JP3788680B2 - Organic-inorganic composite pigment and method for producing the same - Google Patents

Description

【００３５】
表１より、実施例１及び２は比較例１及び２より優れており、特に実施例１はいずれの項目でも優れていることが確認された。
【００３６】
配合例１
表２に示す配合でアイシャドウを作成した。すなわち粉体成分を粉砕器で混合し、更に油分を添加して均一になるまで混合した。これをふるいに通した後、型に入れて圧縮し、固形に成型してアイシャドウとした。得られたアイシャドウは彩度が高く、色調が鮮明で、更に耐久性にも優れたものであった。
【００３７】
【表２】
（成分） （重量％）
タルク １６．７
マイカ １０．０
ステアリン酸亜鉛 ７．０
有機無機複合顔料（実施例１） １８．０
酸化チタン ３．０
群青 ０．３
雲母チタン ２５．０
流動パラフィン １０．０
ミリスチン酸イソプロピル １０．０
【００３８】
【発明の効果】
本発明の方法により製造した有機無機複合顔料は、有機顔料と無機顔料とが複合化したものであり、彩度が高く、特に化粧料に配合した場合色調が鮮明となり、かつ耐久性にも優れたものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic-inorganic composite pigment having good color development, excellent dispersibility, and high durability, and a method for producing the same.
[0002]
[Prior art and problems to be solved by the invention]
A composite pigment having an organic colorant attached to the surface of an inorganic pigment has a higher chroma than in the case of simple mixing, and is particularly effective in sharpening the appearance color when blended in cosmetics. If the organic colorant to be combined is a fine particle and adheres to the surface of the inorganic pigment with high dispersion, the saturation becomes higher.
[0003]
By the way, as a method of attaching the organic colorant to the surface of the inorganic pigment, a method of adsorbing an organic dye using the charge on the surface of the inorganic pigment, or a dye after adsorbing polyvalent ions or a surfactant to the surface of the inorganic white pigment is used. A method of adsorbing is known. If these methods are used, the organic colorant can be adhered to the surface of the inorganic pigment with high dispersion.
[0004]
However, the organic / organic composite pigments obtained by these methods tend to release the organic colorant in water, and the amount of the organic colorant that can be attached to the surface of the inorganic pigment is not sufficient.
[0005]
On the other hand, a method of attaching an organic colorant to the surface of an inorganic pigment using a binder is also widely used. As such a binder, a water-soluble polymer is generally used. However, since the water-soluble polymer is inferior in water resistance, the organic colorant may be detached from the surface of the inorganic pigment or may be discolored with a small amount of water. In addition, a method using various polymers such as acrylic polymers as a binder is also known (Japanese Patent Laid-Open No. 1-294411). However, when fine organic pigments are used, aggregation is likely to occur in a solvent, and saturation is increased. The improvement effect is not so high.
[0006]
Accordingly, an object of the present invention is to provide an organic-inorganic composite pigment that has high chroma, has a high effect of sharpening the color tone when blended with cosmetics, and is excellent in durability.
[0007]
[Means for Solving the Problems]
As a result of intensive research aimed at achieving the above-mentioned object, the present inventors have found that an organic-inorganic composite pigment containing a highly oil-absorbing inorganic pigment, a fine-particle organic colorant and a specific organopolysiloxane has high chroma and is incorporated into cosmetics. As a result, it was found that the appearance color can be clarified and the durability is excellent, and the present invention has been completed.
