JP5469319B2 - Sunscreen cosmetics - Google Patents

Description

  The present invention relates to a sunscreen cosmetic. More specifically, the present invention relates to a sunscreen cosmetic that has a high UV protection ability and is excellent in use feeling and stability.

  The important ultraviolet absorption wavelength regions by sunscreen cosmetics are the UV-A region (320 to 400 nm) and the UV-B region (290 to 320 nm). UV rays in the UV-A region (320 to 400 nm) invade the skin black, but it is considered that sunburn occurs like the ultraviolet rays in the UV-B region (290 to 320 nm) and does not promote skin aging. It was. However, in recent years, ultraviolet rays in the UV-B region stay relatively on the surface of the skin, whereas ultraviolet rays in the UV-A region reach the deep part of the skin, and induce skin cancer as well as skin aging. It has been found to be the cause.

  Cosmetic UV absorbers that have been used to date are classified according to the structure: (1) benzoic acid derivatives, (2) cinnamic acid derivatives, (3) benzophenone derivatives, (4) dibenzoylmethane derivatives, (5) Salicylic acid derivatives and the like. In recent years, the ultraviolet absorbers (2) and (4) are frequently used.

  However, the ultraviolet absorbers listed above have their respective problems from a practical standpoint. For example, in the benzoic acid derivative of (1), for example, p-dimethylaminobenzoic acid-2-ethylhexyl is liquid and transparent, and has advantages that it is easy to handle, but there is a suspicion of safety including these derivatives. It has not been used in recent years. Further, the maximum absorption wavelength is in the vicinity of 290 nm, and the ultraviolet ray only in the UV-B region is absorbed.

  In the cinnamic acid derivative (2), there is p-methoxycinnamic acid-2-ethylhexyl ester as an ultraviolet absorber most frequently used in sun care cosmetics currently on the market. The maximum absorption wavelength is around 310 nm, and the absorption region does not reach the UV-A region. In addition, the color changes due to sunlight and there is a problem in the sustainability of the coloring property and the UV protection effect.

  In the benzophenone derivative of (3), for example, 2-hydroxy-4-methoxybenzophenone has absorption over the UV-A and UV-B regions and has relatively good solubility in a skin external preparation base, but has a maximum absorption wavelength. Slightly close to the UV-B region and the absorbance is not very large. In recent years, a basic skeleton structure (benzophenone) has been pointed out as an environmental hormone and its use has been avoided.

  Of the dibenzoylmethane derivatives of (4), 4-tert-butoxy-4-methoxydibenzoylmethane is often used as a skin external preparation. The maximum absorption is in the vicinity of 360 nm, the absorbance is large, and it is excellent as an ultraviolet absorber in the UV-A region. However, there is a problem in light stability, the compatibility with the oil for skin external preparation is poor, and only a small amount can be mixed.

  In the salicylic acid derivative (5), octyl salicylate is used. It has a maximum absorption wavelength in the UV-B region, is oily, and is excellent in compatibility with paraffin oil or the like, but is not practically used because of its low absorbance.

  For this reason, 2-ethylhexyl p-methoxycinnamate (2) is used in the UV-B region, and 4-tert-butoxy-4-methoxydibenzoylmethane (4) is used in the UV-A region. Often done. Particularly in recent years, there has been an increasing demand for ultraviolet absorption in the UV-A region.

On the other hand, dimethicodiethylbenzalmalonate and 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] are UV It is known as a kind of ultraviolet absorber in the -A region (Patent Documents 1 and 2).
However, both of these UV absorbers have low UV protection ability, and have problems such as squeeze and oiliness due to high blending when increasing the blending amount and aiming for a high SPF product.

  As described above, some ultraviolet absorbers cause problems in the feeling of use, and may be a major problem when blended in sunscreen cosmetics that place importance on the feeling of use. That is, when the blending amount of the ultraviolet absorber is increased in order to exhibit a high ultraviolet absorption effect, the feeling of use becomes extremely worse. Furthermore, aggregation and precipitation of the ultraviolet absorber are likely to occur, resulting in a problem in stability. Therefore, there are cases where the desired ultraviolet absorber cannot be blended in the desired blending amount.

  In general, from the viewpoint of securing a wide absorption region, a plurality of ultraviolet absorbers are blended into a sunscreen cosmetic. However, in order to improve the feeling of use and to ensure stability, it is not usually performed to mix a plurality of ultraviolet absorbers.

