Shampoos are products designed to cleanse, condition, and provide a pleasant fresh, clean residual scent to hair. Consumer shampooing habits vary significantly depending on where you live, with the average European washing their hair three times a week, and 80 percent of North Americans and 90 percent of Japanese washing their hair once a day.
This high level of product consumption results in shampoos being the largest personal care category, representing ~37 percent of the total hair care market. The shampoo category has numerous segments, including:
- two-in-one conditioning
- body enhancing
- volumizing
- color protecting
- shine enhancing
- moisturizing
- damage repairing
- anti-dandruff
The use of shampoos dates to 1762 England, when hair stylists boiled shaved soap in water and added herbs to give the hair shine and fragrance. Commercially-made shampoo became available at the beginning of the 20th century.
Magazine ads in 1914 featured Harmony Hair Beautifier and Shampoo by Rexall, as well as young women in a camp washing their hair with Canthrox shampoo. Hans Schwarzkopf developed the first powder shampoo in 1903 and introduced the first liquid shampoo in 1927. He also opened the first training center for hairdressers.
The development of cheap synthetic surfactants after World War II enabled the development of superior performing shampoos, versus the fatty acid soaps that had been used previously.
The next major shampoo development occurred in 1987 when Procter and Gamble launched Pert Plus, the first broadly successful conditioning shampoo. The technology used in Pert Plus was enabled by the development of a cationic polymer (Polyquaternium 10-Polymer JR, Union Carbide) combined with a high molecular weight Dimethicone which provided conditioning properties that weren’t previously possible. Pert Plus revolutionized the shampoo market and created the two-in-one conditioning shampoo category.
Current typical modern shampoo formulations are comprised of:
Ingredient | Percentage | Function |
deionized water | 73-90% | |
primary surfactant | 8-15% active | foam/lather |
secondary surfactant | 2-6% active | foam boosting/ thickening/mildness improvement |
thickening polymers | 0-2% | |
salt | 0-2% | thickening |
opacifying/pearling agents | 0-1% active | |
chelating agent | .05-.2% | improve hard water performance |
conditioning polymers | 0-1% | anti-static, wet/dry conditioning |
conditioning emollients | 0-1% | mostly Silicones for wet conditioning |
fragrance | 0-.5% | |
preservatives | .001-1% |
Prospector® Personal Care & Cosmetics material searches
Primary surfactants provide the main foaming and lathering properties of the formulation and are typically anionic surfactants. Sodium/Ammonium Lauryl sulfates have been the primary surfactant workhorses for decades, historically used alone or in combination with Sodium Laureth 3 Sulfate. Currently many manufacturers have switched to using only Sodium Laureth 1 or 2 Sulfate as the primary surfactant.
Another recent trend has been to use sulfate-free primary surfactants, especially in color protecting shampoos. The most popular used sulfate-free surfactants include Sodium Methyl 2-Sulfolaurate/Disodium 2-Sulfolaurate, Sodium C14-16 Olefin Sulfonate, and Sodium Lauroyl Methyl Isethionate.
Secondary surfactants are used to improve the mildness, boost foam/lather and help thicken shampoos. Cocamidopropyl Betaine is by far the most commonly used secondary surfactant and is the cheapest. Others used include Coco Betaine, Lauryl/Coco Hydroxypropyl Sultaine, Disodium Cocoamphodiacetate, Cocamide MEA, and Decyl Glucoside. Many formulations contain combinations of secondary surfactants, especially Cocamide MEA combined with Cocamidopropyl Betaine.
Secondary surfactants are often amphoteric, and function by forming mixed micelles with anionic primary surfactants which can associate and form long rod shaped micelles. This process improves mildness and helps thicken the shampoo. Salt thickens shampoos by reducing micelle charge density, helping to promote the conversion of spherical- to rod-shaped micelles, which can entangle and cause increased viscosity.
The most commonly used cationic polymers are Guar Hydroxypropyltrimonium Chloride (the most popular), Polyquaternium 10, Polyquaternium 6, and Polyquaternium 7. These polymers are normally combined with Dimethicone (>100 K cts.) or Amodimethicone in most two-in-one conditioning shampoos for better wet and dry combing properties.
State of the current market
- Shampoos from large producers like L’Oreal, Procter and Gamble, Johnson and Johnson, and Unilever dominate selling nine of the top 10 brands.
- Most popular shampoos utilize similar formulations based on alkyl sulfate/alkyl ether sulfate and Cocamidopropyl Betaine.
- Non-conditioning shampoos are differentiated mostly by fragrance and conceptual ingredients.
- Most key two-in-one conditioning patents from P&G and Unilever have expired, making the technology generic.
- Lack of product innovation and distinctness among currently marketed products. Most innovation is coming from small niche brands.
- Lack of store shelf transparency; everything looks and sounds the same.
- Little correlation between product price and performance.
Current trends
- Greater use of green, natural based, sustainable ingredients
- Development of more premium priced hair care brands
- Greater focus on scalp health - anti-dandruff products are gaining market share.
- Powdered shampoos are gaining in popularity.
- Development of more structured surfactant-based shampoos. Structured Surfactants are novel surfactant blends that form liquid crystal surfactant phases. These phases consist of a close packed network of spherulites that can suspend high concentrations of oils, silicone, exfoliating, and ZPT (antidandruff active). The formulations also are milder, have a rich dense creamy lather, and a lotion-like feel and texture.
