WO2014189069A1 - 防汚塗料組成物、防汚塗膜、防汚塗膜付基材および該基材の製造方法 - Google Patents
防汚塗料組成物、防汚塗膜、防汚塗膜付基材および該基材の製造方法 Download PDFInfo
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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
- C09D5/1656—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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- 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
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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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
- 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
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
- C09D5/165—Macromolecular compounds containing hydrolysable groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
Definitions
- the present invention relates to an antifouling coating composition, an antifouling coating film, a substrate with an antifouling coating, and a method for producing the substrate. More specifically, while reducing the amount of volatile organic compounds (VOC) and reducing the impact on the environment and the human body, it has excellent antifouling properties on the surface of substrates such as ships, underwater structures and fishing gear.
- An antifouling coating composition that can be applied and can form a coating film excellent in damage resistance, an antifouling coating film formed from the antifouling coating composition, and a substrate with an antifouling coating film And a method for producing the substrate.
- Substrates such as ships, underwater structures, and fishing nets can be exposed to water for a long period of time, so animals on the surface such as oysters, mussels and barnacles, plants such as laver, and various aquatic organisms such as bacteria Easy to adhere.
- animals on the surface such as oysters, mussels and barnacles, plants such as laver, and various aquatic organisms such as bacteria Easy to adhere.
- the surface roughness of the ship increases, resulting in a decrease in ship speed and fuel consumption, and damage to the anticorrosion coating formed on the ship surface. Therefore, there is a risk of damage such as a decrease in the strength and function of the ship and a significant shortening of the life.
- an antifouling coating film is conventionally provided on the surface of the substrate.
- the antifouling coating film is required to have characteristics such as a high antifouling property and a stable coating film consumption level over a long period of time.
- an antifouling coating composition capable of forming such an antifouling coating film 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile is used as an antifouling agent.
- the composition containing this is known (patent documents 1 and 2).
- the antifouling coating film has a volatile organic compound (hereinafter referred to as “VOC” (hereinafter “VolatiletiOrganic Compounds”). It is also an important issue to reduce the amount of volatilization.
- VOC volatile organic compound
- the surface of the ship may increase in surface roughness or form on the ship surface due to collisions with the sea surface and suspended matter in the sea, damage due to woodcutting during shipbuilding or damage due to fenders installed on the quay.
- the applied anticorrosive coating film may be damaged.
- the antifouling coating film formed on the ship surface is also required to be resistant to damage.
- Conventional antifouling paint compositions for example, the antifouling paint composition described in Patent Document 2, have poor coating film drying properties, and it is not easy to form an antifouling coating film having excellent damage resistance.
- the present invention has been made in view of the above-mentioned problems, has excellent damage resistance, can form an antifouling coating film having a stable coating film consumption level and high antifouling properties over a long period of time, and has a low VOC content
- An object is to provide an antifouling paint composition.
- an antifouling paint composition containing a specific polymer and an antifouling agent and having a VOC content of a specific value or less As a result of intensive studies on the method for solving the above problems, the present inventors have found that an antifouling paint composition containing a specific polymer and an antifouling agent and having a VOC content of a specific value or less. The present inventors have found that the above problems can be solved, and have completed the present invention.
- the configuration of the present invention is as follows.
- An antifouling paint composition having a volatile organic compound (VOC) content of 400 g / L or less.
- M represents zinc or copper, and R 1 independently represents a hydrogen atom or a methyl group.
- the antifouling agent (B) further contains zinc pyrithione, copper pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, triphenylboron / amine complex, 2-methylthio-4 -Tert-Butylamino-6-cyclopropyl-s-triazine, N, N-dimethyl-N'-phenyl-N '-(fluorodichloromethylthio) sulfamide and N, N-dimethyl-N'-tolyl-N'-
- the antifouling paint composition according to any one of [1] to [3], comprising at least one antifouling agent (b2) selected from the group consisting of (fluorodichloromethylthio) sulfamide.
- the polymer (A) has the formula (2): CH 2 ⁇ C (R 1 ) —COO—MO—CO—C (R 1 ) ⁇ CH 2 [wherein M is Z 1 represents zinc or copper, and R 1 independently represents a hydrogen atom or a methyl group. And a component unit derived from another unsaturated monomer (a2) that can be copolymerized with the monomer (a1). [1] to [6]
- the monomer (a1) includes at least one monomer selected from the group consisting of zinc diacrylate, zinc dimethacrylate, copper diacrylate, and copper dimethacrylate.
- Stain paint composition includes at least one unsaturated monomer selected from the group consisting of alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, and hydroxyalkyl (meth) acrylates.
- the antifouling paint composition includes at least one monomer selected from the group consisting of alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, and hydroxyalkyl (meth) acrylates.
- a substrate with an antifouling coating wherein the substrate is coated with the antifouling coating according to [11].
- a base with an antifouling coating film comprising the steps of forming a coating film comprising the antifouling coating composition according to any one of [1] to [10] on a substrate and curing the coating film A method of manufacturing the material.
- the impact on the environment and the influence on the human body are suppressed to a low level, the coating workability and the drying property are excellent despite the low VOC amount, and the coating film consumption level and the high antifouling property are stable over a long period of time. It is possible to provide a high solids type hydrolyzable antifouling paint composition capable of forming an antifouling coating film excellent in balance in terms of property and mechanical strength (damage resistance). Moreover, according to this invention, it becomes possible to carry out antifouling
- FIG. 1 is a diagram showing evaluation criteria in a damage resistance test (board pressure test) in Examples.
- the antifouling coating composition according to the present invention has a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (1)”).
- An antifouling agent containing 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile hereinafter also referred to as “antifouling agent (b1)”) Containing (B), Content of a volatile organic compound (VOC) is 400 g / L or less.
- M represents zinc or copper, and R 1 independently represents a hydrogen atom or a methyl group.
- Such a composition of the present invention is an excellent coating workability and drying property with a low VOC amount while suppressing an environmental load and an influence on the human body, and a stable coating film over a long period of time. It becomes a high solid type hydrolyzable antifouling paint composition capable of forming an antifouling coating film having a good balance between the degree of wear and the high antifouling property and mechanical strength (damage resistance).
- the conventional antifouling coating composition needs to use a large amount of solvent in order to obtain a viscosity suitable for coating, the amount of VOC in the composition must be increased for practical use. In other words, it was not a preferable composition for the environment and human body.
- a composition suitable for coating can be obtained even if the amount of organic solvent is small. In this case, the initial coating film consumption rate becomes excessively high, and thereafter the coating film consumption rate decreases. Therefore, a coating film having a stable film consumption level and antifouling property over a long period of time is obtained.
- the composition of the present invention is a composition having a low viscosity even if the content of VOC is small, and also forms an antifouling coating film having a stable coating film consumption level and a high antifouling property over a long period of time. It can also be a composition.
- the antifouling coating film can be formed on the substrate by various methods.
- the composition of the present invention it is possible to easily perform spray coating that is suitably employed when forming an antifouling coating film on a substrate such as a ship, an underwater structure, and fishing gear.
- the composition of the present invention is a high solid type coating composition, it can be applied with almost no change in coating conditions and coating environment from conventional solvent type coatings, and the coating equipment and the like can be modified. It is possible to paint while taking the environment and human body into consideration.
- the composition of the present invention has good drying properties. For this reason, when a painted hull block is mounted on a dock in a new ship or the like, the hull block is normally supported by wood blocks, but even in such a case, the composition of the present invention can be used.
- the antifouling coating film formed on the surface of the ship hardly dents or rises in the portion in contact with the board and hardly causes damage.
- the ship may come in contact with fenders and the like installed on the quay.
- the antifouling coating film formed on is hardly damaged by fenders.
- the hydrolyzable polymer (A) has the structural unit (1) and has a weight average molecular weight (Mw) of 1000 to 5000.
- the polymer (A) is hydrolyzable at least in an alkaline atmosphere such as in seawater. Since the composition of the present invention contains such a polymer (A) and an antifouling agent (b1), it has a low VOC amount and a low viscosity, is excellent in drying properties, and is stable over a long period of time.
