by Griffin.
N _HLB =(E+P)/5 (1)
(N _HLB represents the HLB value. E represents the ratio (mass %) of the polyether moiety of the nonionic surfactant (B) to the entire molecule of the nonionic surfactant (B). P represents the ratio (mass %) of the polyhydric alcohol part of the nonionic surfactant (B) to the whole molecule of the nonionic surfactant (B).)

The content of the nonionic surfactant (B) is preferably 1% by mass or more based on 100% by mass of the total amount of the liquid dispersion. Thereby, the dispersibility of the hydrophobized titanium oxide (C) becomes better. It is more preferably 2% by mass or more, still more preferably 3% by mass or more. The upper limit is not particularly limited, but from the viewpoint of cost reduction and uniform dispersion, it is preferably 25% by mass or less. It is more preferably 20% by mass or less, still more preferably 15% by mass or less.

-Hydrophobic treatment titanium oxide (C)-
The hydrophobized titanium oxide (C) has an average particle diameter of 150 to 700 nm. Usually, titanium oxide having such a particle size of pigment grade tends to settle, and according to the conventional common technical knowledge, it is considered that the dispersion stability of a liquid dispersion is not good. Contrary to this technical common sense, however, the liquid dispersion of the present invention has extremely good dispersion stability in spite of containing the hydrophobized titanium oxide (C) having such a particle size, so that it is suitable for use in color pigments. Especially useful. From the viewpoint of producing a more beautiful color, the thickness is more preferably 180 nm or more, and further preferably 200 nm or more. From the viewpoint of dispersion stability, it is more preferably 650 nm or less, still more preferably 600 nm or less.

In the present specification, the average particle diameter of titanium oxide is a method of measuring the particle diameter of 200 particles randomly selected in a scanning electron microscope photograph (SEM photograph) and calculating the average of the primary particle diameters. Means the value measured by. The diameter of the smallest circumscribed circle is used to calculate the individual primary particle size.

The shape of the hydrophobized titanium oxide (C) is not particularly limited, and examples thereof include spherical shapes (including substantially spherical shapes), rod shapes, needle shapes, spindle shapes, plate shapes, hexagonal plate shapes, needle aggregates, and amorphous shapes. Are listed.
The shape can be observed with a scanning electron microscope or the like.

The titanium oxide, which is a raw material of the hydrophobized titanium oxide (C), may be a composite powder whose surface is coated with another inorganic material. In this case, the composite powder is hydrophobized to be used as hydrophobized titanium oxide (C). Other inorganic materials are not particularly limited, and examples thereof include zinc oxide, titanium oxide, cerium oxide, iron oxide, barium oxide, hydrous silicic acid, silica, aluminum hydroxide, alumina, and zirconia. The coating amount of these inorganic materials is preferably, for example, 0 to 25 mass% with respect to 100 mass% of the total amount of titanium oxide after the hydrophobic treatment. More preferably, it is 2 to 20 mass %.

The hydrophobized titanium oxide (C) is obtained by subjecting raw material titanium oxide (which may be the above composite powder) to a hydrophobizing treatment. The hydrophobizing treatment means treating the surface of the raw material titanium oxide with a hydrophobic organic surface treating agent. Since the hydrophilic portion of the surface of the raw material titanium oxide to be treated is blocked by the hydrophobizing treatment, the water resistance and water repellency are improved, and the hydrophobizing treatment is performed, for example, when it is added to a cosmetic containing a water-soluble polymer. The gel formation between titanium oxide (C) and the water-soluble polymer is suppressed, and the tingling sensation during use is sufficiently reduced, which makes it more useful for cosmetics.

Here, the hydrophobized titanium oxide (C) (that is, the hydrophobized titanium oxide) preferably has a high degree of hydrophobicity. Thereby, the stability of the liquid dispersion can be further increased. The degree of hydrophobization can be measured by pressing the hydrophobized titanium oxide into a flat plate having a uniform surface, and measuring the contact angle of water droplets when 1 μL of water is dropped on the surface. The angle is preferably 45 degrees or more, more preferably 60 degrees or more, and further preferably 90 degrees or more.

The hydrophobic organic surface-treating agent is not particularly limited as long as it is an organic surface-treating agent usually used for hydrophobizing the surface of particles. Silicone, alkylsilanes, fatty acids (salts), amino acids (salts) and alkylphosphorus At least one selected from the group consisting of acids (salts) is preferable. Thereby, the effect of the above-mentioned hydrophobic treatment is further exerted, and the release of the surface treatment agent from titanium oxide is sufficiently suppressed, so that the dispersion stability is further improved.

