CN113939565A - Multilayer antifouling coating film and coated article having the same on surface - Google Patents

Multilayer antifouling coating film and coated article having the same on surface Download PDF

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Publication number
CN113939565A
CN113939565A CN202080037675.7A CN202080037675A CN113939565A CN 113939565 A CN113939565 A CN 113939565A CN 202080037675 A CN202080037675 A CN 202080037675A CN 113939565 A CN113939565 A CN 113939565A
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China
Prior art keywords
monomer
coating film
copolymer
mass
antifouling
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Pending
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CN202080037675.7A
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Chinese (zh)
Inventor
安井拓也
松木崇
和久英典
小林慧
伊藤基道
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Nitto Kasei Co Ltd
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Nitto Kasei Co Ltd
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Publication of CN113939565A publication Critical patent/CN113939565A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
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    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
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    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
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Abstract

The present invention provides a multilayer antifouling coating film which has excellent impact resistance and excellent antifouling properties both in the initial stage of immersion and in the long-term antifouling properties. According to the present invention, there is provided a multilayer antifouling coating film comprising a lower coating film and an upper coating film formed thereon, wherein the upper coating film comprises a copolymer A, the lower coating film comprises a copolymer B, the upper and lower coating films each comprise an antifouling agent, the copolymer A is a copolymer of a1 st monomer mixture comprising a monomer (a) and a monomer (c) and optionally a monomer (B), the copolymer B is a copolymer of a2 nd monomer mixture comprising at least one of the monomer (a) and the monomer (B), the monomers (a) to (c) are represented by general formulae (1) to (3), the content of the monomer (a) is 10 to 45 mass%, the content of the monomer (B) is 0 to 15 mass%, and the content of the monomer (c) is 20 to 50 mass% in the copolymer A, based on 100 mass% of the 1 st monomer mixture, the total content of the monomer (a) and the monomer (B) is 10 to 45% by mass, the copolymer B is a copolymer other than the copolymer A, and the total content of the monomer (a) and the monomer (B) is 46 to 65% by mass when the 2 nd monomer mixture is 100% by mass.

Description

Multilayer antifouling coating film and coated article having the same on surface
[ technical field ]
The present invention relates to a multilayer antifouling coating film and a coated article having the coating film on the surface.
[ background art ]
Aquatic fouling organisms such as barnacles, serpula, common mussels, bryozoans, ascidians, green algae, sea lettuce, and slime adhere to underwater structures such as ships (particularly ship bottom parts), fishing nets, fishing net accessories and other fishery tools, power plant aqueducts, and the like, thereby impairing the functions, appearance, and the like of these ships and the like.
In order to prevent such problems, a technique is known in which an antifouling coating film is formed by applying an antifouling coating composition to a ship or the like, and an antifouling agent is slowly released from the antifouling coating film to exhibit antifouling performance for a long period of time (patent document 1).
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent laid-open No. 2000-17203
[ summary of the invention ]
[ problems to be solved by the invention ]
However, a coating film renewability by hydrolysis as in patent document 1 is generally considered to be inferior in the initial stage of immersion in water. Particularly, in the outfitting period, the renewability of the coating film is very poor because the ship is in a standing state. Therefore, the adhesion of slime and the like is likely to occur in the initial stage of water immersion, and then the adhesion of barnacles, coccid and the like continues to occur, which causes problems such as a decrease in fuel consumption rate and a deterioration in appearance.
The present invention has been made in view of such circumstances, and provides a multilayer antifouling coating film which is excellent in impact resistance and is excellent in both initial antifouling property at the time of immersion in water and long-term antifouling property.
[ means for solving the problems ]
According to the present invention, there is provided a multilayer antifouling coating film comprising a lower coating film and an upper coating film formed thereon, wherein the upper coating film comprises a copolymer A, the lower coating film comprises a copolymer B, the upper and lower coating films each comprise an antifouling agent, the copolymer A is a copolymer of a1 st monomer mixture comprising a monomer (a) and a monomer (c) and optionally a monomer (B), the copolymer B is a copolymer of a2 nd monomer mixture comprising at least one of the monomer (a) and the monomer (B), the monomers (a) to (c) are represented by general formulae (1) to (3), the content of the monomer (a) is 10 to 45 mass%, the content of the monomer (B) is 0 to 15 mass%, and the content of the monomer (c) is 20 to 50 mass% in the copolymer A, based on 100 mass% of the 1 st monomer mixture, the total content of the monomer (a) and the monomer (B) is 10 to 45% by mass, the copolymer B is a copolymer other than the copolymer A, and the total content of the monomer (a) and the monomer (B) is 46 to 65% by mass when the 2 nd monomer mixture is 100% by mass.
