DESCRIPTION j
ANTIFOULING COATING COMPOSITION AND USES OF THE SAME
TECHNICAL FIELD
5 [0001]
The present invention relates to an antifouling coating
composition which comprises a hydrolyzable copolymer and an
antifouling agent and is employable for preventing aquatic animals
from fouling a substrate. The present invention also relates to
10 uses of the antifouling coating composition.
BACKGROUND ART
[0002] :
A material to coat a bottom of a ship that is now widely
15 employed is an antifouling coating material containing a camponent
such as a (meth) acrylic acid metal salt copolymer and a silyl ester
copolymer, and various antifouling agents, for its ability to
exhibit'gpod consumption property and good antifouling property.
However, in less often ship-operating, or under certain sea
20 conditions, animals, e.g., barnacles, and slimes (microorganism
coating), e.g., diatoms, adhere onto the substrate of the ship,
often causing a problem. ,
[0003]
In view of the above, conventional antifouling coating
SF-2337
.2
composition contained a copper compound, e.g., cuprous oxide,
aimed at preventing the adhering of the barnacles and the like,
or an organic antifouling agent intended as an anti-slime agent,
e.g.,
5 N,N-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfamide,
2,4,6-trichlorophenylmaleimide, and
2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine. ;
[0004] ;
These conventional antifouling coating compositions,
10 however, need to contain an antifouling agent in a large amount
in order to sufficiently exhibit an antifouling effect, and this
has an adverse effect on coating film property.
[0005]
For this reason, there has been a demand for an antifouling •
15 coating composition excellent in coating film property which has
stable coating film consumption degree on ships, underwater
structures and the like and which exhibits excellent antifouling
property over a long term.
[0006]
20 Patent''document 1 describes the use as an antifouling
component of medetomidine bonded to metal nanoparticles. Patent
document 2 describes the use as an antifouling component of
medetomidine bonded to a skeleton of a polymer such as polystyrene
and an acrylate polymer. Patent document 3 describes a protective
j
SF-2337 ;
.3
t
coating containing medetomidine and an organic antif ouling agent
such as 3-(3,4-dichiorophenyl)-1,1-dimethyl urea serving as an
algal inhibitory substance. Patent document 4 describes the use ;
of medetomidine as a chemical to inhibit marine biofouling, and
5 further describes the blending of medetomidine into a coating
material containing an acrylic polymer.
[0007] ' {
Still, it is difficult for these conventional antifouling ;
coating compositions to form an antifouling coating film which
10 has stable coating film consumption degree on ships, underwater i
structures and the like and which exhibits excellent antifouling
property over a long term.
CITATION LIST
15 PATENT DOCUMENT
[0008]
Patent document 1: JP 2008-533237 A
Patent document 2: JP 2008-535943 A
Patent document 3: JP 2009-503229 A
20 Patent''document 4: JP 2002-535255 A
SUMARRY OF THE INVENTION
PROBLEM TO BE SOLVED BY THE INVENTION
[0009]
SF-2337
.4 |
It is an object of the present invention to provide an
antifouling coating composition capable of forming an antifouling i
coating film which has stable coating film consumption degree on I
ships, underwater structures and the like and which exhibits ;
S, - «... (
5 excellent antifouling property over a long term. It is another object of the present invention to provide uses of the antifouling coating composition.
MEANS EOF SOLVING THE PROBLEM
- i n <• — — "• f~i i
As a result of repeated studies, the present inventors have
found that the use of an antifouling coating composition comprising
a specific hydrolyzable copolymer, and medetomidine as an
antifculir.g ager.r, can form an antifouling coating film that solves •
15 the aforesaid problem. The present invention has been
accomplished based on this finding.
[0011] .. .
That is, the antifouling coating composition of the present
invention is an antifouling coating composition comprising at least
20 one hydrolyzable copolymer (A) selected from the group consisting
of the following (al) to (a3), and an,antifouling agent (B)
comprising at least medetomidine,
(al) a metal salt bond-containing copolymer which is an
acrylic resin or a polyester resin and has a side-chain end group
SF-2337
5 '•
represented by the general formula (I):
-COO-M-O-COR1 (I)
[In the formula (I) , M is zinc or copper, and R1 is an organic
group];
5 (a2) a metal salt bond-containing copolymer having
a component unit derived from a monomer (a21)
represented by the general formula (II):
CH2=C(R2)-COO-M-0-CO-C(R2)=CH2 (II)
[In the formula (II) , Mis zinc or copper, and R2 is a hydrogen
10 atom or a methyl group], and
a component unit derived from other unsaturated
monomer (a22) copolymerizable with the monomer (a21); and
(a3) a silyl ester copolymer having
a component unit derived from a monomer (a31)
15 represented by the general formula (III):
R7-CH=C(R3)-COO-SiR4R5R6 (III)
[In the formula (III), R3 is a hydrogen atom or a methyl
group, ~
R4, R5 and R6 are each independently a hydrocarbon group,
20 and i
R7 is a hydrogen atom or R8-0-CO-- (wherein R8 is an organic
group or a silyl group represented by -SiR9R10Rn, wherein R9, R10
and R11 are each independently a hydrocarbon group) ] , and optionally
a component unit derived from other unsaturated
SF-2337
6 ]
t
monomer (a32) copolymerizable with the monomer (a31). ;
[0012] I
Preferably, an organic group R1 in the metal salt bond-containing copolymer (al) is an organic acid residue formed
5 from a monobasic acid, and is a saturated or unsaturated aliphatic
hydrocarbon group having 2 to 30 carbon atoms, a saturated or !
unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms,
an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a i
substituted group thereof. More specific examples of the organic
10 group R~ include an organic acid residue formed from at least one
monobasic acid selected from the group consisting ofversaticacid,
palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic I
acid, abietic acid, neoabietic acid, pimaric acid, dehydroabietic )
acid, 12-hydroxystearic acid and naphthenic acid. With regard • ;
15 to the metal salt bond-containing copolymers (al) and (a2) and
the silyl ester copolymer (a3), detailed embodiments in other
respects are described later.
[ U U i J j
The medetomidine is contained preferably in an amount of
20 0.01 to 200 £arts by weight based on 100 parts by weight of the •
hydrolyzable copolymer (A) . The antifouling coating composition [
of the present invention may further comprise an antifouling agent ;
other than medetomidine such as cuprous oxide, copper pyrithione
and zinc pyrithione. SF-2337 I
.7 |
i
[0014] t
Anantifouling coating f ilmof thepresent invention is formed from the antifouling coating composition.
In a substrate with a coating film of the present invention,
% - «- ' _ , •
5 a surface of the substrate is coated with a coating film obtained ;
by curing the antifouling coating composition.
A method for producing a substrate with a coating film of
the present invention comprises a step of applying or impregnating the antifouling coating composition to a surface of a substrate, 10 and a step of curing the composition to form a coating film.
EFFECT OF THE INVENTION
[0015]
The use of the antifouling coating composition of the present •
15 invention can form an antifouling coating film which has stable
coating film consumption degree on ships, underwater structures
and the like- and which exhibits excellent antifouling property
over a long term. Furthermore, in the present invention, the
composition does not need to contain a large amount of an antifouling
20 agent to exhibit excellent antifouling property, and thus this
does not have an adverse effect on coating film property.