- High solid type hydrolyzable antifouling paint capable of forming antifouling coating film with excellent balance in wear level, damage resistance, coating film physical properties (for example, crack resistance, adhesion to substrate) and surface smoothness It becomes a composition.
- the polymer (A) is preferably a polymer containing the structural unit (1) in an amount of 1 to 50% by weight, more preferably 10 to 30% by weight based on the whole polymer (100% by weight). It is desirable from the standpoint that an antifouling coating film excellent in a good balance in coating film consumption, damage resistance, and coating film physical properties (for example, crack resistance, adhesion to a substrate) can be obtained over a long period of time.
- the polymer having the structural unit (1) can be obtained, for example, by using the following monomer (a1) as a synthesis raw material.
- the amount of the structural unit (1) in the polymer can be calculated from, for example, the amount of the monomer (a1) used.
- the polymer in which the amount of the structural unit (1) is in the above range can be obtained, for example, by appropriately adjusting the amount of the monomer (a1) used.
- the content of zinc and / or copper in the polymer (A) is antifouling coating that is excellent in a good balance over a long period of time with a stable coating film consumption and coating film physical properties (for example, crack resistance, adhesion to a substrate). From the viewpoint that a film can be obtained, it is preferably 0.5 to 25% by weight (in 100% by weight of the polymer (A)) of the polymer (A), more preferably 1 to 20% by weight. is there.
- “the content of zinc and / or copper” means the total content of zinc and copper when both zinc and copper are included.
- the zinc and / or copper content can be measured by using an ICP emission analyzer, and can be adjusted by the type and amount of the metal-containing compound used to prepare the polymer (A). is there.
- Examples of the polymer (A) include those represented by the formula (2): CH 2 ⁇ C (R 1 ) —COO—MO—CO—C (R 1 ) ⁇ CH 2 [wherein M is zinc or Represents copper, and R 1 independently represents a hydrogen atom or a methyl group. And a component unit derived from another unsaturated monomer (a2) that can be copolymerized with the monomer (a1). A copolymer is preferred. Each of the monomer (a1) and the unsaturated monomer (a2) may be used alone or in combination of two or more.
- the monomer (a1) preferably contains at least one monomer selected from the group consisting of zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylate.
- Such a monomer (a1) includes, for example, an inorganic metal compound (zinc or copper oxide, hydroxide, chloride, etc.) and (meth) acrylic acid or an ester compound thereof, an ether organic solvent, etc. And can be prepared by a known method such as heating and stirring at a temperature lower than the decomposition temperature of the monomer (a1) in the presence of an organic solvent and water.
- the unsaturated monomer (a2) includes at least one unsaturated monomer selected from the group consisting of alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates and hydroxyalkyl (meth) acrylates.
- alkyl (meth) acrylates alkoxyalkyl (meth) acrylates and hydroxyalkyl (meth) acrylates.
- methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate Etc. are particularly preferred.
- the copolymer can be produced by a conventionally known method. Examples of such a method include the method disclosed in Japanese Patent Application Laid-Open No. 2000-234072.
- the copolymer may be a polymer obtained by polymerizing a monomer mixture in a pressurized container at a temperature of 110 ° C. or higher and pressurized so that water does not reflux.
- the antifouling coating film formed from the composition containing the copolymer thus produced is a case where the coating film is formed on a ship and the ship is operated at a low speed. Excellent performance can be maintained for a long time without lowering the self-polishing property of the coating film.
- the monomer (a1) used for synthesizing the copolymer is used so that the amount of the structural unit (1) in the obtained polymer and the content of zinc and / or copper are in the above range.
- the amount of the monomer (a1) used is preferably 1 to 50 mol%, more preferably 100 mol% based on 100 mol% of the total monomers used for synthesizing the copolymer. Is from 5 to 30 mol%.
- the amount of the monomer (a2) used when synthesizing the copolymer is preferably 50 to 99 mol% with respect to 100 mol% of the total monomers used when synthesizing the copolymer. More preferably, it is 70 to 95 mol%.
- the weight average molecular weight (Mw: polystyrene conversion value) of the polymer (A) is preferably 1500 to 5000 from the viewpoint of obtaining a composition having a lower viscosity while having a low VOC amount. Preferably it is 2000-4500. Further, the number average molecular weight (Mn: polystyrene conversion value) of the polymer (A) can be appropriately adjusted in consideration of the viscosity and storage stability of the composition, the dissolution rate of the antifouling coating film, etc. It is preferably 1000 to 3000, more preferably 1000 to 2500.
- the molecular weight can be measured by gel permeation chromatography (GPC), and specifically can be measured by the method described in the following examples.
- the Gardner viscosity (25 ° C.) of the polymer (A) is preferably about L to Z from the viewpoint that a composition having a low VOC amount and low viscosity and excellent coating workability can be obtained. More preferably, it is about O to W.
- the composition of the present invention is excellent in coating workability and drying property while having a low VOC amount, and has a well-balanced balance over a long period of time with a stable coating film consumption level, high antifouling property and mechanical strength (damage resistance).
- the polymer (A) is preferably 1 to 50 parts by weight, more preferably 100 parts by weight of the composition (solid content). 3 to 40 parts by weight, more preferably 5 to 35 parts by weight.
- the said polymer (A) may be used individually by 1 type, and may use 2 or more types together.
- the composition of the present invention contains an antifouling agent (b1) as the antifouling agent (B).
- the composition of the present invention contains such an antifouling agent (b1), so that even when a polymer having a small Mw is used, the coating film consumption level and high antifouling property and mechanical strength are stable over a long period of time. It is possible to form an antifouling coating film excellent in balance (damage resistance).
- the present inventors combine the antifouling agent (b1) with the polymer (A) to greatly reduce the viscosity of the mixture, and hydrolyzability in the resin contained in the antifouling coating composition. It was found that it was possible to suppress the dissolution of only the portion having saccharide first and the remaining portion having no hydrolyzability, so that a composition having the above-described effect could be obtained.
- the composition of the present invention can completely eliminate or greatly reduce the use of cuprous oxide, which has been conventionally used in many cases. It becomes possible to make the hydrolysis rate of the antifouling coating film containing the coalescence (A) substantially constant over a long period of time.
- the specific gravity of the antifouling coating composition can be reduced, and corrosion of the substrate due to cuprous oxide can be suppressed.
- a desired base material can be selected and used.
- the tint of the antifouling coating film obtained can be adjusted by not using or reducing cuprous oxide.
- the content of the antifouling agent (b1) in the composition of the present invention is not particularly limited as long as it does not adversely affect the physical properties of the resulting coating film. From the viewpoint of being obtained, the amount is preferably 1 to 20 parts by weight, more preferably 1 to 15 parts by weight, and further preferably 2 to 15 parts by weight with respect to 100 parts by weight of the composition (solid content) of the present invention. Parts by weight.
- composition of the present invention exhibits excellent antifouling property and the like by containing the antifouling agent (b1) as the antifouling agent (B), but antifouling property, particularly algae resistance (such as algae) In order to further improve (preventing adhesion), other antifouling agent (b2) may be contained as necessary.
- the antifouling agent (b2) is not particularly limited, but preferred examples include zinc pyrithione, copper pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, triphenylboron amine complex, 2-methylthio-4-tert-butylamino-6-cyclopropyl-s-triazine, N, N-dimethyl-N′-phenyl-N ′-(fluorodichloromethylthio) sulfamide, N, N-dimethyl-N′- And tolyl-N ′-(fluorodichloromethylthio) sulfamide.
- zinc pyrithione 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (for example, Cine Nine 211N (ROHM) is obtained in that an antifouling coating film having better antifouling properties can be obtained.
- Zinc pyrithione is particularly preferable from the standpoint that a composition having excellent coating film drying properties can be obtained.
- These antifouling agents (b2) may be used alone or in combination of two or more.
