WO2020156145A1 - 木制品及其制备方法 - Google Patents

木制品及其制备方法 Download PDF

Info

Publication number
WO2020156145A1
WO2020156145A1 PCT/CN2020/071957 CN2020071957W WO2020156145A1 WO 2020156145 A1 WO2020156145 A1 WO 2020156145A1 CN 2020071957 W CN2020071957 W CN 2020071957W WO 2020156145 A1 WO2020156145 A1 WO 2020156145A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
wood
michael addition
wood product
acrylic polymer
Prior art date
Application number
PCT/CN2020/071957
Other languages
English (en)
French (fr)
Inventor
范世刚
赵熙
段刚
Original Assignee
广东华润涂料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东华润涂料有限公司 filed Critical 广东华润涂料有限公司
Priority to EP20748014.6A priority Critical patent/EP3919188A4/en
Priority to US17/424,233 priority patent/US20220025202A1/en
Publication of WO2020156145A1 publication Critical patent/WO2020156145A1/zh

Links

Classifications

    • 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
    • C09D15/00—Woodstains
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/02—Staining or dyeing wood; Bleaching wood
    • 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
    • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09D131/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • 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
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D5/002—Priming 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • 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
    • 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
    • B05D7/06—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood

Definitions

  • the present invention relates to a wood product containing a Michael addition cured coating. More specifically, the present invention relates to the use of a specific seal coating to improve the adhesion of the Michael addition cured coating to a wooden substrate containing acidic substances, and through The seal coating assists the formation of wood products containing Michael addition cured coating.
  • Wood products include wood furniture, which is the most commonly used product in production and life, which is mainly made of wood substrates. It is well-known that wood substrates have special textures, natural color and other materials that are unmatched by other materials. However, the wooden substrate inevitably has the characteristics of complex structure, uneven material, porous, swelling and shrinking when exposed to water, and containing undesirable substances such as grease, tannins and other colored impurities. It is not an ideal industrial material. Therefore, the research on wood lacquers that can provide a protective layer for wooden substrates has attracted particular attention.
  • the Michael addition curing coating system with low volatile organic compounds has received special attention in recent years, and it is expected to replace two-component polyurethane (PU) curing coatings in the fields of ships, aerospace, construction, and metal profiles.
  • VOC volatile organic compounds
  • PU polyurethane
  • the coating industry needs wood products coated with this low-VOC Michael addition curing coating system.
  • a wood product which comprises a wood substrate containing an acidic substance, which has at least one major surface; a seal coat coated on the major surface of the wood substrate; and The Michael addition-cured coating on the seal coat, wherein the seal coat is formed by a sealant, and the sealant comprises an aqueous latex of a polyurethane acrylic polymer, a carboxyl functionalized self-crosslinking acrylic One or more of water-based polymer latex, cationic acrylic polymer water-based latex, polyvinyl acetate water-based latex, and two-component water-based polyurethane coating system; and wherein the Michael addition curing coating
  • the layer is formed from a two-component curing coating composition.
  • the wood product has an adhesiveness of 4B or higher, and the adhesiveness is measured by the cross-hatch method according to ASTM D3359.
  • Another aspect of the present invention provides a method for preparing the above-mentioned wood products, including the following steps: (a) providing a wood substrate containing acidic substances, which has at least one major surface; (b) in the wood The main surface of the substrate is coated with the above-mentioned sealant to form a seal coat; and (c) a two-component curing coating composition is applied on the seal coat to form a Michael addition cured coating.
  • Another aspect of the present invention discloses a method for improving the adhesion of a Michael addition cured coating to a wooden substrate containing an acidic substance.
  • the method includes applying the above-mentioned seal coat on the wooden substrate. At least one step on the main surface; and wherein the Michael addition cured coating is formed from a two-component curing coating composition.
  • Another aspect of the present invention discloses the use of a seal coating for improving the adhesion of a Michael addition cured coating to a wooden substrate containing acidic substances, wherein the seal coating is formed by the above-mentioned sealant; And wherein, the Michael addition curing coating is formed by a two-component curing coating composition.
  • the applicant pioneered the application of a specific sealing agent on the surface of a wooden substrate to form a sealing coating, which provides a new way for the application of Michael addition cured coatings on wooden substrates containing acidic substances.
  • the presence of the seal coating significantly reduces or eliminates the adverse effects of acidic substances such as tannin in the wood substrate on the Michael addition cured coating, which has never been recognized before the present invention.
  • compositions are described as including or containing specific components, it is expected that the composition does not exclude optional components not involved in the present invention, and it is expected that the composition may be composed or composed of the involved components, or
  • a method is described as including or containing specific process steps, it is expected that the method does not exclude optional process steps not involved in the present invention, and it is expected that the method can be constituted or composed of the involved process steps.
  • any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, and any upper limit can be combined with any other upper limit to form an unspecified range.
  • every point or single value between the end points of the range is included in the range. Therefore, each point or single value can be used as its own lower limit or upper limit, combined with any other point or single value, or combined with other lower limit or upper limit, to form an unspecified range.
  • major surface is the surface formed by the length and width dimensions of the wooden substrate for providing decoration.
  • blocking coating is a continuous coating film formed of a blocking agent for blocking undesired substances such as tannin in a wood substrate.
  • adheresion is a parameter used to measure whether a Michael addition cured coating can form an acceptable coating on a wood substrate. The higher the adhesion, the better the film-forming stability of the Michael addition cured coating on the wood substrate.
  • the term “on” includes applying one coating directly or indirectly to another coating.
  • Layer up In some embodiments of the present invention, the Michael addition-cured coating is directly applied to the seal coating and is in direct contact with the seal coating. In other embodiments of the present invention, one or more colorant layers may exist between the Michael addition-cured coating and the seal coating to obtain the desired color.
  • One aspect of the present invention provides a wood product, which comprises a wood substrate containing an acidic substance, the wood substrate having at least one main surface; and a seal coat coated on the main surface of the wooden substrate And a Michael addition cured coating coated on the seal coat, wherein the seal coat is formed by a sealant, and the sealant comprises an aqueous latex of a polyurethane acrylic polymer, carboxyl functionalized One or more of the self-crosslinking acrylic polymer water-based latex, cationic acrylic polymer water-based latex, polyvinyl acetate water-based latex, and two-component water-based polyurethane coating system; and The Michael addition cure coating is formed from a two-component curing coating composition.
  • the wood product according to the present invention has an adhesiveness of 4B or higher, preferably an adhesiveness of 5B or higher, which is measured by the cross-hatch method according to ASTM D3359.
  • the wood product has an adhesion of 4B or higher, preferably 5B or higher.
  • the wood product has an adhesion of 4B or higher, preferably 5B or higher.
  • the wood product has an adhesiveness of 4B or higher, preferably 5B or higher.
  • wood substrate used to manufacture the wood product of the present invention any suitable wood substrate known in the art can be used.
  • woody substrate refers to any cellulose/lignin material derived from the hard, fibrous structural organization in the stems and roots of trees or other woody plants.
  • Wood includes, for example, hardwood and softwood wood cut directly from trees, and engineered wood composite materials made of wood strips, wood chips, wood fibers or wood veneers. Examples of wood composite materials include, but are not limited to, plywood, oriented strand board (OSB), medium density fiberboard (MDF), particle board, and the like.
  • OSB oriented strand board
  • MDF medium density fiberboard
  • the wood product of the present invention includes a wood substrate having an acidic substance.
  • the acidic substance includes tannins, aldehydes and/or hemiacetals.
  • the wood substrate has a tannin content of at least 0.1 wt%, preferably a tannin content of at least 1 wt%, more preferably a tannin content of at least 5 wt%, and even more preferably A tannin content of at least 10% by weight, and even more preferably a tannin content of at least 30% by weight, as determined by CNS4716-2005.
  • Exemplary wooden substrates hardwood, chestnut, oak, red hook chestnut, camellia, press wood, Douglas fir, Japanese cedar, American cypress, Japanese pine, Japanese cypress, water walnut, black walnut, maple, Japanese beech , Japanese paulownia, birch, Sals, magnolia, ash, teak, oak, catalpa, mountain camphor, cedar, oak, rubber wood, one or more.
  • the wood substrate has at least one, preferably two major surfaces facing each other.
  • the "major surface” is the surface for decoration formed by the length and width dimensions of the wooden substrate.
  • the main surface of the wood substrate may have polar groups such as hydroxyl, amino, sulfhydryl and the like.
  • the sealing agent of the present invention is easier to disperse and coat on it.
  • the hydroxyl groups on the surface of the wooden substrate are derived from the cellulose in the wooden substrate, or the surface treatment method is used to make the wooden substrate obtain a main surface with hydroxyl groups, such as oxidation by corona treatment, thereby introducing hydroxyl groups on the surface of the wooden substrate .
  • the application of the Michael addition curing system on wood substrates cannot always meet industrial needs. Therefore, there is no wood product on the market using this low-VOC Michael addition curing coating system.
  • the inventor of the present invention technologically revealed that the acidic substance present in the wooden substrate is the root cause of the adhesion problem of the Michael addition cured coating on the wooden substrate, thereby providing protection for the Michael addition cured coating
  • the wooden base material provides ideas.
  • the seal coat is coated on the main surface of the wooden substrate to seal the acidic substance such as tannin contained therein, thereby providing a coating suitable for Michael addition curing coating.
  • the seal coat is formed by a sealant comprising an aqueous latex of a polyurethane acrylic polymer, an aqueous latex of a carboxyl functionalized self-crosslinking acrylic polymer, and a cationic acrylic polymer
  • a sealant comprising an aqueous latex of a polyurethane acrylic polymer, an aqueous latex of a carboxyl functionalized self-crosslinking acrylic polymer, and a cationic acrylic polymer
  • the sealing agent comprises an aqueous latex of polyurethane acrylic polymer (PUA).
  • PUA polyurethane acrylic polymer
  • this water-based latex is formed by radical polymerization of acrylic monomers in the presence of an aqueous polyurethane dispersion.
  • any polyurethane aqueous dispersion suitable for preparing polyurethane acrylic polymer can be used.
  • an aqueous dispersion of polyurethane with rare unsaturated functional groups can also be used, so this aqueous dispersion can be copolymerized with acrylic monomers added later to form a more stable polyurethane acrylic polymer Of water-based latex.
  • the polyurethane prepolymer with rare unsaturated functional groups can be formed by any suitable preparation method using any suitable reactants.
  • the polyurethane functionalized with rare unsaturated functional groups is formed by making an excess of diisocyanate and at least one polyhydroxy compound, an ethylenically unsaturated compound containing isocyanate-reactive functional groups, and optionally a water-dispersing group
  • the polyhydroxy compound reacts.
  • the reaction conditions for preparing the above-mentioned unsaturated polyurethane can be easily determined by a person of ordinary skill in the art.
  • the monomer used to prepare the aqueous latex of the polyurethane acrylic polymer includes any ethylenically unsaturated compound that can undergo radical polymerization.
  • examples of the ethylenically unsaturated compound are selected from styrenes (such as styrene, ⁇ -methylstyrene, vinyl toluene, vinyl naphthalene), halogenated olefins (such as vinyl chloride, vinylidene chloride).
  • Vinyl fluoride tetrafluoroethylene, hexafluoropropylene
  • allyl ethers such as allyl anisole
  • vinyl acetate vinyl tertiary carbonate
  • vinyl tertiary carbonate for example, the commercially available vinyl tertiary carbonate VeoVa 10
