No.

12

July 1995

In This Issue A New Class of Cosmetic Ingredients APG: Innovative Surfactants Made From Sugar and Fat

Page

A New Class of Cosmetic Ingredients APG: Innovative Surfactants Made From Sugar and Fat Alkyl polyglycosides (APGs) are particularly suited for new formulation concepts with excellent ecological, dermatological and applicational properties. APGs are the surfactants of the nineties and result from a longterm development of fatty alcohols and their derivatives. The historical development of these glucose surfactants comprises almost 2 decades at Henkel. APGs are exclusively made on the basis of regrowable, vegetable raw materials. They display synergistic effects with classic surfactants and have a number of interesting, product specific influences on the hair and the skin. Alkyl polyglycosides are directly synthesized from glucose and fatty alcohol. They are termed the new surfactant generation because only few years ago scientists succeeded in developing synthesis conditions which permit

the production of quantities which are needed today on a technical scale. Natural vegetable oils are transformed on their way from the triglyceride to the cosmetic basic material. Fatty acids and fatty acid methyl esters are basic materials derived by splitting or transesterification and turn into fatty alcohols by catalytic high pressure hydration. These fatty alcohols represent a raw material stream for alkyl polyglycosides. Within the past 60 years Henkel has globally become the leading manufacturer of fatty alcohol on a vegetable basis. In the course of a year, approximately 170 billion tons of biomass develop on earth, 5 % of which are starch and sugar. Only a small portion of this huge, renewable raw material source is used industrially. Glucose substances are polyhydroxy compounds which are practically available without limits, have a high degree of purity and good ecological and toxicological properties. They are an alternative to ethylene oxide and may be used as a hydrophilic element for surfactants. (continued on page 16)

Cosmetic Applications Jrg Kahre Alkyl Polyglycosides Multifunctional Ingredients for the Cosmetics Industry

Skin Compatibility and Mildness Bettina Jackwerth Fatty Alcohol Polyglycosides a New Surfactant Generation with Outstanding Skin Compatibility 4 Biodegradation Josef Steber The Biodegradability of Mild Cosmetic Surfactants Based on Renewable Raw Materials Patent Situation Bernd Fabry APG An Overview of the Patent Situation

10

Skin Cleansing and Washing Effects Mathias Rohr / Karlheinz Schrader In Vivo Tests: Influence of Various Surfactants on the Skin 12

From Oils, Fats and Starch to Oleochemical Derivatives

Raw Materials Starch Oleochemical Basic Materials Glucose Derivatives Alkyl polyglycosides (APGs)

Oils and fats

Fatty acid methyl esters

Fatty alcohols

Fatty acids

Fatty alcohol ethoxylates Guerbet alcohols

Publishers Note This Skin Care Forum publication is intended to be an informal service for cosmetic professionals, researchers, and cosmetic educators /communicators worldwide. While striving to be accurate, we leave to our select readers all confirmations and interpretations provided, authored or published by indicated other sources. The Skin Care Forum is distributed free of charge to qualified recipients. APG, Plantaren and Texapon are trademarks of Henkel KGaA.

Fatty acid derivatives

Glycerine

Partial glycerides

Cosmetic Applications

Jrg Kahre Alkyl Polyglycosides Multifunctional Ingredients for the Cosmetics Industry Alkyl polyglycosides have first been mentioned in literature in 1893 by Emil Fischer (1). Due to their availability on a technical scale and after their market introduction by Henkel under the brand name Plantaren 1200 UP and Plantaren 2000 UP, alkyl polyglycosides have been subjected to numerous tests. Their toxicological, dermatological and ecological behavior can be considered as outstanding (2). From the pont of view of application, the properties of these surfactants have primarily been of major interest (3, 4). Due to their chemical structure (strong hydrophilic part: glucose residue; hydrophobic part: fatty alcohol residue), they have more superior active properties than other nonionic surfactants (Figure 1). Compared to fatty alcohol ethoxylates, the foaming power of alkyl polyglycosides is clearly stronger.
Figure 1 Plantaren Alkyl Polyglycosides

Dr. Jrg Kahre is a chemist and specializes in the sector of cosmetic waving agents and hair analysis. Since 1992 he has been head of the product development of new ingredients for hair treating agents. He furthermore deals with new application areas of alkyl polyglycosides.

Another basic property of surfactants is of great interest. Although alkyl polyglycosides cannot always be compared with specific thickeners, they have properties that modify the rheological properties. For example, alkyl polyglycosides influence the flowing behavior of highly concentrated ether sulfates. This influence is so strong that easily dilutable, well-pumpable, highly concentrated products such as Plantaren PS 10 can be offered on the market (6). Usually, highly concentrated ether sulfates show a distinct gel phase at concentrations of 30 45 % active substance. The integration of Plantaren in the formulation leads to products with easy handling during application. Another interesting application of this property also promotes the development of concentrates. For example a shampoo concentrate must have good flowing, dilution and distribution behavior. From the viewpoint of application, a cosmetic ingredient should in addition to its basic properties also have further positive effects perceivable in the final formulations. In agents for the cleansing of skin and hair, for example, they should influence the interaction between hair fibers and effects on skin and hair. Here, alkyl polyglycosides also display very interesting effects.

The cleansing effect of alkyl polyglycosides as compared to ether sulfates can be demonstrated impressively in the following experiment. Pig skin was soiled with sebum/carbon black and washed with water under defined conditions, a 3 % ether sulfate solution and 3 % alkyl polyglycoside solution; the surfactant content refers to the active substance content. A grey shade was then determined and evaluated with the aid of digital image processing. The results revealed that at this low active content of surfactant only Plantaren 1200 UP provided a wrinkle- and pore-deep cleansing. This result is of special interest for the development of facial cleansers and eye makeup removers. It is also important for shower gels and shampoos, since it is possible to reduce the active content without loosing the cleansing power. On hair it causes an increase of the dry combing work. Short to mediumlength as well as very fine hair is always problematic. In order to arrange a hairdo in the dry state which has stand, volume, hold and body, the interactions between the hair fibers must be increased. Measurements on hair strands show that alkyl polyglycosides increase their dry combing work. Therefore, alkyl polyglycosides are interesting ingredients for the formulation of products for fine hair. Apart from this, the synergistic effect between alkyl polyglycosides and cationic substances can be exploited to obtain particularly positive effects. On fine hair cationic products can lead to excessive load. However, they are necessary in order to reduce the wet combing work.

O H H H H O O O O O O

Plantaren 1200 Lauryl Polyglucose 12-16 Plantaren 2000 Decyl Polyglucose 8-16

1. Surfactant Properties and Applications In mixtures with conventional surfactants, alkyl polyglycosides stabilize the foam. In combination with acyl glutamates, they even produce a foam volume comparable to that of ether sulfates. This allows the development of particularly mild products with good or even very good foaming power. The foam structure of alkyl polyglycosides differs characteristically from that of other surfactants, for example ether sulfates (Figure 2).

Figure 2 Foam Structures of Alkyl Polyglycosides by Comparison with a Classic Standard Surfactant (30 times enlarged after 15 minutes) Standard Surfactant Sodium Laureth Sulfate foam bubbles New Product Type Lauryl Polyglucose foam bubbles

coarse-bubbled dry

polyedric unstable

fine-bubbled wet

round stable

Figure 3a APG A Multifunctional Cosmetic Ingredient (I) Properties extremely mild readily biodegradable good foamer viscosity modifier Use main or co-surfactant for all kind of cleansing preparations: shampoo shower bath foam bath facial wash

Figure 3b APG A Multifunctional Cosmetic Ingredient (II) Properties (Hair care products) emulsifying Use emulsions: hair rinses hair colours setting lotions styling gels permanent wave formulations volume and body formulations shampoos for fine or damaged hair pore and wrinkle-deep cleansing

setting properties curl retention no hydrolysis at alkaline pH-value improves tensile strength of hair modifies interaction of dry hair cleansing power

reduces peak viscosity of FAES pastes (e.g. Plantaren PS 10)

shampoo concentrates

By means of the synergistic effect between alkyl polyglycosides and specific cationic raw materials, the required concentration of cationic substances may be optimized. 2. Alkyl Polyglycosides in Non-surfactant Formulations The synergism with cationic surfactants as well as the emulsifying property of alkyl polyglycosides, in particular of the longer chain APGs, enables their application in O/W emulsions. Such emulsions can be used as rinse-off or leave-on-intensive conditioners for hair aftertreatment (6, 7). Their use in emulsions, the pH stability in the alkaline range, the easy combination with cationic substances and the surface activity also allow the application of alkyl polyglycosides in hair dyes. Another property of alkyl polyglycosides is that they increase the tensile strength of hair strands, which also speaks in favor of their use in dyes. They may furthermore be applied in waving agents. With the alkaline solubility it could be proved that alkyl polyglycosides may be utilized for the production of mild waving lotions with good reshaping effect (8). The alkaline solubility of hair means that under defined conditions cold-waved hair is treated with a caustic soda solution. The mass loss of the hair during this alkaline treatment is determined gravimetrically. It is a measure for the degree of reductive and oxidative damage to the hair.

