JP2001049233A - Ultraviolet-absorbing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having an excellent ultraviolet-absorbing effect by mixing microcapsules containing an ultraviolet absorber with a substance that has the property of scattering ultraviolet rays. SOLUTION: This composition contains microcapsules containing an ultraviolet absorber and a substance that has the property of scattering ultraviolet rays in a weight ratio of 100:1 to 1:100. The microcapsules have each a wall made by polycondensing one or more compounds which are selected from the group consisting of compounds represented by the formula (wherein m is 1-4; n is 0-3; m+n<=4; R is an organic group; and Y is an alkoxy, hydrogen, or siloxy), at least one of which is a compound of the formula (wherein m=2 or 3), and at least one of which is a compound having at least one R that is lyophilic for at least either the continuous phase or the disperse phase. R that is lyophilic is desirably one having a polypeptide or a polyoxyethylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a composition containing microcapsules contained therein and having a property of absorbing ultraviolet rays.
More specifically, the present invention relates to an ultraviolet absorbing composition containing a microcapsule containing an ultraviolet absorbing agent and a substance having a property of scattering ultraviolet light and used as a component of a cosmetic or the like.

[0002]

2. Description of the Related Art In cosmetics, for example, cosmetics for skin and hair, especially sun care cosmetics, an ultraviolet absorber is often blended together with pigments and other components. As the ultraviolet absorber to be blended in cosmetics or the like, those having a high ultraviolet protection effect, particularly those having a high ultraviolet protection effect when used in combination with a pigment or the like having a property of scattering ultraviolet light are desirable. The present inventor has a property of encapsulating an ultraviolet absorber in a microcapsule and scattering the microcapsule, rather than a composition obtained by directly mixing an ultraviolet absorber and a substance having a property of scattering ultraviolet light. The present inventors have found that a composition having a more excellent ultraviolet absorbing effect can be obtained by mixing with a substance, and completed the present invention.

[0003]

SUMMARY OF THE INVENTION The present invention provides an ultraviolet absorbing composition comprising a microcapsule containing an ultraviolet absorbing agent and a substance having a property of scattering ultraviolet light. The weight ratio of the microcapsules containing the ultraviolet absorbent to the substance having the property of scattering ultraviolet rays is usually from 1: 100 to 1
00: 1, preferably from 1:30 to 30:
1, more preferably 1:10 to 10: 1.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, microcapsules include both microcapsules and nanocapsules. Generally, microcapsules have a particle size of 1 μm to 1 m.
m and nanocapsules having a particle size of less than 1 μm. The microcapsule, which is one component of the composition of the present invention, has a space in which a resin matrix or the like does not exist inside the wall film, and a core material such as an ultraviolet absorber is provided inside the space formed by the wall film. Including. The microcapsules used in the present invention may have the general structural formula (II) RnSi (OH) mY (4-mn) (II) wherein m is an integer of 1 to 4, and n is an integer of 0 to 3. so,
m + n ≦ 4. R is an organic group in which a carbon atom is directly bonded to a silicon atom, and the n Rs may be the same or different. Y is a group selected from the group consisting of an alkoxy group, hydrogen and a siloxy group, and (4-mn) Y may be the same or different. One or more compounds selected from the group of compounds represented by the formula: wherein at least one compound has m = 2 or 3;
And at least one compound having at least one R which is amphiphilic in at least one of a continuous phase and a dispersed phase, wherein an organopolysiloxane synthesized by condensation polymerization of a compound (compound (B)) is used as a wall film. It is preferable to use a microcapsule that contains an ultraviolet absorber.

The compound (B) comprises one or several compounds (groups) selected from the compounds represented by the general structural formula (II). However, at least one of one or several compounds constituting the compound (B) is a compound in which m = 2 or 3 in the general structural formula (II). Further, at least one of one or several compounds constituting the compound (B) is a compound having at least one R which is amphiphilic in at least one of a continuous phase and a dispersed phase. Here, the continuous phase and the dispersed phase refer to the dispersion medium and the dispersed phase, respectively, before the formation of the wall film of the microcapsules. In this specification, the external phase and the internal phase after the formation of the wall film of the microcapsules are also referred to, respectively. It is called a continuous phase or a dispersed phase. The polycondensation of the compound (B) means -Si in the general structural formula (II).
-SiL in another molecule in which the OH group constitutes the compound (B)
(L represents a leaving group such as a hydroxyl group.)
This is a reaction for forming iOSi-, and this polycondensation reaction generates an organopolysiloxane to be a wall film.

The compound (B) is usually represented by the following general structural formula (I): RnSiX (4-n) (I) wherein n is an integer of 0 to 3. R is an organic group in which a carbon atom is directly bonded to a silicon atom, and the n Rs may be the same or different. X is at least one group selected from the group consisting of a hydroxyl group, hydrogen, an alkoxy group, a halogen group, a carboxy group, an amino group and a siloxy group, and (4-n) Xs may be the same or different . One or more compounds selected from the group of compounds represented by formula (I), wherein at least one compound has an affinity for at least one of a continuous phase and a dispersed phase.
Can be obtained by hydrolyzing a compound having at least one (compound (A)). Compound (A) is composed of one or more compounds selected from the group of compounds represented by general structural formula (I).

[0007] In the production of the microcapsule used in the present invention, the amount of the core substance not encapsulated in the capsule is minimized, or the aging of the core substance from the capsule during the subsequent use. Preferably, at least one compound selected from the group consisting of hydrolyzable silanes and hydrolyzable polysiloxanes is added to the core material to minimize bleeding (leaching), or The surface of the wall film formed of a hydrolyzate of at least one compound selected from the group consisting of a hydrophilic silane and a hydrolyzable polysiloxane is treated at least once. Here, the hydrolyzable silane or hydrolyzable polysiloxane refers to a silane or polysiloxane that is hydrolyzed to generate a silanol group. Examples of the hydrolyzable silane or the hydrolyzable polysiloxane added to the core material or used for treating the surface of the formed wall film include methyltrichlorosilane.

