Oligoester ammonium salts and their use in compositions for conditioning hair

Abstract

The invention relates inter alia to cosmetic compositions comprising an oligoester ammonium salt (OAS) and a cosmetically component (F), where the OAS is obtained by: (i) heating a mixture of the following components (a) to (d) under continuously removing of reaction water: (a) a certain a diethanolamine compound; (b) a certain dicarboxylic acid; (c) a certain organic triol; and a monocarboxylic acid of formula R.sup.1—COOH (d), wherein R.sup.1 is linear or branched C.sub.12-C.sub.24-alkyl; (ii) reacting the oligoester of step (i) with a quarternization agent.

Claims

1. A cosmetic composition, comprising at least one oligoester ammonium salt (OAS) and at least one cosmetically acceptable component (F), whereby the at least one oligoester ammonium salt (OAS) is prepared by a process comprising the steps of: (i) heating a mixture of components (a) to (d) while continuously removing reaction water: 0.5 to 3.0 molar equivalents of a diethanolamine compound according to formula (a) ##STR00011## wherein R.sup.3 is a linear or branched C.sub.1-C.sub.6-alkyl; 0.5 to 1.5 molar equivalents of a dicarboxylic acid according to formula (b) ##STR00012## wherein R.sup.2 is a linear or branched C.sub.1-C.sub.10-alkylene or a linear or branched C.sub.2-C.sub.10-alkenylene; 0.5 to 1.5 molar equivalents of an organic triol according to formula (c2) ##STR00013## 1.0 molar equivalent of a monocarboxylic acid according to formula (d)
R.sup.1—COOH  (d) wherein R.sup.1 is linear or branched C.sub.20-C.sub.24-alkyl or linear or branched C.sub.20-C.sub.24-alkenyl; to form an oligoester product; (ii) reacting the oligoester product of step (i) with a quaternization agent (e); to form the oligoester ammonium salt (OAS) and (iii) optionally removing and purifying the at least one oligoester ammonium salt (OAS).

2. The cosmetic composition comprising at least one oligoester ammonium salt (OAS) according to claim 1, in which in the diethanolamine component (a), R.sup.3 is methyl.

3. The cosmetic composition comprising at least one oligoester ammonium salt (OAS) according to claim 1, in which the dicarboxylic acid (b) is selected from the group consisting of adipic acid, glutaric acid, succinic acid, sebacid acid, itaconic acid, maleic acid, and combinations thereof.

4. The cosmetic composition comprising at least one oligoester ammonium salt (OAS) according to claim 1, in which the carboxylic acid (d) comprises or is behenic acid.

5. The cosmetic composition comprising at least one oligoester ammonium salt (OAS) according to claim 1, in which the components (a), (b), (c2) and (d) are used in the following molar ratios: from 0.75-3.0, from 0.5-1.5, from 0.5-1.5, and 1, respectively.

6. The cosmetic composition comprising at least one oligoester ammonium salt (OAS) according to claim 1, prepared by first heating the mixture of components (a), (b), (c2) and (d) in step (i) to a temperature from 80 to 220° C., and in step (ii) subsequent reaction of the obtained oligoester product with a quarternization agent (e).

7. The cosmetic composition comprising at least one oligoester ammonium salt (OAS) according to claim 1, in which the oligoester ammonium salt (OAS) has a molecular mass Mn (number average) of from 600 to 4000 g/mol.

8. The cosmetic composition according to claim 1, comprising 0.01 to 20% by weight of one or more oligoester ammonium salts (OAS) and further comprising at least 0.5% by weight of one or more further components (F), wherein the one or more further components (F) is selected from the group consisting of acidity regulators, glossers, lubricants, and further surfactants.

9. A method of preparing a cosmetic composition, according to claim 1, comprising the step of preparing one or more oligoester ammonium salts (OAS) and mixing the OAS with one or more further components (F).

10. A method of treating hair, wherein the cosmetic composition according to claim 1 is a hair conditioner composition, comprising: a) applying the hair conditioner composition onto wet hair and then b) removing the conditioner composition from the hair.

11. The method according to claim 10, comprising: (a) applying a shampoo composition onto the hair; and then (b) washing the hair with the shampoo composition; and then (c) removing the shampoo composition from the hair; and then (d) applying the hair conditioner composition onto wet hair, and then removing the conditioner composition from the hair.

Description

EXAMPLE 1: PREPARATION OF OLIGOESTER PRECURSOR

(1) Methyl diethanol amine (component (a), 119.2 g, 1.0 mol), behenic acid (component (d), 510.9 g, 1.5 mol), adipic acid (component (b), 219.2 g, 1.5 mol) and glycerol (component (c), 138.16 g, 1.5 mol) were charged in a 2 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen. The reaction mixture was heated to 160° C. and the distillation of reaction water started. The temperature was increased to 206° C. when the head temperature decreased. The reaction water was continually removed from the reaction mixture by distillation at 160-206° C. over a period of 5 h.