Waving agents are products for the long-term styling of hair. Blow-drying lotions, styling foams, gels and waxes, in contrast, are intended for short-term reshaping and fixing of the hair. This requires film-forming properties of the ingredient. In addition to the traditionally used film-forming polymers, protein hydrolysates and alkyl polyglycosides also lead to film formation. The hair setting effects of a combination of alkyl polyglycosides with protein hydrolysates are comparable to those of a 2 % polyvinyl pyrrolidone solution (6, 7). The applications of alkyl polyglycosides described so far concerned agents for the cleansing and care of skin and hair. On account of the excellent mucosa compatibility, the good toxicological values as well as the good foaming behavior, alkyl polyglycosides can also be used for dental care both in toothpastes and mouthwashes or in two in one gels. These examples demonstrate that alkyl polyglycosides are cosmetic ingredients having a very broad range of application. With the increasing availability of alkyl polyglycosides, further new formulation concepts will become possible in the future and the range of applications will become even broader, thus opening a promising future for alkyl polyglycosides. Summary As shown in Figures 3a and 3b, alkyl polyglycosides are modern, multi-functional ingredients for the cosmetics industry. Their application spectrum clearly extends beyond that of surfactants. Alkyl polyglycosides are interesting and promising ingredients whose development potential is far from being exhausted. Many interesting

product innovations in cosmetics may be expected for the future, and alkyl polyglycosides will certainly make a major contribution. Bibliography
Fischer E.; Ber. 26 (1893) 2400 Matthies W. H.; Krchter H. U.; Steiling, W.; Weuthen M.; Skin and Mucous Membrane Compatibility of Alkyl Polyglycosides (APG); In: 18th IFSCC International Congress; The Cosmetic Image A Mosaic of Biosciences; Vol. 4; IFSCC (1994) 317-323 (3) Busch P.; Hensen H.; Tesmann H.; Alkylpolyglycoside eine neue Tensidgeneration fr die Kosmetik; Tenside Surfactants Deterg. 30 (1993) 116 -121 (4) Busch P.; Hensen H.; Krchter H. U.; Tesmann H.; Alkyl Polyglycosides Their Use in Cosmetics; Cosmetics and Toiletries Manufacture Worldwide 74 (1993) 123 -130 (5) Salka B.; Alkyl Polyglycosides: Properties and Applications; Cosmetics & Toiletries 108, No. 3 (1993) 89-94 (6) Busch P.; Hensen H.; Kahre J.; Salka B.; Tesmann H.; Alkylpolyglycoside neue Anwendungen in Haarbehandlungsmitteln; In: Verlag fr chemische Industrie (ed.): 40. Jahrestagung der SEPAWA (1993) 23-29 (7) Busch P.; Hensen H.; Kahre J. Tesmann H.; Alkyl Polyglycosides A New Cosmetic Concept for Mildness and Care; Agro-Food-Industry hi-tech 9/10 (1994) 23-28 (8) Kahre J.; Goebels D.; Einflsse von Tensiden auf die Wirkung von Wellmitteln am Haar; In: Verlag fr chemische Industrie (ed.): 41. Jahrestagung der SEPAWA (1994) 36-41
(1) (2)

Skin Compatibility and Mildness

Bettina Jackwerth Fatty Alcohol Polyglycosides a New Surfactant Generation with Outstanding Skin Compatibility 1. Introduction For cosmetics developers fatty alcohol polyglycosides represent a new surfactant generation which is marked by a combination of desired application properties with good environmental compatibility and an outstanding dermatological compatibility. The cleansing properties of surfactants are more or less linked with undesired effects on skin (1). Owing to changing consumer habits and thus altered demands on skin cleansing agents over the last decades, an improved compatibility has become more and more important. This raises new possibilities for particularly skin-friendly surfactants such as fatty alcohol polyglycosides (2). This article describes the outstanding skin compatibility of the fatty alcohol polyglycosides, using the example of Plantaren 1200 (lauryl polyglucose, base: C 12 - C 16 fatty alcohol), Plantaren 2000 (decyl polyglucose, base: C 8 - C 16 fatty alcohol) and Plantaren PS 10 (lauryl polyglucose and sodium laureth sulfate). The example of sodium laureth sulfate (sodium lauryl ether sulfate with 2 EO) reveals how the skin compatibility of conventional surfactants can be improved by adding fatty alcohol polyglycosides. 2. Methods for the Examination of the Skin Compatibility of Surfactants In vitro tests as well as in vivo studies on human skin play a role in evaluating the compatibility of surfactants and surfactant mixtures. The chicken egg test (HET-CAM) is presented as an example for in vitro tests. For in vivo methods, the modified Duhring Chamber test, the arm-flex wash test and a consumer test are described. 2.1 In Vitro Tests Chicken Egg Test (HET-CAM) The local irritation potential of the test substances can be evaluated comparatively on the chorionallantois membrane (CAM) of incubated chicken eggs. The chicken egg test also serves as an 4

Biologist Bettina Jackwerth is in charge of cosmetic products at Henkel's Department of Dermatology. Major emphasis of her work in dermatology lies in a consultant activity with regard to the optimization of formulations under the aspects of skin compatibility and the demonstration of product effects on the skin.

reference substance and reference quantity for the determination of the relative irritation scores of the test samples (Figure 3, 4). This anionic standard surfactant is widely used in all types of washing and cleansing products and is regarded as having a good skin compatibility. This method only takes into consideration effects which can be assessed objectively and is considered to be very skin-friendly. For the interpretation of the findings it must be considered that the modified Duhring Chamber test for rinse off products is carried out under intensified test conditions. Since the contact time is clearly longer than during normal application and since the test conditions are occlusive the superficial skin layers swell, thus making penetration of the substances into the skin easier. Therefore, the results of this test system should only be interpreted together with an evaluation of the compatibility in an application-oriented test. Arm-Flex Wash Test The arm-flex wash test represents a standardized method for the applicationoriented screening of surfactants and surfactant formulations. Under controlled conditions 20 test subjects wash their sensitive arm flex with the test samples. Since the washing occurs twice a day over 2 weeks (weekends excluded) and no care product is applied in the application area, test conditions are also intensified so that highly compatible test substances can also be distinguished. In addition to visible findings such as erythema and squamation, the arm-flex wash test also evaluates subjective findings, e.g. itching, prickling, burning and tension (1). The subjective effects are registered both before and during washing. As in the Duhring Chamber test, on the basis of individual evaluations for every product an irritation score is determined for the

alternative method for the evaluation of mucosa compatibility. A mixture of specific fatty alcohol ether sulfates (Texapon ASV) is used as a reference substance for this method. The irritation potential of the test substances is divided by the irritation potential of Texapon ASV. The resulting irritation ratio Q serves as an evaluation measure for mucosa compatibility (3). 2.2 In Vivo Tests There are standardized methods for the in vivo evaluation of skin compatibility; contact time, contact frequency and type of application are gradually adjusted to practical application conditions (Figure 1). Modified Duhring Chamber Test The occlusive, single application Duhring Chamber Test, modified according to the Soap Chamber test developed by Frosch and Kligman (4), is above all suitable for the screening of surfactants. By means of specific plasters with aluminum chambers, the diluted test substances are applied for 24 hours on the backs of 20 test subjects. The resulting findings, i.e. erythema, squamation and swelling, are evaluated according to a defined system up to 72 hours after removal of the plaster and expressed as irritation score per substance. Sodium laureth sulfate (1% active substance) is used as a
Figure 1 Test Strategy

Test strategy for the dermatological examination of surfactants, surfactant mixtures and finished products with step by step approximation to practical application conditions. Method Modified Duhring Chamber test Arm-flex wash test Test principle single, long-term occlusive application repeated open application under intensified test conditions repeated application under normal test conditions application situation Strategy laboratory model

Consumer test

Figure 2 HET-CAM Test Irritation potential represented as irritation ratio Q for Plantaren 1200 (lauryl polyglucose, orange bars) in relation to Texapon ASV (mixture of specific fatty alcohol ether sulfates, yellow bars) on the chorionallantois membrane. Irritation ratio Q 1,6 1,4 1,2 1,0 0,8 0,6 0,4 0,2 0 50 40 30 20 10 5 5 Test concentration (% AS)

3. Test Results We investigated the following test samples to evaluate the compatibility of Plantaren products as well as that of surfactant mixtures with Plantaren: Surfactants Formulation 1 (F1): Sodium laureth sulfate Formulation 2 (F 2): Lauryl polyglucose (Plantaren 1200) Formulation 3 (F 3): Decyl polyglucose (Plantaren 2000) Formulation 4 (F 4): Sodium laureth sulfate (and) lauryl polyglucose (Plantaren PS 10) Mixtures with Plantaren 1200 Formulation 5 (F 5): Sodium laureth sulfate (3 parts) and lauryl polyglucose (1 part) Formulation 6 (F 6): Sodium laureth sulfate (1 part) and lauryl polyglucose (1 part) Formulation 7 (F 7): Sodium laureth sulfate (1 part) and lauryl polyglucose (3 parts) Mixtures with Plantaren 2000 Formulation 8 (F 8): Sodium laureth sulfate (3 parts) and decyl polyglucose (1 part) Formulation 9 (F 9): Sodium laureth sulfate (1 part) and decyl polyglucose (1 part) Formulation 10 (F10): Sodium laureth sulfate (1 part) and decyl polyglucose (3 parts) Chicken Egg Test In this test system lauryl polyglucose shows an outstanding compatibility. Lauryl polyglucose reaches the irritaFigure 3 Modified Duhring Chamber Test Erythema Formation Improvement of skin compatibility of sodium laureth sulfate mixed with decyl polyglucose using the example of erythema formation. Relative irritation score as compared to pure sodium laureth sulfate (1% AS =100 %). Test concentration 1.4 % AS; n = 20 Relative irritation score (%) 140
120 100 80 60 40 20 0 F1 F8 F9 F10 F3

