JPH0348884B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a cosmetic containing an orange pigment of excellent quality.

For more information: Krill (Euphusia Superba)
For the solvent extract, contaminating unsaturated lipids other than pigments are selectively hydrogenated with a catalyst, then enzymes are added to hydrolyze the lipids, and free fatty acids are removed by urea addition and/or molecular distillation. The resulting product is odorless, does not produce any back-odor, and has excellent color stability.
A cosmetic containing a bright orange pigment, and a cosmetic product obtained by concentrating and purifying the orange pigment thus obtained by column chromatography.
The present invention relates to a cosmetic containing an orange pigment having high coloring power in addition to the above properties.

[Prior Art] Krill contains the orange pigment astaxanthin and can be caught in large quantities, so it is used as a raw material for pigments, but the commercially available pigments have a unique odor and
There were drawbacks such as poor coloring power.

As a method to improve this point, in JP-A-60-4558, after making the pH of the solvent extract of krill neutral, lipase or alkali is added to decompose fatty acids and other impurities to form a liquid system. proposed a method of molecular distillation or washing using dilute alkali.

[Problems to be Solved by the Invention] However, even with this purification method, unsaturated fatty acids cannot be efficiently removed, so a peculiar odor remains, and furthermore, it oxidizes over time, producing a return odor. Therefore, krill pigments have the disadvantage that their use is limited to foods that are consumed in a relatively short period of time and in which specific odor is not a problem, such as kamaboko and fish roe, and cannot be applied to cosmetics. .

[Means for Solving the Problems] In view of the above circumstances, the present inventors have conducted intensive research to solve the above drawbacks, and as a result, the unsaturated lipids contained in krill pigments and the unsaturated lipids that are hydrolyzed to liberate them. unsaturated fatty acids oxidize over time, producing a return odor; unsaturated fatty acids cannot be sufficiently removed by molecular distillation; and in order to sufficiently remove unsaturated fatty acids, It is necessary to selectively hydrogenate only unsaturated lipids in the step, and because lipids cannot be removed sufficiently, only a low concentration of pigment can be obtained, which causes a lack of coloring power. I found out. Based on these findings, they discovered that cosmetics containing purified orange pigments, especially makeup cosmetics, are colored a very vivid orange color and do not change odor or fade over time, and have developed the present invention. It was completed.

In other words, the present invention relates to a solvent extract of krill,
An odorless product obtained by selectively hydrogenating contaminating unsaturated lipids other than pigments with a catalyst, then adding enzymes to hydrolyze the lipids, and removing free fatty acids by urea addition and/or molecular distillation. A cosmetic product characterized by containing a bright orange pigment that does not produce a back-odor and has excellent color stability, and furthermore, the orange pigment thus obtained is concentrated and purified by column chromatography. The present invention relates to a cosmetic product which is characterized by containing an orange pigment having the above-mentioned properties and high tinting power.

Hereinafter, the configuration of the present invention will be explained in detail.

The raw material used is a crude pigment liquid extracted from dried krill with an organic solvent such as n-hexane or acetone.

Purification of the crude pigment solution involves hydrogenation of lipids, their decomposition,
This is accomplished in 4 steps: 3 steps of fatty acid removal and further removal of residual lipids by column chromatography.

Fatty acids can be removed using a distillation method using molecular distillation or a chemical method using urea addition.

First, for the hydrogenation of lipids, add about 0.001 part of catalyst (weight, the same below) or 2 to 10 parts of ethanol to 1 part of the crude dye solution, and at 30 to 70°C the amount of hydrogen absorbed is 10% per 1 kg of the total dye solution. ~40, preferably 20-30
The reaction is carried out under the following conditions. Note that when ethanol is added, the ethanol is distilled off under reduced pressure to recover the dye liquid. Examples of the catalyst used in the present invention include palladium oxide, stabilized nickel, and platinum oxide. Among these, palladium oxide is the most preferred because it causes less decomposition of dyes and can selectively hydrogenate unsaturated lipids. As shown in Figure-1,
If hydrogen absorption is carried out under the above conditions, hydrogenation can be carried out efficiently, but if the hydrogen absorption is less than this, a large amount of unsaturated lipids will remain, resulting in return odor even if further purification is carried out, and If this is the case, the decomposition of the dye will become significant, which is not preferable.

