WO2020224523A1 - 涂料组合物以及由其制成的木制品 - Google Patents

涂料组合物以及由其制成的木制品 Download PDF

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WO2020224523A1
WO2020224523A1 PCT/CN2020/088163 CN2020088163W WO2020224523A1 WO 2020224523 A1 WO2020224523 A1 WO 2020224523A1 CN 2020088163 W CN2020088163 W CN 2020088163W WO 2020224523 A1 WO2020224523 A1 WO 2020224523A1
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reactive
coating composition
coating
present
donor
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PCT/CN2020/088163
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English (en)
French (fr)
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牛松
陈宏彬
范世刚
赵熙
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广东华润涂料有限公司
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Priority to US17/608,187 priority Critical patent/US20220064455A1/en
Priority to EP20801548.7A priority patent/EP3967733A4/en
Publication of WO2020224523A1 publication Critical patent/WO2020224523A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • 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
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; 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
    • 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
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • B05D2203/00—Other substrates
    • B05D2203/20—Wood or similar material
    • 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
    • B05D2502/00—Acrylic polymers
    • 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
    • B05D2504/00—Epoxy polymers
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B05D3/0272—After-treatment with ovens
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0406—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being air
    • 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
    • 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
    • C08G2150/00—Compositions for coatings
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings

Definitions

  • the present invention relates to a coating composition for woodware and wood products made therefrom. More specifically, the present invention relates to a coating composition for woodware that is cured by Michael addition reaction and wood products made therefrom.
  • PCDI polycarbodiimide
  • Michael addition curing has achieved great success.
  • the commercial company Allnex has carried out a large number of commercial promotion and called it "Acure" technology.
  • this coating system has many advantages, including (1) it can be applied at room temperature or even lower temperature; (2) the solvent content is very low (for example, less than 250g/L); (3) activation Very long period (for example, more than 8 hours at 23°C); (3) Excellent appearance properties (for example, gloss at 60° is greater than 90, DOI is greater than 90); (5) Thick layer coating (>150 ⁇ m) ; (6) Very good chemical resistance; (7) Excellent flexibility; (8) Good outdoor durability; and (9) Free from isocyanate, formaldehyde and organotin. Therefore, the market demand for this Michael addition curing coating system is strong. However, the application of this system on wood substrates is not satisfactory. The hardness of the dry coating film cured at room temperature using this Acure curing technology is far lower than that of the traditional two-component polyurethane coating, which cannot meet the application requirements.
  • One aspect of the present invention discloses a coating composition
  • a coating composition comprising:
  • a film-forming resin composition including a reactive donor capable of providing two or more nucleophilic carbanions, and a reactive acceptor containing two carbon-carbon double bond groups;
  • At least one of the reactive acceptor and the reactive donor contains an aromatic ring structure, and the polymer formed by homopolymerization of the reactive acceptor has a Tg of 100°C or higher, and Tg is measured by, for example, differential scanning calorimetry.
  • the reactive receptor can be selected from one or more of the ⁇ , ⁇ -unsaturated carboxylic acid esters represented by the following formula:
  • Another aspect of the present invention also provides a wood product, which comprises a wood substrate, which has at least one major surface; and a cured coating, the cured coating is directly or indirectly coated on the major surface
  • the coating composition of the present invention is formed.
  • the applicant pioneered the design of at least one of the reactive acceptor or donor in the Michael addition curing system containing an aromatic ring structure, and designed to use a bifunctionality (that is, containing two carbons) with a Tg greater than 100°C. Carbon double bond group) reactive acceptor, the cured coating thus obtained can obtain a coating hardness comparable to that of a traditional two-component polyurethane coating.
  • the inventors of the present invention surprisingly discovered that the introduction of an aromatic ring structure in at least one of the reactive acceptor or the reactive donor can significantly increase the hardness of the cured coating.
  • the inventors of the present invention are more surprised to find that a cured coating formed by using a bifunctional reactive receptor with a Tg greater than 100°C is better than using other trifunctional and tetrafunctional reactive receptors (including Tg greater than 100°C).
  • the cured coating formed by the three-functionality and four-functionality reactive acceptor) has a significantly higher hardness, which has never been recognized before the present invention.
  • composition is 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 consist of or consist of the involved components, or Where 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 may 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 numerical value can be used as its own lower limit or upper limit in combination with any other point or single numerical value or in combination with other lower or upper limits to form an unspecified range.
  • Michael addition refers to the nucleophilic addition reaction between the carbanion in the reactive donor and the carbon-carbon double bond in the reactive acceptor.
  • the Michael addition reaction usually follows the following reaction mechanism:
  • B is a catalyst, which reacts with the Michael addition reactive donor through deprotonation to form a carbanion for subsequent addition reaction with the Michael addition reactive acceptor.
  • carbon-carbon double bond group refers to a structure containing a carbon-carbon double bond in the molecule, but does not include a benzene ring.
  • nucleophilic carbanion refers to a reactive intermediate of carbon with two or three strong electronegative groups attached and a pair of lone pairs of electrons.
  • the nucleophilic carbanion is derived from the acidic proton CH in the activated methylene or methine group.
  • aromatic ring structure refers to a rigid closed aromatic ring or ring system, which is different from flexible alkanes or cycloalkyls such as cyclohexyl.
  • aromatic ring structure include, but are not limited to, phenylene, naphthylene, biphenylene, fluorenylene, and indenyl, and heteroarylene (such as closed aromatic or aromatic cyclic hydrocarbon or ring A system in which one or more atoms in the ring are elements other than carbon (such as nitrogen, oxygen, sulfur, etc.).
  • glass transition temperature (Tg) refers to the glass transition temperature of a homopolymer formed by homopolymerization of the reactive acceptor molecule, which is, for example, the use of differential scanning Measured by calorimetry.
  • glass transition temperature (Tg) refers to the glass transition temperature of the reactive donor itself, which is measured by differential scanning calorimetry, for example.
  • EW Epoxy Equivalent Weight
  • the term “Epoxy Equivalent Weight (EEW)” refers to the mass of the reactive donor containing 1 mol of epoxy groups.
  • the epoxy equivalent refers to the mass of the acetoacetate esterified epoxy containing 1 mol of epoxy groups.
  • the lower the epoxy equivalent the more epoxy groups contained in the reactive donor, and the higher the reactivity.
  • major surface is the surface formed by the length and width dimensions of the wooden substrate to provide decoration.
  • the term “on” includes that the coating composition is directly or indirectly coated on the main surface of the substrate.
  • the coating composition according to the present invention is directly coated on the main surface of the wood substrate without adhesion problems.
  • one or more adhesion promoting layers may be present between the coating composition according to the present invention and the wood substrate, so as to obtain the desired adhesion.
  • volatile organic compound refers to any carbon-containing compound that participates in atmospheric photochemical reactions except for carbon monoxide, carbon dioxide, carbonic acid, metal carbides or carbonates. Generally, volatile organic compounds have a vapor pressure of 0.1 mm Hg or higher. As used herein, “volatile organic compound content (VOC content)” refers to the weight of VOC per volume of paint solids, for example, it is reported as g/liter.
  • Figure 1 shows the hardness and VOC comparison results of cured coatings formed by various Michael addition cured varnishes, where the coating thickness is 100 microns or 200 microns.
  • the varnish includes a coating composition formed by three different epoxy equivalent reactive donors (A1, A2 and A3) and a bifunctional reactive acceptor (B4) with a Tg of 180°C, and the same three reactions
  • the coating composition is formulated with a sex donor and trifunctional or tetrafunctional reactive acceptors (B1, B2 and B3) with Tg of 62°C, 98°C and 103°C.
