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Desenvolvimentos Recentes em Surfactantes Catiônicos para Fabric Care e Car Care – Andras Nagy – Evonik
1. Recent Developments in
Cationic Surfactants for
Fabric & Car Care
Andras Nagy, Ph.D.
Applied Technology Manager
Household Care/CS NA
2. Agenda
Traditional and Unique Applications: Substantivity
Antibacterial agents/Corrosion inhibitors/Asphalt emulsion/Ore flotation
Fabric softeners
Vehicle drying agents
Emulsifiers/surfactants: cleaning/drying aids/protectants
Anionic Scavengers – Softergents: car care - fabric care
Silicone Quats: special organomodified silicones
Latest Developments: Smart molecules
Low temperature dispersible fabric softener quat
Readily biodegradable emulsifier for vehicle rinse aids
Consumer Specialties | Business Line Household Care Page | 2
3. What Is a Cationic Surfactant (Quat)
Quats are positively charged ions, R being alkyl or aryl
group(s)
Permanently charged, independent of the pH of their
solution.
Cationic surfactants are salts of quaternary ammonium
cations with an anion.
Made by alkylation of tertiary amines
Have hydrophobic tail(s), polar head(s) with positive
charge(s) and counter-anion(s) with negative charge(s)
X-
-
+
-
Consumer Specialties | Business Line Household Care Page | 3
4. An Important Property
Substantivity
An attractive force is required to deposit caring
agents from dilute formulations to the target
surface
Most surfaces are negatively charged mainly due
to oxidation
The Coulomb attraction between cationic
surfactants and surfaces can be used as a
deposition mechanism
- - - - - - - -
Consumer Specialties | Business Line Household Care Page | 4
5. Traditional and Unique Applications
Antimicrobial Quats:
Disruption of intermolecular interactions (bacteriostatic, fungistatic, algistatic,
antiviral activity)
Corrosion Inhibitors:
Substantivity of the cationics will create protective coatings
Ore Flotation:
Quats will form monomolecular films on negative particles. Air bubbles will
float the hydrophobic components
Asphalt Emulsions:
Cationic emulsions will coat inorganic particles and metal surfaces even in
wet conditions (highway construction, vehicle undercoating)
Miscellaneous Applications:
Cosmetics, Hair conditioners, Pigment dispersants, etc.
Consumer Specialties | Business Line Household Care Page | 5
6. Page | 6
Fabric Softening
1. Overview
2. Rinse Cycle Products
3. Dryer Cycle Products
Consumer Specialties | Business Line Household Care
7. Fabric Softeners Overview
Phase Behaviour of Quats
Double-chain cationic surfactants
form vesicles
from: J.N. Israelachvilli et al., J. Chem. Soc.,
Faraday Trans. II, 72 (1976) 1525-1568
+
Consumer Specialties | Business Line Household Care Page | 7
8. Page | 8
Fabric Softening
1. Overview
2. Rinse Cycle Products
3. Dryer Cycle Products
Consumer Specialties | Business Line Household Care
9. How Are Fabric Softeners Made?
Rinse Cycle Fabric Softeners:
1. Quats are heated and homogenized
-
-
“heat” quat to T °C
T °C
Homogenize
Consumer Specialties | Business Line Household Care Page | 9
10. How Are Fabric Softeners Made?
Rinse Cycle Fabric Softeners:
1. Quats are heated and homogenized
2. Dispersed into warm water
T °C
Disperse quat
into water at T °C; mix
Consumer Specialties | Business Line Household Care Page | 10
11. How Are Fabric Softeners Made?
Rinse Cycle Fabric Softeners:
1. Quats are heated and homogenized
2. Dispersed into warm water
3. Cooled down while being mixed
t °C
Cool to t °C; mix
Consumer Specialties | Business Line Household Care Page | 11
12. How Do Fabric Softeners Work?
Rinse Cycle Fabric Softeners:
1. Quats are heated and homogenized
2. Dispersed into warm water
3. Cooled down while mixed
4. Fragrances and other additives are added
Add dye, fragrance, etc.;
mix thoroughly
Consumer Specialties | Business Line Household Care Page | 12
13. How Do Fabric Softeners Work?
Rinse Cycle Fabric Softeners:
