THE USE AND SAFETY OF HYDROXY ACIDS IN COSMETICS

Date: 16th February 2005

R.J.E.Williams B.Sc., Dip.Env.St.

Abstract.
The use of Hydroxy Acids (Alpha Hydroxy Acids, Beta Hydroxy Acids and Alpha Keto Acids)
represented one of the major breakthroughs in cosmetic technology and achievement towards truly
functional “anti-aging” products. The popularity of Hydroxy Acid based products with the
consumers, stimulated a significant growth in the personal care market. An understanding of
Hydroxy Acids and specifics of formulating with them may assist in the development of safe and
effective personal care formulations.

Preface
The original position paper was published in “Cosmetics, Aerosols and Toiletries in Australia” Vol
10, No1, p 23-26, 1996 - ISSN 0817-637X., and an updated form of this paper is included in the
body of text below.
Since this publication other regulatory action has taken place and a brief synopsis of each of these is
included in further sections below.

Introduction.
Hydroxy Acids are a class of organic chemical compounds which have an Hydroxyl or Keto group
in close proximity to the Carboxyl group. In the case of Alpha Hydroxy Acids (AHAs) and Alpha
Keto Acids (AKAs) the hydroxyl group (with AHAs) and the Keto group (with AKAs) is in the
alpha position (one removed) and in the case of Beta Hydroxy Acids the hydroxy group in the beta
position from the carboxyl group (two removed).
These Hydroxy Acids have been reported to act as common moisturizing agents by absorbing
moisture from the atmosphere, hence when applied topically; they help increase moisture content
and plasticity of the stratum corneum.
It has also been reported that Hydroxy Acids stimulate cell desquamation by reducing corneocyte
adhesion/cohesion and accelerate cell renewal within the basal layer by induction of epidermolysis,
leading to the synthesis of new collagen, and hence their use as exfoliants and skin smoothing
agents. The danger is when, through high levels, low pH and excessive exposure times, more than
the dead skin layers are removed, exposing immature skin cells, blood, nerve or lymphatic systems
to harmful effects of the environment.

Table 1.
In his article “Technology Transfer – Alpha Hydroxy Acids (AHA): Borrowing from
Dermatology”; Morris Herstein lists
The Cosmetic Benefits of AHAs as the Therapeutic Uses of AHAs as
Retexturizing Ichthyosis

Improved Skin Tone Actinic Keratosis

Softer, Smoother Skin Age Spots

Less lines and Wrinkles Skin Peeling

Fading of Age Spots Warts

Photoaging/Wrinkles

This paper discusses the chemical types available, the selection and concentration of Hydroxy
Acids, the pH of products containing Hydroxy Acids, the selection of delivery systems, the
selection of excipients and anti-irritants and the establishment of a skin irritation index through
clinical testing.
Table 2.
Chemical Examples.
Single Alpha Hydroxy Acids
Glycolic Acid CH 2 (OH)–COOH
Lactic Acid CH 3-CH(OH)-COOH
Malic Acid CH 3-CH2-CH(OH)-COOH
Poly-Alpha Hydroxy Acids
Tartaric Acid COOH-CH(OH)-CH(OH)-COOH
Citric Acid COOH-CH 2-HOC(COOH)- CH2-COOH
Glyceric Acid CH 2(OH)-CH(OH)-COOH
Gluconic Acid CH2(OH)-CH(OH)-CH(OH)-CH(OH)-CH(OH)-COOH
Dicarboxylic Acid types
Tartronic Acid HOCH(COOH) 2
Aromatic Hydroxy Acids
Mandelic Acid C6H5-CH(OH)-COOH
Benzylic Acid C6H5-(HO)C(COOH)-C6H5

Beta Hydroxy Acids

Salicylic Acid
Note: these have been used as Kerotylic agents for many years in such products as medicated wipes.
Alpha Keto Acids
Pyruvic Acid CH 3-CO-COOH
Note: Alpha Keto Acids (AKAs) are likely to have two modes of action in that:
a) they exhibit specific effects as AKAs (like AHAs) in the upper layers of skin, and
b) in their reduced form (e.g., after conversion of Pyruvic Acid to Lactic Acid by Lactic
Dehydrogenase) act as AHAs in the lower levels of skin.
Ascorbic Acid (Vitamin C)

Please note that the compounds found in Table 2. are by no means a complete list of possible
compounds and there are many Hydroxy Acids which may prove effective and non-irritant in
commercial use.

Formulating
When formulating with Hydroxy Acids standard product development should be employed.
That is;
1. Select the type and concentration of the Hydroxy Acid
Selection of the type and concentration of the Hydroxy Acid should be based on the end usage of
the product (see tables 1. 2. and 3.)
It seems that there has been an almost direct transfer of technology from Dermatology to Cosmetics
(i.e. the use of high levels of short chain AHAs or Fruit Acids) without sometimes considering the
consequences. That is, some formulators have used materials which have a very high efficacy but
leading to potential skin problems sometimes experienced when not formulated correctly, not
formulated with safety in the forefront of consideration or not used under strict clinical supervision.
These potential skin problems can be simple skin irritations, to short term skin damage (chemical
burns) and possible long term detrimental effects.
It goes without saying that there should be a balance between efficacy and irritation. Products
intended for Dermatologists and Salon use, where the patient is under constant supervision, stronger
levels of Hydroxy Acids may be used, however where the cosmetic customer buys a product and
uses it at home where little or no supervision is available then the formulator must take the potential
for simple skin irritations, to short term skin damage (chemical burns) and possible long term
detrimental effects, into consideration.
2. Select the pH of the Product
In his article “Technology Transfer – Alpha Hydroxy Acids (AHA): Borrowing from
Dermatology”; Morris Herstein states the “optimal pH is between 3.0 and 5.5 … the lower the level
the greater the efficacy … there is a need for the free acid form for maximum efficacy, as 100% salt
form of an AHA is not as effective as the acid form. However, a mixture of acid and salt form can
be effective too.”
The relationship between pH, cellular renewal and irritation has been proven utilizing varying
concentrations of different hydroxy and non-hydroxy acids at different pHs (see table 3. below).
Table 3.
“Relationship Between Cell Renewal, Irritation and pH”
Cell renewal - a higher value indicates greater skin renewal and, Irritation results are based on
standard tests where the lower value indicates a lower irritation potential.

