WO2011074620A1 - 金属架橋型オルガノポリシロキサンチオブロックビニル共重合体および該金属架橋型共重合体を含有する防汚塗料組成物 - Google Patents
金属架橋型オルガノポリシロキサンチオブロックビニル共重合体および該金属架橋型共重合体を含有する防汚塗料組成物 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
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- C—CHEMISTRY; METALLURGY
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/148—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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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
- C09D5/1675—Polyorganosiloxane-containing compositions
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- 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 a metal cross-linked copolymer having a hydrophilic / hydrophobic structure and an antifouling coating composition containing the metal cross-linked copolymer.
- antifouling paints are coated on the surface of the substrate.
- physiologically active substances for example, organic tin compounds
- problems in safety and environmental safety during painting work are recognized. Therefore, development of antifouling paints that can prevent the attachment of aquatic organisms without using such physiologically active substances has been underway.
- Patent Documents 1 and 2 include an organopolysiloxane thioblock vinyl copolymer formed from a polyoxyalkylene group-containing vinyl copolymer block and a specific organopolysiloxane thioblock, and the copolymer and silicone.
- An antifouling paint composition containing oil is described.
- Patent Document 3 describes an antifouling paint obtained by adding a polyether-modified silicone oil of HLB 3 to 12 to a non-silicone film-forming resin.
- Patent Document 4 discloses a copolymer containing both terminal (meth) acryl-modified silicon-containing polymerizable monomer units and a metal atom-containing polymerizable monomer unit containing a divalent metal atom, and the copolymer A coating composition containing is described.
- Patent Documents 5 and 6 describe a polysiloxane-acrylic resin block copolymer having a crosslinked structure of a predetermined metal and an antifouling coating composition containing the copolymer.
- Patent Documents 7 and 8 describe a graft copolymer composed of a (meth) acryl group-containing polyether-modified silicone and another polymerizable monomer, and a coating composition containing the copolymer.
- the antifouling coating film formed from the antifouling coating composition described in the above Patent Documents 1 to 3 has a certain antifouling performance in the part where the water is always submerged, but the wet and dry alternating parts such as a ship and the waterside. It was inferior to the long-term antifouling property in the section and could not be expected to have a long-term antifouling effect. Further, the antifouling paint composition described in Patent Document 3 has a poor compatibility between the non-silicone-based film-forming resin and the polyether-modified silicone oil, and the oil is extremely bleed. Dirtyness could not be maintained.
- the antifouling paint composition containing the polysiloxane-acrylic resin block copolymer described in Patent Document 5 or 6 is not sufficient in antifouling effect unless it further contains an antifouling agent, and long-term antifouling Sex could not be maintained.
- the antifouling coating composition containing the graft copolymer described in Patent Document 7 or 8 is also insufficient in long-term antifouling properties and physical properties such as crack resistance and strength of the coating film. It was.
- the present invention solves the above-mentioned problems, has an excellent long-term antifouling property in alternating dry and wet parts and a waterside part of a ship, etc., and is excellent in mechanical strength and recoatability, and contains an antifouling agent
- An object of the present invention is to provide a silicone copolymer having a high antifouling performance even if not, and an antifouling coating composition containing the copolymer as a vehicle.
- the component unit derived from the polymerizable unsaturated carboxylic acid (a1) and at least one other polymerizable unsaturated monomer copolymerizable with the polymerizable unsaturated carboxylic acid (a2) are used.
- a metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] having a structure in which the polymer [C] is crosslinked with a divalent metal [M] is provided.
- R 11 each independently represents a hydrocarbon group having 1 to 10 carbon atoms
- R 12 , R 13 and R 14 each independently represents R 11 or a divalent group having 1 to 20 carbon atoms.
- t is an integer of 0 or more
- u is 1 or more Indicates an integer.
- the polymerizable unsaturated carboxylic acid (a1) is preferably at least one selected from (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or undecylenic acid.
- the polymerizable unsaturated monomer (a2) is preferably a polymerizable unsaturated carboxylic acid ester (a21), or a polymerizable unsaturated carboxylic acid ester (a21) and a polymerizable group-containing polyether-modified silicone (a22). It is.
- the polymerizable unsaturated carboxylic acid ester (a21) is preferably at least one selected from (meth) acrylic acid esters, styrenes, vinyl esters, (meth) acrylamides or vinyl ethers.
- the polymerizable group-containing polyether-modified silicone (a22) preferably has an HLB of 18 or less.
- the acid value of the organopolysiloxane thioblock vinyl copolymer [C] is preferably 1 to 200.
- the glass transition temperature (Tg) of the organopolysiloxane thioblock vinyl copolymer [C] is preferably ⁇ 50 ° C. to 60 ° C.
- the weight average molecular weight (Mw) of the organopolysiloxane thioblock vinyl copolymer [C] is preferably 1,000 to 200,000.
- the divalent metal [M] is preferably at least one selected from zinc, copper, cobalt, nickel, manganese, magnesium or calcium.
- the metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] has a carboxylic acid-containing vinyl copolymer block [A] of 5 to 98.5 wt% in a solid content of 100 wt%, and an organopolysiloxane thioblock. [B] is preferably 1 to 80% by weight, and the divalent metal accounts for 0.5 to 16% by weight.
- the metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] preferably has a viscosity of 50 to 100,000 mPa ⁇ s / 25 ° C. at a nonvolatile content of 50% by weight.
- a metal-crosslinked organopolysiloxane thioblock vinyl comprising the above-mentioned metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] and a water-repellent component and / or a hydrophilic component.
- a copolymer composition is provided.
- the water-repellent component is preferably at least one selected from dimethyl silicone oil, methylphenyl silicone oil, fluorine-containing silicone oil, fluorine oil or paraffins.
- the hydrophilic component is preferably a polyether-modified silicone oil having an HLB of 12 or less.
- an antifouling coating composition comprising the metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] or the metal-crosslinked organopolysiloxane thioblock vinyl copolymer composition as described above.
- the antifouling coating composition can further contain an antifouling agent.
- an antifouling coating film formed from a metal-crosslinked organopolysiloxane thioblock vinyl copolymer composition or an antifouling paint composition as described above;
- a coated substrate characterized by being coated with a coating formed by curing an organopolysiloxane thioblock vinyl copolymer composition or an antifouling coating composition;
- a substrate antifouling method characterized in that the substrate surface is coated with the antifouling coating film as described above.
- the antifouling paint composition containing the metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] according to the present invention has a wet and dry condition such as a ship in which a characteristic decrease in performance is observed in the conventional silicone antifouling paint.
- An antifouling coating film excellent in long-term antifouling properties can also be formed at alternating portions and waterside portions. Since such antifouling paint composition does not need to contain a poison such as an organotin compound, the coating work environment can be improved and the environmental safety is excellent.
- FIG. 1 is a chart of the IR spectrum of metal cross-linked copolymer A-1 (Example 1).
- FIG. 2 is a chart of the IR spectrum of metal cross-linked copolymer A-2 (Example 2).
- FIG. 3 is a chart of an IR spectrum of metal cross-linked copolymer A-3 (Example 3).
- FIG. 4 is an IR spectrum chart of the metal cross-linked copolymer A-4 (Example 4).
- FIG. 5 is a chart of the IR spectrum of metal cross-linked copolymer A-5 (Example 5).
- FIG. 6 is an IR spectrum chart of the metal cross-linked copolymer A-6 (Example 6).
- FIG. 1 is a chart of the IR spectrum of metal cross-linked copolymer A-1 (Example 1).
- FIG. 2 is a chart of the IR spectrum of metal cross-linked copolymer A-2 (Example 2).
- FIG. 3 is a chart of an
- FIG. 7 is a chart of an IR spectrum of metal cross-linked copolymer A-7 (Example 7).
- FIG. 8 is an IR spectrum chart of metal cross-linked copolymer A-8 (Example 8).
- FIG. 9 is a chart of an IR spectrum of metal cross-linked copolymer A-9 (Example 9).
- FIG. 10 is an IR spectrum chart of the metal cross-linked copolymer A-10 (Example 10).
- FIG. 11 is a chart of an IR spectrum of metal cross-linked copolymer A-11 (Example 11).
- FIG. 12 is an IR spectrum chart of the metal cross-linked copolymer A-12 (Example 12).
- FIG. 13 is an IR spectrum chart of metal cross-linked copolymer A-13 (Example 13).
- FIG. 14 is a chart of an IR spectrum of metal cross-linked copolymer A-14 (Example 14).
- FIG. 15 is a chart of an IR spectrum of metal cross-linked copolymer A-15 (Example 15).
- FIG. 16 is an IR spectrum chart of metal cross-linked copolymer A-16 (Example 16).
- the metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] of the present invention comprises a component unit derived from a polymerizable unsaturated carboxylic acid (a1) and at least a copolymerizable with the polymerizable unsaturated carboxylic acid.
- the carboxylic acid-containing vinyl copolymer block [A] is preferably 5 to 98.5% by weight, more preferably 10%.
- the organopolysiloxane thioblock [B] is preferably 1-80 wt%, more preferably 5-50 wt%, and the divalent metal is preferably 0.5-16 wt%, More preferably, it accounts for 1 to 10% by weight.
- the ratio of the carboxylic acid-containing vinyl copolymer block [A], the organopolysiloxane thioblock [B], and the divalent metal [M] is the same as that of the metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D].
- the viscosity of the metal-crosslinked organopolysiloxathioblock vinyl copolymer [D] is preferably 50 to 100% with a nonvolatile content of 50% by weight from the viewpoint of coating strength, antifouling durability, and handling of the copolymer solution.
- the viscosity is less than 50 mPa ⁇ s / 25 ° C., the coating film strength is lowered and the antifouling durability becomes difficult.
- the viscosity is more than 100,000 mPa ⁇ s / 25 ° C., the fluidity of the solution is lost and handling is difficult.
- nonvolatile content refers to the heating residue after drying for 3 hours in a hot air drier at 108 ° C., as described in Examples below, and “solid content” is also synonymous with this. be able to.
- divalent metal [M] for crosslinking the organopolysiloxane thioblock vinyl copolymer [C] zinc, copper, cobalt, nickel, manganese, magnesium and calcium are preferable, and zinc and copper are particularly preferable.
- Organopolysiloxane thioblock vinyl copolymer An organopolysiloxane thioblock vinyl copolymer [C] formed from a carboxylic acid-containing vinyl copolymer block [A] and an organopolysiloxane thioblock [B] is: , A compound that should also be referred to as a precursor of a metal-crosslinked organopolysiloxatin oblock vinyl copolymer [D].
- the acid value of the organopolysiloxane thioblock vinyl copolymer [C] is preferably 1 to 200, more preferably 10 to 120, from the viewpoints of coating film wear resistance and coating film water resistance.
- the glass transition temperature (Tg) of the organopolysiloxane thioblock vinyl copolymer [C] is preferably ⁇ 50 ° C. to 60 ° C., more preferably ⁇ 30 ° C. 40 ° C.
- the weight average molecular weight (Mw) of the organopolysiloxane thioblock vinyl copolymer [C] is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and even more preferably 3 , 20,000 to 20,000.
