WO2010071181A1 - 防汚塗料組成物、該組成物を用いて形成される防汚塗膜、該塗膜を表面に有する塗装物、及び該塗膜を形成する防汚処理方法 - Google Patents
防汚塗料組成物、該組成物を用いて形成される防汚塗膜、該塗膜を表面に有する塗装物、及び該塗膜を形成する防汚処理方法 Download PDFInfo
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- WO2010071181A1 WO2010071181A1 PCT/JP2009/071061 JP2009071061W WO2010071181A1 WO 2010071181 A1 WO2010071181 A1 WO 2010071181A1 JP 2009071061 W JP2009071061 W JP 2009071061W WO 2010071181 A1 WO2010071181 A1 WO 2010071181A1
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- acid
- coating film
- antifouling
- modified rosin
- salt
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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
- C09D5/1612—Non-macromolecular compounds
-
- 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
- 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
-
- 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
- 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
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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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
- C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
- C09D193/04—Rosin
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates to an antifouling coating composition, an antifouling coating film formed using the composition, a coated product having the coating film on the surface, and an antifouling treatment method for forming the coating film.
- the triorganosilyl group-containing copolymer is a copolymer obtained by copolymerizing a linear silyl ester-containing monomer with an alkyl group such as a tri-n-butylsilyl ester-containing copolymer
- an alkyl group such as a tri-n-butylsilyl ester-containing copolymer
- Patent Documents 1 to 7 when the coating composition containing the copolymer is used, it dissolves at a constant rate in seawater at an early stage. The dissolution rate becomes too high, and the paint design is difficult.
- rosins such as gum rosin, wood rosin, and tall oil rosin have free carboxylic acid and high hydrophilicity, thus reducing the water resistance of the coating film, and may result in coating film abnormalities such as blisters and cracks. is there.
- the metal salts tend to be less hydrophilic than the sodium salts and the like, and thus the coating film abnormality can be suitably prevented.
- the coating film abnormality such as a hair crack (fine crack) may occur.
- the zinc salt or the copper salt it is possible to prevent the attachment of large fouling organisms such as animals and plants, but it cannot sufficiently prevent the attachment of slime.
- the slime is deposited on the antifouling coating film, for example, the frictional resistance of the ship increases, and the fuel efficiency during navigation deteriorates.
- the present invention forms an antifouling coating film with high environmental safety, which is less likely to cause coating film abnormalities such as hair cracks even when immersed in seawater for a long period of time, and in which slime adhesion is prevented or suppressed. It is an object to provide a composition for the purpose.
- the present invention provides the following antifouling paint composition, an antifouling coating film formed using the composition, a coated product having the coating film on the surface, and an antifouling treatment method for forming the coating film.
- A) (a) General formula (1):
- R 1 represents a hydrogen atom or a methyl group
- R 2 , R 3, and R 4 are the same or different and each represents an alkyl group or a phenyl group branched from the ⁇ -position of 3 to 6 carbon atoms.
- a modified rosin which is a salt of zinc and / or copper with a modified rosin containing 80% by weight or more selected from the group consisting of acid, dehydroabietic acid, pimaric acid, isopimaric acid and dihydropimaric acid salt, Antifouling paint composition containing 2.
- the modified rosin in the modified rosin salt (B) has two or more contents selected from the group consisting of dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid and dihydropimaric acid.
- the antifouling coating composition according to Item 1 wherein the antifouling coating composition is 85 to 100% by weight. 3.
- the content ratio of the triorganosilyl ester-containing copolymer (A) and the modified rosin salt (B) is 85 by weight ratio (the copolymer (A) / the modified rosin salt (B)).
- the antifouling coating composition according to item 1 or 2 which is / 15 to 20/80. 4).
- the content ratio of the triorganosilyl ester-containing copolymer (A) and the modified rosin salt (B) is 70 by weight ratio (the copolymer (A) / the modified rosin salt (B)).
- Item 4. The antifouling coating composition according to any one of Items 1 to 3, which is / 30 to 40/60. 5). 5. An antifouling treatment method for forming an antifouling coating film on the surface of a film-forming article using the antifouling coating composition according to any one of items 1 to 4. 6). 5. An antifouling coating film formed using the antifouling coating composition according to any one of items 1 to 4. 7). 7. A coated product having the antifouling coating film according to item 6 on its surface.
- the antifouling paint composition of the present invention even when immersed in seawater for a long period of time, a paint film abnormality such as a hair crack is unlikely to occur, and the antifouling paint film in which slime adhesion is prevented or suppressed is provided. Can be formed.
- the composition of the present invention hardly thickens, gels or solidifies even when stored for a long period of time. Furthermore, the antifouling paint composition of the present invention has high environmental safety, and even when dissolved in seawater, there is almost no problem of marine pollution.
- the antifouling coating film of the present invention is 1) excellent in water resistance, so even if it is in contact with seawater for a long time, cracks, peeling, etc. hardly occur, and hair cracks hardly occur. 2) Appropriate hardness It has the advantage that it does not easily cause coating film abnormalities such as cold flow, 3) has high adhesion to the coating film formation, and 4) it has almost no slime even when immersed in seawater for a long time. .
- the coated product of the present invention has an antifouling coating film having the advantages 1) to 4), it can be suitably used as the above-mentioned ship (especially ship bottom), fishing equipment, underwater structure and the like.
- the antifouling coating film when the antifouling coating film is formed on the ship bottom surface of the ship, the antifouling coating film gradually dissolves from the surface, and the coating film surface is constantly renewed, thereby preventing adhesion of waterpox fouling organisms. it can.
- the antifouling coating film has moderate solubility. Therefore, the ship can maintain antifouling performance for a long time. In particular, the ship can exhibit an antifouling effect for a long period of time because the coating film dissolution rate is stable even when navigating in a sea area with a high water temperature. Further, even when the ship is in a stationary state such as during berthing or during the outfitting period, there is almost no adhesion / accumulation of chickenpox fouling organisms (especially slime), and the antifouling effect can be exhibited for a long time. As a result, the frictional resistance of the ship is reduced, and fuel can be saved during navigation.
- the antifouling coating on the surface basically does not cause coating film defects even after a long period of time. Therefore, an antifouling coating film can be suitably formed by directly overcoating the antifouling coating composition after using the coated product for a certain period of time. Thereby, it is possible to easily and continuously maintain the antifouling performance at a low cost.
- R 1 represents a hydrogen atom or a methyl group
- R 2 , R 3, and R 4 are the same or different and each represents an alkyl group or a phenyl group branched from the ⁇ -position of 3 to 6 carbon atoms.
- a modified rosin which is a salt of zinc and / or copper with a modified rosin containing 80% by weight or more selected from the group consisting of acid, dehydroabietic acid, pimaric acid, isopimaric acid and dihydropimaric acid Contains salt.
- the antifouling paint composition of the present invention can form an antifouling coating film that can suppress or prevent the adhesion of waterpox fouling organisms (effectively exhibiting antifouling performance).
- the antifouling coating composition of the present invention can form an antifouling coating film in which slime adhesion is prevented or suppressed by containing the modified rosin salt (B).
- the slime is different from fouling organisms such as shellfish, algae, etc., and adherent bacteria and diatoms grow and aggregate while secreting adhesive substances, gradually forming large aggregates (colony) and forming a film It is. Sometimes referred to as primary microbial membrane.
- Slime is evaluated by its thickness (largeness) and strength of adhesion. When the slime adherence is strong, fouling organisms such as shellfish and algae tend to adhere on the slime. When the thickness of the slime is large, the resistance on the surface of the coating film increases, and as a result, the fuel consumption during traveling of the ship is deteriorated.
- an antifouling coating film that maintains antifouling performance for a long period of time, even if it is immersed in seawater for a long period of time, does not cause coating film abnormalities such as hair cracks. It can form suitably.
- an antifouling coating film that is hardly affected by the temperature of seawater and that exhibits a stable coating film dissolution rate even when the seawater temperature is high.
- an antifouling coating film having an appropriate coating film hardness and having excellent toughness and water resistance.
- the antifouling paint composition of the present invention is excellent in storage stability and hardly gels or solidifies even when stored for a long period of time.
- R 1 represents a hydrogen atom or a methyl group
- R 2 , R 3, and R 4 are the same or different and each represents an alkyl group or a phenyl group branched from the ⁇ -position of 3 to 6 carbon atoms.
- Methacrylic acid triorganosilyl ester monomer represented by (B) A triorganosilyl ester-containing copolymer (A) obtained from a mixture of the methacrylic acid triorganosilyl ester monomer and a copolymerizable ethylenically unsaturated monomer is contained.
- the glass transition temperature (Tg) of the copolymer (A) is preferably about 30 to 80 ° C., more preferably about 35 to 70 ° C.
- Tg is about 30 to 80 ° C.
- the coating film hardness is hardly affected by the water temperature or air temperature, and can maintain appropriate hardness and toughness for a long period of time, so that cold flow, cracks, peeling, etc. It is difficult for the coating film abnormality to occur.
- the weight average molecular weight (Mw) of the copolymer (A) is about 20,000 to 70,000, preferably about 30,000 to 60,000.
- Mw is about 20,000 to 70,000, the physical properties of the coating film (hardness and toughness of the coating film) are good (because cracks and peeling are not likely to occur), so it will exhibit an antifouling effect for a long time. it can.
- Examples of the measuring method of Mw include gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- Mw is displayed as a value (polystyrene conversion value) obtained by creating and measuring a calibration curve using polystyrene as a standard substance.
- the copolymer (A) is obtained by copolymerization of the monomer (a) and the monomer (b).