JP 10-175836 JP 07-23315

  In view of the above-mentioned viewpoints, the present inventors have conducted extensive research on the feeling of use of an ultraviolet absorber when blended with a sunscreen cosmetic. As a result, dimethicodiethylbenzal is selected from a wide variety of ultraviolet absorbers. Sunscreen cosmetics containing a combination of malonate and 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] In addition, when blended with both-end silicone-modified glycerin having a specific structure, even when producing a product having a high SPF, it exhibits excellent usability and stability, and has excellent cosmetics. The present invention has been completed by finding that it is possible to provide a stop cosmetic.

  The objective of this invention is providing the sunscreen cosmetics which are excellent in a usability | use_condition and stability, and have the ultraviolet absorption effect of especially remarkable UV-A area | region.

式中、Ｒ１は炭素数１〜１２の直鎖又は分岐アルキル基、もしくはフェニル基であり、Ｒ２は炭素数２〜１１のアルキレン基であり、ｍは１０〜１２０、ｎは１〜１１である。
That is, the present invention
(A) dimethicodiethylbenzalmalonate;
(B) 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol];
(C) is to provide a sunscreen cosmetic which is characterized by containing at both ends silicone-modified glycerin represented by the following general formula (a).
(A)

In the formula, R1 is a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group, R2 is an alkylene group having 2 to 11 carbon atoms, m is 10 to 120, and n is 1 to 11. .

Moreover, this invention provides said sunscreen cosmetics characterized by the above-mentioned sunscreen cosmetics being water-in-oil type emulsified cosmetics.

  The sunscreen cosmetics of the present invention have an excellent feeling of use and stability, and are excellent in long-lasting makeup. Therefore, even when the ultraviolet absorber is highly blended, there is no problem in the feeling of use, and a sunscreen cosmetic having a high SPF can be provided. Furthermore, the ultraviolet absorption effect is synergistically increased.

  Hereinafter, the present invention will be described in detail.

ｓ＝３〜６，ｒ＝５０〜７０ Dimethicodiethylbenzalmalonate used in the present invention is a known ultraviolet absorber having the following structure, and Pulsol SLX (INCI name: Polysilicone-15, DSM Nutritional Products, Sisseln) can be suitably used as a commercial product. . This ultraviolet absorbent has low ultraviolet absorbing ability and does not improve SPF. Further, it is an ultraviolet absorber that has been confirmed to exhibit a bad feeling of oiliness in sunscreen cosmetics.

s = 3-6, r = 50-70

2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] used in the present invention has a known ultraviolet absorption having the following structure: As a commercial product, Tinosorb M (50% aqueous dispersion, Ciba Specialty Chemicals) can be suitably used. This ultraviolet absorbent has low ultraviolet absorbing ability and does not improve SPF. Further, it is an ultraviolet absorber that has been confirmed to exhibit a bad feeling of “squeaking” in sunscreen cosmetics.

The amount of dimethicodiethylbenzalmalonate and 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] Depending on the target SPF, the amount is preferably 1 to 10% by mass with respect to the total amount of the sunscreen cosmetic.
More preferably, dimethicodiethylbenzalmalonate is 1 to 7% by mass, and 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3) -Tetramethylbutyl) phenol] is 1 to 5% by mass.
Moreover, the optimal compounding ratio of both is a mass ratio, dimethicodiethylbenzalmalonate is 1, and 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- ( 1,1,3,3-tetramethylbutyl) phenol] is 0.3 to 0.7.

式中、Ｒ１は炭素数１〜１２の直鎖又は分岐アルキル基、もしくはフェニル基であり、Ｒ２は炭素数２〜１１のアルキル基であり、ｍは１０〜１２０、ｎは１〜１１である。 The both-end silicone-modified glycerin used in the present invention is a compound represented by the following general formula (a). In this invention, it mix | blends as a stabilizer of the said ultraviolet absorber.
In addition, when the sunscreen cosmetic of the present invention is an emulsified cosmetic, it also functions suitably as an emulsifier.
(A)

In the formula, R1 is a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group, R2 is an alkyl group having 2 to 11 carbon atoms, m is 10 to 120, and n is 1 to 11. .

