Polyurethane gelling agent

Abstract

The invention relates to new oil gelling polyurethanes useful for preparing clear gels in organic media (oils, solvents) and to a process for their preparation. The invention also relates to the gels formed from these gelling polyurethanes and to compositions containing them, in particular cosmetic compositions.

Claims

1. A polyurethane compound suitable for gelling oils, of formula (I) ##STR00016## A.sub.1 is a linear alkyl radical, comprising 2 to 12 carbon atoms, said radical optionally comprising one or more unsaturations; A.sub.2 is ##STR00017## l and m are, independently of one another, an integer from 1 to 10, the sum of l+m being from 2 to 20; n is an integer from 2 to 12; D is a linear or branched alkyl radical, comprising 6 to 14 carbon atoms, said radical optionally comprising one or more unsaturations; X is a linear or branched C.sub.2-C.sub.10 alkyl radical, having or not having unsaturations; and Y is an oxygen atom.

2. The polyurethane compound of formula (I) according to claim 1, wherein A.sub.1 represents a linear or branched alkyl radical comprising 2 to 6 carbon atoms; A.sub.2 is ##STR00018## l and m represent, independently of one another, an integer from 1 to 10, the sum of l+m being from 5 to 12; n is an integer from 2 to 8; D represents a linear or branched alkyl radical, comprising 6 to 14 carbon atoms, said radical optionally comprising one or more unsaturations; X is a linear or branched alkyl radical, having or not having unsaturations, comprising 2 to 10 carbon atoms; and Y represents an oxygen atom.

3. The polyurethane compound of formula (I) according to claim 1 wherein A.sub.1 represents a linear alkyl radical comprising 3 carbon atoms.

4. The polyurethane compound of formula (I) according to claim 1 having a content of natural origin greater than 80% according to standard NF-16128-2.

5. A process for preparing a polyurethane compound of formula (I) ##STR00019## A.sub.1 is a linear alkyl radical, comprising 2 to 12 carbon atoms, said radical optionally comprising one or more unsaturations; A.sub.2 is ##STR00020## l and m are, independently of one another, an integer from 1 to 20, the sum of l+m being from 2 to 20; n is an integer from 2 to 8; D is a linear or branched alkyl radical, comprising from 6 to 14 carbon atoms, said radical optionally comprising one or more unsaturations; X is a linear or branched C.sub.2-C.sub.10 alkyl radical, having or not having unsaturations; Y is an oxygen an atom, the process comprising the following steps: 1) functionalizing a di-OH estolide of formula (3) by a diisocyanate derivative of formula (4) in order to obtain a diisocyanate estolide of formula (5) ##STR00021## A.sub.1, A.sub.2, l and m are as defined above; X is a linear or branched C.sub.2-C.sub.10 alkyl radical, having or not having unsaturations; 2) performing a chain extension in order to obtain a polyurethane of estolide of formula (7) by adding a diol of formula (6), optionally solubilized in an oil ##STR00022## wherein A.sub.1, A.sub.2, E, X, Y, l and m are as defined above; D is a linear or branched alkyl radical, comprising 6 to 14 carbon atoms, said radical optionally comprising one or more unsaturations; n is an integer from 2 to 12; and 3) optionally, performing chain termination by adding a nucleophilic molecule in excess capable of reacting with the residual isocyanate functions in order to give the gelling polyurethane of formula (I).

6. The process according to claim 5, wherein at least one of the following conditions is fulfilled: the sum of l+m has an average value of 5 to 12; n is an integer from 2 to 8.

7. The process of claim 5 wherein A.sub.1 represents a linear alkyl radical comprising 3 carbon atoms.

8. The process according to claim 5 wherein the step of functionalization of the di-OH estolide by a diisocyanate derivative is carried out by rapid addition of a quantity of diisocyanate (4) comprised between 1.4 and 2.0 equivalents with respect to 1 equivalent (eq) of di-OH estolide (3), calculated according to its OH index, at a temperature comprised between 60° C. and 150° C.

9. The process according to claim 5 wherein the step of functionalization of the di-OH estolide by a diisocyanate derivative is carried out by adding 1 equivalent (eq) of di-OH estolide (3) over a mixture of oil and diisocyanate (4) present in a quantity comprised between 1.4 and 2.0 equivalents, at a temperature greater than or equal to 110° C.

10. The process according to claim 5 wherein chain termination is carried out by the addition in excess of a nucleophilic molecule of the alcohol, thiol, amine or carboxylate type, mono- or difunctional, capable of reacting with the residual isocyanate functions in excess in the reaction medium at a temperature comprised between 110 and 150° C.

11. An oil gelling agent obtained according to the process of claim 5.

12. A process for gelling at least one oil selected from organic oils, the vegetable oils, and mixtures of apolar oils and more-polar oils, wherein the gelling polyurethane of formula (I) according to claim 1 is added to said at least one oil or oils, or to a composition containing the oils.