  • FIG. 2 shows the hardness and VOC comparison results of the cured coating formed by Michael addition curing varnishes containing various bifunctional reactive acceptors with different Tg and conventional two-component polyurethane paints, wherein the coating thickness It is 100 microns or 200 microns.
  • the bifunctional reactive receptors respectively include the bifunctional reactive receptor B7 with a Tg of 62°C, the bifunctional reactive receptor B5 with a Tg of 104°C, and the bifunctional reactive receptor with a Tg of 180°C.
  • Body B4 and bifunctional reactive receptor B6 with a Tg of 107°C.
  • One aspect of the present invention provides a coating composition for woodware, comprising: (A) a film-forming resin composition, including a reactive donor capable of providing two or more nucleophilic carbanions, and two carbon-carbon A reactive acceptor of a double bond group; and (B) a catalyst for catalyzing the Michael addition crosslinking reaction between the reactive donor and the reactive acceptor, wherein the reactive acceptor and the reactive acceptor At least one of the reactive donors includes an aromatic ring structure, and the polymer formed by homopolymerization of the reactive acceptor has a Tg of 100°C or higher.
  • film-forming resin composition refers to the resin composition constituting the main body of the coating formed by the woodware coating composition of the present invention, which may include a reaction capable of providing two or more nucleophilic carbanions Sex donors, reactive acceptors containing carbon-carbon double bond groups, solvents, and optional additional additives.
  • At least one of the reactive acceptor and the reactive donor includes an aromatic ring structure.
  • the aromatic ring structure has a rigid structure, which is different from flexible alkanes or cycloalkyl groups such as cyclohexyl.
  • the inventors of the present invention surprisingly found that the Michael addition cured coating containing this aromatic ring structure showed improvement compared to the Michael addition cured coating with flexible alkyl or cycloalkyl (for example, from Allnex Acure cured coating) The hardness of the coating.
  • the reactive receptor comprises an aromatic ring structure.
  • the reactive donor comprises an aromatic ring structure.
  • both the reactive acceptor and the reactive donor comprise aromatic ring structures.
  • the film-forming resin composition includes a reactive acceptor containing two carbon-carbon double bond groups.
  • a reactive acceptor containing two carbon-carbon double bond groups the higher the functionality of the reactant, the higher the crosslink density of the cured coating, and the higher the hardness of the coating.
  • the inventors of the present invention surprisingly found that, compared to reactive acceptors containing more than two carbon-carbon double bond groups, for example, reactive acceptors containing three or four carbon-carbon double bond groups, two The reactive acceptor of a carbon-carbon double bond group is more beneficial to increase the hardness of the cured coating in the Michael addition curing system. Therefore, reactive acceptors containing more than two carbon-carbon double bond groups are not included in the scope of the present invention.
  • the glass transition temperature of the reactive receptor is also an important parameter that affects the hardness of the cured coating.
  • the reactive acceptor has a glass transition temperature of 100°C or higher, preferably a glass transition temperature of 101°C or higher, and more preferably a glass transition temperature of 102°C or higher The temperature is still more preferably a glass transition temperature of 103°C or higher, but the glass transition temperature of the reactive acceptor should not be too high. If the glass transition temperature of the reactive acceptor is too high, it may adversely affect the degree of crosslinking of Michael addition curing, thereby affecting the hardness of the resulting cured coating.
  • the glass transition temperature of the reactive acceptor does not exceed 200°C, preferably does not exceed 195°C, and more preferably does not exceed 190°C.
  • the glass transition temperature of the reactive acceptor is in the range of 100-190°C, preferably in the range of 104-180°C.
  • the reactive receptor has a relatively low molecular weight and usually exists in a non-polymer form.
  • the reactive acceptor has a molar mass of 1000 g/mol or lower, preferably a molar mass of 500 g/mol or lower, and more preferably a molar mass of 350 g/mol or lower.
  • the carbon-carbon double bond group contained in the reactive acceptor generally has the structure shown in the following formula I:
  • CX represents any one of an alkenyl group, an alkynyl group, an aldehyde group (-CHO), a keto group (-CO-), an ester group (-C(O)O-), and a cyano group (-CN).
  • the carbon-carbon double bond group is derived from one or more of ⁇ , ⁇ -unsaturated aldehyde, ⁇ , ⁇ -unsaturated ketone, ⁇ , ⁇ -unsaturated carboxylic acid ester and ⁇ , ⁇ -unsaturated nitrile Species, preferably derived from ⁇ , ⁇ -unsaturated carboxylic acid esters.
  • the reactive receptor can be selected from one or more of the ⁇ , ⁇ -unsaturated carboxylic acid esters represented by the following formula:
  • the film-forming resin composition includes a reactive donor capable of providing two or more nucleophilic carbanions.
  • the nucleophilic carbanion is a reactive intermediate of carbon, which usually has two or three strong electronegative groups attached to it, and carries a pair of lone pairs of electrons.
  • the nucleophilic carbanion of the reactive donor is derived from the acidic proton C-H in the activated methylene or methine group.
  • Suitable examples that can provide the aforementioned acidic protons include, but are not limited to, dialkyl malonate (e.g., dimethyl malonate, diethyl malonate, etc.); cyanoacetate (e.g., methyl cyanoacetate, Ethyl cyanoacetate, etc.); acetoacetate; propionyl acetate; acetylacetone; dipropionylmethane, etc., and mixtures or combinations thereof.
  • the reactive donor is obtained by reacting an acetoacetate or malonate compound with an aromatic compound.
  • the aromatic compound is an aromatic epoxy resin and/or an aromatic polyester. The inventors of the present invention surprisingly found that the reactive donor containing an aromatic ring structure can provide a cured coating with improved hardness.
  • the aromatic epoxy backbone is derived from bisphenol A, bisphenol F, novolac epoxy resin, and mixtures or combinations thereof.
  • Suitable aromatic epoxy resins that can be functionalized to act as reactive donors include, but are not limited to, bisphenol A epoxy resins, bisphenol F epoxy resins, and novolac epoxy resins.
  • the epoxy resin can be functionalized as follows: for example, reaction with diketene, transesterification with alkyl acetoacetate or dialkyl malonate, and malonic acid or monoester or acid malonate. The polyester is esterified.
  • the reactive donor is obtained by transesterifying epoxy resin with alkyl acetoacetate or dialkyl malonate, wherein the malonate or acetoacetate functional group is present in the main In the chain, in the side chain, or both, it is preferably present in the side chain.
  • the aromatic polyester backbone is derived from containing phthalic acid and its anhydride, terephthalic acid and its anhydride, isophthalic acid and its anhydride, or Dicarboxylic acid components in any combination.
  • a suitable aromatic polyester resin that can be functionalized to act as a reactive donor can be obtained by combining an acid component containing an aromatic dibasic or more polycarboxylic acid or anhydride with an Or a variety of dihydric or polyhydric alcohols for esterification.
  • Examples of the aromatic dibasic or more polycarboxylic acid include, but are not limited to, phthalic acid and its anhydride, terephthalic acid and its anhydride, isophthalic acid and its anhydride, trimellitic anhydride or any combination thereof.
  • Examples of the dihydric or polyhydric alcohols include, but are not limited to, trimethylolpropane, pentaerythritol, neopentyl glycol, diethylene glycol, 1,4-butanediol, ethylhexylpropanediol, 2,4-diethyl -1,5-pentanediol, ditrimethylolpropane, dipentaerythritol or any combination thereof.
