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Economy Premium Shampoos



Heres a look at the science and art behind the formulation of these products.



Published February 6, 2007
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Economy & Premium Shampoos



Here’s a look at the science and art behind the formulation of these products.



Shoaib Arif
Pilot Chemical




Before going to the bench to develop a shampoo formula, it is helpful to know what is already available in the market, as well as the current market trends. Most shampoos on the U.S. market use a combination of alkyl sulfates and alkyl ether sulfates as the primary surfactants. The most common alkyl sulfates are sodium and ammonium lauryl sulfates, while the most frequently used ether sulfates are sodium and ammonium lauryl ether sulfates. Alkyl ether sulfates tend to be slightly milder than the corresponding alkyl sulfates. Ethoxylation may also improve the flash foaming characteristics, solubility and the cloud/freeze points. Alkyl sulfates, on the other hand, may give denser foam and build comparatively higher viscosities with salt. A combination and balance of alkyl sulfates and alkyl ether sulfates will provide more desirable properties than either the alkyl or the alkyl ether sulfates alone.

Typically, betaines and amides are the secondary surfactants in shampoo base formulas. Incorporating other surfactants such as amphoterics, sulfosuccinates and ethoxylated sorbitan esters into a shampoo formula can further improve special properties such as mildness and low eye irritation. Cocamidopropyl betaine, a common secondary surfactant in shampoo formulas, improves mildness, viscosity and enhances the foam properties. Cocamide MEA is the most commonly used alkanolamide for enhanced foam stability and viscosity. Most products in today’s market no longer use the DEA version of cocamide. A plain and simple formula for a shampoo is a combination of lauryl sulfate, lauryl ether sulfate, cocamidopropyl betaine and cocamide MEA. A desirable pH of 5-6 is achievable with the addition of citric acid. An optimum viscosity is usually obtainable by incorporating sodium chloride into the formula. A formulator will typically add preservatives, perfumes and dyes to complete the formula. To realize all end use properties and marketing claims, some modifications with other additives may be necessary. Hair shampoo formulations need to provide some or many of the following benefits to the consumer: Aesthetics, cleansing of hair, fresh and clean appearance, silky, soft after-feel, conditioning and antistatic effects, moisturizing effects, hydrating effects, aroma, shine and luster, body, wet and dry combing ease, nutrients for hair and scalp, split-end repair, sunscreen/UV absorption, color protection and anti-dandruff effects. Before starting the actual formulating work, one should write a detailed product description. For example, a premium, plain shampoo’s description is shown in the table below.
   

Premium, Plain Shampoo Description


Color: Green
Appearance: Clear, transparent
Odor: Herbal/floral
Ammonia odor: Product must not give ammonia odor even at high pH
pH: 5-6
Viscosity: 15,000-25,00 cps  (Brookfield DV-1 +, spindle # 3)
% Solids: 20-25%
Special additives: None
Foam height:  40-50mm cylinder shake test. 1% sol. 10 shakes
Foam stability: Less than 10% loss of foam after 5 minute in cylinder
Flash foaming: High
Product application: Easy to mix and apply to the wet hair
Lather quality: Soft, rich, creamy lather
Feel: Creamy, silky
Cleaning performance: Excellent, must clean grease and dirt
Rinse: Rinses easily
Wet combing: Easy, no tangling
Dry combing:  Easy, smooth
After feel: Silky, soft with volume
Biodegradability:  Readily bio-degradable
Toxicity: None to low
Flash point: High (non-flammable or combustible)
Skin & scalp irritation: None to low
Raw material cost: Not more than $.25/lbs.
Benchmark brand: ABC/XYZ shampoo


Here are some of the important aspects to consider before a formulator goes to the bench to develop a shampoo product.

Cost: It is important for a formulator to have an idea of the cost of the formula’s ingredients as well as the finished product’s target cost. High foaming anionic surfactants such as alkyl sulfates and alkyl ether sulfates are some of the lowest cost surfactants used in shampoo formulas. 