The present inventors have made extensive studies to solve the above problems, and as a result, have found that the above problems can be solved by a multilayer antifouling coating film having the above structure, and have completed the present invention.
[ detailed description of the invention ]
The present invention will be described in detail below.
1. Multilayer antifouling coating film
The multilayer antifouling coating film according to an embodiment of the present invention has a lower coating film and an upper coating film formed thereon. The lower layer coating film and the upper layer coating film are both hydrolysis type antifouling coating films.
1-1. upper layer coating film
The upper coating film contains a copolymer A and an antifouling agent. The upper coating film can be formed using an antifouling paint composition obtained by dissolving or dispersing the components contained in the upper coating film in a solvent.
< copolymer A >
Copolymer A is a copolymer of the 1 st monomer mixture. The 1 st monomer mixture contains the monomer (a) and the monomer (c), and may contain the monomer (b) or monomers other than the monomers (a) to (c).
In the copolymer A, the content of the monomer (a) is 10 to 45% by mass, the content of the monomer (b) is 0 to 15% by mass, the content of the monomer (c) is 20 to 50% by mass, and the total content of the monomer (a) and the monomer (b) is 10 to 45% by mass, based on 100% by mass of the 1 st monomer mixture.
The content of the monomer (a) is, for example, 10, 15, 20, 25, 30, 35, 40, 45 mass%, and may be in a range of 2 out of the numerical values exemplified here. The content of the monomer (b) is specifically, for example, 0, 5, 10, and 15 mass%, and may be in a range between any 2 of the numerical values exemplified herein. The content of the monomer (c) is specifically, for example, 20, 25, 30, 35, 40, 45, 50 mass%, and may be in a range between 2 of the numerical values exemplified here. The total content of the monomer (a) and the monomer (b) is, for example, 10, 15, 20, 25, 30, 35, 40, and 45 mass%, and may be in the range of 2 out of the numerical values exemplified here.
The monomer (a) is a triorganosilyl methacrylate monomer represented by the general formula (1).
[ solution 1]
Figure BDA0003364188980000021
In the formula, R1～R3The groups are the same or different and are branched alkyl or phenyl with 3-8 carbon atoms.
R1～R3Each of which is the same or different and represents a branched alkyl group having 3 to 8 carbon atoms or a phenyl group. Examples of the branched alkyl group having 3 to 8 carbon atoms include: isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpropyl, 1-methylbutyl, 1-methylpentyl, 1-dimethylpropyl, 1-dimethylbutyl, tert-hexyl (thexyl), cyclohexyl, 1-dimethylpentyl, 1-methylhexyl, 1-dimethylhexyl, 1-methylheptyl, 2-methylbutyl, 2-ethylbutyl, 2-dimethylpropyl, cyclohexylmethyl, 2-ethylhexyl, 2-propylpentyl, 3-methylpentyl and the like. R1～R3Preferred are isopropyl, sec-butyl, tert-butyl, phenyl, and 2-ethylhexyl. Isopropyl is particularly preferred.
