JPH02117613A - External application for skin - Google Patents

Abstract

PURPOSE:To an external application for skin having sunscreen effect, excellent practicability and durability of make-up by mixing silicone-based cinnamic acid derivative dissolving in silicone oil, having excellent resistances to water and oil and having ultraviolet light-absorbing properties of wavelength in UV-B region. CONSTITUTION:A silicone-based cinnamic acid derivative composed of an unit expressed by the formula (R<1> is 1-4C alkyl, phenyl or trimethylsiloxy; R<2> is bifunctional hydrocarbon group; X is alkoxy; n is 0-3; a is 2 or 3; R<3> is 1-4C alkyl, phenyl or trimethylsiloxy; m is 0-3) and an unit expressed by the formula O(4-m)/2SiR<3>m is blended to a silicone-based base and made to formulation by conventional method to afford the aimed article. Mixing amount of said derivative is 0.1-20% and capable of preparing in a shape of powdery, liquid-like, spray-like or foundation, etc.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a silicone-based cinnamic acid derivative that is soluble in silicone oil, has excellent water and oil resistance, and has ultraviolet absorption characteristics at wavelengths in the UV-B region. The present invention relates to a novel skin preparation for external use, which is characterized by its ability to prevent sunburn, has excellent usability, and has the effect of increasing the longevity of makeup.

[Prior Art] It is known that ultraviolet rays cause various changes in the skin.

The dermatological classification of ultraviolet rays is 400 to 320 nm.
Long wavelength ultraviolet rays called UV-A, 320-290n
Ultraviolet rays are divided into medium wavelength ultraviolet rays called UV-B, which has a wavelength of 290 nm or less, and short-wavelength ultraviolet rays, which have a wavelength of 290 nm or less, called UV-C.

Normally, most of the ultraviolet rays that humans are exposed to are from sunlight, but the ultraviolet rays that reach the ground are UV-A and UV-B.
UV-C is absorbed in the ozone layer and almost never reaches the ground. Among the ultraviolet rays that reach the ground, UV-B causes changes such as the formation of erythema and blisters when the skin is irradiated with more than a certain amount of light, as well as melanin formation and pigmentation. .

Therefore, protecting the skin from UV-B is extremely important in terms of preventing the acceleration of skin aging and preventing the occurrence and aggravation of age spots and freckles.
-B absorbers have been developed.

Here, as existing UV-B absorbers, PABA derivatives, cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives, urocanic acid derivatives, penduphenone derivatives, and heterocyclic derivatives are known.

These UV-B absorbers are used exclusively by being incorporated into external preparations such as cosmetics and quasi-drugs.

On the other hand, since sun care cosmetics that contain UV absorbers are used in the hot summer, they are easily washed off by sweat and sebum, and products used at the beach or pool are easily washed off by bathing. So there is a problem. Therefore, there is a growing need for cosmetics to last longer, and in recent years, low-molecular-weight silicone bases such as dimethylsiloquine have been widely used as bases for external preparations. This is largely due to the silicone base's ease of use, such as good spreadability, lightness and non-stick properties, and functionality, such as excellent water and oil resistance, and resistance to sweat and water.

[Problem to be solved by the invention] −′. However, existing UV-B absorbers have extremely low compatibility with silicone bases.

Therefore, in order to incorporate a silicone base into an external preparation, it is necessary to further add an oily base, which has the drawback that the above-mentioned usefulness of the silicone base cannot be fully demonstrated.

Furthermore, UV-B absorbers have the disadvantage of being inferior in water resistance and oil resistance.

On the other hand, patents for silicone having ultraviolet absorbing ability include Japanese Patent Publication No. 44-29866, Japanese Patent Application Publication No. 60-58991, and Japanese Patent Application Publication No. 60-108431.

However, these chemical structures have a basic skeleton of unsubstituted cinnamic acid, and in silicone oil, UV-C
It had a maximum absorption wavelength on the side, and was insufficient as a UVB absorber. (Figure 3 shows the UV absorption spectrum of 3-his(trimethylsiloxy)methylsilyl-2-methylpropy)tocinnamate. It can be seen that there is no suitable wavelength range as a UV-B absorber. )
Under these circumstances, there has been a strong desire to develop a UV-B absorber that dissolves in silicone oil, has excellent water and oil resistance, and sufficiently protects against wavelengths in the UV-B iJf region.

The inventors have also discovered that the silicone-based cinnamic acid derivative used in the present invention is a compound that satisfies the above-mentioned properties, and have completed the present invention. An object of the present invention is to provide an external preparation for skin that has an excellent UV-B absorption effect and can stably incorporate a UV-B absorber, and furthermore, a silicone base is used as the external preparation base. An object of the present invention is to provide a skin preparation for external use that is excellent in usability and can exhibit arbitrary UV-B absorption effects.

[Means for Solving the Problems] That is, the present invention provides siloxanes having at least one unit represented by the following general formula, in which other units that may be present in the siloxanes are:
1. A skin external preparation characterized by containing a silicone-based cinnamic acid derivative characterized by the following: general 20.4 to m1zzsiR3.

