TDS-447 Fragrance With Fixate

7/24/2019 TDS-447 Fragrance With Fixate

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TECHNICAL DATA SHEET

TDS-447Edition : March 6, 2015

Previous Edition : February 24, 2009Original Date: Augus t 17, 2006

Use of Fragrance with Fixate Polymers

Summary

Adding fragrance to clear water-based formulations such as styling gels can cause a clear system tobecome hazy in appearance. To maintain clarity in these systems, fragrance solubilizers are typicallyneeded.

Fragrances used in cosmetic products, are mostly complex blends consisting of many notes components which have different odors. Our research in styling gel formulations has shown that theuse of solubilizer blends is the preferred approach to incorporate the various perfume notes of differentpolarity allowing us to achieve optimum clarity in formulations.

Lubrizol Advanced Materials, Inc. conducted a large number of experiments to understand the effect offragrances and solubilizers on the clarity of styling gels based on Fixate and Carbopolpolymers.From this study, preferred fragrance and solubilizer blends for different Fixate and Carbopol polymersystems were identified.

Fixate Hair Fixative Polymers

Fixate polymers are Lubrizol Advanced Materials acrylate-based hair fixative polymers offering thefollowing benefits in formulations:

1. Flexible to stiff hold2. Excellent humidity resistance3. Resistance to flaking4. Superior clarity5. Easy removal from hair6. Natural shine

Fixate G-100 PR polymer is recommended for low to medium viscosity styling applications. FixatePLUS polymer is recommended for medium to high viscosity gels as it is itself a viscosity builder. FixateSuperhold polymer is recommended when formulating styling products which require a hard, stiff hold.

Lubrizol Advanced Materials , Inc. / 9911 Brecksvil le Road, Cleveland , Ohio 44141-3247 / TEL: 800.379.5389 or 216.447.5000

The information contained herein is being furnishedfor informational purposes only, upon the express conditionthat the User makes its own assessment of the appropriateuse of such information. While the information containedherein is believed to be reliable, no representations,guarantees or warranties of any kind are made as to itsaccuracy, suitability for a particular application or theresults to be obtained herefrom. Lubrizol AdvancedMaterials, Inc. ("Lubrizol") cannot guarantee how anyproducts associated with this information will perform in

combinationwithother substances or in the Users process.Due to variations in methods, conditions and equipmentused commercially in processing these materials, nowarranties or guarantees are made as to the suitability ofthe information or products for the applicationsdisclosed. Lubrizol shall not be liable and the Userassumes all risk and responsibility for any use orhandling of any material beyond Lubrizol's directcontrol. LUBRIZOL MAKES NO WARRANTIES, EXPRESSOR IMPLIED, INCLUDING, BUT NOT LIMITED TO,

THE IMPLIED WARRANTIES OF MERCHANTABOR FITNESS FOR A PARTICULAR PURPOSE. It isUsers sole responsibility to determine if there areissues relating to patent infringement of any componecombination of components relating to the supinformation. Nothing contained herein is to considered as permission, recommendation, noan inducement to practice any patented invenwithout permissio n of the patent owner.

For further information, please visit: www.lubrizol.com/personalcare

ubrizol Advanced Materials, Inc. is a wholly owned subsidiary of The Lubrizol Corporationarbopol

, Fixate and Chemonic are trademarks owned by The Lubrizol Corporation

Copyright 2015/The Lubrizol Corporation
http://www.lubrizol.com/personalcarehttp://www.lubrizol.com/personalcarehttp://www.lubrizol.com/personalcarehttp://www.lubrizol.com/personalcare


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TDS-447Use of Fragrance with Fixate Polymers

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Ingredient Interactions in Hair Styling Gels

Typical ingredients in clear commercial styling gels include fixative polymer, thickener, plasticizer,preservative, conditioning materials, UV stabilizer, color, fragrance, and fragrance solubilizer. Fixativepolymers may increase the haze of fragranced styling gels because of the hydrophobic interactionscausing some incompatibility among the ingredients as described in Figure 1. Understanding thescience behind fragrance and fragrance components may provide insights on how to minimize thenegative hydrophobic interactions which cause haziness in the system. The clarity of the system canbe optimized by identifying suitable fragrance solubilizers.

