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Cationic Silicone Complexes as Delivery Systems
31 Cationic Silicone Complexes as Delivery Systems Anthony J. OLenick, Jr. Siltech LLC Dacula, Georgia Charles W. Buffa Biosil Technologies Inc. Paterson, New Jersey
31.1 31.2 31.3 31.4
Introduction ................................................................................... 636 The Eureka! Moment.................................................................. 636 Group Opposites .......................................................................... 636 Silicone Compounds .................................................................... 637 31.4.1 Carboxy Silicone Polymers ............................................... 637 31.5 Fatty Quaternary Ammonium Compounds .................................. 639 31.6 Silicone Complex Improvements .................................................. 639 31.6.1 Organic Quats .................................................................. 639 31.6.2 Silicone Quat Complexes ................................................. 639 31.7 Desirable Properties of Cationic Silicone Complexes .................. 640 31.7.1 Compatibility with Anionic Surfactants .............................. 640 31.7.2 Compatibility with Anionic Surfactants Test ...................... 640 31.8 Fatty Quaternary, Carboxy Silicone Conditioner ........................... 641 31.8.1 Test Method....................................................................... 641 31.8.2 Test Results ...................................................................... 642 31.9 Recent Advancements ................................................................. 644 31.10 Conclusions .................................................................................. 644 31.11 Formulations ................................................................................. 645 References .......................................................................................... 666
Meyer R. Rosen (ed.), Delivery System Handbook for Personal Care and Cosmetic Products, 635666 © 2005 William Andrew, Inc.
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31.1 Introduction The ability to deliver actives to the hair and skin is a key area of interest to the cosmetic formulator. Water-soluble materials that have no affinity for the hair or skin will only be effective in providing a benefit if they are retained on the substrate of choice. To develop cost-effective formulations, it is imperative to increase the substantivity of actives to hair and skin. As we use the term actives, it relates to any material the cosmetic chemist wants to place onto the hair or skin, rather than being restricted to certain traditional actives. For example, if a cationic conditioner is in an aqueous product, it can be considered an active and anything that facilitates the delivery of that conditioner onto the hair or skin is, in the simplest terms, a delivery system. We have developed complexation technology that allows for enhanced delivery to hair and skin. We believe this will become a major new application area for the cosmetic chemist. The successful approach described in this chapter is accomplished by making a salt that, by virtue of its molecular weight, is delivered preferentially to the skin or hair. Since larger molecules disrupt more hydrogen bonding between water molecules in aqueous systems, large sparingly soluble molecules have a tendency to preferentially deposit on substrates to achieve the lowest energy level. This concept of delivery allows for the formulation of products that provide outstanding performance and ease of formulation.
31.2 The Eureka! Moment Complex delivery dates back to May 1981, when pioneering work was done by Lucassen and Giles.[1] They showed that when mixed surfactant systems (anionic/cationic) are evaluated, the mixed surfactant often gave synergistic surface activity. Simply put, when a cationic and an anionic surfactant are mixed, they form a complex. If one mixes sodium lauryl sulfate and stearalkonium chloride together, one obtains sodium chloride, and a stearalkoniumlauryl sulfate complex. This complex is insoluble in water and it will precipitate in order to produce the lowest free-energy state system. If the surfactant molecules are chosen so that the complex is not insoluble and, instead, exhibits a low solubility in wa-
ter in the presence of a substrate, it will then deposit on that substrate in order to achieve the lowest possible energy state. In short, by properly selecting the solubility of the complex, one increases deposition on hair or skin and obtains delivery. The reader is referred to the Journal of Colloid and Interface Sciences, Vol. 81, No. 1, pp. 150157 for a detailed physical chemistry of this phenomenon. We initially became interested in this technique during the study of methods to deliver water-soluble dyes to textile fibers. Such dyes were not terribly substantive, and most of the product was lost in the waste water. Ideally, if there was a charge on the fiber, the opposite charge could be put onto the dye and the process efficiency improved. Most times, however, this was not possible, and we observed that water-insoluble color compounds could not be easily delivered to the textile surfaces. It turned out that the very same emulsifiers that emulsified the color compound in the water also acted as detergents, and could remove the color so deposited. In the textile area, when a hydrophobic treatment is required, one can treat the fiber with silicone or with a hydrocarbon. Both types of treatment will result in a hydrophobic finish. However, if treated with silicone, the fiber will also be oleophobic. If treated with oil, the fiber will also be siliphobic. Thus, for waterproofing fibers, selection of the proper molecule is critical, since improper selection will result in unacceptable oil staining. In search of a solution to this problem, we discovered that when a charged silicone compound was chosen and complexed with a surfactant having the opposite charge, a more efficient mechanism to deliver the active was achieved. We quickly modified this concept to allow for the delivery of many noncolor compounds to the hair and skin and thereby achieved a powerful new approach for the delivery of useful personal care actives to the hair and skin.
31.3 Group Opposites In order to understand the technology described in this chapter, one first needs to understand the concept of group opposites. This concept was developed recently and explained in terms of solubility group opposites.[2] Originally, there were two types
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS of opposites: oil-soluble and water-soluble. Now, with the growing availability of organosilicone materials in personal care products, a new type of opposite needs to be introduced. The presence of silicone groups in the molecule alters the solubility and can result in an improved deposition on hair and skin of silicone-modified materials. When compounds are least soluble in water, they will be more likely to deposit on substrates, or end up at an interface. The trick in designing an effective molecule with enhanced deposition capability is to generate sufficient water-solubility to allow for a cosmetically appealing aqueous product, yet, at the same time, to have limited the water-solubility so that it will preferentially absorb onto the substrate. Charged silicone polymers offer a very attractive delivery system for actives having the opposite charge. This concept extends to standard quaternaries as well as many other useful ionic actives such as polyacrylate type polymers. Table 31.1 describes some very useful definitions, and their opposites, which are critical for understanding and achieving delivery.
31.4 Silicone Compounds In the 1990s, there was a considerable expansion in the number of silicone surfactants available commercially. In fact, there has been a duplication of virtually all classes of compounds available as carbon-based surfactants in the world of silicone surfactants. Table 31.2 outlines a range of products with similar functionality available in both the world of fatty chemicals as well as that of silicone.
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phosphates, sulfates, and sulfosuccinates. Having such an ionic charge is the first requirement for making a delivery complex. The second requirement for making a delivery system complex is to make the silicone compound barely water-soluble. Silicone polymers offer extraordinary opportunities to vary solubility and, therefore, improve delivery and attachment to the desired substrates. A series of new products have been prepared and commercialized that incorporate silicone, fatty, and water-soluble moieties. These materials demonstrate improved substantivity to hair and skin, as expected.
31.4.1
Carboxy Silicone Polymers
As an example of the effective use and application of cationic silicone complexes for enhanced personal care delivery systems, we present below specific complexes obtained between carboxy functional silicone polymers and selected fatty quaternary compounds. Carboxy silicone polymers useful in making delivery complexes have a pendant carboxy group present and consequently are anionic surface-active agents. Appropriate selection of the silicone portion of the molecule, combined with the proper cationic portion, has been found to considerably improve delivery and deposition uniformity of actives on the hair and skin. The delivery complexes have the structure shown in Fig. 31.1. These complexes are large molecules that disrupt hydrogen bonding in water and, as such, are preferentially adsorbed on the substrate in order to obtain an aqueous solution with the minimum free energy.
The new silicone-based products have increased substantivity to hair and skin as a result of the presence of the silicone moiety. In fact, to predict the solubility of Table 31.1. Group Opposites products having oil-soluble, water-soluble, and silicone-soluble Hydrophilic (water loving) Hydrophobic (water hating) portions, an expansion of the wellOleophilic (oil loving) Oleophobic (oil hating) known HLB system has been proposed and has come to be Siliphilic (silicone loving) Siliphobic (silicone hating) known as the 3D HLB System.[3] Note: Many of the compounds listed · Hydrophobic materials can be either oleophilic or siliphilic. in Table 31.2 possess an ionic · Oleophobic materials may be either hydrophilic or siliphilic. charge, and these include func· Siliphobic materials may be either oleophilic or hydrophilic. tional groups like carboxylates,
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Table 31.2. Comparison of Hydrocarbon Compounds with Silicone-modified Compounds[4]
Hydrocarbon Products
Silicone Products
Anionic Compounds Phosphate esters
Silicone phosphate esters[5][6]
Sulfates
Silicone sulfates[7]
Carboxylates
Silicone carboxylates[8][9]
Sulfosuccinates
Silicone sulfosuccinates[10][11]
Cationic Compounds Alkyl quats
Silicone alkyl quats[12]
Amido quats
Silicone amido quats[13]
Imidazoline quats
Silicone imidazoline quats[14]
Amphoteric Compounds Amino proprionates
Silicone amphoterics[15]
Betaines
Silicone betaines[16]
Phosphobetaines
Silicone phosphobetaines[17]
Nonionic Compounds Alcohol alkoxylates
Dimethicone copolyol
Alkanolamids
Silicone alkanolamids[18]
Esters
Silicone esters[19][20][21][22]
Taurine derivatives
Silicone taurine[23]
Isethionates
Silicone isethionates[24]
Alkyl glycosides
Silicone glycosides[25]
CH3 CH3 CH3 CH3 | | | | CH3Si(OSi)a(OSi)bOSiCH3 | | | | CH3 CH3 (CH2) 3 CH3 | O(CH2CH2O)xC(O)RC(O)O CH3 | RN+CH3 | CH3 Figure 31.1 The structure of a delivery complex (Cetylsil®) based on carboxy silicone polymers.
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
31.5 Fatty Quaternary Ammonium Compounds Fatty quaternary compounds are commonly called quats. They are tetra-substituted ammonium compounds in which each of the four groups on the nitrogen atom are comprised of groups other than hydrogen. If any hydrogen groups are present, the compounds are not considered quaternary amines; they are then known as primary or secondary amines. There are several well-known, undesirable attributes of fatty cationic products. In each case, these attributes may be improved by complexation with an anionic silicone moiety. Examples of these undesirable attributes include: Fatty quaternary compounds are incompatible with anionic surfactants since an insoluble complex is frequently formed when the two types of materials are combined. This problem frequently occurs using polyacrylates as thickeners since they are cationic. Many fatty quaternary compounds are eye irritants;[26] such materials are minimally irritating to the eyes at concentrations of 2.5 weight percent.[27] This limits the useful concentration. Fatty quats are generally hydrophobic and, when applied to a substrate, cause a reduction in water absorbency of the substrate. It is not an uncommon situation for a traveler staying in a hotel to encounter a very soft towel that totally fails to absorb water. This is because the fatty quaternary treatment provides softness, but also prevents rewetting as a result of its hydrophobic nature. This situation can be also observed on hair when the absorbed conditioner prevents the hair from rewetting. The phenomenon causes the hair to become gunky and results in undesirable buildup of the material.
31.6 Silicone Complex Improvements Making silicone complexes with carboxy silicone compounds can mitigate many of these undesirable
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attributes of the fatty quaternary ammonium compounds. The complexes of carboxy silicones with quaternary compounds produce altered properties which make them highly desirable in personal care applications such as shampoos, body washes, and other cleansing products. A comparison of two such complexes with two well-known quats is described below.
31.6.1
Organic Quats
Stearalkonium chloride is well known to be an excellent conditioning agent, and imparts outstanding substantivity to hair. The product has detangling properties and improves wet-comb properties when applied after shampooing. The FDA formulation data reports the use of this material in 78 hair conditioners. Of these conditioners, eight are used at levels of less than 0.1%, eighteen at levels of between 0.1% and 1.0%, and fifty-two at levels of between 1.0% and 5.0%. Cetyltrimonium chloride, or CTAC, is well known to be a very substantive conditioner. In addition to providing a non-greasy feel, the material also improves wet-comb properties and also provides a gloss to the hair. The product, however, is classified as a severe primary eye irritant and therefore its useconcentration is generally limited to less than or equal to 1.0% by weight.
