Some problems in Hair care product formulations and manufacturing

1. 11
Some Problems in Hair CareSome Problems in Hair Care
Product Formulations andProduct Formulations and
ManufacturingManufacturing
Assoc. Prof. Dr. Pleumchitt RojanapanthuAssoc. Prof. Dr. Pleumchitt Rojanapanthu
Pharmacy Department, Faculty of PharmacyPharmacy Department, Faculty of Pharmacy
Mohidol University, Bangkok, ThailandMohidol University, Bangkok, Thailand

2. 22
Shampoos ThickenerShampoos Thickener
and Foam Stabilizerand Foam Stabilizer
• ElectrolytesElectrolytes
• Alkalonamides or the alternativesAlkalonamides or the alternatives
• Polymeric materialsPolymeric materials

3. 33
• ElectrolyteElectrolyte
– ionic density of the solutionionic density of the solution
– size and shape of micellesize and shape of micelle
• Adding the same cation as that of primary anionicAdding the same cation as that of primary anionic
surfactantsurfactant
– Eg: amm.chloride amm. lauryl surphateEg: amm.chloride amm. lauryl surphate
sod. chloride sod. lauryl ether sulphatesod. chloride sod. lauryl ether sulphate
Thickener and Foam StabilizerThickener and Foam Stabilizer

4. 44
• Electrolyte should be added as solutionElectrolyte should be added as solution
(25% W/W)(25% W/W)
• Avoiding local concentration gelationAvoiding local concentration gelation
Thickener and Foam StabiliserThickener and Foam Stabiliser

5. 55
Viscosity/electrolyte curve for aViscosity/electrolyte curve for a
well-formulatedwell-formulated
shampooshampoo
Preferred
viscosity
range
% electrolyte

6. 66
Shampoos which need ThiningShampoos which need Thining
• Active matter is highActive matter is high
• Contain high levels of electrolytesContain high levels of electrolytes
• Large amt. of some amphoterics are presentLarge amt. of some amphoterics are present
• Addition of short-chain alcohol or glycol: ethonal,Addition of short-chain alcohol or glycol: ethonal,
isopropanolisopropanol
– Glycols are preferred (less odor/imflammable)Glycols are preferred (less odor/imflammable)

7. 77
AlkalonamidesAlkalonamides
• Mono-ethanolamide > effective than di- ethanolamideMono-ethanolamide > effective than di- ethanolamide
as foam stabiliser and thickeneras foam stabiliser and thickener
• Disadvantage : waxy solidDisadvantage : waxy solid
rrequired hot process of mixingequired hot process of mixing
• Among the group of lauric, lauric/myristic andAmong the group of lauric, lauric/myristic and
coconut mono- and di-ethanolamidecoconut mono- and di-ethanolamide
• Lauric mono-isopropanolamide is the most effectiveLauric mono-isopropanolamide is the most effective
thickener and foam stabiliserthickener and foam stabiliser

8. 88
Alkalonamide alternativesAlkalonamide alternatives
• PEG-6000 distearatePEG-6000 distearate
• PEG-55 propylene glycol oleatePEG-55 propylene glycol oleate
• PEG-120 methyl glucose dioleatePEG-120 methyl glucose dioleate
• Effective in systems based on someEffective in systems based on some
sulphosuccinates, ethoxylated sorbitansulphosuccinates, ethoxylated sorbitan
esters alkane sulphonates, lauryl sulphates,esters alkane sulphonates, lauryl sulphates,
low level of free fatty alcohols.low level of free fatty alcohols.

9. 99
Polymeric materialsPolymeric materials
• Natural gumsNatural gums:: guar, karaya, caragenan,guar, karaya, caragenan,
lacus beanlacus bean
Find little use in today’s shampoosFind little use in today’s shampoos
• Cellulose derivativeCellulose derivative:: hydroxyethyl cellulosehydroxyethyl cellulose
(HEC), carboxymethyl cellulose (CMC),(HEC), carboxymethyl cellulose (CMC),
hydroxypropyl methycellulose (HPMC)hydroxypropyl methycellulose (HPMC)

10. 1010
PerfumesPerfumes
• Simply added after any hot process is completeSimply added after any hot process is complete
• Solubilty problem:Solubilty problem:
– Premixing with a suitable solubiliserPremixing with a suitable solubiliser
– Ratio of mixing being determined by trial andRatio of mixing being determined by trial and
errorerror
• PEG-40 hydrogenated castor oil is mostly usedPEG-40 hydrogenated castor oil is mostly used
• Polysorbates may cause thiningPolysorbates may cause thining
– Premixing with alkalonamide at < 40 CPremixing with alkalonamide at < 40 C

