croda - crothix thickner for shampoos

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CROTHIX™ DS-53R-6 October 31, 2007

CROTHIX™ INCI Name: PEG-150 Pentaerythrityl Tetrastearate

CROTHIX™ is a patented high performance thickener developed for aqueous surfactant systems. As a complex high molecular weight ester, CROTHIX is truly multi-functional. Not only is it superior as a thickener, but it is also effective as a diethanolamine (DEA) replacement, monoethanolamine (MEA) and a mitigator of irritation. As a thickener, CROTHIX is efficient as well as effective, producing substantial viscosity even at low levels. As a DEA and MEA replacement, the product is a safe alternative providing similar viscosity and foam stabilization. As a mitigator of irritation, it is a viable means of lowering the irritancy potential of the surfactant system itself. What’s more—CROTHIX requires no neutralization, forms no nitrosamine by-products, and works especially well in clear systems. Benefits • Superior surfactant thickening • Pastillated for ease of handling • Globally approved • Mild • Minimizes irritation

• Allows for the formulation of DEA free products • Allows for the formulation of MEA free products • Effective in hard to thicken systems • Produces clear systems

Applications • Shampoos • Body Washes • 2-in-1’s

• Shave Gels • Liquid Soaps

* The use of CROTHIX in cosmetic and other formulations is covered under U.S. Patent # 5,192,462 assigned to Croda Inc.CROTHIX™

------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- Croda Inc 300-A Columbus Circle, Edison, NJ 08837 Tel 732-417-0800 Fax 732-417-0804 Website www.crodausa.com Sederma, Inc. Tel 732-692-1652 Fax 732-417-0804 Croda Inc West Coast Sales Office 9545 Santa Anita Ave, Rancho Cucamonga, CA 91730 Tel 909-980-2510 Fax 909-476-7304 Croda Miami Inc 200 South Park Road, Suite 303, Hollywood, FL 33021 Tel 1-888-84CRODA Fax 954-989-8186 Sol Kaplan & Son PO Box 240234 Memphis TN 38124-0234 Tel 901-685-0323 Fax 901-763-3612 Croda Canada Ltd 221A Racco Parkway, Vaughan, Ontario L4J8X9 CANADA Tel 905-886-1383 Fax 905-886-4753 The information in this publication is believed to be accurate and is given in good faith, but no representation or warranty as to its completeness or accuracy is made. Suggestions for uses or applications are only opinions. Users are responsible for determining the suitability of these products for their own particular purpose. No representation or warranty, expressed or implied, is made with respect to information or products including, without limitation, warranties of merchantability, fitness for a particular purpose, non-infringement of any third party patent or other intellectual property rights including, without limit, copyright, trademark and designs. Any trademarks identified herein are trademarks of the Croda group of companies.

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CROTHIX™

Structure of CROTHIX

RCO

O

C

CH 2

CH 2 CH 2

CH 2

(OCH 2 CH 2 ) y

(CH 2 CH 2 O) w (OCH 2 CH 2 ) x

(OCH 2 CH 2 ) z OCR

O

OCR

O

OCR

O

Where R is the stearic acid fatty moiety and (w+x+y+z) = 150

With CROTHIX, formulators can create mild, rheologically balanced shampoos, body washes, shower gels, liquid soaps or other soap based systems and offer products that are free of DEA and substantially less irritating. As a pastille, CROTHIX also allows you to formulate problem-free without the handling hassles or dusting hazards some materials cause. CROTHIX is approved for use in Japan as Polyoxyethylene Pentaerythritol Tetrastearate (150EO) and is suitable for shampoo products you market globally.

Thickening Performance

As seen in Figure 1, CROTHIX provides higher viscosity from an Ammonium Lauryl Sulfate (ALS) shampoo base, at all concentrations, as compared to PEG-6000 Distearate or PEG-120 Methyl Glucose Dioleate. Such dramatic viscosity-modifying effects demonstrate both the effectiveness and the efficiency with which CROTHIX thickens surfactant systems.