Examples of the monomer (a) include: triisopropylsilyl methacrylate, triisobutylsilyl methacrylate, tri-sec-butylsilyl methacrylate, triisopentylsilyl methacrylate, triphenylsilyl methacrylate, diisopropylphenylsilyl methacrylate, diisopropylisobutylsilyl methacrylate, diisopropyl sec-butylsilyl methacrylate, diisopropyl isoamylsilyl methacrylate, isopropyl diisobutylsilyl methacrylate, isopropyl di-sec-butylsilyl methacrylate, tert-butyldiisobutylsilyl methacrylate, tert-butyldiisopentylsilyl methacrylate, tert-butyldiphenylsilyl methacrylate, diisopropyl tert-hexylsilyl methacrylate, diisopropyl cyclohexylsilyl methacrylate, tricyclohexylsilyl methacrylate, tri-1, 1-dimethylpentylsilyl methacrylate, triisopentylsilyl methacrylate, diisopropyl di-tert-butylsilyl methacrylate, and mixtures thereof, Tri-2, 2-dimethylpropylsilyl methacrylate, tricyclohexylmethylsilicyl methacrylate, diisopropylcyclohexylmethylsilicyl methacrylate, tri-2-ethylhexylsilyl methacrylate, tri-2-propylpentylsilyl methacrylate, and the like. Preferred examples thereof include triisopropylsilyl methacrylate, tri-sec-butylsilyl methacrylate, tert-butyldiphenylsilyl methacrylate, and tri-2-ethylhexylsilyl methacrylate. These monomers (a) may be used alone or in combination of 2 or more.
The monomer (b) is a triorganosilyl acrylate monomer represented by the general formula (2).
[ solution 2]
Figure BDA0003364188980000031
In the formula, R1～R3The groups are the same or different and are branched alkyl or phenyl with 3-8 carbon atoms.
R of the general formula (2)1～R3Description of (1) and R of the formula1～R3The same description applies.
Examples of the monomer (b) include monomers obtained by changing "methacrylic acid" to "acrylic acid" which is a name of the compound exemplified as the monomer (a).
The monomer (c) is a (meth) acrylate monomer represented by the general formula (3). The monomer (c) is a monomer having an acryloyloxy group or a methacryloyloxy group and having an alkoxy group or an aryloxy polyethylene glycol group.
[ solution 3]
Figure BDA0003364188980000032
In the formula, R4Is a hydrogen atom or a methyl group, R5Is alkyl or aryl, and n is 1-25.
The polymerization degree (n) of the polyethylene glycol is 1 to 25, preferably 1 to 5, specifically, for example, 1,2, 3,4, 5, 10, 15, 20, 25, and may be in a range of 2 of any of the numerical values exemplified herein.
Examples of alkyl groups include: a linear or branched alkyl group having 12 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group; and cyclic alkyl groups such as cyclohexyl and substituted cyclohexyl.
Examples of the aryl group include an aryl group and a substituted aryl group. Examples of the substituted aryl group include aryl groups substituted with halogen, alkyl groups having up to about 18 carbon atoms, acyl groups, nitro groups, amino groups, and the like.
The monomer (c) is a monomer having a (meth) acryloyloxy group in the molecule, and examples thereof include: methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, hexyloxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxytriethylene glycol (meth) acrylate, and the like.
Examples of the monomers other than the monomers (a) to (c) include ethylenically unsaturated monomers copolymerizable with the monomers (a) to (c). Examples of such monomers include (meth) acrylates other than the monomer represented by the general formula (3), vinyl compounds, aromatic compounds, and dialkyl ester compounds of dibasic acids. In the present specification, a (meth) acrylate means an acrylate or a methacrylate.
Examples of the (meth) acrylate include: methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like.
Examples of the vinyl compound include: vinyl compounds having a functional group such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone.
Examples of the aromatic compound include styrene, vinyltoluene, and α -methylstyrene.
Examples of the dialkyl ester compound of the dibasic acid include dimethyl maleate, dibutyl maleate, and dimethyl fumarate.
< Synthesis of copolymer A >
The copolymer A can be obtained by copolymerizing the 1 st monomer mixture. The copolymerization is carried out, for example, in the presence of a polymerization initiator.
The weight average molecular weight of the copolymer A is preferably 5000 to 300000. If the molecular weight is less than 5000, the coating film of the antifouling paint becomes brittle and peeling and cracking are likely to occur, and if it exceeds 300000, the viscosity of the copolymer solution increases and handling becomes difficult.
Examples of the polymerization initiator used in the polymerization reaction include: azo compounds such as 2,2 ' -Azobisisobutyronitrile (AIBN), 2 ' -azobis-2-methylbutyronitrile, and dimethyl 2,2 ' -azobisisobutyrate; peroxides such as benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroxyoctanoate, t-butyl peroxy2-ethylhexanoate, 1,3, 3-tetramethylbutyl peroxy2-ethylhexanoate, and 1,1,3, 3-tetramethylbutyl peroxyversatate. These polymerization initiators may be used alone or in combination of 2 or more. The polymerization initiator is particularly preferably AIBN, tert-butyl peroctoate and 1,1,3, 3-tetramethylbutyl peroxo2-ethylhexanoate. The molecular weight of the copolymer a can be adjusted by appropriately setting the amount of the polymerization initiator to be used.
Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization. Among them, solution polymerization is preferable from the viewpoint that the copolymer a can be obtained with good accuracy in particular in a simple manner.
An organic solvent may be used in the polymerization reaction as needed. Examples of the organic solvent include: aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ester-based solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate; alcohol solvents such as isopropyl alcohol, butyl alcohol, and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether, and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Among them, ester solvents, alcohol solvents, and aromatic hydrocarbon solvents are particularly preferable, and butyl acetate, isobutyl acetate, butanol, propylene glycol monomethyl ether, toluene, and xylene are more preferable. These solvents may be used alone or in combination of 2 or more.
The reaction temperature in the polymerization reaction may be appropriately set depending on the kind of the polymerization initiator, and is usually 70 to 140 ℃, preferably 80 to 130 ℃. The reaction time in the polymerization reaction may be appropriately set in accordance with the reaction temperature, and is usually about 4 to 8 hours.
The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
< antifouling Agents >
Examples of the antifouling agent include inorganic agents and organic agents.
Examples of the inorganic agent include cuprous oxide, Copper thiocyanate (common name: Copper thiocyanate), and Copper powder. Among these, cuprous oxide and copper thiocyanate are particularly preferable, and cuprous oxide surface-treated with glycerin, sucrose, stearic acid, lauric acid, rishitin (rishitin), mineral oil, or the like is more preferable from the viewpoint of long-term stability during storage.
Examples of the organic drug include: 2-mercaptopyridine-N-copper oxide (generic name: copper pyrithione), 2-mercaptopyridine-N-zinc oxide (generic name: zinc pyrithione), zinc ethylenebisdithiocarbamate (generic name: zinc pum (zineb)), 4, 5-dichloro-2-N-octyl-3-isothiazolinone (generic name: SeaNine 211), 3, 4-dichlorophenyl-N-dimethylurea (generic name: Diuron), 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine (generic name: Irgarol 1051), 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econa 28), 4- [1- (2, 3-dimethylphenyl) ethyl ] -1H-imidazole (common name: Medetomidine (Medetomine)), and the like.
These antifouling agents may be used in 1 kind or 2 or more kinds together.
The content of the antifouling agent in the composition of the present invention is not particularly limited, and is usually 0.1 to 60% by mass, preferably 1 to 50% by mass in terms of solid content. Specifically, the content of the antifouling agent is, for example, 0.1, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60% by mass, and may be in a range between any 2 of the numerical values exemplified herein.
< other additives >
The upper coating film of the present invention may further contain, if necessary, a dissolution adjusting agent, a plasticizer, a pigment, a dye, an antifoaming agent, a filler, a dehydrating agent, a thixotropic agent, and the like.
Examples of the dissolution control agent include: monocarboxylic acids and salts thereof such as rosin, rosin derivatives, naphthenic acids, cycloalkenylcarboxylic acids, bicycloalkenylcarboxylic acids, versatic acids, trimethylisobutenylcyclohexene carboxylic acids, and metal salts thereof, or the aforementioned alicyclic hydrocarbon resins. These may be used alone or in combination of 2 or more.
Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin. Examples of the alicyclic hydrocarbon resin include Quintone 1500, 1525L, 1700 (trade name, manufactured by ZEON corporation, japan) and the like.
Examples of plasticizers include: phosphoric esters, phthalic esters, adipic esters, sebacic esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, tert-nonyl pentasulfide, vaseline, polybutene, tris (2-ethylhexyl) trimellitate, silicone oil, liquid paraffin, chlorinated paraffin, and the like. These may be used alone or in combination of 2 or more.
