Naturally derived solubilizers

High performance PEG-free solubilizers

for all solubilization needs.

TEAMWORKS 2018

Anna Howe & Anne Mu

April 11, 2018

1
Cross Market trends from Personal Care to Household Care

Naturality & Transparency Performance & Safety Multifunctionality Health & Well-being
Sustainability
Improved functionality versus Hygiene-focused product
Transparency presents an not sacrificing safety Less is more development
Natural & eco-friendly
opportunity for companies to
ingredients
engage consumers by Milder formulations still Combining more than a Aroma therapeutic products
addressing ingredient safety require effective ingredients single benefit in one enhance sensory and support
Natural positioning helps
brands build trust with Performance & safety product well-being
Corporate Social important to product‘s
consumers and grow
Responsibility (CSR) matters success Fragrances are associated
consumer engagement
to consumers with cleanliness in beauty
and similarly in home care

Source: Mintel

2 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Why solubilizers are needed for beauty care?

Different kind of hydrophobic oils are used in cosmetics, need to be

solubilized into water phase:
 PERFUME OILS
 Perfume is essential for consumers
 High variation of fragrance types
 NATURAL OILS
 Natural moisturization & care benefits
 EMOLLIENTS
 Moisturization benefits
 Solvents for other ingredients

3 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Why solubilizers are needed for Home Care?

Different kinds of hydrophobic oils are used in home care, like e.g.
 ESSENTIAL OILS
 Perfume is essential for consumers
 Naturally cleaner, antibacterial, degreaser, polish
 NATURAL OILS
 Natural moisturization & care benefits for leather
 ESTER OILS
 Hydrophobisizes surfaces
 Biodegradable

4 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

What makes it challenging?
 e.g. Complex composition of natural oils
Almond Oil Olive Oil Argan Oil
Stearic
Acid Stearic C18:0
Palmitic Acid Stearic
Palmitic Acid
Acid Palmitic
Acid
Linoleic Acid
Linoleic C16:0 Oleic
Acid Acid Acid
C18:1
Oleic Oleic C18:2
Acid Acid Linoleic
Acid

Sunflower Oil Jojoba Oil Avocado Oil

Stearic Palmitic Oleic

Acid Acid Acid Others
Palmitic Oleic Erucic
Acid Acid Acid C22:1
C20:1
Palmitic
Acid Oleic Acid
C22:2 Gadoleic
Linoleic Acid C16:1
Acid Docos- (&
dienoic isomer) Palmitoleic
Acid Acid
Linoleic
Acid

5 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Needs for next generation solubilizers for both Beauty and Home Care

Requirements Common Challenge

Solubilization Providing high clarity x
performance Broad variety of different oils x
Processing Easy to handle & cold processable x
Adapted foaming & thickening x
properties
Sustainability PEG-free x
Fully naturally derived x
Aspect of High stability on olfactory needs x
formulation Colorless product with high color x
stability
Additional Moisturization x
benefits, like Mildness x

6 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Industrial benchmarks for Home Care and Beauty Care
- The industry keeps coming up with new solubilizer solutions
- We tend to see either:
Ethylated Oils
- Harsh chemistries (PEG-40
Hydrogenated
Polysorbates Ethoxylated
- Milder chemistries but low solubilization power Castor Oil)

Safflower
Plant based Oleosomes Propanediol

Sulfoacetate Sorbitan Oleate

decylglucoside
sarcosinate crosspolymer

Hydrotropes Sodium
xylene / Diabasic
(source: http://library.essentialwholesale.com/what-are-emulsifiers-and-solubilizers/)
Or Industrial toluene esters
waste stream sulfonate
7 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers
 The route to natural derived polyglycerol esters
D - H2O
Coconut Oil Castor Oil cat. OH OH
Glycerin HO O OH
n
condensation
and
OH OH
O OH O O
HO O HO OH

Rapeseed Oil Palm Oil HO OH HO OH

HO OH

HO
OH
O
O
OH
and …
Fatty acids
In addition: variation of degree of PG polymerisation:
60

50

esterification 40

Polyglycerol ester

%
30

20
additional modifications possible
10

By varing the condensation degree, polyglycerol esters 0

1 2 3 4 5 6 7 8 9 10
can be tailored to specific applications. DP

8 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Polyglycerin-based solubilization of different oils in water-based systems

