Diethanolamine Esterquats for Hair and Skin and Other Topics: Literature Findings

May 1, 2009 | Contact Author | By: Charles Fox, Independent Consultant
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Title: Diethanolamine Esterquats for Hair and Skin and Other Topics: Literature Findings
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Keywords: patents

Abstract: This month’s survey of recent patent and research literature describes moneymaking ideas for personal care product development including water-induced thickening of hair, surfactant/biopolymer mixures, a foam/aerosol hair conditioner, and yeast glucan carriers, among others.

This month’s survey of recent patent and research literature describes moneymaking ideas for personal care product development including water-induced thickening of hair, surfactant/biopolymer mixures, a foam/aerosol hair conditioner, and yeast glucan carriers, among others.

Skin and Skin Care
Magnesium ascorbyl phosphate in skin lightening: Nakama et al. indicate that magnesium ascorbyl phosphate (MAP) inhibits the transfer of melanin granules from melanocytes to keratinocytes.1 In skin lightening, this transfer is important to control and many studies have been conducted regarding the transfer mechanism of melanin granules; however, few studies have examined the mechanism of intercellular adhesion between melanocytes and keratinocytes. These researchers investigated the role of epithelial cadherin (E-cadherin), a cell adhesion factor, on the UV-induced acceleration of melanin transfer, revealing that nitric oxide, a skin melanogen induced by UV irradiation, accelerates the transfer of melanin granules from melanocytes to keratinocytes. Furthermore, nitric oxide was found to up-regulate the expression of E-cadherin mRNA in human melanocytes and keratinocytes.

On the other hand, MAP, a vitamin C derivative, inhibited nitric oxide-induced acceleration of melanin transfer and the up-regulation of E-cadherin mRNA expression. These results suggest that E-cadherin regulates the transfer of melanin granules, and that MAP inhibits the acceleration of melanin transfer by regulating the expression level of E-cadherin. On the basis of these results, MAP was found top be an effective, multifunctional ingredient with application in skin lightening products. In such products, it has been shown to reduce and inhibit melanin formation and melanocyte proliferation.

In-shower body lotion for dry skin: Ertel et al. have published a controlled exposure method to predict the benefit of an in-shower body lotion for dry skin.2 Since in-shower body lotions are designed to be used in the shower after cleansing and followed by rinsing, existing predictive methods for cleansers or leave-on lotions are not applicable. Protocol parameters were chosen on the basis of consumer habits, practice studies and randomized clinical testing. The resulting protocol is reportedly consumer-relevant and reliably and reproducibly predicts dry skin improvement from in-shower body lotion product forms.

Skin perturbation with surfactant/humectant systems: Ghosh et al. have published on the visualization and quantification of skin barrier perturbation induced by surfactant/humectant systems using two-photon fluorescence microscopy.3 To visualize the effects of aqueous surfactant/humectant systems on the skin barrier, an in vitro two-photon fluorescence microscopy (TPM) study including dual-channel visualization was conducted. TPM is a noninvasive imaging technique with the capability for imaging up to several hundred micrometers deep that is based on photon-induced nonlinear excitations of fluorophores.

The following aqueous solutions were tested in contact with pig full-thickness skin (p-FTS): a harsh surfactant solution of 1% sodium dodecyl sulfate (SDS); a harsh surfactant/humectant solution of 1% SDS and 10% glycerol; a mild surfactant solution of 1% sodium cocoyl isethionate (SCI); a control solution of phosphate-buffered saline (PBS); and a humectant solution of 10% glycerol. Sulforhodamine B (SRB), a hydrophilic fluorescent probe, was used to visualize the effects of the five aqueous contacting solutions on the skin barrier morphology.

The results of the TPM visualization study revealed that SDS induces corneocyte damage by denaturing keratins and creating intracorneocyte penetration pathways. On the other hand, SDS and glycerol did not significantly induce corneocyte damage. The dual-channel TPM images corresponding to the mild surfactant solution, the control solution and the humectant solution showed low SRB penetration into the corneocytes as well as localization of the SRB probe within the lipid bilayers surrounding the corneocytes of the stratum corneum (SC).

