Classifications

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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • 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
  • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/61—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
  • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • C—CHEMISTRY; METALLURGY
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7806—Nitrogen containing -N-C=0 groups
  • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
  • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
• • C—CHEMISTRY; METALLURGY
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • C—CHEMISTRY; METALLURGY
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/06—Polyurethanes from polyesters
• • 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
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/08—Polyurethanes from polyethers
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  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2475/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2475/04—Polyurethanes
  • C08J2475/08—Polyurethanes from polyethers
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2475/04—Polyurethanes
  • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2475/04—Polyurethanes
  • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C08J2475/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

• the present disclosure relates to coating compositions, kits, coating films, and methods of forming coating films.
• Hard coat treatment is a method of forming a coating film with high crosslink density and surface hardness. However, once the coating film formed by the hard coating process is scratched, cracks are generated from that site. In addition, when hard-coated plastic molded products are used for automobile exterior parts, sand, pebbles, etc. collide with the molded products while the automobile is running, and fine dents (dents) may occur on the surface (coating surface). etc.). In the case of hard coat treatment, the problem of scratches on the coating film surface can be avoided by thickening the coating film, but thickening the coating film causes a decrease in design and an increase in the weight of exterior parts.
• Patent Document 1 discloses a polycarbonate diol containing a specific repeating unit and a terminal hydroxyl group, wherein the specific repeating unit has an average carbon number of 3.0 to 4.0. Disclosed is a coating composition comprising a polycarbonate diol, a polyol other than the polycarbonate diol, and an organic polyisocyanate. Patent Document 1 states that this coating composition provides a coating film having both high wound recovery and stain resistance.
• the coating film made from the coating composition of Patent Document 1 has a long wound recovery time, and it cannot be said that the stain resistance is sufficient.
• the silicon content in terms of SiO2 is 0.001 to 0.1% by mass based on the total amount of the organic polyisocyanate (A), the acrylic polyol (B) and the polydimethylsiloxane compound.
• the ratio of the number of moles of isocyanate groups in the isocyanate group-containing compound contained in the coating composition to the number of moles of hydroxyl groups in the hydroxyl group-containing compound contained in the coating composition is 0.8 to 1.3.
• the coating composition according to any one of [1] to [7].
• a coating film containing a cured product of the coating composition according to any one of [1] to [8].
• a method of forming a coating film comprising applying the coating composition according to any one of [1] to [8] onto an adherend and curing it.
• a coating film that has good stain resistance and excellent self-healing properties against scratches. Further, according to another aspect of the present disclosure, it is possible to provide a coating film that has good smoothness, stain resistance, and adhesion, and that has excellent self-repairing properties against scratches. Further, according to another aspect of the present disclosure, it is possible to provide a coating composition that contributes to the preparation of the coating film, a kit for preparing the coating composition, and a method of forming the coating film.
• the numerical range indicated using “-” indicates the range including the numerical values before and after “-” as the minimum and maximum values, respectively.
• the units of numerical values described before and after “-” are the same, unless otherwise specified.
• the upper and lower limits of the numerical ranges may be replaced with the values shown in the examples.
• the upper limit value and the lower limit value described individually can be combined arbitrarily.
• “(meth)acryl” means at least one of acryl and methacryl corresponding thereto.
• a coating composition includes an organic polyisocyanate (A) and an acrylic polyol (B), the organic polyisocyanate (A) includes a modified polyisocyanate (a), and the modified polyisocyanate (a) is a reaction product of a polyisocyanate component (a1) and a polyol component (a2) or a modified product thereof, the polyisocyanate component (a1) contains an organic diisocyanate or a modified product thereof, and the polyol component (a2 ) contains at least one selected from the group consisting of polytetramethylene glycol and polycarbonate polyols having a number average molecular weight of 200 to 750, and the acrylic polyol (B) has a glass transition temperature of 5 to 30° C., and Contains an acrylic polyol (b) having a hydroxyl value of more than 100 mgKOH/g and not more than 150 mgKOH/g.
• the coating composition according to one aspect of the present disclosure it is possible to obtain a coating film that has good stain resistance and excellent self-healing properties against scratches. Moreover, according to the coating composition according to one aspect of the present disclosure, it is also possible to obtain a coating film with good smoothness and adhesion.
• details of the coating composition according to one aspect of the present disclosure and each component that can be contained in the coating composition will be described.
• Organic polyisocyanate (A) includes modified polyisocyanate (a).
• the modified polyisocyanate (a) is a reaction product of the polyisocyanate component (a1) and the polyol component (a2) or a modified product thereof.
• the reaction product may be a urethane-modified polyisocyanate obtained by the reaction of the polyisocyanate component (a1) and the polyol component (a2), an allophanate-modified polyisocyanate obtained by allophanatizing the urethane-modified polyisocyanate, or An isocyanurate-modified polyisocyanate obtained by isocyanurating the urethane-modified polyisocyanate may be used.
• Modified products include, for example, block modified products of the above reaction products.
• a block-modified product has a structure in which a part of the isocyanate group is modified with a blocking agent.
• the blocking agent prevents the reaction between the isocyanate group and water or an active hydrogen group such as a hydroxyl group, thereby suppressing the progress of the reaction in the coating composition. Therefore, according to the block modified product, it is possible to easily make it into one liquid.
• Modified polyisocyanate (a) which is a block-modified product, is a latent curing agent that reacts with active hydrogen groups when the blocking agent is dissociated by heating and the isocyanate groups are activated again. Details of the blocking agent will be described later.
• allophanate-modified polyisocyanate and isocyanurate-modified polyisocyanate include block-modified allophanate-modified polyisocyanate and isocyanurate-modified polyisocyanate.
• the modified polyisocyanate (a) preferably contains allophanate-modified polyisocyanate.
• allophanate-modified polyisocyanate in the modified polyisocyanate (a), it is possible to obtain a flexible yet tough coating film, it can be made into a liquid with a lower viscosity, and the handling property in painting is improved. The effect is exhibited, and the self-healing property of the coating film is further improved.
• the modified polyisocyanate (a) may contain the allophanate-modified polyisocyanate and the isocyanurate-modified polyisocyanate from the viewpoint of obtaining a more flexible and tough coating film.