(2) The product (782 g) was obtained as clear, brown liquid (acid value: 10.2 mg KOH/g; Bas-N: 1.50%; M.sub.n=1246 g/mol, M.sub.w=1354 g/mol).

EXAMPLE 2: OLIGOESTER AMMONIUM SALT

(3) The oligoester of Example 1 (150.0 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 85° C. Dimethyl sulfate (10.1 g, 0.08 mol, 0.5 equivalents/nitrogen atom in the oligoester) was added dropwise over a period of 15 minutes. The reaction mixture was stirred for 5 h at 90° C. The product (151 g) was obtained as light brown solid (Bas.-N: 0.70%).

EXAMPLE 3: OLIGOESTER AMMONIUM SALT

(4) The oligoester of Example 1 (150.0 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 85° C. Dimethyl sulfate (19.9 g, 0.15 mol, 0.98 equivalents/nitrogen atom in the oligoester) was added dropwise over a period of 15 minutes. The reaction mixture was stirred for 5 h at 90° C. The product (154 g) was obtained as light brown solid (Bas.-N: 0.11%).

EXAMPLE 4: PREPARATION OF OLIGOESTER PRECURSOR

(5) Methyl diethanol amine (119.2 g, 1.0 mol), behenic acid (510.9 g, 1.5 mol), adipic acid (219.2 g, 1.5 mol) and triethanolamine (223.8 g, 1.5 mol) were charged in a 2 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen. The reaction mixture was heated to 160° C. for 3 h and reaction water was removed from the reaction mixture by distillation. Afterwards the reaction mixture was heated to 200-205° C. for 8 h and reaction water was removed from the reaction mixture by distillation. The product (963 g) was obtained as brown wax (acid value: 1.7 mg KOH/g; Bas-N: 3.49%;

(6) M.sub.n=1756 g/mol, M.sub.w=2139 g/mol).

EXAMPLE 5 OLIGOESTER AMMONIUM SALT (OAS)

(7) The oligoester of Example 4 (300.0 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 85° C. Dimethyl sulfate (92.2 g, 0.73 mol, 0.98 equivalents/nitrogen atom in the Oligoester) was added dropwise over a period of 20 minutes. During the addition, the resulting product mixture became highly viscous and butyl diglycol (98.1 g) was added. The reaction mixture was stirred for 5 h at 85° C. The product (400 g, 80% active content) was obtained as brown wax (Bas.-N: 0.01%).

EXAMPLE 6: OLIGOESTER AMMONIUM SALT

(8) The oligoester of Example 4 (330.0 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 85° C. Dimethyl sulfate (51.8 g, 0.41 mol, 0.5 equivalents/nitrogen atom in the oligoester) was added dropwise over a period of 20 minutes. During the addition, the resulting product mixture became highly viscous and butyl diglycol (42.4 g) was added. The reaction mixture was stirred for 5 h at 85° C. The product (380 g, 90% active content) was obtained as brown wax (Bas.-N: 1.31%).

EXAMPLE 7: PREPARATION OF OLIGOESTER PRECURSOR

(9) Methyl diethanol amine (238.4 g, 2.0 mol), behenic acid (340.4 g, 1.0 mol), adipic acid (219.2 g, 1.5 mol) and glycerol (138.5 g, 1.5 mol) were charged in a 2 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen. The reaction mixture was heated to 160° C. for 2 h and reaction water was removed from the reaction mixture by distillation. Afterwards the reaction mixture was heated to 200-205° C. for 7 h and reaction water was removed from the reaction mixture by distillation. The product (810 g) was obtained as brown wax (acid value: 3 mg KOH/g; Bas-N: 2.85%; M.sub.n=1314 g/mol; M.sub.w=1445 g/mol).

EXAMPLE 8: OLIGOESTER AMMONIUM SALT

(10) The oligoester of Example 7 (260.0 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 85° C. Dimethyl sulfate (65.3 g, 0.52 mol, 0.98 equivalents/nitrogen atom in the oligoester) was added dropwise over a period of 20 minutes. During the addition, the resulting product mixture became highly viscous and butyl diglycol (81.3 g) was added. The reaction mixture was stirred for 5 h at 85° C. The product (370 g, 80% active content) was obtained as brown wax (Bas.-N<0.01%).

EXAMPLE 9: OLIGOESTER AMMONIUM SALT

(11) The oligoester of Example 7 (280.0 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 85° C. Dimethyl sulfate (35.9 g, 0.29 mol, 0.5 equivalents/nitrogen atom in the oligoester) was added dropwise over a period of 20 minutes. During the addition, the resulting product mixture became highly viscous and butyl diglycol (35.1 g) was added. The reaction mixture was stirred for 5 h at 85° C. The product (320 g, 90% active content) was obtained as brown wax (Bas.-N=1.04%).

