Surfactant blends for emulsifying

and cleaning

F. Rittig*, R. Baur, C. Esper, U. Steinbrenner, J. Tropsch, S. Zimdahl

BASF SE, 67056 Ludwigshafen, E-EMV/GS-J550
 Motivation

motivation
„ search for emulsifiers able to form stable emulsions

solution
„ surfactant combination with excellent emulsification results
(Steinbrenner et al. SEPWA Proceedings 2006, 373)

16.05.2008, F. Rittig SEPWA Nordic 2009 2

 Evaluation of emulsifiers by the marker
method1

The product (oil) to be Determination of

emulsified is marked with droplets of mixed
2 different oil-soluble dyes color

e
blue dy
+
Homogenization
Oil to a fine emulsion
Raw emulsion A Gentle
Emulsifier
mixing
Water

+y
ello Mixture 1:1
wd Microscopic
ye
picture
Raw emulsion B 1 Thomas Danner, Thesis: „Tropfenkoaleszenz in Emulsionen“,
Univ. Karlsruhe, published by GCA, Herdecke 2001

16.05.2008, F. Rittig SEPWA Nordic 2009 3

 Emulsion stabilities with blends based on
C10 Guerbet alcohol (> 60%)
30% sunflower oil, 1% emulsifier, 69% water, storage at 23°C

10% of the droplets blend of (C10-G + long

coalesced after chain alcohol) ethoxilates

month blends of C10

Guerbet with long
weeks chain alcohols work
well, much better
than C10 Guerbet
days
alone.
hours C16C18 blend of (C10-G + C12C15
C12C15 alcohol) ethoxilates

minutes C10-G ethox

6 8 10 12 14 16
HLB

16.05.2008, F. Rittig SEPWA Nordic 2009 4

 The "Surfactant Team"
Coethoxilates of C10 Guerbet + long chain
alcohol

Examples: C10 Guerbet + 6 EO Coethethoxilate Long chain alc. + 9 EO

HLB ca. 12.5 HLB ca. 12.5 HLB ca. 12.5

1) wetting
(EN 1772, 23°C)
0.5 g/l ca. 60 s ca. 60 s > 300 s
1.0 g/l ca. 10 s ca. 10 s > 300 s
2.0 g/l ca. 5 s ca. 5 s > 300 s

2) gel phases in water solid gel at no solid gel solid from 0% to

(23°C) 40 w% water (<25 Pa*s) ca. 90% water

3) foam test
(EN 12728, 2 g/l, 40°C) ca. 250 ml ca. 280 ml ca. 160 ml

4) emulsion stability
paraffin oil, 23°C S = -0.2 S = 0.7 S = 0.9
sunflower oil, 23°C S = -1.0 S = 1.1 S = 0.8

16.05.2008, F. Rittig SEPWA Nordic 2009 5

 Can synergistic properties of ethoxilates
of C10 Guerbet alcohol blends be utilized for
laundry detergents ?

Agenda
„ Laundry performance of surfactant blends
„ Liquid detergents
z high active contents
z low active contents
z fragrance solubilization
„ Eco-tox
„ Summary

16.05.2008, F. Rittig SEPWA Nordic 2009 6

 Can synergistic properties of ethoxilates
of C10 Guerbet alcohol blends be utilized for
laundry detergents ?

Agenda
„ Laundry performance of surfactant blends
„ Liquid detergents
z high active contents
z low active contents
z fragrance solubilization
„ Eco-tox
„ Summary

16.05.2008, F. Rittig SEPWA Nordic 2009 7

 Screening of synergistic surfactant blends
Test conditions

„ In combination with 5% AEO and 15% Na-LAS in a zeolite based powder

formulation
„ launder-o-meter tests

„ water hardness 2.5 mmol/l (4 parts Ca2+, 1 part Mg2+,

8 parts HCO3-)
z wash time 30 min
z wash temperature 30°C and 60°C
z liquor ratio 1 : 12.5
„ test swatches for screening
z wfk10D (pigment/sebum on cotton)
z wfk10PF (vegetable oil on cotton)
z wfk20D (pigment/sebum on PES/cotton blend)
16.05.2008, F. Rittig SEPWA Nordic 2009 8
 Screening of synergistic surfactant blends
Wash tests at 30 °C