13. A gel containing or formed from the gelling polyurethane of formula (I) according to claim 1.

14. The gel according to claim 13, comprising at least one pharmaceutically or cosmetically acceptable oil.

15. The gel according to claim 13, wherein the content by weight of gelling polyurethane of formula (I) is comprised between 0.7% and 10.

16. A pharmaceutical composition comprising the gel according to claim 13.

17. A cosmetic composition comprising the gel according to claim 13.

Description

EXAMPLE 1

Preparation of a Polyurethane of Estolide of PDO (PRIC212) and 1,10-Decanediol in which the Steps 1) and 2) are Carried Out at Two Different Temperatures (GSC16179)

(1) The gelling polyurethane was synthesized in three steps by polyaddition of the estolide of PDO diisocyanate with 1,10-decanediol in the presence of a cosmetic oil. It has a content of natural origin of 92.8% according to the standard NF ISO 16128-2.

(2) 1) Synthesis of the Estolide of 1,3-Propanediol Diisocyanate (5)

(3) ##STR00012##

(4) with:

(5) ##STR00013## X=C.sub.6H.sub.12 A.sub.1=C.sub.3H.sub.6 A.sub.2 represents a group of formula

(6) ##STR00014## l+m=7 (average value)

(7) In a 1 L reactor, 379 g of the estolide of 1,3-propanediol PRIC212 (3) obtained in step 1 dried under vacuum for 2 h 15 at 90° C. and 58 g of HMDI (4) were introduced by rapid addition (<1 min) of (4) over (3). The reaction mixture was left under mechanical stirring at 60° C. for 2.5 h under a nitrogen stream.

(8) 2) Synthesis of the Polyurethane of Estolide of 1,3-Propanediol (7)

(9) ##STR00015##

(10) With: D=C.sub.10H.sub.20 Y=O

(11) 21.2 g 1,10-decanediol and 162 g Labrafac CC (caprylic/capric triglyceride) are added to the reaction medium, then the temperature is increased to 130° C. The reaction is continued for 30 min after the dissolution of the 1,10-decanediol under nitrogen stream.

(12) 3) Synthesis of the Gelling Polyurethane (8)

(13) In order to eliminate the unreacted isocyanate functions and to stop the reaction, 188 g estolide of 1,3-propanediol diOH (3) is added at 130° C. to the 1L reactor of step 3 containing the polyurethane of estolide of 1,3-propanediol (7). The reaction is continued for 1 h until the complete disappearance of the peak associated with NCO in IR (peak at 2250 cm−1).

EXAMPLE 2

Preparation of a Polyurethane of Estolide of PDO (PRIC212) and 1,10-Decanediol in Which the Steps 1) and 2) Are Carried Out at the Same Temperature (GSC17016)

(14) The gelling polyurethane was synthesized in three steps by polyaddition of the estolide of PDO diisocyanate with a chain extender in the presence of a cosmetic oil. It has a content of natural origin of 92.2% according to the standard NF ISO 16128-2.

(15) 1) Synthesis of the Estolide of 1,3-Propanediol Diisocyanate (5)

(16) In a 1 L reactor, 103 g Labrafac CC (caprylic/capric triglyceride) is heated to 80° C. under a nitrogen stream and under mechanical stirring (500 rpm). HMDI (40 g) is then added to the mixture and the temperature is increased to 115° C. 20 mins after the addition of the HMDI, propanediol estolide PRIC212 (Mn 2000 g/mol, 238 g) is added over 15 mins by dropping funnel while maintaining the temperature at 115° C. under nitrogen stream. The reaction is continued for 1 h 15.

(17) 2) Synthesis of the Polyurethane of Estolide of 1,3-Propanediol (7)

(18) 15.5 g 1,10-decanediol is added to the reaction medium at 115° C., and the reaction is continued for 45 mins after the addition.

(19) 3) Stopping the Reaction

(20) In order to eliminate the unreacted isocyanate functions and to stop the reaction, 119 g estolide of 1,3-propanediol diOH PRIC212 (Mn 2000 g/mol) is added to the 1 L reactor. The reaction is continued for 1 h until the complete disappearance in IR of the peak associated with the NCO functions.

EXAMPLE 3

(21) Gelling Tests of different oils were carried out with the gelling polyurethanes of examples 1 and 2 (5% by weight).

(22) The results are presented in Table 1 below. The oils are identified by their INCI name.

(23) The gelling agent was dispersed in the oil at 130° C. under stirring.

(24) The strength of the gels was evaluated in the following manner:

(25) The transparency of the gels is evaluated qualitatively, by observation of a pill bottle containing gel. If it is possible to read written characters very clearly through the pill bottle, then the gelling agent is considered as forming transparent gels. The gel is considered to be strong if it does not flow when the pill bottle is tilted.

