JP2913441B2 - Wrinkle improver - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wrinkle improving agent and an anti-aging cosmetic, and more particularly, to an anti-aging cosmetic having an excellent effect of suppressing wrinkles and eliminating wrinkles.

[0002]

2. Description of the Related Art Maintaining healthy and beautiful skin is a very interesting problem, especially for women. However, the condition of the skin is constantly affected by factors such as humidity, ultraviolet rays, cosmetics, aging, illness, stress, and eating habits. As a result, various skin troubles such as reduced skin functions and aging of the skin may occur. Occur. Among these, wrinkles are caused by aging of the skin due to aging, photoaging due to exposure to sunlight, and the like. In other words, the cells that make up the fibers of the dermis become smaller and smaller with exposure to the sun's rays and increase in age.In particular, collagen fibers are greatly lost, and the skin ages due to degeneration of the dermis and decrease in subcutaneous adipose tissue. It causes wrinkles, relaxation and loss of elasticity.

Conventionally, various compositions and methods have been proposed for suppressing or treating such aging effects such as wrinkles (Japanese Patent Application Laid-Open Nos. 62-185005 and 62-502546). JP-A-2-72157, JP-A-2-288822, etc.). However, none of these was sufficiently satisfactory in the effect of improving wrinkles. Therefore, a cosmetic excellent in the effect of improving wrinkles has been desired.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above circumstances, and as a result, have found that a specific amine derivative described later has an excellent wrinkle improving action, and have completed the present invention. Reached.

That is, the present invention provides the following general formula (1)

[0006]

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(Wherein R ¹ represents a linear, branched or cyclic, saturated or unsaturated hydrocarbon group having 4 to 40 carbon atoms.
² , R ³ , R ⁴ , R ^5, and R ⁶ each have a hydrogen atom or a carbon number of 1 to 2 which may be substituted by one or more hydroxyl groups.
Shows 10 hydrocarbon groups. The present invention provides a wrinkle improver comprising the amine derivative represented by the formula (1) or an acid addition salt thereof.

[0008] The present invention also provides an anti-aging cosmetic comprising the amine derivative represented by the above general formula (1) or an acid addition salt thereof.

Some of the amine derivatives (1) used in the present invention are known compounds, and have been conventionally used as intermediates for producing N-acyl amide derivatives (JP-A-62-228048). JP-A-54-117421 and JP-A-54-13523.
No. 3). However, its effect on the skin, particularly on the epidermal cells, was not known at all.

In the amine derivative represented by the general formula (1), in the formula, R ¹ represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 4 to 40 carbon atoms. As butyl, hexyl, octyl, decyl,
Dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, docosyl, dotriacontyl, methyl-branched isostearyl, 2-ethylhexyl, 2-heptylundecyl, 5,7,7-trimethyl-2- (1,
Examples include hydrocarbon groups such as (3,3-trimethylbutyl) -octyl, 9-octadecenyl, 9,12-octadecadieenyl, cyclohexyl, phenyl, benzyl, cholesteryl and the like. R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by one or more hydroxyl groups, and specific examples thereof. As a hydrogen atom, and methyl, ethyl, butyl, hexyl, phenyl, benzyl, hydroxymethyl, hydroxyethyl, 1,2-dihydroxyethyl,
1,2,3-trihydroxypropyl, 1,2,3,4
And hydrocarbon groups such as -tetrahydroxybutyl and 1,2,3,4,5-pentahydroxypentyl.

In the amine derivative (1), particularly preferred compounds are those represented by the following general formula (1 ')

[0012]

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Wherein R ² is a hydrogen atom or 1 or 2
The above-mentioned hydroxyl group represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted, and m and n are m + n = 11 to 17, m = n
4 to 10, n = 5 to 11, m = 7, and n = 8.).

Amine derivative (1) used in the present invention
Is synthesized by various known methods. For example, as represented by the following reaction formula, the compound is synthesized by adding an amine derivative (3) to a glycidyl ether derivative (2).

[0015]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶
Has the same meaning as described above.) The amine derivative (1) thus obtained may be further used, if necessary, in a conventional manner, using an inorganic acid salt such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, or succinic acid or fumaric acid. Organic acid salts such as acids, hexadecanoic acid, octadecanoic acid, lactic acid, glycolic acid, citric acid, tartaric acid, and benzoic acid can be used. The amine derivative (1) or an acid addition salt thereof has an action of suppressing generation of wrinkles and eliminating wrinkles, as shown in Examples described later.