Examples of the filler include inorganic fillers and/or organic fillers. Examples of the inorganic filler include: calcium carbonate, ground calcium carbonate, light calcium carbonate, colloidal calcium carbonate, precipitated barium sulfate, barite powder, titanium oxide, calcined kaolin surface-treated with aminosilane, diatomaceous earth, aluminum hydroxide, particulate alumina, magnesium oxide, magnesium carbonate, zinc oxide, zinc carbonate, red oxide, iron oxide, fumed metal oxide, quartz powder, talc, zeolite, bentonite, glass fiber, carbon fiber, fine mica, fused silica powder, fine silica powder, fumed silica, precipitated silica, wet silica, dry silica, or hydrophobic fumed silica (fumed silica) surface-treated with an organosilicon compound such as methyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, or the like, Phthalocyanine blue, carbon black, and the like. Examples of the organic filler include: synthetic resin powders such as polypropylene, polyvinyl chloride, polystyrene, acrylic silicone, and the like.
Examples of the dehydrating agent include: synthetic zeolite adsorbents, silicates such as orthoesters, tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, carbonyldiimides, and the like. These may be used alone or in combination of 2 or more.
< method for producing antifouling paint composition >
The antifouling paint composition for the upper layer coating film can be produced, for example, by mixing and dispersing a mixed solution containing the copolymer a, the antifouling agent, and other additives using a dispersing machine.
The mixed solution is preferably a mixed solution obtained by dissolving or dispersing various materials such as a copolymer and an antifouling agent in a solvent.
The dispersion machine can be preferably used, for example, as a user of a micro mill. For example, a commercially available homoemulsifier (homo mixer), sand mill, bead mill, or the like can be used. The mixed solution may be mixed and dispersed by adding glass beads for mixing and dispersing to a container equipped with a stirrer.
1-2. lower layer coating film
The lower coating film contains a copolymer B and an antifouling agent. The lower coating film can be formed using an antifouling paint composition obtained by dissolving or dispersing the components contained in the lower coating film in a solvent.
< copolymer B >
Copolymer B is a copolymer of the 2 nd monomer mixture. The 2 nd monomer mixture contains at least one of the monomer (a) and the monomer (b). The 2 nd monomer mixture may contain only one of the monomers (a) and (b), or may contain both of them. The 2 nd monomer mixture may contain the monomer (c) and may contain monomers other than the monomers (a) to (c). The monomers (a) to (c) and other monomers are explained in the same manner as in the case of the copolymer A.
The copolymer B is a copolymer other than the copolymer A, and the total content of the monomer (a) and the monomer (B) is 46 to 65% by mass when the 2 nd monomer mixture is 100% by mass. Specifically, the total content may be, for example, 46, 50, 55, 60, or 65 mass%, and may be within a range of 2 of any of the numerical values exemplified herein. The content of the monomer (a) may be, for example, 0 to 65% by mass, specifically, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65% by mass, or may be in a range between any 2 of the numerical values exemplified herein. The content of the monomer (b) may be, for example, 0 to 65% by mass, specifically, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65% by mass, or may be in a range between any 2 of the numerical values exemplified herein. The content of the monomer (c) is, for example, 0 to 54% by mass, specifically, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 54% by mass, or may be in a range of 2 or more of the numerical values exemplified herein.
The monomers (a) to (c) are the same as those of the copolymer A.
< Synthesis of copolymer B >
The copolymer B can be obtained by copolymerizing the 2 nd monomer mixture. The physical properties and production method of the copolymer B are the same as those of the copolymer A.
< antifouling Agents >
The description of the antifouling agent is the same as that of the upper coating film. The antifouling agents of the upper coating film and the lower coating film may be the same or different.
< other additives >
The lower layer coating film of the present invention may further contain, if necessary, an elution adjusting agent, a plasticizer, a pigment, a dye, an antifoaming agent, a filler, a dehydrating agent, a thixotropic agent, and the like. These are explained in the same manner as in the upper coating film.
< method for producing antifouling paint composition >
The antifouling paint composition for the lower coating film can be produced, for example, by mixing and dispersing a mixed solution containing the copolymer B, the antifouling chemical, and other additives using a dispersing machine. The other description is the same as the upper coating film.
2. Method for forming multilayer antifouling coating film
The multilayer antifouling coating film of the present invention can be obtained by forming an upper coating film on a lower coating film.