• the modified polyisocyanate (a) contains an isocyanurate-modified polyisocyanate
• the resulting coating film (polyurethane resin in the coating film) has an increased glass transition temperature. Impairment of the self-healing property can be suppressed by increasing the content of the structure derived from the polycarbonate polyol.
• the modified polyisocyanate (a) contains an allophanate-modified polyisocyanate or an isocyanurate-modified polyisocyanate, the smaller the number of urethane groups in the modified polyisocyanate (a), the higher the self-healing property of the coating film. From such a point of view, the modified polyisocyanate (a) may be substantially free of urethane groups.
• Modified polyisocyanate (a) substantially does not have urethane groups means that the content of urethane-modified polyisocyanate confirmed by proton nuclear magnetic resonance ( 1 H-NMR) spectrum is allophanate-modified polyisocyanate, isocyanurate-modified It means 0.5 mol % or less based on the total amount of polyisocyanate and urethane-modified polyisocyanate.
• the content (total amount) of the allophanate-modified polyisocyanate and the isocyanurate-modified polyisocyanate in the modified polyisocyanate (a) is the total mass of the modified polyisocyanate (a) from the viewpoint of further improving the self-healing property of the coating film. may be 80% by mass or more, or 90% by mass or more, or may be 100% by mass.
• the modified polyisocyanate (a) contains an allophanate-modified polyisocyanate and an isocyanurate-modified polyisocyanate
• the content of the isocyanurate-modified polyisocyanate is the allophanate-modified polyisocyanate from the viewpoint of further improving the self-healing property of the coating film.
• the total amount of isocyanurate-modified polyisocyanate it may be 30 mol % or less, 20 mol % or less, or 10 mol % or less.
• the content of the isocyanurate-modified polyisocyanate may be 1 mol% or more based on the total amount of allophanate-modified polyisocyanate and isocyanurate-modified polyisocyanate, from the viewpoint of further improving the stain resistance of the coating film. It may be mol % or more or 3 mol % or more.
• the content of the isocyanurate-modified polyisocyanate may be 1 to 30 mol %, 2 to 20 mol %, or 3 to 10 mol % from the above viewpoint. The above content can be confirmed by proton nuclear magnetic resonance ( 1 H-NMR) spectrum.
• the average number of functional groups of the modified polyisocyanate (a) may be 4.0 or more, or may be 4.5 or more, from the viewpoint of obtaining a coating film having excellent self-healing properties.
• the average number of functional groups of the modified polyisocyanate (a) may be 6.0 or less, or 5.5 or less, from the viewpoint of viscosity.
• the average functionality of the modified polyisocyanate (a) may be 4.0 to 6.0 or 4.5 to 5.5 from the above viewpoint.
• the average number of functional groups of the modified polyisocyanate (a) means the average number of isocyanate groups (--NCO) contained per molecule of the modified polyisocyanate (a).
• the average number of functional groups of the modified polyisocyanate (a) can be calculated from the isocyanate group content (NCO content) of the modified polyisocyanate (a) and the number average molecular weight.
• the average number of functional groups also includes the number of blocked isocyanate groups.
• the NCO content of the modified polyisocyanate (a) may be 13.0 to 23.0% by mass, even if it is 14.0% to 22.0% by mass or 15.0 to 21.0% by mass. good.
• the NCO content of the modified polyisocyanate (a) is 23.0% by mass or less, the self-healing property of the coating film is further improved.
• the NCO content of the modified polyisocyanate (a) is 13.0% by mass or more, the coating film has good stain resistance.
• the NCO content is a value measured by the method described in JISK1603-1 (polyurethane raw material aromatic isocyanate test method).
• the modified polyisocyanate (a) is a block modified product
• the NCO content of the modified polyisocyanate (a) in an unblocked state (with the blocking agent dissociated) shall be measured.
• the modified polyisocyanate (a) may have a number average molecular weight of 500 to 8,000, 600 to 7,500 or 700 to 7,000.
• the modified polyisocyanate (a) has a number average molecular weight of 500 or more, the self-healing property of the coating film is further improved.
• the modified polyisocyanate (a) has a number average molecular weight of 8,000 or less, the smoothness of the coating film is further improved, and the appearance of the coating film is further improved.
• the number average molecular weight is a value measured under the following conditions using GPC (gel permeation chromatography).
• GPC gel permeation chromatography
• the viscosity of the modified polyisocyanate (a) at 25°C may be 500 to 10000 mPa ⁇ s, 800 to 6000 mPa ⁇ s or 1000 to 3000 mPa ⁇ s.
• the viscosity of the modified polyisocyanate (a) at 25°C is a value measured using a Brookfield viscometer.
• the organic polyisocyanate (A) may contain the modified polyisocyanate (a) singly or in combination of two or more. Further, the organic polyisocyanate (A) contains an organic polyisocyanate other than the modified polyisocyanate (a) (for example, the polyisocyanate component (a1) which is a reaction raw material) as long as it does not impair the self-repairing property. good too.
• the content of the modified polyisocyanate (a) in the organic polyisocyanate (A) is preferably 80% by mass or more, more preferably 90% by mass, based on the total mass of the organic polyisocyanate (A). Yes, more preferably 100% by mass.
• the content of the free polyisocyanate component (a1) may be 1.0% by mass or less based on the total mass of the organic polyisocyanate (A).
• polyisocyanate component (a1) and the polyol component (a2) which are reaction raw materials of the modified polyisocyanate (a), and the method for producing the modified polyisocyanate (a) will be described.
• the polyisocyanate component (a1) is a component composed of an organic compound having multiple isocyanate groups, and includes an organic diisocyanate or a modified product thereof.
• An organic diisocyanate is an organic compound having two isocyanate groups.
• Organic diisocyanates include, for example, aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates. Modified products may be modified products of these organic diisocyanates.
• Modified compounds include, for example, allophanate-modified polyisocyanate, isocyanurate-modified polyisocyanate, uretdione-modified polyisocyanate, urethane-modified polyisocyanate, burette-modified polyisocyanate, uretimine-modified polyisocyanate, acyl urea-modified polyisocyanate, and the like.
• the polyisocyanate component (a1) may be one selected from the above organic diisocyanates and modified products, or a mixture of two or more selected from the above organic diisocyanates and modified products.
