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1
Naturally derived solubilizers
High performance PEG-free solubilizers
for all solubilization needs.
TEAMWORKS 2018
Anna Howe & Anne Mu
April 11, 2018
2
Performance & Safety
Improved functionality versus
not sacrificing safety
Milder formulations still
require effective ingredients
Performance & safety
important to product‘s
success
Cross Market trends from Personal Care to Household Care
Source: Mintel
Naturality &
Sustainability
Natural & eco-friendly
ingredients
Natural positioning helps
brands build trust with
consumers and grow
consumer engagement
Transparency
Transparency presents an
opportunity for companies to
engage consumers by
addressing ingredient safety
Corporate Social
Responsibility (CSR) matters
to consumers
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Multifunctionality
Less is more
Combining more than a
single benefit in one
product
Health & Well-being
Hygiene-focused product
development
Aroma therapeutic products
enhance sensory and support
well-being
Fragrances are associated
with cleanliness in beauty
and similarly in home care
3
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
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
4
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
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
5
Oleic Acid
Linoleic Acid
Palmitic Acid
StearicAcid
What makes it challenging? e.g. Complex composition of natural oils
Jojoba Oil
Almond Oil Olive Oil
Avocado OilSunflower Oil
Argan Oil
Oleic Acid
Linoleic Acid
Palmitic Acid
Stearic Acid
Oleic Acid
Linoleic Acid
Palmitic Acid
StearicAcid
Oleic Acid
Linoleic Acid
Palmitic Acid
Stearic Acid
C18:1C18:2
Oleic Acid
Gadoleic Acid (&
isomer)Docos-dienoic
Acid
ErucicAcid
Palmitic Acid
C20:1C22:1
C16:0
C22:2
C18:0
Oleic Acid
Linoleic Acid
Palmitoleic Acid
PalmiticAcid
Others
C16:1
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
6
Needs for next generation solubilizers for both Beauty and Home Care
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Requirements Common Challenge
Solubilization
performance
Providing high clarity x
Broad variety of different oils x
Processing Easy to handle & cold processable x
Adapted foaming & thickening
properties
x
Sustainability PEG-free x
Fully naturally derived x
Aspect of
formulation
High stability on olfactory needs x
Colorless product with high color
stability
x
Additional
benefits, like
Moisturization x
Mildness x
7
Industrial benchmarks for Home Care and Beauty Care
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Polysorbates EthoxylatedEthylated Oils
(PEG-40 Hydrogenated
Castor Oil)
Safflower OleosomesPlant based Propanediol
Sorbitan Oleatedecylglucosidecrosspolymer
Sulfoacetatesarcosinate
Sodium xylene / toluene
sulfonate
Hydrotropes
Or Industrial waste stream
Diabasicesters
- The industry keeps coming up with new solubilizer solutions
- We tend to see either:
- Harsh chemistries
- Milder chemistries but low solubilization power
(source: http://library.essentialwholesale.com/what-are-emulsifiers-and-solubilizers/)
8
The route to natural derived polyglycerol esters
Coconut Oil
Rapeseed Oil
Castor Oil
Palm Oil
- H2OD
cat.
O O
OH
OH
OH
HO
HO
OO
OH
OH
OH
HO
HO
HO O OH
OH O
HO OH
By varing the condensation degree, polyglycerol esters
can be tailored to specific applications.
