COMPOSITION OF ANTI-SCALING COATING, ANTI-SCALING COATING FILM, SUBSTRATE WITH A COATING FILM AND ME

专利摘要:
composition of antifouling coating and uses thereof. An antifouling coating composition capable of forming an antifouling coating film is provided which has a stable coating film consumption degree on ships, underwater structures and others and which exhibits excellent antifouling properties for a long time. the antifouling coating composition includes a hydrolyzable copolymer (a) and a hydrolyzable (a) is, for example, a copolymer containing a metal salt bond that has a component unit derived from a monomer (a21) represented by the general formula (ii): [in formula (ii), m is zinc or copper, and r ^ 2 ^ is a hydrogen atom or a methyl group], and a component unit derived from another unsaturated monomer (a22) copolymerizable with the monomer (a21 ), and where the antifouling agent (b) includes at least medetomidine.
公开号:BR112012023993B1
申请号:R112012023993-7
申请日:2011-03-18
公开日:2020-03-03
发明作者:Satoshi Masuda；Yusuke Hayashi；Yukio Kozono
申请人:Chugoku Marine Paints, Ltd.；
IPC主号:

专利说明:

COMPOSITION OF ANTI-SCALING COATING, ANTI-SCALING COATING FILM, SUBSTRATE WITH A COATING FILM AND METHOD FOR THE PRODUCTION OF A SUBSTRATE WITH A COATING FILM
Technical field
The present invention relates to an antifouling coating composition that comprises a hydrolyzable copolymer and an antifouling agent and is employed to prevent aquatic animals from becoming encrusted on a substrate. The present invention is also related to uses of the antifouling coating composition.
Foundation technique
A material for coating the bottom of a ship that is now widely used is an antifouling coating material that contains a component such as a (meth) acrylic acid metal salt copolymer and a silyl ester copolymer, and various antifouling agents , for its ability to exhibit good consumption properties and good anti-fouling properties. However, in less frequent ship operations, or under certain sea conditions, animals, for example, barnacles, and sludge (microorganism coating), for example, diatoms, adhere to the vessel's substrate, often causing a problem.
In view of the above, the conventional antifouling coating composition contained a copper compound, for example, cuprous oxide, intended to prevent barnacles, and others, or an organic antifouling agent such as an anti-sludge agent. , per
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2/55 example, N, N-dimethyl-N'-phenyl- (Nfluordichloromethylthio) sulfamide, 2,4,6trichlorophenylmaleimide and 2,3,5,6-tetrachloro-4 (methylsulfonyl) pyridine.
Such conventional antifouling coating compositions, however, need to contain an antifouling agent in a large amount to sufficiently exhibit an antifouling effect, and this has an adverse effect on the coating film property.
For that reason, there was a demand for an excellent antifouling coating composition in coating film property that has a stable coating film consumption degree on ships, underwater structures, and others, and that exhibits excellent antifouling property For a long time.
Patent document 1 describes the use as an anti-fouling component of medetomidine bound to metal nanoparticles. Patent document 2 describes the use as an anti-fouling component of medetomidine attached to a polymer backbone like polystyrene and an acrylate polymer. Patent document 3 describes a protective coating containing medetomidine and an organic antifouling agent such as 3- (3,4-dichlorophenyl) -1,1dimethyl urea that serves as an algae-inhibiting substance. Patent document 4 describes the use of medetomidine as a chemical agent to inhibit marine bio-encrustation, and also describes the mixture of medetomidine in a coating material that contains an acrylic polymer.
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In addition, it is difficult for these conventional antifouling coating compositions to form an antifouling coating film that has a stable film consumption grade on ships, underwater structures, and the like, and that exhibits excellent antifouling properties For a long time.
List of citations
Patent documents
Document in patent 1: JP 2008-533237 THE Document in patent 2 : JP 2008-535943 THE Document in patent 3: JP 2009-503229 THE Document in patent 4: JP 2002-535255 THE
Summary of the invention
Problem to be solved by the invention
It is an object of the present invention to provide an antifouling coating composition capable of forming an antifouling coating film that has a stable coating film consumption rate on ships, underwater structures, and the like, and that exhibits excellent antifouling property for a long time. It is another object of the present invention to provide uses of the antifouling coating composition.
Means to solve the problem
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 antifouling agent, can form an antifouling coating film that solves the problem. previous problem. The present invention has been accomplished based on these findings.
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That is, the antifouling coating composition of the present invention is an antifouling coating composition that comprises at least 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 copolymer that contains a metal salt bond which is an acrylic resin or a polyester resin and has a side chain end group represented by the general formula (I):
-COO-MO-COR ¹ (I) [In formula (I), M is zinc or copper, and R ¹ is an organic group];
(a2) a copolymer containing a metal salt bond that has a component unit derived from a monomer (a21) represented by the general formula (II):
CH ₂ = C (R ² ) -COO-MO-CO-C (R ² ) = CH ₂ (II) [In formula (II), M is zinc or copper, and R ² is a hydrogen atom or a group methyl], and a component unit derived from another unsaturated monomer (a22) copolymerizable with the monomer (a21); and (a3) a silyl ester copolymer that has a component unit derived from a monomer (a31) represented by the general formula (III):
R ⁷ -CH = C (R ³ ) -COO- £ iR ⁴ R ⁵ R ⁶ (III) [In formula (III), R ³ is a hydrogen atom or a methyl group,
R ⁴ , R ⁵ and R ⁶ are each independently a group
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5/55 hydrocarbon, and
R ⁷ is a hydrogen atom or R ⁸ -O-CO- (where R ⁸ is an organic group or a silyl group represented by SiR ⁹ R ¹⁰ R ¹¹ , where R ⁹ , R ¹⁰ and R ¹¹ are each one, independently a hydrocarbon group)], and optionally, a component unit derived from another unsaturated monomer (a32) copolymerizable with the monomer (a31).
Preferably, an organic group R ¹ in the metal salt bond copolymer (a1) is an organic acid residue formed 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 substitution group for these. More specific examples of the organic group R ¹ include an organic acid residue formed from at least one monobasic acid selected from the group consisting of versatic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, neoabietic acid, pyramic acid, dehydroabietic acid, 12-hydroxy stearic acid and naphthenic acid. With respect to the copolymers containing metal salt bond (a1) and (a2) and the silyl ester copolymer (a3), detailed modalities in other cases are described later.
Medetomidine is preferably contained in an amount of 0.01 to 200 parts by weight based on 100 parts by weight of the hydrolyzable copolymer (A). THE
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The antifouling coating composition of the present invention may also comprise an antifouling agent other than medetomidine such as cuprous oxide, copper pyrithione and zinc pyrithione.
An antifouling coating film of the present invention is formed from the antifouling coating composition.
On a substrate with a coating film of the present invention, 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, and a step of curing the composition to form a coating film. .
Effect of the invention
The use of the antifouling coating composition of the present invention can form an antifouling coating film that has a stable consumption of coating film on ships, underwater structures, and the like, and that exhibits excellent antifouling properties for A long time. Furthermore, in the present invention, the composition does not need to contain a large amount of an antifouling agent to exhibit excellent antifouling properties, and thus it does not have an adverse effect on the coating film property.
Modalities for carrying out the invention
In the present invention, the weight of a substance that
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7/55 serves as a standard to define a component content is a weight of a component capable of forming a dry coating film that excludes a volatile component, for example, a resin polymerization solvent and a material dilution solvent coating: in other words, a weight of a “solid component. The terms "(meth) acrylic acid and (meth) acrylate refer collectively to an acrylic acid and a methacrylic acid, and acrylate and methacrylate, respectively. In the present specification, each component can be used in a single type or in a combination of two or more types, unless otherwise noted.
[Composition of antifouling coating]
The antifouling coating composition according to the present invention comprises a hydrolyzable copolymer (A) and an antifouling agent (B).
<Hydrolyzable copolymer (A)>
The antifouling coating composition of the present invention comprises, as a resin component, a "hydrolyzable copolymer that is hydrolyzable in an alkaline atmosphere such as in seawater (also referred to as a" hydrolyzable copolymer (A)). The use of hydrolyzable copolymer (A) as a resin component can form an antifouling coating film that has a stable film consumption grade on ships, underwater structures, and others, and that exhibits excellent antifouling properties, for example, crack resistance and adhesion with a substrate, and excellent surface uniformity.
The hydrolyzable copolymer (A) is at least one
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8/55 hydrolyzable copolymer selected from the group consisting of:
a copolymer that contains metal salt (al) (also referred to as a (al) 'copolymer' ' Next), a copolymer that contains metal salt (a2) (also referred to as a copolymer (a2) ' 'below), and a silyl ester copolymer (a3) (also referred to
as a copolymer (a3) below).
The hydrolyzable copolymer (A) can be a copolymer that meets the requirements of the copolymer (al) and the copolymer (a2), that is, a copolymer that contains a structure of a side chain terminal metal salt bond as seen in the copolymer ( al) and a cross-linked metal salt bond structure as seen in copolymer (a2).
