JPH09309818A - Emulsion-type anti-suntan cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject cosmetic improved in reemulsifiability when comes to contact with water, and excellent in water resistance and emulsion stability, etc. SOLUTION: This emulsion-type anti-suntan cosmetic is a composition comprising (A) at least one kind of an acrylic acid-alkyl methacrylate copolymer of formula I (R1 is a 10-30C alkyl; (m) is 12-51 on average; (n) is 1-4 on average), (B) an oily substance, (C) at least one kind selected from ultraviolet absorbers, titanium dioxide and zinc oxide, (D) water, and (E) at least one kind of copolymer selected from vinylpyrrolidone-alkene copolymers of formula II (R2 is a 8-30C alkyl; (x) is 1-34 on average; (y) is 1-14 on average) and polypropylene glycol-4,4'-dicyclohexylmethane diisocyanate copolymers of formula III.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an emulsified sunscreen cosmetic which has improved re-emulsification properties upon contact with water and is excellent in water resistance, emulsion stability and safety. More specifically, 1 of acrylic acid / alkyl methacrylate copolymer
Or two or more, one or more of oily substances, UV absorbers, titanium oxide, zinc oxide, water, and vinylpyrrolidone-alkene copolymer and polypropylene glycol-4,4'-dicyclohexylmethane diisocyanate copolymer The present invention relates to an emulsified sunscreen cosmetic containing one or more types of coalescence.

[0002]

2. Description of the Related Art A sunscreen cosmetic used outdoors, especially in summer, is required to have resistance to sweat and water. In conventional sunscreen cosmetics to which water resistance is imparted, in order to prevent re-emulsification when contacted with water, a lipophilic nonionic surfactant or the like is used to prepare a W / O type emulsion, or a fatty acid is used. A large amount of a water resistant film forming agent such as a silicone resin has been blended with an O / W type emulsion made of soap, a hydrophilic nonionic surfactant or the like.

However, the W / O type emulsion has a problem in stability, such as stickiness, it is difficult to obtain a refreshing feeling during use, and creaming and separation are likely to occur. On the other hand, when a large amount of a water resistant film-forming agent is added to the O / W type emulsion, unfavorable effects such as poor elongation and heavyness are caused in use feeling. Further, in these emulsions, since a surfactant is used upon emulsification, the surfactant is irritating to the skin or eyes, and there is a problem in safety.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the problems of the conventional water resistant sunscreen cosmetics as described above. That is, the present invention has high water resistance with reduced re-emulsification property, good stability, high safety without using conventional surfactants, and light elongation and feeling of use without stickiness. The present invention provides an emulsion type sunscreen cosmetic.

[0005]

In the present invention, an oily substance is prepared by using one kind or two or more kinds of the acrylic acid / alkyl methacrylate copolymer represented by the general formula 1 in place of the conventional surfactant. The above problems could be solved by emulsification and by using one or more specific water-resistant film-forming agents in combination. That is, the sunscreen cosmetic according to the present invention comprises (A) one or more of the acrylic acid / alkyl methacrylate copolymers represented by the general formula 1,
(B) Oily substance, (C) UV absorber, one or more kinds of titanium oxide, zinc oxide, (D) water, and (E) vinylpyrrolidone-alkene copolymer represented by the general formula 2 and general 1 selected from polypropylene glycol-4,4'-dicyclohexylmethane diisocyanate copolymer represented by formula 3
It is composed of two or more species.

[Chemical 1]

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The acrylic acid / alkyl methacrylate copolymer (A) is a copolymer of acrylic acid and alkyl methacrylate, as shown by the general formula 1, and has a hydrophilic moiety derived from a carboxyl group. It has a lipophilic part derived from an alkyl group and has a good emulsifying property, and it is manufactured by BF Goodrich Co.
ULEN) is marketed under the brand name. It is also possible to use carboxyvinyl polymer and the like together.

