Borchers - How To Formulate MEKOfree Alkyds and Achieve High Performance

How to Formulate MEKO-free Alkyds
and Achieve High Performance

Allison Musto
Technical Service Manager, Europe
5 October 2021
1 | Copyright © 2021 Milliken & Company. All rights reserved

Agenda
Revival of Alkyds & Need for Anti-Skins
Replacing MEKO & Regulatory Challenges
Reformulation Paths
Summary & Questions

Revival of Alkyd Paints
CAN BE USED ACROSS A VARIETY OF SEGMENTS
Advantages of alkyd paints: Architectural
• Bio-renewable
• Cost-effective
• Stable with long shelf lives
• Provide relatively hard films Wood Coatings General Industrial
• Good stain block properties
Alkyd formulations are dependent on cobalt
for curing & MEKO for storage stability
• Alkyd-based coatings dry via autoxidation when

oxygen reacts with points of unsaturation based on
fatty acids in the resin
• Driers such as cobalt and high-performance catalysts

are utilized to speed up the curing process
• Driers reactive to oxygen require an anti-skin agent

to prevent the paint surface from forming a film
called skin

Need for an Anti-Skinning Agent
In a container, a solid layer forms on top of the

liquid coating (common in oxidatively cured
coatings, high solids, and low VOC)
without anti-skin with anti-skin

Types of Anti-Skinning Agents
1. Volatile – Ketoximes & 2. Non-Volatile – Amine Type &

Complexing Agents Phenolics
• Prevent skin formation in closed • Prevent skin formation in closed

containers containers
• Little to no effect on drying • Stay in the film and negatively
performance affect through drying
• Toxic
• Not efficient with cobalt replacements

Why are MEKO-free Anti-skin
Agents Needed?
Europe, Canada, and other nations have proposed reduction
levels of MEKO (Methyl-ethyl-ketoxime = 2-Butanone oxime)
in alkyd paints
• Carcinogenic & sensitizer
• Will be classified as a 1B carcinogen, effective March 1, 2022,

with a concentration limit at ≥ 0.1% (European Commission:
ATP 15 part 3 Annex VI)
This means that MEKO cannot be utilized in any

formulation which meets or exceeds the
concentration limits
The Troubling Cobalt Regulatory Trend
• Stricter cobalt regulations have been proposed over the years

• Full restriction of certain cobalt salts is expected by 2023
• Cobalt availability and pricing are in flux

2023
•Full restriction of five
cobalt salts
2020
•Self Classification / EU
and Global (five cobalt
2019 salts)
• ECHA Carcinogenicity •CI Acute Inhalation
(all routes) •Transportation (Co
2018 •CI Skin Sensitization and Dihydroxide)
•CI Reproductive Toxicity Absorption
•CI Food Contact •Reproductive Toxicity
2017 CoS, CoCl, Co Oxalate
•REACH Restriction of
•Cobalt Institute (CI) five cobalt salts
Workplace Exposure
2016 •Inhalation
•Mutagenicity (CLH Carcinogenicity
proposal)

Paths to Reformulate
Alkyds Containing MEKO

Potential Project Paths
PATH #2: MEKO-FREE +

PATH #1: MEKO-FREE HIGH-PERFORMANCE
COBALT-FREE CATALYST
✓
❑ Labeling MEKO-free ✓
❑ Labeling MEKO- and Cobalt-free
✓
❑ Reformulation required ✓
❑ Enhanced performance
❑ Potential reformulation in the ✓

❑ Complexity reduction
future to remove cobalt
✓
❑ Only one reformulation process
Double
work!

Why Replace Cobalt and MEKO Together?
• Cobalt and its salts are classified as carcinogens and may

be regulated out of use
Cobalt-
• Removing labeling from the products free
One
• Improving the general performance of the system Reformulation
Process
• Cobalt alternative driers work differently than cobalt – MEKO-

the anti-skin requires new evaluation free
• Cobalt works well in combination with MEKO, but to

replace MEKO, a new anti-skin evaluation is necessary

Formulating
MEKO-free
NOT A DIRECT 1:1 REPLACEMENT FOR MEKO
• Calculated as supplied on total formula weight

• Recommended dosage varies from 0.2 – 2%
• Too much anti-skin can inhibit dry performance

Formulating MEKO-free
MEKO-FREE REFORMULATION PROCESS
• Choose Step 2 • Measure dry

reformulation times & skin
path (MEKO- • Set up ladder performance,
free only or study evaluating as well as other
MEKO- and all product lines important
Cobalt-free) (each one parameters
interacts slightly
Step 1 different)
Step 3