5
„ Blends of ethoxilates of C10-
Guerbet alcohol and long chain
0
alcohols are better than single
ΔΔ R vs. C13C15 x 7 EO

-5 components

-10
„ At certain ratios performance is
equal than system with standard
-15 wfk10D surfactants
wfk10PF
-20 wfk20D

-25
0 25 50 75 100
weight-% C10 alcohol ethoxilate

16.05.2008, F. Rittig SEPWA Nordic 2009 9

 Screening of synergistic surfactant blends
Wash tests at 60 °C

5
„ Blends of ethoxilates of C10-
Guerbet alcohol and long chain
0
alcohols are better than single
ΔΔ R vs. C13C15 x 7 EO

-5 components

-10
„ At certain ratios performance is in
the range of the system with
-15 wfk10D standard surfactants
wfk10PF
-20 wfk20D

-25
0 25 50 75 100 Î More detailed studies are required
weight-% C10 alcohol ethoxilate

16.05.2008, F. Rittig SEPWA Nordic 2009 10

 Special coethoxilates
Product and performance data

„ fixed alcohol composition (types and ratio)

„ ethoxilation according to cloud point of benchmark
„ full scale tests (washing machine) in powder and liquid detergents

Physical data M5 ST5 M7 ST7

Alcohol G-C10+ C13/15 G-C10+ C13/15
Hydrophilic part 5 EO 7 EO
Cloud points (EN 1890, Method E,
59-63 °C 60-64 °C 73-76 °C 75 °C
BDG)
Foaming 2g/l EN 12728 110 ml 110 ml 300 ml 280 ml
Wetting @ 23°C (1g/l EN1772) 20 s 100 s 20 s 30 s
Wetting @ 70°C (1g/l EN1772) 35 s 160 s 30 s 30 s
M = Coethoxilates, ST = benchmark (e.g. Lutensol AO)
16.05.2008, F. Rittig SEPWA Nordic 2009 11
 Can synergistic properties of ethoxilates
of C10 Guerbet alcohol blends be utilized for
laundry detergents?

Agenda
„ Laundry performance test of surfactant blends
„ Liquid detergents
z high active contents
z low active contents
z fragrance solubilization
„ Eco-tox
„ Summary

16.05.2008, F. Rittig SEPWA Nordic 2009 12

 Formulations with high contents of WAS
Laundry wash test 40°C

30
formulation
FAS 10 ST 7
nonionic surfactant 15
25
M7
soap 10 20

MPG 6

Δ remission
citric acid 3 15

B(OH)3 1.5
Ethanol 2 10

percarbonate 15
Savinase Ultra 16 L 2 5

neutralized with ethanol amine

0
water balance bleachable enzymatic
general soil (w fk 20D, bleachable soil (EMPA enzymatical stain (EMPA
general
EMPA 101; 141/2; PCS 114; BC-1; BC-2; PCS 3) 112; 116; CS 1; CS-10;
stain 4) stain Stain
CS-8; AS-10; PC-5; CS-
28)
16.05.2008, F. Rittig SEPWA Nordic 2009 13
 Different viscosity profile of coethoxilates
in dilution with water

1000000 „ Lower viscosities observed when

coethoxilated samples are diluted
100000 with water

10000 „ Advantages
visc /m Pas

1000 z Faster dilution in water

z In liquid dosing systems,
100
e.g. in I&I laundry
(all concentrations possible)
10
M7 ST 7 z During manufacturing
1 processes
0 20 40 60 80 100
conc. surfactant (%)
„ Special liquid detergent types
need more detailed investigations
16.05.2008, F. Rittig SEPWA Nordic 2009 14
 “super concentrates” with high contents of
washing active substances (WAS)

