WO2025088891A1 - ポリウレタン樹脂形成性組成物、塗装剤セット、塗膜及び塗膜の形成方法 - Google Patents

ポリウレタン樹脂形成性組成物、塗装剤セット、塗膜及び塗膜の形成方法 Download PDF

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WO2025088891A1
WO2025088891A1 PCT/JP2024/030312 JP2024030312W WO2025088891A1 WO 2025088891 A1 WO2025088891 A1 WO 2025088891A1 JP 2024030312 W JP2024030312 W JP 2024030312W WO 2025088891 A1 WO2025088891 A1 WO 2025088891A1
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component
mass
polyurethane resin
group
forming composition
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English (en)
French (fr)
Japanese (ja)
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啓太 久米
慎太郎 南原
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Tosoh Corp
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Tosoh Corp
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Priority to JP2025531784A priority Critical patent/JP7754378B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • This disclosure relates to a polyurethane resin-forming composition, a coating agent set, a coating film, and a method for forming a coating film.
  • a polyurethane resin-forming composition containing polyol and polyisocyanate is used as the coating agent.
  • in-mold coating is a method in which a coating agent is injected into a mold such as a metal die while the substrate is placed inside the mold, and the coating agent is reacted to form a coating film on the surface of the substrate.
  • the mold used to mold the substrate can be used as the mold for the coating, so that the substrate surface can be coated with fewer steps compared to conventional coating methods, and the amount of waste generated and energy consumption associated with coating can be reduced.
  • the polyurethane resin-forming composition used in the coating agent for in-mold painting is used, for example, in painting plastic molded products used in the interior and exterior parts of automobiles.
  • the coating film there is a demand for the coating film to have excellent weather resistance, that is, to have little deterioration in the surface gloss and little yellowing due to the influence of the usage environment such as light, temperature, and humidity.
  • one aspect of the present disclosure aims to provide a polyurethane resin-forming composition that can be used as a coating agent for in-mold coating and that forms a coating film with excellent weather resistance when applied inside the mold.
  • A a polyol
  • B a polyisocyanate
  • C an ultraviolet absorber
  • D a hindered amine light stabilizer
  • the component (A) contains a polycarbonate polyol
  • the component (C) contains at least one of a triazine-based ultraviolet absorber and an oxalic acid anilide-based ultraviolet absorber,
  • a polyurethane resin-forming composition having a volatile organic compound content of 0 to 5 mass %.
  • a coating film comprising a reaction product of the composition according to any one of [1] to [10].
  • a polyurethane resin-forming composition that can be used as a coating agent for in-mold coating and that forms a coating film with excellent weather resistance when applied inside a mold.
  • FIG. 2 is a schematic diagram for explaining one embodiment of the in-mold coating method of the present disclosure.
  • the numerical range indicated by “ ⁇ ” indicates a range including the numerical values before and after “ ⁇ ” as the minimum and maximum values, respectively.
  • the units of the numerical values before and after “ ⁇ ” are the same.
  • the upper limit or lower limit of a certain numerical range may be replaced with the upper limit or lower limit of the numerical range of another stage.
  • the upper limit or lower limit of the numerical range may be replaced with a value shown in the examples.
  • the upper limit and lower limit values described individually can be arbitrarily combined.
  • the materials exemplified below may be used alone or in combination of two or more types. When multiple substances corresponding to each component are present in the composition, the content of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified.
  • composition a polyurethane resin-forming composition (hereinafter, also referred to as “composition”) that contains (A) polyol (hereinafter, also referred to as “component (A)”), (B) polyisocyanate (hereinafter, also referred to as “component (B)”), (C) ultraviolet absorber (hereinafter, also referred to as “component (C)”), and (D) hindered amine-based light stabilizer (hereinafter, also referred to as “component (D)”), in which component (A) contains a polycarbonate polyol, component (C) contains at least one of a triazine-based ultraviolet absorber and an oxalic acid anilide-based ultraviolet absorber, and the content of volatile organic compounds (based on the total mass of the composition) is 0 to 5 mass%.
  • component (A) contains a polycarbonate polyol
  • component (C) contains at least one of a triazine-based ultraviolet absorber and an oxa
  • polyurethane resin-forming property means having a property that can form a polyurethane resin.
  • the above composition contains component (A) and component (B), and a polyurethane resin can be formed by the reaction of component (A) and component (B).
  • volatile organic compound refers to an organic compound having a boiling point of 180° C. or lower at 1 atm.
  • the above composition allows the formation of a coating film with excellent weather resistance by in-mold coating.
  • the coating film formed by the above composition is less susceptible to deterioration of surface gloss and yellowing due to the influence of the usage environment such as light, temperature, and humidity. Therefore, even when used to paint parts that require weather resistance (for example, plastic molded products used for automobile interior parts, exterior parts, etc.), good surface gloss and low b* can be maintained. Therefore, the above composition is suitable for use as a coating agent for in-mold coating (in-mold coating agent), and is particularly suitable for use as a coating agent for plastic molded products used for automobile interior parts, exterior parts, etc.
  • the above composition allows the additives (components (C) and (D)) to be easily dissolved in component (A), and can be prepared at relatively low temperatures (e.g., less than 100°C).
  • the above composition is unlikely to precipitate under general storage temperatures (e.g., 0 to 50°C) and has excellent low-temperature stability. Therefore, the above composition tends to reduce energy consumption during preparation and storage.
  • the above composition makes it possible to easily develop the self-repairing properties of the coating film.
  • the coating film formed by the above composition also tends to have excellent self-repairing properties.