- an organopolysiloxane thioblock vinyl copolymer [C] having a weight average molecular weight in such a range is used as a precursor, a metal having a viscosity suitable for handling at an appropriate concentration as a solution or an antifouling coating composition
- a cross-linked copolymer [D] can be produced, and a coating film formed from the antifouling coating composition containing such a metal cross-linked copolymer [D] has an appropriate strength, There is a tendency to be excellent in dirt persistence.
- Carboxylic acid-containing vinyl copolymer block [A] comprises a component unit derived from a polymerizable unsaturated carboxylic acid monomer (a1) and the polymerizable unsaturated carboxylic acid. And at least one other polymerizable unsaturated monomer (a2) that can be copolymerized with the component unit.
- (A1) Polymerizable unsaturated carboxylic acid
- various known monomers having a carboxyl group and a polymerizable double bond can be used.
- (meth) acrylic acid, dibasic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and the like, monobasic acids thereof, undecylenic acid, and polymerizable hydroxyl group-containing compounds are acid anhydrides. Examples thereof include polymerizable unsaturated carboxylic acid compounds obtained by ring-opening addition of products.
- “(meth) acrylic acid” is a general term for “acrylic acid” and “methacrylic acid”, and the same applies to terms such as “(meth) acrylate” derived therefrom.
- polymerizable unsaturated monomer Other polymerizable unsaturated monomer (a2) copolymerizable with polymerizable unsaturated carboxylic acid (a1) includes polymerizable unsaturated carboxylic acid ester (a21) and A polymerizable group-containing polyether-modified silicone (a22) is included.
- the polymerizable unsaturated monomer (a2) the polymerizable unsaturated carboxylic acid ester (a21) can be used alone, or the polymerizable unsaturated carboxylic acid ester (a21) and a polymerizable group-containing polyether-modified silicone can be used.
- A22 can also be used in combination.
- polymerizable unsaturated carboxylic acid ester examples include the following compounds: Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl ( (Meth) acrylate, oc
- both terminal (meth) acryloxy silicones include “FM-7711”, “FM-7721”, “FM-7725” (trade name, manufactured by Chisso Corporation), “X-22-164”.
- the polymerizable group-containing polyether-modified silicone (a22) is represented by the component unit derived from the polyether-modified silicone (a221) represented by the following formula [II] and / or the following formula [III]. What consists of a component unit induced
- c, d and e are positive integers indicating the total number of each repeating unit. These repeating units may be arranged at random or may be arranged by forming a block.
- R 21 each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms.
- R 21 include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; aryl groups such as phenyl and tolyl groups; Examples thereof include aralkyl groups such as benzyl group and 2-phenylethyl group; halogenated alkyl groups such as 3,3,3-trifluoropropyl group and 3-chloropropyl group.
- a methyl group, an ethyl group, a phenyl group, a vinyl group, and a 2-phenylethyl group are preferable, and a methyl group is particularly preferable. Furthermore, it is particularly preferred that all R 21 are methyl groups.
- R 22 each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms.
- R 22 for example, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH (CH 3 ) CH 2 CH 2 — and the like, among them —CH 2 CH 2 —, —CH 2 CH 2 CH 2 — -CH 2 CH 2 CH 2 -is particularly preferable.
- R 23 and R 24 may be the same or different from each other, and each independently represents an alkylene group having 2 to 4 carbon atoms.
- R 23 and R 24 for example, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH (CH 3 ) —, —CH (CH 3 ) CH 2 —, —CH 2 CH 2 CH 2 CH 2 — and the like, among them —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH (CH 3 ) —, —CH (CH 3 ) CH 2 — -CH 2 CH 2 -is preferable, and -CH 2 CH 2 -is particularly preferable.
- — (R 23 —O) a (R 24 —O) b — includes a polyoxyethylene group, a polyoxypropylene group, a polyether group containing both, and a poly (oxyethyleneoxypropylene) group. preferable.
- a is the total number of repeating units of (R 23 —O)
- b is the total number of repeating units of (R 24 —O), each independently usually from 1 to 30, preferably from 2 to 20, particularly preferably It is an integer from 3 to 15.
- These repeating units may be arranged at random or may be arranged by forming a block.
- R 25 represents a polymerizable unsaturated hydrocarbon group-containing group.
- R 25 include CH 2 ⁇ CH—, CH 2 ⁇ C (CH 3 ) —, CH 3 —CH ⁇ CH—, CH 3 —CH ⁇ C (CH 3 ) —, HOCOCH ⁇ CH—, CH 3
- examples thereof include a polymerizable unsaturated hydrocarbon group-containing group having a total carbon number of 2 to 15, preferably 2 to 10, such as OCOCH ⁇ CH—, which may have a substituent.
- —OCOR 25 represents a polymerizable unsaturated carboxylic acid residue (polymerizable unsaturated group-containing carbonyloxy group).
- Examples of —OCOR 25 include, for example, an acryloyloxy group (CH 2 ⁇ CHCOO—), a methacryloyloxy group (CH 2 ⁇ C (CH 3 ) COO—), and a dibasic polymerizable group.
- X represents a divalent hydrocarbon group or —YNHCOOZ—
- Y represents a diisocyanate compound residue
- Z represents a divalent hydrocarbon group.
- the number of carbon atoms of X is usually 1 to 8, preferably 1 to 4, and the number of carbon atoms of Z is usually 1 to 12, preferably 2 to 6.
- diisocyanate compound of Y examples include aliphatic, aromatic or cycloaliphatic isocyanates and reactive isocyanate oligomers at both ends, such as diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), 1 , 5-Naphthalene diisocyanate (NDI), p-phenylene diisocyanate, trans-1,4-cyclohexane diisocyanate (CHDI), 1,3-bis- (isocyanatomethyl-benzene, 4,4'-dicyclohexylmethane diisocyanate (H12MDI) 1,3-bis- (isocyanatomethyl) -cyclohexane (H6XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), meta-tetramethylxylene diisocyanate or para-
- R 31 , R 32 , R 33 , R 34 and R 35 are respectively synonymous with R 21 , R 22 , R 23 , R 24 and R 25 in the formula [II].
- p is the total number of repeating units of (R 33 —O)
- q is the total number of repeating units of (R 34 —O)
- These repeating units may be arranged at random or may be arranged by forming a block.
- R and s are also positive integers indicating the total number of each repeating unit. These repeating units may be arranged at random or may be arranged by forming a block.
- the polyether-modified silicone (a221) represented by the formula [II] can be produced, for example, by reacting a compound represented by the following formula [IIa] with a compound represented by the following formula [IIb]. it can.
- R 21 , R 22 , R 23 , R 24 , R 25 , a, b, c, d and e are the same as those in the formula [II].
- the polyether-modified silicone (a222) represented by the formula [III] is produced, for example, by reacting a compound represented by the following formula [IIIa] with a compound represented by the following formula [IIIb]. be able to.
- R 31 , R 32 , R 33 , R 34 , R 35 , p, q, r and s are as defined in the formula [III] (therefore, the formula [III] IIIb] is synonymous with formula [IIb]).
- modified silicone represented by the above formula [IIa] commercially available products are “FZ-2191” (trade name, manufactured by Toray Dow Corning Co., Ltd.), “SH-3771” (trade name, Toray Dow Corning ( And KF-353A (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).
- modified silicone represented by the above formula [IIIa] examples include “SF-8427” (trade name), manufactured by Toray Dow Corning Co., Ltd.) and the like as commercial products.
- those in which X is a divalent hydrocarbon group include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxymethyl isocyanate, Examples include 2-acryloyloxymethyl isocyanate, 2-methacryloyloxybutyl isocyanate, and 2-acryloyloxybutyl isocyanate. Among these, 2-methacryloyloxyethyl isocyanate is preferable. Examples of commercially available products include “Karenz MOI” (registered trademark, manufactured by Showa Denko KK) and “Karenz AOI” (registered trademark, manufactured by Showa Denko KK).
- X is —YNHCOOZ—
- Y is a diisocyanate compound residue
- Z is a divalent hydrocarbon group
- a reaction product of the diisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester Is mentioned.
- hydroxyl-containing (meth) acrylic acid esters include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxy Examples include hexyl (meth) acrylate.
- the reaction between the diisocyanate compound and the hydroxyl group-containing (meth) acrylic acid ester is compounded such that the equivalent ratio of isocyanate group / hydroxyl group is 1.0 / 0.5 to 1.0 / 0.7, It is preferable to react.
- the reaction temperature is usually 0 to 150 ° C., preferably 40 to 100 ° C.
- a urethane reaction catalyst such as dibutyltin dilaurate may be used.
- a polymerization inhibitor such as p-methoxyquinone or hydroquinone may be present.
- an organic solvent such as methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, xylene, cellosolve acetate or the like can be used.
- the equivalent ratio of isocyanate group / hydroxyl group is 0.4 / 1.0 to 0.6 / 1.0. It is preferable to mix
- the compound represented by the formula [IIIa] and the compound represented by the formula [IIIb] are preferably mixed and reacted so as to have the same mole.
- these reactions can be performed at the same reaction temperature as the reaction between the diisocyanate compound and the hydroxyl group-containing (meth) acrylic acid ester, and the same urethane reaction catalyst as that reaction may be used.
- a similar polymerization inhibitor may be present, and an organic solvent similar to the reaction may be used.
- the weight average molecular weight (Mw) measured by GPC of the polymerizable group-containing polyether-modified silicone (a22) or the polyether-modified silicone (a221) and / or (a222) used for preparing the same is 300 to 100,000 is preferred.
- the HLB of the polymerizable group-containing polyether-modified silicone (a22) is usually in the range of 0 to 18 (18 or less), preferably in the range of 0 to 10.
- the component unit (a2) contains a component unit (a22) derived from a polymerizable group-containing polyether-modified silicone
- the introduced polyether-modified silicone oil improves the flexibility of the coating film, so that cracks and the like can be prevented.
- the antifouling durability can be increased.
- Organopolysiloxane thioblock [B] is represented by the following formula [I].
- a plurality of R 11 each independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- the monovalent hydrocarbon group having 1 to 10 carbon atoms include 1 to 10, preferably 1 to 8, and particularly preferably 1 to 3 carbon atoms such as methyl, ethyl, propyl, and isobutyl groups.
- R 12 , R 13 and R 14 each independently represent R 11 or a divalent thioorganic group having 1 to 20 carbon atoms. However, at least one of R 12 , R 13 or R 14 is a divalent thioorganic group having 1 to 20 carbon atoms.
- the divalent thio organic group is represented by the formula —S—X— (wherein X is a divalent organic group having 1 to 20 carbon atoms).
- Organic groups such as: Methylene group (—CH 2 —), ethylene group (— (CH 2 ) 2 —), propylene group (—CH 2 CH 2 CH 2 —, —CHCH 3 CH 2 —, —CH 2 CHCH 3 —), dimethylmethylene Group (—C (CH 3 ) 2 —), butylene group (—CH 2 CH (CH 3 ) CH 2 —), dimethylethylene group (—CH 2 C (CH 3 ) 2 —), octamethylene group (— ( CH 2) 8 -) and the like, 2 may be branched divalent aliphatic hydrocarbon group; Organic groups containing a divalent aromatic hydrocarbon group such as a phenylene group (—C 6 H 4 —) and a phenylene ethylene group (—C 6 H 4 — (CH 2 ) 2 —).
- a thiohydrocarbon group having a chain divalent hydrocarbon group (X) having 1 to 5 carbon atoms such as a thiotrimethylene group is preferable.
