JPS60120806A - Pigment stabilizer - Google Patents

Abstract

PURPOSE:A novel pigment stabilizer that is obtained by esterification of acid mixture consisting of 12-hydroxystearic acid, stearic acid and rosic acid with dipentaerythrit, thus showing high stability to pigments used in various fields. CONSTITUTION:Dipentaerythrit of the formula and an acid mixture consisting of 12-hydroxystearic acid, stearic acid and rosic acid (at 1:4:1.5:0.5 molar ratio) are used to effect esterification to give the objective novel pigment stabilizer. The resultant stabilizer can be used in the fields of medicines for external use, non- medicines for external use and cosmetics and develop faithfully the colors after blending a variety of pigments with high stability, water-holding, emulsifiability and dispersibility and high miscibility with any base materials and highly safe for human bodies.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel substance of a pigment stabilizer that stabilizes pigments used in external medicines, quasi-drugs, cosmetics, and other fields.

Conventionally, external medicines, quasi-drugs 11. Pigments are used in a variety of ways in cosmetics and other fields, but the pigments themselves tend to discolor, and there are many restrictions on the selection of blended pigments. It is difficult to express the dye, and in order to stabilize such a dye, 6.
Conventionally, lanolin and the like have been used as dye stabilizing aids, but they do not have sufficient stability and leave oily substances after use, and furthermore, the effects on the human body have not been safely eliminated. , had various difficulties. This invention relates to a new dye stabilizing substance that has not been used as a dye stabilizer at all in the past, and is much safer for the human body than conventional dye stabilizers, and is suitable for compounded dyes. It is an object of the present invention to provide a dye stabilizer that can improve the stabilizing function of the dye, perform excellent dye stabilization, and exhibit a stabilizing function for dyes used in various fields.

- Examples of this invention will be explained in detail below.

First, the materials are dipentaerythritol and 12-
A mixed acid consisting of human O-oxystearic acid, stearic acid, and rosin acid is used, and these are esterified by dehydration from an alcohol or phenol and an acid.

The main components of this dye stabilizer are dipentaerythritoltetra-12-hydroxystearic acid, sesquistearic acid, and hemirodic acid ester.

Here, dipentaerythritol is a polyol produced from a double product obtained by dehydration condensation of pentaerythritol and having six hydroxyl groups represented by the following general formula.

The specific ingredients of the dye stabilizer of the present invention described above include 1 mol of dipentaerythritol, 4 mol of 2-hydroxystearic acid, 1.5 mol of stearic acid,
It is an esterified product using 0.5 mole of rosin acid, and the specific manufacturing method is to use a mixed acid consisting of dipentaerythritol, 12-hydroxystearic acid, stearic acid and rosin acid at a ratio of 1: 4: 1.5
: Mix at o, s (molar ratio), reduce the pressure to about 20111HQ, prevent oxidation and make it easier to remove water, initially react at around 200 ° C for 2 to 4 hours, further heat to 250 ° C, and react for 8 to 12 hours. The reaction is completed over time.

In addition, in cases where the reaction product has a low acid value with little color and odor, and the completion temperature of the reaction is low, 5nCIa is used as a catalyst.
・5H,O,zn CI4” 5)-1!O,zn
It is made into an ester using c12 and Zn F, etc.

Further, such dye stabilizers were produced according to the standard values shown in Table 1.

Regarding other physical properties of the dye stabilizer of the present invention, the solubility in various oil bases and solvents is shown in Table 2, the hydrophobicity is shown in Table 3, the oxidative stability is shown in Graph 1, and the hydrophobic ability is shown in Table 4.
The moisture permeability is shown in Table 5, the consistency is shown in Graph 2, and the measurement methods are shown below each table or graph.

In addition, the miscibility was 3.0 (g/19°C).

The measurement method is as follows: liquid paraffin 10a and castor oil 10a
The amount of ester added (a) required to make the mixture with o and a homogeneous transparent state was measured, and that value was taken as the miscibility.

Furthermore, the dye stabilizing function of the dye stabilizer was as follows.

■) Pigment stabilization function This dye stabilization function is a specific example of cosmetics.
Various pigments and the pigment stabilizer of the present invention were blended into rouge sticks, stick-type lipsticks, bath additives as specific examples of quasi-drugs, and thermal stimulation patches as specific examples of external medical products. A test was conducted on the case.

