Carbinol Functional

Silicon-Based Technologies

for Coatings

ilicone materials have been used for many

years to improve the surface appearance
and properties of various coatings systems. When added to coatings formulations, silicone additives can improve wetting of substrates and give effective defoaming, blocking resistance and mar resistance. This paper discusses a new class of materials that are being developed.
Traditionally, organo modification of silicones has
involved incorporating polyether, alkyl and phenyl
groups onto the silicone backbone. For this study,
carbinol functionality has been incorporated onto the
silicone backbone using a new capability in Dow
Corning to functionalize silicone resins/polymers with
organic moieties etc. These novel materials will be
capable of co-reacting with many organic cure
chemistries, resulting in improved compatibility and
other performance aspects of the final coating.
This paper describes the initial study of carbinol
functional materials where prototype materials were
cold blended into standard parquet lacquer formulations. The next stage of the program will investigate
Figure 1/General structure of silicone-polyether copolymers.

CH 3
CH 3
CH 3
CH 3
|
|
|
|
R- Si - O (- Si - O )n (- Si - O )m -Si - R
|
|
|
|
CH 3
CH 3
R
CH 3

Silicone Additive Benefits

for Parquet Coatings
For many coatings systems, the regulatory drive away
from solventborne towards waterborne formulations
has created performance issues. Coating formulators
are less able to rely on the flow and leveling benefits
provided by solvents. In addition, waterborne polymers may not provide the required level of gloss, foam
control, blocking and mar resistance. New formulations include non-VOC-contributing additives to proTable 1/UV solventless parquet lacquer formulation, courtesy
of UCB.
Ingredients
Ebecryl 6040
OTA 480
Benzophenone
Irgacure 651
Aktisil MAM-R
Total

Parts by Weight
219.7
263.2
17.6
17.6
481.9
1000

Table 2/Waterborne UV parquet lacquer formulation, courtesy

of Alberdingk Boley.

R = (CH2)3 (OCH2 CH2)x(OCH2CH)yOX

|
or R=CH3

chemically reacting the functional groups into the

resin. A range of carbinol fluid structures were evaluated in terms of their performance in UV and waterborne parquet-type formulations. The silicone chemistry is described, as well as the relationship between
chemical structure and suitability for particular parquet lacquer formulations.

CH 3

Ingredients
Alberdingk Lux 399
Dow Corning 68 Additive
Ultralube D816
Acematt TS 100
DSX 300
Irgacure 500
Total

Parts by Weight
951.0
3.0
25.0
5.0
6.0
10.0
1000

By Donna Perry and Vicky James/Dow Corning Ltd., Barry, UK; and Gerald Witucki/Dow Corning, Midland, MI
86

A P R I L 2 0 0 5 / www.pcimag.com

5.0
4.0
3.0
2.0
1.0
0.0

Ca

Ca

AB

AB

A
AB

rb
in
ol
3

l2
no
rb
i

in
Ca
rb

Co

nt

ol

ro

0.5% add
1.0% add

Figure 3/Appearance of ABA linear silicone carbinol fluid with (EO)1OH

functionality in UV solventless parquet lacquers.
2

0.5% add
1.0% add

ol

l2

in
Ca
rb
AB
A

Ca
A
AB

Ca
A
AB

rb
i

rb
i

no

no

ro

l1

nt

ABA Linear Silicone Carbinol Fluid with

(EO)1OH Functionality
Performance in UV Solventless Parquet Coating
Formulation
The ABA linear samples tested varied in the length of
the siloxane unit. Though these materials are soluble

Figure 2/Mar resistance of ABA linear silicone carbinol fluid with (EO)1OH
functionality in UV solventless parquet lacquers.

Co

Traditionally, silicone polyether technology has been

used to impart slip, wetting, leveling and defoaming.
These copolymers will have typical surfactant features, i.e. hydrophobic and hydrophilic segments. The
ratio of the hydrophobic/hydrophilic segments is
important to achieve the required compatibility balance. A high hydrophobic content may lead to de-wetting defects e.g. fish eyes, craters. On the other hand, a
high hydrophilic content can increase the solubility of
the copolymer so that there is no driving force for
accumulation at the coating/air interface during the
drying process.
Figure 1 shows the general structure of a siliconepolyether copolymer. The polyether chains can be
attached at points along the length of the silicone
backbone, giving a comb-like structure. They can also
be attached to the ends of the silicone polymer, giving
telechelic, linear structures. The architecture of the
copolymer has a profound effect on the behaviour as
an additive. Optimized structures have been identified
by designed experimentation to give suitable combinations of compatibility and desired effect, such as slip,
leveling or wetting and defoaming. Compatibility is
particularly important in clear parquet coatings,
where gloss reduction or haze cannot be tolerated.
This type of silicone technology is already widely
known. This paper will attempt to build on the current
understanding by evaluating three alternative polymer structures with a carbinol functional group
attached to the silicone backbone:
ABA linear silicone carbinol fluid with (EO)1OH
functionality;
Silicone carbinol fluids with novel hydrophilic
groups;
Carbinol functional silicone resins.