- the content of the antifouling agent (b2) in the composition of the present invention is not particularly limited as long as it does not adversely affect the physical properties of the obtained coating film. From the viewpoint of being obtained, it is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, and still more preferably 0.1 to 100 parts by weight of the composition (solid content) of the present invention. ⁇ 12 parts by weight.
- the content of the antifouling agent (b2) is preferably 10 to 1000 parts by weight, more preferably 20 to 500 parts by weight, even more preferably 100 parts by weight of the antifouling agent (b1). 20 to 400 parts by weight.
- the content of the antifouling agents (b1) and (b2) in the composition of the present invention is not particularly limited as long as it does not adversely affect the physical properties of the obtained coating film, but is excellent in antifouling properties and the like. From the viewpoint of obtaining a dirty coating film, it is preferably 1 to 40 parts by weight, more preferably 1 to 30 parts by weight, and still more preferably 1 to 22 parts per 100 parts by weight of the composition (solid content) of the present invention. Parts by weight.
- the composition of the present invention preferably contains zinc oxide from the viewpoint of obtaining an antifouling coating film having excellent wear resistance, high antifouling properties, damage resistance and the like.
- the content of zinc oxide is preferably 0.1 to 60 parts by weight, more preferably 100 parts by weight of the composition (solid content) of the present invention. 1 to 50 parts by weight, more preferably 3 to 50 parts by weight.
- composition of the present invention may further include a general coating composition such as a colorant, extender pigment, dehydrating agent, plasticizer, thixotropic agent, solvent, organic compounds such as resins and organic acids, and the like.
- a general coating composition such as a colorant, extender pigment, dehydrating agent, plasticizer, thixotropic agent, solvent, organic compounds such as resins and organic acids, and the like.
- Various components used in products can be blended. Each of these may be used alone or in combination of two or more.
- Colorant examples of the colorant include color pigments (eg, inorganic pigments such as petals, titanium white (titanium oxide), yellow iron oxide, and organic pigments such as carbon black, naphthol red, and phthalocyanine blue) and dyes. Is mentioned.
- the blending amount of the colorant can be appropriately adjusted, but is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the composition (solid content) of the present invention. .
- An extender pigment is a pigment that has a low refractive index and is transparent and does not hide the coated surface when kneaded with oil or varnish.
- extender pigments include talc, silica, mica, clay, potassium feldspar, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, and zinc sulfide.
- talc, silica, mica, clay, potassium feldspar, and barium sulfate are preferable.
- the amount of extender can be adjusted as appropriate, but is preferably 0.1 to 60 parts by weight, more preferably 1 to 50 parts by weight, with respect to 100 parts by weight of the composition (solid content) of the present invention. ⁇ 45 parts by weight is particularly preferred.
- Calcium carbonate, kaolin, and alumina white can also function as an anti-settling agent, and white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, and zinc sulfide can also function as a matting agent.
- the amount of the pigment (colored pigment + extender pigment) is such that the polymer (A) can be obtained from the viewpoint that an antifouling coating film having good antifouling properties and crack resistance can be obtained.
- ) (Residue on heating) is preferably 1 to 6000 parts by weight, more preferably 5 to 5000 parts by weight, per 100 parts by weight.
- a dehydrating agent is a component which contributes to the improvement of the storage stability of the composition of this invention.
- dehydrating agents include inorganic gypsum, hemihydrate gypsum (calcined gypsum), and synthetic zeolite-based adsorbents (eg, trade name “Molecular Sieve”), and other orthoesters (methyl orthoformate). , Orthoacetic acid methyl, orthoboric acid ester, etc.), silicates, isocyanates and the like.
- anhydrous gypsum and hemihydrate gypsum (calcined gypsum) which are inorganic dehydrating agents are preferable.
- the amount of the dehydrating agent can be adjusted as appropriate, but it is preferably 0 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the composition (solid content) of the present invention.
- the plasticizer is a component that contributes to the improvement of crack resistance and water resistance of the antifouling coating film and the suppression of discoloration.
- the plasticizer include n-paraffin, chlorinated paraffin, terpene phenol, tricresyl phosphate (TCP), and polyvinyl ethyl ether. Among these, chlorinated paraffin and terpene phenol are preferable, and chlorinated paraffin is preferable. Particularly preferred.
- n-paraffin is a product such as “N-paraffin” manufactured by Nippon Petrochemical Co., Ltd.
- chlorinated paraffin is “Toyoparax A-40 / A-50 / A-70 / A-145” manufactured by Tosoh Corporation. / A-150 "and the like.
- the blending amount of the plasticizer can be adjusted as appropriate, and is, for example, 1 to 5% by weight based on the total solid content in the composition of the present invention.
- Anti-sagging agents include, for example, organic clay compounds (such as Al, Ca or Zn amine salts, stearate salts, lecithin salts, alkyl sulfonate salts), organic Examples include wax (polyethylene wax, oxidized polyethylene wax, polyamide wax, amide wax, hydrogenated castor oil wax, etc.), synthetic fine powder silica, among these, organoclay compounds, polyamide wax, oxidized polyethylene wax, synthetic fine powder. Silica is preferred.
- the blending amount of the habit modifier can be adjusted as appropriate, and is, for example, a ratio of 0.1 to 5 parts by weight with respect to 100 parts by weight of the composition (solid content) of the present invention.
- the composition of this invention may contain organic compounds, such as resin and an organic acid, as needed other than the said polymer (A).
- the resin include acrylic resin, acrylic silicone resin, polyester resin, unsaturated polyester resin, fluorine resin, polybutene resin, silicone rubber, polyurethane resin, epoxy resin, polyamide resin, vinyl resin (vinyl chloride copolymer, ethylene ⁇ Vinyl acetate copolymer, etc.), chlorinated rubber, chlorinated olefin resin, styrene / butadiene copolymer resin, ketone resin, alkyd resin, coumarone resin, terpene phenol resin, petroleum resin, pineapple, rosin (gum rosin, wood rosin, tall Non-water-soluble or sparingly water-soluble resins such as oil rosin).
- organic acid examples include monobasic organic acids such as naphthenic acid, versatic acid, triphenylisobutenylcyclohexene carboxylic acid (eg, “A-3000” manufactured by Yashara Chemical Co., Ltd.), and the like.
- the various components which comprise the composition of this invention are melt
- the composition of the present invention can be prepared using the same apparatus, means, and the like as known general antifouling paints. For example, after synthesizing the polymer (A) in advance, this polymer (reaction solution), an antifouling agent, and if necessary, zinc oxide and other components are added to the solvent at once or sequentially, It can be prepared by stirring and mixing.
- the composition of the present invention can be used in the same manner as a known general antifouling paint.
- the composition prepared under such a condition that the ratio of the polymer (A) and the pigment falls within the above range is excellent in paintability (can be coated without the addition of a further solvent).
- the VOC content can be obtained by the method described in the following examples, for example. Can be measured.
- the composition of the present invention for example, according to the desired use, after determining the blending amount of components other than the solvent while considering the physical properties of the resulting antifouling coating film, the composition obtained is further solvent The blending amount of the solvent is determined so that the coating can be performed without the addition of an amount of VOC.
- the composition containing the necessary minimum amount of the solvent has a VOC content in the above range. It is preferable.
- the composition of the present invention has a viscosity (KU value) measured by a Stormer viscometer of preferably 85 to 100, more preferably 85 to 98, and still more preferably 85 to 95. Since a composition having a viscosity in the above range shows a low viscosity, the composition of the present invention having such a viscosity has a low viscosity despite a low VOC content. Therefore, a composition having a viscosity in the above range has little impact on the environment and the human body, is excellent in coating workability and drying property, and can be easily applied to spray coating.
- KU value viscosity measured by a Stormer viscometer
- a composition having a viscosity in the above range is excellent in the retention of the composition on the substrate in addition to the paintability when the composition is applied onto the substrate using an applicator or the like.
- the antifouling coating film can be easily formed on the substrate by various methods.
- the antifouling coating film of the present invention is formed from the composition of the present invention.