The wrinkle improving agent of the present invention can be administered by internal use, external use or any other method, but it is preferable to apply it to the skin as an external preparation. When applied to the skin, it can take various forms of use such as external preparations for medicated skin and cosmetics.For example, if it is added to cosmetics, it suppresses the generation of wrinkles and also has the effect of eliminating wrinkles. Excellent anti-aging cosmetics can be obtained.

The amount of the amine derivative (1) or its hydrochloride addition salt to be added to the anti-aging cosmetic is not particularly limited, but is 0.0001 to 0.1% by weight of the total composition (hereinafter simply referred to as%). Is preferred.

In the amine derivative (1), the compounding amount of the amine derivative represented by the general formula (1 ') or the acid addition salt thereof is preferably 0.0001 to 10% of the total composition. Particularly, 0.001 to 2% is preferable.

The anti-aging cosmetic composition of the present invention includes, in addition to the above-mentioned amine derivative, various optional components used in ordinary cosmetics, quasi-drugs, pharmaceuticals, etc., such as oils, humectants, and thickeners. Preservatives, emulsifiers, ultraviolet absorbers, anti-inflammatory agents, whitening agents, pigments, medicinal ingredients, powders, pH adjusters, antioxidants, fragrances, emulsion stabilizers, etc. can be appropriately compounded as necessary. . As anti-aging cosmetics, various uses and forms,
For example, it can be used as a water / oil, oil / water type emulsified cosmetic, cream, cosmetic emulsion, lotion, oily cosmetic, pack, foundation and the like. These cosmetics can be prepared in the above various forms by a conventional method.

[0021]

Industrial Applicability The wrinkle improver and anti-aging cosmetic of the present invention have excellent effects of suppressing wrinkles and eliminating wrinkles.

[0022]

EXAMPLES The present invention will be specifically described below with reference to examples, but it goes without saying that the present invention is not limited to these examples.

Synthesis Example 1 1- (2-hydroxyethylamino) -3-tetradecyloxy-2-propanol [In the general formula (1), R ¹ ＣC
₁₄ H ₂₉ -, synthesis of R ² = R ³ = compound of ^{R 4 = R 5 = R 6} = H ]: stirrer, a dropping funnel, a thermometer, 3l volume equipped with N ₂ inlet tube and a distillation equipment, 5 In a neck flask, 916.2 g (15 mol) of ethanolamine and 183 of ethanol were added.
g, and heated and stirred at 80 ° C. under N ₂ atmosphere.
270.5 g of tetradecyl glycidyl ether
(1 mol) was added dropwise over 3 hours. After completion of the dropwise addition, ethanol and excess ethanolamine are distilled off under reduced pressure.
The residue was recrystallized from methanol to obtain 295.7 g of the target compound (1a) as a colorless powder (yield: 89.
2%).

[0024]

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Synthesis Example 2 In the same manner as in Synthesis Example 1, the following amine derivative (1b)
To (1f) were synthesized.

[0026]

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Synthesis Example 3 1- (2-hydroxyethylamino) -3-methyl-branched isostearyloxy-2-propanol [In the general formula (1), R ¹ = methyl-branched isostearyl, R ² = R ³
= R ⁴ = R ⁵ = R ⁶ = H compound]: 3 equipped with a stirrer, a dropping funnel, a thermometer, a N ₂ inlet tube and a distillation apparatus
916.2 g of ethanolamine in a 1-liter 5-neck flask
(15 mol) and 183 g of ethanol were charged and stirred and heated to 80 ° C. under an N ₂ atmosphere, and 326.6 g (1 mol) of methyl-branched isostearyl glycidyl ether was added thereto.
Was added dropwise over 3 hours. After completion of the dropwise addition, ethanol and excess ethanolamine were distilled off under reduced pressure, and the residue was purified by silica gel flash chromatography to obtain the target compound (1 g) 32 as a pale yellow paste.
0.5 g was obtained (82.7% yield).

[0028]

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Synthesis Example 4 Synthesis of 1- (2-hydroxyethylamino) -3-methyl branched isostearyloxy-2-propanol hydrochloride: 13.2 amine derivative (1 g) obtained in Synthesis Example 3.
To a solution of g (34 mmol) in 100 ml of ethanol, 2.83 ml (34 mmol) of 12N hydrochloric acid was added, and then the solvent was distilled off under reduced pressure to give a pale yellow gel of the desired amine derivative (1 g) hydrochloride (1 g '). 14.4 g were obtained.