EMBODIMENTS FOR CARRYING OUT THE INVENTION
[0016]
SF-2337 i
' • .8 I
In the present invention, the weight of a substance serving
as a standard to define a content of a component, is a weight of ;
a component capable of forming a dried coating film which excludes
a volatile component, e.g., a resin polymerization solvent and
5 a coating material dilution solvent: in other words, a weight of
a "solid component". The terms "(meth)acrylic acid" and
"(meth)acrylate" collectively refer to an acrylic acid and a
methacrylic acid., and acrylate and methacrylate, respectively.
In the present specification,, each component may be used in a single
10 kind or in combination of two or more kinds, unless otherwise noted.
[0017]
[Antifculing Coating Composition]
The antif ouling coating composition according to the present
invention comprises a hydrciyzable copolymer (A) and an antif ouling •
15 agent (3) .
[0018]

Tfie antifculing coating composition of the present invention
comprises, as a resin, component, a "hydrolyzable copolymer" which
/
20 is hydrolyzaBle in an alkali atmosphere such as in sea water (also
referred to as a "hydrolyzable copolymer...(A) ", hereinafter) . The
use of the hydroiyzable copolymer (A) as a resin component can
form an antifouling coating film which has stable coating film
consumption degree on ships, underwater structures and like and
SF-2337 !
9
ft
which exhibits excellent antifouling property, e.g., crack
resistance and adhesion with a substrate, and excellent surface
smoothness.
[0019]
' ' "5 " The hydrolyzable copolymer (A) is at least one hydrolyzable
copolymer selected from the group consisting of: :
a metal salt bond-containing copolymer (al) ( also referred :
to as a "copolymer (al)" hereinafter), ;
a metal salt bond-containing copolymer (a2) ( also referred ;
10 to as a "copolymer (a2)" hereinafter), and
a silyi esrer copolymer (a3) (also referred to as a "copolymer ?
(a3)" hereinafter).
[0020] j
The hydrolyzable copolymer (A) may be a copolymer satisfying . j
15 requirements of both the copolymer (al) and the copolymer (a2), i
i.e., a copolymer containing a structure of a side-chain end metal ;
salt bond as seen in the copolymer (al) and a structure of a •
crossii-rtked metal salt bond as seen in the copolymer (a2) . ;
The hydrolyzable copolymer (A) may be used in a single kind
20 or in combination of two or more kinds. [0021] Metal salt bond-containing copolymer (al)
The metal salt bond-containing copolymer (al) is an acrylic
resin or a polyester resin, and is a metal salt bond-containing
SF-2337 i
10 ;
copolymer having a side-chain end group represented by the general
formula (I) . In the present invention, the above structure is I
also referred to as a "side-chain end metal salt bond".
[0022]
5 -COO-M-O-COR1 (I)
In the formula (I) , Mis zinc or copper, and R1 is an organic
group. In the copolymer (al), usually, plural side-chain end groups each represented by the formula (I) are present, and each
cf Rx ~.ay be the same as or different from one another, and each
10 of M may be the same as or different from one another.
[0023] Preferably, the organic group R1 in the copolymer (al) (an
organic group R1 in the formula (IV) described later) is an organic
acid residue formed from a monobasic acid, and is a saturated or -
15 unsaturated aliphatic hydrocarbon group having 2 to 30 carbon atoms,
a saturated or unsaturated alicyclic hydrocarbon group having 3
to 20 carbon,atoms, -an aromatic hydrocarbon group having 6 to 18
carbon atoms, or substituted groups thereof; more preferably a
saturated or unsaturated aliphatic hydrocarbon group having 10
/
20 to 20 carbon* atoms, a saturated or unsaturated alicyclic
hydrocarbon group having 3 to 20 carbon atoms, or substituted groups
thereof. An example of the substituted group is a hydroxyl group
substituted group. Of these, particularly preferable are organic !
acid residues formed from at least one monobasic acid selected
SF-2337
11 :
from the group consisting of versatic acid, palmitic acid, stearic ;
acid, oleic acid, linoleic acid, linolenic acid, (including
structural isomers of these unsaturated aliphatic acids, e.g.,
isostearic acid; the same applies hereinafter.), abietic acid,
* - ». - , ';
5 neoabietic acid, pimaric acid, dehydroabietic acid,
12-hydroxystearic acid and naphthenic acid. The copolymer (al)
having such R1 is easy to prepare, and the use of the copolymer ;
(al) having such R1 can provide an antifouling coating film with
much superior hydrolysis property and recoatability.
j_ 0 *" 0 Q 2 4 ••

Among the copolymer (al), an acrylic resin type polymer is
preferable. In the copolymer (al) , the acrylic resin type polymer
canbeprepared, for example, throughpolymerization reaction using •
15 a metal salt bond-containing monomer represented by the general
formula (IV), i.e., a monobasic acid metal (meth)acrylate (also
referred to .as a "monomer (all)" hereinafter). ;
j.00Z5] " ;
CH2=C(R2) -COO-M-0-COR1 (IV)
20 In the "'formula (IV), M is zinc or copper, R1 is an organic
group, and R2 is a hydrogen atom or a methyl group (the same definitions as in the formulae (I) and (II) ) . The definition and
preferred types of R1 in the formula (IV) are the same as those
described with regard to the organic group R1 in the formula (I) , 1
SF-2337
12
with the proviso that R1 in the formula (IV) is not a vinyl group
[-CH=CH2] and an isopropenyl group [-C (CH3) =CH2] , in order to be
distinguished from a monomer (a21) represented by the formula (II) ;
capable of forming a crosslinkedmetal salt bond, which is described
5 later. ;
[0026]
The copolymer (al) may be a polymer obtained through
copolymerization reaction between two or more kinds of monomers
(all), or may be a polymer obtained through copolymerization
10 reaction between one kind, or two or more kinds of monomers (all) ,
and one kind, or two or more kinds of "other unsaturated monomers" ;
copolymerizable with the monomer (all) (also referred to as a i
"monomer (al2)", hereinafter), i.e., a copolymer containing a •
component unit derived from the monomer (all) and a component unit •
15 derived from the monomer (a!2).
[0027]
The monomer (al2) is arbitrarily selectable from various
compoun3s used as polymerizable unsaturated monomers for acrylic
resins, and preferred examples thereof include a monomer not
20 containing a!metal salt bond, e.g., alkyl (meth)acrylates,
alkoxyalkyl (meth)acrylates, and hydroxyalkyl (meth)acrylates.
Of these, particularly preferred are methyl (meth) acrylate, ethyl
(meth)acrylate, butyl (meth)acrylate, 2-methoxyethyl
(meth)acrylate, 3-methoxybutyl (meth)acrylate and 2-hydroxyethyl
SF-2337
13
(meth)acrylate, and so on.
