ENDUIT

COATING COMPOSITION

Abrégé anglais

ABSTRACT
An anti-fouling composition contains, as an active
constituent, a diphenylamine of the general formula:-
<IMG>
where R represents a hydrogen atom or an alkyl or alkoxy
group containing up to six carbon atoms; X represents a
halogen atom, m is zero or an integer from one to three,
n is zero or one, p is zero, one or two and q is zero,
one or two, the sum of m, n, p and q being one, two or
three. The composition preferably contains a film-forming
material and may contain an extender or a plasticiser.
Examples of suitable diphenylamines include:
2,5'-bistrifluoromethyl-2'-chloro-4,6-dinitrophenylamine,
2-trifluoromethyl-2',5'-dichloro-4,6-dinitrodiphenylamine
and 2-trifluoromethyl-2'-cyano-4,6-dinitrodiphenylamine.

Revendications

The embodiments of the invention in which an
exclusive property or privilege is claimed are defined
as follows:
1 An anti-fouling coating composition comprising
as an active constituent an effective amount of diphenylamine
of the general formula:-
<IMG>
wherein R represents a hydrogen atom or an alkyl or alkoxy
group containing up to six carbon atoms; X represents a
halogen atom, m is zero or an integer from one to three,
n is zero or one, p is zero, one or two and q is zero,
one or two, the sum of m, n, P and q being one, two or three;
and a film forming material.
2. An anti-fouling coating composition comprising,
as an active constituent an effective amount of a diphenyl-
amine of the general formula:-
<IMG>
wherein R is a hydrogen atom or methyl; X is halogen and
m is zero or an integer from one to three, p is zero, one
or two; the sum of m and p being one, two or three, and a
film forming material.
3. A coating composition according to Claim 2
wherein m is 1 to 3 and p is zero.
14

4. A coating composition according to Claim 3
wherein m is zero and p is one or two.
5. A coating composition according to Claim 1
wherein the solubility of the diphenylamine in water is
less than 200 ppm,
6. A coating composition according to Claim 1
wherein the melting point of the diphenylamine is above
40°C.
7. A coating composition according to Claim 6
wherein the melting point of the diphenylamine is above
100°C.
8. A coating composition according to Claim 1
wherein the coating composition, after application and
drying contains at least 10% by weight of film-forming
material based on the total solids content of the
composition.
9. A coating composition according to Claim 1
which contains a material acting as an extender and/or a
pigment.
10. A coating composition according to Claim 1
which contains a plasticiser.
11. A coating composition according to Claim 1
wherein the composition contains from 5% to 70% by weight
of diphenylamine, based on the combined weight of the
diphenylamine and the film-forming material.

12, A coating composition according to Claim 11
wherein the composition contains from 5 to 50% by weight
of diphenylamine, based on the combined weight of the
diphenylamine and the film-forming material,
13, A coating composition according to Claim 12
wherein the composition contains from 5 to 25% by weight
of diphenylamine, based on the combined weight of the
diphenylamine and the film-forming material,
14. A coating composition according to Claim 1
which contains a solvent for at least a part of the film-
forming material.
15. A coating composition according to Claim 1
wherein the diphenylamine is 2,5'-bistrifluoromethyl-2'-
chloro-4,6-dinitro-diphenylamine.
16. A coating composition according to Claim 1
wherein the diphenylamine is 2-trifluoromethyl-2',5'-
dichloro-4,6-dinitrodiphenylamine.
17. A coating composition according to Claim 1
where the diphenylamine is 2-trifluoromethyl-2'-cyano-4,6-
dinitrodiphenylamine.
16