Synthesis Example 5 In the same manner as in Synthesis Example 3, 1- (2-hydroxyethylamino) -3- (9-octadecenyloxy) -2-propanol (1h) was synthesized.

[0031]

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Synthesis Example 6 1- (2-hydroxyethylamino) -3-phenyloxy-2-propanol [In the formula (1), R ¹ = phenyl, R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = compound of H synthesis of: stirrer, dropping funnel, thermometer, 500 ml capacity equipped with a N ₂ inlet tube and a distillation apparatus, the 4-necked flask, ethanolamine 91.6 g (1.5 mol) and ethanol 20
g, and heated and stirred at 80 ° C. under N ₂ atmosphere.
To this, 15.0 g of phenylglycidyl ether was added dropwise over 2 hours. After completion of the dropwise addition, ethanol and excess ethanolamine were distilled off under reduced pressure, and the residue was distilled under reduced pressure (1.
By performing the reaction at 75 to 180 ° C./0.5 Torr, 18.5 g of the target compound (1i) as a colorless solid was obtained (yield 87.
6%).

[0033]

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Synthesis Example 7 1- [Bis (2-hydroxyethyl) amino] -3-te
Tradecyloxy-2-propanol [in the general formula (2),
R¹= C₁₄H₂₉-, R^Two= -CH_TwoCH_TwoOH, R ^Three= R^Four=
R^Five= R⁶= H compound]: stirrer, dropping row
G, thermometer, and N_Two1-liter, 5-port flask with inlet tube
Add 105.1 g (1 mol) of diethanolamine to
And 100 g of ethanol._Two80 ° C under atmosphere
While stirring with heating, add tetradecylglycidyl ether
270.5 g (1 mol) of ter was added dropwise over 30 minutes.
After the completion of the dropwise addition, the mixture was further stirred at 80 ° C. for 6 hours.
The reaction mixture is subjected to silica gel flash chromatography.
Purification gives the target compound (1j) as a pale yellow oil
232.0 g was obtained (61.8% yield).

[0035]

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Synthesis Example 8 In the same manner as in Synthesis Example 7, the following amine derivative (1
k) to (1o) were synthesized.

[0037]

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Synthesis Example 9 1- (2,3-dihydroxypropylamino) -3-te
Tradecyloxy-2-propanol (1p) [general formula
In (1), R¹= C₁₄H₂₉-, R^Two= R^Three= R^Four= R ⁶=
H, R^Five= -CH_TwoOH compound]: stirrer, drops
Lower funnel, thermometer and N_Two2 l volume with inlet tube, 4
In a flask, 3-amino-1,2-propanediol
Charge 25g (0.27mol) and 100g of ethanol
See, N_TwoWhile heating and stirring at 80 ° C in an atmosphere,
9.9 g of tradidecyl glycidyl ether (0.037mo
l) was added dropwise over 3 hours. After the addition is completed,
After stirring for 1 hour, 1 l of water was added to the resulting reaction mixture.
Then, the produced solid was filtered. Then the resulting solid
Was recrystallized from methanol to give a colorless powder.
10.3 g of the target compound (1p) was obtained (yield 77.8).
%).

[0039]

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Synthesis Example 10 In the same manner as in Synthesis Example 9, the following amine derivative (1
q) to (1s) were synthesized.

[0041]

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Synthesis Example 11 In the same manner as in Synthesis Example 1, the following amine derivative (1t)
~ (1x) was synthesized.

[0043]

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Synthesis Example 12 In the same manner as in Synthesis Example 3, the following amine derivative (1y)
To (1z) were synthesized.

[0045]

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Synthesis Example 13 In the same manner as in Synthesis Example 7, the following amine derivative (1a
a) to (1ac) were synthesized.

[0047]

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Synthesis Example 14 In the same manner as in Synthesis Example 9, the following amine derivative (1a
d) to (1af) were synthesized.

[0049]

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The components represented by the above (1a) to (1af)
Each substituent R of each amine derivative ¹~ R⁶Table 1 below
The results are shown in Tables 2 and 3.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

The obtained amine derivatives (1a) to (1a)
Data on the shape (melting point), IR, and NMR of f) are shown below. (1a) Colorless powder (melting point 69.1-69.5 ° C) IR (KBr, cm ^-1 ) 3448,2920,2852,1464,1374,1330,1120,10
^{90,1054. 1 H-NMR (CDCl} 3, δ) 0.67~1.87 (m, 27H), 2.53~2.90 (m, 4
H), 2.93-3.20 (br, 3H), 3.30-4.07 (m, 7H).