- t and u are integers indicating the total number of each repeating unit, and usually, t is 0 to 1,500 and u is 1 to 100. These repeating units may be arranged at random or may be arranged by forming a block.
- Such an organopolysiloxane thioblock [B] is derived from a mercapto-modified polyorganosiloxane represented by the following formula [Ia].
- R 110 has the same meaning as R 11 in the formula [I]
- R 120 , R 130 and R 140 have a “divalent thioorganic group” (—S—X—) as “monovalent”.
- R 12 , R 13 and R 14 are the same except that the thio organic group of (HS-X—) is replaced.
- the weight average molecular weight (Mw) measured by GPC of the mercapto-modified polyorganosiloxane [Ia] used for deriving the organopolysiloxane thioblock [B] is usually 300 to 100,000, preferably 500 to 50, 000.
- the organopolysiloxane thioblock [B] has the following formula [I] depending on whether R 12 , R 13 or R 14 in the formula [I] is a divalent thioorganic group having 1 to 20 carbon atoms.
- I-1] one-end type represented by formula [I-2], both-end type represented by formula [I-2], side chain type represented by formula [I-3], represented by formula [I-4]
- the organopolysiloxane thioblock [B] is a single terminal type represented by the formula [I-1]
- the block [B] is present at one terminal or both terminals of the carboxylic acid-containing vinyl copolymer block [A].
- the organopolysiloxane thioblock vinyl copolymer [C] becomes a block copolymer having a structure of [A]-[B] or [B]-[A]-[B];
- the organopolysiloxane thioblock [B] is a both-end type represented by the formula [I-2]
- a carboxylic acid-containing vinyl copolymer block [A] is added to both ends of the block [B]
- the organopolysiloxane thioblock vinyl copolymer [C] becomes a block copolymer having a structure of [A]-[B]-[A];
- the organopolysiloxane thioblock [B] is
- organopolysiloxane thioblock vinyl copolymer [C] is estimated to be a copolymer having a star-shaped structure.
- a block structure other than the above may exist due to a complex termination reaction of radicals.
- Examples of the mercapto-modified polyorganosiloxane for deriving the organopolysiloxane thioblock [B] represented by the above formulas include the following preparations and products: Mercapto-modified polyorganosiloxane [I-1] (single terminal type): “F3-076-05”, “F3-076-06” manufactured by Toray Dow Corning Co., Ltd. Mercapto-modified polyorganosiloxane [I-2] (both ends) ... “X-22-167B” manufactured by Shin-Etsu Chemical Co., Ltd. Mercapto-modified polyorganosiloxane [I-3] (side chain type): “KF-2001”, “KF-2004”, “KP-358” manufactured by Shin-Etsu Chemical Co., Ltd.
- the metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] is an organopolysiloxane thioblock vinyl copolymer having a carboxylic acid-containing vinyl copolymer block [A] and an organopolysiloxane thioblock [B].
- C] is prepared by radical polymerization
- the organopolysiloxane thioblock vinyl copolymer [C] and a divalent metal [M] compound can be produced by a metal esterification reaction.
- the organopolysiloxane thioblock vinyl copolymer [C] is typically Copolymerized with polymerizable unsaturated carboxylic acid (a1) (eg methacrylic acid, acrylic acid) and polymerizable unsaturated carboxylic acid (a1), which will constitute carboxylic acid-containing vinyl copolymer block [A]
- polymerizable unsaturated monomer (a2) polymerizable unsaturated carboxylic acid ester (a21) (eg, methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxy) Ethyl (meth) acrylate, trade name “FM-7711”), and optionally a polymerizable group-containing polyether-modified silicone (a22), Mercapto-modified polyorganosiloxane represented by the formula [Ia] that constitutes the organopolysiloxan
- the composition of each monomer, the amount of polymerization initiator, the heating conditions, the reaction time, etc. are as follows.
- the organopolysiloxane thioblock vinyl copolymer [C] has the acid value, glass transition temperature (Tg), and weight average molecular weight as described above. (Mw) and the like can be adjusted.
- the metal cross-linked organopolysiloxane thioblock vinyl copolymer [D] is typically an organopolysiloxane thioblock vinyl copolymer prepared as described above. It can be produced by mixing [C], a divalent metal [M] compound that cross-links them, and water as necessary, and performing a metal esterification reaction.
- the metal compound examples include divalent metal [M] oxides, hydroxides, chlorides, and organic carboxylates such as zinc oxide (zinc white), zinc hydroxide, zinc chloride, and zinc acetate. be able to.
- the mixing ratio of the organopolysiloxane thioblock vinyl copolymer [C], the metal compound and water, the reaction conditions (temperature, time, etc.), etc. are the metal cross-linked organopolysiloxane thio to be produced. It can adjust suitably according to block vinyl copolymer [D].
- copolymer [C] / metal compound / water 1-3 acid equivalent / 1 mol / 0-5 mol in a mixing ratio of copolymer [C], metal compound, and water as necessary.
- the metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] can be produced by stirring or uniformly mixing and allowing to react at a temperature in the range of 20 to 120 ° C. for 1 to 50 hours. .
- the metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] according to the present invention is particularly preferably used as a resin component (vehicle component) of an antifouling paint. It can also be used for antifouling paints, icing / snowing prevention paints, mold release materials, and the like, and its use is not particularly limited.
- the antifouling paint or other paint is used in combination with a water-repellent substance and / or a hydrophilic substance.
- the performance can be improved. That is, a metal-crosslinked organopolysiloxane thioblock vinyl copolymer composition containing a metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] and a water-repellent substance and / or a hydrophilic substance is constituted. .
- Water repellent component Water-repellent components include paraffins such as petrolatum, paraffin wax, liquid paraffin; dimethyl silicone oil, methylphenyl silicone oil, alkyl-modified silicone oil, fluorine-containing silicone oil (fluorosilicone oil), terminal functional group-containing silicone oil, etc.
- Fluorine oil such as fluoropolyether oil; long chain fatty acids such as caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, oleic acid and esters thereof; beef tallow, lard, linseed oil, coconut oil, Examples thereof include natural fats and oils such as palm oil, among which dimethyl silicone oil, methylphenyl silicone oil, fluorine-containing silicone oil, and paraffins are preferable.
- the amount of the water repellent component used is not particularly limited, but it is a metal-crosslinked organopolysiloxane from the viewpoint of film-forming property, drying property, and adhesion of a coating film formed from a (antifouling) paint.
- the ratio is usually 0 to 100 parts by weight, preferably 1 to 50 parts by weight per 100 parts by weight of the thioblock vinyl copolymer [D] (solid content).
- hydrophilic component examples include polyether-modified silicone oil (excluding polymerizable group-containing polyether-modified silicone (a22)).
- the HLB of the polyether-modified silicone oil is usually in the range of 0 to 12 (12 or less), and preferably in the range of 0 to 7.
- any of a pendant type, a both-ends modified type, and a block type may be sufficient.
- the blending amount in the case of using a hydrophilic component is not particularly limited. From the viewpoint of film-forming property, drying property, adhesion property, and antifouling durability of a coating film formed from (antifouling) paint, The ratio is usually 1 to 100 parts by weight, preferably 5 to 50 parts by weight per 100 parts by weight of the cross-linked organopolysiloxane thioblock vinyl copolymer [D] (solid content).
- the antifouling paint containing the metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] as a resin component is sufficient even if it does not contain an antifouling agent unlike conventional antifouling paints.
- an antifouling agent may be blended as necessary in order to further increase the antifouling performance.
- Antifouling agents include metallic copper, cuprous oxide, rhodan copper, basic copper sulfate, basic copper acetate, basic copper carbonate, oxyquinoline copper, naphthenic acid copper, rosin acid copper, copper pyrithione, zinc pyrithione, tetramethyl Thiuram disulfite, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, 4, Examples include 5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2,4,6-trichlorophenylmaleimide, pyridine-triphenylborane, and amine-triphenylborane.
- Various components blended in a known antifouling coating composition such as a coating film forming component (color developing agent), a leveling agent, and an ultraviolet absorber, can be used as necessary.
- a coating film forming component color developing agent
- a leveling agent leveling agent
- an ultraviolet absorber metal-crosslinked organopolysiloxane thioblock vinyl copolymers
- solvent As a solvent, it has moderate volatility at room temperature, a monomer used for the preparation of a metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] and a synthesized organopolysiloxane thioblock vinyl copolymer [C ] And the metal-crosslinked organopolysiloxane thioblock vinyl copolymer [D] are not particularly limited, for example, aromatic hydrocarbons such as toluene and xylene, aliphatics such as hexane and heptane Hydrocarbons; ethers such as diethyl ether, di-n-propyl ether, dibutyl ether, tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; chlorine such as dichloromethane and chloro
- Elution aid As an elution aid, it acts as a surfactant to assist the surface migration of the water repellent compounded as needed, or to effectively release the antifouling agent formulated as necessary.
- the compound which has can be used For example, a rosin, a naphthenic acid, etc. are mentioned.
- plasticizer a compound having an effect of imparting flexibility to the coating film and improving crack resistance and adhesion can be used.
- chlorinated paraffin normal phosphate ester, phthalate ester, etc. Can be mentioned.
- Thixotropic agent As a habit modifier (anti-sagging agent / anti-settling agent), it is possible to use a compound having an effect of improving the thick coating property and anti-sagging property during coating and, if necessary, preventing the anti-settling of the pigment blended in the coating composition.
- organic clay waxes Al, Ca, Zn amine salts, stearate salts, lecithin salts, alkyl sulfonates, etc.
- organic waxes polyethylene wax, oxidized polyethylene wax, polyamide wax, amide wax, Hydrogenated castor oil wax, etc.
- a mixture of organic clay wax and organic wax, synthetic fine silica, and the like are preferable.
- pigment As the pigment (excluding substances used as an antifouling agent), conventionally known various organic and inorganic colored or extender pigments can be used.
- organic pigments include carbon black, phthalocyanine blue, and bitumen
- inorganic pigments include titanium oxide (titanium white), bengara, silica, calcium carbonate, talc, barium sulfate, and zinc oxide (zinc white). ), White lead, red lead, zinc powder and the like.
- Examples of the resin (coating film forming component) other than the metal cross-linked organopolysiloxane thioblock vinyl copolymer [D] include acrylic resin, acrylic silicone resin, polyester resin, fluororesin, polybutene resin, silicone rubber, and urethane resin.
- Rubber polyamide resin
- vinyl chloride copolymer resin chlorinated rubber (resin), chlorinated olefin resin, styrene / butadiene copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl chloride resin, coumarone resin, trialkylsilyl
- acrylate (co) polymers sil resins
- petroleum resins ketone resins
- formaldehyde resins formaldehyde resins
- polyvinyl alkyl ether resins examples include acrylate (co) polymers (silyl resins), petroleum resins, ketone resins, formaldehyde resins, and polyvinyl alkyl ether resins.
- Leveling agent As leveling agents (antifoaming agents), for example, fluorine-based leveling agents, silicone-based leveling agents, ether-based or ester-based leveling agents, etc. can be further improved in the coating properties of the resin composition, resulting in a finished film.
- leveling agents for example, fluorine-based leveling agents, silicone-based leveling agents, ether-based or ester-based leveling agents, etc.
