JP2023145234A - Sunscreen cosmetic - Google Patents

Abstract

To provide a sunscreen cosmetic which has a sufficient ultraviolet protective effect even without substantially containing an organic ultraviolet absorber, is further excellent in lack of a feeling of burden on the applied film and seawater resistance and also has an excellent elution suppression effect of metal ions.SOLUTION: There is provided a sunscreen cosmetic which comprises (A) 10 to 40 mass% of hydrophobic surface treated zinc oxide and/or titanium oxide having an average particle diameter of less than 100 nm and (B) one or two or more monovalent alkali metal salts selected from the group consisting of alginic acid, acylmethyltaurine and acylglutamic acid, and substantially contains no organic ultraviolet absorber.SELECTED DRAWING: None

Description

The present invention relates to sunscreen cosmetics. The present invention also relates to a method for suppressing elution of metal ions from a composition containing zinc oxide and/or titanium oxide, and an elution inhibitor for metal ions.

Ordinary sunscreen cosmetics contain organic ultraviolet absorbers and metal oxides as ingredients that protect the skin from ultraviolet rays. In recent years, consumer preferences have led to a desire for the development of sunscreen cosmetics that do not contain organic ultraviolet absorbers. There is a need to develop a formulation that exhibits a satisfactory UV protection effect using only metal oxides without containing organic UV absorbers. For this purpose, it is necessary to increase the content of the metal oxide, but this causes problems such as a feeling of burden on the coating film and poor spreadability during coating.

It has also been reported that sunscreen cosmetics may have an impact on the marine environment. Among them, research on the effects of metal oxides on the marine environment is also progressing. For example, zinc ions have been found to have an effect on Stylophora pistillata, a type of hard coral, when the concentration in seawater is 0.1 ppm or more. has been suggested (for example, see Non-Patent Document 1). In particular, when the ultraviolet protection effect is expressed only with a metal oxide without containing an organic ultraviolet absorber, it is necessary to take into account the impact on the environment.

Furthermore, sunscreen cosmetics are required to function for a long time, but in daily life, they can be damaged by rubbing against clothing or coming into contact with moisture in the external environment such as sweat or seawater. There is concern that cosmetics may come off and the UV protection effect may decrease. Against this background, technologies to suppress the decline in the UV protection effect are being investigated. For example, oil-in-water emulsions that maintain high UV protection effects even when in contact with water or sweat and have an excellent feel when used. In sunscreen cosmetics, a technology has been disclosed in which the ultraviolet protection ability is improved upon contact with water by blending a specific ratio of an ultraviolet protection agent and a fatty acid that is solid at room temperature (for example, see Patent Document 1). . In particular, in situations where the risk of ultraviolet rays is high, such as swimming in the sea in the summer, and where the sunscreen coating is likely to fall off due to sweat or seawater, there is an even greater need for sufficient ultraviolet protection, and furthermore, to suppress the decline in ultraviolet protection.

Coral Reefs 2019.38:109-122

International Publication No. 2016/068299

However, although the technique disclosed in Patent Document 1 has an excellent ultraviolet protection effect, it contains an organic ultraviolet absorber, and it may be desirable to further improve seawater resistance. In addition to the above, there are cases in which it is desirable to further increase the feeling of less burden on the coating film.

Furthermore, regarding metal oxides, although numerical ranges that may have an impact on the marine environment have been suggested and studied, techniques for suppressing metal oxides based on these numerical ranges have not been sufficiently studied.

The present invention was made in view of the above circumstances, and its main purpose is to provide a sufficient UV protection effect even without substantially containing an organic UV absorber, and to provide a coating film that does not feel burdensome. An object of the present invention is to provide a sunscreen cosmetic that has excellent seawater resistance and also has an excellent effect of suppressing elution of metal ions.

In view of the above problems, the present inventors conducted extensive studies. As mentioned above, in order to maintain a sufficient UV protection effect, it is necessary to maintain sunscreen cosmetics on the skin. However, it is known that metal oxides are eluted upon contact with moisture. Therefore, in order to suppress the elution of metal ions due to contact with moisture, especially contact with seawater, the present inventors created a cosmetic film that reacts with divalent metal ions in seawater upon contact with seawater. We focused on the possibility that membrane strength could be improved by containing a component that generates insoluble salts. As a result of examining various ingredients capable of forming insoluble salts, we found that sunscreen cosmetics contain one or more monovalent alkali metal salts selected from the group consisting of alginic acid, acylmethyltaurine, and acylglutamic acid. It has been found that by doing so, the membrane strength is increased and a particularly excellent effect of suppressing elution of metal ions can be obtained.

That is, the present invention provides the following.
(A) Hydrophobized surface-treated zinc oxide and/or titanium oxide with an average particle diameter of less than 100 nm 10 to 40% by mass
(B) A sunscreen cosmetic containing one or more monovalent alkali metal salts selected from the group consisting of alginic acid, acylmethyltaurine, and acylglutamic acid, and substantially free of organic ultraviolet absorbers. be.
The component (B) is one or more monovalent alkali metal salts selected from the group consisting of alginic acid, stearoylmethyltaurine, myristoylmethyltaurine, lauroylmethyltaurine, stearoylglutamic acid, myristoylglutamic acid, and lauroylglutamic acid. There may be.
The component (B) may be one or more monovalent alkali metal salts selected from the group consisting of alginic acid, stearoylmethyltaurine, and lauroylglutamic acid.
The mass ratio (A)/(B) of the component (A) to the component (B) may be 10 to 3,000.
The content of the component (B) may be 0.01 to 1% by mass in the sunscreen cosmetic.
After applying ^2g of sunscreen cosmetics to an area of 1000cm2 on a glass plate and drying it, the concentration of zinc ions and/or titanium ions in the seawater after being immersed in 50L of seawater for one week was 0. It may be less than .1 ppm.
The following method for suppressing elution of metal ions from a composition containing component (A) using component (B) may also be used.
(A) Hydrophobized zinc oxide and/or titanium oxide having an average particle diameter of less than 100 nm; (B) One or more selected from the group consisting of alginic acid, acylmethyltaurine, and acylglutamic acid. The method for suppressing elution of metal ions may be such that the composition is a sunscreen cosmetic.
The following component (B) may be used as an elution inhibitor for metal ions from a composition containing component (A).
(A) Hydrophobized surface-treated zinc oxide and/or titanium oxide having an average particle diameter of less than 100 nm; (B) One or more selected from the group consisting of alginic acid, acylmethyltaurine, and acylglutamic acid. monovalent alkali metal salts

Furthermore, the present technology can additionally employ the following configuration.
The method may also be a method of suppressing the elution of zinc ions and/or titanium ions into seawater using the component (B). A method for suppressing the elution of zinc ions and/or titanium ions by forming an insoluble salt using the component (B) may also be used. There may also be a method of suppressing elution of zinc ions and/or titanium ions by contact with seawater using the component (B). A method for suppressing elution of zinc ions and/or titanium ions by improving membrane strength using the component (B) may also be used.
It may also be an elution inhibitor for zinc ions and/or titanium ions used in sunscreen cosmetics that do not substantially contain organic ultraviolet absorbers.
It may be an agent for suppressing the elution of zinc ions and/or titanium ions into seawater using the component (B).
It may be an elution inhibitor of zinc ions and/or titanium ions by forming an insoluble salt using the component (B). It may also be an agent that suppresses elution of zinc ions and/or titanium ions upon contact with seawater, using the component (B). It may also be a zinc ion and/or titanium ion elution inhibitor that uses the component (B) to improve membrane strength.

