JPS6094949A - Multivalent metal salt of p-dimethylaminobenzoic acid - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (M is Zn, Ca, Mg, Al or Zr; n is the valence of M). EXAMPLE:Zinc p-dimethylaminobenzoate. USE:An ultraviolet light inhibitor, useful as an antisuntan agent and a base for cosmetics, and having improved ultraviolet light absorption ability and antisuntan effect without irritation to the skin. PREPARATION:An aqueous solution of a water-soluble multivalent metallic salt expressed by the formula M(X)n (X is Cl, NO3, SO4 or CH3COO) is added to an aqueous solution of an alkali salt of p-dimethylaminobenzoic acid expressed by formula II (A is Na, K or NH4) under agitation. When the pH of the system becomes 8.5, an aqueous solution of an alkali is added to adjust the pH to 8.5- 9.0. The reaction is carried out to afford the aimed compound expressed by formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyvalent metal salts of paradimethylaminobenzoic acid.

The product is non-irritating to the skin, has excellent ultraviolet absorption ability, and has sunscreen effects, and is extremely useful as an ultraviolet inhibitor, sunscreen, and cosmetic base (formulation IiJ, ingredient). An object of the present invention is to provide a polyvalent metal salt of valadimethylaminobenzoic acid represented by the general formula (1) below, which is a new compound.

That is, the present invention has the following general formula (1) (wherein, M is Zn, OapMg, Al or Zr, n
is the valence of M. ) is a polyvalent metal salt of varadimethylaminobenzoic acid.

The polyvalent metal salt of valadimethylaminobenzoate represented by the general formula (1) of the present invention includes zinc valadimethylaminobenzoate, calcium baladimethylaminobenzoate, magnesium baladimethylaminobenzoate, and alkaline baladimethylaminobenzoate. Epsilonium and zirconium dimethylaminobenzoate, and their formulas are as shown in the above.

The polyvalent metal salt of valadimethylaminobenzoic acid of the present invention is an aqueous solution of an alkali salt of valadimethylaminobenzoic acid represented by the following general formula (7) (wherein A is sodium, potassium or MHI). % Formula % (8) (In the formula, M is Zn+Ca, Mg, A1 or Zr,
is -01, NOx, So (or -CH, OOO, n
is the valence. ) 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
It is produced by adding an aqueous solution of a polyvalent metal salt and reacting with continued stirring after the addition, and since the substitution reaction is completed in a short time even at room temperature, it is extremely easy to carry out industrially. Usually, the polyvalent metal salt of baladimethylaminobenzoic acid of the present invention is added to an aqueous solution (concentration of 0.1 to 50% by weight) of the alkali salt of baladimethylaminobenzoic acid per mole of the alkali salt. , l, an aqueous solution (concentration: 1 to 50% by weight) containing 2 to 3 times the mole of the polyvalent metal salt is gradually added under stirring, and from the point when the pH of the system reaches 8.5, By adding an alkaline aqueous solution, its pH was adjusted to 8.5.
After adding the polyvalent metal salt aqueous solution while adjusting the temperature to 9.0, the reaction is completed by continuing stirring for an additional 20 minutes to 2 hours. To isolate the target product from the reaction mixture, the reaction mixture is permeated to select the precipitated polyvalent metal salt of baladimethylaminobenzoic acid, and then the precipitate is thoroughly washed with an aqueous alkaline solution, water, and ethanol. Then, the unreacted alkali salt of baladimethylaminobenzoic acid, the polyvalent metal salt, the hydroxide of polyvalent gold admixture, etc. adhering to the precipitate are completely dissolved and removed. By repeating this purification several times, the desired polyvalent metal salt of baladimethylaminobenzoic acid of the present invention can be obtained with high purity.