EXAMPLE 10: PREPARATION OF OLIGOESTER PRECURSOR

(12) Methyl diethanol amine (238.4 g, 2.0 mol), behenic acid (681.2 g, 2.0 mol), adipic acid (219.2 g, 1.5 mol) and glycerol (138.2 g, 1.5 mol) were charged in a 2 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen. The reaction mixture was heated to 170° C. for 2 h and reaction water was removed from the reaction mixture by distillation. Afterwards the reaction mixture was heated to 190° C. for 1 h, then to 200° C. for 1 h and then to 210° C. for 1 h. During heating, reaction water was continually removed from the reaction mixture by distillation. The product (1127 g) was obtained as brown wax (Acid value: 2.9 mg KOH/g; Bas-N: 2.24%; M.sub.n=1029 g/mol; M.sub.w=1329 g/mol).

EXAMPLE 11: OLIGOESTER AMMONIUM SALT

(13) The oligoester of Example 10 (255.1 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 60° C. Dimethyl sulfate (50.4 g, 0.40 mol, 0.98 equivalents/nitrogen atom in the oligoester) was added dropwise over a period of 25 minutes. During the addition, the resulting product mixture became highly viscous and butyl diglycol (30.1 g) was added. The reaction mixture was heated to 80° C. and stirred at this temperature for 0.5 h. Subsequently the reaction mixture was heated to 90° C. and stirred at this temperature for 4.5 h. The product (288 g, 90% active content) was obtained as brown solid (Bas.-N<0.01%).

EXAMPLE 12: PREPARATION OF OLIGOESTER PRECURSOR

(14) Methyl diethanol amine (119.2 g, 1.0 mol), behenic acid (340.6 g, 1.0 mol), adipic acid (219.2 g, 1.5 mol) and glycerol (138.2 g, 1.5 mol) were charged in a 2 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen. The reaction mixture was heated to 170° C. for 1 h and reaction water was removed from the reaction mixture by distillation. Afterwards the reaction mixture was heated to 190° C. for 1 h, then to 200° C. for 1 h and then to 210° C. for 0.5 h. During heating, reaction water was continually removed from the reaction mixture by distillation. The product (703 g) was obtained as brown wax (Acid value: 5.2 mg KOH/g; Bas-N: 1.66%; M.sub.n=1176 g/mol; M.sub.w=1610 g/mol).

EXAMPLE 13: OLIGOESTER AMMONIUM SALT

(15) The oligoester of Example 12 (253.0 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 60° C. Dimethyl sulfate (37.3 g, 0.29 mol, 0.98 equivalents/nitrogen atom in the oligoester) was added dropwise over a period of 15 minutes. During the addition, the resulting product mixture became highly viscous and butyl diglycol (41.2 g) was added. The reaction mixture was heated to 80° C. and stirred at this temperature for 1 h. Afterwards the temperature was increased to 90° C. and the reaction mixture was stirred at this temperature for additional 4 h. The product (303 g, 88% active content) was obtained as brown solid (Bas.-N=0.02%).

EXAMPLE 14: PREPARATION OF OLIGOESTER PRECURSOR

(16) Methyl diethanol amine (119.2 g, 1.0 mol), behenic acid (170.3 g, 0.5 mol), adipic acid (109.6 g, 0.75 mol) and glycerol (23.0 g, 0.25 mol) were charged in a 2 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen. The reaction mixture was heated to 170° C. for 1 h and reaction water was removed from the reaction mixture by distillation. Afterwards the reaction mixture was heated to 180° C. for 2 h, then to 190° C. for 2 h, then to 200° C. for 2 h and then to 210° C. for 1 h. During heating, reaction water was continually removed from the reaction mixture by distillation. The product (343 g) was obtained as brown soil (Acid value: 2.6 mg KOH/g; Bas-N: 3.21%; M.sub.n=1892 g/mol; M.sub.w=3038 g/mol).

EXAMPLE 15: OLIGOESTER AMMONIUM SALT

(17) The oligoester of Example 14 (150.0 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 60° C. Dimethyl sulfate (42.5 g, 0.34 mol, 0.98 equivalents/nitrogen atom in the oligoester) was added dropwise over a period of 30 minutes in a way that the temperature did not exceed 80° C. Due to the high viscosity of the resulting product mixture, butyl diglycol (57.5 g) was added in portions during the addition of dimethyl sulfate. The temperature was increased to 80° C. and the reaction mixture was stirred at this temperature for 1 h. Afterwards the temperature was increased to 90° C. and the reaction mixture was stirred at this temperature for additional 4 h. The product (349 g, 77% active content) was obtained as brown solid (Bas.-N<0.01%).

EXAMPLE 16: PREPARATION OF OLIGOESTER PRECURSOR

(18) Methyl diethanol amine (178.8 g, 1.5 mol), behenic acid (170.3 g, 0.5 mol), adipic acid (109.6 g, 0.75 mol) and glycerol (69.1 g, 0.75 mol) were charged in a 2 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen. The reaction mixture was heated to 170° C. for 2 h and reaction water was removed from the reaction mixture by distillation. Afterwards the reaction mixture was heated to 190° C. for 1.5 h and then to 200° C. for 1 h. During heating, reaction water was continually removed from the reaction mixture by distillation. The product (391 g) was obtained as brown solid (Acid value: 1.2 mg KOH/g; Bas-N: 2.98%; M.sub.n=908 g/mol; M.sub.w=1360 g/mol).