• aromatic diisocyanates examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate/2,6-tolylene diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyanate, diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate/4,4'-diphenylmethane diisocyanate mixture, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4 ,4′-diisocyanate, 2,2′-diphenylpropane-4,4′-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 4,4′-diphenylpropane di
• araliphatic diisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or mixtures thereof, ⁇ , ⁇ '-diisocyanato-1,4-diethylbenzene and the like.
• aliphatic diisocyanates examples include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, and trioxyethylene diisocyanate. be done.
• alicyclic diisocyanates examples include isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tetramethylxylene diisocyanate.
• organic diisocyanates are preferred, and it is more preferred to use at least one selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.
• Polyisocyanates having no unsaturated bonds are preferred from the viewpoint of the weather resistance of the coating film. That is, it is more preferable to use at least one selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates which do not have unsaturated bonds.
• hexamethylene diisocyanate is particularly preferable because it is easily available and synthesized, and a coating film having excellent adhesion and self-healing properties can be obtained.
• the polyisocyanate component (a1) may contain polyisocyanates other than organic diisocyanates and modified products thereof.
• the content (total amount) of the organic diisocyanate and its modified product in the polyisocyanate component (a1) is preferably 80% by mass or more, more preferably 80% by mass or more, based on the total mass of the polyisocyanate component (a1). It is 90% by mass, more preferably 100% by mass.
• the polyol component (a2) is a component composed of an organic compound having multiple hydroxyl groups.
• the polyol component (a2) contains at least one selected from the group consisting of polytetramethylene glycol and polycarbonate polyols having a number average molecular weight of 200-750.
• Polytetramethylene glycol is a compound having an oxytetramethylene group in its molecular skeleton, and is mainly obtained by ring-opening polymerization of tetrahydrofuran.
• the number average molecular weight of polytetramethylene glycol is 200 to 750, may be 220 or more or 250 or more, may be 600 or less or 500 or less, and may be 220 to 600 or 250 to 500 .
• the higher the number average molecular weight of polytetramethylene glycol the easier it is for the self-healing property of the coating film to improve. easy to obtain.
• a polycarbonate polyol is a compound having a plurality of carbonate groups and a plurality of hydroxyl groups, and is mainly obtained from a dealcoholization reaction or a dephenolation reaction between a low-molecular-weight polyol (for example, a polyol having a molecular weight of 500 or less) and a carbonate.
• a low-molecular-weight polyol for example, a polyol having a molecular weight of 500 or less
• the polycarbonate polyol for example, at least one compound selected from the group of compounds represented by ( ⁇ ) below and at least one compound selected from the group of compounds represented by ( ⁇ ) below are subjected to a dealcoholization reaction or dealcoholization reaction.
• a compound obtained from a phenol reaction (reaction product) can be mentioned.
• Polycarbonate polyols obtained from the dealcoholization reaction of 1,6-hexanediol and dialkyl carbonate (reaction products of 1,6-hexanediol and dialkyl carbonate ) is preferred.
• the number average molecular weight of the polycarbonate polyol is 200 to 750, and may be 220 or more, 250 or more, or 300 or more, and may be 600 or less, 500 or less, or 400 or less, 220 to 600, 250 to 500, It may be 300-750 or 200-400.
• the larger the number-average molecular weight of the polycarbonate polyol the easier it is for the self-repairing property of the coating film to be improved.
• the polyol component (a2) may contain polyols other than polytetramethylene glycol and polycarbonate polyols (other polyols).
• the modified polyisocyanate (a) is selected from the group consisting of a polyisocyanate component (a1) (eg, an organic diisocyanate or a modified product thereof), and polytetramethylene glycol and polycarbonate polyols having a number average molecular weight of 200 to 750. It may be a reaction product of at least one and another polyol.
• the content (total amount) of polytetramethylene glycol and polycarbonate polyol in the polyol component (a2) is preferably 80% by mass or more, more preferably 90% by mass, based on the total mass of the polyol component (a2). % by mass, more preferably 100% by mass.
• polystyrene resins include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 3,3- Dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer diol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, bis( ⁇ -hydroxye
• polyester polyols As other polyols, polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, fluorine-based polyols, animal and vegetable oil-based polyols, etc. can also be used.
• Modified polyisocyanate (a) can be obtained, for example, through the following first to fourth steps.
• 1st step The polyisocyanate component (a1) and the polyol component (a2) are charged in such an amount that the isocyanate groups are excessive relative to the hydroxyl groups, and urethanized to obtain an isocyanate group-terminated prepolymer I.
• 2nd step A catalyst is introduced into isocyanate group-terminated prepolymer I, and allophanatization is allowed to proceed at 70 to 150° C. to produce isocyanate group-terminated prepolymer II.
• - Third step The reaction is stopped by adding a reaction terminator to the isocyanate group-terminated prepolymer II.
• - Fourth step The free polyisocyanate component (a1) is removed by thin film distillation or solvent extraction of the isocyanate group-terminated prepolymer II to obtain the modified polyisocyanate (a).
• the reaction proceeds under nitrogen gas or dry air flow.
• the first to third steps may be carried out in the presence of an organic solvent, or may be carried out in the absence of an organic solvent.
• organic solvents that do not affect the reaction can be used as the organic solvent.
• organic solvents include aliphatic hydrocarbons such as octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; ketones such as methyl isobutyl ketone and cyclohexanone; esters such as butyl acetate and isobutyl acetate; glycol ether esters such as glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate and ethyl-3-ethoxypropionate; ethers such as dioxane; halogenated hydrocarbons; polar aprotic solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide and hexamethylphosphonylamide; These organic solvents may be used singly or in combination of two or more
• Step 1 Step of producing isocyanate group-terminated prepolymer I
• an isocyanate group-terminated prepolymer I is produced by reacting the polyisocyanate component (a1) and the polyol component (a2).
• the amounts of the polyisocyanate component (a1) and the polyol component (a2) to be charged are such that the isocyanate groups are in excess of the hydroxyl groups.
• the ratio R' is 40 or less, the increase in the amount of polyisocyanate containing urethane groups contained in the obtained modified polyisocyanate (a) is further suppressed, the decrease in the number of functional groups is further suppressed, and the production The properties and yields are further improved.
• the temperature at which the polyisocyanate component (a1) and the polyol component (a2) are reacted is, for example, 20 to 120°C, and may be 20 to 100°C or 50 to 100°C.