Lather quality and quantity: An experienced formulator knows how to balance the quality and quantity of the lather produced by surfactants. Generally, common shampoo formulas will use a combination of anionic surfactants such as alkyl sulfates and alkyl ether sulfates for building the main body of lather. The ratio of alkyl sulfate to alkyl ether sulfate is important for flash foaming, foam stability, lather quality and flow properties. For higher flash foaming, use more alkyl ether sulfates, whereas higher ratios of alkyl sulfates will produce creamier foam. Formulators commonly use alkanolamides and betaines for foam enhancement, foam stabilization and viscosity.

Skin and eye irritation: Today’s shampoo formulations use several low irritation surfactants. Formulators frequently use betaines because of their lower cost and their high foam and viscosity-building properties. Shampoo formulas may incorporate other amphoterics such as sodium cocoamphoacetate as low irritation additives. Shampoo and body wash formulas can sometimes use sulfosuccinates, alkyl polyglucosides, ethoxylated sorbitan esters and amino acid-based surfactants like sodium cocoyl glycinate to achieve mildness and low irritation characteristics. Highly ethoxylated esters, like PEG-120 methyl glucose dioleate, are also suggested for lowering the skin and eye irritation of the formula.

Viscosity and flow characteristics: A wide variety of viscosity builders can increase viscosity, including alkanolamides, betaines, amine oxides, polymers, PEG esters and salt. Shampoos must have easy, short flow properties out of the bottle, and a consistency that is not stringy. Use of propylene glycol or ethoxylated nonionic surfactants can reduce stringiness of the formula. Another important criterion for viscosity builders is that they should give relatively flat temperature-viscosity and pH-viscosity curves. In other words, reasonable changes in temperature and/or pH must not change the viscosity drastically.

Suggested Formulas: Economy



Economy or low ingredient cost shampoos generally use high foaming anionic surfactants that are relatively lower cost. These formulas commonly use alkyl sulfates and alkyl ether sulfates as primary surfactants. Either ammonium or sodium salts of the surfactants are fine. The ratio of lauryl sulfate to laureth sulfate does affect the foam and lather profile, viscosity response to the salt and the stringiness of the final product. A good place to start is a 50:50 blend. From there, one can fine tune to achieve the desirable properties of the final product.

Some surfactant suppliers offer surfactant blends for formulating shampoos. Blends have the advantage of simplicity, less processing time, fewer chances of blending errors, lower inventories, less warehouse space for storing the raw materials, and so on. For example, Pilot Chemical offers a blend, CalBlend ECO-1, which is DEA-free, readily biodegradable and made with surfactants derived from natural renewable vegetable source. Twenty-five percent of this blend, when diluted with water and thickened with 2.0% sodium chloride, will give a product with a viscosity of 20,000 cps. (Brookfield DV-1 + viscometer, spindle# 3@3rpm). The addition of preservatives, dye and perfume will complete this economy shampoo that has high viscosity, copious foam and good after feel.

Economy Shampoo


Ingredient:            %Wt.
D.I. water                q.s. to 100
CalBlend ECO-1 (Pilot)    25.0
Sodium chloride    2.0
Preservative, perfume, dye    q.s.
Citric acid    to pH 5.5

Procedure: Add all ingredients in the order listed with constant mixing. Mix well after each ingredient’s addition until the batch is uniform, smooth, homogenous and free of any lumps or particles. Mix well after the addition of all ingredients until the batch is clear, uniform and homogenous. Appearance: Clear liquid; Viscosity@ 70°F: 20,000 cps. (Brookfield DV-1 +, spindle # 3); pH: 5.5

Pearlized Economy Shampoo


Ingredient:    %Wt.
D.I. water    q.s. to 100
CalBlend ECO-1 (Pilot)    30.0
CalBlend Pearl (Pilot)    10.0
Sodium chloride    2.0
Preservative, perfume, dye     q.s.
Citric acid    to pH 5.5

Procedure:

Add all ingredients in the order listed with constant mixing. Mix well after each ingredient’s addition until the batch is uniform, smooth, homogenous and free of any lumps or particles. Mix well after the addition of all ingredients until the batch is clear, uniform and homogenous. Appearance: Clear liquid; Viscosity @70°F: 22,000 cps. (Brookfield DV-1 +, spindle # 3); pH: 5.5.