18. A coating composition according to Claim 1
wherein the diphenylamine is selected from the group con-
sisting of
2-trifluoromethyl-2',6'-dichloro-4,6,6'-trinitrodiphenylamine;
2-trifluoromethyl-2',4'-dichloro-4,6-dinitrodiphenylamine;
2-trifluoromethyl-3',4'-dichloro-4,6-dinitrodiphenylamine;
2-trifluoromethyl-3',5'-dichloro-4,6-dinitrodiphenylamine;
2-trifluoromethyl-6'-methyl-4,6,6'-trinitrodiphenylamine;
2-trifluoromethyl-4',5'-dichloro-4,6,6'-trinitrodiphenylamine;
2-trifluoromethyl-3'-chloro-4'-fluoro-4,6-dinitrodiphenylamine;
2-trifluoromethyl-4'-chloro-3',4,6-trinitrodiphenylamine;
2,3'-bistrifluoromethyl-4'-chloro-4,6-dinitrodiphenylamine;
2,3'-bistrifluoromethyl-4,4',6-trinitrodiphenylamine;
2-trifluoromethyl-2'-methyl-4,5',6-trinitrodiphenylamine;
2 trifluoromethyl-2'-methyl-4,4',6-trinitrodiphenylamine;
2-trifluoromethyl-2',5'-dichloro-4,4',6-trinitrodiphenylamine;
2-trifluoromethyl-2',6'-dibromo-4,6-dinitrodiphenylamine;
2-trifluoromethyl-2',5'-dibromo-4,6-dinitrodiphenylamine;
2-trifluoromethyl-4'-chloro-4,6-dinitrodiphenylamine;
2-trifluoromethyl-3'-chloro-4,6-dinitrodiphenylamine;
2-trifluoromethyl-4'-bromo-4,6-dinitrodiphenylamine;
2-trifluoromethyl-3',4,6-trinitrodiphenylamine;
2-trifluoromethyl-2'-fluoro-4,6-dinitrodiphenylamine;
2-trifluoromethyl-3'-iodo-4,6-dinitrodiphenylamine;
2-trifluoromethyl-2'-chloro-4'-bromo-4,6-dinitrodiphenylamine;
2-trifluoromethyl-4'-ethyl-4,6-dinitrodiphenylamine; and
2-trifluoromethyl-2'-bromo-4,4',6,6'-tetranitrodiphenylamine.
17

Description

~079455
MD.28764
: I .
This invention relates to coating compositions (or
paints) suitable for application to surfaces to inhibit
growth of marine or fresh water organisms thereon.
, The formation of marine flora and fauna ~e.g. algae
;~1 5 and barnacles) on the hull of a vessel increases the
frictional drag between the hull and the water causing
~- a fall in speed and an increase in fuel consumption.
:
It is therefore common practice to apply "anti-fouling"
:.~
paints to prevent the formation of the above organisms.
The compositions of the present invention are especially
applicable as marine anti-fouling compositions.
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107~455
According to the present in~ention there is provided
an anti-fouling coating composition comprising, as an
active constituent, a diphenylamine of the general
formula:-
CF3 R
NO2 ~ ~ HL__ ~ (CN)n
(CF3)p
2 ( 2)q
wherein R represents a hydrogen atom or an alkyl or alkoxygroup containing up to six carbon atoms; X represents a
halogen atom, m is zero or an integer from one to three,
n is zero or one, ~ is zero, one or two and q is zero, one
. or two, the sum of m, n, p and q being one, two or three.
: .10 By the term "halogen" as used in this specification is
meant fluorine, bromine, chlorine and iodine.
Particularly suitable diphenylamines are those comprising
halogen atoms, nitro or trifluoromethyl groups as
substituents. Thus in a preferred aspect the invention
provides an anti-fouling coating composition comprising
as an active constituent a diphenylamine of the general
formula:-
: C~3 R
NO~ ~ ~H ~ ( )m
1~0 2