  • the self-repairing properties of the coating film are not necessarily required, the coating film may have self-repairing properties in applications for plastic molded products used in interior and exterior parts of automobiles. The self-repairing properties may be impaired due to the influence of the usage environment such as light, temperature, and humidity, but it is possible to suppress the deterioration of the self-repairing properties by adjusting the content of component (C), etc.
  • a polyol is a compound having a plurality of hydroxyl groups (—OH).
  • component (A) one type of polyol may be used alone, or two or more types of polyols may be used in combination.
  • Component (A) may be liquid at 25°C in order to provide better film-forming properties during in-mold coating.
  • liquid at 25°C means that when heated to 80°C or higher, allowed to stand at 25°C for 24 hours, and then tilted, even a slight degree of fluidity can be confirmed by visual observation.
  • the (A) component contains a polycarbonate polyol.
  • a polycarbonate polyol is a compound having multiple hydroxyl groups (-OH) and multiple carbonate groups (-OCOO-).
  • a polycarbonate polyol is, for example, a reaction product of a polyol component (hereinafter also referred to as "component (a1)”) and a carbonate component (hereinafter also referred to as “component (a2)”), and contains the (a1) component and the (a2) component as monomer units.
  • the polycarbonate polyol may be a non-aromatic polycarbonate polyol from the viewpoint of obtaining better transparency.
  • non-aromatic polycarbonate polyol means a polycarbonate polyol that does not have an aromatic ring (e.g., a benzene ring).
  • the (a1) component may contain glycol.
  • Glycol is a compound having a structure in which one hydroxyl group is substituted for every two carbon atoms of a chain aliphatic hydrocarbon or a cyclic aliphatic hydrocarbon.
  • glycols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexanediol, 1,7-hexanediol, 1,8-hexanediol, 1,
  • the polycarbonate polyol is more likely to become liquid at 25°C, and when three or more (a1) components are used in combination, the more likely it is to become liquid at 25°C.
  • the ratio (mass ratio) of the linear single component the more likely the polycarbonate polyol is to become liquid at 25°C.
  • the closer the ratio (mass ratio) of the two glycols is to 1:1 the more likely the polycarbonate polyol is to become liquid at 25°C.
  • polycarbonate polyol When two or more (a1) components are used in combination, the more likely the polycarbonate polyol is to become liquid at 25°C when it contains an (a1) component with a short carbon chain (for example, an (a1) component with 6 or less carbon atoms) and/or a branched (a1) component.
  • component (a1) contains at least one selected from the group consisting of 1,3-butanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol, and a linear glycol having 3 to 6 carbon atoms
  • the polycarbonate polyol tends to become liquid at 25°C.
  • component (a1) contains at least two types of linear glycols having 3 to 6 carbon atoms (i.e., when the polycarbonate polyol contains at least two types of linear glycols having 3 to 6 carbon atoms as monomer units), the polycarbonate polyol tends to become liquid at 25°C.
  • Component (a1) may contain a polyol having three or more hydroxyl groups, from the viewpoint of further improving the mechanical properties of the coating film and forming a harder coating film.
  • the polyol having three or more hydroxyl groups may be used in combination with at least one selected from the group consisting of 1,3-butanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol, and/or a linear glycol having 3 to 6 carbon atoms.
  • the polyol having three or more hydroxyl groups is, for example, a non-aromatic polyol that does not have an aromatic ring.
  • polyols having three or more hydroxyl groups include trimethylolethane, trimethylolpropane, 2-hydroxy-2-methyl-1,4-butanediol, glycerin, ditrimethylolethane, ditrimethylolpropane, diglycerin, pentaerythritol, xylitol, dipentaerythritol, sorbitol, and 1,3,5-tris(hydroxymethyl)benzene.
  • the content of the polyol having three or more hydroxyl groups in the (a1) component is 0% by mass or more, and from the viewpoint of further improving the mechanical properties of the coating film, it may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, and from the viewpoint of compatibility of the composition and further improving the self-repairing property of the coating film, it may be 45% by mass or less, 35% by mass or less, or 30% by mass or less. From these viewpoints, the content of the polyol having three or more hydroxyl groups may be 0-45% by mass, 5-45% by mass, 10-35% by mass, or 15-30% by mass. The above content is based on the total mass of the (a1) component.
  • the (a2) component may be any compound capable of condensing with a polyol to produce a polycarbonate polyol.
  • Examples of the (a2) component include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and dipropyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, and diaryl carbonates such as diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate, and bistetrahydronaphthyl carbonate. These may be used alone or in combination of two or more.
  • the polycarbonate polyol may be a reaction product obtained by reacting the reaction product of the (a1) component and the (a2) component, or the (a1) component and the (a2) component, with another reaction component (e.g., a polyester polyol) in the presence of a catalyst, for example.
  • a polyester polyol e.g., a polyester polyol
  • the polycarbonate polyol can be called a polyester polycarbonate polyol.
  • the polyester polycarbonate polyol contains the above-mentioned (a1) component and the above-mentioned (a2) component as monomer units, and contains an ester skeleton derived from the polyester polyol.
  • Other reactive components include, for example, cyclic esters such as ⁇ -caprolactone, polycaprolactone oligomers, etc. These may be used alone or in combination of two or more.
  • the amount of the other reactive components may be, for example, 0 to 40 parts by mass, 5 to 35 parts by mass, or 10 to 30 parts by mass per 100 parts by mass of polycarbonate polyol.
  • the hydroxyl value of the polycarbonate polyol may be, for example, 100 to 400 mgKOH/g.