- UV absorber examples include organic UV absorbers such as oxalic anilide, salicylic acid, benzophenone, triazine, benzotriazole, and cyanoacrylate; titanium oxide, zinc oxide, and oxidation Inorganic UV absorbers such as cerium; organic nickel compounds, light stabilizers such as hindered amines, and the like that have been used in conventional paint compositions and have UV absorption and / or light stabilization. Can be mentioned.
- the (antifouling) coating composition of the present invention is conventionally known in the same manner as a general (antifouling) coating composition using the prepared metal-crosslinked organopolysiloxane thioblock vinyl copolymer solution of the present invention. It can manufacture by the method of. After the metal-crosslinked organopolysiloxane thioblock vinyl copolymer solution of the present invention is prepared, it may be used as it is as an antifouling coating composition.
- Water-repellent / hydrophilic components silane coupling agents, antifouling agents, elution aids, plasticizers, dehydrating agents (stabilizers), alteration agents (anti-sagging / precipitating agents), pigments as necessary
- other components such as a coating film forming component and a solvent are blended, they may be added at a predetermined ratio all at once or in any order, and stirred, mixed, and uniformly dissolved / dispersed.
- the antifouling paint composition according to the present invention has a high antifouling performance against aquatic organisms such as sea bream, barnacles, aonori, cell plastics, oysters, mussels, bryozoans, etc., not only in constantly submerged parts but also in wet and dry alternating parts and waterside parts. It is possible to form an excellent antifouling coating film that has a long-term stability.
- ships, fishery materials eg ropes, fishnets, floats, buoys
- underwater structures such as thermal / nuclear power supply / drain ports, gulf roads, submarine tunnels, harbor facilities, canals / waterways, marine civil engineering Ships, underwater structures, and fishery materials coated with excellent antifouling coatings that can prevent the attachment of aquatic organisms for a long period of time by applying an antifouling paint composition to various substrates such as sludge diffusion prevention films or undercoat surfaces Etc. are obtained.
- Antifouling paint composition adheres well to the surface even when the base material is steel, FRP, wood, aluminum alloy, etc., or when it is overcoated on the surface of an undercoat or existing antifouling paint It also has excellent adhesion (recoatability).
- modified silicone S-1 solution Thereafter, 93 parts by weight of butyl acetate was added to obtain a modified silicone S-1 solution.
- the appearance of this modified silicone S-1 solution is transparent, NV (heating residue after drying for 3 hours in a hot air dryer at 108 ° C.) is 88.1% by weight, the viscosity is 296 mPa ⁇ s / 25 ° C., GPC
- the weight average molecular weight (Mw) of the modified silicone S-1 measured in (1) was 10,540.
- MMA methyl methacrylate
- BMA n-butyl methacrylate
- EHA 2-ethylhexyl acrylate
- this copolymer B-1 solution is transparent, the film appearance is transparent, NV (heating residue after drying for 3 hours in a hot air dryer at 108 ° C.) is 52.4% by weight, and the viscosity is Was 111 mPa ⁇ s / 25 ° C., the acid value was 19.6 KOH mg / g, and the weight average molecular weight (Mw) of the copolymer B-1 measured by GPC was 6,510.
- Metal cross-linked copolymer A-1 The same apparatus as above was charged with 824.4 parts by weight of the above copolymer B-1 solution and 5.86 parts by weight of zinc oxide, stirred at 30 ° C. for 30 minutes in a nitrogen gas atmosphere, and then heated to 90 ° C. After adding 3.89 parts by weight of water at 90 ° C., the mixture was stirred for 2 hours, and then 5.86 parts by weight of zinc oxide was further added and stirred for 2 hours to obtain a metal-crosslinked copolymer A-1 solution.
- this metal-crosslinked copolymer A-1 solution is transparent, NV (heating residue after drying for 3 hours in a hot air dryer at 108 ° C.) is 52.7% by weight, and the viscosity is 4,420 mPa ⁇ s. / 25 ° C., the water content was 0.84% by weight, and the film transparency of the metal cross-linked copolymer A-1 was slightly cloudy.
- Table 2 shows properties of the obtained metal cross-linked copolymer A-1 solution and copolymer B-1 solution.
- the contents of the symbols (product names) appearing in the following table, the manufacturer, and the like are as summarized in Table 1.
- FIG. 1 shows an IR spectrum chart of the obtained metal cross-linked copolymer A-1.
- Examples 2 to 4 Organopolysiloxane thioblock vinyl in the same manner as in Example 1 except that the blending amounts of raw materials, catalysts, solvents, etc. (units of numerical values in the table are parts by weight) and reaction times were changed as shown in Table 2.
- the copolymers B-2 to B-4 were synthesized, metal crosslinked copolymer A-2 to A-4 solutions were synthesized, and the physical properties of each copolymer were evaluated in the same manner as in Example 1 above. Production conditions of the copolymer B-2 to B-4 solution and the copolymer A-2 to A-4 solution (blending amounts of raw materials, catalysts, solvents, etc.
- Table 2 shows the reaction temperature, time, etc.
- 2 to 4 show IR spectrum charts of the metal cross-linked copolymers A-2 to A-4.
- Example 5 (Organopolysiloxane thioblock vinyl copolymer B-5) A reactor equipped with a stirrer, thermometer, nitrogen gas inlet tube, dropping device and reflux condenser was charged with 32.1 parts by weight of butyl acetate and 29.2 parts by weight of propylene glycol monomethyl ether (PGM), and nitrogen gas The temperature was raised to 120 ° C. in the atmosphere.
- PGM propylene glycol monomethyl ether
- the liquid mixture A was dripped in 4 hours, and the mixture B was dripped in 2 hours.
- a mixed additional catalyst of 1 part by weight of t-butylperoxy 2-ethylhexisanoate and 4.5 parts by weight of butyl acetate was further added dropwise over 30 minutes. Thereafter, the mixture was stirred for 2 hours to obtain an organopolysiloxane thioblock vinyl copolymer B-5 solution.
- the appearance of this copolymer B-5 solution was transparent, the film appearance was cloudy, and the NV (residue after drying in a hot air dryer at 108 ° C.
- this metal cross-linked copolymer A-5 solution is transparent, NV (heating residue after drying for 3 hours in a hot air dryer at 108 ° C.) is 49.5% by weight, and the viscosity is 3,980 mPa ⁇ s.
- the film transparency of the metal cross-linked copolymer A-5 was clear.
- Table 2 shows properties of the obtained metal cross-linked copolymer A-5 solution and copolymer B-5 solution.
- FIG. 5 shows an IR spectrum chart of the obtained metal crosslinked copolymer A-5.
- Examples 6 to 15 Organopolysiloxane thioblock vinyl in the same manner as in Example 5 except that the blending amounts of raw materials, catalysts, solvents, etc. (units of numerical values in the table are parts by weight) and reaction times were changed as shown in Table 2.
- copolymers B-6 to B-15 were synthesized, metal cross-linked copolymers A-6 to A-15 solutions were synthesized, and the physical properties of each copolymer were evaluated in the same manner as in Example 5 above. Production conditions of the above-mentioned copolymers B-6 to B-15 solutions and metal cross-linked copolymers A-6 to A-15 solutions (mixing amounts of raw materials, catalysts, solvents, etc.
- Table 2 shows the reaction temperature, time, etc.), and properties of the obtained copolymers B-6 to B-15 solutions and metal cross-linked copolymers A-6 to A-15 solutions. Further, IR spectrum charts of the metal cross-linked copolymers A-6 to A-15 are shown in FIGS.
- Example 16 (Organopolysiloxane thioblock vinyl copolymer B-16) A reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a dropping device and a reflux condenser was charged with 40.3 parts by weight of xylene and 21 parts by weight of propylene glycol monomethyl ether (PGM) in a nitrogen gas atmosphere. The temperature was raised to 120 ° C.
- PGM propylene glycol monomethyl ether
- this copolymer B-16 solution is transparent, the film appearance is transparent, NV (heating residue after drying for 3 hours in a hot air dryer at 108 ° C.) is 53.7% by weight, and the viscosity is Was 90 mPa ⁇ s / 25 ° C., the acid value was 36.4 KOH mg / g, and the weight average molecular weight (Mw) of the copolymer B-16 measured by GPC was 6,140.
- Table 2 shows properties of the obtained metal cross-linked copolymer A-16 solution and copolymer B-16 solution.
- FIG. 16 shows an IR spectrum chart of the obtained metal crosslinked copolymer A-16.
- MMA methyl methacrylate
- BMA n-butyl methacrylate
- EHA 2-ethylhexyl acrylate
- Table 3 shows the composition of the copolymer H-1 solution (parts by weight), the catalyst, the solvent, the reaction temperature, and the properties of the obtained copolymer H-1 solution.
- Copolymers H-2 to H-3 solutions were synthesized in the same manner as the copolymer B-1 solution of Example 1 except that the blending composition was changed as shown in Table 3.
- the physical properties of each copolymer were evaluated in the same manner as in Example 1 above.
- the composition of raw materials (parts by weight), catalyst, solvent, reaction temperature, etc. in the production of the copolymer H-2 to H-3 solution, properties of the copolymer H-2 to H-3 solution, etc. Is shown in Table 3.
- a mixture of 3.2 parts by weight of “ABN-E” azo compound, manufactured by Nippon Hydrazine Co., Ltd.
- ABSN-R 2,2′-azobisisobutyronitrile
- Table 3 shows the composition of the copolymer H-4 solution (parts by weight), catalyst, solvent, reaction temperature, etc., and the properties of the obtained copolymer H-4 solution.
- Examples F-2 to F-24, comparative examples HF-1 to HF-4 As shown in Table 4 (Example) and Table 5 (Comparative Example), the antifouling paint composition was prepared in the same manner as in Example F-1, except that the type of copolymer solution and the amount of each component were changed. Prepared.
- Epoxy zinc rich primer (“Epicon Zinc Rich Primer B-2” manufactured by China Paint Co., Ltd., epoxy anticorrosive paint ("Banno 500” manufactured by China Paint Co., Ltd.)
- Epoxy zinc rich primer (“Epicon Zinc Rich Primer B-2” manufactured by China Paint Co., Ltd.
- epoxy anticorrosive paint (“Banno 500” manufactured by China Paint Co., Ltd.)
- sandblasted steel plate 100mm x 300mm x 2.3mm
- An epoxy anticorrosion paint (Chinese Paint Co., Ltd. “Banno 500R”) was applied using air spray so that the dry film thicknesses were 20 ⁇ m, 150 ⁇ m, and 100 ⁇ m, respectively.
- the coating composition was applied so as to have a dry film thickness of 150 ⁇ m, and a test plate was prepared.After drying in a room for a week, it was immersed so that it would be 1 m below the surface of the water from a pot installed in Hiroshima Bay, The state of biofouling for 18 months was visually observed.
- “Banno 500R”) was applied using air spray so that the dry film thicknesses were 20 ⁇ m, 150 ⁇ m, and 100 ⁇ m, respectively.
- the coating composition was applied so that the dry film thickness was 150 ⁇ m, and dried in a room for a week to prepare a test plate.
- the test plate was immersed in half under the surface of the water from the fence installed in Hiroshima Bay. And the state of biological adhesion for 18 months was visually observed.
- “Banno 500R”) was applied using air spray so that the dry film thicknesses were 20 ⁇ m, 150 ⁇ m, and 100 ⁇ m, respectively, and after drying, the antifouling paint was applied using an applicator.
