JPS6094936A - Polyvalent metal salt of p-methoxycinnamic acid - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (M is Zn, Ca, Mg, Al or Zr; n is valence of M). EXAMPLE:Zinc p-methoxycinnamate. USE:Ultraviolet-screening agent, antisuntan agent, and cosmetic base (compounding material). It is white powder, insoluble in ordinary solvents such as water, alcohol, acetone, petroleum ether, etc., safe to the human body, nonirritant to the skin, and has excellent ultraviolet absorbance and antisuntan effect. PREPARATION:The compound of formula I can be produced by (1) adding an aqueous solution of a water-soluble polyvalent metal salt of formula (X is Cl, NO3, SO4 or -CH3COO) to an aqueous solution of p-methoxycinnamic acid alkali salt of formula II (A is Na, K or NH4) slowly under agitation until the pH of the system reaches 8.5, (2) adding an alkaline aqueous solution together with the aqueous solution of polyvalent metal salt to keep the pH of the system to 8.5- 9.0, and (3) continuing the agitation for 20min-2hr after the completion of the addition at room temperature.

Description

[Detailed description of the invention] The present invention relates to polyvalent metal salts of baramethoxycinnamic acid.

The present invention is non-irritating to the skin, has excellent ultraviolet absorption ability, and has a sunscreen effect, and can be used as an ultraviolet inhibitor, sunscreen agent, and cosmetic base (formulation #A ingredient). An object of the present invention is to provide a polyvalent gold scrap salt of paramethoxycinnamic acid represented by the general formula (1) described below, which is an extremely useful new compound.

That is, the present invention has the following general formula (1) (wherein, M is Zri, Ca+Mf, Al or Zr
t n is the valence of M.

It is a polyvalent metal salt of baramethoxycinnamic acid represented by

The polyvalent metal salt of paramethoxycinnamate represented by the general formula (1) of the present invention is zinc paramethoxycinnamate, calcium paramethoxycinnamate, magnesium paramethoxycinnamate, aluminum aluminum paramethoxycinnamate, and zirconium paramethoxycinnamate. , their structural formulas are j
It is ~ri.

The polyvalent metal salt of paramethoxycinnamic acid of the present invention is an aqueous solution of an alkali salt of paramethoxycinnamic acid represented by the following general formula (7) (wherein A is sodium, potassium or NH+). In the following general formula (8) % formula % (8) (wherein, M is Zn, Oa, M&, Al or Ltzr,
X is -C1, -NO3, -$0. Maf: Bar CHs
Coo, n 1. ! &j child value. ) was gradually added under stirring, and when the pH of the system reached 8.5, an alkaline aqueous solution was added to adjust the pH to 8.5 to 9.0. While
Add the polyvalent metal salt aqueous solution, and after the addition, continue stirring for an additional m.
Since the substitution reaction is completed in a short time even at room temperature, industrial implementation is extremely easy. Usually, the polyvalent metal salt of paramethoxycinnamic acid of the present invention is added to an aqueous solution (concentration: 0.1 to 50% by weight) of the alkali salt of paramethoxycinnamic acid at 1.0% per mole of the alkali salt. An aqueous solution containing 2 to 3 times the mole of the polyvalent metal salt (concentration: 1 to 50% by weight) is gradually added under stirring, and from the point when the pH of the system reaches 8.5, an alkaline aqueous solution is added. After adding the polyvalent metal salt aqueous solution while adjusting the pH to 8.5 to 9.0 by adding
The reaction is completed after stirring for 2 hours. To obtain the half-molten target product from the reaction mixture, filter the reaction mixture to remove the polyvalent metal salt of methoxycinnamic acid as a precipitate, and then thoroughly wash the precipitate with an aqueous alkaline solution, water, and ethanol. As a result, unreacted alkali paramethoxycinnamate salts, the polyvalent metal salts, and by-product polyvalent metal hydroxides adhering to the precipitate are completely dissolved and removed.

By repeating this purification several times, the desired polyvalent metal salt of baramethoxycinnamic acid of the present invention can be obtained with high purity.

