CN101336870B - Symmetrical triazine derivatives - Google Patents

Symmetrical triazine derivatives Download PDF

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CN101336870B
CN101336870B CN 200810129737 CN200810129737A CN101336870B CN 101336870 B CN101336870 B CN 101336870B CN 200810129737 CN200810129737 CN 200810129737 CN 200810129737 A CN200810129737 A CN 200810129737A CN 101336870 B CN101336870 B CN 101336870B
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general formula
chemical compound
acid
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phenyl
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CN101336870A (en
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托马斯·埃里斯
斯蒂芬·穆勒
帕斯卡尔·海奥兹
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Lion Corp
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Abstract

Disclosed is the use of the compounds of formula (1) wherein A is a radical of formula (1a) or (1b), R1 and R5 independently from each other are hydrogen; C1-C18alkyl; or C6-C12aryl; R2, R3 and R4 independently from each other are hydrogen; or a radical of formula wherein, in formula (1a), at least one of the radicals R2, R3 and R4 are a radical of formula (1c); R6, R7, R8, R9 and R10 independently from each other are hydrogen; hydroxy; halogen; C1-C18alkyl; C1-C18alkoxy; C6-C12aryl; biphenylyl; C6-C12aryloxy; C1-C18alkylthio; carboxy; -COOM; C1-C18-alkylcarboxyl; aminocarbonyl; or mono- or di-C1-C18alkylamino; C1-C10acylamino; -COOH; M is an alkali metal ion; x is 1 or 2; and y is a number from 2 to 10; for the protection of human and animal hair and skin against the damaging effect of UV radiation. The compounds of formula (1) are high effective UV absorbers for cosmetic formulations and can be-depending on their physical properties be used in micronized or soluble form.

Description

Striazine derivative
The application is the Chinese invention patent application (applying date: on March 19th, 2004; Application number: 200480010224.5; Denomination of invention: dividing an application Striazine derivative).
The present invention relates to the purposes of concrete Striazine derivative in the damage of protection humans and animals hair and the anti-UV radiation of skin, comprise the method for make-up preparation and these chemical compounds of preparation of these pyrrolotriazine derivatives.
Triazines by xenyl or the symmetrical replacement of naphthyl is known, and for example by US-A-6,225,467 is disclosed.They are used as electroluminescent device.
Find that unexpectedly these chemical compounds can be as the effective UV absorbent of height of cosmetics.
Therefore, the present invention relates to the non-therapeutic use of following general formula compound in protection humans and animals hair and the anti-UV radiation damage of skin:
Figure G2008101297378D00011
, wherein
A is general formula (1a)
Figure G2008101297378D00012
Or (1b)
Figure G2008101297378D00013
Group;
R 1And R 5Be hydrogen, C independently of one another 1-C 18Alkyl or C 6-C 12Aryl;
R 2, R 3And R 4Be hydrogen or general formula (1c) independently of one another Group, radicals R wherein 2, R 3And R 4In at least one is the group of general formula (1c);
R 6, R 7,, R 8, R 9And R 10Be hydrogen, hydroxyl, halogen, C independently of one another 1-C 18Alkyl, C 1-C 18Alkoxyl, C 6-C 12Aryl, xenyl, C 6-C 12Aryloxy group, C 1-C 18Alkylthio group, carboxyl, COOM, C 1-C 18-alkyl carboxyl, amino carbonyl, or one-or two-C 1-C 18Alkyl amino, C 1-C 10Acylamino-,-COOH;
M is alkali metal ion;
X is 1 or 2; And
Y is the numerical value of 2-10.
According to the definition of mutual-through type (1) compound group, C 1-C 18Alkyl is the straight or branched alkyl, such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, amyl group, isopentyl, tertiary pentyl, hexyl, 2-ethylhexyl, heptyl, octyl group, iso-octyl, nonyl, decyl, undecyl, dodecyl, myristyl, pentadecyl, cetyl, heptadecyl or octadecyl.
According to the definition of mutual-through type (1) compound group, C 1-C 18Alkyl can be replaced by following groups: methoxy ethyl, ethoxycarbonyl propyl, 2-ethylhexyl, ethoxy, chloropropyl, N, N-lignocaine propyl group, cyano ethyl, phenethyl, benzyl, p-tert-butyl benzene ethyl, p-uncle's Octylphenoxy-ethyl, 3-(2,4-two tertiary pentyl phenoxy groups)-propyl group, ethoxycarbonylmethyl group-2-(2-hydroxyl-oxethyl) ethyl, or 2-furyl ethyl.
According to the definition of mutual-through type (1) compound group, C 1-C 18Alkyl is: for example methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy., tert-butoxy, amoxy, isoamoxy or uncle's amoxy, hexyloxy, heptan oxygen base, octyloxy, different octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, hendecane oxygen base, dodecyloxy, tetradecyloxyaniline, pentadecane oxygen base, hexadecane oxygen base, heptadecane oxygen base or octadecane oxygen base.
According to the definition of mutual-through type (1) compound group, C 6-C 10Aryl is: for example naphthyl and preferably phenyl.
The preferred chemical compound that uses following general formula:
Figure G2008101297378D00021
R wherein 1, R 5, R 6, R 7And R 8Such as in the general formula (1) definition.
In general formula (2), R 1And R 2Be preferably hydrogen.
Most preferably use the chemical compound of general formula (1) or (2), wherein R 6And R 8Be hydrogen.
The chemical compound of the preferred formula (1) of paying close attention to is, wherein:
R 7Be hydrogen, hydroxyl, C 1-C 5Alkyl, C 1-C 5Alkoxyl ,-COOM ,-COOH or COOR 10
M is alkali metal ion; And
R 10Be C 1-C 5Alkyl.
In addition, preferably use the chemical compound of following general formula:
Figure G2008101297378D00031
R wherein 1, R 2, R 3, R 9And R 10Such as in the general formula (1) definition.
The preferred chemical compound that uses general formula (3), wherein:
R 1, R 2, R 3, R 9And R 10For hydrogen or be C independently of one another 1-C 18Alkyl.
The example that is preferred for pyrrolotriazine derivatives of the present invention is the chemical compound of following general formula:
Figure G2008101297378D00032
Figure G2008101297378D00041
Or
Figure G2008101297378D00051
The chemical compound of general formula of the present invention (1) is particularly suitable as the UV filtering agent, namely for the protection of the skin of ultraviolet-sensitive organic matter, particularly humans and animals and the hair illeffects with anti-UV radiation.These chemical compounds are suitable for as the sunscreen in cosmetics, medicine and the veterinary drug preparation thus.Can use these chemical compounds with dissolved form and micronized state.
Triazine aryl R according to general formula (1a), 1 (b) or (1c) 1, R 2, R 5, R 6, R 7, R 8, R 9And R 10Substituent difference, UV absorbent of the present invention can use with dissolved state (organic filtering agent of the organic filtering agent of solubility, dissolving) or with micronized state (nano level organic filtering agent, the organic filtering agent of granule, UV-absorbent pigment).
Without alkyl substituent or only be characterised in that bad oil-soluble and high-melting-point with general formula (1) pyrrolotriazine derivatives of low-grade alkyl substituent.These derivants are particularly suitable for the UV absorbent as the micronized state form thus.
The mean particle size that thus obtained micronization UV absorbent has usually is the 0.02-2 micron, preferred 0.03-1.5 micron, and more preferably 0.05-1.0 micron.
UV absorbent of the present invention can also use as the dry matrices of powder type.
UV absorbent of the present invention can also be used for specific cosmetics carrier, for example in solid lipid nanoparticle (SLN) or the inertia colloidal sol microcapsule, wherein the UV absorbent encapsulated (Pharmazie, 2001 (56), p.783-786).Such as Internat.J.Phar-maceutics, 2002,242, the lipid nanometer microgranule (CLN ,=crystallization lipid nanoparticle) described in P.373-375 can be as the active carrier (for example chemical compound of general formula 6) of UV filtering agent of the present invention.
Make-up preparation of the present invention or pharmaceutical composition can also contain one or more other such as table 1-3 at listed UV filtering agent.
The preparation method of described cosmetic or pharmaceutical preparation is as follows: use common method that UV absorbent and adjuvant are carried out physical property and mix, for example simply each composition is stirred together, especially utilize known cosmetic UV absorbent, such as the dissolution characteristics of OMC, the different monooctyl ester of salicylic acid etc.For example, can be without further processing or using the UV absorbent with micronized state or powder type.
Take the gross weight of described compositions as benchmark, make up or pharmaceutical preparation contains UV absorbent or the UV absorber blend of 0.05-40 % by weight.
The UV absorbent of general formula of the present invention (1) or UV filter compositions for the protection of skin, hair and/or natural or artificial hair color.