  • the polyester resin can be functionalized as follows: for example, reaction with diketene, transesterification with alkyl acetoacetate or dialkyl malonate, and malonic acid or monoester or acid malonate.
  • the polyester is esterified.
  • the reactive donor is obtained by transesterifying polyester resin with alkyl acetoacetate or dialkyl malonate, wherein the malonate or acetoacetate functional group is present in the main In the chain, in the side chain, or both, it is preferably present in the side chain.
  • the reactive donor has a relatively high glass transition temperature.
  • the inventors of the present invention have found that increasing the glass transition temperature of the reactive donor is advantageous for increasing the hardness of the cured coating.
  • the reactive donor has a glass transition temperature of 25°C or higher.
  • the glass transition temperature of the reactive donor should not be too high, otherwise it will affect the curing of the coating. Therefore, the reactive donor according to the present invention preferably has a glass transition temperature in the range of 25°C to 40°C.
  • the epoxy equivalent of the reactive donor is preferably within a specific range.
  • the inventors of the present invention have found that the epoxy equivalent of the reactive donor is directly related to the VOC of the coating composition. This may be due to the correlation between the epoxy equivalent and the viscosity of the epoxy resin, and higher epoxy equivalent corresponds to higher The resin viscosity. Therefore, epoxy resins with lower epoxy equivalents can form better films with the assistance of smaller solvents, and therefore emit less VOC content.
  • the epoxy equivalent of the reactive donor is in the range of 400-2300 g/mol, preferably in the range of 470-1200 g/mol, more preferably in the range of 500-900 g/mol.
  • the reactive donor and the reactive acceptor are mixed together to form a part of the film-forming resin composition.
  • the reactive donor is present in an amount of 50-75% by weight, and the reactive acceptor is present in an amount of 15-30% by weight.
  • the film-forming resin composition in addition to the reactive donors and reactive acceptors described herein, also includes resins that do not participate in the Michael addition reaction, including but not limited to polyester resins, Acrylic resin, epoxy resin, polyurethane resin, etc.
  • the film-forming resin composition described herein may include one or more solvents.
  • Suitable solvents may be aqueous solvents, organic solvents or mixtures thereof.
  • suitable organic solvents include, but are not limited to, aliphatic solvents; aromatic and/or alkylated aromatic solvents (such as toluene, xylene, etc.); alcohols (such as isopropanol, n-butanol); esters ( For example, methoxy propyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, etc.); ketones (such as methyl ethyl ketone, methyl n-amyl ketone, etc.); glycol ether; glycol Ether esters, and their mixtures or combinations.
  • the film-forming resin composition of the present invention may optionally further contain other additional additives commonly used in coating compositions, and these additives will not adversely affect the coating composition or the curing obtained therefrom.
  • Appropriate additives include, for example, that can improve the processing or manufacturing properties of the composition, enhance the aesthetics 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, selected from adhesion promoters, curing promoters, open time regulators, pigments and fillers, surfactants, lubricants, defoamers, dispersants, UV absorbers, colorants, coalescing agents, contact agents, etc.
  • the content of each optional ingredient is preferably sufficient to achieve its intended purpose, but does not adversely affect the coating composition or the cured coating obtained therefrom.
  • the coating composition according to the present invention also contains a catalyst for catalyzing the Michael addition crosslinking reaction between the reactive acceptor and the reactive donor.
  • the catalyst comprises a latent base catalyst.
  • the latent base catalyst described herein is a substituted carbonate having a structure represented by formula (II):
  • X + is a non-acidic cation.
  • non-acidic cations alkali metal ions, alkaline earth metal ions, ammonium ions, phosphonium ions, etc. can be used, but are not limited thereto.
  • X + is lithium ion, sodium ion, potassium ion or the like. More preferably, X + is a quaternary ammonium ion or a phosphonium ion;
  • R is H, optionally substituted C1-10 alkyl, C6-12 aryl, C7-C14 aralkyl, C7-C14 alkaryl, or a combination thereof.
  • R is an unsubstituted alkyl group having 1 to 4 carbon atoms. If the R group is substituted, the substituent is selected so as not to substantially interfere with the crosslinking reaction.
  • acidic substituents such as carboxylic acid substituents
  • the latent base catalyst described herein is a compound having the general structure shown in formula (II), wherein the cation X + is connected to the carbonate group of formula (II) in a single molecule, ie
  • the potential base catalyst has the general structure shown in formula (II-1):
  • X + and R are as defined above.
  • the latent base catalyst described herein is a compound of the general structure shown in formula (II), wherein the group R is a polymer, and/or the cation X + is a quaternary ammonium ion or a phosphonium ion.
  • the latent base catalyst described herein is preferably a quaternary alkyl ammonium carbonate. Suitable examples include, but are not limited to, tetrahexylammonium methyl carbonate, tetradecyl-trihexylammonium-methyl carbonate, tetradecylammonium methyl carbonate, tetrabutylammonium methyl carbonate, tetrabutyl Ammonium ethyl carbonate, benzyl trimethyl ammonium methyl carbonate, trihexyl methyl ammonium methyl carbonate or trioctyl methyl ammonium methyl carbonate, and mixtures or combinations thereof.
  • the latent base catalyst described herein includes tetrabutylammonium alkyl carbonate.
  • the amount of latent base catalyst used herein may vary according to the nature of the coating composition.
  • the composition contains about 0.001 to 1 molar equivalent of catalyst per gram of resin solids, more preferably 0.02 to 0.07 molar equivalent of catalyst.
  • Latent catalysts of this type are known in the art.
  • the commercially available form of the potential catalyst described herein is called A-CURE 500 (Allnex, Frankflirt, Germany).
  • the latent base catalyst represented by formula (II) acts by releasing carbon dioxide when the carbonate is decomposed. This produces a strong base, namely hydroxide, alkoxy base or aralkoxy base. In the storage tank, the reaction proceeds slowly, thereby extending the pot life. When the coating composition is applied, the surface area increases, as the carbon dioxide escapes from the surface, the alkali is rapidly regenerated, thereby allowing the coating to cure faster (ie, drying and hardness development). Therefore, the use of the latent base catalyst of formula (II) allows the best pot life, open time and curing performance of the coating composition described herein.
  • the catalyst may also include conventional catalysts (ie, non-latent catalysts) known to those skilled in the art that are different from the aforementioned latent base catalysts, which can be used alone or in combination with the latent base catalysts described herein. Catalysts are used in combination to accelerate the Michael addition reaction.
  • conventional catalysts ie, non-latent catalysts
  • Catalysts are used in combination to accelerate the Michael addition reaction.
  • non-latent catalysts include, but are not limited to, tetrabutylammonium hydroxide, ammonium hydroxide, DBU (8-diazabicyclo[5.4.0]undec-7-ene), DBN (1,5- Diazabicyclo[4.3.0]non-5-ene) and TMG (1,1,3,3-tetramethylguanidine).
  • non-latent catalysts include, but are not limited to, salts of cations and anions paired, including non-acidic cations, such as K + , Na + , Li + ; or weakly acidic cations, such as strong organic bases (DBU, DBN or TMG), the anion is a basic anion X - derived from a compound containing an acidic XH group, where X is N, P, O, S or C, and the anion X -is derived from a reactive Reactive donors for reactions with bodies such as acrylates.