• the reaction time for the urethanization reaction varies depending on the presence or absence, type and temperature of the catalyst, but is generally within 10 hours, and may be 1 to 5 hours.
• a known urethanization catalyst can be used during the urethanization reaction.
• urethanization catalysts include organometallic compounds such as dibutyltin diacetate, dibutyltin dilaurate, and dioctyltin dilaurate; organic amines such as triethylenediamine and triethylamine, and salts thereof; and the like. These catalysts may be used singly or in combination of two or more.
• Step 2 Step of producing isocyanate group-terminated prepolymer II
• an isocyanate group-terminated prepolymer II is produced by performing an allophanatization reaction after the urethanization reaction in the first step.
• the allophanatization reaction may be performed simultaneously (in parallel) with the urethanization reaction, or may be performed after the completion of the urethanization reaction.
• the reaction may be performed in the presence of the urethanization catalyst and the allophanatization catalyst.
• the allophanatization reaction is performed after the completion of the urethanization reaction, the urethanization reaction is performed for a predetermined time in the presence of the urethanization catalyst and in the absence of the allophanatization catalyst, and then the allophanatization catalyst is added. Allophanatization reaction may be carried out.
• the allophanatization catalyst can be appropriately selected from known catalysts and used.
• metal salts of carboxylic acids metal salts of alkali metals such as lithium, sodium, potassium; metal salts of metals; metal salts of other typical metals such as tin and lead; metal salts of transition metals such as manganese, iron, cobalt, nickel, copper, zinc and zirconium;
• Carboxylic acids include, for example, monocarboxylic acids and polycarboxylic acids.
• allophanatization catalysts include zirconium octylate.
• the allophanatization catalyst may be used singly or in combination of two or more.
• the amount of the allophanatization catalyst used may be 0.001 to 0.1% by mass, and 0.005 to 0.03% by mass, based on the total mass of the polyisocyanate component (a1) and the polyol component (a2). may be When the amount of the allophanatization catalyst used is 0.001% by mass or more, the allophanatization reaction proceeds more easily, the amount of by-products of the urethane-modified polyisocyanate is suppressed, and the decrease in the number of functional groups of the resulting polyisocyanate is further suppressed. be done. Further, when the amount of the allophanatization catalyst used is 0.1% by mass or less, the storage stability is further improved.
• the reaction temperature for the allophanatization reaction is preferably 70 to 150°C, more preferably 90 to 130°C.
• the reaction temperature is 70° C. or higher, the allophanate-modified polyisocyanate is more likely to be produced, and the amount of by-products of the urethane-modified polyisocyanate is further suppressed, so that the decrease in the number of functional groups of the obtained polyisocyanate is further suppressed.
• the reaction temperature is 150° C. or lower, the formation of by-products of the isocyanurate-modified polyisocyanate is suppressed, and the self-healing property is further improved.
• the allophanatization reaction is preferably carried out until substantially no urethane groups are present.
• the urethane group is substantially absent means that the content of the urethane-modified polyisocyanate confirmed by the proton nuclear magnetic resonance ( 1 H-NMR) spectrum is allophanate-modified polyisocyanate, isocyanurate-modified polyisocyanate, It means 0.5 mol % or less based on the total amount of isocyanate and urethane-modified polyisocyanate.
• R′ the ratio of isocyanurate-modified polyisocyanate (based on the total amount of allophanate-modified polyisocyanate and isocyanurate-modified polyisocyanate) can be set to 30 mol % or less.
• reaction stop step In the third step, after the allophanatization reaction in the second step, a reaction terminator for deactivating the catalyst is added to terminate the allophanatization reaction.
• the reaction terminator may be added after completion of the allophanatization reaction (after urethane groups are substantially absent). However, in order to suppress the progress of side reactions, it is preferable to add the reaction terminator immediately after the end of the allophanatization reaction.
• reaction terminator examples include inorganic acids such as phosphoric acid and hydrochloric acid, organic acids having a sulfonic acid group and a sulfamic acid group, esters thereof, and known compounds such as acyl halides. . These may be used individually by 1 type, and may be used in combination of 2 or more types.
• the amount of reaction terminator added varies depending on the type of catalyst, but may be 0.5 to 10 equivalents, or may be 0.8 to 5.0 equivalents, relative to the amount of catalyst added.
• the addition amount of the reaction terminator is 0.5 equivalent or more, the storage stability of the resulting modified polyisocyanate is further improved.
• the amount of the reaction terminator added is 10 equivalents or less, coloration can be further suppressed.
• the polyisocyanate component (a1) is preferably removed to a residual content of 1.0% by mass or less, and more preferably removed to a residual content of less than 1.0% by mass.
• the residual content is 1.0% by mass or less, the odor is further reduced and the storage stability is further improved.
• the removal of the polyisocyanate component (a1) is preferably carried out by thin film distillation.
• Thin film distillation can be carried out at 120 to 140° C. under a high vacuum of 10 to 100 Pa, for example.
• the method for producing the modified polyisocyanate (a) according to one embodiment has been described above, the method for producing the modified polyisocyanate (a) is not limited to the above-described embodiment.
• the isocyanate group-terminated prepolymer I obtained in the first step may be used as the modified polyisocyanate (a) without performing the second to fourth steps.
• a step of modifying (blocking) some of the isocyanate groups with a blocking agent may be performed after the fourth step.
• blocking agents include phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, p-hydroxydiphenyl, t-butylphenol, o-isopropylphenol, o-sec-butylphenol, p-nonylphenol, pt- Phenolic blocking agents such as octylphenol, hydroxybenzoic acid and hydroxybenzoic acid esters; Lactam blocking agents such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; Active methylene-based blocking agents such as ethyl acetoacetate, methyl acetoacetate, and acetylacetone; methanol, ethanol, n-propyl alcohol, isopropyl
• carbamate blocking agents such as phenyl N-phenylcarbamate and 2-oxazolidone
• imine blocking agents such as ethyleneimine and propyleneimine
• sulfite-based blocking agents such as sodium bisulfite and potassium bisulfite; and the like.
• isocyanurate modification may mainly proceed by using an isocyanurate catalyst instead of the allophanat catalyst.
• Acrylic polyol (B) includes acrylic polyol (b).