tion potential of Texapon ASV (5 % AS) (Figure 2) only at a concentration of 40 % AS. In contrast to this the irritation potential of decyl polyglucose (no figure) is higher than that of the reference substance at all concentrations. Therefore lauryl polyglucose should be used for products which claim good mucosa compatibility. Modified Duhring Chamber Test Figures 3 and 4 represent the results for erythema formation. Squamation shows an analogous behavior. The test samples did not cause swellings. In a first step mixtures of sodium laureth sulfate with decyl polyglucose were compared with decyl polyglucose (Figure 3, test concentration 1.4 % AS). If sodium laureth sulfate (F1) is substituted step by step with fatty alcohol polyglycoside (F 8, F 9, F10), this leads to a clear improvement of skin compatibility, which is expressed in the reduction of the relative irritation scores (Figure 3). A mixing ratio of three parts sodium laureth sulfate with one part decyl polyglucose (F 8) improves the skin compatibility by approx. 40 percent points. A mixing ratio of one part sodium laureth sulfate with three parts decyl polyglucose (F10) reduces the irritation potential of the mixture as compared to sodium laureth sulfate by approx. 97 % points. The relative irritation potential of pure Plantaren (F 3) is only 8 % of the irritation potential of sodium laureth sulfate with the same concentration. Furthermore, the Plantaren products 1200 and 2000 were compared in 1% AS and 3 % AS concentrations (Figure 4a, 4b). For both concentrations the irritation potential is clearly lower than that of the reference substance sodium laureth sulfate (1% AS). Consequently, the Plantaren products display an outstanding skin compatibility for surfactants. Unlike the chicken egg test, this test model does not reveal a clear dependence of the compatibility upon the chain length of the alkyl residue. Plantaren PS 10 is a commercial mixture which consists of a highly concentrated ether sulfate as a main component with a medium-chain fatty alcohol polyglucoside as a co-surfactant (5). This mixture was also examined with a concentration of 1% and 3 % AS in the modified Duhring Chamber test (Figure 4c). As expected, this mixture with a concentration of 1% AS shows a better skin compatibility than pure sodium laureth sulfate. With three times 5

different criteria. Again sodium laureth sulfate (10 % active substance) is used as a reference substance. The expressiveness of the arm-flex wash test and the differentiation of the test substances is still improved by means of physical measuring techniques. Before the first and after the last washing the transepidermal water loss (TEWL) is measured with an evaporimeter as a measure of the barrier damage. Both visible and invisible damages of superficial skin layers can be quantified in this way. The visual evaluation by the test conductor, the subjective evaluation of the test subjects and the physical-quantitative measurement, allow precise statements about the effects of the formulations on skin. Consumer Test The consumer test represents the last step prior to product launch. At least 50 test subjects apply the end product (e.g. shower gel or shampoo), at home under usual application conditions over a test period of 6 weeks. This test reveals how the good compatibility of the fatty alcohol polyglycosides is experienced by the consumer under practical conditions. At the end of the test period, the application properties and the skin compatibility of the products are documented with the aid of a questionnaire.

Figure 4 Modified Duhring Chamber Test Erythema Formation Relative irritation potential of Plantaren 1200 (a), Plantaren 2000 (b) and Plantaren PS 10 (c) in a concentration of 1% AS and 3 % AS as compared to sodium laureth sulfate in 1% AS using the example of erythema formation; n = 20 a) Plantaren 1200 Relative irritation score (%) 100
80 60 40 20 0 1% AS 3% AS

Figure 5 Arm-flex Wash Test Improvement of the skin compatibility of sodium laureth sulfate mixed with fatty alcohol polyglucosides. Relative irritation score as compared to sodium laureth sulfate (= 100 %) using the examples of erythema formation (a), squamation (b), sensoric parameters (c) and transepidermal water loss (TEWL) (d). Test concentration 10 % AS; n = 20 a) erythema formation Relative irritation score (%) 120 100 80 60 40 20 0 F1 F5 F8 c) sensoric parameters Relative irritation score (%) 120 100 80 60 40 20 0 F1 F5 F8 b) squamation Relative irritation score (%) 120 100 80 60 40 20 0 F1 F5 F8

F2

F3

F2

F3

b) Plantaren 2000 Relative irritation score (%) 100

80 60 40 20 0 1% AS 3% AS

F2

F3

d) transepidermal water loss (TEWL) Relative TEWL (%) 120 100 *significant at p < 0.001 80 60 40 20 0 E1 E5 E8 E2 E3

c) Plantaren PS 10 Relative irritation score (%) 140 120 100 80 60 40 20 0 1% AS

3% AS

the AS content, the irritation potential is only 17% higher than that of sodium laureth sulfate with 1% AS. Arm-Flex Wash Test In the arm-flex wash test, lauryl polyglucose, decyl polyglucose as well as surfactant mixtures from sodium laureth sulfate with lauryl polyglucose (F 5) and sodium laureth sulfate with decyl polyglucose (F 8), with a ratio of 3 :1 each, were examined at a test concentration of 10 % AS. Pure sodium laureth sulfate (10 % AS) was used as a reference. The irritation score and /or the transepidermal water loss was put in relation to the reference in order to ensure comparability.

Figure 5 illustrates the relative irritation score for erythema formation (Figure 5a) and squamation as an indicator for the drying of skin (Figure 5b), the relative irritation score for the sensorial parameters (Figure 5c) as well as the relative change of the transepidermal water loss (Figure 5d). The substitution of 25 % sodium laureth sulfate with a fatty alcohol polyglucoside (F 5, F 8) leads to a reduction of the visible findings, erythema and squamation, by approximately 20 to 40 %. The skin protective effect can be recognized even more clearly from the subjective, negative sensations. Here, improvements by approximately 70 % can be achieved. As compared to pure sodium laureth sulfate, the Plantaren products (F 2, F 3) reduce erythema formation by 80 % to 90 % and squamation by 70 to 90 %. Subjective negative sensations disappear almost completely. The transepidermal water loss (Figure 5d) is a measure of the barrier damage and therefore of the potential drying of skin. It is reduced by approx. 5 to 20 % through addition of fatty alcohol polyglucoside to sodium laureth sulfate (F 5, F 8). The pure Plantaren products 1200 and 2000 achieve a significant reduction of the barrier damage (p < 0.001) by approx. 65 to 75 % (F 2, F 3). This is an outstanding result for washing-active substances.

The number of negative sensations during washing is represented in Figure 6. Subjective negative sensations during application of a product provide information about the skin sensitivity which is increased by the surfactant application to varying extents in this test system. Over the entire test period, the test subjects describe negative sensations in 74 washings during application of the reference substance sodium laureth sulfate. A substitution of 25 % sodium laureth sulfate with fatty alcohol polyglycoside (F 5, F 8) leads to a reduction of the skin damage and thus the skin sensitivity so clearly that negative sensations are described only in 19 and /or 24 washings. For pure Plantaren products there are almost no subjective findings throughout the entire test period, in spite of intensified test conditions. The positive influence of fatty alcohol polyglycosides on the compatibility of sodium laureth sulfate is also reflected in the smaller number of test subjects who stopped the test early (Figure 7a). Through substitution of 25 % sodium laureth sulfate with a Plantaren product it is already reduced by 50 % (Figure 7a, F 5 and F 8 compared to F1). In the case of pure fatty alcohol polyglycosides, no test subject stopped the test within the entire application period of 14 days in spite of intensified conditions (F 2, F 3).

In accordance with the better compatibility of the mixtures (F 5, F 8) as compared to pure sodium laureth sulfate, the test was stopped at a later time during the two-week test phase (Figure 7b). While 12 test subjects stopped the application of sodium laureth sulfate after 15.8 washings on average, the application of the surfactant mixtures was stopped by only 6 (F 8) and /or 7 test subjects (F 5) after an average of 17 to 18 washings. To sum up, it can be stated that this application-oriented but intensified test model proves the outstanding skin compatibility of the pure Plantaren products in all three evaluation methods, i.e. visually, physically and subjectively. We were able to demonstrate the relevance of the results from the tests with surfactant mixtures and pure fatty alcohol polyglucosides for the practical application situation in consumer tests with shower gel and foam bath formulations. The formulations with Plantaren achieved the best results with respect to a general compatibility and the subjective evaluation by the test subjects. 4. Summary In mixtures, Plantaren products as substitutes of sodium laureth sulfate lead to a significant reduction of the irritation potential of the conventional surfactants on human skin. In different test models, visible skin damage is clearly reduced by the application of the mixtures. An even stronger improvement is obtained with respect to subjective negative sensations. The measurement of the transepidermal water loss objectively
Figure 6 Arm-flex Wash Test Improvement of skin compatibility of sodium laureth sulfate mixed with fatty alcohol polyglucosides using the example of the number of negative sensations during application. Test concentration 10 % AS; n = 20 Number of negative sensations during application 80
60

Figure 7 Arm-flex Wash Test Improvement of skin compatibility of sodium laureth sulfate mixed with fatty alcohol polyglucosides. Figure 7a shows the number of test subjects who stopped the test early. Figure 7b shows the average number of washings per test subject group after which the test was stopped. The mixtures of sodium laureth sulfate with fatty alcohol polyglucosides (F 5, F 8) can on average be applied for a longer time before the test is stopped. In the case of the pure Plantaren products (F 2, F 3) the test is carried out over 14 days by all volunteers. Test concentration 10 % AS; n = 20 a) Number of test subj. who stopped test early 14 12 10 8 10 6 4 2 0 F1 F5 F8 F2 F3 0 F1 F5 F8 F2 F3 5 15 b) Number of washings 20

demonstrates that the skin barrier damage is smaller when fatty alcohol polyglycosides are added. This minimizes the drying of skin, above all in the case of repeated washing. In correlation to this, other tests show that the skin moisture is less impaired by the products Plantaren 1200 and 2000 and /or a mixture of sodium laureth sulfate with decyl polyglucose (F 8) than by the pure sodium laureth sulfate (5). Fatty alcohol polyglycosides, a new generation of non-ionic surfactants, offer the possibility to clearly improve the compatibility of cosmetic cleansing products. This is particularly important where the skin of the user must not be damaged in addition to existing internal and external influences. This is of special importance for aged skin as well as for baby skin. Furthermore, it is relevant for skin changes where the dermatologist often recommends special cosmetic agents, e.g. mild formulations selected from the cleansing sector. Fatty alcohol polyglycosides are not only intended to minimize further damage to the skin. As can be seen from the improvement of the subjective, negative sensations, formulations on the basis of fatty alcohol polyglycosides also show a better compatibility on pre-damaged skin. Fatty alcohol polyglycosides are therefore above all suitable for the formulation of products for sensitive skin that claim outstanding skin compatibility. The constantly growing number of persons with sensitive skin raises new possibilities for the future.

