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Study says adding CAPB beforehand, makes Cetrimonium chloride compatibe with SLES
I got several failures adding Cetrimonium chloride to water first, then SLES and everything else
while I didn’t see any precipitate forming, it got disgustingly sticky and stringy, then it bacame water-thin and it couldn’t be thickened with salt. It seemed to have little conditioning or cleaning activity too.In latter experiments adding CTAC as the last thing, it seemed to work.
I thought it was because SLES doesn’t react with CTAC when it’s dilutedBut this study says that CTAC won’t react with SLES if CAPB is added first:
Advances in shampoo formulation: synergism of anionic/cationic/zwitterionic surfactant ternary system
Abstract
There is a rule among cosmetic formulators of not mixing an anionic
surfactant with a cationic surfactant in the same formulation, especially
if it’s a clear product, since this interaction will result in the appearance
of turbidity (precipitation). Nevertheless, vast reports show not only the
possible but also synergistic combination of surfactants with opposed
charge, conferring unique properties to the final product. The aim of this
study is to evaluate the use of a co-surfactant as a novel tool for
maintaining high levels of both cationic and anionic surfactants mixed in
the same product, without precipitation. Not only we found this possible
at certain rates, but also attributes of the system such as viscosity,
detergency and foam stability, were improved.
http://www.journalbinet.com/uploads/2/1/0/0/21005390/41.17.5.2_advances_in_shampoo_formulation_synergism_of_anionic_cationic_zwitterionic_surfactant_ternary_system.pdf
… Tested samples were prepared by combining variable
amounts of Sodium laureth sulfate (SLES), Cocamidopropyl betaine (CAPB) and Cetrimonium chloride
(CTC)…… When SLES and CTC are mixed at a similar concentration (1 wt%), precipitation occurs as a result of the
formation of a SLES-CTC complex…… On the contrary, when CAPB is introduced in the mixture before the CTC, instead of precipitation, there is an increase in viscosity which continues as the level of CAPB increases, while maintaining a 1 wt% fixed concentration of SLES and CTC…
… But after a peak in viscosity at 1.5 wt% of CAPB, a
gradual descent is followed with every new addition of surfactant. At this point, micelles become less
polar with every CAPB increase, resulting in chain contraction and relative viscosity decrease…… In general, it is easy for the SLES-CTC ion pairs to be precipitated from solution. However, the ion pairs have been “solubilized” by forming mixed micelles with CAPB in the present case, resulting in an increase of the could point, similarly to the observed linear increase in the clouding temperature of Triton X-100 on addition of small amounts of Sodium dodecyl sulfate (Valaulikar, 1985)…
Step 3 – Learn the rational behind the formula
Seems to be the hardest part, so far.
https://chemistscorner.com/making-cosmetics-the-scientific-way/ -
33 Replies
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1% or 1.5% of surfactant is not going to make a shampoo!
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Agree. Weird concentrations were used in the study.
But it kind of proves that cationic surfactants can be made to work with anionic ones.
Do you know if Behentrimonium, either as Chloride or as Methosulfate, can be made to work with SLES/SLS?
This chinese patent claims they used them both and it passed stability tests (too bad the stability test tables are in chinese)
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These sample formulations from Kao
add SLES and Behentrimonium Chloride in the same recipe seemingly without any problems and passed stability tests (1 month 40ºC/RT/5ºC)I wonder if other ingredients (like laureth carboxylates) play a role in their stability, besides CAPB/hydroxysultaine order of addition?
PEARLED SHAMPOOMILD CONDITIONINGRECOMMENDED OPERATIVE METHOD
• Add to the deionized water each component, keeping the abovementioned order and stirring
after each addition until total homogeneity.AKYPO SOFT 100 BVC (Sodium Laureth-11 Carboxylate) 4.0%
EMAL® 227E Sodium Laureth Sulfate 25.0%
BETADET S-20 Lauryl Hydroxysultaine 5.0%
LEVENOL H&B Glycereth - 2 Cocoate 2.0%
AMIDET A 15 Trideceth-2 Carboxamide MEA 1.0%Disperse QUARTAMIN AB in part of the water (10%) at 65ºC, and add it to the rest of the
formulation. By doing this it is not necessary to heat the entire product.
