1
DESCRIPTIOK
ANTIFOULIWG COATING COMPOSITION, i\NTIFOULING COSTING FILM AND
ANTIFOULING SUBSTRATE, AN13 METHOD FOR PRODUCING ANTIhX)ULING
5 SUBSTRATE
TECHNICAL FIELD
[0001]
The present invontion relates to an antifouling coating
10 composition that has lotig-torm storage stability and gives a coating film exhibiting excellent antifouling properties and water resistance (long-term mechanical properties); an antifouling coating film formed therefrom and an antifouling substrate having such a coating film; and antifouling substrate
15 production method.
BACKGROUND ART
[0002J
The surfaces of substrates such as ships, underwater 20 Structures and fishing nets that are exposed to water for a long term easily undergo the adherence thereto of various aquatic creatures including animals such as oyster, mussel and barnacle, plants such as laver, and bacteria. Tho propagation of these aquatic creatures on the substrate surfaces would cause various

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problems: where the substrate is a ship, for eKaniple, the surface roughness increases from the waterline to the bottom of a ship, resulting in the decrease in the speed of a ship and increaso in fuel cost of a ship. Where the substrate is a fishing net such 5 as a culturing net and B. fixed net, the clogging of the mesh by aquatic creatures could cause sorious problems such as the death of cultured creatures and caught fish because of OKygen deficiency Where the substrate is a water supply and exhaust pipe for scawater of e.g., a thermal power plant and a nuclear power pliint, it may
10 happen that the vjator supply and exhaust pipG for seawater (cooling water) is clogged or flow rate is decreased to disturb circulation systems. [0003]
Regarding such problems, in order to prevent the adherence
15 of aquatic creatures onto various substr^ates, the research and devolopinent of antifouling paints to be applied on Lhe substrates [anti fouling coating composition) are underway. [0004]
As a conventional antifouling coating composition, a
20 coating composition containing a hydroly/^able resin as a resin component (binder component) is Icnown. As a typical example thereof, a coating composition containing a hydrolyzable resin having a triorganosilyl group has been developed. Such a coating composition is applied on the bottom of ships and the like in order

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to prevent aquatic creatures from adhering thereto,
[0005J
The hydroiyzable resins having a triorganosilyl group that.
are generally known aro the onea obtained by (co)polymerizing as 5 El monomer component triisopropyisilyl acrylato (TIPSA) and/or
triisopropylsily], raethacrylate (TlPSMA) . For example, the
following }?atent Literatures 1 to 7 disclose antifouling coating
compositions containing these [co)polymers.
[0006] 10 Patent Literature 1 discloses a coating composition
composed of a copolymer containing 55 to 75 parts by weight of
tri-i-propylsilyl (liieth) acrylato in), 2 to 20 parts by weight of
methoxyethyi acryXate (b) and ^3 to 5 parts by weight of other
polymerizable monomer (c), with respect to of 100 parts by weight 15 of total monomer components, and an antifouling agent,
[0007J
Patent Literature 2 discloses an antifouling coating
composition containing, as a vehicle, a copolymer obtainable from
a specific triorganc?siIyI methacrylate fiionomer, a specific 20 alkoxyallcyl methaorylate monomer and an ethyienic unsaturated
monomer copolymerizablc with these monomers.
[QOOa]
Patent Literature d discloses an antifouling coating
composition containing a copolymer obtained from a specific

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triorqanosilyl methacrylate monomer and a specific methoxyaikyl methacrylate monc?Jner; and rosin copper salt or a roain derivative cnpper salt. [0009] 5 Patent Liti^rature 4 discloses a coating composition
containing, as e.^sential components^ a copolymer obtained from silyl-based monomer having an acryloyloKy group and a specific monomer, and an antifouling agent. [0010]
10 Patent Literature 5 discloses a coating composition
containing, as essential components, a rosin-bascd compound, an organosilyl ester group-having polymer obLained from a silyl-based mono^nsj: having acryloyloKy group and the like, and an antifouling agent.
15 [0011]
Patent Literature 6 discloses an antifouling coating composition containing a triisopropylsilyl (meth)acrylate copolymer obtainable by copolyraerizing triisopropylsilyl (meth) acrylate, niothyl methacrylate and another tmeth) acrylic
20 acid ester and having a specific glase transition teinperaturo and a specific number average molecular weight; a rosin copper salt or a rosin derivative copper salt; and cuprous oxide. [0012]
Patent Literature 7 discloses ^n antifouling coating

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composition containing a poiymor obtained by polymerizing a polymerizable unsaturated carboxylic triorganosiiyl ^nd having a number average molecuiaj: weight of 1000 to 20000, 3.nd a ro^in
zinc salt or a Jrosin derivative zinc salt. 5
CITATIOM LIST
PATENT LITERATURE
[0013]
Patent Literature 1: JP-A-2001-22 6440 10 Patent Literature 2: JP-A-2005-82725
Patent Literature 3: WO2010/071ia0
Patent Literature 4: JP-A-07-102193
Patent Literature 5: JP-A-10-30071
Patent Literature 6: JP-B--1340777 15 !.^atent Literature V: KO2009/065632
SUMMARY OF THE INVENTION TECHNICAL PROBLBH
[0014] 20 However, antifouling coating compositions containing, as a hydroiyzable resin component, a homopolymer or copolymer of TIP3A or TIPSMA that are disclosed in Patent Literature 1 to 7 need to be improved in terms of their properties, as follows. [00151

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According to the study of the present inventorS;^ the antifouling coating film formed from the antifouling coating composition containing a homopolymer of TIP3A is good in terms of its coating film consumption property (renewability), but 5 allows hydrolysis reaction within the coating film to take place relatively early and thus tends to undergo cracking not long after iinmorsod in water. In addition, the homopolymer of TIPSA becomes readily decomposed during the production of coating material or the storage of coating matorial by the incorporation of moisture
10 and temperature increase. Particularly in the presence of
divalent metallic ions, the viscosity of the resulting coating material is increased with the passage of time. [0016]
Tho coating material viscosity is increased presumably when
15 the homopolymer, from which a triisopropylsilyl group is released, becomes an acid polymer (having a carbo^yl group at its side chains); and carboxyl groups are bonded to ono another via a, divalent metal ion such as a copper ion and a ^Inc ion derived from cuprous oxide and zinc oxide, respectively, and are
20 three-dimensionally crosslinked. [0017]
On the other hand, the antifouling coating composition containing a homopolymer of TIP3MA has good storage stability and generally has high water resistance, thus making it difficult for

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hydrolysis reaction to progress within the coating film relatively early. However, this composition has poor coating film consumption property (renewability), ^nd therefore gives an antifouJ.ing coating film that has insufficient static antifouling 5 properties. For example, this antifouling coating film, when often used for ships staying in port, exhibits insufficient antifouling properties. In addition, because TIJ7SMA. has a high Tg; thiii antifouling coating film tends to have an excessively high hardness, and thus cannot follow flexure as well as swelling
10 and shrinkage of ship steel plates, easily causing cracking. [0018]
The coating compositions containing any of TIPS?^ and TIPSMA copolyiiiers disclosed in the Patent Literatures 1 to 7 enable its antifouling coating film to have improved coating film consumption
15 property and static antifouling properties. However, appearance properties and adhesion of their antifouling coating films when immersed in seawater (particularly when immersed for a long tcrin) , and storage stability of such coating compositions have not been improved sufficiently in a balanced manner yet.
20 [0019}
As described above, it has been impossible for conventional coating compositions containing a triorganosilyl group-having hydrolyzable resin to form antifouling coating films satisfactorily exhibiting all of antifouling properties,

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appearance properties antJ adhesion and for such conventional coating compositions to exhibit satisfactory storage stability, and thus the respective properties have been under trado-off
relationship among one another. S {0020J
In view of the failure to overcoftie the problems by such conventional antif ouJ.ing coating compos it ions containing tri.isopropyliiilyl (meth) acry.late polyjners, tho present inventors found that by allowing a copolymer of triiscpropylsilyl 10 methacrylate and tri.isopropylsilyl acryiate to have specific ratios of structural units derived from respective monomers, it is possible for an antifouling coating composition to have good long-term storage stability, and for a coating film formed from said coating composition to have good long-term antifouling 15 properties and long-term water resistance, with good balance. [0021J
That is, it is an object of the present invention to provide an antifouling coating composition that is excellent in long-term storage stability and gives a coating film excellent in long-term 20 antifouling properties and long-term water resistance. [0022]
It is another object of the present invention to provide an antifouling coating film snd an antifouling substrate that are prepared by using the coating composition and being excellent in

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long-term antifoaling properties and long-term water resistance; and a method for pj:oducing an antifouling Hubsti^ate excellent in long-term antifouling properties and long-term water res.istance.
5 lECHHICAL SOLUTION
[Q023]
The antifouling coating composition according to the
present invention comprises a silylacrylic copolymer (A) that
comprises a structural unit (1) derived from triisopropylsilyl 10 rnethacrylate {i.) , a monomer structural unit {2] derived from
triisopropylsilyl acrylate (ii) and a structural unit [3) derived
from a polymeri^-able monomer having a polymei:izable double bond (ill), which excludes the above (i) and tii)^ and satisfies the
following Requirements 1 and 2; 15 Requirement 1: the content weight ratio {[{1)-\-{2) ] / [3] ) of
the total weight i{l)+i2)) of the structural unit (IJ and the
structural unit {2) to the content weight of the structural unit
(3) is 50/50 to 90/10; and
Requirement 2: tho content weight ratio {(l}/(2)) of the 20 content weight of the structural unit (1) to the content weight
of the structural unit (2) is more than 50/SO and not more than
95/5.
[0024]
In the antifouling coating composition of the present

