CA1079455A - Coating composition - Google Patents
Coating compositionInfo
- Publication number
- CA1079455A CA1079455A CA277,876A CA277876A CA1079455A CA 1079455 A CA1079455 A CA 1079455A CA 277876 A CA277876 A CA 277876A CA 1079455 A CA1079455 A CA 1079455A
- Authority
- CA
- Canada
- Prior art keywords
- trifluoromethyl
- coating composition
- dinitrodiphenylamine
- diphenylamine
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
ABSTRACT
An anti-fouling composition contains, as an active constituent, a diphenylamine of the general formula:- 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.
An anti-fouling composition contains, as an active constituent, a diphenylamine of the general formula:- 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.
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:-NO2 ~ ~ HL__ ~ (CN)n (CF3)p
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:-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.
. . .
,~ . .
.
.. -.~, 10~455 TABLE I
Compound Rl R2 R3 l R4 R5 No.
1 Cl H N02 H Cl 2 Cl H H Cl H
: .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.
. . .
,~ . .
.
.. -.~, 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
7 N02 H Cl Cl H
8 H Cl F H H
9 H N02 Cl H H
H CF3 Cl 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
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' : .
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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.
~-~ 25 2,5'-bistrifluoromethyl-2~-chloro-4,6-dinitrodiphenyl-amine, incorporated in a paint composition, was tested as , ,:
-:: , ' :
~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:-' i''' '`
,: - .
' -: : .
,, : ~ . . ., :
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 .
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:-.
.` .
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.
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.
- , . . .. - ' . ' .
- .
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 .
. ~ . . . - . , ~
, . ~.
H Cl H Cl H
7 N02 H Cl Cl H
8 H Cl F H H
9 H N02 Cl H H
H CF3 Cl 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
',','' . .
' : .
" '~' , ~ " "
' . .:
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 , . ~ . . . . . . . .. .
. . , . , :
. .
:. .: '~ ' ?
~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.
~-~ 25 2,5'-bistrifluoromethyl-2~-chloro-4,6-dinitrodiphenyl-amine, incorporated in a paint composition, was tested as , ,:
-:: , ' :
~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:-' i''' '`
,: - .
' -: : .
,, : ~ . . ., :
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.
,-.''~
;::
,' ;
iO79455 11 .
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:-.
.` .
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.
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.
- , . . .. - ' . ' .
- .
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 .
. ~ . . . - . , ~
, . ~.
Claims (18)
1 An anti-fouling coating composition comprising as an active constituent an effective amount of diphenylamine of the general formula:- 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.
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:- 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.
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.
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.
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.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB18790/76A GB1525884A (en) | 1976-05-07 | 1976-05-07 | Coating compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1079455A true CA1079455A (en) | 1980-06-17 |
Family
ID=10118475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA277,876A Expired CA1079455A (en) | 1976-05-07 | 1977-05-06 | Coating composition |
Country Status (5)
| Country | Link |
|---|---|
| AU (1) | AU507506B2 (en) |
| CA (1) | CA1079455A (en) |
| GB (1) | GB1525884A (en) |
| NZ (1) | NZ183947A (en) |
| ZA (1) | ZA772577B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4407820A (en) | 1981-03-19 | 1983-10-04 | Eli Lilly And Company | Diphenylamine compounds |
| CA2020826A1 (en) * | 1989-07-11 | 1991-01-12 | Junji Yokoi | Antifouling composition |
| CN102199095B (en) | 2010-03-22 | 2014-04-09 | 中国中化股份有限公司 | Substituted diphenylamine compounds and preparation and application thereof |
| CA2859842C (en) | 2012-03-14 | 2016-11-08 | Sinochem Corporation | Substitute diphenylamine compounds use thereof as antitumor agents |
-
1976
- 1976-05-07 GB GB18790/76A patent/GB1525884A/en not_active Expired
-
1977
- 1977-04-27 NZ NZ183947A patent/NZ183947A/en unknown
- 1977-04-28 AU AU24686/77A patent/AU507506B2/en not_active Expired
- 1977-04-29 ZA ZA00772577A patent/ZA772577B/en unknown
- 1977-05-06 CA CA277,876A patent/CA1079455A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1525884A (en) | 1978-09-20 |
| NZ183947A (en) | 1978-09-20 |
| AU507506B2 (en) | 1980-02-14 |
| AU2468677A (en) | 1978-11-02 |
| ZA772577B (en) | 1978-12-27 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |