JP2002226350A - Ultraviolet light-defending agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ultraviolet light-defending agent, excellent in water proof property and also in applying feeling such as no oily feeling, a good drying property and also a good stability despite having a high content of a lower alcohol. SOLUTION: This ultraviolet light-defending agent contains the following (A) to (D) components: (A) A lower alcohol 30-85 wt.% (B) An ultraviolet light- absorbing agent 1-20 wt.% (C) A thickening agent 0.05-2 wt.% (D) Water 10-68 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet ray protective agent which is excellent in water resistance and has a good application feeling without an oily feeling.

[0002]

2. Description of the Related Art Ultraviolet protection agents (sunscreen agents) for preventing various disorders caused to skin by ultraviolet rays include:
There are various types of dosage forms, generally divided into water-in-oil, oil-in-water and solubilized forms. The oil-in-water type and the solubilized type use a surfactant to emulsify and disperse an ultraviolet absorber and an ultraviolet scattering agent in water, so that they are well compatible with sweat and moisture and have poor water resistance. Was. On the other hand, the water-in-oil type is excellent in water resistance, but has a strong oily feeling when applied, and cannot be erased, and is not preferred.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an ultraviolet protective agent which is excellent in water resistance and has a good application feeling without an oily feeling.

[0004]

SUMMARY OF THE INVENTION The present inventor has found that an aqueous solution containing a large amount of a lower alcohol is thickened and an ultraviolet absorber is added, whereby the SP in a range suitable for UV protection in daily life is obtained.
F, it was found that an ultraviolet protective agent having excellent application feeling such as excellent water resistance, no oily feeling, and good drying property was obtained.

The present invention relates to the following components (A) to (D): (A) 30 to 85% by weight of lower alcohol, (B) 1 to 20% by weight of ultraviolet absorber, (C) thickener 0.05 (D) 10 to 68% by weight of water.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The lower alcohol of component (A) used in the present invention is preferably an aliphatic alcohol having 1 to 4 carbon atoms, more preferably ethanol, isopropanol, and particularly preferably ethanol. In the ultraviolet ray protective agent of the present invention, the component (A) contains 30 to 85% by weight (hereinafter, simply referred to as%) in terms of stability, dryness, refreshing feeling, and non-stickiness.
Although it contains, it is more preferable to contain 40 to 80%.

[0007] The ultraviolet absorbent of the component (B) used in the present invention includes ultraviolet rays such as cinnamic acid, benzophenone, urocanic acid, benzoic acid, salicylic acid, benzoylmethane, triazine, and anthranilic acid. Absorbents. Specifically, benzyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, isopropyl paramethoxycinnamate / diisopropyl cinnamate mixture and the like Cinnamic acid ultraviolet absorbers: hydroxymethoxybenzophenone, hydroxymethoxybenzophenonesulfonic acid, sodium hydroxymethoxybenzophenonesulfonate, dihydroxymethoxybenzophenone,
Benzophenone ultraviolet absorbers such as sodium dihydroxymethoxybenzophenone disulfonate, dihydroxybenzophenone and tetrahydroxybendiphenone;
Urocanic acid ultraviolet absorbers such as urocanic acid and ethyl urocanate; paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, octyl paradimethylaminobenzoate, 4- [N, N- Benzoic acid-based ultraviolet absorbers such as ethyl di (2-hydroxypropyl) amino] benzoate; salicylic acid-based ultraviolet absorbers such as ethylene glycol salicylate, phenyl salicylate, octyl salicylate, benzyl salicylate, p-tert-butylphenyl salicylate, and homomenthyl salicylate Agent; 4-tert-
Butyl-4'-methoxybenzoylmethane, oxybenzone, 2,4,6-tris [anilino-p- (carbo-
2'-ethyl-1'-hexyloxy)]-1,3,5
-Triazine, 2- (2-hydroxy-5-methylphenyl) benzotriazole, menthyl anthranilate, etc., and as the component (B), from the viewpoint of stability, cinnamic acid, benzoylmethane, triazine, etc. Is preferred.

