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VOC compliant resin technology for decorative coatings full text

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 VOC compliant resin technology for decorative
coatings.
Dirk Mestach, Jan Goossen, Richard Esser, Jaap Akkerman

Paper presented at the Eurocoat 2007 Congress,

Genova, Italy, 6-8 November 2007.

Abstract: Within the EU, there is considerable focus on reducing the emissions of
volatile organic compounds (VOCs). As a result of the Solvents Emission Directive, VOC
emissions have been considerably reduced as of January 1st 2007 and a further
reduction of allowable VOCs is due as of 2010. These limiting values are applicable for
decorative coatings that are not applied in installations where emissions can be
controlled.
The emission reductions needed by 2010 can only be achieved by the use of water-
borne or with high solids solvent- borne products. As most of the wall paints are already
waterborne, special attention has to be given to trim paints, varnishes, primers and
performance coatings. In this paper the approaches Nuplex Resins is following for the
development of VOC-compliant solvent-borne trim paints are discussed.

Introduction - European VOC legislation.

Within the EU, there is considerable focus on improving air quality. Particular
attention is being given to the reduction of emissions of volatile organic
compounds (VOCs). This reduction has a significant impact on the coatings
industry. As a result of the Solvents Emission Directive 1, VOC emissions have
been considerably reduced as of January 1st 2007 and a further reduction of
allowable VOCs is due as of 2010. These limiting values are applicable for
decorative coatings that are not applied in installations where emissions can be
controlled. The National Emission Ceilings Directive requires the EU Member
States to reduce their emissions of VOCs, to lower levels, in a staged way from
2007 towards 2010. This directive has lead Member States to require the
decorative coatings sector to take measures that has lead to the reduction in the
emissions arising from the use of its products as outlined in table 1. These
limiting values for VOC reduction in decorative coatings have been outlined in EU
Directive 2004/42/EC. Decorative coatings are currently using either solvent-
borne technologies or water-borne technologies. About 70% of all decorative

NUPLEX Resins BV, Synthesebaan 1, 4600 AB Bergen op Zoom, The
Netherlands.

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coatings used within the EU are water-borne. These are mainly coatings applied
to interior and exterior walls. In this paper we will focus on trim paints and
varnishes.

Table 1. Maximum VOC levels (g/l) per product category.

PRODUCT CATEGORY TYPE 2007 2010
Interior/exterior trim and Water-borne 150 130
cladding paints for wood, metal or Solvent-borne 400 300
plastic
Interior/exterior trim varnishes and Water-borne 150 130
wood stains Solvent-borne 500 400
Minimal build wood stains Water-borne 150 130
Solvent-borne 700 700

The EU Directive 2004/42/EC covers coatings applied to buildings, their trim and
fittings, and associated structures for decorative, functional and protective
purpose2. The VOC in table 1 is defined as any organic compound having an
initial boiling point less than or equal to 250°C, measured at a standard pressure
of 101,3 kPa. The VOC content is expressed in grams of VOC per liter, contained
in a coating when it is ready for use (including all tinters).
Special attention has to be paid to the definition of the different classes of paint in
this table. The definition of “water Borne Coatings” in this table is “A paint, the
viscosity of which is adjusted by the use of water”. Solvent Based Coatings on
the other hand side are paints, the viscosity of which is adjusted by the use of
organic solvents.
The product category classification also requires special attention, as significant
differences in VOC-limits exist.

 Interior/exterior trim varnishes and wood stains: coatings applied to trim

producing a transparent or semi-transparent film for decoration and
protection of wood, metal and plastics.
 Opaque wood stains: coatings producing an opaque film for the decoration
and protection of wood, against weathering, as defined in EN 927-1 (within
the semi-stable category).
 Minimal build wood stains: products in accordance with EN 927-1:1996,
having a mean thickness of less than 5µm when tested according to ISO
2808:1997, method 5A.

The VOC limits set for water-borne products in the first phase are higher than in
the second phase. This is largely to allow for the use, under phase one, of the
existing colorants added to coatings when tinted in-store. The colorants used in
this operation usually contain volatile organic compounds and compounds in
these colorants will need to be significantly reduced or eliminated
The emission reductions needed by 2010 can only be achieved by the use of
water-borne or with high solids solvent-borne products. As most of the wall paints

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are already waterborne, special attention has to be given to trim paints,
varnishes, primers and performance coatings.

High solids solvent borne resins.

