Photostabilizing polymer

Abstract

The present invention is directed to a series of polymers containing end groups that are absorb ultraviolet (UV) light. The invention is also to the use of such compounds in the cosmetic, toiletry and personal care areas. These polymers can be utilized to produce films and provide solvent properties for the formulation of for ultra-violet absorbing formulations (like sunscreens) and provide outstanding dispensability and anti-agglomeration properties for inorganic sunscreens containing ZnO and TiO.sub.2. The ability to provide uniform non agglomerating sun care formulations results in formulations with increase SPF values and improved water-resistant properties in cosmetic formulation. The compounds of the present invention by themselves do not have ultra violet absorption at the particular wavelength that contributes to sun protection and consequently are not themselves sunscreens.

Claims

1. A photostabilizing polymer prepared by the esterification reaction of: 1. a photo-absorbing group having the following structure: ##STR00014## wherein; x is an integer ranging from 1 to 10; 2. a diacid independently selected from the group consisting of: a. a fatty acid having to the following structure:
HOOCR.sup.3COOH wherein; R.sup.3 is alkyl containing 2 to 12 carbon atoms; b. dimer Acid; c. hydrogenated dimer acid; d. mixtures thereof; and 3. a diol having the following structure:
HOR.sup.4OH wherein; R.sup.4 is alkyl ranging from 3 to 12 carbons; and 4. a monofunctional alcohol independently selected from the group consisting of: a. a branched alkyl having the structure: ##STR00015## wherein; a is an integer ranging from 3-15; b is an integer ranging from 5-17; and mixtures thereof; b. a fatty alcohol having the structure:
R.sup.2OH wherein; R.sup.2 is alkyl having 8 to 26 carbon atoms, and mixtures thereof.

2. The photostabilizing polymer of claim 1 wherein the photo-absorbing group has the following structure: ##STR00016## wherein x is 6.

3. The photostabilizing polymer of claim 1 wherein the photo-absorbing group has the following structure: ##STR00017## wherein x is 7.

4. The photostabilizing polymer of claim 1 wherein the diol is propanediol.

5. The photostabilizing polymer of claim 1 wherein the diacid is hydrogenated dimer acid.

6. The photostabilizing polymer of claim 1 wherein the diacid is azelic acid.

7. The photostabilizing polymer of claim 1 wherein the photo-absorbing group has the following structure: ##STR00018## wherein x is 6 and the diacid is dimer acid.

8. The photostabilizing polymer of claim 1 wherein the photo-absorbing group has the following structure: ##STR00019## wherein x is 7 and the diacid is dimer acid.

9. The photostabilizing polymer of claim 2 wherein the diol is propanediol.

10. The photostabilizing polymer of claim 2 wherein diacid is hydrogenated dimer acid.

11. The photostabilizing polymer of claim 2 wherein the diacid is azelic acid.

12. A process of protecting skin, which comprises contacting the skin with a photostabilizing concentration of a photostabilizing polymer prepared by the esterification reaction of: 1. a photo-absorbing group having the following structure: ##STR00020## wherein; x is an integer ranging from 1 to 10; 2. a diacid independently selected from the groups consisting of: a. A fatty acid having to the following structure:
HOOCR.sup.3COOH wherein; R.sup.3 is alkyl containing 2 to 12 carbon atoms; b. dimer Acid; c. hydrogenated dimer acid; and mixtures thereof; 3. a diol having the following structure:
HOR.sup.4OH wherein; R.sup.4 is alkyl moiety having from 3 to 12 carbons; and 4. a monofunctional alcohol independently selected from the group consisting of: a. a branched alkyl having the structure: ##STR00021## wherein; a is an integer ranging from 3-15; b is an integer ranging from 5-17; and mixtures thereof; b. a fatty alcohol having the structure:
R.sup.2OH wherein; R.sup.2 is alkyl having 8 to 26 carbon atoms, and mixtures thereof.