QUARTAMIN Behentrimonium Chloride AB 0.5 %
http://www.kaochemicals-eu.com/sites/default/files/formulations/C-142.pdf
CONDITIONING SHAMPOO
TransparentRECOMMENDED OPERATIVE METHOD
Heat the water up to 70ºC and add the following ingredients: BETADET® HR, QUARTAMIN®
AB,
polyquaternium-10 and polyquaternium-7 and then stir until complete homogenizationBETADET HR Cocomidopropyl Betaine 8.3%
QUARTAMIN AB Behentrimonium Chloride 0.6%
Polyquaternium-7 1.1%
Polyquaternium-10 0.4%Cool down the temperature until 40-35ºC.
Add each one of the remaining ingredients, EMAL®
270D, AKYPO® RLM 45CA, AMIDET® N and
KAO®
SOFCARE GP-1 and stir until complete homogenization after each addition
EMAL 270D Sodium Laureth Sulfate 16.4%
AKYPO RLM 45CA Laureth-6 Carboxylic Acid 4.2%
AMIDET N PEG-4 Rapeseedamide 1.5%
KAO SOFCARE GP-1 PPG-3 Caprylyl Ether 0.6%
Add the other additives…
http://www.kaochemicals-eu.com/sites/default/files/formulations/c-244.pdf -
Update:
I tried
Phase A:
30% deionized water
5% Polyquaternium 7
2% Cetrimonium Chloride
2.8% active Coco-betaine (9.33% as-supplied @ 30%)Phase B:
15% water
0.1% EDTA Na-4
0.1% Menthol
5% erythritol
12% Texapon N70 (8.4% active SLES)
1.5% Cocamide DEA
5% Euperlan PK 771 Benz pearlizerWhile phase B has too little water, after adding Phase B to A, a disgusting, slimy gel formed.
I just realized that I have Coco-betaine and not CAPB. I will retry with CAPB to see if it gets any different,
but I believe it’s failing because bare SLES must be added right after CAPB, and not just a phase B containing it. -
Thanks for the experiment, interested in this. I could probably repeat the Akypo formula ( I have RLM45-CA). I don’t have the Amidet N though, maybe I could sub cocamide MEA? Nor do I have the SOFCARE GP-1, I could try water dispersible silicone to replace it? (Silsense DW18) and I will have to use cetrimonium chloride not behentrimonium chloride.
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Update:
CAPB gave pretty similar effects to Coco-Betaine: a thick slimeI took out most other ingredients as to see what’s causing the problem
Ingredients are listed in order of addition. All ingredients were properly dissolved before adding the next one.- 45% water
- 5% Polyquaternium-7 (too bad Polyquaternium-10 hasn’t arrived yet)
- 2% Cetrimonium Chloride (some bubbles appear, as expected)
- 2.8% active CAPB = 9.33% as supplied @ 30% solution (at this point the whole solution becomes silightly yellow, but likely just because CAPB is a bit yellow/orange itself)
- 8.4% active SLES = 12% Texapon N70 (it sharply thickens to a disgusting white slime)
According to my experimentation notes, a different addition order gave good results.
I’ll repeat the experiment with just the above mentioned ingredients, in another order.
I’ll keep you posted. -
There is a problem with the quoted Akypo formula with the RLM45 CA. I don’t see the neutraliser. It is strongly acidic and must be neutralised, also its pH controls whether it is anionic, or cationic.
If you look at Akypo’s procedure, it is AMPHO->CAT->CAT->CAT. Cool down. Then add AN->CRYPTO AN
AKYPO® RLM 45 CA is a crypto-anionic surfactant - laureth-6 carboxylic acid - (it combines the properties of the anionic and non-ionic surfactants). It improves lathering and enhances quats and hair dyes efficiency. (ULP)
At this point I am getting the distinct impression that you need to use the quoted Akypo surfactant. I will do an experiment if I have the time. -
I suspect you are confusing what Kao used, guar hydroxypropyl trimonium chloride, with simpler, non compatible quats. I can’t replicate this bc I don’t have any cationic gum here.
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Several conditioning shampoos, all around the world seem to use Cetrimonium chloride with laureth-sulfates, seemingly without problems.
