Thickeners are the skeleton structure and core foundation of various cosmetic formulations, and are crucial to the appearance, rheological properties, stability, and skin feel of products. Select commonly used and representative thickeners of different types, prepare them into aqueous solutions with different concentrations, test their physical and chemical properties such as viscosity and p H, and use quantitative descriptive analysis to evaluate their appearance, transparency, and multiple skin and skin properties during and after use. Sensory tests were carried out based on sensory indicators, and the literature was searched to summarize and summarize various types of thickeners, which could provide a certain reference for cosmetic formula design.
1. Description of thickener
There are many substances that can be used as thickeners. From the perspective of relative molecular weight, there are low-molecular thickeners and high-molecular thickeners; from the perspective of functional groups, there are electrolytes, alcohols, amides, carboxylic acids and esters, etc. Wait. Thickeners are classified according to the classification method of cosmetic raw materials.
1. Low molecular weight thickener
1.1.1 Inorganic salts
The system that uses inorganic salt as a thickener is generally a surfactant aqueous solution system. The most commonly used inorganic salt thickener is sodium chloride, which has an obvious thickening effect. Surfactants form micelles in aqueous solution, and the presence of electrolytes increases the number of associations of micelles, leading to the transformation of spherical micelles into rod-shaped micelles, increasing the resistance to movement, and thus increasing the viscosity of the system. However, when the electrolyte is excessive, it will affect the micellar structure, reduce the movement resistance, and reduce the viscosity of the system, which is the so-called “salting out”. Therefore, the amount of electrolyte added is generally 1%-2% by mass, and it works together with other types of thickeners to make the system more stable.
1.1.2 Fatty alcohols, fatty acids
Fatty alcohols and fatty acids are polar organic substances. Some articles regard them as nonionic surfactants because they have both lipophilic groups and hydrophilic groups. The existence of a small amount of such organic substances has a significant impact on the surface tension, omc and other properties of the surfactant, and the size of the effect increases with the length of the carbon chain, generally in a linear relationship. Its principle of action is that fatty alcohols and fatty acids can insert (join) surfactant micelles to promote the formation of micelles. The effect of hydrogen bonding between the polar heads) makes the two molecules arranged closely on the surface, which greatly changes the properties of the surfactant micelles and achieves the effect of thickening.
2. Classification of thickeners
2.1 Nonionic SAA
2.1.1 Inorganic salt
Sodium chloride, potassium chloride, ammonium chloride, monoethanolamine chloride, diethanolamine chloride, sodium sulfate, sodium phosphate, disodium phosphate and pentasodium triphosphate, etc.
2.1.2 Fatty alcohols and fatty acids
Lauryl Alcohol, Myristyl Alcohol, C12-15 Alcohol, C12-16 Alcohol, Decyl Alcohol, Hexyl Alcohol, Octyl Alcohol, Cetyl Alcohol, Stearyl Alcohol, Behenyl Alcohol, Lauric Acid, C18-36 Acid, Linoleic Acid, Linolenic acid, myristic acid, stearic acid, behenic acid, etc.
2.1.3 Alkanolamides
Coco Diethanolamide, Coco Monoethanolamide, Coco Monoisopropanolamide, Cocamide, Lauroyl-Linoleoyl Diethanolamide, Lauroyl-Myristoyl Diethanolamide, Isostearyl Diethanolamide, Linoleic Diethanolamide, Cardamom Diethanolamide, Cardamom Monoethanolamide, Oil Diethanolamide, Palm Monoethanolamide, Castor Oil Monoethanolamide, Sesame Diethanolamide, Soybean Diethanolamide, Stearyl Diethanolamide, Stearin Monoethanolamide, stearyl monoethanolamide stearate, stearamide, tallow monoethanolamide, wheat germ diethanolamide, PEG (polyethylene glycol)-3 lauramide, PEG-4 oleamide, PEG-50 tallow amide etc.
2.1.4 Ethers
Cetyl polyoxyethylene (3) ether, isocetyl polyoxyethylene (10) ether, lauryl polyoxyethylene (3) ether, lauryl polyoxyethylene (10) ether, Poloxamer-n (ethoxylated Polyoxypropylene ether) (n=105, 124, 185, 237, 238, 338, 407), etc.
2.1.5 Esters
PEG-80 Glyceryl Tallow Ester, PEC-8PPG (Polypropylene Glycol)-3 Diisostearate, PEG-200 Hydrogenated Glyceryl Palmitate, PEG-n (n=6, 8, 12) Beeswax, PEG -4 isostearate, PEG-n (n=3, 4, 8, 150) distearate, PEG-18 glyceryl oleate/cocoate, PEG-8 dioleate, PEG-200 Glyceryl Stearate, PEG-n (n=28, 200) Glyceryl Shea Butter, PEG-7 Hydrogenated Castor Oil, PEG-40 Jojoba Oil, PEG-2 Laurate, PEG-120 Methyl glucose dioleate, PEG-150 pentaerythritol stearate, PEG-55 propylene glycol oleate, PEG-160 sorbitan triisostearate, PEG-n (n=8, 75, 100) Stearate, PEG-150/Decyl/SMDI Copolymer (Polyethylene Glycol-150/Decyl/Methacrylate Copolymer), PEG-150/Stearyl/SMDI Copolymer, PEG- 90. Isostearate, PEG-8PPG-3 Dilaurate, Cetyl Myristate, Cetyl Palmitate, C18-36 Ethylene Glycol Acid, Pentaerythritol Stearate, Pentaerythritol Behenate , Propylene Glycol Stearate, Behenyl Ester, Cetyl Ester, Glyceryl Tribehenate, Glyceryl Trihydroxystearate, etc.