式中、Ｒ１は炭素数１〜１２の直鎖又は分岐アルキル基、もしくはフェニル基、ｍは１０〜１２０、ｎは１〜１１である。 Preferably it is a both-ends silicone modified glycerin of the following formula (b).
(B)

In the formula, R1 is a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group, m is 10 to 120, and n is 1 to 11.

式中、Ｒ１はそれぞれ、炭素数１〜１２の直鎖又は分岐アルキル基、もしくはフェニル基、ｍは１０〜１２０の数である。 The basic structure of the both-end silicone-modified glycerin is a BAB type triblock copolymer, and for B, for example, one-end hydrogen residue silicone represented by the following structure (c) can be used.
A is a glycerin residue.
One-terminal hydrogen silicone having the following structure (c) is a known compound. A BAB type triblock copolymer having an arbitrary degree of polymerization can be produced by a known method.
(C)

In the formula, each R1 is a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group, and m is a number of 10 to 120.

式中、ｎは１〜１１の数である。 The bond between A and B is not an essential structure for the present invention, but the both-end silicone-modified glycerin used in the present invention is obtained by binding the compound (c) and the compound represented by the following structural formula (d). It is.
(D)

In formula, n is a number of 1-11.

  The BAB type triblock copolymer can be synthesized by a known method. The synthesis scheme is shown in FIG. Thus, the both-ends silicone modified glycerin represented by the said structural formula (a), (b) is obtained.

The polymerization degree m of the silicone chain is preferably 10 to 120. The side chain substituent is preferably a methyl group, but may be substituted with phenyl or other alkyl.
As for n of the polymerization degree of a glycerol chain, 1-11 are preferable. Moreover, in the outstanding function expression as a stabilizer or an emulsifier, it is preferable that HLB is 0.2-3.0. (HLB can be determined by a known method, but is calculated by, for example, the Griffin equation (HLB value = glycerin molecular weight × 20 / total molecular weight).)
On the other hand, if the molecular weights of both AB blocks are too high, it may be difficult to spread the sunscreen cosmetic, and the weight of the stretch may be felt. Therefore, there is an appropriate range for the molecular weight, and the molecular weight is preferably 2000 to 20000.

Although the compounding quantity of the both-ends silicone modified glycerin mix | blended as a stabilizer in this invention is not restrict | limited in particular, 0.1-10.0 mass% is normally mix | blended with respect to sunscreen cosmetics. A blending amount of 1 to 5.0% by mass is suitable.
When the blending amount is less than 0.1% by mass, the stability may be inferior, and even when the blending amount is more than 10.0% by mass, the effect is not improved.

The present invention improves the stability when the ultraviolet absorber is blended by blending the above-mentioned both-end silicone-modified glycerin into a sunscreen cosmetic.
Moreover, when making the sunscreen cosmetics of this invention into emulsified cosmetics, it functions also as an emulsifier. In this case, other emulsifiers can be used in combination, but a stable emulsified composition can be obtained by blending substantially only both-end silicone-modified glycerin as the emulsifier. Particularly preferred is a water-in-oil type emulsified cosmetic, and especially the makeup is improved.

  When the sunscreen cosmetic of the present invention is made into a particularly preferred dosage form of water-in-oil cosmetic, a polar oil can be suitably blended. Conventionally, when trying to prepare a water-in-oil cosmetic containing a polar oil component using a general emulsifier, the emulsion phase is poor and the water phase and the oil phase are separated, resulting in a remarkable appearance. It sometimes worsened. On the other hand, in this invention, the emulsion stability at the time of using a polar oil-based component can be improved by mix | blending both terminal silicone modified glycerol. And since a polar oil-based component can be stably emulsified, it is possible to stably blend the above-mentioned ultraviolet absorber and a component that is difficult to dissolve in oil components such as non-polar oils and silicone oils (components that are easily dissolved in polar oils). It becomes possible.

The polar oil used in the present invention is not particularly limited, but preferably has an IOB value of 0.05 to 0.80, and more preferably has an IOB value of 0.10 to 0.60. .
The IOB value is an abbreviation of Inorganic / Organic Balance (inorganic / organic ratio), and is a value representing the ratio of the inorganic value to the organic value, and is an index indicating the degree of polarity of the organic compound. It will be. The IOB value is specifically expressed as “IOB value = inorganic value / organic value”. Here, for each of the “inorganic value” and “organic value”, for example, “organic value” is 20 for one carbon atom in the molecule, and “inorganic value” is 100 for one hydroxyl group. As described above, “inorganic value” and “organic value” corresponding to various atoms or functional groups are set, and “inorganic value” and “organic value” of all atoms and functional groups in the organic compound. Can be calculated to calculate the IOB value of the organic compound (see, for example, Fujita, “Chemical Domain”, Vol. 11, No. 10, pages 719 to 725, 1957).