  • the hydroxyl value of the polycarbonate polyol may be 150 mgKOH/g or more or 200 mgKOH/g or more from the viewpoint of further improving the low-temperature processability of the composition, increasing the compatibility of the composition, and further improving the coating film formability.
  • the hydroxyl value of the polycarbonate polyol may be 380 mgKOH/g or less or 350 mgKOH/g or less from the viewpoint of forming a coating film having better mechanical properties. From these viewpoints, the hydroxyl value of the polycarbonate polyol may be 150 to 380 mgKOH/g or 200 to 350 mgKOH/g.
  • the hydroxyl value means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl groups in 1 g of sample, and is measured in accordance with JIS K1557-1.
  • the molecular weight of the polycarbonate polyol may be, for example, 200 or more. From the viewpoint of easily obtaining a coating film having better mechanical properties, the molecular weight of the polycarbonate polyol may be 300 or more, 400 or more, or 450 or more. From the viewpoint of further improving the low-temperature processability of the composition, increasing the compatibility of the composition, and further improving the coating film formability, the molecular weight of the polycarbonate polyol may be 1100 or less, 1000 or less, or 800 or less. From these viewpoints, the molecular weight of the polycarbonate polyol may be 200 to 1100, 300 to 1000, or 400 to 800.
  • the polycarbonate polyol can be obtained, for example, by reacting the (a1) component with the (a2) component in the presence of a catalyst such as tetrabutoxytitanium.
  • the reaction may be carried out, for example, in a reaction apparatus equipped with a stirrer, a thermometer, a heating device, and a distillation column under a nitrogen stream. Specifically, for example, the temperature is gradually increased to 190°C under a nitrogen stream while distilling off ethanol, and the pressure is gradually reduced to 0.5 kPa or less, and the reaction is carried out at a pressure of 0.5 kPa or less for 4 hours or more, thereby obtaining a polycarbonate polyol as a reaction product of the (a1) component with the (a2) component.
  • the mixing ratio of each component may be appropriately adjusted, for example, from the viewpoint of the hydroxyl value.
  • the (A) component may consist of polycarbonate polyol only, or may contain, in addition to polycarbonate polyol, a polyol other than polycarbonate polyol. From the viewpoint of obtaining better weather resistance and from the viewpoint of making it more difficult for additives to precipitate at low temperatures (improved low-temperature stability), the content of polycarbonate polyol may be 30 mass% or more, 50 mass% or more, or 60 mass% or more based on the total mass of the (A) component. From the viewpoint of obtaining better weather resistance, the content of polycarbonate polyol in the (A) component may be 90 mass% or less, 85 mass% or less, or 80 mass% or less based on the total mass of the (A) component. From the above viewpoint, the content of polycarbonate polyol may be 30 to 90 mass%, 50 to 85 mass%, or 60 to 80 mass% based on the total mass of the (A) component.
  • a polyol other than polycarbonate polyol a polyol having a molecular weight of less than 200 (hereinafter referred to as a "low molecular weight polyol”) may be used.
  • the molecular weight of the low molecular weight polyol may be, for example, 50 or more and less than 200, or may be 60 to 180 or 70 to 150.
  • the low molecular weight polyol may be a diol or a polyol having three or more hydroxyl groups.
  • a coating film having better self-repairing properties is easily obtained, and the effect of improving the compatibility of the composition and the effect of further enhancing the coating film formability due to the lower viscosity are obtained.
  • a coating film having better mechanical properties is easily obtained.
  • the low molecular weight polyol may contain a diol and/or a triol, and from the viewpoint of achieving a higher degree of compatibility between the self-repairing properties and the mechanical properties of the coating film, it may contain a diol and a triol.
  • diols examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer diol, etc.
  • 1,3-butanediol and 2-methyl-1,3-propanediol may be used from the viewpoints of obtaining a coating film having superior self-repairing properties, improving the compatibility of the composition, and improving the coating film formability by reducing the viscosity.
  • the above diols can be used alone or in combination of two or more.
  • the diol content may be 5 to 55 mass %, 10 to 50 mass %, or 15 to 40 mass % based on the total mass of component (A), from the viewpoint of obtaining a coating film with better self-repairing properties, improving the compatibility of the composition, and further enhancing the coating film formability by reducing the viscosity.
  • triols examples include trimethylolethane, trimethylolpropane, 2-hydroxy-2-methyl-1,4-butanediol, glycerin, ditrimethylolethane, ditrimethylolpropane, diglycerin, and pentaerythritol.
  • Trimethylolpropane may be used from the viewpoint of forming a harder coating film and of obtaining a coating film having better mechanical properties.
  • the above triols may be used alone or in combination of two or more kinds.
  • the triol content may be 1 to 30 mass%, 3 to 20 mass%, or 5 to 10 mass% based on the total mass of component (A) from the viewpoint of making it easier to form a harder coating film and easier to obtain a coating film with better mechanical properties.
  • the triol content may be 0 to 30 mass% based on the total mass of component (A).
  • the content of the low molecular weight polyol may be 10 to 70 mass %, 15 to 50 mass %, or 20 to 40 mass %, based on the total mass of component (A), from the viewpoint of suppressing a decrease in self-repairing property and a decrease in curing property.
  • the average hydroxyl value of component (A) may be 300 mgKOH/g or more, 400 mgKOH/g or more, or 500 mgKOH/g or more.
  • the average hydroxyl value of component (A) may be 800 mgKOH/g or less, 700 mgKOH/g or more, or 600 mgKOH/g or more. From these viewpoints, the average hydroxyl value of component (A) may be 300 to 800 mgKOH/g, 400 to 700 mgKOH/g, or 500 to 600 mgKOH/g.
  • the average hydroxyl value of component (A) is the weighted average of the hydrogen values weighted by the mass of the various polyols contained in component (A), and is calculated by multiplying the hydroxyl values of the various polyols by their respective masses to obtain the sum, and then dividing the sum by the mass of component (A) (the sum of the masses of the various polyols).
  • the average number of hydroxyl groups in component (A) may be 2.0 to 3.0, or may be 2.0 to 2.5, or 2.0 to 2.3, from the viewpoint of obtaining better weather resistance.
  • the average number of hydroxyl groups in component (A) is a weighted average value of the numbers of hydroxyl groups weighted by the amounts of substance of the various polyols contained in component (A), and is found by multiplying the numbers of hydroxyl groups in the various polyols by their respective amounts of substance to obtain the sum, and dividing the sum by the amount of substance of component (A) (the sum of the amounts of substance of the various polyols).
  • the content of component (A) may be, for example, 10 to 80 mass%, 20 to 70 mass%, or 30 to 60 mass% based on the total mass of the composition.
  • Component (B): Polyisocyanate is a compound having a plurality of isocyanate groups (-NCO).
  • component (B) one type of polyisocyanate may be used alone, or two or more types of polyisocyanates may be used in combination.
  • Component (B) may be liquid at 25°C in order to provide better film-forming properties during in-mold coating.
  • Component (B) may contain a non-aromatic polyisocyanate in order to further improve the weather resistance (particularly resistance to yellowing) of the coating film.
  • non-aromatic polyisocyanate means a polyisocyanate that does not have an aromatic ring (e.g., a benzene ring).
  • Non-aromatic polyisocyanates include, for example, aliphatic polyisocyanates, alicyclic polyisocyanates, and modified products thereof.
  • Modified products include, for example, isocyanurate modified products, allophanate modified products, biuret modified products, urethane modified products, urea modified products, carbodiimide modified products, uretonimine modified products, and uretdione modified products.
  • Aliphatic polyisocyanates include, for example, hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexa
  • Examples of such compounds include methylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diis
  • alicyclic polyisocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanate methyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanate-n-butylidene)pentaerythritol, and hydrogenated dimer acid diisocyanate.
  • component (B) contains at least one selected from the group consisting of an isocyanurate of an aliphatic diisocyanate and an allophanate of an aliphatic diisocyanate
  • the balance between the film formability during in-mold coating e.g., film formability during in-mold coating at low temperatures
  • the curing properties e.g., fast curing at low temperatures
  • component (B) contains an isocyanurate-modified aliphatic diisocyanate
  • the curing properties e.g., fast curing at low temperatures
  • component (B) contains an allophanate-modified aliphatic diisocyanate
  • the film formability during in-mold coating e.g., film formability during in-mold coating at low temperatures
  • the above-mentioned isocyanurate-modified product and the above-mentioned allophanate-modified product may be used in combination.
  • the content of the isocyanurate modified substance in component (B) may be 10% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, or 90% by mass or more, and may be 100% by mass or less, 90% by mass or less, 70% by mass or less, 50% by mass or less, 30% by mass or less, or 10% by mass or less, or may be 0 to 100% by mass, 10 to 90% by mass, or 30 to 70% by mass. Note that the above content is based on the total mass of component (B).
  • the content of the allophanate modified substance in component (B) may be 10% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, or 90% by mass or more, and may be 100% by mass or less, 90% by mass or less, 70% by mass or less, 50% by mass or less, 30% by mass or less, or 10% by mass or less, or may be 0 to 100% by mass, 10 to 90% by mass, or 30 to 70% by mass. Note that the above content is based on the total mass of component (B).
  • the NCO content of component (B) may be 10 to 40% by mass, or may be 15 to 35% by mass, or 19 to 30% by mass. If the NCO content of component (B) is 10% by mass or more, the coating film tends to have higher hardness. If the NCO content of component (B) is 40% by mass or less, the coating film tends to exhibit good self-repairing properties. The above contents are based on the total mass of component (B).
  • the NCO content is a value measured according to the method described in JIS K1603-1 (Test method for aromatic isocyanates as polyurethane raw materials).
  • component (B) may be, for example, 20 to 90 mass%, 30 to 80 mass%, or 40 to 70 mass% based on the total mass of the composition.
  • the ultraviolet absorber is an additive having a function of absorbing ultraviolet rays.
  • the (C) component contains at least one of a triazine-based ultraviolet absorber and an oxalic acid anilide-based ultraviolet absorber.
  • the (C) component may contain only one of a triazine-based ultraviolet absorber and an oxalic acid anilide-based ultraviolet absorber, or may contain both a triazine-based ultraviolet absorber and an oxalic acid anilide-based ultraviolet absorber. From the viewpoint of superior solubility in the (A) component, the (C) component may contain a triazine-based ultraviolet absorber.
  • triazine-based ultraviolet absorber a wide variety of known triazine-based ultraviolet absorbers used in the field of resin materials can be used. From the viewpoint of obtaining superior solubility in the component (A) and superior weather resistance, a compound represented by the following formula (C-1) may be used.
  • R 1 represents a hydrocarbon group having 1 to 15 carbon atoms
  • R 2 to R 5 each independently represent a hydrogen atom, a hydroxyl group, a methyl group, or an ethyl group.
  • the hydrogen atom of the hydrocarbon group represented by R 1 may be substituted with a hydroxyl group, or with an alkoxy group having 1 to 15 carbon atoms.
  • R 2 to R 5 may be a hydrogen atom, a methyl group, or an ethyl group, or may be a methyl group.
