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Coatings Trends and TechnologiesSeptember 11, 2019

Linda Adamson

A New APEO-free Surfactant Solution for the Paint Can

OUTLINE Ingredients in a Paint Can

Surfactants

- Definition

- Key Features and Benefits

APE- Containing Surfactants

Move to APEO-free Surfactants

New APEO-free Surfactant

- Performance in High Quality Flat (all Acrylic)

- Performance in Premium Semigloss (all Acrylic)

- Performance in Economy Flat (PVA)

- Performance in Economy Flat (Styrene Acrylic)

Household Stain Removal

Surfactant Leaching

Summary2

ADDITIVES – Performance, Processing, Storage,

Application

Defoamer - Complex mixtures

Surfactants- Hydrophobe/Hydrophile

Dispersant- monoacid, polyfunctional acid

polymers,

Rheology modifier - Non-Associative, Associative,

cellulosic

Specialty additives - F/T, open time, adhesion

promoters, block resistance, gloss, etc.

BINDER – Continuous film, Adhesion, Durability

Acrylic – Exterior/Interior; Flat to gloss

Styrene Acrylic - Exterior/Interior; Flat to gloss

Vinyl Acrylic – Interior; Flat to gloss (blends for exterior)

VAE – Interior; flat to semi gloss (blends for exterior)

VA/VEOVA – Exterior Flat to gloss

PIGMENTATION – Appearance, Gloss, Performance

TiO2

Extenders

Colorants

Additives

LIQUID – Application and Fluidity

Water

Solvents – glycols, coalescing agents~40%

< 5%

Additives

Pigments

Binder/Resin

Liquid

~25%

~25%

Additives – components of the paint that are

added in small amount to provide special

properties to the wet paint as well as the dry film –

“Small does make a big difference”.

Waterborne Latex PaintFour key ingredient categories in latex paint

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Novecare (Confidential)

4 May 2018

Surfactants: contracted from SURFACE ACTIVE AGENTS, these are ADDITIVES which reduce surface tension of a liquid and may form micelles thereby :

improve WETTING (wetting agents)- overcome the cohesive tendency of water

help DIPSERSE pigments (DISPERSANTS)

- absorbs onto pigment and assists in its wetting in water

- facilitates wetting of gases on pigment surface which cannot be removed via grinding

inhibit foam (DEFOAMERS)

emulsify (EMULSIFERS)

- lower interfacial tension and stabilize polymer particles

Surfactants – Definition

Surfactants are classified by their charge- ANIONIC: negatively charged hydrophile

- CATIONIC: positively charged hydrophile

- NONIONIC: hydrophile with NO charge

- AMPHOTERIC: charge on hydrophile dependent upon pH

Hydrophilic Head Hydrophobic Tail

• Hydrophillic Groups - Water “loving” ,polar, soluble groups

Hydrophobic Groups - Water insoluble (hydrocarbon chain) groups4

Surfactant Features Dynamic Surface Tension Reduction

• Nature and concentration of the Surfactant determines how much the surface

tension can be reduced

• Speed of diffusion determines how fast wetting/surfactant migration will occur

Quick surface tension drop indicates quick migration of

surfactant to interfaces.

Coating systems need good leveling and flow to have an appealing appearance!

Surface Tension related paint film defects:

Orange Peel

Fish-eyes

Craters

De-wetting/Crawling

Pinholes

Silking

Product #1

Product #2

Product #3

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Surfactants in the Paint CanImprove substrate wetting

Development of Color Strength

Nonionic surfactants work best

Surfactants can help with dark rub up (colorant flocculation) or light rub up

(pigment flocculation)

Stability

Need to Monitor Use Level….

