CN1179146A - Liposomogenic uv absorbers - Google Patents
Liposomogenic uv absorbers Download PDFInfo
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- CN1179146A CN1179146A CN 96192625 CN96192625A CN1179146A CN 1179146 A CN1179146 A CN 1179146A CN 96192625 CN96192625 CN 96192625 CN 96192625 A CN96192625 A CN 96192625A CN 1179146 A CN1179146 A CN 1179146A
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Abstract
There are described liposomogenic UV absorbers, comprising a hydrophilic head group (=Z), a spacer (=W), a UV chromophore (Q) having an absorption in the range from 285 to 400 nm and at least one hydrophobic tail group (=A) of the formula (1), in which A1 and A2, independently of one another, are a hydrophobic radical, Q is a UV chromophore, W is an organic radical, Z1 and Z2, independently of one another, are a hydrophilic radical, n1 and n2, independently of one another, are a number from 0 to 4, n1=n2=0 not being additionally included, p is 1 or 2, q is a number from 0 to 3, r1 is 1 or 2, r2 is 0 or 1, and s1 is a number from 1 to 3. The liposomogenic UV absorbers according to the invention are preferably used as sunscreen agents in cosmetic preparations. They are capable of self-organization into bimolecular layers, and can thereby penetrate into the stratum corneum to a high extent and behave there in an extremely wash-resistant manner.
Description
The present invention relates to a kind of UV absorption agent that can form liposome, the preparation method of this compounds, and they in cosmetic formulations as the purposes of sun-screening agent.
Known wavelength is that the ultraviolet ray of 285-400nm can cause or quicken many different human body skins infringements, as erythema, and accelerated deterioration, phototoxicity and photoallergy etc.Be the localised protection human body skin, recommendation can prevent the compound of the cosmetic formulations form of UV radiation deleterious effect.
People further become known for chemical UV absorption agent itself in the cosmetic formulations of anti-UV and can only adhere on the skin deficiently or in the skin.So need to eliminate this deficiency as emulsion, gel or oil by the suitable prescription of exploitation.This prescription should allow UV protection material the long period to rest on the outer skin or in the outer skin.In addition, allow UV absorption agent hypersynchronous to enter stratum corneum, also make these compound long periods rest on the there simultaneously, this improved possibility is with the form of liposome packing (liposomal packaging) corresponding UV absorption agent to be coated on the skin.This method is described in, for example, and among WO-92.05761 and the WO-93.02659.
Unexpectedly, found a kind of UV chromophoric group and unitary compound of special chemical structure that on 285-400nm, has receptivity that contain, this structural unit make these compounds can be in bilayer self, this compound porous works in wash-resistant especially mode there to the stratum corneum depths.
Therefore, the present invention relates to a kind of UV absorption agent that can form liposome, it comprise hydrophilic headgroup (=Z), spacer (=W), on 285-400nm, have the UV chromophoric group (Q) of receptivity and at least one hydrophobic tail base (=A), have general formula (1):
A wherein
1And A
2, be separately hydrophobic grouping mutually, Q is the UV chromophoric group, W is an organic group, Z
1And Z
2, be separately hydrophilic radical mutually, n
1And n
2Be separately the number of a 0-4 mutually, but do not comprise n in addition
1=n
2=0, p is 1 or 2, and q is the number of a 1-3, r
1Be 1 or 2, r
2Be 0 or 1, s
1It is the number of a 1-3.
The compounds of this invention is a kind of synthetic amphipathic compound that can self, i.e. their spontaneous formation two-dimensional double-layers in water.
Hydrophobic grouping A
1And A
2Be alkyl, alkoxyl group, acyl group or alkylamino have at least 8 carbon atoms on the chain.As alkoxyl group, advantageously, A
1And A
2Be have the unsaturated of 8-22 carbon atom or, radical of saturated aliphatic monohydroxy-alcohol preferably.Alkyl can be side chain, or straight chain preferably.A
1And A
2Alkyl or alkenyl that 10-14 carbon atom preferably arranged.
Suitable aliphatic monohydric alcohol can be a natural alcohol, as lauryl alcohol, and tetradecyl alcohol, hexadecanol or Stearyl alcohol can be synthols also, as decyl alcohol, C
10-C
13Oxo alcohol, tridecyl alcohol, different tridecyl alcohol or have the straight chain primary alcohol (Alfols) of 10-22 carbon atom, the representative of these Alfols is Alfol (10-14), Alfol (12-13) or Alfol (16-18).(Alfol is a trade mark).
The unsaturated aliphatic monohydroxy-alcohol is, for example, and lanolin alcohol, hexadecenol or oleyl alcohol.
Alcohol radical can be single or exist with the form of mixture, for example, and by the mixture of two or more components of soya fatty acid, palm kernel fatty acid or animal oil deutero-alkyl and/or alkenyl, preferred one-component.
If A
1And A
2Being alkylamino, then is from C
12-C
22Aliphatics the primary, preferred secondary amine is derived and is obtained.These amine can be from corresponding lipid acid dehydration, and dehydrogenation obtains then.Preferably, as the A of alkylamino
1And A
2Be two C
12-C
18Alkylamino.
Suitable acyl group is C preferably
8-C
22Alkyl-carbonyl; For example octyl group, decyl, dodecyl, tridecyl, hexadecyl or octadecyl carbonyl.
Preferably, n in the UV absorption agent that can form liposome of suitable general formula (1)
1And n
2Be 1 or 2, preferably 2, group A
1And A
2Has identical meaning.
UV chromophoric group Q is by known UV absorption agent deutero-.Preferably, the suitable UV chromophoric group that can form liposome is the compound with structural unit of following this class among the present invention: (Q
1) laurate, (Q
2) pyrrolotriazine derivatives, (Q
3) benzotriazole, (Q
4) benzophenone, (Q
5) para-amino benzoic acid derivative and (Q
6) benzylidene camphor.Laurate Q
1Be the compound of general formula (2):
Wherein R ' is hydrogen, C
1-C
4Alkyl or C
1-C
4Alkoxyl group, R
1Be C
1-C
4Alkoxyl group, preferred methoxy or ethoxy, and R
2Be hydrogen, C
1-C
4Alkyl or-CN.
The example of the compound of general formula (2) is methyl cinnamate or ethyl cinnamate.
Pyrrolotriazine derivatives Q
2Be, for example, general formula (3) hydroxyphenyl-s-triazine
R wherein
3And R
4Be separately C mutually
1-C
5Alkyl is by hydroxyl, C
1-C
5Alkoxyl group, C
1-C
5Alkylthio, amino or C
1-C
5The C that list or dialkyl amido replace
1-C
18Alkyl, unsubstituted, or by chlorine, hydroxyl, C
1-C
18Alkyl and/or C
1-C
18The phenyl that alkoxyl group replaces; R
5Be C
1-C
18Alkyl, C
1-C
18Alkoxyl group, halogen, hydroxyl, or general formula (3a)-(O-CH
2-CH
2-)
t-R
6Group or the group of general formula (3b)
R
7Be C
1-C
5Alkyl or C
1-C
5Alkoxy-C
1-C
5Alkyl, V
1Be C
1-C
4Alkylidene group, m
1Be 0,1 or 2, t is 1-5, and R
6Be hydrogen or C
1-C
5Alkyl.
If substituent R
1-R
6Be alkyl, it can be straight chain or side chain.The example of these alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, tert-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, different nonyl, positive decyl, heptadecyl or octadecyl.
C
1-C
18Alkoxyl group or C
1-C
5Alkylthio is, for example, and methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy, isopentyloxy, positive heptan the oxygen base, n-octyloxy, different octyloxy, positive ninth of the ten Heavenly Stems the oxygen base, different ninth of the ten Heavenly Stems the oxygen base, the last of the ten Heavenly stems oxygen base, n-dodecane oxygen base, heptadecane oxygen base or octadecane oxygen base or methylthio group, ethylmercapto group, rosickyite base, iprotiazem base, butylthio, isobutyl sulfenyl, secondary butylthio, uncle's butylthio, penta sulfenyl, isoamyl sulfenyl or uncle's penta sulfenyl.
The example of alkyl monosubstituted amino is monomethyl, single ethyl, single propyl group, single sec.-propyl, monobutyl or single amyl group amino.Examples of dialkylamino can be dimethyl, methylethyl or diethylamino.
The example of halogen is fluorine, bromine or preferred chlorine.
Important s-triaizine compounds is those of general formula (4)
R wherein
8And R
9Be separately unsubstituted or mutually by C
1-C
5Alkyl and/or C
1-C
5The phenyl that alkoxyl group replaces, and R
10Be hydrogen or C
1-C
5Alkyl.More interested triaizine compounds is those of general formula (5)
R wherein
11Be hydrogen, hydroxyl, C
1-C
15Alkyl, C
1-C
15The group of alkoxyl group or general formula (3b), and R
12And R
13Be separately hydrogen or C mutually
1-C
15Alkoxyl group.