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invention, the polyrtierlzable monomer (iii) is preferably an ester
having a polymerizable double bond, or a carboxylic acid having
a polymorizabie double bond.
[0025J 5 It is preferable that the antifouling coating composition
of the present Invention further comprises a rosin and/or a
monocarboKylic acid compound (B).
[0026]
It Is preferable that in the antifouling coating coipposition 10 of the present: invention; the content weight ratio [WA/WB) of the
content weight (Wa) of the silylacrylic copolymer (A) to the
content weight (WB) of the rosins and/or monocarbozylic acid
compound (B) is 99.9/0.i to 30/70.
[0027]
I'D It is preferable that, the antifouling coating composition
of the present invention further comprises at least one :3elected
from the group consisting of a copper compound (CJ, an organic
antifouling agent {D), and other additive(s) fE) including a
plasticizer (el), an extender pigment {^2], a pigment dispersant 20 {e3), a coloring pigment (e4J, an anti-sagging agent {e5), an
anti-settling agent (eG) and a dehydrating agent Ee7), and a
solvent (F).
[0028]
The antifouling coating film according to the present

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invention is formed by curing the antifouling coating composition. [0029]
The antifouling substrate according to the present invention is formed by coating or impregiiatitig a substrate with 5 the antifouling coating composiLion, and curing the coating composition, which is used to coat or impiregnate the substrate, to thereby form an antifouling coating film on the substrate. [0030]
It is preferable that the antifouling substrate of the 10 present invention contacts with soawater or fresh water, [0031]
It is preferable that in the anLifouling coating film of the present invention, the substrate is at least one selected from the g!:oup consisting of an underwater structure, a ship and a 15 fishing gear, [0032}
A method for producing an antifouling substrate according to the present invention comprises coating or impregnating a substrate with the antifouling coating composition; and cui:ing 20 the coating composition, which is used to coat or impregnate tho substrate, to thereby form an antifouling coating film on the substrate. [0033]
The silylacrylic copolymer, which is used as a binder

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component of tha Eintifouling coating composition/ according to
the present invention comprises a structural unit {!) derived from
triisopropylsilyl methacrylate (i) , a monomer structural unit {?.)
derived from triisopropylsilyl acrylate (ii) and a structural unit 5 £3) de!:ived from a polymerizable jitonosner having a polymerizatale
double bond (iii) , which exc].udes the above [ij and (1.1), the
Hilylacrylic copolymer satisfying the following RequirementE 1
and 2;
Requirement 1: the content weight ratio { [ [1} ■\- {?.)} / {3) ) of 10 the total weight {{l)-^{2)) of the structural unit (1) and the
structural unit (2) to the content weight of the structural unit
(3) is 50/50 to90/10; and
Requirement 2: the content weight ratio [El)/(2)) of the
content weight of the structural unit fl) to the content weight 15 of the structural unit E2) is more than 50/50 and not more than
95/5.
flDVAKTAGEOUS EFFECTS OF THE INVENTION
[003d]
7.0 The antifouling coating composition according to the
present invention is excellent in long-term storage stability (in particular, le&s increase in its viscosity during long-term storage) and gives a coating film excellent in long-term antifouling properties fin particular static antifouling

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properties) and long-term water resisLance [long-term mechanical properties: adhesion, abrasion resistance^ crack resistance, and appearance properties such ^3 fracture, of a coating film when
intmersod in water, particularly soawater), with good balance. 5 The antifouiing coating filin. and the antifouiing substrate
according to the present Invention exhibit excellent long-term antifouiing properties and long-term water resistance {long-term mechanical properties) with good balance Furthermore, the method for producing the antifouiing substrate according to the 10 present invention can providt3 an antifouiing substrate exhibiting excellent long-terin antifouiing properties and long-term water resistance.
EMBODIMENTS OF THE INVENTION 15 [O035]
Hereinafter, the antifouiing coating composition, the
antifouiing coating film and the antifouiing substrate, and the antifouiing substrate production method, according to the present invention, are described in detail, 20 [Antifouiing coating composition]
The antifouiing coating composition of the present invention ^antifouiing paint) comprises a specific silylacrylic copolymer (A). The antifouiing paint of the present invention may contain an optional coniponejit according to purpose.

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[0036]
1. Silylacrylic copolymor {A}
The silylacrylic copolymer (A) comprises a structural unit (1) derived from triisopropylsiiyl mothacrylate fi), a monomer 5 structural unit (2J derived from triisopropylsiiyl acrylato (ii) and £2 structural unit (3) derived from a polymerizable monomer (iii) having a polymerizable double bond, which excludes the above (i) and (ii). [0037] 10 This silylacrylic copolymer satisfies the following Requirements 1 and 7.,
Requirement!: the content weight ratio f [ ED-l-(2) J / f3} ) of the total weight ((1)+{2)J of the structural unit (1) and the structural unit E2) to the content weight of the structural unit 15 (3) is 50/50 to 90/10; desirably 60/40 to 80/20, in terms of improving coating film hydrolyzability (consumption property}, static antifouling properties and the like.
Requirement 2: the content weight ratio E(l)/(2)) of the content weight of the structural unit (1) to the content weight 20 of the structural unit {?-) is more than 50/50 and not more than 95/5, desirably 60/40 to 90/10, in terms of improving coating film water resistance (mechanical properties), coating film hydrolyzability (consumption property), static antifouling properties, storage stability and the like.

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[0038]
For convenience sake, the content weight ratios in the Requirement 1 and the Requireraent 2 are also called the content weight ratio (I) and the conLcnL weight ratio [11) r rcspGCtively. 5 [0039]
It is preferred that the silylacrylic copolymer [A] is contained in the antifouling coating composition of the present invontion usually in an amount of 10 to 505 by weight, preferably 15 to 304; by weight, in tiornis of improving coating workability,
10 long-terra storage stability;- coating film water resistance (mechanical properties), coating film hydrolyzability (consumption property), static antifouling properties, coating filKL appearance and the lik.e. It is preferred that the silylacrylic copolymer (A) is contained, with respect to 10(J% by
I'D weight of the solid content (heat residue or non-volatile content) of the antifouling coating composition of the present invention, usually in an amount of about 5 to 50^ by weight, preferably about 10 to 30% by weight, in terms of improving coating workability, long-term storage stability, coating film water resistance
20 (mechanical properties), coating film hydrolyzability
(consumption property), static antifouling properties and coating film appearance. The solid content (heat residue] contained in the antifouling coating composition is obtained by keeping 1.5 g of the antifouling coating composition in a

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thermostat chamber at 125 "C for 1 hour to remove volabile contents . [0040]
The polymerizable monomer having a polymerizable double bond fiii) refers to a monomer excluding the triisopropylsilyl. 5 methacrylato (i) and the? triisopropylsilyJ acrylate (ii) and having a po].ymeri?able double bond (for eKamplc, vinyl group^ (moth)acryloyl group), and is copolymerized with the above (i), (ii) or the monomer (,ii.,i.). [0041] 10 Tho polymerizable? monomer (ill) is preferably an ester having a polymerizable double bond, or a carboxylic acid having a polymorizable double bond. The polymerizable monomer (iii), by being such compounds, achieves good compatibility with the triisopropylsilyl methacrylate (i) and the triisopropylsilyl 15 acrylate (iij, and has reactivity with the triisopropylsilyl methacrylate (i) that is a similar degree to reactivity with the triisopropylsilyl acrylate (ii). Therefore, the produced silylacrylic copolymer (fi) has structural units derived from rospectivo monomers which are uniformly (randomly) Incorporated, ?.0 and has good compatibility also with respect to a solvent. In other words, when the polymerization reactivity is extremely different among respective monomers and the copolymerization of respective monomers is difficult, a problem such that copolymers having structural units in a non-uniform manner or homopolymors

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are obtained is caused. By conLrast, when the polymer!zable monomer (ill) is the compounds described above, the occurrence
ot the above problem Is redueced, and stable production of the silylacrylic copolymer (A) is achieved. 5 [0042]
Kxamples of the ester and the carboxylic acid used as the polymerizablo monomer (ill) , whj.ch exclude the triisopropylsilyi methacrylate (i) and the triisopropylsilyl acrylate fii) , include (meth)acrylic acid esters, monocarboxylic acids, dicarboKylic 10 acids and half-esters (monoester), diesters and vinyl esters thereof. Examples of the polymerizable monomej: (iii) other than the ostors and the carboxylic acids include styrenes.
Specific examples of the polymerizable monomer (iii) 15 include (meth)acrylic actd esters such as methyl (meth)acrylate, ethyl(raethj acrylate, butyl(meth)acrylate, 2-ethylhexyl
(meth)aerylate, lauryl (meth)acrylate, tridocyl (meth)aerylate, stearyJ. (meth) acrylate, allyl (meth) aery late, cyclohexyl (meth)acrylato, benzyl (meth)acrylate, isobonyl (meth)acrylate, 20 methoxy (meth)acrylate, ethoKy {meth)acrylate, glycidyl
(meth)acrylate, tetrahydrofurfuryl imeth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl {meth)acrylate, hydroxybutyl (meth)acrylate;
monocarboxylic acids such as (moth)acrylic acids;

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dicarboxylic acids such as itaconic acid, maleic acid and succinic acid, and half-esters (nionoesters) and diosters thereof;
sLyrenes such as styrone and cc—methyl styrene; and
vinyl esters such as vinyl acetate and vinyl propionate.
5 Those are used singly, or two or more kinds thereof may be
contbined. [0044]
The silyl acrylic copolynter (A) preferably has a weight average molecular weight of 5000 to 100000, more preferably 10000 10 to 60000. By employing the silylacrylic copolymer (A) having a weight average molecular weight falling within these ranges, the antifouling coating composition gives a coating film that has good hydrolyzability and has much improved static antifouling properties and further excellent long-term mechanical properties 15 (e.g. adhesion of the antifouling coating film of the present invention to a substrate, an under-coating film and the like, and appearance properties such as cracking of the antifoul.i.ng coating film, in the case of immersion in water for a long term). [0045] 20 The value of the weight average molecular weight is that as measured by gel permeation chromatography (GPCJ , and determined by using standard polystyrene calibration curve. The GPC conditions in molecular weight measurement are as follows. GPC conditions