Mar resistance

Current Silicone Technology

in polar solvents, they are extremely hydrophobic and,

therefore, not water soluble or dispersible. Tests were
performed in a UV system only. The evaluations of
ABA linear carbinol functional fluids were performed
using the formulation shown in Table 1.
The performances of these various molecules in
these formulations were studied, and the following
properties were evaluated: mar resistance; gloss/haze;
slip/friction; and surface appearance (leveling, compatibility).
Mar resistance is an important property for parquet.
The three materials all have the effect of improving
the mar resistance compared to no silicone addition,
as shown in Figure 2. The mar resistance also increases as the number of siloxane units in the siloxane
backbone increases in number from left to right (1 =
excellent appearance, 5 = poor appearance).
Another important property is the compatibility in
terms of no cratering or leveling irregularities. The silicone fluids should have no negative effects on the
appearance of the final coating. The results in Figure
3 demonstrate an improvement in the appearance as
the number of siloxane units in the siloxane backbone
increases in number from left to right (1 = excellent
appearance, 5 = poor appearance).

Cratering

vide the needed performance. Silicone additives are

well suited for use in parquet coatings to protect the
coating surface from mechanical damage during processing, transport and use. They can also improve the
visual appearance by helping to produce a smooth
coating surface free of defects.

PA I N T & C OAT I N G S I N D U S T R Y

87

Carbinol Functional Silicon-Based Technologies for Coatings

The slip performance or coefficient of friction was

also tested and compared to the control. This also gives
a measure of whether the silicone tested comes to the
air-liquid interface. As can be seen in Figure 4, the slip
is reduced, showing their presence at the surface for
all three molecules tested.
Performance in Waterborne
Parquet Lacquer Formulations
The advantages of moving to waterborne systems in
terms of healthier, safer and environmentally more
acceptable coatings are obvious. However there is also
one significant disadvantage. Waterborne coatings
usually contain surfactants (e.g. binder, dispersant,

0.50
0.40
0.30
0.20
0.10
0.00

in
rb
Ca
A
AB

Ca
rb
in
ol
3

2
ol

ol
in
rb
Ca
A
AB

AB
A

0.5% add
1.0% add

Co
nt
ro
l

Coefficient of Friction

Figure 4/Coefficient of friction of ABA linear silicone carbinol fluid with

(EO)1OH functionality in UV solventless parquet lacquers.

Figure 5/Structure of a trisiloxane.

CH3
(CH3)3-Si-O-Si-O-Si-(CH3)3
(CH2)3
(EO)nR

Table 3/Waterborne air-drying parquet lacquer formulation,

courtesy of BASF.
Ingredients
Dowanol PnB
1,2-propylene glycol
Dowanol DPM
Dow Corning 68 Additive
Deuteron MK
Water
Luhydran A 848S
Butyl glycol
Poligen WE1
Total

88

A P R I L 2 0 0 5 / www.pcimag.com

Parts by Weight
40.0
10.0
20.0
5.0
10.0
30.0
800.0
20.0
45.0
980

wetting agent etc), which have the negative effect of

stabilizing foam from air incorporation during the production and application of the coating. However, it is
important for these waterborne coatings to contain
wetting agents due to the high surface tension of
water, which can cause surface defects such as craters
and poor wetting on substrates. Dow Corning promotes various silicone polyether technologies to be
used as wetting agents. One successful product in
particular, a trisiloxane polyether (Figure 5), is sold as
an anti-crater additive and acts by lowering the surface tension of the liquid coating and thus improves
substrate wetting.
This product also has good compatibility as seen
with both UV and air-drying waterborne parquet lacquers (Figure 6).
The addition of these surfactant-type siloxane molecules, although achieving excellent wetting even on
difficult-to-wet substrates, can sometimes have a negative effect on the foam behaviour of the coating. In
some cases, the trisiloxane silicone polyether technology can lead to foam stabilization. This problem is usually overcome by the addition of defoamers, which can
sometimes have negative effects on the final appearance of the coating.
A range of silicone carbinol fluids with novel
hydrophilic groups were synthesized for this evaluation with the hope that good wetting and good compatibility could be achieved without compromising
the foaming behaviour of the liquid coatings.
Five different structures were designed and performance tested. These structures contained the same
siloxane chain length but varied in the nature of the
carbinol functional hydrophilic group. (The exact
nature of these structures is proprietary.)
The evaluations of these fluids were performed
using the formulations shown in Tables 2 and 3.
The following properties were tested in these formulations:
1. Mar resistance
2. Gloss/Haze
3. Slip/Friction
4. Surface appearance (leveling, compatibility)
5. Foam stability
6. Blocking
The molecular weight and mol % hydroxy units in
the fluid dictate the compatibility of the siliconecarbinol fluids in the parquet lacquers (Figure 7).
When mixed at high shear, these materials did not
show foam stabilization typically seen with wetting
surfactants (Figure 8).

