1. Faculty of Pharmacy Mahidol University,
Hair Care Products
Assoc. Prof. Dr.Pleumchitt Rojanapanthu Pharmacy Department,
Faculty of Pharmacy Mahidol University,
Bangkok, Thailand

2. Hair Care Products : Shampoos Hair sprays Conditioners Hair gels
“2 in 1” shampoos Perming solutions
Hair dyes., etc.

3. Shampoos Purpose of shampoo is to clean hair
Customer also expect a dense and luxurious lather
Basic or primary surfactants are backbone of the cleansing products are necessary

4. Shampoos Shampoos can be made in various physical form:
Liquids, creams, paste, aerosol and dry
majority are liquids, either clear or pearlised
The principle constituents of most liquid
shampoos can be classified as :
Primary detergents
Secondary detergents
Thickeners

5. Shampoos (con.) Foamers foam stabilizers and booster Perfumes
Preservatives
Diluents (usually water)
conditioning agents

6. Shampoos (con.) Other additives (functional or otherwise)
pearlisers / opacifiers
colours
Remark : many ingredients are multifunctional and therefore do not clearly fall into any one category

7. Shampoos (con.)
The surfactants used in a shampoo need to be selected on the basis of a whole range of properties including:
costs
foam height
foam texture
detergency

8. Shampoos (con.) irritancy ease of handling and mixing
compatibility with other ingredients
color
odor
purity
biodegradability

9. Surfactants Basic anionic surfactants (Primary, anionic surfactants)
Mild anionic surfactants
(Secondary, anionic surfactants)
Amphoteric surfactants
Nonionic surfactants
Cationic surfactants

10. Basic surfactants Basic surfactants
1. Alky ether sulfates (R- (OCHCH2)xSO4M)
are most widely used surfactants
Exhibit well balanced properties
Excellent foamer, through the foam structure is relatively coarse
Low CMC (critical micelle concentration) ideal for cleansing preparation

11. Basic surfactants (con.)
Ideal behavior regarding foam and detergency
Be easily thickened with salt
Show good water solubility
Skin and eye compatibility is acceptable
Lauryl ether sulfate / sod. Laureth sulfate

12. 2. Alkyl sulfates (R-SO4m)
The first synthetic surfactant
Still most popular
Excellent foamer
Producing rich and creamy foam

13. 3. a- Olefin sulfonates
A mixture alkene of sulfonates and hydroxy alkane sulfonates
Milder than alkyl sulfonate
Similar irritation to the alkyl ether sulfate
Stable both in acidic and alkali pH values

14. Mild Anionic Surfactants (Secondary surfactants)
The purpose is to improve skin and eye compatibility of the formulation
Mild surfactant usually show reduction of foaming and cleansing compared with basic surfactant

15. Sulfosuccinate Derivative of sulfosuccinic acid both mono and diesters
Most popular derivative used in Europe is disodium laureth sufosuccinate
Good foamer and relatively cheap
Instability in both low and high pH value
Stable at pH 6-6.5

16. Cocoyl isethionate (RCOOH-CH2-CH2-SO3Na)
Mainly used as a surfactant in syndet bars
Improve skin compatibility
Excellent skin compatibility and emolliency properties
Using in baby products and in facical wash formulations
Maximum stability at pH 5-7

17. Alkyl ether carboxylates (R-(OCH2-CH2)x-OCH2-COOM)
Mild surfactant, reduce foaming and cleansing
Skin compatibility is similar to that of alky; ether sulfate
Stable at low pH value

18. Magnesium surfactant Have significantly better skin compatibility >
Sod., amm. and amine neutralized
Show high foaming and excellent cleansing properties
Their applicational properties are practically unchanged compared with the sodium foam
Magnesium ion increase the resistant of microbe

19. Alkyl phosphate Mono alkyl phosphate is good surfactant
Show high foam with mildness to skin
Suitable for mild shampoo and show both
Di- and tri- are known as emulsifier

20. Amphoteric surfactants
The charge changes as a function of pH value of the formulation
Build complex with anionic surfactant
Exhibit milder properties than individual

21. Alkyl betaines Can be cationic or anionic depend on pH
At pH 5-7 as in shampoo, they form ionic complex with anionic surfactant
Improve the skin compatibility of an anionic formulation
The size of micelle viscosity
Can improve foaming of a formulation (often use for thickening the formulation)
Improve structure of the foam finer and creamy