Examples of R1 defined in the formula include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-7'
Examples include methyl, phenyl group, trimethylsiloxy group, etc., but it is preferable that the methyl group or a part thereof is a phenyl group or a trimethylsiloxy group for reasons such as availability of raw materials. n represents the number of substitutions of R1. Examples of R2 include: (2) The skin external preparation according to claim 1, characterized in that a silicone base is used as the external preparation base.

The present invention will be explained in detail below.

The silicone-based cinnamic acid derivative of the present invention has a unit represented by general formula (1) and a general formula 014-s)/2 SiR3
It is composed of units expressed as , CHZ
(CH3)Z -C)I2CH2CH C1(3 HzCHzCLCHz--CH2CH20CH2CI
(2-hexylene, cyclohexylene, decylene groups, etc. are mentioned, but alkylene groups having 2 to 4 carbon atoms are preferable,
Further, -Cl2CH and CHH3 are particularly preferred because they cause relatively few side reactions in the hydrosilylation reaction.

Examples of X include methoxy, ethoxy, isopropoxy, and the like. Although there is no significant difference in solubility in silicone bases and UV-B absorption wavelengths, methoxy groups are particularly preferred from the viewpoint of easy availability of reagents. a represents the number of substitutions of X.

General 2〇 In the siloxane unit characterized by being represented by +4-□7□3iR'□, R3 is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t
Examples thereof include -butyl, phenyl group, trimethylsiloxy group, etc., but it is preferable that the methyl group or a part thereof is a phenyl group or a trimethylsiloxy group for reasons such as availability of raw materials. m is the number of substitutions of R3.

The silicone-based cinnamic acid derivative of the present invention can be synthesized by reacting a siloxane having the general formula] % formula % (4-ml/2 units) in an organic solvent in the presence of a catalyst. .

The ester of general formula (2) can be obtained by converting the corresponding substituted cinnamic acid derivative into an acid chloride by a conventional method, and then reacting it with a monohydric alcohol having an olefinically unsaturated bond in the presence of an amine. . Usual organic solvents can be used as reaction solvents, among which toluene,
Aromatic solvents such as benzene and xylene are preferably used as organic solvents, and the reaction temperature is preferably high, with reflux temperature being particularly preferred.

Depending on the alcohol used in the reaction, Y in general formula (2)
Although different, it is a monovalent hydrocarbon group having at least two carbon atoms and an olefinically unsaturated bond (including those having zero heteroatoms). For example, as a straight chain hydrocarbon group, CH,=CM-, CH2=C)ICl
3-, CIl□=CHCH2CH2, CH2''CHCH
CH2=CH-CH(Me) as a branched hydrocarbon group such as zCHzCHzCH□: CHCH20CH2CH2-
-, CHz=CH-C(Me)z-.

CHz=CH-CH(Et)-, CH2=CHC(Et
)zCHz=CHCHzCH(Me) +, CH2=
CHCH(Me)-CHz-+CHz=C(Me)CL
Some have a double bond at the end, such as -.

Also, MeCH=CH-, MeCH=CHCHz-, (
Me) zC=CH-.

(Me) zc=cHcHz-, MeCH=CHCH2
-, those with a double bond inside such as MeCHzCH=CH-, and CH2・CH-CH=CHz-1CH,=C
(Me) CH=CHz-, MeCH=CH-CH=C
Examples include those having two double bonds such as Hz-,
Esters having one double bond at the end are desirable because of the superiority of the esterification and hydrosilylation reactions and the stability (including photostability) of silicone-based cinnamic acid derivatives derived from these esters.

The silicone-based cinnamic acid derivative of the present invention can be obtained by subjecting the ester of general formula (2) thus obtained to a hydrosilylation reaction with a siloxane. is a compound expressed as a siloxane having R'nS i O(3-n)/2 units and R", Si0.4-,.1) 72 units. For example, (CIEt
O) 3SiH, (Me3SiO) JeS iH(Me
iS to) ss iH, (MeJS i)MeP
hS iH, (Me, O5i)EtMeS iH, (
MezO5i)EtPhSiH, H(Me), S 1
Examples include O5i (Me), 05i (Me)2H, etc., but 1.1° 1.3 ,5,5.5-hebutamethyltrisiloxane is preferred. However, the method is not limited to this as long as the silicone-based cinnamic acid derivative of the present invention can be produced.

As the reaction solvent, ordinary organic solvents can be used, but aromatic organic solvents such as toluene, benzene and xylene are particularly preferred, and the reaction temperature is preferably high, with reflux temperature being preferred.

As a catalyst for hydrosilylation, commonly known rhodium complexes (Wilkinson complex), ruthenium complexes, platinum complexes, chloroplatinic acid, etc. can be used, but these may be used depending on the ease of obtaining the catalyst and the operational simplicity of the synthetic reaction. A chloroplatinic acid catalyst is preferred from the viewpoint of properties.

The silicone-based cinnamic acid derivatives used in the present invention can be manufactured from low molecular weight ones to high molecular weight ones by selecting various esters of general formula (2) and the above-mentioned siloxanes depending on the purpose. The properties range from liquid to resin-like solid at room temperature.