While I repeat the experiment in a different addition order,
I’ll list some of themI know this is a pet shampoo. It’s weird it doesn’t contain any CAPB along CTAC
Water, Sodium Laureth Sulfate, Sodium C14 – 16 Olefin Sulfonate, Sodium Chloride, Cocamide Diethanolamine, Cetrimonium Chloride, Yucca Schidigera Extract, Fragrance, Dye.
http://quadrupedpetcare.com/wp/ingredientsSatinique® Extra Volume ShampooIngredients: Water/Eau, Sodium Laureth Sulfate, Cocamidopropyl Betaine, Sodium Chloride, Glycereth-26, Fragrance/Parfum, C12-15 Alkyl Lactate, Hydroxypropyl Methylcellulose, PEG-60 Hydrogenated Castor Oil, Polyurethane-14, Cetrimonium Chloride, Guar Hydroxypropyltrimonium Chloride, Tetrasodium EDTA, AMP-Acrylates Copolymer, Citric Acid, Creatine, Macadamia Ternifolia Seed Oil, Dipropylene Glycol, C10-40 Isoalkylamidopropylethyldimonium Ethosulfate, Aloe Barbadensis Leaf Juice, PPG-12-Buteth-16, Triethanolamine, Dicalcium Phosphate Dihydrate, Sodium PCA, Sodium Lactate, Arginine, Limnanthes Alba (Meadowfoam) Seed Oil, Aspartic Acid, PCA, Hydrolyzed Soy Protein, Glycine, Alanine, Methylchloroisothiazolinone, Ceramide 2, Serine, Ceramide 3, Valine, Behenic Acid, Cholesterol, Isoleucine, Proline, Threonine, Methylisothiazolinone, Biotin, Histidine, Phenylalanine, Perilla Ocymoides Leaf Extract.
http://www.amway.ca/Shop/Product/ProductDetailPrintPreview.aspx?itemno=3698&in=1&mi=1&ri=1&rnr=1&apf=1&aprc=1&ihc=0&ici=1&pt=1&ci=1Product INCI Supplier % Di Water 25.55 Celquat® SC-240 (Polyquaternium-10) 1 0.30 Ammonium lauryl sulfate (28%) 30.00 Ammonium laureth-2 sulfate (26%) 30.00 Dimethicone 60000 cS 0.80 Dimethicone 350 cS 1.20 ArlasilkTM Phospholipid PLN 2 4.00 Estol® 3750 3 2.00 Cetearyl Alcohol 1.00 Monamid® CMA 4 3.00 ArlasilkTM Phospholipid® SV 5 1.20 Cetrimonium chloride 0.75 Fragrance 0.20 Preparation:
Procedure
To water slowly add the Celquat SC-240 with high speed agitation
while heating to 70°C.
When the Celquat SC-240 is dissolved,
add the ammonium
lauryl sulfate and ammonium laureth sulfate
with moderate agitation.
Add dimethicone fluids to ArlasilkTM
Phospholipid PLN,
then add to batch.
When temperature reaches 70°C add Estol 3750,
cetearyl alcohol and Monamid CMA.
Add the ArlasilkTM Phospholipid SV and stir.
Begin cooling to 50°C then add the cetrimonium chloride.
Begin cooling to 45°C, then add colour, fragrance,
and preservative as required.https://www.personalcaremagazine.com/formulation-details/419/2-in-1-shampoo?companyid=1287
Ingredient List
Water, Sodium Cocoyl Isethionate, Sodium Lauryl Sulfate, Sodium Laureth Sulfate, Cocamidopropyl Betaine, Sodium Chloride, Lauryl Glucoside, Stearyl Citrate, Disodium Laureth Sulfosuccinate, Polyquaternium-10, Guar Hydroxypropyltrimonium Chloride, Amodimethicone, Cetrimonium Chloride, Fragrance, Trideceth-12, Tetrasodium EDTA, Phenoxyethanol, Caprylyl Glycol, Ethylhexylglycerin, Hexylene Glycol, Sodium Hydroxide
http://phique.com/product/phique-moisturizing-shampoo/
Water, Sodium Laureth Sulfate, Dimethiconol, Cocamidopropyl Betaine, Perfume, Sodium Chloride, Carbomer, TEA-Dodecylbenzenesulfonate, Amodimethicone, Guar Hydroxypropyltrimonium Chloride, Citric Acid, Disodium EDTA, Mica, Sodium Benzoate, Cyclotetrasiloxane, Trideceth-10, DMDM Hydantoin, Phenoxyethanol, Titanium Dioxide, Trideceth-12, Cetrimonium Chloride, Cyclopentasiloxane, Magnesium Nitrate, Mineral Oil, Hydrolyzed Silk, Dimethyl Palmitamine, Methylchloroisothiazolinone, Magnesium Chloride, Methylisothiazolinone, Iodopropynyl Butylcarbamate, Benzoic Acid, Acetic Acid, Sodium Sulfate, CI 17200
https://www.sunsilk.com.ph/hair-products/shampoo/perfect-straight-shampoo.html
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Well the obvious thing to do is to try simply making a 10% solution of AKYPO RLM45 CA, and add say 2% of CETAC to it, and see what happens. I can do this, so I will try it and see. I will add the CETAC prior to neutralising the LS and then I will neutralise it to check if further changes take place.