C C D D
WAS (LAS + soap + AEO) 41 41 51.5 51.5
LAS (Lutensit A-LBS) 7.9 7.9 7.4 7.4
soap (Edenor K12-18) 11 11 14.6 14.6
ST 7 22 26.6
M7 22 26.6
1,2-propylene glycol 8.8 6 9 6 ST 7 M7
ethanol 2 2 2 2
pH 8.7 8.7 8.7 8.7
viscosity (Sp 2, 60 phase Formulation D
200 160 140
rpm)/mPas separated

Concentrations in active matter

16.05.2008, F. Rittig SEPWA Nordic 2009 15

 “highly viscous super concentrates” with high
contents of washing active substances (WAS)

Formulation Formulation Formulation

D E F
WAS (LAS + soap + AEO) 51.5 51.5 51.5
LAS (Lutensit A-LBS) 7.4 7.4 7.4
soap (Edenor K12-18) 14.6 14.6 14.6
M7 26.6 26.6 26.6
1,2-propylene glycol 6 6 6
ethanol 2 2 2
Sokalan AT120 0.9 1.5
pH 8.7 8.7 8.7
viscosity (Sp 2, 60
140 500 1100
rpm)/mPas

Concentrations in active matter

16.05.2008, F. Rittig SEPWA Nordic 2009 16

 Decrease of viscosity in regular formulas
with low WAS

200
Washing active substance
14.25% 19% 23.75%
180 (Nonionic+LAS+soap)
LAS (Lutensit ALBS)* 7.5% 10% 12.5%
160
ST 7 Soap (Edenor K12-18)* 1.5% 2% 2.5%
140 pH
AEO 5.25% 7% 8.75%
120 8.2
EtOH 2.82% 3.76% 4.7%
visc./mPas

8.6 NaCitrate 0.75% 1% 1.25%

100
9.0 water to 100 to 100 to 100
80

60

40
M7

20 Æ different viscosity profile

*viscosities measured with Sp 62, 60 rpm
0
0% 10% 20% 30%
WAS

16.05.2008, F. Rittig SEPWA Nordic 2009 17

 Options to readjust viscosity
in regular liquid detergents

I. Reduce solvents
II. Check if thickeners are an option

16.05.2008, F. Rittig SEPWA Nordic 2009 18

 Option I
Adjusting viscosity by solvent reduction

ST 7 M7
H 2O 43.9 43.9
Na2SO4 1.9 1.9
NaCl 0.1 0.1
HP56 0.2 0.2
Glycerin 1.2 1.2
EtOH 1.7 1.7
MPG 7.2 7.2
Triethylenglycolmonobutylether 1.5 1.5
AEO 16.4 16.4
Soap 6.1 6.1
SAS 11.6 11.6
pH 8 8
Viscosity (mPas) 112 65
Appearance opaque opaque
Cold cloud point <0 <0

Concentrations in active matter

16.05.2008, F. Rittig SEPWA Nordic 2009 19

 Option I
Adjusting viscosity by solvent reduction

ST 7 M7 M7
H 2O 43.9 43.9 53.5
Na2SO4 1.9 1.9 1.9
NaCl 0.1 0.1 0.1
HP56 0.2 0.2 0.2
Glycerin 1.2 1.2 0
EtOH 1.7 1.7 0
MPG 7.2 7.2 2
Triethylenglycolmonobutylether 1.5 1.5 0
AEO 16.4 16.4 16.4
Soap 6.1 6.1 6.1
SAS 11.6 11.6 11,6
pH 8 8 8
Viscosity (mPas) 112 65 126
Appearance opaque opaque opaque
Cold cloud point <0 <0 <0