  • non-acidic cations such as K + , Na + , Li +
  • weakly acidic cations such as strong organic bases (DBU, DBN or TMG)
  • the anion is a basic anion X - derived from a compound containing an acidic XH group, where X is N, P, O, S or C, and the anion X -is derived from a reactive Reactive donors for reactions
  • Suitable examples of these salts include, but are not limited to, the salt formed by the reaction of KOH and benzotriazole, the salt formed by the reaction of TBAH and benzotriazole, or the salt formed by the reaction of KOH and 1,2,4-triazole, the content of which is 0.001 -1meq/g solid resin. Mixtures or combinations of the above can be used.
  • the preferred non-latent catalyst is a solution of potassium benzotriazole formed by the reaction of KOH and benzotriazole in ethanol at an equimolar ratio.
  • 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 operating 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 (e.g., 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 100 to about 400 ⁇ m, preferably in the range of 100-200 ⁇ m.
  • the applied coating can be cured by air-drying or by using various drying devices familiar to those skilled in the art (for example, an oven) to accelerate the curing.
  • the coating composition has a VOC content of 420 g/L or lower.
  • the coating composition is coated with a wet coating thickness of 100 microns and dried for 1 day, and the resulting cured coating shows a pendulum hardness of 70 or longer, preferably 80 or longer. It is more preferable to have a pendulum hardness of about 90 or longer.
  • the coating composition is coated with a wet coating thickness of 200 microns and dried for 1 day.
  • the resulting cured coating exhibits a pendulum hardness of about 50 or more, preferably 60 or more.
  • Another aspect of the present invention provides a wood product, which comprises: a wood substrate having at least one major surface; and a cured coating, the cured coating is formed directly or indirectly on the major surface It is formed from the coating composition according to the present invention.
  • 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 structure of 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% by weight, preferably a tannin content of at least 1% by weight, more preferably a tannin content of at least 5% by weight, and even more preferably A tannin content of at least 10% by weight, even more preferably a tannin content of 30% by weight, as measured by CNS4716-2005.
  • wood substrates hardwood, chestnut, oak, red cedar, camellia, cypress, Douglas fir, Japanese cedar, American cypress, Japanese pine, Japanese cypress, water walnut, black walnut, maple
  • wood Japanese beech, Japanese paulownia, birch, Salina, magnolia, ash, teak, oak, catalpa, mountain camphor, cedar, oak, and rubber wood.
  • 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, mercapto, etc.
  • 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 wood product can be prepared by, for example, the following steps: (1) providing a polished wood substrate; (2) using a coating and curing process to sequentially coat the wood substrate and form one or Multiple Michael addition cured coatings of the present invention.
  • the colorant may be coated on the wooden substrate before step (2), so as to provide the wooden 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.
  • Epoxy resin (NanYa, EEW: 622g/mol), t-BAA and n-BA are 212.54, 87.46 and 101.02g, respectively.
  • the detailed synthesis process is the same as Synthesis Example 1 (A1).
  • the solid content is about 70%.
  • Epoxy resin (NanYa, EEW: 722 g/mol), t-BAA and n-BA are 209.36, 90.64 and 102.96 g, respectively.
  • the detailed synthesis process is the same as Synthesis Example 1 (A1).
  • the solid content is about 70%.
  • Example 1 The influence of the functionality of the reactive receptor on the hardness of the coating