The base used in the present invention may be any base as long as it dissolves the silicone-based cinnamic acid derivative, but in particular, the use of a silicone-based base provides good spreadability, light texture, non-stickiness, etc. It provides features such as excellent water resistance, oil resistance, and resistance to sweat and water.

The silicone base used in the present invention is not particularly limited, but examples include chain polysiloxanes such as dimethylpolysiloxane, methylpolysiloxane, and methylhydrodienepolysiloxane, decamethylpolysiloxane, dodecamethylpolysiloxane, and tetramethyltetra Cyclic polysiloxanes such as hydrogen polysiloxane, polyethers, fatty acid-modified polysiloxanes, higher alcohol-modified polysiloxanes, and amino-modified polysiloxanes are used.

The external skin preparation of the present invention may contain other ingredients normally used in external skin preparations such as cosmetics and quasi-drugs, such as oils, lubricants, ultraviolet absorbers other than those of the present invention, antioxidants, and surfactants. , preservatives, fragrances, hydroalcohols, thickeners, etc. may be appropriately blended as required.

The skin external preparation of the present invention is not particularly limited in its field of application, and can be used in cosmetics, quasi-drugs, etc., depending on the characteristics and purpose of the silicone-based cinnamic acid derivative used in the present invention. .

Here, the dosage form of the skin external preparation of the present invention is arbitrary and may be any dosage form such as powder, cream, paste, tincture, liquid, spray, foundation, etc. It may be emulsified into type and 0/W type.

Further, the blending amount varies depending on the above-mentioned dosage form, but is generally 0.1 to 20%, preferably 0.5 to 10%.

[Example code] EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples.

1. In the following, the present invention will be explained in more detail by giving examples of the synthesis of the novel silicone-based cinnamic acid derivative of the present invention and its physicochemical properties.

Synthesis Example 1 11.94 g of 3.4.5-trimethoxycinnamic acid and 11 ml of thionyl chloride were stirred in 80 ml of benzene at reflux temperature for 3 hours to form an acid chloride, and after removing the solvent, 7.
80 m of toluene containing 20 g of 1-buten-3-ol
1 was added, the reaction system was cooled in a water bath, and 40 ml of toluene containing 5.25 g of triethylamine was slowly added.
Stir for hours. Further, the mixture was stirred at room temperature for 1 day. After filtering and washing the toluene layer with water to remove water, 3,
4.5-) Rimethoxycinnamic acid ester 10.93g (7
4.6%).

GC-MS M”292 NMR (CDCl2) 7.60 (LH, d (J=1
5.77Hz)) , 6, 36 (li(,d(
J16, 14t(z)), 6.74 (2H,s)
, 5.92 (111, m) , 5.49 (IH
, m).

5.29 (IH, d (J=17.60Hz)),
5.15 (LH, d (J=10.64Hz))
.

3.85 (9H, s), 1.38 (31(, d(J=6
．． 60Hz)).

Synthesis Example 2 2.9319 g of ester obtained in Synthesis Example 1 and siloxane (1,1,1,3,5,5,5-Hepjameth
yltrisiloxane (hereinafter abbreviated as MHM) 2
．． Pour 2270g into 50ml of toluene and add 0.
2.3 1M chloroplatinic acid isopropyl alcohol solution
The mixture was added dropwise and stirred at reflux temperature for 5 hours to carry out a hydrosilylation reaction. The product was isolated by silica gel column chromatography using toluene as a solvent, and 3.0880 g of the oily silicone-based cinnamic acid derivative of the present invention was obtained.
(59.8%) was obtained.

This substance was identified by the following analytical values.

Name of substance.

[3-bis(trimethylsiloxy)methylsilyl-1-
Methij1propyl] -]3.4.5-Trimethquine cinnamate e GC-MS 514 NMR (CDC13) 7.59 (LH, d (J = 16.
13Hz)), 6.35 (IHd (J15, 77Hz)
), 6.75 (2H,s), 4.95 (I
H,q), 3.86 (911,s).

1.65 (2H, m), 1.29 (3H, d (J
=6.23Hz)), 0.54 (2H, m).

0.11 (18H, s), 0.09 (3Hs).

FIG. 1 shows the UV spectrum at a concentration of 10 ppm (solvent, ethanol).

From this, it was determined that the silicone-based cinnamic acid derivative, which is a novel compound of the present invention, has an absorption wavelength appropriate for the Uv-B wavelength region.

Synthesis Example 3 A hydrosilylation reaction was carried out according to Synthesis Example 2 except that benzene was used as a solvent. Similarly purified, the product was 3.15
70 g (61.1%) were obtained.

Synthesis Example 4 A hydrosilylation reaction was carried out according to Synthesis Example 2 except that xylene was used as a solvent. Similarly purified, the product was 3.5
240 g (68.2%) were obtained.

Synthesis Example 5 10.48 g of 3.4-dimethoxycinnamic acid and 11 ml of thionyl chloride were stirred in 200 ml of benzene at reflux temperature for 2 hours to form acid chloride, and after removing the solvent, 3.63 g
80 ml of toluene containing 1-buten-3-ol
The reaction system was cooled in an aqueous solution, and 40 ml of toluene containing 5.10 g of triethylamine was slowly added and stirred for 1 hour. Further, the mixture was stirred at room temperature for 1 day.