As the component (B), two or more kinds may be used in combination.
From the viewpoint of the oil-free feel at the time of application and the ultraviolet ray absorbing effect, the ultraviolet ray protective agent of the present invention contains 1 to 20%,
It is more preferable to contain 2 to 10%.

The thickener of the component (C) used in the present invention includes:
It thickens a mixture of the lower alcohol of the component (A) and the water of the component (D), and is preferably a carboxyvinyl polymer, an acrylic acid / alkyl methacrylate copolymer,
Cationic cross-linked polymers are included.

The acrylic acid / alkyl methacrylate copolymer has the following formula (1)

[0011]

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(Wherein, R represents an alkyl group having 10 to 30 carbon atoms, X and Y each represent mol% of each unit in the copolymer, X = 80.0 to 99.9 mol%, Y
= 0.1 to 20.0 mol%). Commercially available products can be used as such a copolymer. F. PEMULEN TR-1, PEMULENT T manufactured by Goodrich
R-2, Carbopol ETD2020 and the like.

The cationic crosslinked copolymer is a substance having a cationic group and a crosslinked structure in a molecule.
At least one kind of cationic group-containing vinyl monomer (hereinafter, monomer (a ₁ )), at least one kind of amide group-containing vinyl monomer (hereinafter, monomer (a ₂ )),
Cationic crosslinked polymer (hereinafter referred to as copolymer) containing at least one crosslinkable vinyl monomer having at least one vinyl group in the molecule (hereinafter referred to as monomer (a ₃ )) as an essential constituent monomer (I).

The copolymer (I) has, as constituent monomers,
Further, other vinyl monomers such as a vinyl monomer containing a (meth) acryloyl group may be contained.

Preferred specific examples of the monomer (a ₁ ) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and acid neutralization of diethylaminopropyl (meth) acrylamide. Or a quaternary ammonium salt quaternized with a quaternizing agent, or dimethyldiallylammonium chloride.

Preferred examples of the monomer (a ₂ ) include, for example, N-methyl (meth) acrylamide, N,
N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, Nn-propyl (meth)
Acrylamide, Nt-butylacrylamide, N-
(Meth) acryloylmorpholine, N-vinylpiperidone, N-vinylpyrrolidone, and the like. Among these, the use feeling is preferable when N, N-disubstituted acrylamide is used, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like are particularly preferable.

As the monomer (a ₃ ), (meth) acrylates of polyhydric alcohols or unsaturated alcohols,
Acrylamide, divinyl compounds, polyallyl compounds and the like can be mentioned. Of these, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, allyl etherified pentaerythritol, vinyl (meth) acrylate, allyl (meth) acrylate, etc. Particularly preferred.

As the cationic cross-linked copolymer, a copolymer using at least one of the preferred examples of each monomer is preferable, and particularly, dimethylaminoethyl (meth) acrylate / N, N-dimethyl (meth) ) Acrylamide / polyethylene glycol di (meth) acrylate is preferred from the viewpoint of the durability of the ultraviolet protection effect.

The proportion of the monomer (a ₃ ) is preferably from 0.002 to 5%, more preferably from 0.002 to 3%, based on the total amount of the monomer.
%, More preferably 0.002 to 1%. Monomer (a
_When the proportion of ₃ ) is within the above range, the feel of the hydrogel formed from the copolymer (I) is soft and slippery.

The copolymer (I) comprises, in addition to one or more of each of the above-mentioned three types of vinyl monomers, which are essential constitutional units,
General formula (2)

[0021]

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Wherein R ¹ represents a hydrogen atom or a methyl group; G represents an oxygen atom or a —NH— group; R ² represents a linear or branched alkylene group having 1 to 17 carbon atoms; (3)

[0023]

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(Where n is an integer of 1 to 4 and m is 1 to 25)
Indicates an integer. ), And R ³ represents a hydrogen atom or a methyl group. )) May be contained as a constitutional unit.

