JPH0672221B2 - Coloring composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color forming composition, and more particularly to a color forming composition comprising an aqueous solution containing a specific nonionic surfactant or an aqueous alcoholic solution.

In today's daily life, color has a great meaning, and especially for items that are deeply related to personal preference, such as clothes and accessories, cosmetics, and upholstery, one of the important factors of consumers' motivation to purchase. It is said.

Conventionally, it has been common to use dyes and pigments for coloring such products, but since compounds that emit these colors have many unsaturated bonds in their molecular structure, they are often chemically unstable, For example, there are many restrictions on its use because it is poorly stable to light and fades over time, or there is a problem with safety for living organisms, and it is often difficult to freely produce a desired color. It was

Coloring with a dye is a phenomenon based on the absorption of light by the dye compound itself, but some coloring phenomena based on other principles are also known. For example, it is a phenomenon that we experience daily that a thin oil film that spreads on the surface of the water has an iridescent color.This is because the thickness of the thin oil film that spreads is about the same as the wavelength of visible light. This is a phenomenon in which lights reflected at the upper and lower interfaces of the oil film interfere with each other to produce a color, and the difference in color is caused by the difference in the thickness of the oil film and the subtle difference in the observation direction.

The inventors of the present invention have conducted intensive research on a coloring means based on an interference phenomenon by a thin film, but nowadays, a dilute aqueous solution of a specific nonionic surfactant or an alcoholic aqueous solution in which a part of water is replaced with alcohol is appropriately used. The present invention has been completed by finding that it exhibits a color tone.

That is, the present invention has the general formula (I): (In the formula, R is a saturated or unsaturated straight-chain or branched-chain aliphatic hydrocarbon group having 12 to 18 carbon atoms, and R'is 1 to 2 carbon atoms.
Diglycerin dialkyl ether 0.8 to 3.5 represented by a saturated or unsaturated aliphatic hydrocarbon group of
It is intended to provide a color-forming composition comprising an aqueous solution containing a weight% (hereinafter simply referred to as "%") or an alcoholic aqueous solution (alcohol content in the total composition should not exceed 50%).

In the present invention, when diglycerin dialkyl ether (I) is mixed with an appropriate amount of water, a stable liquid crystal having a lamellar structure having a thickness of several thousand angstroms is formed, and a vivid color and sometimes a pearly luster are obtained. It is possible to obtain a color forming composition having Further, since the thickness of the lamella layer can be freely changed by changing the composition ratio of the above compound and water, the wavelength of the interfering light is changed accordingly, and various colors can be developed. is there.

Further, in the present invention, it is possible to partially replace the water out of the constituents of the color forming composition with alcohols,
As a result, the temperature resistance of color development of the color composition can be significantly improved.

In the diglycerin dialkyl ether (1,3-di-O-alkyl-2-O-2 ', 3'-cyhydroxypropylglycerin) represented by the general formula (I), R'is a methyl group and R is branched. A group having a chain, for example, the following formula (II) (Wherein m is an integer of 4 to 10, n is an integer of 5 to 11, m + n is 11 to 17 and has a distribution having m = 7 and n = 8 as vertices), Among them, a methyl-branched isostearyl group is preferable and the most vivid color is obtained. When the carbon number of R'is 3 or more or the carbon number of R exceeds 18, the lipophilicity of the compound becomes too strong and the solubility in water becomes small, which is not preferable. On the other hand, even if R ′ has 1 to 2 carbon atoms, but R has less than 12 carbon atoms, it is not preferable because the hydrophilicity is increased and the liquid crystal forming ability is weak.

The diglycerin dialkyl ether (I) according to the present invention is a novel compound, for example, the following reaction formula (Wherein R and R ′ are the same as those described above).

The properties of a representative compound of the diglycerin dialkyl ether (I) thus synthesized are shown in Table 1.

There is no particular limitation in preparing the color-forming composition of the present invention using these compounds, and diglycerin alkyl ether may be used as an aqueous solution or alcoholic aqueous solution having a predetermined concentration. For example, diglycerin dialkyl ether, water and alcohol may be sequentially mixed, diglycerin dialkyl ether may be dissolved in a mixture of water and alcohol, or water may be added to an alcohol solution of diglycerin dialkyl ether. May be. However, finally, it is necessary that these components are uniformly dispersed in a prescribed ratio.