The hydrolyzable copolymer (A) can be used in a
single type or in combination of two or more types.
Copolymer containing metal (al) salt bond
The copolymer that contains metal salt (al)
it is an acrylic resin or a polyester resin, and it is a copolymer that contains a metal salt bond that has a side chain end group represented by the general formula (I). In the present invention, the above structure is also referred to as a side chain terminal metal salt bond.
-COO-MO-COR ¹ (I)
In formula (I), M is zinc or copper, and R ¹ is a group
organic. In the copolymer (al), commonly, terminal groups
side chains represented each by the formula (I
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9/55 are present, and each of R ¹ can be the same or different from each other, and each of M can be the same or different from each other.
Preferably, the organic group R ¹ in the copolymer (al) (an organic group R ¹ in the formula (IV) described later) is an organic acid residue formed from a monobasic acid, and is a saturated or unsaturated aliphatic hydrocarbon group that it has 2 to 30 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group that has 3 to 20 carbon atoms, an aromatic hydrocarbon group that has 6 to 18 carbon atoms, or substitution groups thereof; more preferably a saturated or unsaturated aliphatic hydrocarbon group having 10 to 20 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, or substitution groups thereof. An example of the substitution group is a hydroxyl group substitution group. Of these, particularly preferable are organic acid residues formed from at least one monobasic acid selected 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 , for example, isostearic acid; the same applies below), abietic acid, neoabietic acid, pyramic acid, dehydroabietic acid, 12-hydroxy stearic acid and naphthenic acid. The copolymer (a1) that has such R ¹ is easy to prepare, and the use of copolymer (a1) that has such R ¹ can provide an antifouling coating film with hydrolysis property
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10/55 and much higher coating.
<Type of acrylic resin>
Among the copolymer (al), an acrylic resin type polymer is preferable. In the copolymer (al), the acrylic resin-type polymer can be prepared, for example, through a polymerization reaction using a monomer that contains a metal salt bond represented by the general formula (IV), that is, one ( met) monobasic acid metal acrylate (also referred to as an (all) monomer below).
CH ₂ = C (R ² ) -COO-MO-COR ¹ (IV)
In formula (IV), M is zinc or copper, R ¹ is an organic group, and R ² is a hydrogen atom or a methyl group (the same definitions as in formulas (I) and (II)). The preferred definition and types of R ¹ in formula (IV) are the same as those described with respect to the organic group R ¹ in formula (I), with the proviso that R ¹ in formula (IV) is not a vinyl group [ -CH = CH2] and an isopropenyl group [C (CH3) = CH2], to be distinguished from a monomer (a21) represented by formula (II) capable of forming a cross-linked metal salt bond, which is described later.
The copolymer (al) can be a polymer obtained through the copolymerization reaction between two or more types of monomers (all), or it can be a polymer obtained through the copolymerization reaction between one type, or two or more types of monomers (all) ), and one type, or two or more types of other unsaturated monomers copolymerizable with the monomer (all) (also referred to as a monomer (a! 2), a
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11/55 below), that is, a copolymer containing a component unit derived from the monomer (a11) and a component unit derived from the monomer (a12).
Monomer (a12) is arbitrarily selectable from various compounds used as polymerizable unsaturated monomers for acrylic resins, and preferred examples of these include a monomer that does not contain a metal salt bond, for example, alkyl (meth) acrylates, alkoxyalkyl (met) acrylates, and hydroxyalkyl (meth) acrylates. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate are particularly preferred, and so on. against.
The acrylic resin-type copolymer (a1) can also be prepared, for example, by a method which comprises the preparation of an acrylic resin using a (met) acrylic acid, an alkyl (met) acrylate, an alkoxyalkyl (met) acrylate, a hydroxyalkyl (meth) acrylate etc., and then carrying out a reaction that introduces a structure that has an organic group (R ¹ ) attached to a carboxyl group through zinc or copper (M), where the carboxyl group is present in an acrylic resin side chain where the metal salt bond has not yet been formed, thus forming a side chain end group represented by formula (I).
<Polyester type resin>
Among the copolymer (a1), a polymer of the polyester resin type is a polyester resin that is synthesized from a polybasic acid and a polyhydric alcohol as
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12/55 is a primary crude material, and has an acid value of 50 to 200 mgKOH / g, preferably 80 to 170 mgKOH / g, and which has, at its end, a side chain terminal group represented by formula (I).
Examples of the acid component for generating the polyester resin include monocarboxylic acids such as benzoic acid and pt-butyl benzoic acid; dicarboxylic acids and anhydrides such as terephthalic acid, isophthalic acid, phythalic acid, 1,4-naphthol acid, diphenic acid, 4.4 ^, -oxybenzoic acid ^, 2,5-naphthalenedicarboxylic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, norbornenodicarboxylic acid ^, oxide malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, 1,3-cyclohexyldicarboxylic acid; and alkyl esters having about 1 to 4 carbon atoms of these dicarboxylic acids. These can be used on a single type or in combination of two or more types. Along with these examples, trifunctional acids or more carboxylic acids such as trimellitic acid, trimellitic anhydride, pyromelitic acid and pyromelitic anhydride can be used, and a slight amount of unsaturated dicarboxylic acids and esters such as maleic anhydride, maleic acid, itaconic anhydride, itaconic and fumaric acid can be used in combination.
Examples of the polyhydric alcohol component for generating the polyester resin include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2propylene glycol, 1,3-propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 1,5- pentane diol,
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1,6-hexane diol, 3-methyl-1,5-pentane diol, 2-methyl-1,3propane diol, 2,2-diethyl-1,3-propane diol, 2-butyl-2-ethyl-
1,3-propane diol, bisphenol A, and a hydrogenated bisphenol A. These can be used on a single type or in combination of two or more types. Along with these, trifunctional alcohols or more alcohols such as trimethylolethane, glycerin and pentaerythritol can be used in combination.
The copolymer of the polyester resin type (a1) can be prepared, for example, by a method comprising carrying out an esterification reaction or ester exchange reaction by a process known as a dissolution process using these various acidic components and alcohol components thus preparing a polyester resin, and then carrying out a reaction that introduces a structure that has an organic group (R ¹ ) attached to a carboxyl group through zinc or copper (M), where the carboxyl group is present at the end where a metal salt bond has not yet been formed, thus forming a side chain end group represented by formula (I).
In the case of introduction of the prescribed side chain end group in acrylic resin or polyester resin by the preparation method as described above, also, preferable types of R ¹ in formula (I) are the same as those previously described. In the preparation method as described above, monobasic acids as described above can be used for a reaction to introduce the organic group R ¹ .
In the copolymer (a1), zinc and / or copper assigned to the structure of formula (I) is preferably contained in a
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14/55 amount of 0.5 to 20% by weight, more preferably 1 to 19% by weight of the copolymer. The use of the copolymer (al) that fulfills these requirements can form a much superior antifouling coating film in both antifouling and consumer properties. 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.
The amount of zinc and / or copper may be above the range, for example, by controlling the proportion between the monomer (all) containing these metals and the monomer (al2) that are used for the preparation of the copolymer (al), or adding quantity of the compound (for example, monobasic acid as described above) containing zinc and / or copper to be reacted with the acrylic resin or the polyester resin previously prepared.
Copolymer containing metal salt bond (a2)
The metal salt-containing copolymer (a2) is a copolymer that has a component unit derived from a monomer (a21) represented by the general formula (II) and a component unit derived from another unsaturated monomer (a22) copolymerizable with the monomer (a21).
CH ₂ = C (R ² ) -COO-MQ-CO-C (R ² ) = ch ₂ (II)
In formula (II), M is zinc or copper, and R ² is a hydrogen atom or a methyl group. In the copolymer (a2), commonly, component units derived from the monomer (a21) represented by the formula (II) are present, and each of R ² can be the same or different from each other, and each of M can be the same or different from each other.
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Examples of the monomer (a21) include zinc diacrylate, zinc dimethacrylate, copper diacrylate, and copper dimethacrylate. The monomer (a21) can be used in a single type or in a combination of two or more types.
The monomer (a21) can be prepared by a known method, such as a method in which an inorganic metal compound (for example, an oxide, a hydroxide, a zinc or copper chloride etc.), and a (meth) acrylic acid or its ester compound is heated and stirred, at a temperature no higher than a temperature at which a metal salt is decomposed, in the presence of an organic solvent based on alcohol and water.
The component unit derived from the monomer (a21) has a structure represented by the general formula (V), and that structure is also referred to as a cross-linked metal salt bond in the present invention.
OO I H H> □
RC ~ COM ~ OCC ~ R ch ₂ ch
I (V)