For the developer it is an additional advantage that the outstanding compatibility of the Plantaren products can be combined with a reduced active substance content in the end product while maintaining the same foam volume and /or the same skin cleansing capacity (5). For the respective product type and the specific requirements, e.g. with respect to skin or mucosa compatibility, the ideal surfactant combination must be found and its properties must then be examined in appropriate test systems. Bibliography
(1) Jackwerth, B.; Krchter, H.- U.; Matthies, W.; Dermatologische Prfmethoden zur Optimierung milder Tensidprparate; Parfmerie und Kosmetik 3 (1993) 134 -141 (2) Fabry, B.; Tenside, Vergangenheit, Gegenwart und zuknftige Entwicklungen; SFW Journal 7 (1994) 378 - 386 (3) Sterzel, W.; Bartnik, F. G.; Matthies, W.; Kstner, W.; Knstler, K.; Comparison of Two in Vitro and Two in Vivo Methods for the Measurement of Irritancy; Toxic. in Vitro 4 (4/5) (1990) 698 -701 (4) Frosch, P .; Kligmann, A. M.; The Soap Chamber Test; J. Am. Acad. Dermatol. 1 (1979) 35 - 41 (5) Busch, P.; Hensen, H.; Kahre, J.; Salka, B.; Tesmann, H.; Alkylpolyglycoside Neue Anwendungen in Haarbehandlungsmitteln; SEPAWAJahrestagung (1993); Tagungsband 23 -29 (6) Busch, P.; Hensen, H.; Tesmann, H.; Alkylpolyglycoside Eine neue Tensidgeneration fr die Kosmetik; Tenside Surfactants Det. 30 (1993) 116 -121

40

20

0 F1 F5 F8 F2 F3

The Biodegradability of Mild Cosmetic Surfactants Based on Renewable Raw Materials Josef Steber The major part of cosmetic product ingredients reach the environment after their use. This happens because they are destined to reach the wastewater as rinse-off products or because at least a portion of them is washed off during body cleansing. Due to the physicochemical and biological properties of chemical compounds they spread in the various environmental areas such as surface waters, sediments, sludge, soils, etc. If not removed by degradation processes, they may have a toxic influence on living organisms in the environment. A far-sighted evaluation of potential ecological hazards should be based on the knowledge of fate- and effectrelevant properties of the product ingredients, i.e. particularly of their biodegradability and ecotoxicity of the product components. From these data and by taking the concrete environmental situation into account (e.g. amount of products used, sewage treatment situation, effluent dilution factors in rivers, etc.) an estimation of the predicted environmental concentration (PEC) and the predicted (ecotoxicological) no effect concentration (PNEC) can be made. Mathematically expressed a hazard is given when the ratio PEC/PNEC is 1. No hazard is to be anticipated if PEC < PNEC (1). Primary and Ultimate Biodegradation Biodegradation is the most important mechanism which is responsible for the irreversible removal of organic compounds such as surfactants from aqueous and soil environments. Biodegradation is a multistep process starting with the transformation of the parent compound into a first degradation product (primary degradation) and forming, in the end, mineralization products (carbon dioxide, water) and bacterial biomass (ultimate or total degradation) (2). The primary degradation of a surfactant, which is of significance from an ecological point of view, as well as its ultimate biodegradation, which plays an important long-term role in the environment, can be assessed by standardized and internationally applied test methods (OECD, EC), see Figure 1. Normally the surface-activity and thus the ecotoxicity of a surfactant is significantly reduced in 8

Dr. Josef Steber is head of Henkels Ecological Department. His research topics include experimental tests and evaluations of the biodegradability of cosmetic ingredients.

the primary degradation steps. The primary degradation of many surfactants can be proven by the application of specific analytical procedures. These analytical methods are often applicable to the whole group of chemically related substances. Examples of these are the MBAS (methylene-blue active substance) and BiAS (bismuth active substance) loss for anionic and nonionic surfactants. The so-called DSBAS (disulfin-blue active substance) method is another analytical method for cationic surfactants. With regard to alkyl polyglycosides, which is a very important surfactant group for cosmetic products, there is no specific analysis group procedure. Therefore, an evaluation of the biological degradation behavior of this surfactant group, which is completely

based on renewable raw materials, strictly occurs by determining the ultimate biodegradability. However, the degradation rates associated with the primary degradation of a surfactant are higher than those associated with the ultimate degradation. The ultimate degradation is measured by so-called sum parameters which are not specific for the particular substance. Examples of these sum parameters are the development of CO2 or the oxygen demand due to the mineralization process (Biological Oxygen Demand, BOD) or the reduction of the dissolved organic carbon (DOC) of the test compound. Test Procedures for Determining Biodegradability A determination of the degradability of surfactants usually starts with screening tests which, due to their stringency, are simple but informative test methods. Under the given conditions of the OECD tests for ready biodegradability, which also comprise the closed bottle test (OECD 301 D), another strict test procedure, and the modified OECD screening test (OECD 301 E) many surfactants based on renewable raw materials prove to be readily biodegradable (Figure 2). Examples of this are the following

Figure 1 Standardized Procedures for Determining the Biodegradability of Substances Screening tests Characteristics Sewage treatment plant simul. tests inflow outflow

G G G G

single addition of test substance test substance is C source duration of test up to 4 weeks stringent assessment

continuous dosage of test substance and synthetic wastewater G retention time: 3-6 hours G evaluation close to reality
G

Examples

Primary degradation (relevant for detergent legislation: anionic and nonionic surfactants) OECD confirmatory test: demand 80 % (MBAS, BiAS) OECD screening test: demand 80 % (MBAS, BiAS)

Ultimate degradation (relevant for Chemicals Law, EC classification hazardous for the environment) OECD tests for ready biodegradability: G closed bottle test: 60 % O2 consumption G modi. OECD screen. test: 70% carbon removal* G CO2 evolutions test: 60% CO2 formation * pass value for ready biodegradability Coupled units test: measurement of DOC removal [%]

Figure 2 Biodegradation of Alkyl Polyglycosides (APG) Test method Closed bottle test Modified OECD screening test readily biodegradable? Model sewage treatment plant: Coupled units test Metabolite test free from poorly degradable metabolites? ECETOC screening test anaerobically degradable? *By analogy Analytical parameters % BOD/CAD % C removal % C removal % C removal C12 /16 APG (Plantaren 1200) 71-73 72-> 80 yes 89 2 101.8 2.0 yes 98 yes C8 /16 APG (Plantaren 2000) 73 -78 yes yes* yes*

% CO2 + CH4

groups of surfactants: alkyl polyglycosides, fatty alcohol sulfates, fatty alcohol ether sulfates and fatty alcohol ethoxylates. As agreed internationally, such substances are easily and ultimately biodegraded, namely in sewage treatment plants and in surface water. This thesis was totally confirmed by investigations into alkyl polyglycosides by means of the coupled units test (OECD 303 A). This is a further, internationally applied test system which simulates the degradation situation in a biological sewage treatment plant. The coupled units test requires a continuous dosage of test substances and nutrients and thus represents a realistic model to test the biodegradability of substances in the competitive situation with a surplus of readily degradable substances (synthetic wastewater). Here, an ultimate biodegradation of approximately 90 % can be shown under realistic, yet rather conservative conditions by current standards of wastewater treatment practice (Figure 2). Alkyl polyglycosides remain in the plant for an average of 3 hours, while under practical conditions 6 -12 hours or more are common for modern plants. This high ultimate degradation value means that alkyl polyglycoside surfactants in the wastewater are almost completely transformed into products which are reintegrated into the natural circuit (carbon dioxide, bacterial biomass). Due to their lower bacteria density substances are degraded at low speed in a receiving stream. Since the same degradation processes take place in a receiving river as in the sewage treatment plant, there is principally no doubt that a complete and ready biodegration of materials which have not yet been degraded in the sewage treatment plant is achieved in the surface waters provided that they are readily degradable compounds.

Metabolite Test To improve the evaluation and documentation of the completeness of the ultimate biodegradation of surfactants and other chemical compounds, further tests are performed on such important cosmetic ingredients as alkyl polyglycosides. These tests are more elaborate than the broadly applied standardized tests and are sometimes very comprehensive. Despite positive results achieved in the above mentioned screening and simulation tests the conclusion to be drawn about a ready and ultimately complete degradation is mainly based on the practical experience gained from many chemical

compounds tested and assessed in the past. Nevertheless, the question always comes up again if organic material which was not degraded in the test period might contain small amounts of intermediates with properties which are unknown and thus perhaps critical for the environment. On the experimental basis of the coupled units test the test to detect stable degradation intermediates (metabolite test), which was developed by us, helps answer these questions (2). In contrast to the sewage treatment plant simulation test (OECD 303 A) the wastewater, which is treated in the test plant, is reused each day as an influent after feeding in a concentrate of the test substance and nutrients (Figure 3). Thus a circuit is achieved, which always gives the bacteria the chance to cope with the test compound and its intermediates under competitive conditions (cf presence of readily degradable nutrients). Since these tests are run over several months corresponding to approximately 100 cycles even very small amounts of recalcitrant metabolites accumulate and are detectable analytically. For alkyl polyglycosides it could be shown that the biodegradation of this surfactant is achieved without residues because the measured removal of the organic carbon does not leave room even for the smallest possible

Figure 3 Further Tests on Biodegradation: How Complete is the Degradation? Problem Test method Characteristics Formation of poorly degradable intermediates? Metabolite test
(concentration)