The color-developing state of the color-developing composition will be described by taking R'as a methyl group and R as a methyl-branched isostearyl group as an example. When water is added to the diglycerin dialkyl ether, a liquid crystal is formed in a wide range of water of 10.0 to 99.2%, of which water is 96.5 to 99.2%, and particularly clear color development is observed in the range of 97.5 to 99.0%. Was given. The color of the color-forming composition is different when observed with transmitted light and reflected light, and the two are almost complementary colors, but when viewed with reflected light using natural light, water is 9
The 7.5% composition, which is blue, gradually becomes reddish as it is diluted with water, and when the water content is 99.2% or more, the transparency of the composition decreases and the color almost disappears. On the other hand, when the water content is 96.5% or less, it is a transparent liquid with high viscosity, but again a coloring composition cannot be obtained.

The color-forming composition of the product of the present invention is very stable at low temperatures and shows vivid color up to about 40 ° C. at high temperatures. When the temperature becomes higher than that, it becomes cloudy and the color disappears, but when cooled to 40 ° C or lower, the vivid coloring phenomenon starts to appear again.

Further, in this color-forming composition, part of water can be replaced with alcohols. The alcohols may be monohydric alcohols or polyhydric alcohols, particularly methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin and the like. Are preferred, and propylene glycol is particularly preferred. 5 of these alcohols
It is possible to add up to 0.0%. Although the color of the coloring composition hardly changes by the addition of alcohols,
In particular, the temperature stability on the high temperature side can be improved.
However, if alcohols are used together in an amount of more than 50.0%, the liquid crystal will start to collapse and the desired color tone cannot be obtained.

As described above, the color forming composition of the present invention can freely emit a wide range of colors. Further, the diglycerin dialkyl ether (I) according to the present invention is chemically stable because it does not have a bond such as an ester group that is easily decomposed, and it is assumed that no color change with time or brown occurs at all. Good. Rather, over time, the regularity of the alignment of the liquid crystal structure will be closer to completion, and will always have a vivid color and pearly luster.

If necessary, other components (for example, oil, moisturizer, thickener, preservative, fragrance, etc.) can be added to the color forming composition of the present invention, and cosmetics such as lotion, cleansing lotion and jelly-like pack can be added. First, it can be used for various products such as accessories such as brooches and pendants, and upholstery. In addition, since the color-forming composition of the present invention is an interference color, it has high color purity and can be applied as an interference filter for monochromatic light or a spectroscope.

Hereinafter, the present invention will be described in more detail with reference to Examples and Reference Examples, but the present invention is not limited thereto.

Reference Example 1 Synthesis of methyl-branched isostearyl glycidyl ether: In a round bottom flask equipped with a reflux condenser, a thermometer, a dropping funnel and a stirrer, 50% sodium hydroxide aqueous solution 12
0 g (60 g (1.5 mol) as pure sodium hydroxide), 68 g (0.25 mol) of monomethyl-branched isostearyl alcohol, 200 ml of n-hexane and 2.51 g (0.0075 mol) of stearyltrimethylammonium chloride were added in this order. The reaction mixture was kept at a reaction temperature of 25 ° C. in a water bath, and 93 g (1 mol) of epichlorohydrin was added dropwise from a dropping funnel with vigorous stirring at a stirring speed of 400 rpm. About 1.5
After adding epichlorohydrin dropwise over time, the temperature of the reaction mixture was raised to 50 ° C. and stirring was continued at this temperature for about 8 hours. After completion of the reaction, the product was treated by a conventional method to obtain 68 g (yield: 83%) of monomethyl branched isostearyl glycidyl ether represented by the following formula.