[0008]
That is, the present invention includes the following components (a) to (c),
(A) high oil-absorbing inorganic pigment having an oil absorption (according to JIS K5101 measurement method, the same shall apply hereinafter) of 50 to 300 mL / 100 g, (b) a fine particle organic colorant and (c) an organopolysiloxane dissolved in a cyclic silicone or An organic-inorganic composite pigment containing the derivative;
In addition, an organopolysiloxane or a derivative thereof is dissolved in a cyclic silicone, and an organic colorant is added to the resulting solution for atomization, followed by impregnation with a highly oil-absorbing inorganic pigment, and then the cyclic silicone is volatilized and removed. The present invention provides a method for producing an organic-inorganic composite pigment.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the component (a) is a highly oil-absorbing inorganic pigment having an oil absorption of 50 to 300 mL / 100 g, preferably 70 to 250 mL / 100 g. If it is less than 50 mL / 100 g, the organic colorant does not uniformly adhere to the surface of the highly oil-absorbing inorganic pigment, and if it exceeds 300 mL / 100 g, the amount of oil is reduced when used in an oily solid cosmetic, and the feeling deteriorates. Examples of such highly oil-absorbing inorganic pigments include inorganic minerals such as mica, talc, bentonite and zeolite, and metal oxides such as titanium oxide, zinc oxide, zirconia oxide, boron nitride, alumina and silica. In the present invention, one or more of these can be used. Of these, titanium oxide, zinc oxide, zirconia oxide, boron nitride, silica, and alumina are preferred because of the high effect of enhancing the color development of the organic colorant. Examples of combinations of two or more include zinc oxide and titanium oxide, silica and alumina, or silica and titanium oxide.
[0010]
The average particle size (observed with a scanning electron microscope, the same applies hereinafter) of the component (a) is preferably 1.0 to 50 μm, and particularly preferably 2.0 to 15 μm. If it is 1.0-50 micrometers, an organic-inorganic composite pigment with high chroma can be obtained.
[0011]
There is no restriction | limiting in particular as an organic colorant of a component (b), For example, red No. 2, red No. 3, red No. 102, red No. 104, red No. 105, red No. 106, yellow No. 4, yellow No. 5, green 3 No. 1, Blue No. 1, Blue No. 2, Red No. 227, Red No. 230, Red No. 231, Red No. 232, Orange No. 205, Orange No. 207, Yellow No. 202, Yellow No. 203, Green No. 201, Green No. 204, Green 205, Blue 205, Red 201, Red 401, Red 502, Red 503, Red 504, Red 506, Orange 402, Yellow 402, Yellow 403, Yellow 406, Yellow 407 No., green 402, purple 401, black 401, etc. acid dyes, lake pigments such as aluminum, barium and zirconium salts of such acid dyes, red 213, red 214 etc. basic dyes Red 215, Red 218, Red 223, Orange 201, Orange 206, Yellow 201, Yellow 204, Green 202, Purple 201, Red 501, Red 505, Orange 403, Yellow 404 No., oil-soluble dyes such as yellow 405, blue 403, vat dyes such as red 226, blue 201, blue 204, red 202, red 213, red 404, red 405, orange 203 No., orange 204, orange 401, and the like, as well as lacqueric acid, carminic acid, shikonin, beta-carotene, shisonin, rutin, chlorophyll and the like. Such organic colorants can be used alone or in combination of two or more.
[0012]
The organic colorant of component (b) needs to be fine particles, and its particle size is preferably 0.001 to 1.0 μm in a state dispersed in cyclic silicone, and 0.01 to 0.00. A thickness of 5 μm is particularly preferable. If it is less than 0.001 μm, the coloring power is not always sufficient, and if it is more than 1.0 μm, the saturation is slightly inferior. The average particle size of the colorant fine particles can be measured using a laser Doppler type particle size measuring device or the like.
[0013]
In the present invention, the component (c) is an organopolysiloxane or a derivative thereof that dissolves in the cyclic silicone. In the present invention, the cyclic silicone means a liquid which is liquid at 30 to 50 ° C., preferably 20 to 60 ° C., and volatilizes at 100 ° C. and 10 mmHg. Examples of the cyclic silicone include octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. Examples of commercially available products include SH244 and SH245 (Toray Dow Corning Co., Ltd.).