All of the measurement methods used in these tests require storage conditions at a temperature of 40°C.
, humidity is set at 1175%, and the absorbance of each dye at its maximum absorption wavelength is measured to determine the dye residual rate.

The maximum absorption wavelength of each dye is as follows.

Blue No. 1 630 mμ Yellow No. 4 408 mμ Red No. 202 5201 μ Orange 2018 504-μ Red No. 204 488 + 11/l A) Red No. 202, Tairo No. 201, and Furoshiki No. 1 are blended as pink pigments to produce the pigment of the present invention. Three types of examples were set: control a, in which the stabilizer was blended, and Example 1, Example 2, and Example 3, in which the blended amount of the dye stabilizer of the present invention was sequentially increased, and the dye residual rate was determined. It was measured.

The formulations of control a and each example are shown in Table A. Red 2
The dye residual rate of No. 02 is shown in Table A-1, Graph 8-1, the dye residual rate of Orange No. 201 is shown in Table A-2, graph A-2, and the dye residual rate of Blue No. 1 is shown in Tables A-3, graph Not shown in A and 3, respectively.

From this data, it can be seen that for any dye, Example 3
, Example 2, Example 1, and Control a have the highest dye residual rates.

In particular, in the comparison between Control a and Example 3, the dye residual rates of Red No. 202, Orange No. 201, and Blue No. 1 after 100 days were tt62.1% and 46% for control a, respectively.
2%, 17.8%, which are extremely low, whereas those in Example 3 are very high, 96.8%, 96.4%, 89.8%, indicating that the dye stabilizer of the present invention is almost red. It has been proven that it has excellent stabilization of the pigment inside.

B) Stick type lipstick pigments Red No. 202, Red No. 204, Orange 201
Example 4, Example 5, and Example 6 in which the colored yarn stabilizer of the present invention was used instead of lanolin and the amount was increased sequentially. Three types of Examples were set up and the dye residual rate was measured.

The formulations of control b and each example are shown in Table 8. Red 2
The dye residual rate of No. 02 is shown in Table B-1 and Graph B-1, the dye residual rate of Red No. 204 is shown in Table B-2 and Graph B-2, and the dye residual rate of Orange No. 201 is shown in Table B- 3. Graph B
-3.

From this data, the dye residual rate is highest in all dyes in the order of Example 6, Example 5, Example 4, and Control b.

In particular, in a comparison between Control b and Example 6, the dye residual rates of Red No. 202, Red No. 204, and Orange No. 20'1 after 100 days were 80.7% for 2L Control b, respectively.
, 70.2% and 54.7%, whereas in Example 6
The results are extremely high at 96.6%, 96.1%, and 96.4%.1 It has been proven that the pigment stabilizer of the present invention is superior to lanolin in stabilizing pigments in stick-type lipsticks. Ta.

C) Bath agent An experiment was conducted on a bath agent containing enzymes and crude drug ingredients.

First, this bath additive will be explained. This bath preparation uses two types of enzymes: a proteolytic enzyme derived from microorganisms and an enzyme obtained from animal organs that has proteolytic, lipolytic, and starch-degrading effects.
An example is ASP protease, and one example of the latter is vancreatin. As the protease derived from microorganisms, actinomycete protease, Aspergillus aspergillus protease, etc. may be used.

The reason for using these two types of enzymes is that the bath additive has the ability to decompose proteins, fats, and other substances.
This is to maintain the above-mentioned decomposition effects at a constant high relative activity over a wide DI-1 range and temperature range, and to maintain a high residual activity rate of each enzyme over elapsed time.

In addition, the crude drug ingredients used include ginseng powder, peony powder, cabbage powder, chives powder, bittersweet extract, and chimpi powder. This is for the purpose of stabilizing the enzyme and stabilizing the enzyme.

Hereinafter, the dye stability achieved by the dye stabilizer of the present invention in a bath additive using ASP protease and pancreatin as enzymes and carrot powder, peony powder, chili powder, and Arunca extract as herbal ingredients will be explained below.

As pigments, Blue No. 1 and Yellow No. 4 are used.

As a basic formulation, the dye stabilizer of the present invention is added to 05.1,
Examples 8, 9, and 10 were set in which the proportions were increased sequentially by 0.1.5% by weight. Also, separately
Example 7 was set in which the crude drug ingredients were removed from the basic formulation and the dye stabilizer of the present invention was blended at 1.0% by weight. In addition, for comparison of each example, control CL in which only the dye stabilizer of the present invention was removed from the basic formulation, and control C in which crude drug ingredients and the dye stabilizer of the present invention were excluded from the basic formulation.
2. Control 03 was set, in which the crude drug ingredients were removed from the basic formulation and 1.0% by weight of lanolin was added instead of the pigment stabilizer of the present invention.

