Overcoming Formulation Challenges for Low-VOC Interior Paints with New Binder Solutions

Last update on Oct 5, 2021

Growing concern over indoor air quality is motivating coating manufacturers to reduce or eliminate volatile organic components (VOCs) and other harmful ingredients from their formulations. VOCs are organic chemicals that have a high vapor pressure at ordinary room temperature conditions. Many VOCs are irritants that produce odor and can introduce toxic exposure concerns.

The definition of VOC from a regulatory standpoint depends somewhat on the region and application. 

  • In the US, VOCs are legally defined in the various laws and codes under which they are regulated, and different regulations exist in each state.
  • In the EU, VOC is any organic compound having an initial boiling point less than or equal to 250°C and that can damage human senses.


VOCs have been necessary components in many types of coating systems primarily to adjust viscosity, provide good coating properties, and achieve the end-use performance requirements demanded from architects and builders. VOCs are generally produced from the coalescing agents and additives used in waterborne paint systems.

Regulations limiting VOCs and other harmful additives, such as formaldehyde, are getting stricter. These are primarily enforced through:

  • The Environmental Protection Agency (EPA) in the US, and
  • The Registration, Evaluation, and Authorization of Chemicals (REACH) in the EU


These regulations are designed to limit the use of organic chemical compounds that are harmful to human health and contribute significantly to carbon emission and atmospheric ozone depletion.

VOCs can be measured either by analyzing the components that are contained in the formulation ('in-can' VOC content) or by emissions that are released into a simulated indoor environment over time. It is important to note that a 'low VOC' coating as determined by an in-can analysis and labeling may still produce harmful emissions during and after coating. 

Indoor emission limits were originally promoted by paint consumers such as educational institutions and healthcare organizations. One can expect this market trend to pick up steam throughout the entire interior paint market. As a result, an increasing number of paint manufacturers are reformulating their products to bring their indoor emissions down below mandated levels. 

Let's address the importance and measurement of interior VOCs and then introduce several new binder resins that have extremely low levels of VOC. When used in the indoor paint formulations, these binders improve indoor air quality without compromising performance properties. In addition to extremely low levels of VOCs, these binders have low odor and are free of plasticizers, alkylphenol ethoxylate (APEO), formaldehyde, and ammonia-producing materials.

Indoor Air Quality (IAQ) has Become an Important Obligation

 

VOC Emissions – Common Sources, Examples & Formula

 

Interior wall paints are recognized as a significant source of VOCs in spaces where we occupy 85-90% of our time (e.g., schools, workplaces, leisure areas, etc.). They are the origin of what has been called the 'sick building syndrome' since VOCs can be related to allergies, asthma, carcinogens, and other health issues. New buildings and freshly renovated areas especially contribute to the highest level of VOC emissions because of the abundant concentration of VOCs generated at the same time. 

Common examples of VOCs that can be present are propylene and ethylene glycol, alcohols, aldehydes, butyl propionate, and butoxyethanol among others. In waterborne coatings, the primary source of these VOCs is coalescing agents and additives such as anti-freeze agents, biocides, and amine neutralizers. 

The most widely used approach in determining VOC content in paints and for labeling is to calculate pounds (or grams) of VOC per gallon (or liter) of solution minus exempt solvents (including water and VOC-exempt organic compounds).

 

VOC = pounds of solvent – exempt solvent
           gallon of coating – exempt solvent


 

However, note that:
 

  1. No attempt is made to compare the relative ozone-generation potential of one VOC with another, and
  2. This calculation does not express the amount, rate, or type of indoor emissions during and after paint application.

Thus, 'low-VOCs' or 'no-VOCs' per the manufacturer's label is no guarantee of low or safe indoor emissions.1

 

Regulations, public pressure, and general apprehension regarding the environment have led manufacturers to reduce VOC content from 150-350 g/L to as low as 50 g/L. Concerns with interior air quality have also led to new regulations mandating reduced emission levels.
 