The lower coating film and the upper coating film can be formed by applying the above antifouling paint composition to the surface (whole or part) of a coating film-formed article. Examples of the coating method include a brush coating method, a spray coating method, a dipping method, a flow coating method, and a spin coating method. These may be used in 1 kind or 2 or more kinds together. After coating, it is dried. The drying temperature may be room temperature. The drying time may be appropriately set according to the thickness of the coating film.
The thickness of the lower layer coating film may be suitably set in accordance with the kind of the coating film-formed article, and is usually 50 to 500 μm, preferably 100 to 200 μm. The thickness of the upper layer coating film may be appropriately set according to the ship's speed, sea water temperature, etc., and is usually 50 to 500 μm, preferably 100 to 200 μm.
Examples of the coating film-formed article include antifouling coating films applied to the surfaces of ships (particularly ship bottoms), fishery equipment, underwater structures, and the like, and old coating films after a certain period of use in seawater.
[ examples ]
The features of the present invention will be further described below with reference to examples and the like. However, the present invention is not limited to the examples and the like.
In each of the production examples, examples and comparative examples,% represents% by weight. The viscosity is a value measured at 25 ℃ and determined by a B-type viscometer. The weight average molecular weight (Mw) is a value (polystyrene equivalent) determined by GPC. The GPC conditions were as follows.
HLC-8220GPC manufactured by Tosoh corporation, …
Pipe column … TSKgel SuperHZM-M2
Flow rate … 0.35.35 mL/min
Detector … RI
The temperature of the pipe column thermostatic bath is … 40 DEG C
Eluent … THF
The heating residue was classified according to JIS K5601-1-2: 1999(ISO 3251: 1993) "coating composition test method-heating residue fraction".
In the table, the unit of the amount of each ingredient is g.
1. Production example of copolymer solution
Production example 1 (production of copolymer solution A1) >
A flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 260g of xylene, and a mixed solution of 215g of triisopropylsilyl methacrylate, 135g of methyl methacrylate, 150g of 2-methoxyethyl acrylate and 3g of 1,1,3, 3-tetramethylbutyl peroxy-2-ethylhexanoate as a polymerization initiator was dropped over 2 hours while stirring at 85. + -. 5 ℃ under a nitrogen atmosphere. After that, after stirring at the same temperature for 1 hour, 0.5g of 1,1,3, 3-tetramethylbutyl peroxy-2-ethylhexanoate was added 5 times per 1 hour to complete the polymerization reaction, and then xylene was added to dissolve the product so that the heating residue was 50%, thereby obtaining a copolymer solution a 1. The viscosity of the obtained copolymer solution was 320 mPas (25 ℃), the heating residue was 50.7%, and the Mw was 45,000.
Production examples 2 to 14 (production of copolymer solutions A2 to A6, B1 to B3, and C1 to C5) >
Polymerization was carried out in the same manner as in production example 1 using the monomer mixtures shown in table 1 to obtain copolymer solutions a2 to a6, B1 to B3, and C1 to C5. The obtained copolymer solutions were measured for residual heat, viscosity, and weight average molecular weight. The results are shown in Table 1.
[ Table 1]
Figure BDA0003364188980000091
2. Production example of coating composition
The components shown in table 2 were mixed in the proportions (mass%) shown in the table, and mixed and dispersed with glass beads having a diameter of 1.5 to 2.5mm, thereby producing coating compositions X1 to X8, Y1 to Y3, and Z1 to Z5.
[ Table 2]
Figure BDA0003364188980000101
The ingredients in table 2 are detailed below.
< dissolution control agent >
Rosin solution: solid content 50% xylene solution of gum rosin (WW) produced in china rosin zinc salt solution: a50% xylene solid solution having a trade name of "Bremazit 3050" (manufactured by Kraemer Co., Ltd.)
Hydrogenated rosin solution: solid content 50% xylene solution sold under the trade name HYPALE CH (manufactured by KAKIN CHEMICAL INDUSTRY)
< plasticizer >
Chlorinated paraffin: under the trade name "Paraffin Chlorinated (Cl: 40%)" (manufactured by Wako pure chemical industries, Ltd.)
E-2000H: epoxidized soybean oil: under the trade name "SANSO CIZER E-2000H" (manufactured by Xinri Suibi & chemistry, Ltd.)
