WO2018062267A1 - 構造物上の塗膜、塗膜を形成するための塗料セット及び下塗層用塗料並びに塗工方法 - Google Patents
構造物上の塗膜、塗膜を形成するための塗料セット及び下塗層用塗料並びに塗工方法 Download PDFInfo
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- WO2018062267A1 WO2018062267A1 PCT/JP2017/034951 JP2017034951W WO2018062267A1 WO 2018062267 A1 WO2018062267 A1 WO 2018062267A1 JP 2017034951 W JP2017034951 W JP 2017034951W WO 2018062267 A1 WO2018062267 A1 WO 2018062267A1
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
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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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B59/00—Hull protection specially adapted for vessels; Cleaning devices specially adapted for vessels
- B63B59/04—Preventing hull fouling
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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
- C09D121/00—Coating compositions based on unspecified rubbers
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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
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
-
- 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
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D153/02—Vinyl aromatic monomers and conjugated dienes
- C09D153/025—Vinyl aromatic monomers and conjugated dienes modified
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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
- C09D183/04—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
- C09D201/00—Coating compositions based on unspecified 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
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
-
- 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
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02B—HYDRAULIC ENGINEERING
- E02B1/00—Equipment or apparatus for, or methods of, general hydraulic engineering, e.g. protection of constructions against ice-strains
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02B—HYDRAULIC ENGINEERING
- E02B17/00—Artificial islands mounted on piles or like supports, e.g. platforms on raisable legs or offshore constructions; Construction methods therefor
- E02B17/0017—Means for protecting offshore constructions
- E02B17/0026—Means for protecting offshore constructions against corrosion
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02B—HYDRAULIC ENGINEERING
- E02B5/00—Artificial water canals, e.g. irrigation canals
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D29/00—Independent underground or underwater structures; Retaining walls
- E02D29/06—Constructions, or methods of constructing, in water
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D2300/00—Materials
- E02D2300/0001—Rubbers
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D2300/00—Materials
- E02D2300/0004—Synthetics
- E02D2300/0006—Plastics
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D2300/00—Materials
- E02D2300/0004—Synthetics
- E02D2300/0025—Adhesives, i.e. glues
Definitions
- the present invention relates to a coating film for preventing the adhesion of contaminants to a structure and protecting the structure, in particular, a coating film for preventing the attachment of aquatic organisms to an underwater structure, and a coating material for forming such a coating film. And it is related with the method of forming this coating film.
- the present invention includes, for example, ships, buoys, harbor facilities, offshore oil field facilities, water passages for power plant cooling water, water floating passages, water gates, underwater sensors, underwater cameras, underwater lights, underwater pumps, underwater piping, Underwater organisms adhere to underwater structures such as underwater power generation facilities (for example, tidal power generation facilities, ocean current power generation facilities, wave power generation facilities, offshore wind power generation facilities), underwater rotating bodies such as propellers, and various underwater mooring devices such as underwater wires. It is related with the coating film, coating material, and method for preventing that it propagates.
- underwater power generation facilities for example, tidal power generation facilities, ocean current power generation facilities, wave power generation facilities, offshore wind power generation facilities
- underwater rotating bodies such as propellers
- various underwater mooring devices such as underwater wires. It is related with the coating film, coating material, and method for preventing that it propagates.
- aquatic organisms such as barnacles, oysters, blue mussels, hydra, cell plastics, squirts, bryozoans, Aosa, Aonori, and attached diatoms may adhere to and propagate in areas that come into contact with water.
- aquatic organisms decrease the mechanical performance of facilities such as a decrease in thermal conductivity and the aesthetics of tourist facilities and ships, but especially in ships, the increase in fluid resistance reduces speed and fuel consumption. Causes deterioration.
- aquatic organisms attached to the ship spread to other areas and cause disturbance of the aquatic environment.
- Patent Document 1 discloses an antifouling paint that coats the surface of an underwater structure to prevent marine organisms from adhering.
- Such an antifouling paint uses a composition having low toxicity by using a photocatalyst, unlike a conventional method.
- a composition having an antifouling effect is included in the binder and loses its effect, a surface-side layer containing an antifouling agent, a layer containing such an antifouling agent, and the surface of the structure And means having an adhesive for adhering both.
- Patent Document 2 discloses zinc bisdimethyldithiocarbamoylethylenebisdithiocarbamate, (meth) acrylate resin, polyether silicone having a number average molecular weight of 500 to 20,000, monobasic acid having a molecular weight of 250 or more, or a metal thereof.
- An antifouling composition containing salt is provided. Such an antifouling composition improves not only the antifouling property but also the storage stability.
- Patent Document 1 mentions the ease of removal of the antifouling paint, but does not disclose that the paint film is peeled off in the form of a sheet, and the removal work of the paint film still involves difficulty. It was. From this, it can be said that, after all, Patent Document 2 discloses only an invention that polishes and removes the coating film, and it is heavy labor and high cost.
- Patent Document 2 is intended to extend the life of the coating film, but the extension of the life is to alleviate the deterioration of the antifouling performance.
- the adhesive strength is reduced and the coating film is easily peeled off.
- the coating film may be peeled from the underwater structure because it receives resistance from water.
- the present invention has been made to solve the above-described problems, and is capable of sheet peeling, facilitates the removal operation, and receives, for example, an underwater structure that involves underwater movement and rough waves.
- a coating film that is resistant to water flow, such as an underwater structure used in a place, and is difficult to peel even when used for a long time in a stationary underwater structure.
- the present invention also provides a paint set and an undercoat paint for forming a coating film having the above properties, and a method for forming such a coating film.
- the present invention provides a paint for an undercoat layer for forming a coating film that is difficult to peel off even in structures other than water and that can be easily peeled off.
- the present invention is a coating film on a structure, and includes an undercoat layer that adheres to the structure, and an antifouling layer that adheres to the undercoat layer.
- the ratio of the tensile strength at break (N / 20 mm) after being immersed in pure water at 60 ° C. for 5 weeks to the adhesive force (N / 20 mm) with the underwater structure is 1.
- a coating film characterized by being 5 or more and having a 1 mm square crosscut stretch peeling degree of 0.05 or less with respect to the undercoat layer of the antifouling layer.
- the undercoat layer of such a coating film preferably contains an elastomer.
- the elastomer is preferably modified with a compound containing a polar group in order to increase the adhesion to the antifouling layer.
- the antifouling layer contains a silicone resin from the viewpoint of being hardly deteriorated.
- the underwater constant load peeling degree is preferably less than 3, more preferably less than 1, more preferably less than 0.5, still more preferably less than 0.2, still more preferably less than 0.1, and 0.0 Is most preferred.
- the ratio is preferably 3.0 or more, more preferably 5.0 or more, and even more preferably 15 or more.
- the 1 mm square crosscut stretch peeling degree is preferably 0.04 or less, more preferably 0.03 or less, still more preferably 0.01, and most preferably 0.00.
- the adhesive force is preferably 4.0 to 15.
- the present invention is a paint set for forming a coating film comprising an undercoat layer adhered to a structure and an antifouling layer adhered to the undercoat layer, wherein the undercoat layer is formed.
- the undercoat layer paint adheres to the PMMA as a layer having a thickness of 150 ⁇ m and is used for the antifouling layer.
- the 100-gram water constant load peel rate is less than 5 (mm / 20 mm) and is immersed in pure water at 60 ° C. for 5 weeks.
- the ratio of the tensile strength at break (N / 20 mm) to the adhesive force (N / 20 mm) after the treatment is 1.5 or more, and the antifouling layer paint layer has a 1 mm square cross to the undercoat layer paint layer.
- a paint set characterized by a cut stretch peeling degree of 0.05 or less.
- the undercoat layer coating material preferably contains an elastomer, that is, a thermoplastic elastomer or a thermosetting elastomer, but is particularly preferably a thermoplastic elastomer.
- the elastomer is preferably modified with a compound containing a polar group in order to increase the adhesion to the antifouling layer.
- the antifouling layer coating material contains a silicone resin from the viewpoint of being hardly deteriorated.
- the degree of underwater constant load peeling is preferably less than 3, more preferably less than 1, more preferably less than 0.5, more preferably less than 0.2, and even more preferably less than 0.1. 0 is most preferred.
- the ratio is preferably 3.0 or more, more preferably 5.0 or more, and even more preferably 15 or more.
- the 1 mm square crosscut stretch peeling degree is preferably 0.04 or less, more preferably 0.03 or less, still more preferably 0.01, and most preferably 0.00.
- the adhesive force is preferably 4.0 to 15.
- the present invention is a method of forming a coating film comprising an undercoat layer adhered to a structure and an antifouling layer adhered to the undercoat layer, wherein the structure is used for an undercoat layer. Applying a paint to form an undercoat layer; and applying an antifouling layer paint to the undercoat layer to form an antifouling layer.
- the 100 g underwater constant load peel strength is 5 (mm
- the ratio of the tensile strength at break (N / 20 mm) to the adhesive force (N / 20 mm) after being immersed in pure water at 60 ° C. for 5 weeks is 1.5 or more, and is for an antifouling layer.
- the 1 mm square cross-cut stretch release degree of the paint layer to the undercoat paint layer is 0.05 or less.
- the undercoat paint used in such a method preferably contains an elastomer, that is, a thermoplastic elastomer or a thermosetting elastomer, but is particularly preferably a thermoplastic elastomer.
- the elastomer is preferably modified with a compound containing a polar group in order to increase the adhesion to the antifouling layer. It is preferable that the antifouling layer coating material contains a silicone resin from the viewpoint of being hardly deteriorated.
- the underwater constant load peeling degree is preferably less than 3, more preferably less than 1, more preferably less than 0.5, preferably less than 0.3, more preferably less than 0.2, and less than 0.1. Is more preferable, and 0.0 is most preferable.
- the ratio is preferably 3.0 or more, more preferably 5.0 or more, and even more preferably 15 or more.
- the 1 mm square crosscut stretch peeling degree is preferably 0.04 or less, more preferably 0.03 or less, still more preferably 0.01, and most preferably 0.00.
- the adhesive force is preferably 4.0 to 15.
- an undercoat layer for forming an undercoat layer comprising a primer layer adhered to a structure and a silicone resin antifouling layer adhered to the primer layer.
- the paint for the undercoat layer adheres to PMMA as a layer having a thickness of 150 ⁇ m
- the paint for the antifouling layer adheres to the layer of paint for the undercoat layer as a layer having a thickness of 100 ⁇ m
- 100 g underwater constant load peeling degree is less than 5 (mm / 20 mm)
- the ratio of the tensile strength at break (N / 20 mm) to the adhesive strength (N / 20 mm) after being immersed in pure water at 60 ° C. for 5 weeks is
- An undercoat layer paint characterized in that the antifouling layer paint layer has a 1 mm square cross-cut stretch release degree of 0.05 or less with respect to the undercoat layer paint layer. I will provide a.
- the present invention provides, as another aspect, an undercoat layer for forming an undercoat layer of a coating film comprising an undercoat layer adhered to a structure and a silicone resin antifouling layer adhered to the undercoat layer.
- the undercoat layer paint adheres to PMMA as a layer having a thickness of 150 ⁇ m
- the antifouling layer paint adheres to the undercoat layer paint layer
- the force is 0.5 (N / 20 mm) or more
- the ratio of the tensile strength at break (N / 20 mm) to the adhesive force (N / 20 mm) is 1.5 or more
- the undercoat layer coating composition is characterized by having a 1 mm square cross-cut stretch peeling degree with respect to the undercoat layer coating layer of 0.05 or less.
- the primer coating used in these methods preferably contains an elastomer.
- the elastomer is preferably modified with a compound containing a polar group in order to increase the adhesion to the antifouling layer.
- the degree of underwater constant load peeling is preferably less than 3, more preferably less than 1, more preferably less than 0.5, more preferably less than 0.2, and even more preferably less than 0.1. 0 is most preferred.
- the ratio is preferably 3.0 or more, more preferably 5.0 or more, and even more preferably 15 or more.
- the 1 mm square crosscut stretch peeling degree is preferably 0.04 or less, more preferably 0.03 or less, still more preferably 0.01, and most preferably 0.00.
- the adhesive force is preferably 4.0 to 15.
- FIG. 1 is a schematic cross-sectional view of a coating film 1 applied to an underwater structure 4 according to an embodiment of the present invention.
- the coating film is formed as a laminate including an undercoat layer 2 and an antifouling layer 3 in order from the underwater structure side.
- a paint set comprising a predetermined undercoat layer paint and antifouling layer paint is prepared, and the undercoat layer paint is applied to the underwater structure and dried, followed by the antifouling layer paint.
- the coating film can be prepared by applying and drying.
- the thickness of the undercoat layer may be set according to the application and the later-described tensile breaking strength, and is not particularly limited, but is, for example, 50 ⁇ m to 500 ⁇ m, preferably 70 ⁇ m to 300 ⁇ m, More preferably, it is 100 ⁇ m to 200 ⁇ m. Further, since the tensile rupture strength described later mainly depends on the undercoat layer, the tensile rupture strength can be adjusted by changing the thickness of the undercoat layer. Since the thickness of the antifouling layer usually has almost no influence on the tensile strength at break, it may be appropriately set depending on the application and the like, and is not particularly limited. For example, it is 50 ⁇ m to 500 ⁇ m, preferably 70 ⁇ m. To 300 ⁇ m, and more preferably 100 ⁇ m to 200 ⁇ m.
- the coating film shown in FIG. 1 has the following properties.
- the underwater constant load peeling degree indicates the degree of ease of peeling of the coating film when the coating film receives resistance in water.
- the 100 gram underwater constant load peel degree indicates the amount of the coating film peeled off from the adherend when one hour has passed under a 100 gram load in water, and is a value measured by the following method. is there.
- FIG. 2 is a schematic cross-sectional view showing the technical meaning of a 100 gram underwater constant load peel degree (mm / 20 mm).
- a coating film is prepared by applying a coating for an undercoat layer and a coating for an antifouling layer to the object to be deposited with a width of 20 mm.
- a fixed amount for example, 20 mm is peeled off from the coating film, and a weight adjusted to 100 g in water is attached to the peeled portion.
- the coating film was immersed in a 23 degreeC pure water tank so that a peeling angle might be 180 degree
- the distance [mm] at which the peeled portion peels from each adherend after 1 hour is the 100 gram underwater constant load peel degree (mm / 20 mm).
- Equation 1 is an expression relating to a pressure resistance for calculating a force generated on a surface having a width of 20 mm and a height of 500 ⁇ m by water having a flow rate of 30 knots.
- the reason why the height is 500 ⁇ m is that the thickness of a typical coating film is 250 ⁇ m, and therefore the height becomes 500 ⁇ m when peeled at 180 degrees. That is, when peeled off at less than 180 degrees, the surface of the peeled coating film that receives the water flow becomes large, but for this part, the coating film moves backward (downstream) to release the resistance. Therefore, the influence on peeling of the coating film is small.
- the water pressure applied to the peeled portion of the coating film corresponds to a constant load of 100 grams at a flow rate of 30 knots. And since 30 knots is faster than the speed at which the ship normally travels, if the peeling of the coating film is sufficiently small with a constant load of 100 g, the coating film can be used for ships and other underwater structures. means. Moreover, since the underwater constant load peel degree is generally inversely proportional to the thickness of the coating film, for example, the underwater constant load peel degree of 250 ⁇ m is twice the underwater constant load peel degree of 500 ⁇ m.
- a non-moving underwater structure such as a marine sensor or a dike may be used as the adherend.
- the tidal current is sufficiently slower than 15 knots and is usually about 10 knots at most. Therefore, even if it receives a water flow with a flow rate of 15 knots, it functions as a coating film.
- the resistance force received by the flow rate of 15 knots corresponds to a constant load of 30 g from Equation 1, and the constant load peel degree of 30 g is converted to a constant load peel degree of 100 g according to Eyring's formula (Expression 2). be able to. Therefore, the constant load peeling degree of 100 g is not only a durability against water flow of 30 knots (hardness of peeling) but also an index of durability against water flow of 15 knots.
- the 100 gram underwater constant load peel (mm / 20 mm) of the coating film of the present invention and the structure of the coating film coated using the production method of the present invention is less than 5, and is thicker than a typical thickness. Considering the film, 4 or less is preferable, 3 or less is more preferable, less than 1 is more preferable, less than 0.5 is more preferable, 0.3 or less is preferable, 0.2 or less is more preferable, 0 .1 or less is more preferable, and 0.0 is most preferable.
- the underwater constant load peeling degree of the coating film with respect to PMMA is less than 5, preferably 4 or less, more preferably 3 or less, and more preferably 1 or less.
- the reason why the constant water peel strength was determined using PMMA as an adherend is that a typical material used for the surface of an underwater structure is a gel coat (acrylic polymer / Polystyrene, etc.), epoxy resin, enamel (acrylic polymers, etc.), various metals (aluminum, aluminum alloys such as aluminum bronze, stainless steel, titanium), antifouling paints, and PMMA is an intermediate property between these surface materials It is for having.
- the coating film of the present invention, and the coating film coated using the coating set and the coating for the undercoat layer of the present invention have a small degree of underwater constant load peeling, and the effect that it is difficult to peel off by using an underwater structure. Play.
- materials used for the surface of the underwater structure other than the above include polyurethane, polyethylene, polypropylene, polycarbonate, polyethylene terephthalate, polyacetal resin, and ABS resin.
- the tensile rupture strength is a strength indicating the difficulty of breaking the coating film when the coating film is pulled.
- the tensile strength at break is low, the coating film is broken when the coating film is peeled off from the adherend, and peeling becomes difficult.
- the adhesive force is high, the force required to peel the coating film from the adherend increases, and as a result, the coating film is easily broken. Therefore, in order to peel easily without breaking the coating film, the ratio of the tensile breaking strength to the adhesive strength must be high.
- the coating film of this invention is equipped with the characteristic that the ratio with respect to the adhesive force of the tensile breaking strength after being immersed in the pure water of 60 degreeC for 5 weeks is 1.5 or more. 60 ° C. is higher than the temperature of natural rivers, seas, and lakes, and even if it is immersed for a short time with respect to the use time of the underwater structure until peeling of the coating film, It is possible to make the structure similar to the state after using the structure for a long time.
- immersing in pure water at 60 ° C. for 5 weeks corresponds to immersing in pure water at 23 ° C. for 5 years.
- Adhesion of the coating film of the present invention and the coating film applied using the production method of the present invention to an underwater structure having a tensile strength at break (N / 20 mm) after being immersed in pure water at 60 ° C. for 5 weeks The ratio to the force (N / 20 mm) is 1.5 or more, preferably 3.0 or more, and more preferably 5.0 or more.
- the influence with respect to a coating film is the same with a pure water and seawater, and if it is a coating film which can be practically used in a pure water, it can be used also in seawater.
- the coating film has a temperature of 60 ° C.
- the ratio of the tensile strength at break (N / 20 mm) after being immersed in pure water for 5 weeks to the adhesive strength (N / 20 mm) with PMMA is 1.5 or more, preferably 3.0 or more. Zero or more is more preferable.
- the undercoat layer has a thickness of 150 ⁇ m and is made of a silicone resin (including 90 parts by weight of silicone oil with respect to 100 parts by weight of the silicone resin).
- the tensile strength at break (N / 20 mm) of the coating film after being immersed in pure water at 60 ° C. for 5 weeks (N / 20 mm) / 20 mm) is 1.5 or more, preferably 3.0 or more, and more preferably 5.0 or more. Therefore, the coating film of the present invention and the coating film coated with the coating composition of the present invention and the coating for the undercoat layer are easy even after using an underwater structure for a long time in an actual underwater environment. Can be peeled off.
- the adhesive strength is preferably 3.0 or more, and more preferably 4.0 or more, since the coating film may be peeled off naturally if the value is too low. On the other hand, if the adhesive force is too high, an excessive force is required for peeling the coating film, and workability is lowered. Therefore, 20 or less is preferable, and 15 or less is more preferable.
- the 1 mm square cross-cut stretch peeling degree of the antifouling layer with the undercoat layer is obtained by dividing a laminated body having a plurality of 1 mm square cut cells formed only in the antifouling layer. This is the ratio of the squares peeled off when stretched twice on the diagonal (in the direction indicated by the arrow 5 in FIG. 3), and indicates the degree of difficulty of peeling from the undercoat layer of the antifouling layer.
- the 1 mm square crosscut stretch peeling degree with respect to the undercoat layer of the antifouling layer is 0.05 or less, preferably 0.8. 04 or less, more preferably 0.03 or less, more preferably 0.01 or less, and most preferably 0.00.
- 1 mm square crosscut stretching of the coating film is 0.05 or less, preferably 0.04 or less, more preferably 0.03 or less, still more preferably 0.01 or less, and most preferably 0.00.
- the undercoat layer has a thickness of 150 ⁇ m and is made of a silicone resin (including 90 parts by weight of silicone oil with respect to 100 parts by weight of the silicone resin).
- the coating film has a 1 mm tetragonal cross-cut stretch peeling degree of 0.05 or less, preferably 0.04 or less, more preferably 0.03 or less, more preferably 0.01 or less, and most preferably 0.00.
- the antifouling layer Since the 1 mm square crosscut stretch release degree of the antifouling layer to the undercoat layer indicates the adhesion of the antifouling layer, the antifouling layer is difficult to peel off from the undercoat layer in a coating film having such a low degree of release. Play.
- Typical materials used for the surface of the underwater structure include, for example, PMMA (polymethyl methacrylate resin), gel coat (acrylic polymer / polystyrene, etc.), paint film with epoxy paint, enamel paint ( Examples thereof include a coating film made of an acrylic polymer and the like and aluminum, but the present invention can also be used for other materials.
- PMMA polymethyl methacrylate resin
- gel coat acrylic polymer / polystyrene, etc.
- paint film with epoxy paint examples thereof include a coating film made of an acrylic polymer and the like and aluminum, but the present invention can also be used for other materials.
- the paint for forming the undercoat layer contains a resin component and a solvent.
- the resin component for example, elastomers such as rubber (thermosetting elastomer) and thermoplastic elastomer can be used.