Although the sunscreen cosmetic of the present invention does not substantially contain a UV absorber, it exhibits a high UV protection effect and is excellent in that the applied film does not feel burdensome. Furthermore, it is excellent in seawater resistance and metal ion elution suppressing effect.
In addition, according to the present invention, the elution of metal ions is suppressed and excellent UV protection effects can be achieved without containing film-forming agents, solid oil agents, surfactants, etc., so that the coating film does not feel burdened. It is possible to obtain a sunscreen cosmetic with no stickiness and good spreadability.

Hereinafter, preferred embodiments for carrying out the present invention will be described. Note that the embodiment described below is an example of a typical embodiment of the present invention, and the scope of the present invention should not be interpreted narrowly thereby. Further, in this specification, percentages are expressed by mass unless otherwise specified. In this specification, the range "X to Y" includes X and Y, and means "more than or equal to X and less than or equal to Y."

1. First embodiment according to the present invention

The first embodiment is a group consisting of component (A) hydrophobized surface-treated zinc oxide and/or titanium oxide having an average particle diameter of less than 100 nm, and component (B) alginic acid, acylmethyltaurine, and acylglutamic acid. It is possible to provide a sunscreen cosmetic containing one or more monovalent alkali metal salts selected from the following, and substantially free of organic ultraviolet absorbers.

(Component (A): hydrophobized surface-treated zinc oxide and/or titanium oxide with an average particle diameter of less than 100 nm)

The component (A) used in the present invention, which has an average particle diameter of less than 100 nm, has a hydrophobic surface treated zinc oxide and/or titanium oxide, which absorbs, scatters, and absorbs a wide range of ultraviolet light from UVB to UBA (290 to 400 nm). A metal oxide that blocks ultraviolet rays by reflecting, quenching, etc.

It is preferable to use finely divided zinc oxide and titanium oxide as component (A), and the average particle diameter is less than 100 nm, preferably 80 nm or less, more preferably 50 nm or less, and even more preferably 35 nm or less. . In addition, the lower limit of the average particle size of zinc oxide in sunscreen cosmetics is not particularly limited because the smaller the particle size, the better the transparency etc., but it is usually preferably 1 nm or more, preferably 3 nm or more, and 5 nm or more. The above is more preferable. Further, the average particle diameter of zinc oxide is preferably 1 nm or more and less than 100 nm, more preferably 3 nm or more and less than 100 nm, even more preferably 5 to 50 nm, and even more preferably 5 to 35 nm. By setting it as these ranges, effects such as ultraviolet protection effect and transparency are more excellent, so it is more preferable. In the present invention, the average particle diameter can be measured as an average particle by an image analysis method of a transmission electron microscope image.
About 10 mg of the sample is thoroughly dispersed with 1-propanol on a glass slide to obtain a dispersion. Stretch the dispersion to obtain a thin film sample. A thin film of the sample is placed on a mesh for transmission electron microscopy (TEM) measurement equipped with a support film. The mesh (dried coating film) is set in a transmission electron microscope (S-4800, Hitachi High-Technologies Corporation) and observed to obtain an image of the dry coating film showing individual particles. The image of the dried coating film surface is subjected to image processing using an image analysis type particle size distribution measuring device (Mac-View, manufactured by Mountech Co., Ltd.) with 1000 particles each, and the particle diameter is measured.
Thereby, the average particle diameter D50 of the sample (powder) can be obtained by image analysis of a transmission electron microscope (TEM) image.

The shape of the zinc oxide and titanium oxide of the component (A) is not particularly limited as long as it is commonly used in cosmetics, quasi-drugs, pharmaceuticals, etc. For example, it may be granular, spherical, spindle-shaped, dendritic, balloon-shaped, etc. In the present invention, granular, spherical, or spindle-shaped are preferable. Note that these average particle diameters are measured on the long side. Commercially available products of these zinc oxides include, for example, the FINEX series (manufactured by Sakai Chemical Co., Ltd.) and the MZ series (manufactured by Teika Corporation). In addition, commercially available titanium oxide products include, for example, the TTO-55 series, TTO-51 series (manufactured by Ishihara Sangyo Co., Ltd.), the JR series, the JA series, the MT series (manufactured by Teika), and the STR series (manufactured by Sakai Chemical Industry Co., Ltd.). ) etc.

The zinc oxide and titanium oxide are subjected to surface treatment. Surface treatment is preferred because seawater resistance and the like are improved and the effects of the present application are more excellent. The hydrophobic treatment agent is not particularly limited as long as it is commonly used in cosmetics, quasi-drugs, pharmaceuticals, etc., but examples include silicone treatment agents, fluorine treatment agents, organic titanate treatment agents, Examples include fatty acids, lecithin, and acylated amino acids. Among these, one or more selected from silicone processing agents, organic titanate processing agents, fatty acids, and acylated amino acids should be used from the viewpoint of UV protection effects, seawater resistance, and no burden on the coating film. is preferred, and more preferably one or more selected from silicone processing agents and fatty acids.

Examples of the silicone treatment agent include chain silicones such as low polymerization degree dimethylpolysiloxane, high polymerization degree dimethylpolysiloxane, and methylphenylpolysiloxane; modified silicones such as amino-modified silicone, alkyl-modified silicone, and alkoxy-modified silicone; Examples include silicone resins such as trimethylsiloxysilicic acid and acrylic-silicone graft copolymers, silicone rubbers, partially or fully crosslinked organopolysiloxanes, silylation agents, silane coupling agents, etc., and the group consisting of these One or more types selected from can be used. Among these, it is preferable to use silane coupling agents.

Among the silane coupling agents, although not particularly limited, trialkoxyalkylsilanes are preferred. Trialkoxyalkylsilane is a compound in which three alkoxy groups and one alkyl group are bonded to a silicon atom, and the alkoxy group chemically modifies the powder surface by reacting with hydroxyl groups, etc. on the powder surface. It is a compound. The alkoxy group in the trialkoxyalkylsilane is preferably an alkoxy group having 1 to 3 carbon atoms such as methoxy, ethoxy or propoxy. Further, the alkyl group in the trialkoxyalkylsilane is preferably an alkyl group having 6 to 18 carbon atoms, such as hexyl group, octyl group, decyl group, or octadecyl group. Such trialkoxyalkylsilanes include, for example, trimethoxyhexylsilane, trimethoxyoctylsilane, trimethoxydecylsilane, trimethoxyoctadecylsilane, triethoxyhexylsilane, triethoxyoctylsilane, triethoxydecylsilane, triethoxyoctadecylsilane. etc. Among these, one or more selected from the group consisting of trimethoxyoctylsilane and triethoxyoctylsilane is more preferable.

Examples of the fatty acid include fatty acids and metal salts thereof, among which fatty acids having 12 to 18 carbon atoms are preferred, and stearic acid is more preferred. Further, examples of the salts include calcium, magnesium, zinc, aluminum, etc., and aluminum salts are more preferred.

Examples of the organic titanate treatment agent include long-chain carboxylic acid type, pyrophosphoric acid type, phosphorous acid type, amino acid type alkyl titanates, etc., and alkyl titanates having an alkyl group having 8 to 24 carbon atoms are preferred. Specifically, the alkyl titanate includes long-chain carboxylic acid type alkyl titanate such as isopropyltriisostearoyltitanate, isopropyltrioctanoyltitanate, isopropyldimethacrylylisostearoyltitanate, isopropylisostearoyldiacryltitanate, and diisostearoylethylene. Examples of pyrophosphate-type alkyl titanates include tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, and tetra(2,2-diallyloxymethyl-1-butyl) bis( Examples of phosphorous alkyl titanates include isopropyl tri(dioctyl pyrophosphate) titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate, and the like. Examples of the amino acid type alkyl titanate include isopropyl tri(N-amidoethyl aminoethyl) titanate. In the present invention, among these alkyl titanates, long-chain carboxylic acid type alkyl titanates are preferred, and isopropyl triisostearoyl titanate is more preferred.