- the composition was applied to a dry film thickness of 150 ⁇ m and dried in a room for 1 week to prepare a test piece.
- the test piece was attached to an underwater rotating device installed in Hiroshima Bay and rotated at 15 Kn for 6 months.
- the test piece was collected, washed with fresh water and dried for 1 day, and then the same kind of antifouling coating composition was overcoated with a dry film thickness of 150 ⁇ m.
- a 60 ° cut reaching the antifouling paint was applied, attached to a rotating device and rotated in the sea, and the adhesion between the antifouling coatings was tested.
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Abstract
Description
本発明の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]は、重合性不飽和カルボン酸(a1)から誘導される成分単位と、該重合性不飽和カルボン酸と共重合可能な少なくとも1種の他の重合性不飽和単量体(a2)から誘導される成分単位とから形成されるカルボン酸含有ビニル共重合体ブロック[A]と、特定のオルガノポリシロキサンチオブロック[B]とから形成されるオルガノポリシロキサンチオブロックビニル共重合体[C]が2価の金属で架橋された構造を有する化合物である。
カルボン酸含有ビニル共重合体ブロック[A]とオルガノポリシロキサンチオブロック[B]とから形成されるオルガノポリシロキサンチオブロックビニル共重合体[C]は、金属架橋型オルガノポリシロキサチンオブロックビニル共重合体[D]の前駆体ともいうべき化合物である。
カルボン酸含有ビニル共重合体ブロック[A]は、重合性不飽和カルボン酸単量体(a1)から誘導される成分単位と該重合性不飽和カルボン酸と共重合可能な少なくとも1種の他の重合性不飽和単量体(a2)から誘導される成分単位とから構成される。
重合性不飽和カルボン酸(a1)としては、カルボキシル基と重合性二重結合を有する公知の各種単量体を使用することができる。具体的には、(メタ)アクリル酸や、マレイン酸、フマル酸、イタコン酸、シトラコン酸等の二塩基酸およびそれらのモノエステルの一塩基酸、ウンデシレン酸、さらに重合性水酸基含有化合物に酸無水物を開環付加して得られる重合性不飽和カルボン酸化合物などが挙げられる。なお、本発明において「(メタ)アクリル酸」は「アクリル酸」および「メタクリル酸」の総称であり、これに派生する「(メタ)アクリレート」等の用語についても同様である。
重合性不飽和カルボン酸(a1)と共重合可能な他の重合性不飽和単量体(a2)には、重合性不飽和カルボン酸エステル(a21)および重合性基含有ポリエーテル変性シリコーン(a22)が含まれる。重合性不飽和単量体(a2)としては、重合性不飽和カルボン酸エステル(a21)を単独で用いることも、また重合性不飽和カルボン酸エステル(a21)と重合性基含有ポリエーテル変性シリコーン(a22)とを併用することもできる。
重合性不飽和カルボン酸エステル(a21)としては、たとえば以下の化合物が挙げられる:
メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、iso-プロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、iso-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、ステアリル(メタ)アクリレート、ラウリル(メタ)アクリレート、ベンジル(メタ)アクリレート、ドデシル(メタ)アクリレート、ヘキサデシル(メタ)アクリレート、オクタデシル(メタ)アクリレート、メトキシエチル(メタ)アクリレート、
2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、(ポリ)カプロラクトン(メタ)アクリレート、
(メタ)アクリロキシプロピルポリジメチルシロキサン、3-[トリス(トリメチルシロキシ)シリル]プロピル(メタ)アクリレート、2,2,2-トリフルオロエチル(メタ)アクリレート、1H,1H,2H,2H-ヘプタデカフルオロデシル(メタ)アクリレートなど、炭素原子数が1~30程度で、脂肪族、脂環族または芳香族系の、水酸基またはケイ素もしくはフッ素を有していてもよい、(メタ)アクリル酸エステル;
スチレン、α-メチルスチレンなどのスチレン類;
酢酸ビニル、プロピオン酸ビニルなどのビニルエステル類;
N,N-ジメチルアクリルアミド、ジメチルアミノエチルアクリルアミドなどの(メタ)アクリルアミド類;
エチルビニルエーテル、イソブチルビニルエーテルなどのビニルエーテル類。
重合性基含有ポリエーテル変性シリコーン(a22)としては、より具体的には、前出の特許文献2(特開2008-1896号公報)に記載されている重合性基含有ポリエーテル変性シリコーン[A]などを用いることができる。
オルガノポリシロキサンチオブロック[B]は下記式[I]で表される。
メチレン基(-CH2-)、エチレン基(-(CH2)2-)、プロピレン基(-CH2CH2CH2-、-CHCH3CH2-、-CH2CHCH3-)、ジメチルメチレン基(-C(CH3)2-)、ブチレン基(-CH2CH(CH3)CH2-)、ジメチルエチレン基(-CH2C(CH3)2-)、オクタメチレン基(-(CH2)8-)等、分岐していてもよい2価の脂肪族炭化水素基;
フェニレン基(-C6H4-)、フェニレンエチレン基(-C6H4-(CH2)2-)等、2価の芳香族炭化水素基を含む有機基。
オルガノポリシロキサンチオブロック[B]が式[I-2]で表される両末端型である場合、当該ブロック[B]の両末端にカルボン酸含有ビニル共重合体ブロック[A]が付加し、オルガノポリシロキサンチオブロックビニル共重合体[C]は[A]-[B]-[A]の構造を有するブロック共重合体となり;
オルガノポリシロキサンチオブロック[B]が式[I-3]で表される側鎖型である場合、当該ブロック[B]の側鎖にカルボン酸含有ビニル共重合体ブロック[A]が付加し、オルガノポリシロキサンチオブロックビニル共重合体[C]は櫛形の構造を有するグラフト共重合体となり;
オルガノポリシロキサンチオブロック[B]が式[I-4]で表される側鎖両末端型である場合、当該ブロック[B]の両末端および側鎖にカルボン酸含有ビニル共重合体ブロック[A]が付加し、オルガノポリシロキサンチオブロックビニル共重合体[C]はスター形の構造を有する共重合体となるものと推定される。ただし、ラジカルの複雑な停止反応により、上記以外のブロック構造が存在することもあり得る。
メルカプト変性ポリオルガノシロキサン[I-1](片末端型)…東レダウコーニング(株)製「F3-076-05」、「F3-076-06」
メルカプト変性ポリオルガノシロキサン[I-2](両末端型)…信越化学工業(株)製「X-22-167B」
メルカプト変性ポリオルガノシロキサン[I-3](側鎖型)…信越化学工業(株)製「KF-2001」、「KF-2004」、「KP-358」。
金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]は、まずカルボン酸含有ビニル共重合体ブロック[A]およびオルガノポリシロキサンチオブロック[B]を有するオルガノポリシロキサンチオブロックビニル共重合体[C]をラジカル重合により調製した後、そのオルガノポリシロキサンチオブロックビニル共重合体[C]と2価の金属[M]の化合物とを金属エステル化反応させることにより製造することができる。
オルガノポリシロキサンチオブロックビニル共重合体[C]は、典型的には、
カルボン酸含有ビニル共重合体ブロック[A]を構成することとなる、重合性不飽和カルボン酸(a1)(例:メタクリル酸、アクリル酸)と、重合性不飽和カルボン酸(a1)と共重合可能な他の重合性不飽和単量体(a2)である重合性不飽和カルボン酸エステル(a21)(例:メチル(メタ)アクリレート、ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート、商品名「FM-7711」)と、必要によっては重合性基含有ポリエーテル変性シリコーン(a22)と、
オルガノポリシロキサンチオブロックビニル共重合体[B]を構成することとなる、式[Ia]で表されるメルカプト変性ポリオルガノシロキサン(例:商品名「KP-358」「KF-2001」、信越化学工業(株)製、メルカプト変性シリコーン)とを、
必要によりラジカル重合開始剤などのラジカル発生源の存在下に、通常の反応条件に従って、熱または光で重合させることにより調製することができる。各モノマーの配合組成、重合開始剤の量、加熱条件、反応時間などは、オルガノポリシロキサンチオブロックビニル共重合体[C]が前記のような酸価、ガラス転移温度(Tg)、重量平均分子量(Mw)などを有するものとなるよう調整することができる。
金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]は、典型的には、上記のようにして調製されたオルガノポリシロキサンチオブロックビニル共重合体[C]と、それらを架橋する2価の金属[M]の化合物と、必要に応じて水とを混合し、金属エステル化反応させることにより製造することができる。
本発明に係る金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]は、防汚塗料の樹脂成分(ビヒクル成分)として用いることが特に好適であるが、その他にも、たとえば貼り紙防止塗料、汚れ防止塗料、着氷・着雪防止塗料、離型材料等に用いることもでき、その用途は特に限定されるものではない。
本発明の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]を樹脂成分(ビヒクル成分)として用いることにより、防汚塗料組成物およびその他の組成物を製造することができる。
撥水性成分としては、ペトロラタム、パラフィンワックス、流動パラフィンなどのパラフィン類;ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、アルキル変性シリコーンオイル、フッ素含有シリコーンオイル(フロロシリコーンオイル)、末端官能基含有シリコーンオイルなどのシリコーンオイル;フロロポリエーテルオイルなどのフッ素オイル;カプリル酸、カプリン酸、ラウリン酸、パルミチン酸、ステアリン酸、オレイン酸等の長鎖脂肪酸及びそのエステル類;牛脂、豚脂、鱈脂、ヤシ油、パーム油などの天然油脂などが挙げられ、中でもジメチルシリコーンオイル、メチルフェニルシリコーンオイル、フッ素含有シリコーンオイル、パラフィン類が好ましい。
親水性成分としては、ポリエーテル変性シリコーンオイル(重合性基含有ポリエーテル変性シリコーン(a22)を除く。)が挙げられる。ポリエーテル変性シリコーンオイルのHLBは通常0~12の範囲(12以下)であり、好ましくは0~7の範囲である。ポリエーテル変性シリコーンオイルの種類としては、ペンダント型、両末端変性型、ブロック型のいずれでもよい。これらのポリエーテル変性シリコーンオイルとしては、ペンダント型としては「ST-114PA」(東レダウコーニング(株)製)、「FZ-2130」(東レダウコーニング(株)製)、「FZ-2191」(東レダウコーニング(株)製)、「KF-6016」(信越化学工業(株)製)、両末端変性型としては「X-22-4272」(信越化学工業(株)製)、「SLJ1623/3」(旭化成ワッカーシリコーン(株)製)、ブロック型としては「FZ-2203」(東レダウコーニング(株)製)、「FZ-2207」(東レダウコーニング(株)製)などが挙げられる。