Through quantification of the amount of SRB penetrating the skin as a function of depth, the researchers found that adding glycerol to an SDS aqueous contacting solution could significantly reduce the SDS-induced penetration depth of SRB, providing evidence of the ability of glycerol to mitigate SDS-induced skin barrier perturbation.

The distribution of SRB in the p-FTS samples was analyzed using a theoretical model that quantified changes in the skin aqueous pore characteristics induced by the four aqueous contacting solutions relative to the control solution. The results of the theoretical model indicate the following ranking order in regard to the extent of perturbation to the skin pores, from highest to lowest: harsh surfactant solution > harsh surfactant/humectants > mild surfactant solution > control solution > humectants solution. The development of such an in vitro visual ranking methodology, including quantification using TPM, could potentially reduce costly in vivo screening procedures, thereby significantly reducing the cost and time-to-market of cosmetic formulations containing surfactants and humectants.

Hair and Hair Care
Hair styling gels: Cosmax Co., Ltd. disclosed hair styling gels containing hair-setting polymers and thickeners.4 The described hair styling gel composition comprises: 0.1–10.0% acrylate-polyoxyethylene alkylethyl methacrylate copolymer, 0.1–10.0% acrylate copolymer, 0.1–10.0% acrylate-hydroxy ester acrylate copolymer as the setting polymer, and 0.01–10.0% of a neutralizer, possibly an alkali such as triethanolamine or sodium hydroxide. Acrylate-polyoxyethylene alkylethyl methacrylate copolymer contains 0.1–60.0% hydrophobic monomer as a thickener. The disclosed low viscosity hair styling gel composition is reported to provide high hair fixing ability.

Surfactant/copolymer hair composition: L’Oréal has disclosed a cosmetic hair composition containing an anionic carboxylic surfactant and a vinylamide/vinylamine copolymer comprising 10–90% of -CH2-CH(NH2)- and 90–10% of -CH2CH-(NH(CO)H)- groups.5 An example of a shampoo is shown in Formula 1.

Diethanloamine esterquats for hair and skin: Clariant International Ltd. has disclosed hair and cosmetic compositions containing diethanolamine esterquats.6 The invention concerns diethanolamine esterquats of the general formula:

R1-CO-O-CH2-CH2-N+(CH3)2- CH2-CH2-O-CO-R2 A- Eq. 1

in which R1CO, R2CO are independently linear or branched saturated C18-24 alkyl carboxyl group; A- is a counter ion; and the total amount of C18-23-alkyl-COOH groups relative to all R1COO- and R2COO- groups is 40% or more. The diethanolamine esterquats are used in cosmetic and pharmaceutical compositions for the treatment of hair and skin. Therefore, didocosoylethyl dimonium chloride was prepared in two steps starting with behenic acid and methyldiethanol amine. The obtained methyldiethanolamine dibehenate was reacted with methylchloride under pressure. A similar product was included in a shampoo, shown in Formula 2.

Foam, aerosol hair conditioner: Kosei Co., Ltd. has introduced a foam aerosol-type hair conditioner composition.7 The conditioner is comprised of a solution containing highly polymerized dimethylpolysiloxane, an amino acid and/or its water-soluble derivative, a cationic cellulose derivative and/or its nonionic cellulose derivative, and water. The solution is combined with a propellant that is added to a container at a ratio of 70:30–97:3. An example is shown in Formula 3 where the solution was added to an aerosol container with liquid petroleum gas at 90:10 to produce a foam aerosol-type hair conditioner.

Water-induced thickening for hair: Shiseido Co., Ltd. discloses low-viscous, transparent compositions showing a water-induced thickening property.8 The compositions are suitable for use in a hair-conditioning compositions that provide good handling. The composition is characterized by containing a cationic surfactant; a polar oil selected from a group of ester oils, higher fatty acids and higher alcohols; a lower alcohol; and/or water. The composition shows a viscosity of < 1000 mPa·s. More specifically, the cationic surfactant has a general structure represented by:

[RCOO(CH2)nN+(Me)[(CH2)nOH] (CH2)nOCOR]X- Eq. 2

where R is C11-21 aliphatic hydrocarbon; n is 2,3; X is halogen, methosulfate, methophosphate. An example of a hair conditioner is shown in Formula 4.