The polyvalent metal salt of para-methylaminobenzoic acid, which is expressed by the general formula (1) and obtained in the examples below, is a white powder that can be dissolved in ordinary solvents such as water, alcohol, acetone, and petroleum ether. It is insoluble, has the physical property values and elemental analysis values shown in Table 1, and is identified in Table 1. IR Atomic Absorption MS Spec Elemental Analysis Value θ Decomposition Point
on-Ryl (A) (m/z) CHN Paradimethyl 1016, 1510 Aminobenzoic acid 1510, 1875 2189 B9
8 55.1 5.1 7.1 447.5 Zinc 12
00, 780 (55ω(5,1) (7,1) paradimethyl 1610, 1570 aminobenzoic acid 1510,140 (14227868
58,65,57,6581,0 Calcium 1200
, 783 (58,7) (5,4) (7,6) Paradimethyl 1617 , 1570 Aminobenzoic acid 1500,1880 2852 85
2 61.4 5.5 8.0 509.0 Magnesium 1200 , 790 (61,4) (5,7)
(8,0) Paradimethyl 1610, 1590 Aminobenzoic acid 1520,1420 8098 51
9 62.8 5.7 8.0 497.5 Aluminum 12 (10, 795 (62,4) (5,8) (
8,1) Paradimethyl 1610, 1580 Aminobenzoic acid 1520,1400 36+) 1 7
47 57.7 5.4 7.4 487.5 Zirconium 1200.780 (67,8) (5,4)
(7,5) (Note) In the above table, elemental analysis values ()
The numbers inside are theoretical values.

The polyvalent metal salt of paradimethylaminobenzoic acid of the present invention is unnecessary for water, organic solvents, tactile substances, and sebum, and is in powder form, so it is not absorbed through the skin (skin permeation) and is safe for the human body. It does not cause skin irritation, and these properties are significantly different from related compounds such as paradimethylaminobenzoic acid, potassium paradimethylaminobenzoate, and magnesium paraaminobenzoate.

The skin irritation score was calculated by using a 51% dispersion of Oleaf as a sample solution and conducting an animal skin irritation test and a human chest irritation test according to the method of L+raiz below. are shown in Table 2.

[Draize, J.H., As5ociation
ofoFood anciDrug officialia
ls of the United 5tatesAp
prize of the 5tafety of
Chemicalsin Foods Drug a
Cosmetics, 46 (i959).

Texas Sta,te Department+ent
of 1(altb.

Au5tLn) ρ) Table 2 Baladimethylaminoamic acid! lI! Mountain 0 0 Calcium paradimethylamino dizoate o.

Magnesium paradimethylaminobenzoate o.

Paradimethylaminobenzoic acid aluminum o.

Zirconium paradimethylaminobenzoate 0 0 Paradimethylaminobenzoic acid 67 Potassium paradimethylaminobenzoate 89 Magnesium paradimethylaminobenzoate b6 The polyvalent gold IA salt of paradimethylaminobenzoate of the present invention can be applied to the skin. The absorption ability in the ultraviolet ray U ■-B region (280□-820 nm), which is harmful to .

Table 8 Transmission spectrum of polyvalent metal salt of Baladimethylaminobenzoic acid 275 0 0 0 10 10 20280 0
0 0 6 6 16 285 0 0 0 8 8 15 290 0 0 0 2 2 16 295 0 0 0 2 1 20 800 0 0 0 1 1 28 805 0 0 0 1 1 25 810 0 0 0 2 2 28 fll15 0 0 1 8 8 80 (Note 1): P
The AB-Mg salt is Paradimena 7L+7j magnesium benzoate.

(Note 2): Transmission spectra were obtained using a self-recording spectrophotometer i1MpS-2000 manufactured by Takashi Seisakusho, and the sample compound was immersed in ethanol at 0.02% and turbidity, after ultrasonication on a 5-minute plane. Measurement was performed using an IOM cell.

The polyvalent metal salt of baladimethylaminobenzoic acid of the present invention is safe for the human body, non-irritating to the skin, has excellent ultraviolet absorption (prevention ability), and is used as an ultraviolet inhibitor and sunscreen. For example, it is extremely useful as a sunscreen agent and cosmetic base. When applied to anti-fouling cosmetics, it exhibits remarkable effects, such as excellent ultraviolet pressure prevention effects that cannot be seen in related compounds such as magnesium baladimethylaminobenzoate and valadimethylaminobenzoic acid. We have discovered various effects such as anti-tank effect, sun protection factor (SPP value), ability to imprint on the skin, spreadability, makeup finish (effect), durability of makeup effect, and water resistance. , can be given.