The other unsaturated monomer (a22) copolymerizable with monomer (a21) is arbitrarily selectable from various compounds used as polymerizable unsaturated monomers for acrylic resins, as is the case with the monomer (al2) together with the copolymer (al). Preferred examples of the unsaturated monomer (a22) include alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, and
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16/55 hydroxyalkyl (meth) acrylates. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate are particularly preferred.
The monomer (a11), described above together with the copolymer (a1), that is, the monobasic acid metal (meth) acrylate represented by formula (IV), is also a copolymerizable monomer with the monomer (a21), and thus it corresponds to the monomer (a22), which can be used for the preparation of the copolymer containing the metal salt bond (a2). With respect to monobasic acid metal (meth) acrylate represented by formula (IV) as the unsaturated monomer (a22), also, the definition and preferred modalities of R ¹ are the same as those described with respect to the organic group R ¹ in formula (I).
The unsaturated monomer (a22) can be used in a single type or in a combination of two or more types.
In another preferred embodiment, the unsaturated monomer (a22) comprises the monobasic acid metal (meth) acrylate represented by formula (IV) and at least one unsaturated monomer selected from the group consisting of an alkyl (meth) acrylate, an alkoxyalkyl ( met) acrylate, and a hydroxyalkyl (met) acrylate.
Additional examples of the unsaturated monomer (a22) include styrene and styrene derivatives; vinyl esters like vinyl acetate and vinyl propionate; (met) acrylamide and derivatives thereof; and (meth) acrylonitrile.
In the copolymer (a2), also, zinc and / or copper assigned to the structure of formula (II) are preferably contained in an amount of 0.5 to 20% by weight,
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17/55 more preferably 1 to 19% by weight of the copolymer, from the same point of view as described with respect to the copolymer (a1). The "amount of zinc and / or copper" as used herein refers to a total amount of zinc and copper if both zinc and copper were contained.
The amount of zinc and / or copper can be in the above range, for example, by controlling the mixing ratio of monomers used for the preparation of the copolymer (a2). When the copolymer (a2) has a cross-linked metal salt bond structure and a side chain terminal metal salt bond structure, it is preferable that the total amount of zinc and / or copper assigned to each structure is controlled in a way to be in the above range.
The average numerical molecular weight (Mn: in terms of polystyrene) and the average weight molecular weight (Mw: in terms of polystyrene) of the copolymer (a1) and the copolymer (a2) can be arbitrarily adjusted for viscosity and stability of storage of the antifouling coating composition and an elution rate of the antifouling coating film etc., and Mn is commonly about 1,000 to 100,000, preferably 1,000 to 50,000, and Mw is commonly about 1,000 to 200,000, preferably 1,000 to 100,000.
Silyl ester copolymer (a3)
The silyl ester copolymer (a3) is a copolymer that has a component unit (also referred to as a silyl ester component unit ”below) derived from a monomer (a31) represented by the general formula (III) (also referred to as a monomer silyl ester ”below), and the copolymer optionally has a
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18/55 component derived from another unsaturated monomer (a32) copolymerizable with the monomer (a31).
R ⁷ -CH = C (R ³ ) -COO-SiR ⁴ R ⁵ R ⁶ (III) i ia Luniiuia limp tv and either a muiogen or a methyl group, R ⁴ , R ⁵ and R ⁶ are each one, independently a hydrocarbon group, R ⁷ is a hydrogen atom or R ⁸ -0C0- (where R ⁸ is an organic group or a silyl group represented by -SiR ⁹ R ¹⁰ R ¹¹ , where R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrocarbon group).
silyl ester monomer (a31) where R ⁷ is a hydrogen atom (H) is represented by the general formula (Ilia):
CH ₂ = C (R ³ ) -COO-SYR ⁴ R ⁵ R ⁶ (IIIa)
In the formula (Illa), R ³ , R ⁴ , R ⁵ and R ⁶ are the same that R ³ , R ⁴ , R ⁵ and R ⁶ , respectively, in formula (III ). The hydrocarbon group at the R ⁴ , R ⁵ and R ⁶ is
preferably an 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.
Examples of a silyl ester monomer (a33), represented by the 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 of a resin from the coating film, long-lasting elution property of a resin and coating film property (eg crack resistance).
silyl ester monomer (a31) where R ⁷ is R ⁸ -O-CO-
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19/55 is represented by the formula (Illb):
R ^a -O-CO-CH = C (R ³ ) -C00-SYR ⁴ R ⁵ R ⁶ (Illb)
In formula (Illb), R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁸ are the same as R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁸ , respectively in formula (III) or in formula (Ilia ).
organic group in R ⁸ is preferably an alkyl group having 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms, more preferably an alkyl group such as methyl, ethyl, propyl and isopropyl. The hydrocarbon group in R ⁹ , R ¹⁰ and R ¹¹ is preferably an alkyl group having 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms, more preferably an alkyl group such as methyl, ethyl, propyl and isopropyl.
An example of a silyl ester monomer (a34), represented by the formula (Illb), is a maleate (a compound represented by the formula (Illb) where R ³ is H).
Examples of another unsaturated monomer (a32) copolymerizable with monomer (a31) (or with monomer (a33) and / or monomer (a34)) include the other unsaturated monomer (al2) and the other unsaturated monomer (a22) exemplified as composed of raw materials of copolymer (al) and copolymer (a2), respectively.
Preferred examples of the other unsaturated monomer (a32) include alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, and hydroxyalkyl (meth) acrylates. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate are particularly preferable.
The silyl ester monomer (a31) can be used in a
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20/55 single type or in combination of two or more types. The other
unsaturated monomer (a32) can be used in a unique type or in combination two or more types. In the copolymer in silil ester (a3) , a unity derived component of monomer from silil ester (a31) is
contained commonly in an amount of 10 to 100% per mol, preferably 10 to 90% per mol, and the component unit derived from the “other unsaturated monomer (a32)” is contained in a residual amount, which is, commonly, in an amount of 0 to 90% per mol, preferably 10 to 90% per mol, based on 100% per mol of all the constituents in the copolymer. The quantities of the component units being in the above range are preferable, which provides excellent viscosity of a resin in the coating film (eg crack resistance), storage stability of the coating material, elution of a resin from the coating film. coating etc.
The average numerical molecular weight Mn (in terms of polystyrene) of the silyl ester copolymer (a3) is commonly 1,000 to 200,000, preferably 1,000 to 100,000. Mn being in the above range is preferable, which provides excellent viscosity of a resin in the coating film (e.g. crack resistance), storage stability of the coating material, elution of a resin from the coating film, etc.
In the antifouling coating composition of the present invention, the hydrolyzable copolymer (A) is contained in terms of a solid component, preferably in an amount of 0.1 to 99.999% by weight, more preferably
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21/55 to 99.999% by weight, more preferably 3 to 99.999% by weight.
<Antifouling agents (B)>
The antifouling coating composition of the present invention comprises medetomidine as an antifouling agent (B). Medetomidine (system name: (±) 4 [1- (2,3-dimethylphenyl) ethyl] -IH-imidazole) is a compound represented by the following by structural formula.
The use of medetomidine with the copolymer that contains a hydrolyzable metal salt bond (A) can provide an excellent antifouling coating composition in coating film property that has a degree of consumption of stable coating film on ships, underwater structures and others and that exhibits excellent antifouling property for a long time.
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 0.02 to 100 parts by weight, more preferably 0.05 to 50 parts by weight, based on 100 parts by weight of the hydrolyzable copolymer (A).
In meeting these requirements, the composition of
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The antifouling coating of the present invention becomes more desirable in terms of an antifouling effect. Specifically, the antifouling coating composition comprising the hydrolyzable copolymer (A) and medetomidine, despite the use of a small amount of antifouling agents (medetomidine) (for example, about 0.01 to 10 parts by weight, preferably 0.01 to 2.0 parts by weight), can exhibit an anti-fouling effect for a long time. In the present invention, the composition need not contain a large amount of an antifouling agent as described above, and so it does not have an adverse effect on the coating film's property as crack resistance. However, the antifouling effect is exhibited for a long time even if medetomidine is contained in an amount of some degree (for example, about more than 10 parts by weight to no more than 200 parts by weight).
The antifouling coating composition of the present invention, in containing medetomidine as the antifouling agents (B), exhibits far superior antifouling properties. The antifouling coating composition of the present invention may optionally contain an antifouling agent, in addition to medetomidine, to have even more improved antifouling properties.
Examples of antifouling agents other than medetomidine include cuprous oxide, copper rodanide, bis (2pyridinediol-1-oxide) copper salt (also referred to as copper pyrithione ”below), bis (2-pyridinediol-1-oxide) salt zinc (also referred to as zinc pyrithione ”below), 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one,
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23/55 triphenylboro-amine complex, dichloro-N ((dimethylamino) sulfonyl) fluor-N- (p-tolyl) methane sulfenoamide, and 2- (p-chlorophenyl) -3-cyano-4-bromo-5trifluoromethylpyrrole.