Polyglycerol ester
Fatty acids
Glycerin
condensation
HO O
OH OH
OH
n
and
esterification
and …
additional modifications possible
0
10
20
30
40
50
60
1 2 3 4 5 6 7 8 9 10
DP
%
In addition: variation of degree of PG polymerisation:
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
9
Polyglycerin-based solubilization of different oils in water-based systems
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Efficient PEG-free Solubilizers
For the solubilization of
• Essential oils like:
Rosemary oil, Lemon oil,
Orange oil, Lavender oil,
Lemongrass oil, Sage oil,
Tea tree oil
• Perfume oils
• Benzyl Alcohol
For the solubilization of
• Fatty natural oils like:
Sunflower oil, Almond oil,
Argan oil, Olive oil,
Soy bean oil, Jojoba oil
• Other triglycerides like
Caprylic/Capric Triglyceride
• Heavier lipophilic emollients like
Ethylhexyl Palmitate, Decyl Cocoate,
Cetearyl Isononanoate
Polyglyceryl-4 Caprate (PG 41)
Polyglyceryl-6 Caprylate; Polyglyceryl-4 Caprate
(PG 90)
Polyglyceryl-6 Caprylate; Polyglyceryl-3
Cocoate; Polyglyceryl-4 Caprate;
Polyglyceryl-6 Ricinoleate (PG 61)
For the solubilization of
• Light and/or relatively polar emollient
esters like:
Isopropyl Myristate,
Isopropyl Palmitate,
Isoamyl Cocoate,
Diethylhexyl Carbonate,
C12-15 Alkyl Benzoate
• Short hydrocarbons like Isohexadecane
• Tocopherol
Increasing hydrophobicity
Polyglyceryl-3 Caprate/ Caprylate/Succinate;
Propylene Glycol (PG 55)
10
Polyglycerin-based solubilizers – Properties
Efficient PEG-free Solubilizers
• Almost colorless liquid
• ~3000 – 5000 mPa·s
• HLB ~15
• Surface tension (1%):
~26 mN/m
• ~25% Propylene Glycol
• Bio-based 1,2-Propylene Glycol
and Succinic acid
• RSPO (MB*)
• (Halal pending)
• Slightly yellow liquid
• ~3000 – 5000 mPa·s
• HLB ~11
• Surface tension (0.5%):
~30 mN/m
• ~12% Water
• Ecocert & COSMOS
• RSPO (MB*)
• Halal
Polyglyceryl-4 Caprate (PG 41)Polyglyceryl-3 Caprate/Caprylate/
Succinate; Propylene Glycol (PG 55)
Polyglyceryl-6 Caprylate; Polyglyceryl-3
Cocoate; Polyglyceryl-4 Caprate;
Polyglyceryl-6 Ricinoleate (PG 61)
• Almost colorless liquid
• ~3000 – 5000 mPa·s
• HLB ~14
• Surface tension (0.5%):
~26 mN/m
• ~10% Water
• Ecocert & COSMOS
• RSPO (MB*)
• Halal
PEG- & preservative free products, 100% based on renewable raw materials
• Colorless to yellowish liquid
• ~3000 - 6000 mPa·s
• HLB ~15
• Surface tension (0.5%):
~26 mN/m
• ~10% Water
• Ecocert & COSMOS
• RSPO (MB*)
• (Halal pending)
Polyglyceryl-6 Caprylate;
Polyglyceryl-4 Caprate (PG 90)
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
*MB = mass balanced
11
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
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
12
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.).
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Th
e s
ma
lle
r th
e b
ar
the
hig
he
r
the
so
lub
iliz
ati
on
po
wer
Polyglyceryl esters show similar performance to the PEG containing market standards
0%
2%
4%
6%
8%
10%
12%
14%
16%
18%
20%
Lemon Oil(Supplier 1)
Lemon Oil(Supplier 2)
Rosemary Oil Tea Tree Oil Lavender Oil Lemongras Oil
Am
ou
nt
of
so
lub
iliz
er
ne
ed
ed
to
s
olu
bil
ize
1%
of
the o
ils
in
wa
ter
Polysorbate 20 PEG-40 Hydrogenated Castor Oil
Polyglyceryl-4 Caprate Polyglyceryl-6 Caprylate; Polyglyceryl-4 Caprate
Polyglyceryl-3 Caprate/Caprylate/Succinate
13
Fragrance mapping – Tested perfume oils
A broad variety of perfume oils were tested to show the solubilizing efficacy of : Polyglyceryl-3 Caprate/Caprylate/Succinate
.
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Tendency
Basic
character
Citrus Watery Fruity Floral Aromatic Woody
Citrus
Fruity
Floral
Fougère
B
A
C D E
F
A Aquatic / Floral (Balsamic - Powdery -
Sandalwood)
B Ozonic / Fruity (Citrus - Melon - Musk)
C Floral / Fruity (Apple - Balsamic)
D Balsamic / Floral (Fruity - Aldehyde - Musk)
E Floral (Freesia - Lily Of The Valley -
Rose)
F Fougère / Citrus (Cassis - Lemon - Sandalwood)
G Fougère / Aromatic (Green - Amber - Bergamot)
Supported by Fragrance Resources (now IFF Fragrance GmbH)
G
14
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.).