Color Cosmetics
W/O makeup remover: Kosei Co., Ltd. discloses a w/o cosmetic makeup remover.9 The makeup remover composition is said to provide good handling properties without dripping and leaves a fresh feeling after rinsing. The composition is characterized by containing 0.1–5% silicone-based surfactant, 5–20% isoparaffin, 0.1–5% dextrin fatty acid ester and 70–80% water. An example is shown in Formula 5.

Makeup deposition and removal emulsion: Narisu Cosmetic Co., Ltd. has disclosed w/o emulsions containing silicones, dextrin fatty acid esters and oils that have cleansing and makeup base effects.10 The w/o emulsions for makeup contain polyether-silicones as emulsifiers, volatile cyclosilicones as cleansing ingredients, organic modified clay minerals and/or partially cross-linked silicones as emulsion stabilizers, dextrin fatty acid esters and liquid oils. An example is shown in Formula 6. The emulsion showed good cleansing effects in removing a liquid foundation from the skin and a good makeup base effect in re-application of a liquid foundation to the skin. The emulsion showed no separation after 3 months’ storage at 40°C.

Light-protective preparations: BASF SE discloses UV light-protective preparations, particularly for cosmetics, based on mixed inorganic/organic systems.11 The disclosed invention particularly relates to light-protective preparations containing nanoparticles of at least one metal derivative, at least one light-protective compound chemically bound to said metal derivative nanoparticles, and at least one additional organic UV light-protective agent that is different from the light-protective compound bound to nanoparticles. Therefore, substances termed hybrids were used in various compositions and were defined as titania or zinc oxide chemically bound to derivatives of triazine, hydroxybenzophenone, 4,4’-diaryl butadiene or other referenced UV-filters. An example is shown in Formula 7.

Antimicrobial sunscreen composition: Symrise GmbH & Co., KG rhas eleased compositions comprising benzyl alcohol derivatives and 1,2-alkanediols having 3 to 14 carbon atoms.12 An example of a sunscreen using these antimicrobials is shown in Formula 8.

Photostable composition: Merck Patent GmbH discloses a photostable composition comprising diethylhexyl radical and ethylhexyl methoxycinnamate, preferably in a ratio 5:1 to 1:5.13 An example of a lip balm is shown in Formula 9.

Surfactant/biopolymer mixtures: Tadros et al. have published on personal care emulsions based on surfactant/biopolymer mixtures and the correlation of rheological parameters with sensory attributes.14 The stability of the o/w emulsions also was investigated using rheological techniques.

The biopolymer mixture included konjac mannan and xanthan gum (KX), which was emulsified with a mixture of alcohol ethoxylates or sucrose esters to produce two surfactant/biopolymer

mixturesa. Stress measurements of the individual components of the biopolymer mixture and their combinations showed a higher zero shear viscosity for the mixture than its individual components. This indicated a synergetic effect in the KX blend, which is attributed to the interaction between the two polysaccharide molecules.

Rheological measurements for the surfactant-biopolymer mixtures showed a reduction in the zero shear viscosity when compared with KX alone, indicating that the surfactants reduced the interaction between the two polysaccharides. Rheological investigations were conducted using the mixtures at various intervals of time, and the results showed high stability of the emulsions both at RT and higher temperatures. The emulsions also showed no separation or creaming as a result of the presence of a gel network in the continuous phase. However, the emulsions are shear-thinning and their viscosity reached low values at high shear rates.

Several emulsions were prepared and their sensory attributes were determined using expert panels. The results obtained were assessed using statistical analysis. The sensory attributes of several emulsions based on these surfactant/biopolymer mixtures were compared with those obtained using classical surfactants and hydrocolloids such as carbomer. Generally, the emulsions based on the emulsifier/biopolymer mixtures showed higher spreadability, higher wetness, lower firmness, lower greasiness, lower thickness and lower integrity of shape compared with the other emulsions. This was mainly due to the lower viscosity at high shear rate and the lower (but coherent) gel structure, which can be easily broken under shear. With the emulsions containing thickeners such as carbomer, a higher cohesive energy was obtained and the gel structure could not be easily broken under shear. These results indicate that, in personal care emulsions, surfactant/biopolymer mixtures provide formulating advantages.