Figure 6/Compatiblity of trisiloxane.

With Trisiloxane SPE

Without Additive

Figure 7/Appearance of silicone carbinol fluids with novel hydrophilic groups in

a waterborne air-drying parquet lacquer (Formulation 3).
0.5% add
1.0% add
5.0% add

2.5
1.5

5
id
flu

id

in

Ca

rb

ol
in
rb

Ca

ol

flu

flu
ol
in

rb
Ca

3
id

id

1
Ca

rb
in

ol

ol

flu

id

SP

in
rb

Ca

flu

l
ro

xa
ne

nt

lo

Co

isi

0.5

Tr

Cratering

The addition of the silicone-carbinol fluids to the

lacquers did not adversely affect the slip, blocking or
gloss of the final coating. No change in mar resistance
was observed.
The effect on wetting was measured by surface tension (Figure 9). With the new silicone-carbinol fluids
evaluated, only a small change in surface tension was
observed.
At this time, the trisiloxane material, with three Si
atoms and pendant EO groups, still gives the best
results for wetting. The new hydrophilic siliconecarbinol fluids do not give the problem of foam stabilization as seen with the trisiloxane material, but the
degree of polymerization of the silicone backbone
and/or the molecular weight of the hydrophilic group
is clearly still too high to achieve the excellent mobility in solution and very efficient packing at the interface achieved by the trisiloxane material.
This class of materials was tested to determine their
effect on the hydrophilicity and oleophobicity of the
coating. This was done by incorporating the materials
in an acrylic binder (Rhoplex SG-30, courtesy of

PA I N T & C OAT I N G S I N D U S T R Y

89

Carbinol Functional Silicon-Based Technologies for Coatings

0.9

0.5% add
1.0% add
5.0% add

0.7
0.5

Co
nt
Tr
ro
isi
l
lo
xa
ne
Ca
SP
rb
E
in
ol
flu
Ca
id
rb
1
in
ol
f
lu
Ca
id
rb
2
in
ol
flu
Ca
id
rb
3
in
ol
flu
Ca
id
rb
4
in
ol
flu
id
5

Density after high shear mixing

2800 rpm, 1 min

Figure 8/Appearance of silicone carbinol fluids with novel hydrophilic groups in

a waterborne UV-drying parquet lacquer (Formulation 2).

Figure 9/Surface tension of silicone carbinol fluids with novel hydrophilic

groups in a waterborne UV-drying parquet lacquer (Formulation 2).
Surface tension mN/m

40
30

0.5% add
1.0% add
5.0% add

20

in

in

ol

ol

rb
Ca

Ca

Ca

rb

rb

in

in

ol

ol

1
rb

in
rb

Ca

Ca

SP
ne
xa

Tr

isi

lo

ol

l
ro
nt
Co

10

6
5
4
3
2
1
0

he

EO

ny
l

l
in
o
Ca

rb

in

ol

Ca

-P

rb

ro
Co

nt

M
Q

2.5% addition
5% addition
10% addition

Cratering

Figure 10/Appearance of carbinol functional silicone resins in waterborne airdrying parquet lacquer (Formulation 3).

5
4
3
2
1
0

he
n
ol
-P
in
rb

Ca
A P R I L 2 0 0 5 / www.pcimag.com

EO

yl

l
in
o
rb
Ca

ro
nt
Co

M
Q

2.5% addition
5% addition
10% addition

Cratering

Figure 11/Appearance of carbinol functional silicone resins in waterborne UV

parquet lacquer (Formulation 2).

90

Rohm and Haas), and measuring the contact angle of

water and oil on the cast film (Table 4). Reduced contact angles were found with water showing these
materials will increase hydrophilicity; however the
effect on oleophobicity was minimal.
The next stage in the development of these materials will be to look at lowering the degree of polymerization of the silicone backbone and the molecular
weight and structure of the hydrophilic group to
achieve excellent wetting without foam stabilization.
Finally, the next class of carbinol functional materials, carbinol functional methyl resins, was evaluated
in formulations included previously. A comparison
was also made to non-functional methyl resins. Materials are not soluble in water and therefore were delivered into the coating in emulsion form.
Adding carbinol functionality alone to methyl
resins can lead to a decrease in compatibility of the
resin in the lacquer, for both UV and air-drying waterborne systems. Examples of this are given in Figures
10 and 11. However, it can bee seen that substituting
phenyl groups into the resin can overcome the issue of
poor compatibility.