- the copolymerization ratio of these monomers is generally proportional to the ratio of the content of each monomer in the mixture described in the item “Synthesis of triorganosilyl ester-containing copolymer (A)” below.
- the copolymer (A) may be any copolymer of a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer.
- Methacrylic acid triorganosilyl ester monomer examples include, for example, isopropyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1, Examples thereof include 1-dimethylpropyl group, 1,1-dimethylbutyl group, texyl group and the like.
- R 2 , R 3 and R 4 are the same or different and are preferably an isopropyl group, a s-butyl group, a t-butyl group and a phenyl group. And a phenyl group are more preferable.
- Examples of the monomer (a) include triisopropylsilyl methacrylate, tris-butylsilyl methacrylate, triphenylsilyl methacrylate, diisopropyl s-butylsilyl methacrylate, diisopropyl t-butylsilyl methacrylate, diisopropyltexyl methacrylate.
- Examples thereof include silyl, diisopropylphenylsilyl methacrylate, isopropyl dis-butylsilyl methacrylate, isopropyl diphenylsilyl methacrylate, diphenylhexylsilyl methacrylate, and t-butyldiphenylsilyl methacrylate.
- triisopropylsilyl methacrylate, tris-butylsilyl methacrylate, and t-butyldiphenylsilyl methacrylate are preferred because they are less likely to cause abnormal coating and can form an antifouling coating having excellent water resistance. More preferred are triisopropylsilyl acid and t-butyldiphenylsilyl methacrylate. These methacrylic acid triorganosilyl ester monomers are used alone or in combination of two or more.
- Ethylenically unsaturated monomer (b) The mixture further contains another ethylenically unsaturated monomer (b) copolymerizable with the monomer (a).
- Examples of the monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and (meth) acrylic acid t.
- (meth) acrylic acid esters are particularly preferred, and are methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) acrylic acid.
- 2-Ethylhexyl and 2-methoxyethyl acrylate are more preferred.
- the exemplified monomer (b) can be used alone or in combination of two or more as the monomer component of the copolymer (A).
- the copolymer (A) is obtained from a mixture of the monomer (a) and the monomer (b).
- the content of the monomer (a) in the mixture is preferably about 45 to 65% by weight, more preferably about 50 to 60% by weight.
- the coating film formed using the resulting antifouling coating composition exhibits stable coating film solubility, and is antifouling for a long time. Performance can be maintained.
- the copolymer (A) can be obtained by polymerizing the monomer (a) and the monomer (b) in the mixture.
- the polymerization is performed, for example, in the presence of a polymerization initiator.
- polymerization initiator examples include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile, dimethyl-2,2′-azobisisobutyrate.
- Azo compounds such as: peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexanoate, etc. Is mentioned.
- These polymerization initiators can be used alone or in combination of two or more.
- 2,2′-azobisisobutyronitrile and t-butylperoxy-2-ethylhexanoate are particularly preferable.
- the molecular weight of the triorganosilyl ester-containing copolymer can be adjusted by appropriately setting the amount of the polymerization initiator used.
- polymerization method examples include solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization.
- solution polymerization is particularly preferable in that the copolymer (A) can be synthesized easily and accurately.
- an organic solvent may be used as necessary.
- the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate; isopropyl
- examples include alcohol solvents such as alcohol and butyl alcohol; ether solvents such as dioxane, diethyl ether, and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
- an aromatic hydrocarbon solvent is particularly preferable, and xylene is more preferable. These solvents can be used alone or in combination of two or more.
- the reaction temperature in the polymerization reaction may be appropriately set according to the type of the polymerization initiator and the like, and is usually about 70 to 140 ° C., preferably about 80 to 120 ° C.
- the reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually about 4 to 8 hours.
- the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas.
- the antifouling coating composition of the present invention comprises 80% by weight or more, preferably two or more selected from the group consisting of dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid and dihydropimaric acid. It contains a modified rosin salt which is a salt of 85 to 100% by weight of the modified rosin and zinc and / or copper.
- a certain modified rosin salt it is possible to form an antifouling coating film in which slime adhesion is prevented or suppressed.
- the reason why slime adhesion to the coating film is prevented or suppressed by the modified rosin salt is considered to be a combined effect by including two or more kinds of the resin acids.
- even when immersed in seawater for a long period of time it is possible to suitably form an antifouling coating film that is resistant to coating film abnormalities such as hair cracks and maintains antifouling performance for a long period of time.
- the modified rosin in the modified rosin salt (B) has two or more contents selected from the group consisting of dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid and dihydropimaric acid.
- the amount is less than 80% by weight, the slime tends to adhere to the formed antifouling coating film, and the fuel efficiency is deteriorated during long-term navigation.
- the antifouling coating film tends to crack.
- the crack can be improved somewhat by using a plasticizer in combination, hair cracks (fine cracks) cannot be avoided, and once a hair crack occurs on the surface of the coating film, seawater tends to penetrate gradually.
- Resin acids conventionally used in the field of ship bottom coatings include rosin, hydrogenated rosin, disproportionated rosin, and the like, which are different from the modified rosin salt (B) in its components.
- a rosin such as gum rosin, wood rosin or tall oil rosin contains 65 to 80% by weight of a resin acid having a highly reactive conjugated diene structure in an abietan skeleton such as abietic acid, neoabietic acid, and parastrinic acid.
- the resin acid having no reactive conjugated diene structure in the pimarane skeleton such as pimaric acid and isopimaric acid is contained only about 10 to 25% by weight.
- the hydrogenated rosin and the disproportionated rosin contain about 25 to 50% by weight of a resin acid having a highly reactive conjugated diene structure in an abitane skeleton such as abietic acid, neoabietic acid, and parastrinic acid.
- Resin acids that do not have a highly reactive conjugated diene structure in the abietane skeleton such as tetrahydroabietic acid and dehydroabietic acid are only contained in an amount of about 40 to 65% by
- modified rosin means a material obtained by modifying rosin, and is obtained by hydrogenating or disproportionating rosin.
- modified rosin salt means that each component in the modified rosin forms a salt.
- a resin acid having a highly conjugated diene structure in a diterpene skeleton such as an abiethane skeleton is referred to as a “conjugated diene resin acid” and is reactive in a diterpene skeleton such as an abiethane skeleton or a pimalane skeleton.
- the resin acid having no high conjugated diene structure is referred to as “non-conjugated diene resin acid”.
- the conjugated diene resin acid since the conjugated diene resin acid has a highly reactive conjugated diene structure (conjugated double bond) in the diterpene skeleton, there is a drawback that it is easily oxidized and deteriorated.
- non-conjugated diene resin acids do not have a highly reactive conjugated diene structure in the diterpene skeleton.
- the non-conjugated diene resin acid includes a resin acid having no double bond in the diterpene skeleton, a resin acid having only one double bond, and two double bonds.
- a resin acid having a double bond that is not conjugated (not a conjugated diene), and at least a resin acid that includes three double bonds and that is stabilized by linking the three double bonds to form a benzene ring.
- One resin acid or the like is included.
- non-conjugated diene resin acids that do not have a highly reactive conjugated diene structure in the diterpene skeleton are less reactive and less susceptible to oxidative degradation than conjugated diene resin acids.
- the modified rosin that forms the modified rosin salt (B) is a non-conjugated diene resin acid, which is selected from the group consisting of dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid, and dihydropimaric acid.
- the total content of the non-conjugated diene resin acids in the modified rosin is 80% by mass or more, including two or more selected.
- the modified rosin forming the modified rosin salt (B) is selected from the group consisting of dihydroabietic acid, tetrahydroabietic acid and dehydroabietic acid among the non-conjugated diene resin acids contained in two or more kinds. It is preferable to contain at least one kind.
- the composition of this invention is excellent in long-term storage property.
- the modified rosin in the modified rosin salt (B) it is desirable not to contain conjugated diene resin acids such as abietic acid, neoabietic acid, and parastrinic acid as much as possible.
- the content of the conjugated diene resin acid in the modified rosin is less than 20% by weight, preferably less than 10% by weight.
- the crack resistance and slime resistance of the antifouling coating film may be lowered.
- the modified rosin salt (B) can be prepared, for example, by the following method (I) or (II).
- the hydrogenation reaction produces dihydroabietic acid, tetrahydroabietic acid, dihydropimaric acid and the like as non-conjugated diene resin acids.
- metal catalyst examples include palladium, platinum, nickel and the like. What is necessary is just to set the usage-amount of a catalyst suitably in consideration of hydrogenation efficiency etc.
- rosin examples include gum rosin, wood rosin, tall oil rosin and the like. These can be used individually by 1 type or in combination of 2 or more types.
- the hydrogen pressure is preferably about 0.1 to 20 MPa.
- the reaction temperature in the hydrogenation reaction is usually about room temperature (20 ° C.) to about 300 ° C.
- the reaction time in the hydrogenation reaction can be appropriately set according to the amount of non-conjugated diene resin acid produced.
- the reaction between the obtained modified rosin and the copper compound or zinc compound may be performed according to a known method.
- a method of reacting the modified rosin with a copper compound or a zinc compound while heating in a solvent for example, at about 70 to 80 ° C.
- Examples of the copper compound include copper hydroxide and cuprous oxide. These can be used individually by 1 type or in combination of 2 or more types.
- Examples of the zinc compound include zinc oxide and zinc carbonate. These can be used individually by 1 type or in combination of 2 or more types.
- the amount of the copper compound and the zinc compound used is not particularly limited, and may be set so that all of the resin acid forms a copper salt or a zinc salt.
- the solvent is not particularly limited as long as it does not inhibit the reaction.
- xylene, methanol, etc. are mentioned. These can be used alone or as a mixed solvent of two or more.