(1b) Colorless powder (melting point: 52.7-53.8 ° C.) IR (KBr, cm ^-1 ) 3452,2920,2852,1466,1432,1380,1358,13
^{32,1120,1050,870. 1 H-NMR (CDCl} 3, δ) 0.63~1.97 (m, 19H), 2.52~3.22 (m, 7
H), 3.25-4.10 (m, 7H).

(1c) Colorless powder (melting point: 60.2-61.5 ° C.) IR (KBr, cm ^-1 ) 3452,2920,2852,1464,1356,1382,1120,10
^{50,958,872. 1 H-NMR (CDCl} 3, δ) 0.63~1.80 (m, 23H), 2.54~2.96 (m, 7
H), 3.26-4.13 (m, 7H).

(1d) Colorless powder (melting point: 70.6 to 71.2 ° C.) IR (KBr, cm ⁻¹ ) 3448, 2920, 2852, 1462, 1124, 1050. ¹ H-NMR (CDCl ₃ , δ) 0.67 to 1.67 (m , 31H), 2.60-2.80 (m, 4
H), 3.10-3.90 (m, 10H).

(1e) Colorless powder (melting point: 77.8-78.3 ° C.) IR (KBr, cm ⁻¹ ) 3452, 2920, 2852, 1464, 1376, 1360, 1330, 11
^{20,1052,868. 1 H-NMR (CDCl} 3, δ) 0.67~1.90 (m, 35H), 2.13~3.11 (m, 7
H), 3.30-4.13 (m, 7H).

(1f) Colorless powder (melting point: 177.6-178.9 ° C.) IR (KBr, cm ^-1 ) 3456, 3376, 2936, 2912, 1458, 1368, 1096, 10
^{52,948,860. 1 H-NMR (CDCl} 3, δ) 0.68 (s, 3H), 0.84~1.72 (m, 32H), 1.72
Up to 2.48 (m, 7H), 2.66 to 2.96 (m, 7H), 3.06 to 3.26 (m, 1H), 3.3
6 ~ 3.58 (m, 2H), 3.67 (bt, J = 5.0Hz, 2H), 3.80 ~ 3.96 (m, 1
H), 5.32-5.38 (m, 1H).

[0060] (1 g) pale yellow pasty ^{IR (NaCl, cm -1) 3440,2924,2856,1462,1380,1118,1054} . 1 H-NMR (CDCl 3, δ) 0.65~1.80 (m, 35H) , 2.38-2.92 (m, 4
H), 3.18 to 4.22 (m, 10H).

[0061] (1 g ') light yellow ^{gel:. IR (NaCl, cm -1} ) 3344,2920,2856,1588,1460,1376,1092 1 H-NMR (CDCl 3, δ) 0.62~1.93 (m, 35H), 2.90 to 3.83 (m, 10
H), 3.83-4.67 (m, 5H).

(1h) pale yellow solid (melting point: 36.0-37.2 ° C.) IR (NaCl, cm ⁻¹ ) 3344,2928,2856,1462,1352,1326,1112,1
_{^{058. 1 H-NMR (CDCl 3}} , δ) 0.76~2.33 (m, 33H), 2.60~2.93 (m, 4
H), 3.13 to 4.20 (m, 10H), 5.23 to 5.67 (m, 2H).

(1i) Colorless solid (melting point: 77.0 to 78.4 ° C.) IR (KBr, cm ⁻¹ ) 3308,2872,1596,1496,1440,1244,1062,10
^{44,956,856,754,698. 1 H-NMR (CDCl} 3, δ) 2.70 ~2.90 (m, 4H), 3.44 (bs, 3H), 3.70
(bt, J = 5.0Hz, 2H), 3.94 (d, J = 5.3Hz, 2H), 4.06-4.20 (m, 1
H), 6.85-7.00 (m, 3H), 7.22-7.34 (m, 2H).

(1j) pale yellow oil IR (NaCl, cm ^-1 ) 3364,2924,2856,1460,1376,1118,1076,1
_{^{040. 1 H-NMR (CDCl 3}} , δ) 0.89 (t, J = 6.5Hz, 3H), 1.10~1.75 (m, 24
H), 2.34 to 2.95 (m, 6H), 3.24 to 4.06 (m, 9H), 4.61 (br, 3H).

(1k) pale yellow oil IR (NaCl, cm ^-1 ) 3404,2928,2856,1462,1118,1080,1036,7
_{^{52. 1 H-NMR (CDCl 3}} , δ) 0.88 (t, J = 6.5Hz, 3H), 1.12~1.72 (m, 24
H), 2.30-2.77 (m, 7H), 3.09 (br, 2H), 3.33-3.54 (m, 4H),
3.60 to 3.70 (m, 2H), 3.85 to 4.00 (m, 1H).