After filtering and washing the toluene layer with water to remove water, 6.886 g of 3,4-dimethoxycinnamic acid ester was obtained by silica gel column chromatography using toluene as a solvent.
(52.2%) was obtained.

GC-MS M' 262 HMR (CDCIs) 7.63 (LH, d (J=
15.62)1z)) , 6.32 (LH,d (
J=15.62Hz)), 6.85(LH,d(J=
8.3011z), 7.05(LH,s).

7.10 (LH, d (J=8.30Hz)), 5.92
(IH, m), 5.50 (LH, m).

5.30 (IH, d (J=17.09Hz)),
5.16 (IH, d (J=10.75Hz)).

3.90(6H,s), 1.29(3H,d(J=
6.83Hz)).

Synthesis Example 6 2.6231 g of ester obtained in Synthesis Example 5 and siloxane (
M HM ) 2.2291 g was poured into 50 ml of toluene, and 2.3 drops of 0.1 M chloroplatinic acid isopropyl alcohol solution was added, followed by stirring at reflux temperature for 5 hours to perform a hydrosilylation reaction. The product was isolated by silica gel column chromatography using toluene as a solvent to obtain 2.9157 g (60.1%) of a silicone-based cinnamic acid derivative in the form of an oil. This substance was identified by the following analytical values.

Name of substance.

[3-bis(trimethylsiloxy)methylsilyl-1-
Methylpropyl] -]3,4-dimethoxycinnamate e GC-MS N'' 484HMR
(CDCI:+)7.63(IH,d(J=15.62
Hz)), 6.32 (1, H, d(15,62Hz))
6.85 (IH, d (J=8.30Hz)), 7.05
(LH,s).

7.10(1)1. d(J=8.30Hz)), 4.9
5(IH,q), 3.90(6t(,s).

1.65 (2H, m), 1.29 (3H, d (J
=6.83Hz)), 0.54 (2H, m)0.
11 (18H, s), 0.09 (3H, s) 10 in Figure 2
The UV spectrum at a concentration of ppm (solvent, ethanol) is shown.

From this, it was confirmed that the silicone-based cinnamic acid derivative, which is a new compound of the present invention, has an appropriate absorption wavelength in the UV-B wavelength region.

Synthesis Example 7 3.4. 24.1550 g of trimethoxycinnamic acid and 22 ml of thionyl chloride were stirred in 160 ml of benzene at reflux temperature for 4 hours to form an acid chloride, and after removing the solvent, 5.
160m of toluene containing 8550g of allyl alcohol
1 was added, the reaction system was cooled in a water bath, 80 ml of toluene containing 10.111 g of triethylamine was slowly added, and the mixture was stirred for 12 hours. '6. After filtering and washing the toluene layer with water to remove water, 20.3039 g (72.0%) of 3,4.5-1-dimethoxycinnamic acid ester was obtained by chromatography on silica gel using toluene as a solvent. It is a white crystal with a melting point of 67.0-68.2°C, and MS
(M”278).

Synthesis Example 8 5.6054 g of the ester obtained in Synthesis Example 7 and 4.4713 g of Siloxa 7 (MHM) were added to Henzea 100 m
A few drops of HzP LCI b isopropyl alcohol solution was added thereto, and the mixture was stirred at reflux temperature for 4 hours to carry out a hydrosilylation reaction. The product was isolated by silica gel column chromatography using toluene as a solvent, and the silicone derivative of the present invention in the form of an oil was isolated at 2°7846°C.
g(27,6Z) was obtained. This substance was identified by the following analytical values.

[3-bis(trimethylsiloxy)methylsilylpropyl l-3,4,5,-)rimethquininnascimate GC-MS N” 500 HNMR (CDCI++) 7.55 (IH, d (J=1
6.12Hz)), 6.31(LH,d(J=15.6
3t(z)), 6.70(2H,s), 4.11(2H
, t), 3.82 (9H.

sL 1.69 (2) 1. m), 0.51(2t(,t
), 0.06 (18H, S ).

The UV spectrum of this substance at a concentration of 10 ppm (ethanol solvent) was almost the same as that of the compound obtained in Synthesis Example 2 (FIG. 1).

Synthesis Example 9 5.000 g of the ester obtained in Synthesis Example 7 and 5.500 g of siloxane H5i (O5iMe+) were mixed with benzene 1
A few drops of H, PtCl, and isopropyl alcohol solution were added thereto, and the mixture was stirred at reflux temperature for 4 hours to carry out a hydrosilylation reaction. The product was isolated by silica gel column chromatography using toluene as a solvent, and the oily silicone derivative of the present invention was obtained at 2.077%
g (20.1%) was obtained. This substance was identified by the following analytical values.

[3-Tris(trimethylsiloxy)silylbubyl]
]-3,4,5-)rimethoxycinnamate GC-MS, single component M”574H-NMR(
CDC1,)7.61 (IH,d (J=15.87
)1z) ) , 6.36 (LH, d(J=15.
87Hz)), 6.77(2H,s), 4.17(2H
,t), 3.90(9Hs), 1.74(2H,m
), 0.53 (2H, t), 0.13 (18) 1. S)
.