[0028]
The acrylic resin type copolymer (al) can be also prepared,
for example, by a method comprising preparing an acrylic resin
5 by using a (meth)acrylic acid, an alkyl (meth)acrylate, an
alkoxyalkyl (meth)acrylate, ahydroxyalkyl (meth)acrylate, etc.,
and then performing a reaction which introduces a structure having
an organic group (R1) bonded to a carboxyl group through zinc or
copper (M; , wherein riie carboxyl group is present at a side chain :
10 of the acrylic resin where a metal salt bond has not yet been formed,
thereby forming a side-chain end group represented by the formula
(I). ;
[0029]
^p~"i Y^C-^" resi" "^^e^
15 ^jr.ong the copolymer (al), a polyester resin type polymer
is a polyester resin which is synthesized from a polybasic acid
and a polyhydric alcohol as a main raw material, and has an acid ;
value cf~50 to 200 mgKOH/g, preferably 80 to 170 mgKOH/g, and which l
has, at its end, a side-chain end group represented by the formula |
20 (I). |
[0030] )
Examples of the acid component to generate the polyester ;•
resin include monocarboxylic acids such as benzoic acid and
p-t-butyl benzoic acid; dicarboxylic acids and anhydrides thereof
SF-2337
14
fc
such as terephthalic acid, isophthalic acid, phthalic anhydride,
1,4-naphthol acid,
diphenicacid, 4,4'-oxybenzoicacid, 2,5-naphthalenedicarboxylic
acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride,
5 norbornenedicarboxylic acid, oxalic acid, malonic acid,
dimethylmalonic acid, succinic acid, glutaric acid, adipic acid,
azelaic acid, sebacic acid, 1, 3-cyclohexyldicarboxylic acid; and
aJLkyl esters having about 1 to 4 carbon atoms of these dicarboxylic
acids. These may be used in a single kind or in combination of
10 two or more kinds. Along with these examples, trifunctional or
more carboxylic acids such as trimellitic acid, trimellitic
anhydride, pyromellitic acid and pyromellitic anhydride, may be
used, and a slight amount of unsaturated dicarboxylic acids and
esters thereof such as maleic anhydride, maleic acid, itaconic
15 anhydride,- itaconic acid and fumaric acid 'may be used in
combination,
r n n 311
Examples of the polyhydric alcohol component to generate
the polyester resin include ethylene glycol, diethylene glycol,
20 triethylene glycol, polyethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, dipropylene glycol, polypropylene glycol, ;
neopentyl glycol, 1,5-pentane diol, 1,6-hexane diol, ;
3-methyl-l,5-pentane diol, 2-methyl-l,3-propane diol, j
2,2-diethyl-l, 3-propane diol, 2-butyl-2-ethyl-l,3-propane diol, I
SF-2337
15
bisphenol A, and a hydrogenated bisphenol A. These may be used
in a single kind or in combination of two or more kinds. Along
with these, trifunctional or more alcohols such as
trimethylolethane, glycerin and pentaerythritol may be used in
"5 combination.
[0032]
The polyester resin type copolymer (al) can be prepared,
for example, by a method comprising carrying out esterification
reaction or ester exchange reaction by a known process such as
10 a dissolution process using these various acid components and
alcohol components thereby preparing a polyester resin, and then
performing a reaction which introduces a structure having an
organic group (R1) bonded to a carboxyl group through zinc or copper
;M) , wherein the carboxyl group is present at the end where a metal • ;
15 salt bond has not yet been formed, thereby forming a side-chain
end group represented by the formula (I).
[0033] . ,
Irr the case of introducing the prescribed side-chain end
group into the acrylic resin or the polyester resin by the
20 preparation method as described above, too, preferable types of j
R* in the formula (I) are the same as those previously described. ;
In the preparation method as describe above, the monobasic acids |
as described above can be used for a reaction to introduce the
organic group R1.
SF-2337
16
[0034]
In the copolymer (al) , zinc and/or copper attributed to the
structure of the formula (I) is contained preferably in an amount
of 0.5 to 20% by weight, more preferably 1 to 19% by weight of
5 the copolymer. The use of the copolymer (al) fulfilling such
requirements can form an antifouling coating film much superior
both in antifouling property and in consumption property. The
"amount of zinc and/or copper" as used herein refers to a total
amount of zinc and copper if both zinc and copper are contained.
10 T 0 Q 3 5 "i ':
The amount of zinc and/or copper can be within the above
range, for example, by controlling the blending ratio between the
monomer (all) containing these metals and the monomer (al2) which I
are used for the preparation of the copolymer (al), or the addition • {
15 amount of the compound (e.g., themonobasic acid as described above) 1
containing zinc and/or copper to be reacted with the acrylic resin f
or the polyester resin previously prepared. '
[0036] ~ •
Metal salt bond-containing copolymer (a2)
20 The metal salt bond-containing copolymer (a2) is a copolymer
having a component unit derived from a monomer (a21) represented
by the general formula (II) and a component unit derived from "other
•4
unsaturatedmonomer (a22 ) " copolymerizable with t h e monomer (a21) .
[0037] SF-2337
17
CH2=C (R2) -COO-M-0-CO-C (R2) =CH2 (II)
In the formula (II) , Mis zinc or copper, and R2 is a hydrogen
atom or a methyl group. In the copolymer (a2), usually, plural
component units each derived from the monomer (a21) represented
5 by the formula (II) are present, and each of R2 may be the same
as or different from one another, and each of M may be the same •
as or different from one another.
[0038] :
Examples of the monomer (a21) include zinc diacrylate, zinc
10 dimethacrylate, copper diacrylate, and copper dimethacrylate.
The monomer (a21) may be used in a single kind or in combination
of two or more kinds.
[0039] The monomer .' = 21) can be prepared by. a known method, such • 15 as a method in which an inorganic metal compound (e.g. , an oxide,
a hydroxide, a chloride, etc. of zinc or copper) , and a (meth) acrylic
acid or its ester compound are heated and stirred, at not higher
than a temperature at which a metal sat is decomposed, in the presence
of an alcohol based organic solvent and water.
20 [0040]
The component unit derived from .the monomer (a21) has a
structure represented by the general formula (V), and this
structure is also referred to as a "crosslinked metal salt bond"
in the present invention.
SF-2337
18
*
[0041]
o o
7 : H U , 7
i^C-C-Q^-O-G^C-Fr
•v ...,.«. ( V )
[0042]
The "other unsaturated monomer (a22) " copolymerizable with
5 the monomer (a21) is arbitrarily selectable from various compounds j
employed as polymerizable unsaturatedmonomers for acrylic resins,
as is the case with the monomer (al2) in connection with the copolymer (al) . Preferred examples of the unsaturated monomer (a22) include alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, and 10 hydroxyaikyl (merh)acrylates. Of these, particularly preferred - are methyl (meth)acrylate, ethyl (meth)acrylate, butyl J
(merh)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl [
(meth)acrylate and .2-hydroxyethyl (meth)acrylate. [UUIJJ
15 The monomer (all), described above in connection with the
copolymer (al), i.e., the monobasic acid metal (meth)acrylate
represented by the formula (IV), too, is a monomer copolymerizable
with the monomer (a21) , and thus corresponds to the monomer (a22) ,
employable for the preparation of the metal salt bond-containing
20 copolymer (a2) . With regard to the monobasic acid metal j
SF-2337
19
(meth)acrylate represented by the formula (IV) as the unsaturated
monomer (a22), too, the definition and preferred embodiments of
R1 are the same as those described with regard to the organic group
R1 in the formula (I).
5 The unsaturated monomer (a22) may be used in a single kind
or in combination of two or more kinds.
[0044]
In another preferable embodiment, the unsaturated monomer
(a22^> comprises the monobasic acid metal (meth)acrylate
10 represented by the, formula (IV) and at least one unsaturatedmonomer
selected from the group consisting of an alkyl (meth)acrylate,
an alkoxyalkyl (meth)acrylate, and ahydroxyalkyl (meth)acrylate.
[0045]
Further examples of the unsaturated monomer (a22) include
15 styrene and styrene derivatives; vinyl esters'such as vinyl acetate
and vinyl propionate; (meth)acrylamide and derivatives thereof;
and (meth)acxylonitrile.