Interior wall paints are recognized as a significant source of VOCs in spaces (e.g., schools, workplaces, leisure areas, etc.)


 

Different Approaches Followed by Countries in Characterizing VOC emissions
 

To determine indoor paint emissions, volatile components are investigated in emission test chambers under controlled applications and climatic conditions. Europe and the US follow different approaches in characterizing emissions although there are some commonalities (See table below).2 However, ISO 16000-6 attempts to harmonize emission test methods.
 

CommonalitiesDifferences
Test chamber climate: 23°C and 50% RH
Components studied: VOCs and volatile aldehydes
Paint substrate: Gypsum or other porous substrates (US). Inert surfaces such as glass or metal (Europe)
Time after coating: 14 days (US). 3 and 28 days (Europe)
Chamber ventilation rate: One air change per hour. One-half air change per hour (Europe)
Reference scenario: Multiple situation scenarios (US). One single scenario (Europe)
Targeted VOCs: 35 individual VOCs taken from California list of chronic respiratory exposure test limit values (US). Up to ~200 VOCs depending on region (Europe)


Differences in European (DIN EN16516) and US (ASTM D5116 and ASTM D6670, LEED, etc.) Indoor Paint Emission Testing

 

Indoor emission test results of a specific VOC per ISO 16000-6 can be compared to various set reference limits.
 

  • In Europe, emission concentration limits have been established by French, Italian, and German legislation.
  • In the US, the most widely used comparison standard is the Office of Environmental Health Hazard Assessment (OEHHA) reference levels (RELS).
     

Certification criteria (e.g., Greenguard, LEED) have also been developed by independent organizations, and they may even be stricter than legislation requirements. Examples of such indoor emission limits are shown in the table below.
 

Classes 

FRENCH legislation
(after 28 days) 
(µg/m3)
CAM Italian legislation
(after 28 days)
(µg/m3)
GREENGUARD Gold
(after 96 days)
(µg/m3)
Formaldehyde 

<10

<60

<9

Acetaldehyde 

<200

<300

<70

Toluene 

<300

<450

<150

Tetrachloroethylene 

<250

<350

<17.5

Xylene 

<200

<300

<350

1,2,4-Trimethylbenzene 

<1000

<1500

Not applicable 

1,4-Dichlorobenzene 

<60

<90

<400

Ethylbenzene

<750

<1000

<1000

n-Butylacetate

<4800

/

Not applicable 

2-Butoxyethanol

<1000

<1500

Not applicable 

Styrene

<250

>1500

<450

TVOC [from n-C6 to n-C16]

<1000

<1500

<220


Indoor Emissions Safe Thresholds – Examples by Country


 

Formulation Challenges & Performance Issues

 

Low-VOC paint compositions can have performance issues that challenge formulators in several respects. One of the more promising routes to producing low- or no-VOC paint is to limit volatile coalescing agents and plasticizers by using softer polymer binder compositions. Coalescing agents function by softening the polymer particles in a latex, enabling the formation of a continuous film as the coating cures. Additional functions of a coalescing agent are to improve open time, prevent skinning, and change the rheology of the formulation.

Traditionally acrylic polymers for interior coatings have a relatively high glass transition temperature (Tg) to provide the required performance properties. Elimination of the coalescing agent requires a binder with a lower Tg and minimum film-forming temperature (MFFT) below about 4°C. However, such softer polymers can result in formulations with reduced performance characteristics such as:
 

  • Higher odor
  • Poor stain resistance
  • Poor dirt pick-up resistance and cleanability
  • Low wet scrub resistance
  • Poor color development and fastness
  • Poor adhesion to old paint
  • Lack of sufficient hiding power
     

These poor performance factors can result in reduced service life which necessitates repainting and another cycle of indoor emissions.