- the antifouling coating film of the present invention is applied, for example, to a substrate, particularly a substrate that is constantly or intermittently in contact with seawater or fresh water, such as underwater structures, ships, and fishing gear.
- a substrate particularly a substrate that is constantly or intermittently in contact with seawater or fresh water, such as underwater structures, ships, and fishing gear.
- a method for producing a substrate with an antifouling coating is not particularly limited, but a method of applying the composition of the present invention on a substrate by a conventionally known method, a method of immersing the substrate in the composition of the present invention
- the method including the process of forming the coating film which consists of a composition of this invention on a base material by this etc., and hardening this coating film is mentioned.
- the method of applying is not particularly limited because the composition of the present invention can be applied onto a substrate by various methods, but spray coating is preferable.
- the (dry) film thickness of the antifouling coating film can be appropriately adjusted in consideration of the consumption rate of the coating film, etc., but may be, for example, about 40 to 400 ⁇ m, preferably about 40 to 200 ⁇ m.
- the solid content means a heating residue when a component containing a solvent or the like is dried in a hot air dryer at 105 ° C. for 3 hours to volatilize the solvent or the like.
- Mw and Mn weight average molecular weight (Mw) and number average molecular weight (Mn)> Mw and Mn of the polymer in the hydrolyzable polymer composition obtained in the following production examples were measured using “HLC-8120GPC” manufactured by Tosoh Corporation and “TSK-gel ⁇ ” manufactured by Tosoh Corporation. Measured by gel permeation chromatography (GPC) method using two types of separation columns ( ⁇ -M) and dimethylformamide (DMF) with 20 mM LiBr added as an eluent. As sought.
- GPC gel permeation chromatography
- Preparation Example 2 (Production of metal atom-containing polymerizable monomer mixture (a-2)) A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 85.4 parts of PGM and 40.7 parts of zinc oxide and heated to 75 ° C. while stirring. Subsequently, a mixture composed of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid and 5 parts of water was dropped from the dropping funnel at a constant rate over 3 hours. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and 36 parts of PGM was added to obtain a transparent metal atom-containing polymerizable monomer mixture (a-2). The solid content was 44.8%.
- Mw of the polymer contained in the obtained hydrolyzable copolymer composition (A-1) was 3200, and Mn was 1150.
- Mw of the polymer contained in the obtained hydrolyzable copolymer composition (A-2) was 3100, and Mn was 1200.
- the obtained mixture was filtered through 300 mesh, whereby a light yellow transparent filtrate (hydrolyzable copolymer composition (A-3) free from insolubles having a heating residue of 45.6% and a Gardner viscosity of -Y was obtained. )).
- Mw of the polymer contained in the obtained hydrolyzable copolymer composition (A-3) was 5200, and Mn was 1950.
- Mw of the polymer contained in the obtained hydrolyzable copolymer composition (A-4) was 3600, and Mn was 1350.
- Mw of the polymer contained in the obtained hydrolyzable copolymer composition (A-5) was 55350, and Mn was 9500.
- Antifouling paint compositions were prepared by mixing the components shown in Tables 1 and 3.
- the numerical values in Tables 1 and 3 indicate parts by weight.
- Sineine 211N is an antifouling agent manufactured by Rohm and Haas Japan, which contains 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one. .
- VOC content It computed from the following formula using the specific gravity of the antifouling paint composition obtained by the Example and the comparative example, and the value of a heating residue.
- VOC content (g / L) specific gravity of the composition ⁇ 1000 ⁇ (100 ⁇ residue on heating) / 100
- Specific gravity At 25 ° C. a specific gravity cup having a capacity of 100 mL is filled with the antifouling paint composition obtained in Examples and Comparative Examples, the mass of the antifouling paint composition is measured, and the antifouling paint composition is measured. Was divided by the capacity of the specific gravity cup to calculate the specific gravity of the composition.
- Heating residue The heating residue was calculated based on JIS K 5601-1-2.
- Viscosity (KU value) of antifouling paint compositions obtained in Examples and Comparative Examples was measured using a Stormer viscometer in accordance with JIS K-5600-2-2. The measurement was performed under the following conditions.
- Stormer viscometer Stormer viscometer made by Coating Tester Industry Setting temperature: 25 ° C ⁇ 0.5 ° C Sample volume: 500 mL Weight: 75g-1000g
- Airless spray workability 5000 g of the antifouling coating composition obtained in the examples and comparative examples was left for 60 minutes under a temperature condition of 23 ° C.
- the composition after standing was coated on a substrate (913 mm ⁇ 718 mm ⁇ 0.32 mm, tin plate) using an airless spray so that the target wet film thickness was 300 ⁇ m.
- the coating workability atomization property, coating film appearance at this time was evaluated based on the following evaluation criteria.
- the antifouling paint composition obtained in the Examples and Comparative Examples was applied to the surface of the coating film with an airless spray so that the dry film thickness was 160 ⁇ m, and dried at room temperature (about 20 ° C.) for 1 day. The operation for forming the film was repeated twice to prepare a test plate with an antifouling coating film having a dry film thickness of 320 ⁇ m.
- test plates were prepared using the antifouling paint compositions obtained in the examples and comparative examples, respectively, and further dried at room temperature of 23 ° C. for 1, 3 or 7 days.
- a 30 ⁇ 30 ⁇ 10 mm piece of wood is placed on the coating film (center part) of each test plate, and a pressure of 40 kgf / cm 2 (3.9 MPa) is applied in a vertical direction (coating direction) from the piece of wood for 20 minutes.
- the state of the coating film surface was observed (deformation degree of the coating film was measured).
- Evaluation criteria are shown in FIG. In FIG. 1, 10 is a piece of wood, and 20 is a coating film. Evaluation criteria 5 shows the most favorable state with no deformation of the coating film 20.
- Evaluation Criteria 4 although some deformation of the coating film 20 is recognized, the coating film 20 does not show the trace of the piece of wood 10 and shows a good state.
- Evaluation criteria 3, 2, and 1 show a state in which the coating film 20 is deformed and the trace of the piece of wood 10 is recognized, and the degree of damage (deformation) is in the order of 3 ⁇ 2 ⁇ 1.
- test plate prepared as described above was immersed in Hiroshima Bay, Hiroshima Prefecture for 12 months, and the adhesion area (%) of marine organisms excluding slime on the coating surface was measured every 3 months. Then, the antifouling property of the antifouling coating film was evaluated according to the following [Evaluation criteria of antifouling property by the adhesion area of marine organisms].