  • acrylonitrile such as acrylonitrile and methacrylonitrile
  • C 1 -C 16 alkyl ester of (meth)acrylic acid alkoxyalkyl ester of (meth)acrylic acid.
  • examples of the rarefied unsaturated compound are selected from one or more of C 1 -C 16 alkyl esters of (meth)acrylic acid, including but not limited to methyl (meth)acrylate, (meth) Base) ethyl acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate.
  • C 1 -C 16 alkyl esters of (meth)acrylic acid including but not limited to methyl (meth)acrylate, (meth) Base) ethyl acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate.
  • the inventors of the present invention surprisingly discovered that the introduction of the above ethylenically unsaturated compounds resulted in the formed aqueous dispersion of polyurethane acrylic polymer being particularly suitable for sealing acidic substances in wooden substrates.
  • the aqueous dispersion of polyurethane alone cannot effectively seal the acidic substances in the wood substrate at all, which was difficult to predict before the present invention.
  • the aqueous dispersion of the polyurethane acrylic polymer may be prepared by the above-mentioned method, or may be commercially available.
  • an aqueous dispersion of a polyurethane acrylic polymer PUA1025 commercially available from Sherwin-Williams Corporation can be used.
  • the blocking agent comprises a carboxyl functionalized self-crosslinkable acrylic polymer aqueous latex.
  • the carboxyl functionalized self-crosslinkable acrylic polymer aqueous latex has a carboxyl content of 0.1 to 5% by weight.
  • the carboxyl group content can be determined by Boehm titration, for example.
  • the inventors of the present invention surprisingly found that the above carboxyl functionalized self-crosslinkable acrylic polymer aqueous latex is particularly suitable for sealing acidic substances in wood substrates.
  • self-crosslinkable acrylic polymer water-based latexes that are not functionalized with carboxyl groups, such as DOW 3311, cannot effectively seal acidic substances in wood substrates.
  • the root cause is not known, but the inventor believes that the self-crosslinking acrylic polymer with carboxyl functional groups is one of the important factors for its ability to effectively seal the acidic substances in the wood substrate.
  • a carboxyl functionalized self-crosslinking acrylic polymer aqueous latex may be commercially available.
  • a carboxyl functionalized self-crosslinking acrylic polymer water-based latex commercially available LP2006 SW EPS water-based self-crosslinking acrylic polymer from Sherwin-Williams can be used.
  • the blocking agent comprises an aqueous latex of a cationic acrylic polymer.
  • the aqueous latex of the cationic acrylic polymer has a pH of 6.0 or less, preferably a pH of 4.2-5.2.
  • the inventors of the present invention surprisingly found that the aqueous latex of cationic acrylic polymer with a pH of less than 6.0 is particularly suitable for sealing acidic substances in wood substrates, and the sealing coating formed therefrom will not give the later coating
  • the formation of Michael addition cured coatings will bring about any adverse effects, which were unforeseen before this application.
  • the coating composition forming the Michael addition curing coating should generally not use any acidic components.
  • the use of cationic acrylic polymer aqueous latex breaks the above-mentioned industry prejudices.
  • an aqueous latex of a cationic acrylic polymer with a pH of 6.0 or less, preferably between 4.2-5.2, can be used as the seal coat, and the seal coat formed therefrom will not affect the later coated
  • the curing of the Michael addition cured coating produces any adverse effects, and the resulting Michael addition cured coating still exhibits excellent adhesion.
  • an aqueous latex of a cationic acrylic polymer having a pH of less than 7.0 may be commercially available.
  • DSM XK350 commercially available from DSM can be used.
  • the blocking agent includes an aqueous latex of polyvinyl acetate.
  • the aqueous polyvinyl acetate latex has a pH of 6.0 or less, preferably a pH of 4.0-5.0.
  • the inventors of the present invention surprisingly discovered that the aqueous polyvinyl acetate latex with a pH of less than 6.0 is particularly suitable for sealing acidic substances in wooden substrates, and the sealing coating formed by it will not give the Michael the coating on it.
  • the formation of addition-cured coatings will bring about any adverse effects, which were difficult to foresee before this application.
  • the coating composition forming the Michael addition curing coating should generally not use any acidic components.
  • the use of polyvinyl acetate aqueous latex breaks the above-mentioned industry prejudices.
  • an aqueous polyvinyl acetate latex with a pH of 6.0 or less, preferably between 4.0 and 5.0, can be used as the seal coat, and the seal coat formed therefrom will not add to the Michael that is applied later.
  • the curing of the cured coating produces any adverse effects, and the resulting Michael addition cured coating still exhibits excellent adhesion.
  • an aqueous polyvinyl acetate latex having a pH of less than 6.0 may be commercially available.
  • the water-based polyvinyl acetate latex the water-based polyvinyl acetate latex of LS5042 can be used.
  • the sealing agent comprises a two-component aqueous polyurethane coating system.
  • a two-component waterborne polyurethane coating system comprises: a) a film-forming resin composition comprising an aqueous emulsion containing an active hydrogen polymer; and b) a polyisocyanate hardener.
  • film-forming resin composition herein refers to the resin composition constituting the main body of the seal coat formed by the two-component aqueous polyurethane coating system of the present invention, which may include an aqueous emulsion containing an active hydrogen polymer and optionally Additional additives include fillers.
  • an aqueous emulsion containing an active hydrogen polymer is used.
  • active hydrogen is reactive with isocyanate groups, which can be provided by functional groups such as -COOH, -OH, -SH, secondary amino groups, and primary amino groups.
  • functional groups such as -COOH, -OH, -SH, secondary amino groups, and primary amino groups.
  • some functional groups such as ester groups (especially carboxylic acid ester groups), thioether groups, or acid anhydride groups (especially carboxylic acid anhydride groups) can be converted into functional groups capable of providing active hydrogen, for example, by hydrolysis.
  • active hydrogen-containing polymer refers to any polymer that itself contains a functional group capable of providing active hydrogen and/or contains a functional group capable of providing active hydrogen during the preparation and/or application of the aqueous blocking agent system. Of any polymer.
  • an aqueous emulsion containing an active hydrogen polymer is used to provide a resin component for the film-forming resin composition and the aqueous sealant system.
  • this resin component acts as an adhesive to provide adhesion of the seal coating to the substrate, and to keep the components (such as fillers) in the film-forming resin composition together and give the seal coating
  • the layer has a certain cohesive strength.
  • this resin component has good reactivity with the polyisocyanate hardener, thereby realizing cross-linking of polymer chains, thereby forming a seal coating with a three-dimensional network structure.
  • the seal coat formed by cross-linking the above resin components and the polyisocyanate hardener has the ability to block water-soluble tannins, grease or other undesirable substances, thereby avoiding their migration and exudation.
  • the seal coating obtained by the aqueous polyurethane coating system of the present invention also has good physical and chemical properties, such as non-sticky, high hardness, good water resistance, good solvent resistance and Long-lasting sealing effect.
  • the active hydrogen-containing polymer includes vinyl acetate-ethylene copolymer, vinyl acetate-ethylene-(meth)acrylate copolymer, vinyl acetate-(meth)acrylate copolymer One or more of polyvinyl acetate, polyvinyl alcohol or any combination thereof.
  • the active hydrogen-containing polymer may be a vinyl acetate-ethylene copolymer.
  • the film-forming resin composition relative to the total weight of the film-forming resin composition, contains about 20% to about 55% by weight, preferably about 35% to about 55% by weight of polymer containing active hydrogen.
  • An aqueous emulsion of the substance Specifically, the film-forming resin composition, relative to the total weight of the film-forming resin composition, contains about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight or About 50% by weight aqueous emulsion containing active hydrogen polymer.
  • the solid content of the aqueous emulsion containing active hydrogen polymer is in the range of about 20% to about 60%, preferably in the range of about 45% to about 60%, wherein The solid content is calculated as the ratio of the weight of the active hydrogen-containing polymer to the total weight of the active hydrogen-containing polymer and water.
  • the solid content of the aqueous emulsion containing active hydrogen polymer is about 22.5%, about 25.0%, about 27.5%, about 30.0%, about 32.5%, about 35.0%, about 37.5%, about 40.0%, about 42.5%, about 45.0%, about 47.5%, about 50.0%, about 52.5%, about 55.0%, or about 57.5%.
  • the pH value of the aqueous emulsion containing the active hydrogen polymer is in the range of about 4.2 to about 8.0.
  • aqueous emulsions containing active hydrogen polymers can be prepared by appropriate emulsion polymerization methods known to those of ordinary skill in the art.
  • any suitable commercially available products such as those of Wacker Chemie AG, Germany, can be used. 402 and American Celanese Celvolit 1602.
  • polyisocyanate hardener refers to a polyisocyanate compound, an isocyanate oligomer, or a combination thereof.
  • the polyisocyanate hardener contains two or more isocyanate functional groups, which can undergo chain extension and crosslinking reactions with the active hydrogen polymer, thereby forming a three-dimensional network structure in the seal coating.
  • Suitable polyisocyanate hardeners include aliphatic polyisocyanates, aromatic polyisocyanates or any combination thereof.
  • aliphatic polyisocyanate refers to a polyisocyanate compound in which an isocyanate group is directly connected to an aliphatic chain or ring.
  • aromatic polyisocyanate refers to a polyisocyanate compound in which an isocyanate group is directly attached to an aromatic ring.
  • suitable polyisocyanate compounds hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane-1,4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, Cyclopentane-1,3-diisocyanate, p-phenylene diisocyanate, toluene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, biphenyl-4,4'-diisocyanate, benzene-1,2 ,4-Triisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, diphenylmethane diisocyanate, butane-1,2,3-triisocyanate or polymethylene Phenyl polyisocyanate.
  • polyurethane prepolymers of any of the polyisocyanate compounds listed above can be used as examples of suitable isocyanate oligomers.
  • polyester prepolymers of any of the polyisocyanate compounds listed above or polyisocyanate compounds of any of the polyisocyanate compounds listed above can be used.
  • the polyurethane prepolymer, polyester prepolymer or polyether prepolymer can be made by any suitable method known to those of ordinary skill in the art.
  • a polyurethane prepolymer can be made by reacting one or more of a polyol monomer and a polyisocyanate compound under appropriate conditions; a polyester prepolymer or a polyether prepolymer It can be produced by reacting one or more of the polyester polyol or polyether polyol and the polyisocyanate compound under appropriate conditions.
  • a polyester prepolymer or polyether prepolymer any suitable product can be used, such as those available from Bayer, Germany ME 120 or ME 230.
  • the polyisocyanate hardener may be diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, polyester prepolymer of diphenylmethane diisocyanate, diphenylmethane Polyether prepolymer of diisocyanate or any combination thereof.
  • a polyester prepolymer of polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, or a polyether prepolymer of diphenylmethane diisocyanate is used.
  • the weight ratio of the film-forming resin composition to the polyisocyanate hardener can be varied within a wide range.
  • the weight ratio of the polyisocyanate hardener to the film-forming resin composition can be varied in the range of 3:100 to 20:100.
  • the weight ratio of the polyisocyanate hardener to the film-forming resin composition is less than 3:100, the sealing performance of the resulting sealing coating is limited, and sufficient sealing effect cannot be obtained.
  • the weight ratio of the polyisocyanate hardener to the film-forming resin composition is greater than 20:100, the operating performance of the resulting closed system and/or the mechanical properties of the resulting closed coating may be reduced.
  • the above-mentioned sealing agents i), ii), iii), iv) and v) can be combined in any manner to form a sealing agent suitable for coating the surface of a wooden substrate.
  • the blocking agents i) and ii) may be combined, the blocking agents i and iii) may be combined, the blocking agents i) and v) may be combined, and the blocking agents i), ii) and iii) may be combined.
  • the above-mentioned blocking agent may optionally further comprise additional additives commonly used in blocking agents, which do not adversely affect the blocking agent or the blocking coating obtained therefrom.
  • Suitable additives include, for example, those agents that improve the processability or manufacturing performance of the sealant, or improve the specific functional properties or characteristics (such as adhesion to the substrate) of the sealant composition or the seal coating obtained therefrom.
