Progress in Organic Coatings 42 (2001) 150–158

A new antifouling paint based on a zinc acrylate copolymer

Yoichi Yonehara∗ , Hiroshi Yamashita, Chikara Kawamura, Kei Itoh
Kansai Paint Co., Ltd., 4-17-1 Higashi Yahata, Hiratsuka, Japan
Received 15 October 2000; accepted 18 January 2001

Abstract
A series of novel acrylic copolymers, which contains zinc atom in a form of polymeric salt and can be exchanged with e.g. sodium ions
in sea water, has been developed. As the ion exchange reaction proceeds, the polymers become soluble and leach out by flow of sea water.
The polymers are considered to be suitable for antifouling paints, since erosion rates of antifouling paints formulated with the polymers
could easily be controlled by varying the polymers’ characteristics such as molecular weight, hydrophilicity, etc., without spoiling the
paints’ overall water resistance. After dynamic immersion the copper release rates, which represent efficacy of the main biocide, increased
in most of the paint samples, and the copper release rates also depended upon the leaching out behaviors of the polymers. © 2001 Elsevier
Science B.V. All rights reserved.
Keywords: Antifouling paints; Zinc acrylate copolymer; Copper release rate; Erosion rate

1. Introduction content and the hydrophilicity of comonomers. Antifouling

Responding to requirements for environmental protection,
organic tin-based antifouling paints were completely phased
out in Japan in 1997 replaced by several species of so-called
“tin-free antifoulings”, being ahead of a global regulation
which will be initiated in 2003. The most important issue
for paint manufacturers is to develop an alternative antifoul-
ing paint that achieves the same performance as the organic
tin-based antifouling paints without significant cost increase.
A series of zinc acrylate copolymers have been reported to
be suitable for a binder resin for such alternative antifouling
paints [1,2]. It was found that the series of zinc acrylates
have leached out into sea water and this was considered due
to the ion exchange reaction between zinc in the polymers
and sodium in the sea water (Fig. 1). Here, the dissolved zinc
does not work as a biocide. Fouling prevention mainly relies
on release of other biocidal ingredients contained in the paint
formulations. In order to ensure longlasting antifouling per-
formance, it is essential to keep the sufficient release of the
biocides as long as possible, and therefore, in doing so it is
necessary to control the erosion rates (self-polishing rates) of
the antifouling paints precisely complying with ships’ sailing
conditions such as sailing speeds, sea water temperature, etc.
In the previous reports [1,2], influences of resin composi-
tions such as molecular weight, content of zinc acrylate and
hydrophilicity of comonomers were examined. The leach-
ing out of the polymers depended on both the zinc acrylate
∗ Corresponding author.
E-mail address: yonehara@als.kansai.co.jp (Y. Yonehara).
paint samples formulated with the polymers have also been
examined on their performances in terms of erosion rate in
a dynamic immersion test and the physical properties in an
elongation test.
The erosion rate of the paint samples were closely related
to the leaching of the polymers [1,2]. This means that it is
possible to control the erosion rate of the paints by control-
ling the leaching out of the polymers. With respect to the
physical property, the paints tended to be less flexible as zinc
acrylate content increased. Therefore, it was concluded that
controlling the leaching out of the polymers by varying the
hydrophilicity was more advantageous than by zinc acrylate
content.
In this report, release rates of cuprous oxide, which is
the most widely used biocide, from the paints formulated
with various zinc acrylate copolymers are presented. Then,
a mechanism of biocide release is discussed in conjunction
with leaching out behaviors of the zinc acrylate copolymers.
2. Experimental
2.1. Zinc acrylate copolymers
The zinc acrylate copolymers with various monomer
compositions as described in Fig. 2 were prepared [3]. The
synthesized were two series of polymers, one is for investi-
gating the effects of hydrophilicity (R1–R10) and the other
is for the influences of zinc acrylate content (R11–R15). An
outline of the monomer compositions is indicated in Table 1.

