JPS6390573A - Lipophilic colored composite pigment composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition, by treating a water-swellable clay mineral with a quaternary ammonium salt type cationic surfactant and acid dye, capable of assuming a bright color tone and having improved light and water resistance as well as water repellency and good compatibility with oils without coloring property for the skin. CONSTITUTION:A pigment composition obtained by treating 100g water-swellable clay mineral, e.g. a kind of colloidal hydrous aluminum silicate having a three- layer structure such as montmorillonite, etc., with preferably 60-140 mequiv. quaternary ammonium salt type cationic surfactant, e.g. dodecyl trimethylammonium chloride, etc., and preferably 0.1-100 mequiv. acid dye, Orange II, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to improved lipophilic colored composite pigment compositions. More specifically, water-swellable clay minerals are used as quaternary ammonium salt type cationic surfactants (hereinafter referred to as cationic surfactants).
It exhibits a vivid color tone obtained by processing it with acid dye and
To provide a lipophilic colored composite pigment composition that has excellent light resistance and does not change color over time, has excellent water resistance and water repellency, does not stain the skin, and is compatible with oil.

[Conventional technology]

Conventionally known coloring pigments include inorganic pigments represented by metal oxides, and organic pigments such as toners and lakes obtained by the reaction of water-soluble dyes and several types of polyvalent metal ions.

[Problems to be solved by the invention] However, among the pigments obtained in this way, inorganic pigments exhibit a characteristic dull color tone, making it difficult to obtain a clear color tone (and organic pigments have a characteristic dull color tone). You can get the color tone, but
There are very few products that are harmless to the human body and have excellent light resistance, water resistance, and water repellency (there were also restrictions on the color options).

As a method to improve these drawbacks, montmorillonite and hectorite clay minerals and various salts (Ca++,
Invention relating to a method for producing a pigment composition obtained from a water-soluble dye (Ba'', AI+'', etc.) and a cosmetic (Japanese Patent Application Laid-Open No. 1986-13
5117, JP-A-50-126840, JP-A-50-4
No. 1444), however, the colored pigments obtained by these methods all have the drawbacks of poor water resistance and water reversion properties, as well as poor compatibility with oils and the tendency to bleed.

As a result of intensive research aimed at improving the shortcomings of the prior art, the present inventors have discovered that by treating water-swellable clay minerals with cationic activators and acidic dyes, they exhibit clear color tones and improve light resistance. We have discovered that it is possible to obtain a lipophilic colored composite pigment that has excellent water resistance and water reversion properties, does not stain the skin, and is compatible with oil, and based on this knowledge, we have completed the present invention.

[Means for solving problems]

That is, the present invention is a lipophilic colored composite pigment obtained by treating a water-swellable clay mineral with a cationic activator and an acidic dye.

The configuration of the present invention will be described below.

The water-swellable clay mineral used in the present invention is a type of colloidal hydrated silicate trialuminum having a three-layer structure, and is generally represented by the following general formula %, and specifically includes natural minerals such as montmorillonite, saponite, and hectorite. Or synthesized (in this case, the (OH) group in the formula is substituted with fluorine) montmorillonite group (commercially available products include Veegum; manufactured by Bang-Bilt; Kunipia; Kunimine Mineral; Laponite; manufactured by Lavorte; etc.); ) and synthetic mica known as sodium silicic mica or sodium or lithium taeniolite (commercially available products include daimonite; available from Tobie Industries, etc.).

The cationic activator used in the present invention has the following general formula (wherein R
1 is an alkyl group or benzyl group having 10 to 22 carbon atoms,
R2 is a methyl group or an alkyl group having 10 to 22 carbon atoms,
R3 and R4 represent an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X represents a halogen atom or a methyl sulfate residue. ).

For example, dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aracyltrimethylammonium chloride, behenyltrimethylammonium chloride,
Myristyldimethylethylammonium chloride, Cetyldimethylethylammonium chloride, Stearyldimethylethylammonium chloride, Arakyldimethylethylammonium chloride, Behenyldimethylethylammonium chloride, Myristyldiethylmethylammonium chloride, Cetyldiethylmethylammonium chloride, Stearyldiethylmethylammonium chloride, Araki diethylmethylammonium chloride,
Behenyldiethylmethylammonium chloride, benzyldimethylmyristylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethylbehenylammonium chloride, benzylmethylethylcetylammonium chloride, benzylmethylethylstearylammonium chloride, dibehenyldihydroxyethylammonium chloride , and corresponding bromides, as well as civalmitylpropylethylammonium methyl sulfate and the like. In implementing the present invention, one or more of these may be arbitrarily selected.