Furtherly, in the hydroxyphenyl-s-triazine of preferred general formula (2), R
11, R
12And R
13Be separately C mutually
5-C
15Alkoxyl group, or such compound, wherein R
11Be the group of general formula (3b), and R
12And R
13Be C
5-C
15Alkoxyl group.
Suitable general formula (3), the compound of (4) and (5) for example is: 2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-4,6-dimethyl-s-triazine, m.p.=131 ℃, 2-(2 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl)-4,6-dimethyl-s-triazine, m.p.=177 ℃, 2-(2 '-hydroxyl-4 ', 5 '-3,5-dimethylphenyl)-4,6-dimethyl-s-triazine, λ=349m, T=48%, 2-(2 '-hydroxyl-4 ', 5 '-3,5-dimethylphenyl)-4,6-diethyl-s-triazine, m.p.=98 ℃, 2-(2 '-hydroxyl-5 '-chloro-phenyl-)-4,6-dimethyl-s-triazine, m.p.=160 ℃, 2-(2 '-hydroxyphenyl)-4,6-dimethyl-s-triazine, m.p.=133 ℃, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl)-4,6-dimethyl-s-triazine, λ=352m, T=60%, 2-(2 '-hydroxyphenyl)-4,6-didecyl-s-triazine, m.p.=53 ℃, 2-(2 '-hydroxyphenyl)-4,6-dinonyl-s-triazine, m.p.=45 ℃, 2-(2 '-hydroxyphenyl)-4,6-two-heptadecyl-s-triazine, λ=338m, T=80%, 2-(2 '-hydroxyphenyl)-4,6-dipropyl-s-triazine, m.p.=18-20 ℃, 2-(2 '-hydroxyphenyl)-4, two (Beta-methyl mercapto the ethyl)-s-triazines of 6-, λ=341m, T=60%, 2-(2 '-hydroxyphenyl)-4, two (beta-dimethyl-the amino-ethyl)-s-triazines of 6-, λ=340m, T=63%, 2-(2 '-hydroxyphenyl)-4, two (β-butyl the amino-ethyl)-s-triazines of 6-, λ=341m, T=66%, 2-(2 '-hydroxyphenyl)-4,6-di-t-butyl-s-triazine, λ=338m, T=68%, 2-(2 '-hydroxyphenyl)-4,6-dioctyl-s-triazine, m.p.=40 ℃, 2-(2 '-hydroxyl-4 '-p-methoxy-phenyl)-4,6-phenylbenzene-s-triazine, m.p.=204-205 ℃, 2-(2 '-hydroxyl-4 '-ethoxyl phenenyl)-4,6-phenylbenzene-s-triazine, m.p.=201-202 ℃, 2-(2 '-hydroxyl-4 '-sec.-propyl)-4,6-phenylbenzene-s-triazine, m.p.=181-182 ℃, 2-(2 '-hydroxyphenyl)-4, two (the 4-p-methoxy-phenyls)-1 of 6-, 3, the 5-triazine, 2-(2 ', 4 '-dihydroxy phenyl)-4, two (4-the p-methoxy-phenyl)-1,3,5-triazines of 6-, 2-(2 '-hydroxyl-3 '-aminomethyl phenyl)-4, two (4-the p-methoxy-phenyl)-1,3,5-triazines of 6-, 2-(2 ', 3 '-dihydroxy phenyl)-4, two (the 4-p-methoxy-phenyls)-1,3 of 6-, the 5-triazine, 2-(2 '-hydroxyl-5 '-chloro-phenyl-)-4, two (the 4-p-methoxy-phenyls)-1,3 of 6-, the 5-triazine, 2-(2 '-hydroxyl-4-p-methoxy-phenyl)-4, two (the 4-p-methoxy-phenyls)-1,3 of 6-, the 5-triazine, 2-(2 ', 4 '-dihydroxy phenyl)-4, two (the 4-p-methoxy-phenyls)-1 of 6-, 3, the 5-triazine, 2-(2 '-hydroxyl-4-hexyloxy phenyl)-4, two (the 4-p-methoxy-phenyls)-1 of 6-, 3, the 5-triazine, 2-(2 '-hydroxyl-4-hexyloxy phenyl)-4, two (the 3-p-methoxy-phenyls)-1 of 6-, 3, the 5-triazine, 2-(2-hydroxyl-4-p-methoxy-phenyl)-4-(4-p-methoxy-phenyl)-6-phenyl-1,3, the 5-triazine, 2-(2 '-hydroxyl-4 '-[2-ethyl hexyl oxy])-4, two (2-ethyl hexyl oxy) phenyl-1,3 of 6-, the 5-triazine, 2-(2 '-hydroxy phenyl)-4, two (the 4-p-methoxy-phenyls)-1,3 of 6-, the 5-triazine, 2-(2 ', 4 '-dihydroxy phenyl)-4, two (the 4-p-methoxy-phenyls)-1 of 6-, 3, the 5-triazine, 2-(2 '-hydroxyl-3 '-aminomethyl phenyl)-4, two (the 4-p-methoxy-phenyls)-1 of 6-, 3, the 5-triazine, 2-(2 ', 3 '-dihydroxy phenyl)-4, two (the 4-p-methoxy-phenyls)-1 of 6-, 3,5-triazine, 2-(2 '-hydroxyl-5 '-chloro-phenyl-)-4, two (the 4-p-methoxy-phenyls)-1 of 6-, 3,5-triazine, 2-(2 '-hydroxyl-4-p-methoxy-phenyl)-4, two (the 4-p-methoxy-phenyls)-1 of 6-, 3, the 5-triazine, 2-(2 ', 4 '-dihydroxy phenyl)-4, two (4-the p-methoxy-phenyl)-1,3,5-triazines of 6-, 2-(2 '-hydroxyl-4-hexyloxy phenyl)-4, two (4-the p-methoxy-phenyl)-1,3,5-triazines of 6-, 2-(2 '-hydroxyl-4-hexyloxy phenyl)-4, two (3-the p-methoxy-phenyl)-1,3,5-triazines of 6-, 2-(2-hydroxyl-4-p-methoxy-phenyl)-4-(4-p-methoxy-phenyl)-6-phenyl-1,3,5-triazine, 2-(2 '-hydroxyl-4 '-[2-ethyl hexyl oxy])-4, two (2-ethyl hexyl oxy) phenyl-1 of 6-, 3,5-triazine, 4, two (2-hydroxyl-4-the p-methoxy-phenyl)-2-(2-propoxy-oxyethyl group)-1 of 6-, 3,5-triazine, 4, two (2-hydroxyl-4-propoxy-the phenyl)-2-(2-methoxy ethoxy)-1 of 6-, 3,5-triazine, 4, two (2-hydroxyl-4-the ethoxyl phenenyl)-2-(2-methoxy ethoxy)-1 of 6-, 3,5-triazine, 4, two (2-hydroxyl-4-the p-methoxy-phenyl)-2-(2-methoxyethoxy)-1 of 6-, 3,5-triazine, 4, two (2-hydroxyl-4-the p-methoxy-phenyl)-2-(2-ethoxy ethoxy)-1 of 6-, 3,5-triazine, 4, two (2-hydroxyl-4-p-methoxy-phenyl)-2-[2-(2-ethoxy ethoxy) oxyethyl groups of 6-]-1,3,5-triazine, 4, two (2-hydroxyl-4-the ethoxyl phenenyl)-2-(2-ethoxy ethoxy)-1 of 6-, 3,5-triazine, 4, two (2-hydroxyl-4-ethoxyl phenenyl)-2-[2-(2-ethoxy ethoxy) oxyethyl groups of 6-]-1,3,5-triazine, 4, two (2-hydroxyl-4-the ethoxyl phenenyl)-2-(2-oxyethyl group-2-methyl ethoxy)-1 of 6-, 3,5-triazine, 4, two (2-hydroxyl-4-the ethoxyl phenenyl)-2-(oxyethyl group methoxy base)-1 of 6-, 3,5-triazine, 4, two (2-hydroxyl-4-the p-methoxy-phenyl)-2-octyloxies-1 of 6-, 3,5-triazine, 4, two (2-hydroxyl-4-p-methoxy-phenyl)-2-{2-[2-(2-oxyethyl group) oxyethyl groups of 6-] oxyethyl group } the oxyethyl group triazine, 4, two (2-hydroxyl-4-ethoxyl phenenyl)-2-{2-[2-(2-oxyethyl group) oxyethyl groups of 6-] oxyethyl group } oxyethyl group-1,3, the 5-triazine, with, 4, two (2-hydroxyl-4-the ethoxyl phenenyl)-2-butoxy-1 of 5-, 3, the 5-triazine.(T is solution the percentage transmission when thickness be 1cm of 1mg substance dissolves in the 100ml chloroform, and λ [m] is maximum optical extinction coefficient).
