JPH11209111A - Multiple phosphate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an excellent ultraviolet absorber having no thickness feeling even if being blended in a composition by composing a multiple phosphate of one or more metals among Mn, Cr, Ce, Mg, Al, Ti and Zn and one or more metals among Ca, Na and K. SOLUTION: This multiple phosphate is water-insoluble or hardly soluble, and exhibits ultraviolet absorption action even in a water based carrier. As the concrete multiple phosphate, (Cr, Zn, Na)PO4 , (Cr, Co, Na)3 (PO4 )2 and the like are exemplified. Though the multiple phosphate is produced by an ordinal phosphate producing method, a closed system liquid phase method is particularly preferable. Concretely the method for mixing a solution of water soluble salts of one or more kinds among Mn, Cr, Ce, Mg, Al, Ti and Zn and a solution of water soluble salts of one or more kinds among Ca, Na and K with a solution of a water soluble phosphate such as sodium phosphate in an autoclave and drying a precipitate produced by the reaction is exemplified.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a composite metal phosphate suitable for an ultraviolet absorber useful as a raw material for cosmetics, paints, plastics and the like.

[0002]

2. Description of the Related Art Ultraviolet absorbers have an effect of protecting skin from ultraviolet rays and preventing deterioration of plastics and paints due to light, and are widely used in the fields of cosmetics, plastic materials and paints. Have been done. Such ultraviolet absorbers are roughly classified into organic ultraviolet absorbers such as cinnamic acid-based compounds, paraaminobenzoic acid-based compounds, and benzophenone-based compounds, and inorganic ultraviolet absorbers such as titanium oxide and zinc oxide. Among them, the organic ultraviolet absorber has a drawback that the amount of light that can be absorbed is finite, and there is a problem in that it remains a problem in terms of safety such as allergy to those applied directly to the skin such as cosmetics. The use of an effective amount of an inorganic ultraviolet absorber has disadvantages such as whitening or thickening due to too great a hiding power, and the generation of radicals due to the absorbed light energy to deteriorate the film. Was. In order to solve such problems, with regard to organic UV absorbers, a skeleton having higher safety and a higher absorption amount has been studied, but it still satisfies both UV absorption characteristics and safety such as allergy. Such a promising skeleton has not yet been discovered. With respect to the inorganic ultraviolet absorber, thickening and pure whiteness have been improved to some extent by making the particles finer, but there is still room for improvement. From such a viewpoint, there has been a demand for an inorganic ultraviolet absorber which does not give a thick feeling or a pure white feeling.

On the other hand, the presence or existence of a complex phosphate itself of one or more selected from manganese, chromium, cerium, magnesium, aluminum, titanium and zinc and one or more metals selected from calcium, sodium and potassium Phosphate is effective as an ultraviolet absorber, blended in compositions such as cosmetics and paints as an ultraviolet absorber, and when such a salt is used as an ultraviolet absorber, the composition containing it is thickened. It was not known that there was no time.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and provides a compound useful as an ultraviolet absorber which does not become thick even when incorporated into a composition. That is the task.

[0005]