The suitable UV filtering agent material that table 1. can also use with UV absorbent of the present invention
Para-Aminobenzoic derivant, for example 4-dimethylaminobenzoic acid 2-Octyl Nitrite;
Salicyclic acid derivatives, for example BMDBM;
Benzophenone derivative, for example oxybenzone and 5-sulfonic acid thereof;
The dibenzoyl methane derivant, 1-(4-tert-butyl-phenyl)-3-(4-methoxyphenyl)-the third-1 for example, 3-diketone;
Diphenylacrylate esters, for example octocrylene and 3-(benzofuranyl) 2-cyanoacrylate;
3-imidazol-4 yl acrylicacidandesters class;
Be described in benzofuran derivatives, especially 2-(p-aminophenyl) benzofuran derivatives among EP-A-582 189, US-A-5 338 539, US-A-5 518 713 and the EP-A-613 893;
Polymer UV absorbent for example is described in the benzylidene malonate derivant among the EP-A-709 080;
Cinnamic acid derivative for example is described in Ethylhexyl Methoxycinnamate and isopropyl ester or cinnamic acid derivative among US-A-5 601 811 and the WO97/00851;
Camphor derivatives, 3-(4 '-methyl) benzal-camphane-2-ketone for example, 3-benzal-camphane-2-ketone, N-[2 (with 4)-2-oxygen base Borneolum Syntheticum-3-subunit-methyl)-benzyl] acrylamide polymer, 3-(4 '-trimethyl ammonium)-benzal-camphane-2-ketone Methylsulfate, 3,3 '-(1, and salt, 3-(4 '-sulfo group) benzal-camphane-2-ketone and salt 4-phenylene two methines)-two (7,7-dimethyl-2-oxo-dicyclo [2.2.1] heptane-1-methanesulfonic acid); Camphora benzalkonium mesylate;
The hydroxyphenyltriazinuv chemical compound, 2-(4 '-methoxyphenyl)-4 for example, 6-two (2 '-hydroxyl-4 '-the n-octyloxy phenyl)-1,3,5-triazines; Two { [4-(3-(2-propoxyl group)-2-hydroxyl-propoxyl group)-2-hydroxyl]-phenyl }-6-(4-the methoxyphenyl)-1,3,5-triazines of 2,4-;
Two { [4-(2-ethyl-hexyloxy)-2-hydroxyl]-phenyl }-6-[4-(2-methoxy ethyl-carboxyl)-phenyl aminos of 2,4-]-1,3,5-triazines; 2,4-pair ([4-(three (trimethylsiloxy-silicyl propoxyl group)-2-hydroxyls]-phenyl }-6-(4-methoxyphenyl)-1,3,5-triazines; 2,4-pair [4-(2 " metacryloxy)-the 2-hydroxyl]-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazines; 2,4-pair [4-(1 ', 1 ', 1 ', 3 ', 5 ', 5 ', 5 '-seven methyl trimethoxy silylation-2 " methyl-propoxyl group)-the 2-hydroxyl]-phenyl)-6-(4-methoxyphenyl)-1,3,5-triazines; Two { [4-(3-(2-propoxyl group)-2-hydroxyl-propoxyl group)-2-hydroxyl]-phenyl }-6-[4-ethyl carboxyls of 2,4-)-phenyl amino]-1,3,5-triazines;
Benzotriazole cpd, for example 2,2 '-methylene-two (6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethyl butyl)-phenol;
Disclosed triphenylamine base-s-pyrrolotriazine derivatives among US-A-5 332568, EP-A-517104, EP-A-507691, WO93/17002 and the EP-A-570 838, for example 2,4, the 6-triphenylamine-(p-carbonyl-2 '-ethyl-1 '-the oxygen base)-1,3,5-triazine and UV absorbent;
2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID and and salt;
Ortho-, meta-or p-amino benzoic Acid esters in the Meng;
Titanium dioxide, zinc oxide, ferrum oxide, Muscovitum, MnO, the Fe of coating or uncoated 2O 3, Ce 2O 3, Al 2O 3, ZurO 2The physical sunscreen agent.(face coat: the metallic soap (described in CAS 4086-70-8) of poly-methyl methacrylate base ester, methyl-silicone oil (methylhydrogenpolysi,oxane described in CAS 9004-73-3), simethicone, three stearic acid isopropyl titaniums (described in CAS 61417-49-0), magnesium stearate, the phosphoric acid perfluor alcohol ester (described in CAS74499-44-8, JP5-86984, JP 4-330007) of C9-15 phosphoric acid fluorine alcohol ester).The meansigma methods that main granular size is 15nm-35nm and the granular size in the dispersion are in the 100nm-300nm scope.
Disclosed hydroxy amino-benzophenone derivative among DE 10011317, EP 1133980 and the EP1046391
Such as disclosed phenyl-benzimidizole derivatives among the EP 1167358
" Sunscreens ", Eds.N.J.Lowe, N.A.Shaath, Marcel Dekker, Inc., New York and Basle or Cosmetics﹠amp; Toiletries (107), the UV absorbent described in the 50ff (1992) also can be used as other protective substance.
Preferably following UV being filtered compositions is special concern:
-UV-filters compositions (A), comprising:
(a 1) Striazine derivative of at least a general formula (1); With
(a 2) the ADP ketone derivatives of at least a following general formula:
Figure G2008101297378D00071
Wherein:
R 1And R 2Be C independently of one another 1-C 20Alkyl, C 2-C 20Alkenyl, C 3-C 10Cycloalkyl, C 3-C 10Cycloalkenyl group; Or R 1And R 2Form 5-or 6-unit heterocycle with the nitrogen-atoms that connects;
n 1Numerical value for 1-4;
Work as n 1=1 o'clock,
R 3Be saturated or undersaturated heterocyclic radical, hydroxyl-C 1-C 5Alkyl, optional by one or more C 1-C 5The cyclohexyl that alkyl replaces, optional by heterocyclic radical, amino carbonyl or C 1-C 5The phenyl that alkyl carboxyl replaces;
Work as n 1=2 o'clock,
R 3For optional by carbonyl-or the alkylidene of carboxyl substituted-, ring alkylidene, alkylene group or phenylene, general formula *-CH 2-C ≡ C-CH 2-* group; Or
R 3Form the divalent group of general formula (1a) with A
Figure G2008101297378D00081
Wherein:
n 2Numerical value for 1-3;
Work as n 1Be 3 o'clock,
R 3Be alkane three bases;
Work as n 1Be 4 o'clock,
R 3Be alkane four bases;
A is-O-or-N (R 5)-; And
R 5Be hydrogen, C 1-C 5Alkyl or hydroxyl-C 1-C 5Alkyl.
Most preferably UV-filters compositions (Al), comprising:
(a 3) chemical compound of general formula (6) and/or (9); With
(a 4) chemical compound of following general formula:
Figure G2008101297378D00082
-UV-filters compositions (B), comprising:
(b 1) Striazine derivative of at least a general formula (1); With
(b 2) the ADP ketone derivatives of at least a following general formula:
Figure G2008101297378D00091
Wherein:
R 1And R 2Be hydrogen, C independently of one another 1-C 20Alkyl, C 2-C 20Alkenyl, C 3-C 10Cycloalkenyl group; R wherein 1And R 2Can form 5-or 6-unit ring;
R 3And R 4Be C independently of one another 1-C 20Alkyl, C 2-C 20Alkenyl, C 3-C 10Cycloalkenyl group, C 1-C 20Alkoxyl, C 1-C 20Alkoxy carbonyl group, C 1-C 20Alkylamino, two (C 1-C 20Alkyl) amino, optional aryl or the heteroaryl that replaces;
X is hydrogen, COOR 5, CONR 6R 7
R 5, R 6, R 7Be hydrogen, C independently of one another 1-C 20Alkyl, C 2-C 20Alkenyl, C 3-C 10Cycloalkyl, C 3-C 10Cycloalkenyl group, (Y-O) q-Z, the optional aryl that replaces;
Y is-(CH 2) 2-,-(CH 2) 4-,-CH (CH 3)-CH 2-;
Z is-CH 2-CH 3,-CH 2-CH 2-CH 3,-CH 2-CH 2-CH 2-CH 3, CH (CH 3)-CH 3
M is 0,1,2 or 3;
N is 0,1,2,3 or 4; And
Q is the numerical value of 1-20
Most preferably UV-filters compositions (B1), comprising:
(b 3) chemical compound of general formula (6) and/or (9); With
(b 4) chemical compound of following general formula:
Figure G2008101297378D00092
-UV-filters compositions (C), comprising:
(c 1) Striazine derivative of at least a general formula (1); With
(c 2) at least a general formula benzotriazole derivatives:
Figure G2008101297378D00101
Wherein:
T 2Be C 1-C 10The C that alkyl or phenyl replaces 1-C 4Alkyl.
Most preferably UV-filters compositions (C1), comprising:
(c 3) chemical compound of general formula (6) and/or (9); With
(c 4) micronized compound of following general formula:
Figure G2008101297378D00102
-UV-filters compositions (D), comprising:
(d 1) Striazine derivative of at least a general formula (1); With
(d 2) chemical compound of at least a following general formula:
Figure G2008101297378D00103
Wherein:
R 1And R 2Be C independently of one another 3-C 18Alkyl, C 2-C 18Alkenyl, general formula-CH 2-CH (OH)-CH 2-O-T 1Group; Or
R 1And R 2Group for general formula (4a)
R 12Be direct key, straight or branched C 1-C 4Alkylidene or general formula
Figure G2008101297378D00105
Or
Figure G2008101297378D00106
Group;
R 13, R 14And R 15Be C independently of one another 1-C 18Alkyl, C 1-C 18The group of alkoxyl or following general formula:
Figure G2008101297378D00111
R 16Be C 1-C 5Alkyl;
m 1And m 3Be 1-4 independently of one another;
p 1Be 0 or the numerical value of 1-5;
A 1Group for following general formula:
Figure G2008101297378D00112
R 3Be hydrogen, C 1-C 10Alkyl ,-(CH 2CHR 5-O) N1-R 4Or the group of following general formula :-CH 2-CH (OH)-CH 2-O-T 1
R 4Be hydrogen; M; C 1-C 5Alkyl; Or general formula-(CH 2) M2-O-T 1Group;
R 3Be hydrogen or methyl;
T 1Be hydrogen or C 1-C 8Alkyl;
Q 1Be C 1-C 18Alkyl;
M is metal cation;
m 2Be 1-4; And
N is 1-16.
