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WO2025143186A1 - Composition durcissable pour un revêtement par pulvérisation - Google Patents

Composition durcissable pour un revêtement par pulvérisation Download PDF

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Publication number
WO2025143186A1
WO2025143186A1 PCT/JP2024/046318 JP2024046318W WO2025143186A1 WO 2025143186 A1 WO2025143186 A1 WO 2025143186A1 JP 2024046318 W JP2024046318 W JP 2024046318W WO 2025143186 A1 WO2025143186 A1 WO 2025143186A1
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curable composition
weight
group
parts
groups
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English (en)
Japanese (ja)
Inventor
貴雄 道信
卓宏 橋本
崇 森本
敦史 川上
克浩 安藤
美伸 大西
克勇 若林
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Kaneka Corp
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Kaneka Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • 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
    • C09D7/65—Additives macromolecular

Definitions

  • the present invention relates to a curable composition for spray coating that contains a polyoxyalkylene polymer having a reactive silicon group, and a cured film using the composition or a method for producing the same.
  • polyoxyalkylene polymers containing reactive silicon groups are widely used in applications such as sealants, adhesives, and paints because of their well-balanced performance in the cured product, including mechanical properties, weather resistance, and dynamic durability.
  • the present invention aims to provide a curable composition for spray coating that contains a reactive silicon group-containing polyoxyalkylene polymer, which has both spray coatability and resistance to sagging after coating, and can suppress bleed-out after curing.
  • reaction with alkali metal salts When introducing an olefin group into a polyoxyalkylene polymer (d1) having a hydroxyl group at its terminal, it is preferable to first react an alkali metal salt with the polyoxyalkylene polymer (d1) to convert the terminal hydroxyl group into an alkoxide terminal.
  • a composite metal cyanide complex catalyst can be used instead of the alkali metal salt. In this manner, an alkoxide-terminated polyoxyalkylene polymer (d2) is formed.
  • the alkali metal salt is not particularly limited, but examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. From the viewpoints of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred, and sodium methoxide and sodium tert-butoxide are more preferred. From the viewpoint of availability, sodium methoxide is preferred.
  • the alkali metal salt may be dissolved in a solvent and then subjected to the reaction.
  • the alkoxide-terminated polyoxyalkylene polymer (d2) obtained as described above can be converted to a structure containing an olefin group by reacting an electrophilic agent (d3) having an olefin group, thereby forming a polyoxyalkylene polymer (d4) having an olefin group in the terminal structure.
  • the electrophile (d3) having an olefin group is not particularly limited as long as it is a compound that can react with the alkoxide terminal of the polyoxyalkylene polymer (d2) and introduce an olefin group into the polyoxyalkylene polymer, but examples of the electrophile include an organic halide (d3-1) having an olefin group and an epoxy compound (d3-2) having an olefin group.
  • An organic halide (d3-1) having an olefin group which is one embodiment of the electrophile (d3), can react with the alkoxide terminal through a halogen substitution reaction to form an ether bond, thereby introducing a structure containing an olefin group as the terminal structure of the polyoxyalkylene polymer.
  • a halogenated hydrocarbon compound having a carbon-carbon triple bond can be used as the organic halide (d3-1) having an olefin group.
  • the halogenated hydrocarbon compound having a carbon-carbon triple bond is not particularly limited, but examples thereof include propargyl chloride, propargyl bromide, and propargyl iodide.
  • a halogenated hydrocarbon compound having a carbon-carbon double bond may be used simultaneously with a halogenated hydrocarbon compound having a carbon-carbon triple bond.
  • an epoxy compound (d3-2) having an olefin group can react with the alkoxide terminal through a ring-opening addition reaction of the epoxy group to form an ether bond, thereby introducing a structure containing an olefin group and a hydroxyl group as the terminal structure of the polyoxyalkylene polymer.
  • a single or multiple epoxy compounds (d3-2) can be added to one alkoxide terminal by adjusting the amount of epoxy compound (d3-2) used relative to the alkoxide terminal and the reaction conditions.