ALS Base = 50cps

0.5% 1.0% 2.0% 3.0%10

100

1000

10000

100000

CROTHIXPEG-6000PEG-120Methyl GlucoseDioleate

Figure 1: Viscosity comparison of CROTHIX vs. PEG-6000 Distearate vs. PEG-120 Methyl Glucose Dioleate in an ALS surfactant base.

Comparative Viscosity CROTHIX vs. Other Thickeners

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CROTHIX™

CROTHIX can be used to thicken shampoos, conditioners, soaps and other liquid bath products or to bolster the viscosity of gels and is able to do so at levels as much as 40% below those of conventional thickeners. Because it produces increasing viscosity with increasing concentration, CROTHIX is also a more reliable and consistent means of thickening than salt, with none of the undesirable characteristics such as its tendency to salt-out. CROTHIX is extremely effective as a thickener for clear systems (including clear conditioners) and for hard-to-thicken systems (even iodine-based pet shampoos). For instance, it has successfully thickened a clear, acid-balanced (pH 5.7) shampoo containing sodium lauroyl sarcosinate (CRODASINIC™ LS-30) yielding a viscosity of 2000cps. In a published paper, CROTHIX was cited for its viscosity increasing effects on sarcosine surfactants.¹

DEA Replacement Data

Formulators can use CROTHIX to thicken systems that are being reformulated without DEA. Our Applications Laboratory has found that blends containing CROTHIX and CROSULTAINE™ C-50 (Cocamidopropyl Hydroxysultaine) in various ratios work well as functional equivalents to Lauramide DEA in terms of both viscosity and foam height. CROSULTAINE C-50 was used specifically because of its ability to produce flash foam. (See table below; also refer to the Alkanolamide Replacement Guide, DS132-R1.) Precise use levels, viscosity data and foam heights allow formulators to calculate a ratio that is specific to their own formula. Testing was conducted using single surfactants alone such as Ammonium Laureth Sulfate (ALES) and Ammonium Lauryl Sulfate (ALS), as well as surfactant blend systems of ALES/ALS and of Sodium Laureth Sulfate/Sodium Lauryl Sulfate (SLES/SLS).

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CROTHIX™

ALES (2 mol, 10% Active) If you use… Replace with… Or…

Lauramide DEA: 5%

CROSULTAINE

C-50: 2.5% CROTHIX:

3.1%

CROSULTAINE C-50: 8.12% CROTHIX:

0.01% *Viscosity, cps

Foam Height, ml 9,600 1,033

8,800 883

9,200 820

ALS (10% Active) If you use… Replace with… Lauramide

DEA: 5%



Foam Height, ml 9,400 863

10,200 833

ALS/ALES (2:1, 10% Active) If you use… Replace with… Lauramide

DEA: 5%

CROSULTAINE C-50: 4.0 CROTHIX:


Foam Height, ml 14,800

847 13,000

923 SLS/SLES (2:1, 10% Active)

If you use… Replace with…

Lauramide DEA: 5%


0.3% **Viscosity, cps Foam Height, ml

80 883

60 973

* RVT Spindle #5, 10rpm, @ 25°C/**RVT Spindle #2, 10rpm, @ 25°C

Table1: CROTHIX replacement suggestions for Lauramide MEA in a formulation.

MEA Replacement Data

Diethanolamine (DEA) is a group of synthetic surfactants used to neutralize acids. DEAs are slow to biodegrade and react with natural nitrogen oxides and sodium nitrite pollutants in the atmosphere to form nitrosamines, a family of potent carinogens. Due to some movement away from the use of DEA, many formulators turned to MEA as their solution. Additional studies have shown that, with CROTHIX, formulators still have a superior option for thickening the systems without using Diethanolamine (DEA) or Monoethanolamine (MEA). A number of various combinations were made with CROTHIX in commonly used surfactant systems. The viscosities of these combinations were then compared to those made with Cocamide MEA as can been seen in Figures 2 – 8.