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Pump: "nLC-ai20GPC" Emanufac:tured by Tosoh Corporation) Column: "SuperH2000IH4000" {manufactured by Tosoh Corporation, 6 mm {inner diameter), 15 cm (length) for each ooltjmn) Eluent: tetrahydrofran (THF) 5 Other conditions
Flow rate: 0,500 ml/min.
Detector: RI
column thcrmoHtat chamber Uemperature; 40*C
Standard substance: polystyrene
10 Sample preparation method: To a solution containing the copolymor (A) , a small amount of calcium chl.oride is added to dehydrate the solution, which is followed by filtration with a mcinbrane filter. The obtained filtered material is used as a sample for GPC measurement.
lb [00^6]
In the silylacrylic copolymer [A], the content weight ratio ( [{l)-^{2)]/{3) ) (the content weight ratio (1)) of the total weight { (1) + (2) ) of the structural unit (1) and the structural unit (2) to the content weight of the structural unit (3) is 50/50 to 90/10,
20 preferably 55/45 to 95/15, more preferably 50/40 to 80/20. [0047}
When tho content weight ratio (I) is within the above range, it is po3sib3.e to obtain an antifouling coating composition having good coating film hydroIyzabiliLy (consumption property] , static

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antifouling properties ^nd coating film water resistance (mechanical properties).
The content weight ratio { {!) / [2) ) (the content weight ratio 5 {II)) of the content weight of the structural unit fl) to the content weight of the structural unit (2) is more than 50/50 and not jfiore than 95/5, preferably 55/'15 to 90/10, more preferably 60/40 to B5/15, particularly pjreferably 65/35 to 80/20. [0049]
IQ When the content weight ratio (II) is within the above range, the antifouling coating film formed from the antifouling coating composition, when immersed in water^ particularly seawater, exhibits sufficient coating film consumption property (renowability), and thorofore exhibits good long-term
15 antifouling properties such as static antifouling properties, making it possible for cracking to occur less often for a long term. [0050]
The silylacrylic copolymer (A) is prepared by
20 copolymerizlng the triisopropylsilyl methacrylate (i), the
triisopropylsilyl acrylate (ii) and the poiymerizable monomer having a pclymerizable double bond (itij by a known polymerization method. An exemplary polymerization mothod is a radical or ionic polymerization in solution polymerization, bulk polymerization,

21
SGiiii'-batch polymerization, suspension polymerization,
coordination polymerization, living polymerization or
emulsificatlon polymerization.
[0051]
b In particular. In tei:ms of improving the productivity and
manufacturing workability of tho silylacryiic copolymer (A) as well as preparing the oopoiymer (A) having low viscosity, it is preferable to subject the above fi)-{iii) to solution polymerization by using an organic solvent commonly used such as
10 toluene, xylene, methyl Isobutyl ketone and n~butyl acetate. When the copolymer (A] has a low viscosity us described above, the amount of a solvent added to reduce the viscosity of the antifouling coating composition can bo lowered, leading to the decrease in the VOC value. The reduced viscosity of the
15 antifouling coating composition can enhance the coating
workability of tho coating composition, and the appearance properties (leveling properties) and the like of the antifouling coating film. [0052]
20 As radical polymerization catalysts, known ones can be widely used, such as azo compounds such ^s 2,2'-azobis{2-methylbutyronitrileJ (7\MBN) , 2,2'-azobis{2,4-dimethylvaleronitrile) and 2,2'-azobis-isobutyronitrile; and peroxides such as

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benzoylpero^ide, t-butylperoxy-2-ethyIhexanoate, t-butyiperoxybonzoatc, t-butylperoxyoctoate, as described in Ji.'-A-2001-15l830, paragrijph [0099] E3nd the likie.
[0053] 5 The r£3tio of charge (weight) of the above (i) to (iii) , which are monomers subjected to polymeirization reaction, tends to correspond to the content (weight) ratio of the structural units
(1) to (3) contained in the resultant copolymer, respectively. Thus, regarding the Requirements 1 and 2, the content weight ratio 10 (1) and the content weight ratio (11) can be controlled to be desired ones, based on the amounts (weights) of charge of (i) to
(iii) E3nd on tho weight ratio of charge f(i)/(ii) or
i{i) + (ii))/((i) + (iij + (iiin) . [0054] 15 ^, Rosin or Monoc^rboxylic acid compound (B)
The antifouling coating composition of the present invention may comprise a rosin or a monocarboxylic acid compound (B) , in terms of promoting the elution of the antifouling agent froiit the antifouling coating film formed from tho composition in 20 order to improve particularly static antifouling properties. Examples of the rosin used herein include rosins such as gum rosin, wood rosin and tall oil rosin, and rosin derivatives such as a hydrogenated rosin and a disproportionated rosin. Examples of the monocarboxylic acid compound include aliphatic or alicyclic

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monocarboxylie acids, monocarboxylic acid derivatives thereof
£ind metal salts thereof.
[0055]
Specific eKamples of the monoca3:boxylic acid compounds
5 include naphthonic acid, cycloalkenylcarboxylic acidij,
bicycloalkienylcarboxylio acids, vorsatic acid, trimethyl
isobutenyl cyclohoxene carboxylic acid, stearic acid,
hydrosystoaric acid, salicylic acid, Eind metal salts thereof.
[0056]
10 In the anLifouling coating composition of the present
invention, the content weight ratio (W^^/WBJ of the content weight fWfl) of the copolymer (A) to the content weight (WB) of the rosin or monocarboxylic acid compound [B) is preferably 99.9/0.1 to 30/VO, more preferably 95/5 to 35/65, still more preferably 90/10 15 to ^0/60. When the content weight ratio is within these ranges, the grindability (coating film consumption property) of the antifouling coating film foriiied from the antlfouling coating composition is increased, and thereby the antlfouling properties (in particular static antlfouling properties} can be enhanced, 20 [0057]
3. Copper compound (C)
The antlfouling coating composition of the present invention, in order Lo provide an antifouling coating film formed from the antifouling coating composition that has further improved

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antifouiing properties, may further comprise a copper compound {C) . The copper compound may be any of organic or inorganic coppei: compounds, with examples thereof including cuprous oxide, copper
thiocyanate, cupronickel and copper pyrithione. s [0058]
In the antifouling coating composition of the present invention, the content of the copper compound (C), with respect to 100 parts by weight of the copolymer (A) , is preferably 10 to 800 piirts by weight, more preferably 100 to 750 parts by weight,
10 j.n terms of improving long-term antifouling properties of the antifouling coating film. The content of the copper compound (C) , with respect to 100% by weight of the antifouling coating composition (containing a solvent), is usually about 0,1 to 70% by weight, preferably about 0.1 to G0% by weight.
15 [0059]
It is preferable that these copper compounds are copper compounds that do not contain 2% or more of metallic coppar based on their total weight. [0060]
20 4. Organic antifouling agent {D)_
The antifouling coating composition of the present invention may further comprise an organic antifouling agent (D), in order to provide the antifouling coating film formed from the antifouling coating composition that has further improved

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antif ouling proper tie a, p£\rticularly improved ant 1 fouling effects on plant marine organism. The organic antifouiing agent [D) is not particularly limited as long as boing organic compounds that provide the antifouiing coating film with antifouiing 5 properties, excluding the above-mentioned organic copper coinpoundK. [00 61]
Examples of the organic antifouiing agent [D) include rnetal pyrithiones such as zinc pyrithione, 10 4,5"dichloro-'2-n-octyl'-4"isothiazolin-3-one,
4-bromo-2- f 4-chlorophenyl) -5- (triflucromethyl) -IH-pyrrole^-S-c arbonitrile, pyridinetriphenylborane, N,N-dimethyldichlorophenylu£eay 2,4,6-trichlorophenylmaleimlde, 15 2,4,5,G-tetrachloroisophthalnitrile,
bisdimethyldithiocarbamoylzinc ethyleneblsdithiocarbamate, chloromethy 1-n^-octyldi sul f ide,
N,N'-dimethyl-N'-phenyl-(H-fluorodichloromethylthio)sulfamide, tetraa1ky1thiuramdisulfide, zinc dimethyldithiocarbamatG; zinc 20 ethylenebisdithiocarbamate,
2, 3-dich].oi:o-N- (2' , 6' -diethylphenyljmaleiraide and 2, 3-dichloro-N- (2' -ethyl-6' -ineLhyiphenyl) maleimide . [0062]
In the antifouiing coating composition of the present

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26
invontion, the content of the org^anic antifouling agent [0), with respect to 100 parts by weight of the copolymer (A) , is proforably
0.1 to 500 parts by weight, more preferably 0.5 to 300 part.s by weight, in terms of nllowing the antifouling coating film formed 5 from the antifouling coating composition to have improved
mainlonanco of long-term antifouling properties and coating film water resistance [maintaining of mechanical properties). The content of the organic antifouling agent ED) / with respect to 100% by weight of the antifouling coating composition (containing a 10 solvent) , is usually about 0.1 to 30% by weight, preferably about 0.1 to 20% by weight. [0063] 5. Other additiveis) {E)_
The antifouling coating composition of the present 11? invention may comprise at least one additive (E) selected from the group consisting of a plasticizer (el), an extender pigment fe2), a pigment dispersant (e3], a coloring pigment [e4), an anti-sagging agont (e5), nn anti-settling agent Ee6} and a dehydrating agent {e7). Hereinafter, these additives (E) are 20 described in detail. [00641
It is preferable that the antifouling coating composition of the present invention comprises a plasticizer {elj in order