Suggested Formulas: Premium



While economy shampoos tend to have lower solids and thus lower raw material cost, premium shampoos have relatively higher solid and active levels. Premium shampoo formulas may contain relatively milder surfactants such as sulfosuccinates (disodium laureth sulfosuccinate, disodium oleamido MIPA sulfosuccinate); amphoterics (sodium cocoamphoacetate, sodium lauroamphoacetate, disodium cocoamphodiacetate) and nonionic (PEG 80 sorbitan laurate, polysorbate 20, alkyl polyglucosides), in addition to high foaming anionic surfactants. Premium shampoos may also contain special additives like glycerin, emollient esters, natural oils, proteins, vitamins and herbal extracts. Premium shampoos, which will be detailed in this article, include plain, conditioning and baby shampoos.

Plain Premium Shampoos



Plain premium shampoos contain 15-25% total active surfactants. The primary surfactants include laury sulfates and lauryl ether sulfates. Ammonium or sodium salts are commonly used. Amphoterics, such as sodium cocoamphoacetates, can be incorporated for mildness. The next formula is an example of a plain premium shampoo.

Plain Premium Shampoo, DEA-Free


Ingredients:    %Wt.
D.I water    q.s. to 100
CalBlend ECO-1 (Pilot)    30.0
Mackam HPC-32 (McIntyre)          15.0
    (Sodium cocoamphoacetate)
Sodium chloride     2.0
Preservative, perfume, dye    q.s.
Citric acid    to pH 5.5


Procedure:

Add all ingredients in the order listed with constant mixing. Mix well after each ingredient’s addition until the batch is uniform, smooth, homogenous and free of any lumps or particles. Mix well after the addition of all ingredients until the batch is clear, uniform and homogenous. Appearance: Clear liquid; Viscosity@ 70°F: 15,000 cps. (Brookfield DV-1 +, spindle # 3); pH: 5.5.

Conditioning Premium Shampoos



Conditioning shampoo formulas can use a number of different hair conditioning agents. These conditioning agents can be divided into three major categories: Cationic polymers; fatty amines and quats; silicone and silicone derivatives.

Conditioning shampoo formulas may use cationic polymers such as quaternized cellulose (polyquaternium-10) and quaternized guar (guar hydroxylpropyltrimonium chloride). Condition- ing shampoos can also utilize water dispersible quats (such as hydroxyethyl behenamidopropyl dimonium chloride), fatty amines, dimethicone, cyclopentasiloxanes, dimethiconol and amino functional siloxanes. Silicones provide excellent wet and dry combing benefits as well as shine to the hair.

Light Conditioning Shampoo


Ingredients:    %Wt.


D.I water    q.s. to 100
Mirapol PQ-10 (Rhodia)     0.50
    (Polyquaternium-10)
CalBlend ECO-1 (Pilot)    30.0
Glycerox HE (Croda)      2.0
    (PEG-7 glyceryl cocoate)
Sodium chloride    2.0
Preservative, perfume, dye    q.s.
Citric acid    to pH 5.5

Procedure:

Add all ingredients in the order listed with constant mixing. Mix well after each ingredient’s addition until the batch is uniform, smooth, homogenous, and free of any lumps or particles. Mix well after the addition of all ingredients until the batch is clear, uniform and homogenous.
    Appearance: Clear liquid; Viscosity @ 70°F: 10,000 cps. (Brookfield DV-1 +, spindle # 3); pH: 5.5.

Conditioning Shampoo


Ingredients:    %Wt.


D.I. water    q.s. to 100
CalBlend ECO-1(Pilot)    35.0
Calfoam ES-302 (Pilot)    15.0
    (Sodium laureth sulfate)
Dow Corning 8500      2.0
    (Amodimethicone)   
Crothix liquid (Croda)     2.0
    (PEG-150 pentaerythrityl tetra-
    stearate (and) PEG-6 caprylic/
    capric glycerides  (and) water)
Sodium chloride    2.0
Preservative, perfume, dye        q.s.
Citric acid    to pH 5.5

Procedure: Add all ingredients in the order listed with constant mixing. Mix well after each ingredient’s addition until the batch is uniform, smooth, homogenous and free of any lumps or particles. Mix well after the addition of all ingredients until the batch is clear, uniform, and homogenous.
    Appearance: Clear liquid; Viscosity @ 70°F: 3,000 cps. (Brookfield DV-1 +, spindle # 2); pH: 5.5.