  • epoxy compound (d3-2) having an olefin group are not particularly limited, but allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and butadiene monoxide are preferred in terms of reaction activity, with allyl glycidyl ether being particularly preferred.
  • the polyoxyalkylene polymer (d4) having an olefin group in the terminal structure or the polyoxyalkylene polymer (d5) (precursor polymer) having a carbon-carbon triple bond in the terminal structure obtained as above is subjected to a hydrosilylation reaction with a hydrosilane compound (d6) having a reactive silicon group, thereby producing a reactive silicon group-containing polyoxyalkylene polymer (A).
  • the hydrosilylation reaction has the advantages that it can be easily carried out, the amount of reactive silicon group introduced is easily adjusted, and the physical properties of the obtained polymer are stable.
  • hydrosilane compound (d6) having a reactive silicon group include halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, and bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxysilane.
  • halosilanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(
  • the hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst in order to promote the reaction.
  • a hydrosilylation catalyst include metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium, and complexes thereof.
  • platinum-olefin complexes
  • JP 2021-11456 A proposes the use of a ruthenium complex with a specific ligand.
  • Specific examples include a method in which a ruthenium complex and a halogen-substituted olefin compound (such as 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, and 1,3,5-tribromobenzene) are used in a hydrosilylation reaction.
  • a ruthenium complex and a halogen-substituted olefin compound such as 1,4-dibromobenzene, 1-bromo-3,5-difluorobenzene, 1-bromo-2,6-difluorobenzene, 1,4-diiodobenzene, and 1,3,5-tribromobenzene
  • a ruthenium complex and a halogen-substituted olefin compound such as 1,4-dibro
  • a method for producing the reactive silicon group-containing polyoxyalkylene polymer (A) can be applied in which a compound (d7) having a reactive silicon group and an isocyanate group in one molecule is allowed to react with a polyoxyalkylene polymer (d1) (precursor polymer) having a terminal hydroxyl group to form a urethane bond and introduce a reactive silicon group.
  • a compound (d7) having a reactive silicon group and an isocyanate group in one molecule is allowed to react with a polyoxyalkylene polymer (d1) (precursor polymer) having a terminal hydroxyl group to form a urethane bond and introduce a reactive silicon group.
  • the compound (d7) having a reactive silicon group and an isocyanate group in one molecule is not particularly limited as long as it is a compound having both an isocyanate group capable of undergoing a urethane reaction with the hydroxyl group of the polyoxyalkylene polymer (d1) and a reactive silicon group in one molecule, but specific examples include (3-isocyanatepropyl)trimethoxysilane, (3-isocyanatepropyl)dimethoxymethylsilane, (3-isocyanatepropyl)triethoxysilane, (3-isocyanatepropyl)diethoxymethylsilane, (isocyanatemethyl)trimethoxysilane, (isocyanatemethyl)triethoxysilane, (isocyanatemethyl)dimethoxymethylsilane, (isocyanatemethyl)diethoxymethylsilane, etc.
  • the urethanization reaction may be carried out without using a urethanization catalyst, but may be carried out in the presence of a urethanization catalyst in order to improve the reaction rate or the reaction rate.
  • a urethanization catalyst for example, a conventionally known urethanization catalyst such as the catalysts listed in Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963, may be used. Specific examples include, but are not limited to, base catalysts such as organotin compounds, bismuth compounds, and organic amines.
  • a method for producing the reactive silicon group-containing polyoxyalkylene polymer (A) can also be applied in which an excess of a polyisocyanate compound (d8) is reacted with a polyoxyalkylene polymer (d1) having a hydroxyl group at its terminal to produce a polymer (precursor polymer) having an isocyanate group at its terminal, and then the precursor polymer is reacted with a compound (d9) having a reactive silicon group and a group that reacts with an isocyanate group (e.g., an amino group).
  • an isocyanate group e.g., an amino group
  • polyisocyanate compounds (d8) include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.