The polyvalent metal salts of baramethoxycinnamic acid expressed by the general formula (1) and obtained in the examples below are all white powders that can be dissolved in ordinary solvents such as water, alcohol, acetone, and petroleum ether. It was identified as being insoluble and having the physical properties and elemental analysis values shown in Table 1.

Table 1 Paramethoxy 1650.1610 Paramethoxy 1640, 1605 Paramethoxy 1650, 1605 Cinnamic acid 1550,1265 2852 878 68
．． 5 4.7 500.0 bara methoxy 1640,
1600 Barramethoxy 1640, 1600 Cinnamic acid 1550.1250 3601 751 64
．． 0 4.7 428.0 Zirconium 1170.8
30 (68,9) (4,8) (Note) In the above table A, the numerical values in parentheses for elemental analysis values are theoretical values.

The polyvalent metal salt of rosemethoxycinnamic acid of the present invention is unnecessary for water, organic solvents, oily substances, and sebum, and is in powder form, so it can be absorbed transdermally (skin permeation), is safe for the human body, and is irritating to the skin. These properties are significantly different from related compounds such as paramethoxycinnamic acid, potassium paramethoxycinnamate, and magnesium paraaminobenzoate. Using a 5% by weight dispersion in olive oil as the number of samples, an animal skin irritation test and a human body irritation test were conducted according to the method of Draiz below, and the calculated skin irritation scores are shown in Table 2. It was shown to.

[Draize, J.H., As5ociati
on of Food and Drug official
als of the United 5tatesA
ppraisal of the 5tafety o
f Chemicals in Foods Drug
and Cosmetics + 46 (1959)
+'l'exas 5tate Department
to of Health.

Table 2 Zinc paramethoxycinnamate 00 Calcium paramethoxycinnamate 00 Magnesium paramethoxycinnamate 00 Aluminum paramethoxycinnamate 00 Zirconium paramethoxycinnamate 00 Paramethoxycinnamate 78 Potassium paramethoxycinnamate 89 The polyvalent metal salt of paramethoxycinnamate of the present invention is , ultraviolet radiation in the UV-B range (280-820 nm) that is harmful to the skin.
As shown in Table 2, the absorption capacity of the compound is extremely high, and as shown in Table 2, it is markedly different from that of related compounds such as 1<lamethoxypotassium cinnamate.

Table 3 Transmission spectrum of polyvalent metal salt of paramethoxycinnamic acid Transmission y
$ (%) Wavelength Polyvalent metal salt of paramethoxycinnamic acid of the present invention PMC
- Salt (nm) Znm CajM Mg salt Al salt Zr
Salt (similar compounds) 270 1 1 2 20 20
85275 1 1 1 10 15 80'280
1 1 1 6 10 25285 1 1 1 2
2 20 290 1 1 1 1 1 1 1 20 295 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 20 805 1 1 1 1 1 12 1 25 810 286 6 80 (Note 1): PM (!- is potassium paramethoxycinnamate.

(Note 2): Transmission spectra were obtained using a self-recording spectrophotometer MPS-2000 manufactured by Takashi Seisakusho, with the sample compound suspended in ethanol at a concentration of 0.02 mm%, and after ultrasonication for 5 days. Measurements were made using a cell.

The polyvalent metal salt of rosemethoxycinnamic acid of the present invention is safe for the human body, non-irritating to the skin, and has excellent ultraviolet absorption (prevention ability), and is used as an ultraviolet inhibitor, sunscreen, and cosmetic. Very useful as a base.

For example, when applied to sunscreen cosmetics obtained by blending it into cosmetic bases such as makeup cosmetics, creams, lotions, and ointments as a sunscreen ζ-screening agent, there are significant effects and effects. For example, it exhibits excellent UV protection effect, sunscreen effect, sunscreen factor (SPF value), and adhesion to the skin that cannot be seen in related compounds such as magnesium paramethoxycinnamate and paramethoxycinnamic acid. , extensibility, cosmetic finish (effect), durability of cosmetic effect, water resistance, and other effects can be expressed and imparted.

Examples will be described below.