31.6.2
Silicone Quat Complexes
By contrast to the organic quats described above, it has been found that silicone carboxy fatty quaternary complexes offer significant advantages in personal care applications. Surprisingly, these materials form clear, water-soluble complexes with anionic systems in aqueous solution. They have been demonstrated to provide outstanding wet-comb properties and antistatic properties on hair. Further, these materials also provide non-greasy, softening properties to hair and skin, are minimally irritating to the eyes, and can be used to formulate clear conditioners. Significantly, these properties are seen in shampoo systems at concentrations below 0.5% by weight because the energetics of the solution favor deposition onto hair rather than retention in solution. The
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silicone-quat complex offers considerable enhancement in deposition and conditioning, and enables the formulator to maintain efficacy in shampoos, while significantly reducing the component concentrations.
Stearasil® is compatible with, and forms clear solutions over a range of concentrations.
Commercial examples of such products are described in Table 31.3
31.7.2
31.7 Desirable Properties of Cationic Silicone Complexes
A ten-percent-solids solution of sodium lauryl sulfate (Colonial SLS from Colonial Chemical) was prepared. Separately, a ten-percent-solids solution of the quat (or quat silicone complex) being tested was also prepared. The quat was titrated into 100 ml of the sodium lauryl sulfate solution. The formation of a white, insoluble complex, or a haze, is considered to be the end point of the titration.
Cationic silicone complexes demonstrate major improvements over the original quat precursors in a variety of key areas. These include anionic compatibility, reduction of eye irritation, improved rewetting, improved compatibility with polyacrylates, and improved conditioning and combability of hair.
31.7.1
Compatibility with Anionic Surfactants
Traditional fatty quats like stearalkonium chloride and cetyltrimonium chloride, form water-insoluble complexes when combined with sodium lauryl sulfate in aqueous solution. This phenomenon is due to the formation of an insoluble anionic/ cationic complex. Cetylsil®, like the traditional quats, also forms a complex, but surprisingly however,
Compatibility with Anionic Surfactants Test
As can be seen from the data in Table 31.4, Stearasil is unique in that it is compatible with sodium lauryl sulfate systems. Eye irritation. Eye irritation is a major concern in the formulation of personal care products, particularly when working with quaternary surfactants. Primary eye irritation was tested using the protocol outlined in FHSLA 16 Code of Federal Regulations 1500.42. The products were tested at 25% actives and the results obtained are outlined in Table 31.5. Rewetting properties. When complexes of fatty quaternary compounds and carboxy silicone are used to treat textile fabrics, they make the substrate soft, but they do not make them hydrophobic. This distinguishes their behavior from the standard fatty
Table 31.3. Commercially Available Products
Commercial Name
INCI Name
Fatty Quat
Stearasilâ
Stearalkonium dimethicone copolyol phthalate
Stearalkonium chloride
Cetylsilâ
Cetrimonium dimethicone copolyol phthalate
Cetyltrimonium chloride
Stearasilâ S
Stearalkonium dimethicone copolyol succinate
Stearalkonium chloride
CetylsilâS
Cetrimonium dimethicone copolyol succinate
Cetyltrimonium chloride
Stearasilâ and Cetylsilâ are registered trademarks of Biosil Technologies Inc.
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Table 31.4. Compatibility with Anionic Surfactants Test
Test Compound
End Point (ml)
Appearance
Material Type
Stearalkonium chloride
0.3
White solid
Fatty quat
Cetyltrimonium chloride
0.2
White solid
Fatty quat
Cetylsil®
0.5
White solid
Silicone quat complex
35.8
Haze develops
Silicone quat complex
Stearasil® ®
®
Stearasil and Cetylsil are registered trademarks of Biosil Technologies Inc
Table 31.5. Eye Irritation
Product Cetyltrimonium chloride Cetylsil
®
Stearalkonium chloride* Stearasil
®
Score 106.0 8.3 116.5 11.3
Irritation Level
Material Type
Severely irritating
Fatty quaternary
Minimally irritating
Silicone complex
Severely irritating
Fatty quaternary
Minimally irritating
Silicone complex
* At a concentration of 0.5%, stearalkonium chloride was minimally irritating. This rating of minimally irritating was the same rating achieved by Cetylsil® and Stearasil® when used at 25% (or 50 times the concentration). As the data clearly show, the irritation level for the silicone-quat complex is dramatically reduced when compared to the starting quat.
quats, which only make the substrate hydrophobic. This property is very important in the personal care area, and specifically to their use on hair. Hair treated with the silicone-complexed quat does not show evidence of any buildup on the surface of the hair.
31.8 Fatty Quaternary, Carboxy Silicone Conditioner The highly desirable properties of formulating a conditioner using a fatty quaternary, carboxy silicone compound can be demonstrated using the formulations and test methods described below. A base formulation and a commercial conditioner were selected as controls. Modifications were made to these by the addition of Stearasil and Cetylsil.
31.8.1 Test Method The test hair used was 7-inch, dark brown, virgin hair from DeMeo Brothers. Five two-gram tresses were used per product evaluated. All tresses were pre-washed three times with Prell original shampoo, rinsed in water at 25°C, and air-dried. Performance was rated using the scale shown in Table 31.6. Table 31.6. Numerical Scale Used to Rate Effects of Formulations on Hair
Rating
Description
1
Very poor
2
Poor
3
Satisfactory
4
Good
5
Excellent
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Test formulas T1T6 (see Table 31.7) were produced, tested, and compared to demonstrate the effects of systems with organic quaternary compounds and their silicone counterparts. The components of the base formulation used in the tests are shown Table 31.8.
the advantage of inclusion of the fatty quaternary, carboxy silicone complex in this formulation. Dry comb properties. The formulas in Table 31.7 were also evaluated on dry hair. The qualitative test results are shown in Table 31.10. Dry comb conclusions. 1. Upon comparing Formulas T1, T3, and T5, the following trend emerges:
31.8.2 Test Results Conditioning, wetability, and combability were evaluated for each of these systems according to the prescribed test method. The test results are shown in Table 31.9 and described here. Conditioning and wet combability. 1. Upon comparing Formulas T1, T3, and T5, the following trend emerges: Including stearalkonium chloride into the base formula did not improve the base at all (Formulas T1 and T5). However, inclusion of Stearasil® into the base formula improved residual feel, and wet combability (Formulas T1 and T3). This clearly shows the advantage of inclusion of the fatty quaternary, carboxy silicone complex in this formulation. 2. Upon comparing Formulas T1, T6, and T4, the following trends emerge: Inclusion of CETAC (cetyl trimethyl ammonium chloride) into the base formula did not improve the base at all. (Formulas T1 and T4). However, inclusion of Cetylsil® into the base formula, improved residual feel, and wet combability (Formula T1 and T6). This clearly shows
Inclusion of stearalkonium chloride into the base formula resulted in a marginal improvement (Formulas T1 and T5). However, inclusion of Stearasil into the base formula improved shine and dry comb characteristics, and provided a very significant improvement in fullness of the hair (Formulas T1 and T3). This clearly shows the advantage of including the fatty quaternary, carboxy silicone complex in this formulation. 2. Upon comparing Formulas T1, T6, and T4, the following trends emerge: Inclusion of CETAC into the base formula resulted in an improvement in shine and dry comb characteristics (Formulas T1 and T4). Inclusion of Cetylsil into the base formula improved all properties measured except curl retention (Formula T1 and T6). The above data clearly shows that the incorporation of cationic silicone complexes, called Stearasil and Cetylsil, into the base formula resulted in significant improvements in functionality. These improvements are a direct result of the usefulness of such adjuvants for enhancing delivery of personal care actives to the hair.
Table 31.7. Formulations Include Two Controls and Four Test Formulations
Test Formulation
Description
T1
Base Formula
T2
Commercial Conditioner
T3
Base Formula + 2% Stearasil®
T4
Base Formula + 2% CETAC added
T5
Base Formula + 2% Stearalkonium chloride
T6
Base Formula + 2% Cetylsil®
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Table 31.8. Base Formulation Used for Control and Test Formulations in Table 31.7
Phase
Ingredient
A
B
Function
% Weight
Water
Solvent
Qs 100.00
Tetrasodium ETDA
Chelating agent
0.15
Biosil Basics SPQ
Conditioner
0.55
Rice bran oil
Conditioner
4.00
Cetyl alcohol
Conditioner
3.00
Test ingredient
C
2.00
Glyceryl stearate
Conditioner
2.50
Propylparaben
Preservative
0.10
Germall 115
Preservative
0.20
Procedure 1. In a suitable container, weigh out all items in Phase A in order shown. 2. Mix well and heat to 75°C. 3. In a separate container, weigh out and combine all items in Phase B in the order shown. 4. Heat Phase B to 75°C. 5. Add Phase B to Phase A at 75°C, while agitating for at least 15 minutes. 6. Add Phase C. 7. Cool to 25°C30°C.
Table 31.9. Hair Conditioning Performance Rating (See Table 31.6) of Formulas Listed in Table 31.7
Property
Formula 1
Formula 2
Formula 3
Formula 4
Formula 5
Formula 6
Residual feel
2
4
4
1
1
2
Squeaky feel
1
2.5
1
1
1
3
Shine
1
2
1
1
1
2
Wet comb
4
5
5
4
4
2.5
Spreadability
4
4.5
4
3
3
3
Smoothness
3
3.5
4
3
3
3
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Table 31.10. Dry Comb Performance Rating (See Table 31.6) of Formulas Listed in Table 31.7
Property
Formula 1
Formula 2
Formula 3
Formula 4
Formula 5
Formula 6
Residual feel
3
3
3
3
3
4
Shine
2
3
3.5
2.5
3
4
Dry comb
3
3
4
5
3
3.5
Fly away
2
2
2
2
2.5
2.5
Curl retention
3
2
2
3
2
3
Fullness
2
2
4
2.5
3
3
Manageability
3
3
2
2
2
3
31.9 Recent Advancements
31.10 Conclusions
There has recently been a patent awarded for the composition of complexes based upon alkylamidoquats, rather than the alkyl quats.[31] These complexes have a superior skin feel, and are better conditioners.
The use of silicone carboxy, fatty quaternary complexes as delivery systems offers the personal care formulator an enhanced ability to improve the cost-effectiveness of using water-soluble actives in formulations that provide a benefit to the hair and skin. This improvement is a direct result of the alteration of the original solubility of water-soluble actives. As a result of the described complex formation between anionic carboxy silicone compounds and cationic fatty quaternary actives, improved substantivity to hair in aqueous formulation is achieved. We believe this is a powerful formulation technique that is ripe for further development.
Recently a number of patents[32]-[34] have been issued in which the complexation phenomenon outlined in this chapter has been expanded to compounds in which neither the cationic compound nor anionic compound contain silicone. The anionic and cationic compounds are chosen so that the complex has minimal water solubility and is compatible with non-ionic silicone surfactants. The performance attributes mimic those of the complexes made from silicone anionic compounds and fatty quats.