0300-9440/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 0 - 9 4 4 0 ( 0 1 ) 0 0 1 5 7 - 6
 Y. Yonehara et al. / Progress in Organic Coatings 42 (2001) 150–158 151

Table 2
Paint formulationa
Material g/100 g paint

40% zinc acrylate solution 39.6

Cuprous oxide 39.6
Chlorinated paraffin 4.0
Tinting pigment 4.7
Extender pigment 3.2
Fig. 1. Leaching process of zinc acrylate copolymer. Polyamide wax 1.9
Solvent 7.0
Total 100.0
a Solid content: 67.7 wt.%; viscosity: 72–78 KU by Stomer’s viscome-

ter; cuprous oxide in solid: 25.1 vol.%.

acrylic polymerization was constant. Tg of the polymers was

found to be from 80 to 125◦ C through DSC measurement.
The obtained polymer solutions were 40% solids by weight.

2.2. Antifouling paint formulation

Fig. 2. Structure of synthesized copolymers.
The monomer compositions were varied under the con-
stant zinc acrylate content (Zn = 0.123 mol/100 g resin) in
R1–R10, and the zinc acrylate content was varied under the
same comonomer composition in R11–R15. Changing: (1)
acrylate/methacrylate ratio in zinc-containing monomers;
(2) type of alkyl group in acrylic ester comonomers; (3)
fraction of methoxy ethyl acrylate monomer (hereinafter
called MEA) varied the hydrophilicity of the polymers.
Here, the range of total zinc content was chosen so as
to avoid possible paint defects by poor physical properties
refering to previous experimental reports.
Molecular weight (Mw ) of the polymers was considered
to be almost the same, since an amount of the initiator in the
The prepared polymers were premixed with cuprous ox-
ide, which is a main biocide in this formulation, and other
ingredients as shown in Table 2, and processed in a paint
conditioner (Red Devil) for about 30 min.
2.3. Test specimen preparation
1. The polymer solutions were applied on glass plates with a
film applicator (Ericsen) to a film thickness of 70–80 ␮m,
to measure leaching out and water absorption of the poly-
mers.
2. The antifouling paints were applied by means of air
spray to a thickness of 150–170 ␮m on cold-rolled-steel
panels (0.8 mm thickness), which had been primed with

Table 1
Features of the synthesized polymers
Sample No. Zn (mol/100 g resin) Outline of monomer composition Solubility parameter measured

la Rb nc

R1 0.123 0.5 Ethyl, stearyl 0 9.48

R2 0.123 1 Ethyl, butyl 0 9.94
R3 0.123 0.25 Ethyl, butyl 0 10.21
R4 0.123 0.75 Ethyl, butyl 0 10.22
R5 0.123 0.5 Ethyl, butyl 0 10.23
R6 0.123 0.5 Ethyl, butyl 0.10 10.30
R7 0.123 0.5 Ethyl, butyl 0.18 10.48
R8 0.123 0.5 Ethyl 0 10.59
R9 0.123 0.5 Methyl 0 10.73
R10 0.123 0.5 Ethyl 0.10 10.75
R11 0.107 0.5 Ethyl, butyl 0 10.15
R12 0.115 0.5 Ethyl, butyl 0 10.23
R13 = R5 0.123 0.5 Ethyl, butyl 0 10.23
R14 0.131 0.5 Ethyl, butyl 0 10.24
R15 0.139 0.5 Ethyl, butyl 0 10.25
a Zn-methacrylate/(Zn-methacrylate + Zn-acrylate).
b Type of alkyl group in acrylic ester monomer.
c Mole fraction of methoxy ethyl acrylate (MEA) monomer/total monomers.
152 Y. Yonehara et al. / Progress in Organic Coatings 42 (2001) 150–158

epoxy-polyamide amine coatings under specified proce-

dures. These specimens were used to measure the erosion
rates and copper release rates of the antifouling paints.
Both (1) and (2) were dried at 20◦ C for 1 week prior to
the measurements.