  Specific polar oils include, for example, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, lactic acid Cetyl, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearylate, ethylene glycol di2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl dicaprate Glycol, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, triiso Trimethylol propane terate, pentaerythritol tetra-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, diethylhexyl naphthalene dicarboxylate , Benzoic acid (C12-15) alkyl, cetearyl isononanoate, tri (caprylic acid / capric acid) glycerin, (dicaprylic acid / capric acid) butylene glycol, glyceryl trimyristate, glyceride tri-2-heptylundecanoate Castor oil fatty acid methyl ester, oleyl oleate, cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L Glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, sebatin Examples include diisopropyl acid, di-2-ethylhexyl succinate, and tripropylene glycol dipivalate.

  One or two or more polar oils may be selected and blended. The blending amount of the polar oil is preferably 0.1 to 20.0% by mass, and more preferably 1.0 to 10.0% by mass with respect to the total amount of the sunscreen cosmetic. If the amount of the polar oil is too small, it may become sticky, and if it is too much, emulsification may be poor.

  Moreover, a silicone oil can be suitably mix | blended with the sunscreen cosmetics of this invention with the said essential component. Examples of the silicone oil used in the present invention include chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, Examples thereof include cyclic polysiloxanes such as tetramethyltetrahydrogencyclotetrasiloxane.

  In addition to the above essential components, the sunscreen cosmetics of the present invention include components usually used in cosmetics, such as whitening agents, moisturizers, antioxidants, oily components, other ultraviolet absorbers, surfactants, A sticky agent, alcohol, powder component, colorant, aqueous component, water, various skin nutrients and the like can be appropriately blended as necessary, and can be produced by a conventional method according to the dosage form.

  The sunscreen cosmetic of the present invention may be in any product form such as cream, emulsion, lotion and the like. Although the dosage form is not particularly limited, emulsified cosmetics, particularly water-in-oil emulsified cosmetics are preferred.

  Hereinafter, the present invention will be described specifically by way of examples. The present invention is not limited to these examples. The blending amount is mass% unless otherwise specified.

The water-in-oil emulsified cosmetics shown in Tables 1 to 3 below were produced by a conventional method, and in vitro SPF, stability, feeling of use (oiliness and stains), and makeup feeling were evaluated.
In the table, Pulsol SLX is dimethicodiethylbenzalmalonate, and Tinosorb M is 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3). 3-tetramethylbutyl) phenol].
Initially, the synthesis example of a both terminal silicone modified glycerol is shown. The both-end silicone-modified glycerin in the table is that of Synthesis Example 1 below.

"Synthesis Example 1 Synthesis of Silicone Modified Glycerin at Both Ends"
Charge 100 g of one-terminal hydrogenated dimethylpolysiloxane of formula (e) (Mw≈4600), 3.5 g of triglyceryl diallyl ether, and 100 g of isopropyl alcohol into a reaction vessel, and add 0.05 g of 3% isopropyl platinate isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(E)

“Synthesis Example 2 Synthesis of Silicone Modified Glycerin at Both Ends”
Charge 100 g of one-terminal hydrogenated dimethylpolysiloxane of formula (e) (Mw≈4600), 4.3 g of tetraglyceryl diallyl ether, and 100 g of isopropyl alcohol into a reaction vessel, and add 0.05 g of 3% isopropyl platinate isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(E)

"Synthesis Example 3 Synthesis of Silicone Modified Glycerin at Both Ends"
Charge 100 g of one-terminal hydrogenated dimethylpolysiloxane of formula (f) (Mw≈7600), 2.6 g of tetraglyceryl diallyl ether, and 100 g of isopropyl alcohol, and add 0.05 g of 3% isopropyl platinate isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(F)

式中、Ｐｈはフェニル基を表す。 "Synthesis Example 4 Synthesis of Silicone Modified Glycerin at Both Ends"
Charge 100 g of hydrogenated methylphenylpolysiloxane (Mw≈5600) of formula (g), 2.9 g of triglyceryl diallyl ether and 100 g of isopropyl alcohol into a reaction vessel, and add 0.05 g of 3% isopropyl chloroplatinic acid isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(G)

In the formula, Ph represents a phenyl group.