SF-2590
27
to give an antifouling coating film that has improved crack resistance. Examples of the plasticizer (el) include paraffin chloride (chlorinated paraffin) , petroleutn rosins, ketone resins, TCP (tricresyl phosphate)^ polyvinyl ethyl ether and 5 dialkylphthalate. In terms of allowing the antifouling coating film formed from the antifouling coating composition to have improved coating film water resistance (mechanical properties) and coating film hydrolyzability [consutnption property) , the plasticizer (el), among these, is preferably paraffin chloride
10 (chlorinated paraffin), petroleum resins or Icotono rosins. The plasticizer (el) may be used singly, or. two or moire kinds thereof may be combined. [0065]
Paraffin chloride may have any of linear molecular structure
15 or branched molecular structure, and may be at a liquid state or a solid state (for example: powder state) under room temperature {for example: 23"C) condition. [0066]
Paraffin chloride has carbons in which the average number
20 of carbons in one molecule is usually 8 to 30, preferably 10 to 26. An antifouling coating composition containing such paraffin chloride can form an antifouling coating film that has less cracking (fracture) and peeling. If the average number of carbons Is less than 8, the effect of suppressing the occurrence of cracks

SF-2590
2B
in the antifouling coating film ntay become insufficient. On the other hand, if the average number of carbons is more than 30, an antifouling coating film may have dccrcayod hydrolyzability
(renewability, grindability) , thus tjaving deteriorated 5 antifouling properties. [0057]
The paraffin chloride usually has a viscosity Eunit; Poise, inGasurGiiiGnl; tomporaturc: 25'C) of 1 or more, preferably 1.2 or morS; and usually has a specific gravity {25°C) of 1.05 to 1.80, 10 preferably 1,10 to 1.70. [006S]
The paraffin chloride usually has a chlorination percentage (chlorine contGnt) with respect to 100^ by weight of paraffin chloride, of 35 to 70% by weight, preferably 35 to 65% by weight. 15 By containing the paraffin chloridG having such chlorination percentage, the antifouling coating composition can form a coating film that has less cracking (fracture), pooling and the like. Specific examples of such paraffin chloride Include "TOYOPRRAX 150" and "TOYOPARfiX R-70" [both of which are manufactured by Tosoh 20 Corporation). [0069J
Examples of the petrolGum resins include C5-based ones, C9-based ones, styrene-based ones, dichloropentadiene-based ones, and hydrogenated products thereof. Specific examples of the

SF-2590
29
petroleum resins include "Quintone 1500" and '"Quintone 1700" Eboth
of which are manufactured by Soon Corporation),
[0070J
In the antifoullng coating composition of the present 5 invention, the content of the plasticii^er (elj , with rospeot to
100 p£3rts by weight of the copolymer {A), is preferably 0.1 to
300 parts by weight, more prcforably 0.1 to ?00 parts by weight,
still more profernbly 0,1 to 150 parts by weight; in terms of
allowing the antifoullng coating film formed from the antifoullng 10 coating composition to have improved coating film hydrolyEability
(consumption property), antifoullng properties and coating film
water resistance Et^iechanical properties),
[0071]
The content of the plasticiser (el), with respect to 100^ 15 by weight of the antifoullng coating composition (containing a
solvent) , is usually about 0.1 to 30% by weight, prefeirably about
0.1 to 20% by weight.
[0072]
Extender pigment [e2) 20 The extender pigment (e2) can provide the antifoullng
coating film formed from the antifoullng coating composition with
improved coating film properties such as crack, resistance.
[0073]
Examples of the extender pigment ie2} include talc, silica,

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30
mica, clay, potassium feldspar, zinc oxide, calcium carbonate, kaolin, aluminum white, white carbon, aluminuio hydroxide, EiEigneEjium carbonate, bariutn carbonate and barium sulfate. Among these, preferred are talc, silica, mica, clay, calcium carbonate, 5 kaolin, barium sulfate, potaaHiutn feldspar and zinc oKide. Calcium carbonate and white carbon are used also as sn. anti-settling agent (e6) described later and a matting agent. [0074]
In the antifouling coating composition of the present 10 invention, tho content of the CKtender pigment fe2) , with respect to 100 parts by weight of the copolymer {A), is preferably 0.1 to 500 parts by weight, more preferably 50 to 300 parts by weight, in view of allowing the antifouling coating film formed from the antifouiing coating composition to have improved coating film 15 water reaiatance (iciechanical properties) and antifouling properties and coating film hydrolyzability (consumption property). [0075]
The content of the extender pigment Ee2) is, with respect 20 to 100% by weight of the antifouling coating composition
(containing a solvent), usually about 0.1 to 50% by weight, preferably about 0.1 to ^0% by weight, [0076] Pigment diapersant fe3J

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Examples of the pigRient dispersant (e3) include known various organic and inorganic pigment dispersants. Examples of the pigment dispersants include £iliphatic aminos or organic acids
("Duomeen TDO" manufactured by Lion Co., Ltd,; "Disperbylc-101" 5 manufactured by BYK CHEMIE). [0077]
In the antifouling coating composition of the present invention, the content of the pigtnent dispersant (e3J , with respect to 100 parts by weight of the copolymer fA), is preferably 10 0.01 to 100 parts by weight, more preferably 0.01 to 50 parts by weight in terms of j.mproving the effect of reducing the coating material viscosity of the antifouling coating composition and the effect of preventing the flooding of the antifouling coating film, The content of the pigment dispersant [e3), with respect 15 to 100^ by weight of the antifouling coating composition
(containing a solvent), is usually about 0.1 to IQ% by weight, preferably about 0,1 to 5% by weight. [0073]
Coloring pigment Ee4) 20 The antifouling coating composition of the present
invention may comprise a coloring pigment Ee4] in order to provide the antifouling coating film formed from the antifouling coating composition with controlled hue and desired hue, [0079]

aiP-?590
32
Examples of the coloring pigment (e4) include various known organi c and inorganic coloring pigments , Examples of the organic coloring pigments include carbon black, naphthol red and phth^locyEinine blue. Examples of the inorganic coloring pigrEionts 5 include red iron oxide, barite powder, titanium white, and yellow iron oxide. [0080]
The antifouling coating composition of the present invention may comprise, together with the coloring pigment (e-l) 10 or instead of the coloring pigment (e4J , a colorant exclviding the coloring pigment (e4), such as dyes. [0081]
In the antifouling coating composition of the present invention, the content of the coloring pigment {e4) , with respect J.5 to 100 parts by weight of the copolymer (A), is preferably 0.01 to 100 pEirta by weight, more preferably 0.01 to 10 parts by weight, .i.n terms of allowing the antifouling coating film formed from the antifouling coating composition to have improved coloring properties, shielding properties, exposure discoloration 20 properties, antifouling properties, and coiJting film water resistance (mechanical properties). [0062]
The content of the coloring pigment (e4j, with respect to 100% by weight of the antifouling coating composition [containing

SF-2590
33
a solvent) , is usually about 0.1 to 30^ by weight, preferably about 0.1 to 20% by weight.
[0083]
Anti-sagging agent {e5) S The antifouling coating composition of the present
invention may comprise an anti-sagging agent {e5) (also called an anti-running agent) in terms of reducing the occurrence of the sagging of the coating composition upon coating the substrate with the antifouling coating composition.
10 [0084]
Examples of the anti-sagging agent (e5) include amide waZj-hydrogenated castor oil-based vax, mixtures thereof and synthetic fine powder silica. The anti-sagging agent {e5) is partioula^rly preferably amide wa^ or synthetic fine powder silica. By using
15 amide v/as or synthetic fine powder silica as the anti-sagging agent (e5), it is possible to improve the storage stability of the antifouling coating composition; and moreover when the formation of the antifouling coating film is followed by the formation, on such an antifouling coating film, of a coating film (over-coating
20 filmj made of the same Icind of coating composition (antifouling coating composition) or different kinds of coating compositions, it is possible to prevent decrease of adhesion between the antifouling coating film and the over-coating film (interlayer adhesion, over coating properties).

SF-2590
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[0085J
Kxamples of c:on[me]:cially available products of the anti-sagging agent [eSj include ")]ISPARLON A630-20XC" manufactured by KUSUMOTO CHHMICALS, CO., LTD- and "ASAT-250F" 5 manufactured by ITO Olh CHEMICALS CO., LTD. [0086]
In the antifouling coating composition of the present invention, the content of the anti-sagging agent fe5), with respect to 100 parts by weight of the copolymer [A] , is preferably 10 0,1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight. The content of the anti-sagging agent (e5) , with respect to 100% by weight of the antifouling coating composition (containing a solvent), is usually about 0,1 to 20S by weight, preferably about 0.1 to 10% by weight, When the content of the 15 anti-sagging agent feS) is set at the range described above, it is poKsible to allow the antifouling coating composition to have improved storage stability; and moreover when the form^ation of the antifouling coating film is foliov/ed by the formation, on such an antifouling coating film, of a coating film fovei:-coating film) 20 made of the same kind of coating composition ^antifouling coating composition) or different kinds of" (boating compositions, it Is possible to prevent decrease of adhesion between the antifouling coating film and the over-coating film (Interlayer adhesion, over coating properties),

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[0087] Anti-settling agent fs6)
The antifouJing coating composition of the present invention may comprise an anti-settling agent (e6J in terms of 5 preventing the coating composition during storage from having precipitates and allowing the coating composition to have improved stirring properties. [0068]
Examples of the anti-soLLling agent (eS) include amine salts 10 of Ai, Ca or Sn of organoclay, polyethylene wax and polyethylene oxide-based wax. In particular, the anti-sottling agent {e6) is preferably polyethylene oztde-based wax. hn example of commercially available products of the polyothylene oxide-based wax is '^DISPARLON^200-20X" (manufactured by Kusumoto Chemical
15 Ltd.). [0089]
In the antifouling coating composition of the present invention, the content of the anti-sottling agent {e6), with respect to 100 parts by weight of the copolymer {A) , is preferably
20 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by
weight. The content of the anti-settling agent (e5) , with respect
to 100% by weight of the antifouling coating composition
(containing a solvent), is usually about 0.1 to 20% by weight,
pi:eferably about 0.1 to 10% by weight. When the content of the