Control C11 Control C〉, Control C
3. The formulation of each example is shown in Table C, the dye residual rate of Blue No. 1 is shown in Table C-1, graph C-1, and the dye residual rate of Yellow No. 4 is shown in Table C-2, graph C-2. Each is shown below.

From this data, the dye residual rate is highest for all dyes in the order of Example 10, Example 9, Example 8, Example 7, Control c1, Control C11, and Control c1.

In particular, in comparison with Control C and Control C1, the dye residual rates of Blue No. 1 and Yellow No. 4 after 100 days were extremely poor at 0% and 42.0%, respectively, for Control O≧. ]] Control C significantly improved by 55.9% and 64.1%, respectively, indicating that the herbal drug components stabilized the pigment.

In addition, in comparison with Control C and Control 0), the dye residual rates of Blue No. 1 and Yellow No. 4 after 100 days were as described above for Control C2, while for Control C2 they were 38.0% and 38.0%, respectively. This was a considerable improvement of 60.0%, indicating that the dye was stabilized by lanolin.

In addition, in comparison with Con 1 to Roll C Yu and Example 7, 10
After 0 days, the dye residual rate of Blue No. 1 and Yellow No. 4 was determined by Conte [
In contrast to J-LeC as described above, in Example 7 there was a considerable improvement of 62.0% and 71.0%, respectively.
It can be seen that the dye was stabilized by the dye stabilizer of the present invention.

Furthermore,] Control C3, Control OLs Example 7
The comparison shows that the dye stabilizer of the present invention contributes to dye stabilization most effectively compared to crude drug powder, crude drug extract, and lanolin.

Furthermore, in a comparison of Examples 7 to 10, the dye residual rates of Blue No. 1 and Yellow No. 4 after 100 days were 62.0% and 71.0%, respectively, in Example 7, whereas In Example 8, they were 85.1% and 853%, respectively, and in Example 9
In Example 1, they are 91.9% and 93.8%, respectively.
0 is 95.8% and 97.7%, indicating that the combination of the dye stabilizing agent of the present invention and the crude drug component achieves even better dye stabilization than the dye stabilizing side of the present invention alone. I know that there is.

Therefore, the dye stabilizer of the present invention has an excellent dye stabilizing function in China and Germany, and in combination with crude drug ingredients,
It was also proven that it has an excellent dye stabilizing function.

D) Control d in which Blue No. 1 was blended as the thermal stimulus patch pigment and no dye stabilizer of the present invention was blended, and Example 11 and Examples in which the blending amount of the dye stabilizer of the present invention was sequentially increased. 12. Three types of Examples such as Example 13 were set up and the dye residual rate was measured.

The formulations of control d and each example are shown in the table, blue 1
Table D-1 and graph D-1 show the dye residual rates of the No.

From this data, Example 13. Example 12゜Example 1
1. The dye residual rate of Blue No. 1 is highest in order of control d.

In particular, in the comparison between Control d and Example 13, 100
After a few days, the dye residual rate of Blue No. 1 was 13 in control d.
．． 7%, whereas that of Example 13 was 95.
It was very high at 8%, proving that the dye stabilizer of the present invention is excellent in stabilizing dyes in heat-stimulating patches.

As described above, it has been proven that the pigment stabilizer of the present invention stabilizes various pigments in the formulation of pink lipsticks, stick-type lipsticks, bath additives, and thermal stimulation patches. Next, a test was conducted on the safety of the dye stabilizer of the present invention.

■) Safety Safety test of the dye stabilizer of the present invention.

i) Skin irritation test The backs of three rabbits weighing 2.70 to 3.09 kg were removed with Balino J, and the pigment stabilizer of the present invention was applied to the intact skin (Patch) using a scalpel. Apply to skin injured with (
Patch) and intradermal injections (i, c) were performed.

Administration is 0.05 ml each, 24 and 48 days after administration.
□rat the skin irritation effect of the pigment stabilizer of the present invention
The degree of erythema and floating scale was determined according to the Ze method. In addition, in the case of intradermal administration, the length of the major axis and minor axis of the erythema and the area index, which is the product thereof, were also measured 48 hours later.