Efficient PEG-free Solubilizers

For the solubilization of For the solubilization of For the solubilization of
• Essential oils like: • Light and/or relatively polar emollient • Fatty natural oils like:
Rosemary oil, Lemon oil, esters like: Sunflower oil, Almond oil,
Orange oil, Lavender oil, Isopropyl Myristate, Argan oil, Olive oil,
Lemongrass oil, Sage oil, Isopropyl Palmitate, Soy bean oil, Jojoba oil
Tea tree oil Isoamyl Cocoate,
Diethylhexyl Carbonate, • Other triglycerides like
• Perfume oils Caprylic/Capric Triglyceride
C12-15 Alkyl Benzoate
• Benzyl Alcohol • Heavier lipophilic emollients like
• Short hydrocarbons like Isohexadecane
Ethylhexyl Palmitate, Decyl Cocoate,
• Tocopherol Cetearyl Isononanoate

Polyglyceryl-3 Caprate/ Caprylate/Succinate;
Propylene Glycol (PG 55)
Polyglyceryl-6 Caprylate; Polyglyceryl-4 Caprate
(PG 90)
Polyglyceryl-4 Caprate (PG 41) Polyglyceryl-6 Caprylate; Polyglyceryl-3
Cocoate; Polyglyceryl-4 Caprate;
Polyglyceryl-6 Ricinoleate (PG 61)

Increasing hydrophobicity
9 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Polyglycerin-based solubilizers – Properties

Efficient PEG-free Solubilizers

• Almost colorless liquid • Colorless to yellowish liquid • Almost colorless liquid • Slightly yellow liquid
• ~3000 – 5000 mPa·s • ~3000 - 6000 mPa·s • ~3000 – 5000 mPa·s • ~3000 – 5000 mPa·s
• HLB ~15 • HLB ~15 • HLB ~14 • HLB ~11
• Surface tension (1%): • Surface tension (0.5%): • Surface tension (0.5%): • Surface tension (0.5%):
~26 mN/m ~26 mN/m ~26 mN/m ~30 mN/m
• ~25% Propylene Glycol • ~10% Water • ~10% Water • ~12% Water

• Bio-based 1,2-Propylene Glycol • Ecocert & COSMOS • Ecocert & COSMOS • Ecocert & COSMOS
and Succinic acid • RSPO (MB*) • RSPO (MB*) • RSPO (MB*)
• RSPO (MB*) • (Halal pending) • Halal • Halal
• (Halal pending)

Polyglyceryl-3 Caprate/Caprylate/ Polyglyceryl-6 Caprylate; Polyglyceryl-4 Caprate (PG 41) Polyglyceryl-6 Caprylate; Polyglyceryl-3
Succinate; Propylene Glycol (PG 55) Polyglyceryl-4 Caprate (PG 90) Cocoate; Polyglyceryl-4 Caprate;
Polyglyceryl-6 Ricinoleate (PG 61)

*MB = mass balanced PEG- & preservative free products, 100% based on renewable raw materials
10 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Outline:
Benefits & application tests of polyglycerin-based solubilizers

1. Solubilization performance
 Essential & perfume oils
 Emollients
 Fatty natural oils

2. Processing attributes
 Foaming
 Phase behavior during processing
 Viscosity effects in surfactant systems

3. Additional benefits
 Moisturization (Corneometer studies)
 Mildness (RBC test results)
 Make-up removing properties

11 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Essential oils in water –
Solubilizing efficacy of Ethoxylated vs. Polyglyceryl Esters
1% essential oil + x% solubilizer + slowly add ad. 100% water.
x = necessary amount of solubilizer for a crystal clear solution (after ~30 min at r.t.).

20% Polysorbate 20 PEG-40 Hydrogenated Castor Oil

The smaller the bar the higher

Polyglyceryl-4 Caprate Polyglyceryl-6 Caprylate; Polyglyceryl-4 Caprate
solubilize 1% of the oils in water
Amount of solubilizer needed to

18%

the solubilization power

Polyglyceryl-3 Caprate/Caprylate/Succinate
16%

14%

12%

10%

8%

6%

4%

2%

0%
Lemon Oil Lemon Oil Rosemary Oil Tea Tree Oil Lavender Oil Lemongras Oil
(Supplier 1) (Supplier 2)

Polyglyceryl esters show similar performance to the PEG containing market standards

12 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Fragrance mapping – Tested perfume oils

A broad variety of perfume oils were tested to show the solubilizing efficacy of : Polyglyceryl-3 Caprate/Caprylate/Succinate
.
A Aquatic / Floral
(Balsamic - Powdery - Tendency Citrus Watery Fruity Floral Aromatic Woody
Sandalwood)