2.4. Measurements

1. Solubility parameter of the polymers was determined by

turbidity titration with two different solvents, n-hexane
and water, according to Ref. [4].
2. Leaching out and water absorption of the polymers were
determined by the weight change of the specimens. The
specimens were immersed in natural sea water taken
from Izu-Ohshima area, and the weight of the specimens
was measured before and after immersion periodically.
Amounts of residual solvents were measured with dupli- Fig. 3. Rotary machine used for the dynamic immersion.
cated panels through heating, 105◦ C for 3 h. Here, the
water absorption and the leaching out can be calculated
was also used for the copper release rate measurements
with the following equation:
during aging in the dynamic condition.


Ww − Wd − Wrs 4. The copper release rate of the antifouling paints was de-
water absorption (%) = × 100, termined from copper concentrations in extracted sea wa-
Wd − Wrs

 ter samples. Procedures were according to the draft of
W0 − Wd − Wrs
leaching out (%) = × 100 ISO (International standardization organization) 15181,
W0 − Wrs except for type and size of specimens and immersion
where Ww is the weight of the films immediately after conditions [5].
removing from the sea water, Wd the weight of the films
after 24 h drying from Ww , Wrs the weight of the residual
solvents (measured by heating), and W0 the weight of the 3. Results and discussion
films before the sea water immersion
3. An erosion rate of antifouling paints was determined from 3.1. Solubility parameter of the polymers
the reduction of dry film thickness after sea water immer-
sion in a dynamic condition. The apparatus used in the The solubility parameters of the zinc acrylate copolymers
dynamic immersion is shown in Fig. 3. The specimens are demonstrated in Table 1, together with the outline of
attached on the outer vertical surface of the rotor can ro- their monomer compositions. The effects of the monomer
tate at a circumferential speed of 15 knots. This apparatus compositions are illustrated in Fig. 4.

Fig. 4. Effects of monomer compositions on solubility parameters.

 Y. Yonehara et al. / Progress in Organic Coatings 42 (2001) 150–158
Fig. 5. Leached thickness of the polymers in static immersion.
The type of the alkyl groups in comonomers gave the
most significant influence on the solubility parameter. This
can be attributed to an amount of the comonomers, since
the comonomers are always majority of the total monomers.
On the other hand, the zinc acrylate content did not greatly
affect the solubiity parameter.
3.2. Leaching out and water absorption of the polymers
The leaching out is expressed as decrement of thickness
and the water absorption is expressed as weight % in the
polymers, respectively. The leaching out of the polymers
was fairly constant after 7 days up to 35 days as shown in
Fig. 5. Relatively fast leaching out during the first 7 days
may have been caused by the release of residual solvents in
the films.
Fig. 6. Effects of monomer compositions on leaching out and water absorption.
153
The water absorption, on the other hand, did not remark-
ably increase during the immersion. In this measurement, the
amount of the residual solvents was also determined from
weight loss by heating, and was used to correct the leach-
ing out and the water absorption as previously described in
Section 2.4 (2).
The effects of the monomer compositions on the leaching
out and the water absorption after 35 days’ immersion are
demonstrated in Fig. 6. It should be noted that no major
influence was observed in water absorption. This means all
these polymers are still preserving good water-resistance
after the sea water immersion despite the variation of
the monomer compositions. This is because the monomer
compositions were carefully determined considering past
experimental results to avoid deterioration of the water
resistance.
The leaching of the polymers, on the other hand,
conspicuously increased with the MEA content. No
other factors, including the type of alkyl groups in the
comonomers produced a significant effect on the leached
thickness. Both the leaching and the water absorption
cannot simply be explained from the solubility parameter
variation.
The relationship between the solubility parameter and the
leaching out of the samples examined is demonstrated in
Fig. 7. Both R7 and R10, containing higher amounts of
MEA, are marked exceptionally indicating deep involvement
of MEA content in the leaching behavior.
3.3. Erosion rate of the paints in dynamic immersion
The erosion rate, micrometer per month, was calculated
from the reduction of thickness of the dry paint films
154 Y. Yonehara et al. / Progress in Organic Coatings 42 (2001) 150–158

caused by water flows but the polymer’s leaching is playing

a main role in the erosion.