- some thermoplastic resins such as polyvinyl chloride, which are severely deteriorated by long-term use, are not preferred because they may be cut when the coating film is peeled off.
- the rubber for example, acrylic rubber, diene rubber, butyl rubber, nitrile rubber, hydrogenated nitrile rubber, fluorine rubber, silicone rubber, ethylene propylene rubber, chloroprene rubber, urethane rubber, epichlorohydrin rubber can be used. It is preferable to use rubber or diene rubber.
- diene rubber natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber can be used, and styrene butadiene rubber is preferably used.
- thermoplastic elastomer monovinyl substituted aromatic compound thermoplastic elastomers such as acrylic thermoplastic elastomers and styrene thermoplastic elastomers can be used.
- acrylic thermoplastic elastomer examples include a block copolymer of PMMA (polymethyl methacrylate) and an alkyl acrylate ester.
- acrylic acid alkyl ester examples include butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and the like.
- Such a block copolymer can be adjusted within the ranges of constant load peeling and tensile breaking strength / adhesive force defined in the present invention by changing the proportion of PMMA which is a hard segment. Specifically, when the content ratio of PMMA is increased, the tensile strength at break is increased, and the adhesive force and constant load peeling tend to be reduced.
- styrenic thermoplastic elastomer examples include SBS (styrene / butadiene block copolymer), SIS (styrene / isoprene block copolymer), SEBS (styrene / ethylene / butylene / styrene block copolymer), and SEPS (styrene).
- SBS styrene / butadiene block copolymer
- SIS styrene / isoprene block copolymer
- SEBS styrene / ethylene / butylene / styrene block copolymer
- SEPS styrene
- the tensile strength at break and the adhesive strength can be adjusted by adjusting the styrene content ratio in the resin component, preferably 20 to 40% by weight. More preferably, it is 22 wt% to 35 wt%, and further preferably 25 wt% to 33 wt%.
- the elastomer may be modified with a compound containing a polar group.
- the polar group include hydroxyl groups, carboxyl groups, alkoxysilyl groups, acid anhydride groups such as maleic anhydride, and amino groups.
- the content of the compound containing the polar group in the elastomer is preferably 0.1% by weight to 20% by weight, more preferably 0.3% by weight to 15% by weight, and further preferably 0.5% by weight. % To 5% by weight.
- the paint may contain a compound containing a polar group.
- a compound containing a polar group examples include resins containing the polar group, silane coupling agents, and silicone oil.
- the resin containing a polar group examples include ionomers, rosin resins, and silicone resins.
- the content of these compounds with respect to the resin component in the paint is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, still more preferably 15 to 80% by weight, The amount is preferably 20 to 70% by weight, and most preferably 25 to 60% by weight.
- the content ratio of the resin component in the paint for the undercoat layer is preferably 5% by weight to 95% by weight, more preferably 10% by weight to 90% by weight, and further preferably 15% by weight to 80% by weight. Particularly preferably 20% to 70% by weight, most preferably 25% to 60% by weight.
- the solvent examples include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene; aliphatic hydrocarbons such as hexane and heptane; esters such as ethyl acetate and vinyl acetate; dioxane and diethyl ether Ethers such as: alcohols such as ethanol, isopropanol and n-butanol; ketones such as acetone, diethyl ketone and methyl isobutyl ketone; water and the like can be used.
- aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene
- aliphatic hydrocarbons such as hexane and heptane
- esters such as ethyl acetate and vinyl acetate
- dioxane and diethyl ether Ethers such as:
- the content of the solvent is preferably 5% to 95% by weight, more preferably 10% to 90% by weight, still more preferably 20% to 85% by weight, and particularly preferably 30% by weight. -80% by weight, most preferably 40% -75% by weight.
- the antifouling layer is formed of a silicone-based paint described later, for example, it is possible to use a styrene thermoplastic elastomer modified with 0.1% to 20% by weight of a compound containing a polar group as the undercoat layer. It is preferable for enhancing the adhesion between the dirty layer and the undercoat layer. At this time, for example, the styrene content can be 20 wt% to 40 wt%.
- a silicone-based paint As the paint for forming the antifouling layer, a silicone-based paint, a copper-based paint, a zinc-based paint, or the like can be used. However, it is preferable to use a paint that does not assume repeated coating such as a silicone-based paint.
- the silicone paint contains organopolysiloxane, which is a base polymer. Since the organopolysiloxane has a curing reactive group, the antifouling layer formed by the silicone-based paint contains a silicone resin that is a reaction product of the organopolysiloxane.
- a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, a vinyl group, or a (meth) acryl group may be used.
- hydrolyzable groups other than hydroxyl groups include alkoxy groups such as methoxy group, ethoxy group, and propoxy group; alkoxyalkoxy groups such as methoxyethoxy group, ethoxyethoxy group, and methoxypropoxy group; acetoxy group, octanoyloxy Groups, acyloxy groups such as benzoyloxy groups; alkenyloxy groups such as vinyloxy groups, isopropenyloxy groups, 1-ethyl-2-methylvinyloxy groups; ketoximes such as dimethyl ketoxime groups, methylethyl ketoxime groups, and diethyl ketoxime groups Groups: amino groups such as dimethylamino group, diethylamino group, butylamino group, cyclohexylamino group; aminoxy groups such as dimethylaminoxy group, diethylaminoxy group; N-methylacetamide group, N-ethylacetamide group, N-methyl group It may
- the silicone-based paint preferably further contains silicone oil.
- Silicone oils include dimethyl silicone oils that are all methyl groups, methyl phenyl silicone oils in which some of the methyl groups in these dimethyl silicone oils are substituted with phenyl groups, monoamines, diamines, or amino-polyether groups.
- Amino-modified silicone oil epoxy, cycloaliphatic epoxy, epoxy-polyether or epoxy-modified silicone oil substituted with epoxy-aralkyl group, carbinol-modified silicone oil substituted with carbinol group, mercapto group-substituted Mercapto-modified silicone oil, carboxyl-modified silicone oil substituted with carboxyl group, methacryl-modified silicone oil substituted with methacryl group, polyether-modified silicone oil substituted with polyether Use a long-chain alkyl-modified silicone oil substituted with a long-chain alkyl or a long-chain alkyl-aralkyl group, a higher fatty acid-modified silicone oil substituted with a higher fatty acid ester group, or a fluoroalkyl-modified silicone oil substituted with a fluoroalkyl group. Can do. Further, methylphenyl silicone oil, polyether-modified silicone oil, and long-chain alkyl-modified silicone oil can be used. Only one
- the adhesive strength can be adjusted by adding an adhesive to the paint for the undercoat layer.
- an adhesive for example, a styrene tackifier resin, a terpene tackifier resin, a rosin tackifier resin, an alicyclic saturated hydrocarbon tackifier resin, and an acrylic tackifier resin can be used.
- Other adhesives may be mixed according to the properties of the layer coating.
- any appropriate content ratio can be adopted depending on the content ratio of the other components such as the antifouling agent.
- it may be 30% to 98% by weight. More preferably, it is 35 wt% to 90 wt%, and further preferably 40 wt% to 80 wt%.
- the content of the silicone oil with respect to 100 parts by weight of the silicone resin is preferably 1 part by weight to 150 parts by weight, and more preferably 40 parts by weight to 140 parts by weight.
- Copper-based paints are paints containing copper-based compounds.
- copper-based compounds include copper oxides such as cuprous oxide and cupric oxide, copper alloys such as copper nickel alloys, copper thiocyanate and copper sulfide. Copper salts, organometallic compounds such as pyrithione copper and copper acetate can be used.
- zinc-based paint a paint containing zinc oxide as an antifouling agent can be used.
- the antifouling layer may contain any appropriate other additive as long as the effects of the present invention are not impaired.
- examples of such other additives include a UV absorber as a weathering agent.
- the coating film according to the present embodiment described above is formed on the underwater structure, it may be formed other than the underwater structure, and has the same effect. For example, you may form on the surface of various exterior materials, such as a roof and an outer wall.
- the adhesive force to PMMA is used as an index indicating the difficulty of peeling from the adherend during use, instead of the degree of underwater constant load peeling. It is preferable that the adhesive force with respect to PMMA with respect to the structure of the coating film of this invention and the coating film coated using the manufacturing method of this invention is 0.5 (N / 20mm) or less, 0.3 or less is preferable, 0.2 or less is more preferable, 0.1 or less is more preferable, and 0.0 is most preferable.
- the ratio of the tensile breaking strength (N / 20 mm) to the adhesive strength (N / 20 mm) in the embodiment and the degree of 1 mm square cross-cut stretch peeling with respect to the undercoat layer of the antifouling layer paint layer Other properties such as are the same as those of a paint that forms a coating film on an underwater structure.
- Table 1 shows the resin components of the undercoat layer of each example and comparative example.
- Table 2 shows the test results of each example and comparative example.
- Example 1 Preparation of paint for undercoat layer
- 80 parts by weight of amine-modified hydrogenated styrene thermoplastic elastomer styrene content 30% by weight, trade name “Tuftec MP10”, manufactured by Asahi Kasei Chemicals Co., Ltd.
- 20 parts by weight of toluene are mixed, and 12 at room temperature (23 ° C.).
- the mixture was stirred for a time to obtain a paint for an undercoat layer.
- a coating film was prepared by the following method using a paint set comprising the above-mentioned undercoat layer paint and antifouling layer paint, and the underwater constant load peeling degree was measured.
- a PMMA plate (trade name “Delagrass K”, manufactured by Asahi Kasei Technoplus Co., Ltd., methyl methacrylate polymer 96.6% or more) is coated with an undercoat using an applicator, dried at room temperature for 12 hours, and a thickness of 150 ⁇ m A coating layer was prepared.
- an antifouling layer coating is applied with an applicator and dried at room temperature for 12 hours to produce an antifouling layer having a thickness of 100 ⁇ m.
- a coating film consisting of a dirty layer was prepared.
- the coating film had a size of 20 mm ⁇ 100 mm.
- the coating is then peeled off from the 20 mm PMMA plate from the short side (20 mm side) side, bent 180 °, and applied to the end of a 20 mm ⁇ 100 mm PET film (trade name “Lumirror S10”, Toray Industries, Inc., thickness 75 ⁇ m).
- the film was pasted so that the contact area with the film was 20 mm ⁇ 20 mm.
- a test sample was prepared by attaching a weight adjusted to a weight of 100 g in water to this PET film. In a water tank filled with 23 ° C. pure water, the sample was immersed in pure water in the water tank so that the peeling angle was 180 degrees, and the distance [mm] where the coating film was peeled off from the PMMA plate after 1 hour was calculated. It was measured.
- an undercoat layer coating was applied with an applicator and dried at room temperature for 12 hours to prepare an undercoat layer having a thickness of 150 ⁇ m. .
- an antifouling layer paint is applied with an applicator and dried at room temperature for 12 hours to produce an antifouling layer having a thickness of 100 ⁇ m.
- a coating film composed of a laminate of layers was prepared.
- the obtained undercoat / antifouling layer laminate was immersed in pure water at 60 ° C for 5 weeks, then cut out so that the undercoat / antifouling layer was 20 mm x 60 mm in size, and a tensile tester (equipment)
- the tensile strength at break was evaluated using the name “AUTOGRAPH AGS-X” (manufactured by Shimadzu Corporation).