- dehydroabietic acid dihydroabietic acid, pimaric acid, isopimaric acid, dihydropimaric acid and the like are generated as non-conjugated diene resin acids.
- the catalyst examples include palladium carbon, nickel, iodine and the like. These can be used individually by 1 type or in combination of 2 or more types in the range which does not inhibit reaction. What is necessary is just to set the usage-amount of a catalyst suitably considering reaction efficiency etc.
- the disproportionation reaction is preferably performed in an inert gas (nitrogen gas) atmosphere.
- the reaction temperature in the disproportionation reaction is preferably about 200 to 300 ° C.
- the reaction time in the disproportionation reaction can be appropriately set according to the amount of non-conjugated diene resin acid produced.
- the reaction between the obtained modified rosin and the copper compound or zinc compound may be performed according to a known method.
- the method described in (I) above can be employed.
- the content ratio of the copolymer (A) and the modified rosin salt (B) in the antifouling coating composition of the present invention is a weight ratio (the copolymer (A) / the modified rosin salt (B )) Is preferably about 85/15 to 20/80, more preferably about 70/30 to 40/60.
- the content ratio is about 85/15 to 20/80 by weight, an antifouling coating film that is not easily affected by the temperature of seawater and exhibits a stable coating film dissolution rate even when the seawater temperature is high can be suitably formed.
- an antifouling coating film having an appropriate coating film hardness and having excellent toughness and water resistance can be suitably formed.
- the composition of the present invention preferably contains substantially no rosin or rosin derivative having a free carboxyl group.
- the content of the rosin and rosin derivative in the composition of the present invention is preferably about 1% by weight or less, more preferably about 0 to 0.1% by weight.
- Rosin and rosin derivatives having a free carboxyl group are highly hydrophilic. Therefore, when the said coating film contains the rosin and rosin derivative which have the said free carboxyl group, there exists a possibility that the water resistance of a coating film may fall and abnormality, such as a blister and a crack, may arise in a coating film.
- the coating composition of the present invention preferably further contains cuprous oxide.
- cuprous oxide By containing cuprous oxide, the formed coating film can exhibit antifouling performance more effectively.
- the cuprous oxide can serve as an antifouling agent.
- the shape of the cuprous oxide is not particularly limited as long as it does not hinder the effects of the present invention. For example, a particulate thing can be used as cuprous oxide.
- the average particle size of cuprous oxide is preferably about 3 to 30 ⁇ m.
- cuprous oxide having an average particle size of about 3 to 30 ⁇ m is contained, the dissolution rate of the coating film can be suitably suppressed and the antifouling effect can be sufficiently exhibited for a long period of time.
- the cuprous oxide is preferably one whose periphery is coated with a coating agent.
- a coating agent For example, when using a particulate thing as said cuprous oxide, it is preferable to coat the surface of each particle
- Examples of the coating agent include stearic acid, lauric acid, glycerin, sucrose, lecithin and the like. About these coating agents, 1 type can be used individually or in mixture of 2 or more types.
- the composition of the present invention preferably contains about 100 to 450 parts by weight of the cuprous oxide based on a total amount of 100 parts by weight of the copolymer (A) and the modified rosin salt (B). More preferably, about 400 parts by weight is included.
- the cuprous oxide is contained in an amount of about 100 to 400 parts by weight with respect to the total amount of 100 parts by weight, the coating film can suitably exhibit an antifouling effect.
- composition of the present invention may further contain an inorganic antifouling agent other than the cuprous oxide as long as it does not inhibit the antifouling effect.
- an inorganic antifouling agent include copper thiocyanate (generic name: rhodan copper), cupronickel, copper powder, and the like. These can be used alone or in combination of two or more.
- the coating composition of the present invention preferably further contains an organic antifouling agent.
- the organic antifouling agent is not particularly limited as long as the organic antifouling agent is a substance having a killing or repelling action against marine fouling organisms.
- organic copper compounds such as 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione); 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylenebisdithiocarbamate (generic name: Dinebu ), Bis (dimethyldithiocarbamate) zinc (generic name: diram), bis (dimethyldithiocarbamate), ethylenebis (dithiocarbamate) dizinc (generic name: polycarbamate), etc .; pyridine triphenylborane, 4 Organic boron compounds such as isopropylpyridyl-diphenylmethylborane, 4-phenylpyridyl-diphenylborane, triphenylboron-n-octadecylamine, triphenyl [3- (2-ethylhexyloxy) propylamine] boron; 6-G Maleimide
- organic antifouling agents are used in combination with the above cuprous oxide to further enhance the antifouling effect, so that the antifouling effect can be maintained with a small amount of use even in the sea area where fouling organisms are active. .
- These organic antifouling agents can be used alone or in combination of two or more.
- the content of the organic antifouling agent in the coating composition of the present invention is 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the copolymer (A) and the modified rosin salt (B). About 10 to 30 parts by weight is more preferable.
- the amount is less than 1 part by weight, the antifouling effect by the organic antifouling agent cannot be exhibited sufficiently.
- the amount exceeds 50 parts by weight the antifouling effect is not improved by increasing the content of the organic antifouling agent, which is economically wasteful.
- the coating composition of the present invention may further contain known additives such as a plasticizer, a dehydrating agent, a dispersant, and a known pigment.
- the plasticity of the coating composition can be improved, and as a result, a tough coating can be suitably formed.
- the plasticizer include phosphate esters such as tricresyl phosphate, trioctyl phosphate, and triphenyl phosphate; phthalate esters such as dibutyl phthalate and dioctyl phthalate; adipic acid such as dibutyl adipate and dioctyl adipate Esters; sebacic acid esters such as dibutyl sebacate and dioctyl sebacate; epoxidized oils and fats such as epoxidized soybean oil and epoxidized linseed oil; alkyl vinyl ether polymers such as methyl vinyl ether polymer and ethyl vinyl ether polymer; polyethylene Polyalkylene glycols such as glycol and polypropylene glycol; t-nonyl pentasulfide, petrolatum,
- tricresyl phosphate, epoxidized soybean oil and epoxidized linseed oil are preferable. Particularly preferred are epoxidized soybean oil and epoxidized linseed oil.
- These plasticizers not only improve the physical properties of the coating film, but also improve the water resistance and prevent the penetration of seawater into the coating film, thus preventing coating abnormalities such as cracks and blisters even in high temperature sea areas. I can do it.
- These plasticizers can be used alone or in combination of two or more.
- the content of the plasticizer in the composition of the present invention depends on the content of the modified rosin salt (B), but the total amount of the copolymer (A) and the modified rosin salt (B) is 100 wt.
- the amount is preferably about 1 to 50 parts by weight, and more preferably about 5 to 30 parts by weight. When the amount is less than 1 part by weight, the effect of improving the physical properties (toughness and adhesiveness) of the coating film does not appear.
- the coating composition of the present invention preferably further contains a dehydrating agent.
- the dehydrating agent is a drug for removing water in the coating composition.
- Examples of the water removing agent include a water binder and a dehydrating agent. About a water binder and a dehydrating agent, you may use individually, respectively, and may use both together.
- the water binder is a compound having a property of removing water in the coating composition by reacting with water.
- orthoformate alkyl esters such as methyl orthoformate and ethyl orthoformate; tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrakis (2-ethoxybutoxy) silane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldi
- alkoxysilanes such as ethoxysilane, trimethylethoxysilane, and diphenyldiethoxysilane; and acid anhydrides such as maleic anhydride and phthalic anhydride.
- the dehydrating agent is a compound having a property of removing water in the composition by incorporating water as crystal water.
- Examples thereof include anhydrous gypsum, molecular sieve, magnesium sulfate, sodium sulfate and the like.
- the content of the dehydrating agent in the composition of the present invention is not particularly limited, but is 1 to 50 with respect to 100 parts by weight of the total amount of the copolymer (A) and the modified rosin salt (B). About 2 parts by weight is preferable, and about 2 to 30 parts by weight is more preferable. When the content of the dehydrating agent is about 1 to 50 parts by weight with respect to the total amount of 100 parts by weight, the storage stability of the coating composition of the present invention is further improved.
- the antifouling coating composition of the present invention preferably further contains a dispersant (anti-settling agent).
- a dispersant antioxidant-settling agent
- the components in the composition for example, the cuprous oxide, the following pigments, etc.
- a hard cake hard precipitate
- the problem that the said composition (paint) droops can be solved effectively.
- dispersant examples include polyethylene oxide dispersants, fatty acid amide dispersants, fatty acid ester dispersants, hydrogenated castor oil dispersants, vegetable polymer oil dispersants, polyether ester surfactants, sulfuric acid Ester-type anionic surfactant, polycarboxylic acid amine salt-based dispersant, polycarboxylic acid-based dispersant, polymer polyether-based dispersant, acrylic polymer-based dispersant, special silicon-based dispersant, talc-based dispersant, Examples thereof include bentonite-based dispersants, kaolinite-based dispersants, and silica gel-based dispersants. These dispersants can be used alone or in combination of two or more.
- the coating composition of the present invention preferably contains a fatty acid amide dispersant as the dispersant.
- the coating composition of the present invention is produced, for example, by preparing a mixed solution containing the copolymer (A) and the like and then mixing and dispersing the mixed solution.
- the said liquid mixture contains the said fatty acid amide type dispersing agent, the storage stability of this liquid mixture can be improved, and the composition of this invention can be obtained more simply and reliably.
- a commercially available dispersant can be used as the dispersant.