Additional examples of these include inorganic antifouling agents such as inorganic copper compounds, for example, copper powders; and organic antifouling agents such as N, N-dimethyldichlorophenyl urea, 2,4,6-trichlorophenyl maleimide, 2-methylthio-4-tertbutylamino-6-cyclopropyl-S-triazine, 2,4,5,6tetrachloroisophthalonitrile, bisdimethyldithiocarbonamino zinc, ethylamine bisditi, bisditi chloromethyl-n-octyldisulfide, N, N'-dimethyl-N'-phenyl- (N-fluordichloromethylthio) sulfamide, tetraalkyl thiamide disulfide, zinc dimethyldithio carbamate, zinc ethylene bisditio carbamate, 2,3-dichloro-N- (2 ', 6'dietylphenyl) maleimide, and 2,3-dichloro-N- (2'-ethyl-6'methylphenyl) maleimide.
These antifouling agents can be used in a single type or in a combination of two or more types.
The amount of anti-fouling agents other than medetomidine contained in the anti-fouling coating composition of the present invention is not particularly limited as long as it is in a range that does not have an adverse effect on the coating film's property as crack resistance, and is preferably 0 to 15,000 parts by weight, more preferably 1 to 3,000 parts by weight, even more preferably 5 to 1,500 parts by weight, more preferably 10 to 500 parts by weight, based on 100 parts by weight of the hydrolyzable copolymer (A). The amount of anti-petition agents 870190038072, from 04/22/2019, p. 31/74
24/55 different medetomidine fouling is preferably 0 to 600,000 parts by weight, more preferably 100 to 200,000 parts by weight, more preferably 200 to 100,000 parts by weight, based on 100 parts by weight of medetomidine.
<Other components>
The antifouling coating composition of the present invention may comprise, in addition to the components mentioned above, various components used in a general coating composition, such as color pigments, extending pigments, dehydrating agents, plasticizers, thixotropic agents, resins other than the copolymer hydrolyzable (A), organic acids, and solvents. These can be used on a single type or in combination of two or more types.
Color pigment
Examples of the color pigment include inorganic pigments such as red iron oxide, titanium white (titanium oxide) and yellow iron oxide; and organic pigments such as carbon black, naphthol red and phthalocyanine blue. The color pigment can be used in a single type or in combination of two or more types. The color pigment can also contain various dyes as a dye. The mixing amount of the color pigment can be arbitrarily adjusted, 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).
Extending pigment
The extensor pigment is a low index pigment
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25/55 refractive that is transparent and does not hide from the coated surface when mixed with an oil or varnish. Examples of the extending pigment include talc, silica, mica, clay, zinc oxide, calcium carbonate which is also used as an anti-fixing agent, kaolin, alumina white, white carbon which is also used as a planing agent, hydroxide aluminum, magnesium carbonate, barium carbonate, barium sulfate and zinc sulfide. Of these, zinc oxide, talc, silica, mica, clay, calcium carbonate, kaolin and barium carbonate are preferable. The extending pigment can be used in a single type or in combination of two or more types. The amount of mixing of the extending pigment can be arbitrarily adjusted, and is preferably 0.5 to 750 parts by weight, more preferably 5 to 400 parts by weight, more preferably 10 to 250 parts by weight, based on 100 parts by weight of the copolymer hydrolyzable (A).
Dehydrating agent
The dehydrating agent is a component that contributes to improving the storage stability of the coating material. Examples of the dehydrating agent include inorganic agents that include anhydrite, gypsum hemihydrate (dry gypsum), and an absorbent based on synthetic zeolite (for example, a product named "molecular sieve"). Additional examples include orthoesters (for example, methyl orthoformate, methyl orthoacetate, and ortho boric acid ester), silicates, and isocyanates. Of these, anhydrite and gypsum hemihydrate (dry gypsum), each being an inorganic dehydrating agent, are preferred. O
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26/55 dehydrating agent can be used in a single type or in combination of two or more types. The mixing amount of the dehydrating agent can be arbitrarily adjusted, and is 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).
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. Examples of the plasticizer include n-paraffin, chlorinated paraffin, terpene phenol, tricresyl phosphate (TCP), and polyvinyl ethyl ether. of these, chlorinated paraffin and terpene phenol are preferable; and chlorinated paraffin is particularly preferable. The plasticizer can be used in a single type or in combination of two or more types. Like n-paraffin, an example of a commercially usable product is n-paraffin, manufactured by “Nippon Petrochemicals Co., Ltd. Like clrinated paraffin, examples of commercially usable products are Toyoparax A-40 / A-50 / A- 70 / A-145 / A-150, manufactured by Tosoh Corporation.
The mixing amount of the plasticizer can be arbitrarily adjusted, and is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on 100% by weight of all solid components that include the plasticizer in the composition. anti-fouling coating.
Anti-sinking / anti-fixing agent
Examples of anti-sink / anti-fixation agent
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27/55 (thixotropic agent) include organic clay compounds (for example, an amine salt, a stearate salt, a lecithin salt and an Al, Ca and Zn alkyl sulfonate), organic waxes (for example, polyethylene, oxidized polyethylene wax, polyamide wax, amide wax, and hydrogenated castor oil wax), and finely divided synthetic silica. Of these, organic clay compounds, polyamide wax, amide wax, oxidized polyethylene wax, and finely divided synthetic silica are preferable. The anti-sink / anti-fixation agent can be used in a single type or in combination of two or more types. The amount of anti-sink / antifixation mixture 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).
Other resins and organic acids
The antifouling coating composition of the present invention can comprise one type, or two or more types of other resins, in addition to the metal salt-containing copolymer (A) as described above.
Examples that can be employed include water-insoluble resins or sparingly water-soluble resins, such as an acrylic resin that does not contain a metal salt bond, an acrylic silicone resin, a polyester resin, an unsaturated polyester resin, a fluorine, a resin polybutene, a silicone rubber, a polyurethane resin, an epoxy resin, a polyamide resin, vinyl resin (for example, a vinyl chloride copolymer and an ethylene / vinyl acetate copolymer), a chlorinated rubber, a chlorinated olefin resin, a
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28/55 styrene / butadiene copolymer resin, ketone resin, alkyd resin, coumarone resin, phenol terpene resin and petroleum resin.
Additional examples employable with the hydrolyzable copolymer (A) include water-soluble resins such as pine tar, rosin (rosin gum, wood rosin and liquid rosin), and monobasic organic acids such as naphthenic acid, versatile acid, triphenylisobutenyl cyclohexene carboxylic acid (A-3000 manufactured by Yasuhara Chemical Co. ”, Ltd.).
Solvent
Various components that make up the antifouling coating composition of the present invention are commonly dissolved or 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, examples of which include an aliphatic solvent, an aromatic solvent (for example, xylene and toluene), a ketone solvent (for example, MIBK and cyclohexanone), an ester solvent, an ether solvent (eg, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate), and an alcohol solvent (eg, isopropyl alcohol). The amount of solvent mixture can be adjusted arbitrarily, and is, for example, an amount in which all solid components account for 20 to 90% by weight in the antifouling coating composition. The solvent can also be added in a coating operation for practicality.
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29/55 [Production method and uses of antifouling coating composition]
The antifouling coating composition of the present invention can be prepared with apparatus, means, etc. similarly to those employed for generally known antifouling coating materials. For example, the copolymer containing metal salt bond (a1) or (a2), or the silyl ester copolymer (a3) is prepared in advance, and then this copolymer (reaction liquid) and antifouling agents (B ), optionally with other components as additives, are added in a solvent, in a moment or in series, and stirred and mixed.
The antifouling coating composition of the present invention can be used in modalities 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, the surface of a substrate is coated or impregnated with the antifouling coating composition of the present invention, and then dried for a prescribed period of time, thus forming a cured antifouling coating film on the substrate surface.
For example, on a substrate with a coating film (for example, an antifouling substrate) of the present invention, the 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 this
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The invention comprises the step of applying or impregnating the antifouling coating composition to a surface of a substrate, and the step of curing the composition to form a coating film; and a method for preventing the fouling of a substrate of the present invention comprises the step of applying or impregnating the antifouling coating composition to a surface of a substrate, and the curing step of the composition to form an antifouling coating film. .
Examples of the substrate include a substrate that is (for example, always or intermittently) in contact with sea water or fresh water, and more specific examples include an underwater structure, a ship's outer edge, a fishing net and a gear. fishing.
It can be prevented that the substrate surface, when being coated with such an antifouling coating film, is encrusted by aquatic animals. The thickness of the antifouling coating film can be arbitrarily adjusted in view of the consumption rate of the coating film etc. Examples of this thickness are 40 to 400 pm per coating, preferably about 40 to 200 pm per coating.
EXAMPLES