1. Quats are heated and homogenized
2. Dispersed into warm water
3. Cooled down while mixed
4. Fragrances and other additives are added
5. These liquid softeners are added during the rinse
cycle in the washing machine
Consumer Specialties | Business Line Household Care Page | 13
14. How Do Fabric Softeners Work?
Rinse Cycle Fabric Softeners:
1. Quats are heated and homogenized
2. Dispersed into warm water
3. Cooled down while mixed
4. Fragrances and other additives are added
5. These liquid softeners are
added during the rinse cycle in the washing machine
6. The positively charged molecules are attached to the
negative fibers to make them soft, and antistatic
Consumer Specialties | Business Line Household Care Page | 14
15. Page | 15
Fabric Softening
1. Overview
2. Rinse Cycle Products
3. Dryer Cycle Products
Consumer Specialties | Business Line Household Care
16. How Are Fabric Softeners Made?
Dryer Cycle Fabric Softeners:
1. Quats and other ingredients are heated and
homogenized
-
-
“Melt” ingredients
at T °C
T °C
Homogenize
Consumer Specialties | Business Line Household Care Page | 16
17. How Are Fabric Softeners Made?
Dryer Cycle Fabric Softeners:
1. Quats are heated and homogenized
2. Poured on a hot plate (lab process)
3. Nonwoven substrate is put on the plate
4. Quat is spead evenly with a roller
Consumer Specialties | Business Line Household Care Page | 17
18. How Are Fabric Softeners Made?
Dryer Cycle Fabric Softeners:
1. Quats are heated and homogenized
2. Poured on a hot plate (lab process)
3. Nonwoven substrate is put on the plate
4. Quat is spead evenly with a roller
5. Coated substrate is lifted to solidify
6. Dryer sheet quat is ready for use
Consumer Specialties | Business Line Household Care Page | 18
19. How Are Fabric Softeners Made?
Dryer Cycle Fabric Softeners:
• Industrial process
Supply Roll
Doctor Blade
Squeeze
Roll
Heating
Cans
Cooling
Cans
Cutting Blade
Heated Dip Tank Take-up Roll
Consumer Specialties | Business Line Household Care Page | 19
20. How Do Fabric Softeners Work?
Dryer Cycle Fabric Softeners:
1. Quats are heated and homogenized
2. Poured on a hot plate,
3. Nonwoven substrate is put on the plate
4. Quat is spead evenly with a roller
5. Coated substrate is lifted to solidify
6. Dryer sheet quat is ready for use
7. The positively charged molecules are attached to the negative
fibers to make them soft, and antistatic
Consumer Specialties | Business Line Household Care Page | 20
21. Page | 21
Fabric Softener Actives
1. Chemistry, Biodegradability
2. Chemistry, Performance
3. Physical State
4. Improvement: Room Temperature Dispersible Quat
Consumer Specialties | Business Line Household Care
22. Evonik – The Global Leader in
Fabric Softener Actives
Full Range of Softener Chemistry
Dialkyl cationic surfactants
Nitrile (ADOGEN® 442)
Amidoamine (VARISOFT® 222)
Imidazolinium (VARISOFT® 475)
Ester Quat (REWOQUAT® WE 45)
Monoalkyl Quats
Anionic scavengers
Softening boosters
ADOGEN® 471
Organomodifed Silicones (II)
Fabric care benefits
Easy ironing
Reduced wrinkling
Faster drying
REWOQUAT® SQ 1
2-in-1 Softener
Additives
ADOGEN® 477 D
Consumer Specialties | Business Line Household Care Page | 22
23. Biodegradability
Ester bonds as potential “breaking points”:
O O
-
CH3
O O
N
CH3
O
Consumer Specialties |P Baguesi n| e2s3s Line Household Care
O
R
O
R
CH3
X
N
X
OH
O
R
O
R
R O
R'
Smaller molecules are more easily
accessible by microorganisms
Fatty acids are readily biodegradable
The other molecular fragments are also
completely biodegradable*
* Puchta et al: Tenside Surf. Det. 30 (1993) 3
24. Environmental Impact of
Quaternaries
Dialkyl-dimethyl and Ester Quaternaries
Biodegradation of Quaternaries
%-Degradation
100
10
1
0.1
EC50 [mg/l]
Consumer Specialties | Business Line Household Care Page | 24
100
80
60
40
20
0
Dialkyl-dimethyl Ester
OECD 301 E (5 d) OECD 301 C (30 d)
Aquatic toxicity of Quaternaries
0.01
Dialkyl-dimethyl Ester
OECD 201 (Algae) OECD 202 (Daphnia) OECD 203 (Fish)
Ester quaternaries yielded significantly better data than the standard dialkyl-dimethyl
quaternaries
25. Page | 25
Fabric Softener Actives
1. Chemistry, Biodegradability
2. Chemistry, Performance
3. Physical State
4. Improvement: Room Temperature Dispersible Quat
Consumer Specialties | Business Line Household Care
26. Nitrile Quats
• Premium softening and anti-stat properties
• Yellowing with age, limited biodegradability and rewet
Key Product Offerings
ADOGEN® 442 75% Tallow based
AROSURF® TA 100 Powder, for warm water wash
Consumer Specialties | Business Line Household Care Page | 26
27. Amidoamines
• Wide range of formulations: (up to 25% active)
• Versatile: household, industrial institutional, textile
• Good softening and rewet
Key Product Offerings
VARISOFT® 222 LM 90% Cold water processable
Consumer Specialties | Business Line Household Care Page | 27
28. Imidazoline Quats
• Excellent antistatic benefits with good softening
• Good for clear fabric softener formulation.