  • the effect of improving solubility and weather resistance tends to increase in the order of hydrogen atom, ethyl group, and methyl group.
  • the hydrocarbon group represented by R1 may be, for example, an alkyl group.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tetradecyl group, and a pentadecyl group.
  • the hydrogen atoms of these alkyl groups may be substituted with hydroxyl groups or alkoxy groups having 1 to 15 carbon atoms.
  • alkoxy group having 1 to 15 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a t-butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, a tetradecyloxy group, and a pentadecyloxy group.
  • the triazine-based ultraviolet absorber may contain a compound represented by the following formula (C-2) from the viewpoint of improving solubility in the component (A) and making precipitation at low temperatures less likely to occur (improving low-temperature stability).
  • R 11 represents an alkyl group having 1 to 15 carbon atoms.
  • R 2 to R 5 in formula (C-2) have the same meaning as R 2 to R 5 in formula (C-1).
  • Examples of the alkyl group represented by R 11 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tetradecyl group, and a pentadecyl group.
  • the alkyl group represented by R 11 may be a methyl group from the viewpoint of further improving the solubility in the component (A) and the low temperature
  • triazine-based ultraviolet absorbers include 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (Tinuvin 405 manufactured by BASF), 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-(octyloxy)phenol, and 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 -bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine mixture (BASF's Tinuvin 400), 2-[4-[4,
  • the content of the triazine-based ultraviolet absorber may be 0.05 parts by mass or more per 100 parts by mass of the total content of the (A) and (B) components from the viewpoint of superior weather resistance (particularly yellowing resistance), and may be 5 parts by mass or less per 100 parts by mass of the total content of the (A) and (B) components from the viewpoint of superior mechanical properties. From these viewpoints, the content of the triazine-based ultraviolet absorber may be 0.05 to 5 parts by mass per 100 parts by mass of the total content of the (A) and (B) components.
  • the content of the triazine-based ultraviolet absorber may be 0.1 parts by mass or more, 0.2 parts by mass or more, 3 parts by mass or less, 1 part by mass or less, 0.1 to 3 parts by mass, or 0.1 to 1 part by mass, per 100 parts by mass of the total content of the (A) and (B) components.
  • oxalic acid anilide-based ultraviolet absorber As the oxalic acid anilide-based ultraviolet absorber, a wide variety of known oxalic acid anilide-based ultraviolet absorbers used in the field of resin materials can be used. From the viewpoint of obtaining superior solubility in the component (A) and superior weather resistance, a compound represented by the following formula (C-3) may be used.
  • R 6 represents an alkyl group having 1 to 15 carbon atoms
  • one of R 7 and R 8 represents a hydrogen atom
  • the other represents an alkyl group having 1 to 15 carbon atoms.
  • Examples of the alkyl group represented by R 6 to R 8 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tetradecyl group, and a pentadecyl group.
  • oxalic acid anilide UV absorbers include 2-ethoxy-2'-ethyl oxalic acid bisanilide (HOSTAVIN VSU, manufactured by Clariant Chemicals Co., Ltd.) and 2-ethoxy-3'-dodecyl oxalic acid bisanilide (HOSTAVIN 3206, manufactured by Clariant Chemicals Co., Ltd.).
  • the content of the anilide oxalate ultraviolet absorber may be 0.05 parts by mass or more per 100 parts by mass of the total content of the (A) and (B) components from the viewpoint of superior weather resistance (especially yellowing resistance), and may be 5 parts by mass or less per 100 parts by mass of the total content of the (A) and (B) components from the viewpoint of superior mechanical properties. From these viewpoints, the content of the anilide oxalate ultraviolet absorber may be 0.05 to 5 parts by mass per 100 parts by mass of the total content of the (A) and (B) components.
  • the content of the anilide oxalate ultraviolet absorber may be 0.1 parts by mass or more, 0.2 parts by mass or more, 3 parts by mass or less, 1 part by mass or less, 0.1 to 3 parts by mass, or 0.1 to 1 part by mass, per 100 parts by mass of the total content of the (A) and (B) components.
  • the (C) component may contain an ultraviolet absorber other than a triazine-based ultraviolet absorber and an oxalic acid anilide-based ultraviolet absorber, but from the viewpoint of obtaining better solubility in the (A) component and better weather resistance, the content of the ultraviolet absorber other than a triazine-based ultraviolet absorber and an oxalic acid anilide-based ultraviolet absorber in the (C) component may be 50% by mass or less, 1% by mass or less, or 0.1% by mass or less, based on the total mass of the (C) component.
  • the content of the (C) component may be 0.05 parts by mass or more per 100 parts by mass of the total content of the (A) and (B) components from the viewpoint of superior weather resistance (particularly yellowing resistance), and may be 5 parts by mass or less per 100 parts by mass of the total content of the (A) and (B) components from the viewpoint of superior mechanical properties. From these viewpoints, the content of the (C) component may be 0.05 to 5 parts by mass per 100 parts by mass of the total content of the (A) and (B) components.
  • the content of the (C) component may be 0.1 parts by mass or more or 0.2 parts by mass or more, 3 parts by mass or less, 1 part by mass or less, 0.1 to 3 parts by mass, or 0.2 to 1 part by mass, per 100 parts by mass of the total content of the (A) and (B) components.
  • the hindered amine light stabilizer is an additive having a function of enhancing the light stability of a resin by capturing radicals, which are a deterioration factor of the resin.
  • the hindered amine light stabilizer has, for example, a hindered amine structure represented by the following formula (D-1).
  • X represents a hydrogen atom, a hydrocarbon group, or other substituent, and * represents a bond.