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31.11 Formulations Formulations 31.131.22, provided by Biosil Technologies Inc., illustrate the efficacy of the carboxy silicone, fatty quaternary complexes in a number of personal care products. The formulations cover a range of hair and skin products: Shampoos
Formulations 31.131.4
Body Wash
Formulations 31.531.7
Conditioners
Formulations 31.831.16
Facial Cleansers
Formulation 31.17
Pomade
Formulations 31.1831.19
Hair Growth Treatment
Formulation 31.20
Tanning Product
Formulation 31.21
Makeup Remover Formulation 31.22
Formulation 31.1: Shampoo
Material
Function
Water
Weight % QS to 100.0
Ammonium lauryl sulfate
a
Detergent
23.0
Cocamid DEA
Viscosity builder
2.4
Cocamidopropyl betainea
Detergent
2.9
Tetrasodium EDTA
Chelating agent
0.1
Aloe vera gel
Active
0.1
Peg 6000 distearate
Opacifier
0.5
Conditioning complex
2.5
Biowax® 754b
Emollient
4.0
Sodium chloride
Viscosity builder
Phenonip
Preservative
a
Cetylsil
®b
As desired 1.0
Mixing Procedure In a suitable container, heat water to 75°C, add each ingredient in the order shown, using good agitation, allowing 15 minutes between additions. Cool to 35°C and add preservative. To increase viscosity, add salt. Notes 1. Cetylsil® is the fatty quaternary, carboxy silicone, added for improved conditioning. 2. Biowax® 754 is added for improved combability. 3. Extracts like common nettle, henna extract, etc., can be added as desired. Sources a
Colonial Chemical, South Pittsburg, Tennessee
b
Biosil Technologies, Inc., Paterson, New Jersey
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Formulation 31.2: Shampoo
Material
Function
Water
Weight % QS to 100.00
Ammonium lauryl sulfate
a
Detergent
25.00
Cocamide DEA
Viscosity
2.40
Cocamidopropyl betainea
Detergent
2.90
Tetrasodium EDTA
Chelation
0.50
PEG-150 distearate
Emollient
2.50
Biosil Basics SPQ
Conditioner
1.00
Dowicil 200
Preservative
0.30
Stearasil® b
Conditioner
2.00
a
®
b
Mixing Procedure 1. In a suitable container, begin to heat water to 70°C75°C, adding one ingredient at a time with proper mixing during each addition. 2. Begin to cool to 35°C. Sources a
Colonial Chemical, South Pittsburgh, Tennessee
b
Biosil Technologies, Inc., Paterson, New Jersey
.
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647
Formulation 31.3: Clear Softening Shampoo
Phase
Material
Function
Water
A
B
Weight % Qs to 100.00
Sodium laureth-2 sulfatea
Detergent
30.00
Cocamide DEAa
Viscosity builder
2.50
Cocamido betainea
Detergent
7.00
Biowax® 754 Specialb
Emollient
2.00
SugaQuat La
Glucose quat
1.50
Cetylsil® Sb
Conditioning complex
6.50
Phenonip
Preservative
1.00
Mixing Procedure 1. In a suitable container, combine all ingredients together of Phase A with good agitation, without aerating. 2. Begin to heat to 70°C75°C.When clear and uniform, stop heating and cool to 35°C40°C. 3. Add Phase B. Mix well. 4. Adjust pH to 6.36.8, with 50% citric acid as needed. Sources a
Colonial Chemical, South Pittsburg, Tennessee
b
Biosil Technologies, Inc., Paterson, New Jersey
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Formulation 31.4: Two-in-One Conditioning Shampoo
Material
Function
Water
Weight % QS to 100.00
Ammonium lauryl sulfate
a
Detergent
23.00
Cocamide DEA
Viscosity build
2.40
Cocamidopropyl betainea
Detergent
2.90
Tetrasodium EDTA
Chelation
0.05
Biosil Basics SPQ
Conditioner
1.00
PEG- 150 distearate
a
®
b
Emollient
2.50
®b
Conditioner
4.00
Behenesilb
Conditioner
1.00
Phenonip
Preservative
1.00
Stearasil
Mixing Procedure 1. In a suitable container, add ingredients and heat to 70°C75°C while mixing. 2. When all ingredients are melted and product is uniform, cool to 35°C40°C while stirring. 3. Pearlescence should appear while cooling.
Sources a
Colonial Chemical, South Pittsburgh, Tennessee
b
Biosil Technologies, Inc., Paterson, New Jersey
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Formulation 31.5: Clear Body Wash
Phase
Material
Function
Water
QS to 100.00 a
Sodium laureth sulfate
Detergent
30.00
Detergent
7.00
Preservative
0.15
Preservative
0.10
Viscosity builder
3.00
Conditioner
3.00
Cucumber extract
Active
0.25
Elder extract
Active
0.25
Matricaria extract
Active
0.25
Ginkgo extract
Active
0.25
C
Imidazolidinyl urea
Preservative
0.30
D
Citric acid
pH adjustment
Cocamidopropyl betaine A
a
Methylparaben Propylparaben a
Cocamide DEA Cetylsil
B
®b
Mixing Procedure 1. In a suitable container weigh out Phase A. Heat to 70°C75°C. 2. Mix until clear and begin to cool to 35°C40°C. 3. At 35°C, add Phase B. Mix well. 4. Add Phase C. Mix well. 5. Adjust pH with Phase D to 6.36.8. Sources a
Colonial Chemical, South Pittsburgh, Tennessee
b
Weight %
Biosil Technologies, Inc., Paterson, New Jersey
QS to pH 6.36.8
650
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.6: Body Shampoo
Material
Function
Water
Weight % Qs to 100.0
a
Ammonium laurel sulfate
Detergent
25.0
Cocamide DEA
Viscosity builder
3.0
Tetrasodium EDTA
Chelation
0.1
Aloe vera gel
Active
0.5
Conditioner
1.5
Silamine C-100c
Slip agent
2.5
Sodium chloride
Viscosity builder
As desired
Citric acid
pH control
As desired
Phenonip
Preservative
a
Cetylsil®
b
1.0
Mixing Procedure In a suitable container, heat water to 75°C. Add each ingredient in the order shown, under good agitation, allowing 15 minutes between additions. Cool to 35°C and add preservative. To increase viscosity, add salt. Notes 1. Cetylsil® is a fatty quaternary, carboxy silicone and is added for improved conditioning. 2. Silamine C-100 is dimethicone copolyol amine and is added for skin feel. 3. Extracts like common nettle, henna extract, etc., can be added as desired. Sources a
Colonial Chemical, South Pittsburg, Tennessee
b
Biosil Technologies, Inc. Paterson, New Jersey
c
Siltech LLC, Dacula, Georgia
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
651
Formulation 31.7: Exfoliating Body Scrub
Phase
Material
Function
Water
QS to 100.00
Sodium lauryl sulfate
a
Detergent
30.00
Cocamide DEA
Viscosity builder
2.50
Cocamidopropyl betainea
Detergent
7.00
Biowax® 754b
Emollient
1.00
Conditioner
3.00
Viscosity builder
0.25
Chamomile extract
Active
1.00
Mallow extract
Active
1.00
Cucumber extract
Active
1.00
Jojoba beads 40/60
Active
5.00
Germaben 11
Preservative
1.00
Triethanolamine (99%)
pH adjustment
0.30
Fragrance
Fragrance
0.50
a
A
Cetylsil
®b
Carbopol 1342 B
C D
c
d
Mixing Procedure 1. In a suitable container, disperse Carbopol 1342. 2. Once mixed well, add remaining ingredients from Phase A. 3. Begin to heat to 55°C60°C until homogenous, then cool to 35°C45°C. 4. Add Phase B. Mix well. 5. Add Phase C. Mix well, then add Phase D. Sources a
Colonial Chemical, South Pittsburgh, Tennessee
b
Biosil Technologies, Inc., Paterson, New Jersey
c
Noveon, Cleveland, Ohio
d
Weight %
ISP, Wayne New Jersey
652
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.8: Spray-on, Leave-on Conditioner
Material
Function
Water
Qs to 100.0
Imidazolidinyl urea Cetylsil
Weight %
® a
®
Biosil Basics SPQ Phenonip
a
Preservative
0.30
Conditioner
1.00
Conditioner
0.30
Preservative
1.00
Mixing Procedure In a suitable container add water. Add each ingredient in the order shown, under good agitation, allowing 15 minutes between additions. Add preservative. Notes 1. Cetylsil® is a fatty quaternary, carboxy silicone and is added for improved conditioning. ®
2. Biosil Basic SPQ is a silicone quat that contains panthenol, a pro-vitamin.
Sources a
Biosil Technologies, Inc., Paterson, New Jersey
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
653
Formulation 31.9: Chelating Rinse-off Conditioner
Phase
Material
Function
Water A B
D
Qs to 100.0
Phytic acid
Chelation
Triethanolamine (99%)
pH adjustment
Methylparaben
Preservative
0.2
Cetyl alcohol
Conditioner
3.0
Rice bran oil
Oil phase
4.0
Conditioner
2.0
PEG-100 stearate
Emollient
1.2
Glyceryl stearate
Emollient
3.5
Propylparaben
Preservative
0.1
Biosil® Basics C38 ester a
Oil phase
1.0
Biosil® Basics SPQa
Conditioner
0.55
Phenonip
Preservative
1.00
Stearasil® C
Weight %
a
0.3 As required
Mixing Procedure 1. Into a suitable container add water. 2. Add Phytic acid. 3. Add enough TEA to adjust the pH to 4.04.5. 4. Add Phase B. 5. Heat to 70°C. 6. In another container combine Phase C. 7. Heat to 75°C80°C. 8. Add Phase C to the mixture of Phase A and B, under good agitation. 9. Cool to 40°C add Phase D. Notes 1. Stearasil® is the fatty quaternary, carboxy silicone and is added for improved conditioning 2. Biosil® Basic SPQ is a silicone panthenol quat. 3. Biosil® Basic C38 is a guerbet ester. Sources: a
Biosil Technologies, Inc., Paterson, New Jersey
654
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.10: Spray-on, Rinse-off Conditioner
Material
Function
Water
Weight % Qs to 100.0
Hydroxyethylcellulose
Viscosity builder
0.1
Dowicil 200
Preservative
0.2
Biosil® Basics HMC-1a
Active
1.0
GafQuat 755 Nb
Polymeric conditioner
1.0
Conditioner
5.0
Cetylsil
®a
Mixing Procedure 1. In a suitable container add water, and heat to 70°C75°C. 2. Slowly add hydroxyethylcellulose. 3. Mix 20 minutes. 4. Cool to 45°C50°C . 5. Add Dowicil 200. 6. Allow to cool to 35oC. 7. Add remaining ingredients in order shown under good agitation. Notes 1. Cetylsil is a fatty quaternary, carboxy silicone and is added for improved conditioning. Source a
Biosil Technologies, Inc., Paterson, New Jersey
b
ISP, Wayne, New Jersey
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
655
Formulation 31.11: Exothermic Conditioner
Material
Function
Biowax 754 Speciala
Emollient
PEG 1000
Exothermic additive
Stearasil
®a
Silwax WD-Fb
Weight % 20.0 Qs to 100.0
Skin feel
1.0
Slip agent
0.5
Mixing Procedure 1. In a suitable container combine materials in order shown. 2. Heat to 65°C. 3. Allow to cool under agitation. Notes 1. Stearasil is the fatty quaternary, carboxy silicone and is added for improved conditioning. 2. Silwax WD-F is a fluoro silicone product that is added to improve combability. 3. The product is a white solid. If a liquid product is desired, use a lower molecular weight.PEG like PEG 400. 4. When placed in wet hands, the PEG produces a mild warming effect. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
b
Siltech LLC, Dacula Georgia
656
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.12: Spray-on Conditioner
Phase
Material
A
Water
B
Dowcil 200 ®
Biosil Basics HMW
D
GafQuat 755Nb Cetylsil
a
®a
Preservative
0.20
Actives
3.00
Polymeric conditioner
5.00
Conditioner
5.00
Mixing Procedure 1. In a suitable container, weigh water. 2. Heat to 45°C50°C. Then cool to 35°C40°C. 3. Add Phase B; mix well with good agitation before adding the next phase. 4. Add Phase C; mix well with good agitation before adding the next phase. 5. Add Phase D; mix well with good agitation before adding the next phase. 6. Add Phase E; mix well. 7. Filter product. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
b
Weight % Qs to 100.00
C E
Function
ISP, Wayne, New Jersey
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
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Formulation 31.13: Two-in-One Conditioner
Phase
Material
Function
Water
QS to 100.00 a
Triethanolamine lauryl sulfate
Detergent
25.00
Cocamidopropyl betaine
Detergent
7.00
Cocamide DEAa
Viscosity builder
2.00
Methylparaben
Preservative
0.20
Propylparaben
Preservative
0.10
Chelation
0.05
Biosil Basics Cocosil
Conditioner
5.00
Cetylsil® b
Conditioner
3.00
B
Citric acid, 50% solution
pH adjustment
QS to 6.30-6.80
C
Sodium chloride
Viscosity adjustment
As required for viscosity
a
A
Tetrasodium EDTA ®
b
Mixing Procedure 1. In a suitable container, heat Phase A to 60°C, while stirring. 2. Cool to 50°C55°C. 3. Use citric acid solution to adjust pH to 6.306.80. 4. Cool to 45°C. Mix well. 5. Use sodium chloride to adjust viscosity.