22. Alkylamido betaines Amino betaines are milder than alkyl betaines
Lower price
Much more often use in cosmetics

23. Acylamphoglycinates and acylamphopropionates
Most important products are coco derivative
Good skin compatibility
Show some conditioning properties in shampoos
Excellent foamer but is not stable in hard water

24. Amino oxides Amino oxides are never anionic
Show cationic, non-ionic depend on pH in combination with anionics can act as a foam booster and improve the foam structure
Good thickener for ionic surfactant
Are good conditioning agents in hair rinsing

25. Non-ionic surfactant Ethoxylated products Poor foaming used in shampoo
Often adds as solubilizers for perfume
Extraordinary mildness, used as the main surfactant in ‘non-sting’ baby-shampoo

26. Alkyl polyglycoside (APG)
Not as good as anionic surfactant
Shows good foaming properties
Excellent skin compatibility
Normally use for secondary surfactant

27. Shampoos (con.)
“frequent use” shampoos contain higher levels of milder secondary surfactants
many secondary surfactants exhibit lower irritation to skin and eyes
small addition of secondary surfactant can lead to a significant decrease irritation

28. Evaluation of Detergents as Shampoo Bases
Ease of spreading
Lathering power
Efficient soil removal
Ease of rinsing

29. Evaluation of Bases Ease of combing wet hair Lustre of the hair
Speed of drying
Ease of combing and setting the dry hair
Safety of shampoo

30. Detergency
Detergency : the removal of dirt, involving the following processes :
ability to wet both the dirt and substrate
reducing the interfacial tension
dispersing the dirt particles

31. Shampoos Additives Thickeners
High viscosity is very important both for
Product stability
Handling
The product should have viscosity
between 400 and 4000 m Pas

32. Thickeners (con.)
Pearlescent products should have minimum viscosity of 2,000 m pas it avoid precipitation
Ether sulfate + electrolytes (Cl-) viscosity by the size of the micelle
Alkanolamide the cloud point of the formulation

33. Thickeners (con.)
Using the special high molecular weight thickener ; PEG 6,000, PEG 120
It is either product, remain stable against hydrolysis at higher temperature or extreme pH values
Polymer thickener
Natural gum
Cellulose derivative

34. Foam stabilizer In the present of oil, such as sebum,
Monoethanolamines are the most effective

35. Pearlescent agents
Ethylene glycol mono and ditearate (EGMS,EGDS) are most often used in surfactant formulations.
They have to be incorporate at high temperature (70 -75)
Ready – made liquid pearlescent bases are now popular

36. Conditioning agents
Shampoo with anionic surfactants leave hair difficult to comb while wet fly-away when comb after drying
Addition of conditioning agents
wet – combability
static charge

37. Conditioning agents (con.)
Cationic surfactants show good properties but incompatable with anionic surfactants
Using quaternized polymer
: quaternize hydroxyethyl cellulose (Poly quaternize 10) compatible with most anionic surfactant
Show excellent conditioning properties

38. Conditioning agents (con.)
Impart manage-ability and body to hair very low concentrations are sufficient
Due to its very high substantively to hair, very low concentrations (0.5%) are sufficient
High concentration may lead to over- conditioning and build up on the hair

39. Conditioning agents (con.)
Small amount of fatty component : fatty alcohol, monoglyceride can support condition effect of shampoo
Silicone can be very effective conditioners, but are very difficult to incorporate and may act as antifoaming agents

40. Thickeners and foam stabilizers
 Alkalonamides or their alternatives
 Polymeric materials
 Electrolytes
Many of these ingredients are multifunctional, and most product use more than one.

41. Thickeners (con.)
Some surfactants systems are difficult to thicken not responding well to electrolyte additions
most surfactants systems are non-Newtonian, exhibit
shear – thinning
shear – thickening
time – dependence
time – independence
yield point
etc.

42. Thickeners (con.)  PEG derivatives
Ultimate test viscosity should be carefully considered
Various raw materials manufactures have developed
 PEG derivatives
 Polymeric material : natural gums
Gum-thickened product have a
different Rheology to otherwise similar
electrolyte-thickened product

43. Thickeners (con.) Temperature effect is less for gum systems
than for an electrolyte-thickened system
This can be useful when formulating for
climates where the product might be
subjected to large temperature variations
in storage, distribution and use

44. Thickeners (con.)
Gum will often stabilize foam by strengthening the film at the air/liquid interfaces in the matrix of bubbles
Making foam feel denser (creamy) in use
It is sometimes apparent as soon as the shampoo is poured into the hand

45. Some disadvantages high cost
lengthened processing time (with higher energy consumption if hot process is used)
difficulty of making viscosity adjustment
This problem can often overcome by using a
small amount of electrolyte for final viscosity
adjustments.