- the fatty acid amide-based dispersant for example, Disparon A603-10X (or 20X), Disparon A630-10X (or 20X), Disparon 6900-10X (or 20X), Disparon 6810-10X (or 20X) (all (Enomoto Kasei Co., Ltd.), Talen 7500-20, Flownon SP-1000 (all manufactured by Kyoeisha Chemical Co., Ltd.), etc.
- Dispalon A603-10X (or 20X) is preferable. Since these dispersants do not contain a hydrophilic solvent such as methanol or ethanol, the storage stability of the antifouling coating composition can be further improved.
- the dispersant can be used by dispersing in a hydrophobic organic solvent such as xylene.
- the content of the dispersant in the coating composition of the present invention is not particularly limited, but is 1 to 50 weights with respect to 100 parts by weight of the total amount of the copolymer (A) and the modified rosin salt (B). About 2 to 30 parts by weight is more preferable.
- the content of the dispersing agent is about 1 to 50 parts by weight with respect to 100 parts by weight of the total amount, the effect of using the dispersing agent (that is, the effect of suppressing hard cake formation) is suitably exhibited, and the present invention The storage stability of the coating composition is further improved.
- the coating composition of the present invention preferably further contains a known pigment.
- the pigment include inorganic pigments such as zinc oxide, bengara, talc, titanium oxide, silica, bentonite, dolomite, calcium carbonate, and barium sulfate, and organic pigments exhibiting red, blue, and the like. These pigments can be used alone or in combination of two or more. In particular, by containing zinc oxide, dissolution of the coating film can be promoted and the renewability of the coating film can be enhanced.
- the content of the pigment in the coating composition of the present invention is not particularly limited.
- the content of the zinc oxide is preferably about 1 to 100 parts by weight, preferably about 10 to 75 parts by weight with respect to 100 parts by weight of the total amount of the copolymer (A) and the modified rosin salt (B). Is more preferable.
- the content of the zinc oxide exceeds 20 parts by weight with respect to the total amount of 100 parts by weight, it may be difficult to control dissolution in a high-temperature sea area due to increased penetration of seawater into the coating film.
- the antifouling paint composition of the present invention may further contain those commonly used as additives for paints such as dyes, anti-coloring agents, and antifoaming agents. .
- the coating composition of the present invention is usually dissolved or dispersed in an organic solvent.
- an organic solvent examples include xylene, toluene, mineral spirit, MIBK, butyl acetate and the like. Among these, xylene or MIBK is particularly preferable.
- These organic solvents can be used alone or in admixture of two or more.
- the antifouling coating composition of the present invention for example, the copolymer (A), the modified rosin salt (B), and, if necessary, known additives such as the cuprous oxide and the plasticizer in a solvent. It can manufacture by mixing with.
- the amount of the copolymer (A), the modified rosin salt (B), etc. used is the content of the modified rosin salt (B) described in the item of the antifouling coating composition, respectively. What is necessary is just to adjust suitably.
- solvent examples include xylene, toluene, mineral spirit, MIBK, butyl acetate and the like. Of these, xylene is particularly preferable. These solvents can be used alone or in admixture of two or more.
- various materials such as the copolymer (A) may be dissolved or dispersed in a solvent in advance. It is preferable to make it.
- the copolymer (A) and the modified rosin salt (B) may be mixed with other materials (such as the organic antifouling agent) in a state of being dissolved or dispersed in a solvent.
- the solvent may be used as the solvent.
- a known disperser can be used.
- the disperser for example, one that can be used as a fine pulverizer can be suitably used.
- a mill or a dissolver can be used.
- a mill for example, a mill generally used for mixing and dispersing paints such as a ball mill, a sand mill, a bead mill, a pearl mill, a dyno mill, a cowless mill, a basket mill, and an attritor can be used.
- the dissolver is a disperser provided with a rotary blade type grinder, and the mixed liquid can be mixed and dispersed by rotating the grinder.
- the dissolver is sometimes called a disper.
- cuprous oxide In the case of containing cuprous oxide, it is desirable to change the order of addition and mixing conditions of cuprous oxide according to the average particle size of the cuprous oxide used.
- cuprous oxide having an average particle size of about 3 to 10 ⁇ m, preferably about 3 to 8 ⁇ m is used as cuprous oxide
- the copolymer (A), the modified rosin salt (B), the suboxide It is preferable to mix and disperse the copper oxide and, if necessary, a known additive after mixing with the disperser.
- Cuprous oxide having an average particle size of about 3 to 10 ⁇ m tends to cause secondary aggregation. For this reason, simply mixing each material containing cuprous oxide may cause lumps in the resulting composition, resulting in cracks and the like in the formed coating film. Mixing a liquid mixture containing cuprous oxide with an average particle size of about 3 to 10 ⁇ m using a disperser, and dispersing the cuprous oxide and the like in the liquid mixture breaks the secondary agglomerated cuprous oxide.
- an antifouling coating composition in which the cuprous oxide is suitably dispersed can be obtained.
- the grinder of the dissolver When using a dissolver as the disperser, it is preferable to rotate the grinder of the dissolver at high speed. By rotating the grinder at a high speed, the secondary agglomerated cuprous oxide can be suitably broken.
- cuprous oxide having an average particle size of about 10 to 20 ⁇ m, preferably about 13 to 20 ⁇ m is used as the cuprous oxide
- the copolymer (A), the modified rosin salt (B) It is preferable to add and mix the cuprous oxide after mixing and dispersing known additives by the disperser.
- Cuprous oxide having an average particle size of about 10 to 20 ⁇ m is relatively less likely to agglomerate. Therefore, after the mixed solution containing the copolymer (A) and the modified rosin salt (B) is mixed and dispersed using a disperser, the cuprous oxide is added to the obtained mixed dispersion, It is desirable to mix using a mixing device so that the copper oxide particles are not pulverized as much as possible. According to this method, since the cuprous oxide is hardly pulverized, the surface area of the cuprous oxide in the obtained composition can be kept in a relatively small range.
- the specific surface area of the cuprous oxide can be limited to about 1.3 ⁇ 10 ⁇ 3 mm 2 or less, preferably about 3.0 ⁇ 10 ⁇ 4 to 1.3 ⁇ 10 ⁇ 3 mm 2 .
- the surface area of the cuprous oxide is small, the dissolution rate of the coating film can be effectively suppressed even when the temperature of the seawater is high.
- the processing time by the said disperser can be shortened and the manufacturing cost of the composition of this invention can be held down.
- the grinder when using a dissolver as the disperser, is preferably rotated at a medium speed or a low speed. By rotating at a medium or low speed, pulverization of the cuprous oxide can be effectively prevented.
- the antifouling treatment method of the present invention is characterized in that an antifouling coating film is formed on the surface of an object to be coated using the antifouling coating composition.
- the antifouling coating film gradually dissolves from the surface and the coating film surface is constantly renewed, thereby preventing the adhesion of chickenpox fouling organisms.
- the antifouling effect can be exhibited continuously by overcoating the said composition.
- Examples of the coating film formation include ships (particularly ship bottom), fishing equipment, underwater structures, and the like.
- Examples of the fishery tools include aquaculture or stationary fishing nets, fishing net accessories such as floats and ropes used in the fishing nets, and the like.
- Examples of the underwater structure include a power plant conduit, a bridge, a port facility, and the like.
- the antifouling coating film of the present invention can be formed by applying the above antifouling coating composition to the surface (entirely or partly) of the coating film forming article.
- Examples of the coating method include brush coating, spraying, dipping, flow coating, and spin coating. These may be used alone or in combination of two or more.
- the drying temperature may be room temperature. What is necessary is just to set drying time suitably according to the thickness etc. of a coating film.
- the thickness of the antifouling coating film may be appropriately set according to the type of coating film forming object, the navigation speed of the ship, the seawater temperature, and the like.
- the thickness of the antifouling coating film is usually 50 to 500 ⁇ m, preferably 100 to 400 ⁇ m.
- the antifouling coating film of the present invention is 1) excellent in water resistance, so even if it is in contact with seawater for a long time, cracks, peeling, etc. hardly occur, and hair cracks hardly occur. 2) Appropriate hardness It has the advantage that it does not easily cause coating film abnormalities such as cold flow, 3) has high adhesion to the coating film formation, and 4) it has almost no slime even when immersed in seawater for a long time. .
- the coated product of the present invention has the antifouling coating film on the surface.
- the coated product of the present invention may have the antifouling coating film on the entire surface or a part thereof.
- the coated product of the present invention has an antifouling coating film having the advantages 1) to 4), it can be suitably used as the above-mentioned ship (especially ship bottom), fishing equipment, underwater structure and the like.
- the antifouling coating film when the antifouling coating film is formed on the ship bottom surface of the ship, the antifouling coating film gradually dissolves from the surface, and the coating film surface is constantly updated, thereby preventing adhesion of waterpox fouling organisms. it can.
- the antifouling coating film has a suitably controlled hydrolysis rate in seawater. Therefore, the ship can maintain antifouling performance for a long period of time. For example, even in a stationary state such as during berthing or during outfitting, there is little adhesion and accumulation of Minamata fouling organisms, and the antifouling effect can be exhibited for a long period of time.
- the antifouling coating on the surface basically does not crack or peel off. Therefore, it is not necessary to perform another operation such as forming a coating film after the coating film is completely removed. Therefore, an antifouling coating film can be suitably formed by directly overcoating the antifouling coating film composition. Thereby, it is possible to easily and continuously maintain the antifouling performance at a low cost.
- the viscosity is a measured value at 25 ° C., and is a value determined by a B-type viscometer.
- the weight average molecular weight (Mw) is a value (polystyrene conversion value) determined by GPC.