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anti-settling agent (eG) is set within these ranges, it is poaaible to improvG the storage stability of the antifouling coating composition; and moreover when the foi:mation of the antifouling coating film is followed by the formation, on such an antifouling 5 coating film, of a coating film fover-coatljig film) composed of the same kind of coating composition (antifouling coating composition) or different kinds of coating compositions, it is possible to prevent the decrease in the adhesion between the antifouling coating film and the over-coating film finterlayer
10 adhesion, over coating properties), [0090] Dehydrating agent (eV)
By employing the copolymer (A), which has good storage stability, tho antifouling coating composition of the present
15 invention has excellent storage stability, and as needed, may havo a dehydrating agent (e7) added therein in order to have further excellent long-term storage stability. The dehydrating agent (e?) is preferably at least one dehydrating agont selected from the group consisting of synthetic zeolite, anhydrous gypsum and
20 gypsum hemihydrate, as an inorganic dehydrating agent; and
alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysiXane, tetraphenozysilane, methyltriethoxysilane, dimethyldiethoxysilanc and trimethylethoxysilane, their condensation products, i.e., polyalkozysilanes, orthof ormic acid

SF-2590
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alkyl esters such as methyl orthoformate and ethyl orthotormate, as ^n organic dehydrating agent. The content of these dehydrating agents feV) , with respect to 100 parts by weight of the copolycaor
(A), is preferably 0.1 to 50 parts by weight. 5 6. Solvent (Fj
The antifouling coating composition of the present
invention rviay comprise a solvent (F) suc^h as water and organic
solvents in order to allow the copolymer (A) and the liko to have
increased dispersibility and to conlrol the viscosity of the 10 composition. As the solvent {F) , the anti.touling coating
composition of the present invention may comprise a solvent.
employed whon preparing the copolymer [A), or a solvent separately
added when niixing the copolymer (AJ with other optional
components, 15 [0091]
EKaniples of the organic solvent include aromatic organic
solvents such as xylene, toluene and ethylbenaene; ketones such
as methylethylketone, methylisobutylketone and cyolohexanone;
aliphatic (the number of carbon atoms: about 1 to 10, preferably 20 about 2 to 5J monovalent alcohols such as ethanol, isopropyl
alcohol, n-butanol snd isobutanol; ester solvents such as ethyl
acetate and butyl acetate.
[0092]
The content of the solvent fF) in the antifouling coating

SF-2S90
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composition of the present invention, with reapect to 100% by weight of the antifouling coating composition, is usually 20 to 80% by weight, preferably 30 to 70% by vjeight. [0093] 5 [Production method for antifouling coating composition] The antifouling coating composition of the present invention may be produced through the appropriate use of a known method. An exemplary method is such that the copolymer (A), and components (B) to (F) as noodod are added to a stirring container
10 at a time or in an arbitrary order, and then these components are mixed by known stirring and mixing moans to disperse or dissolve the components in a solvent. [00 94]
As described above, it is preferable that after the
15 copolymer (A) and the like are dispersed or dissolved in a solvent, amide wax [for example, DISPARLON630-20X and the like) is added, and dispersed for example for about 10 to 20 min, to prepare the antifouling coating composition. This is preferable because upon applying the resultant antifouling coating composition on a
^0 substrate, the occurrence of sagging can be decreased. [0095]
EKamples of the stirring and mixing means include a high-speed dispenser and a sand-grinding mill, a basket mill, a ball Erdll, a three-roll mill, a Ross mixer and a planetary mixer

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and a universal Shi.nagawa agitator.
[0095]
[Antifouling coating filni and antifouling aubatrate]
The antifouling coating film of the present invention is 5 prepared by letting the antifouling coating composition of the present invention dry naturally or ijubjecting the antifouling coating composition of the present invention to drying means such as a heater, to thereby cure the composition. [0097] ID The antifouling substrate of the present invention is formed by coating a substrate (target, material to be coated) with the antifouling coating composition of the present invention by coating means such as cin air spray, an airless spray, a brush and a roller, or by impregnating a substrate with tho antifou].ing 15 coating composition of the present invention, and subjecting tho coating composition, which is used to coat or impregnate the substrate, to, for oxajifple, natural drying (temperature of about room temperature) or drying means such as a heater, to dry and cure the composition to thereby form the antifouling coating film 20 on the substrate. [0098]
Tho subsLraLe used herein, which is not particularly limited, is preferably a substrate contacting with seawater or fresh water. Specific e^^amplos thereof include underwater structures such as

SF-2590
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supply and exhaust ports of various power plants (thermal power plants and nuclear power plants) , coastal roads, undersea tunnels, harbor facilities, and sludgo^diffusion prevention films
employed for various ocean/river civil engineering works such as 5 canals and water channels; ships such as FRP ship (particularly, a part of a ship ranging from its waterline part to its ship bottom) ; and fishing materials such as fishing gear such as rope and fishing nets, floats and buoys. [0099]
10 EKamplcs of materials for these substrates, particularly for ships, are steel, aliiminuTn and wood. EKamples of materials for fishing nets are natural or synthetic fibers. Examples of materials for floats and buoys are synthetic resins . The material of the substrate is not particularly limited as long as antifouling
15 properties and the liko in water are required for the substrate. [0100]
In the case of the surface of these substrates, particularly that of a ship bottom and the like, usually, a steel-made substrate surface is under-coated with a primer such as an anticorrosive
20 coating material to give a primer-treated substrate, and the surface of the primer-treated substrate surface is coated by the method as described above one time or plural times with the antifouling coating composition of the present invention (antifouling paint). Then, the antifouling coating composition

SF-2590
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used for. coating or impregnating fin particular when a substrate is fishing net or the lilce) is cured to form Ein anLifouling coating film. As a result, the antifouling coating film is provided which is excellent in properties preventing the adherence of aquatic 5 creatures such as sea lettuce, barnacle, green laver, serpula, oyster and bryozoans for a long term (antifouling properties, particularly static antifouling properties); and particularly when the antifouling coating film contains an antifouling component {for example, copper or copper compounds {component C),
10 organic antifouling agents {component D)), the antifouling
component can be gradually released over a long period of time, [OIOIJ
When the substrate is a ship (particularly its bottom) , an underwater structure or the like (generally, tho substrate surface
15 may be primer-treated or have a layer formed from any of epoxy resins, vinyl resin-based paints, acrylic resin-based paints and urethane resin-based paints), such a substrate surface is coated with the antifouling coating composition plural times (thiclc-coaLing: thickness of the film dried; about 100 to 600 pm) ,
20 and thereby the resultant antifouling substrate exhibits excellent antifouling properties as well as appropriate plasticity and excellent crack resistance with good balance. [01021
Regarding the production of the antifouling substrate, when

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the substrate is, for ej:amp.l.e, a steel plate or fishing net with a deteriorated antifouling coating film, the substrate surface may be directly coated with the antifouJ.ing coating composition of the present invention, or may be directly impregnated with the 5 antifouling coating composition of the present invention (when the substrate is fishing net or the like). Whan the substrate is made of a steel, the substrate surface may be previously coated with a base inateriEil such as an anticorrosive and a primer to form a base layer, and then the surface of the base layer may be coated
10 with the coating composition of the present Invention. For the purpose of repairing, the antifouling coating film of the present invention may further he formed on the surface of a substrate on which the antifouling coating film of the present invention o?: a conventional antifouling coating film has been formed.
15 [0103J
The thickness of the antifouling coating film, which is not particularly limited, is for example about 30 to 250 jam per coating operation when the substrate is a ship or an underwater structure. [0104]
20 As described above, the underwater structure having the antifouling coating film of the present invention can prevent aquatic creatures from adhering thereto over a long period of time, and as a result thereof, the underwater structure can maintain its functions over a long period of time. The fishing net having

SF-2590
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the antifouling coating film of the present invention has less possibility of envirnnmental pollution, and is prevented from clogging ^^ a result of the prevention of the adherence of aquatic creatures. 5
EXAMPLES [0105]
Hereinafter, with reference to Examples, the present invention is further specifioally described, but the present
10 invention is litrdted in no way with those Examples . In the section of "Example", ''%" denotes '''% by weight" unless otherwise noted, [0106] [[Production Example AlJ
A reaction vessel equipped with a stirring device, a reflux
15 condenser, a thermometer, a nitrogen-introducing tube and a dropping funnel was charged with xylene in an amount of 53 parts. Under nitrogen atmosphere, while xylene was stirred with the stirring device, under an atmospheric pressure, the reaction vessel was heated until, the temperature of xylene in the reaction
?.0 vessel reached 85'C. While keeping the temperature of xylene in the reaction vessel at S5 'C, a monomer mixture composed of 75 parts by weight of TlPSMft {triisopropylsiiyl methacrylate) , 5 parts by weight of TIPSA (triisopropylsiiyl acrylato), 10 parts by weight of EA fethyl acrylate], 10 parts by weight of MMA {methyl

sir-25yo
44
niethacrylate) and 1 part by weight of AMBN
{2,2'-azobia(2-methylbutyronitrile)) was added i nto the reaction vessel with the dropping funnel over a period of 2 hours. [0107] 5 Subsequently, 0.5 parts by weight of t-butylperoxyoctoate vjas further added to the reaction vossol. Under atmospheric pressure, while the liquid temperature In the reaction vessel was kept at 85 "C, stirring was performed for 2 hours with the stirring device. Then, the liquid temperature in the reaction vessel was
ID raised from B5"C to llO-Q, and heating was performed for 1 hour. Thereafter, into the reaction vessel, 14 parts by weight of xylene was added and the liquid temperature in the reaction vessel was lowered. When the liquid temperature reached 40'C, iitirring was stopped. Thereby, n copolymer solution (AI) containing a
15 silyl(meth)acrylate copolymer (polymer {A)] was prepared. [0108]
In accordance with test conditions in "Evaluation of properties of Eco)polymer solution and (co)polymer" described later, the heat residue content (% by weight) of the resultant
20 copolymer solution E^l) was calculated, and the weight average molecular weight fMw) of the polymer contained in the solution was measured [Results are set forth in Table IJ.