Most preferably UV-filters compositions (D1), comprising:
(d 3) chemical compound of general formula (6) and/or (9); With
(d 4) chemical compound of following general formula:
Figure G2008101297378D00121
-UV-filters compositions (E), comprising:
(e 1) Striazine derivative of at least a general formula (1); With
(e 2) the hydroxyphenyltriazinuv chemical compound of at least a following general formula:
Wherein:
R 1, R 2And R 3Be C independently of one another 1-C 18Alkyl, C 2-C 10Alkenyl or phenyl-C 1-C 4Alkyl;
R 4Be hydrogen or C 1-C 5Alkyl.
Most preferably UV-filters compositions (E1), comprising:
(e 3) chemical compound of general formula (6) and/or (9); With
(e 4) chemical compound of following general formula:
-UV-filters compositions (F), comprising:
(f 1) Striazine derivative of at least a general formula (1), the chemical compound of preferred formula (6) or (9); With
(f 2) the dibenzoyl methane Derivatives of at least a following general formula:
Figure G2008101297378D00131
Or
Figure G2008101297378D00132
Most preferably UV-filters compositions (F1), comprising:
(f 3) chemical compound of general formula (6) and/or (9); With
(f 4) 1-[4-(1,1-dimethyl ethyl) phenyl]-3-(4-methoxyphenyl the third-1,3-diketone (avobenzone);
-UV-filters compositions (G), comprising:
(g 1) Striazine derivative of at least a general formula (1), the chemical compound of preferred formula (6) and/or (9); With
(g 2) phenyl bisbenzimidazole tetrasulfonic acid sodium (Heliopan AP).
-UV-filters compositions (H), comprising:
(h 1) Striazine derivative of at least a general formula (1), and
(h 2) triazine of benzoxazole-replacement of following general formula:
Figure G2008101297378D00133
Wherein:
R 1, R 2And R 3Be side chain or non-side chain C independently of one another 1-C 12Alkyl.
Most preferably UV-filters compositions, comprising:
(h 3) chemical compound of general formula (6) and/or (9), and
(h 4) 1,3,5-triazines-2,4,6-triamine, N, N '-two [4-[5-(1,1-dimethyl propyl)-2-benzoxazolyl] phenyl]-N " (2-ethylhexyl) (CAS No.288254-16-0).
In addition, preferred UV filters compositions (H2), comprising:
(h 5) chemical compound of general formula (6) or (9), and
(h 6) at least a general formula (h 21) chemical compound, wherein
(h 61) R 1And R 2Be tertiary pentyl and R 3Be the tert-butyl group; Or wherein
(h 62) R 1And R 2Be the tert-butyl group and R 3Be uncle's octyl group; Or wherein
(h 63) R 1And R 2Be the tert-butyl group and R 3Be the 2-ethylhexyl; Or wherein
(h 64) R 1And R 2Be tertiary pentyl and R 3Be the 2-ethylhexyl.
-UV-filters compositions (I), comprising:
(i 1) Striazine derivative of at least a general formula (1), the chemical compound of preferred formula (6) and/or (9); With
(i 2) 2-(2H-benzotriazole-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl) the oxygen base] the disiloxane base] propyl group]-; (CAS-No.155633-54-8; The Drometrizole trisiloxanes; Mexoryl XL);
-UV-filters compositions (K), comprising:
(k 1) Striazine derivative of at least a general formula (1), the chemical compound of preferred formula (6) and/or (9); With
(k 2) siloxanes and silicone, two-Me, 1-[[4-[3-ethyoxyl-2-(carbethoxyl group)-3-oxo-1-acrylic] phenoxy group] methyl] vinyl Me, 3-[4-[3-ethyoxyl-2-(carbethoxyl group)-3-oxo-1-acrylic] phenoxy group]-1-acrylic Me, Me hydrogen (dimethyl siloxane diethyl toluenyl malonic ester (Dimethicodiethylbenzalmalonate); CAS-No.207574-74-1);
-UV-filters compositions (L), comprising:
(1 1) Striazine derivative of at least a general formula (1), the chemical compound of preferred formula (6) and/or (9); With
(1 2) (+/-)-1,7,7-trimethyl-3-[(4-aminomethyl phenyl) methylene] dicyclo [2.2.1] heptan-2-ketone; P-methyl benzylidene camphor;
-UV-filters compositions (M), comprising:
(m 1) Striazine derivative of at least a general formula (1), the chemical compound of preferred formula (6) and/or (9); With
(m 2) α-(2-oxo Borneolum Syntheticum-3-subunit) toluene-4-sulfonic acid and salt (Mexoryl SL) thereof;
-UV-filters compositions (N), comprising:
(n 1) Striazine derivative of at least a general formula (1), the chemical compound of preferred formula (6) and/or (9); With
(n 2) N, N, N-trimethyl-4-[(4,7,7-trimethyl-3-oxo dicyclo [2,2,1] heptan-2-subunit) methyl]-anilinomethyl sulfate (Mexoryl SO);
-UV-filters compositions (O), comprising:
(o 1) Striazine derivative of at least a general formula (1), the chemical compound of preferred formula (6) and/or (9); With
(o 2) 2-cyano group, 3,3-diphenylacrylate 2-ethyl hexyl ester (octocrylene);
-UV-filters compositions (P), comprising:
(p 1) Striazine derivative of at least a general formula (1), the chemical compound of preferred formula (6) and/or (9); With
(p 2) Uvinul MC 80 (OMC);
-UV-filters compositions (Q), comprising:
(q 1) Striazine derivative of at least a general formula (1), the chemical compound of preferred formula (6) and/or (9); With
(q 2) benzoic acid, 4,4 ', 4 " (1,3,5-acetal-2,4,6-three basic three imino groups) three-, three (2-ethylhexyl) ester; 2,4,6-triphenylamine base-(p-carbonyl-2 '-ethylhexyl-1 '-oxygen base (oxi))-1,3,5-triazines (octyl triazone);
-UV-filters compositions (R), comprising:
(r 1) Striazine derivative of at least a general formula (1), the chemical compound of preferred formula (6) and/or (9); With
(r 2) 2-phenyl-1H-benzimidazole-5-sulfonic acid (Phenylbenzimidazolesulfonic acid);
-UV-filters compositions (S), comprising:
(s 1) Striazine derivative of at least a general formula (1), the chemical compound of preferred formula (6) and/or (9); With
(s 2) benzoic acid, 4,4 '-[[the 6-[[4-[[(1-dimethyl ethyl) amino] carbonyl] phenyl] amino] 1,3,5-triazines-2,4-two bases] diimino] two-, two (2-ethylhexyl) ester; Uvasorb HEB (Uvasorb HEB).
In compositions (A)-(S), the chemical compound of general formula (1), (6) and (9) preferably exists with micronization form compositions respectively.
The chemical compound of general formula (1) can also be used as wrinkle resistant sensation regulator (referring to embodiment 29).This is another object of the present invention.
Can be according to for example US-A-6, the known method described in 225,467 prepares the chemical compound of general formula (1).
In addition, can be take corresponding halogenated aromatic compound and three halo triazines as raw material with the chemical compound that obtains general formula (1) in the Grignard reaction.
The ring trimerizing of aromatic nitrile compound is the another kind of good method of the Striazine derivative of preparation general formula (1), and the productive rate that obtains is lower.
Found unexpectedly the straightforward procedure of preparation general formula (1) chemical compound.Three halos-1,3,5-triazines class and aromatic compounds are reacted in friedel-crafts-reaction and are obtained the Striazine derivative of high yield.
Suitable aromatic compounds is:
Figure G2008101297378D00161
And/or
Figure G2008101297378D00162
Wherein: R 1-R 10Such as in the general formula (1) definition.
According to the method, can prepare according to following reaction scheme the chemical compound of general formula (101):
Preferably cyanuric chloride is used as three halos-1,3,5-triazines.
Reaction temperature is-10-250 ℃, and preferred 5-150 ℃, most preferably 70-130 ℃.
Can be listed in the following table as the type of compounds of catalyst:
Acid halide AlCl 3，AlBr 3，SnCl 4，SbCl 5，FeCl 3
Metal alkyl and metal alkoxide AlR 3，BR 3，ZnR 2，Al(OPh) 3
Bronsted acid HCl，HCl-AlCl 3，H 2SO 4，HF，H 3PO 4
Acidic oxide and derivant Zeolites, the oxide of mixing and solid peracid, clay, heteropoly acid, modified clay
Carrier acid H 3PO 4-SiO 2，BF 3-Al 2O 3
Cation exchange resin Permutit Q，Amberlite IR 112，Dowex 50， Nafion-silica，Deloxan
Other catalyst The solid peracid, heteropoly acid, the proton on the carrier or lewis acid, Nafion and Nafion class complex
Preferred catalyst is (as single compound or compositions: AlCl 3, AlBr 3, BF 3, Boys, BBr 3, BeCl 2, CdCl 2, ZnCl 2, GaCl 3, GaBr 3, FeCl 3, SbCl 3, BiCl 3, TiCl 4, ZrCl 4, SnCl 4, UCl 4And SbCl 5
Advantageously with listed chemical compound in the table in stoichiometric amount or the excessive use.