  • Additional additives that may be included are, for example, carriers (e.g., water), emulsifiers, pigments, fillers, anti-migration aids, antifungal agents, preservatives, chain extenders, lubricants, wetting agents, biocides, extenders Plasticizers, defoamers, colorants, waxes, antioxidants, dispersants, adhesion promoters, UV stabilizers, thickeners, defoamers, pH adjusters, or combinations thereof.
  • carriers e.g., water
  • emulsifiers e.g., water
  • pigments e.g., fillers
  • anti-migration aids e.g., antifungal agents
  • preservatives chain extenders
  • lubricants wetting agents
  • biocides extenders
  • extenders Plasticizers defoamers
  • colorants e.g., waxes, antioxidants, dispersants, adhesion promoters, UV stabilizers, thickeners, de
  • the sealing agent can be coated by conventional coating methods known to those of ordinary skill in the art.
  • the coating method includes dip coating, spin coating, spray coating, curtain coating, brush coating, roll coating and other coating methods known in the art.
  • coating is performed using a spraying process.
  • the sealant can be applied in various seal coat thicknesses.
  • the thickness of the seal coat layer is preferably in the range of about 5 to about 100 ⁇ m, preferably in the range of 20-80 ⁇ m.
  • the applied coating can be cured by air-drying or by using various drying devices (for example, an oven) familiar to those skilled in the art to accelerate the curing.
  • a Michael addition cured coating may be coated on the surface of the wood substrate treated by the seal coating.
  • the Michael addition-cured coating can be directly applied to the seal coat and directly contact the seal coat.
  • the Michael addition cured coating thus formed showed very excellent adhesion to the wood substrate.
  • the wood product according to the present invention has an adhesion of 5B or higher, which is measured by the cross-hatch method according to ASTM D3359.
  • the wood product has an adhesion of 5B or higher.
  • the thickness of the Michael addition cured coating according to the present invention is 100 micrometers or more
  • the wood product has an adhesion of 5B or higher.
  • the Michael addition cured coating according to the present invention has a thickness of 200 microns or more
  • the wood product has an adhesion of 5B or higher.
  • the Michael addition curing coating is formed from a two-component curing coating composition.
  • the two-component curing coating composition comprises:
  • the first reactive component has a malonate or acetoacetate functional group as the first reactive functional group, and preferably mainly has a malonate functional group.
  • the first reactive component mainly contains one type of first reactive functional group, preferably greater than 50, 75, 90 and most preferably 100% of the first reactive functional group comes from one type of first reactive functional group, It is preferably derived from malonate or acetoacetate, most preferably from malonate.
  • the second reactive component has an acryl group as the second reactive functional group.
  • the first reactive functional group and the second reactive functional group in the first reactive component and the second reactive component are preferably constructed in the polymer main chain or suspended on the side chain or terminal of the polymer main chain.
  • the first reactive component and the second reactive component are polyesters and alkyd resins having a first reactive functional group and a second reactive functional group in its main chain, side chain, terminal or a combination thereof, respectively , Polyurethane, polyacrylate, epoxy resin, polyamide and polyvinyl resin group.
  • the first reactive component and the second reactive component may be monomeric, but at least one, preferably at least two reactive components are polymers with a weight average molecular weight (Mw) of at least 250 g/mol, preferably Mw To be a polymer between 250, 300 and 5000, more preferably between 400 and 4000 or 500 and 3000 g/mol, the weight average molecular weight is measured by GPC.
  • Mw weight average molecular weight
  • the molar ratio of the reactive group CH is between 0.5 and 2, and preferably between 0.75 and 1.5, more preferably, between 0.8 and 1.2.
  • the first reactive component and the second reactive component are both commercially available, such as Acure 510-170 commercially available from Allnex resin, with a solid content of 85% as the first reactive component, which is commercially available Acure 550-100 of Allnex resin, with a solid content of 85% as the second reactive component.
  • the film-forming resin composition may optionally include one or more fillers.
  • fillers refers to any volume extender suitable for coatings, which may be organic or inorganic, such as in particulate form. There is no particular limitation on the shape of the particles, and they can have any appropriate shape. The average particle size of the filler can vary within a wide range, for example within a range of about 10 nanometers to about 50 microns.
  • Some fillers, in addition to functioning as volume extenders for coatings also impart one or more desired properties to the composition and/or coating formed from the composition. For example, some fillers can impart the desired color to the composition and the coating resulting from the composition. In this case, this filler is also called “pigment”.
  • Some fillers can improve the chemical and/or physical properties, especially the mechanical properties of the coating obtained from the composition. In this case, this filler is also called “reinforcing filler”.
  • the film-forming resin composition may optionally further contain other additional additives commonly used in coating compositions, and these additives will not adversely affect the coating composition or be caused by The resulting cured coating.
  • Suitable additives include, for example, those that can improve the processing or manufacturing properties of the composition, enhance the beauty of the composition, or improve the specific functional properties or characteristics of the coating composition or the cured composition obtained therefrom (such as adhesion to the substrate) Sex) those reagents.
  • the additives that may be included are, for example, one or more selected from solvents, surfactants, UV absorbers, defoamers, dispersants, crosslinking retarders, preservatives, and bactericides.
  • the content of each optional component is sufficient to achieve its intended purpose, but preferably, such content does not adversely affect the coating composition or the cured coating obtained therefrom.
  • the catalyst may be a non-latent catalyst or a latent catalyst.
  • the latent catalyst may be a carbon dioxide-terminated strong base catalyst, preferably a dialkyl or quaternary alkyl ammonium alkyl carbonate (as described in EP2556108). Since the catalyst generates carbon dioxide, it is preferably used in coatings up to 500, 400, 300, 200 or 150 microns thick.
  • EP0326723 describes a homogeneous base catalyst that is more suitable for thicker coatings, which is a catalyst composed of a combination of tertiary amine and epoxide.
  • a preferred homogeneous catalyst is a salt of a basic anion X- from a compound containing an acidic XH group, where X is N, P, O, S, or C, where the anion X- is reactive with the second reactive component
  • the Michael addition donor, and wherein the anion X- is characterized in that the pKa value of the corresponding acid XH is two or more units lower than the pKa value of most of the first reactive components and is lower than 10.5.
  • the details of this catalyst are described in PCT/EP2014/056953, which is incorporated herein by reference.
  • the weight ratio of the catalyst to the film-forming resin composition can be varied in the range of 2:100 to 8:100.
  • the weight ratio of the catalyst to the film-forming resin composition is less than 2:100, the curing performance of the resulting coating is poor.
  • the weight ratio of the catalyst to the film-forming resin composition is greater than 8:100, the operation performance of the resulting Michael addition-cured coating and/or the mechanical properties of the resulting coating may decrease.
  • an additional inert diluent that will not affect the reactivity of the above catalyst and film-forming resin composition can be added during the preparation of the catalyst and/or film-forming resin composition, for example, to reduce the viscosity of each component . Therefore, the weight ratio of the catalyst to the film-forming resin composition is not limited to the above range, and can be adjusted according to actual needs.
  • the two-component curing coating composition can be prepared by simply mixing the film-forming resin composition and the catalyst in a mixing device in a predetermined weight ratio before application.
  • the mixed cured coating composition can be applied using various methods familiar to those skilled in the art, including spraying (for example, air-assisted, airless or electrostatic spraying), brushing, roller coating, overflow coating, and dipping.
  • the mixed cured coating composition is applied by spraying.
  • the cured coating composition can be applied to various wet film thicknesses.
  • the wet film thickness is preferably in the range of about 2 to about 260 ⁇ m, preferably in the range of 30-260 ⁇ m.
  • the applied coating can be cured by air-drying or by using various drying devices (for example, an oven) familiar to those skilled in the art to accelerate the curing.
  • the wooden product can be prepared, for example, by the following steps: (1) providing a polished wooden substrate; (2) using a spraying process to coat the sealant of the present invention on the wooden substrate to form a seal Coating; (3) Using a wet-to-dry coating process, one or more Michael addition cured coatings are sequentially coated on the seal coat.
  • the colorant can be coated on the seal coat before step (3), so as to provide the wood substrate with the desired color.
  • the wood products thus obtained can be used in the following applications, including, but not limited to: household furniture, such as tables, chairs, cabinets, etc.; bedroom and bathroom furniture; office furniture; custom furniture, such as school and children’s furniture, hospitals Furniture, restaurant and hotel furniture, kitchen cabinets and furniture; panels for interior design; indoor and outdoor windows and doors; indoor and outdoor window and door frames; outdoor and indoor wall panels and wooden floors.
  • Another aspect of the present invention provides a method for improving the adhesion of a Michael addition cured coating to a wooden substrate containing an acidic substance, the method comprising applying a sealant coating on at least the wooden substrate A step on a major surface, wherein the sealing coating is formed by a sealing agent selected from the group consisting of an aqueous latex of a polyurethane acrylic polymer copolymer, a carboxyl functionalized self-crosslinking acrylic polymer One or more of the water-based latex, cationic acrylic polymer water-based latex, polyvinyl acetate water-based latex, and two-component water-based polyurethane coating system, and; and wherein, the Michael addition cured coating Is formed by a two-component curing coating composition, the two-component curing coating composition comprising:
  • a seal coating for improving the adhesion of a Michael addition cured coating to a wood substrate containing acidic substances, wherein the seal coating is formed by a sealant
  • the blocking agent is selected from the group consisting of water-based latex of polyurethane acrylic polymer copolymer, water-based latex of carboxyl functionalized self-crosslinking acrylic polymer, water-based latex of cationic acrylic polymer, and water-based polyvinyl acetate latex And one or more of two-component waterborne polyurethane coating systems; and wherein the Michael addition-cured coating is formed by a two-component cured coating composition, the two-component cured coating composition comprising :
  • the seal coating can be applied to various wood substrates containing acidic substances, and solves the problem that the Michael addition cured coating is difficult to adhere to the wood substrate.
  • the wood substrate thus treated is suitable for various applications, including, but not limited to: household furniture, such as tables, chairs, cabinets, etc.; bedroom and bathroom furniture; office furniture; custom furniture, such as school and children’s furniture, hospital furniture , Restaurant and hotel furniture, kitchen cabinets and furniture; panels for interior design; indoor and outdoor windows and doors; indoor and outdoor window and door frames; outdoor and indoor wall panels and wooden floors.
  • the solid wood boards purchased from the timber market are kiln dried. Take a sample with a size of 15 cm * 15 cm * 1.5 cm from the dried board, and adjust it under the conditions of a temperature of 25°C, a relative humidity (RH) of 60% and an air flow rate of 1.8m/s To constant weight, the equilibrium moisture content of the sample is 11%.
  • sealants were sprayed on the treated samples to form a seal coat, and dried in air for 1 hour, in an oven at 70°C for 1 hour, and in air for 7 days.
  • the aqueous latex of polyurethane acrylic polymer, the aqueous latex of carboxyl functionalized self-crosslinking acrylic polymer, the aqueous latex of cationic acrylic polymer, the aqueous polyvinyl acetate latex according to the present invention The closed system formed by the latex and the two-component waterborne polyurethane coating system specifically improves the adhesion of the Michael addition cured coating to the wood substrate containing acidic substances such as tannins, which was difficult to predict before this application.
  • the inventors conducted the following verification test. First, prepare tannin aqueous solutions with concentrations of 0%, 1%, 5%, 10%, and 15%. Then, each aqueous solution was sprayed on the pine wood sample board, and dried in the air for 30 minutes, in a 50-50 oven for 2 hours, and then cooled.
  • Test sample Adhesion Drying time Pencil hardness Samples coated with 0% tannin aqueous solution 4B 35 B Sample coated with 1% tannin aqueous solution 4B 40 2B Sample coated with 5% tannin aqueous solution 2B 51 2B 10% tannin aqueous solution coated sample 0B 81 2B 15% tannin aqueous solution coated sample 0B 90 2B