[0008] The outline of the production of the above-mentioned microcapsules is shown in the order of processes as follows: "Production of compound (B) by hydrolysis of compound (A) → Polycondensation by neutralization of compound (B) This step is performed only when the process is performed → mixing and emulsification with the core substance and / or the second liquid phase → curing treatment. ”Further, preferably, the hydrolyzable silane or hydrolyzable polysiloxane to the core substance is used. And / or addition of at least one compound selected from the group consisting of hydrolyzable silane or hydrolyzable polysiloxane prior to "curing treatment". The film is subjected to a treatment (hereinafter, this treatment is referred to as an overcoat treatment in the present specification.) Further, if necessary, “the surface treatment compound (A) may be used. Management "is added to the front of the" curing process ".

The prepolymer described below formed by condensation of the compound (B) obtained by hydrolyzing the compound (A) is made amphiphilic to at least one of a continuous phase and a dispersed phase, and formed. It is preferable to select the type of the compound (A) and the ratio thereof when a plurality of types of the compound (A) are used in combination so that the prepolymer is stably dispersed.

In the compound (A) having a hydrophilic group,
It is preferable that R in the general structural formula (I) has a hydrophilic group, and it is preferable that R having the hydrophilic group be bonded to one or more silicon atoms. When a plurality of hydrophilic groups are bonded, two or more hydrophilic groups may be bonded.
In addition to the hydrophilic group, a hydrophobic group or a fluorophilic group may be bonded to R having a hydrophilic group.

Examples of the hydrophilic group include polyethers such as polyoxyethylene, polyoxypropylene, polyoxyethylene polyoxypropylene copolymer, saccharides ranging from monosaccharides such as pullulan, sorbitol, chitin and chitosan to polysaccharides or aminosaccharides. , Proteins, antibodies,
Hydrolyzed proteins, polyamino acids, carboxylic acids or salts and derivatives thereof, polycarboxylic acids and salts and derivatives thereof,
Sulfuric acid or a salt or derivative thereof, phosphoric acid or a salt or derivative thereof, sulfonic acid or a salt or derivative thereof, phosphonic acid or a salt or derivative thereof, a quaternary ammonium group, an amine or a salt thereof, and a polyamine or a salt thereof.
However, the hydrophilic group is not limited to those exemplified above. Examples of the group capable of forming a R a hydrophilic bonded to hydrophilic groups exemplified _{above, -CH 2 -, - (CH} 2) 2 -, -
_{(CH 2) 3 -, -} (CH 2) 3 OCH 2 CH (OH)
CH ₂ —, — (CH ₂ ) ₃ NHCO—, — (CH ₂ ) _{3
CH (CH 2 COOH) CO -} , - (CH 2) 3 CH
(COOH) CH ₂ CO—, and the like. In the partial structural formula, a silicon atom is bonded on the left side, and the hydrophilic group is bonded on the right side.

For polyethers such as the above-mentioned polyoxyethylene, polyoxypropylene, polyoxyethylene polyoxypropylene copolymer, the number average degree of polymerization of oxyethylene and oxypropylene is from 4 to 200.
0, particularly preferably 4 to 800.

The above-mentioned N- [2-hydroxy-3-
(3′-trihydroxysilyl) propoxy] propyl hydrolyzing protein, N- [2-hydroxy-3- (3 ′
-Dihydroxymethylsilyl) propoxy] propyl hydrolyzed protein includes collagen, elastin, keratin, fibroin (silk),
Hydrolyzates of animal-derived proteins such as sericin (silk), casein and conchiolin, plant-derived proteins such as wheat protein, soybean protein, sesame protein, zein (corn protein), and microorganism-derived proteins such as yeast protein are preferred. However, it is not limited to this. Further, the number average molecular weight of the hydrolyzed protein is preferably from 100 to 50,000, particularly preferably from 200 to 5,000.

In the compound (A) having a hydrophobic group,
It is preferable that R in the general structural formula (I) has a hydrophobic group, and it is preferable that one or a plurality of Rs having a hydrophobic group be bonded to one silicon atom. When a plurality of hydrophobic groups are bonded, two or more kinds of hydrophobic groups may be bonded.
Moreover, the fluorophilic group may be bonded to R having a hydrophobic group.

Examples of the hydrophobic group include linear hydrocarbons, branched hydrocarbons, unsaturated hydrocarbons, aromatics, esters, and the like. Any one or more of these functional groups is bonded to R. Is preferred. However, the hydrophobic group is not limited to those exemplified above.

Next, the hydrolysis of the compound (A) will be described below. As a medium for hydrolysis of the compound (A),
Usually, water is used. In addition, a small amount of water-soluble organic solvents, salts, protein denaturants such as urea, and the like may be added to water. The addition of these additives is effective when neutralization after hydrolysis of the compound (A) or emulsification by mixing with the second liquid phase is carried out at a temperature of 0 ° C. or lower, and one preferred method. It is. Furthermore, in the process from the hydrolysis of the compound (A) to the formation of the prepolymer via the compound (B), the reaction rate is controlled so that the condensation reaction does not become too fast, and the precipitation accompanying the insolubilization of the prepolymer is prevented. In order to prevent and stabilize the solution, the viscosity before adding the compound (A) is 10 to 2000 mPa.
The medium of s is preferably used. Viscosity 10-2
Examples of the thickening substance for preparing a medium having a viscosity of 000 mPa · s include polyvinyl alcohol, polyacrylamide, sodium carboxymethylcellulose, carboxymethyldextran, hydroxyethylcellulose, carrageenan, chitin, chitosan, polypeptide, gelatin, and sericin. And the like. Particularly, an aqueous gelatin solution having a viscosity of 10 to 2000 mPa · s is exemplified.