Boiling point: 142 ~ 175 ℃ (0.08mmHg) IR (liquid film cm ^-1 ): 3050, 3000, 1250, 1100, 920, 845 (In the formula, m is an integer of 4 to 10, n is an integer of 5 to 11, m + n is 11 to 17, and m = 7, n
= Has a distribution with 8 as the apex) Reference Example 2 Synthesis of 1-O-methyl branched isostearyl-3-O-methylglycerin: 3 equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer
1000g (31.3mol) of methanol, MeONa
Add 11 g (0.2 mol) and heat. The mixture was kept at 60 ° C., and 654 g (2.0 mol) of methyl-branched isostearyl glycidyl ether obtained in Reference Example 1 was added dropwise over about 3 hours by dropping. After the dropping is completed, the reaction mixture is heated to 60 ° C.
Stir for 8 hours. A gas chromatograph of the reaction mixture showed that the glycidyl ether had completely disappeared, so the reaction mixture was cooled, and then methanol was distilled off under reduced pressure.

After removing methanol, vacuum distillation yielded 650 g of a colorless transparent liquid 1-O-methyl branched isostearyl-3-O-methyl-glycerin. Yield 91%, Boiling point 180 ℃ -210 ℃
/0.7MmHg (calculated) as elemental analysis _{C 22 H 46 O 3 C:} 73.6% (73.69%); H: 12.7% (12.93%); O: 13.4%
(13.38%) Hydroxyl value 150 (157) Average molecular weight (VPO method / HCCl ₃ ) 350 (359) IR (cm ^-1 , liquid film) 3100-3600, 1190, 1000-1150 NMR (CDCl ₃ , δ, inside TMS) Standard) 2.80 (double line, 1H, J = 3.0Hz, 3.2 to 3.6 (multi-line, 7H, 3.33 (singlet, 3H, CH ₃ O-) Reference Example 3-7 by reacting accordance connexion various alkyl glycidyl ethers with various alcohols in Reference Example 1 to give the 1,3-di -O- alkyl glycerols. The boiling points and yields of these compounds are
Shown in the table.

Reference Example 8 1-O-methyl branched isostearyl-3-O-methyl-
Synthesis of 2-O-2 ', 3'-epoxypropylglycerin: (i) 50% aqueous sodium hydroxide solution was added to 3 reaction vessels equipped with reflux condenser, thermometer, dropping funnel and stirring device.
416 g (208 g [5.2 mol] as NaOH), hexane 1.5,
1-O-methyl-branched isostearyl-3-O-methylglycerin prepared in Example 1 (467 g, 1.3 mol) was charged, and further tetrabutylammonium hydrogensulfate 33.1 g was added.
Charge (0.097 mol) and stir vigorously at 25 ° C.
Next, let's drip, 301 g of epichlorohydrin (3.
25 mol) is added dropwise little by little. As the dropping of epichlorohydrin proceeds, heat is generated and the dropping is completed in about 1 hour. The reaction mixture is appropriately heated and cooled so that the temperature thereof becomes 50 to 60 ° C. The reaction is almost completed by stirring for about 3 hours.

The reaction product is allowed to stand and the hexane layer is collected. Hexane is distilled off under reduced pressure, and then distilled under reduced pressure.

Colorless transparent liquid 1-O-methyl branched isostearyl-3
430 g of -O-methyl-2-O-2 ', 3'-epoxypropylglycerin are obtained. Yield 80% Boiling point 195 ℃ ~ 211 ℃ /
0.5mmHg Elemental analysis As C ₂₅ H ₅₀ O ₄ (calculated value) C: 72.5% (72.41%); H: 12.1% (12.15%); O: 15.6% (15.43%) Average molecular weight (VPO method / HCCl ₃ ). 410 (415) Oxirane oxygen
3.70% (3.86%) IR (liquid film, cm ⁻¹ ) 1240, 1000 to 1150, 900, 835 NMR (δ, CCl ₄ , TMS internal standard) 2.33 to 3.90 (multiple lines, 12H, 3.28 _{(singlet, 3H, CH 3 O-) 1} -O- methyl-branched isostearyl -3-O-methyl -
Synthesis of 2-O-2 ', 3'-di-O-acetylpropyl glycerin: (ii) In a reaction vessel 2 equipped with a reflux condenser, a dropping funnel, a thermometer and a stirrer, 460 g of acetic anhydride (4.5 mol) ) And triethylamine 7.6g (0.075mol) are charged and heated to 100 ° C while stirring. Then, from the dropping funnel, 311 g (0.75 mol) of glycidyl ether obtained in (i) of Reference Example 8 was obtained.
Is dripped little by little. The addition of glycidyl ether is completed in about 1 hour. During this period, the reaction temperature is maintained at 100 to 120 ° C. by appropriately heating the reaction mixture. About 3 at this temperature
By continuing stirring for a while, the glycidyl ether disappears and the reaction is completed. The reaction product is cooled and then excess acetic anhydride is distilled off under reduced pressure.