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PreservativesPreservatives
• Most surfactants are already preservedMost surfactants are already preserved
• Chosen preservative system should pass aChosen preservative system should pass a
recognised challenge test in the finalrecognised challenge test in the final
formulationformulation
– Freshly preparedFreshly prepared
– AgingAging
– Accompanied by meaningful preservativesAccompanied by meaningful preservatives
assaysassays

12. 1212
Opacifier and PearlisersOpacifier and Pearlisers
• Aesthetic reasonAesthetic reason
• Occasionally used technique for unclear productOccasionally used technique for unclear product
Suggestion methodSuggestion method
• Buying ready made pearlised base (cheap)Buying ready made pearlised base (cheap)
– Make dilution adding to shampoo as hot mixingMake dilution adding to shampoo as hot mixing
• Buying highly concentrated pearlising agent (moreBuying highly concentrated pearlising agent (more
expensive)expensive)
– Adding as cold mix (2%)Adding as cold mix (2%)

13. 1313
Conditioning agentsConditioning agents
• Back-bone surfactants in shampoos mostlyBack-bone surfactants in shampoos mostly
are anionic surfactantsare anionic surfactants
• Majority active conditioning agents areMajority active conditioning agents are
cationic surfactantscationic surfactants

14. 1414
Problem solvingProblem solving
• Including more % of amphotericIncluding more % of amphoteric
surfactantssurfactants
• Reducing charge of anionic and cationicReducing charge of anionic and cationic
surfactants by ethoxylationsurfactants by ethoxylation
• Replacing cationic surfactants by usingReplacing cationic surfactants by using
cationic polymercationic polymer
• Adding high level of nonionic surfactantAdding high level of nonionic surfactant

15. 1515
Colour fadingColour fading
• Stability to pH variation and light can beStability to pH variation and light can be
predictedpredicted
• Interaction between colour and theInteraction between colour and the
complexation of modern shampoo basecomplexation of modern shampoo base
evaluated for each formulationevaluated for each formulation
– Natural sunlight (shelf life)Natural sunlight (shelf life)
– Accelerated conditionsAccelerated conditions

16. 1616
Colour fading (con.)Colour fading (con.)
• Minimised colour fading by incorporationMinimised colour fading by incorporation
of suitable UV absorberof suitable UV absorber
• Benzophenone – 4 and –2 water solubleBenzophenone – 4 and –2 water soluble
absorbers are most popular (0.05 – 0.1%)absorbers are most popular (0.05 – 0.1%)
• Colour should be added as a solutionColour should be added as a solution

17. 1717
ConditionersConditioners
• Hair charge surface negativeHair charge surface negative
• Anionic surfactants for shampooAnionic surfactants for shampoo
(usually C(usually C1212 /C/C1414) negative charge) negative charge
• Cationic surfactants for conditionerCationic surfactants for conditioner
(usually C(usually C1616 / C/ C1818 and quart with Cand quart with C2222))
positive chargepositive charge

18. 1818
Conditioners (con.)Conditioners (con.)
• Some quarts are relatively poorlySome quarts are relatively poorly
biodegradablebiodegradable
• ‘‘Ester quarts’is claimed to be betterEster quarts’is claimed to be better
• Properties related to charge densityProperties related to charge density
• Highly charged cation more stronglyHighly charged cation more strongly
attached to the negative-charged hairattached to the negative-charged hair
surfacesurface

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Conditioners (con.)Conditioners (con.)
• On the hair surface:On the hair surface:
– number., shape and size of fatty acid chain innumber., shape and size of fatty acid chain in
molecule are the determinantmolecule are the determinant
• A quart with two fatty acid chains providesA quart with two fatty acid chains provides
more lubricity than a quart with onemore lubricity than a quart with one
• More longer chainMore longer chain >>effective lubricanteffective lubricant
than shorter onethan shorter one

20. 2020
Conditioners (con.)Conditioners (con.)
• Using single fatty acid chain greasy hairUsing single fatty acid chain greasy hair
/ frequent use/ frequent use
• Using twin fatty acid chain on theUsing twin fatty acid chain on the
dried / damaged hairdried / damaged hair

21. 2121
ManufacturingManufacturing
• Simply diluting down a suitable quart with waterSimply diluting down a suitable quart with water
• The stability and effectiveness maybe limitedThe stability and effectiveness maybe limited
• The appearance of emulsion may be course andThe appearance of emulsion may be course and
grainy in texturegrainy in texture
• Low opacity/ the flow has high yield pointLow opacity/ the flow has high yield point
• Increased viscosity with timeIncreased viscosity with time
• Sensitivity to change manufacturing methodSensitivity to change manufacturing method