The hydrolysis of the compound (A) is preferably carried out at -5 ° C to 90 ° C, particularly 5 ° C to 75 ° C, with sufficient stirring. The hydrolysis of the compound (A) may be on the acidic side or the basic side, but which side is performed depends on the properties of the compound (A).

The compound (B) formed by hydrolysis of the compound (A) is polycondensed by neutralization. Neutralization is performed at -30 ° C to 80 ° C, especially -5 ° C to 55 ° C with sufficient stirring.
It is preferable to carry out. Examples of the acid or alkali used for neutralization are the same as those exemplified above for the hydrolysis. Water is exemplified as a medium for this neutralization.

In the production of the microcapsule of the present invention,
A core material comprising a UV absorber and / or a second liquid phase,
That is, after mixing and emulsification with a hydrophobic substance and / or a non-aqueous solvent, polycondensation by neutralization is performed to produce an organopolysiloxane to be a wall film (curing treatment). But,
It is possible to perform a certain degree of condensation polymerization by formation and neutralization of the compound (B) before mixing and emulsification with the core substance and / or the second liquid phase to prepare a prepolymer of the compound (B) in advance. preferable. It has at least one hydrophilic R, in particular at least one R has a number average molecular weight of 100
Polypeptide of 〜50,000 or a number average degree of polymerization of 1
Compound (B) having up to 2000 polyoxyethylene
Is preferred because at least one of these can be used to stably present the prepolymer. Further, when the prepolymer is unstable and easily precipitated, a method of preparing the prepolymer by hydrolyzing the compound (A) in a viscous solution such as an aqueous gelatin solution makes the prepolymer exist stably. It is preferable because it can be used. After the preparation of the prepolymer, it is preferable to prepare an emulsion by mixing the prepolymer in the aqueous solvent with a hydrophobic substance and / or a non-aqueous solvent. In the above-mentioned method, after mixing the hydrophobic substance and / or the non-aqueous solvent, the prepolymers condense with each other, grow into larger polymers, and become the organopolysiloxane constituting the wall film.

Next, mixing and emulsification with the core substance and / or the second liquid phase will be described. As a method of mixing and emulsifying with the core substance and / or the second liquid phase, in the case of a microcapsule dispersed in water or a hydrophilic dispersion medium, a prepolymer is prepared in an aqueous dispersion medium, and then a liquid core is prepared. Substance (second
Liquid phase) only, or the core substance and its solvent (second liquid phase)
Is added. In the case of a microcapsule dispersed in a hydrophobic dispersion medium or a non-aqueous dispersion medium, when the core substance is soluble or hydrophilic in an aqueous solvent, the core substance is directly added to an aqueous solvent dispersion of a prepolymer. Or a method in which the obtained liquid is dissolved in an aqueous solvent and added, and the obtained liquid is mixed with a solvent that is immiscible with the aqueous solvent (the second liquid phase becomes a continuous phase) to perform inverse emulsification. After inversion emulsification, a core substance may be added. Mixing and emulsification with the core substance and / or the second liquid phase is usually -30C to 95C, especially -5C.
Perform at ６０60 ° C.

Examples of the ultraviolet absorber included as the core substance include 2-hydroxy-4-methoxybenzophenone,
Benzophenone derivatives such as sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, sodium dihydroxydimethoxybenzophenone-sulfonate, 2,4-dihydroxybenzophenone, tetrahydroxybenzophenone, para-aminobenzoic acid, ethyl para-aminobenzoate, para-aminobenzoic acid Glyceryl, amyl paradimethylaminobenzoate, paraaminobenzoic acid derivatives such as octyl paradimethylaminobenzoate, ethyl paramethoxycinnamate, isopropyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate,
Sodium paramethoxycinnamate, potassium paramethoxycinnamate, methoxycinnamic acid derivatives such as glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, octyl salicylate, phenyl salicylate, homomenthyl salicylate, dipropylene glycol salicylate, ethylene glycol salicylate, Myristyl salicylate, salicylic acid derivatives such as methyl salicylate, urocanic acid,
Ethyl urocanate, 4-tert-butyl-4'-methoxydibenzoylmethane, 2- (2'-hydroxy-
5'-methylphenyl) benzotriazole, methyl anthranilate, octyltriazone and the like.
Among them, 2-ethylhexyl paramethoxycinnamate and 4-tert-butyl-4'-methoxydibenzoylmethane are preferably used. However, it is not limited to the above example. Further, the core substance may contain other components other than the ultraviolet absorber as long as the object of the present invention is not impaired.

When the surface of the formed wall film is treated with a hydrolyzate of at least one compound selected from the group consisting of hydrolyzable silane and hydrolyzable polysiloxane, the mixture is usually mixed, emulsified, and then treated. Is performed before the surface treatment of the wall film with the compound (A) or the like, that is, before the aggregation treatment and the curing treatment of the wall film. This overcoating treatment is usually performed by adding at least one compound selected from the group consisting of hydrolyzable silanes and hydrolyzable polysiloxanes to the continuous phase. The overcoating treatment is preferably performed while stirring at the same temperature as the mixing and emulsification. When performing overcoat processing,
The amount of addition of at least one compound selected from the group consisting of hydrolyzable silanes and hydrolyzable polysiloxanes is preferably 0.1 to 30 mol, preferably 100 mol, per 100 mol of Si used for forming the wall film. 0.5 to 10 mol.