“Synthesis Example 5 Synthesis of Silicone-Modified Glycerin at Both Ends”
Charge 100 g of hydrogenated methyldodecyl polysiloxane (Mw≈5900) of formula (h), 2.7 g of triglyceryl diallyl ether and 100 g of isopropyl alcohol into a reaction vessel, and add 0.05 g of 3% isopropyl platinate isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(H)

A synthesis scheme of Synthesis Examples 1 to 5 is shown in FIG. FIG. 2 shows an IR spectrum of the compound obtained in Synthesis Example 1. Polydimethylsiloxane than peak around in 800,1000,1260,2960Cm ^-1 spectrum, and from the peak derived from a secondary alcohol in the polyglycerol around 1400 cm ^-1 is observed each synthesis proceeded Scheme Street It can be seen that the target compound is obtained.

  Next, SPF, stability, feeling of use (oiliness and blotch), and evaluation method for makeup are described.

"In vitro SPF"
The ultraviolet protection effect was performed using a highly accurate in vitro SPF measurement system described in JP-A-7-167781. Specifically, a solar simulator (Solar Ultraviolet Simulator Model 600: Solar Light Co.) was used as the light source. The sample was uniformly applied to the Transpore Tape ™ (3M Co.) used as the application body at an application amount of 2.0 mg / cm ² , dried for 15 minutes, and then irradiated with ultraviolet rays. And the calculation process of the transmitted ultraviolet spectrum was performed, and SPF value was computed.

"Stability"
The sunscreen cosmetic immediately after production was filled in a transparent sample bottle and observed visually.
<Judgment>
○: Aggregation of powder was not recognized.
X: Aggregation of powder was observed.

“Usage: oily”
An actual use test was conducted by five specialist panels.
<Judgment>
A: 4 to 5 people evaluated that they did not feel oily.
Δ: Evaluated that 2 to 3 people did not feel oily.
X: Evaluated that 0 to 1 person did not feel oily.

"Usage feeling: creaking"
An actual use test was conducted by five specialist panels.
<Judgment>
A: Evaluated that 4 to 5 people did not feel squeak.
Δ: Evaluated that 2 to 3 people did not feel squeak.
X: It was evaluated that 0 to 1 person did not feel squeak.

“Make-up Mochi”
An actual use test was conducted by five specialist panels.
<Judgment>
○: Four to five people evaluated that makeup was good.
(Triangle | delta): Two to three people evaluated that makeup was good.
×: 0 to 1 people evaluated that makeup was good.

＊１：５０％水分散体

* 1: 50% aqueous dispersion

＊１：５０％水分散体

* 1: 50% aqueous dispersion

＊１：５０％水分散体

* 1: 50% aqueous dispersion

In the said result, the sunscreen cosmetics of this invention have shown the effect outstanding about all the items of SPF, stability, a feeling of use, and makeup.
In particular, from Comparative Examples 1-3 and Example 1, dimethicodiethylbenzalmalonate (Parsol SLX) and 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1 , 1,3,3-tetramethylbutyl) phenol (Tinosorb M) is deteriorated in stability, but the stability is remarkably improved by the blending of both terminal silicone-modified glycerin.
Moreover, from Examples 2 to 16, it can be seen that the stability is improved at all levels by blending the both-end silicone-modified glycerin and does not affect the usability and the SPF value.
Furthermore, by adding Pulsol SLX, the makeup is improved.
And by using Pulsol SLX and Tinosorb M in combination, SPF is dramatically improved and a synergistic effect is recognized.
On the other hand, when pulsole SLX is highly blended, the oiliness is conspicuous, and when Chinosorb M is blended high, squeak becomes conspicuous, and it can be seen that there is an optimum blending ratio.
From the above, dimethicodiethylbenzalmalonate and 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, both ends When combined with silicone-modified glycerin, the SPF value increases dramatically, and a sunscreen cosmetic excellent in stability, feeling of use and makeup can be provided.

  The prescription example of the sunscreen cosmetics of this invention is given to the following. In addition, the both terminal silicone modified glycerol manufactured in Synthesis Examples 1-5 can utilize the both terminal silicone modified glycerol.