46. Effect of electrolyte on viscosity of surfactant systems
ionic density of the solution
consequent effect on micelle size and shape
Adding an electrolyte with the same cation as that of primary anionic surfactant in the system
e.g: amm.chloride  amm.lauryl sulfate
sod. chloride  sod.lauryl ether sulfate

47. Effect of electrolyte (con.)
Addition of electrolyte beyond a certain point will cause thinning, quite rapid and 
The maximum in viscosity depends on:
Concentration
presence of alkalotamides
level of free fatty alcohol
effect of the perfumes

48. Effect of electrolyte (con.)
Maximum viscosity occurs at low concentration of electrolyte when free fatty ether and alkalonamides are present
Due to formation of mixed micelles
Should have experimental for the relationship of viscosity and electrolyte concentration

49. Preservatives Ensure that the products contain no pathogenic …
Variety of preservatives are available:
parabens
Imidazolidinyl ureas
2-Bromo-2-nitropropane-,1,3-diol
5-Bromo-5-noitro-1,3-dioxane
Dimethyl dimethylol (DMDM) hydantoin

50. Preservatives (con.) Pohenoxethanol Drazolidinyl urea
Methyl chloroisothiazodlione and
methylisothiazodlione
Pohenoxethanol
Drazolidinyl urea
Methy dibromoglutatonitrile
Questernium – 15
Sodium iodate
Glutaraldehyde

51. Preservatives (con.)
Many surfactants used for shampoo manufacture are already preserved
Addition of preservatives must be taken into account
Challenge test of the finished product must be performed

52. Opacifier and pearliser
Opacification of shampoos usually for aesthetic reason
An occasionally a useful technique to use when the product can’t be made completely clear

53. Opacifier (con.) Opacification may be achieved simply by
Adding a small of fine, intensely white polymer dispersion
For ease of dispersion and subsequent product stability dilution of the opacifer to a 10% solution with water before addition to the main mix

54. Three common used ways achieving Pearlescence using stearate
Buying a ready made pearlised base (need dilution before adding)
Adding the chosen pearlising agents to the hot mix (most commonly ethylene glycol mono-desperate)
Buying a highly concentrated pearlising agent in a liquid or semi-liquid form that may be added as a cold mix

55. Factors affecting the appearance of the ‘pearl’
Composition of stearate ester
Presence of alkanolamides and other materials
Rate of cooling
Shear rate of stirring
Composition of the base

56. Conditioning agents
The majority of active conditioning agents are cationic surfactants, incompatible with anionic surfactants which are the basis of nearly all shampoos
The properties of both cationic and anionic can be modified

57. Variety other materials have been used as conditioning agents in shampoo
Various vegetable oil
Vitamin
Lanolin and its derivative
Herbal extracts
Some specialty silicone

58. Color
Using color which meet both EC and US specifications whenever possible
Higher purity colors are more expensive than technical grades
Color stability should be considered
Color fading can be minimize by adding a suitable UV absorber

59. Water u soluble absorbers usually work best in shampoos
u Bensophenone-4 and 2 ( %)
Color should be added in solution, not as solid material
Aqueous solution color required preservative

60. Sequestrants
Such as EDTA (ethylene diamine tetra-acetic acid) salts added in low level
To aid rinsing in hard water
To boost the efficiency of preservative

61. Anti-build-up shampoos
Are formulate to help remove excess build-up of conditioning agents and styling aids

62. Hair conditioners Conditioning Means many things to many people :
Reduction of fly-away
Gloss
Sheen
Manageability
Ease of handling
Simply general overall appearance

63. Conditioner should impart the condition of the hair as follow :
Improved wet and dry combing
Reduced fly-away (antistatic)
Increase gloss and volume
Improve curled retention
Repair the damage of hair shaft
Increase moisturing

64. Basic ingredients in the formulation
Primary surfactants (nearly always cationic)
Polymers
Bodying agents
Auxiliary emulsifiers
Oily components
Other ‘active’ ingredients