SF-2590
'LS
0109
Table 1

Resin Production Example Al A2 A3 A4 A5
Polvraer Solution Ai A2 A3 A4 A5
Monomer
mixture (i) TlPSMAfpart by weight) 75 70 60 50 50

(ii) TIPSA(partbvw-eight) 5 10 20 30 30

(iii) E A(part by weight) 10 10 10 10 0

MMA(part by weight) 10 10 10 10 10

B A(part by weight) 10

Reaction
Initiator AMBN(part by weight) 1 1 1 1 1
„ ^- T ' - ^ t-butylperoxyoctoate ReactionInitialor i . j, . ,^.
(part by wei^t) 0.5 0.5 0.5 0.5 0.5
Properties Evaluation Percentage of heat residue in polymer solution i:wt%) 59-5 59.7 59,8 59.6 593

Weight average molecular weight Mw 31,151 32,404 30,22S 2S,507 31,29

Viscosity of Polymer solution fmPas) 1,108 1,027 793 618 721

(i)/(ii) (weight ratio) * 1 93,8 S7,5 75-0 62.5 62,5

6.3 12,5 25-0 37.5 37-5
(fiHCii)) content fwt%) *2 SO SO SO SO SO

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46

Table 1 (continued)
Resin ProductLon Example A9 AlO All A12 : A13
Polymer Solution A9 AlO All A12 1 A13
Monomer mixture (i) TiPSMAfpajt by weight) 50 40 37 55 50

fii) TPSA(part by weight) 20 30 ' 33 5 10

(iii) E A(part by weight) 10 10 10 10 10

MM A(part by weiqht) 20 20 20 30 30

BA(part by weight)

Reaction Initiator AMBN(parr by weight) 1.2 1.2 1.2 1.3 L4
Reaction Initiator t'butylperoxyoctoate (part by weight) 0.5 0.5 0,5 0,5 0.5
Percentage of heat residue m polymer solution (wt%) 59,5 59,7 60-1 59.S 59-4
Weight average molecular weight Mw 32,741 27,770 ■ 30,333 30^51 29,766
Properties Evaluation Viscosity of Polymer solution (mPas) 1,347 1 1,112 ■ 1,099 2,335 2^38

(iy(ii) (weightratio)*! 71.4 57.1 52.86 9L7 S3.3

28.6 42.9 47.14 8.3 16.7

((iyKli)) content fwt%} ■*2 70 70 70 60 60

1 (i)/(ii)-
Amount of charge of (i) Amount of charge of (ii)
Amount of charge of (i) -I- Amount of chaise of (ii)
'2 ((i)/(ii)) Content (wt%) =
Amount of charge of (i) -r Amount of chaise of (ii)-r Amount of charc:e of (ii

SF-2590
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[0110]
[Production Examples A2 to A16 and Production Examples Bl to 31] The same procedure as in Production l^lsample Al was performed except that a monoraer mixture having a formulation shown in Table 5 1 or Table 2 was used instead of the monomer mixture used in Production Mxample Al. Thereby, a silyl(meth)acrylate (co)polymer solution (fil) containing a silyl(meth)acrylate copolymer (polymer (A) ) was pirepared, and its heat residue was calculated, and the weight average molecular weight (Mw) of the 10 fco)polymer was measured. [0111]
In Tables 1 to A, (co)polymer solutions A2 to A15 and (cojpolymer solutions BI to B7 refer to solutions containing (co)polymers obtained in Production Examples A2 to AI6 and 15 Production Examples Bl to B7, respectively.

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48
[0112]
Table 2

Resia Production Exanople Bl B2 E3 B4
Polymer Solution Bl B2 B3 B4
Monomer mixture (i) Tl?SMA(part by weight) 70 35 20

Cii) T]PSA(partbywei^t) 70 35 50

EA(part by weight) 10 10 10 10

(hi) MMAfpart bv weiahtl 20 20 20 20

B A(part by weight)

Reaction rnitiator AMBN(part by weight) I 1.2 1.2 1
Reactior Initiator t-butylperoxyoctoate (part by weight) 0,5 0.5 0,5 0.5
Percentage of heat residue in polymer solution (wt%) 59.8 60.4 59.8 60,2
Properties Evaluation Weight average molecular weight Mw 29,223 28,578 28,921 30.002 2

Viscosity of Polvmer solution fmPas') 1.924 484 992 808

(i)/(ii) (weight ratio) * 1 100.0 0.0 50,0 28,6

0,0 100.0 50,0 71.4

(fi)+(ii)) content fwt%) *2 70 70 70 70

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49
[0113] [Example 1]
A plastic container (volume: 1000 ml) was charged with 5 xylene in an amount of 18.2 parts by weight aa a solvent, and trimothyl isobiitenyl cyclohexene carboxylic acid (50% xylene solution) as the component B in an amount of 4. 0 parts by weight. These components were mixod with a paint shakier until trimethyl isobutenyl oyclohexenc carboxylic acid became uniformly 10 dissolved in xylene. [0114]
Subsequently, to the plastic container, the polymer solution Al in an amount of 18 parts by weight was added and mixed with a paint shakor until uniformly dispersed or dissolved. 15 'thereafter, to the plastic container:, additives (1) (3.0 parts by weight of talc FC-1, 4.0 paints by weight of zinc oxide (zinc oxide No. 3], 45 parts by weight of cuprous oxide NCaOl, 0.3 part by weight of Novoperm Rod F5RK, 2.0 parts by weight of titanium white R-5N, 1.0 part by weight of copper omadine [copper 20 pyrithione) and 2.0 parts by weight of DISPARLON 4200-20X) were added and stirred with a paint shaker for 1 hour to disperse these components. iOll'S]
After dispersing, 2.5 parts by weight of DISPARLON 630-20X

Sir-2590
50
was added and stirred for 20 minutes with a paint shakor. Then, the mixture was filtered with a filtering net (opening: 80 nsesh), and the residue was removed to obtain a filtered material (coating composition Al) . Manufacturers and the like of Lhe above various 5 additives are set forth in Table 8. [0116]
Using the resultant coating composition, in accordance with test conditions described in "Evaluation of coating material properties'', various properties were evaluated. Results are set 10 forth in Table S. [0117] [Examples 2 to 2^ and Comparative Examples 1 to 9]
The same procedure was performed as in Example 1 except that the solvent, the polymer solution, the component B and the 15 additives (1) that were used in Example 1 were changed as shown in Tables 3 snd 4, to prepare a coating composition, and various coating material properties were evaluated, Kesults are set forth in Tables 5 and G. [0118] 20 The coating compositions fi2 to A24 and the coating
compositions Bl to B9 that are shown in Table 5 and G are the coating compositions obtained in Examples 2 to 2 4 and Comparative Examples 1 to 9, respocLivcly.

•r-i
If)

o
a% ,—,
m IJl
(N i-E
1 i-l
Ui O
Ui '—'

"
s ■J? ■* (J CJ CJ (^ —H ^ »n r-
—H C^ ?3
1—■ F-r < ■^ ^ 1^
C3 CI CI t^ ■— l-
CI f'-
e3
1—■
A < H* n ■^ 1^ r* CI r^ - "1 CI
o
CI CJ C3
—H
IT. 1— (-1 f c^L (-1 r'l ^ :? CI If.
A ^ ^O Ir- ■a- "1 M CI n " -r IM ci c o
r- 5 90 ■V ■^ t^ t-l n 1—1 ^ ■fi F-- in cj g
jj ^ < -t ^ ■A c-t CJ te. - to ci 1—
■A 3 ■^ ^ CI CJ "1 1—1 if. •r-
CI cj 1—
■fl- 3 o? n TT f-1 rJ CJ (^ ■— ^ oi o I-] "1
ci 1

x>
H
H ■A
p3 ^ aa •t ^ n CJ ^cG (crack) Adhesion 0 0 Q 0 0 0 0 0 0
0 0 0 0 0 0 0

1 4 months Appearance (crack) Adhesion 0
0 0 0 0 0 0
0 0 0 0 0 0 0 0 0

Smoolhs Appearance (crack) Adhesion 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
1 ^ 1 month 2.1 3.3 4.1 3.7 5.7 3.7 3,7 4.5

2 months 3.fi 4 5.1 5,9 9.8 5.7 5.5 S.9
^
3 months 4.5 53 5.9 7,9 14.3 6.8 7.5 13.3
1
1
1
4 months 5.1 7 9.1 10 3 19,7 9.8 9.9 1S.9

5 months 7 10.3 13.5 14,2 25.7 14 13.3 24.5

6 months S.6 13.7 18 J 1S,5 30.5 19.7 13.3 29.8

'•a
-- 7 months 1L4 15.7 22.3 23,5 36.7 23 22.1 35.6

S months U.9 [B.7 26.7 23.7 42.3 27.5 26.3 40.3

9 months 16.3 223 31.5 34.5 48.9 32.5 29.5 46.5

10 months 22.3 2S.3 36,7 39.S 55 .S 37,8 35.7 52,3

II monlhs 23 36.9 4o,a 44.3 61.3 42.1 44.5 59,8
i
}2 months 273 42.4 46.3 49.S 68.8 4S.9 5L8 67.g

Monthly average coating film consumption amount (pm) 2.3 3,5 3.9 4.2 5.7 4.1 4.3 5.7

Cojiline film amJcaranceofafter 12 months AA AA AA AA AA AA AA AA
.li 1^ 1 month 0 0 0 0 0 0 0 0

2 months 0 0 0 0 0 0 0 0

3 months 0.5 0 0 0 0 0 0 0

4 months 0.5 0 0 0 0 0 0 0

5 months 0.5 0.5 0 0 0 0 0 0

6monlhs 0,3 0.5 Q 0.5 0 0 0 0.5
?? Initial viseositv fKu) B6 85 S2 84 81 84 85 S3

MscositvaitergJorajiealSO'C fori months S7 86 83 85 83 S6 87 86

Increase of viscusitv- {TCu) +1 +] +1 +1 +2 +2 +2 +3

SF-2590
55

Table 5 (continued)
1 Q
C C
1 Examnb 13 14 15 16 17 18 T9 20

Coatina ComDosMon A13 A14 AI5 A16 A17 AIS A19 A20

■ month , Appc^=c{aack) Adhesion 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