(1 l) pale yellow oil IR (NaCl, cm ^-1 ) 3404,2928,2856,1456,1378,1114,1068,7
^{36,698. 1 H-NMR (CDCl} 3, δ) 0.89 (t, J = 6.5Hz, 3H), 1.09~1.70 (m, 27
H), 2.55-3.08 (m, 6H), 3.25-4.04 (m, 9H), 7.18-7.40 (m,
5H).

(1 m) Colorless solid (melting point: 88.9-90.2 ° C.) IR (KBr, cm ⁻¹ ) 3360, 2924, 2852, 1468, 1348, 1244, 1126, 11
00,1084,1042. ¹ H-NMR (CDCl ₃ , δ) 0.88 (t, J = 6.5Hz, 3H), 1.20-1.80 (m, 27
H), 2.27-2.86 (m, 7H), 3.30-4.02 (m, 11H), 4.57 (br, 5H).

(1n) pale yellow oil IR (NaCl, cm ^-1 ) 3388,2920,2856,1470,1110,1074,1036,1
^{026,744,702. 1 H-NMR (CDCl} 3, δ) 0.88 (t, J = 6.5Hz, 3H), 1.16~1.72 (m, 28
H), 2.46 to 2.82 (m, 4H), 3.22 to 4.00 (m, 13H).

(1o) pale yellow oil IR (NaCl, cm ^-1 ) 3352,2928,2856,1458,1118,1088,1054,1
^{042,756,702. 1 H-NMR (CDCl} 3, D 2 O, δ) 0.86 (t, J = 6.5Hz, 3H), 1.08~1.80
(m, 28H), 2.38-2.90 (m, 4H), 3.13-4.13 (m, 13H), 7.14 (b
r, 5H).

[0070] (1p) colorless powder (mp 100.5~102.2 ℃) IR (KBr, cm -1) 3388,2920,2852,1470,1352,1124,1076. 1 H-NMR (CDCl 3, δ) 0.88 (t , J = 6.5Hz, 3H), 1.05-1.67 (m, 24
H), 1.68-2.20 (m, 4H), 2.58-2.94 (m, 4H), 3.31-3.96 (m,
8H).

(1q) Colorless powder (melting point: 98.4-99.5 ° C.) IR (KBr, cm ^-1 ) 3440, 2920, 2852, 1468, 1344, 1124, 1096, 10
_{^{64. 1 H-NMR (CDCl 3}} , δ) 0.88 (t, J = 6.5Hz, 3H), 1.13~1.67 (m, 28
H), 2.30-2.97 (m, 8H), 3.30-4.00 (m, 8H).

(1r) Colorless powder (melting point—decomposed, unmeasurable) IR (NaCl, cm ⁻¹ ) 3352,2928,2856,1470,1458,1118,1088,1
^{054,1042,756,702. 1 H-NMR (CDCl} 3, D 2 O, δ) 0.86 (t, J = 6.5Hz, 3H), 1.08~1.80
(m, 28H), 2.38-2.90 (m, 4H), 3.13-4.13 (m, 13H), 7.14 (b
r, 5H).

[0073] (1s) colorless powder (mp 85.7~87.1 ℃) IR (KBr, cm -1) 3488,2924,2852,1470,1334,1120,1036. 1 H-NMR (MeOH-d 4, δ) 0.67 ~ 1.93 (m, 31H), 2.50 ~ 2.94 (m, 2
H), 3.17 to 3.98 (m, 13H).

(1t) Colorless powder (melting point 50.3-51.2 ° C.) IR (KBr, cm ^-1 ) 3448,2920,2848,1464,1425,1359,1116,10
^{47,957,912,867. 1 H-NMR (CDCl} 3, δ) 1.18~1.75 (m, 14H), 1.95~2.12 (m, 2
H), 2.55-2.84 (m, 4H), 3.02 (brs, 3H), 3.32-3.52 (m, 4H),
3.60 to 3.74 (m, 2H), 3.82 to 3.98 (m, 1H), 4.85 to 5.07 (m, 2
H), 5.68-5.94 (m, 1H).

[0075] (1u) colorless powder (mp 61.2~62.1 ℃) IR (KBr, cm -1) 3448,2920,2852,1466,1120,1052. 1 H-NMR (CDCl 3, δ) 0.80~0.98 (m , 3H), 1.18-1.70 (m, 18
H), 2.54-2.85 (m, 4H), 3.05-4.00 (m, 10H).