Example 17: Sunscreen emulsion (W / O)
Compounding ingredients Mass%
(1) Decamethylcyclopentasiloxane 30
(2) Polyoxyethylene dimethicone modified organopolysiloxane 2
(3) Cetyl isooctanoate 3
(4) Dimethylpolysiloxane 2
(5) Pulsol SLX 5
(6) Paraben appropriate amount (7) Perfume appropriate amount (8) Organically modified clay mineral 0.5
(9) Hydrophobized titanium oxide 4
(10) Hydrophobized zinc oxide 10
(11) Both ends silicone-modified glycerin 1
(12) Remaining ion exchange water (13) Glycerin 10
(14) Edetate salt (15) Tinosorb M 3
Manufacturing method (1)-(8) is heated and mixed and dissolved at 70 ° C., and the oil phase is adjusted in advance. Next, (9) to (11) are added and dispersed and mixed with a disper. (12) to (14) are dispersed and mixed at 70 ° C. and then gradually added to the oil phase while stirring with a disper, and mixed and dissolved sufficiently and cooled to obtain the desired sunscreen cream.

Example 18: Sunscreen cream (W / O)
Compounding ingredients Mass%
(1) Decamethylcyclopentasiloxane 20
(2) Polyoxyethylene dimethicone modified organopolysiloxane 2
(3) Cetyl isooctanoate 3
(4) Dimethylpolysiloxane 2
(5) Pulsol SLX 5
(6) Paraben appropriate amount (7) Fragrance appropriate amount (8) Organically modified clay mineral 2
(9) Hydrophobized titanium oxide 4
(10) Hydrophobized zinc oxide 10
(11) Both ends silicone-modified glycerin 1
(12) Remaining ion exchange water (13) Glycerin 10
(14) Edetate salt (15) Tinosorb M 3
Manufacturing method (1)-(8) is heated and mixed and dissolved at 70 ° C., and the oil phase is adjusted in advance. Next, (9) to (11) are added and dispersed and mixed with a disper. (12) to (14) are dispersed and mixed at 70 ° C. and then gradually added to the oil phase while stirring with a disper, and mixed and dissolved sufficiently and cooled to obtain the desired sunscreen cream.

Example 19: Sunscreen Latex (O / W)
Compounding ingredients Mass%
<< Aqueous phase component 1 >>
(1) Glycerin 3
(2) POE60 hydrogenated castor oil 1.5
(3) Sodium carboxymethyl cellulose 0.1
(4) Succinoglycan 0.3
(5) Ion-exchanged water Residual (6) Edeto salt Suitable amount << Oil phase component >>
(7) Hydrophobized titanium oxide 4
(8) Hydrophobized zinc oxide 10
(9) Isostearic acid 1
(10) Cyclopentapolysiloxane 10
(11) Pulsol SLX 5
(12) Methylphenylpolysiloxane 1
(13) Both ends silicone-modified glycerin 1
<< Aqueous component 2 >>
(14) Ion exchange water 5
(15) Citric acid appropriate amount (16) Sodium citrate appropriate amount (17) Ethanol 5
(18) Preservative appropriate amount (19) Chinosorb M 3
Production Method Oil phase components (7) to (13) are mixed, and the mixture is crushed by a bead mill to obtain a dispersion. The obtained dispersion is added to the aqueous phase components 1 (1) to (6) and emulsified by a disper treatment. Thereafter, water phase components 2 (14) to (19) are added to and mixed with water phase component 1, and a disper treatment is performed to obtain a target oil-in-water emulsified cosmetic.

  ADVANTAGE OF THE INVENTION According to this invention, the sunscreen cosmetics which solve the fault on the feeling of use which an ultraviolet absorber has, have a high ultraviolet-ray defense capability, and are very excellent in a feeling of use and stability can be provided.

It is a figure explaining the synthetic scheme of both terminal silicone modified glycerol. 2 is an IR spectrum of both-end silicone-modified glycerin of Synthesis Example 1.

Claims (2)

(A) dimethicodiethylbenzalmalonate;
(B) 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol];
(C) sunscreen cosmetic which is characterized by containing at both ends silicone-modified glycerin represented by the following general formula (a).
(A)

In the formula, R1 is a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group, R2 is an alkylene group having 2 to 11 carbon atoms, m is 10 to 120, and n is 1 to 11. .   The sunscreen cosmetic according to claim 1, wherein the sunscreen cosmetic is a water-in-oil emulsified cosmetic.

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