Test Results No abnormalities were observed for up to 3 hours when the pigment stabilizer of the present invention was applied to the skin or injured skin.

24 hours later, 1 out of 3 cases had a wound on the patch.
Mild redness was observed in 2 cases, but all of these symptoms recovered within 48 hours.

When administered intradermally under severe test conditions, no abnormalities were induced until 3 hours later, but after 24 hours, mild redness was observed, and the same condition remained even after 48 hours. Met.

Test results J: The skin irritation effect of the pigment stabilizer of the present invention is considered to be extremely weak on intact skin, and even when there is a wound, it is slightly irritating.
As shown in Table 6, it is considered to be weak.

Therefore, it can be seen that there is no problem at all when the pigment stabilizer of the present invention is used in cosmetics and the like that are used directly on the skin.

ii) Eye mucosal irritation test substance 0.05 ml of the sample was instilled into the eyes of three domestic rabbits with fu of 2.26 to 2.28 ka, and observations were made at 3.24 and 48 hours after administration.

Test results Immediately after administration of the dye stabilizing agent of the present invention, the patient did not close his eyes and was in a normal state. At 3 hours, mild hyperemia of mucous membranes was observed in 2 out of 3 cases, but there were no abnormalities in erythema or nictitating membranes.

After 274 hours, mild hyperemia remained in one case, but the other two cases were normal, and an overall trend towards recovery was observed48
After some time, everything was back to normal.

From the following, it can be seen that the dye stabilizer of the present invention has a weak irritant effect for several hours after being instilled in the eye, but it tends to recover after that, and the irritant effect is temporary and not serious.

Therefore, it can be seen that even when the dye stabilizer of the present invention is used in bath additives and the like, it does not irritate the eye mucous membranes and there is no problem at all.

iii > Oral toxicity test [Test method] 5-week-old ddY male mice (2
0.5-26. BQ) Pigment stabilizer 501/k (] (0.5 ml/l og) of the present invention to 10 animals per group.

60 ml/ku (0.6111/10 (J )) was orally administered using a gastric tube. Three hours after administration, the animals were observed for one day from beginning to end, and thereafter, they were observed twice in the morning and in the evening for one week.

[Results and Discussion] (a) Symptoms Oral administration of the pigment stabilizer of the present invention (50111+/10g) caused almost no abnormality except for mild suppression of spontaneous movement from around 10 minutes.

The same condition continued even after 1 hour, but the suppression of spontaneous movement gradually progressed with the suppression of respiratory movement.

By the next morning (approximately 18 hours after administration), 1 out of 100 cases had died. The other surviving cases were still in a state of suppressed locomotor activity, but had been in a state of recovery since 3 hours after administration on the previous day.

For reference, 60ml/kO (0°6ml/10g>) was administered, but 3 out of 100 cases died by the next morning.

The other seven patients had suppressed spontaneous movements, but were relatively healthy and gradually started to recover.

(b) L~ value The mortality rate (number of deaths/number of administrations) for oral administration of the dye stabilizer of the present invention is C, as shown in the table below.

Pigment stabilizer of the present invention 50ml/ka (0.5ml/1
Oral administration of 0g) resulted in 1 fatality in 100 cases.

When 60ml/kq was administered to Zara, 3 out of 100 cases died. In the case of administration of 501111/kg or more, physical factors such as the load on the stomach are added, so the weight of 3 out of 100 cases due to administration of 60ml/kg is also unclear.

Therefore, the dye stabilizer of the present invention can be administered orally [LD by one administration,
. The value was set as "50 ml/kg or more."

As mentioned above, the dye stabilizer of the present invention 5o1/kill
The fact that only 1 out of 100 patients died after administration of this drug seems to suggest that the toxicity of the dye stabilizer of the present invention is low. This also seems to be suggested by the fact that no serious symptoms of intoxication were observed, other than suppression of respiratory movements and spontaneous movements.

Accordingly, it seems that there is no problem at all when the dye stabilizer of the present invention is used in lipsticks and bath additives.

The pigment stabilizer of the present invention having the performance properties as described above can be widely used in fields such as external medicines, quasi-drugs, cosmetics, and other fields where pigments are used.
By using the dye stabilizer of the present invention, the desired dye expression can be achieved stably even with a combination of various dyes, and the dye is highly stabilized and has excellent water-holding properties, emulsifying properties, dispersibility, etc. It mixes well with any base material, is highly safe for the human body, can be used for dyes in all fields, and is extremely effective as a material for stabilizing dyes, which was previously unthinkable. It brings about a great effect.