Other studies have also shown that at a pH 3.0 all acids significantly stimulated the skin and
produced some degree of irritation. At pH 7.0 little or no irritation was observed, however there was
no stimulation either. Pure 70% Glycolic Acid has been used and with a pH of less than 2 the
irritation potential is so high that some chemical burns have been reported with excessive exposure,
hence should be avoided.

The early Van Scott patents stressed the importance of neutralizing AHAs with specific bases.
Smith’s studies demonstrated no marked changes if neutralization was achieved with Sodium
Hydroxide, Triethanolamine or Ammonium bases.
3. Choose the appropriate delivery system for the hydroxy Acid
Research indicates formulation design is of key importance to ensure optimal delivery of the skin
condition benefits. The performance of Hydroxy Acids can be affected by the delivery system, such
as a lotion, cream or gel, etc. whether it is to be buffered or unbuffered and the incorporation of
percutaneous penetration enhancers.
4. Select Excipients and Anti-Irritants
Firstly, the emulsifying system and excipients must be selected from those which are stable at the
chosen pH and compatible with the Hydroxy Acid. It should also be noted that performance of
Hydroxy Acids can be affected by the presence of various emulsifiers and excipients. The product is
then formulated around the Hydroxy Acid and compatible emulsion system.
If required anti-irritants can be selected from the following chemical groups:
Table 4. Anti-Irritants
 Thickeners: by reducing diffusion on the skin and into the eyes.
 Complexing agents: by reacting with the skin before the Hydroxy Acid can irritate.
 High Molecular Weight Molecules e.g., Proteins, Botanicals and Sterols: by reducing the ability
of the Hydroxy Acid to penetrate the skin.
 Compounds with high levels of Hydroxy groups e.g., Ethoxylated compounds and Glucose
derivatives.

Further Regulatory Action

Cosmetic Ingredient Review (CIR) -1997
The Cosmetic Ingredient Review (CIR) published their findings, with respect to the “Safety
Assessment of Glycolic Acid, Ammonium, Calcium, Potassium and Sodium Glycolate, Methyl,
Ethyl, Propyl, and Butyl Glycolate, and Lactic Acid, Ammonium, Calcium, Potassium, Sodium, and
TEA-Lactate, Methyl Ethyl, Isopropyl, and Butyl Lactate, and Lauryl, Myristyl, and Cetyl Lactate.”
June 6, 1997”. The essence of their findings was that there is some concern when using these
materials, particularly when the concentration is above 10%w/w, and the pH is below 3.0.
The CIR recommendation was that:
cosmetic products should have a concentration of Glycolic Acid, Lactic Acid and their derivatives
no greater than 10.0%w/w and the pH of any product should be greater than 3.5.
and,
salon products should have a concentration of Glycolic Acid, Lactic Acid and their derivatives no
greater than 30.0%w/w and the pH of any product should be greater than 3.0.
It is assumed that this would leave the medical profession (dermatologists) to use higher
concentrations and lower pH products.

Conclusion (or) Position Statement.

Whilst cosmetic products containing Hydroxy Acids generally possess the least potential for harm
to the consumer, formulators should be aware of the potential pitfalls when developing such
products. The ASCC is not able to recommend the precise way you should formulate your product;
however, we recommend that formulators carry out the appropriate development, clinical and
dermatological tests to determine efficacy and potential irritancy of formulations containing
Hydroxy Acids. By following rigorous protocols of testing, we may be able to bring the consumer,
Hydroxy Acid based products which are effective and safe to use.
We suggested that cosmetic limits for a composite of Glycolic Acid (and derivatives), in "skin
renewal products", should be no more than 20.0%w/w and with a pH greater than 3.5. If, however,
the product is likely to meet the eyes, the Australian Society of Cosmetic Chemists would
recommend a maximum level of Glycolic Acid (and derivatives) being 10.0%w/w and with a pH
greater than 3.5. This stand is based on evidence as found in the Cosmetic Ingredient Review (CIR)
Final Report of June 6, 1997 (noted above).
Higher levels of Glycolic Acid (and derivatives) and possibly lower pH’s may be encountered in
specialist areas. A possible overview of this should be determined by the Therapeutic Goods
Administration.
Other chemical forms of Hydroxy Acids, as previously listed, should be exempt from any
regulation, as their action is generally milder than Glycolic Acid (and derivatives) and they have
been used for many years without reported problems. Also new Hydroxy Acids being developed for
the cosmetic industry have sufficient safety and efficacy data provided to ensure safe use of these
chemicals.
All this should also be dependent on the final product (for cosmetic and salon use, containing Alpha
Hydroxy Acids) having undergone some form of safety testing and, as a result, include appropriate
label recommendations as to warnings, contact time and removal.

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