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Forests & Forestry (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Sealing Material Composition (AREA)

Abstract

一种木制品以及制备该木制品的方法。该木制品包含含有酸性物质的木质基材，其具有至少一个主表面；涂覆在该木质基材的主表面上的封闭涂层；和涂覆在该封闭涂层上的迈克尔加成固化涂层，其中，该封闭涂层是由封闭剂形成的，该封闭剂包含选自聚氨酯丙烯酸类聚合物的水性胶乳、羧基官能化的可自交联丙烯酸类聚合物的水性胶乳、阳离子性丙烯酸类聚合物的水性胶乳、聚醋酸乙烯酯水性胶乳和双组分水性聚氨酯涂层体系中的一种或多种；并且其中迈克尔加成固化涂层是由双组分固化涂料组合物形成的。

Description

木制品及其制备方法
相关申请的交叉引用
本申请要求享有于2019年01月29日提交的名称为“木制品及其制备方法”的中国专利申请201910085770.3的优先权，该申请的全部内容通过引用并入本文中。
技术领域
本发明涉及一种含有迈克尔加成固化涂层的木制品，更具体地，本发明涉及利用特定封闭涂层提高迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性，以及经由该封闭涂层辅助形成的含有迈克尔加成固化涂层的木制品。
背景技术
木器产品包括木质家具是生产、生活中最常用的产品，其主要由木质基材制成。公知地，木质基材具有特殊的纹理、自然的材色等其他材料所无法比拟的魅力。但是，木质基材不可避免地具有组织构造复杂、材质不均匀、多孔、遇水膨缩以及含有诸如油脂、单宁和其它有色杂质的不期望物质等特点，并不是一种理想的工业材料。因此，能够为木质基材提供保护层的木器漆的研究特别引人关注。
低挥发性有机化合物(VOC)的迈克尔加成固化涂层体系近年来受到特别的关注，其有望在船舶、航天、建筑、金属型材等领域中替代双组分聚氨酯(PU)固化涂层。特别吸引人的是，这种涂层体系具有诸多优点，包括可以在室温下、甚至更低温度下施工，溶剂含量非常低(例如小于250g/L)，活化期很长(例如在23℃下大于8小时)，优异的外观性能(例如在60°下的光泽度大于90，DOI大于90)，优异的机械性能(包括优异的耐化学品性、优异的耐刮性、优异的柔韧性、良好的户外耐受性 等)，并且不含诸如异氰酸酯、甲醛和有机锡等有害化学品。因此，市场上对这种迈克尔加成固化涂层体系的需求是旺盛的。然而，这种体系在木质基材上的应用却不尽如人意。迄今为止，市场上还没有采用这种低VOC的迈克尔加成固化涂层体系涂覆的木器产品。
涂料工业中需要采用这种低VOC的迈克尔加成固化涂层体系涂覆的木器产品。
发明内容
本发明一方面公开了一种木制品，其包含含有酸性物质的木质基材，其具有至少一个主表面；涂覆在所述木质基材的主表面上的封闭涂层；和涂覆在所述封闭涂层上的迈克尔加成固化涂层，其中，所述封闭涂层是由封闭剂形成的，所述封闭剂包含聚氨酯丙烯酸类聚合物的水性胶乳、羧基官能化的可自交联丙烯酸类聚合物的水性胶乳、阳离子性丙烯酸类聚合物的水性胶乳、聚醋酸乙烯酯的水性胶乳和双组分水性聚氨酯涂层体系中的一种或多种；并且其中所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的。优选地，所述木制品具有4B或更高的粘附性，所述粘附性是根据ASTM D3359采用划格法测定的。
本发明的另一方面提供了一种用于制备上述木制品的方法，包括如下步骤：(a)提供含有酸性物质的木质基材，其具有至少一个主表面；(b)在所述木制基材的主表面上涂覆上述封闭剂以形成封闭涂层；和(c)在所述封闭涂层上涂覆双组分固化涂料组合物以形成迈克尔加成固化涂层。
本发明的另一方面公开了用于提高迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性的方法，所述方法包括将上述封闭涂层涂覆在所述木质基材的至少一个主表面上的步骤；并且其中，所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的。
本发明的还要另一方面公开了封闭涂层用于提高迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性的用途，其中，所述封闭涂层由上述封闭剂形成；并且其中，所述迈克尔加成固化涂层是由双组分固化涂料组 合物形成的。
以上各方面所涉及的双组分固化涂料组合物包含：A)成膜树脂组合物，其包含a)具有至少两个在活化亚甲基或次甲基中的酸性质子C-H的第一反应性组分，b)具有至少两个活化的不饱和C＝C基团的第二反应性组分，和c)任选的附加添加剂，选自溶剂、填料、表面活性剂、消泡剂、分散剂、UV吸收剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种；和B)用于催化所述成膜树脂组合物发生迈克尔加成交联反应的催化剂。
在本发明中，申请人开创性地将特定的封闭剂涂覆到木质基材的表面上形成封闭涂层，为迈克尔加成固化涂层在含有酸性物质的木质基材上的应用提供了新思路。该封闭涂层的存在显著地减少了或消除了木质基材中的酸性物质例如单宁对迈克尔加成固化涂层的不利影响，这在本发明之前从未被认识到。
本发明的一个或多个实施方案的细节在以下的说明书中阐明。根据说明书和权利要求，本发明其它特征、目的和优点将变得清楚。
定义
在本文中使用时，不使用数量词、“至少一种”和“一种或多种”可互换使用。因此，例如包含添加剂的组分可以被解释为表示该组分包含“一种或多种”添加剂。
在组合物被描述为包括或包含特定组分的情况下，预计该组合物中并不排除本发明未涉及的可选组分，并且预计该组合物可由所涉及的组分构成或组成，或者在方法被描述为包括或包含特定工艺步骤的情况下，预计该方法中并不排除本发明未涉及的可选工艺步骤，并且预计该方法可由所涉及的工艺步骤构成或组成。
为了简便，本文仅明确地公开了一些数值范围。然而，任意下限可以与任何上限组合形成未明确记载的范围；以及任意下限可以与其它下限组合形成未明确记载的范围，同样任意上限可以与任意其它上限组合形成未明确记载的范围。此外，尽管未明确记载，但是范围端点间的每个点或单个数值都包含在该范围内。因而，每个点或单个数值可以作为自身的下限 或上限与任意其它点或单个数值组合或与其它下限或上限组合形成未明确记载的范围。
当在木质基材的上下文中使用时，术语“主表面”是由木质基材的长度和宽度尺寸形成的用于提供装饰的表面。
当本文中使用时，术语“封闭涂层”是由封闭剂形成的用于封闭木质基材中的诸如单宁等不期望物质的连续涂膜。
在本文中，术语“粘附性”是用于衡量迈克尔加成固化涂层能否在木质基材上形成可接受涂层的参数。粘附性越高表明，迈克尔加成固化涂层在木质基材上的成膜稳定性越好。
在“将...涂层涂覆在...涂层上”的上下文中使用时，术语“在...上”包括将一种涂层直接地或间接地涂覆在另一种涂层上。在本发明的一些实施方式中，迈克尔加成固化涂层直接涂覆在封闭涂层上，与封闭涂层直接接触。在本发明的另一些实施方式中，迈克尔加成固化涂层和封闭涂层之间可以存在一种或多种着色剂层，从而获得想要的颜色。
当出现在本说明书和权利要求中时，术语“包含”和“包括”及其变体不具有限制性含义。
术语“优选的”和“优选地”是指在某些情况下可提供某些益处的本发明实施方案。然而，在相同或其他情况下，其它实施方案也可能是优选的。另外，一个或多个优选的实施方案的叙述不意味着其他实施方案是不可用的，并且不旨在将其他实施方案排除在本发明范围外。
具体实施方式
本发明一方面提供了一种木制品，其包含，含有酸性物质的木质基材，所述木质基材具有至少一个主表面；涂覆在所述木制基材的主表面上的封闭涂层；和涂覆在所述封闭涂层上的迈克尔加成固化涂层，其中，所述封闭涂层是由封闭剂形成的，所述封闭剂包含聚氨酯丙烯酸类聚合物的水性胶乳、羧基官能化的可自交联丙烯酸类聚合物的水性胶乳、阳离子性丙烯酸类聚合物的水性胶乳、聚醋酸乙烯酯水性胶乳和双组分水性聚氨酯涂层体系中的一种或多种；并且其中所述迈克尔加成固化涂层是由双组分 固化涂料组合物形成的。
优选地，根据本发明的木制品具有4B或更高的粘附性，优选具有5B或更高的粘附性，所述粘附性是根据ASTM D3359采用划格法测定的。在本发明的迈克尔加成固化涂层的厚度具有30微米或更厚的实施方式中，所述木制品具有4B或更高、优选5B或更高的粘附性。在本发明的迈克尔加成固化涂层的厚度具有100微米或更厚的实施方式中，所述木制品具有4B或更高、优选5B或更高的粘附性。在本发明的迈克尔加成固化涂层的厚度具有200微米或更厚的实施方式中，所述木制品具有4B或更高、优选5B或更高的粘附性。
木质基材
作为用于制造本发明木制品的木质基材，可以使用本领域已知的任何合适的木质基材。在本申请中，术语“木质基材”指的是任何来源于树木或其它木本植物的茎和根中的坚硬、纤维状结构组织的纤维素/木质素材料。木材包括，例如从树木直接切下的硬木和软木木材，以及由木材条、木材碎料、木材纤维或木材薄板制成的工程木材复合材料。木材复合材料的实例包括但不限于胶合板、定向刨花板(OSB)、中密度纤维板(MDF)、碎料板等。
本发明的木制品包含具有酸性物质的木质基材，作为示例，所述酸性物质包含单宁、醛类和/或半缩醛类物质。在本发明某些实施例中，所述木质基材具有至少0.1wt％的单宁含量，优选具有至少1wt％的单宁含量，更优选具有至少5wt％的单宁含量，还要更优选具有至少10wt％的单宁含量，甚至还要更优选具有至少30wt％的单宁含量，所述单宁含量是通过CNS4716-2005测定的。示例性的木质基材坚木、栗木、栎木、红钩栗、油茶、按木、花旗松、日本柳杉、美国扁柏、日本赤松、日本扁柏、水胡桃、黑胡桃、槭木、日本山毛榉、日本泡桐、桦木、婆罗双、木兰、白蜡树、柚木、柞木、楸木、山樟木、杉木、橡木、橡胶木中的一种或多种。