[Chemical 1]

Examples of the oily substance (B) include avocado oil, almond oil, olive oil, sesame oil, southern oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, persic oil, castor oil, cottonseed oil, peanut oil. Oils, cacao butter, palm oil, palm kernel oil, plant oils such as oak, coconut oil, hydrogenated castor oil, turtle oil, mink oil, egg yolk oil, animal fats such as beef tallow, lard, carnauba wax,
Candelilla wax, plant waxes such as jojoba oil, beeswax, spermaceti, animal waxes such as lanolin, liquid paraffin, petrolatum, paraffin, ozokerite, ceresin,
Hydrocarbon oils such as microcrystalline wax, squalane, pristane, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, 12-
Fatty acids such as hydroxystearic acid, undecylenic acid, lanolin fatty acid, isostearic acid, lauryl alcohol, cetanol, stearyl alcohol, behenyl alcohol, oleyl alcohol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol, lanolin alcohol, cholesterol Usually used for cosmetics such as alcohols, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, ester oils such as glyceryl 2-ethylhexanoate, silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane. An oily substance can be used, and one or more types are selected from these and used.
Of these, volatile silicone oils such as low-molecular-weight dimethylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane do not remain on the skin when used in cosmetics, resulting in an oily feeling. It is particularly preferable because it gives a refreshing feeling without use. As the compounding amount,
0.5-80.0% by weight is suitable.

Examples of the ultraviolet absorber (C) include paraaminobenzoic acid, paraaminobenzoic acid derivatives such as ethyl paraaminobenzoate, methoxycinnamic acid derivatives such as octyl paramethoxycinnamate, 2-hydroxy-4-methoxybenzophenone, 2, Benzophenone derivatives such as 2'-dihydroxy-4-methoxybenzophenone, octyl salicylate, salicylate derivatives such as phenyl salicylate, 4-tert-butyl-4 '
-Methoxydibenzoylmethane and the like which are usually used for cosmetics can be used. Alternatively, titanium oxide or zinc oxide having an ultraviolet scattering effect can be used. From these, one kind or two or more kinds are selected and used.

The vinylpyrrolidone / alkene copolymer (E) is a copolymer composed of vinylpyrrolidone and an alkene having 10 to 32 carbon atoms from decene to dotriacontene, as represented by the general formula 2. Further, the polypropylene glycol / 4'-dicyclohexylmethane diisocyanate copolymer has an average molecular weight of 4,000 to 18, consisting of polypropylene glycol and 4,4'-dicyclohexylmethane diisocyanate, as shown by the general formula 3.
000 oligomers. All of these forms a highly water-resistant film having high skin compatibility and skin adhesion.
In the present invention, one or more of these are selected and used. The blending amount of these copolymers is such that the weight ratio of the acrylic acid / alkyl methacrylate copolymer of (A) (A) /
A range in which (E) is 8/2 to 1/9 is suitable. Also,
Other film forming agents can also be used in combination. Suitable examples of the film-forming agent include silicone resins such as trimethylsiloxysilicic acid, silylated pullulan, and the like.

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[0010]

The emulsion-type sunscreen cosmetic according to the present invention has good emulsion stability and does not show creaming or separation even after long-term storage. When applied to the skin, it has low re-emulsification property when it comes into contact with water, exhibits excellent water resistance and water repellency, and has good makeup retention. In addition, it has low irritation to the skin and eyes and is excellent in safety. Furthermore, it is not sticky, stretches lightly, and has good usability.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The emulsified sunscreen cosmetic according to the present invention can be provided in product forms such as emulsion, cream, makeup base lotion, makeup base cream, emulsion foundation, creamy foundation and the like.

[0012]

EXAMPLES Further, the features of the present invention will be described in detail with reference to examples.

The formulations of Examples 1 and 2 which are sunscreen emulsions according to the present invention are shown in Table 1 together with Comparative Examples.
In Example 1 and Example 2, (4) to (6) or (7) in Table 1 were mixed and homogenized, and a part of (11) was dispersed and dissolved therein.
(1), (8) and (10) were added, a shearing force was applied by a homogenizer etc. to emulsify, and (9) dissolved in the rest of (11) was added to neutralize, mix and homogenize, and then ( Prepare by adding 12).