The resulting residue is neutralized in a dilute aqueous acid solution and then extracted with ether to obtain a diester compound. A colorless and transparent liquid 1-O-methyl branched isostearyl-3-O-methyl-2-O-2 ', 3'-di-O was obtained by distillation under reduced pressure.
380 g of acetylpropylglycerin are obtained. Yield 98% Boiling point 213 ℃ -240 ℃ / 0.9mmHg Elemental analysis As C ₂₉ H ₅₆ O ₇ (calculated value) C: 68.1% (67.4%); H: 11.1% (10.92%); O: 20.6% (21.67 %) Saponification number 210 (217) Average molecular weight 517 (VPO / HCCl ₃ ) (517) IR (cm ^-1 , liquid film) 1730, 1210, 1000 to 1150 NMR (δ, CDCl ₃ , TMS internal standard) 2.0 ( singlet, 6H, 2 Quai acetyl groups) 3.33 _{(singlet, 3H, CH 3 O-) 3.3~3.6} ( multiplet, 7H, 3.70 (double line, 2H, J = 6.0Hz, 3.85 ~ 4.50 (multiple lines, 2H, 5.15 (multiple lines, 1H, 1-O-methyl branched isostearyl-3-O-methyl-
Synthesis of 2-O-2 ', 3'-dihydroxypropylglycerin: (iii) 30% sodium hydroxide aqueous solution 28 in a reaction vessel 3 equipped with a reflux condenser, a dropping funnel, a thermometer and a stirrer.
Add 0 g (84 g (2.1 mol) as NaOH) and 750 ml of ethanol and stir at room temperature. Then, from the dropping funnel, 359 g (0.70 mol) of the diester compound obtained in (ii) of Reference Example 8 was dropped little by little. The dropping is completed in about 1 hour. Then,
The reaction mixture is heated to reflux at 80 ° C for about 3 hours. After cooling the reaction product, water (1) and ether (500 ml) were added and the mixture was stirred and then separated. The ether layer is collected, and the ether is distilled off under reduced pressure, followed by heat drying at 100 ° C./0.5 mmHg for 3 hours. As a result, a colorless transparent liquid 1-O
-Methyl branched isostearyl-3-O-methyl-2-O
298 g of 2 ', 3'-dihydroxypropylglycerin are obtained.

Yield 99% Elemental analysis As C ₂₅ H ₅₂ O ₅ (calculated value) C: 70.0% (69.40%); H: 12.1% (12.11%) O: 18.2% (18.49%) Hydroxyl value 250 (259) Saponification Valence 0.3 (0.0) Average molecular weight (VPO / HCCl ₃ ): 430 (433) IR (cm ^-1 , liquid film) 3100-3550, 1190, 1000-1150 NMR (CDCl ₃ , δ, TMS internal standard) 3.33 (single) _{line, 3H, CH 3 O-) 3.30~4.0} ( multiplet, 14H, Reference Examples 9 to 14 (i) In accordance with (i) of Reference Example 8, various 1,3-di-O
-Alkyl-2-O-2 ', 3'-epoxypropylglycerin was synthesized. The boiling points and yields of these compounds are shown in Table 3.

(Ii) In accordance with (ii) of Reference Example 9, various 1,3-di-O
-Alkyl-2-O-2 ', 3'-di-O-acetylpropylglycerin was synthesized. The boiling points and yields of these compounds are shown in Table 4.

(Iii) In accordance with (iii) of Reference Example 9, various 1,3-di-
O-alkyl-2-O-2 ', 3'-dihydroxypropylglycerin was synthesized. The melting points and yields of these compounds are shown in Table 3.