O/W moisturizing emulsions: Carlotti et al. have published on o/w moisturizing emulsions with two saccharose esters, saccharose palmitate and saccharose stearate.14 The ability of saccharose esters to form lamellar structure in oil/water/glyceryl stearate mixtures was investigated through ternary phase diagrams. Three different oils were tested including mineral oil, C12-15 alkyl benzoate and cetearyl octanoate.

On the basis of the phase behaviors, several emulsions with liquid crystal structures were obtained and then characterized. Furthermore, the most stable emulsions were combined with one of two moisturizing actives, lauryl pyrrolidone or sodium-d,l-pyroglutamate. After the addition, the stability of the emulsions was assessed. It was observed that emulsions containing sodium-d,l-pyroglutamate were less stable compared to emulsions containing lauryl pyrrolidone.

Interesting Raw Materials and Compositions
Yeast glucan carriers: Freimund et al. discuss yeast-derived beta-glucan as a novel carrier for cosmetic substances.15 In nature, 1,3-beta-d-glucan as structure-providing polysaccharides are common. They are present in the cell walls of bacteria, fungi and algae and contain different health-promoting properties. In particular, the beta-glucan from the common baking or brewer’s yeast has been intensively examined for more than 60 years, where its distinctive activating effect on the immune system has been proven multiple times.

In the meantime, glucan is offered as a natural substance both in capsule or tablet form and as an effective component of skin care products. However, no application has been found for this material as a potential carrier of active substances. Due to its insolubility in water but good swelling capacity, its availability at acceptable prices, and its self-actuation, the glucan from yeast offers new alternatives to conventional carrier systems. The authors present several successful results of recently developed carrier systems on the basis of a glucan yeast.

High unsaponifiables in cosmetics and pharmaceuticals: International Flora Technologies Ltd. disclosed the use of high unsaponifiables for cosmetics and pharmaceuticals.17 Materials with high levels of unsaponifiable matter, such as extracts from plants, result in hydrolyzates with unique properties. Researchers have found that applying a hydrolysis process to materials with a high level of unsaponifiables, e.g., at least 6% of the material, produces a product with properties significantly different than products resulting from conventional saponification and with < 6% unsaponifiables. The resulting hydrolyzates resist both physical and aqueous-based removal from skin and hair, exhibit a unique surfactant property, and are not foaming agents with water.

These hydrolyzates may be used to enhance the performance of cosmetics and pharmaceuticals since they are bioactive agents. They are also natural carrier alternatives for topical treatments, particularly for application of materials to the skin or hair, and provide a substantive support for the materials carried. A dramatic increase in skin hydration was observed for a majority of subjects testing a jojoba hydrolyzate skin lotion versus a control formula.

Glycerol ether/polyol mixtures: Air Liquide Sante discloses compositions that comprise one or more glycerol ethers together with one or more diol/diols and/or polyol/polyols.18 Such compositions were shown to provide microbiocidal efficacy, reducing or avoiding skin whitening and drying effects while regulating moisture content. An example is shown in Formula 10.

Reproduction of all or part of this article is strictly prohibited.