Sources a
Colonial Chemical, South Pittsburgh, Tennessee
b
Weight %
Biosil Technologies, Inc., Paterson, New Jersey
658
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.14: Rinse-off Conditioner
Phase
Material
Function
Water
QS to 100.00
Methylparaben A
B
Preservative
0.15
Biosil Basics SPQ
Conditioner
0.50
Tetrasodium EDTA
Chelant
0.05
Stearasil® a
Conditioning complex
2.00
Rice bran oil
Oil
4.00
Cetyl alcohol
Oil
3.00
Propylparaben
Preservative
0.10
PEG-100 stearate
Emulsifier
1.15
Emulsifier
2.50
Conditioning complex
2.00
Preservative
0.20
®
a
Glyceryl monostearate ®
Biosil Basics Behenesil C
a
Imidazolidinyl urea
Mixing Procedure 1. In a suitable container, weigh and combine ingredients of Phase A. 2. Begin to heat to 75°C80°C. 3. In another container, weigh and combine all ingredients in Phase B. 4. Heat phase B to 75°C80°C. 5. Add Phase B to Phase A. Mix well. 6. Begin to cool to 30°C35°C. 7. Add Phase C. Mix well. Sources a
Weight %
Biosil Technologies, Inc., Paterson, New Jersey
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
659
Formulation 31.15: Creamy Conditioner
Phase
Material
Function
Water
QS to 100.00
Methylparaben A
Preservative
0.15
Biosil Basics SPQ
Conditioner
1.50
Stearasil® a
Conditioning complex
2.00
®
a
Tetrasodium EDTA
Chelation
0.05
a
Oil
4.00
Cetyl alcohol
Oil
3.00
Propylparaben
Preservative
0.10
PEG-100 stearate
Emulsifier
1.15
GMS-450
Emulsifier
2.50
Conditioning complex
1.00
Biosil Basics HMC
Actives
1.00
Biosil® Basics DL-30a
Actives
1.00
Phenonip
Preservative
1.00
Rice bran oil
B
a
Behenesil ®
C
Weight %
a
Mixing Procedure 1. In a suitable container, combine Phase A and with good agitation begin to heat to 70°C75°C. 2. In another suitable container, combine Phase B and begin to heat to 70°C75°C. 3. At temperature, add Phase B to Phase A. Mix well, begin to cool to 35°C40°C. 4. At temperature, add Phase C mixing well between additions. 5. Add Phase D at 35°C. Mix very well. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
660
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.16: Clear, Leave-in Conditioner Detangler
Phase A
B
C
Material
Function
Water
Weight % QS to 100.00
Hydroxyethylcellulose
Thickener
0.09
Propylene glycol
Solvent
4.00
Cocosila
Conditioner complex
2.50
Biosil® Basics SPQa
Conditioner
1.00
Preservative
0.30
Actives
1.00
Dowicil 200 ®
Biosil Basics HMC-1
a
Mixing Procedure 1. In a suitable container, weigh out water of Phase A and disperse hydroxyethylcellulose. 2. Mix until clear, begin to heat to 60°C65°C. 3. Combine Phase B and heat until uniform (60°C65°C). 4. Add Phase B to Phase A. Cool to 40°C45°C. 5. Add Phase C and mix well. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
661
Formulation 31.17: Facial Cleanser (Oily Skin)
Phase
Material
Function
Water A
QS to 100.00
Propylene glycol
Solvent
3.00
Methylparaben
Preservative
0.20
Biowax 754 speciala
Emollient
1.00
Cetylsil® Sa
Conditioning complex
2.00
Oil
5.00
Stearic acid
Oil
3.50
GMS-450
Emulsifer
1.00
Propylparaben
Preservative
0.15
Oil
0.40
Biosil Basics C-38
Oil
1.00
Emulsifying wax
Emulsifier
3.00
TEA lauryl sulfateb
Detergent
3.50
Preservative
0.30
Rhodofiltrat chondrus crispus
Active
1.00
Coralline concentrate
Active
1.00
Witch hazel extract
Active
0.5
Grapefruit extract
Active
0.5
Chamomile extract
Active
0.5
Rice bran oil
B
a
Cetyl alcohol ®
C
a
Unicide U-13 a
D
Weight %
Mixing Procedure 1. In a suitable container, weigh out and combine ingredients in Phase A and begin to heat to 70°C75°C with light agitation. 2. In another container, weigh out and combine ingredients in Phase B and begin to heat to 70°C75°C with light agitation. 3. At desired temperature, add Phase B to Phase A. Mix well and begin to cool to 35°C45°C. 4. Add Phase D, one ingredient at a time; mix well between additions. Add Phase E. 5. Mix well. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
b
Colonial Chemical, South Pittsburgh, Tennessee
662
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.18: Hair Pomade
Material Petrolatum-white IS
Function
Weight %
Oil
QS to 100.00
Oil
2.00
Oil
10.00
Behenesila
Conditioner
1.00
Silwax 418b
Silicone wax
2.00
c
Zenigloss S
Biosil Basics C-38
a
Mixing Procedure 1. Combine all ingredients in a suitable container and heat to 70°C75°C or until uniformly melted. 2. Mix well. Pour product at 65°C70°C. 3. Allow to cool.
Sources a
Biosil Technologies, Inc., Paterson, New Jersey
b
Siltech LLC, Dacula, Georgia
c
Zenitech LLC, Old Greenwich, Connecticut
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
663
Formulation 31.19: Hair Pomade Stick
Phase A
B
Material a
Function
Cyclomethicone
Solvent
Stearyl alcohol
Oil
15.00
Castor Wax MP80
Wax
8.00
Zeniglossc
Gloss additive
2.00
Biosil® Basics C-38b
Oil
3.00
Conditioner
1.50
Behenesil
b
Mixing Procedure 1. Combine all ingredients of Phase B and heat to 75°C80°C. 2. Once uniform, cool to 60°C 65oC and add Phase A. 3. Mix until uniform. Sources a
Siltech LLC, Dacula, Georgia
b
Biosil Technologies, Inc., Paterson, New Jersey
c
Weight %
Zenitech LLC, Old Greenwich, Connecticut
QS to 100.0
664
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.20: Hair Growth Conditioner Treatment
Phase
Material
Function
Water
QS to 100.00
Phytic acid complex
Active
2.00
Biosil Basics SPQ
Conditioner
0.75
Tetrasodium EDTA
Chelation
0.05
Methylparaben
Preservative
0.20
Conditioner
1.25
Cetyl alcohol
Oil
3.00
Propylparaben
Preservative
0.15
Rice bran oil
Oil
4.00
PEG-100 stearate
Emulsifier
1.15
Glyceryl stearate
Emulsifier
2.50
Imidazolidinyl urea
Preservative
0.30
Biosil® Basics HMC-1a
Active
5.00
Complex anti chute N
Active
3.50
Ginkgo extract
Active
0.10
Chamomile extract
Active
0.10
Henna extract
Active
0.10
Fragrance
Fragrance
0.50
®
A
Cetylsil
B
C
D
Weight %
a
®a
Mixing Procedure 1. In a suitable container, add water and phytic acid complex. 2. Add remaining ingredients of Phase A; one at a time with good agitation between additions. 3. Begin to heat to 75°C80°C. 4. In another suitable container, weigh and combine Phase B. Heat to 75°C80°C. 5. Add phase B to Phase A. Mix well and begin to cool to 40°C45°C. 6. At 40°C, add Phase C, one ingredient at a time with good agitation between additions. 7. Add Phase D. Mix well. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
665
Formulation 31.21: Self-Tanning Mousse
Phase A
B
Material Water
D
Weight % Qs to 100.00
Hydroxy celluose
Thickener
0.10
Dowcil 200
Preservative
0.30
Biosil® Basics SPQa
Conditioner
1.00
Cetylsil® a
Conditioner complex
1.25
Biowax 754 special
Emollient
1.00
DHA
Self tanner
5.00
Dermochlorella D
Active
1.00
Cocamido betaine
Surfactant
3.00
a
C
Function
Mixing Procedure 1. In a suitable container, slowly sprinkle hydroxy celluose into water of Phase A. 2. Once well dispersed, weigh and combine ingredients of Phase B and add to Phase A. Mix well. 3. Add Phase C, one ingredient at a time, with good agitation between additions. 4. Add Phase D. Mix well. (NO HEAT REQUIRED). Note: Must use AIRSPRAY BOTTLE to achieve mousse effect. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
b
Colonial Chemical, South Pittsburgh, Tennessee
666
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.22: Water-based Makeup Remover
Material
Function
Water Cocosil
Weight % QS to 100.0
a
Conditioner complex
2.0
Chamomile extract
Active
1.0
Cucumber extract
Active
1.0
Dowicil 200
Preservative
0.3
Mixing Procedure 1. In a suitable container, weigh and combine all ingredients in the order they appear. 2. Mix until completely uniform. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
References 1. Lucassen, E., and Giles, D., Journal of Colloid and Interface Science, Vol. 81, No. 1, pp. 150157 (May 1981)
17. Kollmeier, U.S. Patent 4,654,161 (Mar. 1987) 18. OLenick, U.S. Patent 5,237,035 (Aug. 1993) 19. OLenick, U.S. Patent 5,070,171 (Dec. 1991) 20. OLenick, U.S. Patent 5,070,168 (Dec. 1994)
2. OLenick, A. J., Journal of Surfactants and Detergents, Vol. 3, No. 2, p. 229 (Apr. 2000)
21. Dexter, U.S. Patent 4,724,258 (Feb. 1988)
3. OLenick, A. J., Surfactants: Chemistry and Applications, p. 96, Allured Publishing (1999)
23. OLenick, U.S. Patent 5,280,099 (Jan. 1994)
4. ibid 2, p. 26.
25. OLenick, U.S. Patent 5,120,812 (Jun. 1992)
5. OLenick, U.S. Patent 5,149,765 (Sep. 1992) 6. Dexter, et al., U.S. Patent 4,724,248 (Feb. 1988) 7. OLenick, U.S. Patent 4,960,845 (Oct. 1990) 8. Haluska, U.S. Patent 3,560,544 (Feb. 1971) 9. OLenick, U.S. Patent 5,296,625 (Mar. 1994) 10. Maxon, U.S. Patent 4,717,498 (Jan. 1988) 11. Colas, U.S. Patent 4,777,277 (Nov. 1998) 13. OLenick, U.S. Patent 5,098,979 (Mar. 1992) 14. OLenick, U.S. Patent 5,153,294 (Oct. 1992) 15. OLenick, U.S. Patent 5,196,499 (Feb. 1993) 16. OLenick, U.S. Patent 5,073,619 (Dec. 1991)
22. OLenick, U.S. Patent 6,338,042 (Dec. 2002) 24. OLenick, U.S. Patent 5,300,666 (Apr. 1994) 26. Hunter, A., Encyclopedia of Shampoo Ingredients, pp. 174175, Micelle Press (1983) 27. Sherex Formulary, Witco Chemical, Greenwich CT 28. Hunter, A., Encyclopedia of Conditioning Rinse Ingredients, Micelle Press, p. 99 (1987) 29. OLenick, U.S. Patent 5,296,434 (Mar. 1994) 30. OLenick, U.S. Patent 5,248,783 (Sep. 1993) 31. OLenick, U.S. Patent 6,498,263 (Dec. 2002) 32. OLenick, U.S. Patent 6,461,598 (Oct. 2002) 33. OLenick, U.S. Patent 6,410,679 (Jun. 2002) 34. OLenick, U.S. Patent 6,372,934 (Apr. 2002)
31.1 31.2 31.3 31.4
Introduction ................................................................................... 636 The Eureka! Moment.................................................................. 636 Group Opposites .......................................................................... 636 Silicone Compounds .................................................................... 637 31.4.1 Carboxy Silicone Polymers ............................................... 637 31.5 Fatty Quaternary Ammonium Compounds .................................. 639 31.6 Silicone Complex Improvements .................................................. 639 31.6.1 Organic Quats .................................................................. 639 31.6.2 Silicone Quat Complexes ................................................. 639 31.7 Desirable Properties of Cationic Silicone Complexes .................. 640 31.7.1 Compatibility with Anionic Surfactants .............................. 640 31.7.2 Compatibility with Anionic Surfactants Test ...................... 640 31.8 Fatty Quaternary, Carboxy Silicone Conditioner ........................... 641 31.8.1 Test Method....................................................................... 641 31.8.2 Test Results ...................................................................... 642 31.9 Recent Advancements ................................................................. 644 31.10 Conclusions .................................................................................. 644 31.11 Formulations ................................................................................. 645 References .......................................................................................... 666
Meyer R. Rosen (ed.), Delivery System Handbook for Personal Care and Cosmetic Products, 635666 © 2005 William Andrew, Inc.