EXAMPLE 17: OLIGOESTER AMMONIUM SALT

(19) The oligoester of Example 16 (234.7 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 60° C. Dimethyl sulfate (61.8 g, 0.49 mol, 0.98 equivalents/nitrogen atom in the oligoester) was added dropwise over a period of 45 minutes. The addition was stopped for three times and cooled to 70° C. to prevent reaction temperatures higher than 80° C. in the reaction mixture. During the addition, the resulting product mixture became highly viscous and butyl diglycol (69.6 g) was added in portions. The reaction mixture was heated to 90° C. and stirred at this temperature for 5 h. The product (349 g, 81% active content) was obtained as brown solid (Bas.-N=0.06%).

EXAMPLE 18: PREPARATION OF OLIGOESTER PRECURSOR

(20) Methyl diethanol amine (178.8 g, 1.5 mol), behenic acid (170.3 g, 0.5 mol), adipic acid (109.6 g, 0.75 mol) and glycerol (46.1 g, 0.5 mol) were charged in a 2 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen. The reaction mixture was heated to 170° C. for 2 h and reaction water was removed from the reaction mixture by distillation. Afterwards the reaction mixture was heated to 190° C. for 1 h and then to 200° C. for 1 h. During heating, reaction water was continually removed from the reaction mixture by distillation. The product (446 g) was obtained as brown solid (Acid value: 2.9 mg KOH/g; Bas-N: 4.12%; M.sub.w=985 g/mol).

EXAMPLE 19: OLIGOESTER AMMONIUM SALT

(21) The oligoester of Example 18 (237.9 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 60° C. Dimethyl sulfate (86.5 g, 0.69 mol, 0.98 equivalents/nitrogen atom in the oligoester) was added dropwise over a period of 45 minutes. The addition was stopped for three times and cooled to 70° C. to prevent reaction temperatures higher than 80° C. in the reaction mixture. During the addition, the resulting product mixture became highly viscous and butyl diglycol (62.3 g) was added. The reaction mixture was heated to 90° C. and stirred at this temperature for 5 h. The product (372 g, 84% active content) was obtained as brown solid (Bas.-N=0.03%).

EXAMPLE 20: PREPARATION OF OLIGOESTER PRECURSOR

(22) Methyl diethanol amine (178.8 g, 1.5 mol), behenic acid (170.3 g, 0.5 mol), adipic acid (73.1 g, 0.5 mol) and glycerol (69.1 g, 0.75 mol) were charged in a 2 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen. The reaction mixture was heated to 170° C. for 1 h and reaction water was removed from the reaction mixture by distillation. Afterwards the reaction mixture was heated to 190° C. for 2 h, then to 200° C. for 1 h and then to 210° C. for 1 h. During heating, reaction water was continually removed from the reaction mixture by distillation. The product (386 g) was obtained as brown solid (Acid value: 1.1 mg KOH/g; Bas-N: 3.39%; M.sub.n=768 g/mol; M.sub.w=1037 g/mol).

EXAMPLE 21: OLIGOESTER AMMONIUM SALT

(23) The oligoester of Example 20 (150.0 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 60° C. Dimethyl sulfate (44.8 g, 0.36 mol, 0.98 equivalents/nitrogen atom in the oligoester) was added dropwise over a period of 30 minutes. During the addition, the resulting product mixture became highly viscous and butyl diglycol (41.1 g) was added. The reaction mixture was heated to 80° C. and stirred at this temperature for 1 h. Afterwards the temperature was increased to 90° C. and the reaction mixture was stirred at this temperature for additional 4 h. The product (210 g, 83% active content) was obtained as brown solid (Bas.-N not detected).

EXAMPLE 22: PREPARATION OF OLIGOESTER PRECURSOR

(24) Methyl diethanol amine (178.8 g, 1.5 mol), behenic acid (170.3 g, 0.5 mol), adipic acid (36.5 g, 0.25 mol) and glycerol (69.1 g, 0.75 mol) were charged in a 2 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen. The reaction mixture was heated to 170° C. for 1 h and reaction water was removed from the reaction mixture by distillation. Afterwards the reaction mixture was heated to 190° C. for 2 h and then to 200° C. for 1.5 h. During heating, reaction water was continually removed from the reaction mixture by distillation. The product (382 g) was obtained as brown wax (Acid value: 2.6 mg KOH/g; Bas-N: 3.39%; M.sub.w=842 g/mol).