Figure 1 Interactions of Ingredients in Styling Gel

Fragrance 101: Basic Introduction to Fragrance Chemistry

Fragrances are mixtures of fine aroma chemicals from natural and/or synthetic sources1,2. Mostfragrances contain more than 10 components. Some examples of natural products found in fragrancesare extracts and essential oils. Examples of synthetic aroma materials are hydrocarbons, alcohols,aldehydes, ketones, ethers, acids, esters, acetals, ketals, and nitriles.

Fixative Polymer

Fixate PLUSFixate G-100 PRFixate Superhold

Fragrance

Carbopol Polymer

HomopolymersCarbopol

940

Carbopol980

CopolymerCarbopol

Ultrez 21

Polarity High polarity Medium Low Non-polar

Polarity High Low

Preservative

Solubilizer HLB >14Solubilizer Blends HLB 17 + HLB 8 HLB 17 + HLB 10 HLB 17 + HLB 12 HLB 17 + HLB 8 +

HLB 12

Solubilizer

Clear Hair Gel

>90 wt% water


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Developing desirable and pleasing fragrances is an art. A simplification of their complex composition isshown in Figure 2(3,4)below. Figure 2 shows 3 levels of odor classes based on the ingredients volatilityor vapor pressure at room temperature. Typically the top notes of a fragrance (25 wt%) vaporize orvolatilize at a much faster rate than notes in the middle (25%) and bottom levels (50%). Fragrancesalso contain solvents and/or high boiling carrier fluids. The purpose of these solvents / carrier fluids is

to solubilize the fine aroma chemicals of different polarity and prolong the fragrance release from thecomposition. Examples of typical solvents include propylene glycol and dipropylene glycol. Examplesof high boiling carrier fluids include diethyl phthalate, benzyl benzoate, benzyl acetate, triethyl citrate,and isopropyl myristate. Solvents and carrier fluids may interfere with other ingredients and potentiallycan cause haziness in water-based systems such as styling gels.

Figure 2 Typical Fragrance Composition

Fragrance Odor Classes, Polarity, Solubi lity Parameter (SP) and FragranceSolubilizers

Fragrance Odor Classes: Typically, fragrances contain compounds from a single or combination ofdifferent odor classes. To help classify perfumes all fragrance components are classified into nine

different odor classes(3,4)

as outlined below. Table 1 describes each odor class by polarity andsolubility.

Table 1 Fragrance Odor Classes

# Odor Class Relative Polarity Relative Solubi lity Examples

1 Floral High HighJasmine, rose, lilac, and

carnation

2 Fruity Medium MediumEsters, aldehydes, and fruity

lactones

3 Menthe Medium MediumPeppermint, spearmint, and

menthol

4 Spice / Herbs Medium / Low Medium / Low Spice oils (Eugenol)

5 Citrus Low / Non-polar Low Terpenes, d and llimonene

6 Woods Low / Non-polar Low Cedar and sandal wood oil

7 Woods Low / Non-polar Low Pinene

8 Medicinal Low / Non-polar Low Camphor and thymol

9 Animal Low / Non-polar Low Ambergris, civet and musk

Polarity: Fragrance polarity is a physical property of a fragrance compound that affects its solubility inboth water and oil. The polarity of a material results from an uneven partial charge distribution betweenatoms of a compound. Electronegative atoms such as nitrogen, oxygen and sulfur have a tendency to

~25% TOP

~25% MIDDLE

~50% BOTTOM


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exhibit partial negative charges. Fragrance compounds containing these atoms (alcohols, aldehydes,ketones, ethers, esters, etc.) are more polar and will likely be water soluble or water dispersible.

Molecules whose atoms have equal or nearly equal electro negativities have zero or very small dipolemoments. Atoms, such as carbon and hydrogen, have a tendency to be more neutral or have partial

positive charges. Examples of this class of compounds are mineral oil and silicone oil which are non-polar (water insoluble).

Solubility Parameter(SP): SP is a measure of the cohesive forces of a molecule. SP is often usedas a tool to solve problems caused by fragrance ingredients in emulsion products and surfactant basedcleansing products(1, 3-8). Solubility parameter ranges from 5 for silicone oils (non-polar), to 23.4 forwater (polar). The higher the SP number, the better the water dispersibility or water solubility of thematerial. Figure 3 provides a list of fine chemicals with their respective solubility parameter.