New proprietary resin binder technologies relieve many of these performance problems. The optimal use of materials and processes produces resins with reduced Tg and MFFT. As a result of these efforts, low-VOC interior paints can be manufactured without coalescent and yet have properties that are equivalent or superior to high-VOC paints.

A secondary approach to formulating low-VOC paint is to consider the contributions of conventional paint additives which include – anti-freeze agents, mildewcides, rheology modifiers, defoamers, and surfactants. In conventional VOC coatings, these contributions are not significant, but in low-VOC formulations, they can be the largest source of VOCs. Newly developed additives allow further reduction in VOC.


 

New Low-VOC Binders from Vinavil

 

Vinavil has recently developed three unique polymers (Crilat 4750, Crilat 4816, and Vinavil 04V) that have less VOC content, reduced emission levels, and performance levels at least equivalent to higher VOC paints. Properties of these resin binders are shown in the table below.
 

Property ↓ / Product Name →Crilat 4750Vinavil 04VCrilat 4816
Polymer TypeStyene acrylicVinyl Veova copolymerPure acrylic
VOC Content, %<0.15%<0.1<0.1
Formaldehyde, ppm<10<10<10
Tg, °C10208
MFFT, °C550
Solids Content, %50±152±150±1
Viscosity*, mPas2000±10002500±1000<1000
pH8.0±0.54.5±0.58.0±0.5
*Measured at 23°C with RVT, 20 rpm, spindle 2


Property Comparison of Vinavil Low-VOC Resin Binders

 

With such low VOC levels, the odor of paints made with these resin dispersions is extremely low. The Vinavil products also have the following ideal characteristics for environmentally friendly interior paints:
 

  • Low MFFT of 0-5 °C
  • VOC content less than 0.15%
  • Low residual monomer
  • No formaldehyde producing components
  • Free of hazardous and toxic substances (CMR, sensitizers)
  • No environmental hazardous substances (e.g., APEO)
  • Low odor
  • Excellent compatibility with pigments, fillers, and other additives

 

These resin binders offer excellent versatility in formulating many kinds of waterborne coatings at low, medium, and high pigment volume content (PVC) levels for use in indoor applications. These paint systems have stain resistance, low dirt pick-up, and wet-scrub resistance. This results in improved durability allowing greater intervals between repainting and subsequent reintroduction of indoor emissions.

 

Starting Formulation Developments for Indoor Paints

 

Several starting formulations for indoor paints have been suggested for the new Vinavil dispersions. These all have safe and low-VOC additives. Performance properties, as described in the next section, are comparable to premium interior paints with higher VOC content and indoor emission levels.

The formulation shown in the table below is for a low-VOC interior paint with a relatively high 80% pigment volume content (PVC) typically used in flat paint. As PVC increases, density and paint hiding power increase, but performance properties such as durability (e.g., scrub, stain, and dirt pick-up resistance) typically decrease. The Crilat 4750 formulation, however, shows no reduction in these important performance properties. High PVC paints are often less expensive than lower PVC paints when quality is equal.
 

Component%%FunctionsSuppliers
Water24.5525.30  
Defoamer0.200.20 Various
Natrosol PLUS 330 PA0.600.60CelluloseAshland
NaOH (sol. 10%)0.100.10pH regulatorVarious
Sodium hexametaphosphate (sol. 10%)1.701.70Dispersing agentVarious
 
Nuosperse FN2650.20 0.20Wetting agentElementis
Ecodis P900.20 0.20 Dispersing agentCoatex
Acticide B200.200.20BiocideThor
TiO2 type RXL8.008.00PigmentHuntsman
Kaolin Polestar 200P4.00 4.00FillerImerys
CaCO3 5M type Omyacarb 5AV44.5044.50FillerOmya
TYPICAL STYRENE ACRYLIC BINDER10.00 Bindern.a.
Crilat 4750 10.00BinderVinavil
Texanol / Optifilm 4000.25 Coalescing AgentEastman
Propylene Glycol0.50 Co-solventVarious
Water5.005.00  
TOTAL100.00100.00  


Starting Formulation: Interior Paint at 80% PVC with Crilat 4750 Compared to aTypical Styrene Acrylic Binder


 

The table below describes low-VOC starting formulations with Vinavil 04V or Crilat 4816 having a PVC of 37%. This is a typical PVC level for satin and egg-shell finishes. In high traffic areas, such as hallways, low PVC paint may be preferred for better durability. 
 