However, the chemical shift is hydrogen of CICl3 (7.27 ppm
) was set as the standard. The UV spectrum (ethanol loppm concentration) of this derivative was almost the same as that of the compound obtained in Synthesis Example 2 (FIG. 1).

Synthesis Example 10 3.4.5-Trimethoxycinnamic acid 11. ．． 960 g, thionyl chloride], 1 ml was stirred in 80 ml of benzene at reflux temperature for 3 hours to form acid chloride, and after removing the solvent, 3.
Toluene 8 containing 640 g of 1-buten-4-ol
0 ml was added, the reaction system was cooled in aqueous solution, and 5.340
40 ml of toluene containing 1 g of triethylamine was slowly added and stirred for 24 hours. After filtering, washing the toluene layer with water and removing the water, 10.0342 g (68.4%) of 3.4.5-)rimethoxycinnamate was obtained by chromatography on silica gel using toluene as a solvent. It is a white crystal with a melting point of 61.8-63.8°C, qs
(M゛292).

Synthesis Example 11 2.9303 g of the ester obtained in Synthesis Example 10 and 2.2289 g of siloxane (MHM) were mixed with 1 part of benzene.
00ml, and then added several drops of H2PtCI 6 isopropyl alcohol solution and stirred at reflux temperature for 2 hours.
A hydrosilylation reaction was performed. Using toluene as a solvent,
The product was isolated by silica gel column chromatography, and the silicone derivative of the present invention in the form of an oil was obtained by
88 g (61.0%) were obtained. This substance was identified by the following analytical values.

[3-bis(trimethylsiloxy)methydibutyl] -3,4,5,-)rimethoxycinnamate H,S), 0.01 (3H,s).

The UV spectrum of this derivative (ethanol concentration: 10 ppm) was almost the same as that of the compound obtained in Synthesis Example 2 (FIG. 1).

Synthesis Example 12 According to Synthesis Example 11, siloxane H5i (O5iMea)
A hydrosilylation reaction was carried out using 3. Four oil-like silicone F5i of the present invention were obtained by silica gel column chromatography. This substance was identified by the following analytical values.

[3-tris(trimethylsiloxy)ylbutyl]
-3,4,5-) Rimethoxocinnamate GC-MS N"514H-NMR (CDCI3) 7.59 (LH, d
(J = 15.62t(z)), 6.35 (IH,
d(J=16.11Hz)), 6.74(2H,s),
4.21 (2H, t), 3.87 (9H.

s), 1.75 (2H, m), 1.47 (2H,
m), 0.51 (211, m), 0.10 (18GC
-MS M'588'HNMR (CDCI3) 7.59 (LH, d (J=1
5.62Hz)), 6.35(II, d(J=16.1
1Hz)), 6.74 (28, s), 4.21 (2H,
t), 3.87 (9H.

s), 1.75 (2H, m), 1.47 (2H, m),
0.51 (2H, m), 0.10 (27H, S).

The UV spectrum of this derivative (ethanol concentration at 10 ppm) was almost the same as that of the compound obtained in Synthesis Example 2 (FIG. 1).

(Left below) Synthesis Example 13 According to Synthesis Example 6, siloxane H5i was prepared using the same ester.
A hydrosilylation reaction was performed using (O5iMez)z. An oily silicone derivative of the present invention was obtained by silica gel column chromatography. This substance was identified by the following analytical values.

[3-Tris(trimethylsiloxy)silyl-1-methylbuvir] -]3.4-dimethoxycinnamate GC-MS N"558' H-NMR (CDCI i) 7.63 (LH, d
(J = 15.62Hz) ), 6.32 (I
H, d (J = 15.62 Hz)), 6.85 (IH, d
(J=8.30 Hz)), 7.05 (IH.

s), 7.10 (LH, d (J=8.30 Hz)),
4.95 ((IH, q), 3.90 (6H, s),
1.65 (2H, m), 1.29 (3H, d (J
=6.83 Hz)).

0.54 (2H, m), 0.10 (27H, s).

The UV spectrum of this derivative (ethanol concentration: 10 ppm) was almost the same as that of the compound obtained in Synthesis Example 6 (FIG. 2).

Synthesis Example 14 23.912 g of 3.4.5-trimethoxycinnamic acid and 22 ml of thionyl chloride were stirred in 700 mI of benzene at reflux temperature for 2 hours to form acid chloride, and after removing the solvent, 10
．． 332 g of ethylene glycol monoallyl ether (
160 ml of toluene containing CL=Ct(CHzOCIIzCHzOH) was added, the reaction system was cooled in a water bath, and 1O
, 80 ml of toluene containing 233 g of triethylamine
was added slowly and stirred for 24 hours. After filtering, washing the toluene layer with water and removing water, 23.189 g (71.7%) of 3,4.5-)rimethoxycinnamate was obtained by chromatography on silica gel using toluene as a solvent.

This ester is in the form of an oil.

GC-MS A322'HNMR (CDCI:+)7.62 (IH, d(J")
15.63Hz)), 6.39(LH,d(J=16.
12Hz) ), 6.76(2H,s), 5.9
2(E,m), 5.31 (LH,d(J=17.
09 Hz)), 5.21(LH,d(J=10.74
Hz)), 4.37(2H,t).