The promoter that uses: alcohols, water, HCl, HF, H 2SO 4, H 3PO 4, RCOOH (organic acid), sulphonic acids, for example p-methyl benzenesulfonic acid.
Also can be with stoichiometric amount or with excessive use promoter.
Preferably gas HCl is used as promoter.
As catalyst, promoter or promoter, the classes of compounds of use:
-form cationic chemical compound: preferred alkyl-and acyl group-halogenide and contain oxygen-, sulfur-or the chemical compound of halogen-donor atom.
-adduct: ZnCl 2-AlCl 3, SnCl 4, AlCl 3-ketone, AlCl 3-pyridine, AlCl 3-RNO 2, AlBr 3-RNO 2, GaCl 3-RNO 2, SbF 5, BF 3-OEt 2, BF 3-C 6H 5OH; AlCl 3-sulfolane.(R-NO 2: nitro aliphatic series and nitro-aromatics).
Suitable solvent is: aliphatic hydrocarbon, aromatic hydrocarbons, sulfur-bearing-hydro carbons, halogenated aromatic compound, halogenated aliphatic chemical compound, alkyl (alyl)-aryl ethers, alkyl-alkyl ether, sulfolane, nitro-aromatics and nitro aliphatic compounds.
Most preferably: chlorobenzene, 1,2-dichloro-benzenes, Isosorbide-5-Nitrae-dichloro-benzenes, Nitrobenzol, Nitrocarbol., tetrachloromethane.
In addition; reaction is at ionic liquid, and for example s.1-1-butyl-pyridinium father-in-law chloride-aluminum chloride (III) and 1-butyl-3-Methylimidazole. father-in-law chloride-aluminum chloride (III) (carry out in the solvent of ethyl-3-methylimidazole father-in-law halogenated aluminum hydrochlorate ionic liquid as the friedel-crafts acylation reaction of ferrocene.Journal of theChemical Society，Dalton Transactions：Inorganic Chemistry 1999(1)，63)。
Find unexpectedly reaction not as 1, the solvent of 2-dichloro-benzenes situation under carry out.When gas HCl was put into reactant mixture, reaction was carried out well especially.
This preparation method has special significance, because the application of halogenated aromatic solvent is so that unique what be difficult to remove in end-product is the solvent residues thing.These types of solvents are not suitable for cosmetic applications.
For example, cosmetic or pharmaceutical preparation can be cream, gel, lotion, alcohol and water/alcoholic solution, Emulsion, wax/fat composition, patch, powder or ointment.Except above-mentioned UV filtering agent, cosmetic or pharmaceutical preparation can contain other adjuvant as described below.
As moisture and Emulsion (for example W/O, O/W, O/W/O and W/O/W Emulsion or microemulsion) oil-containing, described preparation contains: for example, 0.1-30 % by weight, one or more UV absorbent (take composition total weight as benchmark) of preferred 0.1-15 % by weight and especially 0.5-10 % by weight; At least a oil component (take composition total weight as benchmark) of 1-60 % by weight, especially 5-50 % by weight and preferred 10 to, 35 % by weight; At least a emulsifying agent (take composition total weight as benchmark) of 0-30 % by weight, especially 1-30 % by weight and preferred 4-20 % by weight; 10-90 % by weight, the especially water of 30-90 % by weight, (take composition total weight as benchmark); With the 0-88.9 % by weight, especially acceptable adjuvant is gone up in other cosmetic of 1 to50 % by weight.
Cosmetic of the present invention or pharmaceutical composition/preparation can also contain one or more other chemical compounds, such as the aliphatic alcohol esters of fatty acid; Natural or synthetic glycerine three esters comprise glyceride type and derivant; Pearlescent waxes: hydrocarbon ils, silicone or siloxanes (organic replacement polysiloxane-based); Fluoridize or the perfluorinate emulsifier; Superfatting agent; Surfactant; Consistency modifiers/thickening agent and rheology modifier; Polymer; Biological active component; The deodorant activities component; Dandruff removing agent; Antioxidant; Hydrotropic agent; Antiseptic and antibacterial; Aromatic oil; Coloring agent; Polymeric beads or hollow ball as SPF promoter.
Comprise in the various cosmetic products and make up or pharmaceutical preparation.Consider, for example, especially descend series preparation: skin protectant, bath shampoo, cosmetic personal nursing agent, foodcare agent; The depilatory (depilation) of lucifuge agent, skin tanning agent, depigmenting agent, anthelmintic, deodorizer, antiperspirant, the preparation that is used for cleaning and nursing stained skin, chemical drugs form, shave a mao agent, aromatic or cosmetic hair nursing agent.
Listed final preparation can exist with various forms, for example:
-liquid preparation form is such as W/O, O/W, O/W/O, W/O/W or PIT Emulsion and all types of microemulsion; Gel, oil, cream, milk or lotion, powder, lacquer, tablet or cosmetics, rod, spray or aerosol, foam or paste form.
Be anti-day photo etching as the make-up preparation with particular importance that is used for skin, such as day cream, astringent, cream, oil, sunscreen or summer using agent after newborn, pre-suntan or the Exposure to Sunlight, also claim the skin tanning agent, for example from shining black frost.The special meaningfully sun-screening agent of sunscreen cream, suntan lotion, sunscreen and spray form.
Be above-mentioned preparation for hair-care as the make-up preparation with particular importance that is used for hair, the shampoo of especially shampoo form, hair conditioner, conditioner, pre-care formulations for example, hair oil, hair styling cream, hair styling gel having, pomade, hair conditioner; The nursing bag, strong conditioner, hair straighten, liquid hair mousse, hair foaming agent and hair jelly.The shampoo of special meaningfully shampoo form.
The marked feature of make-up preparation of the present invention is that application on human skin is to the splendid protective action of daylight detrimental effect.
Embodiment
The preparation of UV absorbent
Embodiment 1: the preparation of general formula (101) chemical compound
Figure G2008101297378D00191
Cyanuric chloride (36.9g, 0.20mol) is dissolved in 1,2-dichloro-benzenes (500ml).Add aluminum chloride (96.0g, 0.72mol) and this reactant mixture is heated to 140 ℃.Slowly drip and be dissolved in 200ml 1, the biphenyl (111.0g, 0.72mol) of 2-dichloro-benzenes also maintains 140-145 ℃ of lower 1-4 hour with temperature.
With this reactant mixture be cooled to about 60 ℃ and join the dense HCl of 150ml and the mixture of 350g ice in.After being separated under about 110 ℃, remove the dichloro-benzenes phase, with Na 2CO 3Stir together and at 100-110 ℃ of lower heat filtering.Make required compound recrystallization from filtrate.
For purification, make this chemical compound from dichloro-benzenes with recrystallization the diox.
13C NMR(90MHz，CDCl 3，TMS)：
The peak δ(ppm) ％Int. Peak Nr. δ(ppm) ％Int.
1 171.8 15.6 6 129.3 98.6
2 145.6 21.6 7 128.4 32.5
3 140.8 18.3 8 127.8 62.9
4 135.6 26.4 9 127.7 100.0
5 129.9 62.2
Embodiment 2:
Provide biphenyl (200.0g, 1.28mol) and fusing under 70-75 ℃.Add cyanuric chloride (9.2g, 0.05mol) and discharged hydrogen chloride 10 minutes.Minute 5 equal portions add aluminum chloride (20.0g, 0.15mol) in 40 minutes, wherein again emit hydrogen chloride after front two parts of addings.Behind reaction terminating, slowly drip 95% ethanol (200ml), under reflux state, this reactant mixture was heated 1 hour.Final adding acetone (400ml) also stirred 1 hour, is cooled to room temperature and filters out defective product under puffing regimens.
The productive rate of three (biphenyl)-1,3,5-triazines (general formula 101): about 65%
Embodiment 3: the preparation of general formula (102) chemical compound
Figure G2008101297378D00201
Obtain the chemical compound of general formula (102) according to the method described in the embodiment 1, condition is to substitute biphenyl with naphthalene.
Embodiment 4: the preparation of general formula (103) chemical compound
Figure G2008101297378D00211
Reaction scheme:
Figure G2008101297378D00212
Embodiment 4a:
With 0.5g 2,4,6-three-(4-bromophenyl)-1,3,5-triazines (CAS Nr.30363-03-2) and 0.816g 4-xenyl boric acid join in the 10m toluene in ar gas environment.The 2.238g cesium carbonate is dissolved in 3.5ml water and joins in the above-mentioned reactant mixture.After adding 0.03 equivalent palladium (II) catalyst, this reactant mixture was heated 4 hours under reflux state.This reactant mixture is cooled to room temperature and then filtration.Filter cake is dissolved in hot DMF, filter and under cooling condition crystallization go out required product.The brilliant fusing point of white fine needle be 360 ℃ and 1H-NM has confirmed this structure.