Componentsw. %FunctionSuppliers
Water12.8  
Tego Antifoam2-890.2DefoamerEvonik
Natrosol Plus 330 PA0.2CelluloseAshland
Sodium hydroxide (10% sol.)0.2pH regulatorVarious
Sodium hexametaphosphate (10% sol.)2.5Dispersant Various
Ecodis P90
 
0.6DispersantArkema
Metolat 3880.3Wetting agentMunzing
Acticide B200.2BiocideThor
Vinavil 04V or Crilat 48166.0BinderVinavil
Titanium dioxide type RXL24.0PigmentHuntsman
Calcium carbonate 5m type Omyacarb 5 AV16.0FillerOmya
Vinavil 04V or Crilat 4816
 
35.0BinderVinavil
Tafigel PUR 800.2PU-thickenerMunzing
Sodium hydroxide (10% sol.)0.2pH regulatorVarious
Tego Antifoam 2-890.2DefoamerEvonik
Total100.0  


Starting Formulation: Interior Paint at 37% PVC with Vinavil 04V or Crilat 4816


 

Comparisons with Conventional Coatings

 

Characteristics of Crilat 4750 vs Styrene Acrylic Copolymers


Crilat 4750 is a styrene acrylic copolymer waterborne dispersion. It is free of APEO, coalescent, plasticizers, formaldehyde, and ammonia. Styrene acrylic copolymers are used as binders for medium and high PVC paints due to their outstanding pigment binding properties.

Crilat 4750 dispersion has lower in-can VOC content and emission levels when compared to conventional styrene acrylic binders. The low indoor emission levels meet Classification A+ according to the Grenelle de l'environnement French legislation (See table below). In comparison to conventional styrene-acrylic copolymers, Crilat 4750 has good flexibility. It is suitable for interior and exterior waterborne paint formulations.
 

 UnitsCrilat 4750Typical Styrene Acrylic Binder
In-can VOC g/l13.5
Emission VOC after 24hµg/m352021200
Emission VOC after 48hµg/m3
 
1709190


Crilat 4750 Emission VOC Compared to a Typical Styrene Acrylic Binder

 

In addition to its exceptional environmental profile, the main features of Crilat 4750 paint formulations are: 
 

  • Water resistance and wet scrub resistance even in high PVC paints
  • High binding power with fillers and pigments, even at high PVC paints
  • Good stain resistance
  • Excellent alkali resistance that allows the formulation of both exterior paint and textured coating
  • Low dirt pick-up and good cleanability
  • Odorless
     

The properties of Crilat 4750 satin paint with 37% PVC are provided in the table below. Its versatility and excellent compatibility with cement and mineral binders make it a good solution for medium to high VOC interior paints and wall texture coatings.
 

AnalysisMethodUnit35% PVC Satin Paint Crilat 4750Market Reference Paint
Brookfield viscosity, 23°C (20 rpm)UNI 8490/3 mPas700026000
pHUNI 8490/41-149.218.27
Web scrub resistanceUNI 10560N° cycles>5000>5000
Web scrub resistance (200 cycles)ISO 11998µm2.5n.d.
Dirt pick-upUNI 10792ΔL0.120.17
Cleanability (Carbon black)UNI 11021ΔE
 
2.344.28
Gloss (85°)MV AT 034bis-136
VOCISO 11890g/l140


Performance Characteristics of Crilat 4750 in Satin Paints


 

Characteristics & Emission Results of Vinavil 04V vs Vinyl Acetate Copolymers


Vinavil 04V is a new generation waterborne dispersion of vinyl acetate – Veova copolymer. The copolymer has a unique, highly branched aliphatic structure which contributes to key polymer performance properties. It shows a lower VOC content than conventional vinyl acetate copolymers, and it is free of APEO, coalescent, plasticizers, and formaldehyde.