4.06 (2H, d (J=5.37 Hz)), 3.8
8(9t(,s), 3.72(2H,t).

Synthesis Example 15 Using the ester (3,2329g) obtained in Synthesis Example 14, toluene was added to siloxane MHM (2,2896g). The mixture was refluxed in the medium (50 ml) for 2 hours to carry out a hydrosilylation reaction.

The silicone HM conductor of the present invention in oil form was collected in an amount of 3.9251 g (7
1.8%) was obtained. This substance was identified by the following analytical values.

GC-MS M''544 UV spectrum of this derivative (ethanol 110PP concentration) was almost the same as that of the compound obtained in Synthesis Example 2 (FIG. 1).

Synthesis example 2. 3. 4. 6. 8. 9.11.12
．． Regarding the solubility of the silicone-based cinnamic acid derivative (dimethoxy, trimethoxy substituted product) obtained in 13.15 in a silicone base, a solubility test in dimethylpolysiloxane and methylphenylpolysiloxane was conducted at 25°C. In either case, 10% by weight
It showed excellent solubility.

Note that the ester as a precursor showed almost no solubility.

Regarding water resistance and oil resistance, the silicone-based cinnamic acid derivative (dimethoxy, trimethoxy substituted product) of the present invention is stirred and mixed with water, 50% ethanol, oil such as liquid paraffin, and left at 50"C for 60 days. However, it was confirmed that it has excellent water resistance and oil resistance because hydrolysis does not occur.

The electronic spectrum of the ultraviolet absorber may shift by about 10 to 20 nm depending on the base (or solvent) in which it is blended. For example, N,N-dimethyl 2-ethylhexylcinnamate shifts by 10 nm in ethanol and dimethylpolysiloxane. Ultraviolet absorbers are required to have little solvent dependence.

The silicone-based cinnamic acid derivative of the present invention has little solvent dependence.

Furthermore, safety as an ultraviolet absorber and stability against heat and light are required.

The silicone-based cinnamic acid derivative of the present invention has no safety problems such as sensitization, mutagenicity, photoconductivity, and phototoxicity, and has good stability against heat (including hydrolysis). In terms of stability against light, it is completely stable under normal sunlight irradiation, and photoisomerization (trans-
cis) reaction, but absorption is observed in the UV-B pJf region, making it an excellent ultraviolet absorber.

Example 1 Sunscreen cosmetic (oil type) ■Decamethylcyclopentasiloxane 48.0%■Dimethylpolysiloxane (l0cs/25°C) 20.0■Methylphenylpolysiloxane (20C5/25°C) 20.0■Silicone resin 10.0■Silicone-based cinnamic acid derivative 11 2.01) Me (Production method) Mix ■~■, sufficiently dissolve, and then filter to obtain a product Comparative example 1 Example 1 A product was obtained in the same manner as in Example 1 except for omitting ■ in the formulation.

"Me Example 2 Sunscreen cosmetic (W10 cream) ■Octamethylcyclotetrasiloxane 28.0% ■Dimethylpolysiloxane 5.0 (100C5
/25°C) ■Dimethylpolysiloxane (2,500,0OOC5/25°C) 3.0■
Liquid paraffin 5.0■ Silicone-based cinnamic acid derivative 2) 1.5■ Polyether-modified silicone 6.0 (400C5
/25°C) (Polyoxyethylene group content 20% by weight) ■Purified water
43.1 ■ Sodium L-glutamate 3.0 ■ 1.3-Butylene glycol 5.0 [Phase] Preservative
0.20 fragrance
0.2 (manufacturing method) Mix ■~■ and ■, heat and melt and maintain at 70''C to form an oil phase. Separately ■~
Heat and dissolve (2) and maintain at 70°C to form an aqueous phase. The aqueous phase is added to this oil field and thoroughly emulsified using an emulsifier.

After emulsifying, cool while stirring, and when the temperature drops below 35°C, pour into a container and leave to cool to solidify.

Comparative Example 2 A product was obtained in the same manner as in Example 2 except for omitting ■ in the formulation of Example 2.

Example 3 Sunscreen cosmetic (0/W cream) ■Decamethylcyclopentasiloxane 9.0%■Liquid paraffin 3.0■Isopropyl myristate 2.0■Vaseline
5.0 ■ Setanol
5.0 ■ Stearic acid
3.0 ■ Glyceryl monoisostearate ■ Silicone-based cinnamic acid derivative 3) ■ Preservative [phase] Fragrance ■ Glycerin @ propylene glycol ■ Hyaluronic acid ■ Potassium hydroxide ■ Purified water 3.0 1.0 0.2 0. 2 10.0 5.0 0.01 0.2 53.39 (Left below) Ae (Manufacturing method) Heat and stir ■ to ■ to form an oil phase at 70°C. After heating 0 to [phases] to 70°C and completely dissolving them, the aqueous phase is obtained. The oil phase is added to the water phase and emulsified using an emulsifier.

The emulsion is cooled to 30°C in a heat exchanger and then filled to obtain a product.