636
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
31.1 Introduction The ability to deliver actives to the hair and skin is a key area of interest to the cosmetic formulator. Water-soluble materials that have no affinity for the hair or skin will only be effective in providing a benefit if they are retained on the substrate of choice. To develop cost-effective formulations, it is imperative to increase the substantivity of actives to hair and skin. As we use the term actives, it relates to any material the cosmetic chemist wants to place onto the hair or skin, rather than being restricted to certain traditional actives. For example, if a cationic conditioner is in an aqueous product, it can be considered an active and anything that facilitates the delivery of that conditioner onto the hair or skin is, in the simplest terms, a delivery system. We have developed complexation technology that allows for enhanced delivery to hair and skin. We believe this will become a major new application area for the cosmetic chemist. The successful approach described in this chapter is accomplished by making a salt that, by virtue of its molecular weight, is delivered preferentially to the skin or hair. Since larger molecules disrupt more hydrogen bonding between water molecules in aqueous systems, large sparingly soluble molecules have a tendency to preferentially deposit on substrates to achieve the lowest energy level. This concept of delivery allows for the formulation of products that provide outstanding performance and ease of formulation.
31.2 The Eureka! Moment Complex delivery dates back to May 1981, when pioneering work was done by Lucassen and Giles.[1] They showed that when mixed surfactant systems (anionic/cationic) are evaluated, the mixed surfactant often gave synergistic surface activity. Simply put, when a cationic and an anionic surfactant are mixed, they form a complex. If one mixes sodium lauryl sulfate and stearalkonium chloride together, one obtains sodium chloride, and a stearalkoniumlauryl sulfate complex. This complex is insoluble in water and it will precipitate in order to produce the lowest free-energy state system. If the surfactant molecules are chosen so that the complex is not insoluble and, instead, exhibits a low solubility in wa-
ter in the presence of a substrate, it will then deposit on that substrate in order to achieve the lowest possible energy state. In short, by properly selecting the solubility of the complex, one increases deposition on hair or skin and obtains delivery. The reader is referred to the Journal of Colloid and Interface Sciences, Vol. 81, No. 1, pp. 150157 for a detailed physical chemistry of this phenomenon. We initially became interested in this technique during the study of methods to deliver water-soluble dyes to textile fibers. Such dyes were not terribly substantive, and most of the product was lost in the waste water. Ideally, if there was a charge on the fiber, the opposite charge could be put onto the dye and the process efficiency improved. Most times, however, this was not possible, and we observed that water-insoluble color compounds could not be easily delivered to the textile surfaces. It turned out that the very same emulsifiers that emulsified the color compound in the water also acted as detergents, and could remove the color so deposited. In the textile area, when a hydrophobic treatment is required, one can treat the fiber with silicone or with a hydrocarbon. Both types of treatment will result in a hydrophobic finish. However, if treated with silicone, the fiber will also be oleophobic. If treated with oil, the fiber will also be siliphobic. Thus, for waterproofing fibers, selection of the proper molecule is critical, since improper selection will result in unacceptable oil staining. In search of a solution to this problem, we discovered that when a charged silicone compound was chosen and complexed with a surfactant having the opposite charge, a more efficient mechanism to deliver the active was achieved. We quickly modified this concept to allow for the delivery of many noncolor compounds to the hair and skin and thereby achieved a powerful new approach for the delivery of useful personal care actives to the hair and skin.
31.3 Group Opposites In order to understand the technology described in this chapter, one first needs to understand the concept of group opposites. This concept was developed recently and explained in terms of solubility group opposites.[2] Originally, there were two types
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS of opposites: oil-soluble and water-soluble. Now, with the growing availability of organosilicone materials in personal care products, a new type of opposite needs to be introduced. The presence of silicone groups in the molecule alters the solubility and can result in an improved deposition on hair and skin of silicone-modified materials. When compounds are least soluble in water, they will be more likely to deposit on substrates, or end up at an interface. The trick in designing an effective molecule with enhanced deposition capability is to generate sufficient water-solubility to allow for a cosmetically appealing aqueous product, yet, at the same time, to have limited the water-solubility so that it will preferentially absorb onto the substrate. Charged silicone polymers offer a very attractive delivery system for actives having the opposite charge. This concept extends to standard quaternaries as well as many other useful ionic actives such as polyacrylate type polymers. Table 31.1 describes some very useful definitions, and their opposites, which are critical for understanding and achieving delivery.
31.4 Silicone Compounds In the 1990s, there was a considerable expansion in the number of silicone surfactants available commercially. In fact, there has been a duplication of virtually all classes of compounds available as carbon-based surfactants in the world of silicone surfactants. Table 31.2 outlines a range of products with similar functionality available in both the world of fatty chemicals as well as that of silicone.
637
phosphates, sulfates, and sulfosuccinates. Having such an ionic charge is the first requirement for making a delivery complex. The second requirement for making a delivery system complex is to make the silicone compound barely water-soluble. Silicone polymers offer extraordinary opportunities to vary solubility and, therefore, improve delivery and attachment to the desired substrates. A series of new products have been prepared and commercialized that incorporate silicone, fatty, and water-soluble moieties. These materials demonstrate improved substantivity to hair and skin, as expected.
31.4.1
Carboxy Silicone Polymers
As an example of the effective use and application of cationic silicone complexes for enhanced personal care delivery systems, we present below specific complexes obtained between carboxy functional silicone polymers and selected fatty quaternary compounds. Carboxy silicone polymers useful in making delivery complexes have a pendant carboxy group present and consequently are anionic surface-active agents. Appropriate selection of the silicone portion of the molecule, combined with the proper cationic portion, has been found to considerably improve delivery and deposition uniformity of actives on the hair and skin. The delivery complexes have the structure shown in Fig. 31.1. These complexes are large molecules that disrupt hydrogen bonding in water and, as such, are preferentially adsorbed on the substrate in order to obtain an aqueous solution with the minimum free energy.
The new silicone-based products have increased substantivity to hair and skin as a result of the presence of the silicone moiety. In fact, to predict the solubility of Table 31.1. Group Opposites products having oil-soluble, water-soluble, and silicone-soluble Hydrophilic (water loving) Hydrophobic (water hating) portions, an expansion of the wellOleophilic (oil loving) Oleophobic (oil hating) known HLB system has been proposed and has come to be Siliphilic (silicone loving) Siliphobic (silicone hating) known as the 3D HLB System.[3] Note: Many of the compounds listed · Hydrophobic materials can be either oleophilic or siliphilic. in Table 31.2 possess an ionic · Oleophobic materials may be either hydrophilic or siliphilic. charge, and these include func· Siliphobic materials may be either oleophilic or hydrophilic. tional groups like carboxylates,
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Table 31.2. Comparison of Hydrocarbon Compounds with Silicone-modified Compounds[4]
Hydrocarbon Products
Silicone Products
Anionic Compounds Phosphate esters
Silicone phosphate esters[5][6]
Sulfates
Silicone sulfates[7]
Carboxylates
Silicone carboxylates[8][9]
Sulfosuccinates
Silicone sulfosuccinates[10][11]
Cationic Compounds Alkyl quats
Silicone alkyl quats[12]
Amido quats
Silicone amido quats[13]
Imidazoline quats
Silicone imidazoline quats[14]
Amphoteric Compounds Amino proprionates
Silicone amphoterics[15]
Betaines
Silicone betaines[16]
Phosphobetaines
Silicone phosphobetaines[17]
Nonionic Compounds Alcohol alkoxylates
Dimethicone copolyol
Alkanolamids
Silicone alkanolamids[18]
Esters
Silicone esters[19][20][21][22]
Taurine derivatives
Silicone taurine[23]
Isethionates
Silicone isethionates[24]
Alkyl glycosides
Silicone glycosides[25]
CH3 CH3 CH3 CH3 | | | | CH3Si(OSi)a(OSi)bOSiCH3 | | | | CH3 CH3 (CH2) 3 CH3 | O(CH2CH2O)xC(O)RC(O)O CH3 | RN+CH3 | CH3 Figure 31.1 The structure of a delivery complex (Cetylsil®) based on carboxy silicone polymers.
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31.5 Fatty Quaternary Ammonium Compounds Fatty quaternary compounds are commonly called quats. They are tetra-substituted ammonium compounds in which each of the four groups on the nitrogen atom are comprised of groups other than hydrogen. If any hydrogen groups are present, the compounds are not considered quaternary amines; they are then known as primary or secondary amines. There are several well-known, undesirable attributes of fatty cationic products. In each case, these attributes may be improved by complexation with an anionic silicone moiety. Examples of these undesirable attributes include: Fatty quaternary compounds are incompatible with anionic surfactants since an insoluble complex is frequently formed when the two types of materials are combined. This problem frequently occurs using polyacrylates as thickeners since they are cationic. Many fatty quaternary compounds are eye irritants;[26] such materials are minimally irritating to the eyes at concentrations of 2.5 weight percent.[27] This limits the useful concentration. Fatty quats are generally hydrophobic and, when applied to a substrate, cause a reduction in water absorbency of the substrate. It is not an uncommon situation for a traveler staying in a hotel to encounter a very soft towel that totally fails to absorb water. This is because the fatty quaternary treatment provides softness, but also prevents rewetting as a result of its hydrophobic nature. This situation can be also observed on hair when the absorbed conditioner prevents the hair from rewetting. The phenomenon causes the hair to become gunky and results in undesirable buildup of the material.
31.6 Silicone Complex Improvements Making silicone complexes with carboxy silicone compounds can mitigate many of these undesirable
639
attributes of the fatty quaternary ammonium compounds. The complexes of carboxy silicones with quaternary compounds produce altered properties which make them highly desirable in personal care applications such as shampoos, body washes, and other cleansing products. A comparison of two such complexes with two well-known quats is described below.
31.6.1
Organic Quats
Stearalkonium chloride is well known to be an excellent conditioning agent, and imparts outstanding substantivity to hair. The product has detangling properties and improves wet-comb properties when applied after shampooing. The FDA formulation data reports the use of this material in 78 hair conditioners. Of these conditioners, eight are used at levels of less than 0.1%, eighteen at levels of between 0.1% and 1.0%, and fifty-two at levels of between 1.0% and 5.0%. Cetyltrimonium chloride, or CTAC, is well known to be a very substantive conditioner. In addition to providing a non-greasy feel, the material also improves wet-comb properties and also provides a gloss to the hair. The product, however, is classified as a severe primary eye irritant and therefore its useconcentration is generally limited to less than or equal to 1.0% by weight.