The compound of general formula (3), (4) and (5) is known, can prepare with currently known methods, as heating amidine and o-hydroxy carboxylicesters, preferably in the ebullient organic solvent with near 2: 1 molar ratios, [referring to US 3 896 125 and Helv.Chim.Acta 55,1566-1595 (1972)].
Furtherly, can use general formula (6)
Triazine UV absorbent structure unit as (Q
2).
R in this situation
14And R
15, be respectively separately hydrogen, hydroxyl, C
1-C
5Alkyl, or C
1-C
5Alkoxyl group.
Benzotriazole Q
3It is the compound of general formula (7)
R wherein
16And R
18, be hydrogen separately respectively, unsubstituted, or by the C of phenyl, halogen or group (7a) replacement
1-C
18Alkyl or C
1-C
8Alkoxyl group
R wherein
19Be hydrogen, C
1-C
10Alkyl, C
5-C
8Cycloalkyl, C
7-C
10Aralkyl or C
6-C
10Aryl, R
20Be hydrogen, C
1-C
20Alkyl, C
2-C
17Alkenyl, C
5-C
8Cycloalkyl, C
7-C
10Aralkyl or C
6-C
10Aryl, and t
2Be 1 or 2, if t
2=1, R
19And R
20Can save with bridge
Form list or multinuclear nitrogen heterocyclic ring, R in this case together
19Be-CO-is unsubstituted or by C
1-C
5Methylene radical and R that alkyl replaces
20Be C
2-C
5Alkylidene group, C
2-C
5Alkylene group, C
6-C
10Two, four or six hydrogen C of arylidene or ortho position keyed jointing
6-C
10Arylidene, R
17Be C
1-C
18Alkyl, C
1-C
18Alkoxyl group, halogen, C
6-C
10Aryl, C
7-C
10Aralkyl, or C
5-C
8Cycloalkyl, ring B can be at 1,2 and 3 by C
1-C
5Alkyl, C
1-C
5Alkoxyl group, carboxyl, C
2-C
9Alkoxy carbonyl, H
2NCO-, SO
2-, C
1-C
5Alkyl sulphonyl, the group of halogen or general formula (7b) replaces
Implication is C
1-C
10Alkyl, C
1-C
20The substituent R of alkyl
19And R
20, can be straight chain or side chain, for example, methyl, ethyl, n-propyl, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, tert-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, different nonyl, positive decyl, dodecyl, heptadecyl, octadecyl or eicosyl.
If R
19And R
20Be C
6-C
10Aryl can be list or bicyclic aryl then, as phenyl or naphthyl.
As C
7-C
10Aralkyl, R
19And R
20For example be benzyl, styroyl, Alpha-Methyl styroyl or α, α-Er Jiajibianji.
If R
19And R
20Be C
5-C
8Cycloalkyl then can be a cyclopentyl, suberyl, ring octyl group or preferred cyclohexyl.
As C
2-C
17The R of alkenyl
20, for example be, vinyl, allyl group, 1-propenyl, crotyl, pentenyl, 2-hexenyl, 2-decene base, 3,6,8-trialkenyl in the last of the ten Heavenly stems or 2-heptadecene base.
Preferred benzotriazole cpd is the compound of general formula (8)
R wherein
21Be C
1-C
18Alkyl or preferred hydrogen, and R
22Be C unsubstituted or that replaced by phenyl
1-C
18Alkyl.
Example as the benzotriazole cpd of general formula (7) and (8) is: 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-acrylamido (acryloylamido) methyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-acrylamido (acryloylamido) methyl-5 '-benzyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-butoxy acetamidomethyl-5 '-benzyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole, and 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole.
It is known that the benzotriazole cpd of general formula (7) and (8) can absorb UV, and major part is disclosed among FR-A-1 195 307 or the US-A-3 629 192.
Benzophenone (Q
4) be the compound of formula (9)
R wherein
23Be hydrogen, hydroxyl, C
1-C
14Alkoxyl group, phenoxy group or amino, wherein C
1-C
14Alkoxyl group can be replaced by the group of general formula (9a) and/or acyloxy
R
24Be hydrogen, halogen or C
1-C
5Alkyl, R
25Be hydrogen, hydroxyl or C
1-C
5Alkoxyl group, and R
26Be hydrogen or hydroxyl.
Acyl group is C
1-C
5Alkyloyl, for example, formyl radical, ethanoyl, propionyl, acryl, methacryloyl or benzoyl.
The compound of general formula (9) can prepare with the method that oneself knows, for example is disclosed among US-A-3 468 938, US-A-3 696 007 and the US-A-4 698 064.
In liposome, be used as the UA chromophoric group (Q of para-amino benzoic acid derivative according to the present invention
5) be the compound of general formula (10)
R wherein
27Be hydroxyl, halogen, cyano group, C
1-C
5Alkyl, C
1-C
5Alkoxyl group, list-C
1-C
5Alkylamino or two C
1-C
5Alkylamino, R
28Be hydrogen or C
1-C
5Alkyl, R
29And R
30Be separately hydrogen or C mutually
1-C
5Alkyl, and m
2Be 0,1 or 2.
Preferably, use from para-amino benzoic acid or its methyl or ethyl ester deutero-structural unit as UV chromophoric group (Q
5).
Suitable UV chromophoric group (Q
5) be Ben Yajiaji camphor.Their general formula is (11)
In order to prepare the UV absorption agent that can form liposome of the present invention, suitable UV chromophoric group (Q
1)-(Q
6), if they are not soluble in water in this case, can be used as water dispersion and use.
In this case; suitable dispersion agent is an all cpds; as the acid ester of alkylene oxide adduct or their salt; polystyrolsulfon acid ester (salt); lipid acid taurides (taurine acid anhydride); alkylation diphenylene-oxide list or disulfonate (salt); polycarboxylate; or by 1-60; preferred 2-30 moles of ethylene oxide and/or propylene oxide and organic di-carboxylic acid or inorganic multivariate acid change into the adduct of acid ester; the fatty amine that 8-22 carbon atom arranged; aliphatic amide; lipid acid or fatty alcohol or have three the sulphonates (salt) of 3-6 carbon atom, the polycondensate of ligninsulfonate and formaldehyde to the hexahydroxy-alkanol.The details of dispersion agent and UV absorption agent dispersion can, for example find among the EP-A-0 523 006.
By the present invention, the following chromophoric group Q of preferred use:
R under every kind of situation
2, R
14, R
16, R
17With identical in the definition of B and general formula (2), (6) and (7).
As a rule, organic group W is an alkylidene group of divalence at least, in case of necessity, can by carbonyl, carboxylate radical (carboxylato) or ether the interval.Especially, W be side chain or the alkylidene group with 2-8 carbon atom of straight chain preferably.Alkylidene group preferably has 2-5 carbon atom.For example, be
-CH
2-；-CH
2CH
2-；
-CH
2CH
2CH
2-；-CH
2CH
2CH
2CH
2-；
Suitable hydrophilic group Z
1And Z
2Preferably, (Z
a) ammonium or amine compound, (Z
b) phosphoric acid ester (salt) compound, (Z
c) carboxylicesters (salt) compound, (Z
d) polyvalent alcohol and (Z
e) sulfuric ester (salt) compound.
They have formed the hydrophilic headgroup that the present invention can form the UV absorption agent of liposome.In these structural units, at positively charged ion (Z
a) negatively charged ion ((Z
b), (Z
c), (Z
e)) and neutral headgroup ((Z
a) and (Z
d)) between difference can be arranged.
Suitable ammonium cation compound (Z
a) be, particularly, single or two C
1-C
5Alkylammonium, they can improve by further replacement.Following group can be used as example:
Suitable neutral amine example is following group:
The basic Z of suitable phosphoric acid ester (salt)
bBe, particularly, the compound of deriving and obtaining by the list or the diester of phosphoric acid.In this case, phosphorus compound normally uses with the form of its sodium salt.
Carboxylicesters (salt) compound (Z
c) deriving from list or di-carboxylic acid obtains, and also is to use with the form of its sodium salt usually.
Suitable polyvalent alcohol (Z
d) be, for example, following compound:
Suitable sulfuric ester (salt) (Z
e) be by the alkyl sulfuric ester deutero-, necessary, also can further replace.Sulfuric ester (salt) base that is suitable for mainly is a sulfate ion, SO
4 2-
According to used initial compounds, headgroup (Z
a)-(Z
e) can be while and organic group W formation-W-Z
1Or-W-Z
2The unit.
The UV absorption agent that can form liposome of the present invention can prepare by currently known methods.Usually, they can be by systematic a series of known response steps, wait as polycondensation, alkylation, esterification, hydrolysis to prepare.The details that carries out these reactions can find in the monograph of organic synthesis, as J.March, and Advanced Organic Chemistry, 2nd Edition, McGraw-Hill, New York, 1977.
The introducing of hydrophobic grouping A can be undertaken by different modes, as carrying out by the etherificate (referring to embodiment 1,2,5 and 7) of the phenol OH on the UV chromophoric group or by acyl chlorides and long-chain dialkylamine reaction (referring to embodiment 4).There are many reactions also to be suitable for introducing hydrophilic headgroup Z, for example, (quaternized) that can from embodiment 1 and 2, see.Yet, utilize suitable reaction promptly in same step, to introduce A and Z simultaneously.For example, this can use a kind of Fatty Alcohol(C12-C14 and C12-C18) to open a suitable acid anhydrides (embodiment 6) to realize.
The specially suitable compound that can form liposome is the compound of general formula (13)
A wherein
1Be hydrophobic group, Q is the UV chromophoric group, and W is an organic group, Z
1Be hydrophilic group, n
1Be the number of a 1-4, p is 1 or 2, and q is 1-3, r
1Be 1 or 2, and s
2Be 1-3.The compound of general formula (14) further preferably
A wherein
2Be hydrophobic group, Q is the UV chromophoric group, and W is an organic group, Z
1Be hydrophilic group, n
2Be 1 or 2, p is 1 or 2, and q is 1-3, r
2Be 1 or 2 and s be 1 or 2.
The UV absorption agent that can form liposome in the present invention contains the cinnamic acid derivative structural unit as the UV chromophoric group, and the compound of its formula of (15) is preferred
W wherein
1It is the group of general formula (15a)
R
29Be hydrogen, C
1-C
4Alkyl or-CN, R
30And R
31Be separately C mutually
1-C
5Alkyl, hydroxyl, hydroxyl-C
1-C
5Alkyl or carboxyl, R
32Be C
1-C
5Alkyl, hydroxyl, hydroxyl-C
1-C
5Alkyl, the group of carboxyl or general formula (15a), A
1And A
2Be separately hydrogen or C mutually
10-C
14Alkoxyl group, one of them group is C always
10-C
14Alkoxyl group, X are halogen atoms, and q is that number and the w of a 2-4 is 0 or 1, or the compound of general formula (16)
R wherein
29Be hydrogen, C
1-C
4Alkyl or-CN, R ' is a hydrogen, C
1-C
4Alkyl or C
1-C
4Alkoxyl group, A
1And A
2Be separately C mutually
10-C
14Alkoxyl group, W are C
2-C
4Alkylidene group in case of necessity can be by-O (CO)-Ji at interval, and Z
1And Z
2Be separately C mutually
1-C
3Carboxylic acid, n
1And n
2Be separately 0,1 or 2 mutually, do not comprise n in addition
1=n
2=0, and r
2Be 1 or 2.
The present invention preferably contains triazine group as the chromophoric UV absorption agent that can form liposome of UV, is the compound of general formula (17)
A wherein
1Be general formula (17a) or group (17b)
And t
3And t
4Be separately the number of 5-13 mutually.
The present invention is preferred, have a benzylidene camphor as the UV absorption agent of the chromophoric generation liposome of UV be general formula (18a) those or
Or those of general formula (18b)
A wherein
1And A
2, W and Z
1With identical in the general formula (1).
The UV absorption agent that the present invention can form liposome is particularly suitable for as the sun-screening agent in the cosmetic formulations.
The invention further relates to a kind of cosmetic formulations, comprise the compound of at least a general formula (1) and make up upward sustainable vehicle or auxiliary agent.
Make-up composition of the present invention is a benchmark with the gross weight of composition, contains 0.1-15%, the UV absorption agent that can form liposome of preferred 0.5-10% weight and make up and go up endurable auxiliary agent.
Cosmetic composition can form the UV absorption agent and the preparation of auxiliary agent physical mixed of liposome by method commonly used, as by stirring two kinds of materials simply.
Cosmetic formulations of the present invention can be prepared into water-in-oil or oil-in-water emulsion, oil bag oleyl alcohol washing lotion (alcohollotion), foaming dispersion liquid, gel, solid paste or the aerosol of ion or non-ionic amphiphilic lipid.
As oil-in-water or water-in-oil emulsion, endurable rib agent preferably contains the oil phase of 5-50% in the cosmetic, the emulsifying agent of 5-20% and the water of 30-90%.In this case, oil phase contains any oil that is suitable for cosmetic formulations, as one or more hydrocarbon ils, and wax, natural oil, silicone oil, fatty acid ester or Fatty Alcohol(C12-C14 and C12-C18).Preferred monohydroxy-alcohol or many alcohol are ethanol, Virahol, propylene glycol, hexylene glycol, glycerine and Sorbitol Powder.
Any conventional emulsifying agent of using may be used to cosmetic formulations of the present invention, one or more ethoxylation esters as natural derivative, the polyethoxylated ester of hydrogenated castor oil for example, or as the silicone oil emulsification agent of siloxane polyol, free or ethoxylated fatty acid soap, ethoxylized fatty alcohol, free or ethoxylation dehydrated sorbitol ester, ethoxylated fatty acid or ethoxylated glycerol ester.
Cosmetic formulations also can and then contain just like softener, emulsion stabilizer, and skin moisturizer, skin tanning promotor, as xanthic thickening material, as the wetting Agent for Printing Inks of glycerine, preservatives or spices and pigment.
According to cosmetic formulations of the present invention, human skin there is fabulous protection, can prevent the infringement of sunlight, can make skin obtain safer tanning with it simultaneously.And it is very good when using on the skin its washable effect according to cosmetic formulations of the present invention.
The preparation embodiment of new compound:
Embodiment 1: two 2-[3-(4-dodecyloxy phenyl) acryloxy] and ethyl } dimethyl methyl ammonium sulfate Or ammonium iodide 
(101a) X=CH
3SO
4(101b) X=I
The preparation of 4-dodecyloxy styracin is by known method, finishes by 4-alkylbenzene formaldehyde and propanedioic acid polycondensation or with dodecyl bromination thing and coumaric acid reaction.The fusing point of this clear crystal is 158-159 ℃.By in benzene, almost having obtained corresponding acyl chlorides (18 hours, room temperature) quantitatively with the oxalyl chloride reaction.
In the chloroform of 150ml, begin to add the 4-dodecyloxy cinnamyl chloride of 28.1g (0.08mol), stir and cooling at room temperature,, use the N methyldiethanol amine of 5.0g (0.04) to handle then earlier with the triethylamine of 4.1g (0.04mol).About 4 hours of this mixture restir also is cooled to 10 ℃, and (this chloroform is to use NH earlier to 250ml to splash into chloroform then in this reaction soln
3Saturated) discharge alkali.This suspension Hyflo
_Filter twice and through evaporation drying.With chromatographic column (silica gel, toluene/ethanol 95: 5) the thick amine of purifying.Theoretical yield is 53%.
Quaternized for realizing, amine be added to earlier in the toluene and 40 ℃ down with the sulfuric acid dimethyl esters of equimolar amount (=101a) or methyl iodide (=101b) react, after 3 hours, do not had initial material on the thin-layer chromatography post.These mixtures evaporation drying in a vacuum also use acetone treatment with crystallization.Earlier use the hexane wash clear crystal then with acetone, and dry down at 40 ℃.Quaternization almost carries out quantitatively.
UV spectrum (10
-5M; Ethanol): λ
Max=313nm ε
Max=53,500M
-1Cm
-1 Embodiment 2:{2-[3-(3,4-couple-the dodecyloxy phenyl) acryloxy] ethyl }-(2-hydroxyethyl) The bromination Dimethyl Ammonium
(102a)：(Y＝O)
(102b)：(Y＝NH)
3, the carrying out of 4-pair-dodecyloxy styracin and the preparation of corresponding acyl chlorides is similar with embodiment 1 described method.For esterification with discharge amine, the method for similar embodiment 1 and the reaction of 2-dimethylaminoethanol.
Under 100 ℃, in toluene, carried out quaternization 12 hours with ethylene bromohyrin.With the thick product of washing with acetone, then with post phase chromatogram purification.
UV spectrum (10
-5M; Ethanol): λ
Max=328nm ε
Max=19.500M
-1Cm
-1 Embodiment 3:{2-[3-(3,4-couple-the dodecyloxy phenyl) acrylamido] ethyl }-(2-hydroxyethyl) Diformazan ammonia brometo de amonio
The synthetic method of this compound is undertaken by the method that embodiment 2 describes.React with it with 2-methylamino ethamine and to replace esterification process to obtain acid amides.Product grinds with acetone, then recrystallization and purifying from methyl alcohol.