In view of such a situation,
The present inventors have conducted intensive studies in search of an ultraviolet absorber that is not thickened even when incorporated into the composition, and as a result, manganese,
The inventors have found that a composite phosphate of two or more metals selected from chromium, cerium, magnesium, aluminum, titanium and zinc has such an effect, and completed the invention. Hereinafter, the present invention will be described in detail focusing on its embodiments.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (1) Composite phosphate of the present invention The composite phosphate of the present invention comprises manganese, chromium, cerium,
It is a composite phosphate of at least one selected from magnesium, aluminum, titanium, and zinc and at least one metal selected from calcium, sodium, and potassium. All of these complex phosphates are novel complex salts that have not been described in the literature. The complex phosphate of the present invention is provided on condition that it is insoluble or hardly soluble in water. This is because it is necessary to exhibit an ultraviolet absorbing effect even in an aqueous carrier. Further, as long as the effects of the present invention are not impaired, anionic components other than the phosphate group can be contained. Examples of such components include carbonate groups and sulfate groups. The content of such anionic component other than the phosphate group is preferably 10% by weight or less, more preferably 5% by weight or less. Further, in the composite phosphate of the present invention, it is preferable that the element composition ratio is constant in any part of the salt. Examples of such salts include the following for each component.
However, depending on the charge ratio of the raw materials and the reaction conditions, it is needless to say that the following example is only an example, because it may contain water of crystallization, may not take an accurate molar ratio, or each constituent salt may be solid-dissolved. . For example, (Cr, Zn, N
a) PO ₄ , (Cr, Co, Na) ₃ (PO ₄ ) ₂ , Ca
(Mn, Zn) ₅ (PO ₄ ) ₄ , (Ca, Co) ₃ (P
O ₄ ) ₂ , K ₂ (Mn, Mg) ₅ (PO ₄ ) ₄ , K (Mn, C
e) (PO ₄ ), (Cr, Mg, Na) ₃ (PO ₄ ) ₂ ,
(Mn, HNa) ₃ P ₂ O ₈ , Na ₂ Mn ₅ (PO ₄ ) ₄ , K
(Al, Cr) PO ₄ , (Cr, K, Ti) ₃ (PO ₄ ) ₄
And the like. Further, for example, (Cr, Zn, Na) P
Taking O ₄ as an example, let the total number of moles of chromium, zinc, and sodium and the number of moles of PO _{4 be} m and n, respectively;
When the number of moles of n and Na is a, b and c, respectively, m:
When n = 1: 1, the mole numbers of Cr, Zn, and Na take values that balance with the valence of PO ₄ . That is, assuming that the valences of Cr, Zn, and Na are 3, 2, and 1, respectively, C
It can be expressed as r _0.5 Zn _0.5 Na _0.5 PO ₄ , which is also in the category of (Cr, Zn, Na) PO ₄ . These are all water-insoluble salts or poorly water-soluble salts which are not described in the literature. These composite phosphates of the present invention have excellent absorption characteristics not only for ultraviolet B but also for ultraviolet A, and are very useful as ultraviolet absorbers.

(2) Method for Producing Composite Phosphate of the Present Invention The composite phosphate of the present invention can be produced by an ordinary method for producing phosphate. Such methods include, for example, solid-phase methods such as a method of firing individually or by mixing hydroxides and carbonates of various metals with phosphoric acid, and a method of firing by mixing phosphates of respective metals. And a liquid phase method in which a solution of chlorides or nitrates of various metals alone or a solution of an alkali salt of phosphoric acid and / or phosphoric acid is mixed and reacted in a water and / or alcohol solution. Further, examples of the liquid phase method include an open system in which the reaction is carried out in a beaker or the like and a closed system in which the reaction is carried out in an autoclave. Of these, the most preferable is the liquid phase method, and the more preferable is the liquid phase method in a closed system. This is because, in the solid phase method, the particle size of the raw material greatly affects the particle size of the final product, the quality of the final product differs depending on the method of mixing the raw materials,
This is because the heat of sintering may cause defects such as inconsistent water of crystallization. Specific examples of the liquid phase method in this closed system include a solution of a water-soluble salt of at least one metal selected from manganese, chromium, cerium, magnesium, aluminum, titanium, and zinc, calcium, sodium, and potassium. A method of mixing a solution of a water-soluble salt of at least one metal selected from the group consisting of a water-soluble salt of phosphoric acid such as sodium phosphate in an autoclave, reacting, and drying the resulting precipitate. As for the autoclave conditions, a mixing method, a reaction temperature, a pressure, an aging time and the like are appropriately selected depending on a target phosphate.

