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Additives for water-borne metallic coatings

1. Introduction
Plastic materials are widely used for various products such as cell
phones and laptops since plastics show good properties likemoldability and lightness. For plastic surfaces, thermoplastic
acrylates, isocyanate cure coatings and UV cure coatings aregenerally used.
Solvent-borne coatings are still major in the coating industry,
however the amount of water-borne coatings is gradually
increasing because of environmental issues.
Photo1. Aluminum pigment
A good example for a water-borne coating is the basecoat and(Toyo Aluminium)
metallic luster is the preferred appearance of plasic basecoats. Soluster pigments like aluminum pigments or pearl pigments are added to a basecoat to get this effect.
To focus on an aluminum pigment, its shape is like a flake, the regular particle size is about 15 µm,
and the regular thickness is about 0.5 µm. We can get a good metallic luster surface if the aluminum
pigments are oriented parallel to the surface. If not, the surface looks dull and darker.
In practice, an aluminum pigment is like a fine flake, so it moves around and swings in the wet film.
Therefore it is difficult to keep the pigments parallel to the surface.
For the above reason, several additives are generally used to set aluminum pigments parallel anduniform. These kind of additives increase the paint viscosity right after spraying and prevent thepigments movement. To fix the pigment is important for a good metallic pigment orientation. Laterthe drying shrinkage of the film brings the pigments parallel to the film surface. (Figure1)

Drying Shrinkage

Figure1. Aluminum pigment orientation
In addition to the above mentioned additives, we have various other additives for water-borne
metallic coatings. Following you can find these additives in this document.

2. Dispersant for aluminum pigments
1) Mechanism
Solid particles may flocculate with attractive forces such as Van der Waals force. If there are some
repulsive forces stronger than the attractive forces, particles are stabily dispersed without any
flocculation. The examples of repulsive forces are electrostatic repulsion by electric double layerand steric hindrance by polymer adsorption layer. (Figure2)

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2/6- - - - - - ++ + ++- - - - ++ + +++ - ++- +--+++- Pigment - Pigment + + - ++- +++++- +- ++- ++ + + - - - + + +- - - - - - Electrostatic repulsion
by surface charge

Pigment

Pigment

Steric hindrance
by polymer adsorption layer

Figure2. Mechanism of dispersing effect
DISPARLON AQ-320 and AQ-330 are dispersants which can work in water or polar solvents.
AQ-320 and AQ-330 are compositions of a phosphate part and a polyether part, and both of them
are water-soluble. The phosphate part works as an adsorption group in a polar solvent and showselectrostatic repulsion by anionic charge in water. On the other hand the polyether part works as
an adsorption group or polymer adsorption layer and also contributes to the solubility to the polar
solvents. We combined these two parts appropriately so that AQ-320 and AQ-330 can act as
dispersants in water and various polar solvent systems.

2) Dispersing effect of aluminum pigment
Following, we show an application example of AQ-320 and AQ-330 dispersing an aluminum
pigment in butyl glycol.
Pigment flocculation increases the viscosity, dispersing of pigments decreases the viscosity.
As shown in figure 3, AQ-320 and AQ-330 brings a lower viscosity of the aluminum slurrycompared to Additive A or B. Thus the pigment dispersing abilities of AQ-320 and AQ-330 weremuch better.
Like this, the improvement of aluminum pigment dispersibility by AQ-320 or AQ-330 decreases
the viscosity (Photo 2). As a result, the amount of solvents can be reduced. Moreover, thealuminum slurry which was well dispersed keeps its dispersibility even after the addition to awater-borne coating. In this way, a stable metallic paint can be created.

Table1. Aluminum slurry formulation

Figure3. Viscosity change by dispersant
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Blank

AQ-330

AQ-320Additive A

Additive B

Photo2. Flow of an aluminium slurry
3. Rheology control agents for water-borne coatings
1) Mechanism
DISPARLON AQ-600 series are paste form
anti-settling agents which are mainly basedon an amine salt of polyamide.
AQ-polyamides disperse uniformly in coatingand form a network structure in thePolyamide
interaction with the resins and pigments as Polyamide
aggregate
shown in the model (Figure 4). This network
structure imparts high viscosity to the paintHydrophobic
on standing condition. However theHydrogen bondinteraction
Particle (resins and pigments)
structure is not fixed strongly and can be
broken by stirring. Thus, viscosity decreases
Figure4. Model structure and mechanism
by increasing the shear rate. This type offlow is called "Thixotropy". If a coating showsa thixotropic flow, storage problems like settling and hard-caking can be prevented without
increasing the application viscosity.