  • the molecular weight of component (D) may be, for example, 400 to 4000. From the viewpoint of superior solubility in component (A), the molecular weight of component (D) may be less than 1000, 700 or less, or 500 or less, or may be 400 or more and less than 1000, 400 to 700, or 400 to 500.
  • the molecular weight of component (D) means the weight average molecular weight of the multiple compounds.
  • the base constant (pKb) of component (D) may be, for example, 4 to 12, and from the viewpoint of superior solubility in component (A), may be 4 to 9.
  • component (D) include a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate and methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate (Tinuvin 292 manufactured by BASF), 1,2,3,4-butanetetracarboxylic acid tetramethyl ester and 1,2,2,6,6-pentamethyl-4-piperidinol and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-2,4,8,10-tetraoxaspiro[5.5 ]Reaction products with undecane-3,9-diethanol (ADEKA STAB LA-63P manufactured by ADEKA CORPORATION), bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (BASF Tinuvin 770), 2,2,6,6-tetramethyl-1-[2-[(3,5,5-trimethyl-1-oxohexyl)oxy]ethyl]-4-piperid
  • the content of the (D) component may be 0.05 parts by mass or more, 0.1 parts by mass or more, or 0.2 parts by mass or more, per 100 parts by mass of the total content of the (A) component and the (B) component.
  • the content of the (D) component may be 5 parts by mass or less, 3 parts by mass or less, or 1 part by mass or less, per 100 parts by mass of the total content of the (A) component and the (B) component.
  • the content of the (D) component may be 0.05 to 5 parts by mass, 0.1 to 3 parts by mass, or 0.2 to 3 parts by mass, per 100 parts by mass of the total content of the (A) component and the (B) component.
  • the total content of the (C) component and the (D) component may be 0.5 parts by mass or more, 0.6 parts by mass or more, or 0.7 parts by mass or more, per 100 parts by mass of the total content of the (A) component and the (B) component.
  • the total content of the (C) component and the (D) component may be 5 parts by mass or less, 3 parts by mass or less, or 1.5 parts by mass or less, per 100 parts by mass of the total content of the (A) component and the (B) component.
  • the total content of the (C) component and the (D) component may be 0.5 to 5 parts by mass, 0.6 to 3 parts by mass, or 0.7 to 1.5 parts by mass, per 100 parts by mass of the total content of the (A) component and the (B) component.
  • volatile organic compounds examples include ketone compounds such as methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, and cyclohexanone; aromatic compounds such as toluene and xylene; glycol ether compounds such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and propylene glycol monomethyl ether acetate; ester compounds such as ethyl acetate, butyl acetate, methyl cellosolve acetate, and cellosolve acetate; Solvesso #100 and Solvesso #150 (all trade names, manufactured by Exxon Mobil Corporation).
  • ketone compounds such as methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, and cyclohexanone
  • aromatic compounds such as toluene and xylene
  • glycol ether compounds such as
  • the volatile organic compound may also be component (A) to component (D). That is, even if it is a compound corresponding to component (A) to component (D), an organic compound having a boiling point of 180° C. or less at 1 atm is a volatile organic compound.
  • the content of the volatile organic compounds is 0 to 5 mass % based on the total mass of the composition. By having the content of the volatile organic compounds in the above range, good in-mold paintability can be obtained.
  • the content of the volatile organic compounds may be 1 mass % or less, or 0.1 mass % or less.
  • the composition may further contain other components other than the above-mentioned components.
  • the other components include catalysts for forming urethane resins.
  • the catalyst include organic tin compounds such as dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin dioctoate, and tin 2-ethylhexanoate, iron compounds such as iron acetylacetonate and iron chloride, lithium compounds such as lithium acetylacetonate, lead compounds such as lead octoate, bismuth compounds such as bismuth octoate, zinc compounds such as zinc octoate, and tertiary amine catalysts such as triethylamine and triethylenediamine.
  • the content of the catalyst may be, for example, 0.001 to 5.000% by mass based on the total mass of the composition.
  • composition may further contain other components such as antioxidants such as 2,6-di-tert-butyl-4-methylphenol, ultraviolet absorbers, pigments, dyes, flame retardants, hydrolysis inhibitors, lubricants, plasticizers, fillers, antistatic agents, dispersants, storage stabilizers, thickeners, internal release agents, surface conditioners, defoamers, antibacterial agents, etc.
  • the composition may further contain, as other components, a hydroxyl group-containing compound (a compound having a hydroxyl group) other than component (A) and an isocyanate group-containing compound (a compound having an isocyanate group) other than component (B).
  • a hydroxyl group-containing compound a compound having a hydroxyl group
  • an isocyanate group-containing compound a compound having an isocyanate group
  • the composition may not contain a hydroxyl group-containing compound having an aromatic ring and an isocyanate group-containing compound having an aromatic ring.
  • the content of the hydroxyl group-containing compound having an aromatic ring may be 5% by mass or less, or may be 0% by mass, based on the total mass of the composition.
  • the content of the isocyanate group-containing compound having an aromatic ring may be 5% by mass or less, or may be 0% by mass, based on the total mass of the composition.
  • the ratio of the number of moles of isocyanate groups in the isocyanate group-containing compound contained in the composition to the number of moles of hydroxyl groups in the hydroxyl group-containing compound contained in the composition may be 0.8 or more, 0.9 or more, or 1.0 or more, from the viewpoint of suppressing an excess of hydroxyl groups and further improving the durability and mechanical properties of the coating film.