3.4. Copper release rate of the paints

As stated in Section 2.2, the antifouling performance relies

Fig. 7. Solubility parameter and leaching of polymers.
during the dynamic immersion. Thickness reduction due to
the residual solvents in the films was corrected by determin-
ing their amounts through heating. The measured erosion
rates are shown in Table 3 and the effects of the monomer
compositions are illustrated in Fig. 8.
The erosion rates remarkably increased with the MEA
content and significantly decreased as the zinc methacrylate
in the total zinc monomers increased. The influence of the
zinc methacrylate in the total zinc monomers cannot be
elucidated by either the water absorption or the leaching of
the polymers. The type of alkyl groups in the comonomers
and the zinc acrylate content did not exhibit any great
influence.
As clearly seen in Fig. 9, the erosion rate of the paints
was closely related to the leaching out of the polymers. This
indicates that the erosion of the paints depends on the leach-
ing out of the polymers as we previously reported. This also
means that the erosion is not a simple physical phenomenon
on the release rate of the biocide, and cuprous oxide was
used as the biocide in this experiment. The released cuprous
oxide can only be detected as copper ions due to immediate
oxidation in the sea water. The release rate of copper was
examined under the two different immersion conditions to
assess their influences. Fig. 10 shows a procedure of the
measurement.
In the case of static immersion, the specimens were firstly
immersed in a testing bath (a 2-l beaker for extraction) for
4 h to extract the copper compounds into sea water, then
transferred to a holding tank (a 100-l container for aging)
and were kept in it for 35 days. After that the specimens were
removed from the tank and were transferred to the testing
bath for the release rate measurement.
In the case of dynamic immersion, the specimens were
attached onto the rotary machine after the initial release
rate measurement. After 26 days of the dynamic immer-
sion, the specimens were taken out from the machine and
were extracted in the testing bath to measure the release rate
again.
Fig. 11 shows the change of copper release rates dur-
ing the test period. A large difference can be seen be-
tween the two immersion conditions. The sample paints
became more easily releasable after dynamic immersion,
while they became slightly less releasable after static
immersion.
The effects of the monomer compositions on the copper
release rate before and after the dynamic immersion are
demonstrated in Fig. 12. The copper release rates after the

Table 3
Erosion rate and copper release rate of the test paints
Sample No. Polymer No. Erosion rate Copper release rate (␮g/cm2 /day)
(␮m/month)
Dynamic immersion Static immersion

Initial After 26 days Initial After 35 days

P1 R1 13 29 33 24 23
P2 R2 4 32 15 31 14
P3 R3 16 39 61 35 19
P4 R4 5 22 45 22 21
P5 R5 12 30 61 28 28
P6 R6 20 45 105 44 21
P7 R7 32 44 124 39 23
P8 R8 19 34 109 27 29
P9 R9 18 33 98 31 32
P10 R10 31 51 113 48 30
P11 R11 10 33 30 32 22
P12 R12 10 27 56 24 25
P13 = P5 R13 = R5 12 30 61 28 28
P14 R14 11 22 67 21 30
P15 R15 12 27 89 25 37
 Y. Yonehara et al. / Progress in Organic Coatings 42 (2001) 150–158 155

Fig. 8. Effects of monomer compositions on erosion rate.

Fig. 9. Leaching of the polymers and Erosion rate of paints.

Fig. 11. Copper release rate of paint samples.

Fig. 10. Procedure of biocide release rate measurement.

156 Y. Yonehara et al. / Progress in Organic Coatings 42 (2001) 150–158

Fig. 12. Effects of monomer compositions onto copper release rate before and after the dynamic immersion.

immersion were greatly increased in the following following equation:

cases:  
Tl
1. the type of alkyl groups in comonomers is methyl and Re = × Cc × dc × Pc × 102
Cp
ethyl;  
Tl
2. the MEA content is higher than 0.10; = × 0.251 × 5.88 × 0.865 × 102
3. the zinc acrylate content is higher than 0.123 Zn 0.517
(mol/100 g resin). = T1 × 2.469 × 102
To summarize the above observations, the more hydrophilic where Re is the estimated copper release rate based on the
polymers became more easily releasable after the dynamic leaching out of the polymers (␮g/cm2 /day), Tl the leached
immersion. thickness measured (␮m/day), Cp the volumetric polymer
The copper release rate after the dynamic immersion can content in the dry film = 0.517, Cc the volumetric cuprous
be related to both the leaching out and the water absorption oxide content in the dry film = 0.251, dc the density of the
of the polymers as shown in Figs. 13 and 14. The polymers cuprous oxide = 5.88 g/cm3 , Pc the purity of copper in the
in the paints contributed to the release of the copper to some cuprous oxide = Cu/Cu2 O = 0.865.
extent by leaching out and absorbing water. The estimated release rates based on the above equation
The contribution of the polymers’ leaching to the cop- were compared with the copper release rate actually mea-
per release from the paint films can be estimated from the sured as indicated in Fig. 15. It is clear that the copper

Fig. 13. Copper release rate after the dynamic immersion and leached Fig. 14. Copper release rate after the dynamic immersion and water
thickness of the polymers. absorption of the polymers.
 Y. Yonehara et al. / Progress in Organic Coatings 42 (2001) 150–158 157

Fig. 15. Comparison between the measured and estimated copper release rates.

Table 4
Summary of the resultsa

Factors (monomer compositions) Characteristics of polymers Performances of paints

Solubility parameter Leaching out Water absorption Erosion rate Copper release rate

After dynamic After static

Zinc monomer content ± + ± + +++ ++

Acrylate/methacrylate (l) ± ± − − − ±
Type of alkyl groups in comonomers (R) −−− − − −− −−− −
MEA content (n) ++ +++ + +++ ++ ±
a (+): increased as either zinc acrylate, l, R or n increased; (±): no clear tendency was observed; (–): decresed as either zinc acrylate, l, R or n increased.

release rate after the dynamic immersion is much higher than
the estimated (Fig. 15, upper). This means the remarkable
increase of the release rate after the dynamic immersion can-
not be elucidated only by the leaching of the polymers. It is
possible to expect some contribution of roughening on the
surface to the increase of the copper release rate. Because
the roughened surface must increase porosity on the surface
and can provide more chance for the sea water to contact the
cuprous oxide even if it is located inside. This roughening
effect was also confirmed by another experiment separately
carried out. That is when the surfaces were treated by a piece
of sand paper (#240), the copper release rate of the sample
paints was greatly increased. Further evidence should have
been obtained by electron micro-spectroscopic observation.
At present, the paint samples after the immersion is too frag-
ile to prepare a very thin piece for the electron microscopic
observation.
On the other hand, the estimated release rate showed
good coincidence with the copper release rate after the static
immersion (Fig. 15, lower). This suggests the copper was
mainly released by the leaching of the polymers even after
the static immersion.
4. Conclusions
The effects of the monomer compositions are summarized
in Table 4. The zinc acrylate content produces a significant
effect on the copper release rate. Almost no effect was ob-
served by the zinc acrylate/zinc methacrylate ratio. The type
of alkyl groups in comonomers produced considerable ef-
fect on the erosion rate and the copper release rate, and the
most powerful effect was produced by the MEA content on
the leaching of the polymers and the erosion rate.
In complying with market demands, it is absolutely nec-
essary to control both the erosion rate and the copper release
rate very precisely according to given sailing conditions. The
zinc acrylate copolymers have been proved to satisfy the
above requirement, since the erosion rate and the copper re-
lease rate can be controlled easily as described in this report.
158 Y. Yonehara et al. / Progress in Organic Coatings 42 (2001) 150–158

References [3] Japan Patent No. 97-286933 Kansai Paint (1997).

[1] Y. Yonehara, et al., Proceedings of the Second Pacific Coating Forum,
Vol. 308, 1997.
[2] Y. Yonehara, et al., Proceedings of the Annual Meeting of Japan
Society of Color Material, Vol. 76, 1998.
[4] K.W. Suh, J.M. Corbett, J. Appl. Polym. Sci. 12 (1968)
2359.
[5] ISO15181-1, Draft for Part 1 (General method for extraction of copper
and tin-based biocides) and Part 2 (Determination of copper ion
concentration in the extract and release rate calculation).