- the conditions of GPC are as follows. Equipment: HLC-8220GPC manufactured by Tosoh Corporation Column: TSKgel SuperHZM-M (Tosoh Corporation) 2 flow rate: 0.35 mL / min Detector ... RI Column thermostatic chamber temperature: 40 ° C Free liquid ... THF
- the heating residue is a value obtained by heating at 110 ° C. for 3 hours.
- the unit of the blending amount of each component in Table 1 is “g”.
- Production Example 1 (Production of Copolymer Solution A-1) After charging 230 g of xylene into a 1000 ml flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel, 270 g of triisopropylsilyl methacrylate and methyl methacrylate were stirred at 100 ⁇ 2 ° C. in a nitrogen atmosphere. A mixed solution of 50 g, 2-methoxyethyl methacrylate 130 g, 2-methoxyethyl acrylate 30 g, ethyl acrylate 20 g, and t-butylperoxy 2-ethylhexanoate 4 g (initial addition) was added dropwise over 1 hour. .
- Triorganosilyl ester-containing copolymer solutions A-2 to A-6 are obtained by conducting a polymerization reaction in the same manner as in Production Example 1 using the organic solvent, monomer, and polymerization initiator shown in Table 1. Obtained. Table 1 shows the viscosity, heating residue, Mw, and Tg of each copolymer solution obtained.
- a portion of this modified rosin is methylated with diazomethane and gas chromatography (column: diethylene glycol succinate (GEGS), 0.24 mm ⁇ ⁇ 25 m, column temperature: 200 ° C., carrier gas: nitrogen, detector: hydrogen flame ion) Component analysis was performed with a detector (FID).
- the content of the non-conjugated diene resin acid in the modified rosin was 87.8% by weight (62.8% by weight dehydroabietic acid, 15.2% by weight dihydroabietic acid, 9.8% by weight dihydropimaric acid). Met.
- the obtained modified rosin was dissolved in xylene to obtain a xylene solution having a solid content of 50%.
- 400 g of the xylene solution was put into a flask, 200 g of cuprous oxide was added so that all the resin acids in the modified rosin formed a copper salt, and 100 g of methanol was further added and mixed uniformly.
- an appropriate amount (about 400 ml) of glass beads (diameter 2.5 to 3.5 mm) was added, stirred at 70 to 80 ° C. for 8 hours, and then kept at 50 ° C. for 2 days.
- the obtained mixed solution was cooled to room temperature (25 ° C.), filtered, and then concentrated under reduced pressure to distill off the methanol component.
- xylene is added to the obtained concentrated solution to obtain a xylene solution of a modified rosin copper salt containing a copper salt of the non-conjugated diene resin acid (dark blue transparent solution, solid content of about 50%) B-1. Obtained.
- the heating residue of the obtained xylene solution was 50.5%.
- Production Example 8 (Production of modified rosin zinc salt xylene solution B-2)
- 400 g of the xylene solution of the modified rosin obtained in Production Example 7 (solid content 50%) was placed in the flask.
- 100 g of zinc oxide was added so that the resin acid would completely form a zinc salt, and the mixture was refluxed and dehydrated at 70 to 80 ° C. for 3 hours.
- the mixture was cooled and filtered to obtain a xylene solution of a modified rosin zinc salt containing a zinc salt of the non-conjugated diene resin acid (dark brown transparent solution, solid content about 50%) B-2.
- the heating residue of the obtained xylene solution was 50.9%.
- a part of the modified rosin was subjected to component analysis in the same manner as in Production Example 7.
- the content of the non-conjugated diene resin acid in the modified rosin was 89.8% by weight (dihydroabietic acid 60.4% by weight, tetrahydroabietic acid 19.3% by weight, dihydropimaric acid 10.1% by weight) Met.
- the obtained modified rosin was dissolved in xylene to obtain a xylene solution having a solid content of 50%.
- 400 g of the xylene solution was put into a flask, 200 g of cuprous oxide was added so that all the resin acids in the modified rosin formed a copper salt, and 100 g of methanol was further added and mixed uniformly.
- an appropriate amount (about 400 ml) of glass beads (diameter 2.5 to 3.5 mm) was added, stirred at 70 to 80 ° C. for 8 hours, and then kept at 50 ° C. for 2 days.
- the obtained mixed solution was cooled to room temperature (25 ° C.), filtered, and then concentrated under reduced pressure to distill off the methanol component.
- xylene is added to the obtained concentrated solution to obtain a xylene solution of a modified rosin copper salt containing a copper salt of the non-conjugated diene resin acid (dark blue transparent solution, solid content of about 50%) B-3. Obtained.
- the heating residue of the obtained xylene solution was 50.3%.
- Production Example 10 (Production of modified rosin zinc salt xylene solution B-4)
- a 1000 ml flask equipped with a thermometer, a reflux condenser and a stirrer 400 g of the xylene solution of the modified rosin obtained in Production Example 9 (solid content 50%) was placed in the flask.
- 100 g of zinc oxide was added so that the resin acid would completely form a zinc salt, and the mixture was refluxed and dehydrated at 70 to 80 ° C. for 3 hours.
- a part of the resin acid was subjected to component analysis in the same manner as in Production Example 7.
- the content of the non-conjugated diene resin acid in the resin acid is 47.3% by weight (dehydroabietic acid 35.5% by weight, dihydroabietic acid 5.3% by weight, dihydropimaric acid 6.5% by weight). there were.
- the obtained resin acid was dissolved in xylene to obtain a xylene solution having a solid content of 50%.
- 400 g of the xylene solution was put in a flask, 200 g of cuprous oxide was added so that all the resin acids formed a copper salt, and 100 g of methanol was further added and mixed uniformly.
- an appropriate amount (about 400 ml) of glass beads (diameter 2.5 to 3.5 mm) was added, stirred at 70 to 80 ° C. for 8 hours, and then kept at 50 ° C. for 2 days.
- the obtained mixed solution was cooled to room temperature (25 ° C.), filtered, and then concentrated under reduced pressure to distill off the methanol component.
- xylene was added to the resulting concentrated liquid to obtain a xylene solution (dark blue transparent solution, solid content about 50%) R-3 containing the copper salt of the non-conjugated diene resin acid.
- the heating residue of the obtained xylene solution was 51.2%.
- Comparative Production Example 4 (Production of resin acid zinc salt xylene solution R-4)
- 400 g of the xylene solution of resin acid (solid content 50%) obtained in Comparative Production Example 3 was placed in the flask, and all the resin acid was zinc.
- 100 g of zinc oxide was added so as to form a salt, followed by reflux dehydration at 70 to 80 ° C. for 3 hours. Thereafter, the mixture was cooled and filtered to obtain a xylene solution (dark brown transparent solution, solid content about 50%) R-4 containing a zinc salt of the non-conjugated diene resin acid.
- the heating residue of the obtained xylene solution was 50.9%.
- Examples 1 to 7 and Comparative Examples 1 to 5 Manufacture of coating compositions
- the components shown in Table 2 were blended in the proportions (% by weight) shown in Table 2, and mixed and dispersed with glass beads having a diameter of 1.5 to 2.5 mm to produce a coating composition.
- Test Example 1 (Paint stability test) The coating compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were put in a 100 ml wide-mouth tin can, sealed, and stored in a thermostat at 40 ° C. for 1 month, and then the viscosity of the coating composition was changed to B Measured with a viscometer.
- Test example 2 film hardness
- the coating compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were applied on a transparent glass plate (75 ⁇ 150 ⁇ 1 mm) so that the thickness as a dry coating film was about 100 ⁇ m, and the coating composition was obtained at 40 ° C. Dried for 1 day.
- the coating film hardness of the obtained dried coating film was measured at 25 ° C. using a pendulum type hardness meter (pendulum hardness meter).
- the results (count number) are shown in Table 3. A count number of 20 to 50 is practically preferable.
- Test Example 3 Coating adhesion test
- a coating adhesion test was performed in accordance with the provisions of JIS K-5600-5-6. Specifically, the coating compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were dried on a blasted tin plate (75 ⁇ 150 ⁇ 2 mm) with a dry coating thickness of about 100 ⁇ m. After being applied and dried at 40 ° C. for 1 day, an adhesion test was conducted.
- Test Example 4 Coating film flexibility test
- the coating compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were applied to a blasted tin plate (75 ⁇ 150 ⁇ 2 mm) so that the dry coating thickness was about 100 ⁇ m. After drying at 0 ° C. for 1 day, the state of the folded coating film was confirmed by visual observation at 90 degrees.
- Test Example 5 (Rotary test) A rotating drum having a diameter of 515 mm and a height of 440 mm was attached to the center of the water tank so that it could be rotated by a motor. In addition, a cooling device for keeping the temperature of the seawater constant and an automatic pH controller for keeping the pH of the seawater constant were attached.
- a rust preventive coating film was formed by applying and drying a rust preventive paint (vinyl A / C) on a hard PVC plate (75 ⁇ 150 ⁇ 1 mm) so that the thickness after drying was about 50 ⁇ m. Thereafter, the coating compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were applied on the rust-preventing coating film so that the thickness after drying was about 300 ⁇ m. The obtained coated material was dried at 40 ° C. for 3 days to prepare a test plate having a dry coating film having a thickness of about 300 ⁇ m.
- One of the produced test plates was fixed to the rotating drum of the rotating device of the above apparatus so as to contact seawater, and the rotating drum was rotated at a speed of 20 knots. Meanwhile, the temperature of the seawater was kept at 25 ° C. and the pH was kept at 8.0 to 8.2, and the seawater was changed every week.