31.6.2
Silicone Quat Complexes
By contrast to the organic quats described above, it has been found that silicone carboxy fatty quaternary complexes offer significant advantages in personal care applications. Surprisingly, these materials form clear, water-soluble complexes with anionic systems in aqueous solution. They have been demonstrated to provide outstanding wet-comb properties and antistatic properties on hair. Further, these materials also provide non-greasy, softening properties to hair and skin, are minimally irritating to the eyes, and can be used to formulate clear conditioners. Significantly, these properties are seen in shampoo systems at concentrations below 0.5% by weight because the energetics of the solution favor deposition onto hair rather than retention in solution. The
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silicone-quat complex offers considerable enhancement in deposition and conditioning, and enables the formulator to maintain efficacy in shampoos, while significantly reducing the component concentrations.
Stearasil® is compatible with, and forms clear solutions over a range of concentrations.
Commercial examples of such products are described in Table 31.3
31.7.2
31.7 Desirable Properties of Cationic Silicone Complexes
A ten-percent-solids solution of sodium lauryl sulfate (Colonial SLS from Colonial Chemical) was prepared. Separately, a ten-percent-solids solution of the quat (or quat silicone complex) being tested was also prepared. The quat was titrated into 100 ml of the sodium lauryl sulfate solution. The formation of a white, insoluble complex, or a haze, is considered to be the end point of the titration.
Cationic silicone complexes demonstrate major improvements over the original quat precursors in a variety of key areas. These include anionic compatibility, reduction of eye irritation, improved rewetting, improved compatibility with polyacrylates, and improved conditioning and combability of hair.
31.7.1
Compatibility with Anionic Surfactants
Traditional fatty quats like stearalkonium chloride and cetyltrimonium chloride, form water-insoluble complexes when combined with sodium lauryl sulfate in aqueous solution. This phenomenon is due to the formation of an insoluble anionic/ cationic complex. Cetylsil®, like the traditional quats, also forms a complex, but surprisingly however,
Compatibility with Anionic Surfactants Test
As can be seen from the data in Table 31.4, Stearasil is unique in that it is compatible with sodium lauryl sulfate systems. Eye irritation. Eye irritation is a major concern in the formulation of personal care products, particularly when working with quaternary surfactants. Primary eye irritation was tested using the protocol outlined in FHSLA 16 Code of Federal Regulations 1500.42. The products were tested at 25% actives and the results obtained are outlined in Table 31.5. Rewetting properties. When complexes of fatty quaternary compounds and carboxy silicone are used to treat textile fabrics, they make the substrate soft, but they do not make them hydrophobic. This distinguishes their behavior from the standard fatty
Table 31.3. Commercially Available Products
Commercial Name
INCI Name
Fatty Quat
Stearasilâ
Stearalkonium dimethicone copolyol phthalate
Stearalkonium chloride
Cetylsilâ
Cetrimonium dimethicone copolyol phthalate
Cetyltrimonium chloride
Stearasilâ S
Stearalkonium dimethicone copolyol succinate
Stearalkonium chloride
CetylsilâS
Cetrimonium dimethicone copolyol succinate
Cetyltrimonium chloride
Stearasilâ and Cetylsilâ are registered trademarks of Biosil Technologies Inc.
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Table 31.4. Compatibility with Anionic Surfactants Test
Test Compound
End Point (ml)
Appearance
Material Type
Stearalkonium chloride
0.3
White solid
Fatty quat
Cetyltrimonium chloride
0.2
White solid
Fatty quat
Cetylsil®
0.5
White solid
Silicone quat complex
35.8
Haze develops
Silicone quat complex
Stearasil® ®
®
Stearasil and Cetylsil are registered trademarks of Biosil Technologies Inc
Table 31.5. Eye Irritation
Product Cetyltrimonium chloride Cetylsil
®
Stearalkonium chloride* Stearasil
®
Score 106.0 8.3 116.5 11.3
Irritation Level
Material Type
Severely irritating
Fatty quaternary
Minimally irritating
Silicone complex
Severely irritating
Fatty quaternary
Minimally irritating
Silicone complex
* At a concentration of 0.5%, stearalkonium chloride was minimally irritating. This rating of minimally irritating was the same rating achieved by Cetylsil® and Stearasil® when used at 25% (or 50 times the concentration). As the data clearly show, the irritation level for the silicone-quat complex is dramatically reduced when compared to the starting quat.
quats, which only make the substrate hydrophobic. This property is very important in the personal care area, and specifically to their use on hair. Hair treated with the silicone-complexed quat does not show evidence of any buildup on the surface of the hair.
31.8 Fatty Quaternary, Carboxy Silicone Conditioner The highly desirable properties of formulating a conditioner using a fatty quaternary, carboxy silicone compound can be demonstrated using the formulations and test methods described below. A base formulation and a commercial conditioner were selected as controls. Modifications were made to these by the addition of Stearasil and Cetylsil.
31.8.1 Test Method The test hair used was 7-inch, dark brown, virgin hair from DeMeo Brothers. Five two-gram tresses were used per product evaluated. All tresses were pre-washed three times with Prell original shampoo, rinsed in water at 25°C, and air-dried. Performance was rated using the scale shown in Table 31.6. Table 31.6. Numerical Scale Used to Rate Effects of Formulations on Hair
Rating
Description
1
Very poor
2
Poor
3
Satisfactory
4
Good
5
Excellent
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Test formulas T1T6 (see Table 31.7) were produced, tested, and compared to demonstrate the effects of systems with organic quaternary compounds and their silicone counterparts. The components of the base formulation used in the tests are shown Table 31.8.
the advantage of inclusion of the fatty quaternary, carboxy silicone complex in this formulation. Dry comb properties. The formulas in Table 31.7 were also evaluated on dry hair. The qualitative test results are shown in Table 31.10. Dry comb conclusions. 1. Upon comparing Formulas T1, T3, and T5, the following trend emerges:
31.8.2 Test Results Conditioning, wetability, and combability were evaluated for each of these systems according to the prescribed test method. The test results are shown in Table 31.9 and described here. Conditioning and wet combability. 1. Upon comparing Formulas T1, T3, and T5, the following trend emerges: Including stearalkonium chloride into the base formula did not improve the base at all (Formulas T1 and T5). However, inclusion of Stearasil® into the base formula improved residual feel, and wet combability (Formulas T1 and T3). This clearly shows the advantage of inclusion of the fatty quaternary, carboxy silicone complex in this formulation. 2. Upon comparing Formulas T1, T6, and T4, the following trends emerge: Inclusion of CETAC (cetyl trimethyl ammonium chloride) into the base formula did not improve the base at all. (Formulas T1 and T4). However, inclusion of Cetylsil® into the base formula, improved residual feel, and wet combability (Formula T1 and T6). This clearly shows
Inclusion of stearalkonium chloride into the base formula resulted in a marginal improvement (Formulas T1 and T5). However, inclusion of Stearasil into the base formula improved shine and dry comb characteristics, and provided a very significant improvement in fullness of the hair (Formulas T1 and T3). This clearly shows the advantage of including the fatty quaternary, carboxy silicone complex in this formulation. 2. Upon comparing Formulas T1, T6, and T4, the following trends emerge: Inclusion of CETAC into the base formula resulted in an improvement in shine and dry comb characteristics (Formulas T1 and T4). Inclusion of Cetylsil into the base formula improved all properties measured except curl retention (Formula T1 and T6). The above data clearly shows that the incorporation of cationic silicone complexes, called Stearasil and Cetylsil, into the base formula resulted in significant improvements in functionality. These improvements are a direct result of the usefulness of such adjuvants for enhancing delivery of personal care actives to the hair.
Table 31.7. Formulations Include Two Controls and Four Test Formulations
Test Formulation
Description
T1
Base Formula
T2
Commercial Conditioner
T3
Base Formula + 2% Stearasil®
T4
Base Formula + 2% CETAC added
T5
Base Formula + 2% Stearalkonium chloride
T6
Base Formula + 2% Cetylsil®
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Table 31.8. Base Formulation Used for Control and Test Formulations in Table 31.7
Phase
Ingredient
A
B
Function
% Weight
Water
Solvent
Qs 100.00
Tetrasodium ETDA
Chelating agent
0.15
Biosil Basics SPQ
Conditioner
0.55
Rice bran oil
Conditioner
4.00
Cetyl alcohol
Conditioner
3.00
Test ingredient
C
2.00
Glyceryl stearate
Conditioner
2.50
Propylparaben
Preservative
0.10
Germall 115
Preservative
0.20
Procedure 1. In a suitable container, weigh out all items in Phase A in order shown. 2. Mix well and heat to 75°C. 3. In a separate container, weigh out and combine all items in Phase B in the order shown. 4. Heat Phase B to 75°C. 5. Add Phase B to Phase A at 75°C, while agitating for at least 15 minutes. 6. Add Phase C. 7. Cool to 25°C30°C.
Table 31.9. Hair Conditioning Performance Rating (See Table 31.6) of Formulas Listed in Table 31.7
Property
Formula 1
Formula 2
Formula 3
Formula 4
Formula 5
Formula 6
Residual feel
2
4
4
1
1
2
Squeaky feel
1
2.5
1
1
1
3
Shine
1
2
1
1
1
2
Wet comb
4
5
5
4
4
2.5
Spreadability
4
4.5
4
3
3
3
Smoothness
3
3.5
4
3
3
3
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Table 31.10. Dry Comb Performance Rating (See Table 31.6) of Formulas Listed in Table 31.7
Property
Formula 1
Formula 2
Formula 3
Formula 4
Formula 5
Formula 6
Residual feel
3
3
3
3
3
4
Shine
2
3
3.5
2.5
3
4
Dry comb
3
3
4
5
3
3.5
Fly away
2
2
2
2
2.5
2.5
Curl retention
3
2
2
3
2
3
Fullness
2
2
4
2.5
3
3
Manageability
3
3
2
2
2
3
31.9 Recent Advancements
31.10 Conclusions
There has recently been a patent awarded for the composition of complexes based upon alkylamidoquats, rather than the alkyl quats.[31] These complexes have a superior skin feel, and are better conditioners.
The use of silicone carboxy, fatty quaternary complexes as delivery systems offers the personal care formulator an enhanced ability to improve the cost-effectiveness of using water-soluble actives in formulations that provide a benefit to the hair and skin. This improvement is a direct result of the alteration of the original solubility of water-soluble actives. As a result of the described complex formation between anionic carboxy silicone compounds and cationic fatty quaternary actives, improved substantivity to hair in aqueous formulation is achieved. We believe this is a powerful formulation technique that is ripe for further development.
Recently a number of patents[32]-[34] have been issued in which the complexation phenomenon outlined in this chapter has been expanded to compounds in which neither the cationic compound nor anionic compound contain silicone. The anionic and cationic compounds are chosen so that the complex has minimal water solubility and is compatible with non-ionic silicone surfactants. The performance attributes mimic those of the complexes made from silicone anionic compounds and fatty quats.
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31.11 Formulations Formulations 31.131.22, provided by Biosil Technologies Inc., illustrate the efficacy of the carboxy silicone, fatty quaternary complexes in a number of personal care products. The formulations cover a range of hair and skin products: Shampoos
Formulations 31.131.4
Body Wash
Formulations 31.531.7
Conditioners
Formulations 31.831.16
Facial Cleansers
Formulation 31.17
Pomade
Formulations 31.1831.19
Hair Growth Treatment
Formulation 31.20
Tanning Product
Formulation 31.21
Makeup Remover Formulation 31.22
Formulation 31.1: Shampoo
Material
Function
Water
Weight % QS to 100.0
Ammonium lauryl sulfate
a
Detergent
23.0
Cocamid DEA
Viscosity builder
2.4
Cocamidopropyl betainea
Detergent
2.9
Tetrasodium EDTA
Chelating agent
0.1
Aloe vera gel
Active
0.1
Peg 6000 distearate
Opacifier
0.5
Conditioning complex
2.5
Biowax® 754b
Emollient
4.0
Sodium chloride
Viscosity builder
Phenonip
Preservative
a
Cetylsil
®b
As desired 1.0
Mixing Procedure In a suitable container, heat water to 75°C, add each ingredient in the order shown, using good agitation, allowing 15 minutes between additions. Cool to 35°C and add preservative. To increase viscosity, add salt. Notes 1. Cetylsil® is the fatty quaternary, carboxy silicone, added for improved conditioning. 2. Biowax® 754 is added for improved combability. 3. Extracts like common nettle, henna extract, etc., can be added as desired. Sources a
Colonial Chemical, South Pittsburg, Tennessee
b
Biosil Technologies, Inc., Paterson, New Jersey
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Formulation 31.2: Shampoo
Material
Function
Water
Weight % QS to 100.00
Ammonium lauryl sulfate
a
Detergent
25.00
Cocamide DEA
Viscosity
2.40
Cocamidopropyl betainea
Detergent
2.90
Tetrasodium EDTA
Chelation
0.50
PEG-150 distearate
Emollient
2.50
Biosil Basics SPQ
Conditioner
1.00
Dowicil 200
Preservative
0.30
Stearasil® b
Conditioner
2.00
a
®
b
Mixing Procedure 1. In a suitable container, begin to heat water to 70°C75°C, adding one ingredient at a time with proper mixing during each addition. 2. Begin to cool to 35°C. Sources a
Colonial Chemical, South Pittsburgh, Tennessee
b
Biosil Technologies, Inc., Paterson, New Jersey
.