2.1.6 Amine oxide
Myristyl amine oxide, isostearyl aminopropyl amine oxide, coconut oil aminopropyl amine oxide, wheat germ aminopropyl amine oxide, soybean aminopropyl amine oxide, PEG-3 lauryl amine oxide, etc.
2.2 Gender SAA
Cetyl Betaine, Coco Aminosulfobetaine, etc.
2.3 Anionic SAA
Potassium oleate, potassium stearate, etc.
2.4 Water-soluble polymers
2.4.1 Cellulose
Cellulose, cellulose gum, carboxymethyl hydroxyethyl cellulose, cetyl hydroxyethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, formazan Base cellulose, carboxymethyl cellulose, etc.
2.4.2 Polyoxyethylene
PEG-n (n=5M, 9M, 23M, 45M, 90M, 160M), etc.
2.4.3 Polyacrylic acid
Acrylates/C10-30 Alkyl Acrylate Crosspolymer, Acrylates/Cetyl Ethoxy(20) Itaconate Copolymer, Acrylates/Cetyl Ethoxy(20) Methyl Acrylates Copolymer, Acrylates/Tetradecyl Ethoxy(25) Acrylate Copolymer, Acrylates/Octadecyl Ethoxyl(20) Itaconate Copolymer, Acrylates/Octadecane Ethoxy(20) Methacrylate Copolymer, Acrylate/Ocaryl Ethoxy(50) Acrylate Copolymer, Acrylate/VA Crosspolymer, PAA (Polyacrylic Acid), Sodium Acrylate/ Vinyl isodecanoate crosslinked polymer, Carbomer (polyacrylic acid) and its sodium salt, etc.
2.4.4 Natural rubber and its modified products
Alginic acid and its (ammonium, calcium, potassium) salts, pectin, sodium hyaluronate, guar gum, cationic guar gum, hydroxypropyl guar gum, tragacanth gum, carrageenan and its (calcium, sodium ) salt, xanthan gum, sclerotin gum, etc.
2.4.5 Inorganic polymers and their modified products
Magnesium aluminum silicate, silica, sodium magnesium silicate, hydrated silica, montmorillonite, sodium lithium magnesium silicate, hectorite, stearyl ammonium montmorillonite, stearyl ammonium hectorite, quaternary ammonium salt -90 montmorillonite, quaternary ammonium -18 montmorillonite, quaternary ammonium -18 hectorite, etc.
2.4.6 Others
PVM/MA decadiene crosspolymer (crosslinked polymer of polyvinyl methyl ether/methyl acrylate and decadiene), PVP (polyvinylpyrrolidone), etc.
2.5 Surfactants
2.5.1 Alkanolamides
The most commonly used is coconut diethanolamide. Alkanolamides are compatible with electrolytes for thickening and give the best results. Alkanolamides
The thickening mechanism is the interaction with anionic surfactant micelles to form a non-Newtonian fluid. Various alkanolamides have great differences in performance, and their effects are also different when used alone or in combination. Some articles report the thickening and foaming properties of different alkanolamides. Recently, it has been reported that alkanolamides have the potential hazard of producing carcinogenic nitrosamines when they are made into cosmetics. Among the impurities of alkanolamides are free amines, which are potential sources of nitrosamines. There is currently no official opinion from the personal care industry on whether to ban alkanolamides in cosmetics.
2.5.2 Ethers
In the formulation with fatty alcohol polyoxyethylene ether sulfate (AES) as the main active substance, generally only inorganic salts can be used to adjust the appropriate viscosity. Studies have shown that this is due to the presence of unsulfated fatty alcohol ethoxylates in AES, which contribute significantly to the thickening of the surfactant solution. In-depth research found that: the average degree of ethoxylation is about 3EO or 10EO to play the best role. In addition, the thickening effect of fatty alcohol ethoxylates has a lot to do with the distribution width of unreacted alcohols and homologues contained in their products. When the distribution of homologs is wider, the thickening effect of the product is poor, and the narrower the distribution of homologues, the greater the thickening effect can be obtained.
2.5.3 Esters
The most commonly used thickeners are esters. Recently, PEG-8PPG-3 diisostearate, PEG-90 diisostearate and PEG-8PPG-3 dilaurate have been reported abroad. This kind of thickener belongs to non-ionic thickener, mainly used in surfactant aqueous solution system. These thickeners are not easily hydrolyzed and have stable viscosity over a wide range of pH and temperature. Currently the most commonly used is PEG-150 distearate. The esters used as thickeners generally have relatively large molecular weights, so they have some properties of polymer compounds. The thickening mechanism is due to the formation of a three-dimensional hydration network in the aqueous phase, thereby incorporating surfactant micelles. Such compounds act as emollients and moisturizers in addition to their use as thickeners in cosmetics.