(26) TABLE-US-00001 TABLE 1 Formation of gels Formation of gels Oils (INCI) (Example 1) (Example 2) Isopropyl myristate Strong transparent gel Strong transparent gel Dicaprylyl carbonate Strong transparent gel Strong transparent gel Pentaerythrityl tetraisostearate Strong transparent gel Strong transparent gel C12-C15 alkyl benzoate Strong transparent gel Strong transparent gel Caprylic/capric triglyceride Strong transparent gel Strong transparent gel Ethylhexyl palmitate Strong transparent gel Strong transparent gel Isononyl isononanoate Strong transparent gel Strong transparent gel Isopropyl palmitate Strong transparent gel Strong transparent gel Ricinus communis seed oil Strong transparent gel Strong transparent gel Dimer dilinoleyl dimer dilinoleate Strong transparent gel Strong transparent gel

EXAMPLE 4

Measurement of the Viscosity and the Liquefaction Temperature of Gels Produced in Caprylic/Capric Triglyceride with the Polyurethanes of Examples 1 and 2

(27) The viscosity measurements were carried out with a TA Instruments AR1500ex viscosimeter by flow rheology measurement, at shear rates of 100 s.sup.−1.

(28) The liquefaction temperature was measured under oscillation at 1 Pa and 1 Hz.

(29) The results show a significant viscosity of the gels starting from the presence of 2% gelling agent in the oil, and a liquefaction temperature greater than 50° C., allowing their use in the cosmetics industry.

(30) TABLE-US-00002 TABLE 2 Viscosity in Pa .Math. s (shear 100.sup.s−1 at 20° C., measured Liquefaction temperature (° C.) at t = 10 s) (oscillation, 1 Pa, 1 Hz) 5% gel in 2% gel in 5% gel in 2% gel in Batch caprylic/capric caprylic/capric caprylic/capric caprylic/capric Example number triglyceride triglyceride triglyceride triglyceride 1 GSC16179 1.33 0.38 Not tested 68.5 2 GSC17016 1.01 0.26 76.3 65.1

EXAMPLE 5

Synthesis of a Polyurethane of Estolide of 1,3-Propanediol, 1,10-Decanediol and Castor Oil (GSC16162)

(31) The gelling polyurethane was synthesized in three steps by polyaddition of the estolide of 1,3-propanediol diisocyanate with 1,10-decanediol in the presence of two cosmetic oils. It has a content of natural origin of 95.0% according to the standard NF ISO 16128-2.

(32) 1) Synthesis of the Estolide of 1,3-Propanediol Diisocyanate (5)

(33) In a 1 L reactor, 194.7 g estolide of 1,3-propanediol (3) and 39.5 g of HMDI (4) were introduced. The reaction mixture was left under mechanical stirring at 60° C. for 2.5 h under a nitrogen stream. Infrared measurements were carried out by monitoring the ratio of —NCO function (peak at 2250 cm−1) with respect to the —CH functions (several bands between 2800 and 3000 cm−1). The reaction is continued until the NCO/CH ratio is constant over at least two measurements separated by 15 mins.

(34) 2) Synthesis of the Polyurethane of Estolide of 1,3-Propanediol (7)

(35) 14.5 g 1,10-decanediol is solubilized at 130° C. in 86.1 g of Labrafac CC (caprylic/capric triglyceride, Gattefossé). The temperature of the 1 L reactor of step 1 containing the estolide of 1,3-propanediol diisocyanate (5) is increased to 130° C., then the mixture of 1,10-decanediol (6) plus Labrafac CC is added once to the reaction medium. The reaction is continued for 30 mins under nitrogen stream.

(36) 3) Synthesis of the Gelling Polyurethane (8)

(37) In order to eliminate the unreacted isocyanate functions and to stop the reaction, 463 g castor oil is added in excess at 130° C. to the 1 L reactor of step 3 containing the polyurethane of estolide of 1,3-propanediol (7). The reaction is continued for 1 h until the complete disappearance of the peak associated with NCO in IR.

EXAMPLE 6

Synthesis of a Polyurethane of Estolide of PDO and Hexanediol (GSC16080)

(38) The gelling polyurethane was synthesized in three steps by polyaddition of the estolide of PDO diisocyanate with 1,6-hexanediol in the presence of a cosmetic oil.

(39) It has a content of natural origin of 92.7% according to the standard NF ISO 16128-2.

(40) 1) Synthesis of the Estolide of 1,3-Propanediol Diisocyanate (5)

(41) In a 100 mL flask, 33.2 g estolide of 1,3-propanediol PRIC212 (Mn 2000 g/mol) (3) and 7.2 g of HMDI (4) were introduced. The reaction mixture was left under mechanical stirring at 60° C. for 3.2 h under nitrogen stream.