Concentrations in active matter

16.05.2008, F. Rittig SEPWA Nordic 2009 20

 Option II
Adjusting viscosity by thickener

e.g. II/A II/B

LAS Lutensit A-LBS 10 10
Soap Edenor K12-18 2 2
KOH pH = 8.6
M7 0 7
ST 7 7 0
EtOH 2 2
MPG 1.2 1.2
NaCitrate 1 1
KOH pH = 8.6
NaCl
Viscosity/mPas 177 70

Concentrations in active matter

16.05.2008, F. Rittig SEPWA Nordic 2009 21
 Option II
Adjusting viscosity by thickener

e.g. II/A II/B III/C III/D

LAS Lutensit A-LBS 10 10 10 10
Soap Edenor K12-18 2 2 2 2
KOH pH = 8.6
M7 0 7 7 7
ST 7 7 0 0 0
EtOH 2 2 2 2.5
MPG 1.2 1.2 1.2 1.2
NaCitrate 1 1 1 1
NaCl
Sokalan AT120 0.26 0.58
Viscosity/mPas 177 70 160 355

Concentrations in active matter

16.05.2008, F. Rittig SEPWA Nordic 2009 22
Make use of superior emulsification properties
Method

„ 1 g Surfactant
„ 0.1 to 0.5 g Perfume (orange
terpene)
„ Mix it 1 g ST
0.5 g orange terpene
1gMX
0.1 g orange terpene
1gMX
0.2 g orange terpene
1gMX
0.4 g orange terpene
1gMX
0.5 g orange terpene

„ Balance with water (100 g)

„ Stir for 5 min at given speed
cloudy Slightly cloudy clear Phase
„ Check samples after 24 h separated

16.05.2008, F. Rittig SEPWA Nordic 2009 23

Make use of superior emulsification properties
Method

Orange terpene
0.1 g 0.2 g 0.3 g 0.4 g 0.5 g 1 g ST
0.5 g orange terpene
1gMX
0.1 g orange terpene
1gMX
0.2 g orange terpene
1gMX
0.4 g orange terpene
1gMX
0.5 g orange terpene

ST 7
MX
Cloudy clear
2 phase slightly cloudy

Lillial C11 aldehyde

0.1 g 0.2 g 0.3 g 0.4 g 0.5 g 0.1 g 0.2 g 0.3 g 0.4 g 0.5 g
ST 7 ST 7
MX M7
Isoamylsalicylate Globalide
ST 7 ST 7
MX M7

16.05.2008, F. Rittig SEPWA Nordic 2009 24

 Eco-tox properties & labeling

M7 ST 7

Aquatic invertebrates: 1-10 mg/l 0.1-1 mg/l

Daphnia
magna/EC50(48h)
Aquatic plants: 1- 10 mg/l 0.1-1 mg/l
Scenedesmus
subspictus/EC50 (72h)
Labeling Xn, R22, R41 Xn, N, R22, R41, R50

Transport No hazardous material Class 9

16.05.2008, F. Rittig SEPWA Nordic 2009 25

 Summary

Surfactant blends and coethoxilates with C10-Guerbet alcohols show

month

weeks

„ Synergistic effects in 30
days

hours C16C18
C12C15

z emulsification (triglycerides)
25
minutes C10-G ethox

20 6 8 10 12 14 16
HLB

Δ remission
z laundry detergents 15

10
200

180

160

140
5

120 8.2

visc./mPas
8.6
0 100
EMPA 101 WFK 10D WFK 20D Triolein Olive oil average
9.0
80

„ Different viscosity profiles vs. standards 60

40

20

0
0% 10% 20% 30%

„ Improved solubilization of fragrances

WAS/%

„ Sustainable eco-tox profile

16.05.2008, F. Rittig SEPWA Nordic 2009 26

 Performance profile

labeling

Emulsification
Laundry
laundry (triglycerides)
emulsification (triglycer
performance

dynamics Emulsification(p
emulsification
(paraffin)

w etting cmc

low foam

Lutensol M
C12C15 ethoxylates

Thank you!
16.05.2008, F. Rittig SEPWA Nordic 2009 27