(1v) Colorless powder (melting point: 67.4-68.4 ° C.) IR (KBr, cm ⁻¹ ) 3444, 2920, 2848, 1464, 1358, 1332, 1120, 10
^{90,1050,952,868,722. 1 H-NMR (CDCl} 3, δ) 0.88 (t, J = 6.24Hz, 3H), 1.10~1.70 (m, 2
2H), 2.54-3.20 (m, 7H), 3.30-3.52 (m, 4H), 3.58-3.74
(m, 2H), 3.80 to 3.98 (m, 1H).

(1w) Colorless powder (melting point: 72.2 to 73.4 ° C.) IR (KBr, cm ⁻¹ ) 3448,2920,2852,1464,1378,1328,1122,10
^{52,956,866,720. 1 H-NMR (CDCl} 3, δ) 0.88 (t, J = 6.19Hz, 3H), 1.08~1.70 (m, 2
6H), 2.50-3.20 (m, 7H), 3.28-3.50 (m, 4H), 3.58-3.72
(m, 2H), 3.80 to 3.98 (m, 1H).

(1x) Colorless powder (melting point 77.4-78.0 ° C) IR (KBr, cm ^-1 ) 3440,3312,2916,2852,1464,1378,1356,13
^{30,1120,1052,954,868,720. 1 H-NMR (CDCl} 3, δ) 0.88 (t, J = 6.24Hz, 3H), 1.10~1.70 (m, 3
0H), 2.50-3.25 (m, 7H), 3.32-3.52 (m, 4H), 3.62-3.72
(m, 2H), 3.82 ~ 3.98 (m, 1H).

[0079] (1y) pale yellow oil ^{IR (NaCl, cm -1) 3388,2926,2856,1461,1377,1110} . 1 H-NMR (CDCl 3, δ) 0.70~0.97 (m, 15H), 0.98 ~ 1.76 (m, 20
H), 2.56 to 2.73 (m, 4H), 3.29 to 3.59 (m, 4H), 3.62 to 4.10 (m,
6H).

(1z) pale yellow oil IR (NaCl, cm ^-1 ) 3296,2924,2856,1458,1374,1118,1052,9
^{40,884. 1 H-NMR (CDCl} 3, δ) 0.70~0.98 (m, 15H), 0.98~1.78 (m, 20
H), 2.56-2.92 (m, 4H), 3.30-3.60 (m, 4H), 3.62-4.10 (m,
6H).

[0081] (1aa) pale yellow oil ^{IR (NaCl, cm -1) 3356,2924,2856,1464,1376,1122,1070} . 1 H-NMR (CDCl 3, δ) 0.78~1.00 (m, 6H) , 1.00 ~ 1.75 (m, 29
H), 2.32 to 2.88 (m, 6H), 3.30 to 4.00 (m, 9H), 4.90 (brs, 3H).

[0082] (1ab) pale yellow oil ^{IR (NaCl, cm -1) 3424,2928,2856,1460,1378,1116,1040} . 1 H-NMR (CDCl 3, δ) 0.72~0.96 (m, 6H) , 1.00 ~ 1.76 (m, 29
H), 2.33 (s, 3H), 2.36 to 2.72 (m, 4H), 3.30 to 3.52 (m, 6H), 3.
57 ~ 3.68 (m, 2H), 3.82 ~ 3.96 (m, 1H).

(1ac) pale yellow oil IR (NaCl, cm ^-1 ) 3388,2924,2856,1454,1370,1118. ¹ H-NMR (CDCl ₃ , δ) 0.63 to 1.92 (m, 35H), 2.40 ~ 4.06 (m, 15
H), 7.18 (brs, 5H).

(1ad) colorless powder (melting point 93.6-94.5 ° C.) IR (KBr, cm ^-1 ) 3404,2924,2852,1470,1350,1120,1102,10
_{^{50. 1 H-NMR (CDCl 3}} , δ) 0.80~1.00 (m, 6H), 1.10~1.68 (m, 24
H), 2.45-2.74 (m, 2H), 3.20-3.64 (m, 12H), 3.78-3.98
(m, 1H).

(1ae) colorless powder (melting point: 84.4 to 85.4 ° C.) IR (KBr, cm ⁻¹ ) 3308, 2924, 2856, 1466, 1378, 1114. ¹ H-NMR (CDCl ₃ , δ) 0.80 to 1.00 (m , 3H), 1.10 to 1.70 (m, 24
H), 2.56 ~ 2.74 (m, 2H), 3.24 ~ 3.74 (m, 15H), 3.88 ~ 4.06
(m, 1H).