Examples will be described below.

In the Examples, % means weight %, and parts means N parts.

Example 1 Synthesis of Zinc Valadimethylaminobenzoate Potassium Valadimethylaminobenzoate 552 and 1 ton of water were placed in a 2 t flask equipped with a stirrer, and under stirring, 0.5 t of zinc acetate 80F was added. While gradually adding an aqueous solution dissolved in water over a period of 60 minutes, from the point when the pH decreased to 8.5, an IN-potassium hydroxide aqueous solution was gradually added little by little to adjust the reaction solution (system). The reaction (exchange reaction) is carried out while maintaining the pH at 8.5 to 9.0. After the addition of the zinc acetate water bath solution is complete, stirring is continued for an additional 30 minutes, after which the precipitate is separated by filtration. Next, this precipitate was washed successively with IN aqueous potassium hydroxide solution, water, and methanol, and then dried to obtain white powder 552. The obtained white powder was confirmed to be the target compound zinc valadimethylaminobenzoate (compound of structural formula (2) above) based on the physical property values and elemental analysis values shown in Table 1 above.

Example 2 Synthesis of Calcium Baladimethylaminobenzoate The procedure of Example 1 was repeated except that an aqueous solution of calcium acetate 662 dissolved in 0.5 L of water was used instead of the zinc acetate solution. Powder 572 was obtained.

The obtained white powder was found to be the target compound of calcium paradimethylaminobenzoate (compound of structural formula (8) above) based on the physical property values and elemental analysis results shown in Table 1 above.
It was confirmed that

Example 3 Synthesis of Magnesium Valadimethylaminobenzoate Instead of an aqueous solution of zinc acetate, 0.5% of magnesium chloride was added.
White powder 6011 was obtained in the same manner as in Example 1, except that an aqueous solution in which T was dissolved was used.

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

Example 4 Synthesis of Aluminum Valadimethylaminobenzoate The procedure of Example 1 was repeated except that an aqueous solution of aluminum nitrate 94F dissolved in 0.51 g of water was used instead of the zinc acetate aqueous solution, and 62 g of white powder was prepared. I got it. The obtained white powder was confirmed to be the target compound aluminum valadimethylaminobenzoate (compound of structural formula (5) above) from the physical property values and elemental analysis values shown in Table 1 above.

Example 5 Synthesis of Zirconium Valadimethylaminobenzoate The procedure of Example 1 was repeated except that an aqueous solution of zirconium sulfate 672 dissolved in 0.5 t of water was used instead of the zinc acetate aqueous solution, and white powder 60 I got it. The obtained white powder was confirmed to be the target compound, zirconium varadimethylaminobenzoate (compound of structural formula (6)) from the physical property values and elemental analysis values shown in Table 1 above.

Application example 1゜ (Application as a sunscreen agent in the production of sunscreen makeup cosmetics) Zinc valadimethylaminobenzoate of the present invention (hereinafter abbreviated as compound A of the present invention), valadimethylaminobenzoate calcium acid (hereinafter abbreviated as compound B of the present invention), magnesium valadimethylaminobenzoate (hereinafter abbreviated as compound C of the present invention), aluminum valadimethylaminobenzoate (hereinafter abbreviated as compound RI of IJ) ), zirconium vara-dimethylaminobenzoate (hereinafter abbreviated as compound E of the present invention), vara-dimethylaminobenzoic acid as a related compound (hereinafter abbreviated as analogous compound A'), magnesium vara-aminobenzoate (hereinafter abbreviated as analogous compound B) ') as a sunscreen, 10 parts each, and 0.2 parts of Red Garla,
Yellow iron oxide 0.4 part, black iron oxide 0.05 part, talc 59.
After stirring and kneading 95 parts of mica, 25.0 parts of mica, 922.0 parts of stuff, 2.0 parts of isopropyl palmitate, and 0.2 parts of fragrance, the mixture was filled into a mold container, molded, and no sunburn was applied. A makeup cosmetic (solid white powder) was obtained. Next, the SPF value (Sun Protect) is a measure of sun protection effectiveness.
ion Factor) was measured.