The salt is not particularly limited, and for example, metal salt, ammonium salt, and organic amine salt are preferable. Examples of the metal atom constituting the metal salt include monovalent metals such as sodium, lithium, potassium, rubidium and cesium; divalent metals such as zinc, magnesium, calcium, strontium and barium; trivalent metals such as aluminum; iron. , Other metals such as titanium; and the like. Examples of the organic amine group constituting the organic amine salt include alkanolamine groups such as monoethanolamine group, diethanolamine group and triethanolamine group; alkylamine groups such as monoethylamine group, diethylamine group and triethylamine group; ethylenediamine group, A polyamine group such as a triethylenediamine group; and the like. Among the above salts, ammonium salts, sodium salts or potassium salts are preferable, and sodium salts are more preferable.

Among the above hydrophobic organic surface treating agents, silicone is preferable. Examples of the silicone include methylhydrogenpolysiloxane, dimethylpolysiloxane, copolymers of methylhydrogenpolysiloxane and dimethylpolysiloxane, organopolysiloxanes containing reactive trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group, and the like. It is suitable.

In the hydrophobizing treatment of titanium oxide, the hydrophobizing treatment is performed in a ratio of 0.1 to 10 mass% with respect to 100 mass% of the total amount of titanium oxide (hydrophobized titanium oxide (C)) after the treatment. Is preferred. When it is 0.1% by mass or more, water repellency and water resistance are further improved. Even if the amount exceeds 10% by mass, the effect of the hydrophobizing treatment reaches the ceiling. It is more preferably 0.2 to 9% by mass, and further preferably 0.5 to 8% by mass.

The content of the hydrophobized titanium oxide (C) is preferably 60% by mass or more based on 100% by mass of the total amount of the liquid dispersion. This is preferable because when a liquid dispersion is used as a raw material for various purposes, a small amount can exert a sufficient effect. It is more preferably 65% by mass or more, and further preferably 70% by mass or more. The upper limit is not particularly limited, but considering the contents of other components, it is preferably 95% by mass or less, and more preferably 90% by mass or less.

-Water (D)-
The content of water (D) is less than 300 parts by mass based on 100 parts by mass of the total amount of the polyhydric alcohol (A) and the nonionic surfactant (B). When it is 300 parts by mass or more, sedimentation or thickening with time becomes remarkable and the dispersion stability is not good, but the average particle size is 150 nm or more only when the content is less than 300 parts by mass. When the hydrophobized titanium oxide (C) is used, sedimentation and thickening with time are sufficiently suppressed, and phase separation and caking are also suppressed. It is preferably 290 parts by mass or less, more preferably 250 parts by mass or less, further preferably 230 parts by mass or less, and particularly preferably 200 parts by mass or less. Further, from the viewpoint of handleability (also referred to as handling property), the lower limit may be an amount exceeding 0 parts by mass, but from the viewpoint of increasing whiteness, the polyhydric alcohol (A) and the nonionic surfactant (B ) And 100 parts by mass, the amount is preferably more than 100 parts by mass, more preferably 110 parts by mass or more, further preferably 120 parts by mass or more, and particularly preferably 130 parts by mass or more.

-Lecithin and/or hydrogenated lecithin (E)-
The liquid dispersion of the present invention preferably further contains lecithin and/or hydrogenated lecithin (E). By containing lecithin and/or hydrogenated lecithin (E), the adhesion of the hydrophobized titanium oxide (C) to the skin is improved, and the makeup retention is improved.
In addition, lecithin and/or hydrogenated lecithin may be collectively referred to as “(hydrogenated) lecithin”.

The content of lecithin and/or hydrogenated lecithin (E) (the total amount when two types are used) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the hydrophobized titanium oxide (C). Is preferred. If the amount is less than 0.01 parts by mass, the improvement of the adhesiveness cannot be expected so much, and if it exceeds 10 parts by mass, problems such as stickiness may occur. The amount is more preferably 0.1 to 8 parts by mass, further preferably 0.5 to 5 parts by mass, and particularly preferably 0.5 to 3 parts by mass.