Adding carbinol functionality alone

to methyl resins can lead to a
decrease in compatibility of the
resin in the lacquer, for both UV and
air-drying waterborne systems.
Earlier we saw that linear silicone-carbinol fluids
gave no benefit in mar resistance in waterborne coatings. The data in Figure 12 shows the positive benefit
of adding a more rigid, three-dimensional structure to
the coating to improve mar resistance. The substitution of phenyl groups into the carbinol resin also
improves the mar resistance at lower addition levels
compared to the non-functional methyl only resins.
Of course it is important to ensure that other properties required in the coatings remain unaffected by
the addition of the silicone resins e.g., gloss, slip. Figures 13 and 14 illustrate that in the UV and air-drying
formulations tested, the phenyl substituted carbinol
resins had no negative impact on slip or gloss.

Conclusions
Silicone additives have progressed enormously since
the first use of PDMS fluids in solventborne coatings.
New chemical structures and delivery forms promise

Carbinol Functional Silicon-Based Technologies for Coatings

Table 4/Contact angle measurements at 1% additive addition into an acrylic

binder.
Water Contact Angle
(deg)
43
<15
<15
<15
<15
<15

Reference
Acrylic binder alone
Carbinol 1
Carbinol 2
Carbinol 3
Carbinol 4
Carbinol 5

Oil Contact Angle

(deg)
50.7
52.8
56.8
48.8
58.6
43.0

even greater improvements. This paper summarizes

he
n

EO

yl

ol
in

-P
Ca

rb

in

ol

Ca

Co

rb

nt

ro

M
Q

Mar resistance

Figure 12/Mar resistance carbinol functional silicone resins in waterborne airdrying parquet lacquer (Formulation 3).
5
2.5% addition
4
5% addition
3
10% addition
2
1
0

EO

ny

ol

olP
rb
in

Ca

Corning Europe. Jerry Witucki is a technical service specialist with Dow

Corning Corporation. The authors wish to thank Frances Fournier, Gary

work. They would also like to thank UCB, Alberdingk Boley, BASF and
Rohm and Haas for their contributions to test formulations.

Ca

Gloss 85 deg

Donna Perry and Vicky James are technical service specialists for Dow

gosch at Worlee Chemie GmBH for their valuable contribution to this

Figure 14/Gloss of carbinol functional silicone resins in waterborne UV parquet

lacquer (Formulation 2).
80

2.5% add
5% add
10% add

60
40

References
1. Owen, MJ, The Surface Activity of Silicones: A short
review, I&EC Prod. Res. Dev., 10 (1980), 97.
2. W.H. Pushaw III in Handbook of Coatings Additives
(L.J. Calbo, ed.), Marcel Dekker, Inc., New York, 1987,
p.271.

20
For further information contact, Donna.perry@dowcorning.com,

he
l-P
ino

Ca
rb
A P R I L 2 0 0 5 / www.pcimag.com

EO

ny
l

l
ino
rb

MQ

Ca

Co

nt
ro

92

Acknowledgements

Wieber and Mike Ferritto at Dow Corning Corporation and Katrin Lan-

he

rb
in

MQ

Co

nt

ro
l

C of F

Figure 13/Slip of carbinol functional silicone resins in waterborne UV parquet

lacquer (Formulation 2).
0.1
0.08
2.5% add
0.06
5% add
10% add
0.04
0.02
0

the performance of different silicone technologies in

various parquet coating formulations.
Short chain ABA linear silicone-carbinol fluids with
(EO)1OH functionality have shown good compatibility
in UV solventless coatings. They can migrate to the
coating surface, giving increased mar resistance and
slip. Their hydrophobicity does not allow them to be
used directly in waterborne coatings. Further work is
planned using an emulsion delivery system to determine their effects in waterborne coatings.
Increasing the hydrophilic character of the siliconecarbinol fluids allows them to be directly incorporated
in waterborne systems. Their compatibility in waterborne coatings is dependent on the balance between
the length of the siloxane backbone and the molecular
weight of the hydrophilic group. They do not cause
foam stabilization seen with other surfactants, but
more work is needed on optimizing the structures of
these materials if benefits in wetting and mar resistance are to be achieved.
Moving from a linear fluid to a rigid, three-dimensional resin brings improvements in mar resistance
without adversely affecting the slip or gloss level of the
coating. Carbinol functional resins show improved
mar resistance compared to non-functional resins, but
this must be balanced with phenyl functionality to
ensure compatibility in the coating. Further work is
planned to determine improvements in performance
by reacting carbinol resins with organic binders.

Vicky.james@dowcorning.com, or Gerald.Witucki@dowcorning.com.
This paper was presented at the European Coatings Conference Parquet
Coatings III, which took place November 2004, in Berlin. Information is
available at Vincentz Network, amanda.beyer@coatings.de.