13. The process of claim 12 wherein the photostabilizing concentration is between 0.1 and 10.0% by weight.

14. The process of claim 12 wherein the photostabilizing concentration is between 0.5 and 5.0% by weight.

15. The process of claim 12 wherein the photo-absorbing group has the following structure: ##STR00022## wherein x is 6.

16. The process of claim 12 wherein the photo-absorbing group has the following structure: ##STR00023## wherein x is 7.

17. The process of claim 12 wherein the diol is propanediol.

18. The process of claim 12 wherein the diacid is hydrogenated dimer acid.

19. The process of claim 12 wherein the diacid is azelic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) One aspect of the present invention is directed towards a photostabilizing polymer prepared by the esterification reaction of: 1. An photo-absorbing group having the following structure:

(2) ##STR00001## wherein; x is an integer ranging from 1 to 10. 2. A diacid independently selected from the groups consisting of: a. A fatty acid having to the following structure:
HOOCR.sup.3COOH wherein; R.sup.3 is alkyl containing 2 to 12 carbon atoms; b. Dimer Acid; c. Hydrogenated Dimer Acid; and mixtures thereof; 3. A diol having the following structure:
HOR.sup.4OH wherein; R.sup.4 is an integer ranging from 3 to 12 carbons; 4. A monofunctional alcohol independently selected from the groups consisting of: a. a branched alkyl having the structure:

(3) ##STR00002## wherein; a is an integer ranging from 3-15; b is an integer ranging from 5-17; and mixtures thereof; b. A fatty alcohol having the structure:
R.sup.2OH wherein; R.sup.2 is alkyl having 8 to 26 carbon atoms, and mixtures thereof.

(4) Another aspect of the present invention is directed towards a process of protecting skin, which comprises contacting the skin with a photostabilizing concentration of a photostabilizing polymer prepared by the esterification reaction of: 1. An photo-absorbing group having the following structure:

(5) ##STR00003## wherein; x is an integer ranging from 1 to 10. 2. A diacid independently selected from the groups consisting of: a. A fatty acid having to the following structure:
HOOCR.sup.3COOH wherein; R.sup.3 is alkyl containing 2 to 12 carbon atoms; b. Dimer Acid; c. Hydrogenated Dimer Acid; and mixtures thereof; 3. A diol having the following structure:
HOR.sup.4OH wherein; R.sup.4 is an integer ranging from 3 to 12 carbons; 4. A monofunctional alcohol independently selected from the groups consisting of: a. a branched alkyl having the structure:

(6) ##STR00004## wherein; a is an integer ranging from 3-15; b is an integer ranging from 5-17; and mixtures thereof; b. A fatty alcohol having the structure:
R.sup.2OH wherein; R.sup.2 is alkyl having 8 to 26 carbon atoms, and mixtures thereof.

PREFERRED EMBODIMENTS

(7) In a preferred embodiment the photo-absorbing group has the following structure:

(8) ##STR00005## wherein x is 6.

(9) In a preferred embodiment the photo-absorbing group has the following structure:

(10) ##STR00006## wherein x is 7.

(11) In a preferred embodiment the diol is propanediol.

(12) In a preferred embodiment the diacid is hydrogenated dimer acid.

(13) In a preferred embodiment the diacid is azelic acid.

(14) In a preferred embodiment the photo-absorbing group has the following structure:

(15) ##STR00007## wherein x is 6 and the diacid is dimer acid.

(16) In a preferred embodiment the photo-absorbing group has the following structure:

(17) ##STR00008## wherein x is 7 and the diacid is dimer acid.

(18) In a preferred embodiment the diol is propanediol.

(19) In a preferred embodiment the diacid is hydrogenated dimer acid.

(20) In a preferred embodiment the diacid is azelic acid.

(21) In a preferred embodiment the photostabilizing concentration is between 0.1 and 10.0% by weight.

(22) In another preferred embodiment the photostabilizing concentration is between 0.5 and 5.0% by weight.