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OK.
1. Added 10g RLM 45CA (.9AS) to 90g water, AS level 9%. Result: milky fluid, acidic.
2. Added 2g CETAC and mixed. No apparent physical change.
3. Tested for foam. Zero foam generation.
4. Neutralised the mixture to pH6 using NaOH. Some foam apparent on mixing.
5. Tested for foam. Now producing foam.
6. Removed excess to get 80g of mixture. Added 20% SLES, .3AS, for 6% SLES.
Mixed.
Some thickening evident but not to the level of a finished product.
No other physical change.
Tested for foam: plentiful.
Aroma: reminiscent of pineapple.I will keep the result under observation but so far it does appear that the laureth-6 carboxylate is able to “protect” the CETAC from reacting with the SLES to produce slime.
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Update:
Now I experimented another addition order:
45% deionized water- 12% Texapon N70 (SLES, 8.4% active)
- 9.33% Dehyton K (CAPB, 2.8% active) as expected it becomes a bit thicker.
- 2% Dehyquart A (Cetrimonium Chloride) now it becomes thicker, but not as much as in the previous addition order, and no slime was formed. Although it became whitish, it seems to have some bubbles in it despite not stirring it hard, unlike the previous flat-white slime.
According to my previous experiments, it should become thinner, clearer and bubble free by tomorrow.
So I left it standing still,
and protected from light (IDK if darkness will make any difference)
I will post results tomorrow.This simple experiment clearly depicts how changing the addition order can have a huge impact on the end result, when working with anionics+cationics.@Belassi did you get the white slime too?
What addition order/concentrations led to slime forming?
Was it
1 CETAC
2 CAPB
3 SLES (or ALES)? -
Please see my post, the entire procedure was explained. The result is still stable.
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I tried the test item as a shampoo this morning. All seemed well until I got a tiny amount in my eye. On a scale of 1-10 the irritation was 11… definitely not something I would want to sell!
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This is CTAC, CAPB, SLES order
disgustingly thick and slimy = useless
This is SLES, CAPB, CETAC order
after being left standing still for 24 hours = pretty clear and not too thick and nicely conditioning.
The same one above.
Even gentle stirring makes it whitish and with some tiny white specs, which I believe this might be mild insolubility or incompatibility.
If left standing still it reverts back to clear.
It doesn’t seem to affect its conditioning properties, and white specs may well be hidden behind pearlizer.
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I just wanna say this thread is super interesting! The contract manufacturer I work for doesn’t really do hair products so it’s really cool to see in depth discussion like this even if I’m not going to use the information. I’ve enjoyed following you guys’ experiments.
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Cetrimonium bromide and cetrimonium chloride were severe ocular irritants that caused irreversible damage at 25% and 10%, respectively, in in vitro studies. Ocular irritation was moderate at 2.0% for cetrimonium chloride and mild for behentrimonium chloride at 3.0%.
Is this something I want to include in a shampoo? -
Here’s the study they (mis)quoted
They probably mistook Cetrimonium Cl for Steartrimonium Cl, which is really irritating.F I N A L R E P O R T O N T H E S A F E T Y A S S E S S M E N T O F
C E T R IM O N IU M C H L O R ID E , C E T R IM O N IU M B R O M ID E ,A N D S T E A R T R IM O N IU M C H L O R ID E1In VivoGroups of six albino male rabbits of the SPF - Russian strain were used to assess the ocular irritation potential of 0.1% , 0.5% , 1.2% , and 2.5% (w /w )Cetrimonium Chloride. The right conjunctival sac of each rabbit wasinstilled with 0.1 m L of Cetrimonium Chloride, and the left eye served asan un treated control. The eyes were examined 24 h later both with an dwithout ¯ uorescein stain in g . All of the eyes were rinsed with 0.9%sodium chloride and examined at 48 an d 72 h . The results are reportedin Table 4. The investigators reported that after 6, 14, and 21 days, all ofthe eyes were restored to normal conditions (D anoch em o, 1983b)…The ocular irritation potentia l of 1 % and 1 0 % solutions ofCetrimonium Chloride was investigated by instilling one conjunctivalsac of each of two rabbits with 0 .2 mL of either solution . Observationswere made after 1 , 24, and 48 h. The overall scores for the 1 % and 1 0%Cetrimonium Chloride solutions were 3.6 and 47.5 , respectively, of apossible maximum score of 110 ( A r m o u r I n d u st r i a l C h e m i c a l sC o m p a n y, 1967).Steartrimonium Chloride ( dose not stated ) was severely irritating to the eyes of nine rabbits. Both r in sed and unr in sed eyes had irritation for up to 13 days after administration . One rabbit had red watery discharge, and six had hemorrhagic peripheral areas ( S h er ex C h e m icalC o m p a n y, Inc., 1986).