• "acrylic polyol” means a polymer containing a (meth)acrylic monomer as a monomer unit and having a plurality of hydroxyl groups.
• the acrylic polyol (b) may be a homopolymer obtained by polymerizing one (meth)acrylic monomer, or may be a copolymer obtained by copolymerizing two or more (meth)acrylic monomers.
• the acrylic polyol (b) may contain monomers other than the (meth)acrylic acrylic monomer as a monomer unit, but from the viewpoint of achieving both a predetermined glass transition temperature and a hydroxyl value, only the (meth)acrylic acrylic monomer is used as a monomer unit. It is preferably included as a unit.
• a homopolymer obtained by polymerizing one type of (meth)acrylic monomer includes a homopolymer of a (meth)acrylic acid hydroxy compound.
• Copolymers obtained by copolymerizing two or more (meth)acrylic monomers include copolymers obtained by copolymerizing (meth)acrylic acid esters and (meth)acrylic acid hydroxy compounds.
• the (meth)acrylic acid ester is at least one selected from the group consisting of acrylic acid esters and methacrylic acid esters.
• the (meth)acrylic acid hydroxy compound is at least one selected from the group consisting of acrylic acid hydroxy compounds and methacrylic acid hydroxy compounds, which has one or more hydroxyl groups that can serve as reaction sites in its molecule.
• the glass transition temperature (glass transition point, Tg) of acrylic polyol (b) is 5 to 30°C. If the acrylic polyol (b) has a glass transition temperature of less than 5°C, the self-healing property against repeated scratches and stain resistance during outdoor use may be lowered. Further, when the glass transition temperature of the acrylic polyol (b) exceeds 30°C, the self-repairing property at room temperature (eg, 5 to 35°C) and low temperature (eg, below 5°C) may deteriorate.
• the glass transition temperature of the acrylic polyol (b) may be 10° C. or higher or 15° C. or higher from the viewpoint of better self-healing properties against repeated scratches and better stain resistance when used outdoors.
• the glass transition temperature of the acrylic polyol (b) may be 25° C. or lower or 20° C. or lower from the viewpoint of better self-healing properties at room temperature and low temperature.
• the glass transition temperature of the acrylic polyol (b) may be 10 to 25°C or 15 to 20°C from the above viewpoint.
• the polyol (b) having a glass transition temperature within the above range can be synthesized by adjusting the type and compounding ratio of the monomer components. For example, when the acrylic polyol (b) is a copolymer, Fox An acrylic polyol (b) having a glass transition temperature within the above range can be obtained by estimating the glass transition temperature from the formula and setting the mixing ratio of the monomer components.
• the glass transition temperature of the above acrylic polyol (b) is determined by measuring the inflection point of DSC in accordance with JIS K7121.
• the hydroxyl value of acrylic polyol (b) is more than 100 mgKOH/g and 150 mgKOH/g or less. If the hydroxyl value of the acrylic polyol (b) is out of this range, the self-healing property, stain resistance and smoothness may be deteriorated.
• the hydroxyl value of the acrylic polyol (b) may be 120 mgKOH/g or more or 140 mgKOH/g or more from the viewpoint of better stain resistance and smoothness.
• the hydroxyl value of the acrylic polyol (b) may be 130 mgKOH/g or less or 110 mgKOH/g or less from the viewpoint of better self-healing properties.
• the hydroxyl value of the acrylic polyol (b) is 120 to 150 mgKOH/g, 140 to 150 mgKOH/g, 120 to 130 mgKOH/g, more than 100 and 130 mgKOH/g or less, or more than 100 and 110 mgKOH/g or less. It's okay.
• the hydroxyl value of the acrylic polyol (b) is a value measured by a method according to JISK1557.
• the acrylic polyol (b) is, for example, a mixture of a (meth)acrylic monomer and a polymerization initiator by applying energy (light energy such as ultraviolet rays, electron beams, heat energy, etc.) to (meth) It can be obtained by polymerizing an acrylic monomer.
• the acrylic polyol (b) can be a thermal polymer or a photopolymer.
• the acrylic polyol (b) may be a thermal polymer in that it tends to be a polymer in which the polymerization reaction and the cross-linking reaction are completed.
• the acrylic polyol (B) may contain one type of acrylic polyol (b) alone, or may contain two or more types in combination.
• the acrylic polyol (B) may also contain an acrylic polyol (b') other than the acrylic polyol (b) (one or both of the glass transition temperature and the hydroxyl value are outside the above ranges).
• the content of the acrylic polyol (b') in the acrylic polyol (B) is based on the total mass of the acrylic polyol (B), from the viewpoint of making it easier to obtain a coating film having better self-healing properties and stain resistance. , 50% by mass or less (eg, 0 to 50% by mass), 30% by mass or less, or 10% by mass or less.
• (Meth)acrylic acid esters include, for example, alkyl esters having an alkyl group having 1 to 20 carbon atoms.
• Examples of such (meth)acrylate esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, ( (Meth)acrylic acids such as hexyl methacrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate and dodecyl (meth)acrylate Alkyl ester; (meth)acrylic acid cycloalkyl ester such as cyclohexyl (meth)acrylate (product of esterification reaction of (meth)acrylic acid and alicyclic alcohol); phenyl (meth)
• the (meth)acrylic acid hydroxy compound has one or more hydroxyl groups in the molecule that can act as reaction points with the polyisocyanate composition.
• Examples of (meth)acrylic acid hydroxy compounds include acrylic acids such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxy-2,2-dimethylpropyl acrylate, and pentaerythritol triacrylate.
• hydroxy compounds such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxy-2,2-dimethylpropyl methacrylate and pentaerythritol trimethacrylate;
• These (meth)acrylic acid hydroxy compounds may be used singly or in combination of two or more.
• the polymerization initiator includes thermal polymerization initiators and photopolymerization initiators.
• a polymerization initiator is appropriately selected depending on the polymerization method.
• thermal polymerization initiators include peroxydicarbonates such as di-2-ethylhexylperoxydicarbonate; t-butyl peroxybenzoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate, t - peroxyesters such as hexylperoxyisopropyl carbonate; di(t-butylperoxy)-2-methylcyclohexane, di(t-butylperoxy)3,3,5-trimethylcyclohexane and di(t-butylperoxy)cyclohexane peroxyketals; and the like.