防汚剤としては、金属銅、亜酸化銅、ロダン銅、塩基性硫酸銅、塩基性酢酸銅、塩基性炭酸銅、オキシキノリン銅、ナフテン酸銅、ロジン酸銅、銅ピリチオン、ジンクピリチオン、テトラメチルチウラムジサルファイト、2,4,5,6-テトラクロロイソフタロニトリル、N,N-ジメチルジクロロフェニル尿素、2-メチルチオ-4-tert-ブチルアミノ-6-シクロプロピルアミノ-s-トリアジン、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン、2,4,6-トリクロロフェニルマレイミド、ピリジン-トリフェニルボラン、アミン-トリフェニルボランなどが挙げられる。
溶剤としては、常温で適度の揮発性を有し、金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]の調製に用いられるモノマーならびに合成されたオルガノポリシロキサンチオブロックビニル共重合体[C]および金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]を溶解させうるものであれば特に制限はないが、例えば、トルエン、キシレン等の芳香族炭化水素、ヘキサン、ヘプタン等の脂肪族炭化水素;ジエチルエーテル、ジ-n-プロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類;酢酸エチル、酢酸ブチル等のエステル類;メチルエチルケトン、メチルイソブチルケトン等のケトン類;ジクロロメタン、クロロホルム等の塩素化炭化水素;メタノール、イソプロパノール、ブタノール等のアルコール類;エチ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等のグリコール誘導体系溶媒等が挙げられる。
溶出助剤としては、必要に応じて配合される撥水剤の表面移行を補助するような、または必要に応じて配合される防汚剤を効率的に除放させるような界面活性剤的作用を有する化合物を用いることができ、たとえば、ロジン、ナフテン酸等が挙げられる。
可塑剤としては、塗膜に可撓性を付与し、耐ワレ性や密着性を向上させる作用を有する化合物を用いることができ、たとえば、塩素化パラフィン、正リン酸エステル、フタル酸エステル等が挙げられる。
搖変剤(タレ止め剤・沈降防止剤)としては、塗装時の厚塗り性、タレ止性の向上や必要により塗料組成物に配合される顔料の沈降防止の作用を有する化合物を用いることができ、たとえば、有機粘土系ワックス(Al、Ca、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)および有機粘土系ワックスと有機系ワックスの混合物や、合成微粉シリカなどが挙げられ、中でも、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。
顔料(防汚剤として用いられる物質を除く。)としては、従来公知の有機系、無機系の各種着色または体質顔料を用いることができる。たとえば、有機系顔料としては、カーボンブラック、フタロシアニンブルー、紺青等が挙げられ、無機系顔料としては、酸化チタン(チタン白)、ベンガラ、シリカ、炭酸カルシウム、タルク、硫酸バリウム、酸化亜鉛(亜鉛華)、鉛白、鉛丹、亜鉛末等が挙げられる。
金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]以外の樹脂(塗膜形成成分)としては、たとえば、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、フッ素樹脂、ポリブテン樹脂、シリコーンゴム、ウレタン樹脂(ゴム)、ポリアミド樹脂、塩化ビニル系共重合樹脂、塩化ゴム(樹脂)、塩素化オレフィン樹脂、スチレン・ブタジエン共重合樹脂、エチレン-酢酸ビニル共重合樹脂、塩化ビニル樹脂、クマロン樹脂、トリアルキルシリルアクリレート(共)重合体(シリル系樹脂)、石油樹脂、ケトン樹脂、ホルムアルデヒド樹脂、ポリビニルアルキルエーテル樹脂等が挙げられる。
レベリング剤(消泡剤)としては、たとえば、フッ素系のレベリング剤、シリコーン系のレベリング剤、エーテル系又はエステル系のレベリング剤など、樹脂組成物のコーティング性をより向上させて、塗膜の仕上がり外観を改善し、薄膜として均一に塗布することができる作用を有するものが挙げられる。
紫外線吸剤(光安定化剤)としては、たとえば、シュウ酸アニリド系、サリチル酸系、ベンゾフェノン系、トリアジン系、ベンゾトリアゾール系、シアノアクリレート系等の有機系紫外線吸収剤;酸化チタン、酸化亜鉛、酸化セリウム等の無機系紫外線吸収剤;有機ニッケル化合物、ヒンダードアミン系等の光安定化剤など、従来より塗料組成物に配合して用いられている紫外線吸収作用及び/又は光安定化作用を有するものが挙げられる。
本発明の(防汚)塗料組成物は、調製された本発明の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体溶液を用いて、一般的な(防汚)塗料組成物と同様の従来公知の方法により製造することができる。本発明の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体溶液を調製した後、それをそのまま防汚塗料組成物として用いてもよい。必要に応じて、撥水性成分・親水性成分、シランカップリング剤、そのほか防汚剤、溶出助剤、可塑剤、脱水剤(安定剤)、搖変剤(タレ止め・沈降防止剤)、顔料、その他の塗膜形成成分、溶剤などの成分を配合する場合には、それらを所定の割合で一度にあるいは任意の順序で添加して撹拌、混合し均一に溶解・分散等すればよい。
本発明に係る防汚塗料組成物は、常時没水部のみならず乾湿交互部および水際部においても、アオサ、フジツボ、アオノリ、セルプラ、カキ、イガイ、コケムシ等の水棲生物に対する高い防汚性能を長期間安定的に有する、優れた防汚塗膜を形成することができる。たとえば、船舶、漁業資材(例:ロープ、魚網、浮き子、ブイ)、火力・原子力発電所の給排水口等の水中構造物、湾岸道路、海底トンネル、港湾設備、運河・水路、海洋土木工事の汚泥拡散防止膜などの各種基材もしくは下塗り表面に防汚塗料組成物を塗布すれば、水棲生物の付着を長期間防止できる優れた防汚塗膜で被覆された船舶、水中構造物、漁業資材などが得られる。防汚塗料組成物は、基材が鋼鉄、FRP、木、アルミニウム合金などである場合にもその表面に良好に付着し、また下塗りの塗膜や既存の防汚塗膜の表面に上塗りした場合の付着性(リコート性)にも優れている。
実施例および比較例で使用した原料(表2~5参照)は下記表に示すとおりである。
GPCおよびIRの測定条件は下記の通りである。
[GPC測定条件]
装置:東ソー社製 HLC-8120GPC
カラム:東ソー社製 Super H2000+H4000 6mm I.D., 15cm
溶離液:THF
流速:0.5ml/min
検出器:RI
カラム恒温槽温度:40℃
[IR測定条件]
装置:パーキンエルマー製 Spctrum One FT-IR
測定方法:KBrセル、塗布法
<重合性基含有ポリエーテル変性シリコーン(a22)の合成>
[合成例1]変性シリコーンS-1
攪拌装置、温度計、および還流冷却管を備えた反応容器に、FZ-2191(商品名「FZ-2191」、東レダウコーニング(株)製、側鎖OH基含有EO変性シリコーン、固形分100%、OH当量1150)1,150重量部を仕込んで、60℃まで昇温した。次いで2-メタクリロイルオキシエチルイソシアネート(商品名「カレンズMOI」、昭和電工(株)製)31重量部とp-メトキシフェノール0.59重量部と酢酸ブチル93重量部の混合液を30分で滴下し更に酢酸ブチル38重量部を投入して、60℃で1時間反応した。反応生成物をIR分析したところ、イソシアナート基吸収ピークは完全に消失した。
攪拌装置、温度計、および還流冷却管を備えた反応容器に、X-22-4272(商品名「X-22-4272」、信越化学工業(株)製、両末端OH基含有EO変性シリコーン、固形分100%、OH当量1122)1,122重量部と2-メタクリロイルオキシエチルイソシアネート(商品名「カレンズMOI」、昭和電工(株)製)77.5重量部とp-メトキシフェノール0.6重量部を仕込んで、95℃まで昇温し16時間反応した。
[実施例1]
(オルガノポリシロキサンチオブロックビニル共重合体B-1)
攪拌装置、温度計、窒素ガス導入管、滴下装置および還流冷却管を備えた反応容器に、酢酸ブチル32.1重量部とプロピレングリコールモノメチルエーテル(PGM)29.2重量部を仕込んで、窒素ガス雰囲気中で120℃まで昇温した。次いで、表2に示すように、メチルメタクリレート(MMA)57.5重量部、n-ブチルメタクリレート(BMA)5重量部、2-エチルヘキシルアクリレート(2EHA)5重量部、メトキシポリエチレングリコールメタクリレート(商品名「NKエステル M-230G」、新中村化学(株)製、-C2H4-O-単位数=23(平均値)、固形分100重量%)2.5重量部、メタクリル酸(MAA)2.5重量部、アクリル酸(AA)2.5重量部、重合開始剤のt-ブチルパーオキシ2-エチルヘキシサノエート(商品名「カヤエステルO」、化薬アクゾ(株)製、過酸化物)12重量部、プロピレングリコールモノメチルエーテル(PGM)3.5重量部の混合物Aと、KP-358(商品名「KP-358」、信越化学工業(株)製メルカプト変性シリコーン、重量平均分子量(Mw)4,400、固形分100重量%、SH基の位置は側鎖型)25重量部と酢酸ブチル12.5重量部の混合物Bとを、内温120℃を保ちながら同時に、上記反応容器に滴下開始した。混合液Aは4時間で滴下し、混合物Bは2時間で滴下した。混合物A滴下終了後に、更にt-ブチルパーオキシ2-エチルヘキシサノエートを1重量部と酢酸ブチル4.5重量部の混合追加触媒を30分で滴下した。その後2時間保温攪拌し、オルガノポリシロキサンチオブロックビニル共重合体B-1溶液を得た。この共重合体B-1溶液の外観は透明であり、フィルム外観は透明であり、NV(108℃の熱風乾燥機中3時間乾燥後の加熱残分)は52.4重量%であり、粘度は111mPa・s/25℃であり、酸価は19.6KOHmg/gであり、GPCで測定した共重合体B-1の重量平均分子量(Mw)は6,510であった。
上記と同様の装置に、上記共重合体B-1溶液824.4重量部と亜鉛華5.86重量部を仕込んで、窒素ガス雰囲気中30℃で30分攪拌後90℃まで昇温した。90℃で水3.89重量部加えた後、2時間保温攪拌した後、更に亜鉛華5.86重量部を加え2時間保温攪拌し、金属架橋型共重合体A-1溶液を得た。この金属架橋型共重合体A-1溶液の外観は透明、NV(108℃の熱風乾燥機中3時間乾燥後の加熱残分)は52.7重量%であり、粘度は4,420mPa・s/25℃であり、水分は0.84重量%であり、金属架橋型共重合体A-1のフィルム透明性は微白濁であった。
原料、触媒、溶剤等の配合量(表中の数値の単位は重量部)や反応時間等を表2に示すように変えた以外は、実施例1と同様にして、オルガノポリシロキサンチオブロックビニル共重合体B-2~B-4溶液を合成後、金属架橋型共重合体A-2~A-4溶液を合成し、各共重合体の物性を上記実施例1と同様に評価した。上記共重合体B-2~B-4溶液および上記共重合体A-2~A-4溶液の製造条件(原料、触媒、溶剤等の配合量(表中の数値の単位は重量部)、反応温度・時間等)、ならびに得られた上記共重合体B-2~B-4溶液および金属架橋型共重合体A-2~A-4溶液の性状などを表2に示す。また、金属架橋型共重合体A-2~A-4のIRスペクトルのチャートを図2~4に示す。
(オルガノポリシロキサンチオブロックビニル共重合体B-5)
攪拌装置、温度計、窒素ガス導入管、滴下装置および還流冷却管を備えた反応容器に、酢酸ブチル32.1重量部とプロピレングリコールモノメチルエーテル(PGM)29.2重量部を仕込んで、窒素ガス雰囲気中で120℃まで昇温した。次いで、表2に示すように、メチルメタクリレート(MMA)15重量部、n-ブチルメタクリレート(BMA)15重量部、n-ブチルアクリレート(BA)20重量部、2-エチルヘキシルアクリレート(2EHA)5重量部、シクロヘキシルアクリレート(CHA)5重量部、メタクリル酸(MAA)7.5重量部、アクリル酸(AA)7.5重量部、重合開始剤のt-ブチルパーオキシ2-エチルヘキシサノエート(商品名「カヤエステルO」、化薬アクゾ(株)製、過酸化物)12重量部、プロピレングリコールモノメチルエーテル(PGM)3.5重量部の混合物Aと、KP-358(商品名「KP-358」、信越化学工業(株)製メルカプト変性シリコーン、重量平均分子量Mw4400、固形分100重量%、SH基の位置は側鎖型)25重量部と酢酸ブチル12.5重量部の混合物Bとを、内温120℃を保ちながら同時に、上記反応容器に滴下開始した。混合液Aは4時間で滴下し、混合物Bは2時間で滴下した。混合物A滴下終了後に、更にt-ブチルパーオキシ2-エチルヘキシサノエートを1重量部と酢酸ブチル4.5重量部の混合追加触媒を30分で滴下した。その後2時間保温攪拌し、オルガノポリシロキサンチオブロックビニル共重合体B-5溶液を得た。この共重合体B-5溶液の外観は透明であり、フィルム外観は白濁であり、NV(108℃の熱風乾燥機中3時間乾燥後の加熱残分)は53.6重量%であり、粘度は74mPa・s/25℃であり、酸価は52.8KOHmg/gであり、GPCで測定した共重合体B-5の重量平均分子量(Mw)は5,860であった。