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Formulation 31.3: Clear Softening Shampoo
Phase
Material
Function
Water
A
B
Weight % Qs to 100.00
Sodium laureth-2 sulfatea
Detergent
30.00
Cocamide DEAa
Viscosity builder
2.50
Cocamido betainea
Detergent
7.00
Biowax® 754 Specialb
Emollient
2.00
SugaQuat La
Glucose quat
1.50
Cetylsil® Sb
Conditioning complex
6.50
Phenonip
Preservative
1.00
Mixing Procedure 1. In a suitable container, combine all ingredients together of Phase A with good agitation, without aerating. 2. Begin to heat to 70°C75°C.When clear and uniform, stop heating and cool to 35°C40°C. 3. Add Phase B. Mix well. 4. Adjust pH to 6.36.8, with 50% citric acid as needed. Sources a
Colonial Chemical, South Pittsburg, Tennessee
b
Biosil Technologies, Inc., Paterson, New Jersey
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DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.4: Two-in-One Conditioning Shampoo
Material
Function
Water
Weight % QS to 100.00
Ammonium lauryl sulfate
a
Detergent
23.00
Cocamide DEA
Viscosity build
2.40
Cocamidopropyl betainea
Detergent
2.90
Tetrasodium EDTA
Chelation
0.05
Biosil Basics SPQ
Conditioner
1.00
PEG- 150 distearate
a
®
b
Emollient
2.50
®b
Conditioner
4.00
Behenesilb
Conditioner
1.00
Phenonip
Preservative
1.00
Stearasil
Mixing Procedure 1. In a suitable container, add ingredients and heat to 70°C75°C while mixing. 2. When all ingredients are melted and product is uniform, cool to 35°C40°C while stirring. 3. Pearlescence should appear while cooling.
Sources a
Colonial Chemical, South Pittsburgh, Tennessee
b
Biosil Technologies, Inc., Paterson, New Jersey
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Formulation 31.5: Clear Body Wash
Phase
Material
Function
Water
QS to 100.00 a
Sodium laureth sulfate
Detergent
30.00
Detergent
7.00
Preservative
0.15
Preservative
0.10
Viscosity builder
3.00
Conditioner
3.00
Cucumber extract
Active
0.25
Elder extract
Active
0.25
Matricaria extract
Active
0.25
Ginkgo extract
Active
0.25
C
Imidazolidinyl urea
Preservative
0.30
D
Citric acid
pH adjustment
Cocamidopropyl betaine A
a
Methylparaben Propylparaben a
Cocamide DEA Cetylsil
B
®b
Mixing Procedure 1. In a suitable container weigh out Phase A. Heat to 70°C75°C. 2. Mix until clear and begin to cool to 35°C40°C. 3. At 35°C, add Phase B. Mix well. 4. Add Phase C. Mix well. 5. Adjust pH with Phase D to 6.36.8. Sources a
Colonial Chemical, South Pittsburgh, Tennessee
b
Weight %
Biosil Technologies, Inc., Paterson, New Jersey
QS to pH 6.36.8
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Formulation 31.6: Body Shampoo
Material
Function
Water
Weight % Qs to 100.0
a
Ammonium laurel sulfate
Detergent
25.0
Cocamide DEA
Viscosity builder
3.0
Tetrasodium EDTA
Chelation
0.1
Aloe vera gel
Active
0.5
Conditioner
1.5
Silamine C-100c
Slip agent
2.5
Sodium chloride
Viscosity builder
As desired
Citric acid
pH control
As desired
Phenonip
Preservative
a
Cetylsil®
b
1.0
Mixing Procedure In a suitable container, heat water to 75°C. Add each ingredient in the order shown, under good agitation, allowing 15 minutes between additions. Cool to 35°C and add preservative. To increase viscosity, add salt. Notes 1. Cetylsil® is a fatty quaternary, carboxy silicone and is added for improved conditioning. 2. Silamine C-100 is dimethicone copolyol amine and is added for skin feel. 3. Extracts like common nettle, henna extract, etc., can be added as desired. Sources a
Colonial Chemical, South Pittsburg, Tennessee
b
Biosil Technologies, Inc. Paterson, New Jersey
c
Siltech LLC, Dacula, Georgia
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Formulation 31.7: Exfoliating Body Scrub
Phase
Material
Function
Water
QS to 100.00
Sodium lauryl sulfate
a
Detergent
30.00
Cocamide DEA
Viscosity builder
2.50
Cocamidopropyl betainea
Detergent
7.00
Biowax® 754b
Emollient
1.00
Conditioner
3.00
Viscosity builder
0.25
Chamomile extract
Active
1.00
Mallow extract
Active
1.00
Cucumber extract
Active
1.00
Jojoba beads 40/60
Active
5.00
Germaben 11
Preservative
1.00
Triethanolamine (99%)
pH adjustment
0.30
Fragrance
Fragrance
0.50
a
A
Cetylsil
®b
Carbopol 1342 B
C D
c
d
Mixing Procedure 1. In a suitable container, disperse Carbopol 1342. 2. Once mixed well, add remaining ingredients from Phase A. 3. Begin to heat to 55°C60°C until homogenous, then cool to 35°C45°C. 4. Add Phase B. Mix well. 5. Add Phase C. Mix well, then add Phase D. Sources a
Colonial Chemical, South Pittsburgh, Tennessee
b
Biosil Technologies, Inc., Paterson, New Jersey
c
Noveon, Cleveland, Ohio
d
Weight %
ISP, Wayne New Jersey
652
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.8: Spray-on, Leave-on Conditioner
Material
Function
Water
Qs to 100.0
Imidazolidinyl urea Cetylsil
Weight %
® a
®
Biosil Basics SPQ Phenonip
a
Preservative
0.30
Conditioner
1.00
Conditioner
0.30
Preservative
1.00
Mixing Procedure In a suitable container add water. Add each ingredient in the order shown, under good agitation, allowing 15 minutes between additions. Add preservative. Notes 1. Cetylsil® is a fatty quaternary, carboxy silicone and is added for improved conditioning. ®
2. Biosil Basic SPQ is a silicone quat that contains panthenol, a pro-vitamin.
Sources a
Biosil Technologies, Inc., Paterson, New Jersey
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
653
Formulation 31.9: Chelating Rinse-off Conditioner
Phase
Material
Function
Water A B
D
Qs to 100.0
Phytic acid
Chelation
Triethanolamine (99%)
pH adjustment
Methylparaben
Preservative
0.2
Cetyl alcohol
Conditioner
3.0
Rice bran oil
Oil phase
4.0
Conditioner
2.0
PEG-100 stearate
Emollient
1.2
Glyceryl stearate
Emollient
3.5
Propylparaben
Preservative
0.1
Biosil® Basics C38 ester a
Oil phase
1.0
Biosil® Basics SPQa
Conditioner
0.55
Phenonip
Preservative
1.00
Stearasil® C
Weight %
a
0.3 As required
Mixing Procedure 1. Into a suitable container add water. 2. Add Phytic acid. 3. Add enough TEA to adjust the pH to 4.04.5. 4. Add Phase B. 5. Heat to 70°C. 6. In another container combine Phase C. 7. Heat to 75°C80°C. 8. Add Phase C to the mixture of Phase A and B, under good agitation. 9. Cool to 40°C add Phase D. Notes 1. Stearasil® is the fatty quaternary, carboxy silicone and is added for improved conditioning 2. Biosil® Basic SPQ is a silicone panthenol quat. 3. Biosil® Basic C38 is a guerbet ester. Sources: a
Biosil Technologies, Inc., Paterson, New Jersey
654
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.10: Spray-on, Rinse-off Conditioner
Material
Function
Water
Weight % Qs to 100.0
Hydroxyethylcellulose
Viscosity builder
0.1
Dowicil 200
Preservative
0.2
Biosil® Basics HMC-1a
Active
1.0
GafQuat 755 Nb
Polymeric conditioner
1.0
Conditioner
5.0
Cetylsil
®a
Mixing Procedure 1. In a suitable container add water, and heat to 70°C75°C. 2. Slowly add hydroxyethylcellulose. 3. Mix 20 minutes. 4. Cool to 45°C50°C . 5. Add Dowicil 200. 6. Allow to cool to 35oC. 7. Add remaining ingredients in order shown under good agitation. Notes 1. Cetylsil is a fatty quaternary, carboxy silicone and is added for improved conditioning. Source a
Biosil Technologies, Inc., Paterson, New Jersey
b
ISP, Wayne, New Jersey
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
655
Formulation 31.11: Exothermic Conditioner
Material
Function
Biowax 754 Speciala
Emollient
PEG 1000
Exothermic additive
Stearasil
®a
Silwax WD-Fb
Weight % 20.0 Qs to 100.0
Skin feel
1.0
Slip agent
0.5
Mixing Procedure 1. In a suitable container combine materials in order shown. 2. Heat to 65°C. 3. Allow to cool under agitation. Notes 1. Stearasil is the fatty quaternary, carboxy silicone and is added for improved conditioning. 2. Silwax WD-F is a fluoro silicone product that is added to improve combability. 3. The product is a white solid. If a liquid product is desired, use a lower molecular weight.PEG like PEG 400. 4. When placed in wet hands, the PEG produces a mild warming effect. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
b
Siltech LLC, Dacula Georgia
656
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.12: Spray-on Conditioner
Phase
Material
A
Water
B
Dowcil 200 ®
Biosil Basics HMW
D
GafQuat 755Nb Cetylsil
a
®a
Preservative
0.20
Actives
3.00
Polymeric conditioner
5.00
Conditioner
5.00
Mixing Procedure 1. In a suitable container, weigh water. 2. Heat to 45°C50°C. Then cool to 35°C40°C. 3. Add Phase B; mix well with good agitation before adding the next phase. 4. Add Phase C; mix well with good agitation before adding the next phase. 5. Add Phase D; mix well with good agitation before adding the next phase. 6. Add Phase E; mix well. 7. Filter product. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
b
Weight % Qs to 100.00
C E
Function
ISP, Wayne, New Jersey
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
657
Formulation 31.13: Two-in-One Conditioner
Phase
Material
Function
Water
QS to 100.00 a
Triethanolamine lauryl sulfate
Detergent
25.00
Cocamidopropyl betaine
Detergent
7.00
Cocamide DEAa
Viscosity builder
2.00
Methylparaben
Preservative
0.20
Propylparaben
Preservative
0.10
Chelation
0.05
Biosil Basics Cocosil
Conditioner
5.00
Cetylsil® b
Conditioner
3.00
B
Citric acid, 50% solution
pH adjustment
QS to 6.30-6.80
C
Sodium chloride
Viscosity adjustment
As required for viscosity
a
A
Tetrasodium EDTA ®
b
Mixing Procedure 1. In a suitable container, heat Phase A to 60°C, while stirring. 2. Cool to 50°C55°C. 3. Use citric acid solution to adjust pH to 6.306.80. 4. Cool to 45°C. Mix well. 5. Use sodium chloride to adjust viscosity.