Anti-Skinning Testing Method
Make sample and store overnight in Flacktek Check after 1 week by tilting vial, but do
cup not open
If skinning is noted after 24 hours, sample is

After 4 weeks, remove from oven
eliminated
and open jar
If there is no skinning, place in glass vial

with 1” head space Make final skinning measurement
Store in 50°C oven

Note any color change over time

Anti-Skinning Testing Method
SKIN RATING SYSTEM

Level Description
0 No visible changes
1 Very thin skin, hardly visible
2 Thin skin
3 Medium thick skin
4 Hard skin
5 Very hard skin
6 No skin, but gelling throughout can

Path #1: MEKO-free
Cobalt-containing Formula

Borchers’ MEKO-Free Anti-Skinning Agents
• Amino compound dissolved in

1,2-propanediol
Ascinin® • Phenol, Oxime & MEKO-Free
• Amino compound Anti-Skin • Waterborne / Solvent borne
dissolved in fatty acid 0445
ester
• Phenol, Oxime &
MEKO-Free
• Solvent borne Ascinin® Ascinin®
Anti-Skin Anti-Skin • Amino compound
0444 1240 dissolved in fatty
MEKO acid ester
-Free • Oxime & MEKO-Free
• Solvent borne
• Cyclohexanone oxime
• MEKO replacement Borchi®
Borchi®
• Minimal impact on Nox
Shield • New anti-skin product
drying times 1640 • Oxime-containing
• Solvent borne • Minimal impact on
drying times
• Solvent borne
• Highly effective antioxidants for solvent borne,

high solids alkyds systems and printing inks
Ascinin® Anti-Skin 0444
• Recommended to work with High-Performance
Catalysts (Borchi® OXY-Coat and Borchi® Dragon)
• The optimum level should be experimentally

Ascinin® Anti-Skin 0445 determined
• Overdosing may lead to longer drying times
• Recommended dosages:
• 0444: 0.2-0.6%
Ascinin® Anti-Skin 1240
• 0445: 0.2-0.6%
• 1240: 0.25-1% (higher volatility than 0444 &
0445)

• Higher volatility than Ascinin® products
Borchi® Nox 1640 • Minimal impact on dry times
• Recommended dosage: 0.2-1.5%

• Designed to prevent skin in high solids and long oil

systems with reduced VOC
• Synergistically designed for use with Borchi®

Dragon High-Performance Catalyst
Borchi® Shield
• Minimal impact on dry times
• Higher volatility than Ascinin® products
• Recommended dosage: 0.2-1%

Evaluation of MEKO-free Anti-skin with Cobalt Formula
Ascinin® Anti- Ascinin® Anti-

Skin 0444 Skin 1240
0.2% 0.4% 0.6% 0.25% 0.5% 1%
Ascinin® Anti-
Borchi® Shield
Skin 0445
0.2% 0.4% 0.6% 0.25% 0.5% 1%

Replacing MEKO with Ascinin® Anti-Skin 1240
L* b*
b*
L*
MEKO free No impact

formulation on color
Ingredient Control Ascinin®

Anti-skin 1240
Supplied Ascinin® Anti-
Ascinin ®
Supplied Control (MEKO) Ascinin

Ascinin
® Anti-Skin
® Anti-Skin 1240 Control Skin 1240
Anti-Skin
System 1 100.00 100.00 1240 (MEKO) 1240
12% Cobalt 0.15 0.15

Dry Time in Standard Conditions and Loss of Dry
4.5
5% Calcium 0.38 0.38 4.13
4
12% Zirconium 0.54 0.54 3.5 3.13
3
MEKO 0.32 2.38 2.25 2.25
2.5 2.13
1.88
2 1.63
Ascinin® Anti-Skin 1240 0.50 1.38 1.5 1.38
1.5 1.13
1
total: 101.39 101.57
0.5
0
Set to Touch Tack Free Through Dry Set to Touch Tack Free Through Dry
Control (MEKO) Ascinin Anti-Skin 1240
Ascinin® Anti-skin 1240
Standard (25C/50%RH) Loss of dry (14 days at 50C)

Path #2: MEKO-free and Cobalt-free
Introducing High-Performance
Catalysts to the Formulation

High-Performance Catalysts
• Patented organometallic ligand technology
Borchi®
OXY-Coat • Faster dry times than cobalt-based driers
• Excellent performance under adverse conditions
• Improved loss of dry over stability testing