UV spectrum (10
-5M; Ethanol): λ
Max=321nm ε
Max=19,500M
-1Cm
-1 Embodiment 4:2, two [(4-carboxyl) the anilino]-6-two-octadecyl amino-s-triazines (sodium salt) of 4-
Under 0-5 ℃, the cyanuryl chloride of 18.5g (0.1mol) is joined earlier in the mixture of the dioxan of 250ml and water (9: 1).Under stirring state, add the 4-subcutin of 16.5g (0.1mol), temperature is brought up to 15 ℃, pH drops to 0.5.The pH value of this white suspension is adjusted to 8.0-8.5 with 30% NaOH, and further handle with the amine of equivalent.Dioxan/water with 250ml dilutes, and is heated to 90 ℃, adds NaOH with automatic gauge and keeps pH to remain on 8.5.After 4 hours, by suction solid filtering is come out, and use dioxan, water and methanol wash.With the method for recrystallization from ethyl cellosolve thick intermediates being purified, (output is 25.7g: 58% of theoretical yield; Fusing point is 264 ℃).
The intermediates of 6.63g (0.015mol) and the 4-dimethylamino pyridine of 1.83g (0.015mol) are joined earlier among the DMF of 70ml, and handle with two-octadecylamine of 8.3g down, it is dissolved in the chloroform of 30ml at 60 ℃.This mixture stirred 3 hours down at 100 ℃, and filtered this hot solution evaporation drying.Residue is purified with toluene/ethyl acetate (80: the 20) extraction of 50ml and with chromatographic column (silica gel), and (output is 4.5g: 33% of theoretical yield; Colourless, wax shape ester).
For hydrolysis, this ethyl ester joins in the mixture of ethanol/NaOH earlier and reflux 2 hours.This gelatinous precipitate is filtered, and use washing with acetone.Almost be hydrolyzed quantitatively.
UV spectrum (10
-5M; Ethanol): λ
Max=301nm ε
Max=60,000M
-1Cm
-1
Embodiment 5: single 3-[3-(3,4-couple-the dodecyloxy phenyl) acryloxy] and the 2-hydroxypropyl } 2.3-
The diacetoxy succinate
3, the preparation of 4-pair-dodecyloxy styracin and its corresponding acyl chlorides is identical with the method that embodiment 1 describes.Direactive glyceride can according to people such as Watanabe (J.Med.Chem.1980,23, step 50-59) by carrying out esterification with isopropylidene glycerine, is removed blocking group with boric acid subsequently, almost obtains quantitatively.
With the mixture of the diacetyl tartaric acid acid anhydride of the direactive glyceride of 5.91g (0.01mol) and 2.16g (0.01mol) under protection gas 120 ℃ of heating 2 hours down.With chromatographic column to the glassy thick product (silica gel of purifying; The ratio of toluene/acetone is 8: 2)
UV spectrum (10
-5M; Ethanol): λ
Max=328nm ε
Max=17,400M
-1Cm
-1 Embodiment 6:1-dodecyl 2-[3-(4-dodecyloxy phenyl) acryloxy] succinate 
The preparation of 4-dodecyloxy cinnamyl chloride such as the described method of embodiment 1.
In inert atmosphere, the acyl chlorides of 30.9g (0.088mol) and the DL-oxysuccinic acid of 5.36g (0.04mol) are joined in the chlorobenzene of 100ml, and be heated to 130 ℃.Stir after 2 hours, just finished emitting of HCl.The 1-dodecanol that is dissolved in the 7.7g (0.04mol) in the chlorobenzene of 10ml is splashed into into, and mixture refluxed stirred 3 hours.After the cooling, the suction filtration precipitation, usefulness toluene and hexane wash, and in vacuum and 80 ℃ of following dryings.(silica gel, toluene/acetone are 80: 20 with chromatographic column.) the thick product of purifying, output is 15.2g (theoretical yield 62%).
UV spectrum (10
-5M; Ethanol): λ
Max=311nm ε
Max=27,300M
-1Cm
-1 Embodiment 7: two 2-[3-(4-dodecyloxy phenyl) acryloxy] and ethyl } Padil
In inert atmosphere, with the 4-dodecyloxy cinnamyl chloride (it prepares referring to embodiment 1) of 26.7g (0.075mol) and the N of 4.9g (0.03mol), two (hydroxyethyl) Padil thorough mixing of N-, and slowly be heated to 130-140 ℃.More than 80 ℃, material becomes and can stir, and has HCl to overflow.Afterreaction was finished in 4 hours.After cooling, add 100ml acetone (95: 5), mixture heated 2 hours under refluxing.Evaporation drying, and with chromatographic column (silica gel, toluene/acetone are 80: 20.) purifying.The output of strong absorbent product is 3.1g (theoretical yield 13%).
UV spectrum (10
-5-M; Ethanol): λ
Max=313nm ε
Max=29,300M
-1Cm
-1 Embodiment 8:1-{2-[3-(4-p-methoxy-phenyl) acryloxy] ethyl } 2-12 carbon-2-thiazolinyl amber Acid esters (triethanolamine salt) 
Press known method (esterification) preparation 2-hydroxyethyl 4-Methoxycinnamate in the document.
9.0g (0.04mol) 2-hydroxyethyl 4-Methoxycinnamate and 10.6g (0.04mol) 2-dodecenyl succinic anhydride is dissolved in the 50ml toluene, and stirs down at 100-110 ℃.After 6 hours, thin-layer chromatography shows almost conversion quantitatively.Mixture is cooled to 55-60 ℃, and handles with 5.35g (0.036mol) trolamine.Restir 6 hours, solvent removed in vacuo.Obtain the high-viscosity products of 24.9g (theoretical yield 97.7%) light colour.
UV spectrum (10
-5M; Ethanol): λ
Max=312nm ε
Max=26,400M
-1Cm
-1 Embodiment 9:1-{[1-hydroxyl-2-(2 benzotriazole the base)-6-tertiary butyl-4-(4-hydroxybutyl)] phenyl } 2- 12 carbon-2-octenyl succinate ester Prepare 2 benzotriazole-2-base-6 tertiary butyls-4-(4-hydroxybutyl) phenol by known method in the document.
8.5g (0.025mol) 2 benzotriazole-2-base-6-tertiary butyl-4-(4-hydroxybutyl) phenol and 6.9g (0.025mol) 2-dodecenyl succinic anhydride are dissolved in the 100ml toluene, and stir down at 100-110 ℃ in the nitrogen atmosphere.After 18 hours, thin-layer chromatography shows almost conversion quantitatively.Solvent removed in vacuo.And with chromatographic column (toluene/ethyl acetate=9: 1, silica gel 40 * 5cm) purifying residues.Obtain the high-viscosity products of 5.4g (theoretical yield 36%) light colour.
UV spectrum (10
-5M; Ethanol): λ
Max=340nm ε
Max=14,500M
-1Cm
-1 Application Example Embodiment 10 A. prepare liposome
The compound (embodiment 1 preparation) of 1-5g general formula (101a) is dissolved in the N-Methyl pyrrolidone (NMP) of 100ml.Then, this drips of solution is added in the NaCl aqueous solution of 900ml 0.9%, or injects, form liposome with syringe.(Basle) volume with the gained Liposomal dispersion is concentrated to 50-100ml for Ultrasette, Skan AG, and correspondingly liposome is concentrated to 1-10% by diafiltration equipment.Then, by diafiltration equipment, replace the volume-exchange solvent of the filtrate of removing simultaneously with pure 0.9%NaCl solution by further filtration.In order to exchange solvent, be benchmark with spissated Liposomal dispersion, use the long-pending pure 0.9%NaCl solution of pentaploid at least.The original content of NMP is 10%, then maximum residual 0.07% NMP in dispersion liquid.The volume of the 0.9%NaCl solution that the NMP residual quantity can be used to exchange by raising reduces.
As a kind of selection, liposome can be by at first preparing the compound dissolution of 1-5g general formula (101a) in the 100ml solvent in (NMP, ethanol or Anaesthetie Ether).Then, add in the round-bottomed flask solution and heating, use the rotatory evaporator solvent removed in vacuo.Then the 0.9%NaCl solution with 50-100ml adds on the film that the bottle inwall obtains, and shaking flasks.Then, (the liposome sonication that Basle) will form by this way 0 minute is to reduce the granularity of liposome for Branson Model 250 Sonifier, Skan AG by the ultrasonic wave rod.B. measure the diameter of liposome
With photon coherence spectrum method (ALV/Monomode Fibre Compact Goniometer System, AVL-Laser GmbH, Langen) diameter of mensuration liposome.In order to accomplish this point, liposome is diluted to 0.02-0.1%, measure the auto correlation function of scan light fluctuation in four scanning angles (30,60,90 and 120).Obtain average diffusion coefficient by CONTlN software, in angular dependence, being extrapolated to scanning angle is 0.Use the Stokes-Einstein relation to draw the diameter of liposome from resulting diffusion coefficient.Compound liposome for the general formula (101a) that uses the injection preparation records: d=(220 40) nm
This Confirmation Of Number has liposome to exist.In the method that will describe below second kind prepares liposome, change the sonication time (10-60 minute) diameter is adjusted between the 1000-200nm.