10794~55
wherein R is a hydrogen atom or methyl; X is halogen
and m is zero or an integer from one to three, ~ is zero,
one or two, the sum o~ m and ~ being one, two or three.
One especially preferred group of compounds within this
definition is that wherein m is 1 to 3 and ~ is zero,
and another especially preferred group of compounds within
this definition is that wherein m is zero and p is one or
two.
Specific diphenylamines which have been found to be
useful in the practice of the invention are listed in the
Table I. The headings to the columns of Table 1 conform
. to the substituent groups on the diphenylamine structure
of the general formula:-
v~ .
: CF3 ~ ~
1~2~ ~R3
: 2 4
The compounds of Table 1 may be prepared by methods .-
described in United Kingdom Patent Specification
Nos.1430046 and 1455207.
. . .
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10~455
TABLE I
Compound Rl R2 R3 l R4 R5
No.
1 Cl H N02 H Cl
2 Cl H H Cl H
3 Cl H Cl H H
4 H Cl Cl H H
H Cl H Cl H
6 N02 H H H CH3
7 N02 H Cl Cl H
8 H Cl F H H
9 H N02 Cl H H
H CF3 Cl H H
11 H CF3 N02 H H
12 CH3 H H N02 H
13 CH3 H N02 H H
14 Cl H N02 Cl H
Br H H H Br
16 Br H H Br H
17 H H Cl H H
18 H Cl H H H
19 - H H Br H H
CN H H H H
21 H N02 H H H
22 F H H H H
23 H I H H H
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1079455
T~BLE I ( continued)
Compound I Rl j R2¦ R3 4 ~ 5
r
2 6 Br H N02 H N02
2 7 _ N H CF 3 H
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~079455
The diphenylamines mentioned above have a low solubility
in water and a relatively high melting point, a high melting
point being indicative of a reduced tendency to migrate
towards the surface of the coating. Preferably the
solubility in water is less than 200 ppm but may be greater.
Preferably the melting point is above 40C, especially
above 100C.
In order to improve the protection of the substrate
against corrosion, the coating composition should
preferably comprise a continuous layer of film-forming
.
; material, accordingly the coating composition preferably
contains a film-forming material. The film-forming
material may be a synthetic or a natural material or a
mixture of such material. Suitable synthetic materials
include vinyl copolymers such as vinyl chloride/vinyl
acetate/vinyl alcohol copolymers, phenolic resins, epoxy
resins, polyurethanes and chlorinated synthetic rubber
(for example '~lloprene~ R10). 'Alloprene' is a trade
mark. Suitable natural materials include rosin and
bituminous materials such as coal tar pitch. Preferably
the coating composition after application and drying
contains at least 10% by weight of film-forming material
based on the total solids content of the composition.
The coating composition may also contain extenders
and/or pigments, for example iron oxide, titanium dioxide,
; silica and carbon black, and plasticisers, for example
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~079455
tricresyl phosphate or a chlorinated paraffin wax (for
example 'Cereclor' 42). 'Cereclor' is a trade mark.
In addition to the above diphenylamines, the
composition may also contain other toxins known in the
art; examples of such toxins are cuprous oxide, zinc
oxide, mercuric oxide and trialkyl tin derivatives. A
particularly suitable co-toxin is cuprous oxide.
Suitably the composition contains 5-70%, preferably
. 5-50%, for example 5-25%, by weight of the above
diphenylamine, based on the combined weight of the
diphenylamine and the film-forming material.
The composition preferably contains a solvent for at
` least a part of the film_forming material, the solvent(s)
, ..
~ evaporating once the composition has been applied to the
. ~ . .
surface. Suitable solvents include the aromatic
hydrocarbons, ketones and esters.
The thickness of the film will depend on such factors
as the nature of the ingredients and the duration of
protection required, but thicknesses of 50 to 200 microns `
are generally suitable.
The composition can be applied to the surface by
methods known in the art.
~-~ The invention is illustrated by the following Examples.
EXAMPLE 1
~-~ 25 2,5'-bistrifluoromethyl-2~-chloro-4,6-dinitrodiphenyl-
amine, incorporated in a paint composition, was tested as
,
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~07g45S
an anti-fouling agent. Polyvinyl sheets were coated with
the paint composition described below dispersed in
1:1 w/w xylene:'Aromasol' ~ as solvent. The paint
thickness was 100 microns. The sheets were then exposed
for 1 month to the sea on a raft. The sheets were
arranged so that part of each sheet was above the water
line. Untreated sheets were similarly mounted and acted
as control. The degree of fouling was estimated, using