(42) 2) Synthesis of the Polyurethane of Estolide of 1,3-Propanediol (7)

(43) 9.72 g estolide of 1,3-propanediol diisocyanate are sampled and placed in a 100 mL flask. 0.48 g 1,6-hexanediol are solubilized at 130° C. in 9.8 g Labrafac CC (caprylic/capric triglyceride, Gattefossé). The temperature of the 100 mL flask containing the estolide of 1,3-propanediol diisocyanate (5) is increased to 130° C., then the mixture of 1,6-hexanediol (6) plus Labrafac CC is added in one go to the reaction medium. The reaction is continued for 2 h 40 under nitrogen stream.

(44) 3) Synthesis of the Gelling Polyurethane (8)

(45) In order to eliminate the unreacted isocyanate functions and to stop the reaction, 3.28 g estolide of 1,3-propanediol is added in excess at 130° C. to the 100 L flask of step 2 containing the polyurethane of estolide of 1,3-propanediol (7). The reaction is continued for 2.5 h after the complete disappearance of the peak associated with NCO in IR.

EXAMPLE 7

Synthesis of a Polyurethane of Estolide of PDO and 1,12-Dodecanediol (GSC16071C)

(46) The gelling polyurethane was synthesized in three steps by polyaddition of the estolide of PDO diisocyanate with 1,12-dodecanediol in the presence of cosmetic oil. It has a content of natural origin of 93.4% according to the standard NF ISO 16128-2.

(47) 1) Synthesis of the Estolide of 1,3-Propanediol Diisocyanate (5)

(48) In a 250 mL reactor, 35.7 g estolide of 1,3-propanediol PRIC212 (Mn 2000 g/mol) (3) and 8.0 g HMDI (4) were introduced. The reaction mixture was left under mechanical stirring at 60° C. for 1 h under a nitrogen stream, then the mixture is drawn under vacuum for 4 h 30. 43.7 g Labrafac CC (caprylic/capric triglyceride) is added.

(49) 2) Synthesis of the Polyurethane of Estolide of 1,3-Propanediol (7)

(50) 21.2 g of the previously obtained mixture of estolide of 1,3-propanediol diisocyanate (5) and Labrafac CC are sampled then added to a 250 mL flask at 130° C., then 0.78 g 1,12-dodecanediol is added. The reaction is continued for 1 h under nitrogen stream.

(51) 3) Synthesis of the Gelling Polyurethane (8)

(52) In order to eliminate the unreacted isocyanate functions and to stop the reaction, 10 g ethanol is added in excess at 130° C. to the 250 mL flask containing the polyurethane of estolide of 1,3-propanediol (7). The reaction is continued for 1 h until the complete disappearance of the peak associated with NCO in IR. The ethanol is then evaporated in a vacuum for 1 h.

EXAMPLE 8

(53) Gelling tests of oils with the polyurethanes of Examples 5, 6 and 7 (5% by weight gelling polyurethane) are presented in Table 3 below.

(54) TABLE-US-00003 TABLE 3 Oils (INCI) Example 3 - 4 - 5 Isopropyl myristate Strong transparent gel Caprylic/capric triglyceride Strong transparent gel

EXAMPLE 9

Synthesis of a Polyurethane of Estolide (PRIC2205H) and 1,10-Decanediol by Addition of Estolide to the Diisocyanate (LZE17009)

(55) This polyurethane has a content of natural origin of 95.7% according to the standard NF ISO 16128-2.

(56) 1) Synthesis of the Estolide PRIC2205H Diisocyanate

(57) In a 250 mL flask, 10 g estolide PRIC2205H (Mn 3000 g/mol) is added dropwise over 15 mins in a mixture containing 0.86 g HMDI and 4 g Labrafac CC (caprylic/capric triglyceride). The reaction mixture was left under magnetic stirring at 115° C. for 1.5 h under a nitrogen stream.

(58) 2) Synthesis of the Polyurethane of PRIC2205H and 1,10-Decanediol

(59) 0.29 g 1,10-decanediol is added to the reaction medium, maintaining the temperature at 115° C. The reaction is continued for 45 mins.

(60) 3) Synthesis of the Gelling Polyurethane

(61) In order to eliminate the unreacted isocyanate functions and to stop the reaction, 5 g estolide PRIC2205H is added in excess to the 250 mL reactor. The reaction is continued for 1 h until the complete disappearance of the peak associated with NCO in IR.

EXAMPLE 10

Synthesis of a Polyurethane of Estolides PRIC2205H and PRIC212, and 1,10-Decanediol by Addition of Estolides to the Diisocyanate (LZE17012)

(62) This polyurethane has a content of natural origin of 94.6% according to the standard NF ISO 16128-2.