Comparative Example 1 is a W / O type emulsion obtained by emulsifying a silicone oil using a sorbitan sesquioleate ester which is a lipophilic nonionic surfactant, and ), (4), (5) are mixed, heated and homogenized, and (10), (11) and (8) dispersed therein are gradually added to emulsify and after cooling. Obtained by adding (12). Comparative Examples 2 and 3 are O / W type emulsions obtained by emulsifying silicone oil with polyoxyethylene (20E.O.) sorbitan monooleate which is a hydrophilic nonionic surfactant. In addition, a water-resistant film forming agent is blended, and (3) to (6) or (7) is mixed and heated to homogenize, and this is heated and dissolved (10) and (11) to (8) Is gradually added to the dispersion to emulsify, and after cooling, (12) is added to obtain. Comparative Example 4 is an emulsion obtained by emulsifying silicone oil using an acrylic acid / alkyl methacrylate copolymer, which is a water resistant film forming agent (6), (7).
It does not contain (1), (8), (10), which is a mixture of (4) and (5) mixed and homogenized, and then dispersed and dissolved in a part of (11).
After adding and emulsifying by applying a shearing force with a homogenizer etc., after neutralizing by adding (9) dissolved in the rest of (11),
Obtained by adding and mixing (12). The pH of each of the emulsions of Examples and Comparative Examples was adjusted to 7.5.

[Table 1]

Examples 1, 2 and Comparative Example 1 of the present invention
-For Comparative Example 3, water repellency, re-emulsification property, usability, safety, and stability were evaluated.

(1) Water repellent 0.1 g of each sample was taken on a slide glass, uniformly applied, dried and evaluated by measuring the contact angle. Table 2 shows the results.

[Table 2]

(2) Re-emulsification property 0.1 g of each sample was taken on a slide glass, uniformly applied and dried, and then placed in a linatsu type tester, dipped in 700 ml of tap water for 5 minutes, then dried and contacted. The angle was measured and evaluated. The results are shown in Table 2.

(3) Usability and Safety A total of 20 female panelists, aged 20 to 50, were used as one group, and each group was used blindly with the Examples and Comparative Examples, and was stretched during application and after application. A sensory evaluation was conducted on the presence or absence of stickiness and the presence or absence of irritation. Regarding growth, "heavy", "slightly heavy", "normal", "slightly light", "light", and "presence", "somewhat", "neither", "somewhat" “No”, “No”, and “I feel very strongly”, “I feel a little strongly” regarding irritation,
The evaluation was made in five levels: "feel", "delicately feel", and "not feel". The results are shown in Table 3 by the number of panelists used for each evaluation.

[Table 3]

The safety was also evaluated by a patch test. A closed patch test for 48 hours was performed on the back of each sample using 30 male panelists. The results are judged according to the judgment criteria shown in Table 4,
The average value of the skin irritation index of 30 persons is shown in Table 5.

[Table 4]

[Table 5]

(4) Stability For each sample, (a) -20 ° C
If the procedure of freezing in and then thawing is repeated 5 times,
(B) When left standing for 3 months while changing the storage temperature in the range of -10 ° C to 40 ° C, (c) When left at 40 ° C for 3 months, (d) Still at 50 ° C for 3 months. When the sample was placed, (e) Changes in the emulsified state in each case when left standing at 5 ° C. for 3 months were observed and evaluated. The results are shown in Table 6.

[Table 6]

As is clear from Table 2, the contact angles of Examples 1 and 2 and Comparative Example 1 of the present invention were larger than those of Comparative Examples 2, 3 and 4, and were very excellent. It was shown to have water repellency. Further, in Examples 1 and 2 and Comparative Example 1 of the present invention, the contact angle after soaking in water was slightly decreased, but in Comparative Examples 2 to 4, a remarkable decrease was observed. . From this, the first embodiment of the present invention
Also, in Example 2, it is shown that the water resistance is good and the re-emulsification property is also small. On the other hand, in Comparative Examples 2, 3, and 4, the water resistance was low and the maximum emulsification property was high.