2 months ■ App«r^e._ (cra^) 1 Adnc&iaD 0
Q 0 0 0 0 0 0 0 0 0 0 0 0 0 0

3 monlhs Appearance (crac^) Adhesion 0 0 0 0 0 0 0 0 0 0 0 0 1 1 0 0

4 months AppMtancc (crack) Adhesion 0 Q 0 0 1 1 0 0 0 0 0 0 1 1 0 0

5 months AppEarance (crack) Adhesion 0 0 0 0 1 ] 0 0 0 0 0 0 1 1 0 0
1
1
1 ■g
'2 I mooth 2.5 4.5 4.7 3.2 3.1 3,5 3.7 1.2

2 months 3.8 6.9 7.1 2.9 3,9 4.1 4.5 3.5

3 months 5.1 10.1 10.5 5.1 5,5 5.6 5,S 4.2

4 months 7.S 13.-^ 14.1 7.3 7,6 S ?.] 4.9

5 months 11.] 16.^ 17.5 9.9 10,6 10,9 11.3 6.7

6 mooths 14.5 2U 24.9 II 123 13.1 13.S 8.3

7 months IS2 26.3 30,1 ■5,5 17.2 18.S 19.3 10.9
i
5 monlhs 22.4 30.9 33.5 IS,4 19.S 20.5 21 13.5
1
9 monlhs 26.S 34.^ 38.9 2? 23.6 24.6 26.6 1S.9
3
^
[0 months 30J 38.5 43.3 27,9 28.S 30 32.S 20.1

11 months 36.3 4S.S 50.3 34. S 35.5 36.9 38.6 22.6
i
12 monlhs UA 54.5 56,3 40.7 42,1 44.3 46.3 24.9

Monthly average coating film consmnpfion amount (urn"! 3.7 4.5 4,7 3.4 3.5 3.7 3.9 2.1

CftUin2rjImam)caiainKofafter[2nionlhs AA AA AA AA AA AA AA AA
'ft h 1 month D 0 0 0 0 0 0 0

2 mouths 0 0 0 0 0 0 0 0

S months 0 0 0 0 0 0 0 o.s

s 3? 4 months 0 0 0 0.5 0 0 0 05

5 months 0.5 0 D 0,5 0,5 0 0 0.5

6 monlhs 0.5 0 D 0.5 0.5 0 0 0,5
IHI Initial viscosll^' (Kul SI S3 S3 S3 83 S2 SI S4

Viscosity BflerstoraK at 50"Cfbi 3 monlhs S5 S9 93 S4 87 90 98 S5

Increase of \'iscositvrKu) +4 -6 -i-lO +1 +4 -8 +17 "1

SF-2590

56

[OI22:

Table 6

1 Comoaralis'e EKamolc 1 2 3 4 5 6

Coatine Composilion Bl B2 B3 B4 S5 66

Imonlh Appcaranct (ciack) Adhesion 3 2 0 0 0 0 0 0 0 0 0 0

2 months Appearance (crack) Adhesion 3 2 0 0 0 0 0 0 2 2 0 0

3 months Appearance (crack) Adhesion 3 2 3 2 1 1 2 2 2 2 3 2

4 months Appearance (crack) Adhesion 3 2 3 2 2
2 2 2 2 2 3 2

Smonlhs Appuarancc (rack) Adhesion 3 2 3 2 3
2 3 2 3 2 2
1
1
1 -□ 1 month 1.7 5.5 3,6 4.9 5.2 2,7

2 [nonlhs 3,2 11,3 4,3 9.3 10.3 5.5

3monlhs 3,9 IS.7 5.6 15 16.2 10.1

4[nonlhs 4.7 25 J &2 20.9 23.1 12.7

5 monlhs 6.7 31.9 11 29.1 29.S 18.1

6 months fi.3 3S.7 13.9 34, [ 36,4 20.7

7m(nilhs 10.7 46 19.3 4D.2 44.e 26.3

SmonLhs 12.3 55.3 22,1 46.9 52.7 313
i
9 months 14,7 68.3 26 35.3 64.7 38.7
I
lOraonlhs 16.7 91.3 32.3 72.3 S7.5 51.2
■ E
11 months 19.3 12Z5 37.9 93.1 105,9 62.^
1
1^ months 23.S 151.3 47.5 118.5 129,5 83,2

Monthly averafia coaling film consumptioii amaunl fum) 1.9 12.6 4.0 9,9 lO.S 6.9
u Coaling film appearance of alter |2 monlhs Crack ine Crack ine Crack Crack inc Crack ine Ctack ing
1"^ ] monrh D 0 D 0 0 0
4
? months 0.5 0 0 0 0 0

3 months 0.5 0.5 0 0 0 0

4 monlhs 1 0.5 0 0 0 0.5

5 months 2 0,5 0 0 0,5 0.5

6 months 3 0.5 0.5 0 0.5 0.5
MUixy^ Initial vTscD^itv (K|i) S7 82 &2 SI S4 83

ViscDsitv-aftersloragealSO'C for Smooths ss 116 110 114 112 113

Increase of ■viscosity (Kul +1 +34 +2& "33 -2S +30

SF-2590
57
[0123]
[Evaluation of properties of (co)polymer solution and (co)polymer]
(1} Content of heat residue in {co}pQlymer solution 5 1.5 g (Xi (g) ) of the {co)polymer solution was k.ept in a thermostat chamber at 1 atmospheric pressure at loyc for 3 hours to remove volatile contents, whereby a heat residue (non-volatile contents) was obtained. Subsequently, the amount (X? {q] ) of the resultant heat residue (non-volatile contents J was measuired. 10 Based on the following equation, the content {%) of the heat residue contained in the (co)polymer solution was calculated. [0124]
Content {%) of heat residue = X2/X1x 100 (2) Average moleoulaj: weight of (co)polymer 15 The weight average molecular weight (Mw) of the (co) polymer was measured by GPC (gel permeation chromatography) under the following conditions. GPC conditions
Apparatus: "HLC-0120GPC" (manufactured by Tosoh Corporation) 20 Columfi: "SupGrH2OOO'|.H4O0O" (manufactured by Tosoh Corporation, 6 mm (inner diameter), 15 cm [length) for each column) Eluent: tetrahydrofran (THF) fcM.ow rate: 0,500 ml/min Detector: RI

58
Column thermostat chamber temperature: 40'C Standard substance: polystyrene
Sample preparation method: to the Eco)poiynter solution prepared in each Production Example, a small amount of calcium chloride 5 was added tc dehydrate the solution, which was followed by filtration with a membrane filter. The obtained filtered material was deJfined as a sample for GPC measurement. [0125} (3) Viscosity of (co)polymer solution
10 By using an E-type viscometer {manufactured by TOKI SfiNGYO CO.; LTD.), the viscosity {unitr mPa-s) at a liquid temperature 25''C of the [co}polymer solution was measured. [0126] {4) Coating film deterioration accelera^tion test (Evaluation of
15 coating film appearance ^nd adhesion)
A sandblasted plate fl50 mm >i 70 mm x 1.5 mm] was coated by using an applicator with an epoxy-based coating rtiaterial (epoxy Z\C coating material, product name: "Bannoh 500'', manufactured by Chugoku Marine i?aints. Ltd,) such that the thickness of the film
20 dried would be 150 ym, followed by curirtg, to form a cured coating film (150 ^m) . .Subsequently, the cured coating film was coated by using an applicator with an epoxy binder coating material (product name: '''Bannoh SOOi^", manufactured by Chugoku Marino Paints, Ltd.) such that the thickness of the film dried would be

SF-2590
59
100 |jm, followed by curing, to form a cured coating film ElOO pmJ -
Thereby^ a test plate was prepared.
[0127]
Subsequently, the test pl^ite (surface of the cured coating
5 film formed from epoxy binder coating material) was coated by using
an applicator with the coating composition of any of the above
Examples and Comparative Examples such that the thickness of the
fi.lm dried would be 150 pm, which was followed by drying at 23'C
for 1 day, to form an antifouling coating film (ISO |jm) . Further,
10 this antijfouling coating film surface was coated with the above
coating composition such that the thickness of the film dried would
be ISO pm, which was followed by drying at 23''C for 1 days, to
f.orm an antifonling costing film. Thereby, a test plate with
an. antifouling coating film was prepared.
15 [012RJ
The resultant test plate with the antifouling coating film was immersed in artificial seawater at SO-C. Every one month after the immersion, the appearance and adhesion of the coating film were investigated based on the following evaluation criteria. 20 [0129J
Evaluation of Appearance
The degree of fracture of the antifouling coating film surface of the test plate with the antifouling coating film was visually observed, and was evaluated in accordance with JIS

SF-2S9Q
60
Kb600-8-4 shown in the following Table.
[0130]
Table?
Hvaluatioii Poinl (RN) Classificalion of Fractuic Amount
0 None
1 Donsity 1
2 Density 2 Density 3
3

[0131] 5 Evaluation of Adhesion
The antifouling coating film surface of thR test pl.ate with the antifouling coating film was slit with an NT cutter so as to have four cut lines both in the longitudinal direction and the transverse direction with one line spaced from another line by
10 4 mm, and this resulted in the formation of 9 squares on the coating film surface. On the coating film surface having the squares, a Cellotape (trade mark) was press-contacted and thon quickly peeled off. Then, the squares were observed. Subsequently, provided that the area of the 9 squares was 100%, the percontage
15 i%) of the area of the coating film remaining on the squares iremaining area) after the peeling operation was calculated, and basod on the following evaluation criteria, adhesion was evaluated, [Adhesion ovaluation criteria]
20 0: the ST^d. of the remaining coating film is 95^ or more.
1: the area of the remaining coating film is 75 to less than 95%.