As the continuous phase, a liquid phase is used throughout the capsule preparation process. In the case of microcapsules dispersed in a hydrophobic continuous phase or a non-aqueous continuous phase, examples of the continuous phase include higher fatty acids, hydrocarbons, organic solvents, esters, silicones, higher alcohols, animal and vegetable oils, and the like. And one or more combinations are used. Any organic solvent having a boiling point lower than that of water may be used as long as it can azeotropically drive water out of the system.

In the preparation of the emulsion, for example, a reaction vessel made of a round bottomed cylindrical glass having an inner diameter of 12 cm and a capacity of 2 liters equipped with a mechanical stirrer and having a particle size of 0.3
When the particle diameter is adjusted within the range of 100 μm and the central particle diameter is within the range of 1 to 20 μm, the reaction liquid is adjusted to 50 to 1000
It is preferable to stir at 300 rpm, especially 300-1000 rpm.

In the preparation of the emulsion, for example, after the reaction solution is stirred with a mechanical stirrer, the mixture is mainly dispersed with a homomixer in the range of 0.1 to 30 μm in particle size and 0.5 to 5 μm in center particle size. When adjusting the diameter, it is preferable to treat the reaction solution with a homomixer at 1,000 to 20,000 rpm, particularly at 5,000 to 10,000 rpm.

In the preparation of the emulsion, for example, the reaction solution is stirred with a mechanical stirrer, treated with a homomixer, and then mainly treated with a microfluidizer.
In the range of 1 μm, the central particle size is 0.2 to 0.8 μm
When the particle size is adjusted within the range, the treatment is preferably performed with a microfluidizer at 300 to 5000 kg / cm 2.

Next, the surface treatment with the compound (A) which is an intermediate for producing microcapsules will be described below. Production of Microcapsules Microcapsules can be produced without surface treatment with compound (A) as an intermediate. However, it is considered that silanol groups not participating in condensation remain on the surface of the uncured capsule immediately after emulsification. This silanol group is formed by the newly added compound (A) or
It condenses with the hydrolyzate, compound (B), and provides a foothold for imparting new properties to the capsule surface. Therefore,
The compound (A) is used to prevent aggregation of the microcapsules, make the surface of the microcapsules cationic, and to impart various functions by modifying the surface properties of the microcapsules in various ways.
Is performed.

In the curing treatment, alcohol generated by hydrolysis of alkoxysilane, which is a kind of the compound (A), is removed, dehydration by elapse of time or heating,
The condensation polymerization reaction can be further advanced by dehydration outside the reaction system or the like, thereby increasing the strength of the wall film of the microcapsule. The heating temperature is preferably 30 ° C. or higher at the temperature of the reaction solution, and the boiling point may be changed depending on the pressure. However, it is particularly preferable to heat at a temperature at which the water in the reaction system boils. The above-mentioned dehydration by the passage of time means that siloxane condensation naturally dehydrates and condenses at a neutral pH, so that dehydration is performed only by the passage of time, and the dehydration to the outside of the reaction system is as follows: For example, distillation (removing the liquid formed by cooling the solvent vapor out of the reaction system without returning it to the reaction system)
And so on.

In the microcapsules thus obtained, the weight of the ultraviolet absorber is preferably 20 to 93% by weight based on the total weight of the encapsulated microcapsules. More preferably, it is 40 to 90% by weight. The ratio of the weight of the core substance to the weight of the encapsulated microcapsules is hereinafter referred to as “encapsulation rate”.

The microcapsules obtained as described above are mixed with a substance having a property of scattering ultraviolet rays by a conventional method to obtain the ultraviolet absorbing composition of the present invention.
As a substance having the property of scattering ultraviolet light, other than pigments such as pigments, a substance which does not scatter visible light but has the property of scattering ultraviolet light, and furthermore, the effect of scattering ultraviolet light is relatively small, so that conventionally, ultraviolet light is not used. A substance not used for the purpose of scattering is also included (hereinafter, a substance having a property of scattering ultraviolet rays is referred to as a “UV scattering agent”). Specifically, for example, colorless white pigments such as titanium dioxide and zinc oxide, inorganic red pigments such as iron oxide (iron oxide) and iron titanate, inorganic brown pigments such as γ iron monoxide, yellow iron oxide, and loess Inorganic yellow pigments such as black iron oxide, carbon black, and lower titanium oxide; inorganic purple pigments such as mango violet and cobalt violet; inorganic inorganic pigments such as chromium oxide, chromium hydroxide, and cobalt titanate Green pigments, inorganic blue pigments such as ultramarine and navy blue, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 218, Red No. 220, Red No. 225
No., Red No. 226, Red No. 228, Red No. 405, Orange No. 201, Orange No. 203, Orange No. 204, Yellow No. 401
No. 2, green 202, blue 404, etc., red 3, red 104, red 106, red 227, red 230, red 401, red 505, orange 205
No. 4, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203
No. 3, Green No. 3, Purple No. 201, Blue No. 11, etc., organic pigments such as barium or aluminum lake, chlorophyll, natural pigments such as β-carotene, mica titanium, mica titanium treated with red iron oxide, mica titanium treated with yellow iron oxide And mica titanium treated with black iron oxide, mica titanium treated with iron oxide and yellow iron oxide, titanium mica treated with navy blue, titanium treated with carmine, titanium treated with chromium oxide, titanium treated with carbon black, and the like. Also, talc, kaolin, mica, mica mica, sericite, muscovite mica, synthetic mica, mica, lithia mica, vermiculite, and the like. Fluoroapatite, hydroxyapatite, ceramic powder, metal soap (zinc myristate, calcium palmitate, aluminum stearate, etc.), boron nitride, silica-alumina, silica-magnesia, bentonite, flours earth, Sansei clay, activated clay, montmorillonite , Attapal guide, inorganic powder such as silica beads, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, styrene / acrylic acid copolymer resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder And organic powders such as cellulose powder. Furthermore, the above-mentioned thing which was made hydrophobic by silicone etc. is also illustrated. The ultraviolet-absorbing composition of the present invention can contain other than the microcapsules containing the ultraviolet absorbent and the substance having the property of scattering ultraviolet rays as long as the object of the present invention is not impaired. The ultraviolet absorbing composition of the present invention can be used, for example, as a cosmetic or the like or as one component of a cosmetic. Here, the cosmetics include not only cosmetics under the Pharmaceutical Affairs Law, but also quasi-drugs, external medicines such as dermatological drugs, and those widely applied to the human body such as skin and hair. Hair cosmetics are included. Examples of skin cosmetics include basic cosmetics such as lotions, emulsions, claims, gels, and essences (essences), solid white powder, liquid foundations, foundations such as solid foundations and dual-use foundations, lipsticks and emulsified lipsticks, and the like. Examples include makeup cosmetics such as lipsticks, blushers, eyebrows, and beautiful nails, sunscreen lotions, sunscreen creams, and emollient creams. Examples of the hair cosmetics include hair wash cosmetics such as shampoos, rinses and treatments, and hair finishing cosmetics such as hair creams and hair treatments.
When the ultraviolet-absorbing composition of the present invention is used as a cosmetic, those which are mixed with the microcapsules, that is, those having the property of scattering ultraviolet rays, and other components include "new cosmetics" (edited by Takeo Mitsui, Minamiyama) (1993, Todo, 1993). Particularly preferred are powders of these components, for example, those obtained by treating the surface of a pigment with a hydrophobic substance such as silicone.