C. test affinity and water-repellancy
In order to test affinity and water-repellancy, the stratum corneum on the use pig ear is as external sample.Pig ear was brought from the slaughterhouse in preparation the cuticular same day.After pig ear is cleaned and shaved hair, be cut into the small pieces of 3 * 3cm.Section is placed in 60 ℃ the redistilled water 1.5 minutes before stratum corneum is peelled off.Then, before using, stratum corneum is peelled off and is kept at (1% redistilled water) in the penicillin/streptomycin solution.
After this, by Franz diffusion cell test affinity and water-repellancy.At first UV absorbent solution is added to the lower floor in pond, and add 0.9%NaCl solution (phosphate buffered saline buffer is adjusted to pH7.4) to upper strata.With a slice stratum corneum be placed into two-layer between, under the lateral, UV absorption agent molecule can be spread in the skin or is adsorbed on the skin like this.In this course, the temperature of diffusion cell is controlled at 32 ℃, the UV absorbent solution in the agitated pool.Under each situation, after 60 minutes, showed absorption dynamics 5 hours with UV spectroscopic analysis stratum corneum prison.The conclusive parameter of estimating affinity is the concentration of the UV absorption agent molecule in skin after 5 hours.Then, shift out the UV agent solution, and replace with 0.9%NaCl solution (regulating pH with phosphate buffered saline buffer is 6.0) from the lower floor in pond.After this, (but the timed interval is longer) measured desorption kinetic in 17 hours in the same way, the important parameter of estimating water-repellancy is to be the concentration that still was retained in the UV absorption agent in the skin after 17 hours on the one hand, on the other hand, be that peak concentration when beginning with desorption is a benchmark, the ratio of this value.
Result in the table 1 shows, and is quite high in the concentration of compound in skin of absorption general formula (101a) after 5 hours.
Can find out further that from table 1 compound of general formula (101a) has very high water-repellancy.The retention rate of material is 79% in the skin handling with the aqueous solution (0.9%NaCl, regulating pH with phosphate buffered saline buffer is 6.0) after 17 hours.
D. spectral quality:
| Table 1 |
| The liposome of the compound 10mM of general formula (101) does not have other additive | |
| C (skin, absorption) adsorbs after 5 hours (affinity) | (1.9??0.6)mM |
| C (skin, desorption), desorption is (water-repellancy) after 17 hours | (1.5??0.6)mM |
| C (skin takes off)/c (skin suction) | 0.79 |
It is the 310nm place that the maximum delustring of the compound of general formula (101a) is positioned at wavelength.On this wavelength, the delustring of 1% solution when optical thickness is 1cm is: and E (1%, 1cm)=612.
The half-breadth of absorption band is 58nm.
E. the sunlight protection factor is definite:
The sunlight protection factor (SPF) is to determine with the method for Diffey and Robson (J.Soc.Cosmet.Chem.40 (1989) 127).With 2 l/cm
2Preparation be applied on the Transpore_ band (3M).Then; with uncoated Transpore_ band contrast; in the spectral range of 290-400nm, measure diffuse transmission (use in conjunction with bead (integration sphere) and measure), calculate the sunlight protection factor, with the sensitivity spectrum of skin and the intensity spectrum weighting of the sun.Carry out nine times and measure under each situation, the minimum and maximum value of the resulting sun protection factor is disregarded interior, uses the measured value calculating mean value at last seven times.Like this for the dispersion liquid of general formula (101a) compound 5%: SPF=8.6 1.7.
Embodiment 11: A. prepare liposome
Method by embodiment 10a prepares liposome, but replaces general formula (101a) compound with general formula (101b) compound, replaces NMP to make injection solvent with the ethanol that is heated to 65 ℃.
B. measure the diameter of liposomeThe method of pressing embodiment 9b is measured the diameter of liposome.The value of the liposome of general formula (101b) compound that obtains is: d=(190 30) nm.
C. test affinity and water-repellancy:
By the method test affinity and the water-repellancy that are similar to embodiment 9c.Table 2 has been listed the result of general formula (101b) compound liposome.Obtained with embodiment 9C in the identical result of general formula (101a) compound that describes, that is to say that the good affinity and the waterproof shape of material that can form liposome is.
D. spectral quality
| Table 2 | |
| The liposome of the compound 10mM of general formula (101b) does not have other additive | |
| C (skin, absorption) adsorbs after 5 hours (affinity) | (2.1??0.7)mM |
| C (skin, desorption), desorption is (water-repellancy) after 17 hours | (1.5??0.5)mM |
| C (skin takes off)/c (skin suction) | ?0.71 |
It is the 310nm place that the maximum delustring of general formula (101b) compound is positioned at wavelength.At this wavelength, the delustring of 1% solution when optical thickness is 1cm is: and E (1%, 1cm)=601.The half-breadth of absorption band is 58nm.
E. measure the sunlight protection factor
The method test sunlight factor by the general formula that is similar to embodiment 10b (101a) compound.Dispersion liquid for general formula (101b) compound liposome 5%: SPF=8.3 1.6.
Embodiment 12 A. prepare liposome
Method by embodiment 10a prepares liposome, and different is to replace general formula (101a) compound with general formula (102a) compound, and the solvent of injection is ethanol or NMP.
B. measure the diameter of liposome
The method of pressing embodiment 10b is measured the diameter of liposome.The value of the liposome of general formula (102a) compound that obtains is:
d＝(250??40)nm。
C. test affinity and water-repellancy:
By the method test affinity and the water-repellancy that are similar to embodiment 9c.Table 3 has been listed the result of general formula (102a) compound liposome.
| Table 3 | |
| The liposome of the compound 10mM of general formula (102a) does not have other additive | |
| C (skin, absorption) adsorbs after 5 hours (affinity) | (3.1??1.0)mM |
| C (skin, desorption), desorption is (water-repellancy) after 17 hours | (1.4??0.5)mM |
| C (skin takes off)/c (skin suction) | 0.45 |
Also the present invention's material that can form liposome has good affinity and waterproof shape is as can be seen.
D. spectral quality
It is the 328nm place that the maximum delustring of general formula (102a) compound is positioned at wavelength.At this wavelength, the delustring of 1% solution when optical thickness is 1cm is: and E (1%, 1cm)=273.
The half-breadth of absorption band is 71nm.
E. measure the sunlight protection factor
By the method test sunlight protection factor that is similar to embodiment 9d.Dispersion liquid for general formula (102a) compound 5%: SPF=3.0 0.3.
Embodiment 13 A. prepare liposome
Method by embodiment 10a prepares liposome, replaces general formula (101a) compound with general formula (102b) compound, and injection solvent is ethanol or NMP.
B. measure the diameter of liposome
The method of pressing embodiment 10b is measured the diameter of liposome.The value of the liposome of general formula (102b) compound that obtains is:
d＝(150??25)nm。
C. test affinity and water-repellancy:
By the method test affinity and the water-repellancy that are similar to embodiment 9c.Table 4 has been listed the result of general formula (102b) compound liposome.
| Table 4 |
| The liposome of the compound 10mM of general formula (102b) does not have other additive | |
| C (skin, absorption) adsorbs after 5 hours (affinity) | (1.4??0.5)mM |
| C (skin, desorption), desorption is (water-repellancy) after 17 hours | (0.9??0.3)mM |
| C (skin takes off)/c (skin suction) | 0.64 |
Also can see the result who is similar to embodiment 10c.
D. spectral quality
It is the 328nm place that the maximum delustring of general formula (102b) compound is positioned at wavelength.At this wavelength, the delustring of 1% solution when optical thickness is 1cm is: and E (1%, 1cm)=274.
The half-breadth of absorption band is 69nm.
E. measure the sunlight protection factor
By the method test sunlight protection factor that is similar to embodiment 10d.Dispersion liquid for general formula (102b) compound 5%: SPF=3.0 0.3.
Embodiment 14 A. prepare liposome
Method by embodiment 10a prepares liposome, and different is to replace general formula (101a) compound with general formula (104) compound (preparation is referring to example 4), and injection solvent is ethanol or NMP.
B. measure the diameter of liposome
The method of pressing embodiment 10b is measured the diameter of liposome.The value of the liposome of general formula (104) compound that obtains is:
d＝(120??15)nm。
C. spectral quality
It is the 303nm place that the maximum delustring of general formula (104) compound is positioned at wavelength.At this wavelength, the delustring of 1% solution when optical thickness is 1cm is: and E (1%, 1cm)=654.