  • component A Mix the components of component A in the amounts shown in Table 3 below to form component A, and then mix components A and B in the amounts shown in Table 3 below to form a Michael addition curing coating Layer coating composition.
  • the resulting coating composition was coated on the test substrate with a wet coating thickness of 100 microns or 200 microns, respectively, and cured at room temperature.
  • Using BYK-Gardner GmbH's pendulum hardness tester test the pendulum hardness of the cured coating according to ASTM D-4366. The obtained pendulum hardness is expressed in the number of times, and the difference is adopted according to the GB/T23985-2009 standard Method to determine the VOC of each cured coating. The results are shown in Figure 1.
  • Example 2 The effect of the glass transition temperature of the reactive receptor on the hardness of the coating
  • component A Mix the components of component A in the amounts shown in Table 4 below to form component A, and then mix components A and B in the amounts shown in Table 4 below to form a Michael addition curing coating Layer coating composition.
  • the coating composition 13-16 obtained was coated on the test substrate with a wet coating thickness of 100 microns or 200 microns, respectively, and cured at room temperature.
  • a commercially available 2K polyurethane coating composition was used.
  • BYK-Gardner GmbH's pendulum hardness tester test the pendulum hardness of each cured coating according to ASTM D-4366. The resulting pendulum hardness is expressed in the number of times, and according to the GB/T23985-2009 standard, the difference is Value method, the VOC of each cured coating was measured, and the results are shown in Figure 2.
  • the results shown in Figure 2 indicate that the glass transition temperature of the reactive receptor is also an important parameter affecting the hardness of the cured coating.
  • the bifunctional reactive receptor with a glass transition temperature of 100°C or higher has significantly better coating hardness than the bifunctional reactive receptor with a lower glass transition temperature.
  • a coating composition formulated with a bifunctional reactive receptor with a glass transition temperature of 100°C or higher can form a cured coating with equivalent hardness, while having obvious Lower VOC emissions.

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Abstract

本发明涉及一种涂料组合物以及由其制成的木制品，包含：（A）成膜树脂组合物，包括能够提供两个或更多个亲核碳负离子的反应性供体，和包含两个碳碳双键基团的反应性受体；和（B）用于催化所述反应性供体和所述反应性受体发生迈克尔加成交联反应的催化剂，其中，所述反应性受体和所述反应性供体中的至少一种包含芳环结构，并且所述反应性受体均聚形成的聚合物具有100℃或更高的Tg。

Description

涂料组合物以及由其制成的木制品
相关申请的交叉引用
本申请要求享有于2019年05月07日提交的名称为“木器用涂料组合物以及由其制成的木制品”的中国专利申请201910377437.X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
本发明涉及一种木器用涂料组合物以及由其制成的木制品，更具体地，本发明涉及采用迈克尔加成反应进行固化的木器用涂料组合物以及由其制成的木制品。
背景技术
传统的溶剂型双组分聚氨酯由于其优异的整体性能，包括干燥速度、丰满度、膜硬度、光泽、耐化学性等，已在木器涂料中得到广泛应用。目前，仍然是木材的首选涂料。然而，由于越来越严格的环境法规，涂料应用中的游离二异氰酸酯(例如TDI)和挥发性有机化合物(VOC)控制标准变得越来越严格。尤其，TDI对人体的危害极大，因此没有任何游离TDI的非异氰酸酯(NICN)固化技术在学术和工业领域受到了极大的关注。
迄今为止，在木器涂料中存在几种可行的NICN固化方法，例如聚碳化二亚胺(PCDI)固化、迈克尔加成固化等。由于适用期较短，PCDI在现阶段很难实现商业化。由于具有长适用期，迈克尔加成固化目前已经取得了巨大的成功，商业公司Allnex已对其进行了大量的商业推广，将其称之为“Acure”技术。特别吸引人的是，这种涂层体系具有诸多优点，包括(1)可以在室温下、甚至更低温度下施工；(2)溶剂含量非常低(例如小于250g/L)；(3)活化期很长(例如在23℃下大于8小时)；(3)优异的外观性能(例如在60°下的光泽度大于90，DOI大于90)；(5)能够厚层 涂覆(>150μm)；(6)非常好的耐化学性；(7)优异的柔韧性；(8)良好的户外耐久性；以及(9)不含异氰酸酯、甲醛和有机锡。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。在室温下固化的采用这种Acure固化技术得到的干涂膜的硬度远远低于传统的双组分聚氨酯涂层，无法满足应用需求。
目前，木器涂料工业急需能够达到所需涂膜硬度的迈克尔加成固化涂层体系以取代传统的双组分聚氨酯体系。
发明内容
本发明一方面公开了一种涂料组合物，包含：
(A)成膜树脂组合物，包括能够提供两个或更多个亲核碳负离子的反应性供体，和包含两个碳碳双键基团的反应性受体；和
(B)用于催化所述反应性供体和所述反应性受体发生迈克尔加成交联反应的催化剂，
其中，所述反应性受体和所述反应性供体中的至少一种包含芳环结构，并且，所述反应性受体均聚形成的聚合物具有100℃或更高的Tg，所述Tg例如采用差示扫描量热法测定。
在本发明的一些实施方式中，所述反应性受体可以选自下式所示的α,β-不饱和羧酸酯中的一种或多种：
Figure PCTCN2020088163-appb-000001
Figure PCTCN2020088163-appb-000002
本发明另一方面还提供了一种木制品，其包含木质基材，其具有至少一个主表面；和固化涂层，所述固化涂层是由直接或间接涂覆在所述主表面上的本发明的涂料组合物形成的。
