TECHNICAL DATA SHEET

TDS-447
Edition: March 6, 2015
Previous Edition: February 24, 2009
Original Date: August 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 to
become hazy in appearance. To maintain clarity in these systems, fragrance solubilizers are typically
needed.
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 the
use of solubilizer blends is the preferred approach to incorporate the various perfume notes of different
polarity allowing us to achieve optimum clarity in formulations.
Lubrizol Advanced Materials, Inc. conducted a large number of experiments to understand the effect of
fragrances and solubilizers on the clarity of styling gels based on Fixate and Carbopol polymers.
From this study, preferred fragrance and solubilizer blends for different Fixate and Carbopol polymer
systems were identified.

Fixate Hair Fixative Polymers

Fixate polymers are Lubrizol Advanced Materials acrylate-based hair fixative polymers offering the
following benefits in formulations:
1.
2.
3.
4.
5.
6.

Flexible to stiff hold

Excellent humidity resistance
Resistance to flaking
Superior clarity
Easy removal from hair
Natural shine

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

Lubrizol Advanced Materials, Inc. / 9911 Brecksville Road, Cleveland, Ohio 44141-3247 / TEL: 800.379.5389 or 216.447.5000
The information contained herein is being furnished
for informational purposes only, upon the express condition
that the User makes its own assessment of the appropriate
use of such information. While the information contained
herein is believed to be reliable, no representations,
guarantees or warranties of any kind are made as to its
accuracy, suitability for a particular application or the
results to be obtained herefrom.
Lubrizol Advanced
Materials, Inc. ("Lubrizol") cannot guarantee how any
products associated with this information will perform in

combination with other substances or in the Users process.

Due to variations in methods, conditions and equipment
used commercially in processing these materials, no
warranties or guarantees are made as to the suitability of
the information or products for the applications
disclosed. Lubrizol shall not be liable and the User
assumes all risk and responsibility for any use or
handling of any material beyond Lubrizol's direct
control. LUBRIZOL MAKES NO WARRANTIES, EXPRESS
OR IMPLIED, INCLUDING, BUT NOT LIMITED TO,

THE IMPLIED WARRANTIES OF MERCHANTABILITY

OR FITNESS FOR A PARTICULAR PURPOSE. It is the
Users sole responsibility to determine if there are any
issues relating to patent infringement of any component or
combination of components relating to the supplied
information. Nothing contained herein is to be
considered as permission, recommendation, nor as
an inducement to practice any patented invention
without permission of the patent owner.

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

Lubrizol Advanced Materials, Inc. is a wholly owned subsidiary of The Lubrizol Corporation
Carbopol, Fixate and Chemonic are trademarks owned by The Lubrizol Corporation
Copyright 2015 / The Lubrizol Corporation

TDS-447
Use 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. Fixative
polymers may increase the haze of fragranced styling gels because of the hydrophobic interactions
causing some incompatibility among the ingredients as described in Figure 1. Understanding the
science behind fragrance and fragrance components may provide insights on how to minimize the
negative hydrophobic interactions which cause haziness in the system. The clarity of the system can
be optimized by identifying suitable fragrance solubilizers.

Figure 1 Interactions of Ingredients in Styling Gel

Fixative Polymer

Carbopol Polymer
Homopolymers

Carbopol 940

Carbopol 980

Fixate PLUS
Fixate G-100 PR
Fixate Superhold
Clear Hair Gel
>90 wt% water

Fragrance

Copolymer

Carbopol Ultrez 21

Preservative
Solubilizer

Polarity
High polarity
Medium
Low
Non-polar

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

Polarity
High
Low

Fragrance 101: Basic Introduction to Fragrance Chemistry

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

TDS-447
Use of Fragrance with Fixate Polymers
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Developing desirable and pleasing fragrances is an art. A simplification of their complex composition is
shown in Figure 2(3,4) below. Figure 2 shows 3 levels of odor classes based on the ingredients volatility
or vapor pressure at room temperature. Typically the top notes of a fragrance (25 wt%) vaporize or
volatilize at a much faster rate than notes in the middle (25%) and bottom levels (50%). Fragrances
also 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 the
composition. Examples of typical solvents include propylene glycol and dipropylene glycol. Examples
of 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 potentially
can cause haziness in water-based systems such as styling gels.
Figure 2 Typical Fragrance Composition

~25% TOP
~25% MIDDLE

~50% BOTTOM

Fragrance Odor Classes, Polarity, Solubility Parameter (SP) and Fragrance

Solubilizers
Fragrance Odor Classes: Typically, fragrances contain compounds from a single or combination of
different 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 and
solubility.
Table 1 Fragrance Odor Classes
#

Odor Class

Relative Polarity

Relative Solubility

Floral

High

High

Fruity

Medium

Medium

Menthe

Medium

Medium

4
5
6
7
8
9

Spice / Herbs
Citrus
Woods
Woods
Medicinal
Animal

Medium / Low
Low / Non-polar
Low / Non-polar
Low / Non-polar
Low / Non-polar
Low / Non-polar