根据本发明，木质基材具有至少一个、优选两个彼此相对的主表面。当在本文中使用时，“主表面”是由木质基材的长度和宽度尺寸形成的用于 装饰的表面。优选地，木质基材的主表面上可以带有诸如羟基、氨基、巯基等极性基团，结果本发明的封闭剂更容易分散和涂覆到其上。木质基材表面的羟基基团来自木质基材中的纤维素，或者通过表面处理方法使得木质基材获得具有羟基的主表面，例如通过电晕处理进行氧化，从而在木质基材的表面引入羟基。
封闭涂层
如背景技术部分所述，迈克尔加成固化体系在木质基材上的应用总是不能满足工业需求。因此，市场上还没有采用这种低VOC的迈克尔加成固化涂层体系制造的木器产品。本发明的发明人开创性地揭示了，木质基材中存在的酸性物质是导致迈克尔加成固化涂层在木质基材上的粘附问题的根本原因，从而为提供迈克尔加成固化涂层保护的木质基材提供了思路。
因此，在根据本发明的木制品中，将封闭涂层涂覆在木质基材的主表面上，以封闭其中所包含的酸性物质如单宁，从而可以提供适于迈克尔加成固化涂层涂覆的木质基材。根据本发明，所述封闭涂层由如下封闭剂形成，所述封闭剂包含聚氨酯丙烯酸类聚合物的水性胶乳、羧基官能化的可自交联丙烯酸类聚合物的水性胶乳、阳离子性丙烯酸类聚合物的水性胶乳、聚醋酸乙烯酯的水性胶乳和双组分水性聚氨酯涂层体系中的一种或多种。
封闭剂i)：聚氨酯丙烯酸类聚合物的水性胶乳
在根据本发明的一个实施方式中，所述封闭剂包含聚氨酯丙烯酸类聚合物(PUA)的水性胶乳。优选地，这种水性胶乳是在聚氨酯水性分散体的存在下通过丙烯酸类单体的自由基聚合形成的。
在聚氨酯丙烯酸类聚合物(PUA)的水性胶乳的制备中，可以使用任何适用于制备聚氨酯丙烯酸类聚合物的聚氨酯水性分散体。可选地，还可以使用带有稀属不饱和官能团的聚氨酯的水性分散体，因而这种水性分散体可以与稍后添加的丙烯酸类单体进行共聚，从而形成更稳定的聚氨酯丙 烯酸类聚合物的水性胶乳。根据本发明，具有稀属不饱和官能团的聚氨酯预聚物可以利用任何适当的反应物通过任何适当的制备方法形成。优选地，稀属不饱和官能团官能化的聚氨酯通过如下形成：使过量的二异氰酸酯与至少一种多羟基化合物、含有异氰酸酯反应性官能团的烯属不饱和化合物以及可选的具有水分散基团的多羟基化合物进行反应。制备上述不饱和聚氨酯的反应条件可由本领域普通技术人员容易地确定。
根据本发明，用于制备所述聚氨酯丙烯酸类聚合物的水性胶乳的单体包括任何可进行自由基聚合的烯属不饱和化合物。适当地，所述烯属不饱和化合物的实例选自苯乙烯类(诸如苯乙烯、α-甲基苯乙烯、乙烯基甲苯、乙烯基萘)、卤代烯烃类(诸如氯乙烯、偏氯乙烯、氟乙烯、四氟乙烯、六氟丙烯)、烯丙基醚类(诸如烯丙基苯甲醚)、醋酸乙烯酯、叔碳酸乙烯酯(例如可商购的叔碳酸乙烯酯VeoVa 10)、丙烯腈类(诸如丙烯腈、甲基丙烯腈)、(甲基)丙烯酸的C 1-C 16烷基酯和(甲基)丙烯酸的烷氧基烷基酯中的一种或多种。优选地，所述稀属不饱和化合物的实例选自(甲基)丙烯酸的C 1-C 16烷基酯中的一种或多种，包括但不限于(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二烷酯。
本发明的发明人惊讶地发现，以上烯属不饱和化合物的引入导致所形成的聚氨酯丙烯酸类聚合物的水性分散体特别适于封闭木质基材中的酸性物质。与之相比，单独的聚氨酯的水性分散体根本无法有效地封闭木质基材中的酸性物质，这在本发明之前是难以预见的。
根据本发明，聚氨酯丙烯酸类聚合物的水性分散体可以采用上述方法制备，或者可以是商购的。作为聚氨酯丙烯酸类聚合物的水性分散体的实例，可以使用商购自宣伟公司的PUA1025。
封闭剂ii)：羧基官能化的可自交联丙烯酸类聚合物的水性胶乳
在根据本发明的一个实施方式中，所述封闭剂包含羧基官能化的可自交联丙烯酸类聚合物的水性胶乳。优选地，所述羧基官能化的可自交联丙烯酸类聚合物的水性胶乳具有0.1-5wt％的羧基含量。根据本发明，所述 羧基含量例如可以通过Boehm滴定法确定。
本发明的发明人惊讶地发现，以上羧基官能化的可自交联丙烯酸类聚合物的水性胶乳特别适于封闭木质基材中的酸性物质。与之相比，未经羧基官能化的可自交联丙烯酸类聚合物的水性胶乳，诸如DOW的3311根本无法有效地封闭木质基材中的酸性物质。并不知晓根本原因，但本发明人认为，可自交联丙烯酸类聚合物带有羧基官能团是其能够有效封闭木质基材中的酸性物质的重要因素之一。
根据本发明，羧基官能化的可自交联丙烯酸类聚合物的水性胶乳可以是商购的。作为羧基官能化的可自交联丙烯酸类聚合物的水性胶乳的实例，可以使用商购自宣伟公司的LP2006 SW EPS水基自交联丙烯酸类聚合物。
封闭剂iii)：阳离子性丙烯酸类聚合物的水性胶乳
在根据本发明的一个实施方式中，所述封闭剂包含阳离子性丙烯酸类聚合物的水性胶乳。优选地，所述阳离子性丙烯酸类聚合物的水性胶乳具有6.0或更小的pH，优选具有4.2-5.2的pH。
本发明的发明人惊讶地发现，pH小于6.0的阳离子性丙烯酸类聚合物的水性胶乳特别适于封闭木质基材中的酸性物质，并且由其形成的封闭涂层不会给稍后涂覆的迈克尔加成固化涂层的形成带来任何不利影响，这在本申请之前是难以预见的。考虑到迈克尔加成固化反应是碱催化的这个事实，所以形成迈克尔加成固化涂层的涂料组合物通常不应使用任何酸性组分。然而，在本发明中，阳离子性丙烯酸类聚合物的水性胶乳的使用打破了上述行业偏见。根据本发明，可以采用pH为6.0或更小、优选介于4.2-5.2的阳离子性丙烯酸类聚合物的水性胶乳作为封闭涂层，而且由此形成的封闭涂层不会对稍后涂覆的迈克尔加成固化涂层的固化产生任何不利影响，所得迈克尔加成固化涂层仍显示优异的粘附性。
根据本发明，pH小于7.0的阳离子性丙烯酸类聚合物的水性胶乳可以是商购的。作为所述阳离子性丙烯酸类聚合物的水性胶乳的实例，可以使用商购自帝斯曼的DSM XK350。
封闭剂iv)：聚醋酸乙烯酯的水性胶乳
在根据本发明的一个实施方式中，所述封闭剂包括聚醋酸乙烯酯的水性胶乳。优选地，所述聚醋酸乙烯酯的水性胶乳具有6.0或更小的pH，优选具有4.0-5.0的pH。
本发明的发明人惊讶地发现，pH小于6.0的聚醋酸乙烯酯的水性胶乳特别适于封闭木质基材中的酸性物质，并且由其形成的封闭涂层不会给涂覆在其上的迈克尔加成固化涂层的形成带来任何不利影响，这在本申请之前是难以预见的。考虑到迈克尔加成固化反应是碱催化的这个事实，所以形成迈克尔加成固化涂层的涂料组合物通常不应使用任何酸性组分。然而，在本发明中，聚醋酸乙烯酯的水性胶乳的使用打破了上述行业偏见。根据本发明，可以采用pH为6.0或更小、优选介于4.0-5.0的聚醋酸乙烯酯的水性胶乳作为封闭涂层，而且由此形成的封闭涂层不会对稍后涂覆的迈克尔加成固化涂层的固化产生任何不利影响，所得迈克尔加成固化涂层仍显示优异的粘附性。
根据本发明，pH小于6.0的聚醋酸乙烯酯的水性胶乳可以是商购的。作为所述聚醋酸乙烯酯的水性胶乳的实例，可以使用牌号为LS5042的聚醋酸乙烯酯的水性胶乳。
封闭剂v)：双组分水性聚氨酯涂层体系
在根据本发明的一个实施方式中，所述封闭剂包含双组分水性聚氨酯涂层体系。
根据本发明，双组分水性聚氨酯涂层体系包含：a)成膜树脂组合物，所述成膜树脂组合物包含含活泼氢聚合物的水性乳液；以及b)多异氰酸酯硬化剂。
术语“成膜树脂组合物”在本文中指构成由本发明的双组分水性聚氨酯涂层体系形成的封闭涂层的主体的树脂组合物，其可以包含含活泼氢聚合物的水性乳液以及任选的附加添加剂包括填料。
根据本发明，使用含活泼氢聚合物的水性乳液。已知的是，活泼氢 与异氰酸酯基团具有反应性，其可以由诸如-COOH、-OH、-SH、仲氨基和伯氨基的官能团来提供。此外，一些官能团，例如酯基(尤其是羧酸酯基)、硫醚基或酸酐基团(尤其是羧酸酐基团)可以例如通过水解转化成能够提供活泼氢的官能团。因此，本文所用的术语“含活泼氢聚合物”指本身含有能够提供活泼氢的官能团的任意聚合物和/或含有在水性封闭剂体系制备和/或应用期间能够转化成能提供活泼氢的官能团的任意聚合物。
根据本发明，含活泼氢聚合物的水性乳液被用于为成膜树脂组合物以及水性封闭剂体系提供树脂组分。一方面，这种树脂组分作为粘合剂，用于提供封闭涂层与基材的粘附性，并且使成膜树脂组合物中的各组分(诸如填料)保持在一起并赋予封闭涂层一定的内聚强度。另一方面，这种树脂组分与多异氰酸酯硬化剂具有良好的反应性，从而实现聚合链的交联，由此形成具有三维网络结构的封闭涂层。
以上树脂组分与多异氰酸酯硬化剂交联形成的封闭涂层具有阻隔水溶性单宁、油脂或其它不期望物质的能力，从而避免它们迁移和渗出。此外，由于形成三维网络结构，所以由本发明的水性聚氨酯涂层体系得到的封闭涂层还具有良好的物理、化学性能，诸如不发粘、高硬度、良好的耐水性、良好的耐溶剂性以及持久封闭效果。
在优选的实施方式中，所述含活泼氢聚合物包括醋酸乙烯酯-乙烯共聚物、醋酸乙烯酯-乙烯-(甲基)丙烯酸酯共聚物、醋酸乙烯酯-(甲基)丙烯酸酯共聚物、聚醋酸乙烯酯、聚乙烯醇或其任意组合中的一种或多种。在特别优选的实施方式中，所述含活泼氢聚合物可以是醋酸乙烯酯-乙烯共聚物。
优选地，所述成膜树脂组合物，相对于所述成膜树脂组合物的总重，包含约20重量％至约55重量％、优选约35重量％至约55重量％的含活泼氢聚合物的水性乳液。具体地，所述成膜树脂组合物，相对于所述成膜树脂组合物的总重，包含约25重量％、约30重量％、约35重量％、约40重量％、约45重量％或约50重量％的含活泼氢聚合物的水性乳液。