在本发明中，申请人开创性地设计迈克尔加成固化体系中的反应性受体或供体的至少一个包含芳环结构，并且设计采用Tg大于100℃的双官能度(即包含两个碳碳双键基团)反应性受体，如此得到的固化涂层可以获得较之传统双组分聚氨酯涂层可比较的涂层硬度。
本发明的发明人惊讶地发现，在反应性受体或反应性供体的至少一个中引入芳环结构可以显著提高固化涂层的硬度。本发明的发明人更惊讶地发现，采用Tg大于100℃的双官能度反应性受体形成的固化涂层，较之采用其它三官能度、四官能度反应性受体(包括Tg大于100℃的三官能度、四官能度反应性受体)形成的固化涂层具有明显更高的硬度，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式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。
当本文中使用时，术语“迈克尔加成”是指反应性供体中的碳负离子与反应性受体中的碳碳双键发生的亲核加成反应。迈克尔加成反应通常遵循如下反应机理：
Figure PCTCN2020088163-appb-000003
在上述反应性示意图中，B:是催化剂，其与迈克尔加成反应性供体通过脱质子反应，从而形成用于随后与迈克尔加成反应性受体的加成反应的碳负离子。
在本文中使用时，术语“碳碳双键基团”是指分子中含有碳碳双键的结构，但不包括苯环。作为碳碳双键基团的实例包括但不限于，-C＝C-C＝C-、-C＝C-C≡C-、-C＝C-CHO、-C＝C-CO-、-C＝C-C(O)O-、-C＝C-CN。
在本文中使用时，术语“亲核碳负离子”是指连有两个或三个强电负性基团，并且带有一对孤对电子的碳的活性中间体，所述强电负性基团可以包括但不限于-NO 2、-C(＝O)-、-CO 2R 1、-SO 2-、-CHO、-CN和-CONR 2等，其中R 1和R 2各自独立地表示烷基。在本发明的一些实施方式中，所述亲核碳负离子衍生自在活化亚甲基或次甲基中的酸性质子C-H。
当本文中使用时，术语“芳环结构”是指刚性的闭合芳香族环或环体系，其不同于柔性的烷烃或环烷基，例如环己基。所述芳环结构的实例包括但不限于亚苯基、亚萘基、亚联苯基、亚芴基和茚基，以及杂亚芳基(例如闭合的芳香族或芳香类环状烃或环体系，其中环中的一个或多个原子是除碳之外的元素诸如氮、氧、硫等)。
在涉及“反应性受体”使用时，术语“玻璃化转变温度(Tg)”是指所述反应性受体分子均聚形成的均聚物的玻璃化转变温度，其例如是采用差示扫描量热法测定的。
在涉及“反应性供体”使用时，术语“玻璃化转变温度(Tg)”是指所述反应性供体本身的玻璃化转变温度，其例如是采用差示扫描量热法测定的。
在涉及“反应性供体”使用时，术语“环氧当量(EEW)”是指含有1mol环氧基的反应性供体的质量。在反应性供体是乙酰乙酸酯化环氧的情况下，环氧当量是指含有1mol环氧基的乙酰乙酸酯化环氧的质量。通常，环氧当量越低，反应性供体中所包含的环氧基越多，反应活性越高。
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。
在“涂料组合物涂覆在基材的主表面上”的上下文中使用时，术语“在...上”包括该涂料组合物直接地或间接地涂覆在基材的主表面上。在本发明的一些实施方式中，根据本发明的涂料组合物直接涂覆在木质基材的主表面上，而没有粘附性问题。在本发明的一些实施方式中，根据本发明的涂料组合物和木质基材之间可以存在一种或多种粘附促进层，从而获得想要的粘附性。
在本发明中使用时，术语“挥发性有机化合物(VOC)”是指除一氧化碳、二氧化碳、碳酸、金属碳化物或碳酸盐以外，任何会参与大气光化学反应的含碳化合物。通常，挥发性有机化合物具有0.1mm Hg或更高的蒸气压。本文中使用时，“挥发性有机化合物含量(VOC含量)”是指每体积的涂料固体中的VOC重量，例如被报道为g/每升。
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式。然而，在相同或其他情况下，其它实施方式也可能是优选的。另外，一个或多个优选的实施方式的叙述不意味着其他实施方式是不可用的，并且不旨在将其他实施方式排除在本发明范围外。
附图说明
图1示出了各种迈克尔加成固化清漆形成的固化涂层的硬度和VOC比较结果，其中所述涂层厚度为100微米或200微米。所述清漆包括三种不同环氧当量的反应性供体(A1、A2和A3)与Tg为180℃的双官能度反应性受体(B4)配制形成的涂料组合物，以及同样三种反应性供体与Tg分别为62℃、98℃和103℃的三官能度或四官能度反应性受体(B1、B2和B3)配制形成的涂料组合物。
图2示出了包含Tg不同的各种双官能度反应性受体的迈克尔加成固化清漆与常规双组分聚氨酯漆料形成的固化涂层的硬度与VOC比较结果，其中所述涂层厚度为100微米或200微米。所述双官能度反应性受体分别包括Tg为62℃的双官能度反应性受体B7，Tg为104℃的双官能度反应性受体B5，Tg为180℃的双官能度反应性受体B4以及Tg为107℃的双官能度反应性受体B6。
具体实施方式
本发明一方面提供了一种木器用涂料组合物，包含：(A)成膜树脂组合物，包括能够提供两个或更多个亲核碳负离子的反应性供体，和包含两个碳碳双键基团的反应性受体；和(B)用于催化所述反应性供体和所述反应性受体发生迈克尔加成交联反应的催化剂，其中，所述反应性受体和所述反应性供体中的至少一种包含芳环结构，并且，所述反应性受体均聚形成的聚合物具有100℃或更高的Tg。
成膜树脂组合物
术语“成膜树脂组合物”在本文中是指构成由本发明的木器用涂料组合物形成的涂层的主体的树脂组合物，其可以包含能够提供两个或更多个亲核碳负离子的反应性供体、包含碳碳双键基团的反应性受体、溶剂、以及任选的附加添加剂。
根据本发明，所述反应性受体和所述反应性供体中的至少一种包含芳环 结构。如上所述，芳环结构具有刚性结构，其不同于柔性的烷烃或环烷基，例如环己基。本发明的发明人惊讶地发现，含有这种芳环结构的迈克尔加成固化涂层较之具有柔性烷基或环烷基的迈克尔加成固化涂层(例如来自Allnex Acure固化涂层)显示改善的涂层硬度。在本发明的一些实施方式中，所述反应性受体包含芳环结构。在本发明的另一些实施方式中，所述反应性供体包含芳环结构。在本发明的还要另一些实施方式中，所述反应性受体和所述反应性供体二者均包含芳环结构。
根据本发明，成膜树脂组合物包含含有两个碳碳双键基团的反应性受体。一般来说，在涂层的固化交联过程中，反应物的官能度越高，固化涂层的交联密度越高，相应地涂层的硬度也越高。然而，本发明的发明人惊讶地发现，较之含有两个以上碳碳双键基团的反应受体，例如含有三个或含有四个碳碳双键基团的反应性受体，含有两个碳碳双键基团的反应性受体在迈克尔加成固化体系中对于提高固化涂层的硬度更有利的。因此，含有两个以上碳碳双键基团的反应性受体并不包括在本发明的范围内。
根据本发明，反应性受体的玻璃化转变温度也是影响固化涂层的硬度的一个重要参数。在本发明的一些实施方式中，反应性受体具有100℃或更高的玻璃化转变温度，优选具有101℃或更高的玻璃化转变温度，更优选具有102℃或更高的玻璃化转变温度，还要更优选103℃或更高的玻璃化转变温度，但反应性受体的玻璃化转变温度不宜过高。如果反应性受体的玻璃化转变温度过高，可能会不利地影响迈克尔加成固化的交联程度，从而影响所得固化涂层的硬度。通常，反应性受体的玻璃化转变温度不超过200℃，优选不超过195℃，更优选不超过190℃。在本发明的具体实施方式中，反应性受体的玻璃化转变温度在100-190℃的范围内，优选在104-180℃的范围内。
根据本发明的实施方式，所述反应性受体具有相对较低的分子量，通常以非聚合物形式存在。优选地，所述反应性受体具有1000g/mol或更低的摩尔质量，优选具有500g/mol或更低的摩尔质量，更优选具有350g/mol或更低的摩尔质量。
根据本发明的实施方式，所述反应性受体包含的碳碳双键基团通常具有 下式I所示的结构：
C＝C-CX   (式I)
其中，CX表示烯基、炔基、醛基(-CHO)、酮基(-CO-)、酯基(-C(O)O-)和氰基(-CN)中的任意一种。优选地，碳碳双键基团衍生自α,β-不饱和醛、α,β-不饱和酮、α,β-不饱和羧酸酯和α,β-不饱和腈中的一种或多种，优选衍生自α,β-不饱和羧酸酯。
在本发明的一个实施方式中，所述反应性受体可以选自下式所示的α,β-不饱和羧酸酯中的一种或多种：
Figure PCTCN2020088163-appb-000004
根据本发明，成膜树脂组合物包含能够提供两个或更多个亲核碳负离子的反应性供体。如上所述，亲核碳负离子是具有反应性的碳的活性中间体，其通常连有两个或三个强电负性基团，并且带有一对孤对电子。作为强电负性基团的实例，可以选取如下中的一种或多种：-NO 2、-C(＝O)-、-CO 2R 1、-SO 2-、-CHO、-CN和-CONR 2等，其中R 1和R 2各自独立地选自烷基。
根据本发明的实施方式，反应性供体的亲核碳负离子衍生自在活化亚甲基或次甲基中的酸性质子C-H。可提供上述酸性质子的合适实例包括但不限于丙二酸二烷基酯(例如丙二酸二甲酯、丙二酸二乙酯等)；氰基乙酸酯(例如氰基乙酸甲酯、氰基乙酸乙酯等)；乙酰乙酸酯；乙酸丙酰酯；乙酰丙酮；二丙酰甲烷等，以及它们的混合物或组合。