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CROTHIX™

Figure 2: SLES (12%) and Cocamidopropyl Betaine (3%) as the surfactant base comparing the viscosities of CROTHIX vs. Cocamide MEA at 0.5% and 1.0% use levels. NOTE: Viscosity scale = 103

Figure3: SLES (12%) and Cocamidopropyl Betaine (1.5%) as the surfactant base comparing the viscosities of CROTHIX vs. Cocamide MEA at 0.5% and 1.0% use levels. NOTE: Viscosity scale = 103

CROTHIX

%w/w

MEA

%w/w

Water QS QS

Sodium Laureth Sulfate 12.0 12.0

Cocamidopropyl Betaine 3.0 3.0

Sodium Chloride 1.0 1.0

CROTHIX 0.5 -1.0 ---

Cocamide MEA --- 0.5 -1.0

CROTHIX

%w/w

MEA

%w/w

Water QS QS




CROTHIX 0.5 -1.0 ---


Sodium Laureth Sulfate & Cocamidopropyl Betaine 3.0%

Sodium Laureth Sulfate & Cocamidopropyl Betaine 1.5%

0

50

100

150

200

250

300

350

0.0 0.5 1.0

% Thickener Added

Visc

osit

y (c

ps)

103

Crothix

Cocamide MEA

0

20

40

60

80

100

120

140

160

180

200

0 0.5 1% Thickener Added

Visc

osity

(cps

) 103

CrothixCocamide MEA

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CROTHIX™

Figure 4: SLES (12%) and Sodium Lauroamphoacetate (1.5%) as the surfactant base comparing the viscosities of CROTHIX vs. Cocamide MEA at 0.5% and 1.0% use levels. NOTE: Viscosity scale = 103

Figure 5: SLES (12%), SLS (4%) and Cocamidopropyl Betaine (1.5%) as the surfactant base comparing the viscosities of CROTHIX vs. Cocamide MEA at 0.5% and 1.0% use levels. NOTE: Viscosity scale = 103

CROTHIX

%w/w

MEA

%w/w

Water QS QS


Sodium Lauroamphoacetate 1.5 1.5


CROTHIX 0.5 -1.0 ---


CROTHIX

%w/w

MEA

%w/w

Water QS QS


Sodium Lauryl Sulfate 4.0 4.0



CROTHIX 0.5 -1.0 ---


Sodium Laureth Sulfate & Sodium Lauroamphoacetate

0

20

40

60

80

100

120

140

160

180

200


Visc

osity

(cps

) 103

Crothix

Cocamide MEA

0

20

4060

80

100

120

140

160

180

200


Visc

osity

(cps

) 103

CrothixCocamide MEA

Sodium Laureth & Lauryl Sulfate with Cocamidopropyl Betaine

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CROTHIX™

Figure 6: ALES (12%) and Cocamidopropyl Betaine (1.5%) as the surfactant base comparing the viscosities of CROTHIX vs. Cocamide MEA at 0.5% and 1.0% use levels. NOTE: Viscosity scale = 103

Figure 7: ALES (8%), ALS (4%) and Cocamidopropyl Betaine (1.5%) as the surfactant base comparing the viscosities of CROTHIX vs. Cocamide MEA at 0.5% and 1.0% use levels. NOTE: Viscosity scale = 103

It can be seen that in every surfactant system tested above, CROTHIX outperformed Cocamide MEA in thickening at both 0.5% and 1.0% active use levels. The most dramatic differences can be seen in the systems where Sodium Laureth Sulfate was the primary surfactant.