  • Examples of compounds (d9) having a group that reacts with an isocyanate group and a reactive silicon group include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyldimethoxymethylsilane, ⁇ -aminopropyltriethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyldimethoxymethylsilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltriethoxysilane, ⁇ -(N-phenyl)aminopropyltrimethoxysilane, ⁇ -(N-phenyl)aminopropyldi Examples include amino group-containing silanes such as methoxymethylsilane, N-ethylaminoisobutyltrimethoxysilane, N-
  • a method for producing a reactive silicon group-containing polyoxyalkylene polymer (A) can be applied in which a polyoxyalkylene polymer (d4) (precursor polymer) having an olefin group in its terminal structure is reacted with a compound (d10) having a reactive silicon group and a mercaptan group in one molecule to form a sulfide bond by addition of the mercaptan group to the olefin group, thereby introducing a reactive silicon group.
  • the compound (d10) having a reactive silicon group and a mercaptan group in one molecule is not particularly limited as long as it is a compound having both a mercaptan group capable of undergoing an addition reaction with an olefin group in the polyoxyalkylene polymer (d4) and a reactive silicon group in one molecule, but specific examples include (3-mercaptopropyl)methyldimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methyldiethoxysilane, (3-mercaptopropyl)triethoxysilane, (mercaptomethyl)methyldimethoxysilane, (mercaptomethyl)trimethoxysilane, (mercaptomethyl)methyldiethoxysilane, (mercaptomethyl)triethoxysilane, etc.
  • the addition reaction of the mercaptan group to the olefin group may be carried out without using a radical initiator, but may be carried out in the presence of a radical initiator in order to improve the reaction rate or the reaction rate.
  • a radical initiator a conventionally known initiator may be used. Specific examples include, but are not limited to, azo-based initiators and peroxide-based initiators.
  • azo initiators such as 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (V-59), and 2,2'-azobis(1-methylcyclohexanecarbonitrile) (V-40) are particularly preferred.
  • AIBN 2,2'-azobis(isobutyronitrile)
  • V-59 2,2'-azobis(2-methylbutyronitrile)
  • V-40 2,2'-azobis(1-methylcyclohexanecarbonitrile)
  • the curable composition for spray coating according to the present disclosure contains a hydrocarbon diluent (B).
  • a hydrocarbon diluent (B) By blending the hydrocarbon diluent (B) together with a plasticizer (C) described below, the viscosity of the curable composition for spray coating can be reduced, and spray coatability can be improved.
  • Hydrocarbon diluent (B) refers to a compound whose main component is a hydrocarbon compound and which is liquid at room temperature.
  • the hydrocarbon diluent may be either an aromatic hydrocarbon or a non-aromatic hydrocarbon, but from the viewpoint of low odor, non-aromatic hydrocarbons are preferred.
  • the hydrocarbon diluent (B) is preferably non-volatile.
  • the boiling point of the hydrocarbon diluent (B) is preferably 250°C or higher, more preferably 280°C or higher, even more preferably 290°C or higher, and particularly preferably 300°C or higher.
  • the above-mentioned "boiling point" refers to the starting point of the boiling point.
  • Examples of the high-boiling point hydrocarbon diluent (B) include naphthenic solvents and paraffinic solvents. These hydrocarbon solvents are preferably hydrogen-treated. They may be used alone or in combination of two or more.
  • the paraffinic solvents referred to here include isoparaffinic solvents.
  • hydrocarbon diluent (B) examples are not particularly limited, but commercially available products can be used, such as TOTAL FLUID D-170, Hydroseal HY, IP Solvent 2835, and Exol D130. Among these, TOTAL FLUID D-170 and Hydroseal HY are preferred.