65. Conditioners (con.) Thickeners Perfumes Preservative
Diluents (usually water)
Colors
Other non-functional ingredient

66. Cationic surfactants The most common active ingredients:
quaternary ammonium compound (quats)
properties related to charge density
Highly charged cationic will be more strongly attracted to the negatively charged hair surface

67. Cationic surfactants (con.)
On the hair surface, the number, shape and size of the fatty chain in mol. are determinants
Two fatty acid chains > lubricity than one chain
Long chain > effective lubricant than short chain

68. Bodying agents
Conditioners are perceived to be more effective when thick and creamy
Using high level of fatty alcohol along with other waxy esters

69. Auxiliary emulsifiers
Some quats are good emulsifiers, some are not
Incompatibility with anionic surfactants
Surfactants emulsion stability can’t be obtained with cationic alone
Non-ionic surfactants are in used
Choosing 2 surfactants : should consider HLB (Hydrophilic Lipophilic Balance)

70. Oil components Should be considered the effect of oil on :
Ease of manufactures
Product stability
Using at typically low level, less affecting stability
Small quantities of exotic oil with attractive names may be included

71. Thickeners Salt solution are in used
Add only very small amount at a time (viscosity will peak at low concentration than in shampoo)
Add salt solution when emulsion is cold (maximum 30 oC)
Use dilute salt solution (10% max) add very slow with continue stirring
Small amount of salt solution with high-shear mixing
Try a small batch and scale up carefully

72. Manufacturing Using two phases method Heating oil and water phases
Combining together
Cooling process
According to high water phase /oil ratio
Only part of water is heated is formed
a concentrate emulsion
Adding the rest of water at cold stage

73. Clear Conditioners Using aqueous solution of quarts, polymers, or both
Conditioning other active ingredients such as :
Parthenol, water-soluble silicone derivative
Thickening by electrolyte as shampoo
Developing quite strong lather

74. “2-in-1” shampoos
- contain both cleansing and high levels of conditioning agents
- over 20% shampoos are sold of this type
- silicone is the basic substance derive from natural substances

75. How 2-in-1 formulations work: (1) surfactant molecules
(blue)and conditioner particles (pink) surround the hair;
each conditioner particle is trapped inside a crystal 'cage'

76. (2) The surfactant molecules are attracted to the
dirt on the hair surface and lift it away, leaving
the hair clean

77. (3) When the hair is rinsed, the conditioner particles are
released from their 'cages'; they are not washed away
but, because of their electrical charge (+), they are drawn towards the (-) charges of the hair

78. 4) They cling to the hair, smoothing out any roughness
on the surface and protecting the cuticle

79. Hair thickener Hair can be made thicken by
Causing it to swell
Coating it to increase its diameter
Hair will be swollen in water / more under alkali conditions
Powerful humectants may be used to increase moisture content of hair
Application of panthenol solution cause the swelling of hair

80. Styling aids Hair Sprays, Hair gels Various description terms :
Light hold, medium hold, strong hold, ultra hold, mega hold
The main ingredients in hair sprays are :
Polymer Solvent
Plastizer Neutralizer
Perfume Other addition n n n

81. Polymers Ideal hair spray polymer should be soluble in ethanol
Hydrophilic enough is be easily removed from hair by shampooing
Hydrophilic enough to compatible hydrocation propellants

82. Polymers (con.) Should give powerful hold without brittleness
Easily remove by combing or brushing
Must be good adhesion and not sticky
For example :
Vinyl pyrrolidone derivative
Vinyl acetate
etc.

83. Solvent Non-aerosol product
Ethanol alone or slightly dilute with water
Excellent solvent for most resins
The addition of water to solvent system may be necessary:
To improve water solubility of ingredients
To retard evaporation salt
To reduce cause
To prevent perception from on acid-resin based system

84. Plasticizers Using to modify the properties of polymer flim
Making it more flexible
Only small quantities are normally required
(0.5% of dry weight polymer)
For examples:
Ester
Various silicone
Protein
Polyol
Lanolin derivatives

85. Neutralizer Calculated from the acid value of the resin
Can be obtained from polymer

86. Hair Gels
Majority of gels on the market are aqueous/ aqueous alcoholic
Carboxyvinyl polymer are the most important/ carbomer 940
Create the clear gel foam
Have some fixative power
Contribute to overall hold of the formulation
As a primative film former