Imidazolinium
VARISOFT® 475 75% Paste, tallow
VARISOFT® 3690 Liquid, oleyl
VARISOFT® 3696 Liquid, 100% active, ethyl sulfate
Consumer Specialties | Business Line Household Care Page | 28
29. Ester Quats
• Readily biodegradable (best in class)
• Wide range of formulations: (up to 25% active)
• Good fragrance impact
Key Product Offerings
REWOQUAT® WE 16 E Tallow based w/ ethanol
REWOQUAT® WE 18 E US High viscosity version w/ ethanol
REWOQUAT® WE 28 E US Vegetable based w/ ethanol
REWOQUAT® WE 45 Clear, liquid, easy to handle
Consumer Specialties | Business Line Household Care Page | 29
30. Rinse Cycle Quat Characteristics
Product
ADOGEN®
442
VARISOFT®
475
VARISOFT®
222
REWOQUAT®
WE 28 E
Type Nitrile Imidazolinium Amidoamine TEA Ester Quat
Softening
Fragrance Impact
Static Control
Range of Formulation
Biodegradation
**** = most favorable
Consumer Specialties | Business Line Household Care Page | 30
31. Page | 31
Fabric Softener Actives
1. Chemistry, Biodegradability
2. Chemistry, Performance
3. Physical State
4. Improvement: Room Temperature Dispersible Quat
Consumer Specialties | Business Line Household Care
32. Consumer Specialties | Business Line Household Care
O O
N
OH
O
R
O
R
CH3OSO3
Ester Quat
CH3OSO3
N
HN
HN
O
R
O
R
((CH2)2O)nH
Amidoamine
N N
CH3OSO3 NH
R
R
O
Imidazolinium
Nitrile R N R Cl
Page | 32
Fabric Softener Actives
33. Consumer Specialties | Business Line Household Care
TEA Ester Quats
Biodegradable
Globally accepted
Regional CAS numbers
Descriptor matches fatty acid
Complex mixture
Mono, di, tri ester quats
Esteramines
Typical concentration of 90%
Paste or solid at 25 °C
O O
N
OH
O
R
O
R
CH3OSO3
Ester Quat
CH3OSO3
N
HN
HN
O
R
O
R
((CH2)2O)nH
Amidoamine
N N
CH3OSO3 NH
R
R
O
Imidazolinium
Nitrile R N R Cl
Page | 33
Fabric Softener Actives
34. Consumption of Surfactants for
Fabric Softeners by Region
Consumer Specialties | Business Line Household Care
+3.8%
+5.7%
Global Demand (t)
328,000 (2009)
361,000 (2014)
+2.5% -0.1%
XX% CAGR 2009 – 2014
*CAGR 2011 – 2016
+6.0%*
Sources: SRI Consulting, Coimbra Consultoria
Representações Comerciais Ltda
35. Fabric Softener Actives
Current Technology
Fabric Softener Actives
Paste or solid products require
continuous heating which impacts
Storage time
Transportation
Color and odor
Solvent level
Consumer Specialties | Business Line Household Care
Page | 35
36. Fabric Softener Actives
Paste or solid products require
continuous heating which impacts
Storage time
Transportation
Color and odor
Solvent level
Fabric Softener Formulations
Paste or solid products impact
Processing and handling conditions
Energy use
Cycle time
Consumer Specialties | Business Line Household Care
Page | 36
Fabric Softener Actives
Current Technology
37. Page | 37
Fabric Softener Actives
1. Chemistry, Biodegradability
2. Chemistry, Performance
3. Physical State
4. Improvement: Room Temperature Dispersible Quat
Consumer Specialties | Business Line Household Care
38. Consumer Specialties | Business Line Household Care
Our Goal
A new product that meets multiple
requirements for processing and use
Easy-to-handle and transport
Room temperature processing
Biodegradable
Globally accepted
Wide range of stable formulations
Competitive softening performance
Fabric Softener Actives
Paste or solid products require
continuous heating which impacts
Storage time
Transportation
Color and odor
Solvent level
Fabric Softener Formulations
Paste or solid products impact
Processing and handling conditions
Energy use
Cycle time
Page | 38
Fabric Softener Actives
Proposed Technology
39. Fabric Softener Active
Attempts to make a liquid product
Additives (solubilizers emulsifiers)
Additional solvent
Highly unsaturated fatty acid raw materials
Partially hydrogenated fatty acids
Fatty Acid Blends
None of these reached the goal!