Foaming

use as little as possible

use appropriate defoamer

Water sensitivity

use as little as possible

nonionics less troublesome than anionics, but are also usually less efficient

and must be used at higher concentrations6

Substrate Wetting

Paint White “Satin” paint

Substrate Silicone release paper

Additive 1% (active) based on total paint

DD Blade with depth

of cut = 150 m (~5 mils)

Application by brush

Surfactant No Surfactant Surfactant No Surfactant

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Color Issues

Some common challenges when colorant is added to paint…

Color Float

Color Acceptance

Color Development

Poor vs. Excellent color

development and

acceptancePoor vs. Excellent resistance to colorant float

The right surfactant package in the paint formulation can help minimize or

eliminate these problems8

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Alkylphenol Ethoxylates (APE)

• Have been around a long time

• Versatile, cost effective surfactants

• Use in a wide variety of applications

Concerns• Biodegradability

- “60% minimum biodegraded within 28 days”

• Toxicity of degradation products

• Bioaccumulation

- low mole APEO’s are not water soluble

- readily absorbed onto surfaces

- can lead to accumulation and sediment in waterways

- can lead to accumulation in aquatic species

• Viewed as an Endocrine Disruptor

- chemicals that interfere with hormone systems in animals

- can cause cancerous tumors, birth defects, etc.

Structure of the hormone estradiol and one of the nonylphenols.

Move to APEO-free Surfactants

• European Parliament: APE’s cannot be used at 0.1% or greater (2003)

• Canada: Proposed regulations to reduce the use of APE’s by 95% (2010)

• EPA Directive – U.S. EPA Office of Pollution an Toxics

“EPA Adds Nonylphenol Ethoxylates to Toxics Release Inventory”

– promoting greater transparency for chemicals used in cleaners,

detergents, paints, etc.

- Effective for the 2019 TRI (Toxics Release Inventory)

Several Companies pushing for “Greener Products”: substances such as

formaldehyde, lead, and APE-containing (Alkyl Phenol Ethoxylate) surfactants

will not be allowed in finished products

• Home Depot

• WalMart

• Target

• Best Buy

• Costco

• CS Health

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Characteristic Non-ionic

Appearance Clear or slightly hazy liquid

Color Gardner 5 maximum

Density, 20°C (g/cm3) 1.01

Active content (%) 90 approx.,

Pour point 5 approx..

pH 5.0 - 7.0

Viscosity (cPs) 30 - 238

Static surface tension (mN/m), 0.1%

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VOC Content (g/L)

Benchmarking Study

Formulations to Span the Regions

50 PVC/33.5VS - All Acrylic

22 PVC/35VS - All Acrylic

70 PVC/28VS – PVA

78 PVC/32VS- Styrene Acrylic

DETAILS

- 23 Wetting Aids (3 APE, 1 Competitive APEO-free, 19

Samples)

- 3 Binder Chemistries

- 4 Formulations

- White and Tinted Paints

tested

184 Total Paints in Study

Wetting Agents were screened at 0.3% level for all formulations

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High Quality Flat - All Acrylic50.5% PVC/33.5% VS; ~22g/L VOC; HEC/HEUR

Sheen, Flow, Sag, Opacity, DPUR, Color Float - all comparable

New RHODOLINE APEO-free WA Overall Performance is Better Than

Competitive APE-containing WA while maintaining Comparable

Appearance Properties in Acrylic Flat Formulation

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Premium Semigloss – All Acrylic 22.2% PVC/35% VS; ~20 g/L VOC; HEUR

Gloss, Flow, Sag, Opacity, DPUR, Color Float - all comparable

Note: All samples scrubbed > 2000 cycles for 50% abrasive scrub

New RHODOLINE APEO-free WA Overall Demonstrates Improved

Adhesion and Colorant Stability in Semigloss Formulation compared to

Competitive APE-containing WA

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Economy Flat : PVA70% PVC/28% VS; ~12 g/L VOC; HEC/HASE

Sheen, Flow, Sag, Opacity, DPUR, Color Float - all comparable

New RHODOLINE APEO-free WA has Comparable Performance to

Competitive APE-containing WA in High PVC PVA Formulation

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Economy Flat : Styrene/Acrylic76% PVC/32% VS; ~33 g/L VOC; HEC/HASE