In the Examples, % means % by weight, and parts means parts by weight. Synthesis of Zinc Paramethoxycinnamate Potassium paramethoxycinnamate 552 and 16 water were placed in a 2 t flask equipped with a stirrer and stirred. Below, add 60% of an aqueous solution of 809 zinc acetate dissolved in 0.56% water.
The pH of the reaction solution (thread) was adjusted to 8.5 by gradually adding a small amount of IN-potassium hydroxide water bath solution once the pH had decreased to 8.5. 5-9.0
The reaction (transformation reaction) is carried out while maintaining the temperature. Vinegar f! It
After the addition of the aqueous zinc solution is complete, stirring is continued for an additional 80 minutes, after which the precipitate is separated. Next, this precipitate
The mixture was sequentially washed with an IN potassium hydroxide aqueous solution, water, and methanol, and then dried to obtain white powder 552.

The obtained white powder was confirmed to be the target compound zinc methoxycinnamate (compound of structural formula (2) above) from the physical property values and elemental analysis values shown in Table 1 above.

Example 2 Synthesis of Calcium Paramethoxycinnamate Instead of an aqueous zinc acetate solution, calcium acetate 66V (
Example 1 except that an aqueous solution of L5t in water was used.
In the same manner as above, white powder 57'J was obtained.

The obtained white powder was confirmed to be the target compound, calcium paramethoxycinnamate (compound of structural formula (3)), based on the physical property values and elemental analysis results shown in Table 1 above.

Example 3 Synthesis of magnesium paramethoxycinnamate A white powder 60f was obtained in the same manner as in Example 1, except that an aqueous solution of magnesium chloride dissolved in 0.5A water was used instead of the zinc acetate aqueous solution. Ta.

The obtained white kernel powder was confirmed to be the target compound, magnesium baramethoxycinnamate (compound of structural formula (4)), based on the physical property values and elemental analysis values shown in Table 1 above.

Example 4 Synthesis of Aluminum Paramethoxycinnamate The procedure of Example 1 was repeated, except that an aqueous solution of aluminum nitrate 94f dissolved in 0.57.0% water was used instead of the zinc acetate aqueous solution. ? I got it. The obtained white powder was found to be the target compound, aluminum paramethoxycinnamate (compound of the structural formula (5)), based on the physical property values and elemental analysis values shown in Table 1 above.

Example 5 Synthesis of zirconium paramethoxycinnamate The procedure of Example 1 was repeated, except that a water bath solution containing 67v of zirconium sulfate dissolved in 0.5t of water was used instead of the zinc acetate aqueous solution, and 60f of white powder was prepared. I got it. This white powder obtained is
From the physical property values and elemental analysis values shown in Table 1 above, it was confirmed that the target compound was zirconium paramethoxycinnamate (compound of structural formula (6) above).

Application Example 1 (Application as anti-sunscreen agent in the production of makeup cosmetics) Zinc paramethoxycinnamate of the present invention (hereinafter abbreviated as compound A of the present invention), calcium paramethoxycinnamate (below
(abbreviated as the compound B of the present invention), magnesium paramethoxycinnamate (hereinafter abbreviated as the compound C of the present invention), aluminum paramethoxycinnamate (hereinafter abbreviated as the compound of the present invention), zirconium paramethoxycinnamate (hereinafter abbreviated as the compound of the present invention) (abbreviated as compound E), paramethoxycinnamic acid as a related compound (hereinafter abbreviated as related compound A'), potassium paramethoxycinnamate (hereinafter abbreviated as related compound B') as a sunscreen agent. 0.2 parts of Benkara, 0.4 parts of yellow iron oxide, 0.05 parts of black iron oxide, and 59.9 parts of talc.
After stirring and kneading 5 parts, 25.0 parts of mica, 2.0 parts of squalane, 2.0 parts of isopropyl palmitate, and 0.2 parts of fragrance, the mixture was filled into a mold container, molded, and the sunbathing was stopped. A makeup cosmetic (solid white powder) was obtained. Next, the SPF value (Sun Protective Value) is a measure of sun protection effectiveness.
on Factor) was measured.

The SPF value is 2 per CIA on the back of 20 panelists.
It was determined from the ratio of the minimum erythema-producing irradiation energy Ea when the cosmetic sample No. 11f was applied uniformly and the minimum erythema-generating irradiation energy Ec when the cosmetic sample was not applied at all.