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Abstract
Description
このように、防汚塗料組成物中のVOC量の低下と、該組成物から得られる防汚塗膜の長期間にわたる、安定した塗膜消耗度および高い防汚性とはトレードオフの関係にあり、これらの特性を両立できる防汚塗料組成物が求められていた。
従来の防汚塗料組成物、例えば、前記特許文献2に記載の防汚塗料組成物は、塗膜乾燥性が劣り、耐ダメージ性に優れる防汚塗膜を形成することは容易ではなかった。
(b1)4-ブロモ-2-(4-クロロフェニル)-5-(トリフルオロメチル)-1H-ピロール-3-カルボニトリルを含む防汚剤(B)を含有し、
揮発性有機化合物(VOC)の含有量が400g/L以下である、防汚塗料組成物。
[5] 前記防汚剤(b2)の含有量が、防汚塗料組成物100重量部(固形分)に対して、1~20重量部である、[4]に記載の防汚塗料組成物。
[9] 前記不飽和単量体(a2)が、アルキル(メタ)アクリレート、アルコキシアルキル(メタ)アクリレートおよびヒドロキシアルキル(メタ)アクリレートからなる群より選ばれる少なくとも1種の不飽和単量体を含む、[7]または[8]に記載の防汚塗料組成物。
[13] 基材上に、[1]~[10]のいずれかに記載の防汚塗料組成物からなる塗膜を形成し、該塗膜を硬化させる工程を含む、防汚塗膜付基材の製造方法。
また、本発明によれば、水中構造物、船舶および漁具等の基材を、長期間防汚することが可能となる。
本発明に係る防汚塗料組成物(以下、単に「組成物」ともいう。)は、下記式(1)で表される構造単位(以下「構造単位(1)」ともいう。)を有し、重量平均分子量(Mw)が1000~5000である加水分解性重合体(A)、および、
(b1)4-ブロモ-2-(4-クロロフェニル)-5-(トリフルオロメチル)-1H-ピロール-3-カルボニトリル(以下「防汚剤(b1)」ともいう。)を含む防汚剤(B)を含有し、
揮発性有機化合物(VOC)の含有量が400g/L以下である。
これは、防汚塗料組成物に含まれる樹脂中の加水分解性を有する部分のみ先に溶け、加水分解性を有さない部分が残ることによると考えられる。
一方、本発明の組成物は、VOCの含有量が少なくても、粘度が低い組成物であり、また、長期間にわたり安定した塗膜消耗度および高い防汚性を有する防汚塗膜を形成できる組成物でもある。これらの効果は、特定の重合体(A)と防汚剤(b1)とを含むことで初めて達成される。
また、本発明の組成物は、ハイソリッド型塗料組成物であるため、塗装条件や塗装環境を従来の溶剤型塗料とほとんど変化させずに塗装が可能であり、塗装設備等を改造しなくても環境や人体に配慮しながら塗装が可能となる。
前記加水分解性重合体(A)は、構造単位(1)を有し、重量平均分子量(Mw)が1000~5000である。
前記重合体(A)は、少なくとも海水中等のアルカリ雰囲気下において加水分解性を示す。本発明の組成物は、このような重合体(A)および防汚剤(b1)を含むため、低VOC量でありながら低粘度であり、乾燥性に優れ、かつ、長期にわたって安定した塗膜消耗度、耐ダメージ性、塗膜物性(例えば、耐クラック性、基材に対する密着性)および表面平滑性にバランスよく優れる防汚塗膜を形成することができるハイソリッド型加水分解性防汚塗料組成物となる。
前記構造単位(1)を有する重合体は、例えば、その合成原料として下記単量体(a1)を用いることで得ることができる。重合体中における構造単位(1)の量は、例えば、用いる単量体(a1)の使用量から算出することができる。構造単位(1)の量が前記範囲にある重合体は、例えば、単量体(a1)の使用量を適宜調整することで得ることができる。
前記亜鉛および/または銅の含有量は、ICP発光分析装置を用いることで測定することができ、重合体(A)の調製に用いる金属含有化合物の種類および使用量等により調整することが可能である。
前記単量体(a1)および不飽和単量体(a2)はそれぞれ、1種類単独で用いてもよく、2種類以上を併用してもよい。
また、前記共重合体は、単量体混合物を110℃以上の温度でかつ、水が還流しないように加圧した加圧容器中で重合したものであってもよい。このように製造された共重合体を含む組成物から形成した防汚塗膜は、該塗膜を船舶上に形成した場合であって、該船舶を低速で運航させる場合であっても、該塗膜の自己研磨性が低下することなく、優れた性能を長期間維持させることができる。
また、前記共重合体を合成する際に用いる単量体(a2)の使用量は、共重合体を合成する際に用いる総モノマー100モル%に対し、好ましくは50~99モル%であり、より好ましくは70~95モル%である。
また、前記重合体(A)の数平均分子量(Mn:ポリスチレン換算値)は、組成物の粘度や貯蔵安定性、防汚塗膜の溶出速度等を考慮し、適宜調整することができるが、好ましくは1000~3000、より好ましくは1000~2500である。
前記分子量は、ゲルパーミエーションクロマトグラフィー(GPC)で測定することができ、具体的には、下記実施例に記載の方法で測定することができる。
前記重合体(A)は、1種類単独で用いてもよく、2種類以上を併用してもよい。
本発明の組成物は、防汚剤(B)として、防汚剤(b1)を含有する。
本発明の組成物が、このような防汚剤(b1)を含有することで、Mwの小さい重合体を用いても、長期間にわたり安定した塗膜消耗度および高い防汚性ならびに機械的強度(耐ダメージ性)にバランスよく優れる防汚塗膜を形成することができる。
本発明者らは、防汚剤(b1)を前記重合体(A)と組み合わせることにより、該混合物の粘度は大きく低下すること、および、防汚塗料組成物に含まれる樹脂中の加水分解性を有する部分のみ先に溶け、加水分解性を有さない部分が残ることを抑制できることを見出したため、前記効果を有する組成物を得ることができた。
また、亜酸化銅の不使用または削減により、防汚塗料組成物の比重を低減することができ、亜酸化銅による基材の腐食を抑制することができるため、基材の材質によらず、所望の基材を選択して使用することができる。さらに、亜酸化銅の不使用または削減により、得られる防汚塗膜の色味を調整することができる。
防汚剤(b2)としては、特に制限されないが、好ましい例として、ジンクピリチオン、銅ピリチオン、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン、トリフェニルボロン・アミン錯体、2-メチルチオ-4-tert-ブチルアミノ-6-シクロプロピル-s-トリアジン、N,N-ジメチル-N'-フェニル-N'-(フルオロジクロロメチルチオ)スルファミド、N,N-ジメチル-N'-トリル-N'-(フルオロジクロロメチルチオ)スルファミド等が挙げられる。これらの中でも、より防汚性に優れる防汚塗膜が得られる等の点から、ジンクピリチオン、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン(例:シーナイン211N(ローム・アンド・ハース・ジャパン(株)製))がより好ましく、さらに、塗膜乾燥性にも優れる組成物が得られる等の点から、ジンクピリチオンが特に好ましい。
これらの防汚剤(b2)は1種類単独で用いてもよく、2種類以上を併用してもよい。
また、前記防汚剤(b2)の含有量は、防汚剤(b1)100重量部に対して、好ましくは10~1000重量部あり、より好ましくは20~500重量部であり、さらに好ましくは20~400重量部である。
本発明の組成物は、安定した消耗性、高い防汚性および耐ダメージ性等に優れる防汚塗膜が得られるなどの点から、酸化亜鉛を含むことが好ましい。
本発明の組成物が酸化亜鉛を含む場合、酸化亜鉛の含有量は、本発明の組成物(固形分)100重量部に対して、好ましくは0.1~60重量部であり、より好ましくは1~50重量部であり、さらに好ましくは3~50重量部である。
本発明の組成物には、前述した成分の他に、さらに、着色剤、体質顔料、脱水剤、可塑剤、揺変剤、溶剤、樹脂や有機酸などの有機化合物等の一般的な塗料組成物に用いられている各種成分を配合することができる。これらはそれぞれ、1種類単独で用いてもよく、2種類以上を併用してもよい。
着色剤としては、例えば、着色顔料(例:弁柄、チタン白(酸化チタン)、黄色酸化鉄等の無機系顔料、カーボンブラック、ナフトールレッド、フタロシアニンブルー等の有機系顔料)および染料が挙げられる。
着色剤の配合量は適宜調整することができるが、本発明の組成物(固形分)100重量部に対して、0.1~20重量部が好ましく、0.5~10重量部がより好ましい。