NMR-data: 1H-NMR (340MHz, CDCl 3): δ=8.83 (d, 6H), 7.82 (d, 6H), 7.75 (d, 6H), 7.67 (d, 6H), 7.62-7.60 (m, 6H), 7.44-7.40 (m, 6H), 7.34-7.30ppm (m, 3H).
Also can use chloride, iodide or toluene fulfonate to replace bromide as raw material.Preferred bromide
Embodiment 4b:
The chemical compound that can synthesize by following approach on the other hand, general formula (103):
Figure G2008101297378D00221
X=Cl, Br, I, adjacent tosyl (the preferred Br of X=)
Embodiment 4c:
Another kind of approach for the preparation of the chemical compound of general formula (103) is as follows:
Figure G2008101297378D00222
Embodiment 4d:
Obtain the chemical compound of general formula (103) according to the method described in the embodiment 1, condition is to substitute biphenyl with para-terpheny.
Embodiment 5: the preparation of general formula (104) chemical compound
Figure G2008101297378D00231
Obtain the chemical compound of general formula (104) according to the method described in the embodiment 1, condition is with right, and quaterphenyl is substituted biphenyl as starting compound.
Embodiment 6: the preparation of micronization UV absorbent
Respectively with the chemical compound of 100 parts of general formulas (101), (102), (103) or (104) with as the Zirconium orthosilicate. grain (bells) of grinding aid (diameter: 0,1-4mm), dispersant (15 parts of C 8-C 16Poly glucoside) and water (85 parts) jointly to be ground to mean particle size in ball mill be d 50=130nm.
Make the little pigment dispersion that has obtained in this way the UV absorbent.
Embodiment 7: the preparation of micronization UV absorbent
Respectively with 100 parts of general formulas (101), (102), (103) or (104) chemical compound with as the Zirconium orthosilicate. grain of grinding aid (diameter: 0,1-4mm), dispersant (15 parts of C 12Glyceride (gyceride)-Polyethylene Glycol 10) and water (85 parts) jointly to be ground to mean particle size in ball mill be d 50=130nm.
Make the little pigment dispersion that has obtained in this way the UV absorbent.
Application Example
Figure G2008101297378D00261
Figure G2008101297378D00262
Figure G2008101297378D00271
Figure G2008101297378D00272
Figure G2008101297378D00281
The preparation explanation of embodiment 8a-8d:
Respectively A part and B partly are heated to 75 ℃.Continuing under the stirring A part impouring B part.To sneak into described mixture from D part cyclopentasiloxane and Polyethylene Glycol-12 simethicone immediately after the emulsifying.After this, use Ultra Turrax with 11000rpm with this mixture homogenize 30 seconds.After being cooled to 65 ℃, sneak into sodium acrylate copolymer (with) liquid paraffin (with) polypropylene glycol-1 tridecyl polyoxyethylene (6) ether.Under＜50 ℃ temperature, add the C part.Under＜35 ℃ temperature, sneak into alpha-tocopherol acetate and subsequently water (with) the Fructus Citri Limoniae acid for adjusting pH.At room temperature add the E part.
Lotion between embodiment 9:UV day
The INCI-title %w/w (providing)
The A part The phosphoric acid cetyl 1.75
Benzoic acid C12-C15 Arrcostab 4.00
16/octadecanol/Polyethylene Glycol-20 stearate 2.00
The ethoxydiglycol oleate 2.00
Stearic acid 1.50
Ethylhexyl methoxy cinnamate 3.00
Isononyl isononanoate 2.00
Bemotrizinol (Tinosorb S) 1.00
The B part Water In right amount to 100
Xanthan gum 0.35
UV-absorbent dispersion as described in example 6 above 5.00
EDETATE SODIUM 0.20
Propylene glycol 2.00
N-(methylol)-N-(the two methylols-2 of 1,3-, 5-dioxy-4-imidazolidinyl-N '-(methylol) urea (with) methyl parahydroxybenzoate (with) propyl p-hydroxybenzoate (with) propylene glycol 0.70
Glycerol 1.50
The C part Cyclopentasiloxane (with) simethicone 1.00
Ethoxydiglycol 3.00
Simethicone 2.00
The D part Triethanolamine In right amount
The preparation explanation:
Prepare the A part by sneaking into all components, then under middling speed, stir and be heated to 75 ℃.Preparation B part also is heated to 75 ℃.In this temperature with progressively increase progressively under the mixing speed B part impouring A part.Then this mixture of homogenize (30 seconds, 15000rpm).Under＜50 ℃ temperature, add the C part.Then this chemical compound of cooling under middling speed stirs detects pH and regulates with triethanolamine.
Embodiment 10: sunscreen
The INCI-title %w/w (providing)
The A part 16/octadecanol/Polyethylene Glycol-20 stearate 4.00
Benzoic acid C12-C15 Arrcostab 2.00
Dicaprylyl ether (Dicaprylyl Ether) 3.00
The ethoxydiglycol oleate 2.00
Stearic acid 1.00
Ethylhexyl methoxy cinnamate 3.00
Sodium acrylate copolymer (with) Glycine Soja (with) polypropylene glycol-1 tridecyl polyoxyethylene (6) ether 0.30
Squalane 3.50
The B part Water In right amount to 100
UV-absorbent dispersion as described in example 6 above 5.00
The C part N-(methylol)-N-(the two methylols-2 of 1,3-, 5-dioxy-4-imidazolidinyl-N '-(methylol) urea (with) butyl carbamic acid iodine propynyl ester 0.15
Propylene glycol 2.50
Water 10.00
The D part Cyclopentasiloxane (with) simethicone 2.00
Ethoxydiglycol 5.00
Cyclopentasiloxane (with) simethicone/vinyl-simethicone friendship 2.00
Linked polymer
The E part Sodium hydroxide 0.10
The preparation explanation:
Prepare the A part by sneaking into all components, then under middling speed, stir and be heated to 75 ℃.Preparation B part also is heated to 75 ℃.In this temperature with progressively increase progressively under the mixing speed B part impouring A part.Be lower than 65 ℃ of lower D parts that add separately.After under middling speed stirs, being cooled to 55 ℃, add the C part.Then detect pH and regulate with sodium hydroxide.With 16000rpm with this mixture homogenize 30 seconds.
Embodiment 11: daily lotion
The INCI-title %w/w (providing)
The A part The phosphoric acid stearyl 5.00
Tricontanyl PVP 1.00
The ethoxydiglycol oleate 3.00
Squalane 5.00
Benzoic acid C12-C15 Arrcostab 5.00
Ethylhexyl methoxy cinnamate 3.00
Tristerin 2.00
Spermol 2.00
Butyl methoxydibenzoylmethise (Parsol 1789) 1.50
The B part Water 20.00
UV-absorbent dispersion as described in example 5 above 3.00
Bisoctrizole (TinosorbM) 2.00
The C part Water In right amount to 100
Stearyl polyoxyethylene (10) ether allyl ether/acrylate copolymer 0.50
Glycerol 2.50
N-(methylol)-N-(the two methylols-2 of 1,3-, 5-dioxy-4-imidazolidine 0.15
Base-N '-(methylol) urea (with) butyl carbamic acid iodine propynyl ester
Sodium lauroyl glutamate 0.70
The D part Cyclopentasiloxane (with) simethicone 1.50
Triethanolamine 1.85
The preparation explanation:
Prepare the A part by sneaking into all components, then under middling speed, stir and be heated to 75 ℃.Preparation C part also is heated to 75 ℃.In this temperature with progressively increase progressively under the mixing speed C part impouring A part.After emulsifying, add immediately the B part, then with the neutralization of part triethanolamine.With this mixture homogenize 30 seconds.After under middling speed stirs, cooling off, the adding cyclopentasiloxane (with) simethicone.Be lower than 35 ℃ of lower pH of inspection and regulating with triethanolamine.
Embodiment 12: sprayable sunscreen
The INCI-title %w/w (providing)
The A part 16/octodecyl alcohol polyoxyethylene (15) ether (with) tristerin 3.00
Octadecanol 1.00
The castor oil acid cetyl 0.80
Dicaprylyl ether 3.00
Benzoic acid C12-C15 Arrcostab 3.00
2-Methylpentadecane 2.50
The stearyl simethicone 1.00
Ethylhexyl methoxy cinnamate 4.00
Spermol 0.80
Tartaric acid two-C12-13 Arrcostab 3.00
The B part Water In right amount to 100
Stearyl polyoxyethylene (10) ether allyl ether/acrylate copolymer 0.45
Polyethylene Glycol-7 glyceryl cocos nucifera oil acid esters 2.50
Glycerol 2.00
Propylene glycol 3.00
The C part N-(methylol)-N-(the two methylols-2 of 1,3-, 5-dioxy-4-imidazolidinyl-N '-(methylol) urea (with) butyl carbamic acid iodine propynyl ester 0.15
Water 20.00
UV-absorbent dispersion as described in example 6 above 12.00
Titanium dioxide (with) silicon dioxide (with) sodium polyacrylate 8.00
The D part Cyclopentasiloxane (with) simethicone 0.85
The E part Sodium hydroxide (with) water In right amount to pH 6.50-7.00
The F part Spice In right amount
The preparation explanation:
A part and B partly are heated to 80 ℃.Under agitation A is partly mixed the B part and use UltraTurrax with 11000rpm homogenize 30 seconds.C partly is heated to 60 ℃ also slowly to be joined in the described emulsion.After being cooled to 40 ℃, at room temperature sneaking into the D part and add the E part.