For many decades air-drying alkyd resins have been the binders of choice for
both decorative trim paints. These resins form the basis of a rich palette of resin
systems, each with its own special properties. Coatings based on alkyd resins
have always been characterized by ease of application and high performance.
Besides their versatility, alkyd resins have the advantage of being partially based
on raw materials from renewable resources such as vegetable oil (from soybean,
for example). With the maximum of 300 grams of solvent per liter in 2010 many
products that have been on the market for many years will have to disappear. It
is theoretically possible to replace all the remaining traditional solvent-borne
products with water-borne versions. However, for certain applications, the latter
do not deliver the quality and performance required.
About one decade ago, very high solids or solvent-free alkyd resins were
developed to formulate enamels with very low VOC levels. Different technological
approaches were used to design these alkyds, but most of the time the oil
content of the alkyd was increased considerably, quite commonly to values of 80
- 85 %. Compared to the 65-70 % oil length usually encountered in conventional
long oil alkyds, this increase resulted in a number of changes in the fundamental
properties of the alkyd resin. Because of the high oil length not only durability but
also drying speed and hardness development and also resistance to yellowing
were compromised. In order to improve the drying behavior, the commonly used
soy bean oil was often partially replaced by oils having higher reactivity such as
linseed or tung oil. This replacement often improved drying behavior but at the
expense of yellowing and (outdoor) durability.

Recently Nuplex Resins has developed new alkyd-technology that does not have
these disadvantages of the first generation of high solids alkyds and is VOC
compliant at the same time. The raw materials used in this new generation of
alkyd resins are very close to those used for conventional alkyds: vegetable oil of
fatty acids (linoleic rich), pentaerythritol and phthalic anhydride.
The main difference is they way these raw materials are combined with each
other during the alkyd synthesis3. In this way we can use the difference in
functionality and reactivity of the raw materials to achieve the build-up of a
strongly branched alkyd molecule.

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 Figure 1. High solids alkyd raw materials and functionality.

Because of the fact that this new generation of alkyds has a strongly branched
polymer backbone (see figure 1) the hydrodynamic volume of the polymer
molecule will be lower than that of a conventional linear alkyd with the same raw
material composition having the same molecular weight. As a consequence it is
possible to increase the solids content of the alkyd resin without influencing
viscosity.

Figure 2. Normally the alkyd resin consists of a linear polyester back-bone with
pendant fatty acid chains. The new generation of alkyds, however, has a strongly
branched polymer backbone.

Using this approach, high solid alkyds can be synthesized with a solids content of
80 – 85 % in D-40 solvent at a viscosity of 4.5 -5.5 Pa.s (at 23 °C and 100 s-1)
that have properties that are very close to those of their conventional
counterparts at a solids content of 69 – 70 %.
In table 2 the properties of five alkyd resins are compared:

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 Alkyd A: solvent-free high solids alkyd resin
Alkyd B: high solids alkyd based on vegetable oil
Alkyd C: high solids alkyd based on vegetable fatty acids
Conv. OL: conventional solids alkyd based on vegetable oil
Conv. FA: conventional solids alkyd based on fatty acids

In the following table the resin properties of the alkyds used are given.

Table 2. Resin properties.

Alkyd Solids acid value Viscosity Color
(%) (mg KOH/g) (Pa.s 23 °C, 100 s-1) (Gardner)
Alkyd A 99 9.5 10.5 Max. 8
Alkyd B 81 7.8 5.5 Max. 7
Alkyd C 83 Max. 7.6 4.8 Max. 9
Conv. OL 70 6.7 5.5 Max. 6
Conv. FA 69 Max. 6.4 4.8 Max. 9

These resins were formulated in simple white gloss enamel formulations

according to the recipe given in table 3.

Table 3. Paint formulations.

Alkyd A Conv. FA Conv. OL B and C
Resin 62 100 100 91.5
Grind

Kaolin gel¹ 15.3 15.3 15.3 15.3

Titanium dioxide 122.7 122.7 122.7 122.7
Resin 92.7 122 119 100
Cobalt (6%) 1.28 1.28 1.28 1.28
Zirconium (12%) 0.93 0.96 0.93 0.93
Let down

Calcium (10%) 3.83 3.83 3.83 3.83

Methyl ethyl ketoxime 1.23 1.12 1.23 1.23
D40 solvent To 4.8 poises²

¹: 87 grams D40 solvent + 10 grams Kaolin + 3 grams butanol

²: ICI Cone & Plate viscosimeter @ 20°C

The paint parameters of these white gloss enamels were determined and
reported in table 4.