The half-breadth of absorption band is 39nm.
D. measure the sunlight protection factor
Press the method test sunlight protection factor of embodiment 10b.Dispersion liquid for general formula (104) compound 5%: SPF=5.0 0.5.
Embodiment 15 A. prepare liposome
Method by embodiment 10a prepares liposome, and different is to replace general formula (101a) compound with general formula (105) compound (example 5 is seen in preparation), and injection solvent is ethanol or NMP.
B. measure the diameter of liposome
The method of pressing embodiment 10b is measured the diameter of liposome.The value of the liposome of general formula (105) compound that obtains is:
d＝(150?25)nm。
C. spectral quality
It is the 328nm place that the maximum delustring of general formula (105) compound is positioned at wavelength.At this wavelength, the delustring of 1% solution when optical thickness is 1 cm is: and E (1%, 1cm)=215.
The half-breadth of absorption band is 68nm.
D. measure the sunlight protection factor
By the method test sunlight protection factor that is similar to embodiment 9d.For general formula (105) compound 5% dispersion liquid: SPF=2.3 0.3.
Embodiment 16 A. prepare liposome
Method by embodiment 9a prepares liposome, and different is to replace general formula (101a) compound with general formula (106) compound (with reference to embodiment 6 preparation compounds), and injection solvent is ethanol or NMP.
B. measure the diameter of liposome
The method of pressing embodiment 10b is measured the diameter of liposome.The value of the liposome of general formula (106) compound that obtains is:
d＝(180??30)nm。
C. test affinity and water-repellancy:
By the method test affinity and the water-repellancy that are similar to embodiment 10c.Table 5 has been listed the result of general formula (106) compound liposome.
| Table 5 | |
| The liposome of the compound 10mM of general formula (106) does not have other additive | |
| C (skin, absorption) adsorbs after 5 hours (affinity) | (5.5??0.9)mM |
| C (skin, desorption), desorption is (water-repellancy) after 17 hours | (2.4??0.6)mM |
| C (skin takes off)/c (skin suction) | 0.44 |
Also the present invention's material that can form liposome has good affinity and waterproof shape is as can be seen.
D. spectral quality
It is the 312nm place that the maximum delustring of general formula (106) compound is positioned at wavelength.At this wavelength, the delustring of 1% solution when optical thickness is 1cm is: and E (1%, 1cm)=451.
The half-breadth of absorption band is 50nm.
E. measure the sunlight protection factor
By the method test sunlight protection factor that is similar to embodiment 9d.Dispersion liquid for general formula (102a) compound 5%: SPF=5.6 0.7.
Embodiment 17 A. prepare liposome
Method by embodiment 10a prepares liposome, and different is to replace general formula (101a) compound with general formula (107) compound (with reference to embodiment 7 preparation compounds), and injection solvent is ethanol or NMP.
B. measure the diameter of liposome
The method of pressing embodiment 10b is measured the diameter of liposome.The value of the liposome of general formula (107) compound that obtains is:
d＝(980??130)nm。
C. spectral quality
It is the 313nm place that the maximum delustring of general formula (107) compound is positioned at wavelength.At this wavelength, the delustring of 1% solution when optical thickness is 1cm is: and E (1%, 1cm)=347.
The half-breadth of absorption band is 52nm.
D. measure the sunlight protection factor
By the method test sunlight protection factor that is similar to embodiment 9d.Dispersion liquid for general formula (107) compound 5%: SPF=3.8 0.4.
Embodiment 18 A. prepare liposome
Method by embodiment 10a prepares liposome, and different is to replace general formula (101a) compound with general formula (108) compound (with reference to embodiment 8 preparation compounds), and injection solvent is ethanol or NMP.
B. measure the diameter of liposome
The method of pressing embodiment 10b is measured the diameter of liposome.The value of the liposome of general formula (108) compound that obtains is:
d＝(170??30)nm。
C. spectral quality
It is the 310nm place that the maximum delustring of general formula (108) compound is positioned at wavelength.At this wavelength, the delustring of 1% solution when optical thickness is 1cm is: and E (1%, 1cm)=418.
The half-breadth of absorption band is 53nm.
D. measure the sunlight protection factor
Press the embodiment 10d method test sunlight protection factor.Dispersion liquid for general formula (107) compound 5%: SPF=4.8 0.5.
Embodiment 19 A. prepare liposome
Method by embodiment 10a prepares liposome, and different is to replace general formula (101a) compound with general formula (109) compound (with reference to embodiment 9 preparation compounds), and injection solvent is NMP.
B. spectral quality
It is the 339nm place that the maximum delustring of general formula (109) compound is positioned at wavelength.At this wavelength, the delustring of 1% solution when optical thickness is 1cm is: and E (1%, 1cm)=237.
C. measure the sunlight protection factor
Press the embodiment 10d method test sunlight protection factor.Dispersion liquid for general formula (108) compound 5%: SPF=5.5.
Claims (24)
1. UV absorption agent that can form liposome, comprise hydrophilic headgroup (=Z), spacer (=W), on 285-400nm, have the UV chromophoric group (Q) of receptivity and at least one hydrophobic tail base (=A), have general formula (1):
A wherein
1And A
2, be separately hydrophobic grouping mutually, Q is the UV chromophoric group, W is an organic group, Z
1And Z
2, be separately hydrophilic radical mutually, n
1And n
2Be separately the number of a 0-4 mutually, but do not comprise n in addition
1=n
2=0, p is 1 or 2, and q is the number of a 0-3, r
1Be 1 or 2, r
2Be 0 or 1, s
1It is the number of a 1-3.
2. according to the UV absorption agent that can form liposome of claim 1, A in general formula (1) wherein
1And A
2Be separately alkoxyl group, acyl group or the alkylamino of at least 8 carbon atoms mutually.
3. according to the UV absorption agent that can form liposome of claim 2, A wherein
1And A
2Be separately alkyl or alkenyl mutually with 10-14 carbon atom.
4. according to any one the UV absorption agent that can form liposome among the claim 1-3, wherein n
1And n
2Be 1 or 2.
5. according to the UV absorption agent that can form liposome of claim 4, wherein, n
1And n
2Be 2.
6. according to any one the UV absorption agent that can form liposome among the claim 1-5, wherein A
1And A
2Identical.
7. according to any one the UV absorption agent that can form liposome among the claim 1-6, wherein UV chromophoric group Q is selected from (Q
1) laurate, (Q
2) pyrrolotriazine derivatives, (Q
3) benzotriazole, (Q
4) benzophenone, (Q
5) para-amino benzoic acid derivative and (Q
6) benzylidene camphor
8. according to any one the UV absorption agent that can form liposome among the claim 1-7, wherein UV chromophoric group (Q
1) be styracin deutero-from general formula (2)
Wherein R ' is hydrogen, C
1-C
4Alkoxyl group or C
1-C
4Alkoxyl group, R
1Be C
1-C
4Alkoxyl group, preferred methoxy or ethoxy, and R
2Be hydrogen, C
1-C
4Alkyl or-CN.
9. according to any one the UV absorption agent that can form liposome among the claim 1-7, wherein UV chromophoric group (Q
2) be from the Alpha-hydroxy phenyl-s-triazine derivatives of general formula (3)
R wherein
3And R
4Be separately C mutually
1-C
5Alkyl is by hydroxyl, C
1-C
5Alkoxyl group, C
1-C
5Alkylthio, amino or C
1-C
5The C that list or dialkyl amido replace
1-C
18Alkyl, unsubstituted, or by chlorine, hydroxyl, C
1-C
18Alkyl and/or C
1-C
18The phenyl that alkoxyl group replaces; R
5Be C
1-C
18Alkyl, C
1-C
18Alkoxyl group, halogen, hydroxyl, or general formula (3a)-(O-CH
2-CH
2-)
t-R
6Group; Or the group of general formula (3b)
R
7Be C
1-C
5Alkyl or C
1-C
5Alkoxy-C
1-C
5Alkyl, V
1Be C
1-C
4Alkylidene group, m
1Be 0,1 or 2, t is 1-5, and R
6Be hydrogen or C
1-C
5Alkyl.
10. according to any one the UV absorption agent that can form liposome among the claim 1-7, wherein UV chromophoric group (Q
2) be from the triazine derivatives of general formula (6)
R wherein
14And R
15Be separately hydrogen, hydroxyl, C mutually
1-C
5Alkyl or C
1-C
5Alkoxyl group.
