Hair Care Products

1
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 gt
• 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.)

• 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.)
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.)

• 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 cant 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

1. Composition of stearate ester
2. Presence of alkanolamides and other materials
3. Rate of cooling
4. Shear rate of stirring
5. 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 (0.05-0.1)
• 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 gt lubricity than one chain
• Long chain gt 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 cant 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 gt 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
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