Premium Baby Shampoos



Baby shampoo formulations combine high foaming anionic surfactants like alkyl ether sulfates and some mild anionic, amphoteric and/or nonionic surfactants. Mild surfactants commonly used in baby shampoos include sulfosuccinates (disodium laureth sulfosuccinate or disodium oleamido MIPA sulfosuccinate); amphoterics (sodium cocoamphoacetate, disodium cocoamphodiacetate or the lauric versions and cocamidopropyl betaine); alkyl polyglucosides (decyl glucoside or coco glucoside); ethoxylated sorbitan esters (PEG-80 sorbitan laurate and/or polysorbate 20).
 

Baby Shampoo, No. 1


Ingredients:    %Wt.


D.I. water    q.s. to 100
Calfoam ES-302 (Pilot)    23.5
    (Sodium laureth sulfate)
Caltaine C-35  (Pilot)    15.7
    (Cocamidopropyl betaine)   
Mackam 2C (McIntyre Group)    3.9
    (Disodium cocoamphodiacetate)
Mackanate OPSV (McIntyre)    3.9
    (Disodium oleamide-MIPA
    sulfosuccinate)
AtlasG-4280 (Uniqema)     11.8
    (PEG-80 sorbitan laurate)
Plantaren 818 (Cognis)    5.0
    (Coco-glucoside)
Preservative, perfume, dye    q.s.
Citric acid    to pH 5.5

Procedure:

Add all ingredients in the order listed with constant mixing. Mix well after each ingredient’s addition until the batch is uniform, smooth, homogenous and free of any lumps or particles. Mix well after the addition of all ingredients until the batch is clear, uniform and homogenous. Appearance: Clear liquid; Viscosity @ 70°F: 3,000 cps. (Brookfield DV-1 +, spindle # 2); pH: 5.5.

Baby Shampoo, No. 2


Ingredient:    %Wt.


D.I. water    q.s. to 100%
CalBlend BSC (Pilot)    32.5
Preservative, perfume, dye    q.s.
Citric acid    to pH 5.5

Procedure:

Add all ingredients in the order listed with constant mixing. Mix well after each ingredient’s addition until the batch is uniform, smooth, homogenous and free of any lumps or particles. Mix well after the addition of all ingredients until the batch is clear, uniform, and homogenous. Appearance: Clear liquid; Viscosity @70°F: 7,000 cps. (Brookfield DV-1+, spindle # 3); pH: 5.5.

Final Thoughts


Any formulation work is not complete without proper safety, physical, chemical, performance, stability and consumer panel testing. It is a good idea to have more than one or two final prototype formulas. Subject the formulas through these tests and then choose the final formula. Have a few back up formulas. Another important aspect of product development is product scale up. A formula is not good enough unless a manufacturing facility can produce it, no matter how good it looks in the lab.

The art of formulating a shampoo is the art of balancing the desirable properties in the formula and keeping the undesirables to a minimum, while achieving a specified raw material cost. In many formulas for example, an increase in viscosity can be associated with an increase in stringiness. The formulator’s job is to reach a high desirable viscosity without having the undesirable property of stringiness. The addition of glycerin, propylene glycol and/or ethoxylated nonionic surfactants like ethoxylated alcohols or ethoxylated sorbitan esters may improve the formula’s short flow characteristics (reduce stringiness), but it is likely to reduce the viscosity. Finding the appropriate balance between viscosity and stringiness is the key.  A formulator is not only a scientist but an artist as well and the art comes from experience and time spent on the bench to learn the small tricks of formulation techniques.


About the Author


Shoaib Arif is manager, home and personal care applications at Pilot Chemical Co., Cincinnati, OH.
Previously, he was technology manager at Degussa Goldschmidt, Hopewell, VA. He has also worked in surfactant applications for home and personal care products at Noveon, Witco and Olin Chemicals. He has more than 30 years of experience in the home and personal care market. For most of his career, Mr. Arif has been involved in the development of new applications for raw materials, particularly surfactants. He has authored many articles and holds several patents. More info: 513-326-0618; E-mail: sarif@pilotchemical.com




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