-Other ingredients-
The liquid dispersion of the present invention contains, if necessary, a polyhydric alcohol (A), a nonionic surfactant (B), a hydrophobized titanium oxide (C), water (D), and lecithin and/or Other components than hydrogenated lecithin (E) may be included. Other components are not particularly limited, but include, for example, paraoxybenzoic acid alkyl ester, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, salicylic acid, carboxylic acid, sorbic acid, parachlormethacresol, hexachlorophene, chloride. Examples include antibacterial preservatives such as benzalkonium, chlorhexidine chloride, photosensitizer, and phenoxyethanol, and antibacterial agents.

The content of other components is, for example, preferably 20% by mass or less based on 100% by mass of the total amount of the liquid dispersion. It is more preferably 15% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less.

The production method for obtaining the liquid dispersion of the present invention is not particularly limited, and it may be produced by mixing the above components. The mixing method is not limited, and a normal method that can uniformly disperse may be used. For example, a dispersing machine/device such as a bead mill, a jet mill, or a high-pressure homogenizer may be used, but the liquid dispersion of the present invention can be easily prepared with a simple stirrer without using these expensive dispersing machines/devices. Therefore, there is also an advantage that an expensive dispersing machine such as a bead mill becomes unnecessary.

The liquid dispersion of the present invention preferably has a viscosity at 25° C. of 1000 mPa·s or more. When the viscosity is within this range, the hydrophobized titanium oxide (C) becomes harder to move (that is, harder to settle), so that the increase in viscosity over time is more sufficiently suppressed and the dispersion stability is further improved. To do. More preferably, it is 2500 mPa·s or more. The upper limit of the viscosity is preferably 500,000 mPa·s or less, more preferably 300,000 mPa·s or less, further preferably 100,000 mPa·s or less, and particularly preferably 50,000 mPa·s or less.

The above-mentioned “viscosity at 25° C.” means polyhydric alcohol (A), nonionic surfactant (B), hydrophobized titanium oxide (C), water (D), and lecithin and/or It is the viscosity of the liquid dispersion in the case of containing no components other than hydrogenated lecithin (E). This liquid dispersion was prepared, allowed to stand at 40° C. for 1 day, and then cooled to 25° C. (LVDV1M, manufactured by Eiko Seiki Co., Ltd.) (value measured at 25° C.).

The liquid dispersion of the present invention preferably has a whiteness of 60 or more in W value. This makes it even more useful as a color pigment for various applications. It is more preferably 62 or more, still more preferably 64 or more.
The W value is calculated from the values of the Hunter color system L (lightness), a (saturation), and b (hue) according to the following formula (2).
W=100-{(100-L) ² +(a ² +b ² )} ^1/2 (2)

[Use]
Since the liquid dispersion of the present invention can maintain a dispersed state stably for a long time, it is easy to store and transport as a dispersion, and a dispersion treatment is performed when the liquid dispersion is dispersed in a dispersion medium. It can be simplified or omitted. Therefore, it is useful as various raw materials, particularly as cosmetic raw materials, coating raw materials, and ink raw materials. Among them, the liquid dispersion of the present invention is very useful as a raw material for cosmetics because it has good color development, feel and handleability, and can give a cosmetic having high water repellency that is strong against sweat and water. Thus, the cosmetic raw material comprising the liquid dispersion of the present invention is one of the present inventions. Further, cosmetics, coating compositions or ink compositions containing the liquid dispersion of the present invention are also included in the invention by the present inventor. The cosmetics will be further described below.

[Cosmetic]
The cosmetic of the present invention contains the liquid dispersion of the present invention described above. The method for producing such a cosmetic is not particularly limited, and may be an ordinary method for producing a cosmetic.

The above-mentioned cosmetics are not particularly limited, and examples thereof include skin care products, hair products, makeup products, UV protection products and the like. The shape of the cosmetic is not particularly limited, and examples thereof include liquid, emulsion, cream, solid, paste, gel, multi-layer, mousse, spray and the like.

The above cosmetics can be preferably applied to any of water-based cosmetics, O/W type cosmetics (oil-in-water type cosmetics) and W/O type cosmetics (water-in-oil type cosmetics). .. In the O/W type cosmetics using the liquid dispersion of the present invention, even when used in combination with the anionic water-soluble polymer, the viscosity is not lowered, gelation is not caused, and the water resistance is improved. In addition, in the W/O type cosmetics, after the cosmetics are applied to the skin, the adhesion of titanium oxide to the skin is improved by the evaporation of water, and the makeup lasting property can be improved. In particular, by adding lecithin or hydrogenated lecithin, the adhesion to the skin is significantly improved.