Figure 3 Solubility parameters of select fine chemicals indicating their relative polarity

5

7.09

8.03

8.83

9.62

11

11.8

12.3

12.6

14

23.4

0 5 10 15 20 25

Silicone Oil

Mineral Oil

Pinene

Citronellal

Linalool

Benzaldehyde

Phenyl ethyl alcohol

Vanillin

Ethanol

Propylene Glycol

Water

Polarity (SP)

Fragrance Solubilizers: Solubilizers used for fragrances in water-based systems are typicallynonionic surfactants. The key criterion in selecting a suitable solubilizer or solubilizer package is the

HLB (hydrophilic/ lipophilic balance) value. Another equally important property will be the solubilityparameter of the fragrance contained in the formulation.

Fine ingredients with a solubility parameter > 9 are readily soluble or dispersible when using afragrance solubilizer that has an HLB >14. If a high HLB solubilizer doesnt work with a particularfragrance, one can assume that the fragrance may contain a large quantity of oil soluble components.Thus, it is best to choose a blend of high and low HLB solubilizers for the solubilizer package. The useof a blended system will help to solubilize both the low and high solubility parameter fragrancecomponents.


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Experiments

I. Baseline study - experiments using a single solubi lizer: A simple styling gel formulation waschosen for the baseline study to understand fragrance interactions using five individual fragrances ofknown solubility parameter, six widely used fragrance solublizers, and Fixate PLUS polymer. Table 2

lists the five fine aroma ingredients with their solubility parameters (SP).

Table 2 Fine aroma ingredients with known solubility parameters

Fragrance Odor Class Solubi lit y Parameter (SP)

Phenyl ethyl alcohol Floral (Rose) 11.79

Benzaldehyde Fruity 11.07

Linalool Floral (w/spicy) 9.62

Citronellal Floral (Rose) 8.83

Pinene Wood 8.03

Table 3 shows six types of commonly used solubilizers of known HLB ranging from 14 to 19. They werescreened at 2:1 ratio of solubilizer to fragrance.

Table 3 Solubilizer List

Solubi lizer INCI HLB Supplier Trade Name

1 Polysorbate 20 16.7 Uniqema Tween20

2 Polysorbate 80 15.0 Uniqema Tween80

3PEG - 60 Hydrogenated

Castor Oil17.0 BASF CremophorRH 60

4 PEG - 40 HydrogenatedCastor Oil 14.6 BASF CremophorRH 40

5 Steareth-100 18.8Jeen

InternationalJeecol SA-100

6 Oleth-20 14.6 LubrizolChemonic OE-20

Surfactant

The details of the simple styling gel screening formulation are found in Table 4.

Table 4 Simple Styling Gel Formulation

Part A wt%Deionized Water Q.SCarbopol940 Polymer 0.50FixatePLUS Polymer 1.67 (0.50 wt% TS)Glydant Plus 0.35

AMPUltra PC 2000 pH 7

Part BSolubilizer 0.20Fragrance 0.10Propylene Glycol 1.00Deionized Water 1.00


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Preparation Procedure:1. Disperse Carbopolpolymer in water with mixing.2. Add the remaining ingredients of Part A in the order listed. Neutralize to pH 7.0 with AMPUltra PC

20003. Mix ingredients in Part B in order. Mix for 5 min or until mixture appears clear.

4. Add Part B to Part A with mixing.5. Mix vigorously to allow fragrance mixture uniformly distributed.

II. Experiments us ing solubili zer blendsThe simple hair gel formulation in Table 4 was repeated using Carbopol Ultrez 21 polymer at 0.5 wt%TS with a non-polar fragrance which comprises citrus, fruity, woody, musky, medicinal, menthol, andfloral. The solubilizer consisted of Cremophor RH 60 (PEG-60 HCO) and Transcutol CG(ethoxydiglycol) from Gattefosse at various ratios (25/75, 50/50 and 75/25 wt/wt ratios).

III. An Optimization studyAn optimization study was conducted using a design of experiments (DOE) based on seven variablesincluding solubilizer packages containing high HLB 17, high/low HLB blend of 17/8 mixture, and high/medium / low HLB blend of 17/8/12 mixture. The details of variables are shown in Table 5.