Embodiment 13: day care liquid
The INCI-title %w/w (providing)
The A part Polyglyceryl methyl glucoside distearate 2.50
16/octadecanol 2.00
Octyl stearate 3.00
Caprylic/capric triglyceride 4.00
2-Methylpentadecane 4.00
Ethylhexyl methoxy cinnamate 2.70
The B part Water 64.80
Glycerol 5.00
Phenyl phenol (with) methyl parahydroxybenzoate (with) butyl p-hydroxybenzoate (with) ethylparaben (with) propyl p-hydroxybenzoate 0.50
UV-absorbent dispersion as described in example 6 above 8.00
The C part The ring simethicone (with) simethicone 3.00
The D part Stearyl polyoxyethylene (10) ether allyl ether/acrylate copolymer 0.50
The preparation explanation:
A part and B partly are heated to 75 ℃.Under continuous stirring, A partly added the B part and with 11000rpm homogenize 1 minute.After being cooled to 50 ℃, under continuous stirring, add the C part.
After being cooled to 30 ℃, add the D part.After this with pH regulator to 6.00-6.50.
Embodiment 14: the day care agent with UV protective action
The INCI-title %w/w (providing)
The A part Tristerin SE 3.00
Tristerin and Polyethylene Glycol-100 stearates 3.50
Spermol 1.50
Myristyl myristate 2.00
Isopropyl palmitate 2.50
Liquid paraffin 5.00
Octyldimethyl PABA 3.00
The B part Water In right amount to 100
Propylene glycol 7.50
Phenyl phenol (with) methyl parahydroxybenzoate (with) butyl p-hydroxybenzoate (with) ethylparaben (with) propyl p-hydroxybenzoate 1.00
The C part Water 30.00
UV-absorbent dispersion as described in example 6 above 10.00
The D part Sodium acrylate copolymer (with) liquid paraffin (with) polypropylene glycol-1 tridecyl polyoxyethylene (6) ether 2.00
The E part Citric acid 0.30
The preparation explanation:
Respectively A part and B partly are heated to 75 ℃.After B partly being added the A part, use UltraTurrax with 11000rpm homogenize 1 minute in this mixture.After being cooled to 50 ℃, add the C part.After this with this mixture with 16000rpm homogenize 1 minute.During in temperature＜40 ℃, add the D part.At room temperature with the E part pH value is adjusted to 6.00-6.50.
Embodiment 15:O/W day is used the UV protective liquid
The INCI-title %w/w (providing)
The A part Tristerin and Polyethylene Glycol-100 stearates 5.00
Octadecanol 1.00
Glyceryl tripalmitate 0.70
Simethicone 2.00
Benzoic acid C12-15 Arrcostab 5.00
Isopropyl palmitate 5.00
Ethylhexyl methoxy cinnamate 3.00
The B part Water In right amount to 100
Polysorbate60 0.50
Glycerol 3.00
The C part Water 10.00
UV-absorbent dispersion as described in example 6 above 8.00
The D part Phenyl phenol (with) methyl parahydroxybenzoate (with) butyl p-hydroxybenzoate (with) ethylparaben (with) propyl p-hydroxybenzoate 0.70
Stearyl polyoxyethylene (10) ether allyl ether/acrylate copolymer 1.50
The E part Water (with) sodium hydroxide In right amount
The F part Spice In right amount
The preparation explanation:
Respectively A part and B partly are heated to 75 ℃, C partly is heated to 60 ℃.After this under agitation with B part impouring A part.With this mixture with UltraTurrax with 11000rpm homogenize 30 seconds and sneak into the C part.After being cooled to 40 ℃, add the D part.At room temperature with sodium hydroxide pH value is adjusted to 6.30-6.70 and adds the F part.
Embodiment 16:O/W day is used the UV protective agent
The INCI-title %w/w (providing)
The A part Tristerin and Polyethylene Glycol-100 stearates 5.00
Octadecanol 1.00
Glyceryl tripalmitate 0.70
Simethicone 2.00
Benzoic acid C12-15 Arrcostab 4.00
Isopropyl palmitate 4.00
Ethylhexyl methoxy cinnamate 3.00
OXYBENZONE 1.00
UVNUL MS-40 1.00
The B part Water In right amount to 100
Polysorbate60 0.50
Glycerol 3.00
The C part Water 10.00
UV-absorbent dispersion as described in example 6 above 8.00
The D part Phenyl phenol (with) methyl parahydroxybenzoate (with) butyl p-hydroxybenzoate (with) ethylparaben (with) propyl p-hydroxybenzoate 0.70
Stearyl polyoxyethylene (10) ether allyl ether/acrylate copolymer 1.50
The E part Water (with) sodium hydroxide In right amount
The F part Spice In right amount
The preparation explanation:
Respectively A part and B partly are heated to 75 ℃, C partly is heated to 60 ℃.After this under agitation with B part impouring A part.With this mixture with UltraTurrax with 11000rpm homogenize 30 seconds and sneak into the C part.After being cooled to 40 ℃, add the D part.At room temperature with sodium hydroxide pH value is adjusted to 6.30-6.70 and adds the F part.
Embodiment 17: sunscreen cream
The INCI-title %w/w (providing)
The A part 16/octadecanol (with) DCP (with) hexadecanol polyoxyethylene (10) ether 4.50
Benzoic acid C12-15 Arrcostab 6.00
Caprylic/capric triglyceride 7.00
Pentaerythritol tetraoctyl stearate 2.00
Ethylhexyl methoxy cinnamate 3.00
Iso-amyl p-methoxycinnamate 2.00
The B part Water In right amount to 100
Glycerol 2.00
Propylene glycol 1.50
Magnesiumaluminumsilicate 1.20
The C part Stearyl polyoxyethylene (10) ether allyl ether/acrylate copolymer 0.50
UV-absorbent dispersion as described in example 5 above 12.00
The D part Phenyl front three silicone oil 1.50
Phenyl phenol (with) methyl parahydroxybenzoate (with) butyl p-hydroxybenzoate (with) ethylparaben (with) propyl p-hydroxybenzoate 0.70
The E part Sodium hydroxide 0.90
The preparation explanation:
Respectively A part and B partly are heated to 75 ℃.Under continuous stirring, B is partly added A partly and after this use UltraTurrax with 11000rpm homogenize 30 seconds.After being cooled to 60 ℃, add the C part.Add the C part at 40 ℃, and with 11000rpm homogenize 15 seconds.At room temperature partly regulate pH value with E.
Embodiment 18:UVA/UVB O/W type day care liquid
The INCI-title %w/w (providing)
The A part Tristerin and Polyethylene Glycol-100 stearates 5.00
Octadecanol 1.00
Glyceryl tripalmitate 0.70
Mineral oil 15.00
The B part Water In right amount to 100
Polysorbate60 0.50
Glycerol 3.00
The C part Water 10.00
UV-absorbent dispersion as described in example 6 above 8.00
The D part Stearyl polyoxyethylene (10) ether allyl ether/acrylate copolymer 1.50
Phenyl phenol (with) methyl parahydroxybenzoate (with) butyl p-hydroxybenzoate (with) ethylparaben (with) propyl p-hydroxybenzoate 0.70
The E part Water (with) sodium hydroxide In right amount
The F part Spice In right amount
The preparation explanation:
Respectively A part and B partly are heated to 75 ℃, C partly is heated to 60 ℃.Under agitation with B part impouring A part., after 1 minute C is partly being joined in the A/B mixture with the 11000rpm homogenize.After being cooled to 40 ℃, sneak into the D part.At room temperature with the E part pH value is adjusted to 6.3-7.0.The final F part that adds.
Embodiment 19:UVA/UVB O/W type day care liquid
The INCI-title %w/w (providing)
The A part Oil base polyoxyethylene (3) ether phosphate 0.60
Stearyl polyoxyethylene (21) ether 2.50
Stearyl polyoxyethylene (2) ether 1.00
Spermol 0.80
The B part Octadecanol 1.50
tribehenin 0.80
2-Methylpentadecane 8.00
The C part Water In right amount to 100
Glycerol 2.00
EDETATE SODIUM 0.10
Cyclopentasiloxane 4.50
Polyethylene Glycol-12 simethicone 2.00
The D part Sodium acrylate copolymer (with) mineral oil (with) polypropylene glycol-1 tridecyl polyoxyethylene (6) ether 1.50
The E part UV-absorbent dispersion as described in example 6 above 10.00
The F part Alpha-tocopherol acetate 0.45
DMDM Hydantoin (with) butyl carbamic acid iodine propynyl ester (with) water (with) butanediol 0.85
The G part Water (with) citric acid In right amount
Spice In right amount
The preparation explanation:
Respectively A part and B partly are heated to 75 ℃.Under continuous stirring with A part impouring B part.Immediately C is partly joined after the emulsifying and also use UltraTurrax with 11000rpm homogenize 30 seconds in the described mixture.After being cooled to 65 ℃, under 50 ℃ with sodium acrylate copolymer (with) mineral oil (with) polypropylene glycol-1 tridecyl polyoxyethylene (6) ether slowly joins in the UV absorbent dispersion.Under about 35-30 ℃, sneak into the F part.With the G part pH value is adjusted to 5.5-6.5.