Examples of the fluorine treatment agent include fluorine compounds such as fluorine-modified silicone, perfluoroalkyl phosphoric acid and its salt, perfluoropolyether, fluoroalkoxysilane, perfluoropolyether alkyl phosphoric acid and its salt, and perfluoroalkyl silane. , one or more of these can be used.

Lecithin is a lipid having a phosphate group, regardless of its animal origin, vegetable origin, hydrogenated or non-hydrogenated, PC (phosphatidylcholine) purity, etc. Specifically, commercially available products such as Ajinomoto Lecithin (manufactured by Ajinomoto Co., Ltd.), which is a soybean phospholipid, and Lecinol S-10 and S-10E (both manufactured by Nikko Chemicals, Inc.), which are hydrogenated soybean lecithins, can be used as they are. . Examples of phospholipid (lecithin) derivatives include copolymers of phospholipids and acrylic polymers.

Acylated amino acids are amino acids in which the hydrogen atom of the amino group is replaced with an acyl group, and the acyl group is a saturated or unsaturated linear or cyclic amino acid having 1 to 20 carbon atoms. Examples include N-acetylglutamic acid, N-lauroylglutamic acid, N-myristylalanine, NN-oleylthreonine, N-cinnamoylglycine, N-nicotinoylglutamic acid, and the like. Further, examples of the salt include sodium salt, potassium salt, and triethanolamine salt.

There are no particular limitations on the method for hydrophobizing the component (A), and it can be produced by a commonly known method. For example, a hydrophobizing agent and powder particles to be treated are added to a solvent, stirred in a ball mill, etc., dried as necessary, washed with water and filtered repeatedly to remove impurities, and then dried. By pulverizing the powder, the desired hydrophobized powder can be obtained. Furthermore, the surface can be treated with several types of compounds as surface treatment agents at the same time, or the surface can be treated with one of the compounds in advance, and then the surface can be further treated with other compounds.

There is no particular limitation on the mass of the hydrophobizing agent in hydrophobized zinc oxide (hereinafter simply referred to as "zinc oxide of component (A)") in which component (A) has an average particle diameter of less than 100 nm. However, from the viewpoint of UV protection effect and seawater resistance, the lower limit is preferably 0.1% by mass or more (hereinafter sometimes simply abbreviated as "%") based on the powder mass before treatment, and 1% or more. is more preferable, and 3% or more is even more preferable. Further, as an upper limit, it is preferably 30% or less, more preferably 20% or less, and even more preferably 15% or less, based on the powder mass before treatment, from the viewpoint of not burdening the coating film.

There is no particular limitation on the mass of the hydrophobizing agent in hydrophobized titanium oxide (hereinafter simply referred to as "component (A) titanium oxide") in which the average particle size of component (A) is less than 100 nm. However, the lower limit is preferably 10% or more, more preferably 15% or more, based on the powder mass before treatment, from the viewpoint of ultraviolet protection effect and seawater resistance. Even more preferably 20% or more. Further, as an upper limit, it is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less based on the powder mass before treatment, from the viewpoint of not feeling burdened by the coating film.

In the present invention, the lower limit of the content of component (A) in the sunscreen cosmetic is 10% or more, preferably 15% or more. The upper limit is 40% or less, preferably 35% or less, and more preferably 30% or less. Further, the content of component (A) in the sunscreen cosmetic is 10 to 40%, preferably 15 to 35%, and more preferably 15 to 30%. This range is more preferable because it provides better ultraviolet protection, less burden on the coating film, and more excellent effect of suppressing elution of metal ions.

In the present invention, the combination of zinc oxide and titanium oxide as component (A) is not essential, but when used together, the content of zinc oxide is not particularly limited, but the lower limit It is preferably 8% or more, more preferably 10% or more, and even more preferably 15% or more. The upper limit is preferably 30% or less, more preferably 25% or less. Further, the content of zinc oxide when used in combination is preferably 8 to 30%, more preferably 10 to 30%, and even more preferably 15 to 25%. This range is more preferable because it provides better ultraviolet protection effects and less burdensome feeling on the coating film. The content of titanium oxide when used in combination with component (A) is not particularly limited, but the lower limit of the content of titanium oxide in the sunscreen cosmetic is preferably 2% or more, more preferably 5% or more. The upper limit is preferably 20% or less, more preferably 15% or less. Further, the content of titanium oxide when used in combination is preferably 2 to 20%, more preferably 2 to 15%, and even more preferably 5 to 15%. This range is more preferable because it provides better ultraviolet protection effects and less burdensome feeling on the coating film.

(Component (B): one or more monovalent alkali metal salts selected from the group consisting of alginic acid, acylmethyltaurine, and acylglutamic acid)

Component (B) used in the present invention: One or more monovalent alkali metal salts selected from the group consisting of alginic acid, acylmethyltaurine, and acylglutamic acid (hereinafter simply referred to as "component (B)") ) is not particularly limited as long as it is commonly used in cosmetics, quasi-drugs, pharmaceuticals, etc.

The acyl in the acylmethyltaurine and acylglutamic acid of component (B) is derived from a long chain fatty acid, and the number of carbon atoms in this fatty acid is not particularly limited, but it generally has 8 to 22 carbon atoms. 12 to 18, more preferably 12 to 18. Further, as the fatty acid, linear or branched fatty acids derived from saturated or unsaturated fatty acids can be used. More specifically, examples of fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, isostearic acid, palmitic acid, oleic acid, linoleic acid, behenic acid, coconut oil fatty acid, palm fatty acid, etc. It will be done. One type of these may be used, or two or more types selected from the above group may be used in combination. Among these, at least one selected from the group consisting of stearic acid, myristic acid, and lauric acid is more preferable, and by using these components, it reacts with divalent metal ions in seawater to produce an insoluble salt. It is more preferable because the film strength during the process is improved and the effects of the present invention such as seawater resistance and metal ion elution suppressing effect are better.

The alkali metal in component (B) is one of the Group 1 elements of the periodic table excluding hydrogen, such as sodium and potassium. Moreover, the alkali metal salt of component (B) may be used as a salt in advance, or may be a salt generated by a neutralization reaction during production. To give a more specific example, examples of the alginate include sodium alginate, potassium alginate, etc., and sodium alginate is more preferred. Examples of the acylmethyltaurate salt include sodium N-stearoyl-N-methyltaurate, sodium N-myristoyl-N-methyltaurate, sodium coconut oil fatty acid methyltauride, sodium laurylmethyltauride, and more preferably N- It is sodium stearoyl-N-methyltaurate, and the acylglutamates include potassium N-lauroyl-L-glutamate, potassium N-myristoyl-L-glutamate, N-stearoyl-L-glutamate arginine salt, and N-stearoyl-L- Examples include potassium glutamate, sodium N-stearoyl-L-glutamate, and sodium N-lauroyl-L-glutamate is more preferred. These may be used alone or in combination of two or more.

In the present invention, the content of component (B) in the sunscreen cosmetic is preferably 0.01% or more, and more preferably 0.05% or more as a lower limit, although it is not particularly limited. The upper limit is preferably 1% or less, more preferably 0.5% or less, even more preferably 0.2% or less. Further, the content of component (B) is preferably 0.01 to 1%, more preferably 0.05 to 1%, even more preferably 0.05 to 0.5%, and even more preferably 0.05 to 0.2%. is even more preferred. This range is more preferable because seawater resistance, the coating film does not feel burdensome, and the effect of suppressing elution of metal ions is more excellent. Note that the content of the component (B) is the content as a salt.

The component (B) has an effect of suppressing the elution of zinc oxide and/or titanium oxide, an effect of suppressing the elution of zinc oxide and/or titanium oxide into seawater, and an effect of suppressing the elution of zinc oxide and/or titanium oxide by forming insoluble salts. It has an inhibitory effect, an effect to suppress elution of zinc oxide and/or titanium oxide due to contact with seawater, an effect to suppress elution of zinc oxide and/or titanium oxide by improving film strength, and the like.