Decomposition of lipids by enzymes is approximately 0.1% per part of dye solution.
After adjusting the pH to 7.0 by adding ~5 parts of water, add lipase dissolved in a small amount of water per 1 kg of pigment solution.
In addition to 50,000 to 200,000 units (international units, the same applies hereinafter),
Stir at about 35-40°C for 10-40 hours. Next about 80~
Heat to 100°C to inactivate the enzyme and leave to stand to separate the upper dye liquid layer. Another method for decomposing lipids is to use an alkali, but this is not preferred because the odor stability of the final dye is poor.

Removal of separated fatty acids, glycerin and other lipids, molecular distillation is about 0.01-0.001Torr
If it is carried out at around 140 to 190 degrees Celsius, there will be less decomposition of the dye and lipids can be removed efficiently. Urea addition is carried out by adding about 1 to 5 parts of a saturated urea ethanol solution to 1 part of the dye solution, stirring at 30 to 75°C for about 10 to 40 hours, cooling, filtering the crystals, distilling off the ethanol under reduced pressure, and adding n.
-Hexane is added and washed with water to remove remaining urea, and n-hexane is distilled off under reduced pressure.

The dye obtained in this way was
Unlike the product obtained by No. 4558, there was no peculiar odor or return odor, and it was a bright orange pigment. In addition, the cosmetic containing the orange pigment of the present invention had a desired clear color tone and was excellent in odor stability and color tone stability.

Furthermore, when a dye with excellent coloring power is desired, residual lipids are removed by column chromatography. In other words, 1 part of the dye solution is adsorbed on a column packed with 0.5 to 2 parts of carrier and 0.5 to 2 parts of Celite, and only the lipids are eluted with a low polar solvent, and then with a mixed solvent of a low polar solvent and a high polar solvent. Elute the dye. The column is regenerated by passing through a highly polar solvent. Examples of carriers used in the present invention include silicic acid, activated clay,
Examples include magnesium silicate, activated alumina, activated carbon, and silica gel. Among these, silicic acid is the most preferred because it can retain and elute dyes well and has a high dye recovery rate. Examples of the low polar solvent used in the present invention include n-hexane,
Examples include petroleum ether, toluene, and benzene. Among these, n-hexane is highly safe;
Most preferred because of low cost. Examples of the highly polar solvent used in the present invention include methanol, ethanol, acetone, and ethyl acetate. Among these, acetone is the most preferred because it can effectively elute highly polar lipids remaining on the column and is inexpensive. Examples of the mixed solvent of a low polarity solvent and a high polarity solvent used in the present invention include combinations of the various solvents listed above. Among these, a mixed solvent of about 1 to 10% acetone-n-hexane is most preferred since it can selectively and efficiently elute the dye.

In addition to the above-mentioned properties aimed at by the present invention, the dye obtained as described above was an orange dye of excellent quality and had extremely high tinting power.

By blending this pigment into cosmetics, the cosmetics can be colored bright orange. Furthermore, according to sensory tests, it had no effect on the odor of cosmetics, and no odor was observed to return over time.

[Example] Next, reference examples, examples, and comparative examples are given to specifically clarify the present invention. The present invention is not limited thereby.

Reference example 1 Krill pigment liquid (pigment content 219mg%) 95 to 100Kg
% ethanol and 0.1 kg of palladium oxide were added, and hydrogenation was carried out at 45° C. and a hydrogen pressure of 4 kg/cm ² for 120 minutes. The amount of hydrogen absorbed during that time is 1kg of pigment liquid.
It was a hit of 30. After the reaction was completed, palladium oxide was collected by filtration, and ethanol was distilled off. The reduced dye solution had an iodine value of 78 and a dye content of 208 mg%.
100% water was added to the reduced dye solution, the pH was adjusted to 7.0 with dilute sulfuric acid, an enzyme solution prepared by dissolving 0.5 kg of lipase (30000 units/g) in 50% water was added, and the mixture was stirred at 38°C for 25 hours. Next, after heating at 90°C for 30 minutes, the mixture was allowed to stand to separate the upper dye liquid layer. This dye solution was heated at 160℃.
By performing molecular distillation at 0.005 Torr to remove low-boiling fatty acids, odor components, etc., 20.2 kg of purified pigment liquid (pigment content 980 mg%) was obtained.