In the following, the present invention is also described with reference to the Examples, but it should be understood that the present invention is not limited to those Examples. In the Examples and Comparative Examples below, the term part (s) means part (s) by weight, and% with respect to the indication of a solid component means% by weight, unless it deviates from the point.
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In the present invention, including the tables as described later, a simple reference, for example, “copolymer (A) basically means a resin which is a film-forming component. The reference, for example, to copolymer (A) with the indication of a solid component also means a resin solution or dispersion that contains a volatile component such as a solvent as well as the resin that serves as the coating film forming component. <Gardner viscosity measurement conditions>
Gardner's viscosity was measured under the conditions of a resin concentration of 35% by weight and 25 ° C according to JIS K 7233-4.3, as described in JP 2003-55890
THE.
<Visit>
Viscosity at 25 ° C was measured with a viscometer type
B.
<Solid component>
A solid component means a residue from the heating given when a reaction mixture, a coating material, an uncured coating film or others containing a polymer, a solvent etc. it is heated and dried for 3 hours in an air dryer heated to 105 ° C to evaporate the solvent etc. The solid component commonly 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 others and capable of forming a resin (solid component) through reaction are also included in the solid component.
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32/55 <Measurement of average numerical molecular weight (Mn) and average weight molecular weight (Mw)>
The average molecular weight (Mw) of a resin was measured by gel permeation chromatography (GPC) with HLC-8120GPC ”, manufactured by Tosoh Corporation, using two separate columns (α-M) of TSK- α type gel ”, manufactured by Tosoh Corporation, and using, as an elution solution, dimethylformamide (DMF) to which 20 mM LiBr were added. The average molecular weight of the resin was determined in terms of polystyrene. The average numerical molecular weight (Mn) of the resin was measured by GPC as described above and determined in terms of polystyrene.
[Production example 1]
Production of side chain terminal copolymer containing metal salt bond (a1-1)
In a four-neck flask equipped with a condenser, a thermometer, a drip 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 drip funnel, a mixture consisting of monomers and a polymerization initiator shown in Table 1 was dripped at a constant rate for 3 hours. After the dripping was complete, 1 part of t-butyl peroctoate and 10 parts of xylene were dripped for 2 hours, and after stirring for 2 hours, 20 parts of xylene were added, thus obtaining a reaction mixture containing a side chain terminal copolymer containing metal salt bond (a1-1).
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Gardner's viscosity and the solid component (%), which are property values of the copolymer (a1-1) or the reaction mixture containing the obtained copolymer (a1-1), were evaluated. The results are shown in Table 5 1.
[Table 1] <Table 1> Example of production of side chain terminal copolymer containing metal salt bond (a1)
Example ofproduction 1 Side chain terminal copolymer containingmetal salt connection (a1) a1-1 (met) acid metal acrylatemonobasic: monomer (a11) versatic acid, zinc methacrylate 35 Another unsaturated monomer copolymerizable with monomer (a11): monomer (a12) 2-methoxyethylacrylate 10 3-methoxybutylacrylate 30 ethyl acrylate 25 Polymerization initiator t-butyl peroxide 6 Property values Viscosity ofGardner + Z Solid component 50.5
* the values of the monomer (a11), the monomer (a12) and the polymerization initiator denote parts by weight.
[Preparation example 1]
Preparation of metal-containing monomer (a21-1)
In a four-neck flask equipped with a
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34/55 condenser, thermometer, drip funnel and stirrer, 85.4 parts of propylene glycol monomethyl ether (PGM) and 40.7 parts of zinc oxide were introduced, and with stirring, they were heated to 75 ° Ç.
Subsequently, from the drip funnel, a mixture consisting of 43.1 parts of methacrylic acid (MAA), 36.1 parts of acrylic acid (AA) and 5 parts of water was dripped at a constant rate for 3 hours. After the dripping was complete, reaction solution 10 became transparent from an opaque white state.
After stirring for 2 hours, 36 parts of propylene glycol monomethyl ether were added to obtain a reaction liquid containing a metal-containing monomer (a21-1). The loaded quantities of the raw materials are presented in terms of molar proportion, and the composition of the resulting reaction liquid is presented in terms of percentage by weight in Table 2.
[Table 2] <Table 2> Preparation of metal-containing monomer (a21-1)
Loaded quantity (molar ratio) Volatile component (%) of reaction liquid containing metal-containing monomer Solid component (%) * of reaction liquid containing metal-containing monomer MMA AA ZnO Water PGM Water Componentsolid
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Preparation example1 a21-1 0.5 0.5 0.5 0.27 53.2 2 44, 8
* Solid component (%) contains a monomer capable of forming a resin through reaction.
[Production example 2] Production of a copolymer containing a cross-linked metal salt bond (a2-1)
In a four-neck flask equipped with a condenser, a thermometer, a drip 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 ° Ç. Subsequently, from the drip funnel, a transparent mixture consisting of 52 parts of the metal-containing monomer reaction liquid (a21-1) obtained in Preparation Example 1, 1 part of methyl methacrylate (MMA), 66.2 parts of ethyl acrylate (EA), 5.4 parts of 2-methoxyethyl acrylate (2-MEA), 2.5 parts of azobisisobutyronitrile (AIBN, manufactured by Japan Hydrazina Company Inc.), 7 parts of azobismethylbutyronitrile (AMBN, manufactured by Japan Hydrazina Company Inc.), 1 part of a chain transfer agent (“Nofmer MSD”, manufactured by Nippon Oil & Fats Co., Ltd.), and 10 parts of xylene were dripped at a constant rate for 6 hours. After the drip was complete, 0.5 part of t-butyl peroctoate (TBPO) and 7 parts of xylene were dripped for 30 minutes. After stirring for 1 hour and 30 minutes, 4.4 parts of xylene were added to obtain an insoluble, light yellow, transparent reaction mixture
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36/55 copolymer containing cross-linked metal salt (a2-1). Mixture composition and property values of the copolymer (a2-1) or of the reaction mixture containing the copolymer (a2-1) obtained are shown in Table 3.
[Table 3] <Table 3> Example of production of a copolymer that contains cross-linked metal salt (a2)
Example ofproduction 2 copolymer containing metal salt bondcrisscross (a2) a2-1 Reaction liquidMonomer that containsmetal: monomer (a21) a21-1 52 Another unsaturated monomer copolymerizable with monomer (a21): monomer (a22) MMA 1 AND THE 66, 2 2-MEA 5, 4 Initiator AIBN 2.5 AMBN 7 TBPO 0.5 Transfer agentof chain Nofmer MSD 1 Property values Gardner viscosity -Y Solid component (%) 45, 6 Average numerical molecular weight (Mn) 1950 Average molecular weight (Mw) 5200
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37/55 [Production example 3]
Production of copolymer that contains cross-linked metal salt (a2-2)
A copolymer containing a cross-linked salt (a2-2) was prepared in the same way as
Production example 1, except that the mixing components of the mixture containing the monomers and the polymerization initiator have been exchanged as shown in the Table
4. The mixture composition and property values of the copolymer (a2-2) or the reaction mixture containing the copolymer (a2-2) obtained are shown in Table 4.
[Table 4] <Table 4> Example of production of a copolymer that contains cross-linked metal salt (a2)
Example ofproduction 3copolymer containing metal salt bondcrisscross (a2) a2-2 Monomer that containsmetal (a21) Zinc diacrylate 8 Dimethacrylatezinc 8 (meth) monobasic acid metal acrylate: monomer (a22) isostearic acidzinc acrylate 12 isostearic acidzinc methacrylate 12 Another monomerunsaturated 2-methoxyethyl acrylate 13 methyl methacrylate 13
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copolymerizable withmonomer (a21): monomer(a22) ethyl acrylate 34 Initiator polymerization t-butyl peroxide 5 Property values Viscosity ofGardner -Y Solid component (%) 49.7
[Production example 4]
Production of silyl ester copolymer (a3-1)
In a reaction flask equipped with a stirrer, a condenser, a thermometer, a drip device, a nitrogen introducing tube and a heating / cooling jacket, 100 parts of xylene were introduced, and heating and stirring was carried out in a nitrogen stream at a temperature condition of 85 ° C. With this temperature maintained, from the drip device, a mixture of 60 parts of triisopropylsilyl acrylate, 40 parts of methyl methacrylate and 0.3 parts of 2,2'-azobisisobutyronitrile were dripped into the reaction flask for 2 hours. After that, stirring was carried out for 4 hours at that temperature, and then 0.4 part of 2,2'-azobisisobutyronitrile was added, and stirring was also carried out for 4 hours at this temperature, in order to obtain a colorless and transparent reaction mixture that contains a silyl ester copolymer (a3-1). The mix composition and property values of the
copolymer (a3-1) or of the mixture in reaction containing the copolymer (a3-1) are presented at Table 5. [Table 5]<Table 5> Example in production of silyl ester copolymer
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39/55 (a3)
Production example 4 Silyl ester copolymer (a3) a3-1 Solvent xylene 100 Componentsdripped triisopropyl silyl acrylate 60 methyl methacrylate 40 2,2'-azobisisobutyronitrile(early stage) 0.3 Total 200.3 Component added 2,2'-azobisisobutyronitrile(later stage) 0.4 Values ofproperty Solid component (%) 51.2 Viscosity (cps / 25 ° C) 408 Average numerical molecular weight(Mn) 9,735 Average molecular weight(Mw) 55,650
[Examples 1 to 3 and Comparative Example 1]
Production of antifouling coating composition-1
The reaction mixture containing the copolymer containing the cross-linked metal salt (a2-1) obtained in
Production example 2, together with the antifouling agents (B) and other components, were homogeneously mixed using a paint stirrer, to thereby produce an antifouling coating composition 10 that has a mixing composition as shown in