[0014]
The term “dissolved in cyclic silicone” means that organopolysiloxane or a derivative thereof is dissolved in cyclic silicone at 5% by weight or more, preferably 10% by weight or more at room temperature or below the boiling point of cyclic silicone.
[0015]
The structure of the organopolysiloxane or derivative thereof is not particularly limited as long as it dissolves in the cyclic silicone, but more preferably, the one having a hydrophilic segment in the molecule improves the dispersibility of the organic colorant, Suitable for uniform adhesion to the surface of inorganic pigments. Examples of such hydrophilic segments include N-acylalkylimines blocked at the end, polyalkylene glycol, polyalkylene glycol monoalkyl ether, acrylic acid, methacrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, Quaternary dimethylaminoethyl methacrylate, methacrylamide, Nt-butylacrylamide, maleic acid, maleic anhydride, half-ester of maleic anhydride, crotonic acid, itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, diallyldimethylammonium Chloride, vinyl pyrrolidone, vinyl ethers, vinyl pyridine, vinyl imidazole, styrene sulfonate, allyl alcohol, vinyl alcohol, vinyl Caprolactam, etc. N- alkylene carbobetaine and sugar derived residues.
[0016]
Among these, the composition ratio (weight) of the hydrophilic segment and the organopolysiloxane segment in the organopolysiloxane derivative is 1/50 to 20/1, and the weight average molecular weight of the organopolysiloxane is a copolymer of 500 to 500,000. Is particularly preferable for improving the dispersibility of the organic colorant.
Furthermore, from the viewpoint of stability and safety, an organopolysiloxane / N-acylalkylimine copolymer is most preferable.
[0017]
The organic-inorganic composite pigment of the present invention is a pigment in which the components (a) to (c) are complexed. Among these, the component (c) is used as a binder and the component (b) adheres to the surface of the component (a) with high dispersion. It is preferable from the viewpoints of color clarity and durability when blended in a chroma, cosmetics and the like. Moreover, the average particle diameter of the organic-inorganic composite pigment of the present invention is preferably 1.0 to 50 μm, particularly preferably 2.0 to 15 μm, from the viewpoint of saturation and durability improvement.
[0018]
Next, the manufacturing method of the organic inorganic composite pigment of this invention is demonstrated. First, an organopolysiloxane or a derivative thereof is added to a cyclic silicone solution, and appropriately stirred and heated to completely dissolve the organopolysiloxane or a derivative thereof. Next, the component (b) is added to this solution, and the mixture is properly stirred and dispersed uniformly. Or the organic colorant which is not atomized may be added and the atomization process of the organic pigment may be performed in this solution. The atomization treatment can be performed according to a conventional method using, for example, a bead mill, a sand mill, a ball mill, a microfluidizer, or a nanomizer.
[0019]
The content of the component (b) in the mixed solution obtained above is preferably 0.01 to 50% by weight, particularly preferably 0.1 to 20% by weight. If it is less than 0.01% by weight, it is difficult to obtain a desired color tone because the amount of the pigment is small, and if it exceeds 50% by weight, it is difficult to disperse the organic colorant in the mixed solution. In the mixed solution obtained above, the content of the organopolysiloxane or its derivative with respect to the component (b) is preferably 1 to 100% by weight, particularly preferably 5 to 50% by weight. If the amount is less than 1% by weight, it is difficult to stably attach the component (b) to the surface of the component (a). If the amount is more than 100% by weight, the organic-inorganic composite pigment tends to aggregate.
[0020]
Next, the mixture (a) obtained above is impregnated with the component (a). At this time, the liquid mixture is preferably in a volume ratio of 0.1 to 1000, particularly 0.5 to 100 with respect to the component (a) to be impregnated. If it is less than 0.1, the component (b) hardly adheres uniformly to the surface of the component (a). If it exceeds 1000, it takes a long time to volatilize and remove the cyclic silicone, and the operation becomes complicated. Thereafter, the cyclic silicone is volatilized and removed under normal pressure or reduced pressure, whereby the organic-inorganic composite pigment of the present invention can be obtained.