Medium / Low
Low
Low
Low
Low
Low

Examples
Jasmine, rose, lilac, and
carnation
Esters, aldehydes, and fruity
lactones
Peppermint, spearmint, and
menthol
Spice oils (Eugenol)
Terpenes, d and llimonene
Cedar and sandal wood oil
Pinene
Camphor and thymol
Ambergris, civet and musk

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

TDS-447
Use of Fragrance with Fixate Polymers
Page 4 of 9
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 dipole
moments. 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 nonpolar (water insoluble).
Solubility Parameter (SP): SP is a measure of the cohesive forces of a molecule. SP is often used
as a tool to solve problems caused by fragrance ingredients in emulsion products and surfactant based
cleansing products(1, 3-8). Solubility parameter ranges from 5 for silicone oils (non-polar), to 23.4 for
water (polar). The higher the SP number, the better the water dispersibility or water solubility of the
material. 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
23.4

Water
14

Propylene Glycol
12.6

Ethanol

12.3

Vanillin

11.8

Phenyl ethyl alcohol

11

Benzaldehyde
9.62

Linalool
Citronellal

8.83
8.03

Pinene

7.09

Mineral Oil
5

Silicone Oil
0

10

15

20

25

Polarity (SP)

Fragrance Solubilizers: Solubilizers used for fragrances in water-based systems are typically
nonionic 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 solubility
parameter of the fragrance contained in the formulation.
Fine ingredients with a solubility parameter > 9 are readily soluble or dispersible when using a
fragrance solubilizer that has an HLB >14. If a high HLB solubilizer doesnt work with a particular
fragrance, 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 use
of a blended system will help to solubilize both the low and high solubility parameter fragrance
components.

TDS-447
Use of Fragrance with Fixate Polymers
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Experiments
I. Baseline study - experiments using a single solubilizer: A simple styling gel formulation was
chosen for the baseline study to understand fragrance interactions using five individual fragrances of
known 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
Phenyl ethyl alcohol
Benzaldehyde
Linalool
Citronellal
Pinene

Odor Class
Floral (Rose)
Fruity
Floral (w/spicy)
Floral (Rose)
Wood

Solubility Parameter (SP)

11.79
11.07
9.62
8.83
8.03

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

INCI

HLB

Supplier

Trade Name

Polysorbate 20

16.7

Uniqema

Tween 20

Polysorbate 80
PEG - 60 Hydrogenated
Castor Oil
PEG - 40 Hydrogenated
Castor Oil

15.0

Uniqema

Tween 80

17.0

BASF

Cremophor RH 60

14.6

BASF

Cremophor RH 40

Steareth-100

18.8

Jeen
International

Jeecol SA-100

Oleth-20

14.6

Lubrizol

Chemonic OE-20
Surfactant

3
4

The details of the simple styling gel screening formulation are found in Table 4.
Table 4 Simple Styling Gel Formulation
Part A
Deionized Water
Carbopol 940 Polymer
Fixate PLUS Polymer
Glydant Plus
AMP Ultra PC 2000

wt%
Q.S
0.50
1.67
0.35
pH 7

Part B
Solubilizer
Fragrance
Propylene Glycol
Deionized Water

0.20
0.10
1.00
1.00

(0.50 wt% TS)

TDS-447
Use of Fragrance with Fixate Polymers
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Preparation Procedure:
1. Disperse Carbopol polymer in water with mixing.
2. Add the remaining ingredients of Part A in the order listed. Neutralize to pH 7.0 with AMP Ultra PC
2000
3. 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 using solubilizer blends
The 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, and
floral. 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 study
An optimization study was conducted using a design of experiments (DOE) based on seven variables
including 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
Ingredient
Category

Fixate Polymer

Preservative

Fragrance Type

Fragrance Level

Carbopol
Polymer

Solubilizer Blends

Description 1
PLUS
Superhold
G-100 PR

Glydant Plus

Kathon CG

Germaben II

Phenonip
High polarity
Med polarity
Low polarity
Non-polar
0.1 wt%
0.3 wt%
Ultrez 21
940
980
S1
S2
S3
S4

Solubilizer:
Fragrance ratio

1:1
2:1
3:1

Description 2

0.5 wt% TS (with 0.5 wt% TS Carbopol polymer for high viscosity gel)

0.5 wt% TS (with 0.5 wt% TS Carbopol polymer for high viscosity gel)

1.0 wt% TS (with 1.0% Carbopol polymer for high viscosity gel)
Iodopropynyl butylcarbamate
Methylchloroisothiazolinone, Methylisothiazolinone
Diazolidinyl Urea, Methyl- and Propylparaben, /Propylene glycol
Methyl-, Ethyl, Propyl-, Butyl-, and isobutylparaben, Phenoxyethanol
Floral (rose) with a touch of citrus
Fruity (strong green apple) with musky notes
Fruity, spicy, floral and musky notes
Citrus, fruity, woody, musky, medicinal, menthol and floral