1. M Nakama et al., Magnesium ascorbyl phosphate inhibits the transfer of melanin granules from melanocytes to keratinocytes, Frag J 36(9) 53–58 (2008) (in Japanese)
2. K Ertel et al., Protocol to predict the dry skin benefit from the unique in-shower body lotion product form, J Cosm Sci 59(4) 253–262 (2008)
3. S Ghosh et al., Visualization and quantification of skin barrier perturbation induced by surfactant-humectant systems using two-photon fluorescence microscopy, J Cosm Sci 59(4) 263–289 (2008)
4. KR 845,745, Hair styling gels containing hair-setting polymers and thickeners, Cosmax Co., Ltd., S. Korea, July 11, 2008
5. FR 2,914,183, Cosmetic hair compositions containing an anionic carboxylic surfactant and a vinylamide/vinylamine copolymer, L’Oréal, France, Oct. 3, 2008
6. DE 102,008,015,899, Hair and cosmetic compositions containing diethanolamine esterquats, Clariant International Ltd., Switzerland, Oct. 9, 2008
7. JP 2008 247,808, Foam aerosol-type hair conditioner compositions, Kosei Co., Ltd., Japan, Oct. 16, 2008
8. JP 2008 239,510, Low-viscous transparent compositions showing water-induced thickening property, Shiseido Co., Ltd., Japan, Oct. 9, 2008
9. JP 2008 247,846, Water-in-oil-type cosmetic makeup remover, Kosei Co., Ltd., Japan, Oct. 16, 2008
10. JP 2008 247,785, W/O emulsions having cleansing effect and makeup base effect, containing silicones, dextrin fatty acid esters, and oils, Narisu Cosmetic Co., Ltd., Oct. 16, 2008
11. WO 2008 122,481, UV light-protective agent based on mixed inorganic-organic systems, BASF SE, Germany, Oct. 16, 2008
12. WO 2008 119,841, Compositions comprising benzyl alcohol derivatives and further antimicrobial active compounds, Symrise G.m.b.H. & Co. KG, Germany, Oct. 9, 2008
13. WO 2008 119,428, Photostable composition comprising diethylhexyl radical and ethylhexyl methoxycinnamate, Merck Patent GmbH, Germany, Oct. 9, 2008
14. TF Tadros et al., Personal care emulsions based on surfactant-biopolymer mixtures: correlation of rheological parameters with sensory attributes, Colloids and Interface Sci Series 4 107–126 (2008)
15. ME Carlotti et al., O/W moisturizing emulsions with saccharose palmitate and saccharose stearate, J Dispersion Sci Tech 29(3) 375–386 (2008) (in English)
16. S Freimund et al., Yeast-derived beta-glucan as a novel carrier for cosmetic substances, SOFW Journal 134(8) 35–36, 38–40 (2008) ( in German)
17. US 7,435,424, High unsaponifiables for cosmetics and pharmaceuticals, International Flora Technologies Ltd., USA, Oct. 14, 2008
18. US 2008 255,015, Composition based on glycerol ether/polyol mixtures, Air Liquide Sante, France, Oct. 16, 2008



Footnote A

aArlatone V-100 (INCI: Steareth-100 (and) Steareth-2 (and) Glycerol Stearate Citrate (and) Sucrose (and) Mannan (and) Xanthan Gum) and Arlatone V-175 (INCI: Sucrose Palmitate (and) Glycerol Stearate  (and) Glycerol Stearate Citrate (and) Sucrose (and) Mannan (and) Xanthan Gum) are products of Croda Inc.

Formula 1. Shampoo Composition5

Laureth-5 carboxylic acid 1.80% w/w
Coco-glucoside (Plantacare-818, Cognis) 11.00
Cocamidopropyl betaine 2.60
Vinylformamide/vinylformamine copolymer (Lupamin-9030, BASF) 1.00
Preservatives qs
Fragrance (parfum) qs
pH-adjusting agents qs
Water (aqua) qs to 100.00

Formula 2. Shampoo with an esterquat6

Ceteareth (Hostacerin T-3, Clariant) 1.50% w/w
Ceteareth-3 (and) cetyl alcohol 3.00
Behentrimonium chloride (Genamin KDMP, Clariant) 2.50
Behentrimonium chloride diethanolamine esterquat 3.00
Fragrance (parfum) 0.30
Pigments qs
Preservative qs
Citric acid, 10% qs
Water (aqua) qs to 100.00

Formula 3. Aerosol hair conditioner7

Dimethicone 18.10% w/w
Sodium dilauramidoglutamide lysine (Pellicer L 30, Asahi Kasei) 1.00
Polyquaternium-10 0.01
Alcohol 5.00
Behenyltrimethylammonium chloride 0.40
Methylparaben 0.10
Glycerin 5.00
Fragrance (parfum) 0.10
Water (aqua) qs to 100.00

Formula 4. Hair conditioner8

Dicocoylethyl hydroxyethyhlmonium methosulfate (and) propylene glycol (Dehyquart l80, Cognis) 30.00%w/w
Isostearyl lactate 30.00
Dipropylene glycol 30.00
Polyoxyethylene glycerin monoisostearate 1.00
Water (aqua) qs to 100.00