上記と同様の装置に、上記共重合体B-5溶液794.8重量部と亜鉛華15.22重量部を仕込んで、窒素ガス雰囲気中で30℃で30分攪拌後90℃まで昇温した。90℃で水10.1重量部加えた後、2時間保温攪拌した後、更に亜鉛華15.22重量部加え13時間保温攪拌した後、酢酸ブチル38.45重量部とプロピレングリコールモノメチルエーテル(PGM)25.66重量部を加えて、金属架橋型共重合体A-5溶液を得た。この金属架橋型共重合体A-5溶液の外観は透明、NV(108℃の熱風乾燥機中3時間乾燥後の加熱残分)は49.5重量%であり、粘度は3,980mPa・s/25℃であり、金属架橋型共重合体A-5のフィルム透明性はクリアであった。
原料、触媒、溶剤等の配合量(表中の数値の単位は重量部)や反応時間等を表2に示すように変えた以外は、実施例5と同様にして、オルガノポリシロキサンチオブロックビニル共重合体B-6~B-15溶液を合成後、金属架橋型共重合体A-6~A-15溶液を合成し、各共重合体の物性を上記実施例5と同様に評価した。上記共重合体B-6~B-15溶液および金属架橋型共重合体A-6~A-15溶液の製造条件(原料、触媒、溶剤等の配合量(表中の数値の単位は重量部)、反応温度・時間等)、ならびに得られた上記共重合体B-6~B-15溶液および金属架橋型共重合体A-6~A-15溶液の性状などを表2に示す。また、金属架橋型共重合体A-6~A-15のIRスペクトルのチャートを図6~15に示す。
(オルガノポリシロキサンチオブロックビニル共重合体B-16)
攪拌装置、温度計、窒素ガス導入管、滴下装置および還流冷却管を備えた反応容器に、キシレン40.3重量部とプロピレングリコールモノメチルエーテル(PGM)21重量部を仕込んで、窒素ガス雰囲気中で120℃まで昇温した。次いで、表2に示すように、メチルメタクリレート(MMA)42.5重量部、n-ブチルアクリレート(BA)10重量部、2-エチルヘキシルアクリレート(2EHA)12.5重量部、メタクリル酸(MAA)5重量部、アクリル酸(AA)5重量部、重合開始剤のt-ブチルパーオキシ2-エチルヘキシサノエート(商品名「カヤエステルO」、化薬アクゾ(株)製、過酸化物)12重量部、プロピレングリコールモノメチルエーテル(PGM)3.5重量部の混合物Aと、KP-358(商品名「KP-358」、信越化学工業(株)製メルカプト変性シリコーン、重量平均分子量(Mw)4,400、固形分100重量%、SH基の位置は側鎖型)25重量部と酢酸ブチル12.5重量部の混合物Bとを、内温120℃を保ちながら同時に、上記反応容器に滴下開始した。混合液Aは4時間で滴下し、混合物Bは2時間で滴下した。混合物A滴下終了後に、更にt-ブチルパーオキシ2-エチルヘキシサノエートを1重量部と酢酸ブチル4.5重量部の混合追加触媒を30分で滴下した。その後2時間保温攪拌し、オルガノポリシロキサンチオブロックビニル共重合体B-16溶液を得た。この共重合体B-16溶液の外観は透明であり、フィルム外観は透明であり、NV(108℃の熱風乾燥機中3時間乾燥後の加熱残分)は53.7重量%であり、粘度は90mPa・s/25℃であり、酸価は36.4KOHmg/gであり、GPCで測定した共重合体B-16の重量平均分子量(Mw)は6,140であった。
上記と同様の装置に、上記共重合体B-16溶液644.2重量部と酢酸銅41.73重量部とキシレン142.03重量部と20%KF-96-1000キシレン溶液(商品名「KF-96-1000」、信越化学工業(株)製ジメチルシリコーンオイル、粘度1000cSt)0.36重量部を仕込んで、窒素ガス雰囲気中30℃で30分攪拌後90℃まで昇温した。90℃で2時間保温攪拌した後、加熱して溶剤を回収しながら4.5時間で150℃まで昇温した。回収溶剤327.6重量部。冷却してキシレン397.5重量部を加え、金属架橋型共重合体A-16溶液を得た。この金属架橋型共重合体A-16溶液の外観は透明、NV(108℃の熱風乾燥機中3時間乾燥後の加熱残分)は40.2重量%であり、粘度は19,610mPa・s/25℃であり、金属架橋型共重合体A-16のフィルム透明性はクリアであった。
(共重合体H-1)
攪拌装置、温度計、窒素ガス導入管、滴下装置および還流冷却管を備えた反応容器に、酢酸ブチル40.5重量部とKF-2001(商品名「KF-2001」、信越化学工業(株)製メルカプト変性シリコーン、重量平均分子量(Mw)9,200、固形分100重量%、SH基の位置は側鎖型)25重量部とメトキシポリエチレングリコールメタクリレート(商品名「NKエステル M-230G」、新中村化学(株)製、-C2H4-O-単位数=23(平均値)、固形分100重量%)2.5重量部を仕込んで、窒素ガス雰囲気中で110℃まで昇温した。次いで、表3に示すように、メチルメタクリレート(MMA)42.5重量部、n-ブチルメタクリレート(BMA)20重量部、2-エチルヘキシルアクリレート(2EHA)10重量部、重合開始剤のt-ブチルパーオキシ2-エチルヘキシサノエート(商品名「カヤエステルO」、化薬アクゾ(株)製、過酸化物)2.5重量部の混合物Aを、内温120℃を保ちながら3時間で滴下した。混合物Aの滴下終了1時間後に、更にt-ブチルパーオキシ2-エチルヘキシサノエートの酢酸ブチル溶液(20重量%)1重量部を45分毎に3回加えた後1.5時間保温攪拌し、共重合体H-1溶液を得た。この共重合体H-1溶液の外観は透明であり、フィルム外観は透明であり、NV(108℃の熱風乾燥機中3時間乾燥後の加熱残分)は64.3重量%であり、粘度は6,800mPa・s/25℃であり、GPCで測定した共重合体H-1の重量平均分子量(Mw)は31,710であった。
配合組成を表3に示すように変えた以外は、実施例1の共重合体B-1溶液と同様にして、共重合体H-2~H-3溶液を合成した。各共重合体の物性を上記実施例1と同様に評価した。共重合体H-2~H-3溶液の製造の際の、原料の配合組成(重量部)、触媒、溶剤、反応温度などの他、共重合体H-2~H-3溶液の性状などを表3に示す。
(共重合体H-4)
攪拌装置、温度計、窒素ガス導入管、滴下装置および還流冷却管を備えた反応容器に、キシレン66.66重量部を仕込んで、窒素ガス雰囲気中で90℃まで昇温した。次いで、表3に示すように、メチルメタクリレート(MMA)40重量部、n-ブチルメタクリレート(BMA)60重量部、重合開始剤の2,2’-アゾビス(2-メチルブチロニトリル)(商品名「ABN-E」、日本ヒドラジン(株)製、アゾ化合物)3.2重量部の混合物Aを、内温90℃を保ちながら2時間で滴下した。混合物Aの滴下終了1時間後に、更に2,2’-アゾビスイソブチロニトリル(商品名「ABN-R」、日本ヒドラジン(株)製、アゾ化合物)0.05重量部4時間で95℃昇温し2,2’-アゾビスイソブチロニトリル0.1重量部を30分毎に2回加えた後、105℃昇温し30分保温攪拌し、共重合体H-4溶液を得た。この共重合体H-4溶液の外観は透明であり、フィルム外観は透明であり、NV(108℃の熱風乾燥機中3時間乾燥後の加熱残分)は59.5重量%であり、粘度は5,640mPa・s/25℃であり、GPCで測定した共重合体H-4の重量平均分子量(Mw)は14,816であった。
[実施例F-1]
表4に示すように、金属架橋型共重合体A-1溶液(NV=52.7%)100重量部、それぞれ撥水性成分および親水性成分としてシリコーンオイルKF-54(商品名「KF-54」信越化学工業(株)製、メチルフェニルシリコーンオイル)5重量部及びKF-6016(商品名「KF-6016」、信越化学工業(株)製、側鎖型ポリエーテル変性シリコーンオイル、HLB 3.5)10重量部、消泡剤としてKF-96-1000(商品名「KF-96-1000」、信越化学工業(株)製、ジメチルシリコーンオイル)0.5重量部、溶剤としてキシレン10重量部、顔料としてフジファーストレッド2305W(商品名「フジファーストレッド2305W」、富士色素(株)製、有機赤色顔料)1.5重量部及び酸化チタン(商品名「R-5N」、堺化学(株)製)3重量部ならびに添加剤(搖変剤)としてディスパロン6900-10X(商品名「ディスパロン6900-10X」、楠本化成(株)製、脂肪酸アマイドワックス、10%キシレンペースト)6重量部をガラスビーズをメディアとしたペイントシェーカーに仕込み2時間振とうした後、120メッシュのフィルターにてろ過して防汚塗料組成物を調製した。
表4(実施例)および表5(比較例)に示すように共重合体溶液の種類および各成分の配合量を換えたほかは実施例F-1と同様にして、防汚塗料組成物を調製した。
上記各防汚塗料組成物の防汚性評価を行った。結果を表4(実施例)および表5(比較例)に示す。各評価の試験方法は下記の通りである。
100mm×300mm×2.3mmのサンドブラスト鋼板にエポキシ系ジンクリッチプライマー(中国塗料(株)製「エピコンジンクリッチプライマーB-2」、エポキシ系防食塗料(中国塗料(株)製「バンノー500」)、エポキシ系防食塗料(中国塗料(株)「バンノー500R」)を、それぞれ乾燥膜厚が20μm、150μm、100μmとなるようエアースプレーを用いて塗装した。形成されたエポキシ系バインダーコート表面に上記防汚塗料組成物を、その乾燥膜厚が150μmとなるように塗装し、試験板を作製した。一週間室内で乾燥した後、広島湾内に設置された筏より水面下1mとなるように浸漬し、18ヶ月間の生物付着状況を目視観察した。
4点 海中生物の付着面積が5%以下
3点 海中生物の付着面積が5%を超える10%以下
2点 海中生物の付着面積が10%を超える25%以下
1点 海中生物の付着面積が25%を超える50%以下
0点 海中生物の付着面積が50%を超える
[半没水防汚試験]
100mm×300mm×2.3mmのサンドブラスト鋼板にエポキシ系ジンクリッチプライマー(中国塗料(株)製「エピコンジンクリッチプライマーB-2」、エポキシ系防食塗料(中国塗料(株)製「バンノー500」)、エポキシ系防食塗料(中国塗料(株)「バンノー500R」)を、それぞれ乾燥膜厚が20μm、150μm、100μmとなるようエアースプレーを用いて塗装した。形成されたエポキシ系バインダーコート表面に上記防汚塗料組成物を、その乾燥膜厚が150μmとなるように塗装し、一週間室内で乾燥して、試験板を作製した。試験板を広島湾内に設置された筏より水面下に半分浸漬する状態で浸漬し、18ヶ月間の生物付着状況を目視観察した。
4点 海中生物の付着面積が5%以下
3点 海中生物の付着面積が5%を超える10%以下
2点 海中生物の付着面積が10%を超える25%以下
1点 海中生物の付着面積が25%を超える50%以下
0点 海中生物の付着面積が50%を超える
[リコート性評価]
70mm×150mm×2.3mmの湾曲サンドブラスト鋼板にエポキシ系ジンクリッチプライマー(中国塗料(株)製「エピコンジンクリッチプライマーB-2」、エポキシ系防食塗料(中国塗料(株)製「バンノー500」)、エポキシ系防食塗料(中国塗料(株)「バンノー500R」)を、それぞれ乾燥膜厚が20μm、150μm、100μmとなるようエアースプレーを用いて塗装した。乾燥後、アプリケーターを用いて上記防汚塗料組成物を乾燥膜厚が150μmとなるように塗装し、1週間室内で乾燥して、試験片を作成した。広島湾内に設置した海中回転装置に試験片を取り付け、6ヶ月間15Knで回転させた。試験片を回収し、真水水洗1日乾燥後、同種防汚塗料組成物を乾燥膜厚が150μmとなるよう上塗り塗装した。試験片中央に下塗り防汚塗料に達する60°のカットを入れ回転装置に取り付け海中で回転させ、防汚塗膜相互の付着性を試験した。
5点 剥離なし
4点 カット線に沿って点状に一部分剥離
3点 カット線に沿って約1mm幅で部分的に剥離
2点 カット線に沿って約2mm幅で殆ど剥離
1点 クロスカット部分がかなり剥離し、一部分の塗膜が残る
0点 殆ど剥離
Claims (22)