Ozonic / Fruity Basic

B (Citrus - Melon - Musk) character

Floral / Fruity Citrus

C (Apple - Balsamic) A
D Balsamic / Floral
(Fruity - Aldehyde - Musk)
Fruity
B
E Floral
(Freesia - Lily Of The Valley - Floral
Rose)
C D E
F Fougère / Citrus
(Cassis - Lemon - Sandalwood)
Fougère
Fougère / Aromatic F G
G (Green - Amber - Bergamot)

Supported by Fragrance Resources (now IFF Fragrance GmbH)

13 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Perfume oils in water –
Solubilizing efficacy of Polyglyceryl-3 Caprate/Caprylate/Succinate

1% perfume oil + x% solubilizer + slowly add ad. 100% water.

x = necessary amount of solubilizer for a crystal clear solution (after ~30 min at r.t.).
25% PEG-40 Hydrogenated Castor Oil
Polyglyceryl-4 Caprate
Amount of solubilizer needed to
solubilize 1% of the fragrances

Polyglyceryl-3 Caprate/Caprylate/Succinate

Increasing solubilization
20%

15%

power
10%

5%

All fragrances from Fragrance Resources

0% (now IFF Fragrance GmbH)
Aquatic / Floral Ozonic / Fruity Floral / Fruity Balsamic / Floral Fougère / Fougère /
(in DPG) (in DPG) (in DPG) Floral (in DPG) Citrus Aromatic
(in DPG) (in DPG) (in IPM)

Polyglyceryl-3 Caprate/Caprylate/Succinate in average is as effective as the PEG-based standard PEG-40

Hydrogenated Castor Oil

14 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Perfume oil in water or a High Electrolyte and low pH environment –
Solubilizing efficacy of standard ingredients in a corrosive environment

1% perfume oil “SPICY HERBS” (100% essential oils, BDIH quality, IFF Fragrance GmbH).
Maximum of 21% solubilizer tested.
25%
Amount of solubilizer needed to
solubilize 1% of the fragrance

Water 20% Electrolyte/Low pH

20% (results
highly
dependent
on quality)
15%

10%

5%

0%
Caprylyl/Capryl Glucoside Polyglyceryl-4 Caprate PEG-free surfactant blend* Isotrideceth-9 PEG-40 Hydrogenated Polyglyceryl-3 Polyglyceryl-6 Caprylate;
Castor Oil Caprate/Caprylate/Succinate Polyglyceryl-4 Caprate

Polyglyceryl esters show superior solubilizing properties in water and high electrolyte low pH systems
*INCI Name: Water; Pentylene Glycol; Sodium Lauryl Sulfoacetate; Sodium Oleyl Sarcosinate; Sodium
Chloride; Disodium Sulfoacetate; Sodium Oleate; Sodium Sulfate
15 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Emollients in water –
Solubilizing efficacy of Polyglyceryl-4 Caprate & Polyglyceryl-6 Caprylate; Polyglyceryl-3 Cocoate; Polyglyceryl-
4 Caprate; Polyglyceryl-6 Ricinoleate

0.5% oil + x% solubilizer + slowly add ad. 100% water.

x = necessary amount of solubilizer for a crystal clear solution. Max. amount of solubilizer tested: 11%.
PEG-40 Hydrogenated Castor Oil
Polysorbate 20
12% Polyglyceryl-4 Caprate
Amount of solubilizer needed to

Polyglyceryl-6 Caprylate; Polyglyceryl-3 Cocoate; Polyglyceryl-4 Caprate; Polyglyceryl-6 Ricinoleate

solubilize 0.5% of the oils

Increasing solubilization
10%

8%

power
6%

opaque o/n
4%

opaque
2%

0%

Polyglyceryl-4 Caprate best Polyglyceryl-6 Caprylate; Polyglyceryl-3 Cocoate;

for light and polar emollients Polyglyceryl-4 Caprate; Polyglyceryl-6 Ricinoleate best for
16 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers highly lipophilic emollients
Natural oils in water –
Solubilizing efficacy of Polyglyceryl-6 Caprylate; Polyglyceryl-3 Cocoate; Polyglyceryl-4 Caprate;
Polyglyceryl-6 Ricinoleate

0.5% oil + x% solubilizer + slowly add water ad. 100%.