- the film thickness per month ( ⁇ m / month) is determined by measuring the residual film thickness of each test plate every 3 months after the start of the test with a laser focus displacement meter and calculating the dissolved film thickness from the difference. ) In addition, the said measurement was performed for 24 months and the said coating-film melt
- Table 4 shows that the coating films formed using the coating compositions of the present invention (Examples 1 to 7) have a dissolution amount in seawater of about 2 to 5 ⁇ m per month (annual average). Recognize. Further, it can be seen that the coating film formed using the coating composition of the present invention is stably dissolved for a long period of time because the coating film dissolution rate is suppressed to some extent. And since the coating film formed using the coating composition of this invention is excellent in water resistance, and does not produce a crack, a hair crack, etc., it can maintain antifouling performance for a long period of time.
- the coating films formed using the coating compositions of Comparative Examples 1, 2, and 5 have low water resistance, coating film abnormalities such as cracks and peeling occur during the test. Moreover, although the coating film formed using the coating composition of Comparative Examples 3 and 4 has good water resistance, hair cracks (fine cracks) occur after a long period of time. Furthermore, the coating film formed using the coating composition of Comparative Example 5 cannot exhibit antifouling performance for a long period because the dissolution rate of the coating film in seawater is too high.
- Test Example 6 Anti-fouling test
- the coating compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were applied on both sides of a hard PVC plate (100 ⁇ 200 ⁇ 2 mm) so that the thickness as a dry coating film was about 200 ⁇ m.
- the obtained coated material was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dry coating film having a thickness of about 200 ⁇ m.
- This test plate was immersed in 1.5 m below the sea surface in Owase City, Mie Prefecture, and the test plate was observed for 24 months for contamination by deposits.
- Evaluation was performed by visually observing the state of the coating film surface, and was judged according to the following criteria. ⁇ : No fouling organisms such as shellfish or algae adhere, and there is almost no slime. ⁇ : No fouling organisms such as shellfish or algae adhere, and the slime adheres thinly (so that the coating surface can be seen). Level that can be removed by lightly wiping with a brush ⁇ : There is no adherence of fouling organisms such as shellfish or algae, but the slime is thin (so that the surface of the coating is visible) and cannot be wiped off with a brush.
- the coating films formed using the coating compositions of the present invention have no adhesion of fouling organisms such as shellfish and algae, and almost no slime. .
Abstract
Description
1. (A)(a)一般式(1):
(b)該メタクリル酸トリオルガノシリルエステル単量体と共重合可能なエチレン性不飽和単量体との混合物から得られるトリオルガノシリルエステル含有共重合体、並びに
(B)ジヒドロアビエチン酸、テトラヒドロアビエチン酸、デヒドロアビエチン酸、ピマール酸、イソピマール酸及びジヒドロピマール酸からなる群から選択される2種以上を80重量%以上含む改質ロジンと、亜鉛及び/又は銅との塩である改質ロジン塩、
を含有する防汚塗料組成物。
2. 前記改質ロジン塩(B)中の改質ロジンにおけるジヒドロアビエチン酸、テトラヒドロアビエチン酸、デヒドロアビエチン酸、ピマール酸、イソピマール酸及びジヒドロピマール酸からなる群から選択される2種以上の含有量が、85~100重量%である上記項1に記載の防汚塗料組成物。
3. 前記トリオルガノシリルエステル含有共重合体(A)と前記改質ロジン塩(B)との含有割合が、重量比(前記共重合体(A)/前記改質ロジン塩(B))で、85/15~20/80である上記項1又は2に記載の防汚塗料組成物。
4. 前記トリオルガノシリルエステル含有共重合体(A)と前記改質ロジン塩(B)との含有割合が、重量比(前記共重合体(A)/前記改質ロジン塩(B))で、70/30~40/60である上記項1~3のいずれかに記載の防汚塗料組成物。
5. 上記項1~4のいずれかに記載の防汚塗料組成物を用いて被塗膜形成物の表面に防汚塗膜を形成する防汚処理方法。
6. 上記項1~4のいずれかに記載の防汚塗料組成物を用いて形成される防汚塗膜。
7. 上記項6に記載の防汚塗膜を表面に有する塗装物。
本発明の防汚塗料組成物は、
(A)(a)一般式(1):
(b)該メタクリル酸トリオルガノシリルエステル単量体と共重合可能なエチレン性不飽和単量体との混合物から得られるトリオルガノシリルエステル含有共重合体、並びに
(B)ジヒドロアビエチン酸、テトラヒドロアビエチン酸、デヒドロアビエチン酸、ピマール酸、イソピマール酸及びジヒドロピマール酸からなる群から選択される2種以上を80重量%以上含む改質ロジンと、亜鉛及び/又は銅との塩である改質ロジン塩
を含有する。
本発明の防汚塗料組成物は、
(a)一般式(1):
(b)該メタクリル酸トリオルガノシリルエステル単量体と共重合可能なエチレン性不飽和単量体との混合物から得られるトリオルガノシリルエステル含有共重合体(A)を含有する。
炭素数3~6のα位が分岐したアルキル基としては、例えば、イソプロピル基、s-ブチル基、t-ブチル基、1-エチルプロピル基、1-メチルブチル基、1-メチルペンチル基、1,1-ジメチルプロピル基、1,1-ジメチルブチル基、テキシル基等が挙げられる。
前記混合物には、前記単量体(a)と共重合可能な他のエチレン性不飽和単量体(b)をさらに含有させる。
前記共重合体(A)は、前記単量体(a)及び前記単量体(b)との混合物から得られる。
本発明の防汚塗料組成物は、ジヒドロアビエチン酸、テトラヒドロアビエチン酸、デヒドロアビエチン酸、ピマール酸、イソピマール酸及びジヒドロピマール酸からなる群から選択される2種以上を80重量%以上、好ましくは85~100重量%含む改質ロジンと、亜鉛及び/又は銅との塩である改質ロジン塩を含有する。ジヒドロアビエチン酸、テトラヒドロアビエチン酸、デヒドロアビエチン酸、ピマール酸、イソピマール酸及びジヒドロピマール酸からなる群から選択される2種以上を80重量%以上含む改質ロジンの亜鉛塩及び/又は銅塩である改質ロジン塩を含有させることにより、スライムの付着が防止又は抑制された防汚塗膜を形成できる。上記改質ロジン塩によって塗膜へのスライムの付着が防止又は抑制される理由として、上記樹脂酸を2種以上含むことによる複合効果が考えられる。また、長期間、海水中に浸漬しても、ヘアークラック等の塗膜異常が生じにくい、長期間防汚性能を維持した防汚塗膜を好適に形成できる。
本発明の塗料組成物は、さらに亜酸化銅を含有することが好ましい。亜酸化銅を含有することにより、形成される塗膜は防汚性能をより効果的に発揮できる。前記亜酸化銅は、防汚薬剤としての役割を果たすことができる。亜酸化銅の形状については、本発明の効果を妨げない範囲であればよく特に限定されない。例えば、亜酸化銅として、粒子状のものを使用できる。