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Problem solvingProblem solving
• Introduction of other waxy component: estersIntroduction of other waxy component: esters
– Decrease H-bonding with OHDecrease H-bonding with OH--
__of fatty alcoholof fatty alcohol
– Decrease the viscosity risingDecrease the viscosity rising
• Addition of small amount of oilAddition of small amount of oil
– Smooth out the emulsionSmooth out the emulsion
– Increase opacityIncrease opacity
– Facilitate processingFacilitate processing
– Easier to obtain repeatable viscosityEasier to obtain repeatable viscosity

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Problem solving (con.)Problem solving (con.)
• Additon of a non-ionic to the emulsionAdditon of a non-ionic to the emulsion
– Can increase grealty in the emulsificationCan increase grealty in the emulsification
– Increase stability due to the formation of mixedIncrease stability due to the formation of mixed
micelles and the presence of mixed surfactantsmicelles and the presence of mixed surfactants
at the oil/water interface of the emulsionat the oil/water interface of the emulsion

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Bodying AgentsBodying Agents
• As shampoos, conditioners perceived to beAs shampoos, conditioners perceived to be
more effective when thick and creamymore effective when thick and creamy
• Using high levels of fatty alcohols withUsing high levels of fatty alcohols with
other waxy estersother waxy esters
– Improvement in handling of hair especiallyImprovement in handling of hair especially
when combingwhen combing

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Auxilliary EmulsifiersAuxilliary Emulsifiers
• Depending on HLBDepending on HLB
• Some quart mols. have emulsifierSome quart mols. have emulsifier
properties, some are notproperties, some are not
• Incompatibilty with anionic emulsifiersIncompatibilty with anionic emulsifiers
• Addition of non-ionic are preferredAddition of non-ionic are preferred
• Recommended to use two emulsifiers (highRecommended to use two emulsifiers (high
and low HLB)and low HLB)

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ThickenersThickeners
• Cationic emulsion do not usually requiredCationic emulsion do not usually required
thickenerthickener
• If needed, they usually response to salt in aIf needed, they usually response to salt in a
similar way as shampoosimilar way as shampoo
• The method of using thickening must beThe method of using thickening must be
treated with extreme cautiontreated with extreme caution
• Irreversible emulsion breakdown should beIrreversible emulsion breakdown should be
avoidedavoided

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SuggestionsSuggestions
• Add only small amount of salt solutionAdd only small amount of salt solution
at a time since viscosity will peak atat a time since viscosity will peak at
much lower salt level than that ofmuch lower salt level than that of
shampooshampoo
• Add salt solution at cold emulsionAdd salt solution at cold emulsion
(max 30 C)(max 30 C)
• Shear rate has effect on the emulsion;Shear rate has effect on the emulsion;
moderate shear rate should be usedmoderate shear rate should be used
• Try small scale before scaling upTry small scale before scaling up

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• Gum-type thickener: cellulose derivativeGum-type thickener: cellulose derivative
dominate for clear conditionerdominate for clear conditioner
• Carbomers incompatibility withCarbomers incompatibility with
cationicscationics
Suggestions (con.)Suggestions (con.)

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Permanent WavingPermanent Waving
Factor affecting the efficiency of the productsFactor affecting the efficiency of the products
• Processing timeProcessing time
• Processing temperatureProcessing temperature
• Concentration of reducing agentConcentration of reducing agent
• Ratio of lotion to hair quantitiesRatio of lotion to hair quantities
• Penetration of the lotionPenetration of the lotion
• pHpH
• The nature and condition of untreatedThe nature and condition of untreated
hairhair

30. 3030
• Procession timeProcession time
– Should not be longer than necessaryShould not be longer than necessary
– Home perm may be designed for longer processingHome perm may be designed for longer processing
• Processing temperatureProcessing temperature
– Will be ambient for most productsWill be ambient for most products
– For hot process: needs external mean of heat orFor hot process: needs external mean of heat or
exothermic chem. reaction (mixing before use)exothermic chem. reaction (mixing before use)
Permanent Waving (con.)Permanent Waving (con.)
Factor affecting the efficiency of the productsFactor affecting the efficiency of the products

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• Concentration of active ingredientsConcentration of active ingredients
– A wide range of concentration is availableA wide range of concentration is available
– Will not be changed during use except by dilutionWill not be changed during use except by dilution
• The ratio of lotion to hairThe ratio of lotion to hair
– Insufficient lotion to treat when very long hair isInsufficient lotion to treat when very long hair is
involvedinvolved
Permanent Waving (con.)Permanent Waving (con.)
Factor affecting the efficiency of the productsFactor affecting the efficiency of the products