x = necessary amount of solubilizer for a crystal clear solution. Max. amount of solubilizer tested: 12%.
PEG-40 Hydrogenated Castor Oil
Polyglyceryl-4 Caprate
Polyglyceryl-6 Caprylate; Polyglyceryl-3 Cocoate; Polyglyceryl-4 Caprate; Polyglyceryl-6 Ricinoleate
Amount of solubilizer needed to

12%

Increasing solubilization
solubilize 0.5% of the oils

10%

8%

power
6%

4%

not 100% clear

not 100% clear

2%

0%
Almond Oil Olive Oil Argan Oil Sunflower Oil Jojoba Oil Avocado Oil Fragrance White
Lily (~90% Soy
Bean Oil)

Polyglyceryl-6 Caprylate; Polyglyceryl-3 Cocoate; Polyglyceryl-4 Caprate; Polyglyceryl-6 Ricinoleate is more

efficient (~15 – 20%) than the PEG-based market standard (PEG-40 Hydrogenated Castor Oil)

17 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Outline:
Benefits & application tests of polyglycerin-based solubilizers

1. Solubilization performance
 Essential & perfume oils
 Emollients
 Fatty natural oils

2. Processing attributes
 Foaming
 Phase behavior during processing
 Viscosity effects in surfactant systems

3. Additional benefits
 Moisturization (Corneometer studies)
 Mildness (RBC test results)
 Make-up removing properties

18 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Foaming during processing

Foam kinetics / Flash foam in water – SITA method,

c=0.5% in water (~10 °dH), T= 30 °C, pH ~6, 1500 rpm
1200

PEG-free surfactant blend product*

1000
Foam volume [ml]

Polyglyceryl-4 Caprate
800
Polyglyceryl-6 Caprylate; Polyglyceryl-3 Cocoate;
Polyglyceryl-4 Caprate; Polyglyceryl-6 Ricinoleate
600
PEG-40 Hydrogenated Castor Oil

Polyglyceryl-6 Caprylate; Polyglyceryl-4 Caprate

400

Polyglyceryl-3 Caprate/Caprylate/Succinate
200

0
10 20 30 40 50 60 70 80 90 100

Foaming interval [sec]

Polyglycerin-based solubilizers are low foaming in water, thus enabling easy processing
*INCI Name: Water; Pentylene Glycol; Sodium Lauryl Sulfoacetate; Sodium Oleyl Sarcosinate; Sodium
Chloride; Disodium Sulfoacetate; Sodium Oleate; Sodium Sulfate
19 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers
 Processing versus PEG-40 Hydrogenated Castor Oil

Test for processing of Almond oil in water: 0.5% Almond oil + 9% solubilizer at r.t., slowly add water ad 100%
after 24 h
Polyglyceryl-6 Caprylate;
Polyglyceryl-3 Cocoate;
Polyglyceryl-4 Caprate;
Polyglyceryl-6 Ricinoleate 2:30 min 6:11 min 15:02 min

TEGO® Solve 61

after 24 h

PEG-40
Hydrogenated
Castor Oil 2:30 min 5:12 min 15:02 min

Polyglycerin-based solubilizers are cold processable and do not form a gel phase in contrast to some PEG-
containing solubilizers in high concentrations
20 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Viscosity effects (I) –
Comparison to PEG-40 Hydrogenated Castor Oil & Polysorbate 20

Influence of solubilizers on the viscosity:

Chassis: 9% SLES, 3% CAPB, 0.2% PQ-10, 0.5% NaCl,
2.5% PEG-18 Glyceryl Oleate/Cocoate; pH 5.5
10000
9000
8000
Viscosity [mPa·s]

7000
6000
5000
4000
3000
2000
1000
0
Chassis + 1% PG 55 + 1% PG 90 + 1% PG 41 + 1% PG 61 + 1% PEG- 1%
40 Hydrog. Polysorbate
Castor Oil 20

Polyglycerin-based solubilizers show significantly lower viscosity reduction than PEG-40 Hydrogenated
Castor Oil or Polysorbate 20

21 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Outline:
benefits & application tests of polyglycerin-based solubilizers

1. Solubilization performance
 Essential & perfume oils
 Emollients
 Fatty natural oils

2. Processing attributes
 Foaming
 Phase behavior during processing
 Viscosity effects in surfactant systems

3. Additional benefits
 Moisturization (Corneometer studies)
 Mildness (RBC test results)
 Make-up removing properties

23 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Moisturizing properties –
In vivo Corneometer test results

In vivo short-term moisturization test with a leave-on O/W treatment.