(63) 1) Synthesis of Estolides PRIC2205H and PRIC212 Diisocyanate

(64) In a 250 mL flask, 1.3 g estolide PRIC212 (Mn 2000 g/mol) then 10 g estolide PRIC2205H (3000 g/mol) is added dropwise in 15 mins to a mixture containing 1.1 g HMDI and 4 g Labrafac CC (caprylic/capric triglyceride). The reaction mixture was left under magnetic stirring at 115° C. for 1.5 h under a nitrogen stream.

(65) 2) Synthesis of the polyurethane of PRIC2205H, PRIC212 and 1,10-decanediol

(66) 0.42 g 1,10-decanediol is added to the reaction medium, maintaining the temperature at 115° C. The reaction is continued for 45 mins.

(67) 3) Synthesis of the Gelling Polyurethane

(68) In order to eliminate the unreacted isocyanate functions and to stop the reaction, 3.25 g estolide PRIC212 is added to the 250 mL reactor. The reaction is continued for 1 h until the complete disappearance of the peak associated with NCO in IR.

(69) The gelling tests of the oils with the polyurethanes of Examples 9 and 10 (5% by weight gelling polyurethane) are presented in Table 4 below.

(70) TABLE-US-00004 TABLE 4 Oils (INCI) Example 9 Example 10 Caprylic/capric triglyceride Weak gel Weak gel PPG 15 Stearyl Ether Strong gel Strong gel Dicaprylyl Carbonate Weak gel Weak gel Squalane Weak gel Strong gel

EXAMPLE 11

Influence of the Polyurethane Synthesis Conditions on the Viscosity of the Gels Obtained by Dissolution of the Polyurethanes in Caprylic/Capric Triglyceride

(71) The flow viscosity measurements at a shear rate of 100 s.sup.−1 and obtained after 10 s, are recorded in Table 5 below.

(72) TABLE-US-00005 TABLE 5 Table GSC16179 GSC17012 5Synthesis (Example 1) (Example 2) Viscosity 1.33 1.08 (Pa .Math. s) - 5% PU T ° liq (° C.) - 78.3 78.4 5% PU Viscosity 0.38 0.22 (Pa .Math. s) - 2% PU T ° liq (° C.) - 69 67 2% PU Viscosity 0.10 Not measured (Pa .Math. s) - 1% PU
It is possible to change the ratio between the PRIC212 (here between Example 1 and Example 2) and the HMDI in order to vary the properties of the gels that will be formed with the gelling agents.

(73) It is also possible to modify the quantities of decanediol during step 2 in order to significantly modify the gelling properties of the polyurethanes, for example by increasing the viscosity of the gels having 5% polyurethane in caprylic/capric triglyceride from 1 to 1.6 Pa.s.

EXAMPLE 12

Incorporating Gelling Polyurethanes in Cosmetic Formulations

(74) Different cosmetic formulas are given below.

(75) For all the cosmetic formulas, the gel was prepared in the following manner: the gelling polyurethane added to the oil is first brought to temperature in a bath, then subjected to vigorous stirring by the Ultra-Turrax® and finally to stirring by a deflocculation blade while maintaining the temperature at 80° C.

(76) The ingredients are named using their INCI name.

(77) 1) Fragrance Formula

(78) TABLE-US-00006 INCI % Caprylic/capric triglyceride 43.525 PU GSC16179 (Example 1) 12.50 Fragrance 43.525 Diethylhexyl syringylidenemalonate (and) caprylic/ 0.05 capric triglyceride Octocrylene 0.20 Butyl methoxydibenzoylmethane 0.20

(79) The gelling polyurethane is compatible with the fragrances currently used in cosmetics and in the perfume industry.

(80) The gelling polyurethane (for example batch GSC16179 [Example 1]) gels fragrances and forms solid gels with pure fragrance contents comprised between 0.2 and 43.5%. These tests were carried out with 10 different fragrances.

(81) The gelling polyurethane also has a suspensory capacity for holding for example nacres, exfoliating agents, powders of variable density in the medium.

(82) 2) Gelled Oil Formula with Nacres in Suspension:

(83) TABLE-US-00007 INCI % Caprylic/capric triglyceride 97.8 PU GSC16179 [Example 1] 1 Synthetic fluorphlogopite (and) iron oxide 0.1 Fragrance 0.1 Caryodendron orinocense nut oil 1

(84) The gelling polyurethane forms transparent gels making it possible to put elements in suspension starting from 1%. This gel can be formed from numerous gelling polyurethanes according to the invention. This gelled oil is very fluid and vaporizable. The nacres are held in suspension by means of the gelling polyurethane throughout the stability of the product. Nacres having variable granulometries and densities can be used, at concentrations comprised between 0.1 and 1% in the gel.