Table 5 Variables used in the optimization study

IngredientCategory

Description 1 Description 2

Fixate PolymerPLUS 0.5 wt% TS (with 0.5 wt% TS Carbopolpolymer for high viscosity gel)

Superhold 0.5 wt% TS (with 0.5 wt% TS Carbopol polymer for high viscosity gel)G-100 PR 1.0 wt% TS (with 1.0% Carbopol polymer for high viscosity gel)

Preservative

Glydant Plus Iodopropynyl butylcarbamate

KathonCG Methylchloroisothiazolinone, Methylisothiazolinone

Germaben

II Diazolidinyl Urea, Methyl- and Propylparaben, /Propylene glycolPhenonip

Methyl-, Ethyl, Propyl-, Butyl-, and isobutylparaben, Phenoxyethanol

Fragrance Type

High polarity Floral (rose) with a touch of citrusMed polarity Fruity (strong green apple) with musky notesLow polarity Fruity, spicy, floral and musky notesNon-polar Citrus, fruity, woody, musky, medicinal, menthol and floral

Fragrance Level0.1 wt%

0.3 wt%

Carbopol

Polymer

Ultrez 21

940

980

Solubilizer Blends

S1 PEG-60 Hydrogenated Castor Oil

S2 PEG-60 Hydrogenated Castor Oil /Ethoxydiglycol(75/25 wt/wt%)

S3PEG-60 Hydrogenated Castor Oil / C12-13 Pareth-3(80/20 wt/wt%); HLB 17/8

S4PEG-60 Hydrogenated Castor Oil / C12-13 Pareth-3 / C12-13 Pareth-6.5(80/10/10 wt/wt%); HLB 17/8/12

Solubilizer:Fragrance ratio

1:1

2:1

3:1


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Results and Discussions

I. Baseline study - experiments using a single solubil izer: Figure 4 shows the clarity data for allsolubilizer/fragrance combinations evaluated. It is obvious that fragrances having a solubility parameterof > 9 offered clear gels with clarities of at least 65% transmittance (T). Compared to the other

solubilizers, PEG-60 Hydrogenated castor oil (Peg 60 HCO or HCO 60) gave better clarity withcitronellal from the floral odor class (SP = 8.83). As predicted, poor clarity was obtained with oil solublepinene (SP = 8.03) from the woody odor class using all 6 solubilizers.

Figure 4 Hair gel clarity using different solubilizer / fragrance combinations withfine aroma ingredients of known solubility parameter

0

20

40

60

80

100

SA-100 Oleth 20 HCO 60 HCO 40 Polysorbate

20

Polysorbate

80

Clarity,

%T SP 11.79 (Phenyl ethyl

alcohol, Rose)

SP 11 (Benzaldehyde)

SP 9.62 (Linalool, Floral)

SP 8.83 (Citronellal,

Rose, Floral)

SP 8.03 (Pinene)

II. Experiments using solubilizer blends: The major components in the floral odor class (eg. Phenylethyl alcohol, SP = 11.79) are either water soluble or water dispersible due to their relatively highpolarity. As expected, clear gels were easily obtained with floral fragrance using PEG-60 HCO. Incontrast, musk (from the animal odor class) is relatively non-polar and it was very difficult to obtain clearhair gels with fragrances containing a considerable amount of musk. Figure 5 illustrates the importanceof the solubilizer blend formulating approach. A solubilizer blend of ethoxydiglycol and PEG-60 HCO at25:75 wt/wt ratio offered clarity (>75% T) in the presence of a musk-based non-polar fragrance in thegel formula with 0.5 wt% TS Fixate PLUS and 0.5 wt% TS CarbopolUltrez 21 polymers.


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Figure 5 Hair gel clarity using blends of ethoxydiglycol and PEG-60 HCO as thesolubilizer for non-polar fragrance

III. Optimization study: A large number of experiments were carried out in the optimization study(DOE) to understand the clarity aspect of styling gels using several variables:

Different combination of Fixate and Carbopolpolymers Fragrances with different polarities Various blends of solubilizers Various preservatives chosen from different solubility ranges

Based on data generated from the design of experiments, the preferred solubilizer blends for typical

fragrance classes are provided for different Fixate and Carbopol polymer combinations in Table 6.