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Table 4. Paint parameters.
Paint based on alkyd D40 Viscosity¹ Density VOC PVC NV
added (g) (poise) (g/l) (g/l) (%) (%)
A 12 4.8 1.37 143 16.6 90
Conv. FA 45.5 5 1.14 371 16.2 67
C 54 4.8 1.17 329 16.1 72
Conv. OL 49 4.9 1.21 388 18.3 68
B 49 5 1.26 341 18 73

¹: ICI Cone & Plate viscosimeter @ 20°C

note: Density, VOC, PVC and Non-Volatiles were calculated not measured.

Table 4 shows that all enamel formulated are compliant with the VOC limits
introduce for 2007. None, however, is 2010 compliant. From table X it also
becomes clear that the paint based on alkyd C gives the most promising results
when it comes to approaching the 2010 VOC limits.
In figure 3 the BK-drying times are given for the different enamels.

Drying time (h)

18
16
14
12
10
8
6 stage 4
4 stage 3
2 stage 2
stage 1
0
FA
L
A

C
O

nv
nv

co
co

Setal

Figure 3. BK-drying comparison between different high solids enamels.

Again alkyd C compares very favorable. Also the other properties of this paint
such as gloss levels were promising as shown in table 5.

Table 5. Comparison of gloss levels.

Setal 20° 60° 85°
A 79,8 88,6 97,8
conv FA 78,2 86,4 97,6
C 82,2 90,1 98,2

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The hardness build-up upon drying of the paint based on alkyd C was only
marginally slower that for that based on the conventional fatty acid based long oil
alkyd (figure 4).

90

80

70
Persoz Hardness (s)

60

50

40

30
A
20
conv FA
10 C

0
0 5 10 15 20 25
Draying time (days)

Figure 4. Comparison of hardness build-up as a function of drying time.

Even though alkyd C has an interesting product profile, the 2010 VOC limits are
just beyond reach. We also found that increasing the degree of polymer
branching in alkyd C did not lead to a even higher solids content, but only
resulted in a more critical production process. Therefore it was decided to
explore blends of alkyd C with alkyd A, using the latter one as a reactive diluent
rather than as a main binder.
The results of blending alkyd C with alkyd A gave encouraging results as can be
seen from figure 5.

380

360

340

320

300
VOC (g/l)
280

260

240

220

200
Conv. FA C C + A (80:20)

Figure 5. Comparison between the VOC properties of alkyd C, with and without
reactive diluent alkyd A and a conventional fatty acid based alkyd.

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Both alkyd C and the blend of alkyd C and C (80:20) were formulated in the gloss
white enamel formulation given in table 3. The BK-drying behavior of both paints
was compared (figure 6). When the hardness build-up as a function of time was
studied (figure 7), it was noticed that when using the standard drier package (
Co: 6 %, Zr: 12 %, Ca: 10 %), the hardness increase for the blend C + A (80:20)
was slower than that of the reference C.
Therefore we investigated the effect of the drier composition on the hardness
build-up and the drying behavior. It was found that used an optimized
commercially available drier4 (dosage based on 0.05 % of Co on solid resin)
gave results that were very close to that of the reference C. Carefully optimizing
the drier package to suit the adopted paint formulation therefore always has to be
considered.

Drying time (min)

900

800

700
600
500
400
300
4
200 3
100 2 Phase
0 1
C
C+A
(80:20)
Alkyd

Figure 6. BK-drying of alkyd C compared to blend of alkyds C and A (80:20).

-8-
 70

60

50

Persoz hardness (s)

40

30

20
C+A (80:20)
10 C+A Optim. Drier
C

0
0 5 10 15
Drying time (days)

Figure 7. Hardness build-up for alkyd C and blends with alkyds A with and
without optimized drier composition.

Conclusion.
It is possible to produce solvent-borne products with a lower solvent content and
modern high-solids technology can be used to formulate products that offer many
of the attributes of traditional solvent-borne products but with significantly
reduced solvent content. The new alkyds can be used easily to formulate high
quality enamels that have VOC levels well below the future VOC limits. An
interesting aspect is that there is no need for time-consuming and expensive re-
formulation of the paint recipe.

Acknowledgements.
The authors would like to tank Mrs. Pascale Teasdale and Mr. Paul Dolphijn for
their valuable contribution to this paper.

1
Council Directive 1999/13/EC of 11 March 1999 on the limitation of emissions of volatile organic
compounds due to the use of organic solvents in certain activities and installations.

2
Also vehicle refinishing products are covered by this directive.
3
T.C. Patton, “Alkyd Resin Technology”, J. Wiley & Sons, Inc. , 1962.
4
Available from Elementis Pigments, UK.

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