Table 1 Standard value measurement method: The dye stabilizer of the present invention was added dropwise to an oil or solvent, and the limit point at which it dissolved transparently was determined (25°C). However, among waxes, the limit point was set at 70°C for solid paraffin (125"F) and 85°C for candelilla and carnauba wax.

Measurement method: Gradually add water to 10 g of sample while stirring to make the sample hydrate. After thoroughly hydrating until the water is dispersed, the mixture is left to stand at room temperature for 11 minutes, and excess water is removed.

Water-retaining property was defined as the percentage of water hydrated per 10 g of sample.

Graph l Oxidation stability measurement method: Put 20 ml of the sample into the blow tube for AOM measurement, and add 2-Bllt of air in an oil bath at 97.8 ± 0.2°C.
/ffj), samples were taken at regular intervals, and the peroxide value (POV) was measured.

Table 4 Hydrophobic capacity (benzene/dioxane method 25°C) Measurement method: 1 g of sample was mixed with benzene/dioxane mixed solvent B
It was dissolved in Omt and titrated with distilled water, and the titration amount until it became cloudy was defined as the water number.

Hydrophobic ability Metco*WN:Water number Table 5 Water permeability measuring method: Using a moisture permeable cup (JI8ZO208), the water permeability of the dye stabilizer of the present invention through an oil film was measured using the following formula.

Graph 2 Consistency 0 10 20 (°C) Temperature - 11 ---- Measurement method: Table A according to J I 8 = 251!4 Habo-Beni table A-1 Dye residual rate measurement results Habo-Beni graph A- 1 Dye residual rate measurement results Habo-Beni Red No. 202 Storage conditions: Temperature 40°C Humidity 75% U 10 20 80 40 50 60 70 80
90 100 Table A-2 Dye residual rate measurement results Habo-red orange No. 201 Storage conditions: Temperature 40°C, humidity 75%
Graph A-2 Dye residual rate measurement results Reddish orange 2011 Storage conditions: Temperature 40°C Humidity 75% ``'''' 80 40 1'''60 70 80 9
0 100 (3) Table A-8 Residual dye rate measurement results Pure blue January Storage strip A'1. Temperature: 40 degrees (1 degree, 75 degrees) Graph A-8 Dye Retention Rate Measurement Results Habo Pure Blue No. 1 Storage Conditions, Temperature 40"C PeIl!l1176% Table 11 Stick Type 10 Red Table Tl-] Dye Retention Rate measurement results Stick type mouth [
Red 202 months Preservation row f'1 Temperature 1!1L 40℃, i'
! i'lsu 75% graph n-1 dye residual rate measurement results Stick type 11 yarn [Nu! I 75% Table 1 I-2 Dye residual rate measurement results Stick type lipstick red No. 204 Storage conditions: Temperature 40℃ 3M degrees 75% Graph H-2 Dye residual rate Mlll Determination results Stick type lipstick red No. 204 Storage conditions: Temperature 40℃ Humidity 7596 Table n-a Dye residual rate 11 test results Stick type IT
I Ail Orange No. 201 Preservation 1'I: Temperature 40°C
1nu! Ilj 75 graph l3-3 Dye residual rate measurement results Stick type 1.1 #1 tul'I 75% ”0 20 30 40 50 60 7080 90
+00. ,,.

Table C-I Dye residual rate measurement results Bath additive Blue No. 1 Storage conditions, temperature 40°C, humidity 75% 10 20 80 40 50 60 70 80 9
0 100 (11) Table C-2 Dye residual rate measurement results Bathing side yellow April Storage conditions: Temperature 40°C, consistency 75% Graph 0
-2 Dye residual rate measurement results Bath removal D Application examples as external pharmaceuticals Heat stimulation patch table r) -1 Dye residual rate measurement results Heat stimulation patch blue 1
No. Preservation article! l:; #A temperature: 0℃, fJ temperature: 75% Graph D-1 Kamemeryu Zaji Danyu Seiri Thermal Stimulation Patch Blue No. 1 Storage Conditions Temperature 40℃ Humidity 75%

Claims (1)

[Claims] 1) A dye stabilizer obtained by esterifying dipentaerythritol and a mixed acid consisting of 12-hydroxystearic acid, stearic acid and rosin acid by dehydrating alcohol or phenol from the acid.