Naturally derived solubilizers High performance PEG-free ...€¦ · 1 Naturally derived...

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


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


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


6

Needs for next generation solubilizers for both Beauty and Home Care


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


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/)

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:


9

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


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


• 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)


• 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


Polyglyceryl-6 Ricinoleate (PG 61)

• Almost colorless liquid

• ~3000 – 5000 mPa·s

• HLB ~14


~26 mN/m

• ~10% Water


• RSPO (MB*)

• Halal

PEG- & preservative free products, 100% based on renewable raw materials

• Colorless to yellowish liquid

• ~3000 - 6000 mPa·s

• HLB ~15


~26 mN/m

• ~10% Water


• RSPO (MB*)

• (Halal pending)

Polyglyceryl-6 Caprylate;

Polyglyceryl-4 Caprate (PG 90)


*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


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.).


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

.


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.).


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.


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


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%.


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



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



Emollients

Fatty natural oils


Foaming








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


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


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%


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


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



Emollients

Fatty natural oils


Foaming








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


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.


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.


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


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


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

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