Consumer Specialties | Business Line Household Care
Page | 39
40. Making a Liquid Active at RT
with Appropriate Synthesis Conditions
Clear, liquid, easy-to-process
TEA ester quat
Liquid at room temperature
Ethanol solvent
Freeze/thaw stable
Dispersible at room temperature
No heating (or cooling) required
As low as 18 °C
Robust formulation range
Formulates from 5% to 20% actives
Base formulas are stable
Softening equal to competitive
products
Consumer Specialties | Business Line Household Care
Page | 40
41. REWOQUAT® WE 45*
Physical/Chemical Property Comparison
Improved Ester
Quat*
Amidoamine Quat
Traditional Ester
Quat
Appearance @ 25 °C
(77 °F) Clear Liquid Opaque Liquid / Paste Solid
Quaternary 84-88% 89-91% 89-91%
Flash Point 24 °C (76 °F) 24 °C (76 °F) 24 °C (76 °F)
Consumer Specialties | Business Line Household Care Page | 41
42. REWOQUAT® WE 45*
Physical/Chemical Property Comparison
Improved Ester
Quat*
Amidoamine Quat
Traditional Ester
Quat
Appearance @ 25 °C
(77 °F) Clear Liquid Opaque Liquid / Paste Solid
Quaternary 84-88% 89-91% 89-91%
Flash Point 24 °C (76 °F) 24 °C (76 °F) 24 °C (76 °F)
Storage Temperature 20 °C (68 °F) 38 °C (104 °F) 45 °C (113 °F)
Pumping Temperature 25 °C (77 °F) minimum
45 °C (113 °F)
minimum
55 °C (131 °F) minimum
Consumer Specialties | Business Line Household Care Page | 42
43. Fabric Softeners
Using a Low Temperature Dispersible Quat
Rinse Cycle Fabric Softeners:
1. Quats are heated and homogenized
-
-
“heat” quat to T °C
T °C
Homogenize
Consumer Specialties | Business Line Household Care Page | 43
44. Fabric Softeners
Using a Low Temperature Dispersible Quat
Rinse Cycle Fabric Softeners:
1. Quats are heated and homogenized
2. Dispersed into warm water
T °C
Disperse quat
into water at T °C; mix
Consumer Specialties | Business Line Household Care Page | 44
45. Fabric Softeners
Using a Low Temperature Dispersible Quat
Rinse Cycle Fabric Softeners:
1. Quats are heated and homogenized
2. Dispersed into warm water
3. Cooled down while mixed
t °C
Cool to t °C; mix
Consumer Specialties | Business Line Household Care Page | 45
46. Fabric Softeners
Using a Low Temperature Dispersible Quat
Rinse Cycle Fabric Softeners:
1. Quats are heated and homogenized
2. Dispersed into warm water
3. Cooled down while mixed
4. Fragrances and other additives are added
Add dye, fragrance, etc.;
mix thoroughly
Consumer Specialties | Business Line Household Care Page | 46
47. Fabric Softener Dispersion
Lab Batch Process – Timeline
Traditional Ester Quat
Heat Water and Quat
EVONIK TEA Ester Quat
Consumer Specialties | Business Line Household Care
Cool
Quat Salt Fragrance
Preservative
Quat Salt Fragrance
Preservative
Time
(min)
20 40 60 80 100
Time
(min)
20 40 60 80 100
Page | 47
48. Fabric Softener Dispersion
Softness Evaluation
Panel Testing PHABROMETER® - Nu Cybertek, Inc.