11. according to any one the UV absorption agent that can form liposome among the claim 1-7, wherein UV chromophoric group (Q
3) be benzotriazole deutero-from general formula (7)
R wherein
16And R
18, be hydrogen separately respectively, unsubstituted, or by the C of phenyl, halogen or group (7a) replacement
1-C
18Alkyl or C
1-C
8Alkoxyl group
R wherein
19Be hydrogen, C
1-C
10Alkyl, C
5-C
8Cycloalkyl, C
7-C
10Aralkyl or C
6-C
10Aryl, R
20Be hydrogen, C
1-C
20Alkyl, C
2-C
17Alkenyl, C
5-C
8Cycloalkyl, C
7-C
10Aralkyl or C
6-C
10Aryl, and t
2Be 1 or 2, if t
2=1, R
19And R
20Can save with bridge-N-CO-forms list or multinuclear nitrogen heterocyclic ring, R in this case
19Be-CO-or unsubstituted or by C
1-C
5Methylene radical and R that alkyl replaces
20Be C
2-C
5Alkylidene group, C
2-C
5Alkylene group, C
6-C
10Two, four or six hydrogen C of arylidene or ortho position keyed jointing
6-C
10Arylidene, R
17Be C
1-C
18Alkyl, C
1-C
18Alkoxyl group, halogen, C
6-C
10Aryl, C
7-C
10Aralkyl, or C
5-C
8Cycloalkyl, ring B can be at 1,2 and 3 by C
1-C
5Alkyl, C
1-C
5Alkoxyl group, carboxyl, C
2-C
9Alkoxy carbonyl, H
2NCO-, SO
2-, C
1-C
5Alkyl sulphonyl, the group of halogen or general formula (7b) replaces
12. according to any one the UV absorption agent that can form liposome among the claim 1-7, UV chromophoric group (Q
4) be benzophenone deutero-from general formula (9)
R wherein
23Be hydrogen, hydroxyl, C
1-C
14Alkoxyl group, phenoxy group or amino, and C
1-C
14Can be by the following formula group
And/or acyloxy replaces R
24Be hydrogen, halogen or C
1-C
5Alkyl, R
25Be hydrogen, hydroxyl or C
1-C
5Alkoxyl group, and R
26Be hydrogen or hydroxyl.
13. according to any one the UV absorption agent that can form liposome among the claim 1-7, wherein UV chromophoric group (Q
5) be para-amino benzoic acid deutero-from general formula (10)
R wherein
27Be hydroxyl, halogen, cyano group, C
1-C
5Alkyl, C
1-C
5Alkoxyl group, list-C
1-C
5Alkylamino or two-C
1-C
5Alkylamino, R
28Be hydrogen or C
1-C
5Alkyl, R
29And R
30Be separately hydrogen or C mutually
1-C
5Alkyl, and m
2Be 0,1 or 2.
14. according to any one the UV absorption agent that can form liposome among the claim 1-7, wherein UV chromophoric group (Q
6) be the benzylidene camphor of general formula (11)
15. according to any one the UV absorption agent that can form liposome among the claim 1-7, wherein UV chromophoric group (Q) uses general formula 2a), 6a) or group 7a)
R wherein
2, R
14, R
16, R
17Identical with the definition of B and general formula (2), (6) with (7).
16. according to any one the UV absorption agent that can form liposome among the claim 1-15, wherein W is straight chain C side chain or preferred
2-C
4Alkylidene group, if necessary, can be at interval by carbonyl, carboxylate radical or ether.
17. according to any one the UV absorption agent that can form liposome among the claim 1-16, wherein Z is a hydrophilic group, is selected from (Z
a) ammonium or amine compound, (Z
b) phosphoric acid ester (salt) compound, (Z
c) carboxylicesters (salt) compound, (Z
d) polyvalent alcohol and (Z
e) sulfuric ester (salt) compound.
18. the UV absorption agent that can form liposome of the general formula according to claim 1 (13)
A wherein
1Be hydrophobic group, Q is the UV chromophoric group, and W is an organic group, Z
1Be hydrophilic group, n
1Be the number of a 1-4, p is 1 or 2, and q is 1-3, r
1Be 1 or 2, and s
2Be 1-3.
19. the UV absorption agent that can form liposome of the general formula according to claim 1 (14)
A wherein
2Be hydrophobic group, Q is the UV chromophoric group, and W is an organic group, Z
1Be hydrophilic group, n
2Be 1 or 2, p is 1 or 2, and q is 1-3, r
2Be 1 or 2 and s be 1 or 2.
20. the UV absorption agent that can form liposome of the general formula according to claim 1 (15)
Wherein, W
1It is the group of general formula (15a)
R
29Be hydrogen, C
1-C
4Alkyl or-CN, R
30And R
31Be separately C mutually
1-C
5Alkyl, hydroxyl, hydroxyl-C
1-C
5Alkyl or carboxyl, R
32Be C
1-C
5Alkyl, hydroxyl, hydroxyl-C
1-C
5Alkyl, the group of carboxyl or general formula (15a), A
1And A
2Be separately hydrogen or C mutually
10-C
14Alkoxyl group, one of them group is C always
10-C
14Alkoxyl group, X are halogen atoms, and q is that number and the w of a 2-4 is 0 or 1.
21. the UV absorption agent that can form liposome of the general formula according to claim 1 (16)
R wherein
29Be hydrogen, C
1-C
4Alkyl or-CN, R ' is a hydrogen, C
1-C
4Alkyl or C
1-C
4Alkoxyl group, A
1And A
2Be separately C mutually
10-C
14Alkoxyl group, W are C
2-C
4Alkylidene group in case of necessity can be by-O (CO)-Ji at interval, and Z
1And Z
2Be separately C mutually
1-C
3The carboxylic acid group, n
1And n
2Be separately 0,1 or 2 mutually, do not comprise n in addition
1=n
2=0, and r
2Be 1 or 2.
22. the UV absorption agent that can form liposome of the general formula according to claim 1 (17)
A wherein
1Be general formula (17a) or group (17b)
And t
3And t
4Be separately the number of 5-13 mutually.
23. general formula according to claim 1 (18a) or the UV absorption agent that can form liposome (18b)
A wherein
1And A
2, W and Z
1With identical in the claim 1.
24. one kind according to any one the UV absorption agent that can form liposome among the claim 1-22 as the purposes of human body skin sun-screening agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96192625 CN1179146A (en) | 1995-03-17 | 1996-03-07 | Liposomogenic uv absorbers |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH772/95 | 1995-03-17 | ||
| CN 96192625 CN1179146A (en) | 1995-03-17 | 1996-03-07 | Liposomogenic uv absorbers |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01123215A Division CN1338252A (en) | 1995-03-17 | 2001-07-17 | UV adsorbent for forming fatty body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1179146A true CN1179146A (en) | 1998-04-15 |
Family
ID=5128379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96192625 Pending CN1179146A (en) | 1995-03-17 | 1996-03-07 | Liposomogenic uv absorbers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1179146A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030917A (en) * | 2010-11-11 | 2011-04-27 | 浙江理工大学 | Azabenzotriazol containing ultraviolet absorber and preparation method thereof |
| CN107157788A (en) * | 2017-05-05 | 2017-09-15 | 海南京润珍珠生物技术股份有限公司 | A kind of suncream for adding ethylhexyl methoxy cinnamate liposome thing |
| CN107847422A (en) * | 2016-07-07 | 2018-03-27 | 浩思特创新科技公司 | Include the acrylic acid of palkoxy benzene base substitution（APP）The stable composition of the light of copolymer derivative |
-
1996
- 1996-03-07 CN CN 96192625 patent/CN1179146A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030917A (en) * | 2010-11-11 | 2011-04-27 | 浙江理工大学 | Azabenzotriazol containing ultraviolet absorber and preparation method thereof |
| CN102030917B (en) * | 2010-11-11 | 2012-10-24 | 浙江理工大学 | Azabenzotriazol containing ultraviolet absorber and preparation method thereof |
| CN107847422A (en) * | 2016-07-07 | 2018-03-27 | 浩思特创新科技公司 | Include the acrylic acid of palkoxy benzene base substitution（APP）The stable composition of the light of copolymer derivative |
| CN107847422B (en) * | 2016-07-07 | 2020-11-27 | 浩思特美容与个人护理创新公司 | Photostable compositions comprising p-alkoxyphenyl substituted acrylic Acid (APP) copolymer derivatives |
| US11098149B2 (en) | 2016-07-07 | 2021-08-24 | HallStar Beauty and Personal Care Innovations Company | Photostable compositions comprising para-alkoxyl phenyl substituted propenoic acid (APP) copolymer derivatives |
| US11767392B2 (en) | 2016-07-07 | 2023-09-26 | HallStar Beauty and Personal Care Innovations Company | Photostable compositions comprising para-alkoxyl phenyl substituted propenoic acid (APP) copolymer derivatives |
| CN107157788A (en) * | 2017-05-05 | 2017-09-15 | 海南京润珍珠生物技术股份有限公司 | A kind of suncream for adding ethylhexyl methoxy cinnamate liposome thing |
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