2.5.4 Amine oxides
Amine oxide is a kind of polar non-ionic surfactant, which is characterized by: in aqueous solution, due to the difference of the pH value of the solution, it shows non-ionic properties, and can also show strong ionic properties. Under neutral or alkaline conditions, that is, when the pH is greater than or equal to 7, amine oxide exists as a non-ionized hydrate in aqueous solution, showing non-ionicity. In acidic solution, it shows weak cationicity. When the pH of the solution is less than 3, the cationicity of amine oxide is particularly obvious, so it can work well with cationic, anionic, nonionic and zwitterionic surfactants under different conditions. Good compatibility and show synergistic effect. Amine oxide is an effective thickener. When the pH is 6.4-7.5, alkyl dimethyl amine oxide can make the viscosity of the compound reach 13.5Pa.s-18Pa.s, while alkyl amidopropyl dimethyl oxide Amines can make the compound viscosity up to 34Pa.s-49Pa.s, and adding salt to the latter will not reduce the viscosity.
2.5.5 Others
A small number of betaines and soaps can also be used as thickeners (see Table 1). Their thickening mechanism is similar to that of other small molecules, and they all achieve the thickening effect by interacting with surface-active micelles. Soaps can be used for thickening in stick cosmetics, and betaine is mainly used in surfactant water systems.
2.6 Water-soluble polymer thickener
Systems thickened with many polymeric thickeners are not affected by solution pH or electrolyte concentration. In addition, polymer thickeners need less amount to achieve the required viscosity. For example, a product requires a surfactant thickener such as coconut oil diethanolamide with a mass fraction of 3.0%. To achieve the same effect, only fiber 0.5% of plain polymer is enough. Most water-soluble polymer compounds are not only used as thickeners in the cosmetic industry, but also used as suspending agents, dispersants and styling agents.
2.6.1 Cellulose ether
Cellulose ether is a very effective thickener in water-based systems and is widely used in various fields of cosmetics. Cellulose is a natural organic matter, which contains repeated glucoside units, and each glucoside unit contains 3 hydroxyl groups, through which various derivatives can be formed. Cellulosic thickeners thicken through hydration-swelling long chains, and the cellulose-thickened system exhibits obvious pseudoplastic rheological morphology. The general mass fraction of usage is about 1%.
2.6.2 Polyacrylic acid
It has been 40 years since Coodrich introduced Carbomer934 into the market in 1953, and now there are more choices for this series of thickeners (see Table 1). There are two thickening mechanisms of polyacrylic acid thickeners, namely neutralization thickening and hydrogen bond thickening. Neutralization and thickening is to neutralize the acidic polyacrylic acid thickener to ionize its molecules and generate negative charges along the main chain of the polymer. The repulsion between the same-sex charges promotes the molecules to straighten and open to form a network. The structure achieves the thickening effect; hydrogen bonding thickening is that the polyacrylic acid thickener is first combined with water to form a hydration molecule, and then combined with a hydroxyl donor with a mass fraction of 10%-20% (such as having 5 or more ethoxy groups) Non-ionic surfactants) combined to untangle the curly molecules in the aqueous system to form a network structure to achieve a thickening effect. Different pH values, different neutralizers and the presence of soluble salts have a great influence on the viscosity of the thickening system. When the pH value is less than 5, the viscosity increases with the increase of the pH value; when the pH value is 5-10, the viscosity is almost unchanged; but as the pH value continues to increase, the thickening efficiency will decrease again. Monovalent ions only reduce the thickening efficiency of the system, while divalent or trivalent ions can not only thin the system, but also produce insoluble precipitates when the content is sufficient.
2.6.3 Natural rubber and its modified products
Natural rubber mainly includes collagen and polysaccharides, but natural gum used as a thickener is mainly polysaccharides (see Table 1). The thickening mechanism is to form a three-dimensional hydration network structure through the interaction of three hydroxyl groups in the polysaccharide unit with water molecules, so as to achieve the thickening effect. The rheological forms of their aqueous solutions are mostly non-Newtonian fluids, but the rheological properties of some dilute solutions are close to Newtonian fluids. Their thickening effect is generally related to the pH value, temperature, concentration and the presence of other solutes in the system. This is a very effective thickener, and the general dosage is 0.1%-1.0%.
2.6.4 Inorganic polymers and their modified products
Inorganic polymer thickeners generally have a three-layer layered structure or an expanded lattice structure. The two most commercially useful types are montmorillonite and hectorite. The thickening mechanism is that when the inorganic polymer is dispersed in water, the metal ions in it diffuse from the wafer, as the hydration proceeds, it swells, and finally the lamellar crystals are completely separated, resulting in the formation of anionic lamellar structure lamellar crystals. and metal ions in a transparent colloidal suspension. In this case, the lamella has a negative surface charge, and its corners are charged due to lattice fracture planes.
Post time: Dec-26-2022