- FIG. 4 is a schematic diagram illustrating a 15 knot water flow test for an undercoat layer.
- the same operation as in the underwater constant load peel test was performed, and a PMMA plate (trade name “Delagrass K”, manufactured by Asahi Kasei Technoplus Co., Ltd., methyl methacrylate polymer 96.6% or more) with an undercoat layer having a thickness of 150 ⁇ m and a thickness of 100 ⁇ m
- a coating film comprising an antifouling layer was prepared, and the periphery was removed so that the coating film had a size of 20 mm ⁇ 100 mm.
- the coating film is peeled off 20 mm from the short side (20 mm side) side, and a water flow (flow velocity of 15 knots) (indicated by arrow 6 in FIG. 4) in a direction parallel to the long side direction of the coating film is 200 hours.
- the time for the undercoat layer to peel off from the PMMA plate was evaluated.
- the direction of water flow was such that the side where the coating film was peeled was upstream.
- FIG. 5 is a schematic diagram illustrating a 15 knot water flow test for the antifouling layer.
- the PMMA plate (trade name “Delagrass K”, manufactured by Asahi Kasei Technoplus Co., Ltd., methyl methacrylate polymer 96.6% or more) is coated with the primer (1) with an applicator, dried at room temperature for 12 hours, and a thickness of 150 ⁇ m.
- An undercoat layer was prepared. On the prepared undercoat layer, the antifouling layer coating (1) is applied with an applicator so as to form a 20 mm ⁇ 50 mm, 100 ⁇ m thick coating film, and dried at room temperature for 12 hours.
- a coating film comprising an undercoat layer / antifouling layer was prepared.
- a water flow (flow velocity of 15 knots) (shown as 6 in FIG. 5) was passed for 200 hours in a direction parallel to the long side direction of the antifouling layer, and the time for the antifouling layer to peel from the undercoat layer was evaluated.
- FIG. 6 is a schematic diagram for explaining a peelability confirmation experiment.
- a PMMA plate (trade name “Delagrass K”, manufactured by Asahi Kasei Technoplus Co., Ltd., methyl methacrylate polymer 96.6% or more) with an undercoat layer having a thickness of 150 ⁇ m and a thickness of 100 ⁇ m
- a coating film comprising an antifouling layer was prepared. After immersing the laminate of the obtained undercoat layer and antifouling layer in pure water at 60 ° C for 5 weeks, remove the other parts so that the undercoat layer / antifouling layer has a size of 20 mm x 100 mm It was. When the coating film was peeled from the PMMA substrate at a peeling angle of 145 to 180 ° (in the direction indicated by the arrow 7 in FIG. 6), it was evaluated whether or not the primer layer was broken.
- Example 1 had an underwater constant load peeling degree of 0.0, a tensile strength at break / adhesive strength of 19.9, and a cross-cut drawing degree of 0.0.
- Example 1 in the 15.30 knot water flow test, neither the undercoat layer nor the antifouling layer was peeled off, and in the peelability test, it was possible to peel off without cutting. Therefore, Example 1 produces the effect that it is hard to peel in the use of an underwater structure, and can be easily peeled off during the maintenance of the structure. Moreover, also about antifouling property, it confirmed that the aquatic organism did not adhere to the surface of a coating film.
- Example 2 The resin composition of the coating for the undercoat layer was changed to maleic acid-modified SEBS (styrene content 30% by weight, trade name “FG1901”, manufactured by Kraton Japan Polymer Co., Ltd.), which has a different modification method from the resin of Example 1. Except for the above, an undercoat layer paint and an antifouling layer paint were prepared in the same manner as in Example 1. In addition, using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, and underwater constant load peel test, adhesive force, tensile breaking strength, cross-cut stretching test, 15/30. A knot running test (undercoat layer), 15.30 knot running test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Example 2 as in Example 1, the underwater constant load peel degree was 0.0, and the crosscut stretch peel degree was also 0.0. Therefore, in the 15.30 knot water flow test, neither the undercoat layer nor the antifouling layer was peeled off. Further, the ratio of the quoted breaking strength to the adhesive force was 14.0, but in the peel test, it was possible to peel from the adherend without breaking the coating, and it was confirmed that the effects of the present invention were exhibited. It was also confirmed that the present invention can be carried out even if the polar group of the compound used for modification is changed to maleic acid.
- Example 3 Adhesive strength is obtained by adding the resin composition of the paint for the undercoat layer to the resin of Example 2 so that the styrene-based tackifying resin (trade name “Picola Stick A75”, manufactured by NN Chemical Co., Ltd.) is 35% by weight.
- the undercoat layer paint and the antifouling layer paint were prepared by carrying out the same operations as in Example 1 except that Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Example 3 as well, as in Example 1, the underwater constant load peel degree was 0.0, and the crosscut stretch peel degree was also 0.0, so in the 15.30 knot water flow test, Neither the layer nor the antifouling layer peeled off.
- the adhesive strength is high, and the ratio of the quoted breaking strength to the adhesive strength is 1.9.
- the coating film can be peeled off without being broken, and the present invention It was confirmed that the effects of Example 3 also showed that the present invention can be carried out by adding a tackifying resin and adjusting the adhesive strength as required by the embodiment.
- Example 4 Example 1 except that the resin composition of the paint for the undercoat layer was changed to a hydroxyl group-modified SEPS (styrene amount 28 wt%, trade name “HG252”, manufactured by Kuraray Co., Ltd.) different from the resin of Example 1. The same operation was performed to prepare an undercoat layer paint and an antifouling layer paint. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- SEPS hydroxyl group-modified SEPS
- Example 4 As well, as in Example 1, the underwater constant load peel degree was 0.0, and the crosscut stretch peel degree was also 0.0, so in the 15.30 knot water flow test, Neither the layer nor the antifouling layer peeled off. Further, the ratio of the quoted breaking strength to the adhesive strength of Example 4 is 21.4, and in the peel test, the coated film can be peeled off without being cut, and Example 4 is an effect of the present invention. It was confirmed that Example 4 shows that the present invention can be implemented even when the resin is changed to SEPS, which is a different styrenic thermoplastic elastomer, and the polar group of the compound used for modification is changed to a hydroxyl group. .
- SEPS which is a different styrenic thermoplastic elastomer
- Example 5 Example 1 except that the resin composition of the paint for the undercoat layer was changed to modified SEBS (trade name “DYNARON 8660P”, manufactured by JSR Corporation), which has a styrene content of 25% by weight lower than the resin of Example 1.
- SEBS trade name “DYNARON 8660P”, manufactured by JSR Corporation
- a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water
- the test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Example 5 As in Example 1, the underwater constant load peel degree was 0.0, and the crosscut stretch peel degree was also 0.0. In the 15.30 knot water flow test, Neither the layer nor the antifouling layer peeled off. Further, the ratio of the quoted breaking strength to the adhesive strength in Example 5 is 6.0, but in the peeling test, the coating film can be peeled off without being cut, and the effect of the present invention can be achieved. It could be confirmed. It was also found that the present invention can be carried out by adjusting the styrene content to adjust the properties of the coating film as necessary.
- Example 6 Example except that the resin composition of the paint for the undercoat layer was changed to an acrylic thermoplastic elastomer (PMMA / 2-ethylhexyl acrylate / butyl acrylate block copolymer, trade name “Clarity LK9333”, manufactured by Kuraray Co., Ltd.) The same operation as in 1 was performed to prepare an undercoat layer paint and an antifouling layer paint. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- PMMA / 2-ethylhexyl acrylate / butyl acrylate block copolymer trade name “Clarity LK9333”, manufactured by Kuraray Co., Ltd.
- Example 6 as in Example 1, the underwater constant load peel degree was 0.0, and the cross-cut stretch peel degree was also 0.0, so in the 15.30 knot water flow test, Neither the layer nor the antifouling layer peeled off. Further, the ratio of the quoted breaking strength to the adhesive strength in Example 6 is 1.8, but in the peel test, the coated film can be peeled off without being cut, and the effect of the present invention can be achieved. It could be confirmed. From Example 6, it was revealed that the present invention can be carried out even with an acrylic thermoplastic elastomer.
- Example 7 SEBS (styrene content 13% by weight, maleic acid modification amount 1% by weight, trade name “GFG1924”, in which the styrene content in Example 2 was changed from 30% by weight to 13% by weight in the resin composition of the primer coating
- the same operation as in Example 1 was carried out except that the product was changed to (Clayton Japan Polymer Co., Ltd.), and an undercoat layer paint and an antifouling layer paint were prepared.
- a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water
- the test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Example 7 since the styrene content of SEBS in the undercoat layer is as low as 13% by weight, the tensile strength at break is as low as 24. However, since the adhesive force is also low, the ratio of the tensile strength at break to the adhesive force is 4.9. In the peel test, the coating film could be peeled off from the adherend without cutting the coating film. Moreover, since the modification
- Example 8 The undercoat paint and antifouling layer were the same as in Example 1 except that the resin composition of the undercoat paint was changed to a urethane emulsion (trade name “Hydran WLS210”, manufactured by DIC Corporation). A paint was prepared. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Example 8 as in Example 1, the underwater constant load peel degree is 0.0, and the crosscut stretch peel degree is also 0.0, so in the 15.30 knot water flow test, Neither the layer nor the antifouling layer peeled off. Further, the ratio of the quoted breaking strength to the adhesive strength in Example 8 is 3.66, but in the peel test, the coating film can be peeled off without being cut, and the effect of the present invention can be achieved. It could be confirmed. From Example 8, it was revealed that the present invention can be carried out even with a urethane emulsion.
- Example 9 The resin composition of the paint for the undercoat layer is 72% by weight of PIB (polyisobutylene) (trade name “B100”, manufactured by BASF), 21% by weight of a tackifier (trade name “Arcon M135”, manufactured by Arakawa Chemical Industries). Under the same conditions as in Example 1, except that the amine-modified silicone oligomer (trade name “x-40-2651”, manufactured by Shin-Etsu Silicone Co., Ltd.) was mixed at a blending ratio of 7% by weight. Paint and antifouling layer paint were prepared.
- PIB polyisobutylene
- a tackifier trade name “Arcon M135” manufactured by Arakawa Chemical Industries
- Example 2 Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Example 9 the ratio of the tensile breaking strength to the adhesive strength was 2.9, and in the peel test, the coating film could be peeled off from the adherend without cutting the coating film. Moreover, since it contains an amine-modified silicone oligomer, the adhesion between the undercoat layer and the antifouling layer is high, and the crosscut stretch peeling degree is 0.00, so the antifouling layer was not peeled off. Moreover, since the underwater constant load peeling degree was 4 and was slightly high, the undercoat layer was peeled off in the 30 knot water flow test, but the undercoat layer was not peeled off in the 15 knot water flow test. It was confirmed that even the undercoat layer of the blended component has practicality and can carry out the present invention.
- Example 10 The resin composition of the coating for the undercoat layer is 91% by weight of fluororesin (trade name “GL252EA”, containing 5 parts by weight of a curing agent (GL200RB), manufactured by Daikin Industries), ionomer (trade name “CHEMIPARA SA100”, Mitsui Chemicals, Inc.). Manufactured) The same operation as in Example 1 was carried out except that the mixture was mixed at a blending ratio of 9% by weight to prepare an undercoat layer paint and an antifouling layer paint.