Degradation also under anaerobic conditions? ECETOC test / 14 C digester test

pressure measurement apparatus

synthetic wastewater + test substance

continuous test with recycling of the effluent and new dosage of substance G duration of test: up to 3 months
G

G G

static test with sludge duration of test: 4 - 8 weeks

Measurement parameters

C concentration in influent and effluent of test and control plants is measured. C removal [%] is investigated for significant difference (theoretical) formation of an intermediate with more than 1 C atom must be excluded (basis of calculation: amount of C atoms of test substance)

measurement of formation of digester gas [% of organic C of test substance]: - measurement of pressure - 14 CO2 + 14 CH4 30 %: indication of anaerobic (primary) degradation 60 %: good anaerobic ultimate biodegradation

Evaluation

metabolite, a C1 compound (Figure 2). Thus the complete biodegradability of alkyl polyglycosides could be proven experimentally. Anaerobic Degradation The question if surfactants can undergo complete ultimate biodegradation in the environment has yet another dimension. Surfactants have a marked tendency to adsorb on sludge and sediment particles. Considerable amounts of surfactants therefore reach environmental areas where no oxygen is present for the biodegradation processes of microorganisms, e.g. in septic tanks, digesters, sewage treatment plants, sediments of strongly polluted aqueous environments and, partly, soils. Thus, a comprehensive evaluation of the environmental fate of surfactants also has to address their anaerobic biodegradation behavior (2). In the ECETOC screening test for the assessment of anaerobic degradability, to whose development we have contributed and which is now widely applied, the ultimate degradation of a test substance is assessed by measurement of the digester gas (carbon dioxide and methane), see Figure 3. In this screening test, which is regarded as a very stringent degradation procedure, alkyl polyglycosides have shown to be very well degradable under anaerobic conditions (Figure 2). This allows us to conclude that the representatives of this new generation of surfactants are biodegraded into natural end products under all microbial conditions, including aerobic and anaerobic conditions. Hence, they can be completely reintegrated into the natural circuit. Summary Due to their favourable ecotoxicological properties and their comprehensive assessment alkyl polyglycosides represent a surfactant group with an excellent environmental compatibility (3). This has led to the fact that alkyl polyglycosides as the first surfactant class have been categorized into a more favorable water hazard class (WGK 1) by the German Commission for the Assessment of Water-endangering Substances (KBwS). Bibliography
(1) Europische Gemeinschaft; Risk Assessment Directive 93/67/ EEC (2) Steber, J.; Wie vollstndig sind Tenside abbaubar? Test- und Auswertemethoden; Textilveredlung 26 (1991) 348 - 354 (3) Andree, H.; Middelhauve, B.; Mglichkeiten des Einsatzes von Alkylpolyglycosiden in Wasch- und Splmitteln; Tenside Surfactants Deterg. 28 (1991) 413 -418

Patent Situation

Bernd Fabry Alkyl Polyglycosides: An Overview of the Patent Situation Introduction Alkyl polyglycosides (APG surfactants) are nonionic surfactants which are based on renewable raw materials. They have excellent ecotoxicological properties and they are similar to anionic surfactants in their foaming and wetting power. The strong interest of the market in this surfactant class is reflected by the statistics of patent and literature publications (Figure 1). After carefully checking more than 1800 patent publications from Henkel and other companies on the alkyl polyglycoside sector as well as after concluding license agreements with Procter & Gamble and Kao Corp., alkyl polyglycosides should not be assessed more critically by Henkel customers than other standard surfactants. As can be seen, the increase in patent publications in particular over the past five years has been virtually exponential. At present approximately 20 to 30 new articles on APG surfactants are published every month; Henkel alone files 20 to 30 patents a year. If it is already quite difficult for the chemist in the patent department to cope with this flood of published or already granted patents or patents in the process of examination, then the product developer must be all the more overstretched by this task. Therefore, this article is intended to provide a short survey of the most important interrelationships and existing patent positions with emphasis being placed on cosmetics.
Figure 1 Development of Patent and Literature Publications Number of publications/patents 250 200 Source: Derwent 150 100 50 0 80 81 82 83 84 85 86 87 88 89 90 91 92 Year of appearance

After studying technical chemistry at the Technical University of Aachen Dr. Bernd Fabry received his doctorate on homogeneous-chemical hydrogenation processes. In 1986 he entered Henkel KGaA, Dsseldorf to work for the Research Department. In the beginning his work focused on the development of anionic surfactants and the analysis of oleochemical raw materials. In 1989 he joined the Patent Department and has been responsible for oleochemicals and surfactants since 1992.

1. Mixtures of Alkyl Polyglycosides with Anionic Surfactants Among the applicational patents, the European patent EP-B1 0070074 of Procter & Gamble plays a central role. This patent relates to foaming mixtures of alkyl polyglycosides with surfactants containing a sulfate, sulfonate and /or a carboxylate group. It can immediately be recognized that this combination covers virtually all anionic as well as all amphoteric surfactants with betaine structures. Corresponding patents exist for example in the U.S., Japan and Australia. The patent may be granted to customers of Henkel on the basis of a contract agreement. In the course of the opposition proceedings, based on a prior publication of Rohm & Haas (1), the patent was limited to mixtures with APG surfactants having a chain length of 12 to 18 carbon atoms. This means that mixtures of short-chain alkyl polyglycosides with for example 8 to 10 carbon atoms and anionic surfactants are largely in the public domain. One point which is often discussed in connection with this key patent is the average degree of polymerization (DP) of alkyl polyglycosides, which allows the characterization of overlapping homologue distributions. With regard to the DP the Procter & Gamble patent contains a lower limit of 1.5, but since this restriction was not necessary for the delimitation from the known state-of-the-art, this numerical value must probably be considered as an approximate value so that mixtures of anionic surfactants with alkyl polyglycosides types having a lower DP, for example 1.3, are covered.

10

Although EP-B1 0070074 basically discloses APG /anionic surfactant mixtures using the example of soaps, alkyl sulfates, alkylether sulfates, alkylbenzene sulfonates, olefin sulfonates, alkanesulfonates and alkyl betaines, the patent does leave room for selection inventions. Some examples are represented in Table 1. For the manufacturer of cosmetic products the combination of alkyl polyglycosides with mono- and /or dialkyl sulfosuccinates is certainly important; it is the subject of the European patent application EP-A1 0358216 of Kao Corp. A licence on this patent may be obtained by customers of Henkel KGaA within the framework of a licence agreement. A synergistic mixture on the basis of alkyl polyglycosides, betaines and protein fatty acid condensates is protected by the European patent EP-B1 0521965 of the Henkel KGaA. An application concerning alkyl polyglycosides /monoglyceride sulfate compounds is expected to be granted soon in the U.S. The European patent EP-B1 0384983 of Hls AG claims mixtures of APG surfactants with ether carboxylic acids. With regard to the state of the art, the patent had to be limited to unsaturated ethercarboxylic acids during the examination procedure. Here it must be mentioned that these patents are selection inventions, which if finally granted are dependent upon EP-B1 0070074. An exception is the combination of APG surfactants with alkyl phosphates (EP-A2 0324451, Kao Corp.) since the latter are not covered by the definition of anionic surfactants chosen in the Procter & Gamble patent.

2. Mixtures of Alkyl Polyglycosides with Nonionic Surfactants European patents EP-B1 0075995 and EP-B1 0075996 (Procter & Gamble) claim mixtures of alkyl polyglycosides and nonionic surfactants. Both patents have meanwhile been revoked in the final instance by the Technical Appeal Board of the European Patent Agency. However, this does not necessarily mean that mixtures of APG surfactants are basically free; with regard to the publication by Rohm & Haas this is at best true for the application of classical nonionic surfactants with shortchain APG surfactants (Table 2). Kao Corp. for example has filed applications for mixtures of alkyl polyglycosides with mixtures of nonionic surfactants with different HLB values as well as with sugar esters. The subject of WO 93 /07249 of Henkel Corp. are synergistic mixtures of short-chain and longer-chain APG types. 3. Mixtures of Alkyl Polyglycosides with Cationic Surfactants Mixtures of alkyl polyglycosides with classical cationic surfactants of the QAV type are to a large extent in the public domain. A patent application for combinations of APG surfactants with esterquats was filed by Henkel KGaA (WO 94 /06899). Cationic polymers are particularly important ingredients for the preparation of hair care and hair treatment agents. In the European patent EP-B1 0337354, which is currently involved in opposition proceedings,

Kao Corp. claims mixtures which contain APG surfactants and cationic polymers. Independent of the further fate of this patent, Henkel can grant licences on this patent to customers within the framework of an agreement with Kao Corp. 4. Mixtures of APG Surfactants with Further Additives From the large number of applications concerning mixtures of APG surfactants with further non-surfactant ingredients, let me list just a few examples: combination of alkyl polyglycosides with silicone derivatives (EP-A1 0398177) and /or selected antibacterial agents (EP-A1 0422508) from Kao Corp. as well as mixtures of long-chain alkyl polyglycosides and the corresponding fatty alcohols as self-emulsifying agents (WO 92 /06778, SEPPIC). However, the latter patent (a corresponding French patent already exists), seems to be neither new nor inventive. In the meantime, Henkel has raised nullity action against the French patent. 5. Summary For the chemist concerned with patent legislation, the question arises which lesson to draw from the extremely complex and complicated patent situation. Is there any chance to use alkyl polyglycosides without colliding with a large number of patents in the process of examination or in the opposition proceedings or of patents already granted? The answer to this question is as mentioned above a clear yes if one considers some simple rules: 1. The application of short-chain alkyl polyglycosides for example on the basis of C8 - C10 fatty alcohols is to a

Table 1 Claimed Combinations of Alkyl Polyglycosides with Anionic Surfactants APG + Soaps, LAS, FAS, FAES, AOS Betaines Protein fatty acid condensates + betaines Sulfosuccinates Ethercarboxylic acids Alkyl(ether)phosphates Fatty acid isethionates Acyl lactylate Reference Patentee

Table 2 Claimed Combinations of Alkyl Polyglycosides with Nonionic Surfactants APG surfactants + Polyglycol ether mixtures Sucrose fatty acid esters Alkyl polyglycosides Anionic surfactants + amineoxides Hydroxycarboxylic acid ester Reference Patentee

EP 0070074 EP 0521965 EP 0358216 EP 0384983 EP 0324451 EP 0075994 EP 0453238

Procter & Gamble Henkel Kao Hls Kao Staley Unilever

EP 0408965 EP 0409005 EO 93/07249 EP 0070076 EP 0258814

Kao Kao Henkel Procter & Gamble R.O.L.