The SPF value is 2 per CIA on the back of 20 panelists.
It was calculated from the ratio of the minimum erythema-producing irradiation energy Ea when the cosmetic sample (2) was applied uniformly and the minimum erythema-producing irradiation energy Ec when the cosmetic sample was not applied at all.

SPF value=Ea/Ec In the measurement, five Toshiba PL-2081-80 lamps were attached to an M-DMI type UV irradiation device for clothing manufactured by Toshiba Clothing Products Co., Ltd., 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 Register 48
．． (166), 88206-88269 (0978). ) The measurement results of SPF values are shown in Table 4. In addition, the measurement results in a practical test (by 20 panelists) when makeup was applied by applying this anti-sun makeup cosmetic (solid white powder) to the face are shown in Table 5 below.

Table 4 Sunscreen SPF value Compound of the present invention A I 6.0 tt B 16.2 // C14,2 // D 14.6 // E 18.5 Related compounds A' 8. O B' 6.1 As is clear from the results in Table 4, 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 larger and superior.

Table 5 Test Items Compounds of the Invention Related Compounds A B CD
E A'B' Extension to skin 4.6 points 4.2 points 4.7 points 4.2 points 4.
2 points 2.5 points 3.8 points Lucent feeling 4.6 4.9
4.8 4.8 4g 4.4 4.2 Color dullness 4
．． 5 4.5 4.5 4.5 4.5 2.1 8.
7 close fi 4.8 4.6 t7 4.6 4.4
2.7 8.9 Makeup discoloration 4.9 4.9 4.9
4.9 4.9 2.4 8.4 The decorative finish is poor 4.
9 4.5 4.6 4.5 4.5 2.6 10 Water resistance 4.5 45 4.5 4.6 4.5 1.6
8.2 (Note) The numerical values listed in Table 5 are the evaluation scores for the relevant effects of the test items. This is the average of the favorable scores of the 20 panelists, where 5 is very good, 4 is good, 8 is fair, 2 is poor, and 1 is very poor.

As is clear from the results in Table 5, the compound of the present invention (
The sunscreen cosmetic (solid white powder) using A, B, C, ·D, E) is a related compound (A').

B') is also significantly superior in cosmetic effects (spreadability on the skin, lucent feel, dullness of color, tightness, makeup fading, and water resistance).

Procedural amendment (method) 1. Indication of the case 1982 Patent 11th No. 2t33589 3. Person making the amendment Relationship with the case Patent applicant address 5-17-4 Sumida, Sumida-ku, Tokyo 534 Bejima, Osaka City Patent Department, Kanebo Co., Ltd., 1-5-90 Tomobuchi-cho, Ward Telephone: (06) 921-1251 4. Date of amendment order 5. Number of inventions increased by amendment None 6. Specification of subject of amendment Miscellaneous notes 7. Amendment contents of

Claims (1)

[Claims] (1) The following general formula (1) (in the formula, M is Zn, Ca, Mg, Al or Zr, n
teeth! , is the atom nine of ri. ) Polyvalent metal salt of valadimethylaminobenzoic acid. (2) The polyvalent metal salt of baladimethylaminobenzoic acid according to claim (1), which is zinc valadimethylaminobenzoate. (8) The polyvalent metal salt of Valadimethylaminobenzoic acid according to Claim (1), which is calcium Valadimethylaminobenzoate. (4) The polyvalent metal salt of paradimethylaminobenzoic acid according to claim (1), which is magnesium baradimethylaminobenzoate. (5) The polyvalent metal salt of Valadimethylaminobenzoic acid according to Claim (1), which is aluminum Valadimethylaminobenzoate. (6) The polyvalent metal salt of Valadimethylaminobenzoic acid according to Claim (1), which is aluminum Valadimethylaminobenzoate.