• peroxydicarbonates such as di-2-ethylhexylperoxydicarbonate
• t-butyl peroxybenzoate t-butylperoxy-2-ethylhexanoate
• t-butylperoxyisopropyl carbonate t -
• photopolymerization initiators include acetophenone, methoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone.
• the coating composition may contain a polydimethylsiloxane compound.
• a polydimethylsiloxane compound By using a polydimethylsiloxane compound, not only can the smoothness and stain resistance of the coating film be further improved, but also the scratch resistance can be further improved while maintaining the self-healing property. Therefore, by using a polydimethylsiloxane compound, even if the thickness of the coating film obtained by coating is a thin film of less than 20 ⁇ m, it is possible to achieve both high self-healing property and scratch resistance. Become.
• the polydimethylsiloxane compound includes not only polydimethylsiloxane (dimethylpolysiloxane) but also modified polydimethylsiloxane.
• Modified polydimethylsiloxane includes, for example, a modified polydimethylsiloxane with a compound having at least one hydroxyl group. Such modifications have at least one hydroxyl group.
• polydimethylsiloxane compounds include dimethylpolysiloxane having an acrylic moiety-acrylic block copolymer, dimethylpolysiloxane having a polyether moiety-polyether block copolymer, and dimethylpolysiloxane having a polyester moiety-polyester block copolymer.
• polymers, and dimethylpolysiloxane-polyether-polyester block copolymers having a polyether portion and a polyester portion. Any of the above copolymers may have at least one hydroxyl group in its structure (in the acrylic portion, polyether portion or polyester portion).
• the additive Since the polydimethylsiloxane compound has at least one hydroxyl group in its structure, the additive reacts with the polyisocyanate, and after the coating film is formed, the additive hardly bleeds out, and the stain resistance is improved. is easily obtained, and excellent recoatability is easily obtained.
• polydimethylsiloxane compounds those having two or more hydroxyl groups and acrylic blocks are not considered to be acrylic polyols (B).
• dimethylpolysiloxane-acrylic block copolymer examples include BYK-SILCLEAN3700 (manufactured by BYK-Chemie Japan, number average molecular weight: 7600, silicon content (in terms of SiO 2 ): 1% by mass).
• dimethylpolysiloxane-polyether block copolymers examples include BYK-377 (number average molecular weight: 1400, silicon content: 18% by mass), BYK-SILCLEAN3720 (number average molecular weight: 1100, silicon content: 17 mass %), BYK-9200 (number average molecular weight: 4600, silicon content: 36% by mass), BYK-9201 (number average molecular weight: 4100, silicon content: 20% by mass), BYK-9204 (number average molecular weight: 5700 , Silicon content: 26% by mass), BYK-9205 (number average molecular weight: 4800, silicon content: 37% by mass), BYK-9206 (number average molecular weight: 5400, silicon content: 34% by mass), BYK- 9210 (number average molecular weight: 4200, silicon content: 14% by mass), BYK-9211 (number average molecular weight: 4900, silicon content: 37% by mass), BYK-
• dimethylpolysiloxane-polyester block copolymer examples include BYK-370 (manufactured by BYK-Chemie Japan, number average molecular weight: 2100, silicon content: 8% by mass).
• dimethylpolysiloxane-polyether-polyester block copolymer examples include BYK-375 (manufactured by BYK-Chemie Japan, number average molecular weight: 2200, silicon content: 15% by mass).
• the number average molecular weight of the polydimethylsiloxane compound may be 1000-15000, 1500-12000 or 2000-8000.
• the polydimethylsiloxane compound has a number average molecular weight of 1,000 or more, the self-healing property of the coating film is further improved.
• the number average molecular weight of the polydimethylsiloxane compound is 15,000 or less, the smoothness of the coating film is further improved, and the appearance of the coating film is further improved.
• the silicon content of the polydimethylsiloxane compound is 0.1% by mass based on the total mass of the polydimethylsiloxane compound, from the viewpoint of further improving the smoothness, slip properties, stain resistance, and scratch resistance of the coating film. or more, and may be 0.5% by mass or more, or 1.0% by mass or more.
• the silicon content of the polydimethylsiloxane compound may be 50% by mass or less based on the total mass of the polydimethylsiloxane compound, from the viewpoint of further suppressing the occurrence of repelling and further suppressing the deterioration of recoatability. % by mass or less, 40% by mass or less, 15% by mass or less, 10% by mass or less, or 5.0% by mass or less.
• the silicon content of the polydimethylsiloxane compound is 0.1 to 50% by mass, 0.1 to 15% by mass, 0.5 to 45% by mass, 0, based on the total mass of the polydimethylsiloxane compound. .5 to 10% by weight, 1.0 to 40% by weight or 1.0 to 5.0% by weight.
• the above silicon content is a value converted to SiO 2 and is a value measured by a thermogravimetric-differential thermal analysis (TG-DTA) method.
• the polydimethylsiloxane compound may be used singly or in combination of two or more.
• the amount of the polydimethylsiloxane compound added is such that the silicon content in terms of SiO 2 in the coating composition (based on the total amount of the organic polyisocyanate (A), the acrylic polyol (B) and the polydimethylsiloxane compound) is within the range described later. You can adjust the amount.
• the polydimethylsiloxane compound may be added when mixing the acrylic polyol (B) and the organic polyisocyanate (A).
• the organic polyisocyanate (A), the acrylic polyol (B), and the polydimethylsiloxane compound may be mixed and stirred when forming the coating film.
• the polydimethylsiloxane compound may be incorporated into the organic polyisocyanate (A) by reacting it with the organic polyisocyanate in advance.
• the organic polyisocyanate (A) (for example, the modified polyisocyanate (a)) may be an organic polyisocyanate modified with a polydimethylsiloxane compound.
• the reaction solution obtained by the reaction of the polydimethylsiloxane compound and the organic polyisocyanate may be mixed and stirred with the acrylic polyol (B) when forming the coating film.
• Paint additives include, for example, not only those that impart leveling properties and stain resistance to paint films, but also those for further improving scratch resistance while maintaining self-healing properties.
• the coating additive makes it easier to achieve both self-repairability and scratch resistance in practical use even when the coating film is thin.
• additives include antioxidants such as 2,6-di-tert-butyl-4-methylphenol, ultraviolet absorbers, pigments, dyes, solvents, flame retardants, hydrolysis inhibitors, lubricants, and plasticizers. , fillers, antistatic agents, dispersants, catalysts, storage stabilizers, thickeners and the like.