CROTHIX

%w/w

MEA

%w/w

Water QS QS

Ammonium Laureth Sulfate 12.0 12.00



CROTHIX 0.5 -1.0 ---


CROTHIX

%w/w

MEA

%w/w

Water QS QS

Ammonium Laureth Sulfate 8.0 8.0

Ammonium Lauryl Sulfate 4.0 4.0



CROTHIX 0.5 -1.0 ---


0

50

100

150

200

250

300


Visc

osity

(cps

) 103 Crothix

Cocamide MEA

Ammonium Laureth Sulfate & Cocamidopropyl Betaine

Ammonium Laureth & Lauryl Sulfate with Cocamidopropyl Betaine ( )

0102030405060708090

100

0 0.5 1

% Thickener Added

Visc

osity

(cps

) 103

Crothix

Cocamide MEA

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CROTHIX™

Combining CROTHIX and Cocamide MEA

The data shown, so far, has been based on complete replacement of Cocamide MEA with CROTHIX. However, in some cases, full 1:1 replacement of MEA is not possible. Additional viscosity tests were run on the combination of CROTHIX with Cocamide MEA at a 1:1 ratio to show that even a partial replacement of MEA with CROTHIX yields a significant viscosity benefit.

The surfactant systems in Table 2 were prepared and their viscosities were measured (Figure 8).

Base A

Base B

Base C

Base D

Base E

Base F

Sodium Laureth Sulfate 12.0 12.0 12.0 12.0 12.0 12.0 Cocadmidopropyl Betaine 3.0 3.0 3.0 Sodium Lauroamphoacetate 3.0 3.0 3.0 Sodium Chloride 0.5 0.5 0.5 0.5 0.5 0.5 CROTHIX 1.0 0.5 1.0 0.5 Cocamide MEA 1.0 0.5 1.0 0.5

Table 2: Surfactant systems for testing viscosity of CROTHIX & Cocamide MEA

Figure 8: Viscosities of CROTHIX & Cocamide MEA (1:1 Ratio) in a SLES / Cocamidopropyl Betaine system and SLES / Sodium Lauroamphoacetate system. NOTE: Viscosity scale = 103

With CROTHIX only

With Cocamide MEA only

With CROTHIX & MEA

CROTHIX & Cocamide MEA Viscosities of the Combination

350

55.5

265

350

24.8

160

0

50

100

150

200

250

300

350

400

A B C D E F

Formula

Visc

osity

(cps

) 103

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CROTHIX™

It can be seen that a 50% replacement of Cocamide MEA (0.5%) with CROTHIX in both surfactant systems significantly increases the viscosity as compared with using the Cocamide MEA alone (1.0%). In addition, CROTHIX on its own was shown to still have superior thickening capabilities as compared with the use of Cocamide MEA only and as compared with the combined use of CROTHIX and Cocamide MEA.

Counter-Irritancy Data

Given the Industry’s focus on mildness, CROTHIX can be of great benefit in both skin care and hair care as the product was shown to actually lower the potential for skin irritation in surfactant-based systems. New data suggests that CROTHIX has mitigating effects that help reduce the irritation potential of surfactant or surfactant blend systems. In one in vitro study evaluating the effects of various CROTHIX concentrations on SLS-induced cell death, our Cell Biology Laboratory found that CROTHIX acts as a counter-irritant to decrease SLS mediated cell death and does so at an optimum concentration of 2%. During testing, changes in cell viability were evaluated over time at one, five, and ten minutes after exposure to 10% SLS with and without CROTHIX.

05

10152025303540

% R

educ

tion

in

Irrit

atio

n

5 Min.

Improvement in Cell ViabilityCROTHIX Concentration Effects vs. SLS Alone

0.5% 1% 2% 3% 4%

Figure 9: The ability of CROTHIX to mitigate irritation may be due in part to the product’s high molecular weight and complex branched structure. Control represented by the baseline. The study was conducted using the EpiOcular™ Tissue Model (MatTek Corporation, Ashland MA). Cell survival rates were measured using the MTT Assay which is an accepted method of assessing cell viability. Values given represent changes in cell viability as compared to the 10% SLS positive control.