2) Anti-settling and orientation improvement of aluminum pigment in W/B metallic coating
In addition to the anti-settling properties, the uniquestructural viscosity of AQ-600 series can prevent
aluminum pigment from moving in films after
spraying and improve the pigment orientation. To
evaluate the performances of AQ-600, we used a W/B
metallic coating (Table 2).
As shown in Figure 5, compared with acrylic type
ASE or urethane thickener, AQ-600 showed excellent
thixotropic flow (very high viscosity at low shear andlow viscosity at high shear). With this behaviour,
AQ-600 gives much better anti-settling effects thanASE and urethane thickener (Photo 3).
In the same system AQ-330 was added to thealuminum slurry as a dispersant. The coating withthis pigment preparation showed a good dispersion
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Table2.W/B metallic coating formulation
Part A
NeoCryl A-662

60.4

Butylglycol

7.8

Butyldigl ycol

3.6

Methoxypropoxypropanol

3.6

Let down
Water

11.0

Aluminum slurry

13.6

Thi xotropeＸ(solid 0.6%)

DMEA (pH= 8.0)
Total

Ｙ100.0state without any flocculation.
FC#4 20 sec

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BLANK
AQ-600ASE
UrethaneAfter 30 days / R.T. / FC#4 20sec

Figure5. Viscosity change by thixotrope

Photo3. Anti-settling of aluminum pigment

A Multi-Angle Spectrophotometer is used for measuring the Flop Index (FI) to evaluate theimprovement of aluminum pigment orientation. FI is measured by the amount of reflected lightfrom the lamp (near specular : 15o, vertical : 45o, and near light source : 110o).

Lamp
75°
110°
45°

45° 25°15°0°Specular45°

Figure6. Flop index measurement
As shown in Figure 6, the film which is densely stuffed with pigments (Solid color) scatters light.
Therefore the amount of reflected light is constant at every angle. In case of a mirror, lightreflects completely to the specular direction. So no reflected light is observed in vertical (45o) ornear light source (110o) direction. The angular distribution of the metallic film is inferior to themirror, but quite similar. Good orientation of aluminum pigments provides closer angular
distribution to the mirror and the FI value becomes higher. On the contrary, poor orientation
scatters light more and the FI value becomes lower. (Figure 7)
Good orientation
Uniform reflection
Strong flop
FI: Large
Poor orientation
Non-directionalreflection
Weak flop
FI: SmallFigure7. Pigment orientation and FI
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Figure8. FI of metallic films

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AQ-600ASE
Photo4. Comparison of metallic films
Figure 8 shows the FI measurement results. AQ-600 imparted excellent thixotropic properties
and improved the aluminum pigment orientation. Therefore, the AQ-600 film provided higher FI
values (over 2.0) than ASE. Generally, if the difference of FI is over 2.0, we can recognize thevisual difference clearly. Photo 4 is the view of the metallic films from specular side. The AQ-600
film is brighter than the ASE film because of the stronger specular light reflection.

4. Leveling agents for water-borne coatings1) Mechanism
Leveling agents are additives which spread on thecoating surface uniformly, reduce the surface
tension and improve leveling and wetting
properties.
A conventional acrylic leveling agent is not soeffective especially in water-based systems to get
Hydrophilic
sufficient leveling and to prevent surface defects.
AlkylSilicone
GroupOn the other hand, a modified silicone can cause
Figure9. Model structure of AQ-7120
some troubles such as intercoat adhesion failures
and recoat problems. For these reasons, weTable3. Contact angle (Water)developed an acrylic-silicone copolymer type.
Contact angle (Water) / oAdditive
Figure 9 is the model structure of AQ-7120, one of
the acrylic-silicone leveling agents. Like this, anBlank70
acrylic-silicone has several types of side chains. AndAQ-7120
71
the balance of the side chains is controlled
Additive C75
appropriately to have sufficient leveling/wetting
Additive D79
abilities without intercoat issues and surface
defects.
In general, larger contact angles of water on a coating film mean there is a higher surface tension
difference between water and a film and more intercoat problems can occur. In Table 3, a film
which contains AQ-7120 shows a smaller contact angle than the conventional modified silicones(Additive C and D) meaning that AQ-7120 will cause less intercoat problems.

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6/62) Anti-cratering in W/B metallic coating
We used a W/B metallic coating (Table 4) to evaluate recoatability (anti-cratering performance) ofAQ-7120.
We put hand-cream, DBP and DBA as contaminants on a substrate, and then applied the coatingby an air-spray.
AQ-7120 showed an excellent anti-cratering effect. Furthermore, the change in color of theAQ-7120's film was much smaller than the conventional modified silicones (Additive C and D).
(Photo 5)

Table4.
W/B metallic coating formulation
Blank

Part A
NeoCryl A-662

60.4

Butylglycol

7.8

Butyldiglycol

3.6

Methoxypropoxypropanol

3.6

Let down
Water

4.0

Aluminum slurry

13.6

30% AQ-600 MB

10.0

DMEA (pH=8.0)

X

Wetting ( Dosage : 0.6% )YTotalDBP

AQ-7120Blank
handcream

103.0

DBP

AQ-7120

AdditiveC

Additive
DDBA
DBP : dibutyl phthalate

DBA : dibutyl adipate

Photo5. Estimation of anti-cratering

As mentioned in this document, for water-borne metallic coatings there are a lot of requirements likealuminum pigment dispersion, anti-settling, improving of metallic orientation, recoatability,levelling (anti-cratering) and we can offer a wide range of additives such as AQ-330, AQ-600 andAQ-7120 to solve these problems.

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