Test area: 5 cm2 (inner forearm); 20 μg test formulation;
Time points: Start & 2 h after application;
14 test persons (Nov. 2013), 22-23 measurements / formula
Skin hydration improvement

25
(DCU value) after 2 h rel. to

20
control [%]

15

10

0
Control Vehicle 3% PG 61 5% PG 61
(untreated skin)

Polyglycerin-based solubilizers act as a humectant and provides moisturization benefits

24 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

In-vitro Mildness Assessment –
Red Blood Cell Test

 Lipids and proteins of the skin surface are comparable with cell membranes of erythrocytes
 Influence of irritating surfactants:
 Damage of the erythrocyte-membrane:
 Haemolysis (release of hemoglobin)
 Damage of the protein (denaturation of hemoglobin)
RBC-Test
 Substrate: animal blood (pig, cow, calf, guinea pig)
 Measurement of:
 Cell membrane destruction
 Protein denaturation
 Reference: Sodium Dodecyl Sulfate
W.J.W. Pape, U. Hoppe, Drug Res. 40 (I), 4, 498-502 (1990)
Test Method p. 30
25
Mildness –
Red Blood Cell (RBC) test results of surfactant mixtures

RBC test results of different surfactants with PG 61.

PG 61 is added on top (as an additive) and not calculated into the surfactant active matter.
1000
SLES / CAPB Cocoampho-
basically non irritant
>400 CAPB diacetate
100
Level of baby shampoo benchmark
L/D Value

slightly irritant
>22
10

moderately irritant

irritant
0.1
PG 55 PG 90 PG 61 SLES / CAPB SLES / CAPB CAPB CAPB AM 2 C NM AM 2 C NM
3:1 (+PG 61 3:1:2) (+20% PG 61) (+33% PG 61)

The Polyglycerin-based solubilizers are basically non irritant and improve the mildness of surfactant mixtures

26 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Make-up removal –
Test results with aqueous solutions

Removal of make-up applied

on
PMMA-plates.
Aqueous solution (3% a.m.
90 81.09
surfactants) was put on a 76.62

Make-Up-Removal [%]
80 75.29 73.50 72.92
cotton pad attached to a sled. 70 63.25
60
50
40
30
20 13.43
9.60
long lasting make-up 10
(L´Oréal) 0

Polyglycerin-based solubilizers efficiently remove make-up in a very mild way

27 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

Polyglycerin-based solubilizers –
Benefits at a glance

Essential & Perfume oils Light and/or relatively polar Fatty natural oils
emollients Heavier lipophilic emollients
• Polyglyceryl-3 Caprate/Caprylate/
Succinate • Polyglyceryl-4 Caprate • Polyglyceryl-6 Caprylate; Polyglyceryl-3
• Polyglyceryl-6 Caprylate; Polyglyceryl-4 Cocoate; Polyglyceryl-4 Caprate;
Caprate Polyglyceryl-6 Ricinoleate

 Crystal clear formulations possible

 Low foaming during processing
 Easy to handle, cold processable (no gel phase)
 Low influence on viscosity in surfactant solutions
 Additional benefits:
 Moisturizing benefits
 Ultra-mild cleansing properties
 PEG- and preservative-free
 100% based on renewable raw materials, suitable for natural beauty and home care formulations

28 | April 2018 | TEAMWORKS | Naturally Derived Solubilizers

29
RBC-Test – in-vitro mildness assessment
Values

Erythrocytes-suspension
 H 50 (Hemolysis) (with phophate-buffer)
 Concentration of surfactant at which 50% of the erythocytes are destroyed [ppm]
 Release of haemoglobin due to cellular damage (UV/VIS at 560 or 530 nm)
 DI (Denaturation-Index)
Addition of surfactant:
 Denaturation of haemoglobin compared to SDS [%] (UV/VIS at 575 and 540 nm) 10 min incubation
 L/D – value (L/D = H50 [ppm] / DI [%]) centrifugation

 quotient lysis/denaturation (H50/DI)

 correlates with mean index of ocular irritation (Draize)

Classification: L/D > 100 basically non irritant

L/D > 10 slightly irritant
Very mild formulas photometric determination of
(e. g. baby shampoos) L/D > 1 moderately irritant
free haemoglobin (proportional
L/D > 0.1 irritant to number of lysed cells) in the
upper layer
L/D < 0.1 very irritant
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