根据本发明的一些实施方式，所述反应性供体是由乙酰乙酸酯类或丙二酸酯类化合物与芳香族化合物反应得到的。优选地，所述芳香族化合物为芳香族环氧树脂和/或芳族聚酯。本发明的发明人惊讶地发现，所述反应性供体包含芳环结构可以提供具有改善硬度的固化涂层。
在反应性供体具有芳族环氧主链的实施方式中，所述芳族环氧骨架衍生自双酚A、双酚F、酚醛环氧树脂及其混合物或组合。可被官能化以充当反应性供体的合适的芳族环氧树脂包括但不限于双酚A环氧树脂、双酚F环氧树脂和酚醛清漆环氧树脂。该环氧树脂可通过如下进行官能化：例如与双烯酮进行反应，与乙酰乙酸烷基酯或丙二酸二烷基酯进行酯交换，与丙二酸或单酯或酸性丙二酸酯化聚酯进行酯化。在优选的实施方式中，反应性供体是通过环氧树脂与乙酰乙酸烷基酯或丙二酸二烷基酯进行酯交换得到的，其中丙二酸酯或乙酰乙酸酯官能团存在于主链中、侧链中或二者中，优选存在于侧链中。
在反应性供体具有芳族聚酯主链的实施方式中，芳族聚酯主链衍生自包含邻苯二甲酸及其酸酐、对苯二甲酸及其酸酐、间苯二甲酸及其酸酐或其任意组合的二元羧酸组分。作为一个示例性说明，可被官能化以充当反应性供体的合适的芳族聚酯树脂可通过如下得到：使含有芳族二元或更多元羧酸或酸酐的酸组分与一种或多种二元或多元醇进行酯化。所述芳族二元或更多元羧酸的实例包括但不限于邻苯二甲酸及其酸酐、对苯二甲酸及其酸酐、间苯二甲酸及其酸酐、偏苯三酸酐或其任意组合。所述二元或多元醇的实例包括但不限于三羟甲基丙烷、季戊四醇、新戊二醇、二甘醇、1,4-丁二醇、乙基己基丙二醇、2,4-二乙基-1,5-戊二醇、双三羟甲基丙烷、二季戊四醇或其任意组合。该聚酯树脂可通过如下进行官能化：例如与双烯酮进行反应，与乙酰乙酸烷基酯或丙二酸二烷基酯进行酯交换，与丙二酸或单酯或酸性丙二酸酯化聚酯进行酯化。在优选的实施方式中，反应性供体是通过聚酯树脂与乙酰乙酸烷基酯或丙二酸二烷基酯进行酯交换得到的，其中丙二酸酯或乙酰乙酸酯官能团存在于主链中、侧链中或二者中，优选存在于侧链中。
根据本发明的实施方式，所述反应性供体具有相对较高的玻璃化转变温度。本发明的发明人发现，提高反应性供体的玻璃化转变温度对于提高固 化涂层的硬度是有利的。在本发明的一个实施方式中，所述反应性供体具有25℃或更高的玻璃化转变温度。但是考虑到实际应用，反应性供体的玻璃化转变温度不宜过高，否则会影响涂料的固化。因此，根据本发明的反应性供体优选具有在25℃至40℃范围内的玻璃化转变温度。
根据本发明的实施方式，在所述反应性供体衍生自芳族环氧树脂的情况下，反应性供体的环氧当量优选在特定的范围内。本发明的发明人发现，该反应性供体的环氧当量与涂料组合物的VOC直接相关，这可能是由于环氧当量与环氧树脂的粘度相关，较高的环氧当量对应于较高的树脂粘度。因此，具有较低环氧当量的环氧树脂可以在较小溶剂的协助下较好地成膜，因此排放的VOC含量较少。根据本发明的实施方式，所述反应性供体的环氧当量在400-2300g/mol的范围内，优选在470-1200g/mol的范围内，更优选在500-900g/mol的范围内。
在本发明的实施方式中，将反应性供体和反应性受体混合在一起以构成成膜树脂组合物的一部分。优选地，基于所述成膜树脂组合物的总重，所述反应性供体以50-75重量％的量存在，并且所述反应性受体以15-30重量％的量存在。
在本发明的实施方式中，除了本文所述的反应性供体和反应性受体以外，所述成膜树脂组合物还包括不参与迈克尔加成反应的树脂，包括但不限于聚酯树脂、丙烯酸类树脂、环氧树脂、聚氨酯树脂等。
在本发明的实施方式中，本文所述的成膜树脂组合物可包含一种或多种溶剂。合适的溶剂可以是水性溶剂、有机溶剂或其混合物。合适的有机溶剂的实例包括但不限于脂族溶剂；芳族和/或烷基化芳族溶剂(例如甲苯、二甲苯等)；醇类(例如异丙醇、正丁醇)；酯类(例如甲氧基乙酸丙酯、乙酸乙酯、乙酸丁酯、乙酸异丁酯等)；酮类(例如甲基乙基甲酮、甲基正戊基甲酮等)；二醇醚；二醇醚酯类，以及它们的混合物或组合。
在本发明的实施方式，本发明的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粘附促进剂、固化促进剂、开放时间调节剂、颜填料、表面活性剂、润滑剂、消泡剂、分散剂、UV吸收剂、着色剂、聚结剂、触变剂、抗氧化剂、稳定剂、防腐剂和杀菌剂中的一种或多种，从而根据需要提供所需的膜性能。每种任选成分的含量优选足以达到其预期的目的，但不会对涂料组合物或由其得到的固化涂层产生不利的影响。
涂料组合物
除了上述成膜树脂组合物以外，根据本发明的涂料组合物还包含用于催化所述反应性受体和所述反应性供体发生迈克尔加成交联反应的催化剂。
在本发明某些实施例中，所述催化剂包含潜在碱催化剂。
在本发明的一个实施方式中，本文所述的潜在碱催化剂是具有式(II)所示结构的取代碳酸盐：
Figure PCTCN2020088163-appb-000005
在式(II)中：
X +是非酸性阳离子。作为非酸性阳离子的实例，可以使用碱金属离子、碱土金属离子、铵离子、鏻离子等，但不限于此。优选地，X +是锂离子、钠离子或钾离子等。更优选地，X +是季铵离子或鏻离子；
R是H、可选被取代的C1-10烷基、C6-12芳基、C7-C14芳烷基、C7-C14烷芳基或其组合。优选地，R是具有1-4个碳原子的未取代的烷基。如果R基团被取代，则选择取代基以便基本上不干扰交联反应。为了避免干扰碱催化剂的作用，酸性取代基(例如羧酸取代基)仅以非实质量存在或者完全不存在。
在一个实施方式中，本文所述的潜在碱催化剂是具有式(II)中所示的通式结构的化合物，其中阳离子X +在单个分子中与式(II)的碳酸酯基团连接，即潜在碱催化剂具有式(II-1)所示的通式结构：
Figure PCTCN2020088163-appb-000006
其中，X +和R如上定义。
在另一个实施方式中，本文所述的潜在碱催化剂是式(II)中所示通式结构的化合物，其中基团R是聚合物，和/或阳离子X +是季铵离子或鏻离子。
在一个优选的实施方式中，本文所述的潜在碱催化剂优选是季烷基铵碳酸酯。合适的实例包括但不限于四己基铵甲基碳酸酯、十四烷基-三己基铵-甲基碳酸酯、四癸基铵甲基碳酸酯、四丁基铵甲基碳酸酯、四丁基铵乙基碳酸酯、苄基三甲基铵甲基碳酸酯、三己基甲基铵甲基碳酸酯或三辛基甲基铵甲基碳酸酯，以及它们的混合物或组合它们。优选地，本文所述的潜在碱催化剂包括四丁基铵烷基碳酸酯。
在一个实施方式中，本文使用的潜在碱催化剂的量可以根据涂料组合物的性质而变化。优选地，该组合物包含每克树脂固体约0.001至1摩尔当量的催化剂，更优选0.02至0.07摩尔当量的催化剂。这种类型的潜催化剂在本领域中是已知的。例如，本文所述的可商购形式的潜在催化剂被称为A-CURE 500(Allnex，Frankflirt，Germany)。
不受理论的限制，式(II)所示的潜在碱催化剂在碳酸盐分解时通过释放二氧化碳起作用。这产生了强碱，即氢氧化物、烷氧基碱或芳烷氧基碱。在储存罐中，反应缓慢进行，从而延长了适用期。当涂料组合物被涂覆后，表面积增加时，随着二氧化碳从表面逸出，碱迅速再生，从而允许涂层更快地固化(即干燥和硬度发展)。因此，使用式(II)的潜在碱催化剂允许本文所述的涂料组合物的最佳适用期、开放时间和固化性能。
在本发明另一些实施例中，所述催化剂还可以包含本领域技术人员已知的不同于上述潜在碱催化剂的常规催化剂(即非潜在催化剂)，其可以单 独使用或与本文所述的潜在碱催化剂组合使用以加速迈克尔加成反应。
合适的非潜催化剂的实例包括但不限于氢氧化四丁基铵、氢氧化铵、DBU(8-二氮杂双环[5.4.0]十一碳-7-烯)、DBN(1,5-二氮杂双环[4.3.0]壬-5-烯)和TMG(1,1,3,3-四甲基胍)。
非潜在催化剂的合适的其它实例包括但不限于如下阳离子和阴离子配对的盐，所述阳离子包括非酸性阳离子，例如K +、Na +、Li +；或弱酸性阳离子，例如强有机碱(DBU、DBN或TMG)的质子化物质，所述阴离子是来自含有酸性XH基团的化合物的碱性阴离子X -，其中X为N、P、O、S或C，阴离子X -来自能够与反应性受体(例如丙烯酸酯)反应的反应性供体。这些盐的合适实例包括但不限于KOH和苯并三唑反应形成的盐、TBAH和苯并三唑反应形成的盐或KOH和1,2,4-三唑反应形成的盐，其含量为0.001-1meq/g固体树脂。可以使用上述的混合物或组合。优选的非潜催化剂是由KOH和苯并三唑在乙醇中以等摩尔比反应形成的苯并三唑化钾的溶液。|
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100至约400μm的范围内，优选在100-200μm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。
在本发明的一些实施方式中，所述涂料组合物具有420g/L或更低的VOC含量。
在本发明的一些实施方式中，将所述涂料组合物以100微米的湿涂厚度进行涂覆并且干燥1天，所得固化涂层显示70或更长的摆杆硬度，优选具有80或更长的摆杆硬度，更优选具有约90或更长的摆杆硬度。