Waterborne formulations manufactured with Vinavil 04V dispersion have an in-can VOC content of less than 0.1% and emission levels significantly below strictly set environmental limits. The table below shows the results of chamber tests according to ISO 16000-6. As a result, Vinavil 04V can be classified Class A+ according to the Grenelle de l'environnement French legislation, and it also passes the Italian minimum environmental criteria (CAM). 
 

Classes

Results after 10 days
(µg/m3)

FRENCH legislation
(limit at 28 days)
(µg/m3)

CAM 
Italian legislation
(µg/m3)

Formaldehyde 

<5

<10

<60

Acetaldehyde 

<5

<200

<300

Toluene 

<5

<300

<450

Tetrachloroethylene 

<5

<250

<350

Xylene 

<5

<200

<300

1,2,4-Trimethylbenzene 

<5

<1000

<1500

1,4-Dichlorobenzene 

<5

<60

<90

Ethylbenzene

<5

<750

<1000

n-Butylacetate

<5

<4800

/

2-Butoxyethanol

<5

<1000

<1500

Styrene

<5

<250

<1500

TVOC [from n-C6 to n-C16]

193 

<1000

<1500


ISO 16000-6 Emission Results for Vinavil 04V 37% PVC Interior PaintCompared to Local Environmental Limits
 

In addition to being low-odor and low-VOC, Vinavil 04V paint is characterized by a combination of features that rival interior paint systems with high VOC levels:
 

  • Good color development and hiding power
  • Good wet / dry scrub resistance and adhesion
  • Low odor
  • Good rheological behavior
  • Low water resistance
  • Good stain and alkali resistance
  • Very good compatibility with fillers, pigments, and other additives

 

The excellent performance properties of Vinavil 04V 37% PVC interior paint are shown in the table below. Vinavil 04V offers great versatility in the preparation of any kind of water-based paints with medium and high PVC.
 

PropertyValues
Brookfield RVT viscosity - 20 rpm (mPas)7.250
pH7.41
Density (g/ml)1.40
Gloss at 60°/85° - 24 hours2.7 / 7.3
Gloss at 60°/85° - 7 days
2.6 / 7.3
Matt
Persoz hardness - 24 hours / 7 days87 / 87
Contrast ratio (hiding powder) UNI EN ISO 6504-3 (%)98.41 Class 2 (*)
Wet scrub resistance DIN 53778 (N° cycles)>5000
Wet scrub resistance ASTM D2486 (N° cycles)1200
Wet scrub resistance ISO 11998 (at 200 cycles) (µm)3.1 class 1 (*)
(*) Classification according to UNI EN 13300


Performance Characteristics of Vinavil 04V 37% PVC Paint


 

Characteristics & Emission Results of Crilat 4816


Crilat 4816 is a pure acrylic water dispersion, free from coalescing agents, plasticizers, and APEO. It has a low in-can VOC level of less than 0.1% and emission levels significantly below strictly set environmental limits. The table below shows the results of chamber tests according to ISO 16000-6. As a result, Crilat 4816 can be classified Class A+ according to the Grenelle de l'environnement French legislation, and it also passes the Italian minimum environmental criteria (CAM).
 