EXAMPLE 23: OLIGOESTER AMMONIUM SALT (OAS)

(25) The oligoester of Example 22 (150.0 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 60° C. Dimethyl sulfate (44.8 g, 0.36 mol, 0.98 equivalents/nitrogen atom in the oligoester) was added dropwise over a period of 30 minutes. During the addition, the resulting product mixture became highly viscous and butyl diglycol (17.5 g) was added. The reaction mixture was heated to 80° C. and stirred at this temperature for 1 h. Afterwards the temperature was increased to 90° C. and the reaction mixture was stirred at this temperature for additional 4 h. The product (177 g, 92% active content) was obtained as brown solid (Bas.-N<0.17%).

EXAMPLE 24: PREPARATION OF OLIGOESTER PRECURSOR

(26) Methyl diethanol amine (178.8 g, 1.5 mol), behenic acid (170.3 g, 0.5 mol), sebacic acid (220.8 g, 0.75 mol) and glycerol (69.1 g, 0.75 mol) were charged in a 2 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen. The reaction mixture was heated to 170° C. for 1 h and reaction water was removed from the reaction mixture by distillation. Afterwards the reaction mixture was heated to 190° C. for 2 h and then to 200° C. for 2 h. During heating, reaction water was continually removed from the reaction mixture by distillation. The product (510 g) was obtained as brown solid (Acid value: 2.6 mg KOH/g; Bas-N: 2.91%; M.sub.n=1405 g/mol; M.sub.w=2205 g/mol).

EXAMPLE 25: OLIGOESTER AMMONIUM SALT

(27) The oligoester of Example 24 (150.0 g) was charged in a 1 L flask equipped with a stirrer, distillation apparatus and thermometer under an atmosphere of nitrogen and heated to 60° C. Dimethyl sulfate (38.6 g, 0.31 mol, 0.98 equivalents/nitrogen atom in the oligoester) was added dropwise over a period of 30 minutes. During the addition, the resulting product mixture became highly viscous and butyl diglycol (15.9 g) was added. The reaction mixture was heated to 80° C. and stirred at this temperature for 1 h. Afterwards the temperature was increased to 90° C. and the reaction mixture was stirred at this temperature for additional 4 h. The product (182 g, 92% active content) was obtained as brown solid (Bas.-N<0.07%).

EXAMPLES 26 TO 66: PREPARATION OF HAIR CONDITIONER COMPOSITIONS

(28) The hair conditioner compositions of examples 26 to 66 are prepared by mixing the components, as listed in Table 1. All cosmetic compositions are creamy white liquids with appearance and physical properties similar to commercially available rinse-off hair conditioner products. The pH-values of the formulations are adjusted to 3.5 to 4.5. INCI names are provided for each ingredient. Xiameter PMX-200 is e.g. a silicone fluid (Dimethicone). CE=comparative example.