- fluororesin trade name “GL252EA”
- GL200RB curing agent
- CHEMIPARA SA100 ionomer
- Example 2 Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Example 10 the underwater constant load peel degree is 0.0 as in Example 1, and the crosscut stretch peel degree is also 0.0, so in the 15.30 knot water flow test, Neither the layer nor the antifouling layer peeled off. Further, the ratio of the quoted breaking strength to the adhesive strength in Example 10 is 1.83, but in the peel test, the coated film can be peeled off without being cut, and the effect of the present invention can be achieved. It could be confirmed. From Example 10, it was revealed that the present invention can be carried out even with the undercoat layer of the above-described blending components.
- the present invention is not limited to the above-mentioned materials, and can be appropriately carried out with other materials satisfying the degree of constant load peel in water, the ratio of tensile strength at break to adhesive force, and the degree of cross-cut stretch peel.
- Comparative Example 1 In Comparative Example 1, the resin composition of the paint for the undercoat layer was changed to SEBS (styrene amount 29% by weight, trade name “Tuftec H1053”, manufactured by Asahi Kasei Chemicals Co., Ltd.) which was not modified unlike Example 1. Except for this, the same operation as in Example 1 was carried out to prepare a paint for an undercoat layer and a paint for an antifouling layer. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- SEBS styrene amount 29% by weight, trade name “Tuftec H1053”, manufactured by Asahi Kasei Chemicals Co., Ltd.
- the coating film is peeled off from the adherend without being cut in the peeling test. I was able to. Moreover, since the underwater constant load peeling degree was 0.0, peeling of the undercoat layer did not occur in the 15.30 knot water flow test. However, since the SEBS was not modified, the adhesion with the silicone resin was low, and the cross-cut stretch peel rate was 1.00, so the antifouling layer was peeled even in the 15.30 knot water flow test. . In addition, since the ratio of the tensile breaking strength to the adhesive force was 15.4, there was no problem in peelability.
- Comparative Example 2 In Comparative Example 2, the resin composition of the paint for the undercoat layer was changed to SEBS (styrene amount 18% by weight, trade name “Tuftec H1062”, manufactured by Asahi Kasei Chemicals Co., Ltd.), which was not modified unlike Example 1. Except for this, the same operation as in Example 1 was carried out to prepare a paint for an undercoat layer and a paint for an antifouling layer. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- SEBS styrene amount 18% by weight, trade name “Tuftec H1062”, manufactured by Asahi Kasei Chemicals Co., Ltd.
- the styrene content of SEBS in the undercoat layer of Comparative Example 2 is lower than that of Comparative Example 1 and 18% by weight, the tensile strength at break is also smaller than that of Comparative Example 1.
- the adhesive force is also low, the ratio of the tensile strength to the adhesive force is 18.3.
- the coating film could be peeled from the adherend without cutting the coating film.
- the underwater constant load peeling degree was 0.2, in the 15.30 knot water flow test, the undercoat layer was not peeled off.
- SEBS was not modified and the adhesion to the antifouling layer was low, so that the crosscut stretch peel rate was 1.00.
- Comparative Example 2 has a large degree of cross-cut stretch peeling and is not an embodiment of the present invention. However, if the underwater constant load peel degree is 0.2, the undercoat layer is deposited in the 15.30 knot water flow test. Indicates that it does not peel from the body.
- Comparative Example 3 In Comparative Example 3, the resin composition of the paint for the undercoat layer was changed to SEBS (styrene content 13% by weight, trade name “G1657”, manufactured by Kraton Japan Polymer Co., Ltd.) which was not modified unlike Example 1. Except for this, the same operation as in Example 1 was carried out to prepare a paint for an undercoat layer and a paint for an antifouling layer. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- SEBS styrene content 13% by weight, trade name “G1657”, manufactured by Kraton Japan Polymer Co., Ltd.
- the styrene content of SEBS in the undercoat layer of Comparative Example 3 is lower than that of Comparative Example 2 and is 13% by weight, the tensile strength at break is also lower than that of Comparative Example 2.
- the adhesive strength is also low, the ratio of tensile strength to adhesive strength is 15.6, and in the peel test, the coating film could be peeled from the adherend without cutting the coating film.
- the underwater constant load peeling degree is 8, the undercoat layer peeled off in the 15.30 knot water flow test.
- the cross-cut stretch peel rate was 1.00, 15.30 knots In the water flow test, the antifouling layer was peeled off.
- Example 4 Other than changing the resin composition of the paint for the undercoat layer to a copolymer of polyvinyl chloride and polyvinyl acetate (trade name “Warba in CH”, manufactured by Shin-Etsu Chemical Co., Ltd.) and changing the solvent to MEK The same operation as in Example 1 was carried out to prepare an undercoat layer paint and an antifouling layer paint. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Comparative Example 4 the underwater constant load peel degree was 0.0, and it did not peel in the 15.30 knot water flow test, but because the adhesive strength is high and the ratio of the tensile breaking strength to the adhesive strength is low, It cut
- Example 5 The resin composition of the coating for the undercoat layer was changed to PVB (polyvinyl butyral) (trade name “B60T”, manufactured by Kuraray Co., Ltd.), and the same operation as in Example 1 was performed except that the solvent was changed to ethanol. A coating layer coating and an antifouling layer coating were prepared. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Comparative Example 5 the underwater constant load peel degree was 0.0 and did not peel in the 15.30 knot water flow test, but the adhesion strength was high and the ratio of the tensile strength to break strength was low. It cut
- Example 6 The undercoat layer paint and antifouling were the same as in Example 1 except that the undercoat layer paint was changed to a commercially available urethane paint (trade name “Masking Color”, manufactured by Taiyo Paint Co., Ltd.). A layer coating was prepared. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Example 7 For the undercoat layer, the same operation as in Example 1 was performed except that the paint for the undercoat layer was changed to a commercially available SBR (styrene butadiene rubber) paint (trade name “1034”, manufactured by PlastiDip). A paint and an antifouling layer paint were prepared. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- SBR styrene butadiene rubber
- Example 8 The same operation as in Example 1 was performed except that the undercoat layer paint was changed to a commercially available SEBS paint (trade name “Liquid Rubber Paint Oiliness”, manufactured by SDesgn). A soil coating was prepared. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Example 9 As the coating for the undercoat layer, maleic acid-modified SEBS used in Example 2 and an acrylic thermoplastic elastomer (styrene amount 30% by weight, maleic acid modification amount 1% by weight, trade name “Clarity LA2330”, manufactured by Kuraray Co., Ltd.) The same operation as in Example 1 was carried out except that the mixture was changed to a mixture at a blending ratio (by weight) of 50%, thereby preparing a primer coating and antifouling coating.
- an acrylic thermoplastic elastomer styrene amount 30% by weight, maleic acid modification amount 1% by weight, trade name “Clarity LA2330”, manufactured by Kuraray Co., Ltd.
- Example 2 Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Comparative Example 9 the adhesive strength was improved by containing an acrylic thermoplastic elastomer, but the tensile strength at break was low, and the ratio of the product length breaking strength to the adhesive strength was as low as 1.2. In the test, the film was cut before peeling.
- Example 10 Example 1 except that the coating material for the undercoat layer was changed to a mixture of 25% by weight of maleic acid-modified SEBS used in Example 2 and 75% by weight of the acrylic thermoplastic elastomer described in Comparative Example 10 The same operation as in Example 1 was carried out to prepare an undercoat layer paint and an antifouling layer paint. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Comparative Example 10 the tensile strength at break was improved by containing an acrylic thermoplastic elastomer at a higher content ratio than in Comparative Example 9, but since the adhesive strength was also increased, the ratio of the tensile strength to the adhesive strength was 1. In the peel test, the film was cut before peeling.
- Example 11 An undercoat layer paint and an antifouling layer paint were prepared in the same manner as in Example 1 except that only the acrylic thermoplastic elastomer described in Comparative Example 9 was used as the undercoat layer paint. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Comparative Example 11 is an acrylic thermoplastic elastomer different from Example 6. Although the adhesive strength was higher than that in Example 6, the tensile strength at break was not changed from 24, so the ratio of tensile strength to adhesive strength was as low as 1.2. It cut
- Example 12 The coating for the undercoat layer was carried out except that it was changed to a mixture of 77% by weight of butyl rubber (trade name “065”, manufactured by JSR) and 23% by weight of the amine-modified silicone oligomer described in Example 9 The same operation as in Example 1 was carried out to prepare an undercoat layer paint and an antifouling layer paint. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Comparative Example 12 contained an amine-modified silicone oligomer, and the adhesive strength was high, but the tensile strength at break was as low as 1. Therefore, in the peel test, the film was cut before peeling.
- Example 13 The undercoat layer paint and antifouling layer were the same as in Example 1 except that the primer for the undercoat layer was changed to a commercially available silicone primer (trade name “Primer T”, manufactured by Shin-Etsu Silicone). A paint was prepared. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Comparative Example 13 is a commercially available primer for silicone and is not supposed to be peeled off. Therefore, in the peeling test, the film was cut before peeling.
- Example 14 The same operation as in Example 1 was performed except that the primer for the undercoat layer was changed to a commercially available silicone primer (trade name “Primer No. 4”, manufactured by Shin-Etsu Silicone Co., Ltd.). A soil coating was prepared. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Comparative Example 14 is a commercially available primer for silicone and is not assumed to be peeled off. Therefore, in the peel test, the film was cut before peeling.
- Example 15 The same undercoat layer paint and antifouling layer paint were prepared as in Example 1, except that the ionomer (trade name “Kemipearl SA100”, Mitsui Chemicals) was used as the undercoat paint. did. Using a paint set composed of these paints, a coating film was prepared in the same manner as in Example 1, underwater constant load peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water The test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- the ionomer trade name “Kemipearl SA100”, Mitsui Chemicals
- Example 16 Except that no undercoat layer paint was used, the same operation as in Example 1 was carried out to prepare an antifouling layer paint.
- the peel test, adhesive strength, tensile breaking strength, cross-cut stretching test, 15.30 knot running water test (undercoat layer), 15.30 knot running water test (antifouling layer), and peelability were evaluated. The results are shown in Table 2.
- Example 7 and Example 9 were 3 and 4, respectively, but in the 15 knot water flow test, they did not peel.
- the underwater constant load peeling degree of the comparative example 3 was 8, it peeled within 200 hours, although it did not peel over a comparatively long time in the 15 knot water flow test.
- the resistance force received by the flow rate of 15 knots corresponds to a constant load of 30 g from Equation 1.
- the 100 g constant load peel rate is 0.5 mm or less, it can be considered to have practically sufficient durability (non-peelability) in an environment receiving a water flow of 30 knots.
- the 30 g constant load peeling degree is 0.5 mm or less, it can withstand a water flow of 15 knots.
- the 30 g constant load peeling degree is 0.5 g or less, and the constant is 100 g. It can be calculated that the degree of load separation does not exceed 5 mm.
- the constant load peel rate of 30 g load is 0.38 (mm / 20 mm).