Reference example 2 Krill pigment liquid (pigment content 219mg%) 100Kg and water
The pH of the solution was adjusted to 7.0 using dilute sulfuric acid, and an enzyme solution prepared by dissolving 0.5 kg of lipase (30000 units/g) in 50% water was added, followed by stirring at 38°C for 25 hours. Next, after heating at 90°C for 30 minutes, the upper dye liquid layer was separated. This dye liquid was subjected to molecular distillation at 160°C and 0.005 Torr to obtain 21.7 kg of purified dye liquid (dye content: 885 mg%).

Reference Example 3 A 200% saturated urea ethanol solution was added to the enzyme-treated dye solution of Reference Example 1, mixed and stirred at 75°C for 20 hours, and then cooled. The generated crystals were filtered, ethanol was distilled off under reduced pressure, n-hexane was added and washed with water to remove remaining urea, and n-hexane was distilled off to obtain 20.8 kg of purified pigment liquid (dye content 911 mg%).
I got it.

Reference Example 4 The purified dye solution of Reference Example 3 was further heated at 160℃.
Purify dye solution by molecular distillation at 0.005Torr
17.9Kg (dye content 1020mg%) was obtained.

Reference example 5 Inner diameter 21 filled with 3.0 kg of silicic acid and 3.0 kg of celite
4.0 kg of the purified dye solution of Reference Example 4 was adsorbed onto a stainless steel column with a height of 60 cm and n-hexane 25 kg.
Low polar lipids were eluted through. Next, the dye was eluted and recovered through 3% acetone-n-hexane mixed solvent 10, and 0.72 kg of purified dye liquid (dye content 4873 mg%) was obtained.

Reference example 6 Krill pigment liquid (pigment content 219mg%) 100Kg at 95%
Add to a solution of 30 kg of caustic potassium dissolved in 600% ethanol, and stir for about 2 hours while blowing nitrogen gas.
The mixture was refluxed for an hour to decompose neutral lipids. Thereafter, the pH was adjusted to 2.5 with dilute sulfuric acid, a large amount of salt water was added, and the pigment oil was extracted using diethyl ether in a conventional manner. The dye solution from which the ether has been distilled off is heated to 160°C.
Concentrate dye solution by molecular distillation at 0.005Torr
19.1Kg (dye content 873mg%) was obtained.

Example 1 Blush (1) Talc 12.5% by weight (2) Mica 66.6 (3) Kaolin 8.6 (4) Red iron oxide 0.4 (5) Ultramarine 0.1 (6) Mica titanium pearl agent 3.0 (7) Krill pigment of Reference Example 1 0.5 (8) Squalane 3.0 (9) Isopropyl myristate 5.0 (10) Preservative 0.3 (11) Fragrance Appropriate amount Manufacturing method Mix (1)(2)(3)(4)(5) with a Henschel mixer, (7), (8), (9), and (10) were heated and mixed, and then (11) was mixed while being gently sprayed onto the mixture. This was pulverized using a pulperizer, and after adding (6) and gently mixing, it was press-molded into a medium plate to obtain a blush.

The resulting blush has the desired tone and is 50
No change in odor or fading of color was observed even after being left at ℃ for one month.

Comparative Example 1 Blusher A blush obtained in the same manner as in Example 1 using the krill pigment of Reference Example 2 instead of Reference Example 1 was 50%
When left at ℃, a significant return odor was observed after one week.

Example 2 Eyeshadow (1) Talc 9.5% by weight (2) Mica 62.0 (3) Kaolin 11.0 (4) Red iron oxide 1.3 (5) Mica titanium pearl agent 7.0 (6) Krill pigment of Reference Example 3 1.0 (7) Scrawane 5.0 (8) Isopropyl myristate 2.0 (9) Sorbitan sesquiolate 1.0 (10) Preservative 0.2 (11) Flavor Appropriate amount Manufacturing method Mix (1)(2)(3)(4) in a Henschel mixer, and add to this (6)(7)(8)(9)(10) were heated and melted and mixed, and further mixed while gently spraying (11). This was pulverized using a pulperizer, and after adding (5) and gently mixing, it was press-molded into a medium tray to obtain eyeshadow.