(29) TABLE-US-00001 TABLE 1 Hair conditioner compositions, components are given in weight %. Example 26 31 32 Ingredient (CE) 27 28 29 30 (CE) (CE) Cetearyl 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Alcohol CTAC 0.5 0.5 0.2 0.5 0.2 0.3 0.2 Example 1 2.0 — — — — — — Example 2 — 2.0 1.8 — — — — Example 3 — — — 2.0 1.8 — — Example 4 — — — — — 1.7 1.8 Example 5 — — — — — — — Example 6 — — — — — — — Example 7 — — — — — — — Example 8 — — — — — — — Example 9 — — — — — — — Xiameter 0.2 0.2 0.2 0.2 0.2 0.2 0.2 PMX-200 Preservative q.s. q.s. q.s. q.s. q.s. q.s. q.s. Water Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Example 35 36 39 Ingredient 33 34 (CE) (CE) 37 38 (CE) Cetearyl 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Alcohol CTAC 0.2 0.2 0.3 0.2 0.2 0.2 0.2 Example 1 — — — — — — 1.8 Example 2 — — — — — — — Example 3 — — — — — — — Example 4 — — — — — — — Example 5 1.8 — — — — — — Example 6 — 1.8 — — — — — Example 7 — — 1.7 1.8 — — Example 8 — — — — 1.8 — Example 9 — — — — — 1.8 Xiameter 0.2 0.2 0.2 0.2 0.2 0.2 0.2 PMX-200 Preservative q.s. q.s. q.s. q.s. q.s. q.s. q.s. Water Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Example Ingredient 40 41 42 43 44 45 46 Cetearyl 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Alcohol CTAC — 0.2 — 0.2 — 0.2 — Example 13 2.0 — — — — — — Example 15 — 1.8 2.0 — — — — Example 17 — — — 1.8 2.0 — — Example 19 — — — — — 1.8 2.0 Example 21 — — — — — — — Example 25 — — — — — — — Xiameter 0.2 0.2 0.2 0.2 0.2 0.2 0.2 PMX-200 Preservative q.s. q.s. q.s. q.s. q.s. q.s. q.s. Water Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Example Ingredient 47 48 49 50 51 Cetearyl alcohol 4.0 4.0 4.0 4.0 4.0 CTAC 0.2 0.2 — — — Example 5 — — — 2.0 — Example 8 — — — — 2.0 Example 13 — — — — — Example 15 — — — — — Example 17 — — — — — Example 19 — — — — — Example 21 1.8 — — — — Example 25 — 1.8 2.0 — — Xiameter PMX-200 0.2 0.2 0.2 — — Preservative q.s. q.s. q.s. q.s q.s Water Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Example Ingredient 52 53 54 55 56 57 58 Cetearyl 4.0 4.0 4.0 — — —  3.50 Alcohol Cetyl Alcohol — — — 4.0 4.0 4.0 — Stearyl — — — 1.0 1.0 1.0 — Alcohol Example 3 0.5 — — 1.0 — — 1.5 Example 5 — 0.5 — — 1.0 — — Example 6 — — 0.5 — — 1.0 — Xiameter 2.0 2.0 2.0 — — — — PMX-200 Dow 2-8566 — — — 2.5 2.5 2.5 — Amino Fluid (Amodimethicone) Wacker Fluid — — — — — — — NH 130D (Polydimethyl- siloxane, 3- aminopropyl terminated) Stearamido- 1.5 1.5 1.5 — — — — propyl dimethylamine Hydroxyethyl- — — — 1.0 1.0 1.0 — cellulose Trideceth 6 — — — 0.5 0.5 0.5 — Crodamol SS — — — — — — 0.8 (cetyl esters wax) Trehalose 0.8 0.8 0.8 — — — — Niacinamide — — — — — — 0.5 Preservative q.s. q.s. q.s. q.s. q.s. q.s. q.s. Water Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Example Ingredient 59 60 61 62 63 64 65 Cetearyl  3.50  3.50 — — — 4.0 4.0 Alcohol Cetyl Alcohol — — 0.8 0.8 0.8 — — Stearyl Alcohol — — 3.5 3.5 3.5 — — Example 3 — — 2.0 — — 1.0 — Example 5 1.5 — — 2.0 — — 1.0 Example 6 — 1.5 — — 2.0 — — Xiameter — — — — —  1.75  1.75 PMX-200 Dow 2-8566 — — — — — — — Amino Fluid (Amodimethicone) Wacker Fluid — — 0.5 0.5 0.5 — — NH 130D (Polydimethyl- siloxane, 3-aminopropyl terminated) Stearamido- — — — — — 1.0 1.0 propyl dimethylamine Hydroxyethyl- — — — — — — — cellulose Trideceth 6 — — — — — — — Crodamol SS 0.8 0.8 — — — — — (cetyl esters wax) Trehalose — — — — — — — Niacinamide 0.5 0.5 — — — — — Preservative q.s. q.s. q.s. q.s. q.s. q.s. q.s. Water Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ad. 100 Ingredient Example 66 Cetearyl Alcohol 4.0 Cetyl Alcohol — Stearyl Alcohol — Example 3 — Example 5 — Example 6 1.0 Xiameter PMX-200  1.75 Dow 2-8566 Amino Fluid — (Amodimethicone) Wacker Fluid NH 130D — (Polydimethylsiloxane, 3-aminopropyl terminated) Stearamidopropyl 1.0 dimethylamine Hydroxyethylcellulose — Trideceth 6 — Crodamol SS (cetyl esters — wax) Trehalose — Niacinamide — Preservative q.s. Water Ad. 100

EXAMPLE 67: TESTING OF THE CONDITIONER COMPOSITIONS

(30) The studies are conducted with hair swatches (using dark brown, straight European hair tresses from Kerling, 15 cm long, ca. 2.6 g hair each). Virgin hair (not chemically treated) and damaged (4 times bleached) hair are used.

(31) Hair swatches are pre-treated (base wash with a 14% by weight sodium lauryl ether sulfate (SLES) solution), and then treated with one of the conditioner as described in examples 26 to 64. The following steps are used:

(32) a) applying a shampoo formulation onto the hair;

(33) b) washing the hair with the shampoo formulation;

(34) c) removing the shampoo composition from the hair;

(35) d) applying the conditioner composition of examples 26 to 64, onto the hair;

(36) e) removing said conditioner composition from the hair.

(37) The combing forces in wet and dry state are measured using a typically used instrument (Diastron (UK) MTT175), wet combing after rinsing off the conditioner, and dry combing after at least 12 hours of drying time in air at 22° C. The hair swatches are pre-combed three times before the measurement.

(38) As benchmarks, analogous conditioner compositions are used containing cetrimmonium chloride (CTAC) or behentrimonium chloride (BTAC) at 2% by weight, active level, as listed in Table 2. The Table 3 then presents the wet (average) combing force (gmf force) for hair treated with selected conditioner compositions of examples 26 to 64 (see formulations in Table 1).