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Inc
rea
sin
g s
olu
biliz
ati
on
po
we
r
0%
5%
10%
15%
20%
25%
Aquatic / Floral(in DPG)
Ozonic / Fruity(in DPG)
Floral / Fruity(in DPG)
Balsamic /Floral
(in DPG)
Floral(in DPG)
Fougère /Citrus
(in DPG)
Fougère /Aromatic(in IPM)
Am
ou
nt
of
so
lub
iliz
er
ne
ed
ed
to
s
olu
bil
ize
1%
of
the f
rag
ran
ce
s
PEG-40 Hydrogenated Castor OilPolyglyceryl-4 CapratePolyglyceryl-3 Caprate/Caprylate/Succinate
Polyglyceryl-3 Caprate/Caprylate/Succinate in average is as effective as the PEG-based standard PEG-40
Hydrogenated Castor Oil
All fragrances from Fragrance Resources
(now IFF Fragrance GmbH)
15
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.
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Polyglyceryl esters show superior solubilizing properties in water and high electrolyte low pH systems
0%
5%
10%
15%
20%
25%
Caprylyl/Capryl Glucoside Polyglyceryl-4 Caprate PEG-free surfactant blend* Isotrideceth-9 PEG-40 HydrogenatedCastor Oil
Polyglyceryl-3Caprate/Caprylate/Succinate
Polyglyceryl-6 Caprylate;Polyglyceryl-4 Caprate
Am
ou
nt
of
so
lub
iliz
er
ne
ed
ed
to
s
olu
bil
ize
1%
of
the f
rag
ran
ce Water 20% Electrolyte/Low pH
(results
highly
dependent
on quality)
*INCI Name: Water; Pentylene Glycol; Sodium Lauryl Sulfoacetate; Sodium Oleyl Sarcosinate; Sodium
Chloride; Disodium Sulfoacetate; Sodium Oleate; Sodium Sulfate
16
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%.
Polyglyceryl-6 Caprylate; Polyglyceryl-3 Cocoate;
Polyglyceryl-4 Caprate; Polyglyceryl-6 Ricinoleate best for
highly lipophilic emollients
Polyglyceryl-4 Caprate best
for light and polar emollients
0%
2%
4%
6%
8%
10%
12%
Am
ou
nt
of
so
lub
iliz
er
ne
ed
ed
to
s
olu
bil
ize
0.5
% o
f th
e o
ils
PEG-40 Hydrogenated Castor Oil
Polysorbate 20
Polyglyceryl-4 Caprate
Polyglyceryl-6 Caprylate; Polyglyceryl-3 Cocoate; Polyglyceryl-4 Caprate; Polyglyceryl-6 Ricinoleate
op
aq
ue
o/n
op
aq
ue
Inc
rea
sin
g s
olu
biliz
ati
on
po
we
r
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
17
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%.
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
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)
Inc
rea
sin
g s
olu
bil
iza
tio
n
po
we
r
0%
2%
4%
6%
8%
10%
12%
Almond Oil Olive Oil Argan Oil Sunflower Oil Jojoba Oil Avocado Oil Fragrance WhiteLily (~90% Soy
Bean Oil)
Am
ou
nt
of
so
lub
iliz
er
ne
ed
ed
to
s
olu
bil
ize
0.5
% o
f th
e o
ils
PEG-40 Hydrogenated Castor Oil
Polyglyceryl-4 Caprate
Polyglyceryl-6 Caprylate; Polyglyceryl-3 Cocoate; Polyglyceryl-4 Caprate; Polyglyceryl-6 Ricinoleate
not
100%
cle
ar
not
100%
cle
ar
18
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
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
19
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
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Polyglycerin-based solubilizers are low foaming in water, thus enabling easy processing
0
200
400
600
800
1000
1200
10 20 30 40 50 60 70 80 90 100
Fo
am
vo
lum
e [
ml]
Foaming interval [sec]
PEG-free surfactant blend product*
Polyglyceryl-4 Caprate
Polyglyceryl-6 Caprylate; Polyglyceryl-3 Cocoate;Polyglyceryl-4 Caprate; Polyglyceryl-6 Ricinoleate
PEG-40 Hydrogenated Castor Oil
Polyglyceryl-6 Caprylate; Polyglyceryl-4 Caprate
Polyglyceryl-3 Caprate/Caprylate/Succinate
*INCI Name: Water; Pentylene Glycol; Sodium Lauryl Sulfoacetate; Sodium Oleyl Sarcosinate; Sodium
Chloride; Disodium Sulfoacetate; Sodium Oleate; Sodium Sulfate
20
