Formulating with HALOX

Tannin Stain Inhibitors

for Improved Coating
Performance

What are tannins?

Tannins (tannic acids) are high molecular weight, water
soluble poly-phenolic molecules found in wood western
red cedar, redwood, oak, wattle, birch, willow, merbau,
white and yellow pine

Manifestation of tannins continued :

No tannin
bleed

Tannin
bleed

Manifestation of Tannins continued :

STEPS:

WOOD
HO

1.

HO

HO
HO
HO

2.

HO
HO

HO
HO

1. Penetration
2. Solubilization
3. Diffusion
4. Migration

HO

HO
HO

TANNIN STAINING

3.
HO

HO

HO

4.

COATING

Methods of Reducing Tannin Staining:

PHYSICAL METHODS
z

Utilize resins or pigments with excellent barrier properties such as low moisture
vapor transmission rates (MVTR) for e.g. solvent borne alkyds

CHEMICAL METHODS
z

Chelation additives (neutral or alkaline)

Charge-bearing pigments or liquids which render tannins insoluble
Substrate pre-treatment additives
Moisture sealants and moisture repellants
Cationic binders (low pH, positively charged)
Electrostatic adsorb and trap tannins (negatively charged) in primer
Sequestrian agents
Sequester cations (e.g. Fe2+) which can form dark colored stains
Ion exchange additives (negatively charged)
Electrostatic exchange negatively charged tannins
Bleaching agents
Oxidative breakdown of tannins

Chelation:
The chelation process is essentially the reaction
of soluble metal cations (M+) from tannin stain
inhibitive pigments with anionic (X-) groups on
the phenolic rings present in the tannins.
HO

Zn2+

OH
HO

OH
HO

Zn

HO

HO

Al3+

HO

OH
OH HO

Zr

Al

HO

HO
OH

HO
OH

HO

HO

Zr4+

HO

HO

HO

WATER SOLUBLE

INSOLUBLE COMPLEX

YOUR DESIRED END GOAL:

(Tannin) Chelation and Precipitation

Proof of the Concept :
O

Fe3+

+ Tannic acid

HO

Fe3+
OH

OH

Soluble colored stain

HO

Al3+
OH

Al3+

+ Tannic acid

OH

Insoluble complex

(Tannin) Chelation and Precipitation

Proof of the Concept (continued):

Tannin Extract
Naturally found
In wood

Fe3+-Tannate
Soluble complex
Formed

Al3+_Tannate
Insoluble complex
formed

An Introduction to.

Tannin Stain Inhibitors:

z

HALOX BW-100 (pigment)

HALOX XTAIN A (pigment)

HALOX XTAIN L-66 (liquid)

HALOX XTAIN L-44 (liquid)

Typical Physical Properties:

BW-100

XTAIN A

XTAIN
L-66

XTAIN
L-44

Cations

Calcium
Barium

Aluminum
Zirconium

Aluminum

Aluminum
Zirconium

pH

7.3

9.5

13.0

9.0

Oil Absorption

38.80

35.40

N/A

N/A

% Water
Solubility

0.17

0.11

100

100

Density g/ml

2.77

3.10

1.23

1.30

Mean Particle
Size

5.1

3.1

N/A

N/A

Color

White
Solid

White
Solid

Clear
Liquid

Clear
Liquid

HALOX BW-100
Calcium Barium Phosphosilicate

White Pigment
Used in Latex Wood Primer
Also Effective in High PVC Alkyd Primers
Lowest cost
Proven Track Record
Has shown synergy with XTAIN L-66
Recommended Loading Levels:
5-10% on total formula weight (t.f.w.)

HALOX XTAIN A
Aluminum Zirconium Phosphosilicate

White Pigment
Barium Free
Antimony Free
Multivalent cations
Recommended Loading Levels:
0.5 - 3.0% on total formula weight (t.f.w.)

HALOX XTAIN L-44

Stabilized Aluminum Zirconium complex

Liquid
Easier to incorporate than a pigment
Highly Efficient / Cost Effective
Can eliminate the need for zinc oxide
Recommended Loading Levels:
1.0 - 3.0% on total formula weight (t.f.w.)

HALOX XTAIN L-66

Stabilized Aluminum Complex

Liquid
Easier to incorporate than a pigment
Highly Efficient / Cost Effective
Recommended Loading Levels:
1.0 - 3.0% on total formula weight (t.f.w.)

HALOX XTAIN L-66 continued:

Chemistry: Aluminate Based
Patented: U.S. Patent 6,533,856
BENEFITS:

Cost effective tannin precipitant

Environmentally Friendly Additive
Heavy-metal free
Reduced amine demand
Possible reduced rheology modifier
demand

OH

HO
N

OH

Al
Na

Na

O
Al

OH

N
HO

OH

Formulating Guidelines
HALOX XTAIN L-66:
Pay Attention to the Following:
1.
2.
3.
4.
5.

Order of addition
Amine content
Dispersant, surfactants, defoamers used
Rheology modifiers used
Zinc Oxide used

Formulating Guidelines
HALOX XTAIN L-66 continued:
1.