在本发明的优选实施方式中，所述含活泼氢聚合物的水性乳液的固体 含量在约20％至约60％的范围内，优选在约45％至约60％的范围内，其中所述固体含量被计算为所述含活泼氢聚合物的重量与所述含活泼氢聚合物和水的总重量的比值。具体地，所述含活泼氢聚合物的水性乳液的固体含量为约22.5％、约25.0％、约27.5％、约30.0％、约32.5％、约35.0％、约37.5％、约40.0％、约42.5％、约45.0％、约47.5％、约50.0％、约52.5％、约55.0％或约57.5％。在本发明的实施方式中，所述含活泼氢聚合物的水性乳液的pH值在约4.2至约8.0的范围内。
以上所公开的含活泼氢聚合物的水性乳液可以采用本领域普通技术人员所熟知的适当的乳液聚合方法制备。或者，作为含活泼氢聚合物的水性乳液的实例，可以使用任合适当的可商购产品，诸如德国Wacker Chemie AG的
Figure PCTCN2020071957-appb-000001
402和美国Celanese
Figure PCTCN2020071957-appb-000002
的Celvolit 1602。
本文使用的术语“多异氰酸酯硬化剂”指多异氰酸酯化合物、异氰酸酯低聚物或其组合。所述多异氰酸酯硬化剂含有两个或更多个异氰酸酯官能团，其能够与活泼氢聚合物发生扩链和交联反应，从而在封闭涂层中形成三维网络结构。
适当的多异氰酸酯硬化剂包括脂族多异氰酸酯、芳族多异氰酸酯或其任意组合。本文使用的术语“脂族多异氰酸酯”指异氰酸酯基直接连接到脂族链或环上的多异氰酸酯化合物。本文使用的术语“芳族多异氰酸酯”指异氰酸酯基直接连接到芳族环上的多异氰酸酯化合物。
作为适当的多异氰酸酯化合物的实例，可以使用六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、环己烷-1,4-二异氰酸酯、4,4’-二环已基甲烷二异氰酸酯、环戊烷-1,3-二异氰酸酯、对苯二异氰酸酯、甲苯-2,4-二异氰酸酯、萘-1,4-二异氰酸酯、联苯-4,4’-二异氰酸酯、苯-1,2,4-三异氰酸酯、二甲苯-l,4-二异氰酸酯、二甲苯-l,3-二异氰酸酯、二苯基甲烷二异氰酸酯、丁烷-1,2,3-三异氰酸酯或多亚甲基多苯基多异氰酸酯。
作为适当的异氰酸酯低聚物的实例，可以使用以上列举的任意多异氰酸酯化合物的聚氨酯型预聚物、以上列举的任意多异氰酸酯化合物的聚酯型预聚物或以上列举的任意多异氰酸酯化合物的聚醚型预聚物及其任意组合。聚氨酯型预聚物、聚酯型预聚物或聚醚型预聚物可以通过本领域普通 技术人员已知的任何适当方法制成。例如，聚氨酯型预聚物可以通过如下制成：使多元醇单体与多异氰酸酯化合物中的一种或多种在适当的条件下进行反应；聚酯型预聚物或聚醚型预聚物可以通过如下制成：使聚酯多元醇或聚醚多元醇与多异氰酸酯化合物中的一种或多种在适当的条件下进行反应。或者，作为聚氨酯型预聚物、聚酯型预聚物或聚醚型预聚物，可以使用任何适当的商品，例如购自Bayer，Germany的
Figure PCTCN2020071957-appb-000003
ME 120或
Figure PCTCN2020071957-appb-000004
ME 230。
在本发明的优选实施方式中，多异氰酸酯硬化剂可以是二苯基甲烷二异氰酸酯、多亚甲基多苯基多异氰酸酯、二苯基甲烷二异氰酸酯的聚酯型预聚物、二苯基甲烷二异氰酸酯的聚醚型预聚物或其任意组合。在本发明的进一步优选实施方式中，使用多亚甲基多苯基多异氰酸酯、二苯基甲烷二异氰酸酯的聚酯型预聚物或二苯基甲烷二异氰酸酯的聚醚型预聚物。
根据本发明，成膜树脂组合物与多异氰酸酯硬化剂的重量比可以在宽范围内变化。例如，多异氰酸酯硬化剂与成膜树脂组合物的重量比可以在3：100至20：100的范围内变化。一般而言，当多异氰酸酯硬化剂与成膜树脂组合物的重量比小于3：100时，对所得封闭涂层的封闭性能有限，无法获得足够的封闭效果。一般而言，当多异氰酸酯硬化剂与成膜树脂组合物的重量比大于20：100时，那么所得封闭体系的操作性能以及/或者所得封闭涂层的机械性质可能会下降。
根据本发明，上述封闭剂i)、ii)、iii)、iv)和v)可以以任何方式进行组合，以便形成适于涂覆木质基材表面的封闭剂。例如，可以将封闭剂i)和ii)进行组合，将封闭剂i和iii)进行组合，将封闭剂i)和v)进行组合，将封闭剂i)、ii)和iii)进行组合。
根据本发明，上述封闭剂可以任选地进一步包含常用在封闭剂中的附加添加剂，这些添加剂不会不利地影响封闭剂或由其得到的封闭涂层。适当的添加剂包括例如会改善封闭剂的加工性能或制造性能、或改善封闭剂组合物或由其得到的封闭涂层的特定功能性质或特性(诸如对基材的粘附性)的那些试剂。可以包含的附加添加剂例如是载剂(例如水)、乳化剂、颜料、填料、抗迁移助剂、防霉剂、防腐剂、扩链剂、润滑剂、润湿 剂、生物杀灭剂、增塑剂、消泡剂、着色剂、蜡、抗氧化剂、分散剂、粘着促进剂、UV稳定剂、增稠剂、消泡剂、pH调节剂、或其组合。各个可选成分的含量足以起到其意欲达到目的，但优选地，这样的含量不会不利地影响封闭剂或由其得到的封闭涂层。
根据本发明，所述封闭剂可以通过本领域普通技术人员已知的常规涂覆方法进行涂布。所述涂覆方法包括浸涂、旋涂、喷涂、帘涂、刷涂、辊涂以及本领域已知的其他涂覆方法。在本发明的一个实施方式中，利用喷涂工艺来实施涂覆。封闭剂可被涂成各种封闭涂层厚度。在本发明的实施方式中，封闭涂层厚度优选地在约5至约100μm的范围内，优选在20-80μm的范围内。可以通过使涂覆的涂层风干或通过使用本领域技术人员熟悉的各种干燥装置(例如，烘箱)加速固化来使其固化。
迈克尔加成固化涂层
在根据本发明的木制品中，可以在经由封闭涂层处理过的木质基材的表面上涂覆迈克尔加成固化涂层。迈克尔加成固化涂层可以直接涂覆到封闭涂层上，与封闭涂层直接接触。可供选择地，该迈克尔加成固化涂层和封闭涂层之间可以存在一种或多种着色剂层，从而获得想要的颜色。
如此形成的迈克尔加成固化涂层对木质基材显示非常优异的粘附性。优选地，根据本发明的木制品具有5B或更高的粘附性，所述粘附性是根据ASTM D3359采用划格法测定的。在根据本发明的迈克尔加成固化涂层的厚度具有30微米或更厚的实施方式中，所述木制品具有5B或更高的粘附性。在根据本发明的迈克尔加成固化涂层的厚度具有100微米或更厚的实施方式中，所述木制品具有5B或更高的粘附性。在根据本发明的迈克尔加成固化涂层的厚度具有200微米或更厚的实施方式中，所述木制品具有5B或更高的粘附性。
根据本发明，所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的。在本发明的一个实施方式中，所述双组分固化涂料组合物包含：
A)成膜树脂组合物，其包含a)具有至少两个在活化亚甲基或次甲基中的酸性质子C-H的第一反应性组分，b)具有至少两个活化的不饱和C＝ C基团的第二反应性组分，和c)任选的附加添加剂，选自溶剂、表面活性剂、UV吸收剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种；和
B)用于催化所述成膜树脂组合物发生迈克尔加成交联反应的催化剂。
US5084536,US5565525,EP2556108和EP2764035详细地描述了成膜树脂组合物、催化剂及迈克尔加成固化涂层的制备方法。除非另有说明，上述专利申请描述的内容通过引用并入本文并且在本文中可适用。
根据本发明的一种实施方式，第一反应性组分具有丙二酸酯或乙酰乙酸酯官能团作为第一反应性官能团，优选主要具有丙二酸酯官能团。优选地，第一反应性组分主要包含一种类型的第一反应性官能团，优选大于50、75、90并且最优选100％的第一反应性官能团来自一种类型的第一反应性官能团，优选地来自丙二酸酯或乙酰乙酸酯，最优选地来自丙二酸酯。根据本发明，第二反应性组分具有丙烯酰基作为第二反应性官能团。
第一反应性组分和第二反应性组分中的第一反应性官能团和第二反应性官能团优选构建在聚合物主链中或悬挂在聚合物主链上的侧链或末端。优选地，第一反应性组分和第二反应性组分分别是在其主链、侧链、末端或其组合中具有第一反应性官能团和第二反应性官能团的聚酯、醇酸树脂、聚氨酯、聚丙烯酸酯、环氧树脂、聚酰胺和聚乙烯基树脂的组。
第一反应性组分和第二反应性组分可以是单体的，但至少一种，优选至少两种反应性组分是重均分子量(Mw)至少为250g/mol的聚合物，优选Mw为在250、300与5000之间，更优选为在400与4000或500与3000g/mol之间的聚合物，所述重均分子量是通过GPC测定的。
选择第一反应性组分和第二反应性组分的相对量，使得第二反应性组分中的活化的不饱和反应性基团C＝C与第一反应性组分中的活化的酸性反应性基团C-H的摩尔比为在0.5与2之间，并且优选地在0.75与1.5之间，更优选地，在0.8与1.2之间。
所述第一反应性组分和第二反应性组分均是可商购的，例如商购自Allnex resin的Acure 510-170，固含量为85％作为第一反应性组分，商购自Allnex resin的Acure 550-100，固含量为85％作为第二反应性组分。
在根据本发明的双组分固化涂料组合物中，成膜树脂组合物可以任选地包含一种或多种填料。本文使用的术语“填料”指适用于涂料的任何体积增量剂，其可以是有机的或无机的例如颗粒形式。对颗粒的形状没有特殊限制，其可以具有任何适当的形状。填料的平均粒径可以在宽范围内变化，例如在约10纳米至约50微米的范围内变化。一些填料除了起到涂料的体积增量剂的作用以外还赋予组合物和/或由该组合物形成的涂层一种或多种所需性质。例如，一些填料可以赋予组合物以及由该组合物得到的涂层所需颜色。在这种情况下，这种填料也被称为“颜料”。一些填料可以改善化学和/或物理性质，特别可以改善由该组合物得到的涂层的机械性质。在这种情况下，这种填料也被称为“增强填料”。