(3) Composition of the Present Invention The composition of the present invention is characterized by containing the composite phosphate of the present invention. As the composition of the present invention, for example,
Examples include cosmetics such as foundation and cheek color, external skin medicines such as antifungal external preparations and anti-inflammatory external preparations, paints such as paints, plastic products and the like. The composition of the present invention is excellent in the action of protecting the skin from ultraviolet rays in cosmetics, is excellent in the action of preventing the active ingredient from being light-degraded in external medicine for skin, and is a film formed by light in paints. It is excellent in preventing deterioration of plastics, and is excellent in preventing cracks due to light in plastics and the like. The preferred content of the composite phosphate of the present invention in the composition of the present invention is 0.0
1 to 10% by weight, more preferably 0.05 to 5% by weight.
% By weight. If the amount is too small, the protective action against ultraviolet rays may not be expected in some cases. If the amount is too large, the amount of other optional components may be restricted. Among such compositions, the composite phosphate of the present invention is particularly preferably applied to cosmetics and external preparations for skin because of its high safety, and is applied to cosmetics because of its properties as a coloring material. Is most preferred. It is also within the technical scope of the present invention to include in these compositions any purpose other than the ultraviolet absorber, for example, as a coloring agent or a gaseous powder. This is because, even if the purpose is different, the effect of the present invention is realized as a result.

The composition of the present invention may contain, in addition to the composite phosphate described above, optional components commonly used in these compositions. As such optional components, for example, in the case of cosmetics, hydrocarbons such as petrolatum and microcrystalline wax, esters such as jojoba oil and gay wax, triglycerides such as tallow, olive oil, cetanol, oleyl alcohol And the like, fatty acids such as stearic acid and oleic acid, polyhydric alcohols such as glycerin and 1,3-butanediol, nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants , Ethanol, carbopol and other thickeners, preservatives, ultraviolet absorbers, antioxidants, pigments, powders and the like can be exemplified, if the external preparation, excipients, binders, coating agents, Lubricants, sugar coatings, disintegrants, bulking agents, flavoring agents, emulsifying / solubilizing / dispersing agents, stabilizers, pH adjusters,
Isotonic agents, active ingredients and the like can be exemplified, and examples of the paint include solvents, dispersants, pigments, film-forming agents, plasticizers and the like.

[0010]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but it goes without saying that the present invention is not limited to only these examples.

<Embodiment 1> According to the following method, (C
(r, Zn, Na) PO ₄ was prepared. That is, the commercially available C
_{rPO 4 · 6H 2 O, Zn} 3 (PO 4) 2 · 4H 2 O, NaH
3.8 g, 36.7 g, and 0.42 g of CO ₃ were collected and mixed well by a raikai machine, and the temperature was increased by an electric furnace at a heating rate of 10 g.
Calcination was performed by mooring at 900 ° C for 1 hour at 900 ° C for 10 minutes. After firing, it was pulverized with a ball mill. The yield of this powder was 20 g, it was pale green, and the powder X-ray diffraction and fluorescence X
It was confirmed by a line analysis that it was Cr _0.15 Zn _0.8 Na _0.05 PO ₄ (composite phosphate 1).

<Embodiment 2> According to the following method, Ca
(Mn, Zn) ₅ (PO ₄ ) ₄ was prepared. That is, Ca (NO ₃ ) ₂ .4H ₂ O, MnCL ₂ .4H
9.8 g, 4.9 g, 30.7 g of ₂ O and ZnCL ₂ respectively
Dissolve to obtain solution A. Separately, to 0.3 L of purified water (NH
₄ ) 26.4 g of ₂ HPO ₄ and 28% NH ₄ OH,
Dissolve 13 g to obtain solution B. The solution A is heated to 85 ° C., and the solution B is added dropwise thereto with stirring. After completion of dropping, the mixture was aged at 85 ° C. for 1 hour, and the resulting precipitate was collected by filtration and dried to obtain 19 g of a powder. This powder has a pale purple color, and was confirmed to be Ca (Mn _0.1 , Zn _0.9 ) ₅ (PO ₄ ) ₄ (composite phosphate 2) by powder X-ray diffraction, X-ray fluorescence and infrared spectroscopy. did.