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CROTHIX™

A second study evaluated CROTHIX in a body wash at normal use dilution strengths and found that the product’s mitigating effects on irritation also hold true under these real-use conditions (see graph on the following page). The study was conducted using the Trans-Epithelial Permeability (TEP) assay which is an in vitro replacement for the Draize Eye Irritation Assay. TEP is a very sensitive and highly reproducible means of assessing surfactant cleanser systems at use dilution levels and is considered a more reliable method than the MTT assay.² In healthy skin, cell membranes composed of lipid bilayers and proteins hold the stratum corneum intact and prevent fluid from leaking through. When the skin experiences insult, the lipid bilayer is perturbed, causing cells to pull apart and leave gaps where cellular leakage can occur. With TEP, layers of cultured kidney cells are grown on tissue culture inserts modeling the non-keratinized epiderm and are treated with test material and controls. Na-fluorescein is added directly onto the cell monolayer. Whatever Na-fluorescein accumulates in the wells below the filter is measured and used as a marker for intercellular leakage.

0

2

4

6

8

10

12

14

1:10 1:100 1:250 1:500 1:1000

Dilution

CROTHIX Lowers Irritation Potential of Body Wash Formula in vitro Change in Intercellular Leakage vs. Control Base

0.5% CROTHIX 1% CROTHIX 1.5% CROTHIX

Figure 10: CROTHIX reduces irritation at all concentrations over the use dilution range. Optimum irritation mitigation is seen with 0.5% CROTHIX. Control based represented by the baseline.

%w/w DI Water QS SLES 20.0 Crosultaine C-50 12.0 Germaben II 1.0 CROTHIX 0.5, 1.0 or 1.5

pH 6.0 – 7.0 Table 3: CROTHIX basic body wash formulation used for testing. Percents are based on % active.

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CROTHIX™

Foam Height Stabilization The effect of varying concentrations of CROTHIX on the foam height of the body wash formula (Table 3) was determined using the ASTM Standard Method of Test for Foaming Properties of Surface-Active Agents. All foam heights were measured at 1:100 dilution in distilled deionized water. The results show that CROTHIX has a stabilizing effect on the foam. Values are expressed as centimeters.

Formula Foam Height (cm) T=0 min T=5 min Base 13 12 0.5% CROTHIX 12 11.5 1.0% CROTHIX 12 11.9 1.5% CROTHIX 12 11.8

Table 4: Foam heights of basic body wash formulation using differing amounts of CROTHIX. Formulating Aids CROTHIX is freely soluble in anionic, nonionic or amphoteric surfactant systems and is compatible with cationic salts. As a surfactant-based thickener, CROTHIX should first be premixed with the surfactant or surfactant blend, preferably with an emulsifier that is nonionic, such as Oleth-20 (VOLPO™ 20), Polysorbate 80 (CRILLET™ 4), PPG-5 Ceteth 20 (PROCETYL™ AWS) or one of the higher ethoxylated vegetable oils (CROVOL™ 70 series). Using a blend of CROTHIX and any one of these materials in a ratio of 2:5 (CROTHIX:nonionic emulsifier) works well and yields a surfactant base that is extremely effective in thickening a variety of formulations. Once this surfactant solution is heated to around 60-70°C, the mixture can be added to the oil phase. CROTHIX is best used at a pH between 5.0 and 9.0, tolerates salt well and unlike carbomers, does not need to be neutralized. Recommended use levels: 0.25-5%.

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CROTHIX™

Typical Analysis

APPEARANCE Pastille

COLOR White to off-white

ODOR Mild, characteristic

ACID VALUE 5.0 max.

HYDROXYL VALUE 10 max.

MOISTURE CONTENT 1.0% max.

References: 1) Crudden, J., et. al.; "Applications of N-acyl Sarcosine Surfactants", Royal Society of Chemistry;

Spring 1992. 2) Drewitt-Barlow, et. al., “No Tears for Baby”, Global Cosmetic Industry, Advanstar

Communications Inc, October, 2000.