在本发明的一些实施方式中，将所述涂料组合物以200微米的湿涂厚度进行涂覆并且干燥1天，所得固化涂层显示约50或更长的摆杆硬度，优选具有60或更长的摆杆硬度，更优选具有70或更长的摆杆硬度。
本申请中的“摆杆硬度”是根据ASTM D-4366测试得到，以计次数表示。
木制品
本发明的另一方面提供了一种木制品，其包含：木质基材，其具有至少一个主表面；和固化涂层，所述固化涂层是由直接或间接形成在所述主表面上的由根据本发明的涂料组合物形成的。
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30wt％的单宁含量，所述单宁含量是通过CNS4716-2005测定的。作为示例性的木质基材，可以使用坚木、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羟基、氨基、巯基等极性基团，结果当将本发明的含有官能化硅烷的组合物涂覆到其上时，连接到官能化硅烷的硅原子上的烷氧基或羟基可以与木质基材表面的羟基基团发生键合反应，从而形成粘附促进层。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。
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)利用涂覆和固化工艺，在所述木质基材上依次涂覆并形成一个或多个本发明的迈克尔加成固化涂层。可选地，可以在步骤(2)之前将着色剂涂覆在木质基材上，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。
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
反应性供体
合成例1：乙酰乙酸酯环氧树脂(A1)
在室温下，将220.30g环氧树脂(NanYa，EEW：471g/mol)和79.70g t-BAA装入安装有温度计、顶部搅拌器、气体入口和蒸馏装置的四颈烧瓶中。通过气体入口供应N 2气体来提供N 2保护。然后，将反应混合物缓慢加热至约130℃，收集馏出物(叔丁醇)并保持在该温度直至蒸馏温度不超过78℃。在此条件下(蒸馏温度<＝78℃)，将混合物温度升至160℃。当混合物温度达到160℃时，保持直至蒸馏温度低于60℃。然后将混合物冷却至100℃以下，然后与乙酸正丁酯(n-BA)混合。固体含量约为70％。
合成例2：乙酰乙酸酯环氧树脂(A2)
环氧树脂(NanYa，EEW：622g/mol)、t-BAA和n-BA分别为212.54,87.46和101.02g。详细的合成过程与合成例1(A1)相同。固体含量约为70％。
合成例3：乙酰乙酸酯环氧树脂(A3)
环氧树脂(NanYa，EEW：722g/mol)、t-BAA和n-BA分别为209.36,90.64和102.96g。详细的合成过程与合成例1(A1)相同。固体含量约为70％。
将上述合成例1-3得到的树脂作为反应性供体，对其进行表征。表征结果汇总在下表1中。
表1：各种反应性供体的性质
Figure PCTCN2020088163-appb-000007
反应性受体
下表2列举了商购反应性受体B1-B7的结构式和它们各自的Tg。
表2：各种反应性受体及其玻璃化转变温度
Figure PCTCN2020088163-appb-000008
Figure PCTCN2020088163-appb-000009
涂料组合物
示例1：反应性受体的官能度对涂层硬度的影响
将下表3所示用量的组分A的各成分混合，从而形成组分A，然后将组分A、组分B以下表3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涂料组合物。
将所得涂料组合物分别以100微米或200微米的湿涂厚度涂覆到测试基板上，并且在室温下进行固化。采用BYK-Gardner GmbH公司的摆杆硬度仪，根据ASTM D-4366，测试固化涂层的摆杆硬度，所得摆杆硬度是以计次数表示的，并且根据GB/T23985-2009标准，采用差值法，测定各固化涂层的VOC，结果如图1所示。
图1所示结果表明了，较之含有两个以上碳碳双键基团的反应受体，例如含有三个碳碳双键基团的反应性受体或含有四个碳碳双键基团的反应性受体，含有两个碳碳双键基团的反应性受体在迈克尔加成固化体系中对于提高固化涂层的硬度更有利的。
Figure PCTCN2020088163-appb-000010
示例2：反应性受体的玻璃化转变温度对涂层硬度的影响
将下表4所示用量的组分A的各成分混合，从而形成组分A，然后将组分A、组分B以下表4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涂料组合物。
表4：涂料组合物13-16的组成
Figure PCTCN2020088163-appb-000011
将所得涂料组合物13-16分别以100微米或200微米的湿涂厚度涂覆到测试基板上，并且在室温下进行固化。作为对比例，采用商购的2K聚氨酯涂料组合物。采用BYK-Gardner GmbH公司的摆杆硬度仪，根据ASTM D-4366，测试各固化涂层的摆杆硬度，所得摆杆硬度是以计次数表示的，并且根据GB/T23985-2009标准，采用差值法，测定各固化涂层的VOC，结果如图2所示。
图2所示结果表明了，反应性受体的玻璃化转变温度也是影响固化涂层的硬度的一个重要参数。玻璃化转变温度为100℃或更高的双官能度反应性受体，较之玻璃化转变温度较低的双官能度反应性受体，具有明显更优的涂层硬度。而且，较之传统的双组分聚氨酯涂料组合物，采用玻璃化转变温度为100℃或更高的双官能反应性受体配制形成的涂料组合物可以形成硬度相当的固化涂层，同时具有明显更低的VOC排放量。
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. 一种涂料组合物，包含：
    (A)成膜树脂组合物，包括能够提供两个或更多个亲核碳负离子的反应性供体，和包含两个碳碳双键基团的反应性受体；和
    (B)用于催化所述反应性供体和所述反应性受体发生迈克尔加成交联反应的催化剂，
    其中，所述反应性受体和所述反应性供体中的至少一种包含芳环结构，并且
    所述反应性受体均聚形成的聚合物具有100℃或更高的Tg。
  2. 如权利要求1所述的涂料组合物，其中，所述反应性受体具有1000g/mol或更低的摩尔质量，优选具有500g/mol或更低的摩尔质量，更优选具有350g/mol或更低的摩尔质量。
  3. 如权利要求1或2所述的涂料组合物，其中，所述碳碳双键基团具有下式I所示的结构：
    C＝C-CX (式I)
    其中，CX表示醛基(-CHO)、酮基(-CO-)、酯基(-C(O)O-)和氰基(-CN)中的任意一种。
  4. 如权利要求1至3中任意一项所述的涂料组合物，其中，所述反应性受体选自下式所示的α,β-不饱和羧酸酯中的一种或多种：
    Figure PCTCN2020088163-appb-100001
    Figure PCTCN2020088163-appb-100002
  5. 如权利要求1至4中任意一项所述的涂料组合物，其中，所述反应性供体包含两个或更多个在活化亚甲基或次甲基中的酸性质子C-H。
  6. 如权利要求1至5中任意一项所述的涂料组合物，其中，所述反应性供体是由乙酰乙酸酯类或丙二酸酯类化合物与芳香族化合物反应得到的。
  7. 如权利要求6所述的涂料组合物，其中，所述芳香族化合物为芳香族环氧树脂和/或芳族聚酯。
  8. 如权利要求6或7所述的涂料组合物，其中，所述芳香族化合物为芳香族环氧树脂，所述反应性供体的环氧当量在400-2300g/mol的范围内，优选在470-1200g/mol的范围内，更优选在500-900g/mol的范围内。
  9. 如权利要求1至8中任意一项所述的涂料组合物，其还包含一种或多种溶剂，所述溶剂选自异丙醇、乙酸乙酯和乙酸丁酯中的一种或多种。
  10. 如权利要求1至9中任意一项所述的涂料组合物，其具有420g/L或更低的VOC含量。
  11. 如权利要求1至10中任意一项所述的涂料组合物，其中，将所述涂料组合物以100微米的湿涂厚度进行涂覆并且干燥1天，所得固化涂层显示70或更长的摆杆硬度，优选具有80或更长的摆杆硬度，更优选具有约90或更长的摆杆硬度。
  12. 如权利要求1至11中任意一项所述的涂料组合物，其中，将所述涂料组合物以200微米的湿涂厚度进行涂覆并且干燥1天，所得固化涂层显示约50或更长的摆杆硬度，优选具有60或更长的摆杆硬度，更优选具 有70或更长的摆杆硬度。
  13. 一种木制品，其包含
    木质基材，其具有至少一个主表面；和
    固化涂层，所述固化涂层是由直接或间接涂覆在所述主表面上的权利要求1至12中任意一项所述的涂料组合物形成的。
  14. 如权利要求13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、橡木、橡胶木中的一种或多种。
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