在根据本发明的双组分固化涂料组合物中，成膜树脂组合物还可以任选地进一步包含常用在涂料组合物中的其它附加添加剂，这些添加剂不会不利地影响涂层组合物或由其得到的固化涂层。适当的添加剂包括例如会改善组合物的加工性能或制造性能、增强组合物的美感、或改善涂层组合物或由其得到的固化组合物的特定功能性质或特性(诸如对基材的粘附性)的那些试剂。可以包含的添加剂例如选自溶剂、表面活性剂、UV吸收剂、消泡剂、分散剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种。各个可选成分的含量足以起到其意欲达到目的，但优选地，这样的含量不会不利地影响涂层组合物或由其得到的固化涂层。
在根据本发明的双组分固化涂料组合物中，催化剂可以是非潜伏型催化剂，也可以是潜伏型催化剂。其中，潜伏型催化剂可以是二氧化碳封端的强碱催化剂，优选二烷基或烷基碳酸季烷基铵(如EP2556108中所述的)。由于该催化剂产生二氧化碳，因此其优选用于厚度达500、400、300、200或150微米的涂层中。
EP0326723中描述了更适合较厚涂层的均相碱催化剂，其是由叔胺和环氧化物的组合组成的催化剂。优选的均相催化剂是来自含酸性X-H基团的化合物的碱性阴离子X-的盐，其中X是N、P、O、S或C，其中阴离子X-是与第二反应性组分可反应的迈克尔加成供体，并且其中阴离子X-的特征在于，相应的酸X-H的pKa值比大多数第一反应性组分的pKa值 低两个以上单位，且低于10.5。该催化剂的细节描述于PCT/EP2014/056953中，其通过引用并入本文。
优选地，根据本发明，催化剂与成膜树脂组合物的重量比可以在2：100至8：100的范围内变化。一般而言，当催化剂与成膜树脂组合物的重量比小于2：100时，所得涂层的固化性能不良。一般而言，当催化剂与成膜树脂组合物的重量比大于8：100时，那么所得迈克尔加成固化涂层的操作性能以及/或者所得涂层的机械性质可能会下降。根据实际需要，可以在催化剂和/或成膜树脂组合物的制备期间添加额外的不会对以上催化剂和成膜树脂组合物的反应性造成影响的惰性稀释剂，以例如降低各组分的粘度。因而，催化剂与成膜树脂组合物的重量比并不局限于上述范围，可以根据实际需要调整。
根据本发明，双组分固化涂料组合物可以通过如下制备：应用前，将成膜树脂组合物与催化剂以预定重量比在混合装置中进行简单混合。混合的固化涂料组合物可使用本领域技术人员熟悉的各种方法来涂覆，包括喷涂(例如，空气辅助、无空气或静电喷涂)、刷涂、辊涂、溢涂和浸渍。在本发明的一个实施方式中，混合的固化涂料组合物通过喷涂来进行涂覆。固化涂料组合物可被涂成各种湿膜厚度。在本发明的实施方式中，湿膜厚度优选地在约2至约260μm的范围内，优选在30-260μm的范围内。可以通过使涂覆的涂层风干或通过使用本领域技术人员熟悉的各种干燥装置(例如，烘箱)加速固化来使其固化。
根据本发明，所述木制品可以例如通过如下步骤制备：(1)提供经打磨的木质基材；(2)利用喷涂工艺，将本发明的封闭剂涂覆到木质基材上，从而形成封闭涂层；(3)利用湿对干涂覆工艺，在所述封闭涂层上依次涂覆一个或多个迈克尔加成固化涂层。可选地，可以在步骤(3)之前将着色剂涂覆在封闭涂层上，从而为木质基材提供所需的颜色。
根据本发明，由此得到的木制品可用于如下应用，包括，但不限于：家用家具，例如桌子、椅子、橱柜等；卧室和浴室家具；办公家具；定制家具，例如学校和儿童家具、医院家具、餐厅和酒店家具、厨房橱柜和家具；室内设计用的板；室内和室外的窗户和门；室内和室外的窗框和门 框；室外和室内的护墙板以及木地板。
本发明的另一方面提供了用于提高迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性的方法，所述方法包括将封闭涂层涂覆在所述木质基材的至少一个主表面上的步骤，其中，所述封闭涂层是由封闭剂形成的，所述封闭剂选自聚氨酯丙烯酸类聚合物共聚物的水性胶乳、羧基官能化的可自交联丙烯酸类聚合物的水性胶乳、阳离子性丙烯酸类聚合物的水性胶乳、聚醋酸乙烯酯水性胶乳和双组分水性聚氨酯涂层体系中的一种或多种，并且；并且其中，所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的，所述双组分固化涂料组合物包含：
A)成膜树脂组合物，其包含a)具有至少两个在活化亚甲基或次甲基中的酸性质子C-H的第一反应性组分，b)具有至少两个活化的不饱和C＝C基团的第二反应性组分，和c)任选的附加添加剂，选自溶剂、填料、表面活性剂、消泡剂、分散剂、UV吸收剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种；和
B)用于催化所述成膜树脂组合物发生迈克尔加成交联反应的催化剂。
本发明的还要另一方面提供了封闭涂层用于提高迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性的用途，其中，所述封闭涂层是由封闭剂形成的，所述封闭剂选自聚氨酯丙烯酸类聚合物共聚物的水性胶乳、羧基官能化的可自交联丙烯酸类聚合物的水性胶乳、阳离子性丙烯酸类聚合物的水性胶乳、聚醋酸乙烯酯水性胶乳和双组分水性聚氨酯涂层体系中的一种或多种；并且其中，所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的，所述双组分固化涂料组合物包含：
A)成膜树脂组合物，其包含a)具有至少两个在活化亚甲基或次甲基中的酸性质子C-H的第一反应性组分，b)具有至少两个活化的不饱和C＝C基团的第二反应性组分，和c)任选的附加添加剂，选自溶剂、填料、表面活性剂、消泡剂、分散剂、UV吸收剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种；和
B)用于催化所述成膜树脂组合物发生迈克尔加成交联反应的催化 剂。
这种封闭涂层可以涂覆到各种含有酸性物质的木质基材上，解决了迈克尔加成固化涂层难以粘附到木质基材上的问题。由此处理过的木质基材适用于各种应用，包括，但不限于：家用家具，例如桌子、椅子、橱柜等；卧室和浴室家具；办公家具；定制家具，例如学校和儿童家具、医院家具、餐厅和酒店家具、厨房橱柜和家具；室内设计用的板；室内和室外的窗户和门；室内和室外的窗框和门框；室外和室内的护墙板以及木地板。
下述实施例更具体地描述了本发明公开的内容，这些实施例仅仅用于阐述性说明，因为在本发明公开内容的范围内进行各种修正和变化对本领域技术人员来说是明显的。除非另有声明，以下实施例中所报道的所有份、百分比、和比值都是基于重量计，而且实施例中使用的所有试剂都可商购并且可直接使用而无需进一步处理。
实施例
实施例1
处理木质基材
将购自木材市场的实木板进行窑炉干燥。从烘干的板材上截取尺寸为15厘米*15厘米*1.5厘米的样本，并将其置于温度为25℃、相对湿度(RH)为60％且空气流速为1.8m/s的条件下调节至恒重，其中该样品的平衡水分含量为11％。采用条式打磨机，通过购自3M T Utility Cloth Sheet 240号砂纸打磨样品，并用气压枪进行清洁，备用。
形成封闭涂层
在经处理的样品上喷涂各种封闭剂，从而形成封闭涂层，并在空气干燥1小时，在70℃的烘箱中1小时，并且空气中干燥7天。
形成迈克尔加成固化涂层
将下表1所示用量的组分A的各组分混合，从而形成组分A，然后将组分A、组分B以及适量稀释剂以下表2所示用量进行混合，从而形成适 用于形成迈克尔加成固化涂层的双组分涂料组合物。
表1：
Figure PCTCN2020071957-appb-000005
表2
Figure PCTCN2020071957-appb-000006
然后，将所形成的涂料组合物喷涂到经由各种不同的封闭涂层处理的木质基材上，并测定所得涂层的粘附性，结果示于下表3中。
表3
Figure PCTCN2020071957-appb-000007
由上表结果可见，根据本发明的聚氨酯丙烯酸类聚合物的水性胶乳、 羧基官能化的可自交联丙烯酸类聚合物的水性胶乳、阳离子性丙烯酸类聚合物的水性胶乳、聚醋酸乙烯酯水性胶乳和双组分水性聚氨酯涂层体系形成的封闭体系特异性地提高了迈克尔加成固化涂层对含有酸性物质如单宁的木质基材的粘附性，这在本申请之前难以预期。
实施例2
为了寻找迈克尔加成固化涂层在木质基材上的粘附性较差的原因，发明人实施了如下验证试验。首先，配制浓度分别为0％、1％、5％、10％和15％的单宁水溶液。然后，将各个水溶液分别喷涂到松木样板上，并在空气中干燥30分钟，在50的烘箱中2小时，接着冷却。
然后，将以上实施例1所配制的用于形成迈克尔加成固化涂层的清漆以120微米的湿膜厚度涂覆到经处理的木质上，并在空气中干燥4天，然后测试。测试结果汇总在下表4中。
表4.
测试样 粘附性 干燥时间(min) 铅笔硬度
经0％单宁水溶液涂覆的样板 4B 35 B
1％单宁水溶液涂覆的样板 4B 40 2B
5％单宁水溶液涂覆的样板 2B 51 2B
10％单宁水溶液涂覆的样板 0B 81 2B
15％单宁水溶液涂覆的样板 0B 90 2B
由上表4结果可见，木质基材中的单宁会影响迈克尔加成固化涂层的粘附问题，导致划格粘附性显著下降，并且导致干燥时间延长。在本发明之前，还未有现有技术揭示木质基材中单宁的存在是导致迈克尔加成固化涂层在木质基材上的粘附问题的根本原因。
尽管本发明参照大量实施方式和实施例进行描述，但是本领域普通技术人员根据本发明公开的内容能够认识到可以设计其它实施方式，这并未脱离本发明的保护范围和精神。