- 重合性不飽和カルボン酸(a1)から誘導された成分単位と該重合性不飽和カルボン酸と共重合可能な少なくとも1種の他の重合性不飽和単量体(a2)から誘導された成分単位とから形成されたカルボン酸含有ビニル共重合体ブロック[A]と、下記式[I]で表されるオルガノポリシロキサンチオブロック[B]とを有するオルガノポリシロキサンチオブロックビニル共重合体[C]が、2価の金属[M]で架橋された構造を有する、金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D];
- 前記重合性不飽和カルボン酸(a1)が、(メタ)アクリル酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸またはウンデシレン酸から選択された少なくとも1種である、請求項1に記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]。
- 前記重合性不飽和単量体(a2)が、重合性不飽和カルボン酸エステル(a21)、または重合性不飽和カルボン酸エステル(a21)と重合性基含有ポリエーテル変性シリコーン(a22)である、請求項1または2に記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]。
- 前記重合性不飽和カルボン酸エステル(a21)が、(メタ)アクリル酸エステル類、スチレン類、ビニルエステル類、(メタ)アクリルアミド類またはビニルエーテル類から選択された少なくとも1種である、請求項3に記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]。
- 前記重合性基含有ポリエーテル変性シリコーン(a22)のHLBが18以下である、請求項3に記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]。
- 前記オルガノポリシロキサンチオブロックビニル共重合体[C]の酸価が1~200である、請求項1~5のいずれかに記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]。
- 前記オルガノポリシロキサンチオブロックビニル共重合体[C]のガラス転移温度(Tg)が-50℃~60℃である、請求項1~6のいずれかに記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]。
- 前記オルガノポリシロキサンチオブロックビニル共重合体[C]の重量平均分子量(Mw)が1,000~200,000である、請求項1~7のいずれかに記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]。
- 前記2価の金属[M]が、亜鉛、銅、コバルト、ニッケル、マンガン、マグネシウムまたはカルシウムから選択された少なくとも1種である、請求項1~8のいずれかに記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]。
- 固形分100重量%中、カルボン酸含有ビニル共重合体ブロック[A]が5~98.5重量%、オルガノポリシロキサンチオブロック[B]が1~80重量%、および2価の金属が0.5~16重量%の割合を占める、請求項1~9のいずれかに記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]。
- 不揮発分50重量%における粘度が50~100,000mPa・s/25℃である、請求項1~10のいずれかに記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]。
- 請求項1~11のいずれかに記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]と、撥水性成分および/または親水性成分とを含有することを特徴とする金属架橋型オルガノポリシロキサンチオブロックビニル共重合体組成物。
- 前記撥水性成分が、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、フッ素含有シリコーンオイル、フッ素オイルまたはパラフィン類から選択された少なくとも1種である、請求項12に記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体組成物。
- 前記親水性成分がHLB12以下のポリエーテル変性シリコーンオイル類である、請求項12または13に記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体組成物。
- 請求項1~11のいずれかに記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]または請求項12~14のいずれかに記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体組成物を含有することを特徴とする防汚塗料組成物。
- さらに防汚剤を含有することを特徴とする請求項15に記載の防汚塗料組成物。
- 請求項12~14のいずれかに記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体組成物または請求項15もしくは16に記載の防汚塗料組成物から形成された防汚塗膜。
- 基材の表面が、請求項12~14のいずれかに記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体組成物または請求項15もしくは16に記載の防汚塗料組成物を硬化させてなる塗膜で被覆されていることを特徴とする塗膜付き基材。
- 基材の表面が請求項17に記載の防汚塗膜で被覆された水中構造物。
- 船舶基材の表面が請求項17に記載の防汚塗膜で被覆された船舶。
- 基材表面を請求項17に記載の防汚塗膜で被覆することを特徴とする基材の防汚方法。
- 前記オルガノポリシロキサンチオブロックビニル共重合体[C]と、前記2価の金属[M]の酸化物、水酸化物、塩化物または有機カルボン酸塩から選ばれる少なくとも1種を混合し、金属エステル化反応させることを特徴とする、請求項1~11のいずれかに記載の金属架橋型オルガノポリシロキサンチオブロックビニル共重合体[D]の製造方法。
Priority Applications (6)
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US13/516,406 US8846821B2 (en) | 2009-12-18 | 2010-12-16 | Metal-crosslinked organopolysiloxane-thio block vinyl copolymer and antifouling coating composition containing the metal-crosslinked copolymer |
EP20100837645 EP2514776B1 (en) | 2009-12-18 | 2010-12-16 | Metal-crosslinked organopolysiloxane-thio block vinyl copolymer, and antifouling coating composition containing the copolymer |
SG2012044970A SG181792A1 (en) | 2009-12-18 | 2010-12-16 | Metal-crosslinked organopolysiloxane-thio block vinyl copolymer, and antifouling coating composition containing the copolymer |
CN201080057461.2A CN102666618B (zh) | 2009-12-18 | 2010-12-16 | 金属交联型有机聚硅氧烷硫代嵌段乙烯基共聚物及包含该金属交联型共聚物的防污涂料组合物 |
JP2011546156A JP5557852B2 (ja) | 2009-12-18 | 2010-12-16 | 金属架橋型オルガノポリシロキサンチオブロックビニル共重合体および該金属架橋型共重合体を含有する防汚塗料組成物 |
KR1020127015211A KR101464055B1 (ko) | 2009-12-18 | 2010-12-16 | 금속 가교형 오르가노폴리실록산 티오 블록 비닐 공중합체 및 그 금속 가교형 공중합체를 함유하는 방오도료 조성물 |
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US (1) | US8846821B2 (ja) |
EP (1) | EP2514776B1 (ja) |
JP (1) | JP5557852B2 (ja) |
KR (1) | KR101464055B1 (ja) |
CN (1) | CN102666618B (ja) |
SG (1) | SG181792A1 (ja) |
WO (1) | WO2011074620A1 (ja) |
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CN102702975A (zh) * | 2012-06-12 | 2012-10-03 | 天长市巨龙车船涂料有限公司 | 防污涂料组合物、防污涂膜以及船舶和水下结构体 |
KR20160091915A (ko) * | 2013-12-03 | 2016-08-03 | 아크조노벨코팅스인터내셔널비.브이. | 기판 상에 에이징된 코팅층의 코팅 방법, 및 이 방법에 사용하기에 적합한 코팅 조성물 |
KR102354241B1 (ko) * | 2013-12-03 | 2022-01-21 | 아크조노벨코팅스인터내셔널비.브이. | 기판 상에 에이징된 코팅층의 코팅 방법, 및 이 방법에 사용하기에 적합한 코팅 조성물 |
JP2018080275A (ja) * | 2016-11-17 | 2018-05-24 | 中国塗料株式会社 | 防汚塗料組成物、防汚塗膜およびこれらの用途 |
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JP2019006982A (ja) * | 2017-06-23 | 2019-01-17 | 中国塗料株式会社 | 耐熱塗料組成物、耐熱塗膜、耐熱塗膜付き基材およびその製造方法 |
JP7089938B2 (ja) | 2017-06-23 | 2022-06-23 | 中国塗料株式会社 | 耐熱塗料組成物、耐熱塗膜、耐熱塗膜付き基材およびその製造方法 |
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JP7417457B2 (ja) | 2020-03-30 | 2024-01-18 | 関西ペイントマリン株式会社 | 防汚塗膜及び塗装物 |
DE112022003486T5 (de) | 2021-09-28 | 2024-06-06 | Autonetworks Technologies, Ltd. | Isolierter Draht, Kabelbaum und Herstellungsverfahren für isolierten Draht |
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Also Published As
Publication number | Publication date |
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US20120258321A1 (en) | 2012-10-11 |
EP2514776A4 (en) | 2014-03-12 |
CN102666618B (zh) | 2014-11-26 |
JPWO2011074620A1 (ja) | 2013-04-25 |
KR20120095416A (ko) | 2012-08-28 |
JP5557852B2 (ja) | 2014-07-23 |
SG181792A1 (en) | 2012-07-30 |
KR101464055B1 (ko) | 2014-11-20 |
US8846821B2 (en) | 2014-09-30 |
EP2514776B1 (en) | 2014-12-10 |
EP2514776A1 (en) | 2012-10-24 |
CN102666618A (zh) | 2012-09-12 |
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