The daily protective liquid of embodiment 20:UV-A/UV-B O/W type
The INCI-title %w/w (providing)
The A part GLYCERYL DILAURATE 2.00
Ethylhexyl palmitate 6.00
Spermol 1.00
Tristerin 2.00
Lauryl polyoxyethylene (23) ether 1.00
Isopropyl palmitate 2.00
Tribehenin 0.80
Cera Flava 1.50
Lanolin oil 1.00
The B part Water In right amount to 100
Propylene glycol 4.00
Water (with) titanium dioxide (with) aluminium oxide (with) Polymeric sodium metaphosphate. (with) phenyl phenol (with) methyl P-hydroxybenzoic acid sodium 4.00
The C part Stearyl polyoxyethylene (10) ether allyl ether/acrylate copolymer 1.00
Phenyl phenol (with) methyl parahydroxybenzoate (with) ethylparaben (with) butyl p-hydroxybenzoate (with) propyl p-hydroxybenzoate (with) p-Hydroxybenzoic acid isobutyl ester 1.00
The D part UV-absorbent dispersion as described in example 6 above 8.00
The E part Water (with) sodium hydroxide In right amount
The preparation explanation:
Respectively A part and B partly are heated to 80 ℃.When stirring, also use UltraTurrax with 11000rpm homogenize 30 seconds A part impouring B part.After being cooled to 60 ℃, sneak into the C part.Under 40 ℃ and continuous stirring, slowly add the D part.With E part with pH regulator to 6.50-7.00.
Embodiment 21: sprayable suntan lotion
The INCI-title %w/w (providing)
The A part The cetyl potassium phosphate 0.20
2-Methylpentadecane 7.00
VP/ eicosylene copolymer 1.50
Tartaric acid two-C12-13 Arrcostab 6.00
Uvinul T 150 2.50
Benzoic acid C12-15 Arrcostab 4.50
Water In right amount to 100
Sorbitol polyoxyethylene (30) ether 2.00
Sorbitan stearate (with) sucrose cocos nucifera oil acid esters 4.00
The B part Titanium dioxide (with) aluminium oxide (with) silicon dioxide (with) sodium polyacrylate 2.50
Water 30.00
UV-absorbent dispersion as described in example 6 above 12.00
Phenyl phenol (with) methyl parahydroxybenzoate (with) ethylparaben (with) butyl p-hydroxybenzoate (with) propyl p-hydroxybenzoate (with) p-Hydroxybenzoic acid isobutyl ester 0.70
Water (with) sodium hydroxide In right amount
The preparation explanation:
Respectively A part and B partly are heated to 80 ℃, C partly is heated to 50 ℃.Also use UltraTurrax with 11000rpm homogenize 1 minute B part impouring A part.After being cooled to 50 ℃, under continuous stirring, add the C part.Under 40 ℃, sneak into the D part also again with 11000rpm homogenize 10 seconds.Partly regulate pH with E.
Embodiment 22:O/W day is used the UV protective liquid
The INCI-title %w/w (providing)
The A part Tristerin and Polyethylene Glycol-100 stearates 5.00
Octadecanol 1.00
Glyceryl tripalmitate 0.70
Simethicone 2.00
Caprylic/capric triglyceride 5.00
Isopropyl palmitate 5.00
Ethylhexyl methoxy cinnamate 3.00
The B part Water In right amount to 100
Polysorbate60 0.50
Glycerol 3.00
The C part Water 10.00
UV-absorbent dispersion as described in example 6 above 8.00
ZnO (Nanox zinc oxide) 3.00
The D part Phenyl phenol (with) methyl parahydroxybenzoate (with) ethylparaben (with) butyl p-hydroxybenzoate (with) propyl p-hydroxybenzoate (with) p-Hydroxybenzoic acid isobutyl ester 0.70
Stearyl polyoxyethylene (10) ether allyl ether/acrylate copolymer 1.50
The E part Water (with) sodium hydroxide In right amount
The F part Spice In right amount
The preparation explanation:
Respectively A part and B partly are heated to 75 ℃, C partly is heated to 60 ℃.After this under agitation with B part impouring A part.With this mixture with UltraTurrax with 11000rpm homogenize 30 seconds and sneak into the C part.After being cooled to 40 ℃, add the D part.At room temperature with sodium hydroxide pH value is adjusted to 6.30-6.70 and adds the F part.
Embodiment 23: the water proofing property sunscreen
The INCI-title %w/w (providing)
The A part Polyglycereol (10) five stearates (with) behenyl alcohol (with) stearyl dilactic acid sodium 2.50
VP/ eicosylene copolymer 1.50
Octadecanol 1.50
Squalane 4.00
Benzoic acid C12-15 Arrcostab 5.50
Octocrylene 1.50
4 methyl benzylidene camphor 3.00
Ethylhexyl methoxy cinnamate 2.00
Neo Heliopan OS (Neoheliopan OS) 2.00
The B part Water In right amount to 100
Glycerol 1.80
Stearyl polyoxyethylene (10) ether allyl ether/acrylate copolymer 0.80
The C part UV-absorbent dispersion as described in example 6 above 9.00
The D part VP/ hexadecylene copolymer 2.70
The ring dimethicone 1.50
Phenyl phenol (with) methyl parahydroxybenzoate (with) ethylparaben (with) butyl p-hydroxybenzoate (with) propyl p-hydroxybenzoate (with) p-Hydroxybenzoic acid isobutyl ester 0.70
The E part Water (with) alpha-tocopherol acetate (with) caprylic/capric triglyceride (with) polysorbate80 (with) lecithin 3.50
The F part Spice In right amount
Water (with) sodium hydroxide In right amount
The preparation explanation:
Respectively A part and B partly are heated to 80 ℃.Under continuous stirring with A part impouring B part.After this use UltraTurrax with 11000rpm with this mixture homogenize 1 minute.After being cooled to 60 ℃, sneak into the C part.Also this mixture is carried out the short time homogenize again 40 ℃ of lower D parts that add.
Also at room temperature add spice 35 ℃ of lower E parts that add.Finally regulate pH with sodium hydroxide.
Embodiment 24:UVA/UVB O/W type suntan lotion
The INCI-title %w/w (providing)
The A part The cetyl potassium phosphate 2.00
Tricotanyl PVP 1.00
Caprylic/capric triglyceride 5.00
Benzoic acid C12-15 Arrcostab 5.00
Different n-nonanoic acid 16/octadecyl ester 5.00
Glyceryl stearate 3.00
Spermol 1.00
Simethicone 0.10
Ethylhexyl methoxy cinnamate 5.00
The B part Water In right amount to 100
Glycerol 3.00
2,2 '-two (Isosorbide-5-Nitrae-phenylene)-1H-benzimidazoles-4,6-disulfonic acid one sodium salt (Neoheliopan AP) 2.00
The C part Stearyl polyoxyethylene (10) ether allyl ether/acrylate copolymer 0.50
The D part UV-absorbent dispersion as described in example 6 above 8.00
The E part Phenyl phenol (with) methyl parahydroxybenzoate (with) ethylparaben (with) butyl p-hydroxybenzoate (with) propyl p-hydroxybenzoate (with) p-Hydroxybenzoic acid isobutyl ester 1.00
The F part Water (with) sodium hydroxide In right amount to pH 7.00
The G part Spice In right amount
The preparation explanation:
Respectively A part and B partly are heated to 80 ℃.Under middling speed stirs with B part impouring A part.After this use UltraTurrax with 11000rpm with this mixture homogenize 1 minute.After being cooled to 70 ℃, under agitation add the C part.After being cooled to 50 ℃, sneak into the D part very slowly.40 ℃ of lower E parts that add.At room temperature with F part with pH regulator to 7.00 and add the G part.
Embodiment 25:UVA/UVB O/W type suntan lotion
The INCI-title %w/w (providing)
The A part The cetyl potassium phosphate 2.00
Tricotanyl PVP 1.00
Caprylic/capric triglyceride 5.00
Benzoic acid C12-15 Arrcostab 5.00
Different n-nonanoic acid 16/stearyl 5.00
Glyceryl stearate 3.00
Spermol 1.00
Simethicone 0.10
Ethylhexyl methoxy cinnamate 4.00
Uvasorb HEB (UVASORB HEB) 1.00
The B part Water In right amount to 100
Glycerol 3.00
The C part Stearyl polyoxyethylene (10) ether allyl ether/acrylate copolymer 0.50
The D part UV-absorbent dispersion as described in example 6 above 20.00
The E part Phenyl phenol (with) methyl parahydroxybenzoate (with) ethylparaben (with) butyl p-hydroxybenzoate (with) propyl p-hydroxybenzoate (with) p-Hydroxybenzoic acid isobutyl ester 1.00
The F part Water (with) sodium hydroxide In right amount to pH 7.00
The G part Spice In right amount
The preparation explanation:
Respectively A part and B partly are heated to 80 ℃.Under middling speed stirs with B part impouring A part.With UltraTurrax with 11000rpm with this mixture homogenize 1 minute.After being cooled to 70 ℃, under agitation add the C part.After further being cooled to 50 ℃, sneak into the D part very slowly.40 ℃ of lower E parts that add.At room temperature with F part with pH regulator to 7.00 and add the G part.