  • the amount of the hydrocarbon diluent (B) is 10 to 50 parts by weight per 100 parts by weight of the polyoxyalkylene polymer (A). If the amount of the (B) component is less than 10 parts by weight, it is difficult to obtain the viscosity reducing effect of the (B) component, and the spray coatability is insufficient, making it difficult to carry out spray coating or requiring a high discharge pressure during spray coating. Furthermore, the coating film obtained by spray coating may have coating spots or the film thickness may be uneven. From the viewpoint of spray coatability, the amount of the (B) component is preferably 20 parts by weight or more, more preferably 30 parts by weight or more, and particularly preferably 40 parts by weight or more.
  • examples include phthalate esters such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; and terephthalate esters such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate.
  • phthalate esters such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate
  • terephthalate esters such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate.
  • the curable composition for spray coating according to the present disclosure may contain a tackifier resin for the purpose of improving adhesion and adhesion to a substrate.
  • a tackifier resin for the purpose of improving adhesion and adhesion to a substrate.
  • the tackifier resin there are no particular limitations on the tackifier resin, and any commonly used tackifier resin may be used.
  • the curable composition for spray coating according to the present disclosure may be used in combination with an epoxy resin, such as bisphenol A type epoxy resins or novolac type epoxy resins.
  • an epoxy resin When an epoxy resin is blended, it is preferable to blend a curing agent that hardens the epoxy resin into the curable composition for spray coating according to the present disclosure.
  • a curing agent that hardens the epoxy resin into the curable composition for spray coating according to the present disclosure.
  • the epoxy resin curing agent There are no particular limitations on the epoxy resin curing agent that can be used, and any commonly used epoxy resin curing agent can be used.
  • the amount is preferably in the range of 0.1 to 300 parts by weight per 100 parts by weight of epoxy resin.
  • the curable composition for spray coating according to the present disclosure has good spray coatability, and therefore has a low viscosity when the composition is spray coated under pressure. Therefore, it is preferable that the viscosity measured in the high shear region shows a low value.
  • the viscosity measured at a temperature of 23° C. and a shear rate of 2000/sec is preferably 1.5 Pa ⁇ s or less. More preferably, it is 1.4 Pa ⁇ s or less.
  • the lower limit is not particularly limited, but may be, for example, 0.1 Pa ⁇ s or more, preferably 0.5 Pa ⁇ s or more, and more preferably 1.0 Pa ⁇ s or more.
  • the curable composition for spray coating according to the present disclosure has the property of being less likely to drip after coating. Therefore, it is preferable that the viscosity measured in the low shear region shows a high value. Specifically, it is preferable that the viscosity measured at a temperature of 23°C and a shear rate of 2/sec is 4 Pa ⁇ s or more. More preferably, it is 6 Pa ⁇ s or more, and even more preferably, it is 8 Pa ⁇ s or more. There is no particular limit to the upper limit, but it may be, for example, 30 Pa ⁇ s or less, preferably 20 Pa ⁇ s or less, and more preferably 15 Pa ⁇ s or less.
  • the curable composition is a one-component type
  • all of the ingredients are mixed in advance, so it is preferable to dehydrate and dry the ingredients containing water before use, or to dehydrate them by reducing pressure during mixing.
  • storage stability can be further improved by adding an alkoxysilane compound such as n-propyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldiethoxysilane, or ⁇ -glycidoxypropyltrimethoxysilane as a dehydrating agent.
  • an alkoxysilane compound such as n-propyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane,
  • the amount of the dehydrating agent, particularly the silicon compound that can react with water, such as vinyltrimethoxysilane, is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A).
  • the curable composition for spray coating according to the present disclosure is used for forming a cured film by spray coating onto a substrate surface and then curing.
  • the equipment used for spray coating is not particularly limited, and examples of the equipment include an air spray device that sprays the paint with air pressurized by a compressor to create a mist; an airless spray device that does not use air, but instead sprays the paint by applying pressure to it and spraying it from a nozzle; an HVLP spray device that uses a large volume of air at low pressure to create a mist of the paint; and an electrostatic spray device that charges the paint.