  • the NCO/OH equivalent may be 1.3 or less, 1.2 or less, or 1.1 or less, from the viewpoint of suppressing an excess of isocyanate groups and further improving the durability and mechanical properties of the coating film.
  • the NCO/OH equivalent may be 0.8 to 1.3, 0.9 to 1.2, or 1.0 to 1.1, from the above viewpoint.
  • the coating agent set is, for example, a coating agent set for in-mold coating.
  • the coating agent set includes a first agent containing the above-mentioned (A), (C) and (D) components, and a second agent containing the above-mentioned (B) component.
  • the coating agent set is composed of the first agent and the second agent, the composition of the above embodiment can be prepared by mixing the first agent and the second agent.
  • the first agent in the above coating agent set contains components (A), (C), and (D). Since the additive components (C) and (D) are easily soluble in component (A), the first agent can be prepared at a relatively low temperature (e.g., below 100°C). In addition, the first agent is unlikely to precipitate at typical storage temperatures (e.g., 0 to 50°C) and has excellent low-temperature stability.
  • the first and second agents may contain the above-mentioned component (E), and may also contain other components that may be contained in the composition.
  • component (E) a hydroxyl group-containing compound other than component (A) may be blended in the first agent, and an isocyanate group-containing compound other than component (B) may be blended in the second agent.
  • the coating agent set may further comprise other agents different from the first agent and the second agent.
  • the other agents may contain other components that may be contained in the above composition, and may contain the above component (E).
  • the composition of the above embodiment can be prepared by mixing the first agent, the second agent and the other agents.
  • the viscosity of the first agent at 25°C may be 1 to 15,000 mPa ⁇ s, or may be 5 to 1,000 mPa ⁇ s or 10 to 5,000 mPa ⁇ s. When the viscosity of the first agent at 25°C is within the above range, a composition (coating agent) with even better film-forming properties is more likely to be obtained.
  • the viscosity of the second agent at 25°C may be 1 to 15,000 mPa ⁇ s, or may be 5 to 1,000 mPa ⁇ s or 10 to 5,000 mPa ⁇ s.
  • the viscosity of the second agent at 25°C is in the above range, it is easy to obtain a composition (coating agent) with even better film-forming properties.
  • the viscosity at 25°C is a value measured using a B-type viscometer.
  • the first agent, the second agent, and any other agents that are used optionally may be mixed so that the NCO/OH equivalent falls within the range described above.
  • ⁇ Coating film> Another embodiment of the present disclosure relates to a coating film comprising a reaction product of the composition of the above embodiment.
  • the reaction product of the composition is a reaction product obtained by reacting the components (at least the (A) component and the (B) component) contained in the composition.
  • the coating film comprises a polyurethane resin produced by the reaction of at least the (A) component and the (B) component.
  • the coating film may also comprise a portion of the components contained in the composition (e.g., unreacted components).
  • the thickness of the coating is, for example, 1 to 10,000 ⁇ m, and may be 5 to 5,000 ⁇ m or 10 to 1,000 ⁇ m.
  • the coating film can be formed by forming a coating film made of the composition of the above embodiment and then reacting the composition. More specifically, it can be formed, for example, by the in-mold coating method described below. Since the reaction of the composition progresses the hardening of the coating film made of the composition, the coating film made of the above composition and the coating film of the above embodiment can also be called an uncured film and a cured film, respectively.
  • the coating film may be provided on a substrate such as a plastic molded product, and may form part of a component (e.g., an interior component of an automobile) that includes the substrate.
  • a component e.g., an interior component of an automobile
  • the present disclosure provides a component that includes a substrate and the coating film provided on the substrate.
  • Another embodiment of the present disclosure relates to an in-mold coating method, comprising: preparing a substrate and a mold in which the substrate is disposed; injecting the composition of the above embodiment into the mold, applying the composition to the surface of the substrate; and reacting the composition to form a coating film on the surface of the substrate. According to this method, the coating film of the above embodiment can be obtained.
  • the in-mold coating method of this embodiment will be described with reference to FIG. 1.
  • FIG. 1 is a schematic diagram for explaining one embodiment of the in-mold coating method.
  • a substrate 1 and a mold 2 with the substrate 1 placed inside are prepared (see FIG. 1(a)).
  • the substrate 1 is, for example, a molded body (plastic molded product) molded from a plastic material.
  • the plastic material include acrylic polyol resin, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene phthalate resin, polystyrene resin, AS resin, ABS resin, polycarbonate-ABS resin, 6-nylon resin, 6,6-nylon resin, MXD6 nylon resin, polyvinyl chloride resin, polyvinyl alcohol resin, polyurethane resin, phenol resin, melamine resin, polyacetal resin, chlorinated polyolefin resin, polyolefin resin, polyamide resin, polyether ether ketone resin, polyphenylene sulfide resin, NBR resin, chloroprene resin, SBR resin, SEBS resin, and combinations thereof.
  • the surface of the molded body may be subjected to a surface treatment such as a corona discharge treatment. Another coating film that can become an intermediate layer may be formed on the
  • the mold 2 has a gap 2a for forming a coating film between the inner wall of the mold 2 and the substrate 1, an opening 2b for injecting the coating agent, and a flow path 2c for supplying the coating agent from the opening 2b to the gap 2a.
  • the mold 2 may be the same mold as that used to mold the substrate 1, and may have an internal structure with the same shape as the desired shape of the substrate 1.
  • the clamping force may be reduced or the gap between the obtained molded product (substrate) and the inner wall of the mold may be opened slightly, providing a gap 2a for forming a coating film between the substrate 1 and the mold 2.