Comparative Example 3 A product was obtained in the same manner as in Example 3 except for excluding ■ in the formulation of Example 3.

Example 4 Sunscreen lotion ■Dimethylpolysiloxane (5C5/25°C) 1
0.0% ■Methylphenylpolysiloxane (20C5/25°C) 7.0 ■Stearic acid 1.0■
Silicone-based cinnamic acid derivative 4ゝ 1o, 0 ■Preservative ■Fragrance ■Glycerin ■Montmorillonite ■Potassium hydroxide [phase] Edge ice making" Me 0.2 0.2 5.0 0.5 0.2 65.9 (Production method) Heat and stir ■ to ■ at 70°C to obtain an oil phase. Heat and dissolve ■ to [phase] to 70°C to obtain an aqueous phase. Add the oil phase to the aqueous phase. Then, emulsify using an emulsifying machine.

The emulsion was cooled to 30°C in a heat exchanger and then filled to obtain a sunscreen lotion.

Comparative Example 4 A product was obtained in the same manner as in Example 4 except for excluding ■ in the formulation of Example 4.

Examples 1 to 4 and Comparative Example 1 obtained as above
-4 were measured for their ultraviolet protection effects.

The ultraviolet ray prevention effect was measured using the following ultraviolet sensitive composition.

The UV protection effect was measured using a UV sensitive composition described in JP-A-62-112020. The method for producing the ultraviolet-sensitive composition will be described below.

A solution consisting of 1.0 g of leuco crystal violet, 0.1 g of tetrabromodimethylsulfone, 10 g of ethylene-vinyl acetate copolymer, and 100 ml of toluene is prepared and used as Solution I. Separately, N, N dimethylvaraminobenzoic acid-2-ethylhexyl ester 7g 1 ethylene-vinyl acetate copolymer Log, ) Luene 1
A solution consisting of 00ml was prepared and used as a solution (■).

First, apply Liquid I to a solid content of 1 g/yr on photographic base paper, and after drying, apply Liquid ■ on top of it to a solid content of 5 g.
/rd to obtain an ultraviolet sensitive composition.

This ultraviolet-sensitive composition is a paper whose color changes from white to pale purple to purple to deep purple when irradiated with ultraviolet rays as the amount of ultraviolet irradiation increases.

40 mg of the sample to be measured is mixed in 12 g of castor oil and uniformly dispersed by roller treatment. A transparent PET film was placed on top of the above ultraviolet sensitive composition in a circular shape with a diameter of 5 cm, and 1.5 g of the film was applied on top of it to a uniform thickness, and the PET film was irradiated with an ultraviolet lamp for 8 minutes. Using a Hitachi 607 spectrophotometer, the color difference of the colored UV-sensitive composition that was removed along with the sample was calculated using the LAB coordinate system based on the color of the UV-sensitive composition when the amount of UV irradiation was zero.

The results are shown in Table 1.

(Hereafter the margin) Table 1 (Hereafter the margin) As can be seen from Table 1, it can be seen that the dyes of the examples have a smaller color difference than the corresponding comparative examples and have a higher ultraviolet protection effect. That is, it can be seen that by blending the silicone-based cinnamic acid derivative of the present invention, an excellent ultraviolet protection effect can be obtained.

Example 5 Dual-use sunscreen foundation ■Silicone-treated titanium oxide 9.5%■Silicone-treated mica 40.0■Silicone-treated talc 20.45■Silicone-treated iron oxide 7.5■Spheroidal nylon powder
10.0 ■ Trimethylolpropane
5.0 Triisostearate ■ Squalane 3.0 ■ Peace wax 2.0 ■ Silicone cinnamic acid derivative 5) 0.5 ■ Sorbitan triolate 1.0 ■ Preservative
0.50 vitamin E
O, 05 ■Fragrance e 0.5 (Production method) Mix ~■ with a Henschel mixer, add and mix ■~@ by heating, mix, and then crush, mold this into a medium plate, and bake in the sun. I got a double-use foundation.

Example 5 applied easily, gave a natural finish, had good makeup retention, and had a long-lasting UV protection effect.

Example 6 Sunscreen stick cosmetic ■Titanium oxide 10.0%
■Zinc oxide 7.0■Mica 16. .

■Red iron oxide 1.5■Yellow iron oxide 1.5■Black iron oxide 1.0■Dimethylpolysiloxa 7 (20C5/25°C) 29.4■Trimethylolpropanetri-2-ethylhexanoate■Fluidity Paraffin [phase] Microuristarine Wanx ■ Ceresin @ solid paraffin ■ Silicone-based cinnamic acid derivative 6) ■ Fragrance ■ Antioxidant ■ Sorbitan sesquiolate 6) Me 10.0 ■0.0 2.0 1.0 6. 0 3.0 0.5 0.1 1.0 (?! Method) Mix ■~■ with a Henschel mixer, and mix ■~
■■■Add [phase] to the dissolved solution by heating and stirring, and mix. Next, a melt of [Phase]~@0 was added to the above mixture, and after thorough mixing, it was molded into a stick to obtain a sunscreen cosmetic.

Example 6 had a high effect of preventing ultraviolet rays and had excellent makeup durability.