Claims (14)

  1. 一种木制品，其包含
    含有酸性物质的木质基材，其具有至少一个主表面；
    涂覆在所述木质基材的主表面上的封闭涂层；和
    涂覆在所述封闭涂层上的迈克尔加成固化涂层，
    其中，所述封闭涂层是由封闭剂形成的，所述封闭剂包含聚氨酯丙烯酸类聚合物的水性胶乳、羧基官能化的可自交联丙烯酸类聚合物的水性胶乳、阳离子性丙烯酸类聚合物的水性胶乳、聚醋酸乙烯酯的水性胶乳和双组分水性聚氨酯涂层体系中的一种或多种；并且其中所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的。
  2. 如权利要求1所述的木制品，其中，所述聚氨酯丙烯酸类聚合物的水性胶乳是在聚氨酯水性分散体的存在下通过丙烯酸类单体的自由基聚合形成的。
  3. 如权利要求1所述的木制品，其中，所述羧基官能化的可自交联丙烯酸类聚合物的水性胶乳包含相对于羧基官能化的可自交联丙烯酸类聚合物的重量0.1-5wt％量的羧基。
  4. 如权利要求1所述的木制品，其中，所述阳离子性丙烯酸类聚合物的水性胶乳具有6.0或更小的pH，优选具有4.2-5.2的pH。
  5. 如权利要求1所述的木制品，其中，所述聚醋酸乙烯酯水性胶乳具有6.0或更小的pH，优选具有4.0-5.0的pH。
  6. 如权利要求1所述的木制品，其中，所述封闭涂层的厚度为在5-100微米范围内。
  7. 如权利要求1所述的木制品，其中，所述酸性物质包括单宁，所述木质基材具有至少0.1wt％的单宁含量，优选具有至少1wt％的单宁含量，更优选具有至少5wt％的单宁含量，甚至更优选至少10wt％的单宁含量，还要更优选具有至少30wt％的单宁含量，所述单宁含量是通过标准CNS4716-2005测定的。
  8. 如权利要求1所述的木制品，其中，所述木质基材选自坚木、栗 木、栎木、红钩栗、油茶、按木、花旗松、日本柳杉、美国扁柏、日本赤松、日本扁柏、水胡桃、黑胡桃、槭木、日本山毛榉、日本泡桐、桦木、婆罗双、木兰、白蜡树、柚木、柞木、楸木、山樟木、杉木、胡桃木、橡木和橡胶木中的一种或多种。
  9. 如权利要求1所述的木制品，其中，所述双组分固化涂料组合物包含：
    A)成膜树脂组合物，其包含a)具有至少两个在活化亚甲基或次甲基中的酸性质子C-H的第一反应性组分，b)具有至少两个活化的不饱和C＝C基团的第二反应性组分，和c)任选的附加添加剂，选自填料、溶剂、表面活性剂、消泡剂、分散剂、UV吸收剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种；和
    B)用于催化所述成膜树脂组合物发生迈克尔加成反应的催化剂。
  10. 根据权利要求9所述的木制品，其中，所述成膜树脂组合物与所述催化剂的重量比在100:2-100:8的范围内。
  11. 如权利要求1所述的木制品，其中，所述迈克尔加成固化涂层具有30微米或更厚的厚度，优选具有100微米或更厚的厚度。
  12. 如权利要求1所述的木制品，其具有4B或更高的粘附性，所述粘附性是根据ASTM D3359采用划格法测定的。
  13. 一种用于制备权利要求1-12中任意一项所述木制品的方法，包括如下步骤：
    (a)提供含有酸性物质的木质基材，其具有至少一个主表面；
    (b)在所述木制基材的主表面上涂覆所述封闭剂以形成封闭涂层；和
    (c)在所述封闭涂层上涂覆所述双组分固化涂料组合物以形成迈克尔加成固化涂层。
  14. 封闭涂层用于提高迈克尔加成固化涂层对含有酸性物质的木质基材的粘附性的用途，
    其中，所述封闭涂层是由封闭剂形成的，所述封闭剂选自聚氨酯丙烯酸类聚合物共聚物的水性胶乳、羧基官能化的可自交联丙烯酸类聚合物的 水性胶乳、阳离子性丙烯酸类聚合物的水性胶乳、聚醋酸乙烯酯水性胶乳和双组分水性聚氨酯涂层体系中的一种或多种，并且
    其中，所述迈克尔加成固化涂层是由双组分固化涂料组合物形成的，所述双组分固化涂料组合物包含：
    A)成膜树脂组合物，其包含a)具有至少两个在活化亚甲基或次甲基中的酸性质子C-H的第一反应性组分，b)具有至少两个活化的不饱和C＝C基团的第二反应性组分，和c)任选的附加添加剂，选自填料、溶剂、表面活性剂、消泡剂、分散剂、UV吸收剂、交联延缓剂、防腐剂和杀菌剂中的一种或多种；和
    B)用于催化所述成膜树脂组合物发生迈克尔加成反应的催化剂。
PCT/CN2020/071957 2019-01-29 2020-01-14 木制品及其制备方法 WO2020156145A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20748014.6A EP3919188A4 (en) 2019-01-29 2020-01-14 WOODEN PRODUCT AND ASSOCIATED PREPARATION METHOD
US17/424,233 US20220025202A1 (en) 2019-01-29 2020-01-14 Wood article and process for the preparation of the wood article

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910085770.3 2019-01-29
CN201910085770.3A CN109877025B (zh) 2019-01-29 2019-01-29 木制品及其制备方法

Publications (1)

Publication Number Publication Date
WO2020156145A1 true WO2020156145A1 (zh) 2020-08-06

Family

ID=66927324

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/071957 WO2020156145A1 (zh) 2019-01-29 2020-01-14 木制品及其制备方法

Country Status (4)

Country Link
US (1) US20220025202A1 (zh)
EP (1) EP3919188A4 (zh)
CN (1) CN109877025B (zh)
WO (1) WO2020156145A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113549388A (zh) * 2021-07-02 2021-10-26 珠海展辰新材料股份有限公司 水性单组份封闭底漆涂料及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109877025B (zh) * 2019-01-29 2022-04-26 广东华润涂料有限公司 木制品及其制备方法
CN112358786A (zh) * 2020-11-30 2021-02-12 上海展辰涂料有限公司 一种防渗色水性封闭底漆及其制备方法
CN115466532B (zh) * 2021-06-10 2023-05-02 广东华润涂料有限公司 可迈克尔加成固化的组合物、包含该组合物的涂料组合物以及涂布制品
CN115491115A (zh) * 2022-10-13 2022-12-20 上海展辰涂料有限公司 一种用于静电涂装的水性双组分石墨烯实色漆

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0326723A1 (en) 1988-02-01 1989-08-09 Rohm And Haas Company Method for reacting two components, compositions, coating compositions and uses thereof
US5084536A (en) 1984-04-04 1992-01-28 Hoechst Ag Reaction product of olefinically unsaturated compounds with compounds containing active hydrogen, processes for their preparation and 2-component lacquers based thereon
US5565525A (en) 1993-10-27 1996-10-15 Nippon Paint Co., Ltd. Unsaturated carbonyl and active hydrogen components with onium salt and epoxy compound
CN101712174A (zh) * 2009-02-19 2010-05-26 潘学扬 一种木制品的表面涂装方法
CN102115630A (zh) * 2009-12-31 2011-07-06 广东华润涂料有限公司 水性封闭剂体系、木制品以及封闭木质基材的方法
EP2556108A1 (en) 2010-04-07 2013-02-13 Nuplex Resins B.V. Crosslinkable composition crosslinkable with a latent base catalyst
EP2764035A1 (en) 2011-10-07 2014-08-13 Nuplex Resins B.V. Crosslinkable composition
CN107660228A (zh) * 2015-04-17 2018-02-02 欧尼克斯荷兰有限公司 用于固化rma可交联树脂涂层的方法、其中使用的rma可交联组合物和树脂
CN109877025A (zh) * 2019-01-29 2019-06-14 广东华润涂料有限公司 木制品及其制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050245636A1 (en) * 2004-04-29 2005-11-03 Ashland Inc. Radiation-curable coatings for wood substrates from multifunctional acrylate oligomers
US20060177649A1 (en) * 2005-02-07 2006-08-10 Clark Mark D Methods of blocking stains on a substrate to be painted, and composites suitable for use in such methods
CN105694644A (zh) * 2014-11-27 2016-06-22 合众（佛山）化工有限公司 一种抗渗色阳离子丙烯酸酯乳液的制备方法
AU2016247589B2 (en) * 2015-04-17 2020-10-29 Allnex Netherlands B.V. Floor coating compositions
AU2019212991B2 (en) * 2018-01-26 2024-05-23 Allnex Netherlands B.V. Powder coating composition
CN108485510A (zh) * 2018-05-02 2018-09-04 广东海顺新材料科技有限公司 一种木器用单组份自干水性封闭剂及其制备方法
CA3052694A1 (en) * 2018-09-11 2020-03-11 Ivm Chemicals S.R.L. Insulating composition and kit comprising such composition
CN110240821B (zh) * 2019-05-07 2021-04-02 广东华润涂料有限公司 木器用涂料组合物以及由其制成的木制品

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5084536A (en) 1984-04-04 1992-01-28 Hoechst Ag Reaction product of olefinically unsaturated compounds with compounds containing active hydrogen, processes for their preparation and 2-component lacquers based thereon
EP0326723A1 (en) 1988-02-01 1989-08-09 Rohm And Haas Company Method for reacting two components, compositions, coating compositions and uses thereof
US5565525A (en) 1993-10-27 1996-10-15 Nippon Paint Co., Ltd. Unsaturated carbonyl and active hydrogen components with onium salt and epoxy compound
CN101712174A (zh) * 2009-02-19 2010-05-26 潘学扬 一种木制品的表面涂装方法
CN102115630A (zh) * 2009-12-31 2011-07-06 广东华润涂料有限公司 水性封闭剂体系、木制品以及封闭木质基材的方法
EP2556108A1 (en) 2010-04-07 2013-02-13 Nuplex Resins B.V. Crosslinkable composition crosslinkable with a latent base catalyst
EP2764035A1 (en) 2011-10-07 2014-08-13 Nuplex Resins B.V. Crosslinkable composition
CN107660228A (zh) * 2015-04-17 2018-02-02 欧尼克斯荷兰有限公司 用于固化rma可交联树脂涂层的方法、其中使用的rma可交联组合物和树脂
CN109877025A (zh) * 2019-01-29 2019-06-14 广东华润涂料有限公司 木制品及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3919188A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113549388A (zh) * 2021-07-02 2021-10-26 珠海展辰新材料股份有限公司 水性单组份封闭底漆涂料及其制备方法

Also Published As

Publication number Publication date
EP3919188A4 (en) 2022-10-19
CN109877025A (zh) 2019-06-14
EP3919188A1 (en) 2021-12-08
US20220025202A1 (en) 2022-01-27
CN109877025B (zh) 2022-04-26

Similar Documents

Publication Publication Date Title
WO2020156145A1 (zh) 木制品及其制备方法
CN111303747B (zh) 双组份涂料组合物以及由其制成的制品
EP3720914B1 (en) Aqueous coating compositions for forming anti-grain-puffing coatings on wood substrate, aqueous paints and articles
WO2020224519A1 (zh) 涂料组合物以及由其制成的木制品
WO2020224523A1 (zh) 涂料组合物以及由其制成的木制品
EP3919189B1 (en) Wood product and preparation method therefor
EP3783070A1 (en) A waterborne white-base coating
EP4347719A1 (en) Two-component aqueous sealing primer for wood substrate, sealing coating formed thereof and article
EP4208512A1 (en) A coating composition, an article made thereof and a process for preparing the same
CN113652132B (zh) 木器用封闭底漆及由其制成的木制品
WO2010037866A1 (de) Wässriger lack zur reduktion der formaldehydemission aus holzwerkstoffen
CN110000882B (zh) 偏氯乙烯/丙烯酸/氯乙烯三元共聚物的水性分散体在木质基材中作为防渗涂层的应用
CN112126330A (zh) 一种水性白漆
CN111423796B (zh) 双组份修色剂以及由其制成的制品
WO2022105603A1 (en) Sealing primer for woodware and article containing the sealing primer layer formed by the sealing primer
WO2023155693A1 (en) Two-component aqueous coating composition, and coated article made therefrom
WO2024023705A1 (en) Water-based coating composition and use thereof
JPS61215608A (ja) 塗装家具

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20748014

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2020748014

Country of ref document: EP

Effective date: 20210830