- the constant load peeling degree (stress) of 5.0 g / 100 mm, so that if the constant load peeling degree of 100 g load is 5.0 (mm / 20 mm), the undercoat is submerged in water. It is understood that the layer is difficult to peel off and is practical.
- the constants c and n of the above-mentioned examples are obtained from the experimental results of peeling 10 mm in a peeling time of 1.5 hours by the method described in the measuring method of 100 g underwater constant load peeling degree.
- Table 3 shows the experimental results when a gel coat (trade name “white coat”, manufactured by Koshin Chemical Co., Ltd.) is used as an adherend.
- Table 4 shows the experimental results when a coating film prepared from an epoxy paint (trade name “SEAJET03”, made in China) is used as an adherend.
- Table 5 shows a case where a coating film prepared from an enamel paint (trade name “SEAJET015”, made in China) is used as an adherend.
- Table 6 shows the experimental results when a coating film prepared from an antifouling paint (trade name “SEAJET033”, manufactured by China Paint) is used as an adherend.
- Table 7 shows the experimental results when aluminum (trade name “A1080”, aluminum purity 99.5% or more, manufactured by Nishiyama Seisakusho) is used as an adherend.
- the adherend was applied to a coating film prepared from a gel coat, an epoxy paint, a coating film prepared from an enamel paint, or an antifouling paint. Also in the case of changing to the film and aluminum, it was confirmed that there was no peeling in the 15.30 knot water flow test, and that the peeling could be done without breaking even in the evaluation of peelability.
- Example 3 when the adherend was changed to a gel coat (trade name “white coat”, manufactured by Koshin Chemical Co., Ltd.) instead of the PMMA plate, there was no peeling in the 15.30 knot water flow test. It was confirmed that the film could be peeled without being cut even in the peelability evaluation.
- a gel coat trade name “white coat”, manufactured by Koshin Chemical Co., Ltd.
- Example 4 a coated film prepared from a gel coat (trade name “White Coat”, manufactured by Koshin Chemical Co., Ltd.) and epoxy paint (trade name “SEAJET03”, manufactured by China Paint) instead of the PMMA plate. Even when changing to a paint film made from enamel paint (trade name “SEAJET015”, made in China), it was confirmed that the 15.30 knot water flow test was not peeled off and the peelability was evaluated without being peeled off. did.
- Example 5 an adherend was prepared from a gel coat (trade name “White Coat”, manufactured by Koshin Chemical Co., Ltd.) and enamel paint (trade name “SEAJET015”, manufactured by China Paint) instead of the PMMA plate. Also when it changed into each coating film, it was confirmed that it was not peeled by the 15.30 knot water flow test and could be peeled without being cut even by the evaluation of peelability.
- Example 6 in the case where the adherend was changed to a coating film prepared from a gel coat (trade name “white coat”, manufactured by Koshin Chemical Co., Ltd.) instead of the PMMA plate, the 15.30 knot water flow test It was confirmed that the film could be peeled without being cut off even in the evaluation of peelability without peeling.
- a gel coat trade name “white coat”, manufactured by Koshin Chemical Co., Ltd.
- a coating film having an undercoat layer having a thickness of 150 ⁇ m and an antifouling layer having a thickness of 100 ⁇ m was prepared, and the 100 g underwater constant load peeling degree of the coating film was 0.5 (mm
- the ratio of the tensile strength at break (N / 20 mm) after being immersed in pure water at 60 ° C. for 5 weeks to the adhesion force (N / 20 mm) with the adherend is 1.5 or more.
- the antifouling layer has a 1 mm square cross-cut stretch peeling degree with respect to the undercoat layer of 0.05 or less, at least any adherend of an underwater structure is used in water.
- the embodiment of the present invention includes a paint set including a paint for an undercoat layer and a paint for an antifouling layer having the above-described characteristics.
- the antifouling layer having a thickness of, for example, 100 ⁇ m is formed by a silicone resin or a copper-based compound which is a material of the undercoat layer having a thickness of 150 ⁇ m and a typical antifouling layer.
- a coating for an undercoat layer having the following characteristics is also included in one embodiment of the present invention.
- Example 11 The undercoat layer coating material was treated in the same manner as in Example 1 except that the resin composition of the undercoat layer paint was changed to a urethane emulsion (trade name “Superflex 470”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). And the coating material for antifouling layers was produced.
- a urethane emulsion trade name “Superflex 470”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- Example 12 Except that the resin composition of the primer coating was changed to Ionomer Butyl (no brand name, manufactured by LANXESS), the same operation as in Example 1 was performed, and the primer coating and antifouling coating were obtained. Produced.
- Example 13 In Example 13, the resin composition of the paint for the undercoat layer was changed to SEBS (styrene amount 30% by weight) which was not modified unlike Example 1, and rosin resin (trade name “Pencel D135”, Arakawa Chemical Industries, Ltd.).
- SEBS styrene amount 30% by weight
- rosin resin trade name “Pencel D135”, Arakawa Chemical Industries, Ltd.
- Example 14 In Example 14, the resin composition of the paint for the undercoat layer was changed to SEBS (styrene amount 30% by weight) which was not modified unlike Example 1, and an alkoxy silicone oligomer (trade name “KC-89S”, Shin-Etsu Silicone Co., Ltd.). Undercoat layer paint and antifouling layer paint were prepared in the same manner as in Example 1 except that the adhesive strength was improved by adding 5% by weight).
- SEBS styrene amount 30% by weight
- an alkoxy silicone oligomer trade name “KC-89S”, Shin-Etsu Silicone Co., Ltd.
- Example 15 In Example 15, the resin composition of the paint for the undercoat layer was changed to SEBS (styrene amount 30% by weight) which was not modified unlike Example 1, and hydrogen-modified silicone oil (trade name “KF9901”, Shin-Etsu Silicone Co., Ltd.). Undercoat layer paint and antifouling layer paint were prepared by carrying out the same operations as in Example 1 except that the adhesive strength was improved by adding 23% by weight.
- SEBS styrene amount 30% by weight
- hydrogen-modified silicone oil trade name “KF9901”, Shin-Etsu Silicone Co., Ltd.
- an undercoat layer coating was applied with an applicator and dried at room temperature for 12 hours to prepare an undercoat layer having a thickness of 150 ⁇ m. .
- an antifouling layer paint is applied with an applicator and dried at room temperature for 12 hours to produce an antifouling layer having a thickness of 100 ⁇ m.
- a coating film composed of a laminate of layers was prepared.
- the obtained undercoat / antifouling layer laminate was cut out so that the undercoat / antifouling layer had a size of 20 mm ⁇ 60 mm, and a tensile tester (device name “AUTOGRAPH AGS-X”, The tensile strength at break was evaluated using Shimadzu Corporation).
- FIG. 6 is a schematic diagram for explaining a peelability confirmation experiment.
- the same operation as in the underwater constant load peel test was performed, and a PMMA plate (trade name “Delagrass K”, manufactured by Asahi Kasei Technoplus Co., Ltd., methyl methacrylate polymer 96.6% or more) with an undercoat layer having a thickness of 150 ⁇ m and a thickness of 100 ⁇ m
- a coating film comprising an antifouling layer was prepared.
- the obtained undercoat layer and antifouling layer were removed from the laminate so that the undercoat layer / antifouling layer had a size of 20 mm ⁇ 100 mm.
- the coating film was peeled from the PMMA substrate at a peeling angle of 145 to 180 ° (in the direction indicated by the arrow 7 in FIG. 6), it was evaluated whether or not the primer layer was broken.
- the adhesive strength is 0.5 (N / 20 mm) or more
- the adherend is On the other hand, it exhibits a sufficiently high adhesive force and does not easily peel off from the adherend even on land exposed to wind and rain. Since the degree of cross-cut stretch release is 0.00, the adhesion between the undercoat layer and the silicone resin that is the antifouling layer is high, and the antifouling layer peels off from the undercoat layer in the same manner as when used in water. Hateful.
- the tensile breaking strength with respect to the adhesive force was sufficiently high as 1.5 or more, it was confirmed that the film could be peeled without breaking after the coating film was formed.
- a primer for silicone paint it has been confirmed that it is useful as an antifouling layer on the surface of various exterior materials such as roofs and outer walls, even for applications other than underwater.