体質顔料は、屈折率が小さく、油やワニスと混練した場合に透明で被塗面を隠さないような顔料である。体質顔料としては、例えば、タルク、シリカ、マイカ、クレー、カリ長石、炭酸カルシウム、カオリン、アルミナホワイト、ホワイトカーボン、水酸化アルミニウム、炭酸マグネシウム、炭酸バリウム、硫酸バリウム、硫化亜鉛が挙げられる。これらの中でも、タルク、シリカ、マイカ、クレー、カリ長石、硫酸バリウムが好ましい。体質顔料の配合量は適宜調整することができるが、本発明の組成物(固形分)100重量部に対して、0.1~60重量部が好ましく、1~50重量部がより好ましく、5~45重量部が特に好ましい。なお、炭酸カルシウム、カオリン、アルミナホワイトは沈降防止剤として、ホワイトカーボン、水酸化アルミニウム、炭酸マグネシウム、炭酸バリウム、硫酸バリウム、硫化亜鉛は艶消し剤としての機能も有し得る。
脱水剤は、本発明の組成物の貯蔵安定性の向上に寄与する成分である。
脱水剤としては、例えば、無機系では、無水石膏、半水石膏(焼石膏)、合成ゼオライト系吸着剤(例:商品名「モレキュラーシーブ」)が挙げられ、その他、オルソエステル類(オルソギ酸メチル、オルソ酢酸メチル、オルソホウ酸エステル等)、シリケート類、イソシアネート類等が挙げられる。これらの中でも、無機系の脱水剤である無水石膏、半水石膏(焼石膏)が好ましい。
脱水剤の配合量は適宜調整することができるが、本発明の組成物(固形分)100重量部に対して、0~10重量部が好ましく、0.5~5重量部がより好ましい。
可塑剤は、防汚塗膜の耐クラック性や耐水性の向上および変色の抑制に寄与する成分である。
可塑剤としては、例えば、n-パラフィン、塩素化パラフィン、テルペンフェノール、トリクレジルホスフェート(TCP)、ポリビニルエチルエーテルが挙げられ、これらの中でも、塩素化パラフィン、テルペンフェノールが好ましく、塩素化パラフィンが特に好ましい。
n-パラフィンとしては、日本石油化学(株)製「n-パラフィン」等の商品、塩素化パラフィンとしては、東ソー(株)製「トヨパラックス A-40/A-50/A-70/A-145/A-150」等の商品が挙げられる。
可塑剤の配合量は適宜調整することができるが、例えば、本発明の組成物中の全固形分に対して1~5重量%の割合である。
搖変剤(タレ止め・沈降防止剤)としては、例えば、有機粘土系化合物(Al、CaまたはZnのアミン塩、ステアレート塩、レシチン塩、アルキルスルホン酸塩等)、有機系ワックス(ポリエチレンワックス、酸化ポリエチレンワックス、ポリアマイドワックス、アマイドワックス、水添ヒマシ油ワックス等)、合成微粉シリカが挙げられ、これらの中でも、有機粘土系化合物、ポリアマイドワックス、酸化ポリエチレンワックス、合成微粉シリカが好ましい。
搖変剤の配合量は適宜調整することができるが、例えば、本発明の組成物(固形分)100重量部に対して、0.1~5重量部の割合である。
本発明の組成物は、前記重合体(A)以外にも、必要に応じて樹脂や有機酸などの有機化合物を含有してもよい。
樹脂としては、例えば、アクリル樹脂、アクリルシリコーン樹脂、ポリエステル樹脂、不飽和ポリエステル樹脂、フッ素樹脂、ポリブテン樹脂、シリコーンゴム、ポリウレタン樹脂、エポキシ樹脂、ポリアミド樹脂、ビニル樹脂(塩化ビニル系共重合体、エチレン・酢酸ビニル共重合体等)、塩化ゴム、塩素化オレフィン樹脂、スチレン・ブタジエン共重合樹脂、ケトン樹脂、アルキッド樹脂、クマロン樹脂、テルペンフェノール樹脂、石油樹脂、パインタール、ロジン(ガムロジン、ウッドロジン、トール油ロジン)等の非水溶性または難水溶性の樹脂が挙げられる。
有機酸としては、ナフテン酸、バーサチック酸、トリフェニルイソブテニルシクロヘキセンカルボン酸(例:ヤスハラケミカル(株)製「A-3000」)等の一塩基性有機酸等が挙げられる。
本発明の組成物を構成する各種成分は、通常の防汚塗料組成物と同様、溶剤に溶解もしくは分散していることが好ましい。本発明では、脂肪族系溶剤、芳香族系溶剤(キシレン、トルエン等)、ケトン系溶剤(メチルイソブチルケトン、シクロヘキサノン等)、エステル系溶剤、エーテル系溶剤(プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等)、アルコール系溶剤(イソプロピルアルコール等)など、防汚塗料用の溶剤として一般的なものを用いることができる。
また、必要により、塗装現場において、作業性に応じてさらに溶剤を添加してもよい。
本発明の組成物は、公知の一般的な防汚塗料と同様の装置、手段等を用いて調製することができる。例えば、予め重合体(A)を合成した後、この重合体(反応液)と、防汚剤と、必要に応じて酸化亜鉛やその他の成分とを、一度にまたは順次溶剤に添加して、撹拌、混合することで調製することができる。
本発明の組成物は、公知の一般的な防汚塗料と同様の態様で使用することができる。
本発明の組成物は、重合体(A)と前記顔料との比率が前記範囲になるような条件で調製された組成物が、塗装性に優れる(さらなる溶媒の添加なしで塗装が可能である)組成物になるように、VOCを含むことが好ましく、本発明の組成物におけるVOC含有量は、より好ましくは390g/L以下である。
本発明の組成物中のVOC含有量を400g/L以下とすることにより、環境への負荷や人体への影響を少なくすることができる。VOC含有量が前記範囲にある組成物は、例えば、本発明の組成物に配合され得る溶剤量を調整することで得ることができ、VOC含有量は、例えば、下記実施例に記載の方法で測定することができる。
なお、本発明の組成物は、例えば、所望の用途に応じ、得られる防汚塗膜の物性等を考慮しながら溶剤以外の成分の配合量を決定した後、得られる組成物が、さらなる溶剤の添加なしで塗装が可能になるように溶剤の配合量を決定するが、このような組成物のうち、必要最低量の溶剤を含む組成物のVOC含有量が前記範囲にある組成物であることが好ましい。
また、粘度が前記範囲にある組成物は、アプリケーター等を用いて基材上に組成物を塗布する際には、塗装性に加え、基材上での該組成物の滞留性にも優れるため、容易に、様々な方法で基材上に防汚塗膜を形成することができる。
本発明の防汚塗膜は、前記本発明の組成物から形成される。
本発明の防汚塗膜は、例えば、基材、特に、水中構造物、船舶および漁具等の、海水または淡水等と常時または断続的に接触する基材に、本発明の組成物からなる塗膜を形成し、該塗膜を硬化させることで、基材上に防汚塗膜(防汚塗膜付基材)を形成することができる。
前記塗布する方法としては、本発明の組成物は様々な方法で基材上に塗布することができるため特に制限されないが、スプレー塗装が好ましい。
本発明において、固形分とは、溶剤等が含まれた成分を105℃の熱風乾燥機中で3時間乾燥して溶剤等を揮散させたときの加熱残分をいう。
下記製造例で得られた加水分解性重合体組成物中の重合体のMwおよびMnは、測定装置として東ソー(株)製「HLC-8120GPC」を用い、東ソー(株)製「TSK-gel αタイプ」の分離カラム(α-M)2本を用い、20mMのLiBrを添加したジメチルホルムアミド(DMF)を溶離液として用いて、ゲルパーミエーションクロマトグラフィー(GPC)法により測定し、ポリスチレン換算の値として求めた。
下記製造例で得られた加水分解性重合体組成物中の重合体のガードナー粘度は、25℃で測定した。
冷却器、温度計、滴下ロートおよび攪拌機を備えた四つ口フラスコに、プロピレングリコールモノメチルエーテル(PGM)59.9部および酸化亜鉛40.7部を仕込み、攪拌しながら75℃に昇温した。続いて、メタクリル酸43部、アクリル酸36部および水5部からなる混合物を滴下ロートから3時間かけて等速滴下した。滴下終了後、さらに2時間攪拌した後、PGMを29.4部添加して、透明な金属原子含有重合性単量体混合物(a-1)を得た。固形分は55.1%であった。
冷却器、温度計、滴下ロートおよび攪拌機を備えた四つ口フラスコに、PGM 85.4部および酸化亜鉛40.7部を仕込み、攪拌しながら75℃に昇温した。続いて、メタクリル酸43.1部、アクリル酸36.1部および水5部からなる混合物を滴下ロートから3時間かけて等速滴下した。滴下終了後、さらに2時間攪拌した後、PGMを36部添加して、透明な金属原子含有重合性単量体混合物(a-2)を得た。固形分は44.8%であった。