  • the substrate to which the curable composition for spray coating according to the present disclosure is applied is not particularly limited, and examples thereof include the exterior wall, roof, and rooftop of a building. In particular, it can be used to form a film that seamlessly covers the entire exterior wall material. Such a film can function as a waterproof film. That is, the curable composition for spray coating according to the present disclosure can be used to form a waterproof film on the surface of a substrate by spray coating. Since the cured product of the polyoxyalkylene polymer (A) generally exhibits moisture permeability, the waterproof film can function as a moisture-permeable waterproof film. It should be noted that the use as a waterproof membrane described herein is distinct from its use as a sealant for filling gaps and joints in substrates.
  • the material constituting the substrate is not particularly limited, but examples include porous materials such as siding boards, concrete, CMU backup walls, mortar, stone, metal, etc.
  • the conditions for hardening the coating film are not particularly limited; for example, after spray coating, the coating film may be left at room temperature for about 1 to 5 days.
  • the thickness of the cured film formed on the surface of the substrate is not particularly limited, but may be within the range of, for example, about 100 ⁇ m to 4 mm. About 200 ⁇ m to 3 mm is preferable, and about 200 ⁇ m to 2 mm is even more preferable.
  • a plasticizer which is a cyclic hydrocarbon group-containing dicarboxylic acid ester
  • D polyamide-based rheology control agent
  • the ratio of the plasticizer (C) to the hydrocarbon diluent (B): (C)/(B) is 0.8 to 3.0 by weight.
  • a ratio of the total of the polyoxyalkylene polymer (A) and the plasticizer (C) to the hydrocarbon diluent (B), [(A)+(C)]/(B), is 2.6 to 7.0 by weight.
  • tem 13 A method for producing a cured film, comprising spraying the curable composition according to any one of items 1 to 11 onto a surface of a substrate and then curing the composition.
  • the average number of silyl groups introduced per terminal or per molecule of the polymers shown in the examples was calculated by NMR measurement.
  • polymer (A-1) having a number average molecular weight of 14,600 and dimethoxymethylsilyl groups at the terminals. It was found that polymer (A-1) had an average of 0.8 dimethoxymethylsilyl groups at one terminal and an average of 1.5 dimethoxymethylsilyl groups per molecule.
  • the mixture was cooled to 50°C or lower, and then A-171 (manufactured by Momentive Performance Materials Holdings Inc.: vinyltrimethoxysilane) as a dehydrating agent, A-1120 (manufactured by Momentive Performance Materials Holdings Inc.: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane) as an adhesion promoter, and Neostan U-220H (Nitto Kasei Co., Ltd.: dibutyltin bisacetylacetonate) as a curing catalyst were successively added thereto, and the mixture was thoroughly mixed with a spatula, and then stirred and defoamed using a planetary centrifugal stirring and defoaming mixer to obtain a curable composition.
  • stirring was carried out using a 50 L twin-shaft mixer (manufactured by Inoue Seisakusho).
  • the obtained curable composition was evaluated for spray coatability at a spray pressure of 14 MPa using a Graco Mark V electric airless spray device equipped with a #531 spray tip.
  • the length of the hose was 30 m.
  • the coating was judged based on the presence or absence of coating spots on the coated surface when spray coating was performed once in the horizontal direction about 110 cm while keeping the distance between the coated surface and the spray nozzle at about 50 cm.
  • the coating spots referred to here refer to the occurrence of streaks in the uncoated area. Those that had coating spots were evaluated as "x", and those that did not were evaluated as " ⁇ ". The results are shown in Table 1.
  • TEG2EH (Shandong Kexing Chemical Co., Ltd.: triethylene glycol bis(2-ethylhexanoate))
  • Tinuvin 328 (BASF: benzotriazole-based UV absorber)
  • Tinuvin 770 (BASF: hindered amine light stabilizer)
  • the mixture was cooled to 50°C or lower, and then A-171 (manufactured by Momentive Performance Materials Holdings Inc.: vinyltrimethoxysilane) as a dehydrating agent, A-1120 (manufactured by Momentive Performance Materials Holdings Inc.: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane) as an adhesion promoter, and Neostan U-220H (Nitto Kasei Co., Ltd.: dibutyltin bisacetylacetonate) as a curing catalyst were successively added thereto, and the mixture was thoroughly mixed with a spatula, and then stirred and defoamed using a planetary centrifugal stirring and defoaming mixer to obtain a curable composition.