[0021]
The organic-inorganic composite pigment of the present invention can be used, for example, in cosmetics, paints, plastics, inks, crayons, paints, toners, daily goods and decorative products. Among these, it is preferable to use it as a cosmetic. Examples of cosmetics include lipstick, eye shadow, blusher, nail enamel, eyeliner, mascara, foundation, and emulsion.
[0022]
When used in the above applications, the organic-inorganic composite pigment of the present invention may be subjected to surface treatment performed on a normal organic or inorganic pigment as necessary, for example, metal soap, higher fatty acid, surfactant, silica, alumina. Surface treatment can be performed with titanium oxide, zirconia, silicon nitride, siloxane, polysiloxane, polysiloxane derivatives, fluorine-based polymers, amino acid derivatives, proteins such as fibroin, polymers such as PMMA, nylon, and the like.
[0023]
【Example】
EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited to a following example.
[0024]
Example 1
To 95 parts by weight of cyclic silicone (SH244, Toray Dow Corning Co., Ltd.), 2.5 parts by weight of poly (N-propionylethyleneimine) modified silicone (Kao Co., Ltd.) was added and completely dissolved. To the resulting solution, 2.5 parts by weight of Red No. 202 (Hatsukasei) was added and treated with a sand mill to disperse the fine particle organic colorant. The average particle size of Red No. 202 in the obtained dispersion was 0.3 μm. Next, 10 parts by weight of highly oil-absorbing silica (Sunsphere H122, oil absorption 205 mL / 100 g, average particle size 12 μm, Asahi Glass) was added to this dispersion and impregnated with sufficient stirring. Next, the cyclic silicone was removed by volatilization at 80 ° C. under reduced pressure using a rotary pump to obtain an organic-inorganic composite pigment. The average particle size of the obtained organic-inorganic composite pigment was 12 μm.
[0025]
Example 2
A solution (resin content 1.5 weight) of 10 parts by weight of a solution of highly polymerized methylpolysiloxane dissolved in cyclic silicone (XF49, Toshiba Silicone) and 90 parts by weight of cyclic silicone (SH245, Toray Dow Corning Co., Ltd.) %) Was added with 3.0 parts by weight of red No. 104 aluminum lake (Kai Kasei) and treated with a microfluidizer to disperse the fine particle organic colorant. The average particle size of red No. 104 aluminum lake in the obtained dispersion was 0.6 μm. Next, 10.3 parts by weight of highly oil-absorbing titanium oxide (titanium microbead 1511, oil absorption 75 mL / 100 g, average particle size 7 μm, catalyst conversion) was added to this dispersion, and the mixture was sufficiently stirred and impregnated. Next, the cyclic silicone was removed by volatilization at 80 ° C. under reduced pressure using a rotary pump to obtain an organic-inorganic composite pigment. The average particle diameter of the obtained organic-inorganic composite pigment was 8 μm.
[0026]
Example 3
A total of 95 parts by weight of cyclic silicone (SH244, Toray Dow Corning Co., Ltd.) and 2.5 parts by weight of acrylic acid / butyl methacrylate / polydimethylsiloxane copolymer (synthesized by Kao Corporation) are completely added. Dissolved in. To the resulting solution, 2.5 parts by weight of Red No. 202 (Hana Kasei) was added and treated with a sand mill to disperse the fine organic colorant. The average particle size of Red No. 201 in the obtained dispersion was 0.5 μm. Next, 10 parts by weight of highly oil-absorbing silica (Sunsphere H122, average particle size 12 μm, Asahi Glass, oil absorption 205 mL / 100 g) was added to this dispersion, and the mixture was impregnated with sufficient stirring. Next, using a rotary pump, the cyclic silicone was removed by volatilization at 80 ° C. under reduced pressure to obtain an organic-inorganic composite powder. The average particle size of the obtained organic-inorganic composite pigment was 12 μm.