Table 6 Preferred solubilizer blends and fragrances for Fixate/Carbopolpolymer systems

FixateChoice

CarbopolUltrez 21

PolymerCarbopol

940

PolymerCarbopol

980

Polymer

Fixate PLUSPolymer

and FixateSuperholdPolymer

Preferred SolubilizerBlends (Refer to Table

5)S4 S4 S4

Preferred Fragrance High polarity High polarity High polarityPreferred ratio of

solubilizer/ fragrance1:1 1:1 1:1

Preferred Preservative Glydant Plus Glydant Plus Glydant Plus

Viscosity, mPa.s ~90,000 ~60,000 ~50,000

Clarity, %T Up to 95 Up to 89 Up to 89

Fixate G-100 PRPolymer

Preferred SolubilizerBlends (Refer Table 5)

S2 S4 S4

Preferred fragrance type Low polarity High polarity High polarityPreferred ratio of

solubilizer/ fragrance1:1 1:1 1:1

Preferred Preservative Kathon CG Glydant Plus Glydant Plus Viscosity, mPa

.s ~30,000 ~25,000 ~20,000

Clarity, %T Up to 95 Up to 80 Up to 80

0

20

40

60

80

Ethoxy

diglycol,

100%

Blend-2,

25/75

Blend-2,

50/50

Blend-2,

75/25

PEG 60 HCO,

100%

Clarit

y,

%T

0

20

40

60

80

Ethoxy

diglycol,

100%

Blend-2,

25/75

Blend-2,

50/50

Blend-2,

75/25

PEG 60 HCO,

100%

Clarit

y,

%T


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With the exception of the Fixate G-100 PR polymer and CarbopolUltrez 21 polymer combination, allsystems exhibit better clarity with high polarity fragrance blend S4 and Glydant Plus as thepreservative.

The combination of Fixate G-100 PR polymer, Carbopol Ultrez 21 polymer, and low polarity fragrancesyielded better clarity using the S2 solubilizer blend (refer Table 5) and KathonCG as the preservative.

Overall, Carbopol Ultrez 21 copolymer provides higher clarity systems when compared to the Carbopolhomopolymers.

Summary of recommendations for choos ing additives for making high clarity hair gels:

Thickener: Carbopol Ultrez 21 polymer > Carbopol 940 polymer > Carbopol 980 polymer

Fragrance polarity: High > medium > low > non-polar

Fragrance level: 0.1 > 0.2 > 0.3

Solubilizer blend package (Refer to Table 5): S4 > S3 > S1 > S2Preservative: Glydant Plus> KathonCG > GermabenII (Phenonipmay cause haze)

Processing Guidelines

Refer to Table 4 and procedure. Prepare microemulsion of fragrances and solubilizers separately,shown Part B. Mix Part B until mixture becomes clear. Add microemulsion to Part A with goodagitation. Mix vigorously to allow fragrance mixture to be uniformly distributed.

Acknowledgements:

S.J. Herman is acknowledged for providing five fine aroma ingredients with known solubility parameterfor this work.

References: 1. Chemistry and Technology of Flavors and Fragrances, D Rowe, ed. Boca Raton Blackwell (2005).2. www.iff.com.3. S.J. Herman, The Art and the Science Fragrance, Chemtec, Aug 1992, p. 458.4. www.Stephen-herman.com.5. Steve Herman, Cosmetic and Toiletries 121 (4) 59-67 (2006).6. C.D. Vaughan, Using Solubility Parameters in Cosmetics Formulation, Journal of the Society of

Cosmetic Chemists, Sept/Oct. 1985, Vol. 36, pp. 319-333.

7. C.D. Vaughan, Solubility Effects in Product, Package, Penetration, and Preservation, Cosmetics &Toiletries, Oct. 1988, Vol. 103, pp. 47-69.

8. S.J. Herman, Smells Great! Whats The CLOG P?, Global Cosmetic Industry, Mar. 1999, p. 22.
http://www.iff.com/http://www.iff.com/http://www.stephen-herman.com/http://www.stephen-herman.com/http://www.iff.com/

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TDS-447 Fragrance With Fixate