DINCH: 1, 2-cyclohexanedicarboxylic acid diisononyl ester: trade name "HEXAMOLL (registered trademark) DINCH (registered trademark)" (manufactured by BASF corporation)
TOTM: tri-2-ethylhexyl trimellitate: under the trade name "Tris (2-ethylhexyl) trimetlite" (manufactured by imperial chemical industry (Egyo)
< antifouling Agents >
Cuprous oxide: trade name "NC-301" (manufactured by Nissin chemco)
Copper pyrithione: trade name "hopper Omadine" (manufactured by Arch Chemical Co., Ltd.)
EcoNea: trade name "Econea 028" … 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)
Medetomidine: the trade name is "4- (1- (2, 3-dimethyl) ethyl) -1H-imidazole" (manufactured by Wako pure chemical industries, Ltd.)
< inorganic Filler >
Talc: trade name "Crown Talc 3S" (manufactured by Sonmura industries, Ltd.)
Zinc oxide: trade name "Zinc oxide 2" (manufactured by Kyoho chemical Co., Ltd.)
Iron oxide pellet: trade name "TODA COLOR EP-13D" (manufactured by HORIZONTAL INDUSTRY (PURSION))
Titanium oxide: trade name "FR-41" (manufactured by Guhe mechanical Metal (strand))
< dehydrating reagent >
Tetraethoxysilane: the trade name "tetra ethyl ortho-silicate" (manufactured by Beijing chemical industry (stock) of Chinese imperial court of China)
< thixotropic agent >
Aliphatic amide thixotropic agent: trade name "Disparlon A603-20X" (manufactured by Nanguchen chemical Co., Ltd.)
< organic solvent >
Xylene: (reagent, manufactured by Tokyo chemical industry Co., Ltd.) containing ethylbenzene
3. Test of
The lower coating film and the upper coating film were formed by using the coating compositions X1 to X8, Y1 to Y3, and Z1 to Z5 shown in table 2 in combination shown in table 3. Thereby, the multi-layer antifouling coating films of examples and comparative examples were obtained. The obtained multilayer antifouling coating film was subjected to an impact resistance test and an antifouling test as shown below. The results are shown in Table 3.
[ Table 3]
Figure BDA0003364188980000121
< test example 1 (impact resistance test) >
A rotary drum having a diameter of 515mm and a height of 440mm was attached to the center of the water tank and was set to be rotatable by a motor. In addition, a cooling device for keeping the temperature of the seawater constant and a pH automatic controller for keeping the pH of the seawater constant are installed. Test panels were produced in the following manner.
First, a rust preventive coating (vinyl A/C) was applied to a steel sheet (75X 150X 1mm) and dried to a thickness of about 50 μm after drying, thereby forming a rust preventive coating film. Thereafter, the coating composition for the lower layer coating film was applied onto the rust-preventive coating film so that the thickness after drying was about 150 μm. The obtained coated article was dried at room temperature for 24 hours, and then the coating composition for the upper coating film was applied so that the thickness after drying became 150 μm. A test panel having a dried multilayer coating film with a thickness of about 300 μm was produced by drying the obtained multilayer coating film at 40 ℃ for 3 days.
The test plate thus produced was fixed to the rotary drum of the above-mentioned rotary apparatus so as to be in contact with seawater, and the rotary drum was rotated at a speed of 20 knots (knot). During the period, the temperature of the seawater is kept at 25 ℃, the pH value is kept at 8.0-8.2, and the seawater is replaced every week. The test panel 36 months after the start of the spin test was washed with water and dried, and then subjected to an impact resistance test. According to JIS K5600-5-3: 1999 "general test method of coating material-mechanical properties of coating film-resistance to falling of heavy object" was measured using the conditions of falling ball type.
As a result, the state of the coating film due to the impact of the tip of the weight was judged by the following criteria.
Very good: without cracking or peeling of the coating film
Good: slight cracking and peeling were observed
And (delta): moderate cracking and flaking were observed
X: severe cracking and flaking were observed
< test example 2 (antifouling test) >
The coating composition for the lower layer coating film was applied to both surfaces of a rigid polyvinyl chloride sheet (100X 200X 2mm) so that the thickness of the dried coating film became about 100. mu.m. The obtained coated article was dried at room temperature for 24 hours, and the coating composition for the upper coating film was applied thereon so that the thickness of the dried coating film became about 100 μm. The obtained multilayer coating was dried at room temperature (25 ℃) for 3 days, thereby producing a test panel having a dried multilayer coating film with a thickness of about 200 μm. The test panel was immersed 1.5m under the sea surface of the eagle city, caucasian prefecture, and fouling of the test panel due to the attachment was observed for 24 months.