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Abstract
Description
水中定荷重剥離度は、塗膜が水中で抵抗を受けた際に、塗膜の剥離しやすさの程度を示す。100グラム水中定荷重剥離度は、水中において、100グラムの荷重をかけて、1時間経過した際に、塗膜が被着対象物から剥離する量を示し、以下の方法で測定される値である。
引張破断強度は、塗膜を引張したときの塗膜の破断しにくさを示す強度である。引張破断強度が低いと、塗膜を被着体から剥離する際に、塗膜が破断し、剥離が、困難になってしまう。また、接着力が高いと被着体から塗膜を剥離するために必要な力が大きくなり、その結果、塗膜が破断しやすくなる。したがって、塗膜を破断させずに容易に剥離するためには、引張破断強度の、接着力に対する比が高くなければならない。
防汚層の下塗層に対する1mm四方クロスカット延伸剥離度は、図3に示すように、防汚層にのみ形成された複数の1mm四方の切り込みのマス目を備える積層体を、マス目の対角線上(図3における矢印5で示される方向)に2倍延伸したときに、剥離したマス目の割合であり、防汚層の下塗層からの剥離しにくさの程度を示す。
水中構造物の表面に用いられる典型的な材料として典型的なものには、例えば、PMMA(ポリメタクリル酸メチル樹脂)、ゲルコート(アクリル系ポリマー/ポリスチレン等)、エポキシ塗料による塗膜、エナメル塗料(アクリル系ポリマー等)による塗膜及びアルミニウムが挙げられるが、本発明は、他の材料に用いることもできる。
下塗層を形成するための塗料は、樹脂成分と溶剤を含む。樹脂成分としては、例えば、ゴム(熱硬化性エラストマー)及び熱可塑性エラストマー等のエラストマーを用いることができる。一方で、長期使用による強度劣化が激しい、ポリ塩化ビニル等の一部の熱可塑性樹脂は、塗膜を剥離する際に切断する虞があるため、好ましくない。
(下塗層用塗料の作製)
アミン変性水添スチレン系熱可塑性エラストマー(スチレン含有割合30重量%、商品名「タフテックMP10」、旭化成ケミカルズ株式会社製)80重量部とトルエン20重量部とを混合し、室温(23℃)で12時間撹拌し、下塗層用塗料を得た。
シリコーン樹脂(商品名「KE445B」、信越シリコーン株式会社製)100重量部とシリコーンオイル(メチルフェニルシリコーンオイル、商品名「KF50-100Cs」、信越シリコーン株式会社製)90重量部とを混合し、室温(23℃)で5分間撹拌し、防汚層用塗料を得た。
上記の下塗層用塗料及び防汚層用塗料からなる塗料セットを用いて、以下の方法で塗膜を作成し、水中定荷重剥離度を測定した。PMMA板(商品名「デラグラスK」、旭化成テクノプラス株式会社製、メタクリル酸メチル重合体96.6%以上)に、下塗用の塗料をアプリケーターで塗工し、室温で12時間乾燥させ、厚み150μmの下塗層を作製した。作製した下塗層の上に、防汚層用塗料をアプリケーターで塗工し、室温で12時間乾燥させ、厚み100μmの防汚層を作製することで、PMMA板上に、下塗層及び防汚層からなる塗膜を作製した。
水中定荷重剥離試験と同様の操作を行い、PMMA板(商品名「デラグラスK」、旭化成テクノプラス株式会社製、メタクリル酸メチル重合体96.6%以上)に、厚み150μmの下塗層、厚み100μmの防汚層からなる塗膜を作製した。得られた塗膜を60℃の純水に5週間浸漬後、塗膜が20mm×100mmの大きさになるように、それ以外の部分を取り除いた。引張試験機(AUTOGRAPH AGS-X、(株)島津製作所製)を用いて、積層体をPMMA基板から、剥離角度180度、剥離速度300mm/minで引きはがした際の力を接着力として測定した。
セパレータ(商品名「MRF38」、三菱樹脂(株)製、厚み50μm)の表面に、下塗層用塗料をアプリケーターで塗工し、室温で12時間乾燥させ、厚み150μmの下塗層を作製した。作製した下塗層の上に、防汚層用塗料をアプリケーターで塗工し、室温で12時間乾燥させ、厚み100μmの防汚層を作製することで、セパレータ上に、下塗層及び防汚層の積層体からなる塗膜を作製した。得られた下塗層/防汚層の積層体を60℃の純水に5週間浸漬後、下塗層/防汚層が20mm×60mmの大きさになるように切り取り、引張試験機(装置名「AUTOGRAPH AGS-X」、(株)島津製作所製)を用いて引張破断強度を評価した。
引張破断強度と同様の操作を行い、セパレータ(商品名「MRF38」、三菱樹脂(株)製、厚み38μm)上に、下塗層及び防汚層からなる塗膜を作製した。得られた下塗層及び防汚層の積層体を20mm×60mmに切り取り、クロスカット試験カッターガイド(商品名「スーパーカッターガイド」、太佑機材(株)製)を用いて防汚層のみに1mm間隔で100マス(1cm□)カッターで切り込みを入れた。マスの対角線上に2倍延伸し、下塗層から剥がれた防汚層のマス目の数を計測した。
図4は、下塗層に対する15ノット水流試験を説明する概略図である。水中定荷重剥離試験と同様の操作を行い、PMMA板(商品名「デラグラスK」、旭化成テクノプラス株式会社製、メタクリル酸メチル重合体96.6%以上)に、厚み150μmの下塗層、厚み100μmの防汚層からなる塗膜を作製し、塗膜が20mm×100mmの大きさになるように周囲を除去した。次に、塗膜を短辺(20mm側辺)側から20mm引き剥がし、塗膜の長辺方向と並行となる方向に水流(流速15ノット)(図4において矢印6で示される)を200時間流し、下塗層がPMMA板から剥がれる時間を評価した。尚、水流の方向は塗膜を引きはがした側が上流となるようにした。
図5は、防汚層に対する15ノット水流試験を説明する概略図である。PMMA板(商品名「デラグラスK」、旭化成テクノプラス株式会社製、メタクリル酸メチル重合体96.6%以上)に、前記下塗塗料(1)をアプリケーターで塗工し、室温で12時間乾燥させ、厚み150μmの下塗層を作製した。作製した下塗層の上に、20mm×50mm、厚み100μmの塗膜を形成するように前記防汚層用塗料(1)をアプリケーターで塗工し、室温で12時間乾燥させ、PMMA板上に、下塗層/防汚層からなる塗膜を作製した。防汚層の長辺方向と並行となる方向に水流(流速15ノット)(図5において6で示される)を200時間流し、防汚層が下塗層から剥がれる時間を評価した。
水流を流速30ノットに変更したこと以外は15ノット流水試験(下塗層)と同様の操作を行い、下塗層がPMMA板から剥がれる時間を評価した。
水流を流速30ノットに変更したこと以外は15ノット流水試験(防汚層)と同様の操作を行い、防汚層が下塗層から剥がれる時間を評価した。
図6は、剥離性の確認実験を説明する概略図である。水中定荷重剥離試験と同様の操作を行い、PMMA板(商品名「デラグラスK」、旭化成テクノプラス株式会社製、メタクリル酸メチル重合体96.6%以上)に、厚み150μmの下塗層、厚み100μmの防汚層からなる塗膜を作製した。得られた下塗層及び防汚層の積層体を60℃の純水に5週間浸漬後、下塗層/防汚層が20mm×100mmの大きさになるように、それ以外の部分を取り除いた。塗膜をPMMA基板から、剥離角度145~180°(図6で矢印7で示される方向)で引きはがした際、下塗層が切れるかどうかを評価した。
水中定荷重剥離試験と同様の方法により、PMMA板(商品名「デラグラスK」、旭化成テクノプラス株式会社製、メタクリル酸メチル重合体96.6%以上)に、厚み150μmの下塗層、厚み100μmの防汚層を作製した。得られた下塗層/防汚層の積層体を姫路市沿岸の水深1mに浸漬した。36か月間浸漬後、防汚層の表面に水生生物が付着するかどうかを評価した。なお、防汚層は、いずれの実施例でも同一材料であるため、防汚性についての試験は、実施例1のみにおいて行われた。
下塗層用塗料の樹脂組成を、実施例1の樹脂とは変性方法が異なるマレイン酸変性SEBS(スチレン含有割合30重量%、商品名「FG1901」、クレイトンジャパンポリマー株式会社製)に変更したこと以外は実施例1と同様の操作によって、下塗層用塗料及び防汚層用塗料を作製した。また、それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料の樹脂組成を、実施例2の樹脂に、スチレン系粘着付与樹脂(商品名「ピコラスティックA75」、エヌエヌケミカル株式会社製)を35重量%になるように加えることで接着力を向上させたこと以外は実施例1と同様の操作を行うことによって、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料の樹脂組成を、実施例1の樹脂とは異なる、水酸基変性SEPS(スチレン量28重量%、商品名「HG252」、クラレ株式会社製)に変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料の樹脂組成を、実施例1の樹脂よりスチレン含有量が25重量%と低い、変性SEBS(商品名「DYNARON 8660P」、JSR株式会社製)に変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料の樹脂組成を、アクリル系熱可塑性エラストマー(PMMA/2-エチルヘキシルアクリレート/ブチルアクリレートブロック共重合体、商品名「クラリティLK9333」、株式会社クラレ製)に変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料の樹脂組成を、実施例2のスチレン含有量を30重量%から13重量%に変更したSEBS(スチレン量13重量%、マレイン酸変性量1重量%、商品名「GFG1924」、クレイトンジャパンポリマー社製)に変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料の樹脂組成を、ウレタンエマルジョン(商品名「ハイドランWLS210」、DIC株式会社製)に変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料の樹脂組成を、PIB(ポリイソブチレン)(商品名「B100」、BASF社製)72重量%、粘着付与材(商品名「アルコンM135」、荒川化学工業社製)21重量%、アミン変性シリコーンオリゴマー(商品名「x-40-2651」、信越シリコーン社製)7重量%の配合比で混合したものに変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料の樹脂組成を、フッ素樹脂(商品名「GL252EA」、硬化剤(GL200RB)5重量部含有、ダイキン工業社製)91重量%、アイオノマー(商品名「ケミパールSA100」、三井化学社製)9重量%の配合比で混合したものに変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
比較例1では、下塗層用塗料の樹脂組成を、実施例1と異なり変性を行っていないSEBS(スチレン量29重量%、商品名「タフテックH1053」、旭化成ケミカルズ社製)にそれぞれ変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
比較例2では、下塗層用塗料の樹脂組成を、実施例1と異なり変性を行っていないSEBS(スチレン量18重量%、商品名「タフテックH1062」、旭化成ケミカルズ社製)にそれぞれ変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
比較例3では、下塗層用塗料の樹脂組成を、実施例1と異なり変性を行っていないSEBS(スチレン量13重量%、商品名「G1657」、クレイトンジャパンポリマー社製)にそれぞれ変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料の樹脂組成を、ポリ塩化ビニルとポリ酢酸ビニルの共重合体(商品名「反る場インCH」、信越化学工業社製)に変更し、溶剤をMEKに変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料の樹脂組成を、PVB(ポリビニルブチラール)(商品名「B60T」、クラレ社製)に変更し、溶剤をエタノールに変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料として市販品のウレタン系塗料(商品名「マスキングカラー」、太洋塗料社製)に変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料として、市販品のSBR(スチレン・ブタジエンゴム)系塗料(商品名「1034」、PlastiDip社製)に変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料として、市販品のSEBS系塗料(商品名「液体ラバーペイント油性」、SDesgn社製)に変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料として、実施例2で用いたマレイン酸変性SEBSとアクリル系熱可塑性エラストマー(スチレン量30重量%、マレイン酸変性量1重量%、商品名「クラリティLA2330」、クラレ社製)とを50%ずつの配合比(重量)%で混合したものに変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料として、実施例2で用いたマレイン酸変性SEBS25重量%と比較例10に記載のアクリル系熱可塑性エラストマー75重量%の配合比で混合したものに変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料として、比較例9に記載のアクリル系熱可塑性エラストマーのみに変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料として、ブチルゴム(商品名「065」、JSR社製)77重量%と実施例9に記載のアミン変性シリコーンオリゴマー23重量%の配合比で混合したものに変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料として、市販のシリコーン用プライマー(商品名「プライマーT」、信越シリコーン社製)に変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料として、市販のシリコーン用プライマー(商品名「プライマーNo.4」、信越シリコーン社製)に変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料として、アイオノマー(商品名「ケミパールSA100」、三井化学社製)に変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。それらの塗料からなる塗料セットを用いて、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