Table 6 (Examples 1-3 and Comparative Example 1) (values in the table denote part (s) by weight).
[Examples 4 to 52 and Comparative Example 2 to 11]
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Production of antifouling coating composition-2
The reaction mixture that contains the copolymer that contains a cross-linked metal salt bond (a1-1), (a2-1) or (a21), obtained in Production Examples 1 to 3, or that contains the silyl ester copolymer ( a3-1) obtained in Production Example 4, together with the antifouling agents (B) and other components, were homogeneously mixed using an ink stirrer, to thereby produce an antifouling coating composition that has a mix composition as shown in Tables 8-1 to 8-6 (Examples 4-52 and Comparative Example 2 to 11) (values in the tables denote part (s) by weight).
[Criteria for assessing static antifouling property based on an adhesion area of underwater organisms, in Examples and Comparative Examples]
The criteria for the assessment of static antifouling property based on an adhesion area of underwater organisms are as follows.
point: The adhesion area of underwater organisms is about 100%.
point: The adhesion area of underwater organisms is about 51 to 99%.
points: The adhesion area of underwater organisms is about 31 to 50%.
3 points: THE area in accession From organisms underwater is about from 11 to 30%. 4 points: THE area in accession From organisms underwater is about from 1 to 10%. 5 points: THE area in accession From organisms
underwater is about 0%.
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41/55 <Experiment with static antifouling property of antifouling coating film [Examples 1 to 52 and Comparative Examples 1 to 11]>
A sanded steel plate (length 300 mm x 100 mm wide x 3.2 mm thick) was coated with an anti-corrosion epoxy coating material (AC epoxy coating material, product name: “Bannoh 500”, manufactured by Chugoku Marine Paints, Ltd.) so that the dry film thickness would be 150 pm, and then it was also coated with an epoxy binder coating material (product name: “Bannoh 500N”, manufactured by Chugoku Marine Paints, Ltd. ) so that the dry film thickness would be 100 pm. Subsequently, the resulting plate was coated with the antifouling coating composition produced in the Example or Comparative Example once so that the thickness of the dry film would be 100 pm, and then dried at room temperature for 7 days, so as to prepare a test plate with an antifouling coating film. The above three coatings were each carried out under the condition of 1 day / 1 coat.
The test plate prepared as described above was immersed and left to stand for 8 months in Hiroshima Bay of Hiroshima ”. During this time, the area (%) of adhesion on the surface of the coating film of underwater organisms excluding sludge was measured every two months. According to the criteria for the evaluation of static antifouling property based on an adhesion area of underwater organisms, the static antifouling property of
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42/55 antifouling coating was evaluated. The results are shown in Tables 7, 9-1 to 9-6.
<Antifouling coating consumption grade experiment [Examples 4 to 52 and Comparative Example 2 to 11]>
A 50 x 50 x 1.5 mm rigid vinyl chloride board was coated with the antifouling coating composition produced in the Example or Comparative Example, using an applicator, so that a dry film thickness would be 250 pm. The coated plate was rotated at 15 knots, and the consumption group (decrease in film thickness) of the antifouling coating film was measured every month. The results are shown in Tables 9-1 to 9-6. One unit of the degree of consumption of the coating film in the tables is pm.
<Antifouling coating property experiment [Examples 4 to 52 and Comparative Examples 2 to 11]>
A substrate that was a sanded steel plate coated with an anti-corrosion coating film was coated with the antifouling coating composition produced in the Example or Comparative Example, so that a thickness of the dry film would be 250 µm. Then, it was immersed in sterile and filtered sea water 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 anti-corrosion coating composition that has the same composition, so that a dry film thickness would be 250 pm, and then the resulting coated plate was dried for 1 week.
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Then, it was immersed in sterile sea water and filtered at 50 ° C for 6 months, to observe cracking and peeling of the coating film. When it found no cracking and peeling it was rated AA;
finding crack and partial peeling it was rated as BB; finding partial peeling it was evaluated as CC; and finding crack and peeling all over the surface it was rated as DD. The results are shown in Tables 9-1 to 9-6.
[Table 6] <Table 6> Composition of antifouling coating-1
Ex.1 Ex.2 Ex.3 Ex.comp. 1 Copolymer containing cross-linked metal salt bond (a2-1) (solid component: 45.6%) 100 100 100 100 medetomidine 0.025 0.05 0.1 - xylene 5 5 5 -
[Table 7] <Table 7> Result of antifouling property
Immersion period Ex.1 Ex.2 Ex.3 Ex.comp.1 2 months 4 4 5 2 Four months 3 4 5 1 6 months 2 3 5 0 8 months 2 3 4 0
Petition 870190038072, of 04/22/2019, p. 51/74 [Table 8-1] <Table 8-1> Composition of antifouling coating-2
Ex. 4 Ex.5 Ex.6 Ex.7 Ex.8 Ex.9 Ex.10 Ex.11 Ex.12 Ex. 13 Side chain end copolymer containing metal salt bond (a1-1) (solid component: 50.5%) 45Copolymer containing cross-linked metal salt bond (a2-1) (solid component: 45.6%)45 45 45 45 5 5 Copolymer containing cross-linked metal salt (a2-2) (solid component: 49.7%)45 Silyl ester copolymer (a3-1) (solid component: 51.2%) 45 30 Rosina 10 10 Laroflex MP25 ** 5 5 Chlorinated paraffin 2 2 2 2 2 2 2 2 2 2 Baby powder 15 15 15 15 15 15 15 3 3 3 Zinc oxide 10 10 10 10 15 10 10 3 3 3 Fixing barium sulfate 3 3 3 3 3 3 3 3 3 3 Dry gypsum 1 1 1 1 1 1 1 1 1 1 Red iron oxide 2 2 2 2 2 2 2 2 2 2 Cuprous oxide 40 40 45 Copper rodanida Bis (2-pyridinatiol-1-oxide) zinc salt 5 5 5 55 5 5 Bis (2-pyridinatiol-1-oxide) copper salt SEA-NINE 211N *** 5Pyridine-triphenylborane Dichloro-N - ((dimethylamino) sulfonyl) fluorine-N- (p- 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluormethylpyrrole medetomidine 0.1 0.4 0.1 0.05 0.05 0.1 0.1 0.1 0.1 0.1 Oxidized polyethylene wax (solid component: 20%) 2 2 2 2 2 2 2 2 2 2 Fatty acid amide wax (solid component: 20%) 3 3 3 3 3 3 3 3 3 3 Xylene 8.9 8.6 8.9 8.95 8.95 8.9 8.9 2.9 12.9 12.9 Propylene glycol monomethyl ether 3 3 3 3 3 3 3 3 3 3 Total parts by weight 100 100 100 100 100 100 100 100 100 100
** Laroflex MP25 (BASF Japan Ltd.) *** SEA-NINE 211 (Rohm and Hass, 4,5-dichloro-2-n-octyl-4isothiazoline-3-one)
Petition 870190038072, of 04/22/2019, p. 52/74 [Table 8-2] <Table 8-2> Composition of antifouling coating-2
Ex. 14 Ex.15 Ex.16 Ex.17 Ex.18 Ex.19 Ex.20 Ex.21 Ex.22 Ex.23 Side chain end copolymer containing metal salt bond (a1-1) (solid component: 50.5%) Copolymer containing cross-linked metal salt bond (a2-1) (solid component: 45.6%) 45 45 45 45 45 45 45 45 45 45 Copolymer containing cross-linked metal salt (a2-2) (solid component: 49.7%) Silyl ester copolymer (a3-1) (solid component: 51.2%) Rosina Laroflex MP25 Chlorinated paraffin 2 2 2 2 2 2 2 2 2 2 Baby powder 10 10 10 10 10 10 10 10 10 10 Zinc oxide 10 10 10 10 10 10 10 10 10 10 Fixing barium sulfate 3 3 3 3 3 3 3 3 3 3 Dry gypsum 1 1 1 1 1 1 1 1 1 1 Red iron oxide 2 2 2 2 2 2 2 2 2 2 Cuprous oxide Copper rodanida Bis (2-pyridinatiol-1-oxide) zinc salt 105 5 5 5 Bis (2-pyridinatiol-1-oxide) copper salt10 SEA-NINE 211N 10 5 Pyridine-triphenylborane 10 5 Dichloro-N - ((dimethylamino) sulfonyl) fluorine-N- (ptolyl) methanesulfenoamide 10 52- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluormethylpyrrole10 5 medetomidine 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Oxidized polyethylene wax (solid component: 20%) 2 2 2 2 2 2 2 2 2 2 Fatty acid amide wax (solid component: 20%) 3 3 3 3 3 3 3 3 3 3 Xylene 8.9 8.9 8.9 8.9 8.9 8.9 8.9 8.9 8.9 8.9 Propylene glycol monomethyl ether 3 3 3 3 3 3 3 3 3 3 Total parts by weight 100 100 100 100 100 100 100 100 100 100
Petition 870190038072, of 04/22/2019, p. 53/74 [Table 8-3] <Table 8-3> Composition of antifouling coating-2
Ex.2 4 Ex.25 Ex.26 Ex.27 Ex.28 Ex.29 Ex.30 Ex.31 Ex.32 Side chain end copolymer containing metal salt bond (a1-1) (solid component: 50.5%)Copolymer containing cross-linked metal salt bond (a2-1) (solid component: 45.6%) 45 45 45 45 45 45 30 30 30 Copolymer containing cross-linked metal salt (a2-2) (solid component: 49.7%)Silyl ester copolymer (a3-1) (solid component: 51.2%)RosinaLaroflex MP25Chlorinated paraffin 2 2 2 2 2 2 2 2 2 Baby powder 10 10 10 10 10 10 3 3 3 Zinc oxide 10 10 10 10 10 10 3 3 3 Fixing barium sulfate 3 3 3 3 3 3 3 3 3 Dry gypsum 1 1 1 1 1 1 1 1 1 Red iron oxide 2 2 2 2 2 2 2 2 2 Cuprous oxide 40 45Copper rodanida 40 Bis (2-pyridinatiol-1-oxide) zinc salt 55 Bis (2-pyridinatiol-1-oxide) copper saltSEA-NINE 211N 5 5 5 Pyridine-triphenylborane 5 5 5 Dichloro-N - ((dimethylamino) sulfonyl) fluorine-N- (ptolyl) methanesulfenoamide555 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluormethylpyrrole 55 5 medetomidine 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Oxidized polyethylene wax (solid component: 20%) 2 2 2 2 2 2 2 2 2 Fatty acid amide wax (solid component: 20%) 3 3 3 3 3 3 3 3 3 Xylene 8.9 8.9 8.9 8.9 8.9 8.9 2.9 2.9 2.9 Propylene glycol monomethyl ether 3 3 3 3 3 3 3 3 3 Total parts by weight 100 100 100 100 100 100 100 100 100
Petition 870190038072, of 04/22/2019, p. 54/74 [Table 8-4] <Table 8-4> Composition of antifouling coating-2
Side chain end copolymer containing metal salt bond (a1-1) (solid component: 50.5%)
Copolymer containing cross-linked metal salt bond (a2-1) (solid component: 45.6%)
Copolymer containing cross-linked metal salt (a2-2) (solid component: 49.7%)
Silyl ester copolymer (a3-1) (solid component: 51.2%)
Rosina
Laroflex MP25
Chlorinated paraffin
Baby powder
Zinc oxide
Fixing barium sulfate
Dry gypsum
Red iron oxide
Cuprous oxide
Copper rodanida
Bis (2-pyridinatiol-1-oxide) zinc salt
Bis (2-pyridinatiol-1-oxide) copper salt
SEA-NINE 211N______________________________________________________
Pyridine-triphenylborane
Dichloro-N - ((dimethylamino) sulfonyl) fluorine-N- (ptolyl) methanesulfenoamide
2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluormethylpyrrole medetomidine
Oxidized polyethylene wax (solid component: 20%)
Fatty acid amide wax (solid component: 20%)
Xylene
Propylene glycol monomethyl ether
Total parts by weight
Ex. 33