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%
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Polyglycerin-based solubilizers are cold processable and do not form a gel phase in contrast to some PEG-
containing solubilizers in high concentrations
TEGO® Solve 61
6:11 min
2:30 min 5:12 min
2:30 min
Polyglyceryl-6 Caprylate;
Polyglyceryl-3 Cocoate;
Polyglyceryl-4 Caprate;
Polyglyceryl-6 Ricinoleate 15:02 min
PEG-40
Hydrogenated
Castor Oil 15:02 min
after 24 h
after 24 h
21
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
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Polyglycerin-based solubilizers show significantly lower viscosity reduction than PEG-40 Hydrogenated
Castor Oil or Polysorbate 20
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
Chassis + 1% PG 55 + 1% PG 90 + 1% PG 41 + 1% PG 61 + 1% PEG-40 Hydrog.Castor Oil
1%Polysorbate
20
Vis
co
sit
y [
mP
a·s
]
23
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
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
24
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
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Polyglycerin-based solubilizers act as a humectant and provides moisturization benefits
0
5
10
15
20
25
Control (untreated skin)
Vehicle 3% PG 61 5% PG 61
Sk
in h
yd
rati
on
im
pro
ve
me
nt
(DC
U v
alu
e)
aft
er
2 h
re
l. t
o
co
ntr
ol
[%]
25
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
26
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.
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
The Polyglycerin-based solubilizers are basically non irritant and improve the mildness of surfactant mixtures
0.1
1
10
100
1000
PG 55 PG 90 PG 61 SLES / CAPB3:1
SLES / CAPB(+PG 61 3:1:2)
CAPB CAPB(+20% PG 61)
AM 2 C NM AM 2 C NM(+33% PG 61)
L/D
Va
lue
basically non irritant
slightly irritant
moderately irritant
irritant
Cocoampho-
diacetate
Level of baby shampoo benchmark
CAPBSLES /
CAPB
>22
>400
27
Make-up removal –Test results with aqueous solutions
Removal of make-up applied
on
PMMA-plates.
Aqueous solution (3% a.m.
surfactants) was put on a
cotton pad attached to a sled.
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
long lasting make-up
(L´Oréal)
63.25
75.29
13.43
81.0976.62 73.50 72.92
9.60
0
10
20
30
40
50
60
70
80
90
Ma
ke
-Up
-Re
mo
va
l [%
]
Polyglycerin-based solubilizers efficiently remove make-up in a very mild way
28
Polyglycerin-based solubilizers –Benefits at a glance
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
| April 2018 | TEAMWORKS | Naturally Derived Solubilizers
Essential & Perfume oils
• Polyglyceryl-3 Caprate/Caprylate/
Succinate
• Polyglyceryl-6 Caprylate; Polyglyceryl-4
Caprate
Fatty natural oils
Heavier lipophilic emollients
• Polyglyceryl-6 Caprylate; Polyglyceryl-3
Cocoate; Polyglyceryl-4 Caprate;
Polyglyceryl-6 Ricinoleate
Light and/or relatively polar
emollients
• Polyglyceryl-4 Caprate
29
30
RBC-Test – in-vitro mildness assessmentValues
H 50 (Hemolysis)
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)
Denaturation of haemoglobin compared to SDS [%] (UV/VIS at 575 and 540 nm)
L/D – value (L/D = H50 [ppm] / DI [%])
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
L/D > 1 moderately irritant
L/D > 0.1 irritant
L/D < 0.1 very irritant
Very mild formulas
(e. g. baby shampoos)
Erythrocytes-suspension
(with phophate-buffer)
Addition of surfactant:
10 min incubation
centrifugation
photometric determination of
free haemoglobin (proportional
to number of lysed cells) in the
upper layer
Back p. 25