Although the present invention can be obtained by appropriately containing component (A) and component (B), seawater resistance and It is preferable because the coating film does not feel burdensome and furthermore, a high effect can be expected due to the effect of suppressing elution of metal ions. Such a content mass ratio (A)/(B) is not particularly limited, but as a lower limit, it is preferably 10 or more, more preferably 30 or more, even more preferably 100 or more, and even more than 100. More preferably, 150 or more is particularly preferable. The upper limit is preferably 3000 or less, more preferably 1000 or less, even more preferably 500 or less, even more preferably 400 or less, particularly preferably less than 400, and more preferably 300 or less. The content mass ratio (A)/(B) is preferably 10 to 3000, more preferably 30 to 3000, even more preferably 100 to 1000, even more preferably more than 100 and not more than 500, particularly preferably 150 to 400. , more preferably 150 or more and less than 400, and more preferably 150 to 300.

In the present invention, by specifying the mass ratio of zinc oxide in component (A) and component (B), it is possible to improve seawater resistance, reduce the burden on the coating film, and further improve the effect of suppressing elution of metal ions. This is preferable because it can be expected. Such a content mass ratio (zinc oxide of component (A))/(B) is not particularly limited, but the lower limit is preferably 20 or more, more preferably 50 or more, and even more preferably 80 or more. It is even more preferable that it exceeds 80, and particularly preferably 100 or more. The upper limit is preferably 2000 or less, more preferably 1000 or less, even more preferably 500 or less, even more preferably 250 or less, particularly preferably less than 250, and more preferably 200 or less. Further, the content mass ratio (zinc oxide of component (A))/(B) is preferably 20 to 2000, more preferably 50 to 1000, even more preferably 80 to 500, and even more preferably more than 80 and not more than 250. It is particularly preferably from 100 to 250, more preferably from 100 to less than 250, and even more preferably from 100 to 200. In addition, in the present invention, by specifying the mass ratio of titanium oxide as the component (A) and the component (B), it is possible to improve the seawater resistance, the lack of burden on the coating film, and the effect of suppressing elution of metal ions. This is preferable because higher effects can be expected. Such content mass ratio (titanium oxide of component (A))/(B) is not particularly limited, but as a lower limit, it is preferably 10 or more, more preferably 20 or more, and even more than 20. It is preferably 40 or more, even more preferably 60 or more. The upper limit is preferably 1000 or less, more preferably 500 or less, even more preferably 300 or less, even more preferably 150 or less, particularly preferably less than 150, and more preferably 100 or less. In addition, the content mass ratio (titanium oxide of component (A))/(B) is preferably 10 to 1000, more preferably 20 to 500, more preferably more than 20 and even more preferably 300, even more preferably 40 to 150, and even more preferably 60 to 1000. -150 is particularly preferable, 60 or more but less than 150 is more preferable, and 60-100 is more preferable.

The cosmetic containing the component (A) and the component (B) has an effect of suppressing the elution of zinc oxide and/or titanium oxide, an effect of suppressing the elution of zinc oxide and/or titanium oxide into seawater, and an insoluble salt. It has the effect of suppressing the elution of zinc oxide and/or titanium oxide by formation, the effect of suppressing the elution of zinc oxide and/or titanium oxide by contact with seawater, the effect of suppressing the elution of zinc oxide and/or titanium oxide by improving the film strength, etc. .

Furthermore, the present invention preferably does not substantially contain an organic ultraviolet absorber, and by substantially not containing an organic ultraviolet absorber, a sunscreen cosmetic that satisfies consumer preference can be obtained. In the present invention, the organic ultraviolet absorber includes any substance used in ordinary cosmetics, including water-soluble organic ultraviolet absorbers and oil-soluble organic ultraviolet absorbers. Specifically, for example, 2-hydroxy-4-methoxybenzophenone, 2,4,6-trianilino-p-(carbo-2'-ethylhexyl-1'-oxy)-1,3,5-triazine, salicylic acid-2 -Ethylhexyl, ethyl paradihydroxypropylbenzoate, 2ethylhexyl paramethoxycinnamate, 4-tert-4'-methoxydibenzoylmethane, 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester, dimethoxy Benzylidene dioxoimidazolidine propionate 2-ethylhexyl, 2,2'-methylenebis[6-(2H-benzotriazol-2yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2, 4-bis[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, dimethicodiethylbenzalmalonate, 2- Examples include hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt. Here, in the present invention, "substantially not contained" means 1% or less in the sunscreen cosmetic, preferably 0.5% or less, more preferably 0.1% or less, 0% (contained) It is more preferable not to do so.

It is more preferable to use the sunscreen cosmetic composition of the present invention in an environment where it can come into contact with water containing salt. This environment is preferable because the effects of the present invention can be easily exhibited. Environments that can come into contact with salty water include, but are not particularly limited to, sandy beaches, beaches, seashores, lakeshores, riversides, banks, beaches, swimming areas such as lakeshores, etc. It is possible to maintain the UV protection effect even in environments where it may come into contact with water containing salt. Therefore, the sunscreen cosmetic of the first embodiment may be a cosmetic for use in an environment where it may come into contact with water containing salt.

In addition, as another aspect of the first embodiment, a product kit comprising a product containing a composition containing the component (A) and a product containing a composition containing the component (B); The component (A) and the component (B) may be used in combination by using a product containing (A) and a product containing the component (B) simultaneously or separately. Further, the sunscreen cosmetic of the first embodiment may be prepared by simultaneously or separately mixing the component (A) and the component (B) contained in the product kit, and such preparation You may also provide a product kit that allows you to: For example, a practitioner or an end user may mix the component (A) and the component (B) before use and apply this mixture to the skin, or ) may be applied to the skin simultaneously or separately, and the composition of the first embodiment may be prepared by mixing these on the skin.

Further, as another aspect of the first embodiment, the above-mentioned elution suppression of zinc oxide and/or titanium oxide, suppression of elution of zinc oxide and/or titanium oxide into seawater, and zinc oxide and titanium oxide by formation of insoluble salts are possible. The above-mentioned components ( Agents containing A) and the component (B) or their uses can be provided, and these can be contained or blended into various agents or compositions.

In addition, as another aspect of the first embodiment, the sunscreen cosmetic of the first embodiment provides a method for suppressing elution of zinc oxide and/or titanium oxide, and a method for suppressing elution of zinc oxide and/or titanium oxide into seawater. Method for suppressing elution of zinc oxide and/or titanium oxide by forming insoluble salts, method for suppressing elution of zinc oxide and/or titanium oxide by contact with seawater, method for suppressing elution of zinc oxide and/or titanium oxide by improving film strength It can be used for elution suppression methods, etc. Further, a method for suppressing elution of zinc oxide and/or titanium oxide using the component (B), a method for suppressing elution of zinc oxide and/or titanium oxide into seawater, and a method for suppressing elution of zinc oxide and/or titanium oxide into seawater, and a method for suppressing elution of zinc oxide and/or titanium oxide by forming an insoluble salt. It can be used for a method of suppressing elution of titanium, a method of suppressing elution of zinc oxide and/or titanium oxide by contact with seawater, a method of suppressing elution of zinc oxide and/or titanium oxide by improving film strength, and the like.

The seawater used in the present invention is not particularly limited, and natural seawater, artificial seawater, a combination of natural seawater and artificial seawater, etc. can be used.

Natural seawater is not particularly limited as long as it is seawater that exists in nature, and includes, for example, surface water and deep ocean water. Deep ocean water is seawater collected from the deep ocean at a depth of 200 m or more, and has excellent properties such as eutrophicity, cleanliness, low water temperature, and water quality stability. Deep ocean water has small fluctuations in water quality and its properties are almost stable throughout the year.