"0046"! - J
In the copolymer (a2), too, zinc and/or copper attributed 20 to the structure of the formula (II) is contained preferably in ;
an amount of 0.5 to 20% by weight, more preferably 1 to 19% by
weight of the copolymer, from the same viewpoint as described with
regard to the copolymer (al) . The "amount of zinc and/or copper"
as used herein refers to a total amount of zinc and copper if both i
SF-2337
20
zinc and copper are contained.
[0047]
The amount of zinc and/or copper can be within the above
range, for example, by controlling the blending ratio of monomers
5 employed for the preparation of the copolymer (a2). When the
copolymer (a2) has a structure of the crosslinked metal salt bond
and a structure of the side-chain end metal salt bond, it is
preferable that the total amount of zinc and/or copper attributed
tc each structure is controlled so as to be within the above range.
- l o r n n ^ G "
-LUi.V.'U'iOJ
The number-average molecular weight (Mn: in terms of
polystyrene) and the weight-average molecular weight (Mw: in terms
of polystyrene) of the copolymer (al) and the copolymer (a2) can
be arbitrarily adjusted in view of a viscosity and a storage 15 stability of the antifouling coating compos-ition and an elution
rate of the antifouling coating film, etc. , and Mn is usually about
1,000 to 100., 000,, preferably 1,000 to 50,000, and Mw is usually
about 17000 to 200,000, preferably 1,000 to 100,000. [0049] ;
/ ' ;
20 Silyl ester copolymer (a3) •
The silyl ester copolymer (a3)-is a copolymer having
a component unit (also referred to as a "silyl ester component unit" hereinafter) derived from a monomer (a31) represented by ;
the general formula (III) (also referred to as a "silyl ester |
SF-2337
21
monomer" hereinafter) , and the copolymer optionally has a component
unit derived from other unsaturated monomer (a32) copolymerizable
with the monomer (a31).
[0050]
5 R7-CH=C(R3)-COO-SiR4R5R6 (III)
In the formula (III) , R3 is a hydrogen atom or a methyl group,
R4, R5 and R6 are each independently a hydrocarbon group,
?.' is a hydrogen atom or R8-0-CO- (wherein R8 is an organic
10 group or a silyl group represented by -SiR9R10R1:L, wherein R9, R10
and RL± are each independently a hydrocarbon group). '
r n n c -] i
[ U O J i j
The silyl ester monomer (a31) wherein R7 is a hydrogen atom j
in) is represented by the general formula (Ilia): j
15 CH2=C(R3)-COO-SiR4R5R6 (Ilia)1 |
In the formula (Ilia), R3, R4, R5 and R6 are the same as R3, R", R5 and R6, respectively, in the formula (III) . j
[0u52j ~
The hydrocarbon group in the R4, R5 and R6 is preferably an 20 alkyl group having 1 to 10 carbon atoms, particularly 1 to 5 carbon
atoms, and more preferably, an alkyl group such as methyl, ethyl,
propyl and isopropyl.
[0053]
Examples of a silyl ester monomer (a33) , represented by the SF-2337
22
4
formula (Ilia), include trialkylsilyl (meth)acrylates such as
trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate and
triisopropylsilyl (meth)acrylate. Of these, triisopropylsilyl
(meth)acrylate is preferable, which provides excellent elution
5 of a resin from the coating film, long-lasting elution property
of a resin and coating film property (e.g., crack resistance).
[0054]
The silyl ester monomer (a31) wherein R7 is "R8-0-CO-" is
represented by the formula (Illb):
10 Rs-0-CG-CH=C(R3)-COO-SiR4R5R6 (Illb)
In the formula (Illb) , R3, R4, R5, R6 and R8 are the same as
R3, R4, R5, Rs and R8, respectively in the formula (III) or the
formula (Ilia).
r A H ; i; I
!_ w w .^^ j . - ;
15 The organic group in the R8 is preferably an alkyl group
having I to 10 carbon atoms, particularly 1 to 5 carbon atoms,
more preferably an alkyl group such as methyl, ethyl, propyl and j
isopropyl. The hydrocarbon group in the R9, R10 and R11 is preferably ;
an alkyl group having 1 to 10 carbon atoms, particularly 1 to 5
20 carbon atoms,'more preferably an alkyl group such as methyl, ethyl, ;
propyl and isopropyl. .. [0056] An example of a silyl ester monomer (a34), represented by !
the formula (Illb), is a maleate (a compound represented by the <
SF-2337
23
«
formula (Illb) wherein R3 is H) .
Examples of the other unsaturated monomer (a32)
copolymerizable with the monomer (a31) (or with the monomer (a33)
and/or the monomer (a34)) include the "other unsaturated monomer
5 (al2)" and the "other unsaturated monomer (a22)" exemplified as
raw materials compound of the copolymer (al) and the copolymer
(a2) ,- respectively.
[0057]
Preferred examples of the other unsaturated monomer (a32)
10 include alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, and
hydroxyaikyl (meth) acrylates . Of these, particularly preferable
are methyl (meth)acrylate, ethyl (meth)acrylate, butyl
(meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl
;-eth)acrylate and 2-hydroxyethyl (meth)acrylate.
15 The silyl ester monomer (a31) may be used in a single kind
or in combination of two or more kinds. The other unsaturated
monomer (a32.) may be used in a single kind or in combination of
two or irtore kinds.
roncoi
L w \j *J O j
/ ;
20 In the silyl ester copolymer (a3) , the component unit derived
from the silyl ester monomer (a31) is contained usually in an amount
of 10 to 100% by mol, preferably 10 to 90% by mol, and the component ;
unit derived from the "other unsaturated monomer (a32)" is {
contained in a residual amount, that is, usually in an amount of
SF-2337
24
ft
0 to 90% by mol, preferably 10 to 90% by mol, based on 100% by
mol of all constituents in the copolymer. The amounts of the
component units being within the above range are preferable, which
provides excellent viscosity of a resin in the coating film (e.g.,
* - ». - • .
5 crack resistance), storage stability of the coating material,
elution of a resin from the coating film, etc.
[0059]
Tiie number-average molecular weight Mn (in terms of
polystyrene) of the silyl ester copolymer (a3) is usually 1,000
10 to 200, 000, preferably 1,000 to 100,000. Mn being within the above j
range is preferable, which provides excellent viscosity of a resin
in the coating film (e.g., crack resistance), storage stability j
of the coating material, elution of a resin from the coating film, :
15 r 0 0 6 Q i • In the antifouling coating composition of the present j
invenrion, the hydrolyzable copolymer (A) is contained in terms I
of a solid component preferably in an amount of 0.1 to 99.999%
by weight, more preferably 1 to 99.999% by weight, most preferably
20 3 to 99.999%*by weight.
[0061] f
{
The antifouling coating composition of the present invention
comprises medetomidine as an antifouling agent (B).
SF-2337
25
Medetomidine (system name:
(±)4-[1-(2,3-dimethylphenyl)ethyl]-lH-imidazole) is a compound
represented by the following structural formula.
[0062]
5
N==ii
i!
!!
I U U O JJ
The use of medetomidine with the metal salt bond-containing
hydrolyzable copolymer (A) can provide an antifouling coating
1C composition excellent in coating film property which has stable •
coating film consumption degree on ships, underwater structures
and the like and which exhibits excellent antifouling property
over a long ..term.