The above-mentioned cosmetics may contain one or more kinds of optional aqueous components and oily components usually used in the field of cosmetics, if necessary. The aqueous component and the oil component are not particularly limited, and examples thereof include an oil agent, a surfactant, a moisturizer, a higher alcohol, a sequestering agent, a natural or synthetic polymer, a water-soluble or oil-soluble polymer, an ultraviolet shielding agent, and various types. Extraction liquid, drug component, colorant (dye, pigment, etc.), preservative, antioxidant, pigment, thickener, pH adjuster, fragrance, cooling sensation, antiperspirant, bactericide, skin activating agent, various Examples thereof include powder.

The following examples are provided to explain the present invention in detail, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "mass% (weight %)" and "part" means "mass part (weight part)", respectively.
Various physical properties and the like were evaluated as follows.

1. After the viscosity liquid dispersion was prepared, it was allowed to stand at 40° C. for 1 day or 1 week, cooled to 25° C., and measured with a B-type viscometer (LVDV1M, manufactured by Eiko Seiki Co., Ltd.) (measurement temperature: 25 C).

2. After the caking and the supernatant liquid dispersion were prepared, they were allowed to stand at 40° C. and visually confirmed 1 week later.
In the table, those in which caking or supernatant had occurred were described as "occurrence", and those which did not occur were described as "none".

3, particle size (particle size distribution)
After diluting the liquid dispersion with water, the median diameter D ₅₀ was measured with “LA-950” manufactured by Horiba Ltd.

4. The whiteness liquid dispersion is diluted with a 5 wt% concentration of 1,3-butylene glycol aqueous solution so that the pigment concentration in the dispersion is 25 wt %, and the diluted solution is applied to a glass plate with an applicator (3 mil). And dried at 120° C. for 1 hour to obtain a coating film. The coating film was measured for L value, a value, and b value with a chromaticity meter, and the W value was determined according to the above equation (2) based on these numerical values, and this W value was taken as whiteness. The whiteness indicates the hiding property.

Example 1
In a metal beaker, 1,3-butylene glycol (manufactured by Daicel) in the amounts shown in Table 1, nonionic surfactant (“KF-6013” manufactured by Shin-Etsu Chemical Co., Ltd., polyether-modified silicone), titanium oxide (Sakai) "MKR-1S" manufactured by Kagaku Kogyo Co., Ltd., titanium oxide 98.5%, hydrogen dimethicone 1.5%, average particle diameter: 200 nm), and water were added in that order. At the time of charging, they were mixed with a gold spatula and mixed with a stirrer. The liquid dispersion obtained in this manner was evaluated as described above. The results are shown in Table 1.

Examples 2, 3
A liquid dispersion was prepared in the same manner as in Example 1 except that the amounts of the respective raw material components were changed to the amounts shown in Table 1, and the above-mentioned evaluation was performed. The results are shown in Table 1.

Example 4
A liquid dispersion was prepared in the same manner as in Example 2 except that the average particle diameter of titanium oxide was changed to 500 nm, and the above-described evaluation was performed. The results are shown in Table 1.

Example 5
In a metal beaker, 1,3-butylene glycol (manufactured by Daicel) in the amounts shown in Table 1, nonionic surfactant (“KF-6013” manufactured by Shin-Etsu Chemical Co., Ltd., polyether-modified silicone), lecithin (J- "Lecithin CL" manufactured by Oil Mills), titanium oxide ("MKR-1S" manufactured by Sakai Chemical Industry Co., Ltd., 98.5% titanium oxide, hydrogen dimethicone 1.5%, average particle diameter: 200 nm), and water in this order. .. At the time of charging, they were mixed with a gold spatula and mixed with a stirrer. The liquid dispersion obtained in this manner was evaluated as described above. The results are shown in Table 1.

Comparative Examples 1 to 4
A liquid dispersion was prepared in the same manner as in Example 1 except that the raw material components shown in Table 1 were used in the amounts shown in Table 1 (in some examples, the liquid dispersion could be obtained without dispersion). There was not). The above-mentioned evaluation was performed for the obtained liquid dispersion. The results are shown in Table 1.
The titanium oxide used in Comparative Example 2 is fine particle titanium oxide “STR-100W-LP” manufactured by Sakai Chemical Industry Co., Ltd. (75% titanium oxide, 17% silica, hydrogen dimethicone 8%, average particle diameter: 90 nm (minimum Circumscribed circle average)).