(23) In another preferred embodiment the photostabilizing concentration is between 1.0 and 3.0% by weight.

EXAMPLES

(24) Raw Materials

(25) Photo-Absorbing Group

(26) Photo-absorbing agents are commercially available from a variety of sources including Mayzo, Inc. of Suwannee, Ga. It has the following structure:

(27) ##STR00009##

(28) The CAS number is 104810-48-2.

(29) TABLE-US-00001 Example x MW 1 2 383 2 6 603 3 7 647 4 10 779

(30) Dicarboxylic Acids

(31) Dicarboxylic acids are useful raw materials in the synthesis of the compounds of the present invention and are commercially available from a variety of sources including Cognis. They have the following structure:

(32) ##STR00010##

(33) TABLE-US-00002 Saturated Dicarboxylic acids Example Common Name c Molecular Weight 5 Malonic 1 104 6 Succinic 2 118 7 Glutaric 3 132 8 Adipic 4 146 9 Pimelic 5 160 10 Subric 6 174 11 Azelaic 7 188 12 Sebacic 8 202 13 Undecanedioic 9 216 14 Dodecanedioic 10 230

Example 15 Dimer Acid

(34) Dimer acid is an item of commerce available commercially from Cognis Corporation. It conforms to the following structure:

(35) ##STR00011##

Example 16 Hydrogenated Dimer Acid

(36) Hydrogenated dimer acid is an item of commerce available commercially from Henkel Corporation. It conforms to the following structure:

(37) ##STR00012##

(38) Fatty Alcohols Names

(39) Fatty alcohols are useful as raw materials in the synthesis of the compounds of the present invention are commercially available from a variety of sources including BASF. They conform to the following structure;
ROH

(40) TABLE-US-00003 Example Formula Name Molecular Weight 17 .sub.C.sub.8H.sub.18O 1-Capryl 130.0 18 .sub.C.sub.9H.sub.20O 1-Nonanol 144.3 19 C.sub.10H.sub.22O 1-Decanol 158.3 20 C.sub.11H.sub.24O Undecanol 172.3 21 C.sub.12H.sub.26O Dodecanol 186.3 22 C.sub.18H.sub.38O Stearyl 270.5 23 C.sub.22H.sub.46O Behenyl 326.6

(41) Guerbet Alcohols

(42) Guerbet alcohols useful as raw materials in the preparation of compounds of the present invention are commercially available from a variety of sources including Sasol North America Incorporated of Houston Tex.

(43) The structures are well known to those skilled in the art.

(44) ##STR00013##

(45) TABLE-US-00004 Example A b Molecular Weight 24 15 17 466.0 25 13 11 410.0 26 9 7 298.0

(46) Diols

(47) Diols are useful as raw materials in the synthesis of the compounds of the present invention are commercially available from a variety of sources including BASF. They conform to the following structure;
HO(CH.sub.2).sub.cOH

(48) TABLE-US-00005 Example Formula Name Molecular Weight 27 HO(CH.sub.2).sub.3OH.sub. 1,3-Propanediol 74.0 28 HO(CH.sub.2).sub.10OH 1,10-Decandiol 174.3 29 HO(CH.sub.2).sub.12OH 1,12-Dodecanediol 202.3

Preparation of the Photo-Absorbing Polymer

(49) Photo-Absorbing Terminated Polymer

(50) General Procedure

(51) To a flask equipped with thermometer, heat and distillation ability is added the specified number of grams of chain terminator (examples 1-4), diacid (examples 6-16) and the specified number of grams of the specified a diol (examples 27-29). The mixture is heated to 160-200 C. under agitation. The temperature is held in this range for 8-10 hours as water distills off. The resulting product is cooled and used without additional purification.