Consumer Specialties | Business Line Household Care
Page | 48
49. Fabric Softening Performance Comparison - Panel
120
100
80
60
40
20
0
Control EVONIK Brand A
Consumer Specialties | Business Line Household Care
Softness Score
Fabric Softener Dispersion
Softening Performance – Panel Test
Methodology – Panel Test and
Statistics
Fabric samples prepared according
to ASTM Method D 5237
Statistical differences reported at
95% confidence level (Friedman
Simple Rank)
Brand A is based on TEA Ester
Quat technology
Softer
EVONIK TEA Ester Quat and Brand A are statistically equal
Page | 49
50. Fabric Softener Dispersion
PHABROMETER® - Force vs. Displacement
Extraction Curve(s) for Class: Unknown
Evaluation Type: Hand
Density Type: Heavy Fabric (H) 3440 μg/cm
2.5
2
1.5
1
0.5
0
1
5
9
13
17
21
25
29
33
37
41
45
49
53
Control REWOQUAT® WE 45 Brand A
57
61
65
69
73
77
81
85
89
93
97
101
105
Force
Displacement
Consumer Specialties | Business Line Household Care Page | 50
51. Fabric Softening Performance Comparison - PHABROMETER
140
130
120
110
100
90
80
70
Control Brand A EVONIK
Consumer Specialties | Business Line Household Care
Softness Score
Fabric Softener Dispersion
Softening Performance – PHABROMETER®
PHABROMETER® – Nu
Cybertek, Inc.
Quantitative fabric softness
comparison
Fabric samples prepared
according to ASTM Method D
5237
Average of five replicates per
sample
Statistical differences reported at
95% confidence level
Brand A is based on TEA Ester
Quat technology
Softer
EVONIK TEA Ester Quat and Brand A are statistically equal
Page | 51
52. REWOQUAT® WE 45
Summary
REWOQUAT® WE 45 offers
Potential cost savings for
Storage and handling
Processing
Energy use cycle time
Formulation flexibility and performance
Ability to produce both non-concentrated and ultra formulas
Stable formulations from 5% to 20%
Softening and anti-stat equal to other ester quats
Patent pending technology
Consumer Specialties | Business Line Household Care Page | 52
53. Dryer Sheet Quats
Chemistry, Improved Biodegradability
Performance Test
Consumer Specialties | Business Line Household Care Page | 53
55. VARISOFT® Dryer Sheet Quats
Antistatic Testing Equipment (ASTM D 5237)
Static Decay Meter
Humidity Chamber
Consumer Specialties | Business Line Household Care Page | 55
56. VARISOFT® Dryer Sheet Quats
Antistatic Test Results
4.00
3.50
3.00
2.50
2.00
1.50
1.00
0.50
0.00
National Brand VARISOFT® DS 355 VARISOFT® DS 362
Static Decay Time (s)
Antistatic tests performed on polyester fabrics (ASTM Method D 5237)
Shorter decay times indicate better performance
Control samples exceeded 300 seconds (not shown on graph)
Product coating weights were 1.4 grams
Consumer Specialties | Business Line Household Care Page | 56
57. Ethoxylated Quats
1. Antistatic Sprays
2. Cleaner blends
Consumer Specialties | Business Line Household Care Page | 57
58. Ethoxylated Quats
Antistatic Sprays
Product
Actives
(%)
R
(C2H5O)xH N+ (C2H5O)yH
R’
x+y R R’ Counter Ion
Adogen 66 100 15 CH2CH3 Tallow Ethyl Sulfate
Variquat
K 1215
100 15 CH3 Coco Methyl Chloride
Rewoquat
CPEM
100 5 CH3 Coco Methyl Sulfate
Variquat
638
100 2 CH3 Coco Methyl Chloride
Consumer Specialties | Business Line Household Care Page | 58
59. Antistatic Spray Performance:
Ethoxylated Quats Work Well
50.00
40.00
30.00
20.00
10.00
0.00
0.25
0.20
0.15
0.10
0.05
0.00
Static Guard Varisoft 137 90 Varisoft 222 LM
Static Decay Time (s)
Static Guard Varisoft 137 90 Varisoft 222 LM
90
90
WE 45 Rewoquat
WE 45 Rewoquat
CPEM
CPEM
Adogen 66
Static Decay Time (s)
Adogen 66
Consumer Specialties | Business Line Household Care Page | 59
60. Ethoxylated Quats
1. Antistatic Sprays
2. Cleaner blends
Consumer Specialties | Business Line Household Care Page | 60
61. Car Care Basics and Challenges
-
Drying
Rinsing
Cleaning
Hannah Carwash System
Consumer Specialties | Business Line Household Care Page | 61
62. Car Care Basics and Challenges
Cleaning
-
Major Factors of Cleaning
1. Mechanical energy
Most carwashes do not use brushes anymore to protect the car
finish
“Touchless” systems are getting more popular
2. Time