[0031]

The ultraviolet absorbing composition of the present invention has an excellent ultraviolet protection effect. That is, as compared with the case where the ultraviolet absorbent contained in the ultraviolet absorbent composition of the present invention is mixed with a substance having a property of scattering ultraviolet light as it is without being encapsulated in the microcapsules and other components, The hydrophilic composition has a high ultraviolet absorption effect (such as an SPF value). Therefore, for example, when the ultraviolet absorbing composition of the present invention is used for cosmetics and the like, a cosmetic having excellent ultraviolet absorbing properties can be obtained. Further, the following effects can be further obtained by using the ultraviolet absorbing composition of the present invention as a cosmetic. 1. Since the penetration of the ultraviolet absorber into the skin, hair and the like is reduced, the safety of the cosmetic is improved. 2. Conventionally, it has been difficult to formulate stably, and a more stable formula can be obtained. 3. Conventionally, when an ultraviolet absorber is directly added to cosmetics, a stabilizer has to be added in some cases to prevent yellowing of the ultraviolet absorber, but this is not necessary. It is possible to prevent a decrease in the feel of the cosmetic. For example,
When an ultraviolet absorber such as ethylhexylmethoxycinnamic acid is directly blended, tackiness or the like occurs, and when an ultraviolet absorber such as methoxybutylbenzoylmethane is directly blended, there are problems such as graininess due to precipitation of crystals. This solves the problem and improves the feeling of use of the cosmetic. In addition, the adhesion of the cosmetic is also improved. 5. The compatibility between the ultraviolet absorber and other compounding components (cosmetic raw materials, oils, solvents, etc.) is improved. For example, when an ultraviolet absorber is directly added to a water-rich formulation such as a lotion, it is necessary to add a surfactant, but according to the present invention, it is not necessary to easily add an ultraviolet absorber. it can. In addition, methoxybutylbenzoylmethane and the like have poor solubility and the solubility is reduced due to the influence of other compounding components, so that the compounding is difficult. However, the present invention facilitates dissolution and is not affected by other compounding components. 6. When blending UV absorbers into cosmetics, they are often emulsified and blended, but when such cosmetics are applied to the skin, the emulsified particles of UV absorbers due to evaporation of water or increased water due to sweat, etc. In general, the SPF value on the skin becomes lower than the value measured by the SPF analyzer because the scattering effect due to the emulsification is reduced. However, in the cosmetic using the composition of the present invention, even if there is a change in the amount of water as described above, the ultraviolet absorbent-encapsulated microcapsules are kept as they are, that is, the ultraviolet absorbent particles in the capsules are kept as they are. Therefore, such a problem can be prevented.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which are provided for illustrative purposes only and do not limit the scope of the present invention.
Further, unless otherwise indicated,% is% by weight. The analysis method used in the following examples will be described first.

Analytical Method 1 About 0.1 g of the obtained microcapsule dispersion was added, and about 5 ml of water was added thereto. One drop of this is prepared as a preparation, covered with a cover glass, observed with an optical microscope at a magnification of 1000 times, and the particle size distribution is determined visually.

Analysis method 2 0.1 g of the obtained microcapsule dispersion was weighed at 27 mm in diameter.
A screw tube having a height of 55 mm is precisely weighed and about 5 mL of water is added. 10 mL of n-hexane is added thereto, and the lid is capped. Immediately, the center is fixed horizontally and the axis of rotational symmetry is rotated vertically at 150 rpm using a motor to extract free 2-ethylhexyl paramethoxycinnamate. . After rotating for 2 minutes, 100 μL of the hexane layer is taken into a 10 mL volumetric flask using a micropipette, and n-hexane is added to the weighing line. This is designated as Sample A. The same process is performed by further rotating for 2 minutes. This is designated as Sample B. The concentration of 2-ethylhexyl paramethoxycinnamate in Samples A and B is measured using liquid chromatography. Assuming that the measurement result of sample A is a and the measurement result of sample B is b, free ethyl-2-methoxyhexyl paramethoxycinnamate in the microcapsule dispersion is included in analysis result a, and analysis result a is obtained from analysis result b. Can be regarded as the amount of leaching in 2 minutes. Since the measurement result a includes the amount of leaching in 2 minutes as well as the amount of liberation,
a- (ba) can be regarded as the amount of free 2-ethylhexyl paramethoxycinnamate.