本発明の塗料組成物は、更に、有機系防汚薬剤を含むことが好ましい。前記有機系防汚薬剤としては、海棲汚損生物に対して殺傷又は忌避作用を有する物質であればよく、特に限定されない。例えば、2-メルカプトピリジン-N-オキシド銅(一般名:カッパーピリチオン)等の有機銅化合物;2-メルカプトピリジン-N-オキシド亜鉛(一般名:ジンクピリチオン)、ジンクエチレンビスジチオカーバメート(一般名:ジネブ)、ビス(ジメチルジチオカルバミン酸)亜鉛(一般名:ジラム)、ビス(ジメチルジチオカルバメート)エチレンビス(ジチオカーバメート)二亜鉛(一般名:ポリカーバメート)等の有機亜鉛化合物;ピリジン・トリフェニルボラン、4-イソプロピルピリジル-ジフェニルメチルボラン、4-フェニルピリジル-ジフェニルボラン、トリフェニルボロン-n-オクタデシルアミン、トリフェニル[3-(2-エチルヘキシルオキシ)プロピルアミン]ボロン等の有機ボロン化合物;2,4,6-トリクロロマレイミド、N-(2,6ジエチルフェニル)2,3-ジクロロマレイミド等のマレイミド系化合物;その他、4,5-ジクロロ-2-n-オクチル-3-イソチアゾロン(一般名:シーナイン211)、3,4-ジクロロフェニル-N-N-ジメチルウレア(一般名:ジウロン)、2-メチルチオ-4-t-ブチルアミノ-6-シクロプロピルアミノ-s-トリアジン(一般名:イルガロール1051)、2,4,5,6-テトラクロロイソフタロニトリル(一般名:クロロタロニル)、N-ジクロロフルオロメチルチオ-N’,N’-ジメチル-N-p-トリルスルファミド(一般名:トリフルアニド)、N-ジクロロメチルチオ-N’,N’-ジメチル-N-フェニルスルファミド(一般名:ジクロフルアニド)、2-(4-チアゾリル)ベンズイミダゾ-ル(一般名:チアベンダゾール)、3-(ベンゾ〔b〕チエン-2-イル)-5,6-ジヒドロ-1,4,2-オキサチアジン-4-オキシド(一般名:ベトキサジン)、2-(p-クロロフェニル)-3-シアノ-4-ブロモ-5-トリフルオロメチルピロール(一般名:Econea28)等が挙げられる。この中でも、ジンクピリチオン、カッパーピリチオン、ピリジン・トリフェニルボラン、ジネブ、シーナイン211及びイルガロール1051が好ましく、更に好ましくは、カッパーピリチオン、ジンクピリチオン、ピリジン・トリフェニルボラン及びシーナイン211である。これらの有機系防汚薬剤は、前記亜酸化銅と併用して使用することにより更に防汚効果を高めるため、汚損生物の活性な海域においても、少量の使用で防汚効果を保つ事ができる。これらの有機系防汚薬剤は単独で又は2種以上を併用して使用できる。
本発明の塗料組成物は、可塑剤、除水剤、分散剤、公知の顔料等の公知の添加剤をさらに含んでいてもよい。
本発明の防汚塗料組成物は、例えば、前記共重合体(A)、前記改質ロジン塩(B)、必要に応じて前記亜酸化銅や前記可塑剤等の公知の添加剤を溶剤中で混合することにより製造できる。
本発明の防汚処理方法は、上記防汚塗料組成物を用いて被塗膜形成物の表面に防汚塗膜を形成することを特徴とする。本発明の防汚処理方法によれば、前記防汚塗膜が表面から徐々に溶解し塗膜表面が常に更新されることにより、水棲汚損生物の付着防止を図ることができる。また、塗膜を溶解させた後、上記組成物を上塗りすることにより、継続的に防汚効果を発揮することができる。
装置・・・ 東ソー株式会社製 HLC-8220GPC
カラム・・・ TSKgel SuperHZM-M(東ソー株式会社製)2本
流量・・・ 0.35 mL/min
検出器・・・ RI
カラム恒温槽温度・・・ 40℃
遊離液・・・ THF
加熱残分は、110℃で3時間加熱して求めた値である。
温度計、還流冷却器、撹拌機及び滴下ロートを備えた1000mlのフラスコに、キシレン230gを仕込んだ後、窒素雰囲気下、100±2℃で攪拌しながら、メタクリル酸トリイソプロピルシリル270g、メタクリル酸メチル50g、メタクリル酸2-メトキシエチル130g、アクリル酸2-メトキシエチル30g、アクリル酸エチル20g、及びt-ブチルパーオキシ2-エチルヘキサノエート4g(初期添加)の混合液を1時間かけて滴下した。滴下後、100±2℃で2時間重合反応を行った。次いで、反応液を100±2℃の温度下で攪拌しながら、t-ブチルパーオキシ2-エチルヘキサノエート1g(後添加)を2時間毎に3回添加しで重合反応を行った後、キシレン270gを添加し溶解させることにより、トリオルガノシリルエステル含有共重合体溶液A-1を得た。A-1の粘度、加熱残分、Mw、Tgを表1に示す。
表1に示す有機溶剤、単量体及び重合開始剤を用いて、製造例1と同様の操作で重合反応を行うことにより、トリオルガノシリルエステル含有共重合体溶液A-2~A-6を得た。得られた各共重合体溶液の粘度、加熱残分、Mw、Tgを表1に示す。
温度計及び撹拌機を備えた1000mlのフラスコに、中国ガムロジン(WW)500gを入れ、窒素気流下180℃に昇温し、これに5%パラジウム炭素0.5gを加え混合しながら270±5℃で4時間反応させた。反応後、200℃まで冷却し加圧ろ過にてパラジウム炭素を除去し、濾液をフラスコに移し、200℃にて減圧濃縮を行い、改質ロジン475g(酸価162mgKOH/g)を得た。この改質ロジンの一部を、ジアゾメタンによりメチル化し、ガスクロマトグラフィー(カラム: ジエチレングリコールサクシネート(GEGS)、0.24mmφ×25m、カラム温度:200℃、キャリアーガス:窒素、検出器: 水素炎イオン検出器(FID))にて成分分析を行った。改質ロジン中における非共役ジエン系樹脂酸の含有量は、87.8重量%(デヒドロアビエチン酸62.8重量%、ジヒドロアビエチン酸15.2重量%、ジヒドロピマール酸9.8重量%)であった。
温度計、還流冷却器及び撹拌機を備えた1000mlのフラスコに、製造例7で得られた改質ロジンのキシレン溶液(固形分50%)400gをフラスコに入れ、更に、前記改質ロジン中の樹脂酸が全て亜鉛塩を形成するように酸化亜鉛100gを加え、70~80℃で3時間還流脱水した。その後、冷却しろ過を行うことにより、前記非共役ジエン系樹脂酸の亜鉛塩を含む改質ロジン亜鉛塩のキシレン溶液(濃褐色透明溶液、固形分約50%)B-2を得た。得られたキシレン溶液の加熱残分は、50.9%であった。
3Lのステンレス製のオートクレーブに、中国産ガムロジン(WW)500g及び5%パラジウム炭素1.0を入れ、系内の酸素を除去した後、系内を水素にて50kg/cm2に加圧し、270±5℃の温度で振とうしながら4時間水素化反応を行った。反応後、200℃まで冷却し加圧ろ過にてパラジウム炭素を除き、濾液をフラスコに移し、200℃にて減圧濃縮を行い、改質ロジン482g(酸価157mgKOH/g)を得た。この改質ロジンの一部を、製造例7と同様の方法にて成分分析を行った。改質ロジン中における非共役ジエン系樹脂酸の含有量は、89.8重量%(ジヒドロアビエチン酸60.4重量%、テトラヒドロアビエチン酸19.3重量%、ジヒドロピマール酸10.1重量%)であった。
温度計、還流冷却器及び撹拌機を備えた1000mlのフラスコに、製造例9で得られた改質ロジンのキシレン溶液(固形分50%)400gをフラスコに入れ、更に、前記改質ロジン中の樹脂酸が全て亜鉛塩を形成するように酸化亜鉛100gを加え、70~80℃で3時間還流脱水した。その後、冷却しろ過を行うことにより、前記非共役ジエン系樹脂酸の亜鉛塩を含む改質ロジン亜鉛塩のキシレン溶液(濃褐色透明溶液、固形分約50%)B-4を得た。得られたキシレン溶液の加熱残分は、50.6%であった。
温度計、還流冷却器及び撹拌機を備えた1000mlのフラスコに、中国産ガムロジン(WW,非共役ジエン系樹脂酸15.5重量%、共役ジエン系樹脂酸72.4重量%)のキシレン溶液(固形分50%)400gをフラスコに入れ、前記ガムロジン中の樹脂酸が全て銅塩を形成するように亜酸化銅200gを加え、更に、メタノール100gを加え、均一に混合した。その後、ガラスビーズ(直径2.5~3.5mm)を適量(約400ml)加え、70~80℃で8時間撹拌した後、50℃で2日間保温した。次いで、得られた混合溶液を室温(25℃)まで冷却し濾過した後、減圧濃縮を行うことによりメタノール分を留去した。そして、得られた濃縮液にキシレンを加えることにより、前記非共役ジエン系樹脂酸の銅塩を含むキシレン溶液(濃青色透明溶液、固形分約50%)R-1を得た。得られた樹脂酸銅塩のキシレン溶液の加熱残分は50.7%であった。
温度計、還流冷却器及び撹拌機を備えた1000mlのフラスコに、中国産ガムロジン(WW,非共役ジエン系樹脂酸15.5重量%、共役ジエン系樹脂酸72.4重量%)のキシレン溶液(固形分50%)400gをフラスコに入れ、更に、前記ガムロジン中の樹脂酸が全て亜鉛塩を形成するように酸化亜鉛100gを加え、70~80℃で3時間還流脱水した。その後、冷却しろ過を行うことにより、前記非共役ジエン系樹脂酸の亜鉛塩を含むキシレン溶液(濃褐色透明溶液、固形分約50%)R-2を得た。得られた樹脂酸亜鉛塩のキシレン溶液の加熱残分は、50.5%であった。
温度計及び撹拌機を備えた1000mlのフラスコに、中国産ガムロジン(WW)500gを入れ、窒素気流下180℃に昇温した。これに5%パラジウム炭素0.5gを加え混合しながら230±5℃で1時間反応させた。反応後、200℃まで冷却し加圧ろ過にてパラジウム炭素を除き、濾液をフラスコに移し、200℃にて減圧濃縮を行い、樹脂酸480g(酸価169mgKOH/g)を得た。この樹脂酸の一部を、製造例7と同様の方法で成分分析を行った。樹脂酸中における非共役ジエン系樹脂酸の含有量は、47.3重量%(デヒドロアビエチン酸35.5重量%、ジヒドロアビエチン酸5.3重量%、ジヒドロピマール酸6.5重量%)であった。
温度計、還流冷却器及び撹拌機を備えた1000mlのフラスコに、比較製造例3で得られた樹脂酸のキシレン溶液(固形分50%)400gをフラスコに入れ、更に、前記樹脂酸が全て亜鉛塩を形成するように酸化亜鉛100gを加え、70~80℃で3時間還流脱水した。その後、冷却しろ過を行うことにより、前記非共役ジエン系樹脂酸の亜鉛塩を含むキシレン溶液(濃褐色透明溶液、固形分約50%)R-4を得た。得られたキシレン溶液の加熱残分は、50.9%であった。
表2に示す成分を表2に示す割合(重量%)で配合し、直径1.5~2.5mmのガラスビーズと混合分散することにより塗料組成物を製造した。
実施例1~7及び比較例1~5で得られた塗料組成物を、100mlの広口ブリキ缶に入れ密封し40℃の恒温器に1ヶ月間保存した後、該塗料組成物の粘度をB形粘度計で測定した。
◎:塗料の粘度変化が500mPa・s/25℃未満のもの(塗料状態が殆ど変化しなかったもの)
○:塗料の粘度変化が500~5000mPa・s/25℃のもの(わずかに増粘したもの)
△:塗料の粘度変化が5000mPa・s/25℃超~100000mPa・s/25℃のもの(大きく増粘したもの)
×:塗料粘度が測定不能まで変化したもの(ゲル状になったもの又は固化したもの)
結果を表3に示す。
実施例1~7及び比較例1~5で得られた塗料組成物を、乾燥塗膜としての厚みが約100μmとなるよう透明ガラス板(75×150×1mm)上に塗布し、40℃で1日間乾燥させた。得られた乾燥塗膜の塗膜硬度を、25℃下、振り子式硬度計(ペンジュラム硬度計)を用いて測定した。結果(カウント数)を表3に示す。カウント数20~50が実用上好ましい。
JIS K-5600-5-6の規定に従って、塗膜の付着性試験を行った。具体的には、実施例1~7及び比較例1~5で得られた塗料組成物を、ブラスト仕上げをしたブリキ板(75×150×2mm)上に、乾燥塗膜としての厚みが約100μmとなるように塗布し40℃で1日乾燥させた後、付着性試験を行った。
(1)テープ処理前の評価
乾燥後の塗膜にカッターで、下地(ブリキ板)に達する縦横各11本の傷をごばん目状に入れて2mm角のマス目を100個作製した。このごばん目部における塗膜の付着状態を目視で調べた。
◎:剥離しなかったごばん目の数が70~100個の場合
○:剥離しなかったごばん目の数が40~69個の場合
△:剥離しなかったごばん目の数が20~39個の場合
×:剥離しなかったごばん目の数が0~19個の場合