3F-2590
61
2: the area of the remaining coating film is 50 to less than 75%. 3: the area of the remaininq coating film is less than 50%. [0132]
(5) Coating film consumpLion property Lost
5 Each coating composition obtaj.tied in P'xarnples ^nd
Comparative Examples was applied by using sn applicator on a hard vinyl chloride plate (50rEini« SOmmN 1,5 mm) such that the thickness of the film dried would be 150 ^m and dried, to prepare a tesL plate.
10 [0133]
The resultant tost piato was attached to a rotating drum, and the rotating drum was immersed in seawater. At a seawater temperature of 30'C, the drum was rotated at a circumferential speed of 15 knots, and the thickiness of the film consumed was
15 measured every one month. In addition, the monthly average
coating film consumption amount from the start of the immersion to 12 months thereafter was ca].culated. Ir\]r'ther, coating film appearance after 12 months from the start of the immersion was observed and evaluated based on the following evaluation criteria.
20 [Evaluation criteria of coating film appearance]
AA: the antifouling coating film surface has no cracking. Cracking: the antifouling coating film surface has cracking. [013^]
(6) Static antifouling properties test

Sb^-2590
62
A sandblasted plate (300 run:! « 100 nun « 3.2 nim) was coated by using an air spray with an cpoxy-based coating material (epoxy AC coating material, product name: ^^Bannoh 500", manufactured by Chugolcu Marine Paints, Ltd.) such that the thickness of the film b dried would be 150 ^m, which was followed by curing, Lo form a cured coating film [150 pm) . Subsequently, the cured coating f i.lm was coated by using an air spray with an epoxy binder coating material (product name: "Bannoh 500N", manufactured by Chugoku Marine Paints, Ltd.J such that the thickness of the film dried
10 would be 100 ijm, which was followed by curing, to form a cured coating film (100 jam), to thereby prepare a test plate. [0135]
Subsequently, the test plate [surface of the cured coating film forined from the epoxy binder coating material} was coated
15 by using an air spray with the coating composition of any of the Examples and Comparative Examples such that the thickness of the film dried would be 150 \im, and then the composition was dried at 23''C for 1 day to form an antifouling coating film (150 |jm) . Further, the antifouling coating film surface was coated with the
20 above coating composition such that the thickness of the film dried would be 150 \im, and the then composition was dried at 23"C for 7 days to fo3:m an antifouling coating film. Thereby, a test plate with an antifouling coating film was prepared. [01361

SF-25 30
63
The resultant test plate with the antifouling coating film
was stationarily immersod in Nagasaki bay, Nagasaki Profocture.
Every one month after the immersion, the percentage {%} of the
area of the antifouling coating film on which aquatic creatures 5 were adhered {adherence area) was mt?aKured wherein thts total area
of the antifouling coating film of the test plate is defined as
100%, and baaed on the following evaluation criLoria Lho static
antifouling properties were evaluated,
[Evaluation criteria] 10 0: the adherence area is 0%.
0.5: the adherence area is 0 to 10%.
1: the adherence area is 10 to less than 20%.
2: the adherence area is 20 to less than 30%,
3: the adherence area is 30 to less than 40%. 15 4r the adherence area is 40 to less than 50%.
5: the adherence area is 50 to 100%.
[01371
{7) Storage stability test
The viscosity at 23"C of each coating composition 20 immediately (within one day) after prepared in Examples and
Comparative Examples {initial viscosity (Ku)) was measured in
accordance with JI5 K 540Q by using a stormer viscometer.
Furthermore, after each coating composition was stored in a 50'C
thermostat for 3 months, the viscosity at 23''C of each coating

Sh-2590
composition (viscosity after storage (Ku)) was measured in accordance with JIS K 5400 by using a stormer viscometer. Subsef^ucntly^ increase of viscosity was calculated based on the follcwing equation, 5 [0138]
Viscosity Increase = Viscosity After Storage (Ku) - Initial Viscosity (Ku)

SF-2590

65

0139
Table 8
Item Maimfacturer PropertLcs
Talc FC-1 Fukuoka Talc d:)., Ltd. Extender pigmen
Zinc oxide IC>TIS1IU Hakusui Ka^ialcu Extender pi^iinen
Novoperai Red F5RK Clariant Noith America Organic red pigm
Copper Omadine (copper pvrithione) Arch Chemical, Inc. Organic antifouling
4,5-dichloro-2-n-oct>d-4-isothiazolii:e-3-one Rohn & Haas Company Oi^anic anttibulina
Rosin Made in China Eluticn assistan
Dis630-20XC Kusumoto Chemicals, Ltd, Anti-sagsina age
Dis4200-20X Kusumotc Chemicals, Ltd, Anti-settling age
Cuprous oxide NC-301 Kissin Chemco Co., Ltd, Antifouling agen
Titanium white R-5N . Sakaj Chemical Industry Co.. Ltd. Color pigment
Versatic acid Resolution Nederland Elution assistan

Sf-2590
66
[01^0]
The present invention is described with reference to
embodiments hereinabove^ but the present invention is limited in
no way by the above. The configuration and detail of the present
^ invention can have various modifications comprehensible within
the scope of the invention by a skilled person in the art. [0141]
The present application claims priority from Japanese Patent Application No. 2011-248877 filed on November lA, :^011, 10 and all of the disclosure therein is incoirporated hereto,
IHDUSTRIAL APPLICABILITY
[0142]
The present invention is applicable to antifouling coating 15 compositions and antifouling coating films, and is therefore
employable for antifouling substrates,

SF-2590
67
CLAIMS
1. An antifouling coating composilion coinpriKing a
silylacrylic copolymei: (A^ that coiriprises a sttructural unit (1)
5 derivod from Lriisopropylsilyl methacrylate Ei), a structural unit [2] derived from triisopropylsilyl acrylate (ii) and a stmctutal unit [3] derived from a polymerizable monomer having a polymerizable double bond (iii), which excludes the above (i) and (ii), and satisfies? the following Requirements 1 and 2;
10 Requirement 1: the content weight ratio ( [ f 1) '^ E2) ] / (3)) of the total weight ({13+12)) of the structural unit fl) and the structural unit {2) to the content weight of the structural unit [3] is 50/50 to yO/10; and
Requirement 2: the content weight ratio {(lJ/(2)) of the
15 content weight of the strucLurai unit El) to the content weight of the structural unit (2) is more than 50/50 and not more than 95/5.
2. The antifouling coating composition according to
7.0 Cl.aiml, wherein the polymerizable monomer (iii) is an ester having
a polymerizable double bond, or a carboxylic acid having a polymerizable double bond.
3. The antifouling coating composition according to

68
Claim 1 or 2, further comprising a roain and/or a itionocarboxylic acid compound (B).
4. The antifouling coaling coiripo^ition according to
5 Claim 3, wherein tho content weight ratio (WA/WH) of the content weight (W/iJ of the si.l ylacrylic copolymer (A) to the content weight (WB) of the rosins and/or monocarboKyllc acid compound (B) is 99-9/0,1 lo 30/70.
10 5. The antifouling coating composition according to any one of Claims 1 to 4, further comprising at least one selected from the group consisting of a copper compound (C), an organic antifouling agent (D}^ other additivG(s) (E) including a plasticizer (elj , an CKtender pigment feZ) , a pigment dispersant
15 (e3), a coloring pigment (e^), ^n anti-sagging agent [eb), an anti-Eiettling agent (e6) and dehydrating agent (e?), and solvent
6. An antifouling coating film formed by curing the
20 antifouling coating composition described in any one of Claims
1 to 5.
7. An antifouling substrate formed by coating or
impregnating a substrate with the antifouling coating composition

SF-25yO
69
described in any on^ of Claims ] to 5, and curing the coating composition, which is used to coaL or Impregnate the substrate,
to thetreby form an antifouling coating film on the substrate.
5 B . The antifouling substrate according to Claint 1, which
contacts with seawater or fresh water.
9. The antifoullng substrate according to Claim 7 or di
wherein the substrate is at least one selected from the group
30 consisting of an underwater structure, a ship and a fishing gear.
10. A method for producing an antifouling substrate, the
method comprising coating or impregnating a substrate with the
antifoullng coating composition described i.n any one of Claims
15 1 to 5; and curing the coating composition, which is used to coat or impregnate the substrate, to thereby form an antifouling coating film on the substrate.
11. A silylacrylic copolymer for use as a binder component
20 of an antifouling coating composition, the silylacrylic copolymer comprising a structural unit (1) derived from triisopropylsilyl
methacrylato {i) , a monomer structural unit (2) derived from triisopropylsilyl acrylate fii) and a structural unit (3) derived from a polymcrizable monomei: having a polymerizable double bond

SK-2590
70
(iiii), which excludes the above Ei) and (ii) , the silylaorylic copolymer SEAtisfying the lollowing Roquj cements 1 and 2;
RequDreiisent 1: the content weight ratio i\ {D-t [2) ] / (3)) of the tntal weight f(l)-r-{2)) of the structural unit [1) and the 5 structural unit (2) tn the content weight of the structural unit (3) is 50/50 to90/10; and
Requirement 2: the content weight ratio i {!)/ (2)) of the content weight of the structural unit (1) to the content weight of the. structural unit {?.} is more than 50/50 and not more than 10 95/5.
/
Dated [111^29.04.2014
[R ANJNA MEiHTA-r:)I (TT]
OP RliMKRY & SAGAR
ATTORNEY K3RTHR ArrLICANl|S|

SF-^590
71
ABSTRACT
The antifouli.ng coating composition accoi:ding to the present invention includes a sllylacrylic copolymer including a structural unit (1) derived from triigopropylsilyl methacrylate 5 {i), a structural unit {2) derived from triiBopropylsilyl acrylate (ii) and a structural unit (3) derived from a polymerizable monomer having a polymerizabIe double bond (ill) , which excludes the above [1) and (ii), the silylacrylic copolymer satisfies specific requirements. Thus, an antifouling coating composition that Is 10 excellent in long-term storage stability and gives a coating film eKcellent in long-term antifoulincj properties and long-term water resistance can be provided.