[0027]
Comparative Example 1
2.5 parts by weight of Red No. 202 (Hana Kasei) was added to 97.5 parts by weight of cyclic silicone (SH244, Toray Dow Corning Co., Ltd.) and treated with a sand mill to disperse the fine organic particles. The average particle size of Red No. 202 in the obtained dispersion was 0.8 μm. Next, 10 parts by weight of highly oil-absorbing silica (Sunsphere H122, oil absorption 205 mL / 100 g, average particle size 12 μm, Asahi Glass) was added to this dispersion and impregnated with sufficient stirring. Next, the cyclic silicone was removed by volatilization at 80 ° C. under reduced pressure using a rotary pump to obtain an organic-inorganic composite pigment. The average particle diameter of the obtained organic-inorganic composite pigment was 13 μm.
[0028]
Comparative Example 2
10.3 parts by weight of titanium oxide (CR50, oil absorption 20 mL / 100 g, average particle size 0.8 μm, Ishihara Sangyo) was added to the dispersion obtained in Example 2, and after stirring gently, a rotary pump was used. The cyclic silicone was volatilized and removed at 80 ° C. under reduced pressure to obtain an organic-inorganic composite pigment. The average particle diameter of the obtained organic-inorganic composite pigment was 0.8 μm.
[0029]
Comparative Example 3
To 95 parts by weight of ethanol, 2.5 parts by weight of N-methacryloylethyl N, N-dimethylammonium / α-N-methylcarboxybetaine / butyl methacrylate copolymer (Yukaformer AM-75, Mitsubishi Yuka) was added. It was completely dissolved. To the resulting solution, 2.5 parts by weight of Red No. 202 (Hatsukasei) was added and treated with a sand mill to disperse the fine particle organic colorant. The average particle size of Red No. 201 in the obtained dispersion was 0.9 μm. Next, 10 parts by weight of highly oil-absorbing silica (Sunsphere H122, average particle size 12 μm, Asahi Glass, oil absorption 205 mL / 100 g) was added to this dispersion, and the mixture was impregnated with sufficient stirring. Next, ethanol was volatilized and removed at 80 ° C. under reduced pressure using a rotary pump to obtain an organic-inorganic composite powder. The average particle size of the obtained organic-inorganic composite pigment was 12 μm.
[0030]
Test example 1
The surface of each organic-inorganic composite pigment obtained in each Example and Comparative Example was observed using a scanning electron microscope, and the adhesion state of the organic colorant to the inorganic pigment surface was evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
○: The organic colorant adheres almost uniformly to the surface of the inorganic pigment. Δ: The organic colorant slightly aggregates and adheres to the surface of the inorganic pigment. ×: The organic colorant hardly adheres to the surface of the inorganic pigment.
Test example 2
0.5 g of each organic-inorganic composite pigment obtained in each Example and Comparative Example was placed in 50 mL of water, and stirred vigorously with a stirrer for 3 hours and then dried. Subsequently, the surface was observed using a scanning electron microscope, and the remaining state of the organic pigment on the surface of the inorganic pigment was evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
○: Most of the organic colorant remains on the surface of the inorganic pigment. Δ: A part of the organic colorant remains on the surface of the inorganic pigment. ×: Almost no organic colorant remains on the surface of the inorganic pigment.
Test example 3
1 g of each organic-inorganic composite pigment obtained in each Example and Comparative Example and 5 ml of squalane were mixed using a paint knife, and saturation (C value) was measured with a colorimeter (Σ80, Nippon Denshoku Industries Co., Ltd.). Was measured. As a control, each organic colorant and inorganic pigment used in each example or comparative example were mixed at the same ratio, and the saturation was measured in the same manner as described above, and the saturation was improved according to the following evaluation criteria. The effect was evaluated. The results are shown in Table 1.