Longer reaction time: better cleaning, but higher chance of
damaging the car finish
Longer time → less capacity → time is money
3. Temperature
Higher temperature: better cleaning, but higher chance of
damaging the car finish, higher energy cost
4. Chemistry
Most important factor
Should be highly efficient, safe, economical
Environmental friendly: minimum waste (water/chemical)
Consumer Specialties | Business Line Household Care Page | 62
63. Car Wash: Step I
1. Removal of contaminants by using surfactants:
Water
Oil
Paint
Consumer Specialties | Business Line Household Care Page | 63
64. REWOQUAT® CQ 100 G
Multipurpose Surfactant Blend
Composition
Specialty blend of cationic and nonionic surfactants
Performance
Excellent degreasing and soap scum removal
Good emulsification, anti-redeposition
Provides antistatic property
Easy rinsing, quick drying
Imparts gloss
Ease of Formulation
Good surfactant compatibility (even with anionics)
100% active liquid, easy to process
No solvent or hydrotrope needed
Moderate foaming
High/low pH, temp., hard/soft water
Consumer Specialties | Business Line Household Care Page | 64
65. REWOQUAT® CQ 100 G
Hard Surface Cleaning Results
Improved Detergency Degreasing
Kitchen soil Soap scum Engine soil
Rating
“2”
National Brand
All Purpose
Cleaner
10.9 % active
Rating
“8”
CQ 100 G based
All Purpose
Cleaner
2.0 % active
Rating
“3”
National Brand
Tub Tile Cleaner
3.5 % active
Rating
“8”
CQ 100 G based
Tub Tile
Cleaner
1.0 % active
Rating
“2”
National Brand
Traffic Film
Remover
10.9 % active
Rating
“9”
CQ 100 G based
Traffic Film
Remover
2.0 % active
Consumer Specialties | Business Line Household Care Page | 65
66. Rinsing (Anionic Scavengers)
1. Car Care
2. Fabric Care
Consumer Specialties | Business Line Household Care Page | 66
67. Car Wash: Step II
2. Rinsing with water:
Water film adheres to the surface upon washing and rinsing
Water
- - - - - - - -
Paint
Consumer Specialties | Business Line Household Care Page | 67
68. Car Care Basics and Challenges
Rinsing
-
Major Challenges
1. Anionic surfactants are efficient cleaners, but difficult to rinse
them off from surfaces.
2. Carry over anionics can react with quaternary emulsifiers –Car
care drying agents will work less efficiently
3. Insoluble soap scums ruin the final aesthetics
Step 1.
Cleaning
(Anionic)
Step 2.
Rinsing
(Water)
Step 3.
Drying -
Softening
Anionic carry over Insoluble scum
Consumer Specialties | Business Line Household Care Page | 68
69. Anionic Scavengers - Softergents
Mechanism
Anionic surfactant
Anionic
surfactant
Anionic surfactant
Cationic emulsifier
Scavenger (monoquat)
Scavenger (diquat)
Inactive, insoluble
Inactive, soluble
Net positive charge
Active, soluble (cationic emulsifier)
A
B
C
Consumer Specialties | Business Line Household Care Page | 69
70. Rinsing (Anionic Scavengers)
1. Car Care
2. Fabric Care
Consumer Specialties | Business Line Household Care Page | 70
71. Anionic Scavengers – Softergents
Chemistry
Recommendations:
• Use level:
Depending on rinse efficiency
Use at least the same amount as the anionic carry-over concentration
• Chemistry:
Monoalkyl diquats are the most efficient
CH3 Cl
N CH3 Cl
R
CH3
N
R
CH3
CH3
Cl
N
CH3
CH3
CH3
R
(CH2-CH2-O)xH
N
CH3
2CH3OSO3
(CH2-CH2-O)yH
(CH2-CH2-O)zH
N
CH3
R = tallow, x, y, z 1
Consumer Specialties | Business Line Household Care Page | 71
72. Drying, Protection
1. Theory and Practice
2. Organomodified Silicones
3. Traditional and Biodegradable Systems
Consumer Specialties | Business Line Household Care Page | 72
73. Car Care Basics and Challenges
Drying
-
Major Factors of Drying
1. Cleaned cars have a thin water film which sticks
strongly to the surface
2. Manual (towel) drying is very inefficient, slow and costly
3. Blow drying is inefficient due to the stubborn water film
4. Water needs to be beaded for
Easy and quick water removal
Dryer, shinier cars
Customers associate semi-wet cars with poor
cleaning: they can easily be resoiled, water droplets
leave spots after drying
Consumer Specialties | Business Line Household Care Page | 73
74. Drying Agents / Rinse Aids
What are they?