Synthesis Example 1 1) Preparation of Prepolymer for Capsule Wall Membrane A dropping funnel and reflux condenser were provided on the upper lid, and a round bottom cylindrical glass reaction vessel having an inner diameter of 12 cm and a capacity of 2 liters equipped with a mechanical stirrer was prepared in advance. 90 g of water and N- [2
-Hydroxy-3- (3'-trihydroxysilyl) propoxy] propyl hydrolyzed sericin (the molecular weight of the hydrolyzed sericin is about 2,000 in number average molecular weight) 10 g and 1 g
3.6 g of 8% hydrochloric acid was added, and methyltriethoxysilane (KBE manufactured by Shin-Etsu Silicone Co., Ltd.) was stirred at 50 ° C.
-13) A mixture of 24 g and 7.5 g of octyltriethoxysilane (A-137 manufactured by Nippon Unicar) was dropped from the dropping funnel. After stirring at 50 ° C. for 4 hours,
The mixture was cooled to ℃, and while stirring, 2.45 g of a 25% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 7.0. 2) Addition and emulsification of core substance After stirring the reaction solution prepared in 1) for 30 minutes,
While stirring at 600 rpm, paramethoxycinnamic acid-2
-A mixture of 250 g of ethylhexyl (Ubinal MC80N manufactured by BSF Japan Co., Ltd.) and 2.5 g of tetraethoxysilane (KBE-04 manufactured by Shin-Etsu Silicone Co., Ltd.) was added, and the mixture was further stirred at 600 rpm for 4 hours. 3) Atomization Transfer the reaction solution prepared in 2) to a homomixer container,
Homomixer at 50 ° C, 8000 rpm for 90 minutes, return to original reaction vessel, 50 ° C, 600 rpm for 14 hours
After stirring, transfer to a homomixer container again,
At 8000 rpm for 60 minutes in a homomixer.
Atomized. 4) Overcoat treatment of wall film The reaction solution prepared in 3) was placed in the original reaction vessel at 50 ° C and 250 ° C.
While stirring at rpm, 0.67 g of methyltrichlorosilane (KA-13 manufactured by Shin-Etsu Silicone) and 3.2 Methyltriethoxysilane (KBE-13 manufactured by Shin-Etsu Silicone)
g of the mixture and further stirred at 250 rpm for 1 hour, and then neutralized by adding 2.2 g of a 25% aqueous sodium hydroxide solution. 5) Prevention of agglomeration and curing treatment of wall film Trimethylchlorosilane (K available from Shin-Etsu Silicone Co., Ltd.) while stirring the reaction solution prepared in 4) at 50 ° C. and 250 rpm.
A-31) 2.0 g was added and stirred for 1 hour, and then 2.8 g of a 25% aqueous sodium hydroxide solution was added dropwise. The temperature of the reaction solution was gradually raised to reflux. The vapor containing alcohol was distilled off, and the mixture was refluxed for 2 hours while stirring at 150 rpm. The reaction solution was cooled at room temperature with stirring at 150 rpm to obtain a dispersion of microcapsules in water. 5 μm diameter
Hereinafter, 59.72% of a component is obtained by removing water in a 1 to 3 μm capsule water dispersion. Paramethoxycinnamic acid-2
-The amount of ethylhexyl was 53.7% based on the weight of the microcapsule dispersion in water.

Synthesis Example 2 N- [2-Hydroxy-3- (3'-trihydroxysilyl) propoxy] propyl Hydrolyzed Sericin, Polycondensate of Hydrolyzate Co-Polymer of Methyltriethoxysilane and Octyltriethoxysilane 2-ethylhexyl paramethoxycinnamate having siloxane as a wall film and 4-t
Preparation of capsules of tert-butyl-4'-methoxydibenzoylmethane 1) Preparation of prepolymer for capsule wall membrane A round bottom with an inner diameter of 12 cm, a capacity of 2 liters equipped with a dropping funnel and a reflux condenser on the top lid, and equipped with a mechanical stirrer. In a cylindrical glass reaction vessel, 90 g of water and N- [2
-Hydroxy-3- (3'-trihydroxysilyl) propoxy] propyl hydrolyzed sericin (the molecular weight of the hydrolyzed sericin is about 2,000 in number average molecular weight) and 10 g of 18% hydrochloric acid, and stirred at 50 ° C. While methyltriethoxysilane (KBE manufactured by Shin-Etsu Silicon Co., Ltd.)
-13) A mixture of 15.9 g and 4.9 g of octyltriethoxysilane (A-137 manufactured by Nippon Unicar) was dropped from a dropping funnel. Further, the mixture was stirred at 50 ° C. for 4 hours.
Next, a 20% aqueous sodium hydroxide solution was added while stirring.
1.0 g of EDTA · 2Na dispersed in 7 g and 20 g of water
Was added dropwise to adjust the pH to 7.0. 2) Addition and emulsification of core substance 2-Ethylhexyl paramethoxycinnamate (UBINAL MC80N manufactured by BSF Japan) while stirring the reaction solution prepared in 1) at 600 rpm.
7 g and 4-tert-butyl-4'-methoxydibenzoylmethane (Nippon Roche's Parsol 1789) 4
A mixture of 2.7 g and 2.1 g of tetraethoxysilane (KBE-04 manufactured by Shin-Etsu Silicone Co., Ltd.) was dropped. 3) Atomization Transfer the reaction solution prepared in 2) to a homomixer container,
The mixture was homogenized at 9000 rpm at 50 ° C. for 90 minutes. Then, return to the original reaction vessel, 50 ° C., 600 rpm
After stirring at 15 m for 15 hours, the mixture was again transferred to a homomixer container, and homogenized at 50 ° C and 9000 rpm for 60 minutes. 4) Overcoat treatment The reaction solution prepared in 3) was placed in the original reaction vessel at 50 ° C and 400 ° C.
With stirring at rpm, 0.67 g of methyltrichlorosilane (KA-13 manufactured by Shin-Etsu Silicone Co.) and 3.1 of methyltriethoxysilane (KBE-13 manufactured by Shin-Etsu Silicone) are used.
8 g of the mixture were added dropwise. After stirring for 1 hour, 2.7 g of a 20% aqueous sodium hydroxide solution was added dropwise. 5) Prevention of agglomeration and curing treatment of wall film The reaction solution prepared in 4) was placed in the original reaction vessel at 50 ° C and 400 ° C.
While stirring at rpm, 1.9 g of trimethylchlorosilane (KA-31 manufactured by Shin-Etsu Silicone Co., Ltd.) was added, and the mixture was stirred for 1 hour, and 3.6 g of a 20% aqueous sodium hydroxide solution was added dropwise. The temperature of the reaction solution was gradually raised to reflux. The vapor containing alcohol was distilled off, and the mixture was further heated and refluxed for 2 hours while stirring at 400 rpm. This reaction solution is heated at room temperature for 150 rpm.
The mixture was cooled while stirring at a speed of m to obtain a dispersion of microcapsules in water. The component excluding water in 304.3 g of a dispersion in water of a capsule having a diameter of 10 μm or less, mainly 1 to 3 μm, excluding water, is 59.97.
%Became. The total amount of 2-ethylhexyl paramethoxycinnamate and 4-tert-butyl-4'-methoxydibenzoylmethane was 54.0% based on the weight of the microcapsule dispersion in water.