Further, other vinyl monomers, for example, anionic group-containing monomers such as acrylic acid and methacrylic acid;
(3-sulfopropyl) -N-acryloyloxyethyl-N, N-dimethylammonium betaine, N-carboxymethyl-N-methacryloyloxyethyl-N,
Betaines such as N-dimethylammonium betaine and the like may be contained as constituent units.

The copolymer (I) is obtained by a conventional method, for example, by radical polymerization, and can be produced by an aqueous solution polymerization method, a reverse phase suspension polymerization method, a precipitation polymerization method or the like.

Component (C) includes carboxyvinyl polymer, acrylic acid / alkyl methacrylate copolymer and cationic crosslinked copolymer, methyl cellulose,
Thickeners such as ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and methylhydroxypropylcellulose may be used in combination, and these thickeners may be used in combination with the total amount of carboxyvinyl polymer and cationic cross-linked copolymer (1 part by weight). 1 part by weight or less,
Particularly, it is preferable to contain 0.01 to 0.5 parts by weight.

As the component (C), two or more kinds may be used in combination. Further, from the viewpoint of a coating effect such as a thickening effect, non-stickiness, and good spreadability, the component (C) may be added in the ultraviolet protective agent of the present invention in an amount of 0.1%. 05-2
%, But more preferably 0.1 to 1%.

The water of the component (D) used in the present invention is 10 to 6 in view of stability, non-stickiness, and application feeling such as refreshing feeling.
The content is 8%, but more preferably 12 to 50%.

When the ultraviolet ray protective agent of the present invention further contains component (E) spherical powder in addition to these essential components, the composition has better spreadability, and a more smooth feeling of application and use can be obtained. preferable. The spherical powder of the component (E) to be used includes nylon, polystyrene, polyethylene, polypropylene, polyurethane, polytetrafluoroethylene, silica, silicone resin, polyvinyl chloride, acrylic acid or acrylate polymer, methacrylic acid or methacrylic acid. Acid ester polymers, acrylic acid / styrene copolymers, styrene / divinylbenzene copolymers and the like can be mentioned. Nylon, polystyrene, polyethylene and silicone resin are preferred, and silicone resin is particularly preferred from the viewpoint of hydrophobicity. Component (E) is
Average particle size measured by laser diffraction / scattering method is 1-50μ
m, and particularly preferably 3 to 20 μm, from the viewpoint of coating feeling. The component (E) may contain two or more kinds, and preferably contains 1 to 20%, particularly preferably 2 to 10%, in the ultraviolet protective agent of the present invention.

The ultraviolet ray protective agent of the present invention may contain the component (F) a polar oil from the viewpoint of adjusting the feel and improving the stability, and its content is 2 to 20%, particularly 5 to 15%. Is preferred. As the component (F), specifically, fats and oils such as sunflower oil and cocoa oil; neopentyl glycol dicaprate;
Ester oils such as isononyl isononanoate and isopropyl myristate; higher alcohols such as stearyl alcohol and cetyl alcohol; and fatty acids such as isostearic acid, undecylenic acid and oleic acid, and ester oils are particularly preferred in terms of feel.

The ultraviolet protective agent of the present invention is excellent in water resistance because it does not substantially contain a surfactant. That is, the content of the surfactant is less than 1%, preferably 0.5% or less, particularly preferably 0.2% or less.

The ultraviolet ray protective agent of the present invention may further contain an ultraviolet ray scattering agent in order to further enhance the ultraviolet ray protective effect. Examples of the ultraviolet light scattering agent include titanium dioxide, zinc oxide, iron oxide, zirconium oxide, aluminum oxide, and the like, as well as fine particles and composites thereof. Particularly, titanium dioxide and zinc oxide are preferable. Two or more ultraviolet scattering agents may be used in combination, but the content is preferably 1% or less, particularly preferably 0.5% or less from the viewpoint of stability.