11

large extent in the public domain. This is also true for the combination of long-chain alkyl polyglycosides with classical nonionic and cationic surfactants. 2. Mixtures of C12 - C18 alkyl polyglycosides with anionics which contain a carboxylate, sulfate and /or sulfonate group are protected by a Procter & Gamble patent. Accordingly, longchain APG surfactants cannot be used freely in combinations with the majority of anionic and amphoteric surfactants. 3. Many publications are unexamined patent applications which will not progress beyond this stage. However, they often confuse competitors and should therefore be thoroughly evaluated. Finally, it should be mentioned that Henkel KGaA concluded a licence agreement with Procter & Gamble Co. in 1993 and with Kao Corp. in 1994. The resulting merger of the most important patent portfolios in the field of APG surfactants (not only in terms of the number of patents), now provides Henkel customers with a broad range of cosmetic formulation possibilities which are sufficiently secure from the viewpoint of patent legislation. Upon request, a detailed description of the APG patent situation (2) as well as a list of the patents covered by the Henkel customer license can be provided. The present survey has been compiled to our best knowledge and reflects the status of February 1995. It cannot claim, however, to be complete nor correct; liability claims are thus excluded. A more precise patent evaluation can only be made in the case of a concrete formulation. Bibliography
(1) Proserpio, G.; Vianello, G.; Applicazioni tensio-cosmetiche di un nuovo glucoside, Rivista Ital., 56 (1974) 567 (2) Fabry, B.; Philipp, M.; Drach, J.; Alkyl Polyglycosides An Overview of the Patent Situation; HAPPI, August (1994) 111

Skin Cleansing and Washing Effects Mathias Rohr and Karlheinz Schrader* In Vivo Tests: Influence of Various Surfactants on the Skin Introduction Surfactants are the main ingredients in the formulation of cosmetic cleansing agents. Thus, skin cleansing should always be seen in a direct relationship with skin compatibility and other skinphysiological parameters for an optimal development which require raw materials for mild but still effective cleansing (1, 2). Under the aspect of meeting these requirements this article deals with the examination of raw materials and their effects on human skin from different points of view. As an interfacial membrane the stratum corneum represents a barrier for surfactants. Scientists suppose that for most surfactants the diffusion resistance of the horny layer is 100 times larger than that of the living epidermis. Undesired reactions may occur only after crossing this barrier, i.e. after damaging the interfacial layer. In this context the rinse-off behavior of surfactants from the skin plays an important role for the irritation potential. Surfactant residues may be adsorbed and penetrate into the resulting so-called V-spaces of the skin where they may trigger undesired reactions. Rough skin may especially easily irritated. Excessive cleansing also leads to a change in the barrier function. The function of skin as a protector against noxious agents such as soil, lubricating oil and detergents and thus against further washing applications is impaired. Other aspects which play a role in the evaluation of surfactants on skin are: Skin elasticity, sebum content, appearance of skin (erythema, squamation, fissures), subjective sensations (itching, tension), pH value, alkali neutralization time and resistance as well as circulation of blood in the skin (3, 4, 5, 6, 7). A variety of methods will be presented to objectify partial aspects of the surfactant effect on the stratum corneum (8, 9). The general compatibility, acceptance as well as the damage to the barrier is examined by means of the arm-flex wash test and TEWL measurements. The cleansing power is quantified by means of a skin washing

machine; changes in the skin surface structure (skin roughness) are examined by means of laser profilometry (10). Material and Methods Table 1 lists the individual surfactants which were examined. The tests were carried out with 1/20 molar solutions. For comparative evaluations, tests in molar concentrations allow a direct comparison of different surfactant molecules with different molecular sizes, since equal numbers of surfactant molecules are compared. However, this automatically means that the products contain different quantities of washing-active substances (WAS content). Since only a limited number of products can be tested on a volunteer collective of 20 persons, sodium lauryl sulphate (Texapon K 12) in a 2 % WAS solution is tested as a further standard product. On the one hand this standard (in the following NaLS-(2 % WAS)) allows a comparison reaching beyond the collective; on the other hand a test-internal evaluation of the respective test result is possible through the comparison of the molar content (NaLSmolar) and /or the percentage (NaLS-2 % WAS). Texapon K 1296 and Texapon K 12 are chemically identical; however, they contain different amounts of active substance. Arm-Flex Wash Test with TEWL Measurement The arm-flex wash test with TEWL measurement is performed on 20 volunteers with healthy skin (11). The product is applied twice a day to the bend of the elbow over 5 days. During each application, one bend of the elbow is foamed with the first test substance and washed with the hand for two minutes. After rinsing with warm water, the product is applied again
Dr. Mathias Rohr has been occupying a leading position at the Institute of Applied Skin Physiology, Holzminden, Germany. In addition to applied research on problems in the cosmetics industry his current field of activity includes the development and introduction of new skin-physiological test methods. Furthermore, part of his occupation is the investigation of the laser profilometry of skin effects of surfactant solutions and the determination of sun protection factors according to COLIPA. Dr. Rohr is also a member of the COLIPA Task Force for sun protection factors.

12

Table 1 Short Overview of the Tested Surfactants with the Respective Molecular Weights, Active Substance Content and pH Values No. Name INCI Name Molecular mass 375 424 396 Active % Content of pH Value of substances 0.05 molar 0.05 molar % mass (WAS) solution ca. 53.0 ca. 50.0 ca. 60.0 3.538 4.240 3.300 11.1 10.8 9.3

AA = colour value after application of the model soil and AW = colour value after washing): AW - AA IV - AA x 100 = Cleansing effect in percent

1 2 3

Plantaren 2000 Plantaren 1200 Plantaren PS 10

Decyl Polyglucose Lauryl Polyglucose Sodium Laureth Sulfate + Lauryl Polyglucose Sodium Lauryl Sulfate (molar) Sodium Lauryl Sulfate (%)

4 5

Texapon K 1296 (NaLSmolar) Texapon K 12 (NaLS%)

289 289

min. 96.0 min. 90.5

1.505 2.0*

7.1 7.9*

* 2 % solution

In order to be able to carry out a standardization beyond the collectives, the cleansing effects (CE) calculated according to the above formula are standardized in relation to the difference between NaLS-2 % WAS and Aqua dest. so that the standardized cleansing effect (SCE) can be calculated according to the following formula: CE Prod. - CE water SCE = CE NaLS % - CE water Laser Profilometry The quantitative differentiation of surfactants with regard to their structureinfluencing properties of the skin surface in the application test is possible by means of data obtained with a laser scanning system. In order to detect the influence of the tested surfactants on the surface structure, 20 volunteers are requested to stop using cosmetic agents on the volar forearm 3 days before the test and for the entire test period. Before the first surfactant application, a silicone skin-print is taken of each test area, documenting the initial state. The products are then issued to the volunteers with the request to apply them to the test areas three times a day over 7 days at intervals of 6 hours. 6 hours after the last application skinprints are taken again. The test products are distributed in the areas to be measured on a permutational basis in order to compensate for possible differences in the skin state of the areas. x 100

and washed for another two minutes. After the second warm rinse the area is carefully dried with a towel (no rubbing). The second bend of the elbow is washed with the second product in the same way. This washing procedure is carried out twice per day of application, i.e. in total nine times. At the end of the test the volunteers are interviewed on the reactions that occurred directly after washing. In a subjective comparison of the test products with respect to cleansing effect and acceptance, the volunteers also evaluate mildness, improved skin feel and the overall impression. Measurement of the Transepidermal Water Loss The Tewameter (Courage and Khazaka, Cologne) is used for the measurement of water vaporization from surfaces, in particular from human skin. For approximately 45 minutes before the measurement and during the entire measurement procedure, the volunteers stay in a draught-free, air-conditioned test laboratory at 22 C and 60 % relative humidity. The transepidermal water loss is measured before the application phase of the arm-flex wash test as well as 6 hours after the last application of the test product. Examination of Cleansing Power The skin cleansing test according to Schrader is used for the examination of the cleansing effects of different surfactant products. With the aid of a skin
* Dr. Karlheinz Schrader is the owner and general manager of the Institute of Applied Skin Physiology in Holzminden, Germany. Skin Care Forum recently published an article by Dr. Schrader entitled An Evaluation of Sunscreen Preparations; See Skin Care Forum No. 10 (1994).

washing machine (Figure 1) a standardized and largely practice-related washing process is carried out and the removal of a model soil (12) is quantified with the aid of the Minolta chromameter CR 300 in the lab-colour room. A W/O emulsion is used as a base for the model soil; the emulsion contains a fat- and a water-soluble dye as well as a pigment which represents the mineral soil. The model soil is composed as follows: 4 % fat-soluble red dye, e.g. CI 12150; 4 % water soluble red dye, e.g. CI 6255; 4 % red pigment, e.g. CI 2490; 17% Protegin, INCI: Mineral Oil (and) Petrolatum (and) Ozokerite (and) Glyceryl Oleate (and) Lanolin Alcohol; 2.5 % Tegin O spezial; INCI: Glyceryl Oleate; 5.5 % Lanolin anhydriquum; INCI: Lanolin; 6.5 % Paraffin oil perliquidum, INCI: Mineral Oil; 10 % Vaselin, INCI: Petrolatum; 46.5 % Aqua dest., INCI: Water The reflection values (L-values) of the colour measurement are used for the evaluation. The cleansing effect is calculated in percent according to the following formula based on the three skin colour values (IV = initial value,

Figure 1 Skin Washing Machine According to Schrader a) Standardized washing procedure b) Quantification of the model soil

13

Figure 2 Automated Laser Profilometry with Robot Support

evaluation. The results of a further arm-flex wash test are described in the article by B. Jackwerth in this issue. TEWL Measurement Figure 4 summarizes the measurement of the transepidermal water loss included in the arm-flex wash test in order to quantify the barrier damage caused by surfactants. The changes in the TEWL values are mean values of 20 volunteers. The significance test of the results in the pairwise t-test yields a significant change (p < 0.05) for every product. On account of the respective standardization of the NaLS-(2 % WAS) change to 100 % all products can be directly compared with each other. Cleansing Effects A summary of the results of the washing tests is represented in Table 3. It shows the initial value (IV), the L-value after application of the model soil (AA) as well as the washing value (AW) after the washing procedure as a mean value of 20 volunteers.