(85) 3) Thick and Vaporizable Pearlized Oil:

(86) TABLE-US-00008 INCI % Caprylic/capric triglyceride 92.55 PU GSC16179 [Example 1] 6.25 Synthetic fluorphlogopite (and) iron oxide 0.1 Fragrance 0.1 Caryodendron orinocense nut oil 1

(87) In this example of oily jelly, the gel formed remains transparent despite the high content of gelling polyurethane, the nacres are perfectly held in suspension throughout the stability of the product. This gel can be formed from several gelling polyurethanes according to the invention. The gelling polyurethane forms a gel that is transparent, thick, pearlized and sprayable due to the thixotropic rheology of the gel formed.

(88) 4) Dry Body Oil

(89) TABLE-US-00009 INCI % Isononyl isononanoate 54.5 Isopropyl palmitate 20 Dicaprylyl carbonanate 20 PU GSC17020 5 Tocopheryl acetate 0.2 Fragrance 0.3

(90) The gelling polyurethane forms a transparent gel in this oil mixture. The gel formed is thick, stable and sprayable. The gelling polyurethane GSC17020 is identical to the batch GSC17016 described in Example 2 but with a quantity of 1,10-decanediol of 0.65 equivalent instead of 0.6 equivalent.

(91) 5) Transparent Lip Balm

(92) TABLE-US-00010 INCI % Isopropyl palmitate 36.9 Caprylic/capric triglyceride 30 Ricinus communis seed oil 11.5 Dimer dilinoleyl dimer dilinoleate 6.4 C10-18 triglycerides 5.8 PU GSC17020 6.4 Bis-diglyceryl polyacyladipate-2 3

(93) The gelling polyurethane forms a transparent gel in this oil and wax mixture. The gelling polyurethane GSC17020 reduces the crystallization of the waxes and butters which makes it possible to formulate transparent gels for the lips. The gel formed is thick and is easily presented in a jar.

(94) 6) Low-Viscosity Lip Gloss

(95) TABLE-US-00011 INCI % Pentaerythrityl tetraisostearate 30 Dimer dilinoleyl dimer dilinoleate 20 Ricinus communis seed oil 46.1 Tocopheryl acetate 0.2 PU16179 [Example 1] 2.5 CI 15850, Synthetic Wax 0.2 Titanium dioxide (and) synthetic fluorphlogopite 1 (and) iron oxide Fragrance 0.5

(96) The gelling polyurethane forms a transparent gel in this oil mixture. The gelling polyurethane holds the nacres and pigments in suspension. The gel formed is not very thick and is easily presented in a gloss bottle. This gel can be formed with polyurethane GSC16179 [Example 1] or GSC17020. According to the example of gelling polyurethane used, the nacres are not held in suspension.

(97) The gelling polyurethane presents no risk to the labial mucous membranes.

(98) 7) Moderate-Viscosity Gloss

(99) TABLE-US-00012 INCI % Pentaerythrityl tetraisostearate 30 Dimer dilinoleyl dimer dilinoleate 20 Ricinus communis seed oil 46.1 Tocopheryl acetate 0.2 PU GSC16179 [Example 1] 5 CI 15850, Synthetic Wax 0.2 Titanium dioxide (and) synthetic 1 fluorphlogopite (and) iron oxide Fragrance 0.5

(100) The gelling polyurethane forms a transparent gel in this oil mixture. The gelling polyurethane holds the nacres and pigments in suspension. The gel formed is moderately thick and is easily displayed in a gloss bottle. This gel can also be formed with the gelling polyurethanes GSC16100 or GSC17020. The nacres are perfectly held in suspension during the entire length of the stability tests.

(101) The gelling polyurethane presents no risk to the labial mucous membrane.

(102) 8) High-Viscosity Gloss That Can Be Presented in a Jar

(103) TABLE-US-00013 INCI % Pentaerythrityl tetraisostearate 30 Dimer dilinoleyl dimer dilinoleate 20 Ricinus communis seed oil 38.6 Tocopheryl acetate 0.2 PU16179 [Example 1] 10 CI 15850, synthetic wax 0.2 Titanium dioxide (and) synthetic 1 fluorphlogopite (and) iron oxide Fragrance 0.5

(104) The gelling polyurethane forms a transparent gel in this oil mixture. The gelling polyurethane holds the nacres and pigments in suspension. The gel formed is thick and is easily presented in a jar. This gel can also be formed with the gelling polyurethane GSC17020. The nacres are perfectly held in suspension throughout the stability tests (several months).

(105) The gelling polyurethane presents no risk to the labial mucous membrane.