I tag ak i et al. ( 1 99 1 ) investigated the ocular irritation potential of Steartrimonium Chloride. The conjunctival sac of one eye of each of three rabbits was instilled with 100 mL o f 10 % aq . Steartrimonium Chloride. Steartr imonium Chloride was highly irritating ; the total irritation score ( maximum possible score, 110 ) was 60.3 , and the maximum corneal score was 36.7.In another study, 100 mL of a 5% ( w /v ) solution of Steartrimonium Chloride was instilled into the conjunctival sac of guinea pigs. The eyes were scored for signs of irritation after 0.5, 1, 2, 3, 4, 5, 6, an d 24 h .Steartrimonium Chloride was extremely irritating , having a total irritationscore of 96 (maximum possible score, 110) (B racher et al., 19 88) .
https://eurekamag.com/pdf/008/008686448.pdf -
I wonder if there is a synergy with the rest of the surfactants that makes it 11/10.
@Gunther you need to consider the pH and how it affects the CAPB. If it behaves as anionic it will most likely fail. Perhaps if you add citric acid before adding the CETAC it will make it compatible.
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The RLM45CA is what we use in our sulphate-free product and it does not cause irritation. So it’s either the SLES or CETAC or both and I suspect the CETAC because I had to wait hours for the irritation to subside.
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Update:
Now Cocamide DEA thickened it again, slime returned.
I’ll have to stick to my old recipe (discovered by accident), where CTAC is added last, perhaps only before pearlizer.@DAS that’s a great idea. I’ll try it.
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In this study they made Silicone Quaternium-20 compatible with SLES
Silicone Anionic / Silicone Cationic Complex Silicone Quaternium 20Just mixing SLES and Silicone Quaternium-20 yields an insoluble separation:
Table 6. Shows that the silicone quaternary itself is not soluble insodium laureth sulfate, while the complex is soluble.Note The SELS/Silicone complex is clear, while the incompatibleSELS/ Quat in two layers.They used to previous phases, before adding cationics
one with SLES+CAPB
the second one with SLES+Cocamide DEA+CAPB+EGDS
I wonder if having a separate phase for Cocamide DEA with CAPB and SLES prevents it from reacting with cationics (even though C-DEA is generally regarded as nonionic).
I believe TEA is only meant to neutralize the Carbopol (acrylates copolymer).A simple formula, certainly worth trying,
I will, with Polyquaterniums and Cetrimoniums instead of SiliconeQ-20. -
After what happened to me, I will not be using CETAC in a shampoo. I’ll stick to polyquaternium 7 I think. Or it will stick to me…
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Update:
I just made an experiment with a similar formulaPhase A
22% deionized water
0.1% EDTA Na-4
0.4% preservative
0.25% menthol
5% eryhthritol
10% Texapon N70 (8.4% active SLES)
5% CAPB solution (1.5% active CAPB)Phase B
18% water
2% Texapon N70 (1.4% active SLES)
4.33% CAPB solution (1.3% active CAPB)
1.2% Cocamide DEA
5% Euperlan PK 771 BenzPhase C
5% water
2% Cetrimonium Chloride
2% Polyquaternium 7%Somehow phase A+B felt thicker than expected, despite no cationic being added yet.
While adding phase C didn’t seem to immediately thicken it or make it slimy
it did when filling up to 100% (q.s.), with about 10% water.I’ll try again with a variation of my previous working recipe, in that order.
It had just 3.5% active SLES + 1.5% active SLS for a low-poo shampoo. As expected it was low foaming (but not that low cleaning power)
But later on I’ll try it with 7-8% active SLES to see how it works -
Lower the DEA to half and you will see a significant decrease of viscosity. Also you should consider DEA has 80 or 90% active.
What’s the purpose of erythritol?. doesn’t make it sticky?.
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