The initial value has approximately the same level for all collectives, so that a direct comparison of the standardized cleansing effect is possible. Figure 5 shows a graphic representation of the standardized cleansing effect comparable to the evaluation of the arm-flex wash test in which the standardized difference as compared to the difference Lauryl sulphate- Aqua dist. is shown. The smaller the negative bar, the smaller is the difference between the standardized cleansing effect and the NaLS-(2 % WAS) solution. Laser Profilometry The DIN parameters Rmax, Ra, RzDIN as well as Rk calculated for the respective surfactant products are summarized in Table 4. The individual data reveal that all parameters lie close together, even beyond the different collectives. Consequently, the randomized distribution of the products allows a direct comparison of all products after standardization. Thus, the parameter RzDIN in the overall representation of the initial values in Table 4 varies around a mean value of approx. 152 7 m, which corresponds to an overall variation (beyond collectives) of approx. 5 %. The variations calculated for the negative standard NaLS-(2 % WAS) varied for all collectives between an approximate increase of 2- 6 %. On average, changes of the empty segment were approx. 2 %. A significance level of 95 % of the documented data was not achieved for all products and parameters, which is due to the relatively low roughness. From the overall representation of all parameters and products, in particular from the continuous level of the negative standard NaLS(2 % WAS) and empty segment beyond the collectives, a safe evaluation of the data is possible.

The volunteers wash the test areas twice for one minute, allow the product to work in for one minute and then rinse it off. Similarly to the test described above, an empty segment as well as an area washed with NaLS-(2 % WAS) is tested in addition to the test products to allow a general evaluation of the test collective. For a non-touch scanning of the skin replica an automated scanning process with an optical autofocus sensor (UBM Optical measuring system Microfocus UBM RC 14) is used. The silicone skin-prints are automatically entered and measured by a robot system of the laser scanning unit controlled by the measuring computer (Figure 2). Upon request, further details may be provided by the authors. The changes of the skin profile are quantified by means of various DIN parameters Table 2 (14, 15, 16). A pairwise Wilcoxon test is carried out to safeguard the changes found between the points of time untreated and treated (13). Significances concerning the change of the end value are calculated as compared to the initial value and compared to the empty segment changes. Results Arm-flex Wash Test Some results of the arm-flex wash test are summarized graphically in Figure 3. In each case the evaluations are summed up where the volunteers made different evaluations for the test surfactant and comparative surfactant NaLS-(2 % WAS). Figure 3 shows the standardized sum scores in the form of differences to NaLS-(2 % WAS) in order to allow a comparison of the individual products beyond the collective. The positive effects are assessed so that a positive bar represents a better 14

Figure 3 Evaluation of the Volunteers as a Sum Score of Milder, Improved Skin Feel and Overall Better in the armflex wash test as Compared to the NaLS-(2 % WAS) Evaluation. NaLS-(2 % WAS) = 0.0 norm. sum score (%) 150 125 100 75 50 25 0 -25 -50 Plantaren Plantaren Plantaren 2000 1200 PS 10 NaLSmolar

Table 2 Definition of DIN Surface Parameters Parameter (Lit.) 2-dimensional / 3-dimensional Rmax (DIN 4768) / Sp (14) Ra (DIN 4768) / Sa (14) RzDIN (DIN 4768-1) / Sz (14) Rk (DIN 4776) Meaning Max. profile height difference; only rough profile characterization Mean value of the profile data; measure for skin roughness Mean value from 5 Rmax values; measure for rough structure change Abbott curve (core roughness); combination of all 3-dimensional measuring data in one parameter

The individual changes in percent after empty segment correction, in relation to the change of the negative standard NaLS-(2 % WAS) are shown in Figure 6 for the products Plantaren 2000, Plantaren 1200, Plantaren PS 10 and NaLSmolar. On account of the standardization chosen, a negative bar shows a slightly less pronounced structural change of the skin surface as compared to NaLS-(2 % WAS). Here, Plantaren 1200 and Plantaren 2000 are clearly distinguishable from the other products. Discussion Table 3 shows that the standardized cleansing effect of NaLS-(2 % WAS) is 90 - 93 %, beyond the collective limits, as compared to approx. 60 % for Aqua dist. In the test-internal comparison of NaLSmolar with NaLS-(2 % WAS) the standardized cleansing effect of 97.95 % for NaLSmolar suggests that the lower active content leads to a reduction of the cleansing effect (17). In the comparison of the three tested sugar surfactants, with 91.7% Plantaren PS 10 shows the highest standardized cleansing effect PS 10, probably due to the addition of sodium lauryl ether sulfate to the basic formulation. A differentiation between different alkyl chain lengths, as e.g. between the products Plantaren 2000 Plantaren 1200 which was theoretically expected, with respect to the influence on the cleansing effect was not revealed in this test. Both Plantaren products have a standardized cleansing effect of approx. 88 - 89 %. This was possibly due to the extremely sticky and covering model soil which might cause a leveling of the results through saturation effects. Therefore, the washing differences to be expected in theory should be checked in further tests with a finer model soil. Within the framework of the laser profilometry test Plantaren 1200 shows the smallest negative skin structure changes as compared to the relative NaLS-(2 % WAS) value. For Plantaren 1200 Figure 6 shows a differentiation of 200 - 250 % for the DIN parameters Ra, RzDIN and Rk as compared to the negative standard NaLS-(2 % WAS). For Plantaren 2000 these three DIN parameters also display a positive tendency. However, the differentiation level is only approx. 50 -75 % as compared to NaLS-(2 % WAS). For Plantaren PS 10 the laser profilometry data vary around the NaLS-(2 % WAS)-level. Especially for Plantaren PS 10, which is no pure sugar surfactant, the mixed

Figure 4 Change of the TEWL Value During the Arm-flex Wash Test in Percent Standardized Against the NaLS-(2 % WAS) Field Change TEWL (%) 90 75 60 45 30 15 0 Plantaren Plantaren Plantaren 2000 1200 PS 10 NaLSmolar

NaLSmolar (Figure 6) in relation to NaLS-(2 % WAS), the effects assigned to the active content. However, the laser profilometry data found for the products Plantaren PS 10 and NaLSmolar should be understood only as tendencies since the differentiation from the NaLS-(2 % WAS)-level is not significant. The arm-flex wash test reveals tendencies comparable to the objective laser profilometry examination. Similar to Figure 6, the positive parameters of the arm-flex wash test represented in Figure 3 show a very positive evaluation for Plantaren 1200. However, in contrast to laser profilometry the other products are not differentiated in the subjective evaluation of the volunteers. In the comparison, the evaluation of the sugar surfactants Plantaren 2000 and Plantaren PS 10 correlate with the laser profilometry which is slightly positive for Plantaren 2000 and slightly negative for Plantaren PS 10 (Figure 3). As shown in Figure 4, the TEWL value changes for Plantaren 2000 and Plantaren 1200 lie in the order of magnitude of only 15 -20 % in the relative NaLS(2 % WAS)-measure. Plantaren PS 10, for example, reaches a level of approximately 50 %. Comparable to laser profilometry, a clear differentiation of Plantaren PS 10 and the two other Plantaren products is revealed in the test. On account of addition of sodium lauryl ether sulfate, a clearly higher damage of the barrier is caused. On the other hand it can also be stated on the basis of the present data that with a standardized cleansing effect of NaLS(2 % WAS) of more than 90 %, the TEWL value increase in the arm-flex wash test is reduced by 50 % through addition of lauryl polyglucose. For the test-internal comparison NaLSmolar NaLS-(2 % WAS), similar to the previous

Figure 5 Comparison of the Standardized Washing Effects in the Washing Test According to Schrader (Water-NaLS-(2% WAS)) = 0.0 norm. cleansing effect (%) 2,5 0 -2,5 -5 -7,5 -10 -12,5 Plantaren Plantaren Plantaren 2000 1200 PS 10 NaLSmolar

character of the product is expressed in the differentiation as compared to Plantaren 1200 and 2000. Thus, the slightly better cleansing effect of Plantaren PS 10 in this test correlates with slightly less positive laser profilometry data. The test-internal comparison of NaLSmolar and NaLS-(2 % WAS) supports the tendentially slightly better DIN parameters Ra, RzDIN and Rk for