From Table 3, Example 1 and Example 2 of the present invention
In the case of No. 1, it is shown that the elongation during application is light, there is no stickiness during use, and there is almost no irritation. In Comparative Example 1, Comparative Example 2 and Comparative Example 3, most of the panelists evaluated that the elongation was heavy and sticky. Also, a slight irritation was observed. In Comparative Example 4, each item had a good evaluation. The patch test results shown in Table 5 also confirmed that the skin irritation index was very low and the safety was excellent in Examples 1 and 2 of the present invention. On the other hand, in Comparative Examples 1 and 2 emulsified with a conventionally used surfactant, some skin irritation was observed.

From Table 6, it was shown that in Examples 1, 2 and Comparative Example 4 of the present invention, no change in the emulsified state was observed under each storage condition and the stability was excellent. On the other hand, in Comparative Examples 1 to 3, remarkable deterioration of the emulsified state was observed.

As described above, Examples 1 and 2 of the present invention were excellent in each item of water repellency, re-emulsification property, usability, safety and stability. On the other hand, in Comparative Example 1, the re-emulsification property was small, but the usability and stability were poor, and the safety was not evaluated very well. Comparative Example 2
In Comparative Example 3, good evaluation was not obtained in any of water repellency, re-emulsification property, feeling of use, safety and stability, and Comparative Example 4 had good stability and safety, but water repellency. It was predicted that the makeup retention would be poor due to its low redispersibility and low water resistance.

Next, the formulation of another embodiment of the present invention will be shown.

Example 2 Sunscreen Cream (1) Acrylic Acid / Alkyl Methacrylate Copolymer 4.0 (wt%) (2) Squalane 10.0 (3) Vaseline 5.0 (4) Stearyl Alcohol 3 .0 (5) Stearic acid 3.0 (6) 2-Hydroxy-4-methoxybenzophenone 2.0 (7) Octyl paramethoxycinnamate 5.0 (8) Vinylpyrrolidone-pentadecene copolymer 1.0 (9) 1,3-Butylene glycol 7.0 (10) Titanium oxide 5.0 (11) Methyl paraoxybenzoate 0.1 (12) Potassium hydroxide 1.6 (13) Purified water 53.2 (14) Perfume 0.1. 1 Manufacturing method: Mix (2) to (8) and dissolve to homogenize.
(1) and (9) to (11) are dispersed and dissolved in a part of and added, and the mixture is emulsified with a homomixer. Then dissolved in the rest of (13) (1
Add 2) to neutralize, then add (14) and mix.

[Example 3] Makeup base lotion for sunscreen (1) Acrylic acid / alkyl methacrylate copolymer 1.5 (wt%) (2) Methylphenylpolysiloxane 5.0 (3) Octamethylcyclo Tetrasiloxane 1.5 (4) Octyl paramethoxycinnamate 2.0 (5) 4-tert-butyl-4'-methoxydibenzoylmethane 3.0 (6) Vinylpyrrolidone-dodecene copolymer 0.5 (7) Vinylpyrrolidone-eicosene copolymer 0.5 (8) Trimethylsiloxysilicic acid 1.0 (9) Dipropylene glycol 6.0 (10) Titanium oxide 1.0 (11) Red iron oxide 0.1 (12) Yellow iron oxide 0.4 (13) Methyl paraoxybenzoate 0.1 (14) Potassium hydroxide 0.6 (15) Purified water 76.7 (16) Perfume 0.1 Manufacturing method: Mix and dissolve (2) to (8) And make it even, and (15)
(1) and (9) to (13) are dispersed and dissolved in a part of and added, and the mixture is emulsified with a homomixer. Then dissolved in the rest of (15) (1
Add 4) to neutralize, then add (16) and mix.