High- Borchi®
Borchi®
Dragon
Performance OXY-Coat • Non-yellowing upon aging or initial
Catalysts 1310
• Reduced need for secondary driers & anti-skins
• Non-wrinkling with high solids systems (thick

film)
Borchi®
OXY-Coat
1101 • Cobalt-free

High-Performance
Catalysts in Alkyds
CAN BE USED IN:
• Solvent borne
• Waterborne
• Solvent borne, high solids, low VOC

Cobalt-free & MEKO-free – Evaluation Process
Secondary driers
addition if needed
Secondary Driers
(optional)
• Borchi® OXY-Coat • Ascinin® 0444,
• Borchi® Dragon 0445, 1240
• Zirconium Cobalt-free and
• Borchi® Shield
• Zinc
• Borchi® Nox 1640 MEKO-free
• Calcium Formulation
Ladder Study of
MEKO-free Anti-
High-Performance
Skin Ladder Study
Catalyst
Optimization and Evaluating different

determining the dosage dosages of anti-skins

Replacing Cobalt & MEKO with Cobalt- & MEKO-free
EXCELLENT SKIN PREVENTION
Skin forming in
jars that are
open/closed
daily No skin in
open/closed
jars
Control (Cobalt & MEKO) Cobalt- & MEKO-free

Path #2: MEKO-free and Cobalt-free
Specific Applications &

Additional Benefits Beyond Skin
Prevention

Replacing Cobalt & MEKO with Borchi® OXY-Coat & Ascinin® Anti-Skin 1240
Solvent borne high gloss white trim paint for decorative use
Cobalt & MEKO free
formulation Drying Time (hours)
20.00
17.50
18.00
Ingredients Control Borchi® OXY-Coat 16.00 Faster drying times
14.00 12.50
12.00 10.25
10.00
100.00 100.00 8.00
Long Oil White Paint 5.25 5.00 5.25
6.00
4.00
0.46 Eliminated Zr
15% Co/Zr Carboxylate Blend 2.00
0.00
0.46 0.92 Control 0.5%®BOC
0.5% Borchi OXY-Coat
0.5% Borchi® OXY-Coat
10% Ca Carboxylate
Set to Touch Tack Free Dry Hard
0.23
Borchi® OXY-Coat
Cobalt Control Borchi® OXY-Coat Yellowing Stability over 2
0.31
MEKO Months (b*)
6 5.62
0.50
Ascinin® Anti-Skin 1240 5 Decreased yellowing
4
101.230 101.650 3 2.35
2.02
1.53
total 2
1
• Arkema Synolac 4060 WP 90 – 90% solids long oil alkyd 0
• 46% resin solids in paint Control Borchi ®Oxy Coat
® OXY-Coat
Borchi OXY-Coat
Dark aged color
Initial Aged
29 | Copyright © 2021 Milliken & Company. All rights reserved (2 months)
Replacing Cobalt & MEKO with Borchi® Dragon & Borchi® Shield
Spray application - direct to metal
Cobalt and MEKO free Dry Hard at Different Conditions (minutes)

formulation 50.00 44.50
45.00 Faster cure in adverse conditions
40.00
35.00 32.50
30.00
Dragon + Dragon + 30.00
Ingredients Control 24.50
MEKO Shield 25.00 19.50 19.00
20.00
15.00
10.00
Short Oil Paint 100.00 100.00 100.00 5.00
0.00
10% Cobalt 0.30 Control Dragon + MEKO Dragon + Shield
12% Zirconium 0.30 Lowered Standard (25C/50%RH) Adverse (10C/80%RH)

Adverese
Borchi® Dragon 0.13 0.13 drier dosage

Initial Color Data (b*)
10% Calcium 0.30 0.26 0.26
1.4 1.29
MEKO 0.50 0.25 1.2 Decreased yellowing
Borchi® Shield 1.10 1
0.79
0.8
101.40 100.65 101.50 0.56
total 0.6
0.4
• Short oil alkyd topcoat based on linseed oil and other oils 0.2
50% reduction in
• 27% resin solids in paint
MEKO dosage 0
Control Dragon + MEKO Dragon + Shield
Replacing Cobalt & MEKO with Borchi® OXY-Coat
Solvent borne wood care products for interior & exterior
Cobalt and MEKO free Dry Times (hours)

formulation 30
25
24 24 Significantly faster drying
Borchi® OXY-
Ingredients Control 20
Coat 15
10 9
10 7
Wood Stain 100.00 100.00 5
5
10% Mn Carboxylate 0.25 0