[0064] -
15 The amount of medetomidine contained in the antifouling •
coating composition of the present invention is preferably 0.01 to 200 parts by weight, more preferably.O ,02 to 100 parts by weight, most preferably 0.05 to 50 parts by weight, based on 100 parts by weight of the hydrolyzable copolymer (A).
20 [0065]
SF-2337
26
By satisfying these requirements, the antifouling coating
composition of the present invention becomes more desirable in
terms of an antifouling effect. Specifically, the antifouling
coating composition comprising the hydrolyzable copolymer (A) and
5 medetomidine, in spite of using a small amount of the; antifouling
agent (medetomidine) (for example, about 0 . 01 to 10 parts by weight,
preferably about 0.01 to 2.0 parts by weight), can exhibit an
antifouling effect over a long term. In the present invention,
the composition does not need to contain a large amount of an
10 antifouling agent as described above, and thus this does not have
an adverse effect on coating film property such as crack resistance.
Meanwhile, the antifouling effect is exhibited over a long term
even if medetomidine is contained in an amount of some degree (for
example, about more than 10 parts by weight to not more than 200 •
15 parts by weight). ' i
r0Q6S!
The antifouling coating composition of the present invention, i
by containing medetomidine as the antifouling agent (B) , exhibits
much superior antifouling property. The antifouling coating [
20 composition 6f the present invention may optionally contain an j
antifouling agent, in addition to medetomidine, in order to have ;
still more improved antifouling property. [0067] j
Examples of the antifouling agent other than medetomidine
SF-2337
27
include cuprous oxide, copper rhodanide,
bis(2-pyridinediol-l-oxide) copper salt (also referred to as
"copper pyrithione" hereinafter), bis(2-pyridinediol-l-oxide)
zinc salt (also referred to as "zinc pyrithione" hereinafter),
5 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one,
triphenylboron-amine complex,
dichicrc—N-((dimethylamino)sulfonyl)fluoro-N-(p-tolyl)methane
sulfeneamide, and
2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethyipyrrol.
10 Further examples thereof include inorganic antifouling
agents such as inorganic copper compounds, e.g., copper powders;
and
organic antifouling agents such as
N,N-dimethyldichlorophenyl urea, 2,4,6-trichlorophenyl ]
- :r -i _ . • _ - • j _
-L u m a i c x i i L x u c,
2-methylthio-4-tert-butylamino-6-cyclopropyl-S-triazine, 2,4,5,6-tetrachlorpisophthalonitrile, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, I
chioromethyl-n-octyldisulfide, i
20 N,N'-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfamide, tetraalkyl thiuram disulfide, zinc dimethyldithio carbamate, zinc
ethylene bisdithio carbamate,
2,3-dichloro-N-(2',6'-diethylphenyl)maleimide, and
2,3-dichloro-N-(2'-ethyl-6'-methylphenyl)maleimide. {
SF-2337
28
These antifouling agents may be used in a single kind or
in combination of two or more kinds.
[0068]
The amount of the antifouling agent other than medetomidine
5 contained in the antifouling coating composition of the present
invention is not particularly limited as long as being within a
range which does not have an adverse effect on coating film property
such as crack resistance, and is preferably 0 to 15000 parts by
weight, more preferably 1 to 3000 parts by weight, still more
10 preferably 5 to 1500 parts by weight, most preferably 10 to 500
parts by weight, based on 100 parts by weight of the hydrolyzable
copolymer (A) . The amount of the antifouling agent other than
medetomidine is preferably 0 to 600000 parts by weight, more preferably 100 tc 2C00C0 parts by weight, most preferably 200 to •
15 lOOOOOpartsby weight, based en lOOpartsby weight of medetomidine.
[0069] |
I
Tfie antifouling coating composition of the present invention !
can comprise, in addition to the aforesaid components, various 20 components used in a general coating composition, such as color !
pigments, extender pigments, dehydrating agents, plasticizers,
thixotropic agents, resins other than the hydrolyzable copolymer
(A), organic acids, and solvents. These may be used in a single [
kind or in combination of two or more kinds. I
I
! f i %
SF-2337
29
[0070]
Color pigment
Examples of the color pigment include inorganic pigments
such as red iron oxide, titanium white (titanium oxide) and yellow
5 iron oxide; and organic pigments such as carbon black, naphthol
red and phthalocyanine blue. The color pigment may be used in
a single kind or in combination of two or more kinds. The color
pigment may further contain various colorants such as dye. The ;
blending amount of the color pigment can be arbitrarily adjusted,
10 and is preferably 0.05 to 250 parts by weight, more preferably
1 to 125 parts by weight, based on 100 parts by weight of the
hydrolyzable copolymer (A).
[0071] !
15 The extender pigment is a pigment of a''low refractive index
that is transparent and does not hide the coated surface when mixed
with an oil or a varnish. Examples of the extender pigment include ;
talc, silica, mica, clay, zinc oxide, calcium carbonate that is
used also as an anti-settling agent, kaolin, alumina white, white
20 carbon that i's used also as a flatting agent, aluminum hydroxide, magnesium carbonate, barium carbonate,.barium sulfate and zinc sulfide. Of these, preferable are zinc oxide, talc, silica, mica, t
clay, calcium carbonate, kaolin and barium carbonate. The
extender pigment may be used in a single kind or in combination i
SF-2337
30
of two or more kinds. The blending amount of the extender pigment
can be arbitrarily adjusted, and is preferably 0.5 to 750 parts
by weight, more preferably 5 to 400 parts by weight, most preferably
10 to 250 parts by weight, based on 100 parts by weight of the
5 hydrolyzable copolymer (A). [0072] I
Dehydrating agent The dehydrating agent is a component that contributes to I
r
the improvement of the storage stability of the coating material. 10 Examples of the dehydrating agent include inorganic ones including i
anhydrite, hemihydrate gypsum (exsiccated gypsum) , and a synthetic '
zeolite based adsorbent (e.g., a product named "molecular sieve") .
Further examples include orthoesters (e.g., methyl orthoformate,
methyl orthoacetate, and orthoboric acid ester), silicates, and •
15 isocyanates. Of these, anhydrite and 'hemihydrate gypsum
(exsiccated gypsum), each of which is an inorganic dehydrating
agent, are preferred. The dehydrating agent may be used in a single s
kind orln combination of two or more kinds. The blending amount j
of the dehydrating agent can be arbitrarily adjusted, and is '
20 preferably 0*to 100 parts by weight, more preferably 0.5 to 25
parts by weight, based on 100 parts by-weight of the hydrolyzable
copolymer (A).
[0073]
SF-2337
31
%
Plasticizer
The plasticizer is a component that contributes to the
improvement of crack resistance and water resistance and the
inhibition of discoloration of the antifouling coating film.
5 Examples of the plasticizer include n-paraffin, chlorinated
paraffin,terpenephenol,tricresylphosphate (TCP),andpolyvinyl
ethyl ether. Of these, chlorinated paraffin and terpene phenol
are preferable; and chlorinated paraffin is particularly
preferable. The plasticizer may be used in a single kind or in
10 combination of two or more kinds. As the n-paraffin, an example
of a commercial product employable is "n-paraffin", manufactured
by Nippon Petrochemicals Co., Ltd. As the chlorinated paraffin, ;
examples of commercial products employable are "Toyoparax
A-40/A-50//A-70/A-145/A-150", manufactured by Tosoh Corporation. • 15 The blending amount of the plasticizer can be arbitrarily adjusted, »
and is preferably 0.5 to 10% by weight, more preferably 1 to 5%
by weight, ba.sed on 100% by weight of all solid components including
the plasticizer in the antifouling coating composition.