Artificial seawater is seawater prepared by containing a well-balanced combination of trace elements essential for the survival of living things contained in natural seawater, and in the present invention, artificial seawater can be used without particular limitations. . The method for preparing artificial seawater is not particularly limited, but it is preferable to use a commercially available artificial seawater base, and it is more preferable to use artificial seawater with a specific gravity value of 1.020 to 1.024. preferable. Commercially available products include, for example, artificial seawater manufactured by GEX.

In addition to the above-mentioned essential ingredients, the agent or sunscreen cosmetic containing the component (A) and the component (B) of the present invention may contain ingredients used in ordinary cosmetics that do not impair the effects of the present invention. It can be contained as necessary in a quantitative and qualitative range. For example, oil-based ingredients, surfactants other than component (B), powders other than component (A), water-soluble polymers other than component (B), aqueous components such as humectants, antioxidants, beauty ingredients, preservatives. It can contain agents, fragrances, refreshing agents, etc.

Examples of oily components include hydrocarbons, oils and fats, hydrogenated oils, and ester oils, regardless of their properties, such as solid oils, semi-solid oils, liquid oils, and volatile oils originating from animal oils, vegetable oils, synthetic oils, etc. Examples include fatty acids, higher alcohols, silicone oils, fluorine oils, and lanolin derivatives. Specifically, hydrocarbons such as liquid paraffin, squalane, polyisobutylene, and polybutene, oils and fats such as olive oil, castor oil, mink oil, and macadamian nut oil, jojoba oil, cetyl 2-ethylhexanoate, and tri2- Glyceryl ethylhexanoate, diglyceryl isostearate, diglyceryl diisostearate, diglyceryl triisostearate, diglyceryl tetraisostearate, isotridecyl isononanoate, isostearyl lactate, octyldodecyl lactate, oleyl lactate, stearyl lactate, diisostearyl malate , isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, pentaerythritol rosin ester, neopentyl glycol dioctoate, neopentyl glycol dioctoate, cholesterol fatty acid ester, phytosterol fatty acid ester, stearic acid, lauric acid , fatty acids such as myristic acid, behenic acid, isostearic acid, and oleic acid, higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, and behenyl alcohol, highly polymerized methylphenyl polysiloxane, crosslinked type Methylpolysiloxane, polyoxy-modified organopolysiloxane, crosslinked polyether-modified methylpolysiloxane, methacrylic-modified polysiloxane, stearyl-modified methylpolysiloxane, oleyl-modified methylpolysiloxane, behenyl-modified methylpolysiloxane, polyvinylpyrrolidone-modified methylpolysiloxane, high Silicones such as polymerized dimethylpolysiloxane, polyoxyalkylene/alkylmethylpolysiloxane/methylpolysiloxane copolymer, alkoxy-modified polysiloxane, fluorine-modified polysiloxane, perfluorodecane, perfluorooctane, perfluoropolyether, etc. Examples include fluorinated oils, lanolin, lanolin acetate, isopropyl lanolin fatty acid, and lanolin derivatives such as lanolin alcohol, and one or more of these can be used. Examples include ester oil, silicone oil, natural oil, hydrocarbon oil, higher fatty acid, and higher alcohol.
In the case of containing an oily component in the present invention, the content of the oily component is not particularly limited, but is preferably 10 to 80%, more preferably 15 to 75%, and 20 to 75%. 70% is more preferred.

The surfactant is not particularly limited as long as it is a surfactant commonly used in cosmetics, such as nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. can be used. For example, glycerol fatty acid ester and its alkylene glycol adduct, polyglycerol fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol adduct, polyoxyethylene hydrogenated castor oil, polyoxyalkylene alkyl co-modified organopolysiloxane, Examples include polyether-modified organopolysiloxane and lecithin.

The aqueous component may be any component that is soluble in water, and in addition to water, examples include alcohols such as ethyl alcohol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, tripropylene glycol, Examples include glycols such as polyethylene glycol, glycerols such as glycerin, diglycerin, and polyglycerin, and plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender, and rose.

The sunscreen cosmetic of the present invention can be produced by a commonly known method, and any production equipment may be used as long as it is a dispersion/emulsification equipment such as a general dispersion machine. For example, it can be produced by uniformly mixing a dispersion of component (A) in a three-roll mill with a liquid oil, and then adding and mixing an aqueous fraction containing component (B).

The dosage form of the sunscreen cosmetic of the present invention is not particularly limited. Examples include oil-based, water-in-oil type, oil-in-water type, etc. Among them, water-in-oil type is preferable because the effects of the present invention are more suitably exhibited.

The form of the cosmetic sunscreen of the present invention is not particularly limited, and examples thereof include liquid, emulsion, cream, gel, solid, aerosol mist, aerosol spray, and the like. Applications include sunscreen, daytime serums, skin care cosmetics such as body cream, foundation, makeup base, face color, control color, concealer, BB cream, CC cream, lip balm, eye shadow, etc. Examples include makeup cosmetics, hair mist, out-of-bath hair cosmetics such as hair essence, and the like. Particularly suitable for obtaining the effects of the present invention are skin care cosmetics such as sunscreens and daytime serums, and makeup cosmetics such as foundations, makeup bases, face colors, BB creams, and CC creams.

2. Second embodiment according to the present invention

In the second embodiment, the component (A) and the component (B), or a combination thereof or a mixture thereof, the sunscreen cosmetic of the first embodiment, etc. are used on the skin, and zinc oxide and the like after use are applied to the skin. / or a method for suppressing the elution of titanium oxide, a method for suppressing the elution of zinc oxide and/or titanium oxide into seawater, a method for suppressing the elution of zinc oxide and/or titanium oxide by forming insoluble salts, a method for suppressing the elution of zinc oxide and/or titanium oxide by contact with seawater, A method for suppressing elution of titanium oxide, a method for suppressing elution of zinc oxide and/or titanium oxide by improving film strength, etc. can be provided.
The use is not particularly limited, but it is preferable to apply, rub, massage, spray, etc. on the skin. The application site on the skin is not particularly limited as long as it is the skin, but one or more types selected from the whole body, scalp, face, arms, legs, hands, etc. are suitable. Further, the user may be a professional practitioner such as a masseuse, esthetician, or beautician, or may be a general user or an end user.
The amount of the sunscreen cosmetic to be used or applied to the subject is not particularly limited, but is preferably 1 to 10 mg/cm ² , more preferably 1 to 5 mg/cm ² , and 1 to 3 mg/cm ² . More preferably, 2 mg/cm ² is particularly preferred.

In the description of the method of the second embodiment, the component (A), the component, which overlaps with the explanation of the above "1. First embodiment according to the present invention" and the following "3. Third embodiment according to the present invention" (B), each content, each content mass ratio, manufacturing method, each structure, each method, each term, etc. will be omitted as appropriate, but the above "1. First embodiment according to the present invention" and the following " 3. The explanation of "Third Embodiment of the Present Invention" also applies to the second embodiment, and can be adopted as appropriate.