0.1
8.9
100
Ex.34


0.1
8.9
100
Ex. 35


0.1
8.9
100
Ex.36


0.1
8.9
100
Ex.37


0.1
8.9
100
Ex. 38


0.1
8.9
100
Ex.39


0.1
8.9
100
Ex.40


0.1
8.9
100
Ex.41


0.1
8.9
100
Ex.42


0.1
8.9
100
Petition 870190038072, of 04/22/2019, p. 55/74 [Table 8-5] <Table 8-5> Composition of antifouling coating-2
Ex.43 Ex.44 Ex.45 Ex.46 Ex.47 Ex.48 Ex.49 Ex.50 Ex.51 Ex. 52 Side chain end copolymer containing metal salt bond (a1-1) (solid component: 50.5%) Copolymer containing cross-linked metal salt bond (a2-1) (solid component: 45.6%) 45 45 45 45 45 45 30 30 30 45 Copolymer containing cross-linked metal salt (a2-2) (solid component: 49.7%) Silyl ester copolymer (a3-1) (solid component: 51.2%) Rosina Laroflex MP25 Chlorinated paraffin 2 2 2 2 2 2 2 2 2 2 Baby powder 10 10 10 10 10 10 10 10 10 15 Zinc oxide 10 10 10 10 10 10 10 10 10 15 Fixing barium sulfate 9 9 9 9 9 9 10 10 10 3 Dry gypsum 1 1 1 1 1 1 1 1 1 1 Red iron oxide 2 2 2 2 2 2 2 2 2 2 Cuprous oxide 20 20 Copper rodanida 20Bis (2-pyridinatiol-1-oxide) zinc salt 11Bis (2-pyridinatiol-1-oxide) copper salt SEA-NINE 211N 2 2 2 Pyridine-triphenylborane 2 2 2Dichloro-N - ((dimethylamino) sulfonyl) fluorine-N- (ptolyl) methanesulfenoamide222 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluormethylpyrrole 22 2 medetomidine 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Oxidized polyethylene wax (solid component: 20%) 2 2 2 2 2 2 2 2 2 2 Fatty acid amide wax (solid component: 20%) 3 3 3 3 3 3 3 3 3 3 Xylene 8.9 8.9 8.9 8.9 8.9 8.9 5.9 6.9 5.9 8.9 Propylene glycol monomethyl ether 3 3 3 3 3 3 3 3 3 3 Total parts by weight 100 100 100 100 100 100 100 100 100 100
Petition 870190038072, of 04/22/2019, p. 56/74 [Table 8-6] <Table 8-6> Composition of antifouling coating-2
Ex.Com. 2 Ex.Com.3 Ex.Com.4 Ex.Com.5 Ex.Com.6 Ex.Com.7 Ex.Com.8 Ex.Com.9 Ex.Com.10 Ex.C om.11 Side chain end copolymer containing metal salt bond (a1-1) (solid component: 50.5%) 45Copolymer containing cross-linked metal salt bond (a2-1) (solid component: 45.6%) 4545 5 5Copolymer containing cross-linked metal salt (a2-2) (solid component: 49.7%)45 Silyl ester copolymer (a3-1) (solid component: 51.2%) 45 30 Rosina 10 10Laroflex MP25 5 5Paraloid B-66 (100%) resin *20.7 20.7 Chlorinated paraffin 2 2 2 2 2 2 2 2 2 2 Baby powder 15 15 15 15 15 15 3 3 3 15 Zinc oxide 10 10 10 10 15 15 3 3 3 15 Fixing barium sulfate 3 3 3 3 3 3 3 3 3 3 Dry gypsum 1 1 1 1 1 1 1 1 1 1 Red iron oxide 2 2 2 2 2 2 2 2 2 2 Cuprous oxide 45 40 45Copper rodanida Bis (2-pyridinatiol-1-oxide) zinc salt 5 5 5 5 Bis (2-pyridinatiol-1-oxide) copper salt SEA-NINE 211N55 Pyridine-triphenylborane Dichloro-N - ((dimethylamino) sulfonyl) fluorine-N- (ptolyl) methanesulfenoamide 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluormethylpyrrole medetomidine0.1 0.1 Oxidized polyethylene wax (solid component: 20%) 2 2 2 2 2 2 2 2 2 2 Fatty acid amide wax (solid component: 20%) 3 3 3 3 3 3 3 3 3 3 Xylene 9 9 9 9 9 28.2 3 13 13 33.2 Propylene glycol monomethyl ether 3 3 3 3 3 3 3 3 3 3 Total parts by weight 100 100 100 100 100 100 100 100 100 100
* Paraloid B-66 (MMA / BMA = 50/50; 100%) resin (Rohm and Hass)
Petition 870190038072, of 04/22/2019, p. 57/74 [Table 9-1] <Table 9-1> Results of antifouling property-2
Ex. 4 Ex. 5 Ex.6 Ex.7 Ex.8 Ex. 9 Ex.10 Ex.11 Ex.12 Ex. 13 Static antifouling property / a total of 5 points (immersion in sea water for 2 months) 5 5 5 5 5 5 5 5 5 5 Static antifouling property / a total of 5 points (immersion in sea water for 4 months) 5 5 5 5 4 5 5 5 5 5 Static antifouling property / a total of 5 points (immersion in seawater for 6 months) 5 5 5 5 3 5 5 5 5 5 Static antifouling property / a total of 5 points (immersion in sea water for 8 months) 5 5 5 5 3 5 5 5 5 5 Degree of consumption of coating film 3 months 30.7 34.2 34.5 34.5 33.2 32.1 32.2 35.2 29.3 28.7 Degree of consumption of coating film 6 months 65.2 72.3 73.2 72.9 60.1 67.6 68.2 74.1 53.3 54.4 Proportion of degree of consumption of coating film (6 months / 3 months) 2,124 2,114 2,122 2,113 1,810 2.106 2,118 2.105 1.819 1,895 Property experiment AA AA AA AA AA AA AA AA AA AA
Petition 870190038072, of 04/22/2019, p. 58/74 [Table 9-2] <Table 9-2> Results of antifouling property-2
Ex. 14 Ex. 15 Ex.16 Ex.17 Ex.18 Ex.19 Ex.20 Ex.21 Ex.22 Ex.23 Static antifouling property / a total of 5 points (immersion in sea water for 2 months) 5 5 5 5 5 5 5 5 5 5 Static antifouling property / a total of 5 points (immersion in sea water for 4 months) 5 5 5 5 5 5 5 5 5 5 Static antifouling property / a total of 5 points (immersion in seawater for 6 months) 5 5 5 5 5 5 5 5 5 5 Static antifouling property / a total of 5 points (immersion in sea water for 8 months) 5 5 5 5 5 5 5 5 5 5 Degree of consumption of coating film 3 months 33, 6 33.9 31.2 31.5 33.5 33.3 34.7 32.9 33.5 34.5 Degree of consumption of coating film 6 months 73.5 72.5 56.4 58.0 62.1 63.1 73.0 69.2 70.7 78.1 Proportion of degree of consumption of coating film (6 months / 3 months) 2,188 2,139 1.808 1,841 1,854 1,895 2.104 2.103 2,110 2,264 Property experiment AA AA AA AA AA AA AA AA AA AA
Petition 870190038072, of 04/22/2019, p. 59/74 [Table 9-3] <Table 9-3> Results of antifouling property-2
Ex.2 4 Ex.25 Ex.26 Ex. 2 7 Ex.28 Ex.29 Ex.30 Ex.31 Ex.32 Static antifouling property / a total of 5 points (immersion in sea water for 2 months) 5 5 5 5 5 5 5 5 5 Static antifouling property / a total of 5 points (immersion in sea water for 4 months) 5 5 5 5 5 5 5 5 5 Static antifouling property / a total of 5 points (immersion in seawater for 6 months) 5 5 5 5 5 5 5 5 5 Static antifouling property / a total of 5 points (immersion in sea water for 8 months) 5 5 5 5 5 5 5 5 5 Degree of consumption of coating film 3 months 30.1 30.9 32.1 32.0 33.8 33.5 34.5 30.1 32.1 Degree of consumption of coating film 6 months 54.5 56.3 59.5 58.0 62.7 62.4 72.8 54.3 68.3 Proportion of degree of consumption of coating film (6 months / 3 months) 1.811 1.822 1,854 1.813 1,855 1,863 2,110 1.804 2,128 Property experiment AA AA AA AA AA AA AA AA AA
Petition 870190038072, of 04/22/2019, p. 60/74 [Table 9-4] <Table 9-4> Results of antifouling property-2
Ex.33 Ex.34 Ex.35 Ex.36 Ex.37 Ex.38 Ex.39 Ex. 40 Ex.41 Ex. 42 Static antifouling property / a total of 5 points (immersion in sea water for 2 months) 5 5 5 5 5 5 5 5 5 5 Static antifouling property / a total of 5 points (immersion in sea water for 4 months) 5 5 5 5 5 5 5 5 5 5 Static antifouling property / a total of 5 points (immersion in seawater for 6 months) 5 5 5 5 5 5 5 5 5 5 Static antifouling property / a total of 5 points (immersion in sea water for 8 months) 5 5 5 5 5 5 5 5 5 5 Degree of consumption of coating film 3 months 33.2 33.1 31.2 32.6 32.3 33.1 32.1 33.2 32.9 34.7 Degree of consumption of coating film 6 months 71.7 71.2 56.5 59.8 59.5 62.5 67.5 69.9 69.2 77.2 Proportion of degree of consumption of coating film (6 months / 3 months) 2,160 2,151 1.811 1,834 1,842 1,888 2.103 2.105 2.103 2,225 Property experiment AA AA AA AA AA AA AA AA AA AA
Petition 870190038072, of 04/22/2019, p. 61/74 [Table 9-5] <Table 9-5> Results of antifouling property-2
Ex.43 Ex.44 Ex.45 Ex.46 Ex.47 Ex.4 8 Ex.4 9 Ex.50 Ex.51 Ex.52 Static antifouling property / a total of 5 points (immersion in sea water for 2 months) in 5 5 5 5 5 5 5 5 5 5 Static antifouling property / a total of 5 points (immersion in seawater for 4 months) in 5 5 5 5 5 5 5 5 5 4 Static antifouling property / a total of 5 points (immersion in sea water for 6 months) in 5 5 5 5 5 5 5 5 5 3 Static antifouling property / a total of 5 points (immersion in sea water for 8 months) in 5 5 5 5 5 5 5 5 5 3 Degree of consumption of coating film months 3 32.5 32, 6 33.4 32.1 34.7 33.5 35.1 31.8 33.0 33.8 Degree of consumption of coating film months 6 58.9 59.3 60, 6 58.2 63.5 62.1 73.9 57.3 69.4 61, 8 Proportion of degree of consumption of coating film (6 months / 3 months)1.812 1.819 1.814 1.813 1.830 1,854 2.105 1.802 2.103 1.828 Property experimentAA AA AA AA AA AA AA AA AA AA
Petition 870190038072, of 04/22/2019, p. 62/74 [Table 9-6] <Table 9-6> Results of antifouling property-2
Ex.Com. 2 Ex.Com.3 Ex.Com.4 Ex.Com.5 Ex.Com.6 Ex.Com.7 Ex.Com.8 Ex.Com.9 Ex.Com.10 Ex.C om.11 Static antifouling property / a total of 5 points (immersion in sea water for 2 months) 2 2 2 2 1 3 3 4 2 2 Static antifouling property / a total of 5 points (immersion in sea water for 4 months) 1 1 2 1 1 0 3 3 2 1 Static antifouling property / a total of 5 points (immersion in seawater for 6 months) 1 1 1 1 0 0 2 2 1 0 Static antifouling property / a total of 5 points (immersion in sea water for 8 months) 1 1 1 1 0 0 1 2 1 0 Degree of consumption of coating film 3 months 29.4 31.0 32.3 29.9 29.3 5.8 29.5 27.2 26.9 3.9 Degree of consumption of coating film 6 months 51.3 55.1 56.3 53.7 51.9 6.6 51.6 47.4 46.3 4.3 Proportion of degree of consumption of coating film (6 months / 3 months) 1,745 1,777 1,743 1,796 1,771 1,138 1,749 1,743 1,721 1.103 Property experiment AA AA AA AA AA CC AA AA AA CC