(1af) Colorless powder (melting point: 79.5-81.2 ° C.) IR (KBr, cm ^-1 ) 3424, 3148, 2914, 2848, 1467, 1347, 1110, 10
^{29,969,870. 1 H-NMR (CDCl} 3, δ) 0.88 (t, J = 6.4Hz, 3H), 1.15 (d, J = 6.1Hz,
3H), 1.21 to 1.73 (m, 24H), 2.38 to 2.90 (m, 7H), 3.30 to 3.60
(m, 4H), 3.72-4.01 (m, 2H).

Example 1 Action of amine derivative on wrinkles formed in hairless mouse by UVB irradiation: (1) Hairless mouse (HR / ICR, 9 weeks old at the start of experiment), 6 Toshiba Health Line lamps 20SE Use U
VB light was irradiated three times a week. Energy amount is TOKYO
OPTICAL UV-Radiometer
It measured using UVR-305 / 365D. The irradiation amount at one time was set to 1 MED or less, and set to 65 mj at an energy amount of 0.28 mW / cm ² . The irradiation period was 20 weeks, and after confirming that wrinkles were formed on the back of the hairless mouse,
Each group was divided into 8 animals, and an ethanol solution of the amine derivative (1) at a concentration of 0.005% was continuously applied 80 μl five times a week for 6 weeks. Ethanol only 80 as control
Each μl was applied in the same manner as the sample. After the completion of the application, the degree of wrinkles was visually evaluated according to the following criteria (wrinkle index). Table 5 shows the results.

[0088]

(Table 4) (Wrinkle index) 1: Wrinkles completely disappeared 2: Whether or not wrinkles are present 3: Wrinkles are slightly present 4: Wrinkles are extremely present

[0089]

[Table 5]

As is clear from the results shown in Table 5, the wrinkles formed on the back of the hairless mouse can be eliminated by applying the amine derivative (1).

(2) In order to analyze the details of wrinkles, replicas of the skin were collected from three places with a size of 1 cm ² in diameter for each mouse using a hydrophilic Exaflex hydrophilic vinyl silicone impression material. did. The replica was placed in a horizontal state and irradiated with light from a direction of 30 degrees, and the ratio of shadow formed by wrinkling was determined as an area ratio using an image analyzer. Table 6 shows the results.

[0092]

[Table 6]

As is clear from the results in Table 6, the wrinkles formed on the back of the hairless mouse can be eliminated by applying the amine derivative (1).

[0094]

Example 2 Preparation of anti-aging W / O cream: (% by weight) (1) Amine derivative (1a) 0.01 (2) Cholesterol 0.5 (3) Cholesterol isostearate 1.0 ( 4) Polyether-modified silicone 1.5 (5) Cyclic silicone 20.0 (6) Methylphenylpolysiloxane 2.0 (7) Methylpolysiloxane 2.0 (8) Magnesium sulfate 0.5 (9) 55% ethanol 5.0 (10) Carboxymethyl chitin (manufactured by Ichimaru Falcos, chitin liquid HV) 0.5 (11) Purified water balance

(1) to (7) were dissolved by heating to 80 ° C., and (8) to (11) were added thereto and mixed uniformly.
A / O cream was prepared.

[0096]

Example 3 Production of O / W cream for anti-aging: (% by weight) (1) Polyoxyethylene (10) hydrogenated castor oil 1.0 (2) Sorbitan monostearate 0.5 (3) Stearoyl Sodium methyltaurine 0.5 (4) Cetostearyl alcohol 2.0 (5) Stearic acid 1.8 (6) Amine derivative (1 g) 0.1 (7) Cholesterol 1.5 (8) Cholesteryl isostearate 1. 0 (9) Neopentyl glycol dicaprate 8.0 (10) Methyl polysiloxane 5.0 (11) Glycerin 5.0 (12) Purified water Balance

(1) to (10) were dissolved by heating to 80 ° C., and (11) to (12) were added thereto and mixed uniformly.
An O / W cream was prepared.