87. Hair gels (con.) Carbomer 940 gives the clearest gel
Degrades by UV light: loss of viscosity and clarity
Overcome by adding UV absorber
Sensitive with metal ion => catalyst gel to be degrade
Addition of EDTA is an effective way

88. Permanent Waving Mode of action is as follows:
Reduction of –S-S- bonds between cystine amino acid groping on an adjacent polypeptides chains
Reassignments of hair into its new position
Reforming of the –S-S- bonds by oxidation the various –SH residues will be linked into new partners on the adjacent chains

89. Factor affecting the efficacy of the product
Processing time
Processing temperature
Concentration of reducing agent
Ratio of lotion to hair quantities
Penetration of the lotion pH
The nature and the condition of untreated hair

90. Permanent waving Waving lotion are available in various physical foams
Clear, cloudy liquid, cream or lotion, gel or thickened liquid
Using low conductivity, demineralised water
Using equipment made of 316 grade stainless steel or prolypropylene for all contact parts
Avoiding heavy metal contamination which may be decompose the products and produce discoloration

91. Permantent waving (con.)
The addtion of sequestrans is needed
Emulsion type or gel-type product:
Required hot processing
Thioglycollate should be added last after cooling the mix

92. Permantent waving (con.)
The products can be extreme:
The products is at high pH and strong reducing
The sulfphide odour emitted during processing of the hair are very hard to mask

93. Neutralisation The reforming of the –S-S- bonds by oxidation
Oxidation is commonly carried out by hydrogen peroxide (easier using than the other oxidizing agent)
With a surfactant added to enhance penetration
The solution may be clouded or produced in form of a pourable emulsion

94. Neutralisation (con.)
Bromated, the second most popular type of neutralizer
Since both waving lotion and neutralizers
Usually have guite extreme pHs and exhibit considerable redox potential
They are not particularly susceptible microbiological contamination

95. Effect of Air and Sunlight

96. Hair dyes Temporary, semi-permanent, permanent dyes Temporary dyes
Any soluble colors can be used
The color does not penetrate to the hair shaft
Complete removable by a single shampoo

97. Hair dyes (con.)
Another mean is by using color spray organic and inorganic pigments can be suspended in gum-thickened or emulsion base

98. Semi-permanent dyes
Using dyestuffs whose cationic characteristic gives them a natural affinity of hair
Metallised dyes are not very compatible with salt
The blend of amphoteric, cationic, non-ionic surfactants with low salt levels is preferred
Performance may be enhanced by the inclusion of solvents

99. Semi-permanent dyes (con.)
Water causes considerable swelling of the hair shaft
Aqueous solution with some solvents cause even more
leading is greatly increasd dye uptake
Hair has more pores near the end than the root
Treated hair has more porous than untreated hair

100. Permanent hair dyes Permanent or oxidation dyes Consist of two parts
- A dye intermediate solution and oxidizing agent
- The latter always being hydrogenperoxide
Dye intermediates are blended of primary intermediates and coupling agents or modifiers in a suitable base

101. Permanent hair dyes (con.)
During the permanent dying of hair, the dye intermediate solution and oxidizing solution are mixed and applied to the hair
The primary intermediate are gradually oxidized
Then undergo coupling reaction with modifier

102. Permanent hair dyes (con.)
The primary intermediate are all small molecules can penetrate the hair shaft, particularly the wet, alkali conditions during the hair application
The oxidation and coupling reactions produce much larger molecules
Many of which are then “trapped” in the hair shaft
Thereby making the effect permanent

103. Some general remarks about product development:
Make sure that the discussion is clear,
the brief should include, as minimum :
Require performance parameters
in as much detail as possible

104. Benchmark product, unless the development is in a completely new area
General remarks (con.)
Benchmark product, unless the
development is in a completely
new area
Guidelines on costs
Purpose claims
The required timing

105. General remarks (con.)
1. Do not produce a Rolls Royce when a mini would be sufficient
2. Do not use new raw materials if one from existing stocks will do
3. Specification often appear virtually identical alternative sources of supplier should be investigated

106. General remarks (con.)
4. Ensure reproducibility on scale up making use of suitable plant and equipment
5. Keep formulations as simple as possible
6. Try to develop products which can be made as cheap as possible:
with minimum energy requirement
minimum time for processing

107. Thank You
Kob Khun Kha