The evaluation was carried out by visually observing the state of the surface of the coating film, and was judged according to the following criteria.
Very good: no attachment of fouling organisms such as shellfish and algae, and almost no adhesion of slime
O: no fouling organisms such as shellfish and algae, and the sludge is attached thinly (to the extent that the film surface can be seen), but can be removed by lightly wiping with a brush
And (delta): although no fouling organisms such as shellfish and algae are attached, the slime is attached thinly (to the extent that the film surface can be seen), and the slime cannot be removed even if the film is rubbed with a brush
X: although no fouling organisms such as shellfish and algae are attached, the slime is attached to such a degree that the film surface is not visible, and the slime cannot be removed even if the slime is rubbed with a brush with force
X: the level of attachment of fouling organisms such as shellfish and algae
4. Investigation of
From the above results, it is clear that the multilayer antifouling coating films of all examples are excellent in both impact resistance and antifouling property. On the other hand, all of the multi-layer antifouling coatings of the comparative examples were poor in either impact resistance or antifouling property.
In comparative example 1, the lower layer coating film had a low silicone ester content, the later half-period coating film was slightly renewed, a skeleton layer was formed, and the coating film was brittle.
In comparative example 2, the upper coating film had high hydrophobicity and the initial dissolution of the coating film was small, so the initial antifouling property was poor.
In comparative example 3, since the amount of the monomer (c) component constituting the copolymer in the upper coating film was small, the initial dissolution of the coating film was small, and the initial antifouling property was poor.
In comparative example 4, the upper layer was a coating film composed of a copolymer of triisopropylsilyl acrylate, and cracks were generated in the latter half of the period to deteriorate the antifouling property and decrease the strength of the coating film.
In comparative example 5, the content of silicone ester in the upper coating film was low, and appropriate renewal of the coating film could not be obtained from the initial stage, and the antifouling property was poor and the coating film was also brittle.
In comparative example 6, the upper layer was a coating film composed of a copolymer containing no monomer (a) to (c), and the initial antifouling property and coating film strength were poor.
In comparative example 7, the silicone ester content in the lower coating film was too high, which resulted in slow renewal of the coating film in the latter half period and rapid deterioration of the antifouling property.

Claims (2)

1. A multilayer antifouling coating film characterized by comprising: a lower layer coating film and an upper layer coating film formed thereon,
the upper coating film contains a copolymer A,
the lower coating film contains a copolymer B,
the upper layer coating film and the lower layer coating film contain an antifouling agent,
the copolymer A is a copolymer of a1 st monomer mixture containing a monomer (a) and a monomer (c) and may also contain a monomer (b),
the copolymer B is a copolymer of a2 nd monomer mixture containing at least one of the monomer (a) and the monomer (B),
the monomers (a) to (c) are represented by the general formulae (1) to (3),
in the copolymer A, the content of the monomer (a) is 10 to 45% by mass, the content of the monomer (b) is 0 to 15% by mass, the content of the monomer (c) is 20 to 50% by mass, and the total content of the monomer (a) and the monomer (b) is 10 to 45% by mass, based on 100% by mass of the 1 st monomer mixture,
the copolymer B is a copolymer other than the copolymer A, and the total content of the monomer (a) and the monomer (B) is 46 to 65% by mass, based on 100% by mass of the 2 nd monomer mixture;
Figure FDA0003364188970000011
in the formula, R1～R3The groups are respectively the same or different and are branched alkyl or phenyl with 3-8 carbon atoms;
Figure FDA0003364188970000012
in the formula, R1～R3The groups are respectively the same or different and are branched alkyl or phenyl with 3-8 carbon atoms;
Figure FDA0003364188970000013
in the formula, R4Is a hydrogen atom or a methyl group, R5Is alkyl or aryl, and n is 1-25.
2. A coated article characterized by: the surface has the multilayer antifouling coating film according to claim 1.
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