They are oil in water microemulsions containing emulsifiers, hydrophobes,
solvents/coemulsifiers and water
How do they work?
They are diluted and sprayed on wet surfaces to make the surface hydrophobic
and to enhance the removal/draining of water
Consumer Specialties | Business Line Household Care Page | 74
75. Drying Aids/Protectants:
Microemulsions of Cationic Emulsifiers and Oils
water film 1. Water film adheres
surface
Consumer Specialties | Business Line Household Care
to the surface upon
washing and rinsing
Water
- - - - - - - -
Paint
Vehicle Rinse Aids
Page | 75
76. Drying Aids/Protectants:
Microemulsions of Cationic Emulsifiers and Oils
water film
Consumer Specialties | Business Line Household Care
rinse aid
2. Sprayed -on rinse aid
penetrates through water film
and spreads over the surface
surface
1. Water film adheres to
the surface upon
washing and rinsing
Water
+
+
+ + +
+
+
+
- - - - - - - -
Paint
+ +
+
+
++ +
+
+
+ +
+
Page | 76
77. Drying Aids/Protectants:
Microemulsions of Cationic Emulsifiers and Oils
water film
surface
Consumer Specialties | Business Line Household Care
hydrophobic film
water film
rinse aid
3. Rinse aid displaces
water film, deposits
hydrophobes (Sheeting)
2. Sprayed-on rinse aid
penetrates through water
film and spreads over the
surface
1. Water film adheres to
the surface upon
washing and rinsing
Water
+
+
+
- - - - - - - - + + + + + +
Paint
+ +
+
+
++ +
Page | 77
78. Drying Aids/Protectants:
Microemulsions of Cationic Emulsifiers and Oils
water film
surface
1. Water film adheres to
the surface upon
washing and rinsing
hydrophobic film
Consumer Specialties | Business Line Household Care
hydrophobic film
water film
rinse aid
water droplets
3. Rinse aid displaces
water film, deposits
hydrophobes (Sheeting)
2. Sprayed-on rinse aid
penetrates through water
film and spreads over the
surface
Water beads up, smaller
droplets combine to bigger ones
(Beading) and removed by
a blower
Water
+-+ +- +-+ +- +- + -+ +- + +-
Paint
Page | 78
79. Increasing the Contact Angle
Why is It Beneficial?
θ
1
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A1
B1
θ
2
A2
B2
If the contact angle increases: θ
2θ
1
the face area increases: A2A1
higher droplet profile (“larger sail”), easier water removal by the blower or driving
wind
the footprint decreases: B2B1
less contact between the droplet and the surface: less sticking, easier
water removal by the blower or driving wind
Page | 79
80. Drying, Protection
1. Theory and Practice
2. Organomodified Silicones
3. Traditional and Biodegradable Systems
Consumer Specialties | Business Line Household Care Page | 80
81. Organomodified Silicones
Compatibility Chart
Siliconophilic
Alkylsiloxanes
Hydrophilic Lipophilic
Polyether-siloxanes
Ionic Siloxanes
Silicone Oil
Alkylpolyether-siloxanes
Consumer Specialties | Business Line Household Care Page | 81
82. Page | 82
Basics of Silicone Quats
+
+ /
+ +
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83. Silicone Quats
Strong Bond Between Surface and Molecule
Consumer Specialties | Business Line Household Care Page | 83
84. Silicone Quats
Strong Bond Between Surface and Molecule
Surface
Consumer Specialties | Business Line Household Care Page | 84
85. Silicone Quats
Strong Bond Between Surface and Molecule
Two anchor points
Silicone Backbone
Surface
Consumer Specialties | Business Line Household Care Page | 85
86. Silicone Quats
Strong Bond Between Surface and Molecule
Two anchor points
Silicone Backbone
Surface
TEGOPREN® 6922 (shorter silicone backbone)
TEGO® Polish Additiv Q70 (longer silicone backbone)
Consumer Specialties | Business Line Household Care Page | 86
87. Silicone Quats
Miracles Can Happen…..