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CROTHIX™

Baby Shampoo SH-86-1

This baby shampoo features CROVOL A-70 and CROSULTAINE C-50, naturally derived surfactants that give this formula its mildness. Besides its ability to reduce the irritation of surfactant/shampoo systems, CROVOL A-70 is also used here as a wetting agent and fragrance solubilizer. CROSULTAINE C-50 is a mild foam booster and produces a creamy lather. CROTHIX is used to thicken the formula. Using a fragrance with a ‘baby-fresh’ smell adds to its appeal. Ingredient %(W/W)

PART A CROVOL A-70 (PEG-60 Almond Glycerides) 15.0 CROTHIX (PEG-150 Pentaerythrityl Tetrastearate) 0.5

PART B SLES, 3 mol 20.0 CROSULTAINE C-50 (Cocamidopropyl Hydroxysultaine) 12.0 Deionized Water 51.3

PART C Propylene Glycol (and) Diazolidinyl Urea (and) Methyl Paraben (and) Propyl Paraben

1 1.0 Fragrance

2 0.2

HCl, 10% solution q.s. pH = 7.0 ±0.5; Brookfield Viscosity = 5,000cps ±10% (RVT #4, @ 10rpm, 25ºC)

PROCEDURE Combine ingredients of Part A with mixing and heat to 65ºC, mixing until uniform. Combine ingredients of Part B with mixing. Add Part A to Part B, mixing until uniform. Add ingredients of Part C individually, mixing until uniform. Adjust pH with HCl solution, if needed, and mix until uniform. Cool with mixing to desired fill temperature. 1) Germaben II (ISP) 2) Florasynth AB5697, Powder Type (Florasynth Inc.) 04/08/92

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CROTHIX™

Anti-Dandruff Conditioning Shampoo SH-89-1

This moderately viscous shampoo conditions as it treats dandruff and reduces the dryness and flakiness associated with it. The high substantivity of HYDROTRITICUM™ QM gives the shampoo greater conditioning properties, especially wet comb. CROSULTAINE C-50 is a mild surfactant used for its excellent foam boosting properties and creamy lather, while INCROMIDE CA is used as a foam stabilizer. CROTHIX is used to thicken the formula. Zinc omadine is the active. Ingredients %(W/W)

PART A Deionized Water 56.3

PART B Magnesium Aluminum Silicate1 1.2 Xanthan Gum2 0.5 Propylene Glycol 3.5

PART C Zinc Pyrithione3 2.0

PART D Ammonium Lauryl Sulfate 20.0

PART E INCROMIDE CA (Cocamide DEA) 3.0 CROSULTAINE C-50 (Cocamidopropyl Hydroxysultaine) 7.0 CROTHIX (PEG-150 Pentaerythrityl Tetrastearate) 0.5

PART F Propylene Glycol (and) Diazolidinyl Urea (and) Methyl Paraben (and) Propyl Paraben

4 1.0 HYDROTRITICUM QM (Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein) 5.0 pH = 7.0 ±0.5; Brookfield Viscosity = 13,000cps ±10% (RVT #5, @ 20rpm, 25ºC)

PROCEDURE Heat Part A to 80-85ºC. Combine ingredients of Part B, mixing until uniform. Add Part B to Part A with mixing and then homogenize. Add Part C with mixing and homogenize again. Remove homogenizer and replace with stirrer. Add Part D with gentle mixing. Combine ingredients of Part E with mixing and add to mixture, maintaining temperature at 80-85ºC for 10 minutes. Cool with mixing to 45-50ºC and then add ingredients of Part F one at a time with mixing. Cool with mixing to desired fill temperature. 1) Veegum HV (R.T. Vanderbilt) 2) Keltrol (Kelco) 3) Zinc Omadine, 48% Aqueous Dispersion (Olin Corporation) 4) Germaben II (ISP)

02/25/93

croda - crothix thickner for shampoos

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