[0074]
20 Anti-sagging/anti-settling agent
Examples of the anti-sagging/anti-settling (thixotropic
agent) include organic clay compounds (e.g., an amine salt, a
stearate salt, a lecithin salt and an alkyl sulfonate of Al, Ca
and Zn) , organic waxes (e.g., polyethylene wax, oxidized I
{
i
SF-2337 l
32 ;
ft
polyethylene wax, polyamide wax, amide wax, and hydrogenated castor
oil wax), and synthetic finely divided silica. Of these, :
preferable are the organic clay compounds, polyamide wax, amide »
wax, oxidized polyethylene wax, andsynthetic finely divided silica.
5 The anti-sagging/anti-settling agent may be used in a single kind
or in combination of two or more kinds. The blending amount of
the anti-sagging/anti-settling agent can be arbitrarily adjusted,
and is, for example, 0.25 to 50 parts by weight based on 100 parts
by weight of the hydrolyzable copolymer (A).
10 [0075]
Other resins and organic acids
The antif ouling coating composition of the present invention
may comprise one kind, or two or more kinds of other resins, in
addition, to the metal salt bond-containing copolymer (A) as
15 described above.
[007 6]
Employable examples include water-insoluble resins or
poorly water-soluble resins,
such as an acrylic resin not containing ametal salt bond, an acrylic .
20 silicone resin, a polyester resin, an unsaturated polyester resin, a fluororesin, a polybutene resin, a- silicone rubber, a I
polyurethane resin, an epoxy resin, a polyamide resin, a vinyl
resin (e.g., a vinyl chloride copolymer and an ethylene/vinyl
acetate copolymer), a chlorinated rubber, a chlorinated olefin SF-2337 •
33
resin, a styrene/butadiene copolymer resin, a ketone resin, an
alkyd resin, a coumarone resin, a terpene phenol resin and a
petroleum resin.
[0077]
5 Further examples employable with the hydrolyzable copolymer
(A) include water-soluble resins such as pine tar, rosin (gumrosin,
wood rosin and tall oil rosin), and monobasic organic acids such
as naphthenic acid, versatic acid, triphenylisobutenyl
cyclohexene carboxylic acid ("A-3000" manufactured by Yasuhara
10 Chemical Co., Ltd.).
[0078]
Solvent
Various components constituting the antifouling coating
composition of the present invention are usually dissolved or •
15 dispersed in a solvent, as is the case with a general antifouling
coating composition. A solvent employable in the present
invention can be a solvent generally used for an antifouling coating
material, the examples of which include an aliphatic solvent, an
aromatic solvent (e . g., xylene and toluene) , a ketone solvent (e.g.,
20 MIBK and cycl6hexanone) , an ester solvent, an ether solvent (e.g.,
propylene glycol monomethyl ether and propylene glycol monomethyl
ether acetate), and an alcohol solvent (e.g., isopropyl alcohol) .
The blending amount of the solvent can be arbitrarily adjusted,
and is, for example, such an amount that all solid components account ;
SF-2337
34
%
for 20 to 90% by weight in the antifouling coating composition.
The solvent may be further added in coating operation in view of
workability.
[0079]
5 [Production Method and Uses of Antifouling Coating Composition]
The antifouling coating composition of the present invention
can be prepared with apparatus, means, etc. similar to those
employed for generally known antifouling coating materials. For
example, the metal salt bond-containing copolymer (al) or (a2) ,
10 or the silyl ester copolymer (a3) is prepared in advance, and then ;
this copolymer (reaction liquid) and the antifouling agent (B),
optionally with other components such as additives, are added into {
a solvent, at a time or in series, and stirred and mixed.
"00801 ; ' I
15 The antifouling coating composition of the present invention
can be used in embodiments similar to those for generally known
antifouling coating, materials, and the antifouling coating film
of the present invention is formed from the antifouling coating
composition. For example, a surface of a substrate is coated or
20 impregnated with the antifouling coating composition of the present
invention, and then dried for a prescribed period of time, thereby
forming a cured antifouling coating film on the surface of the
substrate.
[0081] ;
SF-2337
35
For example, in a substrate with a coating film (e.g., an
antifouling substrate) of the present invention, a surface of the
substrate is coated with a coating film obtained by curing the
antifouling coating composition;
5" a method for producing a substrate with a coating film of
the present invention comprises a step of applying or impregnating
the antifouling coating composition to a surface of a substrate,
and a step of curing the composition to form a coating film; and
a method for preventing a substrate from fouling of the
10 present invention comprises a step of applying or impregnating
the antifouling coating composition to a surface of a substrate,
and a step of curing the composition to form an antifouling coating
film.
[0082] < I
15 Examples of the substrate include a substrate which is (e.g., ;
always or intermittently) in contact with seawater or fresh water,
and more specific examples include an underwater structure, an
outside-board of a ship, a fishing net and a fishing gear.
[0083] ;
20 The surface of the substrate, by being coated with such an
antifouling coating film, can be prevented for a long term from
fouling caused by aquatic animals. The (dried) thickness of the
antifouling coating film can be arbitrarily adjusted in view of
consumption rate of the coating film, etc. Exemplary thickness
SF-2337 !
36 I
*
thereof is 40 to 400 vim per one coating, preferably about 40 to
200 urn per one coating.
EXAMPLES
5 [0084] ;
Hereinafter, the present invention is further described with
reference to Examples, but it should be construed that the present
invention is in no way limited to these Examples. In the following
Examples and Comparative Examples, the term "part(s) "means part(s)
10 byweight, and"%" withrespect to the indicationof a solid component
means % by weight, unless deviating from the point.
[0085]
In the present invention, including tables as described later,
a mere reference, e.g., to "copolymer (A) " basically means a "resin" •
15 which is a coating film-forming component. ' The reference e.g.,
to "copolymer (A) " with the indication of a solid component also !
means a "resin solution or dispersion" containing a volatile I
component such as a solvent as well as the resin serving as the coating film-forming component. I
20 [0086]

Gardner viscosity was measured under the conditions of a
resin concentration of 35% by weight and 25°C in accordance with i
JIS K 7233-4.3, as described in JP 2003-55890 A. I
SF-2337
37
[0087]

The viscosity at 25°C was measured with a B-type viscometer.
[0088]
5
A solid component means a heating residue given when a
reaction mixture, a coating material, an uncured coating film or
the like containing a polymer, a solvent, etc. is heated and dried
for 3 hours in a drier of heated air at 105 °C to evaporate the
10 solvent, etc. The solid component usually includes a resin, a
pigment, etc. and becomes a coating film-forming component. For
the calculation, monomers (examples: Table 2) contained in the
coating material or the like and capable of forming a resin (solid
component) through reaction are also included in the solid
15 component.
[0089]
Measurements of number-average molecular weight (Mn) and ,'
weight-Sverage molecular weight (Mw)> <
Weight-average molecular weight (Mw) of a resin was measured ;
20 by gel permeation chromatography (GPC) method with "HLC-8120GPC", l
manufactured by Tosoh Corporation, using two separation columns
(a-M) of "TSK-gel a type", manufactured by Tosoh Corporation, and
using, as an eluting solution, dimethylformamide (DMF) to which
20 mM of LiBr had been added. The weight-average molecular weight
SF-2337
38
t
of the resin was determined in terms of polystyrene.