(2)テープ処理後の評価
前記(1)の評価後、前記100個のマス目にセロハンテープ(ニチバン(株)製 テープ幅24mm)を気泡の入らないように張りつけ、このテープの一端を手に持って急速にはがして、塗膜の付着状態を目視で調べた。
◎:剥離しなかったごばん目の数が70~100個の場合
○:剥離しなかったごばん目の数が40~69個の場合
△:剥離しなかったごばん目の数が20~39個の場合
×:剥離しなかったごばん目の数が0~19個の場合
結果を表3に示す。
実施例1~7及び比較例1~5で得られた塗料組成物を、ブラスト仕上げをしたブリキ板(75×150×2mm)に、乾燥塗膜としての厚みが約100μmとなるよう塗布し40℃で1日間乾燥させた後、90度に折り曲げ塗膜の状態を肉眼観察により確認した。
◎:殆どクラックが生じなかったもの
○:微細なクラックが生じたもの
△:大きなクラックが生じたもの
×:塗膜の一部が容易に剥離したもの
結果を表3に示す。
水槽の中央に直径515mm及び高さ440mmの回転ドラムを取付け、これをモーターで回転できるようにした。また、海水の温度を一定に保つための冷却装置、及び海水のpHを一定に保つためのpH自動コントローラーを取付けた。
◎:全く異常のない場合
○:僅かにヘアークラックが見られるもの
△:塗膜全面にヘアークラックが見られるもの
×:大きなクラック、ブリスター又はハガレなどの塗膜に異常が見られるもの
結果を表4に示す。
実施例1~7及び比較例1~5で得られた塗料組成物を、硬質塩ビ板(100×200×2mm)の両面に乾燥塗膜としての厚みが約200μmとなるよう塗布した。得られた塗布物を室温(25℃)で3日間乾燥させることにより、厚みが約200μmの乾燥塗膜を有する試験板を作製した。この試験板を三重県尾鷲市の海面下1.5mに浸漬して付着物による試験板の汚損を24ケ月観察した。
◎:貝類や藻類などの汚損生物の付着がなく、かつ、スライムも殆どなし
○:貝類や藻類などの汚損生物の付着がなく、かつ、スライムが薄く(塗膜面が見える程度)付着しているものの刷毛で軽く拭いて取れるレベル
△:貝類や藻類などの汚損生物の付着はないが、スライムが薄く(塗膜面が見える程度)付着しており刷毛で強く拭いて取れないレベル
×:貝類や藻類などの汚損生物の付着はないが、スライムが塗膜面が見えない程度に厚く付着しており刷毛で強く拭いても取れないレベル
××:貝類や藻類などの汚損生物が付着しているレベル
結果を表5に示す。
Claims (7)
- (A)(a)一般式(1):
(b)該メタクリル酸トリオルガノシリルエステル単量体と共重合可能なエチレン性不飽和単量体との混合物から得られるトリオルガノシリルエステル含有共重合体、並びに
(B)ジヒドロアビエチン酸、テトラヒドロアビエチン酸、デヒドロアビエチン酸、ピマール酸、イソピマール酸及びジヒドロピマール酸からなる群から選択される2種以上を80重量%以上含む改質ロジンと、亜鉛及び/又は銅との塩である改質ロジン塩、
を含有する防汚塗料組成物。 - 前記改質ロジン塩(B)中の改質ロジンにおけるジヒドロアビエチン酸、テトラヒドロアビエチン酸、デヒドロアビエチン酸、ピマール酸、イソピマール酸及びジヒドロピマール酸からなる群から選択される2種以上の含有量が、85~100重量%である請求項1に記載の防汚塗料組成物。
- 前記トリオルガノシリルエステル含有共重合体(A)と前記改質ロジン塩(B)との含有割合が、重量比(前記共重合体(A)/前記改質ロジン塩(B))で、85/15~20/80である請求項1又は2に記載の防汚塗料組成物。
- 前記トリオルガノシリルエステル含有共重合体(A)と前記改質ロジン塩(B)との含有割合が、重量比(前記共重合体(A)/前記改質ロジン塩(B))で、70/30~40/60である請求項1~3のいずれかに記載の防汚塗料組成物。
- 請求項1~4のいずれかに記載の防汚塗料組成物を用いて被塗膜形成物の表面に防汚塗膜を形成する防汚処理方法。
- 請求項1~4のいずれかに記載の防汚塗料組成物を用いて形成される防汚塗膜。
- 請求項6に記載の防汚塗膜を表面に有する塗装物。
Priority Applications (9)
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EP09833484.0A EP2360214B1 (en) | 2008-12-19 | 2009-12-17 | Antifouling coating composition, antifouling coating film formed using the composition, coated article having the coating film on the surface, and antifouling treatment method to form the coating film |
PL09833484T PL2360214T3 (pl) | 2008-12-19 | 2009-12-17 | Przeciwporostowa kompozycja powłokowa, przeciwporostowa błona powłokowa wytworzona z użyciem kompozycji, wyrób powlekany zawierający błonę powłokową na powierzchni oraz sposób obróbki przeciwporostowej z wytworzeniem błony powłokowej |
AU2009327937A AU2009327937B2 (en) | 2008-12-19 | 2009-12-17 | Antifouling coating composition, antifouling coating film formed using the composition, coated object having the coating film on the surface, and method of antifouling treatment by formation of the coating film |
US13/061,708 US7989521B1 (en) | 2008-12-19 | 2009-12-17 | Antifouling coating composition, antifouling coating film formed using the composition, coated article having the coating film on the surface, and antifouling treatment method to form the coating film |
KR1020117013782A KR101241747B1 (ko) | 2008-12-19 | 2009-12-17 | 방오 도료 조성물, 조성물을 이용하여 형성되는 방오 도막, 도막을 표면에 가지는 도장물, 및 도막의 형성에 의한 방오 처리 방법 |
CN2009801495723A CN102171294B (zh) | 2008-12-19 | 2009-12-17 | 防污涂料组合物、由该组合物形成的防污涂膜、表面具有该涂膜的被涂物,以及通过形成该涂膜的防污处理方法 |
RU2011110403/05A RU2476469C2 (ru) | 2008-12-19 | 2009-12-17 | Композиция для создания противообрастающего покрытия, пленочное противообрастающее покрытие, полученное при помощи указанной композиции, изделие с покрытием, имеющее на поверхности пленочное покрытие, и способ обработки для придания противообрастающих свойств путем формирования пленочного покрытия |
JP2010501722A JP4505661B1 (ja) | 2008-12-19 | 2009-12-17 | 防汚塗料組成物、該組成物を用いて形成される防汚塗膜、該塗膜を表面に有する塗装物、及び該塗膜を形成する防汚処理方法 |
BRPI0916154-6A BRPI0916154A2 (ja) | 2008-12-19 | 2009-12-17 | A paint thing which has on the surface an antifouling coat formed using an antifouling paint constituent and the constituent, and the coat, and an antifouling treatment method which forms the coat |
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US (1) | US7989521B1 (ja) |
EP (1) | EP2360214B1 (ja) |
JP (1) | JP4505661B1 (ja) |
KR (1) | KR101241747B1 (ja) |
CN (1) | CN102171294B (ja) |
AU (1) | AU2009327937B2 (ja) |
BR (1) | BRPI0916154A2 (ja) |
MY (1) | MY148369A (ja) |
PL (1) | PL2360214T3 (ja) |
RU (1) | RU2476469C2 (ja) |
WO (1) | WO2010071181A1 (ja) |
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Also Published As
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MY148369A (en) | 2013-04-15 |
RU2476469C2 (ru) | 2013-02-27 |
KR101241747B1 (ko) | 2013-03-15 |
JPWO2010071181A1 (ja) | 2012-05-31 |
EP2360214A4 (en) | 2012-08-22 |
CN102171294A (zh) | 2011-08-31 |
PL2360214T3 (pl) | 2013-12-31 |
US20110172325A1 (en) | 2011-07-14 |
BRPI0916154A2 (ja) | 2018-03-13 |
EP2360214A1 (en) | 2011-08-24 |
AU2009327937B2 (en) | 2012-04-05 |
CN102171294B (zh) | 2013-09-18 |
KR20110094069A (ko) | 2011-08-19 |
EP2360214B1 (en) | 2013-07-17 |
AU2009327937A1 (en) | 2010-06-24 |
US7989521B1 (en) | 2011-08-02 |
JP4505661B1 (ja) | 2010-07-21 |
RU2011110403A (ru) | 2013-01-27 |
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