Sheen, Flow, Sag, Opacity, DPUR, Color Float - all comparable

New RHODOLINE APEO-free WA Demonstrates improved Stability and is

Comparable in other properties compared to

Competitive APE-containing WA in High PVC S/A Formulation

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Tint Strength Performance

New RHODOLINE APEO-free WA has Comparable Tint Strength compared

to Competitive APE-containing WA in Various Binder Chemistry/PVC R’xs

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Testing Conditions – what needs to be considered:• How the stain is applied- force of the operator

• How much of the stain is applied – uniform force

• How long the stain “sets” on the test panel- 30 minutes vs. 2 hours

• Brand of the stain- different brands use different “recipes”

• How is the stain “cleaned”- stringent cleansers, sponge/cheesecloth

• Subjective Rating System – resistance vs. removal

Performance may be influenced by• Binder itself

• Film formation

• Formulation Ingredient effects

TiO2, Extenders, Dispersants, Thickeners, Surfactants

House Hold Stain Resistance/Removal

Competitive APE WA New Rhodoline APE Containing WAAPEO-free WA

High Quality Flat - All Acrylic (50.5% PVC/33.5% VS; ~22g/L VOC; HEC/HEUUR)

Pencil

Pen

China Marker

Lipstick

Crayon

Marker

Coffee

Tea

Grape Juice

Wine

Mustard

New RHODOLINE APEO-free WA has slightly better Lipstick and Coffee

stain removal (but may be formulation dependant)

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What is Surfactant Leaching

Surfactant Leaching is the outflow of water soluble materials in the paint

traveling to the air/film interface which can result in a change of

appearance of the dried coatings.

- change in gloss of the film

- blotchy, frosted appearance

- brown residue which can remain on the surface

Also known as:

Water Staining or Spotting, Surfactant Blooming, Exudation

Cause: Migration and concentration of water-soluble species

to the surface

- May include binder/resins, surfactants, thickeners, colorants

Drying condition of film is also critical where high moisture/humidity

is present (exterior coatings, bathroom)

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Surfactant Leaching Test MethodSamples were tested via ASTM D-7190

• DD sample on black vinyl chart (~7 mils thickness)

• Allow to dry 4 hours at standard conditions ( 25oC/50% RH)

• Divide the panel into 3 sections: 4 hours/1 day/4 day dry times)

• Place a row of 4 droplets of distilled water at room temperature across the top

of the designated dry time area

• Allow the water droplets to stand for 10 minutes

• After 10 minutes, lift the panel into a vertical position so the water droplets run

down the section of the paint film being evaluated

• Visually rate the test panel immediately after lifting and after overnight drying

SCALE

1- heavy streaking, gloss change, staining

2- moderate

3- slight

4- very slight

5 -no defects

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Surfactant Leaching

Testing was done using a Neat Binder that had Excellent Surfactant Leaching

Samples were DD and tested via ASTM # 7190

Testing the films after 4 hours dry time showed the most differences

New RHODOLINE APEO-free WA has Better Surfactant Leaching compared to

Competitive APE-containing WA in a neat binder

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“New” Rhodoline® Wetting Agent Features

• APE-free Nonionic Surfactant

• Provides Excellent Wetting

• Low Foaming

• Fully compatible with all waterborne architectural binder technologies

• Zero / Low VOC capable solution

• Eco-label Compliant

Summary

“New” Rhodoline® Wetting Agent Benefits

• Offers “best in class” Tint Strength

• Provides Good Viscosity and Shelf Life Stability

• Excellent Choice to Replace APE-containing WA

- Comparable Appearance Properties in all Binder Chemistries/Formulations

- Equal or Improved Scrub Resistance

- Equal or Improved Alkyd Adhesion

- Improved Surfactant Leaching

• Fully compatible with all waterborne architectural binder technologies

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Thank you!

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Committed to YOUR coatings success!

Linda Adamson - Technical Service Manager

Linda.adamson@solvay.com

215-285-6591

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mailto:Linda.adamson@solvay.com