Formula 5. W/O makeup remover9

Cetyl PEG/PPG-10/ 1 dimethicone (Abil EM-90, Degussa) 1.00% w/w
Isoparaffin (IP Solvent 2028MU) 8.00
Dextrin palmitate/ ethylhexanoate (Rheopearl TT, Ciba) 1.00
Propylene glycol dicaprate (Myritol GTEH, Cognis) 1.00
Mineral oil 1.00
Butylene glycol 16.00
Methylparaben  0.15
Sodium chloride 0.30
Water (aqua) qs to 100.00

Formula 6. W/O skin cleanser10

Cetyl PEG/PPG-10/ 1 dimethicone (Abil EM-90, Degussa) 2.00% w/w
Cyclomethicone 10.00
Dimethicone 6.00
Dimethicone (and) dimethicone/vinyl dimethicone crosspolymer (KSG-16, Shin-Etsu) 5.00
Water (aqua) 60.90
Sodium chloride 1.00
1,3-Butylene glycol 10.00
Ethanol 5.00
Methylparaben 0.10

Formula 7. Inorganic-organic sunscreen11

Ethylhexyl methoxycinnamate 7.50% w/w
Benzophenone-3 2.00
INCI not provided (Rylo PG 11, Danisco) 0.80
Sorbitan stearate 1.00
Vitamin E acetate 0.50
Glyceryl stearate (and) PEG-100 stearate 3.00
PEG-40 hydrogenated castor oil 1.00
BASF Hybrid 3.00
Butyrospermum parkii (shea butter) (Cetiol SB45, Cognis) 1.00
C12-15 alkyl benzoate (Finsolv TN, Finetex) 6.50
Butylene glycol 5.00
Xanthan gum 0.30
Disodium EDTA 0.10
Allantoin 0.10
Polyacrylamide (and) C13-14 isoparaffiin (and) laureth-7 (Sepigel 305, Seppic) 1.00
Water (aqua) qs to 100.00

Formula 8. Sunscreen with new preservatives12

Potassium cetyl phosphate (and) hydrogenated palm glycerides (Emulsiphos 2/918520, Symrise) 1.00% w/w
Alpha-bisabolol 0.10
Cetearyl alcohol 1.50
Myristyl alcohol 1.00
Cetearyl ethylhexanoate 4.00
Stearyl heptanoate (and) stearyl caprylate 1.00
Cyclopentasiloxane (and) cyclohexasiloxane 0.50
Butyl methoxydibenzoylmethane 1.50
4-methylbenzylidene camphor  1.50
Ethylhexyl methoxycinnamate 8.00
VP/hexadecene copolymer 1.00
Acrylates/C10-30 alkyl acrylate crosspolymer 0.10
Pentylene glycol 2.00
Capryl glycol 0.50
Sodium hydroxide 0.50
Fragrance (parfum) 0.20
4-methylbenzyl alcohol 0.50
Water (aqua) qs to 100.00

Formula 9. Lip balm13

Diethylhexyl syringlidenemalonate (and) caprylic/capric triglyceride 5.00% w/w
Ethylene/propylene copolymer 4.00
Polyethylene 3.00
Triethylhexanoin 20.00
Petrolatum 30.00
C14-15 dialkyl dicarbonate 10.00
Ethylhexyl methoxycinnamate 5.00
Polybutene 5.00
Cetyl hexanoate 18.00

Formula 10. Moisturizing cream18

Arachidyl alcohol (and) behenyl alcohol (and) arachidyl glusoside (Montanov 202, Seppic) 5.00% w/w
Cetearyl Ethylhexanoate (Lanol 1688, Seppic) 20.00
Ethylheyl Glycerin (Sensiva SC 50, schülke) 1.00
Polyacrylate-13 (and) polyisobutene (and) polysorbate 20 (Sepiplus 400, Seppic) 0.20
Water (aqua) 64.30
Glycerol 9.40
Benzyl alcohol (and) methylchloroisothiazolinone (and) methylisothiazolinone (Euxyl K 100, schülke) 0.10

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