<Embodiment 3> According to the following method, (C
a, Co) ₃ (PO ₄ ) ₂ was prepared. That is, 1.5 L of ethanol was put into a reactor equipped with a reflux machine, and Ca (OC) was added thereto.
_{2 H 5) 2, Co (} OC 3 H 7) 2 respectively 32.5 g, 8.8
g to dissolve the solution A. Separately, 0.3 L of ethanol is mixed with 0.2 L of purified water and 19.6 g of H ₃ PO ₄ to obtain a solution B. Solution B was added dropwise under reflux of Solution A in the reactor, and after the addition, the mixture was refluxed for 1 hour to ripen. After cooling, the resulting precipitate was collected by filtration, dried, and heated at a rate of 10 ° C./10 minutes 500 ° C.-1
Fired for mooring for hours. The fired product was pulverized with a ball mill to obtain 25 g of pale green powder. This powder was analyzed by powder X-ray diffraction and fluorescent X-ray analysis (Ca _0.83 , Co _0.17 ).
₃ (PO ₄ ) ₂ (composite phosphate 3).

<Embodiment 4> According to the following method, K ₂
(Mn, Mg) ₅ (PO ₄ ) ₄ was prepared. That is, purified water 1L to _{MnCL 2 · 4H 2 O, MgCL} 2 · 6H 2 O , respectively 10 g, and A was allowed to 40.6g dissolved. Separately, 45.6 g and 7 g of (K) ₂ HPO ₄ .3H ₂ O and KOH were dissolved in 0.2 L of purified water to obtain a solution B. The solution A and the solution B were set in an autoclave, the solution B was poured into the solution A, and reacted at a reaction temperature of 85 ° C. and a pressure of 300 kg / cm 2 for 1 hour. After cooling, the crystals were collected by filtration and dried to obtain 27 g of light brown powder. This powder was analyzed by powder X-ray diffraction, X-ray fluorescence and infrared spectroscopy to determine K ₂ (Mn _0.2 , Mg _0.8 ) ₅ (PO ₄ ) ₄
(Composite phosphate 4).

<Embodiment 5> According to the following method, K
(Mn, Ce) (PO ₄ ) was prepared. That is, purified water 1
4 g and 34.7 g of MnCL ₂ .4H ₂ O and Ce (NO ₃ ) ₃ .6H ₂ O are dissolved in L, respectively, to obtain solution A. Separately, 22.8 g and 2.8 g of (K) ₂ HPO ₄ .3H ₂ O and KOH were dissolved in 0.2 L of purified water to obtain a solution B. The solution A and the solution B were set in an autoclave, the solution B was poured into the solution A, and reacted at a reaction temperature of 85 ° C. and a pressure of 300 kg / cm 2 for 1 hour. After cooling, the crystals were collected by filtration and dried to obtain 24 g of a pale ocher powder. This powder was analyzed by powder X-ray diffraction, fluorescent X-ray and infrared spectrum analysis to obtain K (Mn _0.2 , Ce _0.8 ).
(PO ₄ ) (composite phosphate 5) was confirmed.

<Example 6> The composite metal salts 1 to 5 of the present invention produced in the above Examples 1 to 5 by the following method.
The ultraviolet absorption characteristics of No. 5 were confirmed. Ultraviolet absorption properties were examined for ultraviolet absorption capacity and ultraviolet absorption efficiency. These characteristic values were measured as follows. Table 1 shows the measurement results. This indicates that the composite phosphate of the present invention has excellent ultraviolet absorption properties. (Ultraviolet absorption ability evaluation method) A tablet of the composite phosphate powder or the comparative powder is formed into a thickness such that light is no longer transmitted,
Using a spectrometer, the tablet has a wavelength of 290 nm to 400 nm.
Is measured. 290 nm to 320 nm of this reflectance
(B wave) and the average reflectance of 320 nm to 400 nm (A wave) are obtained, and the -LOG value thereof is taken as the absorbance of B wave and A wave. This absorbance was defined as the ultraviolet absorption capacity of the powder. (Ultraviolet absorption efficiency evaluation method) An extender pigment such as talc and a composite phosphate powder or a comparative powder are mixed to prepare a mixed powder. Only the mixed powder and extender pigment are tabletted to a thickness such that light is no longer transmitted.
The reflectance at 400 nm is measured. 290 nm of this reflectance
The average reflectance at 320 nm (B wave) and 320 nm to 400 nm (A wave) is determined. (Average reflectance of extender pigment-average reflectance of mixed powder) / (average reflectivity of extender pigment) indicates how much the composite phosphate or the comparative powder reduced the reflectivity of the extender pigment. The ratio of the composite phosphate or the comparative powder mixed into the extender was unified to 1 V%, which was defined as the ultraviolet absorption efficiency. (Work evaluation method) The ultraviolet absorption capacity is originally the absorbance of the substance, and the ultraviolet absorption efficiency is a ratio of how much the absorption capacity can be exhibited. Therefore, (capacity * efficiency) is the amount of work related to ultraviolet absorption. This work was used as an overall evaluation of the composite phosphate or the comparative powder for the ultraviolet absorption characteristics. <Display of Samples in Table 1> (a) Commercial ZnO (b) Commercial TiO2 (c) Composite phosphate of Example 1 (d) Composite phosphate of Example 2 (e) Composite phosphate of Example 3 (F) Composite phosphate of Example 4 (g) Composite phosphate of Example 5