a scale of 0 to 10 where a score of 0 indicates that the
sheet was fouled to the same extent as the untreated
control and a score of 10 indicates that no fouling
occurred.
Paint Composition:
Inaredient Parts
(bv volume)
2,5'-bistrifluoromethyl-2'_chloro-4,6_ 5
dinitrodiphenylamine
Chlorinated Rubber ('Alloprene' R10) 40
Titanium Dioxide 20
Rosin 25
Chlorinated Paraffin Wax ('Cereclor' 42) 10
20 In duplicate tests, the test composition scored (6) and (6).
EXAMPLE Z
The procedure of Example 1 was repeated using the
following paint composition:-
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10794S5
Paint Composition:
Parts
Ingredient (by volume)
2,5'-bistrifluoromethyl-2'-chloro-4,6- 5
dinitrodiphenylamine
Chlorinated Rubber ('Alloprene' R10) 16
Titanium Dioxide 35
Rosin 40
; Chlorinated Paraffin Wax ('Cereclor' 42) 4
The paint thickness was 96 microns.
The test sheets were exposed to the sea for 11 months,
and the degree of barnicidal activity was estimated using
a scale of 0 to 10 where a score of 0 indicates that the
sheet was fouled with animal growth to the same extent as
the untreated control and a score of 10 indicates that no
fouling with animal growth occurred.
In duplicate tests, the test composition had
barnicidal activity scores of 10 and 8 respectively.
Test sheets coated with the same composition were
exposed to the sea for 1 month and the degree of algicidal
activity was estimated using a scale of 0 to 10 where a
score of 0 indicates that the sheet was ~ouled with weed
to the same extent as the untreated control and a score
of 10 indicates that no fouling with weed occurred.
In duplicate tests, the test composition had algicidal
. .
; activity scores of 4 and 4 respectively.
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iO79455
11 .
EXAMPLE 3
2-trifluoromethyl-2',5'-dichloro-4,6-dinitro-
diphenylamine, incorporated in a paint composition, was
tested as an anti-fouling composition using the
procedure of Exam~le 2
The paint thickness was 96 microns.
The paint composition was as follows:-
Ingredient Parts
(by volume)
2-trifluoromethyl-2',5'-dichloro-4,6- 5
dinitrodiphenylamine
Chlorinated Rubber ('Alloprene' R10) 16
Titanium Dioxide 35
Rosin 40
Chlorinated Paraffin Wax ('Cereclor' 42) 4
In duplicate tests, the test composition had
lS barnicidal activity scores, after exposure to the sea for
~ 11 months, of lO and 10 respectively and algicidal activity
:
scores, after exposure to the sea for 1 month, of ~ and 8
respectively.
EXA~IPLE 4
2-trifluoromethyl-2'-cyano-4,6-dinitrodiphenylamine,
~; incorporated in a paint composition, was tested as an
anti-fouling agent using the procedure of Example 2. The
- paint thickness was 229 microns.
The paint composition was as follows:-
.
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io7s4s5
12.
Parts
Ingredient (by volume)
2-trifluoromethyl-2'-cyano-4,6- 20
dinitrodiphenylamine
Chlorinated Rubber (lAlloprene~ R10) 16
Titanium Dioxide 20
Rosin 40
Chlorinated Paraffin Wax (~Cereclor' 42) 4
In duplicate tests, the test composition had
barnicidal activity scores, after exposure to the sea for
11 months, of 10 and 10 respectively, and algicidal
activity scores, after exposure to the sea for 3 months,
of 6 and 6 respectively.
EXAMPLE 5
The algicidal activity of the dinitrobenzotrifluorides
was determined as follows.
Samples of Enteromorpha (a sea water alga) were placed
in vessels containlng, respectively, sea and fresh water
culture media. Amoun ts (given below in ppm) of the test
compound in Dispersol T (a mixture of sodium sulphate and
~; condensate of a sodium salt of naphthalene sulphonic acid
and formaldehyde) were added and the effect on the algae
visually observed 12 days after adding the compound. The
` results presented in Table II are expressed according to
a scale of 0 to 3 where 0 indicates the compound had no
effect and 3 indicates that the algae were completely
killed.
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1079455 13.
TA~LE I I
Compound ENTEROMORPHA SPIROGYRA
No. 0.05 O. 2 1 5 O .05 O. 2 1 5
_
1 O 0,1 1,2 2 O 0,3 3,3 3
2 1 1,2 2,3 3 2 0,3 3,3 3
3 _ O O _ _ 3 3 _
4 O 0,2 3,3 3 O 0,1 3,3 3
O 0,2,2 2,2, 1 3 O 0,3,3 3,3,3 3
6 O O 0,2 3 O O 1,3 3
7 O O 1,2 3 O 2 3,3 3
8 O O 0,2 2 122 2
_ _ O 1 _ _ 3 3
i 11 _ _ O 2 _ _ 3 3
. 12 _ _ O 2 _ _ 2 3
' 13 _ 1 2,3 3 _ 3 3,3 3
14 O 0,2 2,3 3 O 0,3 3,3 3
. 15 _ O 0,3 3 _ O 3,3 3
.: 16 _ _ O 1 _ _ 3 3
, 17 . - O 1,2 2 _ O 3,3 3
., 18 _ _ 1 2 _ _ O 3
19 _ _ 2 2 _ _ 2 3
`. 2201 ~ ~ 0'3 1 ~ 233 33
22 _ _ 1 1 _ _ 2 3
23 __ O O _ _ 2 3
24 _ _ O 1 _ _ 3 3
., . 25 _ _ O O _ _ O 1
- 26 _ O 0,2 3 _ O 1,3 3
2 7 - -- ! ~ ~ -- _ 2, 3 3,
"- " denotes not tested
.
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