  • A-171 manufactured by Momentive Performance Materials Holdings Inc.: vinyltrimethoxysilane
  • A-1120 manufactured by Momentive Performance Materials Holdings Inc.: N-(2-aminoeth
  • the viscosity of the obtained curable composition was measured using a Hybrid Rheometer Discovery HR-2 manufactured by TA Instruments. The plate diameter was adjusted to 20 mm, the gap between the plate and the sample stage was adjusted to 0.5 mm, and the sample stage temperature was adjusted to 23° C. Under these conditions, the shear rate was changed from 0.1/s to 2000/s in 4 minutes (ascending shear rate), and then changed from 2000/s to 0.1/s in the next 4 minutes (descending shear rate). The spray properties of the curable composition were evaluated based on the viscosity at 2000/s (ascending) and 2/s (descending).
  • the viscosity at 2000/s is in the high shear region and is therefore thought to be close to the viscosity at the time of spray discharge, and compositions with a low viscosity value were evaluated as having good spray applicability (i.e., good workability). Additionally, the viscosity at 2/s (Descending) is in the low shear region after a strong shear force has been applied and is therefore thought to be close to the viscosity of the composition in the coating film immediately after spray application, and the higher this value, the less likely it is to drip after application (i.e., the better the finish after application).
  • the obtained curable composition was filled into a mold and aged for 3 days at 23°C and 50% relative humidity, and then for 4 days at 50°C to produce a sheet-like cured product with a thickness of about 3 mm.
  • the sheet-like cured product was punched into a No. 3 dumbbell shape and subjected to a tensile test in an atmosphere of 23°C and 50% relative humidity to measure the stress at 50% and 100% elongation (M50, M100) and the breaking strength.
  • the measurement was performed at a tensile speed of 500 mm/min using an autograph (Shimadzu Corporation: AGS-J).
  • Examples 8 to 15 which used a polyamide-based rheology modifier, the viscosity was within the desired range at 2000/s (Ascending) and 2/s (Descending), and both spray coatability and resistance to sagging after coating were achieved.
  • Examples 8 to 15 exhibited a viscosity in the range of 1.2 to 1.5 Pa ⁇ s at 2000/s (Ascending) and a viscosity of 4.1 Pa ⁇ s or more at 2/s (Descending). That is, since they exhibit low viscosity when spray coated, they can be coated at relatively low pressure using a spray coater, and can be said to have excellent workability. Moreover, after being attached to the substrate surface by spray coating, they exhibit a moderately high viscosity, are less likely to drip, and have a good finish after coating.
  • Comparative Example 4 in which the amount of polyamide-based rheology modifier was as high as 10 parts by weight, and Comparative Examples 5 to 7, in which a rheology modifier not corresponding to a polyamide-based was used, a viscosity of 1.7 Pa ⁇ s or more was shown at 2000/s (Ascending), so that high pressure was required when applying using a spray coater, and the workability cannot be said to be good.
  • Comparative Example 8 which also used a rheology modifier that is not polyamide-based, the viscosity at 2/s (Descending) was extremely low at less than 2 Pa ⁇ s, and the coating was prone to dripping after application, making it difficult to achieve a clean finish.
  • Comparative Example 9 which used a plasticizer described in Patent Document 2 (glycol diester: TEG2EH in Table 2) that does not correspond to a cyclic hydrocarbon group-containing dicarboxylate, the viscosity was 1.8 Pa s at 2000/s (Ascending), and the spray coatability was therefore insufficient.