• a known urethanization catalyst can be used as the catalyst.
• organometallic compounds such as dibutyltin diacetate, dibutyltin dilaurate, and dioctyltin dilaurate, and organic amines such as triethylenediamine, triethylamine, diazabicycloundecene, and diazabicyclononene, and salts thereof.
• organometallic compounds such as dibutyltin diacetate, dibutyltin dilaurate, and dioctyltin dilaurate
• organic amines such as triethylenediamine, triethylamine, diazabicycloundecene, and diazabicyclononene, and salts thereof.
• Ratio R (M NCO /M OH ) further suppresses excessive hydroxyl groups, further improves water resistance and moist heat resistance, and further suppresses a decrease in crosslink density, and improves durability (stain resistance, etc.) and coating film properties.
• the mechanical strength it may be 0.8 or more, 0.9 or more, or 1.0 or more.
• the ratio R is selected from the viewpoints of 1. It may be 3 or less, and may be 1.2 or less or 1.1 or less.
• the ratio R may be 0.8 to 1.3, 0.9 to 1.2 or 1.0 to 1.1 from the above viewpoint.
• the ratio of the number of moles of the isocyanate groups in the organic polyisocyanate (A) to the sum of the number of moles of the hydroxyl groups in the acrylic polyol (B) and the hydroxyl groups in the polydimethylsiloxane compound is 0.8. ⁇ 1.3.
• the silicon content in terms of SiO 2 in the coating composition is 0.001 to 0.1% by mass based on the total amount of the organic polyisocyanate (A), the acrylic polyol (B) and the polydimethylsiloxane compound. is preferred.
• the silicon content is 0.001% by mass or more, the smoothness, slip properties, stain resistance, and scratch resistance of the obtained coating film are further improved.
• the silicon content is 0.1% by mass or less, it is possible to further suppress the occurrence of cissing and further suppress the deterioration of recoating properties.
• the silicon content may be 0.002% by mass or more, 0.005% by mass or more, or 0.01% by mass or more, and 0.09% by mass or less, or 0.05% by mass. % or less.
• the "total amount of the organic polyisocyanate (A), the acrylic polyol (B) and the polydimethylsiloxane compound” can be rephrased as "the total resin solid content”.
• the coating composition comprises, for example, the organic polyisocyanate (A), the acrylic polyol (B), and optionally the polydimethylsiloxane compound and/or the additive, and the ratio R and the silicon content are in the above ranges. It can be prepared by mixing so that
• the coating composition according to one aspect of the present disclosure it is possible to obtain a coating film that has both high self-repairability and stain resistance.
• the coating composition according to one aspect of the present disclosure is a surface coating film of automobile exterior materials that require fine workability, high designability, and weight reduction of exterior parts, and plastic molded products. It can be suitably used for forming applications.
• the coating composition contains the organic polyisocyanate (A) and at least It may contain a reaction product with a polydimethylsiloxane compound having one hydroxyl group.
• a kit according to an aspect of the present disclosure is a kit for preparing the coating composition described above (a coating composition preparation kit), for example, the first agent containing the organic polyisocyanate (A), the acrylic and a second agent containing a polyol (B).
• the organic polyisocyanate (A) contained in the first agent includes a modified polyisocyanate (for example, polyisocyanate component (a1) and the reaction product of the polyol component (a2) or its modified product, and the reaction product of the polydimethylsiloxane compound).
• the paint composition preparation kit may further comprise agents other than the first agent and the second agent.
• Other agents may include, for example, the polydimethylsiloxane compounds described above.
• the first agent and the second agent may be prepared by mixing them so that the above coating composition is obtained, and the first agent, the second agent, and the first agent and the second agent It may be prepared to obtain the coating composition by mixing other agents.
• the polydimethylsiloxane compound when preparing a coating composition containing the above polydimethylsiloxane compound, the polydimethylsiloxane compound may be blended in the first agent and / or the second agent, and the polydimethylsiloxane compound is added to the other agent. may be blended.
• the above-described additives that can be contained in the coating composition may be contained in any of the first agent, the second agent and other agents.
• the first agent, the second agent, and optionally other agents may be mixed so that the ratio R falls within the range described above.
• a coating film according to an aspect of the present disclosure is a self-repairing coating film and includes a cured product of the coating composition described above.
• the coating film can exhibit self-repairing properties within 1 hour at room temperature (eg, 5 to 35° C.) or by heating at 40 to 60° C., for example.
• the coating film can exhibit good smoothness under high humidity conditions and good stain resistance.
• the present inventors presume that the smoothness is improved by improving the drying property and moisture resistance, and the staining resistance is improved by improving the crosslink density.
• the cured product of the coating composition contains a polyurethane resin having a urethane structure produced by the urethanization reaction between the organic polyisocyanate (A) and the acrylic polyol (B).
• the urethane structure contained in the polyurethane resin includes, in addition to the urethane group (--CONH--), the reaction residue of the organic polyisocyanate (A) and the reaction residue of the acrylic polyol (B), and optionally polydimethylsiloxane. Contains reactive residues of compounds (polydimethylsiloxane compounds with at least one hydroxyl group).
• the thickness of the coating film is, for example, 5 to 40 ⁇ m.
• the coating may be a thin film with a thickness of less than 20 ⁇ m.
• the thickness of the coating film is less than 20 ⁇ m (for example 5 ⁇ m), the smoothness, stain resistance and adhesion are good, and the self-healing property against scratches is excellent.
• a coating film is usually formed on an adherend. That is, one aspect of the present disclosure includes an adherend and a coating film formed on the adherend. The adherend will be described later.
• a method of forming a coating film according to one aspect of the present disclosure includes applying the coating composition described above onto an adherend and curing the coating composition. The details of the adherend are as described above.
• adherends include stainless steel, phosphate-treated steel, zinc steel, iron, copper, aluminum, brass, glass, acrylic polyol, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene phthalate resin, polystyrene resin.
• the surface-treated material may be a molded article (surface-treated molded article) of olefin resin such as polyethylene or polypropylene that has been subjected to surface treatment such as corona discharge treatment.
• the adherend may have another coating film on its surface that can serve as an intermediate layer.