Table 3 Skin Washing Test: L-Colour Values of the Different Test Collectives with Respective Cleansing Effect and Standardized Cleansing Effect in Relation to the Difference Aqua dist. NaLS-(2 % WAS)
Product Starting value (IV) Plantaren 2000 Plantaren 1200 Aqua dest NaLS-(2 % WAS) Plantaren PS 10 Aqua dist. NaLS-(2 % WAS) NaLSmolar Aqua dest NaLS-(2 % WAS) 64.58 64.61 64.48 64.86 64.86 64.92 65.00 64.69 64.67 64.95 Parameters Colour value Model soil (AA) 36.67 36.36 36.28 36.50 36.22 36.29 36.80 35.68 35.76 35.96 Cleansing effect (%) Standardized cleansing effect (%)

Washing value (AW) 61.54 61.48 53.56 62.77 61.23 52.16 62.24 62.45 52.49 62.92

89.11 88.92 61.28 92.63 87.33 55.43 90.21 92.28 57.87 93.00

88.76 88.17 0.00 100.00 91.70 0.00 100.00 97.95 0.00 100.00

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Table 4 Laser Profilometry: Individual Data of the DIN Parameters Rmax, Ra, RzDIN and Rk with Respective Changes in Percent (delta %) and Changes in Percent After Empty Segment Correction in Percent (delta % - U)
Produkt A Plantaren 2000 NaLS (2 % WAS) Leerfeld Plantaren 1200 NaLS (2 % WAS) Leerfeld Plantaren PS 10 NaLS (2 % WAS) Leerfeld NaLSmolar NaLS (2 % WAS) Leerfeld 167.62 176.67 167.45 166.46 171.60 150.25 167.02 176.56 166.85 160.46 175.09 158.27 Rmax / [m] E % 171.99 188.17 172.85 166.87 173.02 156.87 177.07 185.18 169.80 169.50 183.76 165.86 2.60 6.51 3.22 0.24 0.83 4.40 6.02 4.88 1.77 5.63 4.95 4.80 Rx / [m] E % 19.77 20.89 19.42 18.72 20.42 16.81 19.66 20.83 18.74 18.53 21.09 17.05 1.43 4.58 1.08 -3.61 3.42 0.32 2.56 2.65 1.39 1.43 5.14 4.11 RzDIN / [m] E % 155.52 164.25 155.70 149.15 156.54 139.73 158.87 166.44 149.79 149.56 161.76 144.31 0.76 3.14 1.68 -2.64 1.84 1.86 5.31 4.07 0.19 1.59 2.66 2.51 Rk / [m] E % 24.61 26.35 23.77 23.03 24.71 20.66 24.97 24.84 24.83 23.60 26.35 20.76 2.61 4.98 2.96 -2.92 2.06 -0.70 4.42 6.58 0.72 3.60 5.42 -1.05

%-U -0.62 3.29 -4.16 -3.58 4.25 3.12 0.84 0.15

A 19.49 19.98 19.21 19.42 19.74 16.76 19.17 20.29 18.49 18.27 20.05 16.38

%-U 0.35 3.50 -3.93 3.10 1.17 1.26 -2.68 1.04

A 154.34 159.24 153.13 153.19 153.71 137.18 150.85 159.93 149.51 147.22 157.57 140.78

%-U -0.92 1.46 -4.50 -0.02 5.12 3.88 -0.92 0.15

A 23.99 25.10 23.09 23.73 24.21 20.81 23.91 23.31 24.65 22.78 25.00 20.98

% -U -0.35 2.02 -2.21 2.76 3.71 5.87 4.65 6.47

tests for NaLSmolar in relation to NaLS(2 % WAS), the TEWL value increase is slightly reduced, in accordance with the different active contents. In general the TEWL measurements also correlate with the results of the arm-flex wash test and laser profilometry after 6 hours after product application. A high TEWL value correlates with a bad evaluation of the arm-flex wash test as well as with negative laser profilometry data. Summary The tests reveal that with the aid of skin-physiological in vivo tests subjective evaluation parameters of the arm-flex wash test can be objectified and correlated by means of objective measurements, e.g. measurement of the TEWL value or of the surfactantinduced skin structure changes by means of objectified laser profilometry.
Figure 6 Laser Profilometry: Change of the DIN Parameters Ra, RzDIN and Rk in Percent Standardized After Empty Segment Correction on the Difference of the NaLS-(2 % WAS) Test Area Ra: mean roughness according to DIN 4768 (15); RzDIN: average roughness according to DIN 4768 /1; Rk: Core roughness depth of the surface profile with exclusion of profile peaks and ridges (16) Ra / RzDIN / Rk (%) 50 25 0 -25 -50 -75 -100 -125 -150 -175 -200 -225 -250 Plantaren Plantaren Plantaren 2000 1200 PS 10

In the case of the observed washing effects and taking into consideration the possibly covering model soil, all test products with molar character show good to very good washing effects. Of the four surfactants tested within the framework of this test (Plantaren 2000, Plantaren 1200, Plantaren PS 10 as well as Texapon K 1296) the product Plantaren 1200 was judged best, followed by Plantaren 2000. References
Schrader, K.; Grundlagen und Rezepturen der Kosmetika; Hthig Verlag Heidelberg (1979) (2) Raab W.; Kindl, U.; Pflegekosmetik; Govi-Verlag, Frankfurt (1991) 186 (3) Braun-Falco, O.; Korting, H.C. (ed.); Hautreinigung mit Syndets; Springer Verlag Berlin (1990) 151 (4) Modd, H.; Schuster, G.: Tronnier, H.; Experimentelle Untersuchungen zum Problem der Hautvertrglichkeit anionaktiver Tenside in der Arbeitsmedizin; Tenside 2 (1965) 368 - 373 (5) Frosch, P. J.; Irritancy of soaps and detergents bars; Chapter 1 in: Frost, P.; Horwitz, S. N. (Eds); Principles of cosmetics for the dermatologist; C. V. Mosby Company, St. Louis Toronto (1982) 5 -12 (6) Frosch, P. J.; Kligman, A. M.; The soap chamber test. A new method for assessing the irritancy of soaps; J. Am. Acad. Dermatol. 1 (1979) 35 - 41 (7) Frosch, P. J.; Tests am Menschen Testmodelle fr Hautirritation am Menschen; rztl. Kosmetol. 13 (1983) 397- 406 (8) Schrader, K.; Rohr, M.; Tenside Ihre Beurteilung hinsichtlich Wirkung und Nebenwirkungen; Euro Cosmetics 1-2 (1994) 18 - 22 (9) Schrader, K.; Memethoden zur Prfung von Kosmetika; SFW 118 (1992) 411 (10) Rohr, M.; Schrader, K.; Surfactant induced Skin Roughness: Quantitative Analysis of the Surface Structure of the Skin Via Automated Non-touch Laser Scanning; Euro Cosmetics (1994) 24-28 (11) Schrader, K.; Praxisbezogene hautphysiologische Untersuchungskriterien mit Seifen und Syndets; Parfmerie Kosmetik 71 (1990) 686 - 695 (12) Tronnier, H.; Zur Standardisierung von Waschversuchen an der menschlichen Haut; FSA 67 (1965) 7 (13) Hartung, J.; Statistik Lehr- und Handbuch der angewandten Statistik; R. Oldenbourg Verlag Mnchen, 9. Auflage (1993) (14) Stout, J.; Sullivan, P. J.; Dong, W. P.; Mainsah, E.; Luo, N.; Mathia, T.; Zahouani, H.; The Development of Methods for the Characterization of Roughness in Three Dimensions (1993)
(1)

(15) DIN 4768 Ermittlung der Rauheitskenngren Ra, Rz, Rmax mit elektrischen Tastschrittgerten Begriffe, Mebedingungen (16) DIN 4776 Kenngren, Rk, Rpk, Rvk, Mr1, Mr2 zur Beschreibung des Materialanteils im Rauheitsprofil Mebedingungen und Auswerteverfahren (1990) (17) Schrader, K.; Die hautphysiologische Bewertung von Tensiden; Parfmerie Kosmetik 75 (1994) 80 - 85

(page 1 continued) By variation of the chain length of the fatty alcohol and the number of glucose groups the structures of the properties of the APGs may be influenced. As a specialist in this field, Henkel provides an APG product range for a wide variety of applications.

Ra RzDIN Rk NaLSmolar

Publisher: Henkel KGaA, Ressort Oleochemie, COSPHA, D- 40191 Dsseldorf, Germany Editors: K. Raabe, S. Einemann, Dr. S. Wallat France: Jean-Franois Herb, Tel. (1) 60.65.21.00; Fax (1) 60.65.21.01; Sidobre-Sinnova S.A., St-Fargeau-Ponthierry Great Britain: Mark Leonard, Tel. 081- 311- 4149; Fax 081- 310-06 20; Henkel Limited Spain: Esther Prat, Tel. (34) 32 90 48 50; Fax (34) 32 90 48 78; Pulcra S.A., Barcelona USA: Patricia Mayer, Tel. (215) 628-14 76; Fax (215) 628-14 50; Henkel Corp., Ambler, Pennsylvania Japan: Katsumi Sasaki, Tel. 81- 3 - 36 64 - 25 58; Fax 81- 3 - 36 64 - 25 59; Henkel Hakusui Corp., Tokio Correspondence: Skin Care Forum, c/o Henkel KGaA, CFC PM Wissenschaftlicher Service, Z 20; D- 40191 Dsseldorf; Germany Tel. (0211) 797 24 43, Fax (0211) 798 76 96 Translations: TTP Sprachendienst, H. Khler, S. Einemann Realization: CPC Werbung/Advertising, H.- J. Tasch, Y. Kppers Design: Bhm & Kleinhans GmbH, D- 40859 Ratingen, Germany Litography: Rheinische Reprotechnik GmbH, D- 40231 Dsseldorf, Germany Printed by: Druck und Verlagsgesellschaft mbH D- 40008 Dsseldorf, Germany All contributions and original articles published in the Skin Care Forum may only be reproduced with special permission and provided that the source is acknowledged. The Skin Care Forum accepts no responsibility for any opinion expressed or statements made in contributions or reproductions from other sources.

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