(Evaluation criteria)
○: C value increased by 5% or more compared to the control Δ: Difference in C value compared to the control was less than 5% ×: C value decreased by 5% or more compared to the control
Test example 4
0.5 g of each organic-inorganic composite pigment obtained in each Example and Comparative Example was added to 50 ml of a linear paraffin solvent, dispersed for 30 seconds using an ultrasonic disperser, allowed to stand for 5 minutes, and then dispersed. Was visually evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
○: Organic / inorganic composite pigment is almost uniformly dispersed Δ: Organic / inorganic composite pigment is partially dispersed ×: Organic / inorganic composite pigment is almost completely precipitated [0034]
[Table 1]

[0035]
From Table 1, it was confirmed that Examples 1 and 2 were superior to Comparative Examples 1 and 2, and in particular, Example 1 was superior in all items.
[0036]
Formulation Example 1
Eye shadows were prepared with the formulation shown in Table 2. That is, the powder components were mixed with a pulverizer and further mixed with oil until uniform. After passing this through a sieve, it was put into a mold and compressed, and then molded into a solid to form an eye shadow. The obtained eye shadow had high saturation, a clear color tone, and excellent durability.
[0037]
[Table 2]
(Ingredient) (wt%)
Talc 16.7
Mica 10.0
Zinc stearate 7.0
Organic-inorganic composite pigment (Example 1) 18.0
Titanium oxide 3.0
Ultramarine 0.3
Mica titanium 25.0
Liquid paraffin 10.0
Isopropyl myristate 10.0
[0038]
【The invention's effect】
The organic-inorganic composite pigment produced by the method of the present invention is a composite of an organic pigment and an inorganic pigment, and has high saturation, especially when blended in cosmetics, has a clear color tone, and is excellent in durability. It is a thing.

Claims (8)

The following components (a) to (c),
(A) a highly oil-absorbing inorganic pigment having an oil absorption (according to JIS K5101 measurement method) of 50 to 300 mL / 100 g;
(B) a fine particle organic colorant,
(C) an organopolysiloxane or a derivative thereof that dissolves in the cyclic silicone;
An organic-inorganic composite pigment containing The organic material according to claim 1, wherein the component (a) is one or more selected from the group consisting of mica, talc, bentonite, zeolite, titanium oxide, zinc oxide, zirconia oxide, boron nitride, silica and alumina. Inorganic composite pigment. The organic-inorganic composite pigment according to claim 1 or 2, wherein the component (a) has an average particle size of 1.0 to 50 µm. The organic-inorganic composite pigment according to any one of claims 1 to 3, wherein the component (b) has an average particle size of 0.001 to 1.0 µm. Component (c) is a N-acylalkylimine whose end is blocked, polyalkylene glycol, polyalkylene glycol monoalkyl ether, acrylic acid, methacrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternary dimethylamino Ethyl methacrylate, methacrylamide, Nt-butylacrylamide, maleic acid, maleic anhydride, half-ester of maleic anhydride, crotonic acid, itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, diallyldimethylammonium chloride, vinylpyrrolidone , Vinyl ethers, vinyl pyridine, vinyl imidazole, styrene sulfonate, allyl alcohol, vinyl alcohol, vinyl caprolactam, N-alkyl Emissions carbobetaines and one or organic and inorganic composite pigments according to any one of claims 1 to 4 is an organopolysiloxane derivative having a functional group derived from two or more selected from the group consisting of sugar residues. The organic-inorganic composite pigment according to any one of claims 1 to 5, having an average particle size of 1.0 to 50 µm. The organic-inorganic composite pigment according to any one of claims 1 to 6, which is used for cosmetics. Dissolve organopolysiloxane or its derivative in cyclic silicone, add organic pigment to the resulting solution and atomize it, impregnate with powder mainly composed of highly oil-absorbing inorganic pigment, then volatilize cyclic silicone It removes by making it remove, The manufacturing method of the organic inorganic composite pigment of any one of Claims 1-7 characterized by the above-mentioned.