  • Example 15 which used polymer (A-2) having an average of 0.93 dimethoxymethylsilyl groups at one end, showed higher tensile properties for the cured product than Example 14, which used polymer (A-1) having an average of 0.83 dimethoxymethylsilyl groups at one end. In other words, it can be said that the cured film after coating is more resistant to impact and abrasion.
  • Example 16 to 20 According to the composition (weight ratio) shown in Table 4, first, polymer (A-1) was mixed with a plasticizer, a diluent, a filler (calcium carbonate and titanium oxide), a rheology modifier, an ultraviolet absorber, and a light stabilizer, and the mixture was stirred using a planetary centrifugal stirring and degassing mixer (manufactured by Samsung Industries Co., Ltd., product name: Hi-Rotor HR005-04V).
  • a planetary centrifugal stirring and degassing mixer manufactured by Samsung Industries Co., Ltd., product name: Hi-Rotor HR005-04V.
  • the mixture was cooled to 50°C or lower, and then A-171 (manufactured by Momentive Performance Materials Holdings Inc.: vinyltrimethoxysilane) as a dehydrating agent, A-1120 (manufactured by Momentive Performance Materials Holdings Inc.: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane) as an adhesion promoter, and Neostan U-220H (Nitto Kasei Co., Ltd.: dibutyltin bisacetylacetonate) as a curing catalyst were successively added thereto, and the mixture was thoroughly mixed with a spatula, and then stirred and defoamed using a planetary centrifugal stirring and defoaming mixer to obtain a curable composition.
  • stirring was carried out using a 50 L twin-shaft mixer (manufactured by Inoue Seisakusho).

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Abstract

La présente invention concerne une composition durcissable pour un revêtement par pulvérisation, ladite composition contenant 100 parties en poids d'un polymère à base de polyoxyalkylène (A) qui présente un groupe silicium réactif, 10 à 50 parties en poids d'un diluant hydrocarboné (B), 30 à 90 parties en poids d'un plastifiant (C) qui est un ester d'acide dicarboxylique contenant un groupe hydrocarboné cyclique, et 0,6 à 7 parties en poids d'un modificateur de rhéologie à base de polyamide (D). Un film durci est produit en revêtant par pulvérisation la surface d'un matériau de base avec la composition durcissable et, par la suite, en faisant durcir la composition durcissable.
PCT/JP2024/046318 2023-12-28 2024-12-27 Composition durcissable pour un revêtement par pulvérisation Pending WO2025143186A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59122541A (ja) * 1982-12-28 1984-07-16 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
JPH09511268A (ja) * 1994-03-31 1997-11-11 ミネソタ マイニング アンド マニュファクチャリング カンパニー 硬化性珪素含有ポリエーテル接着剤組成物
JPH11500759A (ja) * 1995-01-05 1999-01-19 ミネソタ マイニング アンド マニュファクチャリング カンパニー 硬化性シーラーおよび／または接着剤組成物、該組成物のコーティング法およびコーティングされた基材
WO2005108500A1 (fr) * 2004-05-07 2005-11-17 Kaneka Corporation Composition durcissable améliorée en termes d'adhésivité
WO2006006620A1 (fr) * 2004-07-14 2006-01-19 Kaneka Corporation Processus de production d’une composition résineuse curable

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59122541A (ja) * 1982-12-28 1984-07-16 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
JPH09511268A (ja) * 1994-03-31 1997-11-11 ミネソタ マイニング アンド マニュファクチャリング カンパニー 硬化性珪素含有ポリエーテル接着剤組成物
JPH11500759A (ja) * 1995-01-05 1999-01-19 ミネソタ マイニング アンド マニュファクチャリング カンパニー 硬化性シーラーおよび／または接着剤組成物、該組成物のコーティング法およびコーティングされた基材
WO2005108500A1 (fr) * 2004-05-07 2005-11-17 Kaneka Corporation Composition durcissable améliorée en termes d'adhésivité
WO2006006620A1 (fr) * 2004-07-14 2006-01-19 Kaneka Corporation Processus de production d’une composition résineuse curable

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