What a difference!!! ☺
Consumer Specialties | Business Line Household Care Page | 87
88. Drying, Protection
1. Theory and Practice
2. Organomodified Silicones
3. Traditional and Biodegradable Systems
Consumer Specialties | Business Line Household Care Page | 88
89. Drying Agent / Rinse Aid Trends
HISTORICAL EVOLVING
Fast drying
Spot free
surface
Visual:
Aesthetics
Low price
Unlimited water
Environmental,
Safety concern
is low
Nitrile Quats
Mineral Seal Oil
Fast drying
Spot free surface
Visual cues
Competitive price
/ performance
Waste water
restrictions
Environmental,
Biodegradability,
Safety issues
New regulations
Ester Quats
Ester Oils
PERFORMANCE
ENVIRONMENTAL
FORMULATIONS
Consumer Specialties | Business Line Household Care Page | 89
90. Biodegradable Rinse Aids
Drying and Protection of Surfaces
Goal:
Develop an emulsifier that enables the formulation of rinse aids/drying
agents to address the needs of the evolving market
Biodegradability
Environmental friendliness (low aquatic toxicity)
Formulation versatility (for both traditional and biodegradable ingredients)
Water reclaim system friendly formulations (due to droughts)
Performance: improved drying/protection for less spotting
Safety: low toxicity
Raw materials from renewable resources
Price/performance advantages
Consumer Specialties | Business Line Household Care Page | 90
91. Traditional and New Emulsifiers
Dialkyl Quats:
good performance, stable products
low biodegradability
(high di-fatty-alkyl content)
Ester Quats:
TEA type:
medium performance, limited formulas
good biodegradability, low toxicity
(1:2:1 mixture of mono-, di- and tri-fatty-alkyl ratio)
MDEA type:
good performance, versatile formulas
good biodegradability, low toxicity
(enhanced di-fatty-alkyl content)
CH3
R N R
CH3
R=Fatty Alkyl
CH3
O O
N
(+ monoquat and triquat)
(R = Fatty Alkyl)
CH3
X
O
-
X
X
OH
O O
N
CH3
O
R
R
O
O
R
R
(+ monoquat)
(R = Fatty Alkyl)
Consumer Specialties | Business Line Household Care Page | 91
92. Traditional and New Hydrophobes
Mineral Seal Oil:
good performance, stable products
low biodegradability
unpleasant odor (aromatics)
source dependent characteristics
Ester Oils:
Alkyl Laurate, Palmitate, Stearate, etc.
good performance, versatile formulas
good biodegradability
low toxicity
low odor
Aliphatic petroleum naphtas
(Middle distillate)
O
R O
R'
R = Fatty Alkyl
R'=straight or branched Alkyl C5
Consumer Specialties | Business Line Household Care Page | 92
94. Readily Biodegradable Emulsifier
Carspray 800
MDEA Ester Quat emulsifier for vehicle rinse aids/drying agents
to address the needs of the evolving market:
Readily Biodegradable
Environmental friendly, safe (low toxicity)
Formulation versatility (for both traditional and
biodegradable ingredients)
Water reclaim system friendly formulations
Performance: improved drying/protection for less
spotting
Raw materials from renewable resources
Price/performance advantages
Patented technology
O O
N
CH3
-
O
R
O
R
CH3
(+ monoquat)
(R = Fatty Alkyl)
X
Consumer Specialties | Business Line Household Care Page | 94
95. Acknowledgements
BL Household Care – Hopewell, Virginia
• Dennis Parrish
• Miyako Hisamoto
• Gonglu Tian
• Erin King
• Jennifer Goodyear
• Saiid Mohammed
• Phuong Le
• Dana Nystrand
Evonik Industries – Janesville, WI, Mapleton, IL
BL Household Care – Hanau, Germany
Interfacial Technology – Essen, Germany
Evonik Degussa Brasil Ltda
Consumer Specialties | Business Line Household Care
Page | 95