下塗層用塗料を用いなかったこと以外は実施例1と同様の操作を行い、防汚層用塗料を作製し、実施例1と同様の操作により、塗膜を作成して、水中定荷重剥離試験、接着力、引張破断強度、クロスカット延伸試験、15・30ノット流水試験(下塗層)、15・30ノット流水試験(防汚層)、剥離性の評価を行った。結果を表2に示す。
上述した実施例及び比較例に示した下塗層用塗料並びに以下に示す実施例11~15に示される下塗層用塗料と上述した防汚層用塗料とからなる塗料セットを用いて、接着力、引張破断強度、クロスカット延伸度、剥離性の各評価を行った。結果を表8に示す。接着力、引張破断強度および剥離力は下記方法によって測定し、クロスカット延伸度は上述した方法により測定した。
下塗層用塗料の樹脂組成を、ウレタンエマルジョン(商品名「スーパーフレックス470」、第一工業製薬株式会社製)に変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。
下塗層用塗料の樹脂組成を、アイオノマーブチル(商品名なし、ランクセス株式会社製)に変更したこと以外は実施例1と同様の操作を行い、下塗層用塗料および防汚層用塗料を作製した。
実施例13では、下塗層用塗料の樹脂組成を、実施例1と異なり変性を行っていないSEBS(スチレン量30重量%)に、ロジン樹脂(商品名「ペンセルD135」、荒川化学工業株式会社製)を23重量%になるように加えることで接着力を向上させたこと以外は実施例1と同様の操作を行うことによって、下塗層用塗料および防汚層用塗料を作製した。
実施例14では、下塗層用塗料の樹脂組成を、実施例1と異なり変性を行っていないSEBS(スチレン量30重量%)に、アルコキシシリコーンオリゴマー(商品名「KC-89S」、信越シリコーン株式会社製)を5重量%になるように加えることで接着力を向上させたこと以外は実施例1と同様の操作を行うことによって、下塗層用塗料および防汚層用塗料を作製した。
実施例15では、下塗層用塗料の樹脂組成を、実施例1と異なり変性を行っていないSEBS(スチレン量30重量%)に、ハイドロジェン変性シリコーンオイル(商品名「KF9901」、信越シリコーン株式会社製)を23重量%になるように加えることで接着力を向上させたこと以外は実施例1と同様の操作を行うことによって、下塗層用塗料および防汚層用塗料を作製した。
水中定荷重剥離試験と同様の操作を行い、PMMA板(商品名「デラグラスK」、旭化成テクノプラス株式会社製、メタクリル酸メチル重合体96.6%以上)に、厚み150μmの下塗層、厚み100μmの防汚層からなる塗膜を作製した。得られた塗膜を塗膜が20mm×100mmの大きさになるように、それ以外の部分を取り除いた。引張試験機(AUTOGRAPH AGS-X、(株)島津製作所製)を用いて、積層体をPMMA基板から、剥離角度180度、剥離速度300mm/minで引きはがした際の力を接着力として測定した。
セパレータ(商品名「MRF38」、三菱樹脂(株)製、厚み50μm)の表面に、下塗層用塗料をアプリケーターで塗工し、室温で12時間乾燥させ、厚み150μmの下塗層を作製した。作製した下塗層の上に、防汚層用塗料をアプリケーターで塗工し、室温で12時間乾燥させ、厚み100μmの防汚層を作製することで、セパレータ上に、下塗層及び防汚層の積層体からなる塗膜を作製した。得られた下塗層/防汚層の積層体を、下塗層/防汚層が20mm×60mmの大きさになるように切り取り、引張試験機(装置名「AUTOGRAPH AGS-X」、(株)島津製作所製)を用いて引張破断強度を評価した。
図6は、剥離性の確認実験を説明する概略図である。水中定荷重剥離試験と同様の操作を行い、PMMA板(商品名「デラグラスK」、旭化成テクノプラス株式会社製、メタクリル酸メチル重合体96.6%以上)に、厚み150μmの下塗層、厚み100μmの防汚層からなる塗膜を作製した。得られた下塗層及び防汚層の積層体を、下塗層/防汚層が20mm×100mmの大きさになるように、それ以外の部分を取り除いた。塗膜をPMMA基板から、剥離角度145~180°(図6で矢印7で示される方向)で引きはがした際、下塗層が切れるかどうかを評価した。
2 下塗層
3 防汚層
4 被着体
5 延伸方向
6 水流方向
7 剥離方向
Claims (37)
- 水中構造物上の塗膜であって、
前記水中構造物に接着する下塗層と、前記下塗層に接着する防汚層とを備え、
100グラム水中定荷重剥離度が、5(mm/20mm)未満であり、
60℃の純水に5週間浸漬した後における引張破断強度(N/20mm)の、前記水中構造物との接着力(N/20mm)に対する比率が、1.5以上であり、
前記防汚層の前記下塗層に対する1mm四方クロスカット延伸剥離度が、0.05以下である、
ことを特徴とする塗膜。 - 前記下塗層は、エラストマーを含む、
ことを特徴とする請求項1に記載の塗膜。 - 前記エラストマーは、極性基を含有する化合物で変性されている、
ことを特徴とする請求項2に記載の塗膜。 - 前記下塗層は、極性基を含有する化合物を更に含む、
ことを特徴とする請求項2に記載の塗膜。 - 前記防汚層は、シリコーン樹脂を含む、
ことを特徴とする請求項1から4のいずれか1項に記載の塗膜。 - 前記水中定荷重剥離度は、0.5未満であることを特徴とする、
請求項1から5のいずれか1項に記載の塗膜。 - 前記水中定荷重剥離度は、0.1未満であることを特徴とする、
請求項6に記載の塗膜。 - 前記比率が、5.0以上である、
ことを特徴とする請求項1から7のいずれか1項に記載の塗膜。 - 前記接着力は、4.0から15である、
ことを特徴とする請求項1から8のいずれか1項に記載の塗膜。 - 水中構造物に接着した下塗層と、前記下塗層に接着した防汚層とを備える塗膜を形成するための塗料セットであって、
前記下塗層を形成するための下塗層用塗料と、前記防汚層を形成するための防汚層用塗料とを含み、
前記下塗層用塗料が、150μmの厚さの層としてPMMAに接着し、前記防汚層用塗料が前記下塗層用塗料の層に接着する場合に、
100グラム水中定荷重剥離度が、5(mm/20mm)未満であり、
60℃の純水に5週間浸漬した後における引張破断強度(N/20mm)の接着力(N/20mm)に対する比率が、1.5以上であり、
前記防汚層用塗料の層の、前記下塗層用塗料の層に対する1mm四方クロスカット延伸剥離度が、0.05以下である、
ことを特徴とする塗料セット。 - 前記水中定荷重剥離度は、0.5未満であることを特徴とする、
請求項10に記載の塗料セット。 - 前記水中定荷重剥離度は、0.1未満であることを特徴とする、
請求項11に記載の塗料セット。 - 構造物に接着した下塗層と、前記下塗層に接着した防汚層とを備える塗膜を形成するための塗料セットであって、
前記下塗層を形成するための下塗層用塗料と、前記防汚層を形成するための防汚層用塗料とを含み、
前記下塗層用塗料が、150μmの厚さの層としてPMMAに接着し、前記防汚層用塗料が前記下塗層用塗料の層に接着する場合に、
PMMAに対する接着力が0.5(N/20mm)以上であり、
引張破断強度(N/20mm)の接着力(N/20mm)に対する比率が、1.5以上であり、
前記防汚層用塗料の層の、前記下塗層用塗料の層に対する1mm四方クロスカット延伸剥離度が、0.05以下である、
ことを特徴とする塗料セット。 - 前記下塗層用塗料は、エラストマーを含む、
ことを特徴とする請求項10から13の何れか1項に記載の塗料セット。 - 前記エラストマーは、極性基を含有する化合物で変性されている、
ことを特徴とする請求項14に記載の塗料セット。 - 前記下塗層用塗料は、極性基を含有する化合物を更に含む、
ことを特徴とする請求項15に記載の塗料セット。 - 前記防汚層用塗料は、シリコーン樹脂を含む、
ことを特徴とする請求項10から16のいずれか1項に記載の塗料セット。 - 前記比率が、5.0以上である、
ことを特徴とする請求項10から17のいずれか1項に記載の塗料セット。 - 前記接着力は、4.0から15である、
ことを特徴とする請求項10から18のいずれか1項に記載の塗料セット。 - 水中構造物に接着した下塗層と、前記下塗層に接着した防汚層とを備える塗膜を形成する方法であって、
前記水中構造物に、下塗層用塗料を塗工して、前記下塗層を形成するステップと、
前記下塗層に、防汚層用塗料を塗工して、前記防汚層を形成するステップとを備え、
前記下塗層用塗料が、150μmの厚さの層としてPMMAに接着し、前記防汚層用塗料が前記下塗層用塗料の層に接着する場合に、
100グラム水中定荷重剥離度が、5(mm/20mm)未満であり、
60℃の純水に5週間浸漬した後における引張破断強度(N/20mm)の接着力(N/20mm)に対する比率が、1.5以上であり、
前記防汚層用塗料の層の、前記下塗層用塗料の層に対する1mm四方クロスカット延伸剥離度が、0.05以下である、
ことを特徴とする方法。 - 前記下塗層用塗料は、エラストマーを含む、
ことを特徴とする請求項20に記載の方法。 - 前記エラストマーは、極性基を含有する化合物で変性されている、
ことを特徴とする請求項21に記載の方法。 - 前記下塗層用塗料は、極性基を含有する化合物を更に含む、
ことを特徴とする請求項21に記載の方法。 - 前記防汚層は、シリコーン樹脂を含む、
ことを特徴とする請求項20から23のいずれか1項に記載の方法。 - 前記水中定荷重剥離度は、0.5未満であることを特徴とする、
請求項20から24のいずれか1項に記載の方法。 - 前記水中定荷重剥離度は、0.1未満であることを特徴とする、
請求項25に記載の方法。 - 前記比率が、5.0以上である、
ことを特徴とする請求項20から26のいずれか1項に記載の方法。 - 前記接着力は、4.0から15である、
ことを特徴とする請求項20から27のいずれか1項に記載の方法。 - 構造物に接着した下塗層と、前記下塗層に接着したシリコーン樹脂製の防汚層とを備える塗膜の下塗層を形成する下塗層用塗料であって、
前記下塗層用塗料が、150μmの厚さの層としてPMMAに接着し、前記防汚層用塗料が前記下塗層用塗料の層に接着する場合に、
100グラム水中定荷重剥離度が、5(mm/20mm)未満であり、
60℃の純水に5週間浸漬した後における引張破断強度(N/20mm)の接着力(N/20mm)に対する比率が、1.5以上であり、
前記防汚層用塗料の層の、前記下塗層用塗料の層に対する1mm四方クロスカット延伸剥離度が、0.05以下である、
ことを特徴とする下塗層用塗料。 - 前記水中定荷重剥離度は、0.5未満であることを特徴とする、
請求項29に記載の下塗層用塗料。 - 前記水中定荷重剥離度は、0.1未満であることを特徴とする、
請求項30に記載の下塗層用塗料。 - 構造物に接着した下塗層と、前記下塗層に接着したシリコーン樹脂製の防汚層とを備える塗膜の下塗層を形成する下塗層用塗料であって、
前記下塗層用塗料が、150μmの厚さの層としてPMMAに接着し、前記防汚層用塗料が前記下塗層用塗料の層に接着する場合に、
PMMAに対する接着力が0.5(N/20mm)以上であり、
引張破断強度(N/20mm)の接着力(N/20mm)に対する比率が、1.5以上であり、
前記防汚層用塗料の層の、前記下塗層用塗料の層に対する1mm四方クロスカット延伸剥離度が、0.05以下である、
ことを特徴とする下塗層用塗料。 - 前記下塗層用塗料は、エラストマーを含む、
ことを特徴とする請求項29から32のいずれか1項に記載の下塗層用塗料。 - 前記エラストマーは、極性基を含有する化合物で変性されている、
ことを特徴とする請求項33に記載の下塗層用塗料。 - 前記下塗用塗料は、極性基を含有する化合物を更に含む、
ことを特徴とする請求項33に記載の下塗層用塗料。 - 前記比率が、5.0以上である、
ことを特徴とする請求項29から34のいずれか1項に記載の下塗層用塗料。 - 前記接着力は、4.0から15である、
ことを特徴とする請求項29から35のいずれか1項に記載の下塗層用塗料。
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JP6730493B1 (ja) * | 2019-06-14 | 2020-07-29 | アァルピィ東プラ株式会社 | 積層体及び搬送部材 |
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US20210107044A1 (en) | 2021-04-15 |
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