Classes

Results after 10 days
(µg/m3)

FRENCH legislation
(limit at 28 days)
(µg/m3)

CAM 
Italian legislation
(µg/m3)

Formaldehyde 

<5

<10

<60

Acetaldehyde 

<5

<200

<300

Toluene 

<5

<300

<450

Tetrachloroethylene 

<5

<250

<350

Xylene 

<5

<200

<300

1,2,4-Trimethylbenzene 

<5

<1000

<1500

1,4-Dichlorobenzene 

<5

<60

<90

Ethylbenzene

<5

<750

<1000

n-Butylacetate

<5

<4800

/

2-Butoxyethanol

<5

<1000

<1500

Styrene

<5

<250

<1500

TVOC [from n-C6 to n-C16]

275

<1000

<1500


ISO 16000-6 Emission Results for Crilat 4816 37% PVC Interior PaintCompared to Local Environmental Limits
 

In addition to being environmentally friendly, Crilat 4816 paints are characterized by a combination of features that rival interior paint systems with high VOC levels:
 

  • Good color development and hiding power
  • Good wet scrub resistance
  • Low odor
  • Low dirt pick-up
  • Low sensitivity to water and weathering
  • Good stain resistance
  • Very good compatibility with fillers, pigments, and other additives

 

The excellent performance properties of Crilat 4816 37% PVC interior paint are shown in the table below. Paints formulated with Crilat 4816 are also noted for their excellent weathering resistance and durability. They can be used in interior and exterior applications.
 

PropertyValues
Brookfield RVT viscosity - 20 rpm (mPas)6.200
pH8.24
Density (g/ml)1.40
Gloss at 60°/85° - 24 hours2.7 / 4.7
Gloss at 60°/85° - 7 days
2.7 / 4.5
very matt
Persoz hardness - 24 hours / 7 days47 / 50
Wet scrub resistance DIN 53778 (N° cycles)>5000
Wet scrub resistance ASTM D2486 (N° cycles)1600
Wet scrub resistance ISO 11998 (at 200 cycles) (µm)3.7 class 1 (*)
(*) Classification according to UNI EN 13300


Performance Characteristics of Crilat 4816 37% PVC Paint


 

Conclusion

 

Architects and builders view indoor air quality as one of the most important attributes when considering interior paint. Indoor air quality is assessed by international certifications, regulatory standards, and third-party agencies. Paint manufacturers are responding to this challenge by formulating products that have low VOC content and provide safe, low levels of emissions when tested according to ISO 16000-6.

The major source of indoor emissions are coalescents or co-solvents and certain formulation additives. To eliminate these environmentally harmful elements, one must use binder resins with a low Tg and MFFT. This can be done with softer resins so that they self-coalesce. However, these softer resins can adversely affect drying times, dirt pickup, scrub ability, and other durability and appearance factors.

Vinavil has developed three unique binder resins (Crilat 4750, Crilat 4816, and Vinavil 04V) that provide ultra-low levels of VOCs and indoor air emissions without compromising the performance of the paint. These resins have the requisite low Tg and MFFT to reduce VOC content to less than 0.15% and still provide excellent film formation without the need for coalescing agents or plasticizers. These resins also have low odor, no APEO, no formaldehyde producing elements, and both Crilat 4750 and Vinavil 04V are free of ammonia.

A series of starting formulations have been provided for formulators to take advantage of these eco-friendly resins and to provide indoor emission levels that are within the limits mandated by legislation. In addition to being environmentally responsible, these paint systems also provide fast drying times, low dirt pick-up, stain resistance, and good wet scrubability. Their performance and durability are comparable to or surpass conventional indoor paint systems having high VOC content and emission levels.

 

References

 

  1. Schiewreck, A. and Bock, M-C., “Emissions for Low-VOC and Zero-VOC Paints – Valuable Alternatives to Conventional Formulations Also for Use in Sensitive Environments?”, Building and Environment, Vol. 85, 2015, pp. 243-252.
  2. Oppi, R., “Clearing the Air Indoors”, European Coatings Journal, April 2013, pp. 114-117.
  3. Geurts, J., et. al., “New Waterborne Acrylic Binders for Zero VOC Paints”, J. Coating Technology Research, Vol. 8, No. 1, 2008, pp. 57-63.