From Table 1, the following was confirmed.
Examples 1 to 5 are liquid dispersions containing a polyhydric alcohol (A), a nonionic surfactant (B), a hydrophobized titanium oxide (C) having an average particle size of 150 to 700 nm, and water (D). Example 5 is a liquid dispersion further containing lecithin and/or hydrogenated lecithin (E), wherein the content of water (D) is a polyhydric alcohol (A) and a nonionic surfactant ( B) is less than 300 parts based on 100 parts, and the content of the polyhydric alcohol (A) is less than 10% based on 100% of the liquid dispersion. A stable liquid dispersion was obtained in which the occurrence of supernatant and caking was suppressed. The median diameter D ₅₀ was also small, the dispersion of the hydrophobized titanium oxide (C) was good, and the whiteness was at a sufficient level.

On the other hand, as in Comparative Example 1, when the content of water (D) is 300 parts or more based on 100 parts of the total amount of the polyhydric alcohol (A) and the nonionic surfactant (B). The viscosity was too low and the supernatant and caking occurred (see Comparative Example 1). In addition, when polyhydric alcohol (A) and nonionic surfactant (B) are not used and titanium oxide that has not been subjected to hydrophobizing treatment is used, the viscosity increases remarkably with time, and supernatant and caking also occur. (See Comparative Example 3). When the nonionic surfactant (B) and water were not used, they were not dispersed and a liquid dispersion could not be obtained (see Comparative Example 4). Although not shown in the table, the case where polyvinylpyrrolidone was used in place of the nonionic surfactant in Example 1 was also examined, and in this case as well, no dispersion occurred and a liquid dispersion could be obtained. There wasn't. On the other hand, when fine particle titanium oxide having a small average particle size was used as the hydrophobized titanium oxide (C), although the supernatant and caking did not occur, the whiteness was low and it was more useful as a color pigment. It did not occur (see Comparative Example 2).

From the above, the polyhydric alcohol (A), the nonionic surfactant (B), the hydrophobized titanium oxide (C) and water (D) having an average particle size of 150 to 700 nm, and further lecithin and/or water are contained. Even when the additive lecithin (E) is blended, the content of water (D) is less than 300 parts based on 100 parts of the total amount of the polyhydric alcohol (A) and the nonionic surfactant (B), and A liquid dispersion capable of stably maintaining a dispersed state for a long time only when the composition is such that the content of the polyhydric alcohol (A) is less than 10% with respect to 100% of the liquid dispersion. I found out.

Claims (8)

A liquid dispersion containing a polyhydric alcohol (A), a nonionic surfactant (B), a hydrophobized titanium oxide (C), and water (D),
The content of the polyhydric alcohol (A) is less than 10 mass% with respect to 100 mass% of the liquid dispersion,
The average particle diameter of the hydrophobized titanium oxide (C) is 150 to 700 nm,
The content of the water (D) is more than 100 parts by mass and less than 300 parts by mass based on 100 parts by mass of the total amount of the polyhydric alcohol (A) and the nonionic surfactant (B). Characteristic liquid dispersion. The liquid dispersion according to claim 1, further comprising lecithin and/or hydrogenated lecithin (E). The liquid dispersion according to claim 1 or 2, wherein the content of the hydrophobized titanium oxide (C) is 60% by mass or more based on 100% by mass of the liquid dispersion. The hydrophobized titanium oxide (C) is titanium oxide surface-treated with at least one selected from the group consisting of silicone, alkylsilane, fatty acid (salt), amino acid (salt) and alkylphosphoric acid (salt). The liquid dispersion according to claim 1, wherein the liquid dispersion is present. The polyhydric alcohol (A) is at least one selected from the group consisting of ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, pentylene glycol, glycerin, diglycerin, triglycerin and polyglycerin. The liquid dispersion according to any one of claims 1 to 4, wherein The liquid dispersion according to any one of claims 1 to 5, wherein the nonionic surfactant (B) is a polyether-modified silicone. The liquid dispersion according to any one of claims 1 to 6, which has a viscosity at 25°C of 1000 mPa·s or more. A cosmetic raw material comprising the liquid dispersion according to any one of claims 1 to 7.