32. 3232
• The penetration of the lotionThe penetration of the lotion
– Enhanced by the inclusion of surfactantEnhanced by the inclusion of surfactant
– Mostly non-ionic and anionicMostly non-ionic and anionic
– Hydrogen bond breaker: ureaHydrogen bond breaker: urea
Permanent Waving (con.)Permanent Waving (con.)
Factor affecting the efficiency of the productsFactor affecting the efficiency of the products

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• pHpH
– Too low product doesn’t work wellToo low product doesn’t work well
– Too high severe hair damageToo high severe hair damage andand high irritationhigh irritation
of the skin of scalpof the skin of scalp
– Maximum bond cleavage occurs at pH 9Maximum bond cleavage occurs at pH 9
> 8.5 bond reformation is less complete> 8.5 bond reformation is less complete
< 7.5 amt. of bond cleavage is low and< 7.5 amt. of bond cleavage is low and
reformation is more completereformation is more complete
Permanent Waving (con.)Permanent Waving (con.)
Factor affecting the efficiency of the productsFactor affecting the efficiency of the products

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- Conventional ammonium thio-glycollate lotion- Conventional ammonium thio-glycollate lotion
Approx 9.2Approx 9.2++ 0.20.2
- pH is currently restricted by law to a max 9.5- pH is currently restricted by law to a max 9.5
and total thio-glycollate to 8% (free acid)and total thio-glycollate to 8% (free acid)
Permanent Waving (con.)Permanent Waving (con.)
Factor affecting the efficiency of the productsFactor affecting the efficiency of the products

35. 3535
• Hair type and conditionHair type and condition
– Coarse hair require more severe treatmentCoarse hair require more severe treatment
– Fine and damaged hair require gentleFine and damaged hair require gentle
treatmenttreatment
Permanent Waving (con.)Permanent Waving (con.)
Factor affecting the efficiency of the productsFactor affecting the efficiency of the products

36. 3636
• Other Variables:Other Variables:
– Number and diameter of the rollerNumber and diameter of the roller
– Tension of the hair on the rollerTension of the hair on the roller
– The speed at which the operation is carried outThe speed at which the operation is carried out
Permanent Waving (con.)Permanent Waving (con.)
Factor affecting the efficiency of the productsFactor affecting the efficiency of the products

37. 3737
Product Evaluation and TestingProduct Evaluation and Testing
Methods of testing and evaluating productsMethods of testing and evaluating products
are essential to confirm that products areare essential to confirm that products are
met the requirementsmet the requirements
• In vitro method: lab-based instrumentalIn vitro method: lab-based instrumental
techniques for initial screeningtechniques for initial screening
• In vivo method: salon or consumer testingsIn vivo method: salon or consumer testings

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• EC “Cosmetic Directives specify that : “ProductsEC “Cosmetic Directives specify that : “Products
should remain safe and effective for two andshould remain safe and effective for two and
a half years”a half years”
The Test Methods:The Test Methods:
– High and low temperature storageHigh and low temperature storage
– Freeze / thawing cyclingFreeze / thawing cycling
– CentrifugationCentrifugation
– etcetc
Stability TestingStability Testing

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Compatibility TestingCompatibility Testing
• The compatibility testing should be carried outThe compatibility testing should be carried out
• Two sets of tests to be runned in parallelTwo sets of tests to be runned in parallel
– One set in actual containers to be usedOne set in actual containers to be used
– The other in inert container, usually glassThe other in inert container, usually glass
• Should give valuable comparative dataShould give valuable comparative data

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Claim JustificationClaim Justification
• If there is specific claim, the manufacturerIf there is specific claim, the manufacturer
mustmust be able to justify:be able to justify:
– Known properties of raw materialsKnown properties of raw materials
– Usage level and condition of useUsage level and condition of use
– Lab testing, salon trialsLab testing, salon trials
• consumer panel test: the no. and type of subjectsconsumer panel test: the no. and type of subjects

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Product SafetyProduct Safety
• If a formulation is a ‘standard’ one, no furtherIf a formulation is a ‘standard’ one, no further
action is necessaryaction is necessary
• If new raw material/unusual combinations ofIf new raw material/unusual combinations of
materials are usedmaterials are used
• If any ingredient is present at an unusually highIf any ingredient is present at an unusually high
levellevel

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Product Safety (con.)Product Safety (con.)
• The opinion of a qualified dermatologist,The opinion of a qualified dermatologist,
ophthalmologist, toxicologist may be an valuableophthalmologist, toxicologist may be an valuable
backup to the cosmetic chemist’s judgementbackup to the cosmetic chemist’s judgement
• If there is real doubt about the total safety,If there is real doubt about the total safety,
further testing should be in the form of humanfurther testing should be in the form of human
volunteer studyvolunteer study

43. 4343