The obtained eyeshadow had the desired color tone, and no odor or fading was observed even after it was left at 50° C. for one month.

Example 3 Nail enamel (1) Nitrocellulose 13.0% by weight (2) Modified alkyd resin 13.0 (3) Acetyl tributyl citrate 4.0 (4) n-butyl acetate 33.0 (5) Ethyl acetate 5.0 (6) n-butyl alcohol 2.0 (7) Toluene 22.0 (8) Krill pigment of Reference Example 4 4.0 (9) Organically modified montmorillonite 1.0 (10) Mica titanium pearl agent 3.0 Manufacturing method (1)(2)(3)(5)(6)(7 )(8) and part of (4) are dissolved and added to this.
(9)
and the remainder of (4) were mixed to form a gel, which was then added and mixed. Furthermore, (10) was gradually added and dispersed while stirring, and the mixture was filled into a container to obtain nail enamel.

The obtained nail enamel has a clear orange color and does not change odor even if left at 50℃ for one month.
No fading was observed.

Example 4 Lipstick (1) Guyanderilla wax 9.0% by weight (2) Solid paraffin 8.0 (3) Beeswax 5.0 (4) Carnauba wax 5.0 (5) Lanolin 11.0 (6) Refined castor oil 51.0 (7) Isopropyl myristate ester
10.0 (8) Krill pigment of Reference Example 5 1.0 (9) Flavor Appropriate amount Manufacturing method (1)(2)(3)(4)(5)(6)(7)(8) was heated and melted at 80℃, After dispersing with a disperser, remelt at 80℃ and add (9).
After defoaming, it was poured into a mold and rapidly cooled to room temperature to solidify. This was loaded into a container and passed through a flame to make the surface uniform.

The resulting lipstick had a very clear orange tone, and no odor or fading was observed even after it was left at 45°C for one month.

Comparative Example 2 Lipstick A lipstick obtained in the same manner as in Example 4 using the krill pigment of Reference Example 6 instead of Reference Example 5 had less peculiar odor immediately afterward, but the color density was weak, and it was heated at 45°C.
If left for a week, a strong odor developed, making it unusable.

Example 5 Emollient lotion (1) Stearic acid 2.0% by weight (2) Setanol 1.4 (3) Vaseline 3.0 (4) Lanolin alcohol 2.0 (5) Liquid paraffin 10.0 (6) Krill pigment of Reference Example 5 0.1 (7) Poly Oxyethylene monooleate (10E.O.) 2.0 (8) Fragrance 0.5 (9) Preservative, antioxidant appropriate amount (10) Glycerin 3.0 (11) Propylene glycol 5.0 (12) Triethanolamine 1.0 (13) Purification Water 70.0 Manufacturing method Add (10), (11), and (12) to (13) and heat mix at 70°C. (1
)
(2)(3)(4)(5)(6)(7)(8)(9) were melted by heating to 70°C.
The aqueous phase component described above was gradually added to this oil phase component with stirring, and then uniformly emulsified using a homomixer. After emulsification, an emollient lotion was obtained by cooling to 30°C using a heat exchanger.

The obtained emollient lotion had a clear orange color tone, and no odor or fading was observed even after it was left at 50° C. for one month.

[Effects of the Invention] The cosmetic containing the orange pigment according to the present invention has a desired clear color tone and is excellent in odor stability and color tone stability.

[Brief explanation of drawings]

Figure 1 is krill pigment liquid (pigment content 219mg%)
This shows the iodine value and pigment content relative to the amount of hydrogen absorbed when 100 kg was hydrogenated using 0.1 kg of palladium oxide at 45°C.

Claims (1)

[Claims] 1. Regarding the solvent extract of krill, unsaturated lipids other than pigments are selectively hydrogenated with a catalyst, lipase is added to hydrolyze the lipids, and the released fatty acids are subjected to urea addition and/or A cosmetic characterized by containing an orange pigment obtained by removal by molecular distillation. 2 For the solvent extract of krill, unsaturated lipids other than pigments are selectively hydrogenated with a catalyst, then lipase is added to hydrolyze the lipids, and free fatty acids are removed by urea addition and/or molecular distillation,
A cosmetic characterized by containing an orange pigment obtained by further concentrating and purifying by column chromatography.