• the coating composition may be applied directly onto the surface of the above-described molded body, or may be applied over another coating film that has been base-coated on the surface of the above-described molded body.
• the other coating film may be a single layer or multiple layers.
• the coating composition may be applied by a method such as spraying, brushing, or immersion. According to the coating composition according to one aspect of the present disclosure, a coating film having excellent smoothness and self-repairing properties can be obtained even by spray coating, which is easily affected by humidity.
• the coating composition may be cured, for example, by heating. Heating for curing may be heating for drying. That is, when the coating composition contains a solvent, the coating composition may be cured at the same time as (in parallel with) drying to remove the solvent.
• the heating temperature may be, for example, 60-150°C.
• the heating time may be, for example, 1 to 10 hours.
• the NCO content disclosed in this example is a value measured according to the method described in JISK1603-1 (Polyurethane raw material aromatic isocyanate test method).
• the viscosity disclosed in the examples is a value obtained by measuring the viscosity at 25° C. with a No. 4 rotor using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd., model "DVL-BII").
• the free HDI content disclosed in this example is a value calculated from the peak area ratio of hexamethylene diisocyanate in the polyisocyanate composition by performing GPC (HLC-8120 manufactured by Tosoh) measurement.
• the silicon content disclosed in this example is determined by the thermogravimetric-differential thermal analysis (TG-DTA) method by determining the mass residual rate after holding at 500 ° C. for 30 minutes in a nitrogen atmosphere, and the mass residual rate is the silica residual rate. This is a value obtained by calculating the SiO 2 equivalent value as a value equivalent to .
• TG-DTA thermogravimetric-differential thermal analysis
• Synthesis example 1 890 g of hexamethylene diisocyanate (manufactured by Tosoh Corporation, NCO content: 49.9% by mass, hereinafter referred to as "HDI") is placed in a 1 L four-necked flask equipped with a stirrer, thermometer, condenser and dropping funnel. , and 110 g of PTMG-250 (manufactured by BASF, polytetramethylene glycol, trade name: Poly THF250, number average molecular weight 250) were charged, and the urethanization reaction was carried out at 80° C. for 2 hours under a nitrogen stream.
• PTMG-250 manufactured by BASF, polytetramethylene glycol, trade name: Poly THF250, number average molecular weight 250
• zirconium octylate (trade name: zirconyl octylate, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., hereinafter referred to as "OctZr") was added, and an allophanatization reaction was carried out at 110°C for 2 hours.
• NCO content reached 37.0% by mass
• JP-508 (trade name, manufactured by Johoku Kagaku Kogyo Co., Ltd., acid phosphate ester) was added to terminate the reaction, and the reaction solution was cooled to room temperature. cooled. This reaction liquid was subjected to thin film distillation at 130° C. and 0.04 kPa to remove unreacted HDI to obtain polyisocyanate P1.
• Polyisocyanate P1 has an NCO content of 16.2% by mass, a transparent liquid in appearance, a number average molecular weight of 1,400, and an average functional group number of 5 calculated from the NCO content and the number average molecular weight. .4, a viscosity at 25° C. of 2,000 mPa ⁇ s and a free HDI content of 0.2% by weight. It was confirmed by proton nuclear magnetic resonance ( 1 H-NMR) spectrum that polyisocyanate P1 mainly contained allophanate-modified polyisocyanate and slightly contained isocyanurate-modified polyisocyanate. Also, the content of the isocyanurate-modified polyisocyanate was 2 mol % based on the total amount of allophanate-modified polyisocyanate and isocyanurate-modified polyisocyanate.
• Polyisocyanate P2 has an NCO content of 15.9% by mass, a transparent liquid in appearance, a number average molecular weight of 1,350, and an average functional group number of 5 calculated from the NCO content and the number average molecular weight. .1, a viscosity at 25° C. of 4,000 mPa ⁇ s and a free HDI content of 0.2% by weight. It was confirmed by proton nuclear magnetic resonance ( 1 H-NMR) spectrum that polyisocyanate P2 mainly contained allophanate-modified polyisocyanate and slightly contained isocyanurate-modified polyisocyanate. Also, the content of the isocyanurate-modified polyisocyanate was 2 mol % based on the total amount of allophanate-modified polyisocyanate and isocyanurate-modified polyisocyanate.
• Polyisocyanate P3 has an NCO content of 13.2% by mass, a number average molecular weight of 1,450, an average functional group number of 4.6 calculated from the NCO content and the number average molecular weight, and a temperature of 25°C. It had a viscosity of 6,000 mPa ⁇ s and a free HDI content of 0.2% by mass. It was confirmed by proton nuclear magnetic resonance ( 1 H-NMR) spectrum that polyisocyanate P3 mainly contained allophanate-modified polyisocyanate and slightly contained isocyanurate-modified polyisocyanate. The content of the isocyanurate-modified polyisocyanate was 3 mol % based on the total amount of allophanate-modified polyisocyanate and isocyanurate-modified polyisocyanate.
• Examples 1 to 10 and Comparative Examples 1 to 5 [Preparation of coating composition]
• the materials shown in Tables 2 and 3 were mixed in the amounts (unit: g) shown in Tables 2 and 3 to prepare coating compositions 1 to 15 of Examples 1 to 10 and Comparative Examples 1 to 5, respectively.
• the ratio R in Tables 2 and 3 is the number of moles of hydroxyl groups in the hydroxyl-containing compound contained in the coating composition (the sum of the number of moles of hydroxyl groups in the acrylic polyol and the number of moles of hydroxyl groups in the polydimethylsiloxane compound) [M OH ], the ratio [M NCO /M OH ] of the number of moles of isocyanate groups in the isocyanate group-containing compound contained in the coating composition (the number of moles of isocyanate groups in the organic polyisocyanate) [M NCO ]. .
• Si content in Tables 2 and 3 is the silicon content in terms of SiO 2 in the coating composition measured by the method described above (based on the total amount of organic polyisocyanate, acrylic polyol and polydimethylsiloxane compound). is shown.
• Stain resistance was evaluated according to the following evaluation criteria. If the evaluation was A, it was determined that the stain resistance was good. [Evaluation criteria] ⁇ A: Color difference is less than 1 ⁇ B: Color difference is 1 or more and less than 2 ⁇ C: Color difference is 2 or more

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