(106) 9) Exfoliant for the Body

(107) TABLE-US-00014 INCI % Caprylic/capric triglyceride 83.40 PU GSC17020 6.00 Sucrose 4.00 Synthetic Wax (and) CI 77891 (and) CI 77510 1.00 PEG-20 Glyceryl triisostearate 5.00 Fragrance 0.50 Diethylhexyl syringylidenemalonate (and) 0.10 caprylic/capric triglyceride Hydrogenated palm kernel glycerides and 5.00 hydrogenated palm glycerides

(108) The gelling polyurethane makes it possible for example to hold exfoliants of variable density in suspension in an oily gel containing between 5 and 10% gelling polyurethane. The gelling polyurethane holds in suspension, for example, 4% sugar or salt or synthetic wax, or corundum alpha-alumina or pumice stone. The base gel is transparent. The thixotropic aspect of the gel allows fluid spreading, while the product is very thick in a jar.

(109) 10) Gelled Sun Oil with Organic Filters

(110) TABLE-US-00015 INCI % Butyl methoxydibenzoylmethane 3 Octocrylene 8 Ethylhexyl salicylate 5 Homosalate 10 Trimethoxybenzylidene pentanedione 1 C12-C15 Alkyl benzoate 67.8 PU GSC16179 [Example 1] 5 Fragrance 0.2

(111) The gelling polyurethane forms a transparent gel in mixtures containing octocrylene, ethylhexyl salicylate, homosalate, and/or butyl methoxydibenzoylmethane. The gelling polyurethane is compatible and stable with most organic filters. The gel can also be formed with the gelling polyurethane GSC17020.

(112) 11) Gelled Sun Oil with Organic and Mineral Filters

(113) TABLE-US-00016 INCI % Butyl methoxydibenzoylmethane 1.5 Octocrylene 4 Ethylhexyl salicylate 2.5 Homosalate 5 Trimethoxybenzylidene pentanedione 0.5 Caprylic/capric triglyceride 50 C12-C15 Alkyl benzoate 32.4 PU GSC16179 [Example 1] 2.5 Fragrance 0.1 Titanium dioxide 1.5

(114) The gelling polyurethane holds inorganic filters in suspension such as for example titanium dioxide in a thick and sprayable gel.

(115) The gel can also be formed with the gelling polyurethane GSC17020.

(116) 12) Make-Up Remover Jelly

(117) TABLE-US-00017 INCI % Ethylhexyl cocoate (and) Cocos nucifera oil 20 C12-C15 alkyl benzoate 20 Cocos nucifera oil (and) hydrogenated coconut oil 3 Caprylic/capric triglyceride 41.3 PU GSC17020 5 PEG-40 Sorbitan peroleate 10 Tocopheryl acetate 0.2 Fragrance 0.5

(118) The gelling polyurethane makes it possible to form gels in cleansing oils with a high content of emulsifying agent. The gelling polyurethane is compatible with the oily emulsifying agents.

(119) The gel formed is thick, completely transparent and stable.

(120) 13) Water-in-Oil Emulsion

(121) TABLE-US-00018 INCI % Water/aqua 64.4 Magnesium sulfate 0.7 Glycerin 5 Phenoxyethanol (and) ethylhexylglycerin 0.8 Propanediol 1 Octyldodecanol (and) octyldecyl xyloside 4 (and) PEG-30 dipolyhydroxystearate Caprylic/capric triglyceride 21.6 PU GSC16179 [Example 1] 2.4 Fragrance 0.1

(122) The gelling polyurethane is easily incorporated in water-in-oil emulsion formulas and increases the viscosity. This emulsion can also be formed with the gelling polyurethane GSC17020.

(123) 14) Repairing Night Cream

(124) TABLE-US-00019 INCI % Butyrospermum parkii Butter 5 Polyglyceryl-3 diisostearate 4 Dicaprylyl carbonate 15 PU GSC16179 [Example 1] 5 Water/aqua 57 Magnesium sulfate 0.7 Glycerin 10 1,2-Hexanediol (and) caprylyl glycol 0.5 Water (and) alcohol (and) onopordum acanthium 2 flower/leaf/stem extract Perfume 0.5 Tocopheryl acetate 0.3

(125) This repairing night cream does not show instability when it contains the gelling polyurethane, while the formula that does not contain it is unstable. This emulsion can also be formed with the gelling polyurethane GSC17020.

(126) 15) Sun Cream

(127) TABLE-US-00020 INCI % Caprylic/capric triglyceride 12.85 PU GSC17020 5 Octyldodecanol (and) octyldodecyl xyloside 4 (and) PEG-30 dipolyhydroxystearate C12-C15 alkyl benzoate 12.85 Sodium chloride 0.5 Aqua 44.5 Glycerin 5 Phenoxyethanol (and) ethylhexylglycerin 0.5 Zinc oxide (and) caprylic/capric triglyceride 14.3 (and) polyhydroxystearic acid (and) polyglyceryl-3 polyricinoleate (and) isostearic acid (and) lecithin Fragrance 0.5

(128) The gelling polyurethane makes it possible to increase the viscosity and to stabilize sun emulsions containing mineral filters. This example does not show instability when it contains the gelling polyurethane, while the formula that does not contain it is unstable.