[0098]

Example 4 Preparation of anti-aging moisturizing sunscreen cream: (% by weight) (1) Amine derivative (1 g) 0.2 (2) Silicon-coated zinc oxide 7.0 (3) p-methoxycinnamic acid 2-Ethylhexyl 3.0 (4) Cholesteryl isostearate 1.0 (5) Polyether-modified silicone 2.0 (6) Methylpolysiloxane 5.0 (7) Cyclic silicone 15.0 (8) Magnesium sulfate 1. 0 (9) Glycerin 5.0 (10) Purified water balance

(1) to (7) were dissolved by heating to 80 ° C., and (8) to (10) were added thereto and uniformly mixed to prepare a moisturizing sunscreen cream.

[0100]

Example 5 Production of anti-aging ointment: (% by weight) (1) Amine derivative (1a) 0.05 (2) White petrolatum balance (3) Cholesteryl isostearate 3.0 (4) Liquid paraffin 10.0 (5) Glyceryl ether 1.0 (6) Glycerin 10.0

(1) to (6) were heated and dissolved at 80 ° C., and then cooled to prepare an ointment.

[0102]

Example 6 Preparation of pack for anti-aging: (% by weight) (1) Amine derivative hydrochloride (1 g ′) 1.0 (2) Polyvinyl alcohol 15.0 (3) Sodium carboxymethyl cellulose 5.0 (4) Propylene glycol 3.0 (5) Ethanol 8.0 (6) Purified water 67.5 (7) Fragrance 0.5 (8) Preservative, oxidizing agent

[0103] (1) to (8) were heated to 70 ° C to dissolve and then cooled to produce a pack.

[0104]

Example 7 Preparation of anti-aging lotion: (% by weight) (1) 1,3-butylene glycol 8.0 (2) glycerin 4.0 (3) Sodium hyaluronate 1.0 (4) Ethanol 3.0 (5) Polyoxyethylene polyoxypropylene decyltetradecyl ether 0.3 (6) Amine derivative (1a) 0.05 (7) Remaining purified water (8) Preservative proper amount (9) Fragrance trace amount

(Preparation method) After the components (1) to (3) were stirred and dispersed, 60% of purified water was added thereto to obtain A. On the other hand, after the components (4), (5), (6), (8), and (9) are stirred and dissolved, the remaining amount of purified water is added to the mixture to obtain B. While stirring A, B was added and stirred to prepare a lotion.

[0106]

Example 8 Production of aging preventive essence (cosmetic): (% by weight) (1) 1,3-butylene glycol 8.0 (2) glycerin 4.0 (3) xanthan gum 0.3 (4) ) Sodium chondroitin sulfate 0.1 (5) Sodium hyaluronate 0.05 (6) Ethanol 3.0 (7) Polyoxyethylene polyoxypropylene decyltetradecyl ether 0.3 (8) Amine derivative (1 g) 2 (9) Remaining purified water (10) Preservative appropriate amount (11) Fragrance trace

(Preparation method) After the components (1) to (5) were dispersed by stirring, 65% of purified water was added thereto to obtain A. On the other hand, after the components (6), (7), (8), (10), and (11) are stirred and dissolved, the remaining amount of purified water is added to the mixture to obtain B. B was added to A while stirring, and the mixture was stirred to prepare an essence (serum).

The anti-aging cosmetics of the present invention prepared in Examples 2 to 8 were excellent in the effect of suppressing or eliminating wrinkles.

Continuation of the front page (72) Inventor Yukihiro Yada 1-15-1 Kusuda Nishi, Ninomiya-machi, Haga-gun, Tochigi Prefecture (72) Inventor Yukihiro Ohashi 30-19 Koshido-cho, Utsunomiya-shi, Tochigi Prefecture (72) Inventor Taketoshi Fujimori Haga, Tochigi Prefecture 4594 Hanawa, Kakaicho, Gunichi (72) Inventor Genji Imokawa 1022-89, Himurocho, Utsunomiya, Tochigi Prefecture (56) References JP-A-5-194185 (JP, A) (58) Fields investigated (Int. Cl. ⁶⁾ , DB name) A61K 7 / 48,7 / 00

Claims (2)

(57) [Claims] [Claim 1] The following general formula (1) (Wherein, R ¹ represents a linear, branched or cyclic, saturated or unsaturated hydrocarbon group having 4 to 40 carbon atoms. R ² , R ³ ,
R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom or 1 or 2
It represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by the above hydroxyl group. A wrinkle improver comprising the amine derivative represented by the formula or an acid addition salt thereof. 2. The following general formula (1 ′): [Wherein, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by one or more hydroxyl groups, and m and n are m + n = 11 to 17, m = 4 to 10 , N
= 5 to 11 and a number having a distribution having a peak at m = 7 and n = 8]], a wrinkle improver comprising an amine derivative or an acid addition salt thereof.