Order of addition (recommended)

Add XTAIN L-66, as the last additive in the pigment grind

phase, once the desired grind has been achieved

XTAIN L-66 can be added to the letdown phase, but should be

premixed with an equal amount of water to reduce shocking the
system

Example 1:1 or 2:1 (Water: XTAIN L-66)

Formulating Guidelines
HALOX XTAIN L-66 continued:
2. Amine Content

Due to the strong alkalinity of XTAIN L-66, any additional

amines in the formula can be eliminated

Formulating Guidelines
HALOX XTAIN L-66 continued:

3. Dispersant, Surfactants, Defoamers used

Best results have been obtained with all of the following:

Dispersants Tamol 681, 731, and 850 (R&H), Dispex HDN and
DP6-7200 (Ciba), Disperse Ayd W-28 (Elementis)

Surfactants Triton CF-10 (Dow), Surfynol 104A and 104PG (Air

Products), and Coatex A-122 (Coatex)

Defoamers - Drewplus L-475 (Ashland/Drew), Byk 035 (Byk

Chemie), and Rhodoline 643 (Rhodia)

Formulating Guidelines
HALOX XTAIN L-66 continued:

4. Rheology Modifiers used

Thickener levels may be reduced because XTAIN L-66 has a

thickening effect

Due to the strong alkalinity of XTAIN L-66, ASE or HASE type,

ionic thickeners are NOT recommended

HEUR type and cellulosic thickeners give the best

compatibility and efficiency

Formulating Guidelines
HALOX XTAIN L-66 continued:

5. Zinc Oxide used

Can eliminate or reduce levels of zinc oxide in the formula,

when using XTAIN L-66

In Europe Zinc Oxide (ZnO) is a marine TOXIC hazard, which

mandates special labeling of the finished paint (For e.g.
Designation of N, R50/53). Pay close attention to the amount
used in the formulation

More Formulating Tips

All HALOX XTAIN Tannin Stain Inhibitors:
Pay Attention to the Following:
1.

Extender Pigment(s) usedCertain pigment morphologies can improve the barrier

properties of the coating (e.g. platy talc). The alkaline nature
of certain pigments can help to buffer the paint (e.g. calcium
carbonate).

2.

Coalescent Solvent UsedEster alcohols and glycols are preferred. Glycol ethers can
adversely affect the chelation mechanism. [next slide]

More Formulating Tips

All HALOX XTAIN Tannin Stain Inhibitors
Why glycol ether solvents are NOT good in combination with our
tannin stain inhibitors: They can tie up the active metal cations
found in our products

Stain blocking
reactive cation
Ether
(acts as a Lewis base)

Complexed metal
cation unavailable
to react with tannin

HALOX Test Method

(Tannin Stain Characterization):
z

z
z
z
z
z
z
z
z
z

Post-add or high speed disperse into latex paint

2-5% t.f.w. liquid tannin stain inhibitor or
5-7% t.f.w. tannin stain reactive pigment
Apply 1st coat to board @ desired spread rate (ft2/gal or m2/L)
Air dry for 24 hrs
Apply 2nd coat to half of the board @ desired spread rate (ft2/gal
or m2/L)
Air dry for 24 hrs
Colorimetry: measure CIE L.a.b. values (before testing)
Expose boards to 90-100% RH, 100F (38C) for 16-24 hrs to
accelerate tannin or stain bleeding through the coating
Air dry for 2 hrs
Colorimetry: measure CIE L.a.b. values (after testing)
Quantify degree of staining
L = lightness, a = red/green , b = yellow/blue

XTAIN L-44 (3%) vs. BW-100 (5%)

WB Acrylic Latex Primer
(24 hr Humidity)
Blank
Control

3%
XTAIN L-44

5%
BW-100 w/ZnO

Two-coats

One-coat

E3232

Redwood Boards

Post-add XTAIN L-66 to

WB Exterior Latex Flat Primer
(24 hrs Humidity)
Blank
Control

3%
XTAIN L-66

Two-coats

One-coat

Redwood Boards

WB Acrylic Alkyd Tannin Stain Primer

(24 hrs Humidity)

Two-coats

One-coat

Redwood Boards

Frequently Asked
Questions (FAQs)
z

Do our stain blocking additives also prevent nicotine, crayons, ketchup, mayonnaise,
mustard, lipstick and coffee stains?

Do our stain blocking additives also prevent rosin bleeding?

They are a class of solid or semisolid viscous (sticky) substances obtained either as exudations from
certain plants (e.g. pine)

Can our additives react adversely with the binder?

Yes. This are available on the website under Formulations

What is rosin?

The liquids products XTAIN L-44 and XTAIN L-66 are followed by XTAIN-A and BW-100.

Do HALOX have any nicotine stain blocking formulations?

No. However a combination of ZnO and our stain blocking additives may prevent rosin bleed?

Which are the most effective stain blockers?

Yes. For example XTAIN L-44 is most commonly used for this application especially in Europe

Yes. XTAIN L-44 has been shown to react with polyurethanes. XTAIN L-66 has been shown to react
with acrylic latexes and increase the paint viscosity during storage

Are HALOX stain blocking additives compatible with cationic stain blocking binders?

No. All our additives have pH > 7 which renders them unsuitable for such binders

HALOX Contacts:
HALOX Laboratory Phone (219) 933-1560

Dr. Tony Gichuhi HALOX R&D Manager ext 237

Andrew Thorn HALOX Technical Service Manager ext 243
Wendy Novelli HALOX Sr. Project Chemist ext 254
Amanda Adams HALOX Project Chemist ext 241
For an immediate response to your question(s): email
techservice@halox.com