冷却器、温度計、滴下タンクおよび攪拌機を備えた加圧重合可能なオートクレーブに、PGM 10部、キシレン35部およびエチルアクリレート4部を仕込み、攪拌しながら350kPaに加圧し、135℃に昇温した。続いて、滴下タンクからメチルメタクリレート15部、エチルアクリレート48部、n-ブチルアクリレート15部、金属原子含有重合性単量体混合物(a-1)40部、キシレン10部、連鎖移動剤(日油(株)製ノフマーMSD)1.8部、2,2'-アゾビスイソブチロニトリル(AIBN)4部および2,2'-アゾビス(2-メチルブチロニトリル)(AMBN)2部からなる透明な混合物を2.5時間かけて等速滴下した。滴下終了後、30分かけて110℃に降温し、t-ブチルパーオクトエート0.5部とキシレン5部とを30分かけて滴下し、さらに1時間30分攪拌した後、キシレンを3部添加した。得られた混合物を300メッシュでろ過することで、加熱残分55.3%、ガードナー粘度Rを有する不溶解物のない淡黄色透明なろ液(加水分解性共重合体組成物(A-1))を得た。
冷却器、温度計、滴下ロートおよび攪拌機を備えた四つ口フラスコに、PGM 10部、キシレン37部およびエチルアクリレート4部を仕込み、攪拌しながら100℃に昇温した。続いて、滴下ロートからメチルメタクリレート15部、エチルアクリレート52部、n-ブチルアクリレート8部、金属原子含有重合性単量体混合物(a-1)47部、キシレン10部、連鎖移動剤(日油(株)製ノフマーMSD)2部、AIBN 3部およびAMBN 8部からなる透明な混合物を2.5時間かけて等速滴下した。滴下終了後、t-ブチルパーオクトエート0.5部とキシレン7部とを30分かけて滴下し、さらに1時間30分攪拌した後、キシレンを3部添加した。得られた混合物を300メッシュでろ過することで、加熱残分54.8%、ガードナー粘度Rを有する不溶解物のない淡黄色透明なろ液(加水分解性共重合体組成物(A-2))を得た。
冷却器、温度計、滴下ロートおよび攪拌機を備えた四つ口フラスコに、PGM 15部およびキシレン57部を仕込み、攪拌しながら100℃に昇温した。続いて、滴下ロートからメチルメタクリレート1部、エチルアクリレート66.2部、2-メトキシエチルアクリレート5.4部、金属原子含有重合性単量体混合物(a-2)52部、キシレン10部、連鎖移動剤(日油(株)製ノフマーMSD)1部、AIBN 2.5部およびAMBN 7部からなる透明な混合物を6時間かけて等速滴下した。滴下終了後、t-ブチルパーオクトエート0.5部とキシレン7部とを30分で滴下し、さらに1時間30分攪拌した後、キシレンを4.4部添加した。得られた混合物を300メッシュでろ過することで、加熱残分45.6%、ガードナー粘度-Yを有する不溶解物のない淡黄色透明なろ液(加水分解性共重合体組成物(A-3))を得た。
冷却器、温度計、滴下ロートおよび攪拌機を備えた四つ口フラスコに、PGM 30部およびキシレン37部を仕込み、攪拌しながら100℃に昇温した。続いて、バーサチック亜鉛メタクリレート35部、2-メトキシエチルアクリレート10部、3-メトキシブチルアクリレート30部、エチルアクリレート25部およびt-ブチルパーオキサイド10部からなる混合物を滴下ロートから2時間かけて等速滴下した。滴下終了後にt-ブチルパーオクトエート1部とキシレン10部とを2時間かけて滴下し、さらに2時間攪拌した後、キシレンを10部添加した。得られた混合物を300メッシュでろ過することで、加熱残分53.9%、ガードナー粘度Yを有する不溶解物のない淡黄色透明なろ液(側鎖末端型である加水分解性共重合体組成物(A-4))を得た。
攪拌機、コンデンサー、温度計、滴下装置、窒素導入管、および、加熱・冷却ジャケットを備えた反応容器にキシレン80部を仕込み、窒素気流下、85℃の温度条件下で加熱攪拌を行った。同温度を保持しつつ滴下装置より、トリイソプロピルシリルアクリレート60部、メチルメタクリレート40部およびAIBN 0.3部からなる混合物を2時間かけて前記反応容器内に滴下した。その後、同温度で4時間攪拌を行った後、AIBN 0.4部を加え、更に同温度で3時間攪拌を行い、加熱残分55.0%、ガードナー粘度+Zを有する無色透明の加水分解性共重合体組成物(A-5)得た。
表1および3に示す通りの成分を混合し防汚塗料組成物を調製した。表1および3中の数値は、重量部を示す。
なお、表1および3中のシーナイン211Nは、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オンを含むローム・アンド・ハース・ジャパン(株)製の防汚剤である。
実施例1~16および比較例1~22で得られた防汚塗料組成物およびそれらから形成した防汚塗膜の物性は、以下のように評価した。得られた結果を表2または4に示す。
実施例および比較例で得られた防汚塗料組成物の比重および加熱残分の値を用いて、下記式から算出した。
VOC含有量(g/L)=組成物の比重×1000×(100-加熱残分)/100
(2)比重
25℃において、容量が100mLの比重カップに、実施例および比較例で得られた防汚塗料組成物を満たし、その防汚塗料組成物の質量を量り、該防汚塗料組成物の質量を比重カップの容量で割ることにより、組成物の比重を算出した。
(3)加熱残分
加熱残分は、JIS K 5601-1-2に基づいて算出した。具体的には、実施例および比較例で得られた防汚塗料組成物1gを平底皿に量り採り、質量既知の針金を使って均一に広げ、125℃で1時間乾燥後、残渣および針金の質量を量り、加熱残分(重量%)を算出した。
実施例および比較例で得られた防汚塗料組成物の粘度(KU値)を、JIS K-5600-2-2の規定に従ってストーマー粘度計を用い、下記条件で測定した。
ストーマー粘度計:コーティングテスター工業製ストーマー粘度計
設定温度 :25℃±0.5℃
サンプル量 :500mL
重り :75g~1000g
実施例および比較例で得られた防汚塗料組成物5000gを、23℃の温度条件下で60分放置した。ついで、放置後の組成物をエアレススプレーを用いて基材(913mm×718mm×0.32mm、ブリキ板)上に、目標ウェット膜厚が300μmになるように塗装した。この時の塗装作業性(霧化性、塗膜外観)を下記評価基準に基づいて塗装作業性を評価した。
A:防汚塗料組成物をエアレススプレーを用いて基材上に塗装した際に、防汚塗料組成物が微細な粒子として(霧状で)噴霧され、かつスプレーパターンがスジ等を生じることなく、均一なパターンであった(霧化性が良好である)。
B:防汚塗料組成物をエアレススプレーを用いて基材上に塗装した際に、防汚塗料組成物が微細な粒子として(霧状で)噴霧されず、スプレーパターンがスジを引いたようなパターンであった(霧化性に劣る)。
C:エアレススプレーでの塗装が非常に困難であった。
A:基材上に形成された塗膜の表面に、微粒子の発生、光沢低下、レベリング不良などの問題がなかった(外観状態が良好である)。
B:基材上に形成された塗膜の表面に、微粒子の発生、光沢低下、レベリング不良などの問題が生じた(外観状態が劣る)。
C:エアレススプレーでの塗装が非常に困難であり、通常の塗膜(均一な塗膜)にならなかった。
150×70×3.2mmのサンドブラスト処理鋼板に、エポキシ系防食塗料(中国塗料(株)製「バンノー500」)を乾燥膜厚が150μmとなるように塗装し、室温(約20℃)で1日乾燥させて塗膜を形成し、この塗膜表面にさらにエポキシ系バインダー塗料(中国塗料(株)製「バンノー500N」)を乾燥膜厚が100μmとなるように塗装し、室温(約20℃)で1日乾燥させて塗膜を形成した。この塗膜表面に、実施例および比較例で得られた防汚塗料組成物をその乾燥膜厚が160μmとなるようにエアレススプレーで塗装し、室温(約20℃)で1日乾燥させて塗膜を形成する操作を2度繰り返し、乾燥膜厚が320μmである防汚塗膜付試験板を作成した。
50×50×1.5mmの硬質塩化ビニル板にアプリケーターを用いて、実施例および比較例で調製した防汚塗料組成物を乾燥膜厚が150μmになるように塗布し、これを室内で室温(約20℃)にて7日間乾燥させ、試験板を作成した。
25℃の海水を入れた恒温槽に設置した回転ドラムの側面にこの試験板を取り付け、周速15ノットで回転させ、3ヶ月毎の防汚塗膜の消耗度(膜厚減少)を測定した。
サンドブラスト処理鋼板(縦300mm×横100mm×厚み3.2mm)に、エポキシ系防食塗料(中国塗料(株)製「バンノー500」)をその乾燥膜厚が150μm厚になるように塗布した後室温で1日乾燥させて塗膜を形成し、この塗膜表面にさらにエポキシ系バインダー塗料(中国塗料(株)製「バンノー500N」)をその乾燥膜厚が100μm厚となるように塗布し、室温で1日乾燥させた。さらにその上に、前記実施例および比較例で調製した防汚塗料組成物をその乾燥膜厚が100μmとなるように塗布し、室温で7日間乾燥させて、防汚塗膜付試験板を作成した。
0:海中生物の付着無し
0.5:海水生物の付着面積が、0%を超え10%以下
1:海水生物の付着面積が、10%を超え20%以下
2:海水生物の付着面積が、20%を超え30%以下
3:海水生物の付着面積が、30%を超え40%以下
4:海水生物の付着面積が、40%を超え50%以下