(39) TABLE-US-00002 TABLE 2 Formulations of comparative Example (CE) hair conditioner compositions (active levels of ingredients in weight %, Silicone from Dow Corning (DC200)). Ingredient Example (CE1) Example (CE2) Cetearyl Alcohol 4.0 4.0 CTAC 2.0 — BTAC (Behentrimonium — 2.0 Chloride) Example 1 Xiameter PMX-200 0.2 0.2 Preservative q.s. q.s. Water Ad. 100 Ad. 100

(40) TABLE-US-00003 TABLE 3 Wet combing force results of hair treated with conditioner compositions (Examples 30 to 64) compared to benchmark formulations (CE1 or CE2). wet combing force, wet combing force, damaged hair virgin hair (average), (average), Example gmf gmf CE1 — 12.1 CE2 10.7 — Example 30 9.9 — Example 33 9.5 — Example 34 9.7 — Example 35 10.6 — Example 37 9.0 — Example 41 10.2 — Example 46 10.0 11.4 Example 50 8.8 11.8 Example 51 7.5 — Example 52 9.9 11.8 Example 53 10.2 9.2 Example 54 9.6 9.6 Example 56 — 10.2 Example 62 8.6 — Example 66 9.3 —

(41) Table 4 presents the dry (maximum) combing force (gmf force) for hair treated with selected conditioner compositions of Example 33 to Example 46. As benchmark, comparative example CE1 is used (formulation in Table 2).

(42) TABLE-US-00004 TABLE 4 Dry combing force results of hair treated with conditioner compositions (Examples 33 to Example 46), compared to benchmark formulation CE1. dry combing force, dry combing force, virgin hair (max), damaged hair (max), Example gmf gmf CE1 140.8 117.2 Example 33 — 116.4 Example 36 132.0 — Example 37 135.1 77.9 Example 38 111.7 — Example 46 — 106.5 Example 50 67.3 55.3 Example 51 79.5 45.8

(43) The dry hair after treatments with all conditioner compositions of examples 26 to 64 showed good tactile results and led to nice hair appearance. In particular, conditioner compositions of examples 29 to 33 and 35 to 37 produced an effect of very soft hair.

(44) After using the method of treating hair with the conditioning composition, comprising an optional pre-treatment with silicone-free shampoo and a conditioner treatment, the hair probes are tested for hair shine (using a classical testing with Samba Hair System, from Bossa Nova Tech). This measurement technique allows for quantitative evaluation of the light intensity reflected from hair swatches mounted on a drum in a half-circle arrangement.

(45) Results of the shine measurements are illustrated in Table 5, for hair swatches treated with compositions of examples 26 to 49, which in general show stronger shine than the prior art formulation CE1.

(46) TABLE-US-00005 TABLE 5 Hair shine results for swatches treated with conditioner compositions hair shine, virgin hair shine, Example hair damaged hair CE 1 15.5 6.8 Example 26 16.7 — Example 27 16.0 — Example 28 19.0 7.4 Example 29 16.1 — Example 30 19.3 — Example 31 16.7 — Example 32 17.5 — Example 33 18.4 7.4 Example 34 17.5 — Example 35 18.4 — Example 36 18.2 — Example 37 20.2 7.7 Example 39 18.8 7.5 Example 40 17.1 7.3 Example 41 18.2 7.2 Example 42 17.6 7.5 Example 43 17.6 7.5 Example 44 18.0 7.6 Example 45 18.5 7.7 Example 46 18.6 7.5 Example 47 18.4 7.4 Example 48 17.3 7.7 Example 49 17.1 8.0 Example 50 15.6 — Example 51 — 6.9
Evaluation of Hair Volume and Frizz

(47) Hair volume was measured by digital image analysis using ImageJ software. Hair swatches were mounted on a holder in front of a light box, images were taken and evaluated. For each measurement, nine images were used, and the swatch area corresponding to the continuous dark signal intensity was measured. Volume increase or reduction was compared to that of an untreated hair swatch. The frizz component of hair volume was calculated with the ImageJ software as the area in the image on the perimeter of the continuous hair swatch, in which single fibres were visible. The results are reported as volume or frizz change in % of the volume/frizz of the untreated hair (increase—positive; reduction—negative).

(48) The following formulations were tested:

(49) TABLE-US-00006 TABLE 6 Ingredient Example 68 Example 69 CE 1 CE 3 Cetearyl Alcohol 4.0 4.0 4.0 4.0 Example 5 1.7 1.7 — — CTAC 0.3 0.3 2.0 2.0 Xiameter PMX-200 0.2 — 0.2 — Preservative q.s. q.s. q.s. q.s. Water Ad. 100 Ad. 100 Ad. 100 Ad. 100

(50) TABLE-US-00007 TABLE 7 Hair volume changes, virgin European hair: Example Product tested CE 3 CE 1 Example 69 68 Volume change, % +11.3 +4.2 +10.1 −2.1

(51) It is clear and consistent with the knowledge in the field that hair cosmetics without silicone increase hair volume (CE 3 and Example 69). To the contrary, products with silicone reduce hair volume to give the effect of smooth and sleek hair. Volume reduction by using the product with Example 5 is stronger than for a conventional conditioner (CE 1).