Elimination of Control Borchi OXY-Coat
Borchi®Oxy Coat
10% Co Carboxylate 0.16 additional driers

Set to Touch Tack Free Dry Hard
12% Zn Carboxylate 1.80
0.15 Control Borchi® OXY-Coat

Borchi® OXY-Coat Drying time greater than 24 hours Drying time less than 10 hours
0.20
MEKO
102.41 100.15
total
• Long oil alkyd wood stain

• 25% resin solids in paint Anti-skin free formulation

Summary & Conclusion
Replacing MEKO and cobalt at once meets upcoming regulatory requirements

without sacrificing performance
Using HPC and MEKO-free anti-skinning agents together

provides:
• Saved time and resources when replacing MEKO
• Faster dry times
• Improved performance under adverse conditions
• Better color initially / non-yellowing of coatings
• Formula complexity reduction
Formulations that improve paint labeling:
• Cobalt-free
• MEKO-free
“Future-proofing” alkyd formulations

to meet global regulatory requirements
Thank You!
Allison Musto
Technical Service Manager, Europe
allison.musto@borchers.com

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How to Formulate MEKO-free Alkyds

and Achieve High Performance

1 | Copyright © 2021 Milliken & Company. All rights reserved

Revival of Alkyds & Need for Anti-Skins

Replacing MEKO & Regulatory Challenges

Summary & Questions

2 | Copyright © 2021 Milliken & Company. All rights reserved

CAN BE USED ACROSS A VARIETY OF SEGMENTS

Advantages of alkyd paints: Architectural

• Alkyd-based coatings dry via autoxidation when

• Driers such as cobalt and high-performance catalysts

• Driers reactive to oxygen require an anti-skin agent

4 | Copyright © 2021 Milliken & Company. All rights reserved

In a container, a solid layer forms on top of the

without anti-skin with anti-skin

5 | Copyright © 2021 Milliken & Company. All rights reserved

1. Volatile – Ketoximes & 2. Non-Volatile – Amine Type &

• Prevent skin formation in closed • Prevent skin formation in closed

6 | Copyright © 2021 Milliken & Company. All rights reserved

• Carcinogenic & sensitizer

• Will be classified as a 1B carcinogen, effective March 1, 2022,

This means that MEKO cannot be utilized in any

• Stricter cobalt regulations have been proposed over the years

• Cobalt availability and pricing are in flux

8 | Copyright © 2021 Milliken & Company. All rights reserved

9 | Copyright © 2021 Milliken & Company. All rights reserved

PATH #2: MEKO-FREE +

❑ Potential reformulation in the ✓

10 | Copyright © 2021 Milliken & Company. All rights reserved

• Cobalt and its salts are classified as carcinogens and may

• Cobalt alternative driers work differently than cobalt – MEKO-

• Cobalt works well in combination with MEKO, but to

11 | Copyright © 2021 Milliken & Company. All rights reserved

• Calculated as supplied on total formula weight

12 | Copyright © 2021 Milliken & Company. All rights reserved

MEKO-FREE REFORMULATION PROCESS

• Choose Step 2 • Measure dry

13 | Copyright © 2021 Milliken & Company. All rights reserved

If skinning is noted after 24 hours, sample is

If there is no skinning, place in glass vial

Store in 50°C oven

14 | Copyright © 2021 Milliken & Company. All rights reserved

SKIN RATING SYSTEM

15 | Copyright © 2021 Milliken & Company. All rights reserved

16 | Copyright © 2021 Milliken & Company. All rights reserved

• Amino compound dissolved in

• Highly effective antioxidants for solvent borne,

• The optimum level should be experimentally

• Overdosing may lead to longer drying times

18 | Copyright © 2021 Milliken & Company. All rights reserved

• Higher volatility than Ascinin® products

Borchi® Nox 1640 • Minimal impact on dry times

• Recommended dosage: 0.2-1.5%

19 | Copyright © 2021 Milliken & Company. All rights reserved

• Designed to prevent skin in high solids and long oil

• Synergistically designed for use with Borchi®

• Higher volatility than Ascinin® products

• Recommended dosage: 0.2-1%

20 | Copyright © 2021 Milliken & Company. All rights reserved

Ascinin® Anti- Ascinin® Anti-

0.2% 0.4% 0.6% 0.25% 0.5% 1%

0.2% 0.4% 0.6% 0.25% 0.5% 1%

21 | Copyright © 2021 Milliken & Company. All rights reserved