Example 4 Sunscreen Foundation (Emulsion Type) (1) Acrylic Acid / Alkyl Methacrylate Copolymer 1.0 (wt%) (2) Dimethylpolysiloxane 4.0 (3) Decamethylcyclo Pentasiloxane 2.0 (4) Octyl paramethoxycinnamate 8.0 (5) Polypropylene glycol-4,4'-dicyclo 3.0 hexylmethane diisocyanate copolymer (6) Trimethylsilyl pullulan 3.0 (7) Glycerin 3 0.0 (8) Titanium oxide 5.0 (9) Zinc oxide 3.0 (10) Talc 4.0 (11) Red iron oxide 3.0 (12) Yellow iron oxide 2.5 (13) Black iron oxide 0.5 (14) Methyl paraoxybenzoate 0.1 (15) Sodium hydroxide 0.4 (16) Purified water 57.4 (17) Perfume 0.1 Production method: Mix (2) to (6) and dissolve to homogeneity And to this (16)
Disperse and dissolve (1) and (7) to (14) in a part of the mixture, and emulsify with a homomixer. Then dissolved in the rest of (16) (1
Add 5) to neutralize, then add (17) and mix.

[Example 5] Sunscreen foundation (cream type) (1) Acrylic acid / alkyl methacrylate copolymer 5.0 (% by weight) (2) Vaseline 5.0 (3) Cetostearyl alcohol 1. 0 (4) Glyceryl tri-2-ethylhexanoate 5.0 (5) Dimethylpolysiloxane 2.0 (6) Methylphenylpolysiloxane 1.0 (7) Octyl paradimethylaminobenzoate 5.0 (8) 2 2,4-Dihydroxybenzophenone 2.5 (9) Vinylpyrrolidone-eicosene-3.5 Docosene copolymer (10) Polypropylene glycol-4,4'-dicyclo 1.0 hexylmethane diisocyanate copolymer (11) Trimethylsiloxysilica Acid 1.0 (12) 1,3-butylene glycol 5.0 (13) Titanium oxide 8.0 (14) Zinc oxide 4.0 (15) Talc 2.0 (16) Bentonite 1.0 (17) Ngara 2.6 (18) Yellow iron oxide 2.1 (19) Black iron oxide 0.3 (20) Methyl paraoxybenzoate 0.1 (21) Sodium hydroxide 2.0 (22) Purified water 40.8 ( 23) Perfume 0.1 Manufacturing method: Mix (2) to (11) and dissolve to homogenize.
Disperse and dissolve (1) and (12) to (20) in part of 2) and emulsify with a homomixer. Next, (21) dissolved in the rest of (22) is added to neutralize, and (23) is further added and mixed.

Good water resistance was observed in all of the above Examples 2 to 5, and no decrease in water resistance was observed even if these were subjected to the water immersion treatment as described above. In addition, when freezing and thawing at −20 ° C. is repeated 5 times, −
When the temperature is changed within the range of 10 ° C to 40 ° C and stored for 3 months, when stored at 40 ° C for 3 months, it is stored at 50 ° C for 3 months.
In either case of storage for 5 months or storage at 5 ° C. for 3 months, no change in state such as separation of aqueous phase or oil phase, aggregation of pigment, or sedimentation was observed. Further, the feeling of use such as elongation was good, and no irritation during use, skin irritation or sensitization due to use was observed at all.

[0031]

As described in detail above, according to the present invention, it has excellent water repellency, has good water resistance, has no re-emulsification property, and has a good feeling of use with light elongation and lightness.
Furthermore, it was possible to provide an emulsion-type sunscreen cosmetic that is highly safe, has no irritation, and is extremely stable.

Claims (3)

[Claims] 1. (A) one or more of acrylic acid / alkyl methacrylate copolymers represented by the general formula 1, (B)
An oily substance, (C) an ultraviolet absorber, one or more selected from titanium oxide and zinc oxide, (D) water, and (E) a vinylpyrrolidone-alkene copolymer represented by the general formula 2,
And polypropylene glycol represented by the general formula 3,
An emulsified sunscreen cosmetic comprising one or more selected from 4'-dicyclohexylmethane diisocyanate copolymer. Embedded image Embedded image Embedded image 2. The ratio (A) / (E) of the compounding amounts of (A) and (E) is 8/2 to 1/9 by weight.
The emulsified sunscreen cosmetic described in. 3. The blending amount of the oily substance (B) is 0.5 to 8
The emulsified sunscreen cosmetic according to claim 1 or 2, which is 0.0% by weight.