(52) TABLE-US-00008 TABLE 8 Hair frizz changes, virgin European hair: Product tested CE 1 Example 69 Example 68 Frizz change, % −33 −49.3 −84.5

(53) Hair frizz is a component of hair volume, and is generally unwelcome among consumers, as it decreases hair gloss and makes hair less manageable. Typical conditioners are able to reduce hair frizz, and those with added silicone normally have a stronger effect. Material of Example 5 reduces hair frizz stronger than a benchmark conditioner CE 1 (with silicone). Whether silicone-free or with silicone, Example 5 has a much stronger effect in frizz reduction, and can be used in smoothing, frizz reducing products. Hair gloss of frizz-free hair is also expected to be higher.

(54) Evaluation of Hair Smoothness and Repair

(55) Hair smoothness and repair was measured on various types of hair using Diastron (UK) MTT 175 tester with the friction accessory. Friction coefficient for hair when moved in the root-to-tip direction under external weight is interpreted as smoothness, and in the opposite direction (tip-to-root) as hair repair.

(56) The following formulations were tested:

(57) TABLE-US-00009 TABLE 9 Ingredient Example 68 CE 1 CE 2 Cetearyl Alcohol 4.0 4.0 4.0 Example 5 1.7 — — CTAC 0.3 2.0 — BTAC — — 2.0 Xiameter PMX-200 0.2 0.2 0.2 Preservative q.s. q.s. q.s. Water Ad. 100 Ad. 100 Ad. 100

(58) Hair Smoothness

(59) The measurement error is +/−2%. The following results were obtained for friction coefficient for European (virgin and 4 h bleached) and Asian (virgin) hair:

(60) TABLE-US-00010 TABLE 10 Product tested CE 1 CE 2 Example 68 Friction coefficient root-to-tip - 0.5838 0.5462 0.5378 EU virgin Friction coefficient root-to-tip - — 0.5728 0.5458 EU bleached Friction coefficient root-to-tip - 0.5856 — 0.5650 Asian virgin

(61) A lower friction coefficient corresponds to smoother hair, and differences of 0.01 are already significant. The conditioner of Example 68 shows improved performance on that benefit in comparison with typical conditioners (CTAC and BTAC).

(62) Hair Repair

(63) The measurement error is +/− 2%. The following results were obtained for return friction coefficient for European (virgin and 4 h bleached) and Asian (virgin) hair:

(64) TABLE-US-00011 TABLE 11 Example Product tested CE 1 CE 2 68 Friction coefficient tip-to-root - 1.217 1.202 1.031 EU virgin Friction coefficient tip-to-root - 1.120 1.077 1.070 EU bleached Friction coefficient tip-to-root - 1.155 — 1.115 Asian virgin

(65) Material of Example 5, when formulated in a hair conditioner, shows a significantly improved benefit of hair repair in comparison with conventional conditioners (CE 1 and CE 2), on all hair types used for the test.

(66) Evaluation of Hair Gloss/Shine with and without Silicone

(67) Glossy hair is among the largest consumer needs when hair care products are considered. A number of commonly known hair glossers are used in the industry, most frequently silicones. However, with the silicone-free product segment increasing, and with more consumers perceiving silicones as environmentally unfriendly, it is important that a hair conditioner without silicone also provides a high level of hair gloss. Hair gloss on the dry swatches was measured with Samba Hair System (Bossa Nova Tech, CA, USA). BNT numbers for hair gloss calculated by the Bossa Nova algorithm are reported.

(68) TABLE-US-00012 TABLE 12 Product tested CE 1 CE 3 Example 68 Example 69 EU virgin hair 15.9 — 17.0 16.9 EU bleached hair 6.6 6.5 7.0 7.2

(69) Conditioner examples 68 (with silicone) and 69 (silicone-free), both containing the material of Example 5, provide higher shine than a prior-art formulations with cetrimonium chloride.

(70) Analytics

(71) The molecular mass Mn (number average) aka number average molecule weight used herein is measured by GPC. GPC is a special type of liquid chromatography in which the sample is separated according to the hydrodynamic volumes of the individual constituents. Detection is effected by e.g. refractive index and yields a simple distribution curve. To attribute actual molecular weight values to the curve, it is necessary to calibrate the column by passing down polymers of known molecular weight. GPC herein was determined under the following conditions:

(72) Column: 1×PSS SDV Guard, 5 micron, 50 mm×8.0 mm ID

(73) 1×PSS SDV 100 Angstroms, 5 micron, 300 mm×8.0 mm ID 1×PSS SDV 1000 Angstroms, 5 micron, 300 mm×8.0 mm ID 1×PSS SDV 100000 Angstroms, 5 micron, 300 mm×8.0 mm ID
Detector: RID (refractive index detector)
Oven temperature: 40° C.
Flow: 1 ml/min
Injection volume: 50 μl
Eluent: THF
Calibration method: Conventional
Standards: Polyethylene glycol standards in the range from 430 to 44700 Dalton Internal Standard: Toluene.