(52) TABLE-US-00006 Photo-absorbing Diacid Diol Example Example Grams Example Grams Example Grams DP 30 1 82.25 6 46.08 27 21.67 3 31 1 47.35 9 53.95 28 48.70 5 32 1 25.62 11 62.87 29 61.51 10 33 1 63.69 14 69.54 27 16.78 5 34 1 23.83 15 101.66 28 24.51 4 35 1 13.34 16 104.64 29 32.02 10 36 2 98.48 6 35.04 27 16.48 3 37 2 63.11 9 45.67 28 41.22 4 38 2 36.73 11 57.26 29 56.01 10 39 2 80.61 14 55.90 27 13.49 3 40 2 34.39 15 93.16 28 22.46 5 41 2 19.98 16 99.56 29 30.47 10 42 3 100.84 6 33.44 27 15.73 3 43 3 65.70 9 44.31 28 39.99 5 44 3 38.72 11 56.25 29 55.03 10 45 3 83.23 14 53.79 27 12.98 3 46 3 36.29 15 91.62 28 22.09 5 47 3 21.23 16 98.60 29 30.17 10 48 4 106.77 6 29.40 27 13.83 3 49 4 72.61 9 40.67 28 36.71 5 50 4 44.29 11 53.44 29 52.28 10 51 4 90.02 14 48.32 27 11.66 3 52 4 41.64 15 87.31 28 21.05 5 53 4 24.84 16 95.83 29 29.33 10 54 2 50.34 16 91.22 27 8.44 3 55 2 37.52 16 102.00 27 10.48 5 56 2 22.93 16 114.26 27 12.81 10

(53) Mono-Terminated Photo-Absorbing Polymers

(54) General Procedure

(55) To a flask equipped with thermometer, heat and distillation ability is added the specified number of grams of chain terminator (examples 1-4), diacid (examples 6-16), diol (examples 27-29), and the specified number of grams of the monofunctional alcohol (examples 17-26). The mixture is heated to 160-200 C. under agitation. The temperature is held in this range for 8-10 hours as water distills off. The resulting product is cooled and used without additional purification.

(56) TABLE-US-00007 Photo-absorbing Diacid Diol Monoalcohol Example Example Grains Example Grains Example Grains Example Grains DP 57 1 50.22 6 56.27 27 17.05 17 26.46 3 58 1 24.83 9 56.57 28 17.53 22 51.06 5 59 1 12.97 11 63.68 29 11.06 23 62.29 10 60 1 30.44 14 66.48 27 37.04 24 16.04 3 61 1 11.85 15 101.09 28 12.69 25 24.37 5 62 1 6.73 16 105.68 29 5.24 26 32.34 10 63 2 66.32 6 47.19 27 14.30 17 22.20 3 64 2 35.70 9 51.66 28 16.01 22 46.63 5 65 2 19.46 11 60.66 29 10.54 23 59.34 10 66 2 42.92 14 59.54 27 33.17 24 14.37 3 67 2 17.85 15 96.70 28 12.13 25 23.31 5 68 2 10.34 16 103.03 29 5.11 26 31.53 10 69 3 68.93 6 45.72 27 13.85 17 21.50 3 70 3 37.65 9 50.78 28 15.74 22 45.83 5 71 3 20.68 11 60.09 29 10.44 23 58.79 10 72 3 45.11 14 58.32 27 32.49 24 14.07 3 73 3 18.98 15 95.87 28 12.03 25 23.11 5 74 3 11.04 16 102.51 29 5.08 26 31.37 10 75 4 78.88 6 41.80 27 12.66 17 19.66 3 76 4 43.12 9 48.31 28 14.97 22 43.60 5 77 4 24.22 11 58.45 29 10.15 23 57.18 10 78 4 51.18 14 54.95 27 30.62 24 13.26 3 79 4 22.28 15 93.46 28 11.73 25 22.53 5 80 4 13.09 16 101.00 29 5.01 26 30.91 10 81 2 27.51 16 99.69 27 13.59 26 9.21 3 82 2 20.03 16 108.90 27 9.90 26 11.17 5 83 2 11.93 16 118.87 27 5.89 26 13.31 10