The acidic dyes used in the present invention are not particularly limited, and include, for example, yellow-orange dyes known as legal dyes such as orange ■, sunset yellow, and tartrazine, red dyes such as acid red, erythrosine, and feroxine B, and brilliant blue and aliphatic dyes. Examples include dyes such as Zonin Cyanine Green F, Arizurol Purple, and Nithole Blue Black, among which one or two or more of these may be arbitrarily selected when a mixed color is required.

The lipophilic colored composite pigment composition of the present invention can be prepared, for example, by dispersing and stirring a water-swellable clay mineral, a cationic activator, and an acidic dye in water, or by dispersing and stirring a water-swellable clay mineral, a cationic activator, and an acidic dye in water, or by dispersing and stirring a water-swellable clay mineral, a cationic activator, and an acidic dye in water. It can be obtained by a method such as processing to obtain a cation-modified clay mineral, then treating with an acid dye, and then removing water.

The content of the cationic activator in the lipophilic colored composite pigment composition of the present invention is 60 to 100 g per 100 g of water-swellable clay mineral.
It is preferably 140 meq (hereinafter abbreviated as meq). In addition, the content of acidic dye in the present lipophilic colored composite pigment composition is 0.1 per 100 g of water-swellable clay mineral.
~100 meq is preferable, more preferably 0.5
~60 meq.

The reason why the lipophilic colored composite pigment composition of the present invention exhibits vivid coloring is due to the adsorption of the hydrophobic colored complex formed by a part of the cationic activator and the acidic dye into the water-swellable clay mineral. it is conceivable that. The presence or absence of adsorption is determined by the fact that the composite pigment of the present invention does not decolorize even after sufficient washing with water.
Furthermore, this can be confirmed by the fact that the interlayer spacing of the water-swellable clay mineral becomes wider due to adsorption of the hydrophobic colored complex to the glabella (confirmed by measuring the long-plane spacing using X-ray diffraction).

Furthermore, if the lipophilic colored composite pigment composition obtained in the present invention is subjected to Soxhlet extraction using chloroform, ether, etc., the hydrophobic colored complexes adsorbed between the eyebrows will be washed away, and the extract will be subjected to gas chromatography. graphography, spectrophotometer, thermal decomposition temperature measurement or thermal decomposition measurement (DTA-TG
Its existence can be confirmed by measurements.

〔Effect of the invention〕

Since the lipophilic colored composite pigment composition of the present invention is composed of a water-soluble dye, it exhibits a vivid color tone unprecedented for lipophilic pigments, has excellent light fastness, water resistance, and water reversion properties, and has excellent coloring properties on the skin. It is a colored pigment composition that has the great advantage of being neutral and having good compatibility with various oils. The lipophilic colored composite pigment composition of the present invention, which has such great advantages, can be used in a wide range of fields such as cosmetics and paints by taking advantage of its characteristics.

[Example] Next, in order to further understand the present invention, the present invention will be described in more detail by giving examples. The present invention is not limited thereto. In the 6 examples, parts and % are all parts by weight and % by weight.
It is.

Example 1 Benzyldimethylstearylammonium chloride 45
g (equivalent to about 100 meq) and 10 g of acid red (
To 500 d of the aqueous solution (equivalent to about 1 meq) was added 100 g of Veegum (trade name of Bang-Bilt, USA), which is a water-swellable clay mineral, and thoroughly dispersed and mixed with a disper for about 30 minutes.

Next, after removing water using a filter, the mixture was dried for about 1 day and night to obtain the desired lipophilic colored composite pigment.

The adsorption of benzyldimethylammonium chloride (abbreviated as (A)) and the adsorption of a hydrophobic colored complex (abbreviated as (B)) produced from a part of benzyldimethylammonium chloride and acid red were determined by X-ray diffraction and , D.T.A.
- The amount of thermal decomposition of each component was measured by the TG method, and the determination was made by comparing it with a water-swellable clay mineral (veegum).

(The following is a blank space) As is clear from Table 1, the lipophilic colored composite pigment of Example 1 has a significantly wider layer spacing than the clay mineral before treatment. As is clear from the DTA-TG measurement results, this is caused by the adsorption of a hydrophobic colored complex produced by a part of benzyldimethylstearylammonium chloride and acid red, similar to benzyldimethylstearylammonium chloride. I understand.

Example 2 Bentone-38, an organically modified clay mineral, was dissolved in 500 meq of water in which 5 g (14 meq/100 g) of Orange II was dissolved.
distearyldimethylammonium chloride [hereinafter abbreviated as (C)]. 100g of organically modified clay mineral treated with (trade name manufactured by National Red Company, USA) was thoroughly dispersed and mixed using a lab homogenizer.

Next, water was removed using a filter, and the mixture was dried at 50° C. for about 24 hours to obtain the target lipophilic colored composite pigment.