5:海水生物の付着面積が、50%を超える
20:防汚塗膜
Claims (13)
- ストーマー粘度計で測定した粘度(KU値)が85~100である、請求項1に記載の防汚塗料組成物。
- 前記防汚剤(b1)の含有量が、防汚塗料組成物100重量部(固形分)に対して、1~20重量部である、請求項1または2に記載の防汚塗料組成物。
- 前記防汚剤(B)がさらに、ジンクピリチオン、銅ピリチオン、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン、トリフェニルボロン・アミン錯体、2-メチルチオ-4-tert-ブチルアミノ-6-シクロプロピル-s-トリアジン、N,N-ジメチル-N'-フェニル-N'-(フルオロジクロロメチルチオ)スルファミドおよびN,N-ジメチル-N'-トリル-N'-(フルオロジクロロメチルチオ)スルファミドからなる群より選ばれる少なくとも1種の防汚剤(b2)を含む、請求項1~3のいずれか一項に記載の防汚塗料組成物。
- 前記防汚剤(b2)の含有量が、防汚塗料組成物100重量部(固形分)に対して、1~20重量部である、請求項4に記載の防汚塗料組成物。
- さらに、酸化亜鉛を、防汚塗料組成物100重量部(固形分)に対して、0.1~60重量部含有する、請求項1~5のいずれか一項に記載の防汚塗料組成物。
- 前記重合体(A)が、式(2):CH2=C(R1)-COO-M-O-CO-C(R1)=CH2[式(2)中、Mは亜鉛または銅を示し、R1は独立に水素原子またはメチル基を示す。]で表される単量体(a1)から誘導される成分単位と、前記単量体(a1)と共重合し得る他の不飽和単量体(a2)から誘導される成分単位とを有する、請求項1~6のいずれか一項に記載の防汚塗料組成物。
- 前記単量体(a1)が、亜鉛ジアクリレート、亜鉛ジメタクリレート、銅ジアクリレートおよび銅ジメタクリレートからなる群より選ばれる少なくとも1種の単量体を含む、請求項7に記載の防汚塗料組成物。
- 前記不飽和単量体(a2)が、アルキル(メタ)アクリレート、アルコキシアルキル(メタ)アクリレートおよびヒドロキシアルキル(メタ)アクリレートからなる群より選ばれる少なくとも1種の不飽和単量体を含む、請求項7または8に記載の防汚塗料組成物。
- 前記重合体(A)中の亜鉛および/または銅の含有量が、前記重合体(A)の0.5~25重量%である、請求項1~9のいずれか一項に記載の防汚塗料組成物。
- 請求項1~10のいずれか一項に記載の防汚塗料組成物から形成される防汚塗膜。
- 基材が、請求項11に記載の防汚塗膜で被覆されている、防汚塗膜付基材。
- 基材上に、請求項1~10のいずれか一項に記載の防汚塗料組成物からなる塗膜を形成し、該塗膜を硬化させる工程を含む、防汚塗膜付基材の製造方法。
Priority Applications (7)
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EP14801563.9A EP3000857B1 (en) | 2013-05-22 | 2014-05-21 | Antifouling paint composition, antifouling paint film, substrate having an antifouling paint film, and production method for said substrate |
SG11201509576QA SG11201509576QA (en) | 2013-05-22 | 2014-05-21 | Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, and production process for the substrate |
US14/892,835 US9969892B2 (en) | 2013-05-22 | 2014-05-21 | Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, and production process for the substrate |
CN201480029447.XA CN105392852B (zh) | 2013-05-22 | 2014-05-21 | 防污涂料组合物、防污涂膜、具有防污涂膜的基材以及该基材的制造方法 |
ES14801563.9T ES2690562T3 (es) | 2013-05-22 | 2014-05-21 | Composición de pintura antiincrustante, película de pintura antiincrustante, sustrato que tiene una película de pintura antiincrustante y método de producción para dicho sustrato |
KR1020157035192A KR101821475B1 (ko) | 2013-05-22 | 2014-05-21 | 방오 도료 조성물, 방오 도막, 방오 도막 부착 기재 및 그 기재의 제조방법 |
JP2015518271A JP6228600B2 (ja) | 2013-05-22 | 2014-05-21 | 防汚塗料組成物、防汚塗膜、防汚塗膜付基材および該基材の製造方法 |
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KR (1) | KR101821475B1 (ja) |
CN (1) | CN105392852B (ja) |
ES (1) | ES2690562T3 (ja) |
PT (1) | PT3000857T (ja) |
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WO2018008166A1 (ja) * | 2016-07-05 | 2018-01-11 | 三菱ケミカル株式会社 | 重合体含有組成物および防汚塗料組成物 |
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CN109476932B (zh) * | 2016-07-19 | 2022-12-02 | 贝洱工艺公司 | 抗微生物涂料组合物及相关方法 |
JP6948391B2 (ja) * | 2017-06-01 | 2021-10-13 | 中国塗料株式会社 | 積層防汚塗膜、積層防汚塗膜付き基材及びその製造方法、積層防汚塗膜形成用塗料キット、上層防汚塗料組成物、並びに防汚方法 |
WO2019151265A1 (ja) * | 2018-02-01 | 2019-08-08 | Agc株式会社 | 基材および共重合体 |
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KR102664718B1 (ko) * | 2018-07-05 | 2024-05-10 | 한화오션 주식회사 | 온도 반응형 캡슐을 활용한 방오도료 |
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Publication number | Publication date |
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EP3000857A4 (en) | 2016-11-23 |
PT3000857T (pt) | 2018-11-05 |
ES2690562T3 (es) | 2018-11-21 |
US9969892B2 (en) | 2018-05-15 |
CN105392852B (zh) | 2018-04-06 |
JP6228600B2 (ja) | 2017-11-08 |
JP2017122228A (ja) | 2017-07-13 |
EP3000857B1 (en) | 2018-09-12 |
CN105392852A (zh) | 2016-03-09 |
KR20160008592A (ko) | 2016-01-22 |
EP3000857A1 (en) | 2016-03-30 |
KR101821475B1 (ko) | 2018-01-23 |
US20160168392A1 (en) | 2016-06-16 |
SG11201509576QA (en) | 2015-12-30 |
JPWO2014189069A1 (ja) | 2017-02-23 |
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