Analysis Method 3 Measurement of SPF Value and Ultraviolet Transmittance A measurement sample was applied to a surgical tape (manufactured by TRANSPORTATEPE 3M) at ² μl / cm ² .
This was irradiated with ultraviolet rays, and the amount of transmitted light was measured with an SPF analyzer UV-1000S (manufactured by LABSPHERE, USA). The numerical values in the examples are average values of 40 times. Calculation of SPF value

Example 1 The aqueous dispersion of microcapsules obtained in Synthesis Example 1 and a UV scattering agent were mixed in the proportions shown in the table (weight ratio of ultraviolet absorber and pigment in the microcapsules) and mixed with the ultraviolet light of the present invention. An absorbent composition was prepared. As a comparison, instead of the dispersion in water of the microcapsules obtained in Synthesis Example 1, paramethoxycinnamic acid-
An ultraviolet-absorbing composition was prepared in the same manner except that 2-ethylhexyl (Ubinal MC80N manufactured by BFSF Japan) was used. The wavelength 310 of these compositions
The ultraviolet transmittance and the SPF value in nm were measured by the method of analytical method 3. The results are shown in the following table. In addition,
The UV scattering agents used in the present Example and Example 2 are as follows, and are represented by the following abbreviations in the following table and Example 2 table. Scattering agent 1 Polymethyl methacrylate: PMMA G
MX-0610 (manufactured by Nikko Chemtech Co., Ltd.) Scattering agent 2 Nylon powder: sp-500 (manufactured by Nikko Chemtech Co., Ltd.) Scattering agent 3 Silica beads: SPHERICA P-15
00 (manufactured by Catalyst Chemical Industry Co., Ltd.) Scattering agent 4 Titanium mica: TIHIRON MP-10
05 (manufactured by Miyoshi Kasei Co., Ltd.) Scattering agent 5 Titanium oxide: TIPAQUE A-100
(Ishihara Sangyo Co., Ltd.) Scattering agent 6 Yellow iron oxide: TAROX LL-XLO (Titanium Co., Ltd.) Scattering agent 7 Red iron oxide: TAROX R-110-7
Scattering agent 8 Fine particle zinc oxide: ZnO-350 (manufactured by Sumitomo Osaka Cement Co., Ltd.) Scattering agent 9 Fine particle titanium oxide: TTO-S-1 (manufactured by Ishihara Sangyo Co., Ltd.) Scattering agent 10 Soft talc ( Scattering agent 11 Sericite FSE (manufactured by Miyoshi Kasei Co., Ltd.) Scattering agent 12 Mica M-102 (manufactured by Miyoshi Kasei Co., Ltd.) Further, in the following table and the table of Example 2, mixed with UV scattering agent In the case of microcapsules, that is, in the case of the present invention, MC and UV absorber are directly mixed, that is, in the case of comparison, the symbol of UV is shown in the sample column.

[Table 1] Although the amount of 2-ethylhexyl paramethoxycinnamate in the applied microcapsules of Synthesis Example 1 was almost equal to the amount of 2-ethylhexyl paramethoxycinnamate applied as a comparison, the examples of the present invention were mostly This result shows that the case of No. shows a high SPF value and a low transmittance, and the ultraviolet absorbing effect is improved.

Example 2 The dispersion of microcapsules in water obtained in Synthesis Example 2 and a UV scattering agent were mixed at the ratio shown in the table to prepare an ultraviolet absorbing composition of the present invention. For comparison, 2-ethylhexyl paramethoxycinnamate (Ubinal MC80N, manufactured by BSF Japan) and 4-tert-butyl-in place of the aqueous dispersion of microcapsules obtained in Synthesis Example 2 were used.
An ultraviolet absorbing composition was prepared in the same manner except that a 4: 1 (weight ratio) mixture of 4'-methoxydibenzoylmethane (Palsol 1789, manufactured by Nippon Roche) was used.
The ultraviolet transmittance and SPF value at wavelengths of 310 nm and 360 nm of these compositions were measured by the method of Analysis Method 3. The results are shown in the following table.