Embodiment 26: suntan lotion
The INCI-title %w/w (providing)
The A part 16/octadecanol (with) DCP (with) hexadecanol polyoxyethylene (15) ether phosphate 4.00
Benzoic acid C12-15 Arrcostab 2.00
Dicaprylyl ether 3.00
Oleic acid ethoxydiglycol ester 2.00
Stearic acid 1.00
Ethylhexyl methoxy cinnamate 2.00
Sodium acrylate copolymer (with) Glycine soja (with) polypropylene glycol-1 tridecyl polyoxyethylene (6) ether 0.30
Squalane 3.50
VP/ eicosylene copolymer 2.00
Toluenyl malonic ester polysiloxanes (Parsol SLX) 2.00
The B part Water In right amount to 100
UV-absorbent dispersion as described in example 6 above 5.00
The C part N-(methylol)-N-(the two methylols-2 of 1,3-, 5-dioxy-4-imidazolidinyl-N '-(methylol) urea (with) butyl carbamic acid iodine propynyl ester 0.15
Propylene glycol 2.50
Water 10.00
The D part Cyclopentasiloxane (with) simethicone 2.00
Ethoxydiglycol 5.00
Cyclopentasiloxane (with) simethicone/vinyl-dimethyl silicone oil cross linked polymer 2.00
The E part Water (with) sodium hydroxide In right amount
The F part Spice In right amount
The preparation explanation:
Respectively A part and B partly are heated to 75 ℃.Increasing progressively under the mixing speed B part impouring A part.During in temperature＜65 ℃, add separately the component of D part.After being cooled to 55 ℃, under stirring, middling speed adds the C part.During in temperature＜35 ℃, detect pH and with sodium hydroxide regulate and with UltraTurrax with 11000rpm homogenize 30 seconds.At room temperature add the F part.
Embodiment 27:W/O suntan lotion
The INCI-title %w/w (providing)
The A part Polyethylene Glycol-7 castor oil hydrogenated 3.00
Two isostearic acid polyglycereol (3) esters 4.00
Microwax 1.00
Magnesium stearate 1.50
Propyl p-hydroxybenzoate 0.10
Mineral oil 15.00
Octyl dodecanol 8.30
Uvinul T 150 1.00
Ethylhexyl methoxy cinnamate 2.00
Uvinul A+ (Uvinul A+) 1.50
The B part Water In right amount to 100
Water (with) citric acid 0.05
Methyl parahydroxybenzoate 0.15
Magnesium stearate 0.50
The C part UV-absorbent dispersion as described in example 6 above 9.00
Spice In right amount
The preparation explanation:
When stirring, A partly is heated to 80 ℃.B is partly added the A part and uses UltraTurrax with 11000rpm homogenize 1 minute.After being cooled to 30 ℃, sneak into the C part.
Embodiment 28:W/O type skin protection suntan lotion
The INCI-title %w/w (providing)
The A part Dimerization hydroxy stearic acid polyglycereol (2) ester 3.00
Olein 3.00
Different n-nonanoic acid 16/stearyl 7.00
Lauric acid hexyl ester 6.00
Dicaprylyl ether 6.00
Propyl p-hydroxybenzoate 0.10
Hexyldecanol 3.00
Magnesium stearate 1.00
Cera Flava 1.00
Ethylhexyl methoxy cinnamate 4.00
The B part Water In right amount to 100
Methyl parahydroxybenzoate 0.15
Magnesium sulfate 1.00
The C part UV-absorbent dispersion as described in example 6 above 6.00
The preparation explanation:
When slowly stirring, separately A partly is heated to 80 ℃.B partly added A part and with 11000rpm homogenize 1 minute.After being cooled to 30 ℃, under continuous stirring, add the C part.
Embodiment 29: sunscreen
The INCI-title %w/w (providing)
The A part Hexyldecanol 2.70
Polyoxyethylene (2) octadecane alcohol ether 2.20
Dimerization hydroxy stearic acid Polyethylene Glycol (30) ester 1.10
Dispersion UV-absorbent dispersion as described in example 6 above; Regulate pH=7 with citric acid 6
The B part The thylhexoic acid cetyl 4.00
2-Methylpentadecane 4.00
Ethylhexyl methoxy cinnamate 0.00
Bemotrizinol (Tinosorb S) 0.00
Phenyl phenol (with) methyl parahydroxybenzoate (with) ethylparaben (with) butyl p-hydroxybenzoate (with) propyl p-hydroxybenzoate (with) p-Hydroxybenzoic acid isobutyl ester 0.60
The C part Water In right amount to 100
Glycerol 3.00
The D part Sodium acrylate copolymer (with) mineral oil (with) polypropylene glycol-1 tridecyl polyoxyethylene (6) ether 2.00
The E part Cyclopentasiloxane 2.00
This sunscreen also can be used as wrinkle resistant sensation regulator.
The preparation explanation
Mix the A part and be heated to 60 ℃-65 ℃ and slowly adding split under rapid stirring.
Under stirring, 60 ℃ and middling speed add the B part.
60 ℃-75 ℃ and stir under B is partly added the A part.
Under agitation add C part to homogenize (can with ultra turrax emulsifying when the rapid stirring).
Under stirring, middling speed adds D part (60 ℃).
Finally under agitation add E part (60 ℃) and cooling under middling speed stirs.
Embodiment 30: the sunscreen that does not contain Polyethylene Glycol
The INCI-title %w/w (providing)
The A part Hexyldecanol 2.30
Polyglycereol (3) methyl glucoside distearate 1.40
Polyglycereol gathers hydroxy stearic acid ester 1.40
Dispersion UV-absorbent as described in example 6 above; Regulate pH=7 with citric acid 5.00
The thylhexoic acid cetyl 3.00
2-Methylpentadecane 3.00
Ethylhexyl methoxy cinnamate 3.00
Bemotrizinol (Tinosorb S) 2.00
Phenyl phenol (with) methyl parahydroxybenzoate (with) ethylparaben (with) butyl p-hydroxybenzoate (with) propyl p-hydroxybenzoate (with) p-Hydroxybenzoic acid isobutyl ester 0.60
The B part Water In right amount to 100
Glycerol 3.00
Sodium acrylate copolymer (with) mineral oil (with) polypropylene glycol-1 tridecyl polyoxyethylene (6) ether 1.50
The C part Cyclopentasiloxane 1.50

Claims (1)

1. make-up preparation comprises that the UV of 0.05-40 % by weight filters compositions (A1), and said composition (A1) comprising:
(a 3) general formula (6)
Figure FSB00000903054100011
Or
(9)
Figure FSB00000903054100012
Chemical compound; With
Following chemical compound any:
(a 4) chemical compound of following general formula:
(b 4) chemical compound of following general formula:
Figure FSB00000903054100021
(c 4) chemical compound of following general formula:
Figure FSB00000903054100022
(d 4) chemical compound of following general formula:
Figure FSB00000903054100023
(f 2) dibenzoylmethane derivative of at least a following general formula:
Figure FSB00000903054100024
(g 2) Neo Heliopan AP,
(h 4) 1,3,5-triazines-2,4,6-triamine, N, N '-two [4-[5-(1,1-dimethyl propyl)-2-benzo
Figure FSB00000903054100025
The azoles base] phenyl]-N " (2-ethylhexyl),
(i 2) 2-(2H-benzotriazole-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethyl silyl) the oxygen base] the disiloxane base] propyl group]-,
(k 2) siloxanes and silicone, two-Me, 1-[[4-[3-ethyoxyl-2-(carbethoxyl group)-3-oxo-1-acrylic] phenoxy group] methyl] vinyl Me, 3-[4-[3-ethyoxyl-2-(carbethoxyl group)-3-oxo-1-acrylic] phenoxy group]-1-acrylic Me, wherein: Me is hydrogen
(l 2) (+/-)-1,7,7-trimethyl-3-[(4-aminomethyl phenyl) methylene] dicyclo [2.2.1] heptan-2-ketone,
(m 2) α-(2-oxo Borneolum Syntheticum-3-subunit) toluene-4-sulfonic acid and salt thereof,
(n 2) N, N, N-trimethyl-4-[(4,7,7-trimethyl-3-oxo dicyclo [2,2,1] heptan-2-base subunit) methyl]-anilinomethyl sulfate,
(o 2) 2-cyano group, 3,3-diphenylacrylate 2-ethyl hexyl ester,
(p 2) Uvinul MC 80,
(q 2) benzoic acid, 4,4 ', 4 " (1,3,5-triazines-2,4,6-three basic three imino groups) three-, three (2-ethylhexyl) ester,
(r 2) 2-phenyl-1H-benzimidazole-5-sulfonic acid, or
(s 2) benzoic acid, 4,4 '-[[the 6-[[4-[[(1-dimethyl ethyl) amino] carbonyl] phenyl] amino] 1,3,5-triazines-2,4-two bases] diimino] two-, two (2-ethylhexyl) ester;
The chemical compound of wherein said formula (6) or formula (9) is present in the described compositions with micronized state.
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