Number-average molecular weight (Mn) of the resin was measured
by GPC as described above and determined in terms of polystyrene.
[0090]
5 [Production Example 1]
Production of side-chain end metal salt bond-containing copolymer
(al-1)
Into a four-necked flask equipped with a condenser, a
thermometer, a dropping funnel and a stirrer, 30 parts of propylene
10 glycol monomethyl ether (PGM) and 40 parts of xylene were introduced,
and with stirring, they were heated to 100 °C . Subsequently, from
the dropping funnel, a mixture consisting of monomers and a
polymerization initiator shown in Table 1 was dropped at a constant
rate over-3 hours. After the dropping was completed, 1 part of .
15 t-butyl peroctoate and 10 parts of xylene were^dropped over 2 hours,
and after stirring for 2 hours, 20 parts of xylene was added, to
thereby obtain a reaction mixture containing a side-chain end metal
salt bond-containing copolymer (al-1).
[0091]
20 The Gardner viscosity and the solid component (%), which
are property values of the copolymer (al-1) or the reaction mixture I
containing the copolymer (al-1) obtained, were evaluated. The
results are set forth in Table 1.
[0092]
SF-2337 !
39
[Table 1]
Production Example of side-chain end metal salt bond-containing copolymer (a1)
Production
Example 1
Side-chain end metal salt bond-containing copolymer (a1) a1-1
Monobasic acid metal (meth)acrylate: monomer(a11) versatic acid zinc methacrylate 35
Other unsaturated monomer 2-methoxyethyl acrylate 10
copolymerizable with monomer (a11): 3-methoxybutyl acrylate 30
monomer (a12) ethyl acrylate 25
Polymerization initiator t-butyl peroxide 6
_. , . Gardner viscosity +Z
Praoerty values -=-^ ~\ FFTE—
I - } I Solid component (%) ] 50.5
Tne values of the monomer (a11), the monomer (a12) and the polymerization initiator denote parts
by weight.
r n n n n I
j_ '\J \J S ^f J
[Preparation Example 1]
Preparation of metal-containing monomer (a21-l)
Into a four-necked flask equipped with a condenser, a
10 thermometer, a dropping funnel and a stirrer, 85.4 parts of
propylene glycol monomethyl ether (PGM) and 4 0.7 parts of zinc
oxide were introduced, and with stirring, they were heated to 75 °C.
Subsequently, from the dropping funnel, a mixture consisting of
43.1 parts of methacrylic acid (MAA), 36.1 parts of acrylic acid
15 (AA) and 5 parts of water was dropped at a constant rate over 3
hours. After the dropping was completed, the reaction solution
turned transparent from an opaque white state. After stirring
for 2 hours, 36 parts of propylene glycol monomethyl ether was
added, to thereby obtain a reaction liquid containing a
20 metal-containing monomer (a21-l). The charged amounts of the raw
SF-2337 40 '
materials are set forth in terms of molar ratio, and the composition
of the resultant reaction liquid is set forth in terms of weight
percentage in Table 2.
[0094]
5 [Table 2]
Preparation of metal-containing monomer (a21-1)
[ i Volatile I Solid
component (%) of component (%)*
«. . ., , ,. . reaction liquid of reaction liquid
Charged amount (molar ratio) ... . . .
3 v ' containing containing
metal-containing metal-containing
monomer monomer
MMA AA ZnO water PGM water solid component
Preparation ^ ^ Q5 Q5 Q2J 532 2 448
Example 1 j | [ [ | | | [ _ _ _ ^_
*Solid component (%) contains a monomer capable of forming a resin through reaction.
10
[0095]
[Production Example 2]
Production of crosslinked metal salt bond-containing copolymer
(a2-l)
15 Into a four-necked flask equipped with a condenser, a
thermometer, a dropping funnel and a stirrer, 15 parts of propylene
glycol monomethyl ether (PGM) and 57 parts of xylene were introduced,
and with stirring, they were heated to 100°C. Subsequently, from ;
the dropping funnel, a transparent mixture consisting of 52 parts
20 of the reaction liquid of the metal-containing monomer (a21-l)
obtained in Preparation Example 1, 1 part of methyl methacrylate
(MMA), 66.2 parts of ethyl acrylate (EA), 5.4 parts of
SF-2337
41
2-methoxyethyl acrylate (2-MEA), 2.5 parts of
azobisisobutyronitrile (AIBN, manufactured by Japan Hydrazine
Company Inc.), 7 parts of azobismethylbutyronitrile (AMBN,
manufactured by Japan Hydrazine Company Inc.), 1 part of a chain
*5 transfer agent ("Nofmer MSD", manufactured by Nippon Oil & Fats
Co., Ltd. ) , and 10 parts of xylene was dropped at a constant rate
over 6 hours. After the dropping was completed, 0 . 5 part of t-butyl
peroctoate (TBPO) and 7 parts of xylene were dropped over 30 minutes.
After stirring for 1 hour and 30 minutes, 4.4 parts of xylene was
10 added, to thereby obtain an insoluble-free, light yellow,
transparent reaction mixture containing a crosslinked metal salt
bond-containing copolymer (a2-l). Blending composition and
property values of the copolymer (a2-l) or the reaction mixture
containing the copolymer (a2-l) obtained are set forth in Table
15 3.
[0096]
[Table 3]
Production Example of crosslinked metal salt bond-containing copolymer (a2)
SF-2337
42
fc . : , .
Production
Example 2
Crosslinked metal salt bond-containing copolymer (a2) a2-1
Reaction liquid of metal-containing „, , ,.„
monomer: monomer (a21) ~
Other unsaturated monomer MMA 1
copolymerizable with monomer (a21): _EA 66.2
monomer (a22) 2-MEA 5.4
• , -" AIBN 2.5
Initiator AMBN 7
TBPO 0.5
Chain transfer agent Nofmer MSP 1
Gardner viscosity -Y
p , , Solid component (%) 45.6
p ^ Number-average molecular weight (Mn) 1950
I Weight-average molecular weight (Mw) | 5200 |
[0097]
[Production Example 3]
Production of crosslinked metal salt bond-containing copolymer
(a2-2)
A crosslinked-metal salt bond-containing copolymer (a2-2)
5 was prepared in the same manner as in Production Example 1, except
that the blending components of the mixture containing the monomers ,
and the polymerization initiator were changed as shown in Table
4. Blending composition and property values of the copolymer
(a2-2) of the reaction mixture containing the copolymer (a2-2) [
10 obtained are•set forth in Table 4.
[0098] !