SPF value = Ea / Ec In the measurement, five Toshiba FL-2081-80 lamps were attached to a clothing ultraviolet irradiation device manufactured by Toshiba Clothing & Accessories Co., Ltd. @ M-DMI, and irradiation was performed from a distance of 15 crn. The irradiation energy was measured using an ultraviolet intensity meter (UVR-805/865 manufactured by Toshiba Optical Machinery Co., Ltd.). (In addition, SP
The definition of F value is Federal Regi-ster
4B, (166), 88206-88269 (1978
) is described in the literature. ) The measurement results of SPF values are shown in Table 4. In addition, the measurement results in a practical test (by 20 panelists) when this sunscreen makeup cosmetic (solid white powder) was applied to the face to make up are shown in Table 5 below.

Table 4 Compounds of the present invention A 14.0 // B 14.2 tt C14,2 tt D 1B, 6 // B 14.5 Analogous compounds A' 7.0 // B' 6.1 Table 4 As is clear from the results, the compound of the present invention (
Sunscreen makeup cosmetics (solid white powder) using A, B, C, D, and E) have a higher sunscreen effect than those using related compounds (A', B'). (SPF' value) is significantly large, and the test items in Table 5 Compounds of the present invention Related compounds A B (!
D E A'B' Extension to skin 4.7 points 4.8 points 4.7 points 4.3 points 4.
2 points 2.4 points 8.9 points Lucent feeling 4.7 4.9
4.8 4.9 4.8 4.5 4.8 Color dullness
4.6 4.5 4.6 4.5 4.6 2.1 8
．． 7 Cs S feeling 4.8 4.7 4.7 4.7 4.4
2.6 B, 8 Makeup deterioration 4.9 4.9 4.9
4.9 4.9 2.8 3.4 Makeup finish 4.
9 4.6 4.6 4.5 4.7 2.6 8.0
Water resistance 4.5 4.6 4.5 4.6 4.6 1
．． 6 8.2 (Note) The figures listed in Table 5 are as follows:
This is the evaluation score for the relevant effect of the test item. As is clear from the results in Table 5, where 5 is very good, 4 is good, 3 is fair, 2 is poor, and 1 is very poor, the compounds of the present invention (A, B, C!,
The sunscreen cosmetic (solid white powder) using D and E) is a related compound (A').

Compared to those using related compounds (A/ , B/ ), the cosmetic (solid white powder) has a higher cosmetic effect (spreading on the skin, It is also extremely excellent in terms of lucent feel, dull color, adhesion, makeup fading, and water resistance).

Procedural amendment (method) 1. Indication of the case Patent Application No. 208540 filed in 1982 2. Name of the invention paramethoxycinnamic acid polyvalent gold salt 3. Relationship with the ministry case making the amendment Patent applicant address Sumida-ku, Tokyo 5-17-4 Sumida, 1-5-90 Tomobuchi-cho, Bejima-ku, Osaka 534, Japan Patent Department, Kanebo Co., Ltd. Telephone: (06) 921-1251 5. Number of inventions to be increased by the amendment. Details subject to the amendment. Document 7: Engraving of the detailed statement of the amendments (the contents remain unchanged). Street of 90 papers.

Claims (1)

[Claims] (1) The following general formula (1) (in the formula, M is Zn + C, FL r Mf/ +
Al + or Zr, n is the atomic sum of M. ) Polyvalent metal salt of baramethoxycinnamic acid. Q) Claim No. (
1) The polyvalent metal salt of baramethoxycinnamic acid as described in item 1). (8) The polyvalent metal salt of paramethoxycinnamate according to claim (1), which is calcium paramethoxycinnamate. (4) The polyvalent metal salt of paramethoxycinnamate according to claim (1), which is magnesium paramethoxycinnamate. (5) The polyvalent metal salt of paramethoxycinnamic acid according to Claim No. (1)M, which is aluminum paramethoxycinnamate. (6) The polyvalent metal salt of paramethoxycinnamate according to claim (1), which is aluminum paramethoxycinnamate.