PEG-60 Hydrogenated Castor Oil

PEG-60 Hydrogenated Castor Oil / Ethoxydiglycol (75/25 wt/wt%)
PEG-60 Hydrogenated Castor Oil / C12-13 Pareth-3
(80/20 wt/wt%); HLB 17/8
PEG-60 Hydrogenated Castor Oil / C12-13 Pareth-3 / C12-13 Pareth-6.5
(80/10/10 wt/wt%); HLB 17/8/12

TDS-447
Use of Fragrance with Fixate Polymers
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Results and Discussions

I. Baseline study - experiments using a single solubilizer: Figure 4 shows the clarity data for all
solubilizer/fragrance combinations evaluated. It is obvious that fragrances having a solubility parameter
of > 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 with
citronellal from the floral odor class (SP = 8.83). As predicted, poor clarity was obtained with oil soluble
pinene (SP = 8.03) from the woody odor class using all 6 solubilizers.
Figure 4 Hair gel clarity using different solubilizer / fragrance combinations with
fine aroma ingredients of known solubility parameter
100

Clarity, % T

80
SP 11.79 (Phenyl ethyl
alcohol, Rose)

60
SP 11 (Benzaldehyde)

40

SP 9.62 (Linalool, Floral)

20

SP 8.83 (Citronellal,
Rose, Floral)
SP 8.03 (Pinene)

0
SA-100

Oleth 20

HCO 60

HCO 40

Polysorbate Polysorbate
20
80

II. Experiments using solubilizer blends: The major components in the floral odor class (eg. Phenyl
ethyl alcohol, SP = 11.79) are either water soluble or water dispersible due to their relatively high
polarity. As expected, clear gels were easily obtained with floral fragrance using PEG-60 HCO. In
contrast, musk (from the animal odor class) is relatively non-polar and it was very difficult to obtain clear
hair gels with fragrances containing a considerable amount of musk. Figure 5 illustrates the importance
of the solubilizer blend formulating approach. A solubilizer blend of ethoxydiglycol and PEG-60 HCO at
25:75 wt/wt ratio offered clarity (>75% T) in the presence of a musk-based non-polar fragrance in the
gel formula with 0.5 wt% TS Fixate PLUS and 0.5 wt% TS Carbopol Ultrez 21 polymers.

TDS-447
Use of Fragrance with Fixate Polymers
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Figure 5 Hair gel clarity using blends of ethoxydiglycol and PEG-60 HCO as the
solubilizer for non-polar fragrance
C l a r i t y, % T

80
60
40
20
0
Ethoxy
diglycol,
100%

Blend-2,
25/75

Blend-2,
75/25

Blend-2,
50/50

PEG 60 HCO,
100%

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 Carbopol polymers

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/Carbopol polymer systems
Fixate Choice
Fixate PLUS
Polymer
and Fixate
Superhold
Polymer

Fixate G-100 PR
Polymer

Preferred Solubilizer
Blends (Refer to Table
5)
Preferred Fragrance
Preferred ratio of
solubilizer/ fragrance
Preferred Preservative
.
Viscosity, mPa s
Clarity, %T
Preferred Solubilizer
Blends (Refer Table 5)
Preferred fragrance type
Preferred ratio of
solubilizer/ fragrance
Preferred Preservative
.
Viscosity, mPa s
Clarity, %T

Carbopol Ultrez 21
Polymer

Carbopol 940
Polymer

Carbopol 980
Polymer

S4

S4

S4

High polarity

High polarity

High polarity

1:1

1:1

1:1

Glydant Plus
~90,000
Up to 95

Glydant Plus
~60,000
Up to 89

Glydant Plus
~50,000
Up to 89

S2

S4

S4

Low polarity

High polarity

High polarity

1:1

1:1

1:1

Kathon CG
~30,000
Up to 95

Glydant Plus
~25,000
Up to 80

Glydant Plus
~20,000
Up to 80

TDS-447
Use of Fragrance with Fixate Polymers
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With the exception of the Fixate G-100 PR polymer and Carbopol Ultrez 21 polymer combination, all
systems exhibit better clarity with high polarity fragrance blend S4 and Glydant Plus as the
preservative.
The combination of Fixate G-100 PR polymer, Carbopol Ultrez 21 polymer, and low polarity fragrances
yielded better clarity using the S2 solubilizer blend (refer Table 5) and Kathon CG as the preservative.
Overall, Carbopol Ultrez 21 copolymer provides higher clarity systems when compared to the Carbopol
homopolymers.
Summary of recommendations for choosing 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 > S2
Preservative: Glydant Plus > Kathon CG > Germaben II (Phenonip may 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 good
agitation. 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 parameter
for this work.

References:
1.
2.
3.
4.
5.
6.

Chemistry and Technology of Flavors and Fragrances, D Rowe, ed. Boca Raton Blackwell (2005).
www.iff.com.
S.J. Herman, The Art and the Science Fragrance, Chemtec, Aug 1992, p. 458.
www.Stephen-herman.com.
Steve Herman, Cosmetic and Toiletries 121 (4) 59-67 (2006).
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.