[0017]

[Table 1]

<Examples 7 to 11> UV protection cosmetics were prepared according to the following formulations. That is, the prescription ingredients are charged into a double planetary mixer, kneaded well at 95 ° C,
It was filled in a mold, molded by heating press, and mounted in a container to obtain a cosmetic. All of these had an excellent ultraviolet protection effect. Silicone treated titanium dioxide 10 parts by weight Zinc oxide 2 parts by weight Yellow iron oxide 3 parts by weight Bengala 1 part by weight Silicone treated sericite 20 parts by weight Silicone treated mica 10 parts by weight Silicone treated talc 20 parts by weight Nylon powder 14 parts by weight Octyldodecyl oleate 5 parts by weight Dimethicone 13 parts by weight Carnauba wax 1 part by weight Candelilla wax 0.8 part by weight Sorbitan sesquiolate 0.2 part by weight Complex phosphate * 10 parts by weight * Details of the complex phosphate are shown in Table 2.

[0019]

[Table 2]

<Examples 12 to 16> An anti-inflammatory skin external preparation was prepared according to the following formulation. That is, the ingredients were kneaded well with a kneader to obtain a skin external preparation. It suppressed the onset of phototoxicity of indomethacin. Indomethacin 1 part by weight Vaseline 89 parts by weight Complex phosphate ** 10 parts by weight ** Details of the complex phosphate are shown in Table 3.

[0021]

[Table 3]

Example 17 A paint was prepared according to the following recipe. That is, the ingredients were charged into a Dynomill and dispersed uniformly to obtain an aqueous paint. Alkyl acrylate resin emulsion 60 parts by weight Triethyl citrate 5 parts by weight Complex phosphate *** 35 parts by weight *** Details of the complex phosphate are shown in Table 4.

[0023]

[Table 4]

[0024]

According to the present invention, it is possible to provide a compound which is not thickened even when incorporated into a composition and is useful as an ultraviolet absorber.

Claims (8)

[Claims] 1. A composite phosphate of at least one selected from manganese, chromium, cobalt, cerium, magnesium, aluminum, titanium, and zinc and at least one metal selected from calcium, sodium, and potassium. 2. The composite phosphate according to claim 1, wherein the composite phosphate is water-insoluble or hardly soluble. 3. A chromium / zinc / sodium composite phosphate,
Chromium-cobalt-sodium complex phosphate, calcium-zinc-manganese complex phosphate, calcium-cobalt complex phosphate, potassium-manganese-magnesium complex phosphate, potassium-manganese-cerium complex phosphate, chromium-magnesium-sodium complex phosphate Salt, sodium
3. The composite phosphate according to claim 1, wherein the composite phosphate is one of a manganese composite phosphate, a potassium-aluminum-chromium composite phosphate, and a chromium-potassium-titanium composite phosphate. 4. An ultraviolet absorber comprising the composite phosphate according to claim 1. 5. A composition comprising the ultraviolet absorbent according to claim 4. 6. The composition according to claim 5, which is a cosmetic. 7. A composition containing the composite phosphate according to claim 1. 8. The composition according to claim 7, which is a cosmetic.