Example 7 Sunscreen makeup base ■ Dimethylpolysiloxane 2C5/25°C ■ Glyceryl triisostearate ■ Isopar (registered trademark) G ■ Sorbitan sesquiolate ■ Polyoxyethylene modified organopolysiloxane ■ Purified water ■ 1.3 -Butylene glycol ■ Fine particle titanium oxide ■ Silicone-based cinnamic acid derivative 7) [Phase] Preservative ■ Antioxidant ■ Fragrance Me 19.0% 10.0 5.0 1゜0 3.0 45.0 5.0 10.0 2.0 Appropriate amount Appropriate amount Appropriate amount (manufacturing method) ■~■■0@ is stirred and dissolved at 70°C, and to this is added ■~■ [phase] heated to 70°C in advance,
After emulsification and dispersion, the mixture was cooled to obtain the desired sunscreen makeup base.

Example 7 had a high UV protection effect and had excellent makeup longevity.

Example 8 Anti-tanning stick cosmetic ■Titanium oxide IO30%
■Zinc oxide 7.0■Mica 16.0■Red iron oxide 1.5■Yellow iron oxide 1.5■Black iron oxide 1.0■Dimethylpolysiloxane (20C5/25 ”C) 29.4■Trimethylolpropane 10.0 Tory 2
-Ethylhexanoate ■Liquid paraffin 10.0 [
Phase] Microcrystalline wax 2.00
Ceresin 1.0＠Solid paraffin 6.0＠Silicone-based cinnamic acid derivative! l) 3. Q■Fragrance ■Antioxidant [Phase] Sorbitan Sesquiolate" O5+Me.

0.5 0.1 1.0 (Production method) Mix ■～■ with a Henschel mixer, and mix ■～■
(1) Add 0■ to the dissolved solution while heating and stirring, and mix. Next, a melt of [Phase]~@0 was added to the above mixture, and after thorough mixing, it was molded into a stick shape to obtain a sunscreen stick cosmetic.

Example 8 has a high UV protection effect similar to Example 6,
Moreover, the makeup had excellent long-lasting properties.

Example 9 Sunscreen makeup base ■Dimethylpolysiloxane 2C5/25°C19,0
%■Glyceryl triisostearate 10.0■
Isopar (registered trademark) G 5.0■
Sorbitan sesquiolate 1.0 ■ Polyoxyethylene modified 3.0 organopolysiloxane ■ Purified water ■ 1.3-butylene glycol ■ Fine particle titanium oxide ■ Silicone-based cinnamic acid derivative 9) [Phase] Preservative ■ Antioxidant ■ Fragrance ” O5iMe.

45.0 5.0 10.0 2.0 Appropriate amount Appropriate amount Appropriate amount (manufacturing method) Stir and dissolve ■~■■■@ at 70'C, and add ■~■ [phase] heated to 70'C in advance. death,
After emulsification and dispersion, the mixture was cooled to obtain the desired sunscreen makeup base.

Example 9 has a high UV protection effect similar to Example 7,
Moreover, the makeup had excellent long-lasting properties.

[Effects of the Invention] The external preparation for skin according to claim 1 sufficiently protects against wavelengths in the UV-B region. In addition, the UV-B absorber used in the present invention has excellent water resistance and oil resistance, so it is possible to provide a skin preparation for external use in which the base and other ingredients can be freely selected. It has the advantage of being excellent in stability even when left as a cosmetic under harsh conditions such as under the scorching sun. Since the skin external preparation according to claim 2 uses a silicone base, in addition to the above-mentioned effects, it has excellent usability such as good spreadability (light feeling, non-stickiness), and is resistant to sweat and water. It has the advantage that it does not run easily (good makeup retention), and since it can contain any amount of UV-B absorber, it has the effect of providing a skin preparation that has the desired UV protection effect.

[Brief explanation of the drawing]

Figure 1 shows the U of the silicone-based cinnamic acid derivative obtained in Synthesis Example 2 at a concentration of 10 ppm (solvent, ethanol).
The V spectrum is shown. Figure 2 shows the U of the silicone-based cinnamic acid derivative obtained in Synthesis Example 6 at a concentration of 10 ppm (solvent, ethanol).
The V spectrum is shown. Figure 3 shows a lop of unsubstituted silicone, a known compound.
The UV spectrum at a concentration of p m (solvent, ethanol) is shown. Patent applicant Shiseido Co., Ltd. WAVELENGTH (nm) WAVELENGTH (nm) WAVELENGTH (nm)

Claims (2)

[Claims] (1) Siloxanes having at least one unit represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I), in which other units that may exist in the siloxane are
A skin external preparation characterized by containing a silicone-based cinnamic acid derivative represented by the general formula O_(_4_-_m_)_/_2SiR^3m. [In the above general formula, R^1 is an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a trimethylsiloxy group, and R^2 is a divalent hydrocarbon group having at least 2 carbon atoms (
(including those having a hetero atom O), X is an alkoxy group,
n is an integer of 0 to 3, a is an integer of 2 or 3, R^3 is an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a trimethylsiloxy group, and m is an integer of 0 to 3. ] (2) The skin external preparation according to claim 1, characterized in that a silicone base is used as the external preparation base.