- Sulfate-free color protection shampoos
- Use of greener surfactants that don’t use petroleum-derived Ethylene Oxide (Sodium Laureth 1, 2, or 3 Sulfate). Several suppliers soon will be producing Sodium ether sulfates using Ethylene Oxide produced from fermentation produced Ethanol
- Less use of Silicones in two-in-one shampoos, and more natural based oils
- Significantly less use of Methylchloroisothiazolinone and Methylisothiazolinone as preservatives due to safety/public relations concerns
- Biodegradable packaging
Further reading:
Two-in-one shampoo technology: Double the benefits, or double the trouble?
The views, opinions and technical analyses presented here are those of the author or advertiser, and are not necessarily those of ULProspector.com or UL Solutions. The appearance of this content in the UL Prospector Knowledge Center does not constitute an endorsement by UL Solutions or its affiliates.
All content is subject to copyright and may not be reproduced without prior authorization from UL Solutions or the content author.
The content has been made available for informational and educational purposes only. While the editors of this site may verify the accuracy of its content from time to time, we assume no responsibility for errors made by the author, editorial staff or any other contributor.
UL Solutions does not make any representations or warranties with respect to the accuracy, applicability, fitness or completeness of the content. UL Solutions does not warrant the performance, effectiveness or applicability of sites listed or linked to in any content.
Hi Very interesting article. Perhaps this is a silly question – but in the list of ingredients and functions, there is no ingredient which has been assigned a function of “cleaning” or “de-greasing” Presumably shampoo is intended to clean your hair – so what ingredient is doing that? Is it largely the water? Or are the surfactants added for foam/lather purposes doing double duty, As I understand it foam/lather is an aesthetic component of the shampoo experience rather than a functional one, as non-foaming shampoos do exist. Thanks very much
Hi!
Look at the list. Both primary and secondary surfactants deliver the cleaning function to the formulation. Even toothpaste usually contains surfactants like Sodium Lauryl Sulfate or Sodium Lauroyl Sarcosinate.
Alexandra,
Surfactants and cosurfactants provide cleaning however only a small amount is needed to do this. Higher levels are necessary to provide consumers with the rich lather and foam that they perceive is necessary to clean hair.
George
Thanks very much for responding – that is so helpful!
Basically what does the work in shampoo are the surfactants. Primary surfactants which usually the sulfate family is, are anionic detergents (has negative charge). They are excellent in foaming and cleansing. However, depending from for what category of people/customers are you creating the product, you should carefully pick the primary and secondary surfactant (usually mild surfactant with some conditioning effect). For men’s hair is lauryl sulfate is better. They do not bleach the hair, do not have damaged hair. Lauryl sulfate is better for normal non-damaged, non-bleached hair.
However, the sulfate family cleans very well stripping all oils from the hair which also causes “frizz” hair. Another con for sulfate family is they create 1,4-dioxane
Have you seen the latest patents by P&G using Polyquat-6? They go beyond the coacervate effect.
Have you seen the scientific paper by Brown from P&G in the topic of hair conditioning. It is innovation at its best and already marketed in some Pantene products.
What is the innovation coming from small niche brands? Any examples that offer real technology progress rather than marketing crap?
Thanks
Ricardo Diez
Good Right -up
Hello! I mean no offence, but is this article reliable and recommended for use as an academic source? It seems to be a really helpful article!
Is it preferable to use ionized or non-ionized Sodium chloride to thicken?
I recommend using a 30 or 40% aqueous solution.
Hi George,
Do you maybe have a source for the 73-90% of water?
Thanks in advance!
Right on George!
Simple Chemistry explained.
Thanks so much!
James
Ohhh thanks for this article it was really usefull ad have tried to write my formulation ingredients pleaase have alook at them, i want to formulate for my first time
Water,sodium laureth chloride,cocomidopropylbetaine,guar hydroxypropyltrimonium chloride, amodimethicone,dimethicone,cocomide MEA, peppermint oil,aloevera oil,apricot extract oil,rice protein,gylcol stearate, disodium EDTA,sodium hydroxide ,citric acid ,trideceth-12,potassium sorbate and bloom extract
PLEASE GUIDE ME WHERE AM WRONG ????
Hi, Nassinzi.
The formulation looks reasonable. I think you meant Sodium Laureth Sulfate not chloride.
Thanks for reading,
George
Hi, I have a question in regards of Methyl Ester Sulfonates (MES). We have abundant of MES supply in our country (and its the cheapest) – primarily to replace Linear Alkyl Benzoate Sulfonate in detergent formulas.
I can’t find the reference anywhere for soap or shampoo using this material except for someone asking about the formula below in a forum. Sadly no one give any comment to her query.
MES 10%
Cocamydopropyl betaine 9%
Natrium chloride 1.2%
Propylene glycol 0.1%
Caprylic capric triglyceride 3%
Castor oil 2%
Sunflower oil 2%
Fragrances 1 %
Phenoxyethanol 0.5%
Appreciate you view on this.
Hi, Ida:
Stephan Chemical sells MES and there are numerous shampoo formulations containing MES listed on the UL Prospector Stephan site.
Thanks for reading!
George