Example 1 In order to prove the diversity of the color forming composition of the present invention, a composition with water using a diglycerin dialkyl ether in which R = methyl branched isostearyl group and R ′ = methyl group in the formula (I) is used. The color of various coloring compositions (diglycerin dialkyl ether 1.0 to 2.0% by weight) obtained by changing the ratio was measured by a spectrophotometer. The results are shown in Table 6. In the table, the wavelength of the maximum scattered light corresponds to the maximum absorption wavelength obtained by a spectrophotometer. In addition, the transparency of the coloring composition depends on the wavelength.
The comparison was made by the transmittance of 550 nm light and visual observation. The results are shown in Table 6.

Evaluation criteria Pearl luster: ○ Strong △ Weak × None Transparency: ○ High △ Medium × Low As shown in Table 6, for example, a coloring composition containing 2.0% by weight of diglycerin dialkyl ether mainly scatters light around 420 nm, and therefore, when viewed with reflected light, it appears blue-purple to blue. When this coloring composition was diluted with water, the wavelength of the scattered light continuously shifted to the long wavelength side, and accordingly, the color changed to blue, blue green, yellow green, yellow and red. Further, the transparency of the color forming composition increases as the amount of diglycerin dialkyl ether increases, but diglycerin dialkyl ether is 1.
Even a composition of 0% by weight has a transparency of about 70%, which is considered to be practically sufficient.

As described above, the color-forming composition of the present invention could freely produce a wide variety of colors by only slightly changing the composition ratio of diglycerin dialkyl ether and water.

Example 2 Next, the effect of adding alcohols to the color forming composition of the present invention was tested. In the formula (I), diglycerin dialkyl ether (1.7% by weight) in which R = methyl branched isostearyl group and R ′ = methyl group, and water (98.3
%), The temperature at which the color of the color-forming composition disappears was measured in order to examine the temperature stability of the color-forming composition in which a part of water was sequentially replaced with alcohols.
The results are shown in Table 7.

When propylene glycol was used as the alcohol, the temperature stability of the color forming composition was improved with the concentration of propylene glycol, and the color of the composition containing 40% by weight of propylene glycol was kept vivid up to about 70 ° C. On the other hand, the addition of propylene glycol did not change the color type of the color forming composition.

As described above, the coloring composition of the present invention was able to stably retain a bright color even at high temperature by adding alcohols.

Example 3 A lotion containing the following composition was prepared using the color forming composition of the present invention.

Composition Diglycerin dialkyl ether (R = methyl-branched isostearyl group, R '= methyl group) 1.7 (%) Propylene glycol 10.0 Ethanol 10.0 Polyoxyethylene cetyl ether 1.0 Fragrance 0.2 Purified water balance Remaining components other than the purified water After mixing at room temperature, slowly add a predetermined amount of purified water while stirring well,
A light green lotion having a translucent and pearly luster was obtained. This lotion looked yellow to green depending on the viewing direction, and when it was made to pass light, it turned red and had a very beautiful appearance. Also, this lotion fits well on the skin, and when applied to the skin, the color immediately disappeared.

Example 4 Using the color forming composition of the present invention, a mixed solution having the following composition was prepared.

Composition Diglycerin dialkyl ether (R = cetyl group, R ′
= Methyl group) 1.2-1.8 (%) Glycerin 30.0 Purified water Remaining amount Mix the above components at room temperature and disperse evenly, and then fill the glass containers of various shapes with air. . The color differs subtly depending on the content of diglycerin dialkyl ether, and it has an opal-like appearance, and since it exhibits various colors depending on the direction of the light and the direction of viewing,
It was suitable as an interior decoration.

Claims (1)

[Claims] 1. A general formula (I) (In the formula, R is a saturated or unsaturated straight-chain or branched-chain aliphatic hydrocarbon group having 12 to 18 carbon atoms, and R'is 1 to 2 carbon atoms.
Diglycerin dialkyl ether 0.8 to 3.5 represented by a saturated or unsaturated aliphatic hydrocarbon group of
A coloring composition comprising an aqueous solution containing 1% by weight or an alcoholic aqueous solution (alcohol content in the total composition should not exceed 50% by weight).