The ultraviolet protective agent of the present invention comprises the components (A) to
It is a gel dosage form having a high content of lower alcohol, in which the essential components of (D) and other appropriately used components including component (E) are mixed. Its pH (25 ° C.) is mildly acidic to the skin, that is, 4 to 7, 5 to 7, especially 5.5 to 5.
Preferably it is 6.5.

[0035]

EXAMPLES Production Example 1 N, N-dimethylaminoethyl methacrylate diethyl sulfate (MOEDES: 80% manufactured by Nitto Chemical Industry Co., Ltd.) was placed in a reaction vessel.
Aqueous solution) 50.6 g, N, N-dimethylacrylamide 51.55 g, polyoxyethylene (14) glycol dimethacrylate (NK-14G: manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.09
A monomer aqueous solution consisting of 6 g and 350 g of ion-exchanged water, which had been subjected to nitrogen replacement in advance, was added thereto, and nitrogen was further blown in for 20 minutes to raise the temperature to 55 ° C. while replacing the inside of the reaction system with nitrogen. Next, 0.19 g of a polymerization initiator (2,2'-azobis (2-amidinopropane) dihydrochloride) was added. 30 minutes to 1
After an hour, polymerization started, and the whole became a soft gel.
The stirring was continued as it was, and the polymerization was stopped 4 hours after the addition of the polymerization initiator. The mochi-like content was taken out, washed with stirring in 5 L of ethanol for 10 minutes, and dried. Thereafter, the mixture was pulverized with a coffee mill or a jet mill, and the pulverized particles were classified with a high voltter to obtain a copolymer (I).

Example 1 A gel UV protective agent having the composition shown in Table 1 was produced and evaluated as follows. Evaluation items: Stability: 50 g of an ultraviolet protective agent was placed in a 100-mL glass bottle, sealed, placed in a thermostat at 50 ° C., and the appearance after one month was evaluated based on the following evaluation criteria. ；: No sediment or separation was observed. Δ: Slight separation was observed. ×: sediment or separation was observed. -Drying speed, refreshing feeling, non-stickiness: Paneler 10
Sensory evaluation when the name used the ultraviolet protection agent of Table 1
Evaluation was made based on the following evaluation criteria. ；: 7 or more out of 10 subjects recognized the effect. Δ: 3 to 6 out of 10 subjects recognized the effect. ×: 2 or less out of 10 recognized the effect.・ Water resistance: 2 mg / cm ² of the UV protection agent shown in Table 1 was applied to dry pig leather (2 × 4 cm) and air-dried at room temperature for 30 minutes.
0 ° C, put in 500 mL of water, 250 r / min, 8
After stirring for 0 minutes, air-dry at room temperature for 30 minutes, extract with ethanol, measure the absorbance at 310 nm with an ultraviolet spectrometer,
The residual rate was calculated.

[0037]

[Table 1]

Table 1 shows the results of the evaluation.
All were excellent in stability, speed of drying, refreshing feeling, non-stickiness and water resistance.

[0039]

EFFECTS OF THE INVENTION The ultraviolet protective agent of the present invention is excellent in coating feeling such as excellent water resistance, no oily feeling, good drying property, etc., and is stable despite its high content of lower alcohol. Is good.

Continued on the front page F term (reference) 4C083 AB051 AB052 AC101 AC212 AC342 AC432 AC542 AC852 AD072 AD092 AD152 BB26 BB46 CC19 DD27 EE06 EE07 EE17

Claims (2)

[Claims] 1. The following components (A) to (D): (A) 30 to 85% by weight of lower alcohol, (B) 1 to 20% by weight of ultraviolet absorber, (C) Thickener 0.05 to 2 (D) 10 to 68% by weight of water, containing substantially no surfactant and being weakly acidic. 2. The ultraviolet protective agent according to claim 1, further comprising component (E) a spherical powder.