[Table 4] ' '
Production Example of crosslinked metal salt bond-containing copolymer (a2) •
Production
I Example 3 |
SF-2337 43 |
Crosslinked metal salt bond-containing copolymer (a2) a2-2
.. . . ~ . 777 I Zinc diacrylate 8
Metal-containing monomer (a21) -=—-r.—fr — =
v ' Zinc dimethacrylate 8
Monobasic acid metal (meth)acrylate: isostearic acid zinc acrylate 12
monomer (a22) isostearic acid zinc methacrylate 12
Other unsaturated monomer 2-methoxyethyl acrylate 13
copolymerizable with monomer (a21): methyl methacrylate 13
monomer (a22) ethyl acrylate^ 34
' Polymerization initiator ' t-butyi peroxide . 5
r, , . Gardner viscosity -Y
Property values [ Solid component (%) I ~ 4 9 ^—
[0099]
[Production Example 4]
Production of siiyl ester copolymer (a3-l)
Into a reaction vessel equipped with a stirrer, a condenser,
5 a thermometer, a dropping device, a nitrogen introducing pipe and
a heating/cooling jacket, 100 parts of xylene was introduced, and
heating and stirring were carried out in a stream of nitrogen at
a temperature condition of 85°C. With this temperature kept, from
the dropping device, a mixture of 60 parts of triisopropylsilyl :
10 acrylate, 40 parts of methyl methacrylate and 0.3 part of
2, 2' -azobisisobutyronitrile was dropped into the reaction vessel
over 2 hours. Thereafter, stirring was carried out for 4 hours
at this temperature, and then 0.4 part of
2,2'-azobisisobutyronitrile was added, and stirring was further
15 carried out for 4 hours at this temperature, to thereby obtain ;
a colorless and transparent reaction mixture containing a silyl
ester copolymer (a3-l). Blending composition and property values
SF-2337
44
of the copolymer (a3-l) or the reaction mixture containing the
copolymer (a3-l) are set forth in Table 5.
[0100]
[Table 5]
5 * Production Example of silyl ester copolymer (a3)
Production
Example 4 •
Silyl ester copolymer (a3) a3-1
Solvent xylene 100
triisopropyl silyl acrylate 60
Components methyl methacrylate 40
dropped 2,2'-azobisisobutyronitrile (initial stage) 0.3
Jotal 200.3
Component added 2,2'-azobisisobutyronitrile (later stage) 0.4
Solid component (%) : 51.2 .
D . . ViscosityJcps/25°C) 408
Property values -r.—, 'v r >-.—; . , , . . . . =-=r=
r J Number-average molecular weight (Mn) 9,735
I Weight-average molecular weight (Mw) | 55,650 [
[0101]
[Examples 1 to 3 and Comparative Example 1]
Production of antifouling coating composition-1
The reaction mixture containing the crosslinked metal salt
10 bond-containing copolymer (a2-l) obtained in Production Example
2, along with the antifouling agent (B) and other components, were
homogenously mixed using a paint shaker, to thereby produce an
antifouling coating composition having a blending composition as •
shown in Table 6 (Examples 1-3 and Comparative Example 1) (values ;
15 in the table de'note part(s) by weight). ;;
[0102] J- ' ;
[Examples 4 to 52 and Comparative Examples 2 to 11]
SF-2337
45
Production of antifouling coating composition-2
The reaction mixture containing the crosslinked metal salt
bond-containing copolymer (al-1), (a2-l) or (a2-l), obtained in
Production Examples 1 to 3, or containing the silyl ester copolymer
5 (a3-l) obtained in Production Example 4, along with the antifouling
agent (B) and other components, were homogenously mixed using a
paint shaker, to'thereby produce an antifouling coating composition
having a blending composition as shown in Tables 8-1 to 8-6 (Examples
4-52 and Comparative Examples 2 to 11) (values in the tables denote
10 part(s) by weight).
[0103]
[Criteria for evaluation of static antifouling property based on
an area of adhesion of undersea organisms, in Examples and
Comparative Examples]
15 Criteria for evaluation of static antifouling property based
on an area of adhesion of undersea organisms are as follows. i
0 point: The area of adhesion of the undersea organisms is i
about 160%. I
1 point: The area of adhesion of the undersea organisms is
20 about 51 to 09%. ;
2 points: The area of adhesion.of the undersea organisms
is about 31 to 50%.
3 points: The area of adhesion of the undersea organisms
is about 11 to 30%.
SF-2337
4 6
4 points: The area of adhesion of the undersea organisms
is about 1 to 10%.
5 points: The area of adhesion of the undersea organisms
is about 0%.
5 [0104]

A sandblasted steel plate (length 300 mm * width 100 mm *
thickness 3.2 mm) was coated with an epoxy anticorrosive coating
10 material (epoxy AC coating material, product name: "Bannoh 500",
manufactured by Chugoku Marine Paints, Ltd.) so that the dried
film thickness would be 150 urn, and then was further coated with
an epoxy binder coating material (product name: "Bannoh 500N",
manufactured by Chugoku Marine Paints, Ltd.) so that the dried
15 film thickness would be 100 urn. Subsequently, the resultant plate
was coated with the antifouling coating composition produced in ;•
the Example or Comparative Example one time so that the dried film !
thickness would be 100 um, and then dried at room temperature for
7 days, to thereby prepare a test plate with an antifouling coating l
I
20 film. The above three coatings were each carried out under the
condition of 1 day/1 coat.
[0105]
The test plate prepared as described above was immersed and
allowed to stand still for 8 months in Hiroshima Bay of Hiroshima
SF-2337
47
Prefecture. Duringthisperiodof time, thearea (%) of the adhesion
onto the coating film surface of undersea organisms excluding slime,
was measured every two months. In accordance with the [Criteria
for evaluation of static antifouling property based on an area
5 of adhesion of undersea organisms] , the static antifouling property
of the antifouling coating film was evaluated. The results are
set forth in Tables 7, 9-1 to 9-6.
[0106]

A hard vinyl chloride plate of 50 x 50 x 1.5 mm was coated
with the antifouling coating composition produced in Example or
Comparative Example, using an applicator, so that a dried film
thickness- would be 250 urn. The coated plate was rotated at 15 .
15 knots, and the consumption degree (decrease In the film thickness)
of the antifouling coating film, was measured every month. The
results are set forth in Tables 9-1 to 9-6. A unit of the consumption
degree -of the coating film in the tables is "um".
[0107]
20 _
A substrate which was a sandblasted steel plate coated with
an anticorrosive coating film was coated with the antifouling
coating composition produced in Example or Comparative Example,
SF-2337
48
so that a dried film thickness would be 250 urn. Then, this was
immersed in sterilized and filtered seawater for 3 months, and
then dried at room temperature for 1 week. Each of the deteriorated
antifouling coating films thus obtained was coated with an
5 anticorrosive coating composition having the same composition,
so that a dried film thickness wouldbe 250 um, and then the resultant
coated plate was dried for 1 week. Then, this was immersed in
sterilized and filtered seawater at 50 °C for 6 months, to observe the coating film about crack and peeling. Finding no crack and
10 peeling was evaluated as AA; finding partial crack was evaluated
as BB; finding partial peeling was evaluated as CC; and finding ;
crack and peeling throughout the entire surface was evaluated as ]
DD. The results are set forth in Tables 9-1 to 9-6. :
[0108] ?
15 [Table 6]
Antifouling coating composition-1
I Ex.1 I Ex.2 l Ex.3 l Com.Ex.1 [ I
Crosslinked metal-salt, bond-containing 1QQ 10Q ,QQ 10Q
copolymer (a2-1) (solid component: 45.6%)
medefomidine 0.025 0.05 0.1 -
xylene | 5 | 5 | 5 [ - ~|
[0109] , • [Table 7]
2 0 ' Result of antifouling property
- Immersion period Ex.1 Ex.2 Ex.3 Com.Ex.1
J ' 2 months 4 4 5 2
4 months 3 4 5 1 6 months [ 2 | 3 [ 5 | 0 |
SF-2337
49
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