3. Third embodiment according to the present invention

The third embodiment provides an elution inhibitor for zinc oxide and/or titanium oxide, which is used for blending in a sunscreen composition or sunscreen cosmetic, and an elution inhibitor for zinc oxide and/or titanium oxide in seawater. agent, elution inhibitor of zinc oxide and/or titanium oxide due to insoluble salt formation, elution inhibitor of zinc oxide and/or titanium oxide due to contact with seawater, elution inhibitor of zinc oxide and/or titanium oxide due to improvement of film strength. An inhibitor can be provided. In addition, an elution inhibitor of zinc oxide and/or titanium oxide using the component (B), an elution inhibitor of zinc oxide and/or titanium oxide into seawater, and a zinc oxide and/or oxidation agent by forming an insoluble salt. It can be used as a titanium elution inhibitor, a zinc oxide and/or titanium oxide elution inhibitor by contact with seawater, and a zinc oxide and/or titanium oxide elution inhibitor by improving film strength. The agent of the third embodiment is more preferably added in an amount of 10 to 50% in the sunscreen composition or sunscreen cosmetic, and the total amount of the component (A) and the component (B) is It is more preferable to add it to a sunscreen composition or sunscreen cosmetic in an amount of 10 to 50%.

In the description of the agent of the third embodiment, component (A), component ( B), descriptions of each content, each content mass ratio, manufacturing method, each structure, each method, each term, etc. will be omitted as appropriate, but the descriptions of "1. First embodiment according to the present invention" and "2. The description of the second embodiment of the present invention also applies to the third embodiment, and can be adopted as appropriate. The content and the content mass ratio may also be used as the usage amount and the usage mass ratio. Furthermore, a composition containing the agent of the third embodiment, preferably the composition, can provide a cosmetic or an external skin preparation. The agent of the third embodiment is contained in the content and mass ratio of component (A) and component (B) in the composition described in "1. First embodiment according to the present invention". Or it is suitable to mix.

The present technology will be described in more detail below based on examples and the like. Note that the embodiments and the like described below are examples of typical embodiments of the present technology, and the scope of the present technology should not be interpreted narrowly thereby.

Examples 1 to 10 and Comparative Examples 1 to 10: Water-in-oil sunscreen cream Water-in-oil sunscreen creams having the compositions shown in Tables 1 and 2 were prepared by the following manufacturing method, and "A. Ultraviolet protection effect" , "B. Seawater resistance,""C. No burden on the coating film," and "D. Effect of suppressing elution of metal ions." The following evaluation methods and criteria were used to evaluate the results. are shown in Tables 1 and 2.

*1: MZX-304OTS (manufactured by Teika) (average particle size 35 nm)
*2: MT-01 (manufactured by Teika) (average particle size 10 nm)
*3: XZ-300F (manufactured by Sakai Chemical Industry Co., Ltd.) (average particle size 300 nm)
*4: OTS-MP1133 (manufactured by Daito Kasei Kogyo Co., Ltd.) (average particle size 250 nm)
*5: MZ-300 (manufactured by Teika) (average particle size 35 nm)
*6: A3189 (manufactured by Teika) (average particle size 15 nm)
*7: Snow Algin M (manufactured by Fuji Chemical Industry Co., Ltd.)
*8: Nikkor SMT (manufactured by Nikko Chemicals)
*9: Amisoft LS-11 (manufactured by Ajinomoto Co.)
*10: SR1000 (manufactured by Momentive Performance Materials)
*11: KP-545 (polymer purity 30%, manufactured by Shin-Etsu Chemical Co., Ltd.)
*12: CITHROL DPHS (manufactured by Croda)
*13: KF-6028P (manufactured by Shin-Etsu Chemical)
*14: God Ball E-90C (manufactured by Suzuki Yushi Kogyo Co., Ltd.)

(Production method)
A: Components (1) to (6) and components (14) to (18) are uniformly dispersed in a three-roll mill.
B: Components (19) to (22) are mixed uniformly at 80°C.
C: Components (7) to (13) and components (23) to (26) are uniformly mixed at 70°C.
D: A and C were added and mixed in this order while stirring B at 25°C to obtain a water-in-oil sunscreen cream.

(Evaluation item)
stomach. UV protection effect b. Seawater resistance c. No feeling of burden from the coating film d. Metal ion elution suppression effect

〔stomach. UV protection effect]
After applying each sample to a PMMA plate (HELIOPLATE HD6, manufactured by Labsphere) with a finger in an amount of 2 mg/cm ² , the samples were left to stand for 20 minutes, and SPF simulation measurements were performed using an SPF analyzer (UV-2000S, manufactured by Labsphere). and measured the SPF simulation value.
Based on the obtained SPF simulation value, the UV protection effect was judged according to the following criteria.

[3-stage judgment criteria]
(Judgment criteria): (Judgment)
SPF simulation value 50 or more: ◎ (Excellent)
SPF simulation value 30 or more, less than 50: ○ (Good)
SPF simulation value less than 30: × (not allowed)

〔B. Seawater resistance]
After applying each sample to a PMMA plate (HELIOPLATE HD6, manufactured by Labsphere) with a finger in an amount of 2 mg/cm ² , the samples were left to stand for 20 minutes, and SPF simulation measurements were performed using an SPF analyzer (UV-2000S, manufactured by Labsphere). and measured the SPF simulation value.
Next, a sea bathing test was conducted. As the seawater, 108 g of artificial seawater base (manufactured by GEX) was dissolved in 3000 g of purified water. The sea bathing conditions were as follows: At a room temperature of 25°C, the coating sample was pasted on the side of a container (diameter 14 cm x height 15 cm) containing 2 L of seawater, and the seawater in the container was stirred at 300 rpm for 5 minutes using a paddle mixer. I went with the conditions. After stirring, the coated sample was taken out of the container and left to dry for 20 minutes under conditions of 25° C. and 60% humidity, and then the SPF simulation value after sea bathing was measured using the SPF analyzer. Based on the obtained SPF simulation values before and after sea bathing, seawater resistance was judged according to the following criteria.

[4-stage judgment criteria]
(Judgment criteria): (Judgment)
(SPF measurement value after sea bathing) / (SPF measurement value before sea bathing) = 0.9 or more: ◎ (Excellent)
(SPF measurement value after sea bathing) / (SPF measurement value before sea bathing) = 0.7 or more, less than 0.9: ○ (Good)
(SPF measurement value after sea bathing) / (SPF measurement value before sea bathing) = 0.5 or more, less than 0.7: △ (slightly unacceptable)
(SPF measurement value after sea bathing) / (SPF measurement value before sea bathing) = less than 0.5: × (impossible)

[c. No feeling of burden from the coating film]
A panel of 10 cosmetics experts was selected, consisting of women in their 20s to 40s who have received training in sensory evaluation and are capable of evaluating based on certain standards. A cosmetics expert panel applied 0.5 g of each sample to the skin at a concentration of 2 mg/cm ² , and after drying, evaluated the lack of burden on the applied film using the following 5-level absolute evaluation scale. The average value was calculated from the total scores of all the panelists, and the results were judged according to the following 4-level criteria.

[Absolute evaluation criteria]
(Rating) : (Evaluation)
4 points: I don't feel a burden 3 points: I hardly feel a burden 2 points: I feel a burden 1 point: I feel a great burden

[4-stage judgment criteria]
(Average score): (Judgment)
3.2 points or more: ◎ (excellent)
2.8 points or more, less than 3.2 points: ○ (Good)
1.6 points or more, less than 2.8 points: △ (slightly poor)
Less than 1.6 points: × (defective)

[d. Metal ion elution suppression effect]
Regarding the effect of suppressing elution of metal ions, 100 mg of each sample was applied uniformly with a finger to an area of 10 cm wide and 5 cm long on a glass plate (20 cm wide, 10 cm long, and 0.5 cm thick), and then left to stand for 12 hours. The sample was used as a coating sample. The applied sample was pasted on the side of a glass water tank (capacity 68 L, width 65 cm x length 30 cm x height 35 cm) containing 50 L of seawater (1800 g of artificial seawater base (GEX company system) dissolved in 50 kg of purified water). The seawater in the container was stirred at 50 rpm for one week using a paddle mixer. 20 mL of the stirred seawater was taken and centrifuged at 50,000 rpm for 30 minutes using an ultracentrifuge (CS100FNX: manufactured by Eppendorf Hymac Technologies, Inc.) to precipitate insoluble matter. 5 mL of the supernatant after centrifugation was collected, and zinc ions and titanium ions were quantified using ICP-OES (Optima 5300DV, manufactured by PerkinElmer). The metal ion concentration (total of zinc ion and titanium ion concentrations) in seawater was calculated based on the obtained quantitative value, and the effect of suppressing elution of metal ions was judged based on the following criteria. The following criteria are based on the experiment in Reference 1, based on a zinc ion concentration of 0.1 ppm in seawater, which had a significant negative effect on the growth of Stylophora pistillata, a type of hard coral. A concentration sufficiently lower than 0.05 ppm is preferred, and a concentration of less than 0.01 ppm is even more preferred.

[4-stage judgment criteria]
(Evaluation) : (Judgment)
Metal ion concentration in seawater = less than 0.01 ppm: ◎ (Excellent)
Metal ion concentration in seawater = 0.01 ppm or more and less than 0.05 ppm: ○ (Good)
Metal ion concentration in seawater = 0.05 ppm or more and less than 0.1 ppm: △ (slightly impossible)
Metal ion concentration in seawater = 0.1 ppm or more: × (not allowed)

As is clear from Tables 1 and 2, the water-in-oil sunscreen creams of Examples 1 to 10 of the present invention have "ultraviolet protection effect," "seawater resistance," "no burden on the coating film," and " It was excellent in all items regarding the effect of suppressing elution of metal ions.

On the other hand, Comparative Example 1, in which the content of component (A) exceeds 40%, has an excellent UV protection effect, but is not satisfactory in terms of seawater resistance, no feeling of burden on the coating film, and metal ion elution suppression effect. I couldn't get anything. On the other hand, in Comparative Example 2 in which the content of component (A) was less than 10%, a satisfactory ultraviolet protection effect was not obtained. Furthermore, in Comparative Example 3, in which zinc oxide and titanium oxide with an average particle size of 100 nm or more were used instead of component (A), a satisfactory ultraviolet protection effect and no burden on the coating film were obtained. . In addition, in Comparative Example 4, in which unhydrophobicized zinc oxide and titanium oxide with an average particle diameter of less than 100 nm were used instead of component (A), there was no ultraviolet protection effect, no feeling of burden on the coating film, and no metal ion A satisfactory elution suppression effect was not obtained. Comparative Example 5 or 6 using agarose or dextran that has high gelling performance and is easy to form a film instead of component (B), and further neutralized carbomer (in the form of sodium salt) or (acrylates/alkyl acrylate) In Comparative Examples 7 and 8 using crosspolymers, satisfactory seawater resistance and metal ion elution suppression effect were not obtained. Furthermore, in Comparative Examples 9 and 10, in which trimethylsiloxysilicic acid or acrylate silicone, which is commonly used as an oil-soluble film forming agent, was used instead of component (B), seawater resistance, no feeling of burden on the coating film, and metal ion A satisfactory elution suppressing effect was not obtained.

Example 11: Water-in-oil sunscreen lotion (ingredients) (mass%)
(1) Isopropyl titanium triisostearate treated fine particle zinc oxide
(Average particle diameter: 25 nm) *15 18
(2) Dimethicone/hydrogen dimethicone treated fine particle titanium oxide
(Average particle diameter: 10 nm) *16 10
(3) Polyhydroxystearic acid 0.4
(4) Propylene glycol dicaprate 5
(5) Dimethicone (kinematic viscosity 6 mm ² /s at 25°C) 5
(6) Methyl trimethicone 3
(7) Decamethylcyclopentasiloxane 15
(8) Lauryl PEG-9 polydimethylsiloxyethyl dimethicone
*17 1.5
(9) Neopentyl glycol diethylhexanoate 5
(10) Decyltetradecanol 5
(11) Isononyl isononanoate 1
(12) Methylphenylpolysiloxane 3
(13) (PEG-15/lauryl dimethicone) crosspolymer
*18 5
(14) Spherical PMMA *19 3
(15) Fragrance 0.03
(16) Purified water remaining amount (17) Sodium alginate *7 0.1
(18) 1,3-butylene glycol 5
(19) Sodium chloride 0.1
(20) Ethanol 2
(21) Phenoxyethanol 0.05
*15: ITT MZ-500 (manufactured by Daito Kasei Kogyo Co., Ltd.)
*16: MTY-110M3S (manufactured by Teika)
*17: KF-6038 (manufactured by Shin-Etsu Chemical Co., Ltd.)
*18: KSG-310 (polymer purity 30%, manufactured by Shin-Etsu Chemical Co., Ltd.)
*19: Matsumoto Microsphere M311 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.)

(Production method)
A: Components (1) to (6) are uniformly dispersed using a three-roll mill.
B: Components (7) to (15) are mixed uniformly at room temperature.
C: Components (16) to (21) are mixed uniformly at room temperature.
D: A and C were added in this order while stirring B at 25°C to obtain a water-in-oil sunscreen lotion.

The water-in-oil sunscreen lotion of Example 11 was excellent in "ultraviolet light protection effect", "seawater resistance", "no feeling of burden on the coating film", and "effect in suppressing elution of metal ions".

Example 12: Oil-in-water sunscreen cream (ingredients) (mass%)
(1) Dimethicone/octyl silylation treated fine particle zinc oxide
(Average particle diameter: 25 nm) *20 12
(2) Stearic acid treated fine particle titanium oxide
(Average particle diameter: 7 nm) *21 4
(3) Polyhydroxystearic acid 0.3
(4) (Dimethicone/vinyl dimethicone) crosspolymer *22 1
(5) Di(caprylic acid/capric acid) PG 5
(6) Isotridecyl isononanoate 5
(7) Caprylic/capric triglyceride 3
(8) PEG-80 hydrogenated castor oil *23 1
(9) Sorbitan sesquioleate *24 0.2
(10) Cetostearyl alcohol 0.3
(11) Behenyl alcohol 0.3
(12) Glycerin fatty acid ester 0.3
(13) (Na acrylate/Na acryloyldimethyltaurine) copolymer
*25 1
(14) Xanthan gum 0.1
(15) Carbomer *26 0.1
(16) (Acrylates/alkyl acrylate (C10-30)) crosspolymer
*27 0.1
(17) Purified water remaining amount (18) Myristoylmethyltaurate Na *28 0.1
(19) Spherical polymethylsilsesquioxane *29 1
(20) Ethanol 5
(21) 1,3-butylene glycol 5
(22) Water-dispersible zinc oxide *30 8
(23) Phenoxyethanol 0.05
(24) Purified water 5
*20: SALT MZ-500 (manufactured by Miyoshi Kasei Co., Ltd.)
*21: MT-N1 (manufactured by Teika)
*22: KSG-16 (polymer content 25%, manufactured by Shin-Etsu Chemical Co., Ltd.)
*23: HCO-80 (manufactured by Nikko Chemicals)
*24: Rheodor AO-15V (manufactured by Kao Corporation)
*25: SIMULGEL EG (polymer purity 37.5%, manufactured by SEPPIC)
*26: CARBOPOL 980 (manufactured by LUBRIZOL)
*27: CARBOPOL 1382 (manufactured by LUBRIZOL)
*28: Nikkor MMT (manufactured by Nikko Chemicals)
*29: TOSPEARL 3000A (manufactured by LUBRIZOL)
*30: MZX-304OTSW (manufactured by Teika)

(Production method)
A: Components (1) to (5) are uniformly dispersed using a three-roll mill.
B: Mix A and components (6) to (12) uniformly at 80°C.
C: Components (13) to (18) are mixed uniformly at 80°C.
D: Components (19) to (24) are mixed uniformly at room temperature.
E: While stirring C, add B and emulsify at 80°C.
F: After cooling E to 40°C, D was added while stirring to obtain an oil-in-water sunscreen cream.

The oil-in-water sunscreen cream of Example 12 was excellent in "ultraviolet light protection effect," "seawater resistance," "no burdensome feeling on the coating film," and "metal ion elution suppression effect."

Example 13: Oil-based solid sunscreen stick (ingredients) (mass%)
(1) Hydrogen dimethicone/isostearic acid/hydrated silica treated fine particle zinc oxide
(Average particle diameter: 25 nm) *30 15
(2) Silica/aluminum hydroxide treated fine particle titanium oxide
(Average particle diameter: 10 nm) *31 10
(3) (Acrylates/Ethylhexyl acrylate/Dimethicone methacrylate)
Copolymer *32 0.5
(4) (ethylene/propylene) copolymer *33 3
(5) Silylated fumed silica *34 1
(6) Diglyceryl triisostearate 10
(7) Diisostearyl malate 3
(8) Isononyl isononanoate 5
(9) Sodium stearoyl glutamate *35 0.1
(10) Synthetic wax *36 7
(11) Microcrystalline wax *37 1
(12) Candelilla Row *38 0.5
(13) Carnauba wax *39 0.5
(14) Glyceryl tri-2-ethylhexanoate *7 Remaining amount (15) Ethylhexyl palmitate *40 5
(16) Cyclomethicone 15
(17) Methylphenylpolysiloxane *41 5
(18) Liquid paraffin *42 5
(19) Methyl methacrylate crosspolymer *43 5
(20) Spherical silica *44 3
(21) Phenoxyethanol 0.1
(22) Dibutylhydroxytoluene 0.02
*30: MZY-500SHE (manufactured by Teika)
*31: MT-05 (manufactured by Teika)
*32: KP-578P (manufactured by Shin-Etsu Chemical Co., Ltd.)
*33: EPS wax (manufactured by Japan Natural Products)
*34: AEROSIL R972 (manufactured by Nippon Aerosil Co., Ltd.)
*35: Amisoft HS-11P (manufactured by Ajinomoto Co.)
*36: CIREBELLE 109L (manufactured by CIREBELLE)
*37: MULTIWAX W445 (manufactured by SONNNEBORN)
*38: Purified Candelilla Wax SR-3 (manufactured by Japan Natural Products)
*39: TOWAX-1F3 (manufactured by Toa Kasei Co., Ltd.)
*40: PALMESTER 1543 (manufactured by PALM OLEO)
*41: KF-56 (manufactured by Shin-Etsu Chemical Co., Ltd.)
*42: KLEAROL (manufactured by SONNNEBORN)
*43: Matsumoto Microsphere M305 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.)
*44: Cylysia 550 (manufactured by Fuji Silysia Chemical Co., Ltd.)

(Production method)
A: Components (1) to (9) are heated and dissolved at 90°C, and then uniformly dispersed using a three-roll mill.
B: Add components (10) to (22) to A and heat to 90°C to dissolve.
C: B was poured into a stick container at 90°C and cooled to 5°C to obtain an oil-based solid sunscreen stick.

The oil-based solid sunscreen stick of Example 13 was excellent in "ultraviolet protection effect," "seawater resistance," "no burdensome feeling on the coating film," and "metal ion elution suppression effect."

Example 14: Water-in-oil sunscreen foam (aerosol)
(Component) (mass%)
(1) Hydrogen dimethicone treated fine particle zinc oxide
(Average particle diameter: 35 nm) *45 16
(2) Octyl silylation treated fine particle titanium oxide
(Average particle diameter: 15 nm) *46 5
(3) PEG-9 polydimethylsiloxyethyl dimethicone *13 0.5
(4) Cetyl 2-ethylhexanoate 5
(5) Cyclomethicone 2
(6) Red 226 0.1
(7) Mica titanium *47 1
(8) Alkyl benzoate (C12-15) 5
(9) Isopropyl myristate 3
(10) Dioctyl succinate 10
(11) Neopentyl glycol diethylhexanoate 5
(12) Cetyl 2-ethylhexanoate remaining amount (13) Cyclomethicone 15
(14) (Dimethicone/Polyglycerin-3) Crosspolymer *48 3
(15) Talc 5
(16) Nylon-12 *49 3
(17) Purified water 10
(18) Ethanol 5
(19) 1,3-butylene glycol 4
(20) Sodium myristoyl glutamate *50 0.1
*45: FINEX-30S-LPT (manufactured by Sakai Chemical Industry Co., Ltd.)
*46: STR-100W-OTS (manufactured by Sakai Chemical Industry Co., Ltd.)
*47: FLAMENCO RED (manufactured by Shin-Etsu Chemical Co., Ltd.)
*48: KSG-710 (polymer purity 24%, manufactured by Shin-Etsu Chemical Co., Ltd.)
*49: Orgasol 2002D (manufactured by Arkema)
*50: Amisoft MS-11 (manufactured by Ajinomoto Co.)

(Production method)
A: Components (1) to (7) are uniformly dispersed using a three-roll mill.
B: Add components (8) to (16) to A and mix uniformly.
C: Components (17) to (20) are mixed uniformly at room temperature.
D: C was added to B and mixed uniformly to obtain a water-in-oil emulsion type sunscreen stock solution.
E: After filling 90 g of the cosmetic stock solution obtained in D into a pressure-resistant container, the valve was fixed, and 10 g of LPG 0.15 was filled into the pressure-resistant container through the valve to obtain a water-in-oil sunscreen foam (aerosol).

The water-in-oil sunscreen foam (aerosol) of Example 14 was excellent in "ultraviolet protection effect,""seawaterresistance,""no burden on the coating film," and "metal ion elution suppression effect." Ta.

Claims (8)

(A) Hydrophobized surface-treated zinc oxide and/or titanium oxide with an average particle diameter of less than 100 nm 10 to 40% by mass
(B) A sunscreen cosmetic containing one or more monovalent alkali metal salts selected from the group consisting of alginic acid, acylmethyltaurine, and acylglutamic acid, and substantially free of organic ultraviolet absorbers. The component (B) is one or more monovalent alkali metal salts selected from the group consisting of alginic acid, stearoylmethyltaurine, myristoylmethyltaurine, lauroylmethyltaurine, stearoylglutamic acid, myristoylglutamic acid, and lauroylglutamic acid. A sunscreen cosmetic according to claim 1. The sunscreen cosmetic according to claim 1 or 2, wherein the content mass ratio (A)/(B) of the component (A) to the component (B) is 10 to 3,000. The sunscreen cosmetic according to any one of claims 1 to 3, wherein the content of the component (B) is 0.01 to 1% by mass in the sunscreen cosmetic. After applying 2 g of the sunscreen cosmetic to an area of 1000 cm ² on a glass plate and drying it, the concentration of zinc ions and/or titanium ions in the seawater after being immersed in 50 L of seawater for one week is as follows: The sunscreen cosmetic according to any one of claims 1 to 4, which has a content of less than 0.1 ppm. A method for suppressing elution of metal ions from a composition containing component (A) using the following component (B).
(A) Hydrophobized surface-treated zinc oxide and/or titanium oxide having an average particle diameter of less than 100 nm; (B) One or more selected from the group consisting of alginic acid, acylmethyltaurine, and acylglutamic acid. monovalent alkali metal salts The method for suppressing elution of metal ions according to claim 6, wherein the composition is a sunscreen cosmetic. A metal ion elution inhibitor from a composition containing component (A) using the following component (B).
(A) Hydrophobized surface-treated zinc oxide and/or titanium oxide having an average particle diameter of less than 100 nm; (B) One or more selected from the group consisting of alginic acid, acylmethyltaurine, and acylglutamic acid. monovalent alkali metal salts