权利要求:
Claims (18)
[1]
Claims
1. Antifouling coating composition, characterized by comprising a hydrolyzable copolymer (A) and an antifouling agent (B), in which the hydrolyzable copolymer (A) is at least one hydrolyzable copolymer selected from the group consisting of:
(al) a copolymer that contains a metal salt bond which is an acrylic resin or a polyester resin and has a side chain end group represented by the general formula (I):
-COO-MO-COR ¹ (I) [In formula (I), M is zinc or copper, and R ¹ is an organic group];
(a2) a copolymer containing a metal salt bond that has a component unit derived from a monomer (a21) represented by the general formula (II):
CH ₂ = C (R ² ) -CQO-MO-CQ-C (R ² ) = CH ₂ (II) [In formula (II), M is zinc or copper, and R ² is a hydrogen atom or a group methyl], and a component unit derived from another unsaturated monomer (a22) copolymerizable with monomer (a21), where the unsaturated monomer (a22) contains at least one unsaturated monomer selected from the group consisting of an alkyl (meth) acrylate, an alkoxyalkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate, or the unsaturated monomer (a22) contains a monobasic acid metal (meth) acrylate represented by the general formula
Petition 870190130000, of 12/09/2019, p. 9/24
[2]
2/8 (IV):
CH ₂ = C (R ² ) -coo-mo-cor ¹ (IV) [In formula (IV), M is zinc or copper, R ¹ is an organic group, and R ² is a hydrogen atom or a methyl group ]; and (a3) a silyl ester copolymer that has a component unit derived from a monomer (a31) represented by the general formula (III):
R ⁷ -CH = C (R ³ ) -COO-SYR ⁴ R ⁵ R ⁶ (III) [In formula (III), R ³ is a hydrogen atom or a methyl group,
R ⁴ , R ⁵ and R ⁶ are each independently a hydrocarbon group, and
R ⁷ is a hydrogen atom or R ⁸ -O-CO- (where R ⁸ is an organic group or a silyl group represented by SiR ⁹ R ¹⁰ R ¹¹ , where R ⁹ , R ¹⁰ and R ¹¹ are each one, independently a hydrocarbon group)], and optionally a component unit derived from another unsaturated monomer (a32) copolymerizable with the monomer (a31), and wherein the antifouling agent (B) comprises at least one compound represented by the following formula structural:

[3]
3/8
An antifouling coating composition according to claim 1, characterized in that it comprises 0.01 to 200 parts by weight of a compound represented by the following structural formula:

[4]
Antifouling coating composition according to claim 3, characterized by the fact that the antifouling agent is different from a compound represented by the following structural formula:
Petition 870190130000, of 12/09/2019, p. 11/24
4/8

[5]
Anti-fouling coating composition according to any one of claims 1 to 4, characterized in that the copolymer containing the metal salt bond (al) is a copolymer of two or more types of (meth) acrylate metal of monobasic acids each represented by the general formula (IV):
CH ₂ = C (R ² ) -COO-MO-COR ¹ (IV)
Petition 870190130000, of 12/09/2019, p. 12/24
5/8 [In formula (IV), M is zinc or copper, R ¹ is an organic group, and R ² is a hydrogen atom or a methyl group].
[6]
Antifouling coating composition according to any one of claims 1 to 5, characterized in that the copolymer containing the metal salt bond (al) is a copolymer containing a component unit derived from a (met ) monobasic acid metal acrylate represented by the general formula (IV):
CH ₂ = C (R ² ) -coo-mo-cor ¹ (IV) [In formula (IV), M is zinc or copper, R ¹ is an organic group, and R ² is a hydrogen atom or a methyl group ], and a component unit derived from at least one unsaturated monomer selected from the group consisting of an alkyl (meth) acrylate, an alkoxyalkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate.
[7]
Antifouling coating composition according to any one of claims 1 to 6, characterized by the fact that in the copolymer containing a metal (al), zinc and / or copper salt bond attributed to the structure of the formula (I ) is contained in an amount of 0.5 to 20% by weight of the copolymer (al).
[8]
Antifouling coating composition according to any one of claims 1 to 7, characterized in that the monomer (a21) contains at least one monomer selected from the group consisting of zinc diacrylate, zinc dimethacrylate, diacrylate copper and copper dimethacrylate.
[9]
9. Composition of antifouling coating,
Petition 870190130000, of 12/09/2019, p. 13/24
6/8 according to claim 1, characterized by the fact that the unsaturated monomer (a22) contains the monobasic acid metal (meth) acrylate represented by the general formula (IV) and at least one unsaturated monomer selected from the group consisting of an alkyl (meth) acrylate, an alkoxyalkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate.
[10]
Antifouling coating composition according to any one of claims 1 to 9, characterized by the fact that in the copolymer containing a metal (a2), zinc and / or copper salt bond assigned to the structure of formula (II) it is contained in an amount of 0.5 to 20% by weight of the copolymer (a2).
[11]
An antifouling coating composition according to any one of claims 1 to 10, characterized in that the organic group R ¹ in the metal salt bond copolymer (a1) is an organic acid residue formed from of a monobasic acid, and the organic acid residue is a saturated or unsaturated aliphatic hydrocarbon group that has 2 to 30 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group that has 3 to 20 carbon atoms, an aromatic hydrocarbon group that has 6 to 18 carbon atoms, or a substitution group.
12. Composition in antifouling coating in according to any an of claims 1, 5, 6 or 9, characterized by fact in that the group organic_R 1 of
(meth) monobasic acid metal acrylate represented by formula (IV) is an organic acid residue formed from a monobasic acid, and the acid residue
Petition 870190130000, of 09 /
[12]
12/2019, p. 14/24
Organic 7/8 is a saturated or unsaturated aliphatic hydrocarbon group that has 2 to 30 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group that has 3 to 20 carbon atoms, an aromatic hydrocarbon group that has 6 to 18 carbon atoms, or a replacement group like that.
[13]
Antifouling coating composition according to any one of claims 1 to 12, characterized in that the monomer (a31) contains a trialkylsilyl (meth) acrylate.
[14]
Antifouling coating composition according to any one of claims 1 to 13, characterized in that the unsaturated monomer (a32) contains at least one unsaturated monomer selected from the group consisting of an alkyl (meth) acrylate, an alkoxyalkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate.
[15]
15. Antifouling coating composition according to claim 1, characterized in that it further comprises copper pyrithione or zinc pyrithione as the antifouling agent (B).
[16]
16. Antifouling coating film, characterized in that it is formed from the antifouling coating composition as defined in any one of claims 1 to 15.
[17]
17. Substrate with a coating film, characterized in that a surface of the substrate is coated with a coating film obtained by curing the antifouling coating composition as defined in any of claims 1 to 15.
Petition 870190130000, of 12/09/2019, p. 15/24
8/8
[18]
18. Method for the production of a substrate with a coating film, characterized in that it comprises a step of applying or impregnating the antifouling coating composition as defined in any one of claims 1 to 15 to a surface of a substrate, and a stage of curing the composition to form a coating film.

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法律状态:
2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: B63B 59/04 (2006.01), A01N 43/50 (2006.01), C09D 5 |

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2018-05-15| B15K| Others concerning applications: alteration of classification|Ipc: C09D 133/00 (2006.01), C09D 5/16 (2006.01), C09D 1 |

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2018-05-22| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-02-19| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-09-10| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-01-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-03-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/03/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2010-065965|2010-03-23|

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JP2010065965|2010-03-23|

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PCT/JP2011/056571|WO2011118526A1|2010-03-23|2011-03-18|Antifouling coating composition and use for same|

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