In the same manner as in Example 1, the presence or absence of surface treatment was determined by X-ray diffraction and a hydrophobic colored complex (hereinafter referred to as (D) It was evaluated using a spectrophotometer based on the amount of

The results are shown in Table 2.

Displayed in the same manner as in Table 1 (hereinafter in the margin) As is clear from Table 2, the organically modified clay mineral (bentone-38
), it was found that by treatment with the acidic dye Orange (2), part of the cationic surfactant in Bentone 38 and Orange (2) bonded, and the interlayer spacing was further expanded. This is because, as in Example 1, the cationic activator IJ (12 meg) shown in (C) of Table 2 reacts with orange (1) in equimolar amounts to produce a hydrophobic colored complex.

The amount of cationic activator extracted by Soxhlet extraction (C) is the amount of cationic activator physically adsorbed in the organically modified clay mineral (Bentone-38) that has been organically modified by cation exchange reaction (C). Example 1 shows that chemically adsorbed substances are not extracted) and that the amount of all cationic activators can be quantified by the DTA-TG method.
As shown in

And this physically adsorbed cation activator ((C) = 1
2 meg) is reacted with an equimolar amount of acidic dye to form a hydrophobic colored complex ((D) = 12 meg). This reaction produces the lipophilic colored composite pigment of the present invention.

Example 3 and Comparative Example 1 Three parts of the colored composite pigment obtained in Example 1 were dispersed in 100 parts of the oil base shown in Table 3, and a normal coloring agent prepared by laked acid red with aluminum was dispersed. are referred to as Example 3 and Comparative Example 1.

Regarding the colored samples obtained in Example 3 and Comparative Example 1, (11
The color change when left at 95°C for 10 hours was measured using a color difference meter (color tone heating stability), and (2) the color change when left in a 2000 lux glass showcase for 100 hours was measured using a color difference meter. (color dimming stability).

(Left below) Table 3 Oil-based microcrystalline wax 15% Candelilla wax 5 Liquid paraffin 12 Squalane
45 Glycerol Isostearate The heat stability and light stability test results for 15 shades are shown in Table 4.

Pure dye placement heating showcase (ΔE) (ΔE) Example 3 10% 2.14.3 (Left below) It was found that both heat stability and light stability tended to be excellent.

Example 4 and Comparative Example 2 Lipstick Example 4 Comparative Example 2 Polyethylene wax 33 Ceresin wax 77 Carnauba wax 22 Candelilla wax 55 Liquid paraffin 1515 Castor oil
2525 Glycerin di-2-heptylundecate 101O Olive oil 2020 Pigment obtained in Example 1 2.0 = Acidoleft-^l lake
2.0 (Manufacturing method) Oil and wax are heated and melted at 85 to 95°C, and pigment is added and dispersed. The mixture was immediately degassed under reduced pressure, transferred to a designated container, and cooled and solidified to obtain a lipstick.

Example 4 and Comparative Example 2 were heated to a xenon lamp at 25°C for 30
When irradiated for a period of time, the color difference before and after irradiation was 0 in Example 4.
．． 6, whereas Comparative Example 2 had a large value of 4.3.

(Left below) Example 5 Lipstick carnauba wax 2 Candelilla wax 8 Microcrystalline wax 4 piece wax
4 Liquid paraffin
2 hexadecyl stearate
5 Castor oil 24.7
Lanolin 20 Oleyl alcohol 12 Composite pigment obtained in Example 2 3 Barium sulfate
15 (Production method) The Orange H composite pigment obtained in Example 2 and barium sulfate were ground together with castor oil using a roller, dispersed in the dissolved oil and wax, degassed, and added with fragrance. , and then poured into a molding machine to form a product.

Example 6 Blush Ceresin 2 Carnauba wax 1 Bieswa Nox
10 whale wax
5 Liquid paraffin
31.5 isopropyl myristate
10 Titanium dioxide 1 Composite pigment obtained in Example 1 5 Fragrance
0.3, Kaolin
24 (blank below) (Manufacturing method) The acid red composite pigment obtained in Example 1, kaolin, and titanium dioxide are treated with a roller together with a mixture of other components excluding fragrance, and then melted and degassed to produce fragrance. and an antioxidant are added, and the product is poured and filled at 60 to 70°C.

Claims (3)

[Claims] (1) A lipophilic colored composite pigment composition obtained by treating a water-swellable clay mineral with a quaternary ammonium salt type cationic surfactant and an acid dye. (2) The content of quaternary ammonium salt type cationic surfactant is 60 to 140 per 100 g of water-swellable clay mineral.
The lipophilic colored composite pigment composition according to claim 1, which is milliequivalent. (3) The lipophilic colored composite pigment composition according to claim 1, wherein the content of the acidic dye is 0.1 to 100 milliequivalents or less per 100 g of water-swellable clay mineral.