(129) 16) Oil-in-Water Formula

(130) TABLE-US-00021 INCI % Aqua Water 30.9 Glycerin 30 Ethylhexylglycerin & phenoxyethanol 1 Cetearyl alcohol 10 Cetyl alcohol (and) glyceryl stearate (and) 2.5 PEG-75 stearate (and) ceteth-20 (and) stearath-20 Caprylic/capric triglyceride 20 Sodium stearoyl glutamate 0.5 PU GSC17020 5 Fragrance 0.1

(131) This formula example shows the gelling polyurethane in a formula having a continuous aqueous phase. The gelling polyurethane is correctly incorporated into the mixture and the formula is stable.

(132) 17) Gel-Cream Emulsion

(133) TABLE-US-00022 INCI % Water 73 Acrylate/C10 C30 alkyl acrylate crosspolymer 0.6 Tetrasodium EDTA 0.05 Ethylhexylglycerin & phenoxyethanol 0.8 Caprylic/capric triglyceride 20 PU GSC17020 5 Triethanolamine 0.55

(134) This formula example shows the gelling polyurethane in a formula having a continuous aqueous phase without emulsifying agent. The gelling polyurethane is correctly incorporated into the mixture and the formula is stable.

(135) 18) Waterless Emulsion

(136) TABLE-US-00023 INCI % Propylene glycol 30.40 Glycerin 30.00 Sodium polyacrylate 0.10 Cetearyl alcohol 2.00 Cetyl alcohol (and) glyceryl stearate (and) 2.00 PEG-75 stearate (and) ceteth-20 (and) stearath-20 Sodium stearoyl glutamate 0.50 Caprylic/capric triglyceride 31.00 PUGSC17020 4.00

(137) This formula example shows the gelling polyurethane in a formula having a continuous glycol phase. The gelling polyurethane is correctly incorporated into the mixture and the formula is more stable with the gelling polyurethane than without the gelling polyurethane, where it breaks up completely.

(138) 19) Oil-in-Water Foam

(139) TABLE-US-00024 INCI % Caprylic/capric triglycerides 23 PU GSC16179 (Example 1) 2 Polyglyceryl-6 distearate (and) jojoba esters 3 (and) polyglyceryl-3 beeswax (and) cetyl alcohol Hydrogenated palm kernel glycerides and 2 hydrogenated palm glycerides Water/aqua 64.15 Phenoxyethanol (and) ethylhexylglycerin 0.8 Propanediol 2 Tetrasodium EDTA 0.05 Poloxamer 407 (and) PPG-12/SMDI copolymer 3

(140) The gelling polyurethane can be incorporated into oil-in-water emulsions of the expanded foam type. The gelling polyurethane is correctly incorporated into the mixture and the formula is stable.

(141) 20) Waterproof Mascara Formula

(142) TABLE-US-00025 INCI % Water/Aqua 55 Magnesium sulfate 0.63 Glycerin 5 Phenoxyethanol (and) ethylhexylglycerin 0.8 Propanediol 1 Octyldodecanol (and) octyldecyl xyloside (and) 4 PEG-30 dipolyhydroxystearate Caprylic/capric triglyceride 19.57 PU GSC16179 (Example 1) 2.55 C10-18 triglycerides 3 Iron oxides, triethoxycaprylylsilane, isononyl 6.5 isononanoate, ethylene/propylene/styrene copolymer, sorbitan oleate ozokerite 2

(143) The gelling polyurethane makes it possible to formulate highly tinted emulsions such as a mascara. The gelling polyurethane increases the viscosity of the mixture, stabilizes the waxy networks, improves the hold on the brush and application to the lash. The gelling polyurethane is correctly incorporated into the mixture and the formula is stable.

EXAMPLE 13

Measurement of the Viscosity of the Gelling Polyurethane of Example 2 According to the Invention and of the Polyurethane of Example 5 of Application WO2016/090081 in Caprylic/Capric Triglyceride (Comparative Example)

(144) The compound of Example 5 of application WO2016/090081 was prepared as described.

(145) The viscosity measurements were carried out on a 5% by weight gel of each of the polyurethanes under the conditions described in application WO2016/090081 with a TA Instruments AR1500ex viscosimeter by flow rheology measurement, at shear rates of 1 s.sup.−1 and at 20° C.

(146) The results are presented in Table 6 below.

(147) TABLE-US-00026 Viscosity Example Batch number in Pa .Math. s Appearance 2 GSC17016 53.6 transparent 5 — 1.7 translucent application WO2016/090081 (comparative example)

(148) The results show that the gel containing the polyurethane of Example 2 according to the invention have completely different properties to those of the gel containing the polyurethane of Example 5 of application WO2016/090081, namely a significantly greater viscosity and a transparent appearance.