Sources a
Colonial Chemical, South Pittsburgh, Tennessee
b
Weight %
Biosil Technologies, Inc., Paterson, New Jersey
658
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.14: Rinse-off Conditioner
Phase
Material
Function
Water
QS to 100.00
Methylparaben A
B
Preservative
0.15
Biosil Basics SPQ
Conditioner
0.50
Tetrasodium EDTA
Chelant
0.05
Stearasil® a
Conditioning complex
2.00
Rice bran oil
Oil
4.00
Cetyl alcohol
Oil
3.00
Propylparaben
Preservative
0.10
PEG-100 stearate
Emulsifier
1.15
Emulsifier
2.50
Conditioning complex
2.00
Preservative
0.20
®
a
Glyceryl monostearate ®
Biosil Basics Behenesil C
a
Imidazolidinyl urea
Mixing Procedure 1. In a suitable container, weigh and combine ingredients of Phase A. 2. Begin to heat to 75°C80°C. 3. In another container, weigh and combine all ingredients in Phase B. 4. Heat phase B to 75°C80°C. 5. Add Phase B to Phase A. Mix well. 6. Begin to cool to 30°C35°C. 7. Add Phase C. Mix well. Sources a
Weight %
Biosil Technologies, Inc., Paterson, New Jersey
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
659
Formulation 31.15: Creamy Conditioner
Phase
Material
Function
Water
QS to 100.00
Methylparaben A
Preservative
0.15
Biosil Basics SPQ
Conditioner
1.50
Stearasil® a
Conditioning complex
2.00
®
a
Tetrasodium EDTA
Chelation
0.05
a
Oil
4.00
Cetyl alcohol
Oil
3.00
Propylparaben
Preservative
0.10
PEG-100 stearate
Emulsifier
1.15
GMS-450
Emulsifier
2.50
Conditioning complex
1.00
Biosil Basics HMC
Actives
1.00
Biosil® Basics DL-30a
Actives
1.00
Phenonip
Preservative
1.00
Rice bran oil
B
a
Behenesil ®
C
Weight %
a
Mixing Procedure 1. In a suitable container, combine Phase A and with good agitation begin to heat to 70°C75°C. 2. In another suitable container, combine Phase B and begin to heat to 70°C75°C. 3. At temperature, add Phase B to Phase A. Mix well, begin to cool to 35°C40°C. 4. At temperature, add Phase C mixing well between additions. 5. Add Phase D at 35°C. Mix very well. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
660
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.16: Clear, Leave-in Conditioner Detangler
Phase A
B
C
Material
Function
Water
Weight % QS to 100.00
Hydroxyethylcellulose
Thickener
0.09
Propylene glycol
Solvent
4.00
Cocosila
Conditioner complex
2.50
Biosil® Basics SPQa
Conditioner
1.00
Preservative
0.30
Actives
1.00
Dowicil 200 ®
Biosil Basics HMC-1
a
Mixing Procedure 1. In a suitable container, weigh out water of Phase A and disperse hydroxyethylcellulose. 2. Mix until clear, begin to heat to 60°C65°C. 3. Combine Phase B and heat until uniform (60°C65°C). 4. Add Phase B to Phase A. Cool to 40°C45°C. 5. Add Phase C and mix well. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
661
Formulation 31.17: Facial Cleanser (Oily Skin)
Phase
Material
Function
Water A
QS to 100.00
Propylene glycol
Solvent
3.00
Methylparaben
Preservative
0.20
Biowax 754 speciala
Emollient
1.00
Cetylsil® Sa
Conditioning complex
2.00
Oil
5.00
Stearic acid
Oil
3.50
GMS-450
Emulsifer
1.00
Propylparaben
Preservative
0.15
Oil
0.40
Biosil Basics C-38
Oil
1.00
Emulsifying wax
Emulsifier
3.00
TEA lauryl sulfateb
Detergent
3.50
Preservative
0.30
Rhodofiltrat chondrus crispus
Active
1.00
Coralline concentrate
Active
1.00
Witch hazel extract
Active
0.5
Grapefruit extract
Active
0.5
Chamomile extract
Active
0.5
Rice bran oil
B
a
Cetyl alcohol ®
C
a
Unicide U-13 a
D
Weight %
Mixing Procedure 1. In a suitable container, weigh out and combine ingredients in Phase A and begin to heat to 70°C75°C with light agitation. 2. In another container, weigh out and combine ingredients in Phase B and begin to heat to 70°C75°C with light agitation. 3. At desired temperature, add Phase B to Phase A. Mix well and begin to cool to 35°C45°C. 4. Add Phase D, one ingredient at a time; mix well between additions. Add Phase E. 5. Mix well. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
b
Colonial Chemical, South Pittsburgh, Tennessee
662
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.18: Hair Pomade
Material Petrolatum-white IS
Function
Weight %
Oil
QS to 100.00
Oil
2.00
Oil
10.00
Behenesila
Conditioner
1.00
Silwax 418b
Silicone wax
2.00
c
Zenigloss S
Biosil Basics C-38
a
Mixing Procedure 1. Combine all ingredients in a suitable container and heat to 70°C75°C or until uniformly melted. 2. Mix well. Pour product at 65°C70°C. 3. Allow to cool.
Sources a
Biosil Technologies, Inc., Paterson, New Jersey
b
Siltech LLC, Dacula, Georgia
c
Zenitech LLC, Old Greenwich, Connecticut
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
663
Formulation 31.19: Hair Pomade Stick
Phase A
B
Material a
Function
Cyclomethicone
Solvent
Stearyl alcohol
Oil
15.00
Castor Wax MP80
Wax
8.00
Zeniglossc
Gloss additive
2.00
Biosil® Basics C-38b
Oil
3.00
Conditioner
1.50
Behenesil
b
Mixing Procedure 1. Combine all ingredients of Phase B and heat to 75°C80°C. 2. Once uniform, cool to 60°C 65oC and add Phase A. 3. Mix until uniform. Sources a
Siltech LLC, Dacula, Georgia
b
Biosil Technologies, Inc., Paterson, New Jersey
c
Weight %
Zenitech LLC, Old Greenwich, Connecticut
QS to 100.0
664
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.20: Hair Growth Conditioner Treatment
Phase
Material
Function
Water
QS to 100.00
Phytic acid complex
Active
2.00
Biosil Basics SPQ
Conditioner
0.75
Tetrasodium EDTA
Chelation
0.05
Methylparaben
Preservative
0.20
Conditioner
1.25
Cetyl alcohol
Oil
3.00
Propylparaben
Preservative
0.15
Rice bran oil
Oil
4.00
PEG-100 stearate
Emulsifier
1.15
Glyceryl stearate
Emulsifier
2.50
Imidazolidinyl urea
Preservative
0.30
Biosil® Basics HMC-1a
Active
5.00
Complex anti chute N
Active
3.50
Ginkgo extract
Active
0.10
Chamomile extract
Active
0.10
Henna extract
Active
0.10
Fragrance
Fragrance
0.50
®
A
Cetylsil
B
C
D
Weight %
a
®a
Mixing Procedure 1. In a suitable container, add water and phytic acid complex. 2. Add remaining ingredients of Phase A; one at a time with good agitation between additions. 3. Begin to heat to 75°C80°C. 4. In another suitable container, weigh and combine Phase B. Heat to 75°C80°C. 5. Add phase B to Phase A. Mix well and begin to cool to 40°C45°C. 6. At 40°C, add Phase C, one ingredient at a time with good agitation between additions. 7. Add Phase D. Mix well. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
OLENICK, BUFFA: CATIONIC SILICONE COMPLEXES AS DELIVERY SYSTEMS
665
Formulation 31.21: Self-Tanning Mousse
Phase A
B
Material Water
D
Weight % Qs to 100.00
Hydroxy celluose
Thickener
0.10
Dowcil 200
Preservative
0.30
Biosil® Basics SPQa
Conditioner
1.00
Cetylsil® a
Conditioner complex
1.25
Biowax 754 special
Emollient
1.00
DHA
Self tanner
5.00
Dermochlorella D
Active
1.00
Cocamido betaine
Surfactant
3.00
a
C
Function
Mixing Procedure 1. In a suitable container, slowly sprinkle hydroxy celluose into water of Phase A. 2. Once well dispersed, weigh and combine ingredients of Phase B and add to Phase A. Mix well. 3. Add Phase C, one ingredient at a time, with good agitation between additions. 4. Add Phase D. Mix well. (NO HEAT REQUIRED). Note: Must use AIRSPRAY BOTTLE to achieve mousse effect. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
b
Colonial Chemical, South Pittsburgh, Tennessee
666
DELIVERY SYSTEM HANDBOOK FOR PERSONAL CARE AND COSMETIC PRODUCTS
Formulation 31.22: Water-based Makeup Remover
Material
Function
Water Cocosil
Weight % QS to 100.0
a
Conditioner complex
2.0
Chamomile extract
Active
1.0
Cucumber extract
Active
1.0
Dowicil 200
Preservative
0.3
Mixing Procedure 1. In a suitable container, weigh and combine all ingredients in the order they appear. 2. Mix until completely uniform. Sources a
Biosil Technologies, Inc., Paterson, New Jersey
References 1. Lucassen, E., and Giles, D., Journal of Colloid and Interface Science, Vol. 81, No. 1, pp. 150157 (May 1981)
17. Kollmeier, U.S. Patent 4,654,161 (Mar. 1987) 18. OLenick, U.S. Patent 5,237,035 (Aug. 1993) 19. OLenick, U.S. Patent 5,070,171 (Dec. 1991) 20. OLenick, U.S. Patent 5,070,168 (Dec. 1994)
2. OLenick, A. J., Journal of Surfactants and Detergents, Vol. 3, No. 2, p. 229 (Apr. 2000)
21. Dexter, U.S. Patent 4,724,258 (Feb. 1988)
3. OLenick, A. J., Surfactants: Chemistry and Applications, p. 96, Allured Publishing (1999)
23. OLenick, U.S. Patent 5,280,099 (Jan. 1994)
4. ibid 2, p. 26.
25. OLenick, U.S. Patent 5,120,812 (Jun. 1992)
5. OLenick, U.S. Patent 5,149,765 (Sep. 1992) 6. Dexter, et al., U.S. Patent 4,724,248 (Feb. 1988) 7. OLenick, U.S. Patent 4,960,845 (Oct. 1990) 8. Haluska, U.S. Patent 3,560,544 (Feb. 1971) 9. OLenick, U.S. Patent 5,296,625 (Mar. 1994) 10. Maxon, U.S. Patent 4,717,498 (Jan. 1988) 11. Colas, U.S. Patent 4,777,277 (Nov. 1998) 13. OLenick, U.S. Patent 5,098,979 (Mar. 1992) 14. OLenick, U.S. Patent 5,153,294 (Oct. 1992) 15. OLenick, U.S. Patent 5,196,499 (Feb. 1993) 16. OLenick, U.S. Patent 5,073,619 (Dec. 1991)
22. OLenick, U.S. Patent 6,338,042 (Dec. 2002) 24. OLenick, U.S. Patent 5,300,666 (Apr. 1994) 26. Hunter, A., Encyclopedia of Shampoo Ingredients, pp. 174175, Micelle Press (1983) 27. Sherex Formulary, Witco Chemical, Greenwich CT 28. Hunter, A., Encyclopedia of Conditioning Rinse Ingredients, Micelle Press, p. 99 (1987) 29. OLenick, U.S. Patent 5,296,434 (Mar. 1994) 30. OLenick, U.S. Patent 5,248,783 (Sep. 1993) 31. OLenick, U.S. Patent 6,498,263 (Dec. 2002) 32. OLenick, U.S. Patent 6,461,598 (Oct. 2002) 33. OLenick, U.S. Patent 6,410,679 (Jun. 2002) 34. OLenick, U.S. Patent 6,372,934 (Apr. 2002)