[Table 2] 2-Ethylhexyl paramethoxycinnamate and 4-tert- in the aqueous dispersion of the microcapsules of Synthesis Example 2 applied
The amount of butyl-4'-methoxydibenzoylmethane was approximately the same as the amount of 2-ethylhexyl paramethoxycinnamate and 4-tert-butyl-4'-methoxydibenzoylmethane applied as a comparison. The results show that the invention examples show a high SPF value and a low transmittance in most cases, and the ultraviolet absorbing effect is improved.

Reference Examples 2 and 3 Using the aqueous dispersion of microcapsules obtained in Synthesis Example 1, a dual-use foundation having the following formulation was obtained by a conventional method.

[Table 3] SPF value and UV of the obtained dual-use type foundation
A (310 nm) transmittance and UVB (360 nm) transmittance are shown below.

[Table 4] The dual use type foundation of Reference Example 2 was more excellent in the effect of preventing ultraviolet rays than Reference Example 3 using an ultraviolet absorber not encapsulated in microcapsules.

Reference Examples 4, 5 Using the aqueous dispersions of the microcapsules obtained in Synthesis Examples 1 and 2, liquid foundations (w / o type) having the following formulation were obtained by a conventional method.

[Table 5] SPF value of the obtained liquid foundation, UVA
The transmittance and the UVB transmittance are shown below.

[Table 6]

Reference Examples 6 and 7 Using the aqueous dispersion of microcapsules obtained in Synthesis Example 1, a solid white powder having the following formulation was obtained by a conventional method.

[Table 7] The SPF value, UVA transmittance, and UVB transmittance of a sample obtained by diluting the obtained solid white powder by a factor of 2 with liquid paraffin are shown below.

[Table 8]

Reference Examples 8 and 9 Using the aqueous dispersion of microcapsules obtained in Synthesis Example 2, emulsification type lipsticks having the following formulation were obtained in the same manner as in Example 1 and Comparative Example 1.

[Table 9] The SPF value, UVA transmittance and UVB transmittance of a sample obtained by diluting the obtained emulsified lipstick with liquid paraffin twice are shown below.

[Table 10]

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Sueko Oumi 1-2-14 Fukuichicho, Higashiosaka-shi, Osaka F-term (reference) 4C083 AA122 AB172 AB212 AB232 AB242 AB322 AB432 AB442 AC012 AC022 AC122 AC211 AC212 AC231 AC242 AC341 AC342 AC352 AC371 AC372 AC421 AC422 AC442 AC551 AC791 AC792 AC842 AC851 AD052 AD072 AD092 AD152 AD161 AD162 AD411 AD512 BB46 CC01 CC12 CC19 DD23 DD32 EE17 4G005 AA01 AB14 AB15 BA01 DC12X DC15X DC22XDD26 DD26 DCX DD22 DD57Z DD65Z EA03

Claims (7)

[Claims] 1. An ultraviolet absorbing composition comprising a microcapsule containing an ultraviolet absorbing agent and a substance having a property of scattering ultraviolet light. 2. The weight ratio of a microcapsule containing an ultraviolet absorber to a substance having a property of scattering ultraviolet light is 100:
The ultraviolet absorbing composition according to claim 1, wherein the ratio is from 1 to 1: 100. 3. A microcapsule containing an ultraviolet absorber is represented by the general structural formula (II): RnSi (OH) mY (4-mn) (II) wherein m is an integer of 1 to 4, and n is An integer from 0 to 3,
m + n ≦ 4. R is an organic group in which a carbon atom is directly bonded to a silicon atom, and the n Rs may be the same or different. Y is a group selected from the group consisting of an alkoxy group, hydrogen and a siloxy group, and (4-mn) Y may be the same or different. One or more compounds selected from the group of compounds represented by the formula: wherein at least one compound has m = 2 or 3;
And at least one compound having at least one R which is amphiphilic in at least one of a continuous phase and a dispersed phase, wherein an organopolysiloxane synthesized by condensation polymerization of a compound (compound (B)) is used as a wall film. The ultraviolet absorbent composition according to claim 1 or 2, wherein 4. The method according to claim 1, wherein R having at least one of a continuous phase and a dispersed phase is amphiphilic has a number average molecular weight of 100 to 5,000.
2. The composition according to claim 1, which has 0 polypeptide or polyoxyethylene having a number average degree of polymerization of 1 to 2,000.
Or the ultraviolet absorbing composition of 3. 5. The ultraviolet absorbing composition according to claim 1, wherein the encapsulation ratio of the ultraviolet absorbing agent is 25% by weight or more. 6. The method according to claim 1, wherein the ultraviolet absorbent is 2-hydroxy-4-.
Methoxybenzophenone, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, sodium dihydroxydimethoxybenzophenone-sodium sulfonate, 2,4-dihydroxybenzophenone, tetrahydroxybenzophenone, paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate Amyl paradimethylaminobenzoate, octyl paradimethylaminobenzoate, ethyl paramethoxycinnamate, isopropyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, sodium paramethoxycinnamate, potassium paramethoxycinnamate, dipara Glyceryl mono-2-ethylhexanoate methoxycinnamate, octyl salicylate, phenyl salicylate, homomenthyl salicylate, salicyl Dipropylene glycol, ethylene glycol salicylate, salicylic acid, myristyl, methyl salicylate, urocanic acid, ethyl urocanate, 4-
tert-butyl-4'-methoxydibenzoylmethane, 2- (2'-hydroxy-5'-methylphenyl)
6. The ultraviolet absorbing composition according to claim 1, which is at least one selected from benzotriazole, methyl anthranilate and octyltriazone. 7. A cosmetic comprising the ultraviolet absorbing composition according to claim 1.