  • the first agent 3 and the second agent 4 are supplied to the tank 5 and mixed to prepare the composition 6 (polyurethane resin forming composition) of the above embodiment, and the composition 6 is injected into the mold 2 to apply the composition 6 to the surface 1a of the substrate 1 (see FIG. 1(b)).
  • the first agent and the second agent may be heated to mix the first agent 3 and the second agent 4 more uniformly.
  • the composition 6 and the mold 2 may be heated to a degree that does not cause the composition 6 to significantly thicken.
  • the temperature of the composition 6 at the time of injection may be 30° C. or less, and the temperature of the mold 2 at the time of injection may be 85° C. or less.
  • composition 6 is reacted to form a coating film 7 (e.g., a cured film) containing the reaction product of composition 6 on the surface of substrate 1 (see FIG. 1(c)).
  • the reaction of composition 6 may be caused to proceed by injecting composition 6 into a heated mold.
  • the heating temperature may be any temperature that does not exceed the heat resistance of the substrate, and may be 50 to 150°C or 50 to 85°C from the viewpoint of coating film formability.
  • the substrate may be removed from the mold and the coating film may be heated again.
  • the obtained polycarbonate polyol was heated to 100° C., then placed in a transparent glass bottle, and allowed to stand for 24 hours in an environment of 25° C. After standing, the glass bottle was tilted at 25° C., and visually observed to see whether the polycarbonate polyol had fluidity. It was confirmed that the polycarbonate polyol had fluidity (i.e., was liquid).
  • the hydroxyl value of the polycarbonate polyol obtained in Synthesis Example 1 was evaluated by a method using an acetylation reagent in accordance with JIS K1557-1. Based on the hydroxyl value, the number of hydroxyl groups was set to a theoretical value (calculated value) of 2, and the molecular weight of the polycarbonate polyol was calculated. The hydroxyl value of the polycarbonate polyol was 226.8 mg KOH/g, and the molecular weight calculated from the hydroxyl value and the number of hydroxyl groups was 495.
  • Examples 1 to 13 and Comparative Examples 1 to 10> (Preparation of the first agent) Component (A) (polyol), component (C) (ultraviolet absorber), and component (D) (hindered amine light stabilizer) shown in Tables 1 to 3 were charged in a warming device equipped with a stirrer, a thermometer, and a heating device in the amounts shown in Tables 1 to 3, and the temperature inside the device was gradually increased under a nitrogen stream. At this time, in Comparative Example 10, 10.00 parts by mass of butyl acetate was added as a solvent (volatile organic compound). After the solids were dissolved and became uniform, the mixture was cooled to room temperature to obtain a first agent.
  • Component (A) (polyol), component (C) (ultraviolet absorber), and component (D) (hindered amine light stabilizer) shown in Tables 1 to 3 were charged in a warming device equipped with a stirrer, a thermometer, and a heating device in the amounts
  • Average number of hydroxyl groups (number of hydroxyl groups in (A) component 1 ⁇ amount of charged component (A) 1 + number of hydroxyl groups in (A) component 2 ⁇ amount of charged component (A) 2 + number of hydroxyl groups in (A) component 3 ⁇ amount of charged component (A) 3) / total amount of charged components (A)
  • Average hydroxyl value (hydroxyl value of (A) component 1 ⁇ charged mass of (A) component 1 + hydroxyl value of (A) component 2 ⁇ charged mass of (A) component 2 + hydroxyl value of (A) component 3 ⁇ charged mass of (A) component 3) / total mass of charged components (A)
  • component (A) 1, component (A) 2, and component (A) 3 refer to the individual materials blended as component
  • Dioctyltin dilaurate (DOTDL in the table) was added to the first agent, and Coronate HXLV (C-HXLV in the table) was prepared as the second agent.
  • the first and second agents prepared above were thoroughly mixed at room temperature to obtain a uniform composition.
  • the coating liquid made of the obtained composition was applied onto a white steel plate as a substrate.
  • two guides with a height of 600 ⁇ m were provided on the substrate, and the coating liquid was poured between the two guides to adjust the cured film thickness to 600 ⁇ m.
  • release-treated glass was placed on the guides so as to cover the coating film (uncured film made of the coating liquid), and the coating film was then cured at 80°C for 1 hour. Thereafter, it was cured at 60°C for 12 hours to form a coating film (cured film) containing a reaction product of the composition.
  • the laminate made of the substrate and coating film (cured film) obtained in this way was used as a test piece and the following evaluations were performed.
  • Gloss retention rate is 90% or more; B: Gloss retention rate is 85% or more and less than 90%; C: Gloss retention rate is 80% or more and less than 85%; D: Gloss retention rate is less than 80% [Evaluation criteria for 60° gloss retention rate]
  • D Gloss retention rate is less than 85%.
  • test pieces were: A: Sa was less than 0.2 ⁇ m; B: Sa was 0.2 ⁇ m or more and less than 0.4 ⁇ m; C: Sa was 0.4 ⁇ m or more and less than 0.6 ⁇ m; D: Sa was 0.6 ⁇ m or more, or the coating surface was too uneven to measure.
  • 1,3-BG 1,3-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl group number 2, hydroxyl value 1245 mg KOH/g)
  • TMP Trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl group number 3, hydroxyl value 1254 mgKOH/g)
  • GP250 Sannix GP-250 (manufactured by Sanyo Chemical Industries, Ltd., polyether polyol, number of hydroxyl groups: 3, hydroxyl value: 670 mg KOH/g)
  • GK400 Sannix GK-400 (manufactured by Sanyo Chemical Industries, Ltd., polyether polyol, hydroxyl group number 2, hydroxyl value 400 mg KOH/g)

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